AU779924B2

AU779924B2 - Novel color former and recording material

Info

Publication number: AU779924B2
Application number: AU36029/01A
Authority: AU
Inventors: Tetsurou Iwaya; Kazuo Kabashima; Hiroshi Kobayashi
Original assignee: Asahi Kasei Corp; Asahi Chemical Industry Co Ltd
Current assignee: Chemipro Kasei Kaisha Ltd
Priority date: 2000-03-02
Filing date: 2001-03-01
Publication date: 2005-02-17
Anticipated expiration: 2021-03-01
Also published as: WO2001066515A1; CA2399054A1; CN1303064C; AU3602901A; KR20030007444A; CN1496346A; KR100549037B1

Description

NOVEL COLOR-PRODUCING COMPOSITION AND RECORDING MATERIAL TECHNICAL FIELD The present invention relates to a novel urea-urethane compound. The present invention relates also to a novel color-producing composition obtained by using the urea-urethane compound, and to a recording material obtained by using the color-producing composition.

The color-producing composition of the present invention is useful as a color-producing composition for recording materials which use a recording energy such as heat, pressure or the like, and the present invention relates to, in particular, a color-producing composition capable of giving an improved storage stability to an uncolored portion (an original recording material surface) and a developed color image, and a recording material, in particular, a heat-sensitive recording material, which is obtained by using the color-producing composition.

BACKGROUND ART S 15 Various chemical color-producing systems which use a recording energy such as heat, pressure or the like have been known. Of these systems, colore• **o o• go• co** ooe ooo producing systems usually composed of a two-component color-producing system consisting of a colorless or light-colored dye precursor and a developer capable of causing color development on contact with the dye precursor have been known since early times and are commonly utilized in recording materials. There are, for example, pressure-sensitive recording materials which record using pressure, heat-sensitive recording materials which record using heat, and light-sensitive recording materials which record using light.

Pressure-sensitive recording materials have been generally used in the planar forms, similar to paper. In general, the pressure-sensitive recording material is obtained by dissolving a dye precursor in a suitable solvent, emulsifying the resulting solution to several microns, and forming the emulsion into microcapsules. A first layer (also referre to herein as upper paper) of paper obtained by coating a substrate with the microcapsules and a second layer (also referred to herein as under paper) of paper obtained by coating another substrate with a developer layer containing a developer are placed one upon the other so that the microcapsule-coated surface and the developercoated surface face each other. When a pressure is applied to the resulting assembly by writing, striking or the like, the microcapsules are destroyed to release the contents including the dye precursor. The dye precursor transfers to the developer layer to come into 0@ 3 contact with the developer, so that color development reaction occurs, resulting in recording of an image.

In recent years, a heat-sensitive recording method comprising recording by means of heat energy has been often adopted in various information machines such as facsimiles, printers, recorders and the like. A heat-sensitive recording material used in the heatsensitive recording method has many excellent characteristics such as a high whiteness, appearance and feel which are similar to those of ordinary planar paper, and an excellent aptitude for recording, for example, a high color development sensitivity. The heat-sensitive recording method is advantageous, for example, in that an apparatus used in the method is small, requires no maintenance and produces no noise.

Therefore, the range of use of the heat-sensitive recording method has been increased in various fields of, for instance, recorders for measurement, facsimiles, printers, terminals of computer, labels, and automatic vending machines for railroad tickets or the like.

In the heat-sensitive recording method, a recording material obtained by forming on a substrate a color-producing layer containing a two-component colorproducing composition is mainly used, and the components of the heat-sensitive composition are brought into contact with each other by treating the recording material with heat supplied as the recording 0@ 4 energy from a thermal head, a hot stamp, laser beams or the like, whereby color development and recording are carried out. Many compositions used as the colorproducing composition are those obtained by using a colorless or light-colored, electron-donating dye precursor (in particular, a leuco dye) and an acidic developer such as a phenolic compound. An example of a recording material obtained by using a dye precursor is thermal paper obtained by using a combination of Crystal Violet lactone and 4,4'-isopropylidenediphenol (bisphenol A) as a heat-sensitive color-producing composition (see U.S. Patent 3539375, etc.).

As the dye precursor and developer used in each of the recording methods described above, an electron-donating compound and an electron-accepting compound, respectively, are mainly used. This is because the electron-donating compound and the electron-accepting compound have, for example, the following excellent characteristics: the dye precursor as electron-donating compound and the developer as electron-accepting compound come into contact with each other to give a nearly instantaneous developed color image with a high density; and a nearly white appearance can be obtained and various hues such as red, orange, yellow, green, blue, black, etc. can be obtained. However, the developed color image obtained is so poor in chemical resistance that the record disappears easily on contact with a plasticizer 0O contained in a plastic sheet or an eraser, or a chemical contained in food or cosmetics. Also the developed color image is so poor in record storage stability that the record fades or, worse yet, disappears when exposed to sunlight for a relatively short period of time. Therefore, color-producing compositions comprising the dye precursor and the developer are limited in their use to a considerable extent, and their improvement is eagerly desired.

In recent years, phenolic compounds represented by bisphenol A are considered unsuitable for use because they are likely to be endocrine disrupters, and hence a non-phenolic developer is preferred.

For fulfilling such a request, for example, JP-A-59-115887 and U.S. Patent 4521793 disclose recording materials comprising a combination of colorproducing compositions comprising an aromatic isocyanate compound and an imino compound, as recording materials having a high shelf stability. These references disclose various recording materials in which the two color-producing compositions are brought into contact with each other to be reacted, by application of recording energy such as heat, pressure, light or the like. The references describe the fact that various colors such as red, orange, yellow, light brown, dark brown, etc. can be developed by properly selecting the color-producing compositions. However, 0@ 6 in the inventions disclosed in the references, the development of a black color is not yet sufficient and is eagerly desired in the case of recording materials commonly used at present.

JP-A-8-2111 and JP-A-8-2112 disclose heatsensitive recording materials having a color-producing layer containing a colorless or light-colored dye precursor and a urea compound, as heat-sensitive recording materials obtained by using a non-phenolic developer. These recording materials, however, give a low coloring density and have an insufficient shelf stability.

JP-A-5-116459 discloses a heat-sensitive recording material having a heat-sensitive colorproducing layer containing a colorless or light-colored dye precursor and a sulfonylurea compound. This recording material, however, gives a low whiteness and has an insufficient shelf stability.

DISCLOSURE OF THE INVENTION The present invention is intended to provide a novel urea-urethane compound or urea-urethane composition that exhibits excellent performance characteristics when used as developer in a colorproducing composition.

The present invention is also intended to provide a novel color-producing composition excellent in image preservability and coloring density, and a recording material, in particular, a heat-sensitive recording material, which is obtained by the use of the color-producing composition, by using any of various urea-urethane compounds or urea-urethane compositions.

In addition, the present invention relates to a novel color-producing composition possessing further improved performance characteristics by virtue of the addition of various additives to a urea-urethane compound or a urea-urethane composition and a dye precursor, and a recording material obtained by using said color-producing composition.

The present inventors earnestly investigated the synthesis of various compounds for color-producing composition and consequently found that specific compounds exhibit surprisingly excellent performance characteristics, whereby the present invention has been accomplished. Furthermore, the present inventors found that specific compounds exhibit surprisingly excellent performance characteristics in combination with a specific dye precursor, 15 whereby the present invention has been accomplished.

In one aspect, the invention provides a urea-urethane compound S.. represented by the following formulae to oo

H

3 C (s-1 o 0 N N N"C H H H H0 I 0 C2Hs _C 7a 0 n-C 3 H7>, 0 -Cl N

H

3

C

0 1x i-C 3

H

7 .1C"N' 0~3 n-C 4

H

9 0

H

7b 0 0 i- C 4 H 9g 0 1 N l l N H H H 0 0

S-C

4

H

9 0 1 I llN a l~ H H H 3 C N

N

H H H

H

3 C 11 I 9 n-C 6 Hl 3 N- lcl.. ,lN *0 N N N' H H

H

3

C

01 1 *n-CIoH21N 0.cl c 0 N N NC .H H H

H

3

C

0 0 11 n-ClaH3 7 -N

I

0 N a N N"' H H H

H

3

C

(S-12) 09 C-0 CN N'

H

2 H H H (S-13) 0 0OH 3 o II 1 H 3 C 0

H

3 0 "fK2 <CH 3 0 N NN N N 01 H H H H H H (Or-S) (61-S)

S

S. S S S 5*

S

S S S S S. S S S 555 (8T-S)

H

0H'-L" o N 0 6 HV'O-u

(LT-S)

H

0 (9T-S)

(ST-S)

(r'T-S) (S-21)

OH

3 H C I I M2 (S-22) H 1 H SH 0H H H (S-1 03)3)

KICHTOC

2

H

4 O0 NCI (N Vr N~Z JONN)L-C2HO0nIIA H YHH H H (S-23) H OH (S-24) COH3> 11 j3C oA Ha I1 )JC H H HC (S-27)

CH

3

H

3

O<

H

3 -O Ncx N lk N K H HA (S-28) ~IIINXN CI3~ H 2 H H HH 3 3C Hoa2 H2

H

(S-29) CH3 H 3 C 4 o, NC-C- N N N I H 2 H H H H 2 H H H 3 H 3

C

(S3)0 0 0~NJIh~ o CH II C- N O-C- ICoN N H H HI H (S-31) C:H H 3 CH H 3 2 0 H 3

C

(S-32) H 0 HC C-N N NJO

H

H I H2C- H H3CH SHC O C Da

INJ

0 H

H

H N NJ:) Wf (S-33) CH 3 C-N ,l N

H

2 0 HH 3

H

C

2

H

5 O-0-C-N I H 2

H

2 C-0 OJ H 3 H H H H (S-34) H 11N~ N NJ: 4 13

HHH

99 (S-36)00 99 9 H 3 3 0* :101C-N N CN' HH H 9

OH

3 (S-38) 0 j0 :H 0 lN N l l N' C H H H (S-39) (S-41) (S-42) 0 11 i-C 4

H

9 0 llc

H

0 11 s-C 4

H

9 0 -ClN

H

sea 0.00 r* s *4S* (S-43) (S-44) 0 n-CloH21N. 0 1CN

H

0 n-Cl8H37-,, 0 cN' (S-46) (S-47) (S-48)

:H

3 N0 H

,H

(S-49) 0 n-C 3

H

7 0 A 0 N k0

ACH

H

(S-51) 0 0 e 0e 00 4 0 0 To 6.

*go*

SS

(S-52)

H

3 1 0 n-C 4

H

9 0K

-A

(S-53)

H

3 0 i-0 4

H

9 0 (S-54)

S-C

4

H

9 0 00h (S-56)

H

2 I (S-57) (S-58) (S-59) 0 HA CH3 0 H3+-C13H O- -v D, v J v C FC N 19, C3H7- CH3 H y H 2 0

H

3

N'

(S-61) (S-62) (S-63) o, H 3 C~ op H

H

2

H

2 O kl 'I NAo- -C I I H. H (S-64) cL~ (S-66) (S-67) (S-68) 7k (S-69) f ICH 9H N- -c-C-o-c-N N H H H 3

CH

3 2I II 14,9' 7 H2_ 0 :N N.

H

In another aspect, the invention provides a color-producing composition comprising a urea-urethane compound, wherein the melting point of the ureaurethane compound is not higher than 5000C and not lower than 400C, and the 5 urea-urethane compound is at least one selected from the group consisting of the following general formulas (III), (VI) and (VII): e':0 0 II II X-O-C-N-Y0-N-C-N-Z (I) H H H wherein X and Z are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each of the S. 10 residues may have one or more substituents, and Yo is a group selected from the group consisting of tolylene group, xylylene group, naphthylene group, hexamethylene group and -4)-CH 2 group wherein is a phenylene group; 0 0 0 II II II X-O-C-N-Y-N-C-N-Y--N-C-O-X (I H H H H wherein X and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, and each of the residues may have one or more substituents; 0 0 II II a (III) H H H n wherein X and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, a is a residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents; 0 oo C-1N-

(IV)

S" H H H S+n

II

I( 10 wherein Z and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, 13 is a residue having a valence of 2 or more, n is an integer of 2 or more, and each of the a residues may have one or more substituents; a a 15 a

I

-rY- 4 (v) K Y-0 Ky'H HO wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue though the substituent may be a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom, each of the residues may have one or more substituents, y is a group selected from the group consisting of -SO 2

-(CH

2 -CONH- and any of groups represented by the formulas

OH

3

OH

3 0- (a) Q-0-

-I

or is absent, and n is 1 or 2; 6H

(VI)

wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue though the substituent may be a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, each of the residues may have one or more substituents, 8 is a group selected from the group consisting of -SO 2

-(CH

2 -CONH-,

CH(COOR

1

-C(CF

3 2 and -CR 2

R

3 or is absent, each of R 1

R

2 and R 3 is an alkyl group, and n is 1 or 2; O O II H H II H X-O-C-N-Y-N-C-N-Z

(VII)

wherein X, Y and Z are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each of the 15 residues may have one or more substituents, and each of X, Y and Z is preferably an aromatic compound residue or a heterocyclic compound residue.

In another aspect, the invention provides a color-producing composition which comprises a urea-urethane composition obtained by reacting an amino compound with a polyisocyanate adduct obtained by the reaction of a 20 polyisocyanate compound with a hydroxy compound, so that the equivalent ratio of isocyanate group to amino group becomes 2/1 to 1/100, to form one or more urea groups, and then removing the unreacted amino compound.

In another aspect, the invention provides A color-producing composition which comprises a urea-urethane composition obtained by reacting a hydroxy compound with a polyisocyanate adduct obtained by the reaction of a polyisocyanate compound with an amino compound, so that the equivalent ratio of isocyanate group to hydroxyl group becomes 2/1 to 1/100, to form one or more urethane groups, and then removing the unreacted hydroxy compound.

The following describes other various aspects of the invention. The first of them is directed to a urea-urethane compound characterized by being represented by the following formula and having a molecular weight of 5,000 or less: O O II II R-0 N-AI-N N-A 2 H H H wherein R is an aliphatic compound residue, A, and A 2 are independently an aromatic compound residue, the nitrogen atoms of the urea group are directly bonded to the carbon atoms, respectively, of the aromatic rings of AI and A 2 and R, A, and A 2 may have one or more substituents.

A second aspect of the invention is directed to a urea-urethane compound characterized by being represented by the following formula O 0 II II /C C (d) fT I R-O N -N N- H LH H wherein R is an aliphatic compound residue, hydrogen atom(s) of each benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, and R may have one or more substituents.

A third aspect of the invention is directed to a urea-urethane compound characterized by being represented by the following formula or having at least one urethane group and at least one urea group in a total number of not more than 10 and not less than 3, and having a molecular weight of 5,000 or less: (e) R- N-Y-N N--ai H H H n wherein R is an aliphatic compound residue, Y is an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, c is an aromatic, heterocyclic or aliphatic compound residue which is different from Y and has a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents; or N-Y-N N--Z 1 H H H n wherein Zi and Y are independently an aromatic compound residue or a heterocyclic compound residue, P0 is an aliphatic compound residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents.

A fourth aspect of the invention is directed to a urea-urethane compound characterized by being represented by the following formula or r ?1 C C\ (g) 1- N--oN N- HH H n wherein hydrogen atom(s) of each benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, P, is an aliphatic compound residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents; or 0 0 0 0 R -C/Y1 N ANNF 4J \O (h) H HH KK H H H wherein Rs are independently an aliphatic compound residue, hydrogen atom(s) of each benzene ring may be replaced by an aromatic compound residue, an aliphatic 11 compound residue or a heterocyclic compound residue, each of the residues may have one or more substituents, Yi is a group selected from the group consisting of

-SO

2

-(CH

2 -CONH-, -NH-, -CH(COOR) -C(CF 3 2

-CR

2

R

3 and any of groups represented by the formulas

CH

3 -I I -I

CH

3

CH

3

CH

3 Q C0 (a)

CH

3

CH

3 OO -oQ 00- 0 12 or is absent, each of R 1

R

2 and R 3 is an alkyl group, and n is 1 or 2.

A fifth aspect of the invention is directed to a urea-urethane composition which is characterized by comprising a urea-urethane compound and a diluent.

A sixth aspect of the invention is directed to a urea-urethane composition according to the fifth aspect of the invention, wherein the diluent is a urea compound and/or a urethane compound.

A seventh aspect of the invention is directed to a urea-urethane composition according to the fifth aspect of the invention, wherein the diluent is a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound.

An eighth aspect of the invention is directed to a urea-urethane composition obtained by reacting a polyisocyanate compound with a hydroxy compound and an amino compound, which is characterized by comprising wt% or more of a urea-urethane compound having at least one urea group and at least one urethane group in a total number of 2 to 10 in the molecular structure and having a molecular weight of 5,000 or less.

A ninth aspect of the invention is directed to a urea-urethane composition according to the eighth aspect of the invention, wherein the hydroxy compound is a phenolic compound.

A tenth aspect of the invention is directed to a urea-urethane composition according to the eighth 13 aspect of the invention, wherein the hydroxy compound is an alcohol compound.

An eleventh aspect of the invention is directed to a urea-urethane composition according to any one of the eighth to tenth aspects of the invention, wherein the amino compound is an aromatic amino compound.

A twelfth aspect of the invention is directed to a urea-urethane composition according to any one of the eighth to eleventh aspects of the invention, wherein the polyisocyanate compound is an aromatic polyisocyanate compound.

A thirteenth aspect of the invention is directed to a process for producing a urea-urethane composition which is characterized by reacting a polyisocyanate compound with a hydroxy compound so that the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound becomes 100/1 to 1/2, to form one or more urethane groups from some of the isocyanate groups of the polyisocyanate compound, and then adding an amino compound thereto to react the same with the remaining isocyanate group(s) of the polyisocyanate compound to form one or more urea groups.

A fourteenth aspect of the invention is directed to a process for producing a urea-urethane composition which is characterized by reacting a polyisocyanate compound with an amino compound so that *0 14 the ratio of the number of moles of the polyisocyanate compound to the number of amino equivalents of the amino compound becomes 100/1 to 1/2, to form one or more urea groups from some of the isocyanate groups of the polyisocyanate compound, and then adding a hydroxy compound thereto to react the same with the remaining isocyanate group(s) of the polyisocyanate compound to form one or more urethane groups.

A fifteenth aspect of the invention is directed to a process for producing a urea-urethane composition according to the thirteenth or fourteenth aspect of the invention, which is characterized by successively carrying out the reaction for forming one or more urethane groups and the reaction for forming one or more urea groups.

A sixteenth aspect of the invention is directed to a process for producing a urea-urethane composition which comprises reacting an amino compound with a polyisocyanate adduct obtained by the reaction of a polyisocyanate compound with a hydroxy compound, so that the equivalent ratio of isocyanate group to amino group becomes 2/1 to 1/100, to form one or more urea groups, and then removing the unreacted amino compound.

A seventeenth aspect of the invention is directed to a process for producing a urea-urethane composition which comprises reacting a hydroxy compound with a polyisocyanate adduct obtained by the reaction *0 of a polyisocyanate compound with an amino compound, so that the equivalent ratio of isocyanate group to hydroxyl group becomes 2/1 to 1/100, to form one or more urethane groups, and then removing the unreacted hydroxy compound.

An eighteenth aspect of the invention is directed to a process for producing a urea-urethane composition according to any one of the thirteenth to seventeenth aspects of the invention, which is characterized by carrying out the reaction for forming one or more urethane groups and/or the reaction for forming one or more urea groups, without a solvent, or carrying out the reaction for forming one or more urethane groups and the reaction for forming one or more urea groups, by the use of the same solvent.

A nineteenth aspect of the invention is directed to a process for producing a urea-urethane composition according to any one of the thirteenth to eighteenth aspects of the invention, wherein the reaction for forming one or more urethane groups and/or the reaction for forming one or more urea groups are carried out at a temperature of 0 300 0

C.

A twentieth aspect of the invention is directed to a process for producing a urea-urethane composition according to any one of the thirteenth to nineteenth aspects of the invention, wherein the reaction for forming one or more urethane groups and/or the reaction for forming one or more urea groups are *0 16 carried out in the presence of a catalyst.

A twenty-first aspect of the invention is directed to a color-producing composition comprising a developer comprising a urea-urethane compound.

A twenty-second aspect of the invention is directed to a color-producing composition comprising a developer comprising a urea-urethane compound, and a colorless or light-colored dye precursor.

A twenty-third aspect of the invention is directed to a color-producing composition according to the twenty-second aspect of the invention, wherein the colorless or light-colored dye precursor is a leuco dye.

A twenty-fourth aspect of the invention is directed to a color-producing composition according to the twenty-first to twenty-third aspects of the invention, wherein said developer is a urea-urethane compound according to any one of the first to fourth aspects of the invention, a urea-urethane composition according to any one of the fifth to twelfth aspects of the invention, or a composition produced by a production process according to any one of the thirteenth to twentieth aspects of the invention.

A twenty-fifth aspect of the invention is directed to a color-producing composition according to either of the twenty-third and twenty-fourth aspects of the invention, which is characterized in that the leuco dye is at least one leuco dye selected from triaryl- 17 methane type leuco dyes, fluoran type leuco dyes, fluorene type leuco dyes and diphenylmethane type leuco dyes.

A twenty-sixth aspect of the invention is directed to a color-producing composition according to either of the twenty-third and twenty-fourth aspects of the invention, which is characterized in that the leuco dye is a compound represented by the following formula Y2

Y-N'

4 3

Y

6 C=0 wherein both Y 2 and Y 3 are alkyl groups or alkoxyalkyl groups, Y 4 is a hydrogen atom, an alkyl group or an alkoxy group, and each of Y 5 and Y, is a hydrogen atom, a halogen atom, an.alkyl group or an alkoxy group.

A twenty-seventh aspect of the invention is directed to a color-producing composition according to either of the twenty-third and twenty-fourth aspects of the invention, which is characterized in that the leuco dye is a compound represented by the following formula S(j) R R10 Rg wherein each of Rs and R, is a group represented by the formula or the formula R11

R

1 (k) R 21 x R14

R

13 (wherein each of R, through R 1 is a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or -NR 6

,R,

1 wherein each of and is an alkyl group of 1 to 8 carbon atoms), or

R

18 R19 (1) (wherein each of and R 1 is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms, or a phenyl group), and each of R, through R 10 is a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or -NR 20

R

21 wherein each of 19

R

20 and R,2 is an alkyl group of 1 to 8 carbon atoms.

A twenty-eighth aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to twenty-seventh aspects of the invention, which is characterized in that the melting point of the urea-urethane compound developer is not higher than 500 0 C and not lower than 40 0

C.

A twenty-ninth aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to twenty-seventh aspects of the invention, which is characterized in that the urea-urethane compound developer comprises a compound selected from compounds represented by the following general formula or (VI): SH H H L H H H) wherein hydrogen atom(s) of each benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom, each of the residues may have one or more substituents, y is a group selected from the group consisting of -SO 2

-(CH

2 -CONH- and any of groups represented by the formulas OOb CH3 CH3 -CH CH I I

CH

3 CH3 OOo-

^O

or is absent, and n is 1 or 2; and 6 HO (VI) H H H H H H wherein hydrogen atom(s) of each benzene ring may be replaced by an aromatic compound residue, an aliphatic 21 compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, each of the residues may have one or more substituents, 6 is a group selected from the group consisting of -SO 2

-CONH-,

-CH(COOR

1

-C(CF

3 2 and -CR 2

R

3 or is absent, each of Ri, R 2 and R 3 is an alkyl group, and n is 1 or 2.

A thirtieth aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to twenty-seventh aspects of the invention, which is characterized in that the urea-urethane compound developer comprises a compound selected from compounds represented by the following structural formulas (XX) and (XXI):

(XX)

22

(XXI)

N-C-O C O-C-N NH CH 3 N. 0 C C, NH

NH

o0 0 A thirty-first aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to thirtieth aspects of the invention, which further comprises a heat-meltable material.

A thirty-second aspect of the invention is directed to a color-producing composition according to the thirty-first aspect of the invention, which is characterized in that the heat-meltable material is at least one compound selected from 0-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di(m-methylphenoxy)ethane, di-p-methylbenzyl oxalate, 1,2-diphenoxymethylbenzene, m-terphenyl and stearamide.

A thirty-third aspect of the invention is directed to a color-producing composition according to the thirty-first aspect of the invention, wherein the heat-meltable material is that represented by the following structural formula (XVIII):

O(XVIII)

23 wherein Y is any of -SO 2

-CH

2

-CH(C

6

-C(CH

3 -COCO-, -C0 3

-COCH

2 CO-, -COOCH 2 -CONH-, -OCH 2 and n is 1 or 2, and hydrogen atom(s) of each benzene ring may be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue.

A thirty-fourth aspect of the invention is directed to a color-producing composition according to the thirty-third aspect of the invention, wherein the heat-meltable material is that represented by the following structural formula (XIX): 0 S

(XIX)

0 wherein hydrogen atom(s) of each benzene ring may be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue.

A thirty-fifth aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to thirty-fourth aspects of the invention, which further comprises an isocyanate compound.

A thirty-sixth aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to thirty-fourth aspects of the invention, which further comprises an isocyanate compound and an imino compound.

A thirty-seventh aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to thirty-sixth aspects of the invention, which further comprises an amino compound.

A thirty-eighth aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to thirty-seventh aspects of the invention, wherein the developer further comprises an acidic developer.

A thirty-ninth aspect of the invention is directed to a color-producing composition according to the thirty-eighth aspect of the invention, which is characterized in that the acidic developer is at least one developer selected from 2,2-bis(4-hydroxyphenyl)propane, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis(3-ally-4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone and 4,4'-[oxybis(ethyleneoxy-pphenylenesulfonyl)]diphenol.

A fortieth aspect of the invention is 0O directed to a color-producing composition according to any one of the twenty-first to thirty-ninth aspects of the invention, which further comprises a fluorescent dye.

A forty-first aspect of the invention is directed to a color-producing composition according to any one of the twenty-first to fortieth aspects of the invention, which further comprises a shelf-stabilityimparting agent.

A forty-second aspect of the invention is directed to a recording material comprising a substrate and a color-producing layer formed thereon, said colorproducing layer comprising a urea-urethane compound according to any one of the first to fourth aspects of the invention, a urea-urethane composition according to any one of the fifth to twelfth aspects of the invention, or a color-producing composition according to any one of the twenty-first to forty-first aspects of the invention.

A forty-third aspect of the invention is directed to a recording material according to the forty-second aspect of the invention, which is characterized in that a protective layer for the colorproducing layer is formed on the color-producing layer.

A forty-fourth aspect of the invention is directed to a recording material according to the forty-third aspect of the invention, which is characterized in that the protective layer comprises a 0O 26 water-soluble polymer.

A forty-fifth aspect of the invention is directed to a recording material according to either of the forty-third and forty-fourth aspects of the invention, which is characterized in that the protective layer comprises an inorganic pigment and/or an organic pigment.

A forty-sixth aspect of the invention is directed to a recording material according to any one of the forty-third to forty-fifth aspects of the invention, which is characterized in that the protective layer comprises a lubricant.

A forty-seventh aspect of the invention is directed to a recording material according to the forty-second aspect of the invention, which is characterized in that an intermediate layer is formed on the substrate and that the color-producing layer is formed on said intermediate layer.

A forty-eighth aspect of the invention is directed to a recording material according to the forty-seventh aspect of the invention, which is characterized in that the intermediate layer comprises a water-soluble polymer.

A forty-ninth aspect of the invention is directed to a recording material according to either of the forty-seventh and forty-eighth aspects of the invention, which is characterized in that the intermediate layer comprises an inorganic pigment and/or an organic pigment.

A fiftieth aspect of the invention is directed to a recording material according to the forty-second aspect of the invention, which is characterized in that a back coating layer is formed on the substrate on the side reverse to the side having the color-producing layer formed thereon.

A fifty-first aspect of the invention is directed to a recording material according to the fiftieth aspect of the invention, which is characterized in that the back coating layer comprises a watersoluble polymer.

A fifty-second aspect of the invention is directed to a recording material according to either of the fiftieth and fifty-first aspects of the invention, which is characterized in that the back coating layer comprises an inorganic pigment and/or an organic pigment.

A fifty-third aspect of the invention is directed to a recording material according to any one of the forty-second to fifty-second aspects of the invention, which is characterized by using at least one compound selected from water-soluble polymers and anionic surfactants, as a dispersing agent for the urea-urethane compound.

A fifty-fourth aspect of the invention is directed to a recording material according to any one of the forty-second to fifty-second aspects of the 28 invention, which is characterized by using at least one compound selected from poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate, polycarboxylic acid ammonium salts, watersoluble low-molecular weight copolymers, and sodium 2ethylhexylsulfosuccinate, as a dispersing agent for the urea-urethane compound.

A fifty-fifth aspect of the invention is directed to a recording material according to any one of the forty-second to fifty-fourth aspects of the invention, which is characterized by using at least one compound selected from water-soluble polymers, nonionic surfactants and anionic surfactants, as a dispersing agent for a dye precursor.

A fifty-sixth aspect of the invention is directed to a recording material according to any one of the forty-second to fifty-fourth aspects of the invention, which is characterized by using at least one compound selected from methyl cellulose, hydroxypropylmethyl cellulose, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ether sulfates and sodium 2-ethylhexylsulfosuccinate, as a dispersing agent for a dye precursor.

A fifty-seventh aspect of the invention is directed to a recording material according to any one of the forty-second to fifty-sixth aspects of the invention, which is a heat-sensitive recording material.

A fifty-eighth aspect of the invention is directed to a heat-sensitive recording material according to the fifty-seventh aspect of the invention, which is characterized in that the average particle size of the urea-urethane compound is not more than 5 pm and not less than 0.05 pm.

A fifty-ninth aspect of the invention is directed to a heat-sensitive recording material according to the fifty-seventh and fifty-eighth aspects of the invention, which is characterized in that a liquid temperature at grinding of the urea-urethane compound is 60 0 C or lower.

A sixtieth aspect of the invention is directed to a heat-sensitive recording material according to any one of the fifty-seventh to fifty-ninth aspects of the invention, which is characterized in that a pH at grinding of the urea-urethane compound is to A sixty-first aspect of the invention is directed to a heat-sensitive recording material according to any one of the fifty-seventh to sixtieth aspects of the invention, which is characterized by using at least one compound selected from water-soluble polymers and anionic surfactants, as a dispersing agent for a heat-meltable material.

A sixty-second aspect of the invention is directed to a heat-sensitive recording material accord- 0 ing to any one of the fifty-seventh to sixtieth aspects of the invention, which is characterized by using at least one compound selected from poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate, polycarboxylic acid ammonium salts, water-soluble low-molecular weight copolymers, and sodium 2-ethylhexylsulfosuccinate, as a dispersing agent for a heat-meltable material.

A sixty-third aspect of the invention is directed to a heat-sensitive recording material according to any one of the fifty-seventh to sixty-second aspects of the invention, which is characterized in that the urea-urethane compound and a heat-meltable material are finely ground together.

A sixty-fourth aspect of the invention is directed to a heat-sensitive recording material according to any one of the fifty-seventh to sixty-third aspects of the invention, which is characterized in that the pH of the substrate surface to be coated with the heat-sensitive recording layer of the heatsensitive recording material is 3 to 9.

A sixty-fifth aspect of the invention is directed to a process for producing a heat-sensitive recording material according to any one of the fiftyseventh to sixty-fourth aspects of the invention, which is characterized by applying on the substrate a heatsensitive coating liquid of pH 5 to 12 for forming the 0@ 31 heat-sensitive recording layer of the heat-sensitive recording material.

A sixty-sixth aspect of the invention is directed to a recording material according to the forty-second aspect of the invention, which is a heatsensitive magnetic recording material.

A sixty-seventh aspect of the invention is directed to a heat-sensitive magnetic recording material according to the sixty-sixth aspect of the invention, which is characterized in that a heatsensitive recording layer comprising a urea-urethane compound developer is formed on one side of the substrate, and a magnetic recording layer on the other side.

A sixty-eighth aspect of the invention is directed to a railroad ticket that is a heat-sensitive magnetic recording material according to the sixtysixth or sixty-seventh aspect of the invention.

A sixty-ninth aspect of the invention is directed to a ticket that is a heat-sensitive magnetic recording material according to the sixty-sixth or sixty-seventh aspect of the invention.

A seventieth aspect of the invention is directed to a recording material according to the forty-second aspect of the invention, which is a label for heat-sensitive recording.

A seventy-first aspect of the invention is directed to a label for heat-sensitive recording according to the seventieth aspect of the invention, which is characterized in that a heat-sensitive recording layer comprising a urea-urethane compound developer is formed on one side of the substrate, and an adhesive layer on the other side.

A seventy-second aspect of the invention is directed to a label for heat-sensitive recording according to the seventy-first aspect of the invention, which is characterized in that a back coating layer is formed between the adhesive layer and the substrate.

A seventy-third aspect of the invention is directed to a label for heat-sensitive recording according to either of the seventy-first and seventysecond aspects of the invention, which is characterized in that an intermediate layer is formed between the heat-sensitive recording layer and the substrate.

A seventy-fourth aspect of the invention is directed to a label for heat-sensitive recording according to any one of the seventy-first to seventythird aspects of the invention, which is characterized in that a protective layer is formed on the heatsensitive recording layer.

A seventy-fifth aspect of the invention is directed to a recording material according to the forty-second aspect of the invention, which is a multicolor heat-sensitive recording material.

A seventy-sixth aspect of the invention is directed to a multicolor heat-sensitive recording 0@ 33 material according to the seventy-fifth aspect of the invention, wherein at least two heat-sensitive recording layers are formed on one side of the substrate, said recording material being characterized in that at least one of said heat-sensitive recording layers comprises a urea-urethane compound developer.

A seventy-seventh aspect of the invention is directed to a multicolor heat-sensitive recording material according to the seventy-sixth aspect of the invention, which is characterized in that an intermediate layer is formed between the heat-sensitive recording layers.

A seventy-eighth aspect of the invention is directed to a multicolor heat-sensitive recording material characterized by comprising a substrate and two heat-sensitive recording layers laminated on one side of the substrate which have different color development temperatures, respectively, and undergo color development in different color tones, respectively, the upper heat-sensitive recording layer comprising either an agent used both as developer and tone reducer, or a reversible developer, and the lower heat-sensitive recording layer comprising a ureaurethane compound developer.

A seventy-ninth aspect of the invention is directed to a multicolor heat-sensitive recording material according to the seventy-eighth aspect of the invention, which is characterized in that, of the two heat-sensitive recording layers, the upper layer is a low-temperature color-producing layer capable of undergoing color development at a low temperature and undergoing achromatization at a high temperature, and the lower layer is a high-temperature color-producing layer capable of undergoing color development at a high temperature.

An eightieth aspect of the invention is directed to an article for laser marking characterized by having on the surface a heat-sensitive recording layer comprising a urea-urethane compound developer.

An eighty-first aspect of the invention is directed to an article for laser marking characterized by having on the surface a heat-sensitive recording layer comprising a colorless or light-colored dye precursor, a urea-urethane compound developer and a recording sensitivity improving agent.

An eighty-second aspect of the invention is directed to an article for laser marking according to either of the eightieth and eighty-first aspects of the invention, which is characterized by having on the heat-sensitive recording layer a protective layer comprising an aqueous binder having a glass transition point of 20 An eighty-third aspect of the invention is directed to an article for laser marking according to the eighty-first aspect of the invention, wherein the recording sensitivity improving agent is at least one 0@ compound selected from aluminum hydroxide, muscovite, wollastonite and kaolin.

An eighty-fourth aspect of the invention is directed to an article for laser marking according to any one of the eightieth to eighty-third aspects of the invention, which is any of labels, packaging materials and containers.

An eighty-fifth aspect of the invention is directed to a process for producing an article for laser marking which is characterized by applying on a substrate a color-producing marking composition comprising a urea-urethane compound developer, and drying the thus treated substrate.

An eighty-sixth aspect of the invention is directed to a process for producing an article for laser marking which is characterized by applying on a substrate a color-producing marking composition comprising a colorless or light-colored dye precursor, a urea-urethane compound developer and a recording sensitivity improving agent, and drying the thus treated substrate.

An eighty-seventh aspect of the invention is directed to a method for marking an article which is characterized by irradiating the heat-sensitive recording layer of an article for laser marking according to any one of the eightieth to eighty-fourth aspects of the invention, with laser beams.

An eighty-eighth aspect of the invention is 0@ 36 directed to a color-producing marking composition characterized by comprising a urea-urethane compound developer.

An eighty-ninth aspect of the invention is S directed to a color-producing marking composition characterized by comprising a colorless or lightcolored dye precursor, a urea-urethane compound developer and a recording sensitivity improving agent.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is explained below in detail.

Each of the urea-urethane compounds of the first to fourth aspects of the present invention has both at least one urea group and at least one urethane group.

In the urea-urethane compounds of the first to fourth aspects of the present invention, an aliphatic compound residue is bonded to the terminal oxygen atom of the urethane group. Therefore, the urea-urethane compounds can be obtained as compounds excellent in physical and chemical stability, in particular, heat stability. Moreover, the ureaurethane compounds can be obtained by using relatively inexpensive materials.

In addition, a starting alcohol compound for the aliphatic compound residue bonded to the terminal oxygen atom of the urethane group can easily be removed 37 even if it remains unreacted in the synthetic reaction of the urea-urethane compound. Therefore, the ureaurethane compounds can be obtained with a high purity.

Preferable forms at the ends of the urea group vary depending on the molecular size of the ureaurethane compound. In the urea-urethane compound of the formula each end of the urea group should be bonded to an aromatic compound residue. The aromatic compound residue is preferably an aromatic ring shown in the formula In the urea-urethane compounds of the formulas and having a relatively large molecular size, a group at each end of the urea group is, for example, as follows: in the formula the group at each end may be any of an aromatic compound residue, a heterocyclic compound residue and an aliphatic compound residue, and in the formula the group at each end may be either an aromatic compound residue or a heterocyclic compound residue. In both the formulas and the group at each end of the urea group is preferably an aromatic compound residue.

The urea group and the urethane group are adjacent to each other through at least one compound residue (such a structure portion is hereinafter referred to as a urea-urethane structure portion). It is preferable that only one compound residue be present between the urea group and the urethane group. In addition, this residue is preferably an aromatic ring.

Although a concrete mechanism by which the urea-urethane compounds of the first to fourth aspects of the present invention function as a developer is unknown, it is conjectured that the function is due to the interaction between the urea group and the urethane group in the urea-urethane structure portion. The number of urea-urethane structure portions is two or more in the formulas and On the other hand, the number of urea-urethane structure portions is one in some cases in the urea-urethane compound of the formula or In this case, the following is conjectured: in the urea-urethane compound of the formula or a residue to be bonded to each end of the urea group is limited to the most preferable residue, an aromatic compound residue in order to enable the compound to function as a developer to a cetain extent; on the other hand, in the formulas (e) and a residue to be bonded to each end of the urethane group need not always be an aromatic compound residue.

It is sufficient that the number of ureaurethane structure portions present in the molecule be 1 to 10, preferably 1 to 5, more preferably 2 to 4.

The urea-urethane compound may have in the molecule one or more other urea groups and urethane groups in addition to the urea-urethane structure portion(s).

The term "aliphatic" used in the case of the first to fourth aspects of the present invention includes the term "alicyclic".

The term "aliphatic compound residue" used in the case of the first to fourth aspects of the present invention means a residue bonded by the carbon atom of the aliphatic hydrocarbon portion in the residue. The term "aromatic compound residue" used therein means a residue bonded by the carbon atom of the aromatic ring such as benzene ring in the residue. The term "heterocyclic compound residue" used therein means a residue bonded by a carbon atom forming the heterocyclic ring in the residue.

Preferable examples of the substituents of the aliphatic compound residue, the heterocyclic compound residue and the aromatic compound residue are alkyl groups, cycloalkyl groups, phenyl group, amide group, alkoxyl groups, nitro group, nitrile group, halogen atoms, formyl group, dialkylamino groups, toluenesulfonyl group and methanesulfonyl group.

When it is considered that the urea-urethane compounds of the first to fourth aspects of the present invention are used as a developer or in a heatsensitive recording material, the total number of one or more aliphatic urethane groups and one or more urea groups, which are present in the molecular structure of each of the urea-urethane compounds of the first to fourth aspects of the present invention is not more than 11 and not less than 2, preferably not more than 11 and not less than 3, more preferably not more than 0@ 11 and not less than 4. The ratio of the urethane group(s) to the urea group(s) is preferably 1 3 to 3 1, more preferably 1 2 to 2 i, most preferably 1 i. The molecular weight of the urea-urethane S compounds is 5,000 or less, preferably 2,000 or less.

In a heat-sensitive recording material, a compound having a melting point is preferably used.

The melting point or the urea-urethane compounds of the first to fourth aspects of the present invention ranges preferably from 400C to 5000C, more preferably from to 3000C, most preferably from 600C to 2500C.

A process for synthesizing each of the ureaurethane compounds of the first to fourth aspects of the present invention is not particularly limited. A process in which the urea-urethane compound is synthesized by the reaction of an isocyanate compound with an alcohol compound and an amine compound is preferable because of its ease.

A process for producing the urea-urethane compound of the formula of the first aspect of the present invention is not limited. This compound can be obtained, for example, by reacting an alcohol compound of the following formula with an isocyanate compound of the following formula and an amine compound of the following formula according to, for example, the reaction formula or shown below: R -OH (m) wherein R is an aliphatic compound residue which may 41 have one or more substituents;

OCN-A

1 -NCO (n) wherein A, is an aromatic compound residue which may have one or more substituents; and

A

2

-NH

2 (o) wherein A 2 is an aromatic compound residue which may have one or more substituents.

0

II

R-OH OCN-A 1 -NCO R-O 'C N-A1-NCO H o 0 0 O O O R-O CN-A 1 -NCO A 2

-NH

2 R-O N-AI -N IN-A 2 H H H H 0

A

2

-NH

2 OCN-A-NCO OCN-A--N r -A 2 0 0 0 O O O R-OH OCN-Ai-N -A 2 R-O" -AN N-A 2 A process for producing the urea-urethane compound of the formula of the second aspect of the present invention is not particularly limited. This compound can be obtained, for example, by reacting an alcohol compound of the formula with an isocyanate compound of the following formula and an amine compound of the following formula according to, for example, the reaction formula or shown below: 42 OCN--- NCO (p) wherein hydrogen atom(s) of the benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, and each of the residues may have one or more substituents; and

NH

2 (q) wherein hydrogen atom(s) of the benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue, and each of the residues may have one or more substituents.

0 R-OH OCN- NCO R-O n NCO O O co.

R-0 0 -NCO+ c-NH 2 R-O'

N-

H

0 H (D' O O O 0 0 0 R-OH OCN R-O- A process for producing the urea-urethane compound of the formula of the third aspect of the present invention is not limited. This compound can be obtained, for example, by reacting an alcohol compound of the general formula with an isocyanate compound of the following general formula and an amine compound of the following general formula according to, for example, the reaction formula or shown below: OCN--Y-NCO (r) wherein Y is an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, and each of the residues may have one or more substituents; and -X -NH 2 (s) n wherein x, is an aromatic, aliphatic or heterocyclic compound residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents.

0 44 0 R-OH OCN-Y-NCO-- R-O N-Y-NCO H O O O l 1rNH R-O Y--N H n H H H On 0 a-(NH 2 OCN-Y-NCO OCN-Y-N/' SNH[n H H n R-OH OCN-Y-N -a i R- N-Y-N/ N- -a H H H H H n A process for producing the urea-urethane compound of the formula of the third aspect of the present invention is not limited. This compound can be obtained, for example, by reacting an amine compound of the following general formula with an isocyanate compound of the general formula and an alcohol compound of the following general formula according to, for example, the reaction formula or shown below:

Z

1

-NH

2 (t) wherein Z, is is an aromatic compound residue or a heterocyclic compound residue, and each of the residues may have one or more substituents; and 01- OH] (u) wherein Pi is an aliphatic compound residue which has a valence of 2 or more and may have one or more substituents, and n is an integer of 2 or more.

0

Z

1

-NH

2 OCN-Y-NCO OCN-Y-N 'N-Z 1 H H S04OH n 0 PiOH n niOCN-Y-NCO P-0 -Y-NCO

(H'

O n o o Y-NCO n Z-NH 2 0- 0 C Y-Zi n n A process for producing the urea-urethane compound of the formula of the fourth aspect of the present invention is not limited. This compound can be obtained, for example, by reacting an alcohol compound of the formula with an isocyanate compound of the formula and an amine compound of the formula (q) according to, for example, the reaction formula or shown below: PiOH nOC-- -NCO O NCO nn -O O O- N N 0 NH+ OCN-- NCO OCN -N HN- 0 0 0 n OCN--N 1 3 -4H Pf- -N-O A process for producing the urea-urethane compound of the formula of the fourth aspect of the present invention is not limited. This compound can be obtained, for example, by reacting an amine compound of the following formula (XVII) with an isocyanate compound of the formula and an alcohol compound of the general formula according to, for example, the reaction formula or shown below:

NH

2 y 2

(XVII)

wherein hydrogen atom(s) of each benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a hydroxyl group, a carboxyl group, a 47 nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom, each of the residues may have one or more substituents, y, is a group selected from the group consisting of -SO 2 -(CH2 -CONH-, -CH(COORj)-,

-C(CF

3

-CR

2

R

3 and any of groups represented by the formulas O b

~H

3

CH

3

-C

CH

3

C;H

3 0- -oQ Qo or is absent, each of R 1

R

2 and R 3 is an alkyl group, and n is 1 or 2.

R-OH OCN-- NCO [2 L RN NCO 2R-O N

H

0 R-O N- -NCO

H

2 N- -NH 2 K l H O O O O 0 0 0 0 R-O N- 'N N 1 N N- N O-R H kH HHK.H

H

2 N 1- -NH 2 2 OCN-L -NCO 0 0 OCN- -N 71 -N N- -NCO H H H HQK: 0 0 OCN- -N N- Y1 N H N H H H H NC 2R-OH 0 0 0 0 O O O O R-O N- N N 76- -N N- N H H H H H H The compounds of the formulas to (u) which can be used for synthesis of the urea-urethane compounds of the above formulas to are explained below in further detail.

j As the alcohol compound of the general formula any alcohol compound may be used so long as it has one or more OH groups bonded to one or more carbon atoms, respectively, of an aliphatic compound.

Examples of the alcohol compound are the alcohols described in Solvent Handbook, Kodansha Scientific Co., Ltd., the ninth impression (1989), pp. 327-420 and pp.

772-817. The alcohol compound includes, for example, aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tertbutanol, pentanol, cyclopentanol, tert-amyl alcohol, 2pentanol, isoamyl alcohol, hexanol, 3-hexanol, cyclohexanol, cyclohexylmethanol, 4-methyl-2-pentanol, heptanol, isoheptanol, octanol, 2-ethyl-l-hexanol, capryl alcohol, nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, isostearyl alcohol, etc.; unsaturated aliphatic alcohols such as ally alcohol, 2methyl-2-propen-l-ol, crotyl alcohol, propargyl alcohol, etc.; aliphatic alcohols having an aromatic compound residue bonded thereto, such as benzyl alcohol, cinnamyl alcohol, etc.; aliphatic alcohols having a heterocyclic compound residue bonded thereto, such as 2-pyridinemethanol, 3-pyridinemethanol, 4pyridinemethanol, furfuryl alcohol, etc.; halogenated aliphatic alcohols such as 2-chloroethanol, l-chloro-3hydroxypropane, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene 51 glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monophenyl ether, etc.; diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol, etc.; aliphatic polyols such as glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, c-methyl glucoside, sorbitol, sucrose, etc.; polyols such as polyethylene glycols, polypropylene 52 glycols, polytetramethylene glycols, adipate-derived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, amine-modified polyols, polyether polyols obtained by adding one of or a mixture of two or more of alkylene oxides ethylene oxide and propylene oxide) to one of or a mixture of two or more of polyhydric alcohols (glycerin and propylene glycol), acryl polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, castor-oil-derived polyols, polymer polyols, halogen-containing polyols, phosphorus-containing polyols, etc.; and alkanolamines such as N,N-dialkylethanolamines, N,N-dialkylisopropanolamines, Nalkyldiethanolamines, N-alkyldiisopropanolamines, triethanolamine, triisopropanolamine, tetrakis(2-hydroxyethyl)ethylenediamine, tetrakis(2-hydroxypropyl)ethylenediamine, etc.

Of the above-exemplified alcohol compounds, monoalcohols having one OH group are preferable, and aliphatic alcohols and glycol ethers, which have 10 or less carbon atoms are more preferable.

The isocyanate compound of the formula is not particularly limited so long as it is an aromatic isocyanate having two or more isocyanate groups bonded to carbon atoms, respectively. The isocyanate compound includes, for example, p-phenylene diisocyanate, mphenylene diisocyanate, o-phenylene diisocyanate, dimethoxybenzene-1,4-diisocyanate, 2,4-toluene 53 diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris(4phenylisocyanate) thiophosphate, 4,4',4"-triisocyanatoand 4,4',4"-triisocyanatotriphenylamine. As the isocyanate compound of the formula there may also be used diisocyanate dimers such as N,N'-(4,4'-dimethyl-3,3'-diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), a toluene diisocyanate dimer; and diisocyanate trimers such as 4,4',4"-trimethyl-3,3',3"-triisocyanato-2,4,6triphenylcyanurate. There may also be used water adduct isocyanates of toluene diisocyanate, diphenylmethane diisocyanate and the like, such as 1,3-bis(3isocyanato-4-methylphenyl)urea; polyol adducts such as trimethylolpropane adducts of toluene diisocyanate (Desmodule L and Coronate L, trade names); and amine adducts. There may also be used compounds having two or more isocyanate groups, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171 (the contents of these references are hereby incorporated herein by reference).

Of the above-exemplified isocyanate compounds, aromatic isocyanates having isocyanate groups bonded to a benzene ring are preferable. More preferable are p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, l,5-naphthylene diisocyanate, triphenylmethane triisocyanate, N,N'-C4,4'-dimethyl-3,3'diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), 4,4',4"-trimethyl-3,3',3"-triisocyanato-2,4,6triphenylcyanurate, 1,3-bis(3-isocyanato-4-methylphenyl)urea, and trimethyloipropane adducts of toluene diisocyanate (Desmodule L and Coronate L, trade names) Especially preferable examples of the isocyanate compound of the formula are toluene dilsocyanates.

Of the toluene diisocyanates, 2.4-toluene diisocyanate is preferable. Besides 2.4-toluene diisocyanate, mixtures of 2.4-toluene diisocyanate and 2,6-toluene diisocyanate are generally on the market and available at a low price and may also be used as the isocyanate compound of the formula (n) As the amine compound of the general formula there are mentioned, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N,N-dimethylp-phenylenediamine, N,N-diethyl-p-phenylenediaMine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4aminobenzonitrile, anthranilic acid, p-cresidine, dichioroaniline, 2, 6-dichioroaniline, 3, 4-dichioroaniline, 3,5-dichioroaniline, 2,4,5-trichioroaniline, a -naphthylamine, aminoanthracene, o-ethylaniline, ochioroaniline, m-chloroaniline, p-chloroaniline, Nmethylaniline, N-ethylaniline, N-propylaniline, Nbutylaniline, acetoacetic acid anilide, trimethylphenylarnmonium bromide, 4, 4'-diamino-3, 3'-diethyldiphenylmethane, 4, 4'-diaminobenzanilide, diaminochlorobenzene, diaminodiphenyl ether, 3,3'dichloro-4, 4'-diaminodiphenylmethane, 3,3'-dimethyl- 4,4'-diaminodiphenylmethane, tolidine base, ophenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl paminobenzoate, dodecyl p-aminobenzoate, benzyl paminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, oaminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4methoxybenzamide, 3-amino-4-chlorobenzamide, p- (Nphenylcarbamoyl) aniline, (4-chiorophenyl) carbamoyl] aniline, p- (4-amit nophenyl) carbamoyl]aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2- -methyl-3' -chlorophenyl) carbamoyl] aniline, 2-methoxy-5- -chlorophenyl) carbamoyl]aniline, 5-acetylamino-2-methoxyaniline, 4-acetylamino- 56 aniline, 4- (N-methyl-N-acetylanino) aniline, diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (Nbenzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) methylaniline, 4-sul famoylaniline, 3-sul famoylaniline, 2- (N-ethyl-N-phenylaininosulfonyl)aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosul fonylaniline, sul fathiazole, 4-aminodiphenyl sulfone, phenylsulfamoylaniline, sulfamoylaniline, 2, 5-dimethoxy-4-N-phenysulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis[4- Cmaminophenoxy)phenyl] sulfone, bis (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy)phenyl] sulfone, 3, 3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'dimethyl-4, 4'-diaminobiphenyl, 2,2'-dichloro-4,4'- 2,2' 4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2, 2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diarninobiphenyl, 3,3'-dichloro-4,4'diaminobiphenyl, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-clithiodianiline, 4,4'dithiodianiline, 4, 4'-diaminodiphenyl ether, 3,3'diarninodiphenyl ether, 3,4' -diarninod'ihenyl ether, 4,4' -diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4diaminophenyl) sulfone, 4, 4'-diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3, 4'-diaminodiphenyl sulfone, 3,3' -diaminodiphenylmethane, 4, 4-diaminodiphenylamine, 4, 4'-ethylenedianiline, 4, 4'-diamino- 2,2'-dimethylclibenzyl, 3,3'-diaminobenzophenone, 4,4'diaminobenzophenone, 1, 4-bis (4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene, 1,3-bis (3-aminophenoxy)benzene, 9, 9-bis (4-aminophenyl) fluorene, 2,2bis (4-aminophenoxyphenyl)propane, 4, 4'-bis (4-aminophenoxy)diphenyl, 4,4'-tetraaminodiphenyl ether, 3,3',4,4'-tetraaminodiphenyl sulfone, tetraaminobenzophenone, 3-aminobenzonitrile, 4phenoxyaniline, 3-phenoxyaniline, 4, 4'-methylenebis-otoluidine, (p-phenyleneisopropylidene)-bis- (2,6xylidine), o-chloro-p-nitroaniline, o-nitro-pchioroaniline, 2, 6-dichloro-4-nitroaniline, 5-chloro-2nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4nitroaniline, m-nitro-p-toluidine, nitrobenzonitrile, Metol, 2, 4-diaminophenol, N- (fhydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4- fluoroaniline, 2,4-difluoroaniline, 2, 3,4-trifluoroaniline, maminobenzotrifluoride, m-toluylenediamine, 2aminothiophenol, 2-amino-3-bromo-5-nitrobenzoni-tril-e, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N,Ndiphenyl-p-phenylenediamine, dianisidine, 3,3'dichlorobenzidine, 4, 4'-diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino- 2,3-dichloroanthraquinone, etc.

The aromatic isocyanate compound of the formula includes 2,4-toluene diisocyanate, 2,6toluene diisocyanate, m-phenylene diisocyanate, pphenylene diisocyanate, o-phenylene diisocyanate, etc.

Of these, the toluene diisocynates are preferable, and 2,4-toluene diisocyanate is more preferable.

The aromatic amine compound of the formula is not particularly limited so long as it has one or more amino group directly bonded to one or more carbon atoms, respectively, of the benzene ring. In addition, hydrogen atom(s) of the benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom. The aromatic amine compound of the formula includes, for example, aromatic monoamines such as aniline, otoluidine, m-toluidine, p-toluidine, o-anisidine, panisidine, p-phenetidine, 2,4-dimethoxyaniline, dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxy-substituted anilines p- 59 aminobenzoic acid), hydroxyl-substituted anilines (e.g.

o-aminophenol, m-aminophenol, p-aminophenol and 2amino-4-chlorophenol), 2,3-xylidine, 2,4-xylidine, 3,4xylidine, 2, 6-xylidine, nitrile-substituted anilines 4-aminobenzonitrile), anthranilic acid, pcresidine, halogen-substituted anilines dichioroaniline, 2, 6-dichioroaniline, 3, 4-dichioroaniline, 3, 5-dichioroaniline, 2,4, o-chloroaniline, m-chloroaniline and p-chloroaniline), a -naphthylamine, aminoanthracene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl paminobenzoate, dodecyl p-aminobenzoate, benzyl paminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, oaminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4methoxybenzamide, 3-amino-4-chlorobenzamide, carbamoylanilines p- (N-phenylcarbamoyl) aniline, (4chiorophenyl) carbamoyl] aniline, p- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline and 2-methoxy-5- -chlorophenyl) carbamoyl] aniline), 5-acetylarnino-2-methoxyaniline, 4acetylaminoaniline, 2-methoxy-4- (N-benzoylamino) methylaniline, sulfamoylanilines 4-sulfamoylaniline, 3-sulfamoylaniline, sulfarnoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline and 2, 5-dimethoxy-4-N-phenysulfamoylaniline), 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosul fonylaniline, 4-diethylaminosul fonylaniline, sul fathiazole, 4-aminodiphenyl sul fone, benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- chicrophenoxy) sulfonylaniline, 3-anilinosulfonyl-4methylaniline, nitro-substituted anilines achloro-p-nitroaniline, o-nitro-p-chloroaniline, 2, 6dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, onitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl- 4-nitroaniline, m-nitro-p-toluidine and nitrobenzonitrile), sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2, 4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2etc.; aromatic monoamines having one or more substituents including carboxyl group, nitroso group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group, etc.; and aromatic diamines such as 4,4'-diamino-3,3'diethyldiphenylmethane, 4, 4'-diaminobenzanilide, diaminochlorobenzene, diaminodiphenyl ether, 3,3'dichloro-4, 4'-diaminodiphenylmethane, 3, 3'-dimethyl- 4, 4'-diaminodiphenylmethane, tolidine base, dianisidine, bis (m-aminophenoxy)phenyl] sulfone, bis[4- (p-aminophenoxy)phenyl] sulfone, bis[3-methyl-4- (p-aminophenoxy)phenyl] sulfone, 3, 3'-dimethoxy-4, 4'diaminobiphenyl, 3,3' -dimethyl-4, 4'-diaminobiphenyl, 2,2' -dichloro-4, 4'-diamino-5, 5' -dimethoxybiphenyl, 2,2' ,5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2, 4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-ciiaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'dimethyl-4, 4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'diaminodiphenyl ether, 3,3' -diaminocliphenyl ether, 3, 4'-diaminodiphenyl ether, 4, 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4chiorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4,4' -diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3, 4'-ciaminodiphenyl sulfone, 3, 3'-diaminodiphenylmethane, 4,4' -diaminodiphenylamine, 4,4' ethylenedianiline, 4, 4'-diamino-2, 2'-dimethyldibenzyl, 3,3' -diaminobenzophenone, 4,4' -diaminobenzophenone, 1,4-bis (4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene, 1, 3-bis C3-aminophenoxy)benzene, 9,9bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl)propane, 4, 4'-bis (4-aminophenoxy)diphenyl, dianisidine, 3,3'-dichlorobenzidine, etc. Of these, the aromatic monoamines are preferably used, and aniline or the aniline derivatives are more preferably used.

The isocyanate compound of the formula is not particularly limited so long as it has two or more isocyanate groups bonded to carbon atoms, respectively.

This compound includes, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-dilsocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane trilsocyanate, tris(4-phenylisocyanate) thiophosphate, 4,4',4"-triisocyanato-2,5-dimethoxytriphenylamine, 4,4',4"-triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexylisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane dilsocyanate.

As the isocyanate compound of the formula there may also be used diisocyanate dimers such as N,N'-(4,4'-dimethyl-3,3'-diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), a toluene diisocyanate dimer; and diisocyanate trimers such as 4,4',4"-trimethyl-3,3',3"-triisocyanato-2,4,6triphenylcyanurate. There may also be used water adduct isocyanates of toluene diisocyanate, diphenylmethane diisocyanate and the like, such as l,3-bis(3isocyanato-4-methylphenyl)urea; polyol adducts such as trimethylolpropane adducts of toluene diisocyanate (Desmodule L and Coronate L, trade names); and amine adducts. There may also be used compounds having two or more isocyanate groups, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171 (the contents of these references are hereby incorporated herein by reference) Of the above-exemplified isocyanate compounds, aromatic isocyanates having isocyanate groups bonded to a benzene ring are preferable. More preferable are p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, triphenylmethane triisocyanate, N,N'-(4,4'-dimethyl-3,3'diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), 4,4',4"-trimethyl-3,3',3"-triisocyanato-2,4,6triphenylcyanurate, 1,3-bis(3-isocyanato-4-methylphenyl)urea, and trimethylolpropane adducts of toluene diisocyanate (Desmodule L and Coronate L, trade names) Especially preferable examples of the isocyanate compound of the formula are toluene diisocyanates.

Of the toluene diisocyanates, 2.4-toluene diisocyanate is preferable. Besides 2.4-toluene diisocyanate, mixtures of 2.4-toluene diisocyanate and 2,6-toluene diisocyanate are generally on the market and available at a low price and may also be used as the isocyanate compound of the formula The amine compound of the general formula Cs) is not particularly limited so long as it has two or more amino groups. This compound includes, for example, aromatic amines such as 4,4'-diamino-3,3'diethyldiphenylmethane, 4,4' -diaminobenzanilide, diaminochlorobenzene, diaminodiphenyl ether, 3,3'dichloro-4, 4'-diaminodiphenylmethane, 3, 3'-dimethyl- 4,4' -diaminodiphenylnethane, tolidine base, dianisidine, bis[4- (m-aminophenoxy)phenyl] sulfone, bis[4- (p-aminophenoxy)phenyl] sulfone, bis[3-methyl-4- (p-aminophenoxy)phenyl] sulfone, 3, 3'-dirnethoxy-4, 4'diaminobiphenyl, 3,3' -dimethyl-4, 4'-diaminobiphenyl, 2,2' -dichloro-4, 4' -diamino-5, 2,2' 5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2, 4'-diaminobiphenyl, 2,2' -diaminobiphenyl, 4, 4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diaminobiphenyl, 3, 3'-dichloro-4,4'-diaminobiphenyl, 2,2'dimethyl-4, 4'-diaminobiphenyl, 4,4' -thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'diaminodiphenyl ether, 3,3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, bis (3-amino-4chlorophenyl1) sulfone, bis 4-diaminophenyl) sulfone, 4, 4'-diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, 3, 3'-diaminodiphenylmethane, 4,4' -diaminodiphenylamine, 4,4' ethylenedianiline, 4, 4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1, 3-bis (3-aminophenoxy)benzene, 9,9bis(4-aminophenyl)fluorene, 2,2-bis(4-aminophenoxyphenyl)propane, 4,4'-bis(4-aminophenoxy)diphenyl, dianisidine, 3,3'-dichlorobenzidine, tolidine base, ophenylenediamine, m-phenylenediamine, p-phenylenediamine, etc.; heterocyclic compound amines such as guanamine, acetoguanamine, 2,4-diamino-6-[2'methylimidazolyl-(l)]ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diarinopyridine, 2,3,5-triaminopyridine, bis(aminopropyl)piperazine, etc.; and aliphatic amines such as methanediaine, 1,2-diaminopropane, 1,3diaminopropane, 1,4-diaminobutane, 1,3-diamino-2hydroxypropane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-methyl- 3,3'-iminobis(propylamine), hexamethylenediamine, bis(aminomethyl)cyclohexane, isophoronediamine, isopropylidenebis(aminocyclohexane), 4,4'-diaminodicyclohexylmethane, xylylenediaine, etc. Of the above-exemplified amine compounds, the aromatic amines are preferable, and aniline derivatives having at least two amino groups and represented by the following formula (VIII) are especially preferable:

(VIII)

66 wherein R 1

R

2

R

3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group, Xi and X 2 are independently an amino group or a group represented by the formula -0 NH2 (b)

NH

2 and Yj is any of -SO 2

-CO-,

-CONH-, -CH(COOR)-, -C(CF 3 2

-CR

2

R

3 and a group represented by any of the formulas

CH

3 d-b0

CH

3 CH3 CH3 -C0 C (a) I I

CH

3

CH

3 0 0

II

O

or is absent, each of R 2 and R 3 is an alkyl group, and n is 1 or 2.

The amine compound of the general formula (t) includes aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, pphenetidine, N,N-dimethyl-p-phenylenediamine, N,Ndiethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 68 dimethoxyaniline, 3, 4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, maminophenol, p-aminophenol, 2, 3-xylidine, 2, 4-xylidine, 3, 4-xylidine, 2, 6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2, 6-dichioroaniline, 3,4-dichioroaniline, dichioroaniline, 2,4, 5-trichioroaniline, C-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, Nmethylaniline, N-ethylaniline, N-propylaniline, Nbutylaniline, N,N-diglycidylaniline, N,N-diglycidyl-otoluidine, acetoacetic acid anilide, trimethyiphenylammonium bromide, 4, 4'-diamino-3, 3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, benzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'diaminodiphenylmethane, 3,3' -dimethyl-4, 4' -diaminodiphenylmethane, tolidine base, o-phenylenediamine, Inphenylenediamine, p-phenylenediamine, 2-chloro-pphenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, oarinobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-arninobenzamide, paminobenzanide, p-ainino-N-methylbenzamide, 3-amino-4methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p-EN- (4chlorophenyl) carbamoyl] aniline, p-EN- (4-aminophenyl) 69 carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5-[N- (2'-methyl-3'-chlorophenyl)carbamoyllaniline, 2-methoxy-5- (2'-chlorophenyl) carbamoyllaniline, 5-acetylamino-2-methoxyaniline, 4acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2, 5-diethoxy-4- (N-benzoylamino) aniline, 4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenyl sulfone, 2-chloro-5-N-phenylsul famoylaniline, 2- 2, 5-dimethoxy-4- N-phenysulfamoylaniline, aniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4methylaniline, bis (m-aminophenoxy)phenyl] sulfone, bis (p-aminophenoxy)phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy)phenyl] sulfone, 3,3'-dimethoxy-4, 4'diaminobiphenyl, 3,3' -dimethyl-4, 4'-diaminobiphenyl, 2,2' -dichloro-4, 4' -diamino-5, 5' -dimethoxybiphenyl, 2,2' ,5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4' -diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4' -diaminobiphenyl, 2,2'-dichloro-4, 4'-diaminobiphenyl, 3, 3'-dichloro-4,4'-diarninobiphenyl, 2,2'dimethyl-4, 4'-diaminobiphenyl, 4, 4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'diaminodiphenyl ether, 3,3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, bis (3-amino-4chiorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4,4' -diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3, 4'-diaminodiphenyl sulfone, 3, 3'-diaminodiphenylmethane, 4, 4-diaminocliphenylamine, 4,4' ethylenedianiline, 4,4' -ciamino-2,2'-dimethyldibenzyl, 3,3' -diaminobenzophenone, 4,4' -diaminobenzophenone, 1, 4-bis (4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene, 1,3-bis (3-aminophenoxy)benzene, 9,9bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4k -bis (4-aminophenoxy) diphenyl, 3,3',4,4'-tetraaminodiphenyl ether, tetraaminodiphenyl sulfone, 4, 4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3phenoxyaniline, 4, 4'-methylenebis-o-toluidine, (pphenyleneisopropylidene) -bis- 6-xylidine), o-chlorop-nitroaniline, o-nitro-p-chloroaniline, 2, 6-dichioro- 4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4chiorophenol, o-nitroaniline, m-nitroaniline, pnitroaniline, 2-methyl-4-nitroaniline, m-nitro-ptoluidine, 2-amino-5-nitrobenzonitrile, Metol, 2,4diaminophenol, N- (f-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3chloro-4-fluoroaniline, 2, 4-difluoroaniline, 2,3,4trifluoroaniline, m-aminobenzotrifluoride, mtoluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5- 71 nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4,4'-diaminostilbene-2,2'disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4diamino-2,3-dichioroanthraquinone, etc.; and heterocyclic compound amines such as 3-amino-1,2,4triazole, 2-aminopyridine, 3-aminopyridine, 4aminopyridine, a-amino-c-caprolactam, acetoguanamine, 2,4-diamino-6-[2'-methylimidazolyl-(l)lethyl-Striazine, 2,3-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl)piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl)morpholine, etc. Of these, the aromatic monoamines are preferably used.

The alcohol compound of the general formula is not particularly limited so long as it is a polyol compound having two or more OH groups. The alcohol compound includes diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4butanediol, 1,5-pentanediol, 1,6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol, etc.; aliphatic polyols such as glycerin, castor oil, trimethylolpropane, trimethylolethane, 72 hexanetriol, pentaerythritol, a-methyl glucoside, sorbitol, sucrose, etc.; polyols such as polyethylene glycols, polypropylene glycols, polytetramethylene glycols, adipate-derived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, amine-modified polyols, polyether polyols obtained by adding one of or a mixture of two or more of alkylene oxides (e.g.

ethylene oxide and propylene oxide) to one of or a mixture of two or more of polyhydric alcohols (e.g.

glycerin and propylene glycol), acryl polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, castor-oil-derived polyols, polymer polyols, halogen-containing polyols, phosphorus-containing polyols, etc.; and alkanolamines such as N-alkyldiethanolamines, N-alkyldiisopropanolamines, triethanolamine, triisopropanolamine, tetrakis(2-hydroxyethyl)ethylenediamine, tetrakis(2-hydroxypropyl)ethylenediamine, etc. Of these, the diols, the aliphatic polyols, the alkanolamines, and polyols having a molecular weight of 2,000 or less are preferably used.

The amine compound of the general formula (XVII) includes, for example, aromatic diamines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'dimethyl-4,4'-diaminodiphenylmethane, tolidine base, dianisidine, bis (m-aminophenoxy)phenyl] sulfone, bis[4- (p-aminophenoxy)phenyll sulfone, bis[3-methyl-4- (p-aminophenoxy)phenyl] sulfone, 3, 3'-dimethoxy-4,4'diaminobiphenyl, 3,3' -dimethyl-4, 4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diamino-5, 2,2' ,5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-ciiaminobiphenyl, 2,2' -diaminobiphenyl, 4,4'-diaininobiphenyl, 2,2'-dichloro-4, 4'-diaminobiphenyl, 3,3'-dichloro-4,4'--diaminobiphenyl, 2,2'dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'diaminodiphenyl ether, 3,3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, 3,4'-diaminocliphenylmethane, bis (3-amino-4chiorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4,4' -diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3, 4'-diaminodiphenyl sulfone, 3, 3'-diaminodiphenylmethane, 4,4' -diaminodiphenylamine, 4,4' ethylenedianiline, 4, 4'-diamino-2,2'-dimethyldibenzyl, 3,3' -diaminobenzophenone, 4, 4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene, 1,3-bis (3-aminophenoxy)benzene, 9,9bis (4-aminophenyl) fluorene, 2, 2-bis (4-aminophenoxyphenyl)propane, 4,4' -bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, etc. Amine compounds of the general formula (XVII) in which y 1 is a sulfonyl group or a methylene group are preferable.

For obtaining each of the urea-urethane *0 74 compounds of the first to fourth aspects of the present invention, the isocyanate and the corresponding reactants are mixed to be reacted in an organic solvent or without a solvent, after which filtration, crystallization, desolvation, etc. are carried out to collect crystals, whereby the desired compound is obtained.

The reaction may be carried out by a method in which a material having two or more groups in the molecule is used in large excess and another material to be reacted with the groups is added thereto in small portions.

When this method is adopted, it is possible to react only one of the two or more groups. In the addition, it is preferable to stir the system thoroughly to effect sufficient dispersion of the added material immediately after the addition. The above applies to any of the urea-urethane compounds exemplified herein.

A method for the reaction is not limited to the above method and any method may be adopted so long as the same result as above can be obtained. As each of the reactants, one or more compounds may be used depending on purposes. As the solvent, any solvent may be used so long as it does not react with an isocyanate group and the functional groups of the reactants. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and ketones. Methyl ethyl ketone, toluene and the like are especially preferable which dissolve the isocyanate and in which the reaction product has a low solubility. The reaction product obtained by the above reaction procedure is not always a single compound, but is obtained as a mixture of compounds different in the position of a substituent, in some cases.

Specific examples of the urea-urethane compounds of the first to fourth aspects of the present invention are the following compounds to (S- O H 0 H3 0 N N CO N N H H H (sO4) N N N 0 0 H H H H3C 0 0 i-C3H 7 N 0 aN 0 N N N H H H

(S-

4 0o 0 0 C n-C4H9C (S-6) (S-7) (S-8) (S-9) (S-11) (S-12) (S-13) 0 N

H

0 11 n-Cl8H37N, 0 lc',N

H

(6T-S)

H

0 N, 0

H

0, 0 (8T-S)

(LT-S)

H

O

N.

0

H

LHCOV 0>Y 0 (9 T-S)

H

.Nr 0'HEu 0

(ST-S)

H

'IN Ir0

-SZ

0 T7-S) (S-21) (S-22) n-C 4

HO-C

2 H Ja N K~NO -C 2

H

4 -O-n-C 4

H

9 H HH HH (S-23) 0 A- u N N z N A ~NOC2;HA- (S-24) 0 HC(0-CHy.0'k 0

H

3 C-0 A N' (S-26)

H

3 C-0 ru N (S-27) aC 3 3

N

H

3 C- 0 N IhINN N O-A0CH 3 (S-28) (S-29) (S-31) (S-32) H H (S-34) (S-36) (S-37) (S-38) 0

H

2

H

0 11

H

3 Cl- ooc~ .C.

H

0 11

C

2

H

5 0 lC~l 0 11 n-37,,0 ,ClN'

H

(S-39) (S-41) (S-42) (S-43) (S-44) (S-46)

'.CH

3 N N I-cN" H H H 0 i-C 4

H

9

I~C.

0 O-6 l N'

H

0

H

0 11 n-Cl 8

H

37 oe CN'

H

(S-47) N Ir0 -1 0

(GS-S)

H

0

H

A NI 0 0 (cs-s)

H

O N, 6 H0-! 1 0

H

0

H

0

(TS-S)

(os-S) (6k-S) (8k-s) 0 (S-56) (S-57)

H

3 0 n-C 4 H-0 -C 2 Hr-0 l N (S-58)

H,(

L-0-C 2

H

4 -0 N' (S-59) 0 *I9I 0-C 2

H

4 -0-n-CH 9 lz CH 3

H

0 'N 0R -CH 3

H

(S-61) 0 (S-62) (S-63) 0O0 (S-64) cK 0 l P (S-66) (S-67) CN N N' H I I

H

2 C-o a

CH

3 't

H

2 C-O H H Q CH 3 C-N N H N I HI (S-68)

H

3 C 0 C-N N N"

H

2 C-0 a H 3 C H' HI

H

2 I

C

2

H

5

N

a2 H C H H C-N N H N N' I I (S-69) 3- CH 3

H

2

H

2 0 C1 N C-C-O--C-N N H H

CH

3 0I H H

H

Each of the urea-urethane compositions according to the fifth to twelfth aspects of the present invention and the urea-urethane compositions produced by the production processes of the thirteenth to twentieth aspects of the invention preferably comprises 50 wt% or more, more preferably 60 wt% or more, further preferably 70 wt% or more of a ureaurethane compound having in the molecule at least one urethane group (-NHCOO- group) and at least one urea group (-NHCONH- group) in a total number of 2 to 10 and having a molecular weight of 5,000 or less.

Such a urea-urethane composition can be used in combination with a colorless or light-colored dye precursor in order to obtain a color-producing composition for a heat-sensitive recording material or a pressure-sensitive recording material. This colorproducing composition is so effective that it is excellent in both color-producing capability and print preservability.

86 The urea-urethane compound as the main constituent of the urea-urethane composition has at least one urea group and at least one urethane group in the molecule. The urea group and the urethane group are preferably adjacent to each other through at least one compound residue (such a structure portion is hereinafter referred to as a urea-urethane structure portion). The total number of the urethane group(s) and the urea group(s) is not more than 10 and not less than 2, preferably not more than 10 and not less than 3, more preferably not more than 10 and not less than 4.

The ratio of urethane group(s) to urea group(s) in a molecule of the urea-urethane compound is preferably 1 3 to 3 1, more preferably 1 2 to 2 1, most preferably 1 1. The molecular weight of the urea-urethane compound is 5,000 or less, preferably 2,000 or less.

The content of the urea-urethane compound in each of the urea-urethane compositions according to the fifth to twentieth aspects of the present invention is wt% or more. Such a urea-urethane composition can be produced by a relatively simple production process.

On the other hand, it can exhibit excellent performance characteristics because of the high proportion of the urea-urethane compound capable of exhibiting excellent color-developing capability and preserving capability which are required of a color-producing composition.

*0 87 In addition, as the urea-urethane compound, either a single compound or a mixture of two or more compounds including isomers may be used.

Furthermore, a mixture of two or more compounds including isomers may be used as the ureaurethane compound in order to improve the colordeveloping capability, preserving capability and the like.

On the other hand, the urea-urethane compound of the present invention may be properly diluted with a material that does not lessen the effects of the present invention. Such a diluent includes, for example, the heat-meltable materials, acidic developers, amine compounds, isocyanate compounds, urea compounds, urethane compounds and the like, which are described hereinafter. Of these, the urea compounds and the urethane compounds, which have a structure similar to that of the urea-urethane compound, are preferable because they can improve the sensitivity.

In addition, compounds obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound are preferable. Such a diluent is preferably contained in the resulting dilution in a proportion of 0.0001 to 50 wt% based on the total weight of the urea-urethane compound and the diluent.

The content of the diluent is more preferably 40 wt% or less, still more preferably 30 wt% or less, for the exhibition of the preserving capability. The content 88 of the diluent is more preferably 0.01 wt% or more, still more preferably 1 wt% or more, for improving the sensitivity. Such a diluent is produced during the synthetic reaction of the urea-urethane compound in some cases. When the diluent is added, its addition during the synthetic reaction is preferable for improving the sensitivity. For example, preferable is a urea-urethane composition comprising a diluent and a urea-urethane compound having at least one urea group and at least one urethane group in a total number of 2 to 10 in the molecular structure and having a molecular weight of 5,000 or less, which is characterized by comprising the diluent in a proportion of 0.0001 to wt%. The same effect is observed also in the case of the compositions of the eighth to twelfth aspects of the present invention and the compositions produced by the production processes of the thirteenth to twentieth aspects of the invention.

Each of the urea-urethane compositions according to the fifth to twentieth aspects of the present invention is preferably a colorless or lightcolored solid having a melting point, from the viewpoint of utility in a heat-sensitive recording material. The melting point of the composition is preferably 40 0 C to 300 0 C, more preferably 60 0 C to 260 0

C.

As a process for producing any of the ureaurethane compositions according to the fifth to twentieth aspects of the present invention, there is preferably adopted a process of forming one or more urethane groups from at least one of the isocyanate groups of a polyisocyanate compound and the hydroxyl group(s) of a hydroxy compound, and then forming one or more urea groups from the remaining unreacted isocyanate group(s) of the same polyisocyanate compound and the amino group(s) of an amino compound; or a process of forming one or more urea groups from at least one of the isocyanate groups of a polyisocyanate compound and the amino group(s) of an amino compound, and then forming one or more urethane groups from the remaining unreacted isocyanate group(s) of the same polyisocyanate compound and the hydroxyl group(s) of a hydroxy compound.

When one or more urethane groups are formed from a polyisocyanate compound and a hydroxy compound, the urea-urethane composition can be efficiently obtained by using the polyisocyanate compound in an excess amount over hydroxyl group(s), bonding the polyisocyanate compound to the hydroxy compound in an amount of one molecule per hydroxyl group of the hydroxy compound to react only one of the isocyanate groups of the polyisocyanate compound and leave at least one of the isocyanate groups unreacted, and then reacting the remaining unreacted isocyanate group(s) with an amino compound to form one or more urea groups.

In this case, it is preferable to form one or more urethane groups by reacting the polyisocyanate compound with the hydroxy compound so that the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound becomes 100/1 to 1/2, and that the ratio of the number of isocyanate group equivalents of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound becomes 1000/1 to 1/1.

In adding the hydroxy compound to the polyisocyanate compound, the hydroxy compound is preferably added in small portions so that the polyisocyanate compound is always present in the reaction system in an excess amount over hydroxyl group(s). Such an adding method is preferable particularly when the reaction is carried out at a ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound of near 1/1, for example, 5/1 to 1/2.

Similarly, when one or more urea groups are formed from a polyisocyanate compound and an amino compound, the urea-urethane composition can be efficiently obtained by using the polyisocyanate compound in an excess amount over amino group(s), bonding the polyisocyanate compound to the amino compound in an amount of one molecule per amino group of the amino compound to react one of the isocyanate groups of the polyisocyanate compound and leave at least one of the isocyanate groups unreacted, and then reacting the remaining unreacted isocyanate group(s) with a hydroxy compound to form one or more urethane groups. In this case, it is preferable to form one or more urea groups by reacting the polyisocyanate compound with the amino compound so that the ratio of the number of moles of the polyisocyanate compound to the number of amino equivalents of the amino compound becomes 100/1 to 1/2, and that the ratio of the number of isocyanate group equivalents of the polyisocyanate compound to the number of amino equivalents of the amino compound becomes 1000/1 to 1/1.

In adding the amino compound to the polyisocyanate compound, the amino compound is preferably added in small portions so that the polyisocyanate compound is always present in the reaction system in an excess amount over amino group(s). Such an adding method is preferable particularly when the reaction is carried out at a ratio of the number of moles of the polyisocyanate compound to the number of amino equivalents of the amino compound of near 1/1, for example, 5/1 to 1/2.

In a process for producing any of the urethane-urea compositions according to the fifth to twentieth aspects of the present invention, the reaction of a polyisocyanate compound with a hydroxy compound for forming one or more urethane groups is preferably carried out without a solvent or by adding, dropping or pouring the hydroxy compound without a 92 solvent, a dilution of the hydroxy compound with a solvent or a dispersion of the hydroxy compound in a solvent continuously or by portions to a dilution of the polyisocyanate compound with a solvent or a dispersion of the polyisocyanate compound in a solvent.

Similarly, the reaction of a polyisocyanate compound with an amino compound for forming one or more urea groups may be carried out without a solvent or by adding, dropping or pouring the amino compound without a solvent, a dilution of the amino compound with a solvent or a dispersion of the amino compound in a solvent continuously or by portions to a dilution of the polyisocyanate compound with a solvent or a dispersion of the polyisocyanate compound in a solvent.

The above production process comprising adding a hydroxy compound or an amino compound to a polyisocyanate compound in small portions is preferable particularly in the following case: in a reaction process for the production of the urea-urethane composition, while leaving at least one of the isocyanate groups in molecules of the polyisocyanate compound, the other isocyanate group(s) is reacted with the hydroxy compound or the amino compound to form one or more urethane groups or urea groups, respectively.

Moreover, said production process is preferable when a hydroxy compound having two or more hydroxyl groups or an amino compound having two or more amino groups is reacted with a polyisocyanate compound having two or more isocyanate groups.

In carrying out the above reactions, it is preferable to stir the system thoroughly so that the hydroxy or amino compound added, dropped or poured into the polyisocyanate is immediately and sufficiently dispersed. It is preferable to stir the reaction system thoroughly, for example, by adjusting the stirring rate in a reactor, choosing an agitating blade or setting a baffle plate.

It is preferable to carry out the reaction for forming one or more urethane groups and the reaction for forming one or more urea groups, individually and successively. When they are carried out at the same time, the urea-urethane compound content of the urea-urethane composition is undesirably decreased.

It is preferable to carry out these urethane group forming reaction and urea group forming reaction continuously. In the process of the present invention, since separation and purification steps are not necessary in the course of the production, the production can be simplified by carrying out the two reaction steps continuously.

In the production of any of the urea-urethane compositions according to the fifth to twentieth aspects of the present invention, when a polyisocyanate adduct with a hydroxy compound is used which is an isocyanate already having one or more urethane groups in the molecule, the urea-urethane composition can be 94 obtained by reacting this adduct with an amino compound. In this case, it is preferable to form one or more urea groups by carrying out the reaction at an equivalent ratio of isocyanate group to amino group of 2/1 to 1/100, and remove the unreacted amino compound.

In the production of any of the urea-urethane compositions according to the fifth to twentieth aspects of the present invention, when a polyisocyanate adduct with an amino compound is used which is an isocyanate already having one or more urea groups in the molecule, the urea-urethane composition can be obtained by reacting this adduct with a hydroxy compound. In this case, it is preferable to form one or more urethane groups by carrying out the reaction at an equivalent ratio of isocyanate group to hydroxyl group of 2/1 to 1/100, and remove the unreacted hydroxy compound.

When a solvent is used for carrying out the reaction(s) in the production of any of the ureaurethane compositions according to the fifth to twentieth aspects of the present invention, the solvent is not particularly limited so long as it does not react with an isocyanate group and the like. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, ketones and phosphoric esters. Acetone, methyl ethyl ketone, toluene and the like are especially preferable which dissolve the isocyanate and in which the reaction product has a low solubility.

When a high dissolving power for the isocyanate is necessary, the phosphoric esters, in particular, trimethyl phosphate are preferable.

When such a solvent is used, the formation of one or more urethane groups and the formation of one or more urea groups are preferably carried out in one and the same solvent in order to make it easy to reuse the solvent and carry out the reaction for the urea group formation and the reaction for the urethane group formation continuously.

The reaction temperature at which a polyisocyanate is reacted with a hydroxy compound and/or an amino compound to form one or more urethane groups and/or one or more urea groups is 00C to 3000C, preferably 50C to 2000C, more preferably 100C to 150°C. The reaction temperature is properly adjusted depending on the polyisocyanate compound, hydroxy compound and amino compound selected. It is also possible to carry out the urethane group formation and the urea group formation at different temperatures suitable for the formations, respectively.

A catalyst may be used for reacting a polyisocyanate with a hydroxy compound and/or an amino compound to form one or more urethane groups and/or one or more urea groups. The catalyst includes, for example, tertiary amine compounds such as triethylamine, 1,4-diazabicyclo(2,2,2)octane, etc.; and organic acid tin salts such as dibutyltin dilaurate, etc.

Usually, the catalyst concentration is 1 to 10,000 ppm, preferably 10 to 2,000 ppm, relative to the isocyanate compound. Of the above-exemplified catalysts, the tertiary amine compounds are preferable.

A urea-urethane composition containing a urea-urethane compound having a plurality of ureaurethane structure portions in the molecule can be obtained by repeating the steps of the production process of the present invention two or more times by using, for example, an amino compound having two or more amino groups and a hydroxy compound having two or more hydroxyl groups. Since a sufficiently high yield from reaction can be attained in each step, the production process of the present invention permits relatively easy production of a urea-urethane composition having high performance characteristics.

The polyisocyanate compound used in each of the fifth to twentieth aspects of the present invention is not particularly limited so long as it has two or more isocyanate groups bonded to carbon atoms, respectively. The polyisocyanate compound includes, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, benzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'diphenylmethane diisocyanate, hexamethylene dilsocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris(4-phenylisocyanate) thiophosphate, 4,4',4"-triisocyanato-2,5-dimethoxytriphenylamine, 4,4',4"-triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexylisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane diisocyanate. As the polyisocyanate compound, there may also be used diisocyanate dimers such as N,N'-(4,4'-dimethyl-3,3'-diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), a toluene dilsocyanate dimer; and diisocyanate trimers such as 4,4',4"-trimethyl-3,3',3"-triisocyanato-2,4,6triphenylcyanurate. There may also be used water adduct isocyanates of toluene diisocyanate, diphenylmethane diisocyanate and the like, such as 1,3-bis(3isocyanato-4-methylphenyl)urea; polyol adducts such as trimethyloipropane adducts of toluene diisocyanate (Desmodule L and Coronate L, trade names); and amine adducts. There may also be used compounds having two or more isocyanate groups, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171 (the contents of these references are hereby incorporated herein by reference).

The above-exemplified compounds may be used singly or in combination.

Of the above-exemplified compounds, preferable examples of the polyisocyanate compound are aromatic polyisocyanates having isocyanate groups bonded to a benzene ring, such as p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, naphthylene diisocyanate, triphenylmethane triisocyanate, N,N'-(4,4'-dimethyl-3,3'-diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), 4,4',4"-trimethyl-3,3',3"-triisocyanato-2,4,6triphenylcyanurate, 1,3-bis(3-isocyanato-4methylphenyl)urea, trimethylolpropane adducts of toluene diisocyanate (Desmodule L and Coronate L, trade names), etc. Especially preferable examples of the polyisocyanate compound are toluene diisocyanates. Of the toluene diisocyanates, 2.4-toluene diisocyanate is preferable. Besides 2.4-toluene diisocyanate, mixtures of 2.4-toluene diisocyanate and 2,6-toluene diisocyanate are generally on the market and available at a low price and may also be used as the polyisocyanate compound.

As the hydroxy compound that is reacted with the polyisocyanate compound to form one or more urethane groups, phenolic compounds and alcohol compounds are mentioned.

The phenolic compounds include, for example, phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tertoctyiphenol, 2-cyclohexyiphenol, 2-allylphenol, 4indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl)propane, 2,2-bis (hydroxyphenyl)butane, 2, 2-bis (hydroxyphenyl)pentane, 2,2-bis (hydroxyphenyl)heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methyihydroquinone, 4phenylphenol, p,p' -biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl)acetate, bis (4-hydroxyphenyl) sulfone, bis (3methyl-4-hydroxyphenyl) sulfone, bis 5-dimethyl-4hydroxyphenyl) sul fone, 4 -hydroxyphenyl- 4'-me thylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4' -methyiphenyl sulfone, 3, 4-dihydroxyphenyl-4' -methylphenyl sulfone, 4-isopropyloxyphenyl-4' -hydroxyphenyl sulfone, bis (2allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4' benzyloxyphenyl sulfone, 4-isopropylphenyl-4'hydroxyphenyl sulfone, 4-hydroxy-4' -isopropoxydiphenyl sulfone, bis (2-net--hyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'thiodiphenol, 4, 4'-dihydroxybenzophenone,.2, 2-bis (4hydroxyphenyl) hexafluoropropane, 4,4' -dihydroxydiphenylmethane, 3,3' -dihydroxydiphenylamine, bis (4- 100 hydroxy-3-methylphenyl) sulfide, bis(4-(2-hydroxy)phenyl) sulfone, 2,4-dihydroxybenzophenone, tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis(4'-hydroxybenzoate), pentyl 1,5-bis(4'hydroxybenzoate), hexyl 1,6-bis(4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-noctyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid and 4-n-octanoyloxycarbonylaminosalicylic acid.

Of the above-exemplified phenolic compounds, phenol, phenol derivatives represented by the following formula and diphenol compounds represented by the following formula (XVI) are preferable.

OH (w) wherein hydrogen atom(s) of the benzene ring may be replaced by an alkyl group, a cycloalkyl group, a phenyl group, an amide group, an alkoxyl group, a nitro group, a nitrile group, a halogen atom, a formyl group, a dialkylamino group, a toluenesulfonyl group, a methanesulfonyl group or an OH group; and 101 HO-- OH (xvI) wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue though the substituent may be a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, each of the residues may have one or more substituents, 6 is a group selected from the group consisting of -SO2-,

-(CH

2 -CONH-, -CH(COORi)-, -C(CF 3 2 and

-CR

2

R

3 or is absent, R 2 and R 3 are independently an alkyl group, and n is 1 or 2.

The term "aliphatic" used in the case of the fifth to twentieth aspects of the present invention includes the term "alicyclic".

The term "aliphatic compound residue" used in the case of the fifth to twentieth aspects of the present invention means a residue bonded by the carbon atom of the aliphatic hydrocarbon portion in the residue. The term "aromatic compound residue" used therein means a residue bonded by the carbon atom of the aromatic ring such as benzene ring in the residue.

102 The term "heterocyclic compound residue" used therein means a residue bonded by the carbon atom forming the heterocyclic ring in the residue.

Preferable examples of the substituent of the aliphatic compound residue, heterocyclic compound residue or aromatic compound residue are alkyl groups, cycloalkyl groups, phenyl group, amide group, alkoxyl groups, nitro group, nitrile group, halogen atoms, formyl group, dialkylamino groups, toluenesulfonyl group and methanesulfonyl group.

As the alcohol compounds, compounds having at least one OH group bonded to the carbon atom of an aliphatic compound are mentioned. Examples of the alcohol compounds are the alcohols described in Solvent Handbook, Kodansha Scientific Co., Ltd., the ninth impression (1989), pp. 327-420 and pp. 772-817. The alcohol compound includes, for example, aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tertbutanol, pentanol, cyclopentanol, tert-amyl alcohol, 2pentanol, isoamyl alcohol, hexanol, 3-hexanol, cyclohexanol, cyclohexylmethanol, 4-methyl-2-pentanol, heptanol, isoheptanol, octanol, 2-ethyl-l-hexanol, capryl alcohol, nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, isostearyl alcohol, etc.; unsaturated aliphatic alcohols such as ally alcohol, 2- 103 methyl-2-propen-l-ol, crotyl alcohol, propargyl alcohol, etc.; aliphatic alcohols having an aromatic compound residue bonded thereto, such as benzyl alcohol, cinnamyl alcohol, etc.; aliphatic alcohols having a heterocyclic compound residue bonded thereto, such as 2-pyridinemethanol, 3-pyridinemethanol, 4pyridinemethanol, furfuryl alcohol, etc.; halogenated aliphatic alcohols such as 2-chloroethanol, l-chloro-3hydroxypropane, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene 104 glycol monoisobutyl ether, dipropylene glycol monophenyl ether, etc.; diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol, etc.; aliphatic polyols such as glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, a-methyl glucoside, sorbitol, sucrose, etc.; polyols such as polyethylene glycols, polypropylene glycols, polytetramethylene glycols, adipate-derived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, amine-modified polyols, polyether polyols obtained by adding one of or a mixture of two or more of alkylene oxides ethylene oxide and propylene oxide) to one of or a mixture of two or more of polyhydric alcohols (glycerin and propylene glycol), acryl polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, castor oil-derived polyols, polymer polyols, halogen-containing polyols, phosphorus-containing polyols, etc.; and alkanolamines such as N,N-dialkylethanolamines, N,N-dialkylisopropanolamines, Nalkyldiethanolamines, N-alkyldiisopropanolamines, triethanolamine, triisopropanolamine, tetrakis(2-hydroxyethyl)ethylenediamine, tetrakis(2-hydroxypropyl)ethylenediamine, etc.

105 Of the above-exemplified alcohol compounds, aliphatic alcohols having 10 or less carbon atoms, the glycol ethers, the diols, the aliphatic polyols, polyols having a molecular weight of 2,000 or less, and the alkanolamines are preferable.

The above-exemplified alcohol compounds may be used singly or in combination, and the aboveexemplified phenolic compounds may also be used singly or in combination.

As the amino compound that is reacted with the polyisocyanate compound to form one or more urea groups, any compound may be used so long as it has one or more amino groups bonded to carbon atoms, respectively. The amino compound includes, for example, aromatic amines such as aniline, o-toluidine, mtoluidine, p-toluidine, o-anisidine, p-anisidine, pphenetidine, N,N-dimethyl-p-phenylenediamine, N,Ndiethyl-p-phenylenediamine, 2,4-dimethoxyaniline, dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, maminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,6-dichloroaniline, 3,4-dichloroaniline, dichloroaniline, 2,4,5-trichloroaniline, a-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butyl- 106 aniline, N,N-diglycidylaniline, N,N-diglycidyl-otoluidine, acetoacetic acid anilide, trimethyiphenylammonium bromide, 4, 4'-diamino-3, 3'-diethyldiphenylmethane, 4, 4'-diaminobenzanilide, 3, benzene, diaminodiphenyl ether, 3, 3'-dichloro-4, 4'diaminodiphenylmethane, 3,3' -dimethyl-4, 4'diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2chloro-p-phenylenediamine, dianisidine, methyl paminobenzoate, ethyl p-aminobenzoate, n-propyl paminobenzoate, isopropyl p-aminobenzoate, butyl paminobenzoate, dodecyl p-aminobenzoate, benzyl paminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, oaminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4methoxybenzamide, 3-amino-4-chlorobenzamide, p- (Nphenylcarbamoyl) aniline, p-EN- (4-chlorophenyl)carbamoyl]aniline, p- (4-aminophenyl) carbamoyl]aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2- -methyl-3' -chlorophenyl) carbamoyl] aniline, 2-methoxy-5- (2'-chlorophenyl) carbamoyl]aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, diethoxy-4- (N-benzoylamino)aniline, 2,5-dimethoxy-4- (Nbenzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) methylaniline, 4-sulfamoylaniline, 3-sul famoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethyl- 107 aminosul fonylaniline, 4-diethylaminosulfonylaniline, sul fathiazole, 4-aminodiphenyl sulfone, phenylsulfamoylaniline, sulfamoylaniline, 2, 5-dimethoxy-4-N-phenysulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis[4- (Iaminophenoxy) phenyl] sulfone, bis (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-ciiaminobiphenyl, 3,3'dimethyl-4, 4'-diaminobiphenyl, 2,2'-dichloro-4,4'- 5'-dimethoxybiphenyl, 5, 4, 4'-diaminobiphenyl, o-tolidine sulfone, 2,4'diaminobiphenyl, 2,2' -diaminobiphenyl, 4,4' -diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'dichloro-4,4'-diaminobiphenyl, 2,2'-dirnethyl-4,4'diaminobiphenyl, 4, 4'-thiodianiline, 2,2'dithiodianiline, 4,4' -dithiodianiline, 4,4' diaminodiphenyl ether, 3,3' -ciaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4, 4'-diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, bis (3-amino-4chiorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4,4' -diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3,4'-diam~iinodiphenyl sulfon-e, 3,3'-diarninodiphenylmethane, 4, 4-diaminodiphenylamine, 4,4' ethylenedianiline, 4, 4'-diamino-2,2'-dimethyldibenzyl, 3,3' -diaminobenzophenone, 4,4'-diarninobenzophenone, 1,4-bis (4-aminophenoxy)benzene, 1,3-bis (4-amino- 108 phenoxy)benzeie, 1,3-bis(3-aminophenoxy)benzene, 9,9bis (4-aminophenyl) fluoreie, 2,2-bis (4-aminophenoxyphenyl)propane, 4,4' -bis (4-aminophenoxy) diphenyl, 3,3',4,4-tetraaminodiphenyl ether, tetraaminodiphenyl sulfone, 3,3' ,4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3phenoxyaniline, 4, 4'-methylenebis-o-toluiline, (pphenyleneisopropylidene)-bis- 6-xylidine), o-chlorop-nitroaniline, o-nitro-p-chloroaniline, 2, 6-dichioro- 4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4chiorophenol, o-nitroaniline, m-nitroaniline, pnitroaniline, 2-methyl-4-nitroaniline, m-nitro-ptoluidine, 2-amino-5-nitrobenzonitrile, Metal, 2,4diaminophenol, N- (P-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4trifluoroaniline, m-aminobenzotrifluoride, mtoluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4,4'-diaminostilbene-2,2'disulfonic acid, benzylethylaniline, 1, 8-naphthalenediamine, sodium naphthionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4diamino-2, 3-dichioroanthraquinone, etc.; heterocyclic compound amines such as 3-amino-1,2,4-triazole, 2- 109 aminopyridine, 3-aminopyridine, 4-aminopyridine, aamino- E -caprolactam, acetoguanamine, 2,4-diamino-6- methylimidazolyl-(l)lethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1-(2-aminoethyl)piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl)morpholine, etc.; and aliphatic amines such as methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethyihexylamine, ethanolamine, 3- (2-ethyihexyloxy)propylamine, 3-ethoxypropylamine, dilsobutylamine, 3-(diethylamino)propylamine, di-2ethyihexylamine, 3-(dibutylamino)propylamine, tbutylamine, propylamine, 3-(methylamino)propylamine, 3- (dimethylamino)propylamine, 3-methoxypropylamine, methyihydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2methoxyethylamine, 2-ethoxymethylamine, 2-amino-lpropanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine, etc.

In addition, of the above-exemplified amino compounds, the aromatic amines are preferable, and aniline derivatives having at least one amino group and represented by the following formula or (VIII) are especially preferable: 110

RI

NH2 (Z) R2 wherein R, and R 2 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group; or

R

1

X

1 2 R3 KJ (VIII)

R

2 R4 wherein Ri, R 2

R

3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group, X, and X 2 are independently an amino group or a group represented by the formula -0 -NH2 (b)

NH

2 and YI is any of -S02-, -(CH 2

-CO-,

-CONH-, -CH(COORi)-, -C(CF 3 2

-CR

2

R

3 and a group represented by any of the formulas 0 111 OOl

CH

3 CH 3 -C C-

CH

3 CH 3 -oOQ 0 0or is absent, each of R 1

R

2 and R 3 is an alkyl group, and n is 1 or 2.

Such amine compounds may be used singly or in combination.

The urea-urethane compound used as a developer in each of the twenty-first and twenty-second aspects of the present invention refers to a compound 0@ 112 having at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) in the molecule.

It has been known that compounds having one or more urea groups have color-developing effect, but they have not been practical because they give a low coloring density and have an insufficient shelf stability. However, surprisingly, a urea-urethane compound having at least one urea group and at least one urethane group in the molecule is an excellent developer for a colorless or light-colored dye precursor, and a color-producing composition comprising the urea-urethane compound and the dye precursor and a recording material obtained by using the colorproducing composition give a high coloring density and have an excellent shelf stability.

Although a mechanism by which such a ureaurethane compound exhibits an excellent colordeveloping effect is unknown, it is conjectured that the effect is due to the interaction between the urea group(s) and the urethane group(s) in the molecule.

As the urea-urethane compound used as developer in each of the twenty-first and twenty-second aspects of the present invention, any compound may be used so long as it has both at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) in the molecule. The urea-urethane compound is preferably an aromatic compound or a 113 heterocyclic compound. In addition, the urea-urethane compound is preferably a compound in which an aromatic compound residue or heterocyclic compound residue is directly bonded to each end of each of the urea group(s) and the urethane group(s). It is more preferable that besides the urea group(s) (-NHCONH- group(s)) and urethane group(s) (-NHCOO- group(s)), one or more sulfonic acid groups (-SO 2 groups), amide groups (-NHCO- groups) or isopropylidene groups (-C(CH 3 2 groups) be present in the molecule without binding directly to the urea group(s).

The molecular weight of the urea-urethane compound is preferably 5,000 or less, more preferably 2,000 or less. The total number of urea group(s) and urethane group(s) in the urea-urethane compound is preferably 20 or less, more preferably 10 or less. The ratio of urea group(s) to urethane group(s) in the molecular structure of the urea-urethane compound is preferably 1 3 to 3 1, in particular, 1 2 to 2 1.

When used in a heat-sensitive recording material, the urea-urethane compound is preferably one that has a melting point. The melting point ranges preferably from 40 0 C to 500 0 C, in particular, from 60 C to 300 0

C.

A process for synthesizing the urea-urethane compound used as developer in each of the twenty-first and twenty-second aspects of the present invention is 114 not particularly limited so long as at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) are formed. A process in which the urea-urethane compound is produced by the reaction of an isocyanate compound with an OH group-containing compound and an amine compound is preferable because of its ease.

In detail, in the case of the urea-urethane compound used as developer in the present invention, an isocyanate having at least two isocyanate groups is used as a starting material and one or more urethane groups are formed by reacting all the isocyanate groups except at least one with an OH group-containing compound, after which one or more urea groups can be formed by reacting the remaining isocyanate group(s) with an amine compound. It is also possible to form one or more urea groups by reacting all the isocyanate groups except at least one with an amine compound at first, and then form one or more urethane groups by reacting the remaining isocyanate group(s) with an OH group-containing compound.

The starting isocyanate is not particularly limited so long as it has two or more isocyanate groups. The starting isocyanate includes, for example, p-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 115 naphthylene diisocyanate, dianisidine diisocyanate, 9ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris(4-phenylisocyanato)thiophosphate, 4,4',4"-triisocyanato-2,5-dimethoxytriphenylamine, 4,4',4"-triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexylisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane diisocyanate. As the starting isocyanate, there may also be used diisocyanate dimers such as (4,4'-dimethyl-3, 3'-diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), a toluene diisocyanate dimer; and diisocyanate trimers such as 4,4',4"-trimethyl-3,3',3"-triisocyanato-2,4,6triphenylcyanurate. There may also be used water adduct isocyanates of toluene diisocyanate, diphenylmethane diisocyanate and the like, such as 1,3-bis(3isocyanato-4-methylphenyl)urea; polyol adducts such as trimethyloipropane adduct of toluene diisocyanate (Desmodule L, a trade name); and amine adducts. There may also be used compounds having two or more isocyanate groups, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-8-225445 and the specification of JP-A- 8-250623.

Especially preferable examples of the 116 starting isocyanate are toluene diisocyanates. Of the toluene diisocyanates, 2.4-toluene diisocyanate is preferable. Besides 2.4-toluene diisocyanate, mixtures of 2.4-toluene diisocyanate and 2,6-toluene diisocyanate are generally on the market and available at a low price and may also be used as the staring isocyanate.

As the amine compound that is reacted with the starting isocyanate for the urea-urethane compound as developer to form one or more urea groups, any compound may be used so long as it has one or more amino groups. The amine compound includes, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, pphenetidine, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-pphenylenediamine, 2,4-dimethoxyaniline, aniline, 3,4-dimethoxyaniline, p-aminoacetanilide, paminobenzoic acid, o-aminophenol, m-aminophenol, paminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, pcresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5trichloroaniline, a-naphthylamine, aminoanthracene, oethylaniline, o-chloroaniline, m-chloroaniline, pchloroaniline, N-methylaniline, N-ethylaniline, Npropylaniline, N-butylaniline, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, acetoacetic acid anilide, 117 trimethyiphenylammonium bromide, 4, 4'-diamino-3, 3'diethyldiphenylmethane, 4,4' -ciaminobenzanilide, diaminochlorobenzene, diaminodiphenyl ether, 3,3'dichloro-4, 4'-diaminodiphenylmethane, 3,3'-dimethyl- 4,4'-diaminodiphenylmethane, tolidine base, ophenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-amiriobenzoate, isopropyl p-aminobenzoate, butyl paminobenzoate, dodecyl. p-aminobenzoate, benzyl paminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, i-aminobenzamide, 0aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4methoxybenzamide, 3-amino-4-chlorobenzamide, p- (Nphenylcarbamoyl) aniline, p-EN- (4-chiorophenyl) carbamoyl] aniline, p-EN- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2- -methyl-3' -chiorophenyl) carbamoyl] aniline, 2-methoxy-5- (2'-chlorophenyl) carbamoyl]aniline, S-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, diethoxy-4- (N-benzoylamino) aniline, 2, 5-dimethoxy-4- (Nbenzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosul fonylani line, sulfathiazole, 4-aminodiphenyl sulfone, 118 phenylsulfamoylaniline, sulfamoylaniline, 2, 5-dimethoxy-4-N-phenysulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis[4-(maminophenoxy) phenyl] sulfone, bis (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy)phenyl] sulfone, 3, 3'-dimethoxy-4, 4'-diaminobiphenyl, 3,3'dimethyl-4, 4'-diaminobiphenyl, 2,2'-dichloro-4,4'diamino-5,5'-dimethoxybiphenyl, 2,2' 4,4'-diarninobiphenyl, o-tolidine sulfone, 2,4'diaminobiphenyl, 2, 2'-diarninobiphenyl, 4, 4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diaminobiphenyl, 3,3'dichloro-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4, 4'diaminobiphenyl, 4,4'-thiodianiline, 2,2'dithiodianiline, 4,4'-dithiociianiline, 4,4'diaminodiphenyl ether, 3,3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, bis (3-arnino-4chiorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4,4' -diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3, 4'-diaminodiphenyl sulfone, 3, 3'-diaminodiphenylmethane, 4, 4-diaminodiphenylamine, 4,4' ethylenedianiline, 4, 4'-diamino-2,2'-dirnethyldibenzyl, 3, 3'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene, 1,3-bis (3-aminophenoxy)benzene, 9,9bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxy- 119 phenyl) propane, 4,4' -bis (4-aminophenoxy) diphenyl, 3,3',4,4'-tetraaminodiphenyl ether, tetraaminodiphenyl sulfone, 4, 4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3phenoxyaniline, 4, 4'-methylenebis-o-toluidine, (pphenyleneisopropylidene) -bis- 6-xylidine), o-chlorop-nitroaniline, o-nitro-p-chloroaniline, 2, 6-dichioro- 4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4chiorophenol, o-nitroaniline, m-nitroaniline, pnitroaniline, 2-methyl-4-nitroaniline, m-nitro-ptoluidine, 2-amino-5-nitrobenzonitrile, Metol, 2,4diaminophenol, N- (f-hydroxyethyl) -o-aminophenol sulfate, sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N,N-diphenyl-p- phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4, 4'-diaminostilbene-2,2'disulfonic acid, benzylethylaniline, 1, 8-naphthalenediamine, sodium naphthionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4diamino-2, 3-dichioroanthraquinone, etc.; heterocyclic compound amines such as 3-amino-1,2,4-triazole, 2aminopyridine, 3-aminopyridine, 4-aminopyridine, axamino-6-caprolactam, acetoguanamine, 2, 4-diamino-6- 120 methylimidazolyl-(l)lethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1-(2-aminoethyl)piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl)morpholine, etc.; and aliphatic amines such as methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, ciisopropylamine, 2-ethyihexylamine, ethanolamine, 3- (2-ethyihexyloxy)propylamine, 3-ethoxypropylamine, dilsobutylamine, 3-(diethylamino)propylamine, di-2ethyihexylamine, 3-(dibutylamino)propylamine, tbutylamine, propylamine, 3-(methylamino)propylamine, 3- (dimethylamino)propylamine, 3-methoxypropylamine, methyihydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2methoxyethylamine, 2-ethoxymethylamine, 2-amino-lpropanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine, etc.

Of the above-exemplified amine compounds, aniline derivatives having at least one amino group and represented by the following formula (VIII) are especially preferable: (VI I I) 121 wherein R 2

R

3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group, X, and X 2 are independently an amino group or a group represented by the formula -NH2 (b)

NH

2 and Y, is any of -(CH 2

-CO-,

-CONH- and a group represented by any of the formulas 122

CH

3

C--

C C- (a) CH3

CH

3 CH3 -iC 0- (a) CH3 CH3 0 -o IS0or is absent, and n is 1 or 2.

As the OH group-containing compound that is reacted with the isocyanate to form one or more urethane groups, any compound may be used so long as it contains one or more OH groups. The OH groupcontaining compound includes, for example, phenols such as phenol, cresol, xylenol, p-ethylphenol, o-isopropyl- 123 phenol, resorcinol, p-tert-butylpheiol, p-tertoctyiphenol, 2-cyclohexyiphenol, 2-allyiphenol, 4indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl)propane, 2,2-bis (hydroxyphenyl)butane, 2, 2-bis (hydroxyphenyl) pentane, 2, 2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methyihydroquinone, 4phenyiphenol, p,p' -biphenol, 4-cumyiphenol, butyl bis (4-hydroxyphenyl)acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3methyl-4-hydroxyphenyl) sulfone, bis 5-dimethyl-4hydroxyphenyl) sUl fone, 4-hydroxyphenyl- 4' -rethyiphenyl sulfone, 3-chloro-4-hydroxyphenyl-4' -methyiphenyl sulfone, 3, 4-dihydroxyphenyl-4' -iethyiphenyl sulfone, 4-isopropyloxyphenyl-4' -hydroxyphenyl sulfone, bis (2al lyl- 4-hydroxyphenyl) sul fone, 4-hydroxyphenyl-4' benzyloxyphenyl sulfone, 4-isopropylphenyl-4' hydroxyphenyl sul fone, 4-hydroxy- 4'-is opropoxydiphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4, 4'-dihydroxydiphenyl ether, 4,4'thiodiphenol, 4, 4'-dihydroxybenzophenone, 2, 2-bis (4hydroxyphenyl) hexafluoropropane, 4,4' -dihydroxydiphenylmethane, 3,3' -dihydroxydiphenylamine, bis (4hydroxy-3-methylphenyl) sulfide, bis (2-hydroxy) phenyl) sulfone, 2, 4-dihydroxybenzophenone, 4,4'tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4- 124 hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis(4'-hydroxybenzoate), pentyl 1,5-bis(4'hydroxybenzoate), hexyl 1,6-bis(4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-noctyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid, etc. However, as such phenols, those having an amino group are not desirable. Since the amino group has a higher reactivity towards an isocyanate group than does an OH group, the amino group reacts with the isocyanate group before the OH group, so that it is difficult in some cases to obtain the desired compound.

The OH group-containing compound also includes alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, iosbutanol, isopentanol, 2-ethyl-lhexanol, 1-decanol, 2-pentanol, 3-hexanol, tertbutanol, tert-amyl alcohol, methyl Cellosolve, butyl Cellosolve, methyl Carbitol, allyl alcohol, 2-methyl-2propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenyl Cellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, l-chloro-3hydroxypropane, glycerin, glycerol, etc.; polyether 125 type polyols such as polypropylene glycols, polytetramethylene ether glycols, adipate-derived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols, etc.; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6hexane glycol, 1,9-nonanediol, acryl polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor-oil-derived polyols, polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, amethylglucoside, sorbitol, sucrose, etc.

The urea-urethane compound used as developer in each of the twenty-first and twenty-second aspects of the present invention is preferably a urea-urethane compound having a molecular structure in which the number of urea groups and the number of urethane groups satisfy the following numeral formula: R (A B) 3 wherein each of A and B is an integer of 1 or more.

The urea-urethane compound in which the number of urea groups and the number of urethane 126 groups satisfy the numeral formula 10 2 (A B) 3 (wherein each of A and B is an integer of 1 or more) is a compound having a molecular structure in which at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) are present in a total number of not more than 10 and not less than 3.

Such a compound has not been reported and is quite novel. This novel compound is useful in the case of recording materials which use a recording energy such as heat, pressure or the like.

A process for synthesizing the urea-urethane compound in which the number of urea groups and the number of urethane groups satisfy the numeral formula 10 (A B) 3 (wherein each of A and B is an integer of 1 or more) is not particularly limited so long as at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) are formed in a total number of 3 to 10. A process in which the urea-urethane compound is produced by the reaction of an isocyanate compound with an OH group-containing compound and an amine compound is preferable because of its ease.

In detail, as the urea-urethane compound used as developer in each of the twenty-first and twentysecond aspects of the present invention, a ureaurethane compound having at least one urea group and at least one urethane group in a total number of at least 3 can be obtained, for example, by using an isocyanate 0O 127 having at least two isocyanate groups, as a starting material, reacting all the isocyanate groups except at least one with an OH group-containing compound to form one or more urethane groups, and then reacting the remaining isocyanate groups of two molecules of the resulting urethane compound with each other by the use of water to bond them to each other.

In addition, a urea-urethane compound having at least one urea group and at least one urethane group in a total number of at least 3 can be obtained, for example, by using an isocyanate having at least two isocyanate groups, as a starting material, reacting all the isocyanate groups except at least one with an OH group-containing compound to form one or more urethane groups, reacting the remaining isocyanate group(s) with an amine compound having two or more amino groups, to form one or more urea groups, and reacting the remaining amino group(s) with an isocyanate compound.

Furthermore, a urea-urethane compound having at least one urea group and at least one urethane group in a total number of at least 3 can be obtained also by reacting all the isocyanate groups except at least one with an amine compound at first to form one or more urea groups, reacting the remaining isocyanate group(s) with a compound containing two or more OH groups, to form one or more urethane groups, and then reacting the resulting compound with an isocyanate compound. In this case, a urea-urethane compound having at least one 128 urea group and at least one urethane group in a total number of 3 to 10 can be obtained by using an isocyanate compound having two or more isocyanate groups, as the isocyanate to be lastly reacted, and repeating a procedure of reacting the remaining isocyanate group(s) with a compound containing two or more OH groups or an amino compound having two or more amino groups.

The starting isocyanate is not particularly limited so long as it has two or more isocyanate groups. The starting isocyanate includes, for example, p-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, naphthylene diisocyanate, dianisidine diisocyanate, 9ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris(4-phenylisocyanate) thiophosphate, 4,4',4"-triisocyanato-2,5-dimethoxytriphenylamine, 4,4',4"-triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexylisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane diisocyanate.

As the starting isocyanate, there may also be used diisocyanate dimers such as N,N'-(4,4'-dimethyl- 129 3,3'-diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), a toluene diisocyanate dimer; and diisocyanate trimers such as 4,4',4"-trimethyl-3,3',3"triisocyanato-2,4,6-triphenylcyanurate. There may also be used water adduct isocyanates of toluene diisocyanate, diphenylmethane diisocyanate and the like, such as 1,3-bis(3-isocyanato-4-methylphenyl)urea; polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (Desmodule L, a trade name); and amine adducts. There may also be used compounds having two or more isocyanate groups, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171 (the contents of these references are hereby incorporated herein by reference).

Especially preferable examples of the starting isocyanate are toluene diisocyanates. Of the toluene diisocyanates, 2.4-toluene diisocyanate is preferable. Besides 2.4-toluene diisocyanate, mixtures of 2.4-toluene diisocyanate and 2,6-toluene diisocyanate are generally on the market and available at a low price and may also be used as the staring isocyanate. The mixtures of these toluene diisocyanate isomers are liquid at ordinary temperatures.

As the amine compound that is reacted with the starting isocyanate for the urea-urethane compound to form one or more urea groups, any compound may be used so long as it has one or more amino groups. The 130 amine compound includes, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, paminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, aniline, 2,6-dichloroaniline, 3,4-dichioroaniline, dichloroaniline, 2,4,5-trichioroaniline, a-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N,N-diglycidylaniline, N,N-diglycidyl-otoluidine, acetoacetic acid anilide, trimethylphenylammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, benzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'diaminodiphenylmethane, 3,3'-dimethyl-4,4'diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2chloro-p-phenylenediamine, dianisidine, methyl paminobenzoate, ethyl p-aminobenzoate, n-propyl paminobenzoate, isopropyl p-aminobenzoate, butyl paminobenzoate, dodecyl p-aminobenzoate, benzyl paminobenzoate, o-aminobenzophenone, m-aminoaceto- 131 phenone, p-aminoacetophenone, m-aminobenzamide, aaminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4methoxybenzamide, 3-amino-4-chlorobenzamide, p- (Nphenylcarbamoyl) aniline, p-EN- (4-chiorophenyl) carbamoyl] aniline, p-EN- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2- -methyl-3' -chiorophenyl) carbamoyl] aniline, 2-methoxy-5- (2'-chlorophenyl) carbamoyl]aniline, S-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, diethoxy-4- (N-benzoylamino) aniline, 2, 5-dimethoxy-4- (Nbenzoylamino) aniline, 2-methoxy-4- methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenyl sulfone, phenylsulfamoylaniline, sulfamoylaniline, 2, 5-dimethoxy-4-N-phenysulfanoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-rnethylaniline, bis [4-(inaminophenoxy) phenyl] sulfone, bis (p-aminophenoxy) phenyl] su'lfone, bis E3-inethyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-dianinobiphenyl, 3,3'dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'- 5'-dimethoxybiphenyl, 2,2' 4,4'-diarainobiphenyl, o-tolidine sulfone, 2,4'- 132 diaminobiphenyl, 2,2' -diaminobiphenyl, 4,4' -diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4, 4'diaminobiphenyl, 4, 4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 4, 4'-diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4, 4'-diaminodiphenyl sulfone, 3, 3'-diaminodiphenyl sulfone, 3, 4'-diaminodiphenyl sulfone, 3,3' -diaminodiphenylmethane, 4,4diaminodiphenylamine, 4, 4'-ethylenedianiline, 4,4'diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenoie, 4, 4'-diaminobenzophenone, 1, 4-bis (4amirnophenoxy)benzene, 1, 3-bis (4-aminophenoxy)benzene, 1,3-bis (3-aminophenoxy)benzene, 9, 9-bis(4-aminophenyl)fluorene, 2,2-bis (4-aminophenoxyphenyl)propane, 4,4'bis (4-aminophenoxy) diphenyl, 4,4'-tetraaminodiphenyl ether, 4, 4'-tetraaminodiphenyl sulfone, 3,3' ,4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4, 4'-methylenebiso-toluidine, (p-phenyleneisopropylidene)-bis- (2,6xylidine), o-chloro-p-nitroaniline, o-nitro-pchioroaniline, 2, 6-dichloro-4-nitroaniline, 5-chloro-2nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, rn-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, nitrile, Metol, 2,4-diaminophenol, N- (j-hydroxyethyl)- 133 o-aminophenol sulfate, sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2, 4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, mtoluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4, 4'-diaminostilbene-2,2'disulfonic acid, benzylethylaniline, 1, 8-naphthalenediamine, sodium naphthionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diaminoanthraquinone, 1,4diamino-2, 3-dichloroanthraquinone, etc.; heterocyclic compound amines such as 3-amino-1,2,4-triazole, 2aminopyridine, 3-aminopyridine, 4-aminopyridine, cLamino-6-caprolactam, acetoguanamine, 2, 4-diamino-6- methylimidazolyl-(1) ]ethyl-S-triazine, 2,3-diaminopyridine, 2, 5-diaminopyridine, 2,3, 1-amino-4-methylpiperazine, 1- (2-aminoethyl)piperazine, bis (aminopropyl)piperazine, N- (3-aminopropyl) morpholine, etc.; and aliphatic amines such as methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino)propylamine, di-2ethylhexylamine, 3- (dibutylamino) propylamine, tbutylamine, propylamine, 3- (methylamino) propylamine, 3- 134 (dimethylamino)propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2methoxyethylamine, 2-ethoxymethylamine, 2-amino-lpropanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine, etc.

Of the above-exemplified amine compounds, aniline derivatives having at least one amino group and represented by the following formula (VIII) are especially preferable:

R

1

X

1 X 2

R

3 Y, (VIII) R2 R4 wherein R 1

R

2

R

3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group, X, and X 2 are independently an amino group or a group represented by the formula -0NH2 (b)

NH

2 and Y, is any of (CH2) -CO-, -CONH- and a group represented by any of the formulas 135

CH

3 C 0

CH

3

CH

3 CH 3 (a I I

CH

3 CH3 0-0-0-0- 0 -0 0 or is absent, and n is 1 or 2.

As the OH group-containing compound that is reacted with the isocyanate to form one or more urethane groups, any compound may be used so long as it contains one or more OH groups. The OH groupcontaining compound includes, for example, phenols such as phenol, cresol, xylenol, p-ethylphenol, o-isopropyl- 136 phenol, resorcinol, p-tert-butylphenol, p-tertoctyiphenol, 2-cyclohexyiphenol, 2-allyiphenol, 4indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl)butane, 2, 2-bis (hydroxyphenyl)pentane, 2,2-bis (hydroxyphenyl)heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methyihydroquinone, 4phenyiphenol, p,p' -biphenol, 4-cumyiphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3methyl-4-hydroxyphenyl) sulfone, bis 5-dimethyl-4hydroxyphenyl) sul fone, 4-hydroxyphenyl- 4'-me thylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4' -methyiphenyl sul fone, 3, 4-dihydroxyphenyl- 4' -methyiphenyl sul fone, 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone, bis (2allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4' benzyloxyphenyl sulfone, 4-isopropylphenyl-4' hydroxyphenyl sul fone, 4 -hydroxy-4 isopropoxydiphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4, 4'-cihydroxydiphenyl ether, 4,4'thiodiphenol, 4, 4'-dihydroxybenzophenone, 2,2-bis (4hydroxyphenyl) hexafluoropropane, 4,4' -dihydroxydiphenylmethane, 3,3' -di-hydroxydiphenylamine, bis (4hydroxy-3-methylphenyl) sulfide, bis (2-hydroxy)phenyl) sulfone, 2, 4-dihydroxybenzophenone, 2,2' 4'tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4- 137 hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis(4'-hydroxybenzoate), pentyl 1,5-bis(4'hydroxybenzoate), hexyl 1,6-bis(4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-noctyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid, etc. However, as such phenols, those having an amino group are not desirable.

Since the amino group has a higher reactivity towards an isocyanate group than does an OH group, the amino group reacts with the isocyanate group before the OH group, so that it is difficult in some cases to obtain the desired compound. The OH group-containing compound also includes alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, iosbutanol, isoheptanol, 2-ethyl- 1-hexanol, 1-decanol, 2-pentanol, 3-hexanol, tertbutanol, tert-amyl alcohol, methyl Cellosolve, butyl Cellosolve, methyl Carbitol, allyl alcohol, 2-methyl-2propen-1-ol, benzyl alcohol, 4-pyridinemethanol, phenyl Cellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, l-chloro-3hydroxypropane, glycerin, glycerol, etc.; polyether type polyols such as polypropylene glycols, polytetra- 138 methylene ether glycols, adipate-derived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols, etc.; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6hexane glycol, 1,9-nonanediol, acryl polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor-oil-derived polyols, polymer polyols, methylpentanediol, halogen-containing polyols, phosphorus-containing polyols, ethylenediamine, amethylglucoside, sorbitol, sucrose, etc.

As the urea-urethane compound used as developer in each of the twenty-first and twenty-second aspects of the present invention, urea-urethane compounds represented by any of the following general formulas to (VII) are also preferable: 0 0 II II X-0-C-N-Yo-N-C-N-Z (I) H H H wherein X and Z are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each of the residues may have one or more substituents, and Y 0 is a group selected from the group consisting of tolylene group, 139 xylylene group, naphthylene group, hexamethylene group and -4-CH 2 group wherein is a phenylene group; 0 0 0 II II II H H H H wherein X and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, and each of the residues may have one or more substituents; 0 0 X-0-C-N-Y-N-C-N (III) SH H H n wherein X and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, a is a residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents; O 0 Z-N-C-N-Y-N-C-PO

(IV)

H H H wherein Z and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, 0 is a residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents; K H H ~H

H

H (V 140 wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue though the substituent may be a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom, each of the residues may have one or more substituents, y is a group selected from the group consisting of -(CH 2

-CONH-

and any of groups represented by the formulas 141

CH

3 I I CH3

CH

3

CH

3 0 O \II O-S--O II O or is absent, and n is 1 or 2; i 2 rf S t 9 (VI) wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound 142 residue or a heterocyclic compound residue though the substituent may be a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, each of the residues may have one or more substituents, 6 is a group selected from the group consisting of

-(CH

2 -CONH-, -CH(COORI)-,

-C(CF

3 2 and -CR 2

R

3 or is absent, each of R 2 and R 3 is an alkyl group, and n is 1 or 2; and 0 0 II H H II H X-O-C-N-Y-N-C-N-Z (VI I) wherein X, Y and Z are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each of the residues may have one or more substituents, and each of X, Y and Z is preferably an aromatic compound residue or a heterocyclic compound residue.

The urea-urethane compounds of the formulas to (VII) are also quite novel. These novel compounds are useful in the case of recording materials which use a recording energy such as heat, pressure or the like.

A process for producing the urea-urethane 143 compound of the formula used in each of the twentyfirst and twenty-second aspects of the present invention is not limited. This compound can be obtained, for example, by reacting an OH group-containing compound of the following general formula (IX) with an isocyanate compound of the following general formula and an amine compound of the following general formula (XI) according to, for instance, the reaction formula shown below: X-OH

(IX)

OCN-YO-NCO (X)

Z-NH

2

(XI)

wherein X and Z are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each of the residues may have one or more substituents, and Yo is a group selected from the group consisting of tolylene group, xylylene group, naphthylene group, hexamethylene group and -4-CH 2 group wherein is a phenylene group.

The term "aliphatic" used herein includes the term "alicyclic".

0

II

X-OH OCN-YO-NCO X-O-C-N-YO-NCO

H

(A)

O O O (A) II II II X-O-C-N-Yo-NCO Z-NH 2 X-O-C-N--Yo-N-C-N-Z H H H H 144 A process for producing the urea-urethane compound of the formula (II) used in each of the twenty-first and twenty-second aspects of the present invention is not limited. This compound can be obtained, for example, by reacting an OH groupcontaining compound of the general formula (IX) with an isocyanate compound of the following general formula (XII) and water according to, for instance, the reaction formula shown below: OCN-Y-NCO

(XII)

wherein Y is an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, and each of the residues may have one or more substituents.

0 X-OH +OCN-Y-NCO X-0-O--N-Y-NCO

(B)

2 (X-0--N-Y-NCO) H 2 X-0-6--Y-N-6--Y-N-8-0-X A process for producing the urea-urethane compound of the formula (III) used in each of the twenty-first and twenty-second aspects of the present invention is not limited. This compound can be obtained, for example, by reacting an OH groupcontaining compound of the general formula (IX) with an isocyanate compound of the general formula (XII) and an amine compound of the following general formula (XIII) according to, for instance, the reaction formula or shown below: 145 -tNH2) n (XIII) wherein a is a residue having a valence of 2 or more, and n is an integer of 2 or more.

0 X-OH +OCN-Y-NCO X-O- 6

-N-Y-NCO

(C)

n X-o---Y-NCO a -NH 2 n a 0n a- NH 2 n (oCN-Y-NCO) a N-6-N-Y-NCO n 4 H H n a N-6-N-Y-NCO n X-OH

(D)

H H A process for producing the urea-urethane compound of the formula (IV) used in each of the twenty-first and twenty-second aspects of the present invention is not limited. This compound can be obtained, for example, by reacting an amine compound of the general formula (XI) with an isocyanate compound of the general formula (XII) and an OH group-containing compound of the following general formula (XIV) according to, for instance, the reaction formula or shown below: OH n(XIV) 146 wherein 0 is a residue having a valence of 2 or more, and n is an integer of 2 or more.

0

Z-NH

2 +OCN-Y-NCO Z-N-6-N-Y-NCO H H (E) 0 0 n

P

Z H H (Z H H H n(OCN-Y-NCO) P o-0--N-Y-NCO n H n Z-N-Y-N-Y-N-6-

P

O O H H H The compounds of the general formulas (IX) to (XIV) are explained below in further detail which can be used for synthesis of the urea-urethane compounds of the above formulas to (IV).

The OH group-containing compound of the general formula (IX) is not particularly limited so long as it has one or more OH groups. This compound includes, for example, monophenols such as phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4-phenylphenol, 4-hydroxyphenyl-4'-methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl 0O 147 sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, 4i sopropyloxyphenyl- 4'-hyciroxyphenyl sul fone, 4hydroxyphenyl-4' -benzyloxyphenyl sulfone, 4-isopropylphenyl-4' -hyciroxyphenyl sulfone, 4-hydroxy-4' isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4hydroxybenzoate, -chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis hydroxybenzoate), hexyl 1, 6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalcylic acid, 4-n-butyloxysalcylic acid, 4-npentyloxysalcylic acid, 3-n-dodecyloxysalcylic acid, 3n-octanoyloxysalcylic acid, 4-n-octyloxycarbonylaminosalcylic acid, 4-n-octanoyloxycarbonylaminosalcylic acid, etc. The compound of the general formula (IX) also includes diphenols such as 2,2-bis(4hydroxyphenyl) propane, 2, 2-bi s(hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl)pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4phenylphenol, 4,4' -biphenol, 4-cuinylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3methyl-4-hydroxyphenyl) sulfone, bis 5-dimethyl-4hydroxyphenyl) sulfone, 3, 4-dihydroxyphenyl-4' methyiphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) 148 sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis(4hydroxyphenyl)hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis(4hydroxy-3-methylphenyl) sulfide, etc. However, as such OH group-containing compounds, those having an amino group are not desirable. When the amino group is present together with the OH group(s), the amino group has a higher reactivity towards an isocyanate group than does the OH group and hence reacts with the isocyanate group before the OH group, so that it is difficult in some cases to obtain the desired compound.

The compound of the general formula (IX) further includes monohydric alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl- 1-hexanol, 1-decanol, 2-pentanol, 3-hexanol, tertbutanol, tert-amyl alcohol, methyl Cellosolve, butyl Cellosolve, methyl Carbitol, allyl alcohol, 2-methyl-2propen-l-ol, benzyl alcohol, 4-pyridinemethanol, phenyl Cellosolve, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, cyclopentanol, 2-chloroethanol, l-chloro-3hydroxypropane, glycerin, glycerol, etc. As the compound of the general formula there may also be used polyether type polyols such as polypropylene glycols, polytetramethylene ether glycols, adipatederived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone 149 diols, phenolic polyols, amine-modified polyols, etc.; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,6-hexane glycol, 1,9-nonanediol, acryl polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor-oil-derived polyols, polymer polyols, methylpentanediol, halogencontaining polyols, phosphorus-containing polyols, ethylenediamine, x-methylglucoside, sorbitol, sucrose, etc. Of these, the monophenols are preferably used.

The isocyanate compound of the general formula includes 2,4-toluene diisocyanate, 2,6toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, diisocyanate, m-xylylene diisocyanate, etc. Of these, the toluene diisocyanates are preferable.

The isocyanate compound of the general formula (XII) is not particularly limited so long as it has two or more isocyanate groups. This compound includes, for example, p-phenylene diisocyanate, dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diisocyanate, dianisidine diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'- 150 diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris(4-phenylisocyanato)thiophosphate, 4,4',4"-triisocyanato-2,5-dimethoxytriphenylamine, 4,4',4"-triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexylisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane diisocyanate. As the isocyanate compound of the general formula (XII), there may also be used diisocyanate dimers such as N,N'-(4,4'-dimethyl-3,3'diphenyldiisocyanato)urethodione (Desmodule TT, a trade name), a toluene diisocyanate dimer; and dilsocyanate trimers such as 4,4',4"-trimethyl-3,3',3"-triisocyanato-2,4,6-triphenylcyanurate. There may also be used water adduct isocyanates of toluene dilsocyanate, diphenylmethane diisocyanate and the like, such as 1,3bis(3-isocyanato-4-methylphenyl)urea; polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (Desmodule L, a trade name); and amine adducts.

There may also be used compounds having two or more isocyanate groups, among the isocyanate compounds and isocyanate adduct compounds described in the specifications of JP-A-l0-76757 and JP-A-l0-95171.

An especially preferable example of the isocyanate compound of the general formula (XII) is toluene diisocyanate.

151 The amine compound of the general formula (XI) is not particularly limited so long as it has one or more amino groups. This compound includes, for example, aromatic monoamines such as aniline, otoluidine, m-toluidine, p-toluidine, o-anisidine, panisidine, p-phenetidine, 2,4-dimethoxyaniline, dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, maminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,6-dichloroaniline, 3,4-dichloroaniline, dichloroaniline, 2,4,5-trichloroaniline, a-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl paminobenzoate, ethyl p-aminobenzoate, n-propyl paminobenzoate, isopropyl p-aminobenzoate, butyl paminobenzoate, dodecyl p-aminobenzoate, benzyl paminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, oaminobenzamide, p-aminobenzamide, p-amino-Nmethylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4methoxybenzamide, 3-amino-4-chlorobenzamide, p-(Nphenylcarbamoyl)aniline, p-[N-(4-chlorophenyl)carbamoyl]aniline, p-EN-(4-aminophenyl)carbamoyl]aniline, 2-methoxy-5-(N-phenylcarbamoyl)aniline, 2methoxy-5-[N-(2'-methyl-3'-chlorophenyl)carbamoyl]aniline, 2-methoxy-5-[N-(2'-chlorophenyl)carbamoyl]- 152 aniline, S-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 2-methoxy-4- (N-benzoylamino) methylaniline, 4-sul famoylaniline, 3-sul famoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosul fonylaniline, 4-diethylaminosul fonylaniline, sul fathiazole, 4-aminodiphenyl sulfone, phenylsulfamoylaniline, sulfamoylaniline, 2, 5-dimethoxy-4-N-phenysulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosul fonyl-4-methylaniline, o-chloro-pnitroaniline, o-nitro-p-chloroaniline, 2, 6-dichloro-4nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4chiorophenol, o-nitroaniline, m-nitroaniline, pnitroaniline, 2-methyl-4-nitroaniline, m-nitro-ptoluidine, 2-amino-5-nitrobenzonitrile, sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, pfluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile, etc.; and aromatic diamines such as 4,4'diamino-3, 3'-diethyldiphenylmethane, 4, 4'-diaminobenzanilide, 3, 5-diaminochlorobenzene, diaminodiphenyl ether, 3,3-''-diLchloro-4, 4'-diaminodiphenylmethane, 3,3'dimethyl-4, 4'-diaminodiphenylmethane, tolidine base, dianisidine, bis (r-aminophenoxy)phenyl] sulfone, bis[4- (p-aminophenoxy)phenyl] sulfone, bis[3-methyl-4- (p-aminophenoxy)phenyll sulfone, 3, 3'-dimethoxy-4, 4'- 153 diaminobiphenyl, 3,3' -dimethyl-4, 4'-diaminobiphenyl, 2,2' -dichloro-4, 4' -diamino-5, 5' -dimethoxybiphenyl, 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2, 4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4, 4'-diaminobiphenyl, 2,2'dimethyl-4,4'-ciiaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'diaminodiphenyl ether, 3,3' -diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, bis (3-amino-4chiorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4,4' -diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3, 4'-diaminodiphenyl sulfone, 3, 3'-diaminodiphenylmethane, 4,4' -diaminodiphenylamine, 4,4' ethylenedianiline, 4, 4'-diamino-2,2' -dimethyldibenzyl, 3, 3'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene, 1, 3-bis (3-aminophenoxy)benzene, 9,9bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4' -bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, etc. The amine compound of the general formula (XI) also includes, for example, heterocyclic compound amines such as 3-amino- 1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4aminopyridine, ax-amino-e-caprolactam, acetoguanamine, 2, 4-diamino-6-[2'-methylimidazolyl- (1)lethyl-Striazine, 2, 3-diaminopyridine, 2, 154 2,3, 5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl)piperazine, bis (aminopropyl)piperazine, N-(3-aminopropyl)morpholine, etc.; and aliphatic amines such as methylamine, ethylamine, stearylamine, allylamine, isopropylamine, 2-ethyihexylamine, ethanolamine, 3- (2-ethylhexyloxy)propylamine, 3ethoxypropylamine, 3- (diethylamino) propylamine, 3- (dibutylarnino) propylamine, t-butylamine, propylamine, 3- (rethylamino)propylamine, 3- (dimethylamino)propylamine, 3-methoxypropylamine, methyihydrazine, 1methylbutylamine, methanediamine, 1, 4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-l-propanol, 2aminobutanol, 3-amino-l,2-propanediol, 1, 3-diamino-2hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine, etc. Of these, the aromatic monoamines are preferably used.

The amine compound of the general formula (XIII) is not particularly limited so long as it has two or more amino groups. This compound includes, for example, aromatic amines such as 4,4'-diamino-3,3'diethyldiphenylmethane, 4, 4'-diaminobenzanilide, diaminochloroben.-ene, diaminodiphenyl ether, 3,3'dichloro-4, 4'-diaminodiphenylmethane, 3, 3'-dimethyl- 4,4' -diaminodiphenylmethane, tolidine base, dianisidine, bis (m-aminophenoxy)phenyl] sulfone, bis (p-aminophenoxy)phenyl] sulfone, bis [3-methyl-4- 155 (p-aminophenoxy)phenyl] sulfone, 3,3' -dimethoxy-4, 4'diaminobiphenyl, 3,3' -cimethyl-4, 4'-diaminobiphenyl, 2,2' -dichloro-4, 4'-diamino-5, 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolicline sulfone, 2, 4'-ciaminobiphenyl, 2, 2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diaminobiphenyl, 3,3'-dichloro-4, 4'-diaminobiphenyl, 2,2'dimethyl-4, 4'-diaminobiphenyl, 4, 4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, 3, 4'-diaminodiphenylnethane, bis (3-amino-4chiorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4,4' -diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3, 4'-diaminodiphenyl sulfone, 3,3' -diaminodiphenylmethane, 4,4' -diaminodiphenylamine, 4,4' ethylenedianiline, 4,4' -diamino-2,2'-dimethyldibenzyl, 3,3' -diaminobenzophenone, 4, 4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene, 1, 3-bis (3-aminophenoxy)benzene, 9,9bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4' -bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, tolidine base, ophenylenediamine, m-phenylenediamine, p-phenylenediamine, etc. of the above-exemplified amine compounds, aniline derivatives having at least two amino groups and represented by the following formula (VIII) are especially preferable: 156 R Xi X2 R3 R2Z wherein R 2

R

3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group, X 1 and X 2 are independently an amino group or a group represented by the formula -0NH2 (b)

NH

2 and Y 1 is any of -S02-, -(CH 2

-CO-,

-CONH- and a group represented by any of the formulas 0 157

OO

CH 0 0

CH

3 (a) -00 O-- 0or is absent, and n is 1 or 2.

The OH group-containing compound of the general formula (XIV) is not particularly limited so long as it has two or more OH groups. This compound includes, for example, diphenols such as 2,2-bis(4hydroxyphenyl)propane, 2,2-bis(hydroxyphenyl)butane, 158 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methyihydroquinone, p,p'biphenol, butyl his(4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl) sulfone, bis(3-methyl-4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4dihydroxyphenyl-4'-methylphenyl sulfone, bis(2-allyl-4hydroxyphenyl) sulfone, bis(2-methyl-3-tert-butyl-4hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2bis(4-hydroxyphenyl)hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis(4hydroxy-3-methylphenyl) sulfide, etc. However, as such diphenols, those having an amino group are not desirable. Since the amino group has a higher reactivity towards an isocyanate group than does an OH group, the amino group reacts with the isocyanate group before the OH group, so that it is difficult in some cases to obtain the desired compound. The OH groupcontaining compound of the general formula (XIV) also includes polyether type polyols such as polypropylene glycols, polytetramethylene ether glycols, adipatederived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols, etc.; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, 159 dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,6-hexane glycol, 1,9-nonanediol, acryl polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythritol, castor-oil-derived polyols, polymer polyols, methylpentanediol, halogencontaining polyols, phosphorus-containing polyols, ethylenediamine, a-methylglucoside, sorbitol, sucrose, etc.

A process for producing the urea-urethane compound of the formula used in each of the twentyfirst and twenty-second aspects of the present invention is not limited. This compound can be obtained, for example, by reacting a monophenol compound with an aromatic diisocyanate compound and a diamine compound of the following general formula (XV) according to, for instance, the reaction formula or shown below:

H

2 N 7 NH 2

(XV)

wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue though the substituent may be a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a 160 mercapto group, a sulfa group, a sulfamoyl group or a halogen atom, each of the residues may have one or more substituents, and 'y is any of -SO 2

-(CH

2 -CONH- and a group represented by any of the formulas

CH

3

CH

3

OH

3

CH

3 OC io- -0 0- (a)

OH

3

OH

3 -oQ Qo or is absent, and n is 1 or 2.

161 OH OC NCO -c

(G)

2 -N-I NCO H2N y NH 2

O

2 (OCNL -NCO H 2N- -H2 0 OC N Hr II H 2 N-C-N- -NCO O OH OiN II H 11 I O O

O

OCN Y T- -C-N--NCO 2 I§y N -6 40- Q A process for producing the urea-urethane compound of the formula (VI) used in each of the twenty-first and twenty-second aspects of the present invention is not limited. This compound can be obtained, for example, by reacting an aniline derivative with an aromatic diisocyanate compound and a dihydroxy compound of the following general formula (XVI) according to, for instance, the reaction formula 162 or shown below: HO 8 OH (XVI) wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue though the substituent may be a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, each of the residues may have one or more substituents, 6 is any of -CONH-, -CH(COORI)-,

-C(CF

3 2 and -CR 2

R

3 or is absent, R i

R

2 and R 3 are independently an alkyl group, and n is 1 or 2.

0@ 163 NH2+ OCN, NCO -N-C-N-I NCO 3IC H I

(J)

2 N-C-N- NCO HO -8 OH (DH H 0 O 0 Q -O o 2 OCN- 'NCO HO- OH 0 0 CN li li? I H li SOCN- 5 C-N- -NCO 0

NH

2 OCN- C-O 8 O-C-N- -NCO 2 0N 0 0 N N -t -N N-6-N-- H H H H H H

(K)

The compounds usable for synthesizing the urea-urethane compound of the formula or (VI) used in each of the twenty-first and twenty-second aspects of the present invention are explained below in detail.

The phenolic compound usable for synthesizing the urea-urethane compound of the formula is not particularly limited so long as it has one or more OH groups on the benzene ring. In addition, hydrogen atom(s) of the benzene ring may be replaced by a 164 substituent other than OH group, an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom.

Preferable examples of the phenolic compound are phenols such as phenol, cresol, xylenol, pethylphenol, o-isopropylphenol, resorcinol, p-tertbutyiphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2allylphenol, 4-indanol, thymol, 2-naphthol, nitrosubstituted phenols p-nitrophenol), halogensubstituted phenols o-chlorophenol and pchlorophenol), 4-phenylphenol, 4-hydroxyphenyl-4' methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4' methylphenyl sulfone, 4-isopropylphenyl-4' -hydroxyphenyl sulfone, 4-isopropyloxyphenyl-4' -hydroxyphenyl sul fone, 4-hydroxyphenyl-4' -benz yloxyphenyl sul fone, 4isopropylphenyl-4' -hydroxyphenyl sulfone, 4-hydroxy-4' isopropoxydiphenyl sulfone, phenyl salicylate, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4hydroxybenzoate, -chlorobenzyl) 4-hydroxybenzoate, dimethyl 3-hydroxyphthalate, 4-methoxyphenol, 4- (benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-npentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonyl- 165 aminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid, etc. As the phenolic compound, there may also be used phenolic compounds having one or more substituents including carboxyl group, nitroso group, nitrile group, carbamoyl group, ureido group, isocyanate group, mercapto group, sulfo group, sulfamoyl group, etc. However, as such phenols, those having an amino group are not desirable. Since the amino group has a higher reactivity towards an isocyanate group than does an OH group, the amino group reacts with the isocyanate group before the OH group, so that it is difficult in some cases to obtain the desired compound.

The aromatic diisocyanate compound usable for synthesizing the urea-urethane compound of the formula or (VI) is not particularly limited so long as it has two isocyanate groups bonded to its benzene ring.

The aromatic diisocyanate compound includes, for example, p-phenylene diisocyanate, benzene-1,4-diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. Especially preferable examples of the aromatic diisocyanate compound are toluene diisocyanates. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferable. Besides 2,4toluene diisocyanate, mixtures of 2.4-toluene diisocyanate and 2,6-toluene diisocyanate are generally on the market and available at a low price and may also be used as the aromatic diisocyanate. The mixtures of 166 these toluene diisocyanate isomers are liquid at ordinary temperatures.

The diamine compound of the general formula (XV) which is usable for synthesizing the urea-urethane compound of the formula includes, for example, aromatic diamines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, 4, 4'-diaminobenzanilide, diaminochlorobenzene, diaminodiphenyl ether, 3,3'dichloro-4, 4'-diaminodiphenylmethane, 3, 3'-dimethyl- 4, 4'-diaminodiphenylmethane, tolidine base, dianisidine, bis (m-aminophenoxy)phenyl] sulfone, bis (p-aminophenoxy)phenyl] sulfone, bis[3-methyl-4- (p-aminophenoxy)phenyl] sulfone, 3, 3'-dimethoxy-4, 4'diaminobiphenyl, 3,3' -dimethyl-4, 4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5, 5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2, 4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4, 4'-diaminobiphenyl, 2,2' -dichloro-4, 4'-diaminobiphenyl, 3, 3'-dichloro-4, 4'-diaminobiphenyl, 2,2'dimethyl-4, 4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'diaminodiphenyl ether, 3,3' -diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, bis (3-amino-4chlorophenyl) sulfone, bis 4-diaminophenyl) sulfone, 4, 4'-diaminodiphenyl sulfone, 3, 3'-diaminodiphenyl sulfone, 3, 4'-diaminodiphenyl sulfone, 3,3' diaminodiphenylmethane, 4,4' -diaminodiphenylamine, 167 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(4-aminophenoxyphenyl)propane, 4,4'-bis(4-aminophenoxy)diphenyl, dianisidine, 3,3'-dichlorobenzidine, etc.

The aniline derivative usable for synthesizing the urea-urethane compound of the formula (VI) is not particularly limited so long as it is an aniline compound having one or more amino groups on the benzene ring. In addition, hydrogen atom(s) of the benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom.

Preferable examples of such an aniline compound are aniline, o-toluidine, m-toluidine, ptoluidine, o-anisidine, p-anisidine, p-phenetidine, N,N-dimethyl-p- phenylenediamine, N,N-diethyl-pphenylenediamine, 2,4-dimethoxyaniline, aniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxy-substituted anilines p-aminobenzoic acid), hydroxyl-substituted anilines o-amino- 168 phenol, m-aminophenol, 2-amino-4-chlorophenol and paminophenol), 2, 3-xylidine, 2, 4-xylidine, 3, 4-xylidine, 2,6-xylidine, nitrile-substituted anilines 4aminobenzonitrile), anthranilic acid, p-cresidine, halogen-substituted anilines 2, 6-dichloroaniline, 3, 4-dichloroaniline, 3, aniline, 2,4, 5-trichloroaniline, o-chloroaniline, mchloroaniline and p-chloroaniline), ax-naphthylamine, aminoanthracene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, paminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4chlorobenzamide, carbamoylanilines p- (N-phenylcarbamoyl) aniline, p- (4-chlorophenyl) carbamoyl]aniline, p-EN- (4-aminophenyl) carbamoyl]aniline, 2methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline and 2- (2'-chlorophenyl) carbamoyl] aniline), acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2, 5-diethoxy-4- (Nbenzoylamino) aniline, 2, 5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) sulfamoylanilines 4-sulfamoylaniline, 3sul famoylanilime, 2-chloro-5-N-phenylsul famoylaniline, 169 and dimethoxy-4-N-phenysulfamoylaniline), 2-(N-ethyl-Nphenylaminosulfonyl)aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfathiazole, 4-aminodiphenyl sulfone, benzylsulfonylaniline, 2-phenoxysulfonylaniline, chiorophenoxy)sulfonylaniline, 3-anilinosulfonyl-4methylaniline, nitro-substituted anilines ochloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, onitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl- 4-nitroaniline, m-nitro-p-toluidine and nitrobenzonitrile), p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4trifluoroaniline, r-aminobenzotrifluoride, 2-amino-3etc.

As the aniline derivative, there may also be used aniline derivatives having one or more substituents including carboxyl group, nitroso group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group, etc.

The dihydroxy compound of the general formula (XVI) which is usable for synthesizing the ureaurethane compound of the formula (VI) includes diphenols such as 2,2-bis(4-hydroxyphenyl)propane, 2,2bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, 4,4'-biphenol, 170 butyl bis(4-hydroxyphenyl)acetate, benzyl bis(4hydroxyphenyl)acetate, bis(4-hydroxyphenyl) sulfone, bis(3-methyl-4-hydroxyphenyl) sulfone, dimethyl-4-hydroxyphenyl) sulfone, bis(2-allyl-4hydroxyphenyl) sulfone, bis(2-methyl-3-tert-butyl-4hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2bis(4-hydroxyphenyl)hexafluoropropane, 4,4'dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis(4-hydroxy-3-methylphenyl) sulfide, etc. However, as such diphenols, those having an amino group are not desirable. Since the amino group has a higher reactivity towards an isocyanate group than does an OH group, the amino group reacts with the isocyanate group before the OH group, so that it is difficult in some cases to obtain the desired compound.

A process for synthesizing the urea-urethane compound of the formula (VII) used in each of the twenty-first and twenty-second aspects of the present invention is not particularly limited. This compound can be obtained, for example, by reacting an OH groupcontaining compound of the general formula (IX) with an isocyanate compound of the general formula (XII) and an amine compound of the general formula (XI) according to, for instance, the following reaction formula 0 11 H X-OH OCN-Y-NCO X-0-C-N-Y-NCO

(L)

II H 1 H H I H X-O-C-N-Y-NCO Z-NH 2

X-O-C-N-Y-N-C-N-Z

As the substituent of X bonded to the urethane group of the urea-urethane compound of the general formula (VII), alkyl groups, alkenyl groups, phenyl group, cycloalkyl groups, amide group, alkoxyl groups, nitro group, nitroso group, nitrile group, toluenesulfonyl group, methanesulfonyl group, acetyl group, halogen atoms, formyl group, dialkylamino groups and isocyanate group are preferable.

Of such urea-urethane compounds of the general formulas to (VII) as developer, compounds of the general formulas (II) to (VI) are preferable and compounds of the general formulas and (VI) are especially preferable.

Furthermore, a compound of the following structural formula (XX) or (XXI) is especially preferable.

(XX)

172

(XXI)

CH

3 H 3

C

C -O-C-N 0 NH CH 3 Q N. O NH

NH

In the case of the urea-urethane compound used as developer in each of the twenty-first and twenty-second aspects of the invention and the compounds of the formulas to (IV) and (VII) as developer, if a residue bonded to their urea group or urethane group is an aliphatic compound residue, the coloring density and the print-preserving capability are deteriorated in some cases. Therefore, the residue bonded to the urea group or urethane group is preferably an aromatic compound residue or a heterocyclic compound residue. However, the deterioration of the coloring density and the print-preserving capability which is likely to be caused by the introduction of the aliphatic compound residue is reduced by an increase in the total number of urea group(s) and urethane group(s). In the case of compounds of the formula (III) and the formula even if an aliphatic compound residue is among residues bonded to the urea group(s) or urethane group(s), almost no problem about performance characteristics is caused.

The urea-urethane compound used in each of 173 the twenty-first and twenty-second aspects of the present invention may be obtained by mixing the isocyanate with the corresponding reactants in an organic solvent or without a solvent, reacting them, and then collecting the resulting crystals by filtration. As each of the reactants, one or more compounds may be used depending on purposes. As the solvent, any solvent may be used so long as it does not react with an isocyanate group and the functional groups of the reactants. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and ketones. Methyl ethyl ketone, toluene and the like are especially preferable which dissolve the isocyanate and in which the reaction product has a low solubility. The reaction product obtained by the above reaction procedure is not always a single compound, but is obtained as a mixture of compounds different in the position of a substituent, in some cases.

Specific examples of the urea-urethane compound used in each of the twenty-first and twentysecond aspects of the present invention are the following compounds to 174 0 N-C-N

CH

3 H HN- 0 N-C-N

CH

3 H N, C:o 0 OCH 3 (E-3) (E-4) 175 (E 0 HN, c 0 0

CI

0

H

3 CO N-C-N CH 3 H N, Co 00t~r

H

3 CCO 0 CN-c HH H OO-CN

CH

3

HN,

Co 176 0-C.N

CH

3 H N, co

OCH

3 0 H1 0-C-N CH3 Co

CH

3 (E-11) (E-12) 177 (E-13) (E-14) 16) (E-17)

H

3 CO S N, 0 C 2

H

O- &CNN CH 3

HN

Co

HN-C-CH

3 0 (N K) H CD -C- H II L11 CH3 H3C 00 6 0 178 (E-18) (E-1 9) (E-21) 179 (E-22) (E-23) (E-24) PN. 0 0

-CH

3 0 b 180 (E-26) H3C 0 -i0 QCH3 HG ONH H H

'CC

(E-27) H3C 0 0 aCH0 C

C

(E-28) (E-2 9) 0O 181 (E-31) 0 (E-32) oH (E-33) H3CQ Q 0QaQ0CH3 yNH 0N H

NH

0 C0 0@ 182 (E-34)

H

3 C 0C <H 3 0c H 0 GH2 0

H

O\NH HN. C

C

0 (E-36) Q -N N-8 N J 0 Nu8- c 0 (E-37) (E-38) (E-39) 183 00 00 0 (E-41) 0 0 H 3

C

H3C~ N -a 1- J H H 0 ,N H H N/ 0 ~NH (IE-42) H- I0HNN

NHH

(E-42) 04H 3 184 (E-44) O-CN CH3

NH

oC

NH

CH

2

CH

3 The urea-urethane compound used as developer in the present invention is usually a colorless or light-colored compound that is solid at ordinary temperatures.

The molecular weight of the urea-urethane compound used as developer in the present invention is preferably 5,000 or less, more preferably 2,000 or less.

The total number of urea group(s) and urethane group(s) in the urea-urethane compound used as developer in the present invention is preferably 20 or less, more preferably 10 or less. The ratio of urea group(s) to urethane group(s) in the molecular structure of the urea-urethane compound.is preferably 1 3 to 3 1, in particular, 1 2 to 2 1.

For producing a recording material by using the urea-urethane compound as developer, the ureaurethane compound of one kind or, if necessary, a combination of the urea-urethane compounds of two or more kinds may be used.

When used in a heat-sensitive recording material, the urea-urethane compound is preferably one that has a melting point. The melting point of the 185 urea-urethane compound used as developer in the present invention ranges preferably from 40 0 C to 500 0 C, in particular, from 600C to 300 0

C.

The colorless or light-colored dye precursor used in the twenty-second aspect of the present invention is a compound well known as a color former used in pressure-sensitive recording materials and heat-sensitive recording materials and is not particularly limited. As the dye precursor, leuco dyes are especially preferable, and triarylmethane type leuco dyes, fluoran type leuco dyes, fluorene type leuco dyes, diphenylmethane type leuco dyes and the like are more preferable. Typical examples of the leuco dyes are given below.

Triarylmethane type compounds 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (Crystal Violet lactone), 3,3-bis(pdimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(pdimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindol-3yl)phthalide, 3,3-bis(1,2-dimethylindol-3-yl)-5dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol- 3-yl)-5-dimethylaminophthalide, 3,3-bis(2-phenylindol- 3-p-dimethylaminophenyl-3-(l-methylpyrrol-2-yl)-6- dimethylaminophthalide, etc.

186 Diphenylmethane type compounds 4,4' -bis-dimethylaminophenylbenzhydryl benzyl ether, N-halophenylleucoauramines, N-2, 4, phenylleucoauramine, etc.

Xanthene type compounds Rhodamine B anilinolactam, Rhodamine B-pchioroanilinolactam, 3-dimethylamino-6-methyl-7-(intrifluorornethylanilino) fluoran, 3-diethylamino-6methyl-fluoran, 3-diethylamino-7-methyl-fluoran, 3diethylamino-7-chloro-fluoran, 3-diethylamino-7dibenzylaminofluoran, 3-diethylamino-6-methyl-7chiorofluoran, 3-diethylamino-7-octylaminofluoran, 3diethylamino-7-phenylfluoran, 3-diethylamino-6-methyl- 7-anilinofluoran, 3-diethylamino-6-inethyl-7-pmethylanilinofluoran, 3-diethylamino- 6-chloro-7methyifluoran, 3-diethylainino-7- 4-dichioroanilino) fluoran, 3-diethylamino-7- (2-chioroanilino) fluoran, 3diethylainino-6-methyl-7- (o,p-dimethylanilino) fluoran, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-diethylarino-6-methyl-7- (m-trifluoromethylanilino) fluoran, 3diethylamino-6-methyl-7- Co-chioroanilino) fluoran, 3diethylainino-6-methyl-7- (p-chloroanilino) fluoran, 3diethylamino-6-inethyl-7- (o-fluoroanilino) fluoran, 3diethylamino-6-methyl-7- (p-n-butylanilino) fluoran, 3diethylamino-6-inethyl-7-n-octylaninofluoran, 3diethylamino- 6-chloro-7-anilinofluoran, 3-diethylarnino- 6-ethoxyethyl-7-anilinofluoran, 3-diethylamino- 187 benzo fluoran, 3-diethylainino-benzo fluoran, 3diethylamino-6-methyl-7-benzylaminofluoran, 3diethylamino-6-methyl-7-dibenzylaminofluoran, 3diethylamino-7-di (p-methylbenzyl) aminofluoran, 3diethylamino-6-methyl-7-diphenylmethylaminofluoran, 3diethylamino-7-dinaphthylmethylaminofluoran, diethylamino-4-dimethylaminobenzo fluoran, 3diethylamino-7, 8-benz fluoran, 3-diethylamino-6-methyl- 7- (r-trichloroanilino) fluoran, 3-diethylamino-7- Cochioroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-diethylamino-6--methyl-7- dimethylanilino) fluoran, 3- (N,N-diethylamino) 7- N-dibenzylamino) fluoran, 3-morpholino-7- (Npropyltrifluoromethylanilino) fluoran, 3-pyrrolidino-7trifluoromethylanilinofluoran, 7- (N-benzyl-trifluoromethylanilino) fluoran, 3pyrrolidino-7- (di-p-chlorophenyl)methylaminofluoran, 3diethylamino-5-chloro-7- ((-phenylethylamino) fluoran, 3- (N-ethyl-N-p-toluidino) ((-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylethyl) fluoran, 3-diethylamino-5-methyl-7- ((-phenylethylamino) fluoran, 3-diethylamino-7-piperidinoaminofluoran, 2-chloro-3- (Nmethyltoluidino) (p-N-butylanilino) fluoran, 3- (Nethyl-N-cyclohexylamino) 6-benzo-7-ct-naphthylamino- 4'-bromofluoran, 3-diethylamino-6-methyl-7-mesitidino- 4' ,5'-benzofluoran, 3-dibutylamino-6-methyl-fluoran, 3dibutylamino-6-methyl-7-chlorofluoran, 3-dibutylamino- -methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-p- 188 methylanilinofluoran, 3-dibutylamino-6-methyl-7- (o,pdimethylanilino) fluoran, 3-dibutylamino-6-methyl-7- Cmtrifluoromethylanilino) fluoran, 3-dibutylamino-6methyl-7- Co-chioroanilino) fluoran, 3-dibutylamino-6methyl-7- (p-chloroanilino) fluoran, 3-dibutylamino-6methyl-7- Co-fluoroanilino) fluoran, 3-dibutylamino-6methyl-7- (p-n-butylanilino) fluoran, 3-dibutylamino-6methyl-7-n-octylaminofluoran, 3-cibutylamino-6-chloro- 7-anilinofluoran, 3-dibutylamino-6-ethoxyethyl-7anilinofluoran, 3-ci-n-pentylamino-6-methyl-7-anilinofluoran, 3-di-n-pentylamino-6-methyl-7- (o,p-dimethylanilino) fluoran, 3-di-n-pentylamino-6-methyl-7-(intrifluoromethylanilino) fluoran, 3-di-n-pentylamino-6methyl-7- (o-chioroanilino) fluoran, 3-di-n-pentylamino- 6-methyl-7- (p-chloroanilino) fluoran, 3-di-npentylamino-6-methyl-7- Co-fluoroanilino) fluoran, 3pyrrolidino-6-methyl-7-anilinofluoran, 3-piperidino-6methyl-7-anilinofluoran, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethylfluoran, 3- (Nmethyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3- (Nmethyl-N-n-propylamino) -6-methyl-7-anilinofluoran, 3- (N-methyl-N-amylamino) -6-methyl-7-anilinofluoran, 3- N-di-n-ainylamino) -6-inethyl-7-anilinofluoran, 3- (Nmethyl-N-isopropylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-n-propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isopropylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-n-butylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluoran, 189 3- CN-ethyl-N-n-hexylamino) -6-methyl-7-p-methylanilinofluoran, 3- (N-ethyl-N-n-hexylamino) -6-methyl-7- (o,pdimethylanilino) fluoran, 3- (N-ethyl-N-n-hexylamino)-6methyl-7- (m-trifluoromethylanilino) fluoran, 3- (N-ethyl- N-n-hexylamino) -6-methyl-7- (o-chloroanilino) fluoran, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamylamino) -6-chloro-7-anilinofluoran, 3- (N-ethyl-N-3-methylbutylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-p-toluidino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-p-toluidino) -6-methyl-7- (pmethylanilino) fluoran, 3- (N-ethyl-N-p-toluidino) -6methyl-7- (o,p-dimethylanilino) fluoran, 3- (N-ethyl-Ntetrahydrofurfurylamino) -6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-rnethyl amino) -6-methyl-7-anilinofluoran, 3- (N-cyclohexyl-N-methylamino) -7-anilinofluoran, 3- (Nethyl-N-3-methoxypropylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-3-ethoxypropylamino) -6-methyl-7anilinofluoran, 2- (4-oxahexyl) -3-ciimethylamino-6methyl-7-anilinofluorai, 2- (4-oxahexyl) -3-diethylamino- 6-methyl-7-anilinofluoran, 2- (4-oxahexyl) -3-dipropylamino-6-methyl-7-anilinofluoran, 3, 6-bis (diethylamino) fluoran-y- -nitro) anilinolactam, 3, 6-bis (diethylamino) f luoran-y- -nitro) ani linolactan, 3,6bis (diethylamino) f luoran-y- -nitro) anilinolactam, 3, 6-bis (diethylamino) fluoran-y-anilinolactam, etc.

Thiazine type compounds benzoylleucomethylene blue, p-nitrobenzoylleucornethylene blue, etc.

190 Spiro-compounds 3-methylspirodinaphthopyran, 3-ethyispirodinaphthopyran, 3, 3-dichlorospirodinaphthopyran, 3benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo)spiropyran, 3-propylspirobenzopyran, etc.

The leuco dyes also includes, for example, the following compounds that can absorb a near infrared ray: 3, 6-bis (dimethylamino) fluorene-9-spiro-3'- dimethylamino-phthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3'- -dimethylaminophthalide), 3, 6-bis (diethylamino) fluorene-9-spiro-3'- dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3 -dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene-9-spiro-3'- dimethylaminophthalide), 3, 6-bis (dimethylamino) fluorene-9-spiro-3'-(6'-diethylaminophthalide), 3diethylamino-6-dimethylaminofluorene-9-spiro-3 diethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3 -diethylaminophthalide), 3, 6-bis (diethylamino) fluorene-9-spiro-3'- diethylaminophthalide), 3, 6-bis (dimethylamino) fluorene- 9-spiro-3'- (6'-dibutylaminophthalide), 3-dibutylamino- 6-diethylaminofluorene-9-spiro-3 -diethylaminophthalide), 3-diethyllamino-6-dimethylaminofluorene-9spiro-3'-(6'-dibutylaminophthalide), 3,3-bis[2-(4dimethylaminophenyl) (4-methoxyphenyl) ethenyl] 4,5,6, 7-tetrachlorophthalide, etc.

Of the above-exemplified leuco dyes, the 191 triarylmethane type leuco dyes, fluoran type leuco dyes, fluorene type leuco dyes and diphenylmethane type leuco dyes are preferable from the viewpoint of sensitivity and plasticizer resistance, and compounds having a structure represented by the following chemical formula or are more preferable: Y2 Y3-N Y4

C=W

H

Y

6 wherein both Y 2 and Y 3 are alkyl groups or alkoxyalkyl groups, Y 4 is a hydrogen atom, an alkyl group or an alkoxy group, and each of Y 5 and Y 6 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; or

R

6 R 0 j, R8

R

8

R

9 wherein each of Rs and R 6 is a group represented by the formula or the formula R,I

R

1 (k) f (k) 192 (wherein each of R 11 through R 1 is a hydrogen atom, a halogen atom, a alkyl group, a C-C8 alkoxy group or -NRi 6 R, wherein each of R 16 and R 1 is a C--C 8 alkyl group); or R18 (wherein each of R 18 and R, is a hydrogen atom, a Cl-C, alkyl group or a phenyl group), and each of R 7 through Rio is a hydrogen atom, a halogen atom, a alkyl group, a alkoxy group or -NR 20

R

21 wherein each of R 2 0 and Rn 2 is a Cl-C 8 alkyl group.

Such colorless or light-colored dye precursors may be used in combination of two or more thereof if necessary.

The urea-urethane compound as developer is used in a proportion of preferably 5 to 1,000 parts by weight, more preferably 20 to 500 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor. As the proportion of the urea-urethane compound as developer, 5 parts by weight or more is sufficient to allow the dye precursor to develop a color. At such a proportion, the coloring density is high. When the proportion of the urea-urethane compound as developer is 1,000 parts by weight or less, the urea-urethane compound as developer hardly remains as a surplus, and this is economically advantageous and 193 hence preferable.

As the urea-urethane compound or ureaurethane composition used as developer in the nineteenth aspect of the present invention, any of the urea-urethane compounds of the first to fourth aspects of the present invention or any of the urea-urethane compositions of the fifth to twelfth aspects of the present invention can be used. Synthesis processes of these compounds and compositions are as already described in detail in the explanations of the first to twelfth aspects of the present invention.

The incorporation of an isocyanate compound into the color-producing composition of the present invention improves the shelf stability of the composition. The isocyanate compound incorporated into the color-producing composition of the present invention refers to a colorless or light-colored, aromatic or heterocyclic isocyanate compound that is solid at ordinary temperatures. For example, one or more of the following isocyanate compounds are used.

The isocyanate compound incorporated includes 2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene- 2,4-diisocyanate, l-methoxybenzene-2,5-diisocyanate, 1ethoxybenzene-2,4-diisocyanate, 1,4-diisocyanate, 2,5-diethoxylbenzene-1,4- 194 diisocyanate, 2, 5-dibutoxybenzene-1, 4-diisocyanate, azobenzene-4, 4'-diisocyanate, diphenyl ether-4, 4'diisocyanate, naphthalene-1, 4-diisocyanate, naphthalene-1, 5-ciiisocyanate, naphthalene-2, 6dilsocyanate, naphthalene-2,7-diisocyanate, 3,3'dimethyl-biphenyl-4, 4'-diisocyanate, 3, 3'-dimethoxybiphenyl-4, 4'-diisocyanate, diphenylmethane-4, 4'cilisocyanate, diphenylciirethylmethane-4, 4'diisocyanate, benzophenone-3, 3'-diisocyanate, fluorene- 2, 7-diisocyanate, anthraquinone-2, 6-diisocyanate, 9ethylcarbazole-3, 6-diisocyanate, pyrene-3, 8diisocyanate, naphthalene-1, 3,7-triisocyanate, biphenyl-2,4,4'-triisocyanate, 4,4' ,4"-triisocyanato- 2, 5-dimethoxytriphenylamine, 4"-triisocyanatotriphenylamine, p-dimethylaminophenyl isocyanate, tris (4-phenylisocyanato)thiophosphate, etc. if necessary, these isocyanates may be used in the form of a so-called block isocyanate, an addition compound with a phenol, lactam, oxime or the like, they may be used in the form of a diisocyanate dimer such as l-methylbenzene-2,4-diisocyanate dimer, or a diisocyanurate trimer as an isocyanurate, and they may be used in the form of a polyisocyanate obtained as an adduct by the use of any of various polyols and the like. There may also be used water adduct isocyanates of 2,4-toluene diisocyanate, diphenylmethane diisocyanate and the like, such as 1,3-bis(3isocyanato-4-methylphenyl)urea; polyol adducts such as 195 trimethylolpropane adduct of toluene diisocyanate (Desmodule L, a trade name); phenol adduct isocyanates; amine adduct isocyanates; and the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171.

The isocyanate compound is used in a proportion of preferably 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor.

When the proportion of the isocyanate compound is parts by weight or more, a sufficient improving effect on the shelf stability can be obtained and the coloring density is high. When the proportion of the isocyanate compound is 500 parts by weight or less, the isocyanate compound hardly remains as a surplus, and this is economically advantageous and hence preferable.

The incorporation of an imino compound into the color-producing composition of the present invention further improves the shelf stability.

The imino compound that can be incorporated into the color-producing composition of the present invention is a colorless or light-colored compound that has at least one imino group and is solid at ordinary temperatures. Two or more imino compounds may be incorporated in combination, depending on purposes. As the imino compound, those described in JP-A-9-142032 can be mentioned, and the contents of this reference 196 are hereby incorporated herein by reference. Of the imino compounds described in the reference, iminoisoindoline derivatives are preferable, and 1,3diimino-4,5,6,7-tetrachloroisoindoline, 3-imino- 4,5,6,7-tetrachloroisoindolin-l-one and 1,3-diimino- 4,5,6,7-tetrabromoisoindoline are more preferable.

The imino compound is used in a proportion of preferably 5 to 500 parts by weight, more preferably to 200 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor. When the proportion of the imino compound is 5 parts by weight or more, an improving effect on the shelf stability is obtained. When the proportion of the imino compound is 500 parts by weight or less, the imino compound hardly remains as a surplus, and this is economically advantageous and hence preferable.

In addition, the incorporation of an amino compound into the color-producing composition of the present invention improves the preservability of an original recording material surface and print. The amino compound that can be incorporated is a colorless or light-colored substance having at least one primary, secondary or tertiary amino group. As such an amino compound, those described in JP-A-9-142032 can be mentioned. Of the amino compounds described in this reference, aniline derivatives having at least one amino group and represented by the following formula (VIII) are especially preferable: 0 197

(VIII)

wherein Ri, R 2

R

3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group, X, and X 2 are independently an amino group or a group represented by the formula NH2 (b) and Y 1 is any of -SO 2

-CO-,

-CONH- and a group represented by any of the formulas 198

CH

3

CH

3

CH

3

CH

3 -C C (a) -0 0

CH

3

CH

3

II

0 or is absent, and n is 1 or 2.

These amino compounds may be used singly or as a mixture thereof. For improving the print preservability in the plasticizer resistance, the proportion of the amino compound is preferably 1 to 500 parts by weight per 100 parts by weight of the colorless or light-colored dye precursor. When the content 199 of the amino compound is 1 part by weight or more per part of the urea-urethane compound, the print preservability can be improved. When the content is 500 parts by weight or less, performance characteristics of the resulting composition can be sufficiently improved and such a content is advantageous from the viewpoint of cost.

The incorporation of also an acidic developer into the color-producing composition of the present invention improves the sensitivity and enables the color-producing composition to produce a brilliant color.

As the acidic developer that is used when the color-producing composition of the present invention is used in a heat-sensitive recording material, conventional electron-accepting materials are used and, in particular, phenol derivatives; aromatic carboxylic acid derivatives or their metal compounds; salicylic acid derivatives or their metal salts; N,N-diarylthiourea derivatives; sulfonylurea derivatives; etc.

are preferable. The phenol derivatives are especially preferable. Specific examples of the phenol derivatives are 2,2-bis(4-hydroxyphenyl)propane, 2,2bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, l,l-bis(4hydroxyphenyl)cyclohexane, butyl bis(4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4hydroxyphenyl) sulfone, bis(3-methyl-4-hydroxyphenyl) 200 sulfone, 4-hydroxyphenyl-4'-methylphenyl sulfone, 3chloro-4-hydroxyphenyl-4' -methyiphenyl sulfone, 3,4dihydroxyphenyl-4' -methyiphenyl sulfone, 4-isopropylphenyl-4' -hydroxyphenyl sulfone, 4-isopropyloxyphenyl- 4'-hydroxyphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4' -benzyloxyphenyl sulfone, 4isopropylphenyl-4' -hydroxyphenyl sulfone, bis (2-methyl- 3-tert-butyl-4-hydroxyphenyl) sulfide, methyl 4hydroxybenzoate, benzyl 4-hydroxybenzoate, (4chlorobenzyl) 4-hydroxybenzoate, ethyl l,2-bis(4'hydroxybenzoate), pentyl 1, 5-bis (4'-hydroxybenzoate), hexyl 1, 6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, etc. The salicylic acid derivatives include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-npentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid, etc. The sulfonylurea derivatives include, for example, compounds containing one or more arylsulfonylarninoureido groups, such as 4,4-bis(ptoluenesulfonylaminocarbonyl amino) diphenylmethane, 4, 4-bis (o-toluenesulfonylaminocarbonylamino)diphenylmethane, 4, 4-bis (p-toluenesulfonylaininocarbonylamino) diphenyl sulfide, 4, 4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl ether, N- (p-toluenesulfonyl) phenylurea, etc. In addition, there may also be used, for example, [oxybis (ethyleneoxy-p-phenylene- 201 sulfonyl)]diphenol and mixtures composed mainly of this compound D-90 (a trade name, mfd. by Nippon Soda Co., Ltd.)).

Of the above-exemplified acidic developers, 2,2-bis(4-hydroxyphenyl)propane, 4-isopropyloxyphenyl- 4'-hydroxyphenyl sulfone, bis(3-allyl-4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone and 4,4'- [oxybis(ethyleneoxy-p-phenylenesulfonyl)]diphenol are especially preferable because they improve sensitivity and make it possible to obtain a heat-sensitive recording material capable of producing a brilliant color.

In order to improve fog, the thermal response and the like, it is also possible to add phenolic compounds such as N-stearyl-N'-(2-hydroxyphenyl)urea, N-stearyl-N'-(3-hydroxyphenyl)urea, N-stearyl-N'-(4hydroxyphenyl)urea, p-stearoylaminophenol, o-stearoylaminophenol, p-lauroylaminophenol, p-butyrylaminophenol, m-acetylaminophenol, o-acetylaminophenol, pacetylaminophenol, o-butylaminocarbonylphenol, ostearylaminocarbonylphenol, p-stearylaminocarbonylphenol, 1,1,3-tris(3-tert-butyl-4-hydroxy-6-methylphenyl)butane, 1,1,3-tris(3-tert-butyl-4-hydroxy-6ethylphenyl)butane, 1,1,3-tris(3,5-di-tert-butyl-4hydroxyphenyl)butane, 1,1,3-tris(3-tert-butyl-4hydroxy-6-methylphenyl)propane, 1,2,3-tris(3-tertbutyl-4-hydroxy-6-methylphenyl)butane, 1,1,3-tris(3phenyl-4-hydroxyphenyl)butane, 1,1,3-tris(3-cyclohexyl- 202 1,1,3-tris(3cyclohexyl-4-hydroxy-6-methylphenyl)butane, 1,1,3tetra(3-phenyl-4-hydroxyphenyl)propane, 1,1,3,3tetra(3-cyclohexyl-4-hydroxy-6-methylphenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxy-6-methylphenyl)butane, 1,1-bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)butane, etc.

The above-mentioned acidic developer is used in a proportion of preferably 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor. When the proportion of the acidic developer is 5 parts by weight or more, the color development of the dye precursor is satisfactory and the coloring density is high.

When the proportion of the acidic developer is 500 parts by weight or less, the acidic developer hardly remains, and this is economically advantageous and hence preferable.

Also when the color-producing composition of the present invention is used in a pressure-sensitive recording material, the incorporation of an acidic developer into the color-producing composition improves the coloring density and enables the pressure-sensitive recording material to produce a brilliant color.

Also as this acidic developer, an electronaccepting material is used. The acidic developer includes, for example, inorganic compounds such as acid 203 clay, activated clay, attapulgite, bentonite, zeolite, colloidal silica, magnesium silicate, talc, aluminum silicate, etc.; phenol, cresol, butylphenol, octylphenol, phenylphenol, chlorophenol, salicylic acid and the like, or aldehyde condensation novolak resins derived therefrom and their metal salts; and salicylic acid derivatives such as 3-isopropylsalicylic acid, 3phenylsalicylic acid, 3-cyclohexylsalicylic acid, di-t-butylsalicylic acid, salicylic acid, 3,5-di-t-octylsalicylic acid, 3-methylacid, 3,5-di (,a-dimethylbenzyl)salicylic acid, salicylic, etc. and metal salts thereof.

The incorporation of also a fluorescent dye into the color-producing composition of the present invention improves the whiteness. As the fluorescent dye to be incorporated into the color-producing composition of the present invention, various wellknown ones can be used, and there are mentioned stilbene derivatives, coumarin derivatives, pyrazoline derivatives, bisstyrylbiphenyl derivatives, naphthalimide derivatives, bisbenzoxazolyl derivatives, etc. Although the fluorescent dye is not limited to them, diaminostilbenedisulfonic acid derivatives are especially preferable.

As to the amount of the fluorescent dye used, the fluorescent dye is made present in an amount of preferably 0.01 to 3 wt%, more preferably 0.1 to 2 wt%, 204 based on the total weight (in terms of solids) of the color-producing composition. When the amount of the fluorescent dye used is more than 3 wt%, the colorproducing composition is colored in some cases. When the amount is less than 0.01 wt%, the effect of the fluorescent dye on the whiteness is lessened.

Next, the color-producing composition of the present invention may contain shelf-stability-imparting agents. The shelf-stability-imparting agents usable in the present invention are additives such as imagestabilizing agents, light stabilizers, antioxidants, etc.

By using these shelf-stability-imparting agents in combination with a urea-urethane compound developer a developer comprising a urea-urethane compound) and a colorless and light-colored dye precursor, the light resistance of the color-producing composition can be improved and a recording material excellent in light resistance can be obtained.

The image-stabilizing agents as preferable examples of the shelf-stability-imparting agents used in the present invention include, for example, 1,1,3tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, hindered phenol compounds 4,4'- 4,4'- 2,2'-thiobis(6tert-butyl-4-methylphenol) and 2,2'-methylenebis(6- 205 tert-butyl-4-methylphenol)], 4-benzyloxy-4'-(2methylglycidyloxy)diphenyl sulfone, 4,4'-diglycidyloxydiphenyl sulfone, 1,4-diglycidyloxybenzene, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, 2propanol derivatives and salicylic acid derivatives.

Usually, these image-stabilizing agents are used in a proportion of preferably 5 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor. When the proportion of the imagestabilizing agents is 5 parts by weight or more, the light resistance is good and the coloring density is high. When the proportion of the image-stabilizing agents is more than 1,000 parts by weight, their effect on the light resistance is not heightened and moreover, such a proportion is economically disadvantageous.

The light stabilizers as preferable examples of the shelf-stability-imparting agents used in the present invention include, for example, 2-(2'-hydroxy- 5'-methylphenyl)benzotriazole, 2-(3',5'-di-t-butyl-2'hydroxyphenyl)benzotriazole, 2-(5'-t-butyl-2'hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3tetramethylbutyl)phenyl]benzotriazole, butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(3',5'-di-t-pentyl-2'-hydroxyphenyl)benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-octyloxycarbonylethylphenyl)- 206 and the like; 4-hydroxy-, 4methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4benzyloxy-, 4'-trihydroxy-, 2'-hydroxy-4, 4'dimethoxy- or 4- (2-ethyihexyloxy) -2-hydroxybenzophenone derivatives and the like; 4-t-butylphenyl salicylate, phenyl salicylate, octyiphenyl salicylate, dibenzoylresorcinol, bis (4-t-butylbenzoyl) resorcinol, 2, 4-di-t-butylphenyl 3, 5-di-t-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate and the like; ethyl ax-cyano-O343-diphenylacrylate, isooctyl acyano-3,Of-diphenylacrylate, methyl c-carbomethoxycinnamate, methyl cx-cyano-f-methyl-p-methoxycinnamate and the like; bis 6-tetramethyl-4-piperidyl) sebacate, bis 6-tetramethyl-4-piperidyl) succinate, bis 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4piperidyl) sebacate, bis 6-pentamethyl-4piperidyl) adipate and the like; 4,4'-di-octyloxyoxanilide, 2,2' -diethoxyoxyoxanilide, 2,2'-di-octyloxy- 5, 5'-di-t-butyloxanilide, 2,2'-di-dodecyloxy-5,5'-di-tbutyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis (3dimethylaminopropyl) oxanilide, 2-ethoxy-5-t-butyl-2'ethoxyoxanilide and the like; and 2,4,6-tris(2-hydroxy- 4-octyloxyphenyl)-1, 3,5-triazine, 2- (2-hydroxy-41octyloxyphenyl) 6-bis (2,4-dimethylphenyl) triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4dimethylphenyl)-1,3, 5-triazine, 2,4-bis (2-hydroxy-4propyloxyphenyl-6- 4-dimethylphenyl) 207 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and the like. Usually, these light stabilizers are used in a proportion of preferably 5 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor. When the proportion of the light stabilizers is 5 parts by weight or more, the light resistance is good and the coloring density is high. When the proportion of the light stabilizers is more than 1,000 parts by weight, their effect on the light resistance is not heightened and moreover, such a proportion is economically disadvantageous.

The antioxidants as preferable examples of the shelf-stability-imparting agents used in the present invention include, for example, 2,6-di-t-butyl- 4-methylphenol, 2-t-4,6-dimethylphenol, 2,6-di-t-butyl- 4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-dit-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-dinonyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,4-dimethyl-6-(1'-methyl-undeca-l'-yl)phenol,, 2,4-dimethyl-6-(1'-methyl-heptadeca-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyl-trideca-l'-yl)phenol, and mixtures thereof; 2,4-di-octylthiomethyl-6t-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecyl- 208 thiomethyl-4-nonylphenol, and mixtures thereof; 2,6-dit-butyl-4-methoxyphenol, 2, 2, 5-di-t-amylhydroquinone, 2, 6-diphenyl-4-octadecyloxyphenol, 2, 6-di-t-butylhydroquinone, 2, 5-di-t-butyl-4hydroxyanisole, 3, 5-di-t-butyl-4-hydroxyanisole, di-t-butyl-4-hydroxyphenyl stearate, bis butyl-4-hydroxyphenyl) adipate, and mixtures thereof; 2, 4-bis-octylmercapto-6- 5-di-t-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5di-t-butyl-4-hydroxyanilino) 5-triazine, 2octylmercapto-4, 6-bis 5-di-t-butyl-4-hydroxyphenoxy) 1,2,3-triazine, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3, 5-tris (4-t-butyl-3-hydroxy- 2, 6-dimethylbenzyl) isocyanurate, 2,4, 6-tris butyl-4-hydroxyphenylethyl) 5-triazine, 1,3,5tris 5-di-t-butyl-4-hydroxyphenylpropionyl) hexahydro-1, 3,5-triazine, 1,3,5-tris 4-hydroxybenzyl) -isocyanurate and the like; 2,2kmethylenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis(6-t--butyl-4-ethylphenol), 2,21-ethylidenebis(4,6di-t-butylphenol), 2,2'-ethylidenebis(6-t-butyl-4isobutyiphenol), 4,4k -methylenebis 6-di-t-butylphenol), 4, 4'-methylenebis (6-t-butyl-2-methylphenol), 1, 1-bis -(5-t-butyl-4-hydr-oxy-2-methylphenyl)butane, ethylene glycol bis[3,3'-bis(3'-t-butyl-4'-hydroxyphenyl) butyrate] and the like; l,3,5-tris(3,5-di-tbutyl-4-hydroxybenzyl) 6-trimethylbenzene, 1,4bis 5-di-t-butyl-4-hydroxybenzyl) 3,5, 6- 209 tetramethylbenzene, 2,4,6-tris(3,5-di-t-butyl-4hydroxybenzyl)-phenol and the like. Usually, these antioxidants are used in a proportion of preferably to 1,000 parts by weight, more preferably 10 to 500 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor. When the proportion of the antioxidants is 5 parts by weight or more, the light resistance is good and the coloring density is high. When the proportion of the antioxidants is more than 1,000 parts by weight, their effect on the light resistance is not heightened and moreover, such a proportion is economically disadvantageous.

The color-producing composition of the present invention can be made into a recording material by forming a color-producing layer of the composition on some substrate by a method such as coating. The structure of the recording material is varied depending on the kind of the recording material.

The color-producing composition of the present invention can be used in any of various recording materials such as heat-sensitive recording materials, pressure-sensitive recording materials and the like, and is suitable particularly for the heatsensitive recording materials.

When the color-producing composition is used in a heat-sensitive recording material, a heatsensitive recording layer capable of producing a color 210 on heating is formed on a substrate. Specifically, the above-mentioned urea-urethane compound, the abovementioned colorless or light-colored dye precursor such as a leuco dye, the heat-meltable material described hereinafter, and the like should be applied on a substrate, each in the form of a dispersion together with other necessary components to form a heatsensitive recording layer. The dispersion is prepared by finely grinding one or more compounds as each of the components described above, with a sand grinder or the like in an aqueous solution containing a compound having dispersing capability, such as a water-soluble polymer, a surfactant or the like. The particle size of each of the dispersions thus obtained is preferably adjusted to 0.1 to 10 pm, in particular, to about 1 pmn.

Specific examples of the compound having dispersing capability which can be used in the present invention are water-soluble polymers such as poly(vinyl alcohol)s, carboxylic acid-modified poly(vinyl alcohol)s, sulfonic acid-modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, etc.; anionic surfactants such as condensed naphthalenesulfonates, polyoxyethylene alkyl ether sulfuric acid ester salts sodium polyoxyethylene lauryl ether sulfates, sodium polyoxyethylene alkyl ether sulfates and sodium polyoxyethylene alkyl phenyl ether sulfates), dialkylsulfosuccinic acid ester sodium, alkylphosphates (e.g.

211 diethanolamine alkylphosphates and potassium alkylphosphates), specialty carboxylic acid-based polymers, etc.; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alky phenyl ethers, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, polyethylene glycol fatty acid esters, etc.; and cationic surfactants such as dicyanamidopolyamines, tertiary amine salts, quaternary ammonium salts, etc. Of these, the polyvinyl alcohols, carboxylic acid-modified polyvinyl alcohols, sulfonic acid-modified polyvinyl alcohols and methyl cellulose are especially preferable. The above-exemplified compounds may be used singly or as a mixture thereof.

When the urea-urethane compound developer according to the present invention is used in a heatsensitive recording material, the adjustment of the average particle size of the urea-urethane compound developer to not more than 5 pm and not less than 0.05 pm makes it possible to obtain a heat-sensitive recording material which has a sufficient color development sensitivity, gives a very stable printed developed color image, and has a good plasticizer resistance. The average particle size is more preferably not more than 3 pm and not less than 0.1 mn.

When the average particle size is less than 0.05 pm, the preservability of the original recording material surface against plasticizers is deteriorated. On the other hand, when the average particle size is more than 0@ 212 pim, the sensitivity of the heat-sensitive recording material is decreased.

Particularly when the urea-urethane compound is subjected to wet grinding in an aqueous medium, the temperature of the aqueous medium is preferably 600C or lower. At the time of the grinding, the urea-urethane compound developer comes into contact with water, so that hydrolysis of its urethane group(s) proceeds depending on conditions. Therefore, the sensitivity of a heat-sensitive recording material obtained by the use of the urea-urethane compound developer tends to be decreased. Particularly when the medium temperature at the grinding is higher than 600C, the sensitivity is remarkably decreased. The medium temperature at the grinding is more preferably 400C or lower.

In addition, when the urea-urethane compound developer is ground, it is preferably ground in a neutral pH range of 5 to 10. When the pH at the grinding is lower than 5, an inorganic pigment and the like are decomposed in the production of a heat-sensitive coating liquid, so that the sensitivity tends to be decreased. On the other hand, when the pH is higher than 10, the urea-urethane compound developer is hydrolyzed, so that the sensitivity is decreased in some cases. Specific examples of dispersing agent usable for preparing a dispersion of the urea-urethane compound developer by grinding in the present invention are water-soluble polymers such as poly(vinyl 213 alcohol)s, carboxylic acid-modified poly(vinyl alcohol)s, sulfonic acid-modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, etc.; anionic surfactants such as condensed naphthalenesulfonates, polyoxyethylene alkyl ether sulfuric acid ester salts sodium polyoxyethylene lauryl ether sulfates, sodium polyoxyethylene alkyl ether sulfates and sodium polyoxyethylene alkyl phenyl ether sulfates), dialkylsulfosuccinic acid ester sodium, alkylphosphates (e.g.

diethanolamine alkylphosphates and potassium alkylphosphates), specialty carboxylic acid-based polymers, etc.; nonionic surfactants such as polyoxyethylene alkyl phenyl ethers, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, polyethylene glycol fatty acid esters, etc.; and cationic surfactants such as dicyanamidopolyamines, tertiary amine salts, quaternary ammonium salts, etc. Of these, the water-soluble polymers and the anionic surfactants are especially preferable because they make it possible to obtain a heat-sensitive recording material that has a high sensitivity irrespective of conditions of dispersing the urea-urethane compound developer and has an improved preservability of the original recording material surface against plasticizers irrespective of the average particle size of the urea-urethane compound developer. The poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropyl- 214 methyl cellulose, condensed sodium naphthalenesulfonate, polycarboxylic acid ammonium salts, watersoluble low-molecular weight copolymers and sodium 2ethylhexylsulfosuccinate are more preferable. Of these, methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate, and watersoluble low-molecular weight copolymers are still more preferable, and hydroxypropylmethyl cellulose is the most preferable. The above-exemplified dispersing agents may be used singly or as a mixture thereof.

As a dispersing agent usable for preparing a dispersion of the colorless or light-colored dye precursor by grinding in the present invention, the same compounds as those used as the dispersing agent for dispersing the urea-urethane compound developer can be used. Of such compounds, the water-soluble polymers, the anionic surfactants and mixed dispersing agents of these two kinds of the compounds are especially preferable for improving a heat-sensitive recording material in sensitivity and in preservability of the original recording material surface against plasticizers. Mixed dispersing agents consisting of methyl cellulose or hydroxypropylmethyl cellulose as a water-soluble polymer and a polyoxyethylene alkyl ether sulfate or sodium 2-ethylhexylsulfosuccinate as an anionic surfactant are more preferable. A mixed dispersing agent of hydroxypropylmethyl cellulose and sodium 2-ethylhexylsulfosuccinate is the most 215 preferable.

The pH of a coating liquid containing the urea-urethane compound and the colorless or lightcolored dye precursor is preferably 5 to 12.

The heat-sensitive recording layer may contain, besides the components described above, pigments such as diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formaldehyde resin, etc. In addition, the heat-sensitive recording layer may, if necessary, contain metal salts of higher fatty acids, such as zinc stearate, calcium stearate, etc.; and waxes such as paraffin, oxidized paraffin, polyethylenes, oxidized polyethylenes, stearamide, cator wax, etc., for the purpose of, for example, preventing the wear of a head and sticking. If necessary, the heatsensitive recording layer may also contain dispersing agents such as sodium dioctylsulfosuccinate, etc.; ultraviolet absorbers of benzophenone type, benzotriazole type and the like; surfactants; fluorescent dyes; etc.

As a binder usable for forming the heatsensitive recording layer, there can be mentioned, for example, water-soluble binders such as starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, sodium poly(acrylate)s, 216 acrylamide-acrylic ester copolymers, acrylamide-acrylic ester-methacrylic acid terpolymers, alkali salts of styrene-maleic anhydride copolymers, alkali salts of ethylene-maleic anhydride copolymers, etc.; and latex type water-insoluble binders of styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, methyl acrylate-butadiene copolymers, etc.

As the substrate for the heat-sensitive recording layer, paper is mainly used, though any of various woven fabrics, nonwoven fabrics, synthetic resin films, laminated papers, synthetic papers, metal foils, and composite sheets obtained by combining two or more of them may be used besides paper, depending on their purpose. The basis weight of the substrate is preferably 40 g/m 2 to 200 g/m 2 The substrate is preferably excellent in surface smoothness and flatness because a heat-sensitive recording material obtained by the use of the substrate is desired to have as high a flatness as possible. Therefore, the substrate is preferably subjected to surface treatment by applying heat and pressure by means of any of a machine calender, soft calender, supercalender and the like.

The surface pH of the substrate is preferably 3 to 9, more preferably 5 to 9, most preferably 6 to 8.

When the surface pH of the substrate is lower than 3, fog tends to occur. When the surface pH of the substrate is higher than 12, the urea-urethane compound developer is decomposed, so that the coloring density 217 is decreased in some cases.

The heat-sensitive recording layer may be composed of either a single layer or two or more layers. The heat-sensitive recording layer may have, for example, a multilayer structure formed by incorporating each color-producing component into one layer. A protective layer composed of a single layer or two or more layers may be formed on the heatsensitive recording layer, and an intermediate layer composed of a single layer or two or more layers may also be formed between the substrate and the heatsensitive recording layer. The heat-sensitive recording layer can be obtained by mixing aqueous dispersions prepared by fine grinding of each colorproducing component or any other component, with a binder and the like, applying the resulting mixture on the substrate, and drying the mixture. The coating amount of this coating liquid is preferably 1 to 15 g/m 2 when the coating liquid is in a dried state.

When the color-producing composition of the present invention is used in a heat-sensitive recording material, a heat-meltable material may be incorporated into the color-producing composition in order to improve the sensitivity. The heat-meltable material is preferably one which has a melting point of 60 0 C to 1800C, in particular, one which has a melting point of to 1400C. The heat-meltable material includes, for example, benzyl p-benzyloxybenzoate, stearamide or 218 its emulsified product, palmitamide, N-methylolstearamide, J-naphthyl benzyl ether, N-stearylurea, N,N'-distearylurea, phenyl f-naphthoate, phenyl 1hydroxy-2-naphthoate, f-naphthol (p-methylbenzyl) ether, 1, 4-dimethoxynaphthalene, l-methoxy-4-benzyloxynaphthalene, N-stearoylurea, p-benzylbiphenyl, 1,2di (m-methylphenoxy) ethane, 1-phenoxy-2- (4-chiorophenoxy)ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate, m-terphenyl, dibenzyl oxalate and (pchlorobenzyl) oxalate.

In addition, 4,4' -dimethoxybenzophenone, 4, 4'-dichlorobenzophenone, 4, 4'-difluorobenzophenone, diphenyl sulfone, 4, 4'-dichlorodiphenyl sulfone, 4,4'di fluorodiphenyl sul tone, 4, 4'-di chiorodiphenyl disulfide, diphenylamine, 2-methyl-4-methoxydiphenylamine, N,N' -diphenyl-p-phenylenediamine, 1- (Nphenylamino)naphthalene, benzil, 1, 3-diphenyl-1, 3propanedione, etc. are preferable as the heat-meltable material because they are very effective in improving the sensitivity.

As the heat-meltable material, there may also be used benzyl 4-hydroxybenzoate, 4-(benzyloxy)phenol, 2, 4-dihydroxybenzophenone, 4, 4'-tetrahydroxybenzophenone, 4,4' -dihydroxybenzophenone, 12,2-bis (4-hydroxyphenyl)propane, 4,4' -dihydroxydiphenyl sulfone, bis (3methyl-4-hydroxyphenyl) sulfone, bis 5-dimethyl-4hydroxyphenyl) sulfone, 3, 4-dihydroxyphenyl-4' methylphenyl sulfone, bis (2-methyl-3-tert-butyl-4- 219 hydroxyphenyl) sulfide, 4,4' -dihydroxydiphenyl ether, 4,4' -thiodiphenol, 4,4' -dihydroxydiphenylmethane, 3,3'dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4,4'thiobisbenzenethiol, salicylanilide, 4,4'-diamino-3, 3'diethyldiphenylmethane, 4, 4'-diaminobenzanilide, 3,3'dichloro-4, 4'-diaminodiphenylmethane, 3,3' -dimethyl- 4, 4'-diaminodiphenylmethane, 4,4'-thiodianiline, 2,2'dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis(3,4-diaminophenyl) sulfone, 4,4'diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, 3,3' -diaminodiphenylmethane, 4, 4'-diaminodiphenylamine, 3, 3'-diaminobenzophenone, 4, 4'-diaminobenzophenone, acetoacetic 0chioroanilide, acetoacetic anilide, acetoacetic atoluidide, acetoacetic p-toluidide, acetoacetic oanisidide, acetoacetic m-xylidide and p-acetotoluidide, etc.

Of these, diphenyl sulfone, di-p-methylbenzyl oxalate, benzil, 0-naphthyl benzyl ether, p-benzylbipheriyl, 1, 2-di (m-methylphenoxy) ethane, 1, 2-diphenoxymethylbenzene, m-terphenyl and stearamide are preferably used.

In addition, employment of a heat-meltable material of the following structural formula (XVIII), 220 among the above-exemplified heat-meltable materials, in a heat-sensitive recording material is markedly effective in increasing the sensitivity of the recording material and improving the plasticizer resistance of a print portion and the heat resistance of the original recording material surface. Heat-meltable materials represented by the structural formula (XIX) shown below are especially preferable.

0 -0 (XVIII) wherein Y is any of -SO 2

-CH

2 -CH(CsHs)-, -C(CH 3 -COCO-, -C03-, -COCH 2 CO-, -COOCH 2 -CONH-, -OCH 2 and n is 1 or 2, and hydrogen atom(s) of each benzene ring may be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfone group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue.

0

(XIX)

wherein hydrogen atom(s) of each benzene ring may be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a 221 sulfamoyl group, a sulfone group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue.

The above-exemplified heat-meltable materials may be used singly or as a mixture thereof. For attaining a sufficient thermal response, the heatmeltable material is used in a proportion of preferably to 300 parts by weight, more preferably 20 to 250 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor.

As a dispersing agent usable for preparing a dispersion of the heat-meltable material by grinding in the present invention, the same compounds as those used as the dispersing agent for dispersing the ureaurethane compound developer can be used. Of such compounds, the water-soluble polymers and the anionic surfactants are especially preferable for improving a heat-sensitive recording material in preservability of the original recording material surface against plasticizers. The poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate, polycarboxylic acid ammonium salts, watersoluble low-molecular weight copolymers and sodiumr 2ethylhexylsulfosuccinate are more preferable. Of these, the modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate, polycarboxylic acid 222 ammonium salts are still more preferable, and hydroxypropylmethyl cellulose is the most preferable.

The above-exemplified dispersing agents may be used singly or as a mixture thereof.

When the urea-urethane compound developer is ground, fine grinding of the developer together with the above-mentioned heat-meltable material (cogrinding) further improves the sensitivity and plasticizer resistance of a heat-sensitive recording material as compared with fine grinding of each compound followed by mixing of the ground compounds.

The reason why these effects are obtained is not completely clear.

Furthermore, the moisture resistance of the non-print portion (the original surface) of a heatsensitive recording material can be improved by using at least one dispersing agent for the urea-urethane compound developer selected from methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate and water-soluble low-molecular weight copolymers, and at least one dispersing agent for the heat-meltable material selected from modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate and polycarboxylic acid ammonium salts.

The color-producing composition of the present invention can be used in various heat-sensitive recording materials and is especially suitable for 0@ 223 heat-sensitive magnetic recording materials, labels for heat-sensitive recording, multicolor heat-sensitive recording materials, and heat-sensitive recording materials for laser marking.

When the color-producing composition of the present invention is used in a heat-sensitive magnetic recording material, the recording material is preferably in the following form: a heat-sensitive recording layer containing the urea-urethane compound developer is formed on one side of a substrate and a magnetic recording layer is formed on the other side.

The magnetic recording layer of the heatsensitive magnetic recording material is formed by coating a substrate with a coating material prepared by uniformly dispersing ferromagnetic powder such as barium ferrite, strontium ferrite, Co-y-Fe 2 0 2 y-Fe 2 0 2 or the like in an aqueous binder such as an aqueous emulsion resin, and drying the coated substrate. In this case, various additives such as antistatic agents carbon graphite), lubricants wax), color pigments for hue adjustment, coating-film flexibilizers poly(ethylene oxide)s], etc. may be added depending on their purpose.

The heat-sensitive magnetic recording material of the present invention is suitable as heatsensitive magnetic recording materials used as rail road tickets, tickets, prepaid cards, etc.

When the color-producing composition of the 224 present invention is used in a label for heat-sensitive recording, the label is preferably in the following form: a heat-sensitive recording layer containing the urea-urethane compound developer is formed on one side of a substrate and an adhesive layer is formed on the other side.

The adhesive layer of this heat-sensitive recording material is composed mainly of a pressuresensitive adhesive. The pressure-sensitive adhesive includes, for example, synthetic-rubber-based emulsion type adhesives, acrylic emulsion type adhesives, natural-rubber-based solvent type adhesives, acrylic solvent type adhesives and silicon-based solvent type adhesives. Of these, the acrylic emulsion type adhesives are especially preferable.

When a reverse-side layer (a back coating layer) is, if necessary, formed between the adhesive layer and the substrate in the label for heat-sensitive recording produced by a process according to the present invention, taking-out of curl, prevention of electrostatic charge, and adjustment of coefficient of friction are possible in the label for heat-sensitive recording. As the components of a coating liquid for the reverse-side layer, a coating method for the coating liquid, and the like, the same components, method and the like as in the formation of the heatsensitive recording layer may be employed. The dry spread of the coating liquid ranges preferably from 0.2 *0 225 to 10.0 g/m 2 The order of coating in the production of the label for heat-sensitive recording is not particularly limited. For example, either of the following orders may be employed: the heat-sensitive recording layer is formed on one side of the substrate and then the back coating layer is formed on the other side, after which the adhesive layer is formed on the back coating layer; or the back coating layer is formed on one side of the substrate and then the heat-sensitive recording layer is formed on the other side, after which the adhesive layer is formed on the back coating layer.

As to a method for forming the adhesive layer on the back coating layer, a liquid for forming the adhesive layer may be directly applied on the back coating layer and dried, or a material obtained by previously applying a liquid for forming the adhesive layer, on release paper, followed by drying may be attached to the back coating layer side of a heatsensitive recording material having no adhesive layer formed thereon.

In addition, the thermal response can be improved by forming an intermediate layer composed of a single layer or two or more layers, between the heatsensitive recording layer and the substrate. The intermediate layer is composed mainly of an organic or inorganic pigment, hollow particles and an aqueous binder such as a water-soluble polymer or a latex. As *0 226 the organic or inorganic pigment and the aqueous binder, the same organic or inorganic pigment and aqueous binder as used in the heat-sensitive recording layer can be used. A method for forming the intermediate layer is not particularly limited. As this method, the same method as the method for forming the heat-sensitive recording layer can be adopted. The dry spread for forming the intermediate layer ranges preferably from 2.0 to 15.0 g/m 2 When the color-producing composition of the present invention is used in a multicolor heatsensitive recording material, this recording material is preferably in the following form: at least two heatsensitive recording layers are formed on one side of a substrate and at least one of said heat-sensitive recording layers contains the urea-urethane compound developer.

As the substrate used, there can be used synthetic paper produced by kneading a polyolefin resin and a white inorganic pigment with heating, extruding the kneaded product through a die, stretching the extruded product in a lengthwise direction, laminating one or two films made of a polyolefin resin and a white inorganic pigment on each side of the stretched product, and stretching the resulting assembly in a crosswise direction to make the same semitransparent or opaque; films obtained by kneading one of or a mixture of two or more of thermoplastic resins such as 227 polyethylenes, polypropylenes, ethylene-vinyl acetate copolymer resins, poly(vinyl chloride)s, polystyrenes, polyesters, etc. with heating, extruding the kneaded product through a die, and then stretching the kneaded product biaxially; opaque films obtained by mixing a white inorganic pigment with any of the aboveexemplified resins, followed by biaxial stretching; and substrates produced from pulp fiber, such as woodfree paper, medium-duty paper, machine glazed paper, regenerated paper, coated paper, etc. The substrates made of pulp fiber are preferably coated with a heatsensitive layer after previous formation of a layer for coating in order to improve the uniformity of image.

The heat-sensitive color-producing layer according to the present invention comprises as its main constituents an adhesive and a color-producing composition capable of causing color development reaction owing to the contact of materials with each other made by heating. Specific examples of the colorproducing composition are combinations of a colorless or light-colored dye precursor and the above-mentioned urea-urethane developer capable of allowing said dye precursor to develop a color, on heating, and combinations of a diazo compound and a coupler capable of developing a color by its reaction with a diazo compound. If necessary, crosslinking agents, pigments and heat-meltable materials may be incorporated into the color-producing composition. Usually, the coating

S.

228 amount of the heat-sensitive color-producing layer is preferably 3 to 15 g/m 2 from the viewpoint of color development sensitivity and coloring density.

As a color-developable dye, the colorless or light-colored dye precursor already described is used which can develop a color when reacted with the ureaurethane compound developer with heating.

On the other hand, in a heat-sensitive recording layer comprising as its main constituents a diazo compound and a coupler capable of developing a color by its reaction with said diazo compound, these compounds are a well-known light-decomposable diazo compound and a coupler capable of forming a pigment by its reaction with said diazo compound. If necessary, a basic material and the like may be added in order to accelerate the reaction of the diazo compound with the coupler. The coupler and the basic material are preferably used as a mixture thereof in proportions of to 1,000 parts by weight and 10 to 2,000 parts by weight, respectively, per 100 parts by weight of the diazo compound.

The term "light-decomposable diazo compound" used herein means a diazo type photosensitive material capable of forming a pigment by its reaction with a coupling component on heating, such as a diazonium salt, diazosulfonate compound, diazoamino compound, quinonediazide compound or the like. The diazonium salt refers to a compound represented by the general 229 f ormula: Ar-N 2

X

wherein Ar is an aromatic portion, N 2 is a diazonium group, and X- is a counter anion. Such compounds have various maximum absorption wavelengths, depending on the positions and kinds of substituents of the Ar portion.

Specific examples of the diazonium. compound used in the present invention are 4-dimethylaminobenzenediazonium, 4-diethylaminobenzenediazonium, 4dipropylaminobenzenediazonium, 4-methylbenzylaminobenzenediazonium, 4-dibenzylaminobenzenediazoniun, 4ethylhydroxyethylaminobenzenediazoniun, 4-diethylamino- 2-methoxybenzenediazonium, 4 -dimethyl-3-methylbenzenediazonium, 4-benzoylamino-2, 4-morpholinobenzenediazoniun, 4-morpholino-2, diethoxybenzenediazonium, 4-morpholino-2, dibutoxybenzenediazonium, 4-anilinobenzenediazonium, 4toluylmercapto-2, 5-diethoxybenzenediazonium, 4- (N,Ndioctylcarbamoyl) benzenediazonium, 2-octadecyloxybenzenediazonium, 4- (4-tert-octylphenoxy)benzenediazonium, 4- 4-di-tert-amylphenoxy)benzenediazonium, 2- (4-tert-octylphenoxy)benzenediazonium, 5-chloro-2- (4tert-octylphenoxy)benzenediazonium, 2, octadecyloxybenzenediazonium, 2, 4-bis-octadecyloxybenzenediazonium, 4- (N-octyllauroylamino)benzene- 230 diazonium, etc. Specific examples of the counter anion of the diazonium salt used in the present invention are Cl1l/2ZCl 2

BF

4 ,1 PFJ-, B (ph) C,,F 2 1 COO- (n is 3 to 9), CmF 2 mliSOj- (m is 2 to 8) (CkF 2 klSO 2 2 CH- (k is 1 to 18), etc.

The diazosulfonate compound used in the present invention is a compound represented by the general formula: Ar-N 2

-SO

3 Na wherein Ar is an aromatic portion. Specific examples of the diazosulfonate compound used in the present invention are sodium benzenediazosulfonates having one or mrore substituents including 2-methoxy, 2-phenoxy, 2methoxy-4-phenoxy, 2, 4-dimethoxy, 2-methyl-4-methoxy, 2,4-dimethyl, 2,4,6-trimethyl, 2,4,6-trimethoxy, 2,4- 2-methoxy-5-nitro, acetamido, 2-methoxy-5-N,N-diethylsulfonamido, 2- 3-methyl, 4-methyl, 4methoxy, 4-ethoxy, 4-phenyl, 4-phenoxy, 4-acetamido, etc.; and sodium benzenediazosulfonates having one or more substituents including 4- (N-ethyl-N-benzylamino), 4- (N,N-dimethylamino), 4- N-diethylamino), 4- (N,Ndiethylamino) -3-chloro, 4- (N-ethylamino) -3-methyl, 4- N-diethylamino) -2-methyl, 4- (N-ethyl-N-j3-hydroxyethylamino), 4-pyrrolidino-3-chloro, 4-pyrrolidino-3,5dichloro, 4-morpholino, 4-morpholino-3-chloro, 4morpholino-2-methoxy, 4-morpholino-2, 5-diethoxy, 4- 231 4-(4'-tolylmercapto)-2,5dibutoxy, 4 4 '-tolylmercapto)-2,5-diethoxy, 4-diphenylamino, etc. When any of these diazosulfonate compounds is used, the diazosulfonate compound is preferably activated by light irradiation before printing.

The diazoamino compound usable in the present invention is a compound obtained by coupling a diazo group with dicyandiamide, sarcosine, methyltaurine, Nethylanthranilic acid-5-sulfonic acid, monoethanolamine, diethanolamine, guanidine or the like.

The quinonediazide used in the present invention is considered as an internal-salt type diazonium salt from the viewpoint of structure and is, for example, o-quinonediazide or o-naphthoquinonediazide. The quinonediazide includes salts, esters and amide compounds of 1,2-quinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, 1,2naphthoquinonediazide-4-sulfonic acid, etc. Specific examples of the quinonediazide used in the present invention are sodium 1,2-quinonediazide-4-sulfonate, sodium 1,2-naphthoquinonediazide-5-sulfonate, sodium 1,2-naphthoquinonediazide-4-sulfonate, p-cumylphenyl 1,2-naphthoquinonediazide-5-sulfonate, p-cumylphenyl 1,2-naphthoquinonediazide-4-sulfonate, methyl 1,2ethyl 1,2- 1,2-naphthoquinoneacid dimethylamide, esters of 1,2- 232 acid and a novolak resin, etc. In addition, these light-decomposable diazo compounds may be used singly or in combination.

The coupler used in the present invention is one that reacts with the diazo compound to form a pigment. For example, typical couplers capable of forming a yellow pigment are compounds which have a methylene group activated by a carbonyl group adjacent thereto and are represented by the general formula

RCOCH

2 CO-R' wherein R is an alkyl group or an allyl group, and R' is an aromatic amine. Magenta couplers are, for example, 1) cyanoacetyl derivatives of cyclic compounds, or 2) heterocyclic compounds having active methylene or any other coupling portion on the heterocyclic ring. The magenta couplers include, for example, pyrazolone compounds and indazolone compounds.

Cyan couplers include, for example, phenols and naphthols.

Specific examples of the coupler used in the present invention are 4-(p-toluenesulfonylamino)-obenzoylacetanilide, a-benzoyl-o-methoxyacetanilide, 2cyanoacetyl-coumarone, 1-(2,4,6-trichlorophenyl)-3-presorcin, phloroglucin, 2,3-dihydroxynaphthalene, 2,6-dibromo-1,5-dihydroxynaphthalene, N-(o-acetamidophenethyl)-l-hydroxy-2napthoamide, etc. In addition, these couplers may be used singly or in combination.

For smoother progress of the coupling 233 reaction of the diazo compound with the coupler under a basic atmosphere, a basic material is preferably incorporated into the heat-sensitive color-producing layer. As the basic material, a slightly water-soluble or water-insoluble basic material or a material capable of producing an alkali on heating is used. The basic material includes, for example, nitrogen-containing compounds such as inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formamidines, pyridines, etc.

Specific examples of these compounds are tricyclohexylamine, tribenzylamine, octadodecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methylimidazole, 2-undecylimidazoline, 2,4,5-trifuryl-2imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2dicyclohexylguanidine, 1,2,3-tricyclohexylguanidine, guanidine trichloroacetate, N,N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-aminobenzothiazole, 2-benzoylhydrazinobenzothiazole, etc. These basic materials may be used singly or in combination.

In the present invention, the storage 234 stability can be improved by adding a weakly acidic material such as citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid or the like to the heat-sensitive color-producing layer formed of a combination of the diazo compound and the coupler.

Needless to say, the color-producing components used in the present invention can be used in a solid dispersion state attained by dispersing the components in an aqueous solution of a water-soluble polymer, followed by coating and drying, as in a conventional method adopted in heat-sensitive recording materials. It is also possible to improve the green stability by encapsulating a color former to form microcapsules and preventing the contact of the color former with a developer at ordinary temperatures by utilizing the isolating effect of the capsule walls, as described in JP-A-59-190886, JP-A-60-49991, JP-A-61- 169281, etc. The microcapsules are characterized in that they enable the color former and the developer to come into contact with each other only during heating at a certain temperature or higher. The temperature at the starting of the contact of the color former with the developer can be controlled by properly choosing a material for the capsule wall, a core material for the capsule, additives, etc.

As a material for the walls of the microcapsules in the present invention, there are mentioned 235 conventional materials for microcapsule wall, such as polyurethanes, polyureas, polyesters, polycarbonates, urea-formaldehyde resins, melamine resins, polystyrenes, styrene-methacrylate copolymers, gelatin, poly(vinylpyrrolidone)s, poly(vinyl alcohol)s, etc.

These polymers may be used singly or in combination.

In the present invention, as the adhesive contained in the heat-sensitive color-producing layer, either water-soluble resins or water-dispersible resins may be used. However, when any of these resins is mixed with dispersions of the above-mentioned colordevelopable dye and developer, respectively, the resulting mixture should be free from coloration, aggregation and a high viscosity. In addition, a coating film formed as heat-sensitive recording layer should be tough and should not have desensitizing effect. The content of the adhesive in the heatsensitive color-producing layer is preferably 8 to based on the amount (in terms of solids) of the heatsensitive color-producing layer. A content of less than 8% is disadvantageous in that the strength of the coating film is low. A content of more than involves a problem of sensitivity decrease. In order to improve the water resistance of the heat-sensitive color-producing layer, a crosslinking agent for curing the resin can be used.

In the multicolor heat-sensitive recording material of the present invention, forming an inter- 0O 236 mediate layer between heat-sensitive recording layers is effective in improving the thermal partitionment.

The intermediate layer comprises as its main constituent the same resin as the water-soluble or water-dispersible resin used as the adhesive in the heat-sensitive recording layers, and may further comprises pigments, crosslinking agents, etc. The coating amount of the intermediate layer is preferably to 5.0 g/m 2 When the coating amount is less than 1.0 g/m 2 no sufficient preventive effect on diffusion between the recording layers can be obtained, resulting in a deteriorated quality of image. When the coating amount is more than 5.0 g/m 2 the sensitivity is disadvantageously decreased.

As an especially preferable form of the multicolor heat-sensitive recording material of the present invention, there can be mentioned a multicolor heat-sensitive recording material in which two heatsensitive recording layers which have different color development temperatures, respectively, and undergo color development in different color tones, respectively, are laminated on one side of a substrate, and of these recording layers, the upper heat-sensitive recording layer contains either an agent used both as developer and tone reducer, or a reversible developer, and the lower heat-sensitive recording layer contains the urea-urethane compound developer.

Of these, the agent used both as developer 237 and tone reducer in the upper heat-sensitive recording layer is an amphoteric compound having an acidic group having a color-developing function and a basic group having an achromatizing function, which performs the color-developing function on heating at a low temperature and performs the achromatizing function on heating at a high temperature. A typical example of the acidic group is phenolic hydroxyl group or carboxyl group. A typical example of the basic group is amino group.

Although the amphoteric compound may have the basic group as a functional group, it is preferably has the basic group as a portion of a salt compound, as in a complex of a phenolcarboxylic acid compound and an amine compound. Specific examples of such an agent used both as developer and tone reducer are as follows.

The phenolcarboxylic acid compound that constitutes the agent used both as developer and tone reducer includes 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6dihydroxybenzoic acid, gallic acid, bis(4-hydroxyphenyl)acetic acid, 3,3-bis(4-hydroxyphenyl)propionic acid, etc.

The amine compound that forms the salt or complex salt together with the phenolcarboxylic acid compound includes octylamine, nonylamine, decylamine, laurylamine, tetradecylamine, heptadecylamine, 238 stearylamine, behenylamine, 3-methoxypropylamine, hexamethylenediamine, etc.

The reversible developer is, for example, a phenolic compound or a phosphonic acid compound, which has an aliphatic hydrocarbon group of 8 or more carbon atoms. Specific examples of such a reversible developer are those mentioned below. The reversible developer is not limited to those mentioned below, and any reversible developer may be used so long as it performs a color-developing function on heating at a low temperature and performs an achromatizing function on heating at a high temperature.

The reversible developer includes 4- (octadecylthio)phenol, 4-(dococylthio)phenol, 4- (octadecyloxy)phenol, 4-(dococyloxy)phenol, Noctadecyl-4-hydroxybenzamide, 4'-hydroxydocosaneanilide, N-(4-hydroxyphenyl)-N'-n-octadecylurea, docosylphosphonic acid, etc. When recording is conducted with a thermal printer or the like by using the multicolor heat-sensitive recording material of the present invention, printing by heating at a low temperature causes color development only in the lowtemperature color-producing layer, and printing by heating at a high temperature causes achromatization in the low-temperature color-producing layer in a print portion and causes color development only in the hightemperature color-producing layer.

Employment of the urea-urethane compound *0 239 makes it possible to obtain an article for laser marking which is sufficient in coloring density and gives such a very stable printed developed color image that the image is hardly discolored or faded even by fats and oil, chemicals, fingerprints, etc. Therefore, the employment is especially advantageous from the viewpoint of long-term preservation of records.

The heat-sensitive recording layer of the article for laser marking of the present invention preferably contains a recording sensitivity improving agent.

As the recording sensitivity improving agent usable therein, compounds capable of absorbing laser beams used for irradiation are used. Specific examples thereof are various inorganic compounds such as aluminum hydroxide, wollastonite, bentonite, micas muscovite and phlogopite), calcium silicate, talc, kaolin, clay, and silicate minerals (e.g.

foyaite, hornblende and albite). Aluminum hydroxide, muscovite, wollastonite and kaolin are especially preferable. These inorganic compounds may be used singly or as a mixture thereof.

The proportions of the colorless or lightcolored dye precursor and recording sensitivity improving agent used in the heat-sensitive recording layer in the present invention are not particularly limited and may be properly chosen depending on the kinds of the dye precursor and recording sensitivity *0 240 improving agent used. Usually, the recording sensitivity improving agent can be used in a proportion of to 5,000 parts by weight, preferably 100 to 2,000 parts by weight, per 100 parts by weight of the color former.

The contents of the dye precursor, the ureaurethane compound developer and the recording sensitivity improving agent in the heat-sensitive recording layer can be adjusted as follows: based on the total weight (in terms of solids) of said layer, the content of the dye precursor ranges from 5 to 30 wt%, preferably from 10 to 25 wt%, the content of the ureaurethane compound developer ranges from 10 to 60 wt%, preferably from 20 to 50 wt%, and the content of the recording sensitivity improving agent ranges from 5 to wt%, preferably from 10 to 30 wt%.

The incorporation of also an acidic developer into the heat-sensitive recording layer of the article for laser marking of the present invention improves the sensitivity and enables the article for laser marking to produce a brilliant color. As the acidic developer, the above-exemplified conventional electron-accepting materials are used.

For further improving the sensitivity of the article for laser marking of the present invention, a heat-meltable material can be incorporated into the heat-sensitive recording layer. The heat-meltable material is preferably one which has a melting point of 241 600C to 1800C, in particular, 800C to 140 0

C.

The color-producing marking composition of the present invention can be obtained by using the above-mentioned colorless or light-colored dye precursor, urea-urethane compound developer, recording sensitivity improving agent and aqueous binder and water as essential constituents, and mixing various assistants therewith if necessary.

The water used in the color-producing marking composition has a pH in a range of 5 to 12, preferably 6 to 9. When the pH is lower than 5, fog is caused.

When the pH is higher than 12, there are likely to be undesirable influences such as loss of the colordeveloping capability of the urea-urethane compound developer. The water may be used in admixture with a water-soluble organic solvent such as methanol, ethanol or the like.

In addition to the essential constituents described above, various assistants may, if necessary, be incorporated into the color-producing marking composition used in the present invention, in order to, for example, facilitate the application of the composition on a substrate. The various assistants include, for example, dispersing agents sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, lauryl alcohol sulfuric acid ester sodium salt, and fatty acid metal salts), opacifying agents titanium oxide), defoaming agents, viscosity modifiers, fluorescent 0@ 242 dyes, and coloring agents.

A substrate on which the color-producing marking composition of the present invention is printed (applied) is not particularly limited so long as it requires marking. As the substrate, there are mentioned, for example, the predetermined portions of food containers, packaging materials, electronic parts and the like, and articles substrates for label) to be attached thereto. As the substrates for label, papers paper and synthetic paper), synthetic resin films, plastics, metallized paper and synthetic paper, metallized films, metals, wood, etc. are properly used depending on their purpose.

The color-producing marking composition is prepared, for example, as follows. The binder is dissolved or dispersed in water or a solvent composed mainly of water. Among the color former, the developer, the recording sensitivity improving agent and the like, components that should be dispersed in water or a solvent composed mainly of water are treated together or individually in water or an aqueous solvent, which contains a dispersing agent such as a poly(vinyl alcohol), by using a dispersing machine such as a ball mill, attritor, sand grinder or the like, whereby one or more dispersions are prepared. The average particle size of each component after the dispersing operation is usually about 2 p or less, preferably about 1 p or less. Then, the binder and the 0O 243 dispersion(s) are mixed to obtain the color-producing marking composition of the present invention. The solid content of said color-producing marking composition is 20 to 70 wt%, preferably about 30 to about wt%.

The color-producing marking composition may be applied directly on the substrate, or it may be applied on the substrate that has been previously subjected to surface treatment, undercoating or the like. The application can be carried out by using a suitable coater such as a roll coater, gravure coater, micro-gravure coater, knife coater, spray coater or the like. The thickness of the coating film (the heatsensitive recording layer) obtained by the application and drying can be usually adjusted to 1 to 4 p. When the thickness is less than 1 g, color development by laser irradiation is not sufficient and moreover, the coating film tends to be peeled off. On the other hand, when the thickness is more than 4 p, the drying characteristics and the label attachability tend to be deteriorated. The drying is varied depending on coating conditions such as the speed of line and may be conducted either at room temperature, or by heating under conditions which do not cause color development in the heat-sensitive recording layer.

The protective layer of the article for laser marking of the present invention is formed by applying a transparent clear coating liquid on the heat- 244 sensitive recording layer. The clear coating liquid is an aqueous composition consisting of an aqueous binder, water and the like.

As the aqueous binder used in the clear coating liquid for the protective layer in the present invention, there are mentioned those obtained by using as a base a per se known water-soluble or waterdispersible resin used in a coating material or ink.

Such a resin has a hydrophilic group carboxyl group or amino group) optionally introduced thereinto for impartment of the water-solubility or waterdispersibility. As said resin for the aqueous binder, a resin having a glass transition temperature in a range of 20 80'C, preferably 35 700C is used. When the glass transition temperature is lower than the scuff resistance, chemical resistance, water resistance and the like of the protective layer are deteriorated. On the other hand, when the glass transition temperature is higher than 800C, the protective layer is brittle, is poor in flexibility and the like, and is easily cracked. Therefore, both of such glass transition temperatures are not desirable. If necessary, leveling agents, slip-properties-imparting agents, defoaming agents and the like may be incorporated into said clear coating liquid in addition to the components described above.

As the aqueous binder used in the clear coating liquid, an acrylic resin can be obtained by 245 using an alkyl (number of carbon atoms: 1 to 24) ester of acrylic acid or methacrylic acid as a main component in combination with any of, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, etc.; hydroxy-containing unsaturated monomers such as hydroxyethyl acrylate, hydroxypropyl methacrylate, etc.; amino-containing unsaturated monomers such as acrylamide, methacrylamide, etc.; and other unsaturated monomers such as styrene, acrylonitrile, vinyl acetate, vinyl chloride, etc., and copolymerizing the alkyl ester with such a comonomer.

A polyester resin can be obtained by the ester reaction of a polybasic acid (including acid anhydrides) having two or more carboxyl groups in the molecule with a polyhydric alcohol having two or more hydroxyl groups in the molecule. The glass transition point of such an aqueous binder can be adjusted to any temperature by properly choosing the kinds, combination and proportions of components that constitute said binder.

Said clear coating liquid is prepared by dissolving or dispersing the above-mentioned aqueous binder in suitable water, and if necessary, is incorporated with leveling agents, slip-propertiesimparting agents, defoaming agents and the like. The solid content of said clear coating liquid ranges preferably from 20 to 70 wt%, in particular, from 30 to wt%.

Said clear coating liquid can be printed 246 (applied) on the surface of a dried coating film formed as the heat-sensitive recording layer. A method for the printing (application) is not particularly limited.

The application can be carried out by means of a roll coater, gravure coater, micro-gravure coater, spray coater or the like.

The thickness of the coating film thus formed can be usually adjusted to 3 to 10 p. When the thickness is less than 3 p, the protection of the heatsensitive recording layer afforded by said clear coating is not sufficient and the chemical resistance, rub resistance and the like are deteriorated. On the other hand, when the thickness is more than 10 the drying characteristics and physical performance of the coating film tend to be deteriorated. Drying of said clear coating liquid is varied depending on coating conditions such as the speed of line and may be conducted either at room temperature, or by heating under conditions which do not cause color development in the heat-sensitive recording layer.

When the thus formed heat-sensitive recording layer of the article for marking is irradiated with laser beams, the irradiated portion is heated, so that the urea-urethane compound developer and the dye precursor react with each other to develop a color, resulting in marking. Although the amount of energy of laser beams used for the irradiation is not particularly limited, it is preferably 1.4 J (joule)/cm 2 or 247 less when the possibility of fracture of the coating film is taken into consideration. On the other hand, although the lower limit of the amount of energy required for color development is unknown because there is no apparatus capable of producing low energy, sufficient color development takes place even at an amount of energy of 0.4 J/cm 2 Therefore, the suitable amount of energy for color development by the irradiation ranges from 0.4 to 1.4 J/cm 2 in particular, from 0.45 to 1.2 J/cm 2 As a laser used for the irradiation, a pulsed laser or a scanning laser is suitable. As to the kind of the laser, any of, for example, gas lasers, excimer lasers and semiconductor lasers may be used.

Specific examples of the laser are carbon dioxide lasers, mixed gas lasers, YAG lasers, ruby lasers, etc.

As a method for irradiating a portion of a desirable form with laser beams, there are mentioned a method of irradiating the coating film with laser beams through a metal mask to irradiate the coating film with laser beams in conformity with the form of the opening of the metal mask; and a method of inputting a desirable form to a computer and irradiating the coating film with laser beams in accordance with the desirable form in a manner of so-called drawing with a single stroke. When the heat-sensitive recording layer is irradiated with laser beams, the irradiated portion is increased in temperature to undergo color development caused by melting and mixing of the color- 248 producing components in the heat-sensitive recording layer, resulting in the appearance of letters or a figure, which has a clear desirable form. This color change by the irradiation can be carried out in a moment because the energy density of laser beams is high.

A label as the article for laser marking of the present invention can be produced by forming a heat-sensitive recording layer and a protective layer by the above-mentioned methods on a substrate for label properly selected depending on its purpose from papers paper and synthetic paper), synthetic resin films, plastics, metallized paper and synthetic paper, metallized films, metals, etc. Although the label thus obtained can be used in all the fields of conventional labels, it is preferably used in the fields of, in particular, food, medicine, toiletries, publications, and electric and electronic parts, etc.

A packaging material as the article for laser marking of the present invention is produced by forming a heat-sensitive recording layer and a protective layer by the above-mentioned methods on any of various conventional packaging materials such as boxes, packing paper and packages, which are obtained by the use of a substrate properly selected depending on its purpose from papers paper and synthetic paper), synthetic resin films, plastics, metallized paper and synthetic paper, metallized films, metals, glass, wood, etc.

249 Although said packaging material can be used in all the fields of conventional packaging materials, it is preferably used in the fields of, in particular, food, medicine, toiletries, publications, and electric and electronic parts, etc.

A container as the article for laser marking of the present invention is produced by forming a heatsensitive recording layer and a protective layer on a substrate such as glass, plastic, metal or the like by the above-mentioned methods. This food container can be used in all the fields of conventional food containers, such as the fields of bottles for liquors and refreshing drinks, retort-food containers, instantfood containers, cosmetics containers, medicine container, toiletry products, etc.

When the color-producing composition of the present invention is used in a pressure-sensitive recording material, the recording material can have, for example, the forms disclosed in U.S. Patent Nos.

2505470, 2712507, 2730456, 2730457 and 3418250, etc.

That is, various forms such as the following forms can be employed: a pressure-sensitive recording paper obtained by dissolving the dye precursor or a mixture of the dye precursors in a solvent consisting of one of or a mixture of two or more of alkylated naphthalenes, alkylated diphenyls, alkylated diphenylmethanes, alkylated diarylethanes, synthetic oils (e.g.

chlorinated paraffin), vegetable oils, animal oils, *0 250 mineral oils, etc., dispersing the resulting solution in a binder or incorporating the solution into microcapsules, applying the dispersion on a substrate or applying the microcapsules on a substrate together with a binder, and placing the upper paper thus obtained and under paper coated with a dispersion of the ureaurethane compound (and an amino compound and/or a developer, etc.), one upon the other so that their coated surfaces face each other; a pressure-sensitive recording paper obtained by holding, between the abovementioned upper paper and under paper, an intermediate paper coated with a dispersion of the urea-urethane compound on one side and the dye precursor on the other side; a self-type pressure-sensitive recording paper obtained by applying the above-mentioned dispersion of the urea-urethane compound (and an amino compound and/or a developer) and the above-mentioned dispersion containing the dye precursor, on the same surface of a substrate as a mixture or in a multilayer form; and a self-type pressure-sensitive recording paper obtained by making each of the dye precursor and the ureaurethane compound (and an amino compound and/or a developer) into microcapsules, and applying a mixture of the microcapsules of the two kinds on the same surface of a substrate.

As a process for producing microcapsules, there can be adopted, for example, the coacervation processes disclosed in U.S. Patent Nos. 2800457 and 251 2800458, the interfacial polymerization processes disclosed in JP-B-38-19574, JP-B-42-446, JP-B-42-771, etc., the in-situ processes disclosed in JP-B-36-9168, JP-B-51-9079, etc., the melt dispersion cooling processes disclosed in Brit. Patent Nos. 952807 and 96- 5074, etc., and the spray drying processes disclosed in U.S. Patent No. 311140, Brit. Patent No. 930422, etc.

The color-producing composition of the present invention corresponds to the combination of a dye precursor and a developer described in each of the above references and the like.

For forming a pressure-sensitive recording layer, each component such as the urea-urethane compound may be used in the form of a solution or dispersion in a solvent. In the case of a colorproducing system further comprising an amino compound and/or a developer, each component may be used in the form of a solution or dispersion in a solvent, or a combination of the urea-urethane compound, the amino compound and optionally the developer may be used in the form of a solution or dispersion in a solvent.

In the above-mentioned interfacial polymerization processes adopted for forming microcapsules, a film is formed on an interface by using two kinds of monomers, an oil monomer and a water-soluble monomer. There are known, for example, a process in which a polybasic acid chloride is used as an oil phase and a polyvalent amine as an aqueous phase, and a 252 polyamide film is formed on the interface; a process in which a polybasic acid chloride is used as an oil phase and a polyhydric hydroxy compound as an aqueous phase, and a polyester film is formed on the interface; a process in which a polyvalent isocyanate is used as an oil phase and a polyhydric alcohol or a polyhydric phenol as an aqueous phase, and a polyurethane film is formed on the interface; and a process in which a polyvalent isocyanate is used as an oil phase and a polyvalent amine as an aqueous phase, and a polyurea film is formed on the interface. Thus, when the interfacial polymerization process is adopted for producing microcapsules, an isocyanate compound is used in some cases as a reactive monomer for forming a film.

In this case, said isocyanate compound is consumed in forming a film for microcapsules and is not directly concerned with a developed color image, and it is absolutely necessary to use a water-soluble monomer together with the isocyanate compound. In these points, its employment is distinguished from the employment of the isocyanate compound according to the present invention.

Dispersions of compounds which are not made into microcapsules are prepared by finely grinding one or more compounds as each component in an aqueous solution containing a compound having dispersing capability, such as a water-soluble polymer, a surfactant or the like. The urea-urethane compound may 253 be dispersed together with an amino compound and an acidic developer.

As the substrate used in the pressuresensitive recording material, paper is mainly used, though any of various woven fabrics, nonwoven fabrics, synthetic resin films, laminated papers, synthetic papers, metal foils, and composite sheets obtained by combining two or more of them may be used besides paper, depending on their purpose.

As a binder, conventional various binders can be used. The binder includes, for example, watersoluble binders such as starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, sodium poly(acrylate)s, acrylamide-acrylic ester copolymers, acrylamide-acrylic ester-methacrylic acid terpolymers, alkali salts of styrene-maleic anhydride copolymers, alkali salts of ethylene-maleic anhydride copolymers, etc.; and latex type water-insoluble binders of styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, methyl acrylate-butadiene copolymers, etc.

In the recording material of the present invention, the recording layer may contain a hindered phenol compound or an ultraviolet absorber. The hindered phenol compound or ultraviolet absorber includes, for example, 1,1,3-tris(3'-cyclohexyl-4'hydroxyphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5- 254 tert-butylpheny)butane, 4,4'-thiobis(3-methyl-6-tertbutylphenol), 1,3,5-trimethyl- 2,4,6-tris(3,5-di-tertbutyl-4-hydroxybenzyl)benzene, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, p-octylphenyl salicylate, hydroxy-5'-methylpheny)benzotriazole, ethyl-2-cyano- 3,3'-diphenyl acrylate and tetra(2,2,6,6-tetramethyl-4piperidyl)-1,2,3,4-butanetetracarbonate.

A method for forming the color-producing layer is not particularly limited. The color-producing layer is formed, for example, by applying a coating liquid for the color-producing layer on a substrate by a suitable coating method such as free-fall curtain coating, air-knife coating, Bariber blade coating, Pure blade coating, short-dwell coating or the like, and drying the thus treated substrate. The coating amount of the coating liquid for the color-producing layer is not particularly limited and is usually controlled in a range of 1 to 15 g/m 2 preferably about 3 to about g/m 2 in terms of dry weight.

The thermal response can be improved by forming an intermediate layer between the heatsensitive recording layer and the substrate. In the case of conventional heat-sensitive recording materials, a technique for improving the color development sensitivity, for example, by co-using a heat-meltable material in a color-producing layer has been employed. The improvement of the sensitivity by such a method is disadvantageous in that fog tends to *0 255 be caused by heat or friction. It facilitates the occurrence of fog particularly in heat-sensitive recording materials obtained by using the urea-urethane compound developer excellent in color development sensitivity. In the case of conventional heatsensitive recording materials without print preservability, even if fog is caused, it disappears like a print, so that, in particular, fog in the case of using the recording material after long-term storage is seldom taken into account. However, in the case of heat-sensitive recording materials obtained by using the urea-urethane compound developer especially excellent in long-term print preservability, the following problem characteristic of them is caused in some cases: when fog is once caused, it is preserved and hence it is accumulated each time the recording material is stored and then used, so that the recording material surface becomes dirty when the recording material is used after long-term storage. In such a case, by forming the intermediate layer, a practical color development sensitivity can be attained without using a heat-meltable material or by using only a small amount of a heat-meltable material, and a heatsensitive recording material can be obtained which is so excellent in resistance to fog caused by heat or friction that the fog is hardly accumulated even if the recording material is used after long-term storage.

The intermediate layer is composed mainly of 256 an organic or inorganic pigment, hollow particles and an aqueous binder such as a water-soluble polymer or a latex. As the organic or inorganic pigment and the aqueous binder, the same organic or inorganic pigment and aqueous binder as used in the heat-sensitive recording layer can be used. A method for forming the intermediate layer is not particularly limited. As this method, the same method as the method for forming the heat-sensitive recording layer can be adopted. The dry spread for forming the intermediate layer ranges preferably from 2.0 to 15.0 g/m 2 In this case, the surface pH of the intermediate layer formed on the substrate is preferably 3 to 9, more preferably 5 to 9, most preferably 6 to 8.

In addition, in the present invention, the rub resistance of the resulting recording paper can be improved by forming a protective layer composed mainly of a water-soluble polymer, on the heat-sensitive recording layer if necessary. When the urea-urethane compound developer of the present invention is used which is excellent in color development sensitivity and resistance of print to long-term storage, a trace of rubbing tends to be left because of the high sensitivity. On the other hand, the trace of rubbing once left is preserved for an indefinite time and hence traces of rubbing are accumulated each time the recording material is stored and then used. Therefore, the paper surface becomes dirty in some cases when the 257 recording paper is used after long-term storage. In such a case, by forming the protective layer, the accumulation of traces of rubbing can be made difficult even if the recording paper is used after long-term storage. Specific examples of the water-soluble polymer contained in the protective layer are the water-soluble polymer binders mentioned in relation to the above-mentioned heat-sensitive recording layer.

The water-soluble polymer can be used together with a conventional waterproofing agent capable of waterproofing the water-soluble polymer. Specific examples of the waterproofing agent are formaldehyde, glyoxal, chrome alum, melamine, melamine-formaldehyde resins, polyamide resins, polyamide-epichlorohydrin resins, etc.

Furthermore, pigments, metal soaps, waxes, crosslinking agents, etc. are incorporated into the protective layer for the purpose of, for example, improving the matching with a thermal head during printing and improving the water resistance of the protective layer.

The pigments include zinc oxide, calcium carbonate, barium sulfate, titanium oxide, lithopone, talc, pagodite, kaolin, aluminum hydroxide, silica, amorphous silica, etc. The amount of the pigments added is 0.5 to 4 times, preferably 0.8 to 3.5 times, the total weight of the polymers. When the amount is below the lower limit of the above range, the pigments 258 are not effective in improving the matching with a thermal head. When the amount is above the upper limit, the sensitivity of the heat-sensitive recording material is remarkably decreased, so that the commercial value of the recording material is impaired.

The metal soaps include, for example, emulsions of higher fatty acid metal salts such as zinc stearate, calcium stearate, aluminum stearate, etc.

The metal soaps are added in a proportion of 0.5 to wt%, preferably 1 to 10 wt%, based on the total weight of the protective layer. The waxes include, for example, emulsions of paraffin wax, microcrystalline wax, carnauba wax, methylolstearoamide, polyethylene wax, etc. The waxes are added in a proportion of 1 to 20 wt%, preferably 1 to 10 wt%, based on the total weight of the protective layer.

In forming the protective layer on the heatsensitive recording layer, a surfactant is added to a coating liquid for forming the protective layer, in order to obtain a uniform coating layer. The surfactant includes alkali metal salts of sulfosuccinic acids, fluorine-containing surfactants, etc. Specific examples of the surfactant are sodium salts or ammonium salts of di-(2-ethylhexyl)sulfosuccinic acid, di-(nhexyl)sulfosuccinic acid, etc. In general, any surfactant is effective so long as it is anionic.

Conventional auxiliary additives such as fillers, heatmeltable materials (lubricants), surfactants, *0 259 fluorescent dyes, etc. may also be incorporated into the protective layer. Specific examples of the fillers, heat-meltable materials and fluorescent dyes are those mentioned in relation to the above-mentioned heat-sensitive recording layer. The dry spread of the protective layer is preferably about 0.5 to about g/m 2 in particular, about 1 to about 5 g/m 2 When a reverse-side layer (a back coating layer) is, if necessary, formed on the side reverse to the recording layer of the recording material produced by the process of the present invention, curling of the resulting recording paper can be made difficult.

Particularly in the case of the urea-urethane compound developer of the present invention, the formation of the reverse-side layer is effective for the following reason: said developer is superior to other developers in dispersibility, gives a dispersion with a small particle size easily, and has a high sensitivity, but when a coating liquid prepared by mixing said developer with other necessary components is applied on a substrate, the cohesive force of a binder is increased at the time of drying because of the small particle size of the developer, so that the recording layer is eaily shrunk, resulting in easy curling. As the components of the coating liquid for the reverse-side layer and a coating method for the coating liquid, the same components and method as in the case of the protective recording layer may be employed. The dry 260 spread of the coating liquid ranges preferably from 0.2 to 10.0 g/m 2 The present invention is explained in further detail with the following examples.

The analyses of materials and the evaluation of physical properties were carried out by the following methods.

<IR spectrum> Measured by diffuse reflectance spectroscopy by the use of FTIR-8100M manufactured by Shimadzu Corp.

<Mass spectrum> Measured by using JMS-HX100 manufactured by JEOL LTD., nitrobenzyl alcohol as a matrix, and xenon as a primary gas.

<Color development sensitivity of thermal paper> Coloring density at an applied voltage of 24 V and a pulse width of 1.5 msec was measured with an optical densitometer by using a printing tester manufactured by Ohkura Denki and a thermal head KJT-256-8MG manufactured by Kyocera Co., Ltd.

<Plasticizer resistance> A heat-sensitive recording material was held between vinyl chloride wrap films or in a vinyl chloride file, and a load of 300 g/cm 2 was applied thereto from above. After standing at 40 0 C for 24 hours, the coloring density of the printed portion and the non-printed portion (the original recording material surface) was visually estimated. When there 261 was only a slight decrease in print density, the print preservability was rated as good.

<Heat resistance> A heat-sensitive recording material was allowed to stand at 60 0 C and 25% RH for 24 hours and the degree of fading of print was visually estimated.

When the degree of fading is low, the print preservability was rated as good.

In addition, a heat-sensitive recording material was allowed to stand at 80 0 C and 25% RH for 24 hours and the degree of fading of print was visually estimated. When the degree of fading was low, the print preservability was rated as good. The coloring density of the original recording material surface was also visually estimated. When the color development was slight, the preservability of original recording material surface was rated as good.

<Coloring density of pressure-sensitive paper> Upper paper and under paper were placed one upon the other so that their coated surfaces might face each other. A pressure was applied thereto from above to obtain a developed color image on the under paper.

The color density of the developed color image was measured by means of a densitometer Macbeth RD9i7.

<Solvent resistance> Hand cream (Atrix, a trade name, mfd. by Kao Corp.) was thinly applied on the developed color image portion obtained in the coloring density estimation, 262 and after standing at ambient temperature for 7 days, the color density of print portion was visually estimated. When there was only a slight decrease in print density, the print preservability was rated as good.

Example 1 To 27.8 g of 2,4-toluene diisocyanate was added 111 g of toluene as a solvent, followed by adding dropwise thereto a solution of 7.4 g of aniline in 37 g of toluene at room temperature over a period of 1 hour, and the reaction was carried out for another 1 hour.

The white solid precipitated was recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 20 g of white crystals. Subsequently, 5 g of the thus obtained compound was added to 50 mL of methanol, and the reaction was carried out at 60 0 C for minutes, after which the excess methanol was removed by the use of an evaporator, and toluene was added to the residue to effect crystallization. The resulting white crystals were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 5.4 g of white crystals. The melting point of these white crystals was 196 0

C.

Analytical measurement of these white crystals was as follows.

Result of IR measurement: Characteristic peaks appeared at 1060 cm-', 263 1250 1600 cm 1650 cm 1670 1700 cm and 3300 cm The structural formula of the major component of this compound is presumed to be the structural formula of the above-mentioned compound Next, a dispersion was prepared by dispersing 2 g of this compound by grinding it together with 8 g of a 2.5 wt% aqueous solution of a poly(vinyl alcohol) (Gohseran L-3266, a trade name, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) in a paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersing operation was 25 0

C.

The diameter of dispersed particles of the compound was about 0.6 pm.

Another dispersion was prepared by dispersing g of 3-dibutylamino-6-methyl-7-anilinofluoran by grinding it together with 130 g of a 8 wt% poly(vinyl alcohol) aqueous solution in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

Further another dispersion was prepared by dispersing 70 g of diphenyl sulfone by grinding it together with 130 g of a 5.4 wt% poly(vinyl alcohol) aqueous solution in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

Still another dispersion was prepared by mixing 10 g of calcium carbonate with 30 g of water and 264 stirring the mixture by the use of a stirrer.

A coating liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (dry basis proportions); the dispersion of the above-mentioned compound in terms of dry solids: 30 parts by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran dispersion in terms of dry solids: 15 parts by weight, the diphenyl sulfone dispersion in terms of dry solids: parts by weight, the calcium carbonate dispersion in terms of dry solids: 20 parts by weight, a zinc stearate dispersion (solid content: 16 wt%) in terms of dry solids: 10 parts by weight, and a 15 wt% poly(vinyl alcohol) in terms of dry solids: 7 parts by weight.

The coating liquid was applied on base paper with a basis weight of 50 g/m 2 by the use of a bar coater of rod number 10. After drying, supercalendering was conducted to obtain a heat-sensitive recording material. The coating amount of the coating liquid was 4 g/m 2 in terms of dry weight.

The result of evaluating the sensitivity of the heat-sensitive recording material obtained was so good that the optical density was 1.2. The result of estimating the degree of a thermal color change of the original recording material surface (the heat resistance) was so good that the color change was slight.

The thermal fading of the print portion was desirably slight. These evaluation results are summarized in 265 Table 1.

Example 2 To 17 g of 2,4-toluene diisocyanate was added g of methyl ethyl ketone as a solvent, followed by adding dropwise thereto 3.8 g of methanol, and the reaction was carried out with stirring at 60 0 C for hours. Then, 9.9 g of 4,4'-diaminodiphenyl sulfone was added thereto, and the reaction was carried out with stirring at 60 0 C for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and poured into 800 g of acetonitrile, and the crystals precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 15 g of a compound as white crystals.

The melting point of the white crystals was 169 0 C, and their analytical measurements were as follows.

Result of IR measurement: Characteristic peaks appeared at 1220 cm 1 1550 cm 1 1590 cm 1 1660 cm 1740 cm and 3300 cm-.

Result of mass spectrum measurement: was detected at m/z 661.

The structural formula of the major component of this compound is presumed to be the structural formula of the above-mentioned compound (S-13).

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for 0@ 266 using the compound obtained above, in place of the urea-urethane compound synthesized in Example i, and was evaluated. The results obtained are summarized in Table i.

Example 3 In 100 mL of ethyl acetate was dissolved 3.46 g of aniline, and the resulting solution was stirred at room temperature. A solution of 10 g of trimethylolpropane adduct of toluene diisocyanate (Coronate L, a trade name, mfd. by Nippon Polyurethane Industry Co., Ltd.; a 75% ethyl acetate solution) in 50 mL of ethyl acetate was added dropwise thereto over a period of 1 hour, and the reaction was carried out for another minutes. The crystals formed were recovered by filtration and dried overnight in a vacuum to obtain 5.1 g of a compound as white crystals. The melting point of the white crystals was 1610C, and their analytical measurement was as follows.

Result of IR measurement: Characteristic peaks appeared at 1070 cm 1220 cm 1550 cm 1600 cm 1700 cm and 3300 cm-'.

The structural formula of the major component of this compound is presumed to be the structural formula of the above-mentioned compound (S-33) Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the compound obtained above, in place of the 267 urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 1.

Example 4 To 10.4 g of 2,4-toluene diisocyanate was added 20 g of methyl ethyl ketone as a solvent, followed by adding dropwise thereto a dilution of 3.7 g of 4,4'-diaminodiphenyl sulfone with 30 g of methyl ethyl ketone, and the reaction was carried out at ambient temperature for 20 hours. After completion of the reaction, the methyl ethyl ketone was removed by concentration and then toluene was added to the residue, and the white solid precipitated was recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 8.8 g of a compound as white crystals. Subsequently, 15 g of phenol and then a small amount of dibutyltin dilaurate were added to 4 g of the obtained compound, and the reaction was carried out at 50°C for 4 hours. After completion of the reaction, toluene was added to the reaction solution and the crystals precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 5.2 g of a ureaurethane compound as white crystals.

Then, 30 g of toluene was added as solvent to g of 2,4-toluene diisocyanate, followed by adding thereto 30 g of phenol, and the reaction was carried *0 268 out at 100 0 C for 3 hours. After completion of the reaction, the toluene was removed by concentration and hexane was added to the residue. The white crystals precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain g of a urethane compound as white crystals.

The structural formula of the major component of this compound is presumed to be the structural formula of the compound described hereinafter.

Next, 3 g of the above-mentioned ureaurethane compound and 2 g of the urethane compound were mixed to obtain a urea-urethane composition. Thereafter, 2 g of the urea-urethane composition was ground together with 8 g of a 2.5 wt% methyl cellulose aqueous solution in a paint shaker for 45 minutes to be dispersed, whereby a dispersion was obtained.

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dispersion of said composition in place of the dispersion of the compound obtained in Example 1, and was evaluated. The results obtained are summarized in Table 1.

Example A heat-sensitive recording material was produced in the same manner as in Example 4 except for using a urea-urethane composition obtained by mixing g of the urea-urethane compound and 0.5 g of the 269 urethane compound which had been synthesized in Example 4, in place of the urea-urethane composition used in Example 4, and was evaluated. The results obtained are summarized in Table 1.

Example 6 A heat-sensitive recording material was produced in the same manner as in Example 4 except that in place of the urea-urethane composition used in Example 4, there was used 7.4 g of a urea-urethane composition obtained as white crystals in the same manner as in Example 4 except for adding 2.2 g of diphenyl sulfone to the reaction system before the precipitation by the addition of toluene after the synthetic reaction of the urea-urethane compound, stirring the resulting mixture, adding toluene to the mixture, recovering the crystals precipitated, by filtration, washing the crystals with hexane, and then drying the crystals overnight in a vacuum. The heatsensitive recording material was evaluated. The results obtained are summarized in Table 1.

Example 7 To 31.5 g of 2,4-toluene diisocyanate was added dropwise a solution of 21.5 g of 4,4'-diaminodiphenyl sulfone in 60 mL of MEK at 70 0 C with stirring at 300 to 500 rpm over a period of 4 hours, and the reaction was carried out for another 4 hours to obtain 0@ 270 a white viscous slurry reaction mixture. Then, the reaction mixture was cooled to 500C, and 17.1 g of phenol was poured into the reaction mixture to be dissolved therein, after which 0.015 g of triethylamine was added thereto as a catalyst, and the reaction was carried out for 4 hours to obtain a yellow, transparent and viscous reaction mixture. This reaction mixture was freed from the solvent and concentrated under reduced pressure to be solidified, after which the resulting solid was ground and then dried overnight in a vacuum to obtain about 70 g of a urea-urethane composition as light-yellow powder.

The melting point of the light-yellow powder was 160 1800C. In IR measurement of the powder, a wide peak formed by overlapping of characteristic peaks due to urea group and urethane group, respectively, appeared at 1700 cm 1 The content of the urea-urethane main constituent in the urea-urethane composition was 68% as measured by liquid chromatography.

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned composition in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 1.

271 Example 8 To 158.5 g of 2,4-toluene diisocyanate was added 240 g of methyl ethyl ketone as a solvent, and 107.5 g of 4,4'-diaminodiphenyl sulfone was added thereto in the form of powder at 30 0 C with stirring at 400 rpm over a period of 8 hours. After 1 hour, 26 g of methyl ethyl ketone was added thereto and stirred for another 15 hours to obtain a white viscous slurry reaction mixture. Then, a solution of 89.5 g of phenol in 15.8 g of methyl ethyl ketone was poured into the reaction mixture to be dissolved therein, after which 9.3 g of a 1 wt% solution of triethylamine in methyl ethyl ketone was added thereto as a catalyst over a period of 2 hours, and the reaction was continued for 1 hour. Thereafter, the reaction mixture was cooled to and continuously stirred for 3 hours to obtain a slurry containing slightly yellow crystals precipitated therein. The slurry was freed from the solvent and concentrated under reduced pressure to be solidified, after which the resulting solid was ground and then dried overnight in a vacuum to obtain 355 g of a ureaurethane composition as slightly yellow powder.

The melting point of the slightly yellow powder was 130 170°C. In IR measurement of the powder, a wide peak formed by overlapping of characteristic peaks due to urea group and urethane group, respectively, appeared at 1700 cm The content of the urea-urethane main constituent in the urea-urethane 272 composition was 65% as measured by liquid chromatography.

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned composition in place of the urea-urethane compound synthesized in Example i, and was evaluated. The results obtained are summarized in Table i.

Example 9 To 27.8 g of 2,4-toluene diisocyanate was added 100 g of toluene as a solvent, followed by adding dropwise thereto a solution of 7.4 g of aniline in 37 g of toluene at room temperature over a period of 1 hour, and the reaction was carried out for another 1 hour.

The white solid precipitated was recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 20 g of white crystals. Subsequently, g of the thus obtained compound was added to 50 mL of methanol, and the reaction was carried out at 60 0 C for 30 minutes, after which the excess methanol was removed by the use of an evaporator, and the residue was dried overnight in a vacuum to obtain 5.4 g of a ureaurethane composition as white crystals. The melting point of the white crystals was 196 0 C. In IR measurement of the crystals, characteristic peaks due to a urea-urethane compound appeared at 1670 cm and 1700 cm The content of the urea-urethane main constituent 273 in the urea-urethane composition was 92% as measured by liquid chromatography.

Example To 17 g of 2,4-toluene diisocyanate was added g of methyl ethyl ketone as a solvent, followed by adding dropwise thereto 3.8 g of methanol, and the reaction was carried out with stirring at 60 0 C for hours. Then, 9.9 g of 4,4'-diaminodiphenyl sulfone was added thereto, and the reaction was carried out with stirring at 60 0 C for 4 hours. After completion of the reaction, the methyl ethyl ketone as solvent was removed by the use of an evaporator, and the residue was dried overnight in a vacuum to obtain 16 g of a urea-urethane composition as white crystals. The melting point of the white crystals was 169 0 C. In IR analysis on the crystals, characteristic peaks due to a urea-urethane compound appeared at 1660 cm 1 and 1740 cm 1 The content of the urea-urethane main constituent in the urea-urethane composition was 52% as measured by liquid chromatography.

Then, a heat-sensitive recording material was 274 produced in the same manner as in Example 1 except for using the above-mentioned composition in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 1.

Example 11 In 253 mL of toluene was dissolved 27.5 g of 2,4-toluene diisocyanate, followed by adding dropwise thereto a solution of 14.7 g of aniline in 85 mL of toluene at 40 0 C with stirring at 200 rpm over a period of 30 minutes, and the reaction was carried out for another 30 minutes. To the thus obtained white slurry were added 18.0 g of 2,2-bis(4-hydroxyphenyl)propane, 262 mL of toluene and 0.42 mg of triethylamine as catalyst, and the stirring rate was increased to 400 rpm. In order to prevent the aggregation of particles in the slurry in the initial reaction by controlling the reaction rate, the reaction was carried out while raising the reaction temperature stepwise as follows: 60 0 C for 5 h, 65 0 C for 2 h, 70 0 C for 1 h, and 75 0 C for 1 h. Then, 0.42 mg of triethylamine was added, and the reaction was carried out at 800C for another 8 h. The reaction mixture was cooled to room temperature and the resulting white crystals were recovered by filtration.

The white crystals were dried overnight in a vacuum to obtain 59 g of a urea-urethane composition as white crystals. The melting point of these white crystals 275 was 170 0 C. In IR analysis on the crystals, a wide characteristic peak due to urea-urethane appeared at 1720 cm The content of the urea-urethane main constituent in the urea-urethane composition was 81% as measured by liquid chromatography.

Examples 12 to 23 Heat-sensitive recording materials were produced in the same manner as in Example 8 except for using 4,4'-dichlorodiphenyl sulfone (Example 12), 4,4'dihydroxydiphenyl sulfone (Example 13), 2,4'-dihydroxydiphenyl sulfone (Example 14), 4-(benzyloxy)phenol (Example 15), salicylanilide (Example 16), 4,4'diaminodiphenyl sulfone (Example 17), 4,4'-dichlorobenzophenone (Example 18), 4,4'-diaminodiphenylmethane (Example 19), 4,4'-dimethoxybenzophenone (Example diphenyl carbonate (Example 21), 4,4'-dimethoxydiphenyl sulfone (Example 22) or 4,4'-diallyloxydiphenyl sulfone (Example 23) in place of diphenyl sulfone, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 1.

276 Comparative Example 1 A heat-sensitive recording material was produced in the same manner as in Example 1 except for using 2,2-bis(4-hydroxyphenyl)propane in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 1.

Comparative Example 2 To 17.4 g of 2,4-toluene diisocyanate was added 5 mL of methyl ethyl ketone as a solvent, followed by adding dropwise thereto a solution of 3.2 g of methanol in 5 mL of methyl ethyl ketone, and the reaction was carried out with stirring at room temperature for 2 hours. Then, a solution of 7.3 g of nbutylamine in 100 mL of methyl ethyl ketone was added dropwise thereto with stirring at room temperature, and the resulting mixture was stirred for 1 hour. The crystals precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 27 g of a compound as white crystals. The melting point of the white crystals was 156 0 C, and their analytical measurement was as follows.

Result of IR measurement: Characteristic peaks appeared at 1240 cm 1550 1640 cm l 1720 cm and 3300 cm The presumed structural formula of the major component of this compound is the formula shown 277 hereinafter.

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the compound obtained above, in place of the urea-urethane compound synthesized in Example i, and was evaluated. The results obtained are summarized in Table 1.

Comparative Example 3 To 10.0 g of 2,4-toluene diisocyanate was added 100 g of toluene. While stirring the resulting mixture at 25'C, a solution of 15.5 g of stearylamine in 100 mL of toluene was added thereto, and the reaction was continued at 25 0 C for 22 hours. After completion of the reaction, the white solid precipitated was recovered by filtration, washed with toluene and then dried overnight in a vacuum to obtain 20.4 g of white crystals. Thereafter, 5 g of the thus obtained compound was added to 50 mL of methyl ethyl ketone. While stirring the resulting mixture at 80 0

C,

a solution of 8.6 g of p-hydroxybenzylcarboxylic acid in 20 ml of methyl ethyl ketone and then 5 mg of dibutyltin laurate as catalyst were added thereto, and the reaction was continued at 80 0 C for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the crystals precipitated were recovered by filtration, washed with methyl ethyl ketone and then dried overnight in a *0 278 vacuum to obtain 5.6 g of white crystals.

Analytical measurements of these white crystals were as follows.

Result of IR measurement: Characteristic peaks appeared at 1220 cm 1520 cm 1630 cm 1710 cm 2900 cm and 3300 cm-.

Result of mass spectrum measurement: was detected at m/z 596.

The presumed structural formula of the major component of this compound is the formula shown hereinafter.

A heat-sensitive recording material was produced in the same manner as in Example 1 except for using the compound obtained above, in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 1.

Comparative Example 4 To 100 mL of dioxane was added 3.0 g of paminophenol. While stirring the resulting mixture at 0 C, a solution of 5.4 g of toluene sulfonylisocyanate in 30 mL of dioxane was added dropwise thereto over a period of 1 hour, and the reaction was continued at 0 C for 5 hours. After completion of the reaction, the reaction solution was concentrated and then poured into hexane to effect crystallization, and the solid precipitated was recovered by filtration, washed with 0 279 hexane and then dried overnight in a vacuum to obtain 4.9 g of brown crystals. Thereafter, 2 g of the thus obtained compound was added to 50 mL of dioxane. While stirring the resulting mixture at 80°C, a solution of 3.8 g of octadecyl isocyanate in 10 mL of dioxane and then 2 mg of dibutyltin laurate as catalyst were added thereto, and the reaction was continued at 80 0 C for hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the crystals precipitated were recovered by filtration, washed with dioxane and then dried overnight in a vacuum to obtain 2.7 g of slightly pink crystals.

Analytical measurement of these slightly pink crystals was as follows.

Result of IR measurement: Characteristic peaks appeared at 1230 cm 1 1470 1510 cm 1570 cm 1 1620 cm 1 1700 2900 cm 1 and 3300 cm The presumed structural formula of the major component of this compound is the formula shown below.

280 O

O

II ni C C

H

3 C-O N N N-n-C 4 Hg H H H IIH H 3

C

HO-C-C

o o C0 N NC IN-(CH 2 17

CH

3 H H H 0 0 II o 0

C

1 2

H

2 5 -N N I-N CH 3 H \0 H H II 0 Comparative Example To 10 g of 2,4-toluene diisocyanate was added g of toluene as a solvent, followed by adding thereto 30 g of aniline, and the reaction was carried out at 250C for 3 hours. After completion of the reaction, the white solid precipitated was recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 17 g of a compound as white crystals.

The presumed structural formula of the major component of this compound is the structural formula of the compound shown hereinafter.

Next, 2 g of this compound was ground together with 8 g of a 2.5 wt% poly(vinyl alcohol) aqueous solution in a paint shaker for 45 minutes to be dispersed, whereby a dispersion was obtained.

Then, a heat-sensitive recording material was 281 produced in the same manner as in Example 1 except for using this dispersion of said compound in place of the dispersion of the compound obtained in Example i, and was evaluated. The results obtained are summarized in Table 1.

Comparative Example 6 To 10 g of 2,4-toluene diisocyanate was added g of toluene as a solvent, followed by adding thereto 30 g of phenol, and the reaction was carried out at 100 0 C for 3 hours. After completion of the reaction, the toluene was removed by concentration and hexane was added to the residue, and the white solid precipitated was recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 15 g of a compound as white crystals.

The presumed structural formula of the major component of this compound is the structural formula of the compound shown below.

Next, 2 g of the obtained compound was ground together with 8 g of a 2.5 wt% poly(vinyl alcohol) aqueous solution in a paint shaker for 45 minutes to be dispersed, whereby a dispersion was obtained.

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dispersion of said compound in place of the dispersion of the compound obtained in Example 1, and was evaluated. The results obtained are summarized in 282 Table 1.

(C-l) 0 N CH3 H H K.)

HN,

c=o

NH

0 (C-2)

HN

q=o 0 0 Comparative Example 7 A heat-sensitive recording material was produced in the same manner as in Example 1 except for using 1,3-diphenylurea in place of the urea-urethane compound synthesized in Example 1, and was evaluated.

The results obtained are summarized in Table 1.

S. S S S S S S *S S S S *S *S*S 283 Table 1 Main constituents of urea-urethane Heat resistance Color Plasticizer Preservdeveloptent resistance Print ability of G l Stct sensitivity (print preserv- original formua fomala of thermal preserv- ability at recording eauto paper ability) 60 0 C material surface at Exa eL Ic LdH 1 SJ~ 1 -2 A0fl PEm pl 3 PJ 4g (V3P3- J 1 1 A l EX= 1leL. M X L 2 4 1 -2 Pv le.A(VI (E 1-2 ___Oft_0_a Er,=1eS P3L R~A~ (V J-91 1.2. FaIM la Lc4.r..Ld... 1 l- A C) nRlelfL. P 11 (V 9 41 1- 1 Ex lp1 9~f. 1 3 &am- L 4~ 1 (P 1.

a. a. a. *aa* a a a a a a *a a a a* a 284 Ccnpaai6 L.Le2L Exap1eL. P 16 1 2 A A~ M Fnp2.e t- 17 F 2 4 1 1 0 no A 0 9o) Fb~nrml P 18 (VI F, 2 L) 1 2 A_ _n a_ Rypa2.Le.21.F 1 -2 n F-,7n P 22.. 9.E 2.L 1 -9 Cciparative 1.3 x Ccrparative 0.3 0 0.3 x 0 x Ccrparatlve 0.3 x 0 x CcxTparative 0.4 Ccxt(rativ 0.5 x x Ccrlparative 0.4 x x 0 x CcTparative 0.6 x x x R p_7 P_ 7_ 1_ 1. Sensitivity becomes higher with an increase of optical density (OD value).

2. Plasticizer resistance (print preservability) Oe *9 9 S S S S S S *SSS S 55 **SS 285 o x 3. He o

A

Substantially no fading.

A slight color tone change without blur and the like.

Marked fading.

Complete loss of the color of print.

at resistance (print preservability at 60 0

C)

Substantially no fading.

A slight color tone change without blur and the like.

Marked fading.

Complete loss of the color of print.

at resistance (the preservability of an original recording material surface at

X

4. H 0

C)

[e 0 Substantially no fog was caused.

o Reading of a print portion was possible though there was a slight color tone change.

Reading of a print portion was difficult owing to fog.

x Reading of a print portion was impossible owing to serious fog.

286 EXAMPLE 24 While stirring 31.5 g of 2,4-toluene diisocyanate at 60°C, a dilution of 21.5 g of 4,4'-diaminodiphenyl sulfone with 120 ml of methyl ethyl ketone was added dropwise thereto over a period of 4 hours, and the reaction was continued at 60°C for another 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature and then toluene was added thereto, and the white solid precipitated was recovered by filtration, washed with toluene and then dried overnight in a vacuum to obtain 47 g of a compound as white crystals.

Subsequently, 9.5 g of phenol and 95 ml of methyl ethyl ketone were added to g of the obtained compound, followed by adding thereto 30 mg of triethylamine, and the reaction was carried out at 250C for 4 hours. After completion of the reaction, toluene was added to the reaction solution and the crystals precipitated were recovered by filtration, washed with toluene and then dried overnight in a vacuum to obtain 38.5 g of a compound as white crystals. IR measurement of 15 these white crystals was carried out to find characteristic peaks appeared at 990 cm 1 1110 cm 1 1320 cm- 1 1590 cm' 1 1700 cm' 1 and 3350 cm 1 Next, a dispersion was prepared by dispersing 2 g of the obtained compound by grinding it together with 8 g of a 2.5 wt% poly(vinyl alcohol) aqueous solution in a paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersing operation was 250C. The diameter of dispersed particles of the compound was 0.6 lpm.

S

Another dispersion was prepared by dispersing 70 g of 3-dibutylamino-6- S. methyl-7-anilinofluoran by grinding it together with 130 g of a 5.4 wt% aqueous solution of hydroxypropylmethyl cellulose (Metlose 60SH-03, mfd. by Shin-Etsu 25 Chemical Co., Ltd.) in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

Further another dispersion was prepared by dispersing 70 g of diphenyl sulfone by grinding it together with 130 g of a 8 wt% poly(vinyl alcohol) aqueous solution in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

Still another dispersion was prepared by mixing 10 g of calcium carbonate with 30 g of water and stirring the mixture by the use of a stirrer.

287 A coating liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (dry basis proportions); the dispersion of the above-mentioned compound in terms of dry solids: 20 parts by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran dispersion in terms of dry solids: 10 parts by weight, the diphenyl sulfone dispersion in terms of dry solids: 25 parts by weight, the calcium carbonate dispersion in terms of dry solids: 40 parts by weight, a zinc stearate dispersion (solid content: 16 wt%) in terms of dry solids: 20 parts by weight, and a 15 wt% poly(vinyl alcohol) in terms of dry solids: 15 parts by weight.

The coating liquid was applied on base paper with a basis weight of g/m 2 by the use of a bar coater of rod number 10. The coating amount of the coating liquid was 5 g/m 2 in terms of dry weight. After drying, supercalendering was conducted to obtain a heat-sensitive recording material.

The result of evaluating the sensitivity of the heat-sensitive recording 15 material obtained was so good that the optical density was 1.3. The print '9 preservability evaluated by the use of vinyl chloride wrap films was good. The whiteness of the original recording material surface was as good as 82. These evaluation results are summarized in Table 2.

SEXAMPLES 25 AND 26 Heat-sensitive recording materials were produced in the same manner as *:in Example 24 except for using 3-diethylamino-6-methyl-7-anilinofluoran (Example 25) or 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (Example 26) in place of 3-dibutylamino-6-methyl-7-anilinofluoran, and were evaluated. The results obtained are summarized in Table 2.

8 25 EXAMPLES 27 TO 29 Heat-sensitive recording materials were produced in the same manner as in Example 24 except for using methyl cellulose (Metlose M-15, mfd. by Shin-Etsu Chemical Co., Ltd.) (Example 27), a polyoxyethylene alkyl ether sulfate (Rebenol WX, mfd. by Kao Corp.) (Example 28) or sodium 2-ethylhexylsulfosuccinate (Neocol SWC, mfd. by Dai-ichi Kogyo Seiyaku Co., Ltd.) (Example 29) in place of the hydroxypropylmethyl cellulose used in Example 24 for dispersing 3dibutylamino-6-methyl-7-anilinofluoran, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 2.

288 EXAMPLE A urea-urethane compound developer dispersion, a 3-dibutylamino-6methyl-7-anilinofluoran dispersion, a diphenyl sulfone dispersion and a calcium carbonate dispersion were prepared in the same manner as in Example 24.

On the other hand, a dispersion was prepared by dispersing 70 g of 2,2bis(4-hydroxyphenyl)propane by grinding it together with 130 g of a 5.4 wt% poly(vinyl alcohol) aqueous solution in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

A coating liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (dry basis proportions); the urea-urethane compound dispersion in terms of dry solids: parts by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran dispersion in terms of dry solids: 10 parts by weight, the diphenyl sulfone dispersion in terms of dry solids: 20 parts by weight, the 2,2-bis(4-hydroxyphenyl)propane dispersion in 15 terms of dry solids: 10 parts by weight, the calcium carbonate dispersion in terms of dry solids: 20 parts by weight, a zinc stearate dispersion (solid content: 16 wt%) in terms of dry solids: 10 parts by weight, and a 15 wt% poly(vinyl alcohol) in terms of dry solids: 10 parts by weight.

A heat-sensitive recording material was produced in the same manner as in Example 24 except for using the coating liquid obtained above, and was evaluated. The results obtained are summarized in Table 2.

EXAMPLES 31 TO 34 Heat-sensitive recording materials were produced in the same manner as in Example 30 except for using 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone 25 a trade name, mfd. by Nippon Soda Co., Ltd.), (Example 31), bis(3-allyl-4hydroxyphenyl) sulfone (TG-SA, a trade name, mfd. by Nippon Kayaku Co., Ltd.) (Example 32), 2,4'-dihydroxydiphenyl sulfone (24BPS, a trade name, mfd. by Nicca Chemical Co., Ltd.) (Example 33) or a mixture composed mainly of 4,4'- [oxybis(ethyleneoxy-p-phenylenesulfonyl)]diphenol (D-90, a trade name, mfd. by Nippon Soda Co., Ltd.) (Example 34) in place of 2,2-bis(4-hydroxyphenyl)propane, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 2.

289 EXAMPLES 35 TO 64 Heat-sensitive recording materials were produced in the same manner as in each of Examples 30 to 34 except for using P-naphthylbenzyl ether (BON, a trade name, mfd. by Ueno Fine Chemicals Industry Ltd.) (Examples 35 to 39), pbenzylbiphenyl (PBBP, a trade name, mfd. by Nippon Steel Chemical Co., Ltd.) (Examples 40 to 44), 1,2-di(m-methylphenoxy)ethane (KS-235, a trade name, mfd. by SANKOSHA CO., LTD.) (Examples 45 to 49), di-p-methylbenzyl oxalate (HS3520, a trade name, mfd. by Dainippon Ink and Chemicals, Inc.) (Examples to 54), 1,2-diphenoxymethylbenzene (PMB-2, a trade name, mfd. by Nicca Chemical Co., Ltd.) (Examples 55 to 59) or m-terphenyl (mtp, a trade name, mfd.

by Nippon Steel Chemical Co., Ltd.) (Examples 60 to 64) in place of diphenyl sulfone, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 2.

EXAMPLES 65 AND 66 S" 15 Heat-sensitive recording materials were produced in the same manner as in Example 24 except for using a stearamide emulsified product (Highmicron G- 270, a trade name, mfd. by Chukyo Yushi Co., Ltd.) (Example 65) or acetoacetic o-chloroanilide (mfd. by Mitsuboshi Chemical Co., Ltd.) (Example 66) in place of Sdiphenyl sulfone, and were evaluated. The results obtained are summarized in Table 2.

EXAMPLE 67 A heat-sensitive recording material was produced in the same manner as in Example 30 except for adding a stilbene type fluorescent dye (Kayahol 3BS, a trade name, mfd. by Nippon Kayaku Co., Ltd.) to the coating liquid prepared in 25 Example 30, in a proportion of 1 part by weight per 100 parts by weight (in terms of dry solids) of the coating liquid, and was evaluated. The results obtained are summarized in Table 2.

EXAMPLE 68 A dispersion was obtained by dispersing 70 g of 1,1,3-tris(2-methyl-4hydroxy-5-tert-butylphenyl)butane by grinding it together with 130 g of a 5.4 wt% poly(vinyl alcohol) aqueous solution in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

290 Then, a heat-sensitive recording material was produced in the same manner as in Example 30 except for adding the aforesaid 1,1,3-tris(2-methyl-4dispersion to the coating liquid prepared in Example 30, in a proportion of 10 parts by weight per 100 parts by weight (in terms of dry solids) of the coating liquid, and was evaluated. The results obtained are summarized in Table 2.

EXAMPLE 69 To 30 g of 2,4-toluene diisocyanate was added 30 g of toluene as a solvent, followed by adding thereto 3.24 g of phenol, and the reaction was carried out at 100 0 C for 1 hour and 30 minutes. After completion of the reaction, the toluene was removed by concentration and hexane was added to the residue, and the white solid precipitated was recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 6.9 g of a compound as white crystals. Subsequently, 100 g of toluene was added as a solvent to 5.0 g of the 15 obtained compound, followed by adding thereto 3.50 g of aniline, and the reaction was carried out at 25 0 C for 3 hours. The crystals precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain g of a compound as white crystals. IR measurement of these white crystals was carried out to find that characteristic peaks appeared at 890 cm' 1 1000 cm 1 20 1030 cm' 1 1440 cm' 1 1720 cm' 1 and 3350 cm 1 Then, a heat-sensitive recording material was produced in the same manner as in Example 68 except for using the compound obtained above, in place of the urea-urethane compound used in Example 68, and was evaluated.

The results obtained are summarized in Table 2.

25 EXAMPLES 70 TO Heat-sensitive recording materials were produced in the same manner as in Example 68 except for using 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane (Adecaarcles DH-43, mfd. by Asahi Denka Kogyo (Example 4-benzyloxy-4'-(2,3-epoxy-2-methylprop-1-yloxy)diphenyl sulfone mfd. by Nippon Soda Co., Ltd.), (Example 71), methylenebis(2-hydroxy-3- (Example 72), 2-(2'-hydroxy-5'methylphenyl)benzotriazole (Adecaarcles DN-13, mfd. by Asahi Denka Kogyo (Example 73), 1 ,3,5-tris(2,6-dimethyl-4-tert-buty-3-hydroxybenzyi) 291 isocyanurate (Adecaarcles DH-48, mfd. by Asahi Denka Kogyo (Example 74) or sodium 2,2-methylenebis(4,6-di-tert-butylphenyl)phosphate (Adecaarcles mfd. by Asahi Denka Kogyo (Example 75) in place of 1,1,3-tris(2and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 2.

COMPARATIVE EXAMPLE 8 A heat-sensitive recording material was produced in the same manner as in Example 24 except for using 2,2-bis(4-hydroxyphenyl)propane in place of the urea-urethane compound synthesized in Example 24, and was evaluated. The results obtained are summarized in Table 2.

e 292 Table 2 Main constituents Plasticizer of urea-urethane Sensitivity resistance To =Y~riIAJ- ti of thermal (print Witeness General Structural paper preservformi.la fonrula ability) Ex -24. (E2113 no___ 5(y) (E-24) 13 Co9n ExaTT 1- 26 2 4 13 1 oR2n Pal,27(y) (E-24) 1 3 A 8 n PWqlf29(y) (FE-2 4) 1 3 no82n F -3 1t 4n(y) (R-24 13 '1 0 (B Ri Exal03 (F-24) 1 3 n noR1 RwAmnl1132 P 2 4 1 3 Rip Exan1e 33 (F-24) 13 2 0 Rip Exa 4le.3; (E-24) 19 R2 I rpa3. (R-24) 1 4 0 p n.

P-'mIC 1 (12-24) 1 4 p no~ R2 p n Exampei3'A F 24 1 -4 o no R2 C p f- I R 24 1 2 no R2.. C) -n R~aqn1 P40 M .V 24 1 3 1 o-e C. R9 P- n Contin'd 0 .00 00 00 0 0 so 0 000 0000 0 00 0 0 :0 0: 00. 00 0. 0. 0.

00 0000 00 00 0000 0 00 00 0 0 0 0 0 0 0 00 0 0 0 **00 0 00 *000 0 293 E!ca~ 14I 1 Pl 0 A~ c- 4e 2 E 2 4) 13 ~9 (0)R_2__n F:3capl, 41 (E-24 13 Co) R o F ni144 E2 4. 1 290 R9 2 Tr14c; (VI 4F24 10 A. 3 no Pxn(V'P 446()E.-24 10 no R3 A 1'vAml 47 4 2 4 1) A9 R 2 E 4R. E-2A4 1 3 ~_no R 2 C) P P-v~l-4q(VI 24 29 0 n F~~~lrn(y) 1. 2 4~ 0P)R3 0) o, 1L F. 24. 1 4 -0 n. IS 2 Pxa lf 2(y) E.-24 1 4 0- (0 R20 o iz ~1S3. (VI E-2 4. 13 '1 c) no? PA lm A(y) E-2419 no R) 2 0 EYa~lk-1; S E-2 4 13 '1 C) Co Rl0 a PBY~q 15S C E.-2 44 1 n~ A R C) o E'c~1lS7. (NV r) A p9 1) n EXA1e Ss E2 4 1-A 0 o R9 2 0 ~C Exap C) E-2 4 1 29 C) A~ Fixam1a60L. 4E-2 4 1 3 c) no 20 0 E2=1 e 61 (VI 4E-2 44 131 n )C Fba~l e62 (E-2 4 13' R 2 0 f-Al P- A E 413 n) A R) 2 EAnl P 64 R 24 1 1 2 R9 2) 0 (6 Contin'd a. *9 a *a a a a a a a a. 294 Contin'd EamI P 65 (-24 1 3 0 R 0_ S .aD 66 (Ve) (E-24) 1 2 R R ExnanP 67 2 4 1 3 A R 9 a A FrmDIP AR (VI 24) 1 3 A 27 ro Exanpl e69. T 4 1 3 9 Elampl 0 (V )E4) 1 3 A R7 9 VExam P 7n (yV) E 2 4 1 3 A n o xampI P1 71 E 2 4) 1 3 o -1 R2 in2 72 (E-2 4) 13 0 A R 0 n ExamDIP 71 (VI (E.-24 1 1 0 P A 0 n enlt 7; 4 1o c) R Camparative R- 1 .3 x 78 x 1. Sensitivity becomes higher with an increase of optical density (OD value).

2. Plasticizer resistance (print preservability) Substantially no fading.

o A slight color tone change without blur and the like.

A -Marked fading.

x Complete loss of the color of print.

3. Whiteness becomes higher with an increase of its numeral value. Whiteness is sufficient in practice when its numeral value is 80 or more.

295 <Rub resistance> The surface of a heat-sensitive recording material was strongly rubbed with a nail, and whether color development had been caused in the rubbed portion was visually judged. When the recording material showed no remarkable trace of the rubbing, it was rated good in rub resistance.

<Accumulation of traces of rubbing> A cylinder (weight: 2 kg) having a face with a diameter of 5 cm was moved times on one and the same portion with a length of 20 cm of the recording surface of each heat-sensitive recording material produced, at a rate of cm/sec, and then the recording material was allowed to stand at room temperature for one week. After one week of the standing, whether a printed image could be read was visually judged. When the printed image could be sufficiently read, the recording material was rated good.

EXAMPLE 76 15 A heat-sensitive coating liquid was obtained in the same manner as in Example 24. Then, the coating liquid was applied on base paper with a basis weight of 50 g/m 2 by the use of a bar coater of rod number 10. After drying, supercalendering was conducted to form a heat-sensitive color-producing layer on the substrate. The coating amount of the coating liquid was 5 g/m 2 in terms of dry weight.

Then, a dispersion was prepared by dispersing 40 g of kaolin by grinding it together with 60 g of a 0.7 sodium hexametaphosphate aqueous solution in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

A coating liquid for forming a protective layer was obtained by stirring and mixing the kaolin dispersion and other components in the following proportions (dry basis proportions); the kaolin dispersion in terms of dry solids: 20 parts by weight, a zinc stearate dispersion (solid content: 16 wt%) in terms of dry solids: parts by weight, a carboxy-modified poly(vinyl alcohol) aqueous solution in terms of dry solids: 40 parts by weight, and a polyacrylamidoepichlorohydrin crosslinking agent aqueous solution in terms of dry solids: 5 parts by weight.

296 The coating liquid for forming a protective layer was applied on the heatsensitive color-producing layer by the use of a bar coater of rod number 5. After drying, supercalendering was conducted to obtain a heat-sensitive recording material. The coating amount of the coating liquid for forming a protective layer was 2 g/m 2 in terms of dry weight.

The result of evaluating the sensitivity of the heat-sensitive recording material obtained was so good that the optical density was 1.3. The print preservability evaluated by the use of vinyl chloride wrap films was good. The surface of the heat-sensitive recording material was strongly rubbed with a nail and whether color development had been caused in the rubbed portion was visually judged to find that there was no remarkable trace of the rubbing, namely, the rub resistance was good. The result of a long-term test for evaluating the rub resistance was so good that a printed image could be sufficiently read. These evaluation results are summarized in Table 3.

15 EXAMPLES 77 AND 78 Heat-sensitive recording materials were produced in the same manner as in Example 76 except for using a poly(vinyl alcohol) (Example 77) or an acrylic copolymer (Example 78) in place of the carboxy-modified poly(vinyl alcohol), and were evaluated. The results obtained are summarized in Table 3.

o. 20 EXAMPLES 79 TO 81 Heat-sensitive recording materials were produced in the same manner as in Example 76 except for using aluminum hydroxide (Example 79), a crosslinkable poly(methyl methacrylate) resin (Example 80) or silica dioxide (Example 81) in place of kaolin, and were evaluated. The results obtained are 25 summarized in Table 3.

EXAMPLE 82 A coating liquid for intermediate layer was obtained by stirring and mixing a 33 wt% calcined kaolin dispersion and a 50 wt% styrene/butadiene based latex aqueous dispersion in proportions (dry basis proportions) of 100 parts by weight and 12 parts by weight, respectively.

Then, a back coating liquid was obtained by stirring and mixing a 20 wt% acrylic emulsion and a 10 wt% silica fine powder dispersion (Fineseal SP-10) in 297 proportions (dry basis proportions) of 100 parts by weight and 7 parts by weight, respectively.

The aforesaid coating liquid for intermediate layer was applied on one side of base paper (50 g/m 2 in an amount of 10 g/m 2 in terms of solids and dried, and the heat-sensitive coating liquid prepared in Example 76 was applied on the same side in an amount of 5 g/m 2 in terms of solids and dried, after which the coating liquid for protective layer prepared in Example 76 was applied on the same side in an amount of 2 g/m 2 in terms of solids and dried. Then, the aforesaid back coating liquid was applied on the uncoated side in an amount of 1 g/m 2 in terms of solids and dried, and calendering was conducted to produce a heat-sensitive recording material, which was evaluated. The results obtained are summarized in Table 3.

COMPARATIVE EXAMPLE 9 A heat-sensitive recording material was produced in the same manner as in Example 76 except that no coating liquid for forming a protective layer was applied on the heat-sensitive color-producing layer, and the recording material was evaluated. The results obtained are summarized in Table 3.

•o o*oo o *oo o•* •go• ooo* oo 8b8. 8** 8 C C 88 98 8 *8 88 88 88 8888 8. 88 *888 8 88 *8 8 8 C 8 88 8 8 8 8*8@ J 298 Table 3 Main constituents Plasticizer of urea-urethane Sensitivity resistance Accunulation Rub Total canposition of themal (print of traces of Resistance evaluation General Structural paper preserv- rubbing fornula fonrula _ilitv) xn l e 76 (yV) (E-24) 1 a a Exawl e 77 (E-24) 1 3 LExaml.e.78 (E-24) 1.3 a 0 a 0 0 xwmle. 79 (E-24) 13.3 a a a a FyxnLa... P 0 (yV) (E-24) 1 a 0 d 0 a Ex=1l t 1 (E-24) 1 3 a m 8 (E-24) 14 a a a Couparative Cparative (E-24) 1.3 -o X Examml e 9 1 1 1. Sensitivity becomes higher with an increase of optical density (OD value).

2. Plasticizer resistance (print preservability) Substantially no fading.

o A slight color tone change without blur and the like.

A Marked fading.

x Complete loss of the color of print.

o 4 9 6 299 3. Rub resistance o A trace of rubbing shows no development of a black color.

o A trace of rubbing shows slight color development but is not remarkable.

S~ A trace of rubbing shows color development to a limited extent and is remarkable.

x A trace of rubbing shows development of a black color and is remarkable.

4. Accumulation of traces of rubbing A good result is obtained without difficulty in reading a printed image.

o Traces of rubbing show slight color development but a printed image can be sufficiently read.

A Traces of rubbing show color development, so that a printed image is difficult to read.

x Traces of rubbing show development of a black color, so that a printed image cannot be read.

300 EXAMPLE 83 A dispersion was prepared by dispersing 2 g of the compound obtained in Example 24, by grinding it together with 8 g of a 2.5 wt% aqueous solution of a poly(vinyl alcohol) (Gohsenol KL-05, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) in a paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersing operation was 250C and the pH of the dispersion was 8. The diameter of dispersed particles of the compound was 0.6 jpm.

Another dispersion was prepared by dispersing 70 g of 3-dibutylamino-6methyl-7-anilinofluoran by grinding it together with 130 g of a 5.4 wt% poly(vinyl alcohol) aqueous solution in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

Further another dispersion was prepared by dispersing 70 g of diphenyl sulfone by grinding it together with 130 g of a 5.4 wt% aqueous solution of a 15 poly(vinyl alcohol) (Gohsenol KL-05, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours.

20 A coating liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (dry basis proportions); the dispersion of the above-mentioned compound in terms of dry solids: 30 parts by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran dispersion in terms of dry solids: 15 parts by weight, the diphenyl sulfone dispersion in terms 25 of dry solids: 30 parts by weight, the calcium carbonate dispersion in terms of dry solids: 20 parts by weight, a zinc stearate dispersion (solid content: 16 wt%) in terms of dry solids: 10 parts by weight, and a 15 wt% poly(vinyl alcohol) in terms of dry solids: 7 parts by weight. The pH of the coating liquid was 8.2.

Then, the coating liquid was applied on the surface of woodfree paper with a basis weight of 50 g/m 2 in an amount of 5 g/m 2 in terms of dry weight and dried, followed by supercalendering, to produce a heat-sensitive recording material.

The result of evaluating the color development sensitivity of the heat-sensitive recording material obtained was so good that the optical density was 1.3. The 301 print preservability evaluated by the use of vinyl chloride wrap films was so good that no fading occurred. The results obtained are summarized in Table 4.

EXAMPLE 84 A dispersion was prepared by dispersing 2 g of the same urea-urethane compound as used in Example 83 and 2 g of diphenyl sulfone by grinding them together with 16 g of a 2.5 wt% aqueous solution of a modified poly(vinyl alcohol) (Gohsenol KL-05, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) in a paint shaker for 6 hours.

Then, a heat-sensitive recording material was produced in the same manner as in Example 83 except for adding the aforesaid co-dispersion in a proportion of 60 parts by weight in terms of dry solids, in place of the dispersion of the urea-urethane compound used in Example 83 and the diphenyl sulfone dispersion, and the recording material was evaluated. The results obtained are summarized in Table 4.

15 EXAMPLE To 61 g of 2,4-toluene diisocyanate was added 450 g of toluene as a solvent, followed by adding dropwise thereto a solution of 26 g of aniline in 150 g of toluene over a period of 6 hours, and the reaction was carried out at 5 0 C for 7 hours. After completion of the reaction, the white solid precipitated was 20 recovered by filtration, washed with toluene and then dried overnight in a vacuum to obtain 70 g of a compound as white crystals. Subsequently, 365 g of toluene was added as a solvent to 30 g of the obtained compound, followed by adding thereto 12.2 g of 2,2-bis(4-hydroxyphenyl)propane and 0.3 mg of triethylamine, *o o and the reaction was carried out with stirring at 60 0 C for 4 hours, at 70 0 C for 3 25 hours, and then at 80 0 C for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the crystals precipitated were recovered by filtration, washed with toluene and then dried overnight in a vacuum to obtain 42 g of a compound as white crystals. IR measurement of these white crystals was carried out to find that characteristic peaks appeared at 750 cm- 1 840 cm- 1 1020 cm' 1 1500 1600 cm- 1 1720 cm-' and 3320 cm 1 A dispersion was prepared by dispersing 2 g of this compound and 2 g of diphenyl sulfone by grinding them together with 16 g of a 2.5 wt% aqueous

S

302 solution of a modified poly(vinyl alcohol) (Gohseran L-3266, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) in a paint shaker for 6 hours.

Then, a heat-sensitive recording material was produced in the same manner as in Example 83 except for adding the co-dispersion of the abovementioned compound and dipheny sulfone in a proportion of 60 parts by weight in terms of dry solids, in place of the dispersion of the urea-urethane compound used in Example 83 and the diphenyl sulfone dispersion, and the recording material was evaluated. The results obtained are summarized in Table 4.

EXAMPLE 86 A dispersion was prepared by dispersing 2 g of the compound obtained in Example 69 and 2 g of dimethylbenzyl oxalate by grinding them together with 16 g of a 2.5 wt% aqueous solution of a modified poly(vinyl alcohol) (Gohseran L- 3266, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) in a paint shaker for 6 hours.

Then, a heat-sensitive recording material was produced in the same manner as in Example 83 except for adding the co-dispersion of the abovementioned compound and dimethylbenzyl oxalate in a proportion of 60 parts by weight in terms of dry solids, in place of the dispersion of the urea-urethane compound used in Example 83 and the diphenyl sulfone dispersion, and the 20 recording material was evaluated. The results obtained are summarized in Table 4.

EXAMPLE 87 A dispersion was prepared by dispersing 2 g of the compound obtained in Example 2, by grinding it together with 8 g of a 2.5 wt% aqueous solution of methyl cellulose (Metlose SM-15, mfd. by Shin-Etsu Chemical Co., Ltd.) in a paint shaker for 6 hours.

Then, a heat-sensitive recording material was produced in the same manner as in Example 83 except for using the dispersion of the aforesaid compound in place of the dispersion of the urea-urethane compound used in Example 83, and the recording material was evaluated. The results obtained are summarized in Table 4.

303 EXAMPLES 88 TO 92 Heat-sensitive recording materials were produced in the same manner as in Example 83 except for using a polycarboxylic acid ammonium salt (Dispersant 5027, mfd. by Sunnopco Co., Ltd.) (Example 88), a water-soluble low-molecular weight copolymer (Discort N14, mfd. by Dai-ichi Kogyo Seiyaku Co., Ltd.) (Example 89), sodium 2-ethylhexylsulfosuccinate (Neocol SWC, mfd. by Dai-ichi Kogyo Seiyaku Co., Ltd.) (Example 90), hydroxypropylmethyl cellulose (Metlose 60SH-03, mfd. by Shin-Etsu Chemical Co., Ltd.) (Example 91), or condensed sodium naphthalenesulfonate (Roma D, mfd. by Sunnopco Co., Ltd.) (Example 92) in place of the poly(vinyl alcohol) (Gohsenol KL-05, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersing agent for the ureaurethane compound in Example 83, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 4.

i EXAMPLES 93 TO 98 15 Heat-sensitive recording materials were produced in the same manner as in Example 83 except for using methyl cellulose (Metlose SM-15, mfd. by Shin- Etsu Chemical Co., Ltd.) (Example 93), a water-soluble low-molecular weight copolymer (Discort N14, mfd. by Dai-ichi Kogyo Seiyaku Co., Ltd.) (Example 94), sodium 2-ethylhexylsulfosuccinate (Neocol SWC, mfd. by Dai-ichi Kogyo Seiyaku 20 Co., Ltd.) (Example 95), hydroxypropylmethyl cellulose (Metlose 60SH-03, mfd.

by Shin-Etsu Chemical Co., Ltd.) (Example 96), condensed sodium e** naphthalenesulfonate (Roma D, mfd. by Sunnopco Co., Ltd.) (Example 97) or a polycarboxylic acid ammonium salt (Dispersant 5027, mfd. by Sunnopco Co., :Ltd.) (Example 98) in place of the poly(vinyl alcohol) (Gosenol KL-05, mfd. by The 25 Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersing agent for diphenyl sulfone in Example 83, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 4.

EXAMPLES 99 TO 101 Heat-sensitive recording materials were produced in the same manner as in Example 87 except for using methyl cellulose (Metlose SM-15, mfd. by Shin- Etsu Chemical Co., Ltd.) (Example 99), hydroxypropylmethyl cellulose (Metlose 60SH-03, mfd. by Shin-Etsu Chemical Co., Ltd.) (Example 100) or a modified poly(vinyl alcohol) (Gohseran L-3266, mfd. by The Nippon Synthetic Chemical 304 Industry Co., Ltd.) (Example 101) in place of the poly(vinyl alcohol) (Gohsenol KLmfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersing agent for diphenyl sulfone in Example 87, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 4.

EXAMPLE 102 A heat-sensitive recording material was produced in the same manner as in Example 99 except for using a modified poly(vinyl alcohol) (Gohseran L-3266, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) in place of the methyl cellulose (Metlose SM-15, mfd. by Shin-Etsu Chemical Co., Ltd.) used as a dispersing agent for the urea-urethane compound in Example 99, and the recording material was evaluated. The results obtained are summarized in Table 4.

EXAMPLES 103 AND 104 15 Heat-sensitive recording materials were produced in the same manner as in Example 89 except for using methyl cellulose (Metlose SM-15, mfd. by Shin- Etsu Chemical Co., Ltd.) (Example 103) or hydroxypropylmethyl cellulose (Metlose 60SH-03, mfd. by Shin-Etsu Chemical Co., Ltd.) (Example 104) in place of the poly(vinyl alcohol) (Gohsenol KL-05, mfd. by The Nippon Synthetic 20 Chemical Industry Co., Ltd.) used as a dispersing agent for diphenyl sulfone in Example 89, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 4.

EXAMPLES 105 TO 106 Heat-sensitive recording materials were produced in the same manner as in Example 91 except for using methyl cellulose (Metlose SM-15, mfd. by Shin- Etsu Chemical Co., Ltd.) (Example 105) or hydroxypropylmethyl cellulose (Metlose 60SH-03, mfd. by Shin-Etsu Chemical Co., Ltd.) (Example 106) in place of the poly(vinyl alcohol) (Gohsenol KL-05, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) used as a dispersing agent for diphenyl sulfone in Example 91, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 4.

305 EXAMPLES 107 AND 108 Heat-sensitive recording materials were produced in the same manner as in Example 104 except for using hydroxypropylmethyl cellulose (Metlose 03, mfd. by Shin-Etsu Chemical Co., Ltd.) (Example 107) or a mixed dispersing agent of hydroxypropylmethyl cellulose (Metlose 60SH-03, mfd. by Shin-Etsu Chemical Co., Ltd.) and sodium 2-ethylhexylsulfosuccinate (Neocol SWC, mfd. by Dai-ichi Kogyo Seiyaku Co., Ltd.) (weight ratio: 1/1) (Example 108) in place of the poly(vinyl alcohol) used as a dispersing agent for 3-dibutylamino-6-methyl-7anilinofluoran in Example 104, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in Table 4.

COMPARATIVE EXAMPLE A heat-sensitive recording sheet was produced in the same manner as in Example 83 except for using 2,2-bis(4-hydroxyphenyl)propane in place of the urea-urethane compound used in Example 83, and was evaluated. The results 15 obtained are summarized in Table 4.

COMPARATIVE EXAMPLES 11 AND 12 i th. The same urea-urethane compound as used in Example 83 was dispersed in the same manner as in Example 83 except for changing the dispersion time, and the average particle sizes of the resulting dispersions were measured and 20 found to be 0.04 lpm (Comparative Example 11) and 6.5 pm (Comparative Example 12). Heat-sensitive recording sheets were produced in the same S* manner as in Example 83 except for using each of the above-mentioned ::dispersions, and were evaluated. The results obtained are summarized in Table 4.

COMPARATIVE EXAMPLE 13 The same urea-urethane compound as used in Example 83 was dispersed in the same manner as in Example 83 except for maintaining the dispersing temperature at 65 0 C during the dispersing operation. Except for using the dispersion thus obtained, a heat-sensitive recording sheet was produced in the same manner as in Example 83, and was evaluated. The results obtained are summarized in Table 4.

306 COMPARATIVE EXAMPLE 14 The same urea-urethane compound as used in Example 83 was dispersed in the same manner as in Example 83 except for adjusting the pH of the dispersion medium used for the dispersing operation to 4. Except for using the dispersion thus obtained, a heat-sensitive recording sheet was produced in the same manner as in Example 83, and was evaluated. The results obtained are summarized in Table 4.

COMPARATIVE EXAMPLE The same urea-urethane compound as used in Example 83 was dispersed in the same manner as in Example 83 except for adjusting the pH of the dispersion medium used for the dispersing operation to 11. Except for using the dispersion thus obtained, a heat-sensitive recording sheet was produced in the same manner as in Example 83, and was evaluated. The results obtained are summarized in Table 4.

15 COMPARATIVE EXAMPLE 16 The pH of the coating liquid prepared in Example 83 was adjusted to with 1N-sulfuric acid. Except for using the coating liquid thus adjusted, a heatsensitive recording sheet was produced in the same manner as in Example 83, and was evaluated. The results obtained are summarized in Table 4.

glee 20 COMPARATIVE EXAMPLE 17 The pH of the coating liquid prepared in Example 83 was adjusted to 12.5 with 1N-sodium hydroxide. Except for using the coating liquid thus adjusted, a heat-sensitive recording sheet was produced in the same manner as in Example 83, and was evaluated. The results obtained are summarized in Table 4.

or 307 Table 4 Plasticizer Plasticizer Main constituents resistance resistance of urea-urethane ccrposition Sensitivity of iTotal (print (preservability of General Structural preserv- original recording fon. i formi ii abilitv) material surface) Examl -8R (E-24) 1.3 a 0 a 0 o a FEwamol e 84 (E-24) 1.4 r xm tRC; (VI) (E-30) 1.3 0 -0 Fbcil P R6 r) 0 R =l e 87 (S-13) 1 3 o0 Exarul P 88 (E-24) 1 3

R-=

1 iP 89 (E-24) 1 txamo e 90 (E-24) 1.2 a a 0 nphmml91 (E-24) 1.3 0 PxWRM1e- 992 (E-24) 1 2 a -C tRxaIrple93 (E-24) 1'a Fnpl 94 (E-24) 1 3 txaml P95 (E-24) 1.3 Encmle 96 (E-24) 1 3 0 -a iExp1 e 97 (E-24) 1 3 .p Eaoe98(V) (E-24) 1.3 1 p 0 .0C)- Contin'd S. 55 5 *5 55 5 '00* 0S S S *00 5 55 *5 S 308 Contin'd 99 1- 3 Ex<=IP e100 q -1 -4 1.3 Fwarl e 0 q 1.4 Examl e 102 (q-13 1. 4 PYAonI P11 MV (E-24) 1.3 ExMVrt-104 (E-24) 1.3 0 0 a~nP 105 13 a a Maipl 106 (E-24) 1-3 a Exanl P107 (E-24) 1.3 a_ ExG=I P 108 M'F) 2 4 Carparative pyn 1 ni- Pi 1 .3 x 0 x Ccxrparative (E-24) 1.3 a x x Carparative 12(V) (E-24) 0.7 A 0 x Cmzparative iaMMa Pe 13A MV (E-24) 0 .8 a Ax Ccxparative Exa=1 t- 14 MV (E-24) 1.0 a X x Cczrprative PYATMp P 15 (E-24) 0 .8 a A Caqparative P-ynpl e 16 MV (E-24) 1 .1 A x x Canparative Fc~lP 17 MV (E-24) 0 .9 K A 1. Sensitivity becomes higher with an increase of optical 2. Plasticizer resistance (print preservability) density (OD value).

a 4 a a a a. a a as a a a ee e 309 Substantially no fading.

o A slight color tone change without blur and the like.

S- Marked fading.

x Complete loss of the color of print.

3. Plasticizer resistance (the preservability of an original recording material surface) The original recording material surface is hardly colored.

o The original recording material surface is very slightly colored though there is a subtle color tone change.

a The original recording material surface is markedly colored.

x The original recording material surface is so seriously colored that reading of print is difficult 310 EXAMPLE 109 The coating liquid prepared in Example 83 was applied on woodfree paper with a surface pH of 3.2 in an amount of 5 g/m 2 in terms of dry weight and dried, followed by supercalendering, to produce a heat-sensitive recording material.

The result of evaluating the color development sensitivity of the heat-sensitive recording material obtained was so good that the optical density was 1.3. The print preservability evaluated by the use of vinyl chloride wrap films was so good that no fading occurred. The preservability or the original recording material surface was so good that the surface was hardly colored. The results obtained are summarized in Table EXAMPLES 110 AND 111 Heat-sensitive recording materials were produced in the same manner as in Example 109 except for using woodfree paper with a surface pH of 5 (Example :q 110) or woodfree paper with a surface pH of 6.8 (Example 111) in place of the 15 woodfree paper with a surface pH of 3.2, and were evaluated. The results obtained are summarized in Table COMPARATIVE EXAMPLES 18 AND 19

S*

Heat-sensitive recording materials were produced in the same manner as in Example 109 except for using woodfree paper with a surface pH of 2.8 (Comparative Example 18) or woodfree paper with a surface pH of (Comparative Example 19) in place of the woodfree paper with a surface pH of 3.2, and were evaluated. The results obtained are summarized in Table

I

311 Table Plasticizer Plasticizer Main constituents main cnstituents resistance resistance of urea-urethane coiposition Sensitivity of Total th__ ,(print (preservability of thermal paper evaluation Structural preserv- original recording General formula form la ah__ ility) material su rface) PFraplp 109 (E-24) 1 3 )o Exrrmle 110 (E-24) 1 3 0 @a FvmMl e 111 (E-24) 1 3 a A Comparative C arative (E-24) 1.3 A x x FnaMle 18 Ccnparative (E-24) 1. 0 Aa x F!mMw le 19 1. Sensitivity becomes higher with an increase of optical density (OD value).

2. Plasticizer resistance (print preservability) Substantially no fading.

o A slight color tone change without blur and the like.

A Marked fading.

x Complete loss of the color of print.

oo 50 o5 5* o 5555 5 *o oooo 312 o The original recording material surface is very slightly colored though there is a subtle color tone change.

A The original recording material surface is markedly colored.

x The original recording material surface is so seriously colored that reading of print is difficult.

313 EXAMPLE 112 A) Preparation of a coating liquid for magnetic recording layer A coating liquid for magnetic recording layer was prepared by subjecting 100 parts by weight of barium ferrite (coercive force: 2,700), 25 parts by weight of sodium polyacrylate (a 20 wt% aqueous solution), 100 parts by weight of a poly(vinylidene chloride) (a 49 wt% dispersion), 15 parts by weight of carbon black (a 36 wt% dispersion), 10 parts by weight of paraffin wax (a 20 wt% dispersion obtained by the use of methyl cellulose) and 100 parts by weight of water to dispersion in a ball mill for 10 hours.

B) Preparation of a coating liquid for heat-sensitive recording layer A coating liquid for heat-sensitive recording layer was obtained in the same manner as in Example 24.

Next, the coating liquid for magnetic recording layer prepared in A) was applied on one side of woodfree paper with a basis weight of 150 g/m 2 in an 15 amount of 30 g/m 2 in terms of dry weight and dried to obtain a magnetic recording •layer. Then, the coating liquid for heat-sensitive recording layer prepared in B) was applied on the other side of the substrate having the aforesaid magnetic recording layer, in an amount of 6 g/m 2 in terms of dry weight and dried, followed by supercalendering, to obtain a heat-sensitive magnetic recording material.

20 The result of evaluating the color development sensitivity of the heatsensitive recording layer of the heat-sensitive magnetic recording material obtained was so good that the optical density was 1.3. The print preservability evaluated by the use of vinyl chloride wrap films was so good that no fading occurred. The results obtained are summarized in Table 6.

EXAMPLE 113 C) Preparation of a coating liquid for protective layer Twenty parts by weight of zinc stearate, 20 parts by weight of a 5 wt% methyl cellulose aqueous solution and 60 parts by weight of water were mixed and then subjected to dispersion in a sand grinder for 2 hours. Then, 20 parts by weight of a 10 wt% carboxy-modified poly(vinyl alcohol) aqueous solution, parts by weight of silica, 6.5 parts by weight of a 12.5 wt% 314 polyamidoepichlorohydrin aqueous solution and 15.0 parts by weight of water were mixed and then subjected to dispersion in a sand grinder for 2 hours.

Subsequently, 0.7 part by weight of the zinc stearate dispersion obtained above, 45.0 parts by weight of the silica dispersion obtained above and 11.3 parts by weight of water were mixed to prepare a coating liquid for protective layer. A heat-sensitive magnetic recording material was produced in the same manner as in Example 112 except for forming a protective layer by applying the aforesaid coating liquid for protective layer on the heat-sensitive recording layer of the heatsensitive magnetic recording material of Example 112 in an amount of 3 g/m 2 in terms of dry weight, followed by drying, and the heat-sensitive magnetic recording material was evaluated. The results obtained are summarized in Table 6.

EXAMPLE 114 D) Preparation of a coating liquid for intermediate layer A coating liquid for intermediate layer was prepared which was composed 15 of 80 parts by weight (in terms of dry solids) of a 48% dispersion of polystyrene fine particles and 20 parts by weight (in terms of dry solids) of a 40% styreneacrylic ester copolymer emulsion.

A heat-sensitive magnetic recording material was produced in the same manner as in Example 113 except for forming an intermediate layer by applying 20 the aforesaid coating liquid between the heat-sensitive recording layer and substrate of the heat-sensitive magnetic recording material of Example 113 in an amount of 8 g/m 2 in terms of dry weight, followed by drying, and the heatsensitive magnetic recording material was evaluated. The results obtained are summarized in Table 6.

25 COMPARATIVE EXAMPLE A heat-sensitive recording sheet was produced in the same manner as in Example 112 except for using 2,2-bis(4-hydroxyphenyl)propane in place of the urea-urethane compound used in Example 112, and was evaluated. The results obtained are summarized in Table 6.

315 Table 6 Plasticizer Main constituents rssac of urea-urethane cczposition Sensitivity of (print ev alto thermal paper praluarv- General fornula Structural fornula hi I i tyv n 1in 1 (E-24) 1 -3 no__ F.ampl L 113 (E-24) 1 -2 )0 F~xapl P 114 (E-24) 1 Comparative1. x 1. Sensitivity becomes higher with an increase of optical density (OD value).

2. Plasticizer resistance (print preservability) Substantially no fading.

0 A slight color tone change without blur and the like.

A- Marked fading.

x Complete loss of the color of print.

316 EXAMPLE 115 A) Preparation of a coating liquid for heat-sensitive recording layer A coating liquid for heat-sensitive recording layer was obtained in the same manner as in Example 24.

The coating liquid for heat-sensitive recording layer prepared in A) was applied on the surface of woodfree paper with a basis weight of 150 g/m 2 in an amount of 7 g/m 2 in terms of dry weight and dried, followed by supercalendering, to produce a sheet coated with a heat-sensitive recording layer.

B) Production of a release sheet A mold release agent composed of oily dimethyl silicone was applied on base paper with a basis weight of 40 g/m 2 in an amount of 1 g/m 2 by the use of a gravure coater to form a release layer. Then, an adhesive layer component consisting of 100 parts by weight of chlorinated rubber, 20 parts by weight of S ester gum and 120 parts by weight of dibutyl phthalate was applied on the release 15 layer in an amount of 10 g/m 2 C) Production of a label for heat-sensitive recording e The uncoated surface of the sheet coated with a heat-sensitive recording layer which had been produced in the above item A) and the surface coated with an adhesive layer of the release sheet produced in the above item B) were stuck *O 20 together so that they might face each other, whereby a label for heat-sensitive recording was produced.

The result of evaluating the color development sensitivity of the obtained label for heat-sensitive recording was so good that the optical density was 1.3.

The print preservability evaluated by the use of vinyl chloride wrap films was so good that no fading occurred. The results obtained are summarized in Table 7.

EXAMPLE 116 D) Preparation of a coating liquid for back coating layer A coating liquid for back coating layer was prepared by mixing 100 parts by weight of a styrene-maleic acid copolymer with 50 parts by weight of kaolin. A label for heat-sensitive recording was produced in the same manner as in 317 Example 115 except for forming a back coating layer by applying the aforesaid coating liquid on the side reverse to the side coated with a heat-sensitive recording layer of the label for heat-sensitive recording of Example 115 in an amount of 1 g/m 2 in terms of dry weight, followed by drying, and the label was evaluated. The results obtained are summarized in Table 7.

EXAMPLE 117 E) Preparation of a coating liquid for intermediate layer A coating liquid for intermediate layer was prepared which was composed of 80 parts by weight (in terms of dry solids) of a 48% dispersion of polystyrene fine particles and 20 parts by weight (in terms of dry solids) of a 40% styreneacrylic ester copolymer emulsion.

A label for heat-sensitive recording was produced in the same manner as in Example 116 except for forming an intermediate layer by applying the aforesaid coating liquid between the heat-sensitive recording layer and substrate of the 15 label for heat-sensitive recording of Example 116 in an amount of 8 g/m 2 in terms of dry weight, followed by drying, and the label was evaluated. The results obtained are summarized in Table 7.

e°o EXAMPLE 118 F) Preparation of a coating liquid for protective layer Twenty parts by weight of zinc stearate, 20 parts by weight of a 5 wt% methyl cellulose aqueous solution and 60 parts by weight of water were mixed and then subjected to dispersion in a sand grinder for 2 hours. Then, 20 parts by weight of a 10 wt% carboxy-modified poly(vinyl alcohol) aqueous solution, parts by weight of silica, 6.5 parts by weight of a 12.5 wt% polyamidoepichlorohydrin aqueous solution and 15.0 parts by weight of water were mixed and then subjected to dispersion in a sand grinder for 2 hours.

Subsequently, 0.7 part by weight of the zinc stearate dispersion obtained above, 45.0 parts by weight of the silica dispersion obtained above and 11.3 parts by weight of water were mixed to prepare a coating liquid for protective layer. A label for heat-sensitive recording was produced in the same manner as in Example 117 except for forming a protective layer by applying the aforesaid 318 coating liquid on the heat-sensitive recording layer of the label for heat-sensitive recording of Example 117 in an amount of 3 g/m 2 in terms of dry weight, followed by drying, and the label was evaluated. The results obtained are summarized in Table 7.

COMPARATIVE EXAMPLE 21 A heat-sensitive recording sheet was produced in the same manner as in Example 115 except for using 2,2-bis(4-hydroxyphenyl)propane in place of the urea-urethane compound used in Example 115, and was evaluated. The results obtained are summarized in Table 7.

o *•*oo *oe• *oo *o oooo* *o o 9 9 9 319 Table 7 Main constituentsPlsize of urea-urethane caxposition Sensitivity of rssac oa thermal paper (print evaluation General forriula Structural fornuila preserv- I 1 ii- Y ~xm1 (E-24) 1 1 0~ p3)C A FxAinlpl t 116 (E-24) 1 3 p 0 Rv~mplfn 117 (E-24) 1-4 p 0 EXAmpale 1 hR (E-24) 1 -3 Comparative1. x 1. Sensitivity becomes higher with an increase of optical density (OD value).

2. Plasticizer resistance (print preservability) 0 -Substantially no fading.

0 A slight color tone change without blur and the like.

A-Marked f ading.

X -Complete loss of the color of print.

320 EXAMPLE 119 The coating materials for heat-sensitive color-producing layer and coating material for intermediate layer described below were applied on one side of a commercial poly(ethylene terephthalate) film of 75 lam in thickness (Lumilar E, a trade name, Toray Industries, Inc.) so that the following multiple layers might be formed on the substrate in the following order: a cyan color development heatsensitive recording layer, an intermediate layer, a magenta color development heat-sensitive recording layer, an intermediate layer, a yellow color development heat-sensitive recording layer, and an intermediate layer. The application was carried out by bar coating so that the coating amounts of each heat-sensitive recording layer and each intermediate layer after drying might be 6.5 g/m 2 and g/m 2 respectively, whereby a multicolor heat-sensitive recording material was obtained.

Preparation of a coating material for cyan color development heat-sensitive 15 recording layer Liquid A (a heat-sensitive color-developable dye dispersion) Twenty parts by weight of 3,3-bis(p-dimethylaminophenyl)-6dimethylaminophthalide, 20 parts by weight of a 10% poly(vinyl alcohol) aqueous solution and 10 parts by weight of water were mixed and then subjected to 20 dispersion and grinding in a sand grinder (mfd. by AIMEX CO., LTD.) to prepare a S: dispersion having an average particle size of 0.7 lam.

C

Liquid B (a developer dispersion) A urea-urethane compound was synthesized in the same manner as in Example 24, and a dispersion was prepared by dispersing 30 g of this compound by grinding it together with 120 g of a 2.5 wt% poly(vinyl alcohol) aqueous solution in a sand grinder for 3 hours. The temperature of the dispersion immediately after the dispersing operation was 25°C. The diameter of dispersed particles of the compound was 0.6 lam.

A coating material for cyan color development heat-sensitive colorproducing layer was prepared by mixing 30 parts by weight of the liquid A, 120 parts by weight of the liquid B, 52 parts by weight of a 60% calcium carbonate 321 slurry, 40 parts by weight of a 10% poly(vinyl alcohol) aqueous solution, 28 parts by weight of an SBR latex (L-1537, a trade name, ASAHI Chemical Industry, Co., Ltd.; solid content 11 parts by weight of stearamide (Celozol A-877, a trade name, mfd. by Chukyo Yushi Co., Ltd.; solid content 26.5%) and 82 parts by weight of water.

Preparation of a coating material for magenta color development heatsensitive recording layer Liquid A (a heat-sensitive color-developable dye dispersion) Twenty parts by weight of 4-N-(2-(2,4-di-tertamylphenoxy)butyryl)piperazinobenzenediazonium hexafluorophosphate, parts by weight of a 10% poly(vinyl alcohol) aqueous solution and 10 parts by weight of water were mixed and then subjected to dispersion and grinding in a sand grinder to prepare a dispersion having an average particle size of 0.7 I.m.

Liquid B (a coupler dispersion) 15 Fifty parts by weight of 1-(2'-octylphenyl)-3-methyl-5-pyrazolone, 50 parts by weight of 1,2,3-triphenylguanidine, 50 parts by weight of a 10% poly(vinyl alcohol) aqueous solution and 25 parts by weight of water were mixed and then subjected to dispersion and grinding in a sand grinder to prepare a dispersion having an average particle size of 1.0 lm.

20 A coating material for magenta color development heat-sensitive colorproducing layer was prepared by mixing 30 parts by weight of the liquid A, parts by weight of the liquid B, 52 parts by weight of a 60% calcium carbonate slurry, 40 parts by weight of a 10% poly(vinyl alcohol) aqueous solution, 28 parts by weight of an SBR latex (L-1537, a trade name, ASAHI Chemical Industry, Co., Ltd.; solid content 11 parts by weight of stearamide (Celozol A-877, a trade name, mfd. by Chukyo Yushi Co., Ltd.; solid content 26.5%) and 82 parts by weight of water.

Preparation of a coating material for yellow color development heatsensitive recording layer 322 Liquid A (a heat-sensitive color-developable dye dispersion) Twenty parts by weight of 2,5-dibutoxy-4tolylthiobenzenebenzenediazoniurn hexafluorophosphate, 20 parts by weight of a poly(vinyl alcohol) aqueous solution and 10 parts by weight of water were mixed and then subjected to dispersion and grinding in a sand grinder to prepare a dispersion having an average particle size of 0.7 pim.

Liquid B (a coupler dispersion) Fifty parts by weight of 2-chloro-5-(3-(2,4-di-tertpentyl)phenoxypropylamino)acetanilide, 50 parts by weight of 1,2,3triphenylguanidine, 50 parts by weight of a 10% poly(vinyl alcohol) aqueous solution and 25 parts by weight of water were mixed and then subjected to dispersion and grinding in a sand grinder to prepare a dispersion having an average particle size of 1.0 pm.

A coating material for yellow color development heat-sensitive color- 15 producing layer was prepared by mixing 30 parts by weight of the liquid A, parts by weight of the liquid B, 52 parts by weight of a 60% calcium carbonate slurry, 40 parts by weight of a 10% poly(vinyl alcohol) aqueous solution, 28 parts by weight of an SBR latex (L-1537, a trade name, ASAHI Chemical Industry, Co., Ltd.; solid content 11 parts by weight of stearamide (Celozol A-877, a trade 20 name, mfd. by Chukyo Yushi Co., Ltd.; solid content 26.5%) and 82 parts by weight of water.

SI*: Preparation of a coating material (solid content: 15%) for intermediate layer A coating material for intermediate layer was prepared by mixing 42 parts 25 by weight of a 60% kaolinite clay (average particle size: 0.6 pm) dispersion, 200 parts by weight of a carboxylic acid-modified poly(vinyl alcohol) aqueous solution (Gohsenol T-330, a trade name, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.; solid content 100 parts by weight of an acrylic emulsion (SC- 2250, a trade name, mfd. by Nippon Shokubai Co., Ltd.; solid content 33 parts by weight of a dimethylolurea solution (J-001, a trade name, mfd. by Showa Denko solid content 13 parts by weight of a 40% zinc stearate dispersion (Highmicron F-930, a trade name, mfd. by Chukyo Yushi Co., Ltd.; average 323 particle size 0.9 pim), 70 parts by weight of heavy calcium carbonate (NS-1000, a trade name, mfd. by Nitto Funka Kogyo Co., Ltd.), 25 parts by weight of a urethane acrylate emulsion (EM90, a trade name, mfd. by Arakawa Chemical Industries Ltd.; solid content 5 parts by weight of a polysiloxane (SM7025, a trade name, mfd. by Dow Corning Toray Silicone Co., Ltd.; solid content 33%) and 40 parts by weight of water.

EXAMPLE 120 An example of the production of a two-color heat-sensitive recording material is described below.

Leuco dye for high-temperature color-producing layer: dibutylamino-2'-hydroxyphenyl)-3-(5'-anilino-4'-methyl-2'methoxyphenyl)phthalide.

Leuco dye for low-temperature color-producing layer: 3-diethylamino- 7-chlorofluoran.

15 Developer: the urea-urethane compound synthesized in Example 119.

Sensitizer: diphenyl sulfone.

Forty grams of each of the above-mentioned organic compounds to (D) was mixed with 40 g of a 10% poly(vinyl alcohol) solution (degree of polymerization 500, and degree of saponification 90%) and 20 g of water, and each of the 20 thus obtained compositions was subjected to dispersion in a vertical sand mill (a sand grinder manufactured by AIMEX CO., LTD.) so that the particle size might be 1 pm, whereby dispersions were prepared as liquids to corresponding S: to the compounds to respectively.

On the other hand, 40 g of light calcium carbonate (Brilliant 15, mfd. by 25 Shiraishi Industrial Co., Ltd.; average particle size 0.15 jim) and 60 g of a 0.7% sodium hexametaphosphate solution were mixed, and the resulting composition was subjected to dispersion in a Cowles dispersing machine.

Separately, a 21% zinc stearate dispersion was prepared as a lubricant dispersion, a liquid and a 10% poly(vinyl alcohol (NM11, mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) was prepared as an adhesive liquid Preparation of a coating liquid for high-temperature color development heat-sensitive layer 324 A coating liquid for high-temperature color development heat-sensitive layer was prepared by blending the above-mentioned liquids and (G) so that their weight ratio after drying might be as follows: 20 25: Formation of a high-temperature color development heat-sensitive layer A high-temperature color development heat-sensitive layer was formed by applying the aforesaid coating liquid for high-temperature color development heat-sensitive layer on woodfree paper (neutral paper) with a basis weight of g/m 2 in an amount of 8 g/m 2 in terms of dry weight by means of a Mayer bar.

Preparation of a coating liquid (11) for low-temperature color development heat-sensitive layer A coating liquid for low-temperature color development heat-sensitive layer was prepared by blending the above-mentioned liquids and so that their weight ratio after drying might be as follows: (E) (G)=10 20 20 20 10 Production of a two-color heat-sensitive recording material The coating liquid (11) for low-temperature color development heat-sensitive layer was applied on the above-mentioned high-temperature color development heat-sensitive layer in an amount of 5 g/m 2 in terms of dry weight. Then, the 20 Bekk smoothness (JIS-P8119) of the heat-sensitive recording surface was adjusted to 150 seconds by smoothing treatment by means of a supercalender, whereby a two-color heat-sensitive recording material was obtained.

oooo COMPARATIVE EXAMPLE 22 multicolor heat-sensitive recording material was produced in the same 25 manner as in Example 119 except for using 2,2-bis(4-hydroxyphenyl)propane in place of the urea-urethane compound synthesized in Example 119, and was evaluated. The results obtained are summarized in Table 8.

COMPARATIVE EXAMPLE 23 A two-color heat-sensitive recording material was produced in the same manner as in Example 120 except for using 2,2-bis(4-hydroxyphenyl)propane in place of the urea-urethane compound used in Example 120, and was evaluated.

The results obtained are summarized in Table 8.

Evaluation of the multicolor heat-sensitive recording materials 325 The multicolor heat-sensitive recording materials obtained in Examples 119 and 120 and Comparative Examples 22 and 23 were subjected to printing by the use of a commercial thermal printer (NC-1, a trade name, mfd. by Fuji Photo Film Co., Ltd.), and the quality of image and the image preservability were evaluated by the following methods.

<Quality of image> For 5 sheets of each recording material, the definition, contrast, density nonuniformity of image, and the like were visually judged and they were evaluated in the following 5 grades; o: good, 0 A: somewhat good, mediocre, A x: somewhat bad, x: bad.

<Image preservability> Each recording material was held between vinyl chloride wrap films or in a vinyl chloride file, and a load of 300 g/cm 2 was applied thereto from above. After standing at 40 0 C for 24 hours, the coloring density of the printed portion and the 15 non-printed portion (the original recording material surface) was visually estimated. When there was only a slight decrease in print density, the image preservability was rated good.

The results obtained are as shown in Table 8. That is, the recording materials of Examples 119 and 120 were good in quality of image and exhibited 20 an excellent image preservability, while the recording materials of Comparative Examples 22 and 23 were inferior to the recording materials of Examples 119 and 120.

S. S 55

S

S S S S S S *S S 326 Table 8 Main constituents of urea-urethane carosition Quality of Image Total Structural image preservability evaluation General formila foy 11 a 19(y) (E-24) no__ Eape120 (E-24) o Comparative

A-

Fxnmipl 22 Comparative x Fxgmpl I 3 u- 2 1. Quality of image 0 Good.

a -Mediocre.

x Bad.

2. Print preservability -Substantially no fading.

0 A slight color tone change without blur and the like.

A Marked fading.

x Complete loss of the color of print.

327 EXAMPLE 121 A urea-urethane compound was synthesized in the same manner as in Example 24, and a dispersion was prepared by dispersing 2 g of this compound by grinding it together with 8 g of a 2.5 wt% poly(vinyl alcohol) aqueous solution in a paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersing operation was 25°C. The diameter of dispersed particles of the compound was 0.6 gm.

Further another dispersion was prepared by dispersing 70 g of diphenyl sulfone by grinding it together with 130 g of a 5.4 wt% poly(vinyl alcohol) aqueous solution in a sand grinder (mfd. by AIMEX CO., LTD.; vessel capacity 400 ml) at a 15 number of revolution of 2,000 rpm for 3 hours.

On the other hand, an aluminum hydroxide dispersion was prepared by treating a mixture of 60 parts by weight of aluminum hydroxide and 40 parts by 20 weight of a 12.5 wt% poly(vinyl alcohol) aqueous solution for 2 hours by the use of a sand grinder to disperse aluminum hydroxide so that the average particle size might be about 1 pm.

SA coating liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (dry basis 25 proportions); the dispersion of the above-mentioned compound in terms of dry solids: 20 parts by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran dispersion in terms of dry solids: 10 parts by weight, the diphenyl sulfone dispersion in terms of dry solids: 25 parts by weight, the calcium carbonate dispersion in terms of dry solids: 40 parts by weight, the aluminum hydroxide dispersion in terms of dry solids: 13 parts by weight, a zinc stearate dispersion (solid content: 16 wt%) in terms of dry solids: 20 parts by weight, and a 15 wt% poly(vinyl alcohol) in terms of dry solids: 15 parts by weight.

328 Subsequently, this coating liquid for heat-sensitive recording layer was applied on aluminized paper at a rate of 50 m/min by the use of a gravure coater (200 mesh; plate depth 20 The aluminized paper thus treated was dried at for 3 seconds to obtain a heat-sensitive recording layer of 2 in thickness.

Then, a clear coating liquid composed of an aqueous dispersion of an acrylic resin (composed mainly of methyl methacrylate units, 2-ethylhexyl acrylate units and styrene units, and having a glass transition point of about 40 0 C) was applied on the coated surface of the aluminized paper to a thickness of 8 p. by the use of a roll coater and dried at 80°C for 10 seconds to obtain metallized paper for laser marking according to the present invention.

The metallized paper was irradiated with laser beams from a carbon dioxide laser. A clear mark could be obtained and the color developability was good. A plasticizer resistance test was carried out by holding the metallized paper between wrap films, to find that the plasticizer resistance was so good that 15 no fading of print portion was caused. The results obtained are summarized in Table 9.

EXAMPLE 122 i A urea-urethane compound was synthesized in the same manner as in Example 85, and a dispersion was prepared by dispersing 2 g of this compound by grinding it together with 8 g of a 2.5 wt% poly(vinyl alcohol) aqueous solution in a paint shaker for 6 hours.

Then, metallized paper for laser marking was produced in the same e manner as in Example 121 except for using the dispersion of the aforesaid compound in place of the dispersion of the compound obtained in Example 121, 25 and using diphenyl sulfone in place of aluminum hydroxide, and was evaluated.

The results obtained are summarized in Table 9.

COMPARATIVE EXAMPLE 24 Metallized paper for laser marking was produced in the same manner as in Example 121 except for using 2,2-bis(4-hydroxyphenyl)propane in place of the urea-urethane compound synthesized in Example 121, and was evaluated. The results obtained are summarized in Table 9.

329 <Color development sensitivity> An article for laser marking was irradiated with laser beams in a dose of 0.6 J/cm 2 from a carbon dioxide laser (Unimark, mfd. by USHIO INC.) through a stencil capable of permitting appearance of figures. When a clear mark was obtained and the coloring density was high, the color development sensitivity was rated good.

<Pasticizer resistance> Three vinyl chloride wrap films were placed on each of the top and under surfaces of the marked article for laser marking, and the resulting assembly was allowed to stand under a load of 300 kg/cm 2 at 400C for 24 hours. After the standing, the color density of print portion was visually estimated. When there was only a slight decrease in print density, the print preservability was rated good.

e *oo 330 Table 9 Main constituents of urea-urethane Plasticizer ccnpositiofl Marking resistance Total Structural sensitivity (print preserv- evaluation General forula fnrnil Fx m~l 121 (E-24) Fxamplte 122 (VI) 0 -0 Comparative Rxa~mnlte 24 0 X x 1. Marking sensitivity @-Good color developability. A clear mark can be obtained.

0o Somewhat insufficient color development without a problem about visibility.

x Low color developability and unclear print.

2. Plasticizer resistance (print preservability) @o Substantially no fading.

o A slight color tone change without blur and the like.

X -Complete loss of the color of print.

331 EXAMPLE 123 Production of upper paper A solution prepared by dissolving 2.5 parts by weight of 3-diethylamino-7chlorofluoran in 80 parts by weight of NISSEKI HISOL N-296 (an oil, a trade name, mfd. by Nippon Sekiyu Kagaku was emulsified in 100 parts by weight of a 5% aqueous solution of pH 4.0 prepared by dissolving a styrene-maleic anhydride copolymer together with a small amount of sodium hydroxide. On the other hand, when a mixture of 10 parts by weight of melamine, 25 parts by weight of a 37% aqueous formaldehyde solution and 65 parts by weight of water was adjusted to pH 9.0 with sodium hydroxide and heated at 60°C, the mixture became transparent after 15 minutes and a melamine-formaldehyde precondensate was obtained. The precondensate was added to the emulsion obtained above, and the resulting mixture was continuously stirred for 4 hours while maintaining the mixture at 60°C, and then was cooled to room temperature.

15 The solid content of the resulting microcapsule dispersion was The thus obtained microcapsule dispersion was applied on paper and 4 dried to obtain upper paper.

Production of under paper A dispersion was prepared by dispersing 15 g of a composition 20 synthesized in the same manner as in Example 7, by grinding it together with g of a 2 wt% poly(vinyl alcohol) aqueous solution in a paint shaker at ambient temperature for 45 minutes.

Another dispersion was prepared by mixing 60 g of calcium carbonate with 90 g of water and stirring the mixture by the use of a stirrer.

A coating liquid was prepared by mixing and stirring 40 parts by weight of the dispersion of the aforesaid composition, 125 parts by weight of the calcium carbonate dispersion and 120 parts by weight of a 10 wt% poly(vinyl alcohol) aqueous solution.

The coating liquid was applied on base paper with a basis weight of g/m 2 by the use of a bar coater of rod number 10 to obtain under paper.

332 The result of color density evaluation was so good that the optical density was 0.7.

The result of evaluating the solvent resistance by the use of hand cream was so good that reading of a print portion was possible. The results obtained are summarized in Table COMPARATIVE EXAMPLE A pressure-sensitive recording material was produced in the same manner as in Example 123 except for using activated clay as developer in place of the urea-urethane compound used in Example 123, and was evaluated. The results obtained are summarized in Table g *o *a* 90 0* 0 9 333 Table Main ccrlstitueflts Coloring density of Sletrssac of urea-Uretame carposition pressure- sensitive (hand cream) General forimila, Structural formula ape'r Exarrple 123 (E-24) 1.3o Ccrriarative activated clay 0.9 E'xFArpt- 2' 5_ 1. Coloring density becomes higher with an increase of optical density (OD value).

2. Solvent resistance (hand cream) -Substantially no fading.

0 A slight color tone change without blur and the like.

a Marked fading.

X Complete loss of the color of print.

INDUSTRIAL APPLICABILITY Employment of a specific urea-urethane compound makes it possible to provide at a low price a color-producing composition and a recroding material which are excellent in image preservability and color development sensitivity.

334 EXAMPLES 124-134 In the same manner as in Example 9, to 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of toluene as a solvent, followed by adding dropwise thereto a solution of 7.4 g of aniline in 37 g of toluene at room temperature over a period of 1 hour. The reaction was then carried out for another 1 hour. The white solids precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 20 g of white crystals (intermediate compound Subsequently, 5 g of thus obtained intermediate compound (I) was added to ethanol (Example 124), 1-propanol (Example 125), 2-propanol (Example 126), n-butyl alcohol (Example 127), isobutyl alcohol (Example 128), sec-butyl alcohol (Example 129) cyclohexanol (Example 130), 1-hexanol (Example 131), 1-decanol (Example 132), stearyl alcohol (Example 133) and benzyl alcohol (Example 134), respectively, instead of methanol used as an aliphatic alcohol in Example 9. The reaction was carried out at 60°C, after which 15 the excess solvent was removed by use of an evaporator and toluen was then o o added thereto. The resulting slurry was filtered to obtain white solids matter on a filter paper. The white solids matter was washed with n-hexane and then dried overnight in a vacuum to obtain a urea-urethane composition as white powder.

o* The molar ratio of materials fed, reaction conditions, HPLC purity (area ratio), melting point and estimated structure of the main constituent of the resulting ureaurethane composition in each reaction are collectively shown in Table 11.

6 Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned compositions (S- 1) to (S-11) in place of the urea-urethane compound synthesized in Example 1, 25 and was evaluated. The results obtained are summarized in Table 14.

EXAMPLES 135-138 In the same manner as in Example 9, to 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of toluene as a solvent, followed by adding dropwise thereto a solution of 7.4 g of aniline in 37 g of toluene at room temperature over a period of 1 hour. The reaction was then carried out for another 1 hour. The white solids precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 20 g of white crystals (intermediate compound Subsequently, 5 g of thus obtained intermediate compound (I) 335 was reacted dropwise with phenol (Example 135), o-methoxyphenol (Example 136), p-methylphenol (Example 137) and p-chlorophenol (Example 138) as an aromatic alcohol dissolved in 30 ml of MEK, instead of methanol used in Example 9. The reaction was carried out at 60°C, after which the excess solvent was removed by use of an evaporator and toluen was then added thereto. The resulting slurry was filtered to obtain white solids matter on a filter paper. The white solids matter was washed with n-hexane and then dried overnight in a vacuum to obtain a urea-urethane composition as white powder. The molar ratio of materials fed, reaction conditions, HPLC purity (area ratio), melting point and estimated structure of the main constituent of the resulting urea-urethane composition in each reaction are collectively shown in Table 11.

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned compositions (Eand in place of the urea-urethane compound synthesized in 15 Example 1, and was evaluated. The results obtained are summarized in Table 14.

EXAMPLES 139-144

V*

To 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of Stoluene as a solvent, followed by adding dropwise thereto a solution of 7.5 g of phenol in 37 g of toluene at 40°C over a period of 1 hour. The reaction was then carried out at 400C for another 1 hour. The white solids precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum

SO

to obtain 20.5 g of white crystals (intermediate compound Subsequently, 5 g o of thus obtained intermediate compound (II) was reacted dropwise with aniline (Example 139), 4-methylaniline (Example 140), 4-chloroaniline (Example 141), 2- (Example 142), ethyl amine (Example 143) and 4-methoxy benzene (Example 144) as an amine compound dissolved in ml of MEK. The reaction was carried out at 300C, after which the excess solvent was removed by use of an evaporator and toluen was then added thereto.

The resulting slurry was filtered to obtain white solids matter on a filter paper.

The white solids matter was washed with n-hexane and then dried overnight in a vacuum to obtain a urea-urethane composition as white powders. The molar ratio of materials fed, reaction conditions, HPLC purity (area ratio), melting point and 336 estimated structure of the main constituent of the resulting urea-urethane composition in each reaction are collectively shown in Table 12.

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned compositions (E- (E-44) and in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 14.

EXAMPLE 145 In the same manner as in Example 9, to 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of toluene as a solvent, followed by adding dropwise thereto a solution of 9.8 g of p-anisidine in 37 g of toluene at room temperature over a period of 1 hour. The reaction was then carried out for another 1 hour.

The white solids precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 22 g of white crystals.

15 Subsequently, 5.6 g of the thus obtained white crystals were reacted with 10g of phenol in 30 ml of MEK at 60°C, after which the excess solvent was removed by use of an evaporator and toluene was then added thereto. The resulting slurry was filtered to obtain white solids matter on a filter paper. The white solids matter was washed with n-hexane and then dried overnight in a vacuum to obtain 4.3 g 20 of a urea-urethane composition as white powder. The HPLC purity (area ratio) was 95%, the melting point was 176°C and the estimated structure of the main S constituent of the resulting urea-urethane composition was Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned composition (E-6) in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 14.

EXAMPLE 146 In the same manner as in Example 9, to 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of toluene as a solvent,. followed. by.adding dropwise thereto a solution of 10.7 g of p-aminoacetophene in 37 g of toluene at room temperature over a period of 1 hour. The reaction was then carried out for another 1 hour. The white solids precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 23 g of white 337 crystals. Subsequently, 5.8 g of the thus obtained white crystals were reacted with 10 g of phenol in 30 ml of MEK at 600C, after which the excess solvent was removed by use of an evaporator and toluen was then added thereto. The resulting slurry was filtered to obtain white solids matter on a filter paper. The white solids matter was washed with n-hexane and then dried overnight in a vacuum to obtain 4.5 g of a urea-urethane composition as white powder. The HPLC purity (area ratio) was 95%, the melting point was 1940C and the estimated structure of the main constituent of the resulting urea-urethane composition was Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned composition (E-7) in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 14.

EXAMPLE 147 15 To 39.9 g of 4,4'-diphenylmethane diisocyanate (MDI) instead of 2,4- *toluene diisocyanate in Example 9 was added 100 g of toluene as a solvent, followed by adding dropwise thereto a solution of 7.4 g of aniline in 37 g of toluene at room temperature over a period of 1 hour. The reaction was then carried out at room temperature for another 1 hour. The white solids precipitated 20 were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 25.7 g of white crystals. Subsequently, 6.4 g of the thus obtained white crystals were reacted with 10 g of phenol in 30 ml of MEK at 600C, after which the excess solvent was removed by use of an evaporator and toluene was then added thereto. The resulting slurry was filtered to obtain white solids matter on a filter paper. The white solids matter was washed with n-hexane and then dried overnight in a vacuum to obtain 4.8 g of a urea-urethane composition as white powders. The HPLC purity (area ratio) was 95%, the melting point was 210 0C and the estimated structure of the main constituent of the resulting ureaurethane composition was Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned composition (E- 338 in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 14.

EXAMPLE 148 The same procedures as in Example 4 were repeated except for using 3.7 g of 3,3'-diaminodiphenylsulfone instead of 3.7 g of 4,4'-diaminodiphenylsulfone, to obtain 5.0 g of a urea-urethane composition as white crystals. The estimated structure of the main constituent of the resulting urea-urethane composition was (E-21).

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned composition (E- 21) in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 14.

EXAMPLE 149 The same procedures as in Example 4 were repeated except for using 15 2.95 g of 4,4'-diaminodiphenylmethane instead of 3.7 g of 4,4'diaminodiphenylsulfone, to obtain 8.0 g of white crystals. Of these crystals, 3.6 g was taken to which 15 g of phenol was added to carry out the samer reaction as in Example 4. 4.7 g of a urea-urethane composition as white powders were obtained. The estimated structure of the main constituent of the resulting ureaurethane composition was (E-27).

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned composition (E- 27) in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 14.

EXAMPLES 150-153 In the same manner as in Example 9, to 27.8 g of 2,4-toluene diisocyanate in a flask was added 100 g of toluene as a solvent, followed by adding dropwise thereto a solution of 7.4 g of aniline in 37 g of toluene at room temperature over a period of 1 hour. The reaction was then carried out for another 1 hour. The white solids precipitated were recovered by filtration, washed with hexane and then dried overnight in a vacuum to obtain 20 g of white crystals (intermediate compound Subsequently, thus obtained intermediate compound was reacted with dipropylene glycol (Example 150), glycerin (Example 151), triethanol 339 amine (Example 152) and pentaerythriol (Example 153) at 30°C in 60 ml of trimethyl phosphate as a solvent, with 5 mg of dibutyltin laurate added as a catalyst. The reaction mixture was added to distilled water and filtered to obtain white solids matter on a filter paper. The white solids matter was dried overnight in a vacuum to obtain a urea-urethane composition as white powder. The molar ratio of intermediate compound and polyol, reaction conditions, HPLC purity (area ratio), melting point and estimated structure of the main constituent of the resulting urea-urethane composition in each reaction are collectively shown in Table 13.

Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using the above-mentioned compositions (S- 31), (S-34) and (S-35) in place of the urea-urethane compound synthesized in Example 1, and was evaluated. The results obtained are summarized in Table 14.

e* *S 6 S. S 5 .555 *5 S 5 55 55 S* *5S* *S *.55 340 Table 11 Materials used Reaction conditions Urea-urethane composition produced Inter- Molar Structural HPLC purity mediate Aliphatic alcohol used r Reaction Reaction Melting ratio Yield formula of of the main compound for the reaction temperature time point of the main constituent alcohol constituent (area ratio) Kind Amount [hr] [Co] Example 9 5 g Methanol 50 ml 1/67 60 0.5 5.4 92 196 Example 124 5 g Ethanol 50 ml 1/46 60 0.5 5.6 92 195 Example 125 5 g 1-Propanol 50 ml 1/36 60 0.5 5.7 91 179 Example 126 5 g 2-Propanol 150 ml 1/105 60 1.5 5.8 93 220 Example 127 5 g n-Butyl alcohol 35 ml 1/20 60 1.0 4.1 92 165 Example 128 5 g Isobutyl alcohol 100 ml 1/58 60 1.0 5.3 96 189 Example 129 5 g Sec-Butyl alcohol 100 ml 1/58 60 1.0 4.6 80 196 Example 130 5 g Cyclohexanol 100 ml 1/51 60 1.5 3.6 81 214 Example 131 5 g n-Hexanol 75 ml 1/32 60 1.5 4.3 99 161 Example 132 5 g 1-Decanol 100 ml 1/28 60 1.5 5.2 (S-10) 85 146 Example 133 5 g Stearyl alcohol *10 g 1/2 60 8.0 5.4 (S-11) 85 131 Example 134 5 g Benzyl alcohol 100 ml 1/52 60 1.5 5.3 (S-12) 90 209 Example 135 5 g Phenol *10 g 1/6 60 3 4.0 95 168 Example 136 5 g o-Methoxyphenol *10 g 1/4 60 3 4.6 90 135 Example 137 5 g p-Methylphenol *10 g 1/5 60 3 4.3 92 170 Example 138 5 g p-Chlorophenol *10 g 1/4 60 3 4.6 90 178 A solution of 10g of the alcohol in 30 ml of MEK was added to a flask and subjected to the reaction.

0 0 *0 00 0. 0 0* **00 00 00 0 0 0 0 0 @00 0 0 0 0 0 *000 0 00 00*0 341 Table 12 Materials used Reaction conditions Urea-urethane composition produced Inter- Molar mediate Amine compound used for ratio Reaction Reaction Yieldura fl of ofthrminy Melting compound the reaction of temperature time Yed fruao ftemi on (I)(I/the main constituent pon constituent (area ratio) 0 Kind Amount alcohol [CO] (hr] Example 139 5 g Aniline 1.65 g 1/0.95 30 0.25 5.94 97 177 Example 140 5 g 4-Methylaniline 1.90 g 1/0.95 30 0.25 6.17 (E-10) 97 215 Example 141 5 g 4-Chioroaniline 2.26 g 1/0.95 30 0.25 6.50 (E-11) 97 220

N-

Example 142 5 g diethylsulfamoyl 4.57 g 1/0.95 30 1 8.34 (E-13) 95 148 Example 143 5 g Ethyl amine 0.8 0 g 1/0.95 30 0.25 5.04 (E-44) 98 175 Example 144 5 g b-ehen y 2.18 g 1/0.95 30 0.25 6.43 97 173 9 60 Ob9 a too S e a* 4: to. 00 00 to 9 0 a 0.0 342 Table 13 Materials used Reaction conditions Urea-urethane composition produced Iner olrStructural HPLC purity Metn mediate Polyol used for the ratio Reaction Reaction Yild fomuaof ofthnmi compound reaction of temperature time Yil oml f o h an point* the main constituent (I plyl/constituent (area ratio) 0 Kind Amount [CO] [hr] Example 150 5.87 g Dpoye 1.34 g 1/2.2 30 89 3.5 (S-31) 68 186 Example 151 5.87 g Glycerin 0.61 g 1/3.3 30 97 3.3 (S-32) 62 217 Example 152 5.87 g Triethanol amine 0.99 g 1/3.3 30 23 3.5 (S-34) 73 1 251 Examle 153 4.81 g jPentaerythritol 0.51 g 1/4.8 30 20 3.1 (S-35) 70 225 Melting point was shown as a broad peak in each Example.

343 Table 14 Main constituents of urea-urethane Heat resistance OClifffrnI.gi t17 flf n_ Sensitivity Print Preservaof thernal Plasticizer preserva- bility of Total Genral S a paper resistance bility at original evaluation fornula fornula COD value) 60 0 C recording material surface at DrrlpS 8Ld 1 (q-1 1 -20 A ~PVA~I 14. AR- A E~n lP 1 9 5 S3.L-I 1 -1 5 F'm l P126 J4( r 4 5CS 1 1 7. A iP 127l (r (r q 1 1 7 A nl Rn.leJ1 Lc.LP Lr,) 1 1 7 A C vAnlP 13 2C 1j) q- 0 n Rmaple..2 P 110LL 1r 05 A A A5 0A F-%apl eJ 1,41 (Sr)LL. 1 0 0 A AA Rm= P 12.L H I dL. 1.21L 1 .05 A FbmEM1 j P 1 r C s 19 1 1 9, A Fb-C e.J3.P 15 2J 1 -1 R A Eknr=1 P 1 'if (T 1 1l. A A Contin'd 344 Contin'd E nD:I VAR (T )E5F-5 1 1 -9.1 n f Ean, 1ai.3i. (T IE(. -R 1 -2 7 a RmLM e 40l (T I P, 1 1 1 0 a Exa=1 JA P1 141 V.1 1 1 n A Eru1 F, 42. T EL&L -I EKagl P 143. (T (F-44) 0 95 FbnM eL 144 0 9 AA F!,Aa lP 14. 1~i 122 A A Em~l t- 46. 7 1L 1 1 C; A E~m= e 147. TL) 4P. 15L; 1 0 0 l 1aJ4R (R-21 1 -A 0A E-,npl P 49. P, E921 1 1 2A e 190D 4f)4 gL 1 0 1 P~kAu 1 5L 4...qL -3.Z 1 20 P 59, f I g(a) S-3 4L 1 2t EnM=1 F 11 a) 44- 4S1 1 1 n A 1. Sensitivity becomes higher with an increase of optical density (OD value).

2. Plasticizer resistance (print preservability) @o Substantially no fading.

0 A slight color tone change without blur and the like.

A- Marked fading.

x Complete loss of the color of print.

345 3. Heat resistance (print preservability at 60 0

C)

Substantially no fading.

o A slight color tone change without blur and the like.

S~ Marked fading.

x Complete loss of the color of print.

4. Heat resistance (the preservability of an original recording material surface at 0

C)

S~ Substantially no fog was caused.

S~ Reading of a print portion was difficult owing to fog.

x Reading of a print portion was impossible owing to serious fog.

346 Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

;i oooo *o o** oo o

Claims

1- ,C :0 N N N" H H H OH3 (S-37) 0 0 N N II- N"' H H H (S-38) 0 3 n-C3H7N,

11- 0 0 N N N' H H H 353 (S-39) (5-40) (S-41) (S-42) (S-43) (S-44) 0 11 H 0 11 i-C 4 H 9 0 ll N H 0 11 S-C 4 H 9 0 .cl~ H 9 9* *4*9 9 0 9000 4 9~ .9 4 0 9. 4. 9 9 4 9 9 4994 9 (S-46) (S-47) 0 o- I H 2 I 354 (S-48) H3 (S-49) r r r P C O C n 3 H 7 0 N (S-51) H31 (S-52) (S-53) (S-54) 355 (S-56) (S-57) (S-58) 0 (S-59) (S-61) 0 'Aj 0-OH 3 H (S-62) (S-63) 356 (S-64) H H H 3 C CH3 x, O-C-CHO N H HH (S-66) ?H 3 H N IN 0(C CH-0 N N N H2 kH H OH 3 (S-67) Nj 01iN Hi I H H H 2 C-O C H 3 HC-OC j I H NH H 2 -U HT OH 3 C-N IC3 N I H H (S-68) H3C H H I 357 (S-69 H OH 3 1 H2 H2 0 J N--C-cO--C-N H H H 3 OCH 3 H2 9 C C--c-0-C-N N N H H 2. A color-producing composition comprising a urea-urethane compound, wherein the melting point of the urea-urethane compound is not higher than 5000C and not lower than 400C, and the urea-urethane compound is at least one 5 selected from the group consisting of the following general formulas (111), (VI) and (VII): O O 0 0 II II X-0-C-N-Y-N-C-N-Z (I) S: H H H wherein X and Z are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each of the 10 residues may have one or more substituents, and Yo is a group selected from the group consisting of tolylene group, xylylene group, naphthylene group, hexamethylene group and -<-CH 2 group wherein is a phenylene group; 0 0 0 11 II II X-0-C-N N-C--YN-CC--OX I I H H H H 358 wherein X and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, and each of the residues may have one or more substituents; 0 0 fX-O-C-N-Y-N-C-N ja(l) H H H/ n wherein X and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, a is a residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents; II II o Z-N-,,C-N-Y-N-C0#10 (IV) H H H n wherein Z and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, 13 is a residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or more substituents; O U r*~ DI Y iH-- 0 L (V) HK^^H HK K^ 1 H HK>^H wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue though the substituent may be a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, a sulfamoyl group or a halogen atom, each of the residues may have one or more substituents, y is a group selected from the group 359 consisting of -(OH 2 -CONH- and any of groups represented by the formulas OH 3 O H 3 OH 3 OH 3 OH 3 IOH 3 0- or is absent, and n is 1 or 2; 3H ~N--N-jT (VI) HC KH H 0, 360 wherein hydrogen atom(s) of each benzene ring may be replaced by a substituent which is preferably an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue though the substituent may be a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, each of the residues may have one or more substituents, 8 is a group selected from the group consisting of -SO 2 -(CH 2 -CONH-, CH(COOR 1 -C(CF 3 2 and -CR 2 R 3 or is absent, each of R 1 R 2 and R 3 is an alkyl group, and n is 1 or 2; 0 0 II H H II H X-O-C-N-Y-N-C-N-Z (VI I) wherein X, Y and Z are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each of the S" 15 residues may have one or more substituents, and each of X, Y and Z is preferably an aromatic compound residue or a heterocyclic compound residue. 3. A color-producing composition according to claim 2, further comprising a diluent. 4. A color-producing composition according to claim 3, wherein the diluent is 20 a urea compound and/or a urethane compound. A color-producing composition according to claim 3, wherein the diluent is a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound. 6. A color-producing composition according to any one of claims 3 to wherein the urea-urethane composition is one obtained by reacting a polyisocyanate compound with a hydroxy compound and an amino compound, which is characterized by comprising 50 wt% or more of a urea-urethane 361 compound having at least one urea group and at least one urethane group in a total number of 2 to 10 in the molecular structure and having a molecular weight of 5,000 or less. 7. A color-producing composition according to any one of claims 3 to 6, wherein the urea-urethane composition is one obtained by reacting a polyisocyanate compound with a hydroxy compound so that the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents of the hydroxy compound becomes 100/1 to 1/2, to form one or more urethane groups from some of the isocyanate groups of the polyisocyanate compound, and then adding an amino compound thereto to react the same with the remaining isocyanate group(s) of the polyisocyanate compound to form one or more urea groups. 8. A color-producing composition according to any one of claims 3 to 6, Swherein the urea-urethane composition is one obtained by reacting a A 15 polyisocyanate compound with an amino compound so that the ratio of the number of moles of the polyisocyanate compound to the number of amino equivalents of the amino compound becomes 100/1 to 1/2, to form one or more urea groups from some of the isocyanate groups of the polyisocyanate S compound, and then adding a hydroxy compound thereto to react the same with 20 the remaining isocyanate group(s) of the polyisocyanate compound to form one or more urethane groups. 9. A color-producing composition according to claim 7 or 8, wherein the urea- urethane composition is one obtained by successively carrying out the reaction for forming one or more urethane groups and the reaction for forming one or more urea groups. A color-producing composition which comprises a urea-urethane composition obtained by reacting an amino compound with a polyisocyanate adduct obtained by the reaction of a polyisocyanate compound with a hydroxy compound, so that the equivalent ratio of isocyanate group to amino group 362 becomes 2/1 to 1/100, to form one or more urea groups, and then removing the unreacted amino compound. 11. A color-producing composition which comprises a urea-urethane composition obtained by reacting a hydroxy compound with a polyisocyanate adduct obtained by the reaction of a polyisocyanate compound with an amino compound, so that the equivalent ratio of isocyanate group to hydroxyl group becomes 2/1 to 1/100, to form one or more urethane groups, and then removing the unreacted hydroxy compound.

12. A color-producing a composition according to any one of claims 7 to 11, wherein the urea-urethane composition is one obtained by carrying out the reaction for forming one or more urethane groups and/or the reaction for forming one or more urea groups, without a solvent, or carrying out the reaction for forming one or more urethane groups and the reaction for forming one or more urea groups, by the use of the same solvent. :15 13. A color-producing composition according to any one of claims 7 to 12, wherein the urea-urethane composition is one obtained by carrying out the reaction for forming one or more urethane groups and/or the reaction for forming one or more urea groups at a temperature of 0 3000C.

14. A color-producing composition according to any one of claims 7 to 13, 20 wherein the urea-urethane composition is one obtained by carrying out the reaction for forming one or more urethane groups and/or the reaction for forming one or more urea groups in the presence of a catalyst. A color-producing composition according to any one of claims 5 to 14, wherein the hydroxy compound is a phenolic compound.

16. A color-producing composition according to any one of claims 5 to 14, wherein the hydroxy compound is an alcohol compound. 363

17. A color-producing composition according to any one of claims 5 to 16, wherein the amino compound is an aromatic amino compound.

18. A color-producing composition according to any one of claims 5 to 17, wherein the polyisocyanate compound is an aromatic polyisocyanate compound.

19. A color-producing composition according to any one of claims 2 to 18, further comprising a colorless or light-colored dye precursor. A color-producing composition according to claim 19, wherein the colorless or light-colored dye precursor is a leuco dye.

21. A color-producing composition according to claim 20, wherein the leuco dye is at least one leuco dye selected from triarylmethane type leuco dyes, fluoran type leuco dyes, fluorene type leuco dyes and diphenylmethane type leuco dyes. :22. A color-producing composition according to claim 20, wherein the leuco dye is a compound represented by the following formula N Y 2 :o Y 3 4 C=O "20 wherein both Y2 and Y3 are alkyl groups or alkoxyalkyl groups, Y4 is a hydrogen atom, an alkyl group or an alkoxy group, and each of Ys and Y6 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; or the following formula 364 R6 Rs R C O (j) R8 R1io R9 wherein each of R 5 and R 6 is a group represented by the formula or the formula R 11 (k) R12 R14 R13 (wherein each of R 11 through R 15 is a hydrogen atom, a halogen atom, a Ci-C 8 alkyl group, a Ci-Cs alkoxy group, or -NRI 6 R 17 wherein each of R 16 and R 17 S is an alkyl group of 1 to 8 carbon atoms), or 718 1 5 R19 (1) (wherein each of R 18 and R 1 9 is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms, or a phenyl group), and each of R 7 through Rio is a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or -NR 20 R 21 wherein each of R 20 and R 21 is an alkyl group of 1 to 8 carbon atoms. 365

23. A color-producing composition according to any one of claims 2 to 22, which further comprises a heat-meltable material.

24. A color-producing composition according to claim 23, wherein the heat- meltable material is at least one compound selected from p-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di(m-methylphenoxy)ethane, di-p-methylbenzyl oxalate, 1,2-diphenoxymethylbenzene, m-terphenyl and stearamide. A color-producing composition according to claim 23, wherein the heat- meltable material is that represented by the following structural formula (XVIII): 0Y (XVIII) 10 wherein Y is any of -SO 2 -CH 2 -CH(C 6 H 5 C(CH 3 2 -COCO-, -CO3-, -COCH 2 CO-, -COOCH 2 -CONH-, -OCHz and NH-, n is 1 or 2, and hydrogen atom(s) of each benzene ring may be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue.

26. A color-producing composition according to claim 23, wherein the heat- meltable material is that represented by the following structural formula (XIX): ~(xx) *0 wherein hydrogen atom(s) of each benzene ring may be replaced by a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a sulfamoyl group, a sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. 366

27. A color-producing composition according to any one of claims 2 to 26, which further comprises an isocyanate compound.

28. A color-producing composition according to claim 27, which further comprises an amino compound.

29. A color-producing composition according to claims 27 or 28, which further comprises an amino compound. A color-producing composition according to any one of claims 2 to 29, which further comprises an acidic developer.

31. A color-producing composition according to claim 30, wherein the acidic developer is at least one developer selected from 2,2-bis(4-hydroxy- phenyl)propane, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis(3-ally-4- hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone and 4,4'- [oxybis(ethyleneoxy-p-phenylenesulfonyl)]diphenol.

32. A color-producing composition according to any one of claims 2 to 31, 15 which further comprises a fluorescent dye. 0*

33. A color-producing composition according to any one of claims 1 to 32, S which further comprises a shelf-stability-imparting agent.

34. A recording material comprising a substrate and a color-producing layer formed thereon, said color-producing layer comprising a color-producing 20 composition according to any one of claims 2 to 33. A recording material according to claim 34, wherein in that a protective layer for the color-producing layer is formed on the color-producing layer.

36. A recording material according to claim 35, wherein the protective layer comprises a water-soluble polymer. 367

37. A recording material according to either of claims 35 and 36, wherein the protective layer comprises an inorganic pigment and/or an organic pigment.

38. A recording material according to any one of claims 35 to 37, wherein the protective layer comprises a lubricant.

39. A recording material according to any one of claims 34 to 38, wherein an intermediate layer is formed on the substrate and that the color-producing layer is formed on said intermediate layer. A recording material according to claim 39, wherein the intermediate layer comprises a water-soluble polymer.

41. A recording material according to claim 39 or 40, wherein the intermediate layer comprises an inorganic pigment and/or an organic pigment.

42. A recording material according to any one of claims 34 to 41, wherein a back coating layer is formed on the substrate on the side reverse to the side having the color-producing layer formed thereon. 15 43. A recording material according to claim 42, wherein the back coating.layer comprises a water-soluble polymer.

44. A recording material according to claim 42 or 43, wherein the back coating layer comprises an inorganic pigment and/or an organic pigment.

45. A recording material according to any one of claims 34 to 44, characterized by using at least one compound selected from water-soluble polymers and anionic surfactants, as a dispersing agent for the urea-urethane compound.

46. A recording material according to any one of claims 34 to 44, characterized by using at least one compound selected from poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate, polycarboxylic acid ammonium salts, water-soluble 368 low-molecular weight copolymers, and sodium 2-ethylhexylsulfosuccinate, as a dispersing agent for the urea-urethane compound.

47. A recording material according to any one of claims 34 to 46, characterized by using at least one compound selected from water-soluble polymers, nonionic surfactants and anionic surfactants, as a dispersing agent for a dye precursor.

48. A recording material according to any one of claims 36 to 46, characterized by using at least one compound selected from methyl cellulose, hydroxypropylmethyl cellulose, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ether sulfates and sodium 2-ethylhexylsulfosuccinate, as a dispersing agent for a dye precursor.

49. A recording material according to any one of claims 34 to 48, which is a heat-sensitive recording material.

50. A heat-sensitive recording material according to claim 49, wherein the average particle size of the urea-urethane compound is not more than 5 pm and 15 not less than 0.05 gm.

51. A heat-sensitive recording material according to claim 49 or 50, wherein a liquid temperature at grinding of the urea-urethane compound is 60°C or lower.

52. A heat-sensitive recording material according to any one of claims 49 to 51, wherein a pH at grinding of the urea-urethane compound is 5 to 20 53. A heat-sensitive recording material according to any one of claims 49 to 52, characterized by using at least one compound selected from water-soluble polymers and anionic surfactants, as a dispersing agent for a heat-meltable material.

54. A heat-sensitive recording material according to any one of claims 49 to 52, characterized by using at least one compound selected from poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl 369 cellulose, condensed sodium naphthalenesulfonate, polycarboxylic acid ammonium salts, water-soluble low-molecular weight copolymers, and sodium 2- ethylhexylsulfosuccinate, as a dispersing agent for a heat-meltable material. A heat-sensitive recording material according to any one of claims 49 to 54, wherein the urea-urethane compound and a heat-meltable material are finely ground together.

56. A heat-sensitive recording material according to any one of claims 49 to wherein the pH of the substrate surface to be coated with the heat-sensitive recording layer of the heat-sensitive recording material is 3 to 9.

57. A process for producing a heat-sensitive recording material according to any one of claims 49 to 56, characterized by applying on the substrate a heat- sensitive coating liquid of pH 5 to 12 for forming the heat-sensitive recording layer of the heat-sensitive recording material.

58. A recording material according to any one of claims 34 to 48, which is a S 15 heat-sensitive magnetic recording material.

59. A heat-sensitive magnetic recording material according to claim 58, wherein a heat-sensitive recording layer comprising a urea-urethane compound developer is formed on one side of the substrate, and a magnetic recording layer on the other side. -020 60. A railroad ticket that is a heat-sensitive magnetic recording material according to claim 58 or 59.

61. A ticket that is a heat-sensitive magnetic recording material according to claim 58 or 59.

62. A recording material according to any one of claims 34 to 48, which is a label for heat-sensitive recording. 370

63. A label for heat-sensitive recording according to claim 62, wherein a heat- sensitive recording layer comprising a urea-urethane compound developer is formed on one side of the substrate, and an adhesive layer on the other side.

64. A label for heat-sensitive recording according to claim 63, wherein a back coating layer is formed between the adhesive layer and the substrate. A label for heat-sensitive recording according to claim 63 or 64, wherein an intermediate layer is formed between the heat-sensitive recording layer and the substrate.

66. A label for heat-sensitive recording according to any one of claims 63 to 65, wherein a protective layer is formed on the heat-sensitive recording layer.

67. A recording material according to any one of claims 34 to 48, which is a multicolor heat-sensitive recording material.

68. A multicolor heat-sensitive recording material according to claim 67, wherein at least two heat-sensitive recording layers are formed on one side of the substrate, said recording material being characterized in that at least one of said heat-sensitive recording layers comprises a urea-urethane compound developer.

69. A multicolor heat-sensitive recording material according to claim 68, wherein an intermediate layer is formed between the heat-sensitive recording "layers. loll l• 20 70. A multicolor heat-sensitive recording material characterized by comprising a substrate and two heat-sensitive recording layers laminated on one side of the substrate which have different color development temperatures, respectively, and undergo color development in different color tones, respectively, the upper heat- sensitive recording layer comprising either an agent used both as developer and tone reducer, or a reversible developer, and the lower heat-sensitive recording layer comprising the urea-urethane compound of any one of claims 1 to 14 as a developer. 371

71. A multicolor heat-sensitive recording material according to claim wherein, of the two heat-sensitive recording layers, the upper layer is a low- temperature color-producing layer capable of undergoing color development at a low temperature and undergoing achromatization at a high temperature, and the lower layer is a high-temperature color-producing layer capable of undergoing color development at a high temperature.

72. An article for laser marking characterized by having on the surface a heat- sensitive recording layer comprising the urea-urethane compound of any one of claims 1 to 14 as a developer.

73. An article for laser marking characterized by having on the surface a heat- sensitive recording layer comprising a colorless or light-colored dye precursor, the urea-urethane compound of any one of claims 1 to 14 as a developer and a recording sensitivity improving agent.

74. An article for laser marking according to claim 72 or 73, characterized by having on the heat-sensitive recording layer a protective layer comprising an S aqueous binder having a glass transition point of 20 to 800C.

75. An article for laser marking according to claim 73, wherein the recording sensitivity improving agent is at least one compound selected from aluminum S" hydroxide, muscovite, wollastonite and kaolin. 20 76. An article for laser marking according to any one of claims 72 to 75, which is any of labels, packaging materials and containers. S 77. A process for producing an article for laser marking, characterized by i: applying on a substrate a color-producing marking composition comprising the urea-urethane compound of any one of claims 1 to 14 as a developer, and drying the thus treated substrate.

78. A process for producing an article for laser marking, characterized by applying on a substrate a color-producing marking composition comprising a colorless or light-colored dye precursor, the urea-urethane compound of any one 372 of claims 1 to 14 as a developer and a recording sensitivity improving agent, and drying the thus treated substrate.

79. A method for marking an article, characterized by irradiating the heat- sensitive recording layer of an article for laser marking according to any one of claims 72 to 76, with a laser beam. A color-producing marking composition characterized by comprising the urea-urethane compound of any one of claims 1 to 14 as a developer.

81. A color-producing marking composition characterized by comprising a colorless or light-colored dye precursor, a urea-urethane compound developer and a recording sensitivity improving agent.

82. A urea-urethane compound substantially as hereinbefore described with reference to the examples.

83. A colour-producing composition substantially as hereinbefore described with reference to the examples. 15 84. A recording material substantially as hereinbefore described with reference to the examples.

85. A process for producing a heat-sensitive recording material substantially as hereinbefore described with reference to the examples.

86. A label for heat-sensitive recording substantially as hereinbefore described 20 with reference to the examples.

87. An article for laser marking substantially as hereinbefore described with O: ~reference to the examples.

88. A process for producing an article for laser marking substantially as hereinbefore described with reference to the examples.

89. A method for marking an article substantially as hereinbefore described with reference to the examples. 373 A colour-producing marking composition substantially as hereinbefore described with reference to the examples. DATED this 3 d day of September 2004 ASAHI KASEI KABUSHIKI KAISHA WATERMARK PATENT TRADE MARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA CJH/GHO/MEH S oe o o go•