JP3501308B2 - Method for producing reversible thermosensitive recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
And a reversible thermosensitive recording material that can be erased and erased.
In particular, reversible thermosensitive recording material with excellent transparency of reversible thermosensitive recording layer
About. [0002] 2. Description of the Related Art In general, a thermosensitive recording material is formed on a support by an electronic recording medium.
Usually colorless or light-colored dye precursor and electron-accepting
A heat-sensitive recording layer containing a developer as a main component.
Heating with a thermal head, hot pen, laser light, etc.
The dye precursor and the developer react instantaneously to obtain a recorded image.
No. 43-4160, No. 45-
It is disclosed in, for example, JP-A-14039. In general, such a heat-sensitive recording material is once
When an image is formed, that part is erased and the state before image formation is returned.
It is impossible to revert, so record more information
In the case where the image is not
Was. For this reason, when the area of the thermal recording part is limited,
Means that the recordable information is limited and all necessary information can be recorded.
There was a problem of not being able to do so. In recent years, image formats have been developed to address
Consider a reversible thermosensitive recording material that can be repeatedly formed and erased.
For example, Japanese Patent Laid-Open No. 54-119377 discloses
, JP-A-63-39377, JP-A-63-41
In Japanese Patent Publication No. 186, a resin base material and a resin base material dispersed in the resin base material are disclosed.
Describes a reversible thermosensitive recording material composed of selected organic low molecules
Have been. However, this method uses heat energy
A material that reversibly changes the transparency of a reversible thermosensitive recording material
Therefore, the contrast between the image forming part and the image non-forming part is not sufficient.
Minutes. On the other hand, the color development state and the color erasure state are reversibly repeated.
A reversible thermosensitive recording material of color development / decoloration type
Have been. JP-A-2-188293, JP-A-2-
188294, International Publication No. WO 90/1189
No. 8 develops leuco dye by heating with leuco dye.
Reversible thermosensitive recording medium composed of color-degrading color erasing agent
Is described. Further, Japanese Patent Application Laid-Open No. 63-173684,
Japanese Unexamined Patent Publication (Kokai) No. 4-247895 discloses a leuco dye.
Additives and ascorbic acid derivatives, leuco dyes and organic phosphones
A reversible thermosensitive recording medium composed of a combination of an acid compound and the like is described.
Have been. [0007] The inventors of the present invention have developed the above-described color-developing / erasing type reversible feeling.
Better color / decoloration contrast than thermal recording materials
A reverse thermosensitive recording material is disclosed in JP-A-6-210954.
Proposed. [0008] Of these color-forming and decoloring type reversible thermosensitive recording materials,
The recording layer is the same as the recording layer of a general thermosensitive recording material.
Smear the coating solution containing the components to be contained in the layer on the support
It is formed. Coating liquid containing components to be contained in the recording layer
Method of dispersing each component in water or organic solvent, water or
Dissolve some components in organic solvent and disperse other components
Method, one that dissolves all components in water or organic solvent
It can be obtained by a method or the like. Of these, each component is dissolved in water or an organic solvent.
Dispersion method and some components in water or organic solvent
Dissolve and disperse other components
The resulting recording layer is cloudy and has a transparent recording layer.
Can not get. Also, soak in water or organic solvents.
Obtained using a coating liquid prepared by a method in which all components are dissolved.
To obtain a relatively transparent recording layer
May occur, but the refractive index of the components contained in the recording layer
Is greatly different or included in the recording layer when the recording layer is formed.
If the components to be crystallized, it is necessary to obtain a transparent recording layer.
Can not be. Therefore, a transparent reversible thermosensitive recording material must be obtained.
The recording layer is white even if a transparent support is used.
The purpose cannot be achieved because of the turbid state. Also,
Even for reversible thermosensitive recording materials whose support is not transparent,
If the reverse thermosensitive recording layer is cloudy, the sharpness of color development will be deteriorated,
In addition, characters and figures are placed between the support and the reversible thermosensitive recording layer.
When such information is formed, the visibility of this information
There was a very bad problem. As a method for dealing with such a problem, there is a special method.
JP-A-5-270127 discloses a color former and a developer.
Are fine particles each mixed with at least one binder.
Has been proposed. Also, JP
JP-A-5-104859 discloses an electron donating color compound.
, An electron-accepting compound and a refractive index of 1.45 to 1.6 at room temperature.
A thermosensitive recording layer containing a binder resin of
A binder having a refractive index of 1.45 to 1.6 on the thermal recording layer
A method of providing an overcoat layer containing a resin has been proposed. However, the above-mentioned method is applied to a reversible thermosensitive recording material.
If applied to the recording layer, isn't sufficient transparency obtained?
Or problems such as reduced color sensitivity or erasability
The reversible thermosensitive recording layer is transparent,
An image and a colorless and transparent decolored part can be formed,
A reversible thermosensitive recording material with good decoloring contrast can be obtained.
Could not be. [0013] The object of the present invention is to provide a reversible
The heat-sensitive recording layer is transparent, and the color-developed image and the colorless transparent decolored area
Can be formed and can be made transparent by using a transparent support.
A reverse thermosensitive recording material is obtained, and an opaque support is used.
In this case, the coloring is clear and the reversible
When characters or figures are formed between the thermal recording layer
Is a reversible thermosensitive recording with very good visibility of this information.
To provide recording materials. [0014] Means for Solving the Problems The present inventors have made intensive studies.
As a result, the reversible thermosensitive recording layer on the support is usually colorless or pale.
Difference between electron donating dye precursor of color and cooling rate after heating
Causes a reversible color change in the dye precursor
Coloring / decoloring type reversible heat sensitive mainly containing reversible developer
Reversible developer, electron donating
Dye precursor and carboxyl group-modified polyvinyl alcohol
And apply a coating solution containingTransparentReversible thermal recording
A method for forming a layer, wherein the coating liquid comprises a carboxyl group.
Modified polyvinyl alcohol aqueous solution, reversible developer and electron
The donor dye precursor is mixed, and the reversible developer in this mixed solution is mixed.
And the electron-donating dye precursor are simultaneously wet-milled.
The reversible thermosensitive recording material manufacturing method
Was. A reversible developer, an electron-donating dye precursor and
The coating solution containing ruboxyl group-modified polyvinyl alcohol,
It can be created using various methods. Then,
A specific example will be described. A reversible developer, an electron-donating dye precursor and
Ruboxyl-modified polyvinyl alcohol contained in coating liquid
One way to do this is to combine all these ingredients in water at the same time.
To dissolve the carboxyl group-modified polyvinyl alcohol
How to solve, carboxyl group modified polyvinyl alcohol in water
Dissolving the dye and adding it to the reversible developer and electron-donating dye.
Method of mixing precursor, reversible developer and / or electron donation
Water-soluble dye precursors alone or coexist
After pulverized, mixing with other components
You. The thus obtained reversible developer, electron
Donor dye precursor and carboxyl group-modified polyvinyl alcohol
Liquids containing alcohol, such as ball mills and sand mills
Before reversible developer and electron-donating dye in liquid
Forming a reversible thermosensitive recording layer by simultaneously grinding the precursor
To obtain a coating liquid. Wet crusher is acceptable
Powder reverse developer and electron-donating dye precursor to desired particle size
If it can be crushed, it can be used regardless of the method. The transparency of the recording layer includes a reversible developer, an electron donor
Dye precursor and carboxyl group-modified polyvinyl alcohol
Developer and electron donation dispersed in a coating solution containing a polymer
The smaller the volume average particle size of the dye precursor, the higher the
Particularly good transparency when their particle size is 1.5 μm or less
Shows sex. Therefore, the reversible developer and the electron-donating dye precursor
The volume average particle size of the body is preferably 1.5 μm or less. Ma
In addition, making these particle diameters extremely small is extremely difficult for grinding.
It takes a long time and is difficult to grind.
There is no. Thus, particularly preferred reversible developers and electron donors
The volume average particle size of the dye precursor is 0.1 to 1.5 μm.
is there. The reversible thermosensitive recording layer comprises a reversible developer, an electron donor
Dye precursor and carboxyl group-modified polyvinyl alcohol
Formed by applying a coating solution containing
It is. The smearing method is used for the production of general thermal recording materials.
Any smearing method can be used as well
You. According to the method for producing a reversible thermosensitive recording material of the present invention,
If you use a reversible developer that is hardly soluble in solvents,
A high reversible thermosensitive recording layer can be obtained. Also, the manufacturing method
The method is simple and can be used to manufacture other transparent thermosensitive recording materials.
Can be manufactured very easily and stably.
You. The method of the present invention is applied to a method having no reversibility.
When applied to general thermosensitive recording materials, color developer and electron donating property
After mixing with the dye precursor, wet pulverization
The precursor becomes a colored state, and the purpose can be achieved.
Absent. For this reason, the manufacturing method of the present invention has been
It was unthinkable. For reversible thermosensitive recording materials
After mixing the reversible developer and the electron-donating dye precursor, wet
The electron-donating dye precursor is very colored
Difficult to color
Heating at a lower temperature makes the colorless and colorless
And a transparent recording layer that is not used can be obtained. The carboxyl group-modified polyvinyl used in the present invention
Nyl alcohol has a carboxyl group or carboxy group on the side chain.
Polyvinyl alcohol having an acid salt group
No. 53-91995, vinyl acetate and male
Ethylenically unsaturated dica such as acid, fumaric acid, itaconic acid, etc.
Obtained by saponifying a copolymer with rubonic acid
However, there is no particular limitation on the manufacturing method.
No. Use carboxyl group-modified polyvinyl alcohol
To obtain a reversible thermosensitive recording layer with excellent transparency
Can be. Of carboxyl group-modified polyvinyl alcohol
Instead, use native polyvinyl alcohol or carboxy
Modified polyvinyl alcohol other than phenyl group, synthetic resin emulsion
The use of John or the like makes it possible to obtain a transparent reversible thermosensitive recording layer.
I can not do such a thing. Further, the carboxyl group modification used in the present invention
Polyvinyl alcohol is the carboxyl contained in the side chain
The number of groups or carboxylic acid groups is
1 to 1 of the number of hydroxyl groups contained in the side chain of the vinyl alcohol
20% is preferable, and 2-10% is preferable.
Particularly preferred. Carboxyl group-modified polyvinyl alcohol
Carboxyl group or carboxylate in the side chain of
If the number of groups is less than the above preferred range, reversible
The transparency of the heat-sensitive recording layer becomes insufficient and
The number of carboxyl groups or carboxylic acid groups
If it is more than the preferred range, color development / decoloration characteristics and image
It is not preferable because the stability becomes insufficient. Mosquito used in the present invention
Commercially available ruboxyl group-modified polyvinyl alcohol
For example, T. manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
-330, T-330H, T-350, etc.
Re KL-118, KL-318, KL-506, KM
-118 and KM-618, but are not limited to these.
It is not specified. Carboxyl group-modified poly in the reversible thermosensitive recording layer
The content of vinyl alcohol depends on the transparency of the reversible thermosensitive recording layer.
Affects the properties, color development / decoloration characteristics, and image stability. Mosquito
Low content of ruboxyl-modified polyvinyl alcohol
If not, the transparency of the reversible thermosensitive recording layer becomes insufficient
However, the coloring / decoloring characteristics and image stability are good. vice versa,
High content of carboxyl group-modified polyvinyl alcohol
In this case, good transparency of the reversible thermosensitive recording layer can be obtained.
However, the coloring / decoloring characteristics and image stability are insufficient. Good
Transparency of the reversible thermosensitive recording layer, good color development and
To obtain image stability at the same time, a carboxyl group-modified poly
Vinyl alcohol is usually colorless or light-colored electron-donating dye
1 to 200 weights based on the total amount of the colorant precursor and the reversible developer
%, Preferably 5 to 100% by weight
It is particularly preferred to do so. As the reversible developer used in the present invention, heating
Causes a reversible color change in the electron-donating dye precursor
The compound is not particularly limited as long as it is a compound to be used.
From the trust, repetition durability, etc.
Phenolic properties proposed in JP-A-6-210954
Including the reversible developer consisting of a compound,
The electron accepting compound used is preferably used. [0026] Embedded image In Formula 1, n represents 1, 2 or 3. m
Represents 0, 1 or 2. Q is an aliphatic hydrocarbon group,
Represents a xy group or a halogen atom. The ring represented by A is aromatic
It is a ring. X is an aromatic ring represented by A via a nitrogen atom
Divalent group (hereinafter referred to as the first category)
Huh. ), A divalent group containing two or more heteroatoms,
Groups that do not belong to the first category (hereinafter referred to as the second category)
Huh. ), An aromatic ring represented by A containing a nitrogen atom and the number of carbon atoms
A divalent group linked by one or more hydrocarbon groups,
Groups that do not belong to Class 2 (hereinafter referred to as Class 3)
Huh. ) Or a sulfone group, a carbon-carbon having 2 or more carbon atoms
A group containing an elementary multiple bond, a phenylene group, -CH = N-,
A group containing any one of the first, second, and third categories
A group that does not belong to the deviation (hereinafter, this is referred to as a fourth classification).
Represents R represents an aliphatic hydrocarbon group. Included in X and R
Excluding hydrogen atoms and atoms that make up the aromatic ring
The total number of atoms is eight or more. Specific examples of the substituent represented by Q include
Chill, ethyl, propyl, isopropyl, n-
Butyl group, t-butyl group, t-pentyl group, 2-ethyl
Aliphatic carbon such as hexyl group, cyclohexyl group and allyl group
Hydride group, methoxy group, ethoxy group, n-propyloxy
Si group, i-propyloxy group, n-butyloxy group, n
An alkoxy group such as an octyloxy group, fluorine, chlorine,
And halogen atoms such as iodine and iodine. As an example of the case where X is of the first class, -N
HCO-, -NH-, -NHCONH-, -NHCON
HNH-, -N = CH-, -N = N-, -NHSO
_Two-, -NHCO (p-C₆H_Four) NHCO-, -NHC
O (p-C₆H_Four) NHCONH-, -NHCO (p-C
₆H_Four) NHCOCONH-, -NHCO (p-C₆H_Four)
CONH-, -NHCO (p-C₆H_Four) CONHNHC
O-, -NHCO (p-C₆H_Four) OCONH-, -N
HCO (p-C₆H_Four) NHCOO-, -NHCOCH_Two
(M-C₆H_Four) NHCO-, -NHCOCH_Two(P-C₆
H_Four) NHCO-, -NHCOCH_Two(P-C₆H_Four) NH
CONH-, -NHCOCH_Two(P-C₆H_Four) NHCO
CONH-, -NHCOCH_Two(P-C₆H_Four) CONH
-, -NHCOCH_Two(P-C₆H_Four) CONHNHCO
-, -NHCOCH_Two(P-C₆H_Four) CONHNHCO
NH-, -NHCOCH_Two(P-C₆H_Four) CONHNH
COO-, -NHCOCH_Two(P-C₆H_Four) OCONH
-, -NHCOCH_Two(P-C₆H_Four) NHCOO-,-
NHCOCH_TwoCH_Two(P-C₆H_Four) NHCO-, -NH
COCH_TwoCH_Two(P-C₆H_Four) NHCONH-, -NH
COCH_TwoCH_Two(M-C₆H_Four) NHCOO-, -NHC
OCH_TwoCH_Two(P-C₆H_Four) NHCOCONH-, -N
HCOCH_TwoCH_Two(P-C₆H_Four) CONH-, -NHC
OCH_TwoCH_Two(P-C₆H_Four) CONHNHCO-, -N
HCOCH_TwoCH_Two(P-C₆H_Four) CONHNHCONH
-And the like. A hydrogen atom is bonded to a nitrogen atom
In such a case, the hydrogen atom is a methyl group, a cyclohexyl group, etc.
It may be substituted with an aliphatic hydrocarbon group. Among these
In this case, a urea bond is more preferable in terms of decoloring property and image density.
It is interesting that X is -CONH-, -COO-, -S-
In some cases, either the decolorability or the image density is unsatisfactory.
Become. Examples of the case where X is of the second class are as follows:
SO_TwoNH-, -SS-, -CONHNH-, -CO
NHNHCO-, -CONHCH_TwoCO-, -CONH
NHCOO-, -CONHCH_TwoCOO-, -CONH
NHCONH-, -CONHCH_TwoCONH-, -CO
NHNHCONHNH-, -CONHCH_TwoCONNHN
H-, -CH_TwoNHCONH-, -CH_TwoCH_TwoNHCO
NH-, -CH_TwoCH_TwoCH_TwoNHCONH-, -CH_TwoC
H_TwoCH_TwoNHCONH-, -SCH_TwoCONH-, -S
CH_TwoCH_TwoCONH-, -S (CH_Two)_FiveCONH-,
-S (CH_Two)_TenCONH-, -S (p-C₆H_Four) CO
NH-, -SCH_TwoNHCO-, -SCH_TwoCH_TwoNHC
O-, -S (CH_Two)₆NHCO-, -S (p-C₆H_Four)
NHCO-, -SCH_TwoNHCONH-, -SCH_TwoCH
_TwoNHCONH-, -S (CH_Two)₆NHCONH-,-
S (p-C₆H_Four) NHCONH-, -S (CH_Two)_TenN
HCONH-, -SCH_TwoCH_TwoNHCOO-, -S (C
H_Two)₆NHCOO-, -S (p-C₆H_Four) NHCOO
-, -S (CH_Two)₆OCONH-, -S (p-C₆H_Four)
OCONH-, -S (CH_Two)₁₁OCONH-, -SC
H_TwoCH_TwoCONH-, -S (CH_Two)_FiveCONH-,-
SCH_TwoCH_TwoNHCO (p-C₆H_Four)-, -SCH_TwoC
ONHNHCO-, -SCH_TwoCH_TwoCONHNHCO
-, -S (CH_Two)₆CONHNHCO-, -S (C
H_Two)₆CONNHNHCO (p-C₆H_Four)-, -S (CH
_Two)_TenCONHNHCO-, -S (p-C₆H_Four) CON
HNHCO-, -SCH_Two(P-C₆H_Four) CONHNH
CO-, -SCH_TwoCH_TwoNHCOCONH-, -SCH
_TwoCH_TwoCH_TwoNHCOCONH-, -S (CH_Two)₁₁NH
COCONH-, -S (p-C₆H_Four) NHCOCONH
-, -SCH_TwoCONHCONH-, -SCH_TwoCH_TwoC
ONHCONH-, -S (p-C₆H_Four) CONHCON
H-, -SCH_TwoCH_TwoNHCONHCO-, -S (p-
C₆H_Four) NHCONHCO-, -SCH_TwoCH_TwoCONH
NHCONH-, -S (CH_Two)_TenCONHNHCON
H-, -SCH_TwoCH_TwoNHNHCONH-, -S (p-
C₆H_Four) NHNHCONH-, -SCH_TwoCH_TwoNHCO
NHNH-, -S (p-C₆H_Four) NHCONHNH-,
-SCH_TwoCONHCONHNH-, -SCH_TwoCH_TwoC
ONHCONHNH-, -S (CH_Two)_TenCONHCO
NHNH-, -S (p-C₆H_Four) CONHNHCON
H-, -S (p-C₆H_Four) CONHCONHNH-,
-SCH_TwoCONHCONHNHCO-, -SCH_TwoCH
_TwoCONHCONHNHCO-, -S (CH_Two)_TenCO
NHCONHNHCO-, -S (p-C₆H_Four) CONH
NHCONHCO-, -S (p-C₆H_Four) CONHCO
NHNHCO-, -SCH_TwoCONH (CH_Two) NHCO
-, -SCH_TwoCH_TwoCONH (CH_Two) NHCO-,-
S (p-C₆H_Four) CONH (CH_Two) NHCO-, -S
(CH_Two)_TenCONH (CH_Two) NHCO-, -SCH_Two
CON (CH_Two) NHCONH-, -SCH_TwoCH_TwoCO
N (CH_Two) NHCONH-, -S (CH_Two)_TenCONH
CONH (CH_Two) NHCO-, -S (p-C₆H_Four) C
ONH (CH_Two) NHCO-, -SCH_TwoCH_TwoNHCO
NH (CH_Two) NHCO-, -SCH_TwoCH_TwoNHCOC
H_TwoCONH-, -S (p-C₆H_Four) NHCONH (C
H_Two) NHCO-, -S (p-C₆H_Four) NHCOCH_TwoC
ONH-, -CH_TwoCONHNHCO-, -CH_TwoCH_Two
CONHNHCO-,-(CH_Two)_FiveCONHNHCO
-,-(CH_Two)_FiveCONNHNHCO (p-C₆H_Four)
-,-(CH_Two)_TenCONHNHCO-,-(p-C₆H
_Four) CONHNHCO-, -CH_Two(P-C₆H_Four) CON
HNHCO-, -CH_TwoCH_TwoNHCOCONH-, -C
H_TwoCH_TwoCH_TwoNHCOCONH-,-(CH_Two)_TenNH
COCONH-,-(p-C₆H_Four) NHCOCONH
-, -CH_TwoCONHCONH-, -CH_TwoCH_TwoCON
HCONH-,-(p-C₆H_Four) CONHCONH-,
-CH_TwoCH_TwoNHCONHCO-,-(p-C₆H_Four) N
HCONHCO-, -CH_TwoCH_TwoNHCONHNH-,
− (P−C₆H_Four) NHCONHNH-, -CH_TwoCH_TwoN
HNHCONH-,-(p-C₆H_Four) NHNHCONH
-, -CH_TwoCONHNHCONH-, -CH_TwoCH_TwoC
ONHNHCONH-,-(CH_Two)_TenCONNHNHC
ONH-,-(p-C₆H_Four) NHNHCO-, -CH_Two
CONHCH_TwoNHCO-, -CH_TwoCH_TwoCONHCH_Two
NHCO-,-(CH_Two)_TenCONHCH_TwoNHCO-,
− (P−C₆H_Four) CONHCH_TwoNHCO-, -CH_Two
CONHCH_TwoNHCONH-, -CH_TwoCH_TwoCONH
CH_TwoNHCONH-,-(CH_Two)_TenCONHCH_TwoN
HCONH-,-(p-C₆H_Four) CONHCH_TwoNHC
ONH-, -CH_TwoCH_TwoNHCONHCH_TwoNHCO
-,-(P-C₆H_Four) NHCONHCH_TwoNHCO-,
-CH_TwoCH_TwoNHCOCH_TwoCONH-,-(p-C₆H
_Four) NHCOCH_TwoCONH- and the like. Heterogeneous
Specific examples of the child include a nitrogen atom, a sulfur atom, a phosphorus atom,
Boron atom, silicon atom, selenium atom, fluorine atom, chlorine atom
And carbon atom, bromine atom, iodine atom and tin atom. An example of the case where X is of the third category is as follows:
CH_TwoCONH-, -CH_TwoCH_TwoCONH-, -CH_TwoN
HCO-, -CH_TwoCH_TwoNHCO-, -CH_TwoCH_TwoCH
_TwoNHCO-, -CH_TwoCH_TwoNHCOO-,-(C
H_Two)₆NHCOO-,-(p-C₆H_Four) NHCOO-,
-CH_TwoCH_TwoOCONH-,-(CH_Two)₁₁OCONH
-,-(P-C₆H_Four) OCONH-, -CH_TwoCH_TwoCO
NHCO-,-(CH_Two)_FiveCONHCO-, -CH_TwoC
H_TwoCONHCO (p-C₆H_Four)-And the like. As an example of the case where X is of the fourth category, -C
H = CH-, -CH = N-, -SO_Two-, Phenylene
And a group containing a carbon-carbon triple bond and the like. As the aliphatic hydrocarbon group represented by R,
Hexyl group, octyl group, nonyl group, cyclohexyl
Group, decyl group, undecyl group, dodecyl group, cyclodode
Sil group, tridecyl group, tetradecyl group, pentadecyl
Group, hexadecyl group, heptadecyl group, 16-methyl
Butadecyl group, octadecyl group, 9-octadecenyl
Group, nonadecyl group, eikosyl group, henicosyl group,
Docosyl group, tricosyl group, tetracosyl group, 2-nor
Bornyl group, 7,7-dimethylnorbornyl group, 1-A
Damantyl group, cholesteryl group, 5-phenylpentyl
And the like. These may be branched
And may be polycyclic and contain unsaturated bonds
You may. However, among the atoms contained in X and R,
The total number of atoms excluding the atoms that make up the aromatic ring with the
Above, especially 14 or more is necessary for the decoloring property. Next, a reversible microscope preferably used in the present invention.
Specific examples of coloring agents will be given, but the present invention is not limited thereto.
Not. 4'-hydroxyheptaneanilide, 4 '
-Hydroxy-3-methyloctaneanilide, 4'-h
Droxynonadecananilide, 3'-hydroxynonade
Cananilide, 4'-hydroxy-10-octadecene
Anilide, 15-cyclohexyl-4'-hydroxype
Ntadecananilide, 4'-hydroxy-5-tetrade
Senanilide, 3'-cyclohexyl-4'-hydroxy
Cyheptadecaneanilide, 3'-allyl-4'-hydro
Xypentadecaneanilide, 3'-chloro-4'-hydr
Roxyoctadecaneanilide, 3'-hydroxydodeca
Anilide, 2 ', 4'-dihydroxyheptadecane
Nilide, 4'-hydroxy-4-hexylbenzure
Nilide, 4'-hydroxy-4-octadecylbenzure
Nilide, 4'-hydroxy-4-pentadecylaminoca
Rubonyl benzanilide, 4'-hydroxy-4-hex
Silcarbonylaminobenzanilide, 4'-hydroxy
4- (heptylthio) benzanilide, 4'-hydr
Roxy-4-octadecyloxybenzanilide, 4 '
-Hydroxy-4-dodecylsulfonylbenzanili
4'-Hydroxy-4-nonylsulfonyloxy
Nsanilide, 4'-hydroxy-4-dodecyloxy
Sulfonylbenzanilide, 4'-hydroxy-4-pe
Antadecylaminosulfonylbenzanilide, 4'-h
Droxy-4- (N-heptadecylideneamino) benz
Anilide, 4'-hydroxy-3,4-dioctylio
Xybenzanilide, 4'-hydroxy-3-octyl
-4- (octylthio) benzanilide, 4'-hydro
Xy-3- (heptadecylthio) -5-pentadecylo
Xibenzanilide, 4'-hydroxy-3-heptade
Silcarbonylamino-5-dodecylbenzanilide,
4'-hydroxy-3-octadecylaminocarbonyl
-5-tetradecylaminocarbonylbenzanilide,
4'-hydroxy-3-octadecylsulfonylamino
-5-octadecyloxybenzanilide, 4'-hydr
Roxy-3-heptadecyloxysulfonyl-5-tet
Radecyloxysulfonylbenzanilide, 4'-hydr
Roxy-3,5-bis (N-docosylideneamino) ben
Zanilide, 4'-hydroxy-4-octadecylcal
Bonylaminobenzanilide, 4'-hydroxy-3-
Octadecylcarbonylamino-5-octadecyloxy
Sivenzanilide, 3'-allyl-4'-hydroxy-
4-pentadecylbenzanilide, 4'-hydroxy-
3'-methyl-4-nonyloxybenzanilide, 4 '
-Hydroxy-3'-propyl-4-nonadecylcarbo
Nyloxybenzanilide, 3'-butyl-4'-hydr
Roxy-4-octadecyloxycarbonyl benzani
Lido, 3'-hydroxy-4-pentadecylcarbonyl
Oxybenzanilide, 3'-hydroxy-4-nonade
Silsulfonyl benzanilide, 3 ', 4', 5'-to
Lihydroxy-4-tetracosylaminosulfonylben
Zuanilide, 3 ', 5'-dihydroxy-4-pentaco
Silaminocarbonylbenzanilide, 3'-hydroxy
C-4- (N-dodecylideneamino) benzanilide,
N- [4- (3-hydroxyphenylaminocarboni
Le) benzylidene] pentadecylamine, N-cyclohexyl-4-hydroxyben
Zhydrazide, N-cyclohexylmethyl-4-hydro
Xybenz hydrazide, N-cyclohexyl-4-hydride
Roxybenzamide, N-cyclohexylmethyl-4-
Hydroxybenzamide, N-methyl-N-octadecy
4-hydroxybenzamide, N- (3-methyl
Xyl) -4-hydroxybenzamide, N-octade
Sil-4-hydroxybenzhydrazide, N- (8-O
Cutadecenyl) -4-hydroxybenzamide, 4-hydroxy-4'-dodecylbenzure
Nilide, N-methyl-4-hydroxy-4'-octade
Silbenzanilide, 4-hydroxy-4'-octade
Siloxybenzanilide, 4-hydroxy-4'-
(Octadecylthio) benzanilide, 4-hydroxy
-4'-hexadecylcarbonylbenzanilide, 4-
Hydroxy-4'-heptadecyloxycarbonyloxy
Sivenzanilide, 4-hydroxy-4'-dodecylo
Xycarbonyl benzanilide, 4-hydroxy-4 '
-Heptadecylcarbonyloxybenzanilide, 4-
Hydroxy-4'-cyclohexylaminobenzanili
De, 4-hydroxy-4'-octadecylaminobenz
Anilide, 4-hydroxy-4'-heptadecylcal
Bonylaminobenzanilide, 4-hydroxy-4'-
Octadecylaminocarbonylbenzanilide, 4-h
Droxy-4'-dodecylsulfonylbenzanili
Do, 4-hydroxy-4'-octadecyloxysulfur
Onylbenzanilide, 4-hydroxy-4'-dodeci
Rusulfonyloxybenzanilide, N-4-hydro
Xybenzoyl-N'-octadecylidene-1,4-f
Enylenediamine, N-4- (4-hydroxyphenyl
Carbonylamino) benzylidenedecylamine, 4-
Hydroxy-4'-tetradecyloxycarbonylamido
Novenzanilide, 4-hydroxy-4'-octadecy
Luureylene Benzanilide, 3-hydroxy-4'-dodecyloxybe
Nsanilide, N-methyl-4-hydroxy-3'-o
Kutadecyloxybenzanilide, 3-hydroxy-
4'-tetradecylbenzanilide, N-methyl-3-
Hydroxy-4'-octadecylbenzanilide, N-
Dodecyl-4-hydroxy-3-methylbenzamide,
3-methoxy-4-hydroxy-4'-octadecylo
Xybenzanilide, 3-chloro-4-hydroxy-
4'-octadecylbenzanilide, N-octadecyl
-4-hydroxy-2,5-dimethylbenzamide, 4
-Hydroxy-4'-octadecyloxy-3'-chloro
Robenzanilide, 4-hydroxy-3 ', 4'-dide
Siloxybenzanilide, 4-hydroxy-3'-o
Cutadecylamino-4'-octadecyloxybenzure
Nilide, 4-hydroxy-2'-chloro-3 ', 5'-
Didecyloxybenzanilide, 4-hydroxy-
3 ', 4'-dioctadecyloxybenzanilide, 4
-Hydroxy-4'-octyl-3'-methylbenzure
Nilide, 3-hydroxy-4-methyl-4'-tetrade
Silbenzanilide, N-methyl-4-hydroxy-
3'-octadecylbenzanilide, 4- (N-octadecylsulfonylamido)
No) phenol, 4- (N-methyl-N-octadecyl)
Sulfonylamino) phenol, 4- (N-3-methyl)
Hexylsulfonylamino) phenol, 4'-hydro
Xy-4-cyclohexylbenzenesulfonanilide,
4'-hydroxy-4-octadecyloxybenzenes
Rufonanilide, 4'-hydroxy-4- (dodecylchi
E) benzenesulfonanilide, 4'-hydroxy-4
-Hexylcarbonylbenzenesulfonanilide, 4 '
-Hydroxy-4- (8-heptadecenyl) carbonyl
Benzenesulfonanilide, 4'-hydroxy-4-o
Butyloxycarbonyloxybenzenesulfoneanily
Do, 4'-hydroxy-4-dodecylcarbonyloxy
Benzenesulfonanilide, 4'-hydroxy-4-o
Kutadecylaminobenzenesulfonanilide, 4'-hydroxy-4-heptadecylcal
Bonylaminobenzenesulfonanilide, 4'-hydro
Xy-4-dodecylaminocarbonylbenzenesulfone
Anilide, 4'-hydroxy-4-dodecylsulfonyl
Benzenesulfonanilide, 4'-hydroxy-4-o
Kutadecyloxysulfonylbenzenesulfoneanily
4,4'-hydroxy-4-dodecylsulfonyloxy
Benzenesulfonanilide, N-dodecylidene-4-
(4-hydroxyphenyl) aminosulfonylanily
, N-4- (4-hydroxyphenylaminosulfoni
B) benzylideneoctadecylamine, 4'-hydroxy
C-4-octyloxycarbonylaminobenzenesul
Honanilide, 4'-hydroxy-4-octadecylo
Xycarbonylaminobenzenesulfonanilide, 4 '
-Hydroxy-4-octadecylureylenebenzenes
Ruhonanilide, N-methyl-4'-hydroxy-3-oct
Tadecyloxybenzenesulfonanilide, 3'-hydr
Roxy-4-dodecylbenzenesulfonanilide, 3-
Methyl-4- (N-dodecylsulfonamino) pheno
3'-methoxy-4'-hydroxy-4-octade
Siloxybenzenesulfonanilide, 3'-chloro-
4'-hydroxy-4-octadecylbenzenesulfone
Anilide, 4'-hydroxy-2,5-dimethyl-4-
Octadecylbenzenesulfonanilide, 3-methyl-
4- (N-octadecylsulfonamino) phenol,
4'-hydroxy-3,4-dioctadecyloxyben
Zensulfone anilide, 1- (4-hydroxyphenyldithio) o
Kutadecane, 1- (4-hydroxyphenyldithio)-
9-octadecene, 1- (2-fluoro-4-hydroxy
Cyphenyldithio) octadecane, 1- (2-ethoxy)
-4-hydroxyphenyldithio) octadecane, 1-
(3-chloro-4-hydroxyphenyldithio) octa
Deccan, 4'-hydroxy-4-tetradecyl dif
Phenyl sulfide, 4'-hydroxy-4-octadecy
Rudiphenyl sulfide, 4'-hydroxy-4-oct
Tadecylcarbonylaminodiphenyl sulfide, 4 '
-Hydroxy-4-octadecyloxydiphenylsul
Fido, 4'-hydroxy-4-octadecyloxys
Rufonyl diphenyl sulfide, 4'-hydroxy-4
-Octadecylsulfonylaminodiphenylsulfyi
Do 4'-hydroxy-3,4-didecyloxy
Sidiphenyl sulfide, 4'-hydroxy-3,4-
Dioctadecyloxydiphenyl sulfide, 4- (1
5-cyclohexylpentadecyl) -4'-hydroxy
Diphenyl sulfide, 4'-hydroxy-4- (5-
Tetradecenyl) diphenyl sulfide, 3'-chloro-4'-hydroxy-4-o
Cutadecyl diphenyl sulfide, 3'-hydroxy-
4-dodecyldiphenyl sulfide, 3'-hydroxy
-4-octadecyldiphenyl sulfide, 3'-hydr
Roxy-4-dodecyloxycarbonyldiphenylsul
Fido, N- (4-hydroxyphenyl) -N'-
Hexylurea, N- (4-hydroxyphenyl) -N '
-Dodecyl urea, N- (4-hydroxyphenyl)-
N'-hexadecyl urea, N- (4-hydroxyphenyl
L) -N'-octadecyl urea, N- (4-hydroxy
Phenyl) -N'-icosyl urea, N- (4-hydro
(Xyphenyl) -N'-cyclododecyl urea, N- (4
-Hydroxyphenyl) -N'-docosylurea, N-
(4-hydroxyphenyl) -N'-cholesteryl urine
Element, N- (4-hydroxyphenyl) -N '-(2-he
Butyloctyl) urea, N- (4-hydroxyphenyl)
Ru) -N '-(9-octadecenyl) urea, N- (3-allyl-4-hydroxyphenyl)
L) -N'-octadecyl urea, N- (2-hydroxy
Phenyl) -N'-octylurea, N- (3-hydroxy
(Ciphenyl) -N'-octadecyl urea, N- (3,4
-Dihydroxyphenyl) -N'-octadecylurea,
N- (3,4,5-trihydroxyphenyl) -N'-
Trichosyl urea, N- (4-hydroxyphenyl)-
N '-(4-tetradecylphenyl) urea, N- (4-
(Hydroxyphenyl) -N′-hexadecylthiourea,
N- (4-hydroxyphenyl) -N'-octadecyl
Thiourea, 4-undecanoylamino-1- (4-h
Droxyphenylaminocarbonyl) benzene, 4-O
Kutadecanoylamino-1- (4-hydroxyphenyl
Aminocarbonyl) benzene, 4- (octadecylamino)
Nocarbonyl) amino-1- (4-hydroxyphenyl)
Aminocarbonyl) benzene, 4-octadecylamino
-1- (4-hydroxyphenylamino) carbonyl
Butylbenzene, N-octadecyl-N'-p- (4-h
Droxyphenylcarbamoyl) phenyloxamide,
4- (octadecylaminocarbonyl) amino-1-
(4-hydroxyphenylcarbamoyl) methylbenze
4- (octadecylamino) carbonyl-1- (4
-Hydroxyphenylcarbamoyl) methylbenzene,
N-octadecanoyl-N'-p- (p-hydroxyf
Enylcarbamoylmethyl) benzoylhydrazine, N
-Dodecanoyl-N'-p- [2- (p-hydroxyf
Enylcarbamoyl) ethyl] benzoylhydrazine, N- (4-hydroxyphenylmethyl)-
N'-n-tetradecyl urea, N- (4-hydroxy
Enylmethyl) -N'-n-octadecylurea, N-
[2- (4-hydroxyphenyl) ethyl] -N'-n
-Tetradecyl urea, N- [2- (4-hydroxy
Nyl) ethyl] -N'-n-octadecylurea, N-
[3- (4-hydroxyphenyl) propyl] -N'-
n-dodecyl urea, N- [3- (4-hydroxy
Nyl) propyl] -N'-n-octadecylurea, N-
[6- (4-hydroxyphenyl) hexyl] -N'-
n-dodecyl urea, N- [2- (3-hydroxyphenyl)
L) ethyl] -N'-n-octadecylurea, N- [2
-(3,4-dihydroxyphenyl) ethyl] -N'-
n-octadecyl urea, Nn-octadecyl- (4-hydroxy
Phenyl) acetamide, Nn-dodecyl-3- (4
-Hydroxyphenyl) propanamide, Nn-oct
Tadecyl-3- (4-hydroxyphenyl) propana
Mido, N- (4-hydroxyphenylmethyl) octade
Canamide, N- [2- (4-hydroxyphenyl) e
Tyl] octadecaneamide, N- [3- (4-hydroxy
[Ciphenyl) propyl] octadecanamide, N- [3
-(3-hydroxyphenyl) propyl] octadecane
Amide, N- [3- (3,4-dihydroxyphenyl)
Propyl] octadecaneamide, N- (4-hydroxybenzoyl) -N '
-N-octanoylhydrazine, N- (4-hydroxy
Benzoyl) -N'-n-tetradecanoylhydrazide
, N- (4-hydroxybenzoyl) -N'-n-o
Kutadecanoylhydrazine, N- (2,4-dihydroxy
Cibenzoyl) -N'-n-octanoylhydrazine,
N- (2,4-dihydroxybenzoyl) -N'-n-
Octadecanoylhydrazine, N- (4-hydroxy
Nzoyl) -N'-n-tetradecylaminocarbonyl
Hydrazine, N- (4-hydroxybenzoyl) -N '
-N-octadecylaminocarbonylhydrazine, N-
(2,4-dihydroxybenzoyl) -N'-n-tet
Radecylaminocarbonylhydrazine, N- (2,4-
Dihydroxybenzoyl) -N'-n-octadecyl
Minocarbonylhydrazine, N- (4-hydroxyben
Zoyl) -N'-n-octyloxycarbonylhydra
Gin, N- (4-hydroxybenzoyl) -N'-n-
Dodecyloxycarbonylhydrazine, N- (2,4-
Dihydroxybenzoyl) -N'-n-tetradecylio
Xycarbonylhydrazine, N- (2,4-dihydroxy
(Cibenzoyl) -N'-n-octadecyloxycarbo
Nylhydrazine, N- (4-hydroxybenzoyl)-
N'-n-tetradecylhydrazinocarbonylhydrazide
, N- (4-hydroxybenzoyl) -N'-n-o
Kutadecylhydrazinocarbonylhydrazine, N-
(2,4-dihydroxybenzoyl) -N'-n-tet
Radecylhydrazinocarbonylhydrazine, N- (2,
4-dihydroxybenzoyl) -N'-n-octadecy
Ruhydrazinocarbonylhydrazine, N- (4-hydroxybenzoyl) -N '
-N-octanoylmethylenediamine, N- (4-hydrido
Roxybenzoyl) -N'-n-tetradecanoylmethyl
Rangeamine, N- (4-hydroxybenzoyl)-
N'-n-octadecanoylmethylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-tet
Ladecanoylmethylenediamine, N- (2,4-dihydrogen
Roxybenzoyl) -N'-n-octadecanoylmethyl
Rangeamine, N- (4-hydroxybenzoyl)-
N'-n-octylaminocarbonylmethylene diamine
, N- (4-hydroxybenzoyl) -N'-n-do
Decylaminocarbonylmethylenediamine, N- (4-
(Hydroxybenzoyl) -N'-n-tetradecylamido
Nocarbonylmethylenediamine, N- (4-hydroxy
Benzoyl) -N'-n-octadecylaminocarboni
Lmethylenediamine, N- (2,4-dihydroxyben
Zoyl) -N'-n-octadecylaminocarbonyl
Tylenediamine, N- (4-hydroxybenzoyl)-
N'-n-tetradecyloxycarbonylmethylenedia
Min, N- (4-hydroxybenzoyl) -N'-n-
Octadecyloxycarbonylmethylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-tet
Radecyloxycarbonylmethylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-oct
Tadecyloxycarbonylmethylenediamine, N- (4
-Hydroxybenzoyl) -N'-n-octylhydra
Dinocarbonylmethylenediamine, N- (4-hydroxy
(Cibenzoyl) -N'-n-dodecylhydrazinocarbo
Nylmethylenediamine, N- (2,4-dihydroxybe
Nzoyl) -N'-n-tetradecylhydrazinocarbo
Nylmethylenediamine, N- (2,4-dihydroxybe
Nzoyl) -N'-n-octadecylhydrazinocarbo
Nilmethylenediamine, Nn-octadecyl-2- (p-hydro
(Xyphenylthio) acetamide, Nn-octadecy
R-3- (p-hydroxyphenylthio) propanami
, N-n-decyl-11- (p-hydroxyphenyl
Thio) undecaneamide, N- (pn-octylfe)
Nyl) -6- (p-hydroxyphenylthio) hexane
Amide, Nn-octadecyl-p- (p-hydroxy
Phenylthio) benzamide, N- [2- (p-hydro
[Xiphenylthio) ethyl] -n-octadecaneami
, N- [p- (p-hydroxyphenylthio) phenyl
Ru] -n-octadecaneamide, N- (p-hydroxy
Phenylthio) methyl-N′-n-octadecyl urea,
N- [2- (p-hydroxyphenylthio) ethyl]-
N'-n-tetradecyl urea, N- [2- (p-hydro
Xyphenylthio) ethyl] -N'-n-octadecyl
Urea, N- [2- (3,4-dihydroxyphenylthio)
E) ethyl] -N'-n-octadecylurea, N- [p
-(P-hydroxyphenylthio) phenyl] -N'-
n-octadecyl urea, N- [10- (p-hydroxy
Phenylthio) decyl] -N'-n-decylurea, N-
[2- (p-hydroxyphenylthio) ethyl] carba
N-octadecyl formate, N- [p- (p-hydroxy
[Ciphenylthio) phenyl] carbamic acid-n-dodeci
, N-n-octadecylcarbamic acid- [2- (p-
Hydroxyphenylthio) ethyl], N- [3- (p-
Hydroxyphenylthio) propionyl] -Nn-o
Kutadecanoylamine, N- [2- (p-hydroxyf
Enylthio) aceto] -N'-n-octadecanohydra
Zide, N- [3- (p-hydroxyphenylthio) pro
Piono] -N'-n-octadecanohydrazide, N-
[3- (3,4-dihydroxyphenylthio) propio
No] -N'-n-octadecanohydrazide, N- [6-
(P-Hydroxyphenylthio) hexano] -N'-n
-Tetradecanohydrazide, N- [6- (p-hydroxy
Cyphenylthio) hexano] -N'-n-octadecano
Hydrazide, N- [6- (p-hydroxyphenylthio)
E) Hexano] -N '-(pn-octylbenzo) h
Drazide, N- [11- (p-hydroxyphenylthio)
E) Undecano-N'-n-decanohydrazide, N-
[11- (p-hydroxyphenylthio) undecano-
N'-n-tetradecanohydrazide, N- [11- (p
-Hydroxyphenylthio) undecano-N'-n-o
Kutadecanohydrazide, N- [11- (p-hydroxy
Phenylthio) undecano-N '-(6-phenyl)
Oxanohydrazide, N- [11- (3,4,5-trihi
Droxyphenylthio) undecano] -N′-n-oct
Tadecanohydrazide, N- [p- (p-hydroxyphene)
Nylthio) benzo] -N'-n-octadecanohydrazide
, N- [p- (p-hydroxyphenylthiomethyl)
Benzo] -N'-n-octadecanohydrazide, N-
[3- (p-hydroxyphenylthio) propyl] -N
'-N-octadecyloxamide, N- [3- (3,4
-Dihydroxyphenylthio) propyl] -N'-n-
Octadecyl oxamide, N- [11- (p-hydroxy
[Ciphenylthio) undecyl] -N'-n-decyloxy
Samide, N- [p- (p-hydroxyphenylthio) phenyl
Enyl] -N'-n-octadecyloxamide, N-
[2- (p-hydroxyphenylthio) acetyl] -N
'-N-octadecyl urea, N- [3- (p-hydroxy
[Ciphenylthio) propionyl] -N'-n-octade
Silurea, N- [2- (p-hydroxyphenylthio)
Ethyl] -N'-n-octadecanoyl urea, N- [p
-(P-hydroxyphenylthio) phenyl] -N'-
n-octadecanoyl urea, 3- [3- (p-hydroxy
[Ciphenylthio) propionyl] carbazic acid-n-o
Kutadecyl, 4- [2- (p-hydroxyphenylthio)
E) ethyl] -1-n-octadecylsemicarbazide,
1- [2- (p-hydroxyphenylthio) ethyl]-
4-n-octadecyl semicarbazide, 1- [p- (p
-Hydroxyphenylthio) phenyl] -4-n-tetra
Radecyl semicarbazide, 1- [3- (p-hydroxy
Phenylthio) propionyl] -4-n-octadecyl
Semicarbazide, 1- [p- (p-hydroxyphenyl)
Thio) benzoyl] -4-n-octadecylsemicarba
Zide, 4- [2- (p-hydroxyphenylthio) ethyl
1] -n-tetradecanoyl semicarbazide, 4-
[P- (p-hydroxyphenylthio) phenyl] -1
-N-octadecanoyl semicarbazide, 1- [2-
(P-Hydroxyphenylthio) acetamide] -1-
n-octadecanoylaminomethane, 1- [11- (p
-Hydroxyphenylthio) undecaneamide] -N '
-N-decanoylaminomethane, 1- [p- (p-hydrido
Roxyphenylthio) benzamide] -1-n-octa
Decanoylaminomethane, 1- [3- (p-hydroxy
Phenylthio) propanamide] -1- (N′-n-o
Kutadecylureido) methane, 1- [11- (p-hydrido)
Roxyphenylthio) undecaneamide] -N '-(N
'-N-decylureido) methane, 1- {N'-[2-
(P-Hydroxyphenylthio) ethyl] ureido｝-
1-n-octadecanoylaminomethane, N- [2-
(P-hydroxyphenylthio) ethyl] -N'-n-
Octadecylmalonamide, N- [2- (p-hydroxyphenyl) d
Tyl] -n-octadecyl carbamate, Nn-oct
Tadecylcarbamic acid- [2- (p-hydroxyphenyl)
Ru) ethyl], N- [3- (p-hydroxyphenyl)
Propionyl] -Nn-octadecanoylamine, N
-[6- (p-hydroxyphenyl) hexanoyl]-
Nn-octadecanoylamine, N- [3- (p-
Droxyphenyl) propionyl] -N- (p-n-o
Octylbenzoyl) amine, N- [2- (p-hydroxy
Cyphenyl) aceto] -N'-n-dodecanohydrazine
, N- [2- (p-hydroxyphenyl) aceto]-
N'-n-octadecanohydrazide, N- [3- (p-
Hydroxyphenyl) propiono] -N'-n-octa
Decanohydrazide, N- [3- (p-hydroxyphenyl)
L) propiono] -N'-n-docosanohydrazide, N
-[6- (p-hydroxyphenyl) hexano] -N '
-N-tetradecanohydrazide, N- [6- (p-hydr
Roxyphenyl) hexano] -N′-n-octadecano
Hydrazide, N- [6- (p-hydroxyphenyl)
Xano] -N '-(pn-octylbenzo) hydrazine
Do, N- [11- (p-hydroxyphenyl) undeca
No-N'-n-decanohydrazide, N- [11- (p-
(Hydroxyphenyl) undecano-N′-n-octade
Canohydrazide, N- [p- (p-hydroxyphenyl)
L) benzo] -N'-n-octadecanohydrazide, N
-[P- (p-hydroxyphenylmethyl) benzo]-
N'-n-octadecanohydrazide, N- [3- (p-
Hydroxyphenyl) propyl] -N'-n-octade
Siloxamide, N- [3- (3,4-dihydroxy
Enyl) propyl] -N'-n-octadecyloxamine
, N- [p- (p-hydroxyphenyl) phenyl]
-N'-n-octadecyloxamide, N- [2- (p
-Hydroxyphenyl) acetyl] -N'-n-octa
Decylurea, N- [3- (p-hydroxyphenyl) p
Lopionyl] -N'-n-octadecylurea, N- [p
-(P-hydroxyphenyl) benzoyl] -N'-n
-Octadecyl urea, N- [2- (p-hydroxyphene)
Nyl) ethyl] -N'-n-octadecanoyl urea, 4
-[2- (p-hydroxyphenyl) ethyl] -1-n
-Octadecyl semicarbazide, 1- [2- (p-hydrido)
Roxyphenyl) ethyl] -4-n-tetradecylsemi
Carbazide, 1- [2- (p-hydroxyphenyl) e
Tyl] -4-n-octadecylsemicarbazide, 1-
[2- (p-hydroxyphenyl) acetyl] -4-n
-Tetradecyl semicarbazide, 1- [3- (p-hydrido)
Roxyphenyl) propionyl] -4-n-octadecy
Lucemicarbazide, 1- [11- (p-hydroxyphene)
Nil) undecanoyl] -4-n-decylsemicarbadi
, 4- [2- (p-hydroxyphenyl) ethyl]-
1-n-octadedecanoyl semicarbazide, 4- [p
-(P-hydroxyphenyl) phenyl] -1-n-o
Kutadecanoyl semicarbazide, 1- [2- (p-hydrido)
Roxyphenyl) acetamide] -1-n-octadeca
Noylaminomethane, 1- [3- (p-hydroxyphene)
Nyl) propanamide] -1-n-octadecanoylua
Minomethane, 1- [2- (p-hydroxyphenyl) a
Cetamide] -1- (3-n-octadecylureido)
Methane, 1- [3- (p-hydroxyphenyl) propa
Amido] -1- (3-n-octadecylureido) me
Tan, 1- [11- (p-hydroxyphenyl) unde
Canamide] -1- (3-n-decylureido) meta
1- {3- [2- (p-hydroxyphenyl) ethyl]
Ureido} -1-n-octadecanoylaminometh
, N- [2- (p-hydroxyphenyl) ethyl]-
N'-n-octadecylmalonamide, 4-n-octadecylaminophenol,
4- (1-octadecynyl) phenol, 4- (1,3
-Octadecadinyl) phenol and the like. These may be used alone or in combination of two or more.
May be used in combination, usually colorless or pale electron donation
5 to 5000% by weight, preferably based on the dye precursor
Is used in an amount of 10 to 3000% by weight. The colorless or pale-colored color used in the present invention
Generally, pressure-sensitive recording paper or heat-sensitive dye
Typified by those used for recording paper, etc.
Absent. Specific examples include the following:
However, the present invention is not limited to this. (1) Triarylmethane compound 3,3-bis (p-dimethylaminophenyl) -6-di
Methylaminophthalide (crystal violet lacto
), 3,3-bis (p-dimethylaminophenyl) phenyl
Talide, 3- (p-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (2-methyl
Ruindol-3-yl) phthalide, 3- (p-dimethyl)
Ruaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethyl
Indole-3-yl) -5-dimethylaminophthaly
, 3,3-bis (1,2-dimethylindole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis
(9-ethylcarbazol-3-yl) -5-dimethyl
Aminophthalide, 3,3-bis (2-phenylindole
Ru-3-yl) -5-dimethylaminophthalide, 3-p
-Dimethylaminophenyl-3- (1-methylpyrrole
-2-yl) -6-dimethylaminophthalide and the like. (2) Diphenylmethane compounds 4,4'-bis (dimethylaminophenyl) benzhydride
Lil benzyl ether, N-chlorophenyl leuco-o
Lamin, N-2,4,5-trichlorophenylleuquo
-Ramin and others. (3) Xanthene compounds Rhodamine B Anilinolactam, Rhodamine B-p-co
Loroanilinolactam, 3-diethylamino-7-dive
Ndylaminofluoran, 3-diethylamino-7-o
Cutylaminofluoran, 3-diethylamino-7-fu
Enylfluoran, 3-diethylamino-7-chloroph
Luoran, 3-diethylamino-6-chloro-7-methyl
Rufluoran, 3-diethylamino-7- (3,4-di
Chloroanilino) fluoran, 3-diethylamino-7
-(2-chloroanilino) fluoran, 3-Diethylamino-6-methyl-7-a
Nilinofluoran, 3- (N-ethyl) tolylamino-
6-methyl-7-anilinofluoran, 3-piperidino
-6-methyl-7-anilinofluoran, 3- (N-E
Tyl) tolylamino-6-methyl-7-phenethylfur
Oran, 3-diethylamino-7- (4-nitroanily
G) Fluoran, 3-dibutylamino-6-methyl-7
-Anilinofluoran, 3- (N-methyl) propyla
Mino-6-methyl-7-anilinofluoran, 3- (N
-Ethyl) isoamylamino-6-methyl-7-anili
Nofluoran, 3- (N-methyl) cyclohexylamido
No-6-methyl-7-anilinofluoran, 3- (N-
Ethyl) tetrahydrofurylamino-6-methyl-7-
Anilino fluoran and the like. (4) Thiazine compounds Benzoyl leucomethylene blue, p-nitrobenzoy
Leroycomethylene blue and the like. (5) Spiro compound 3-methylspirodinaphthopyran, 3-ethylspirodi
Naphthopyran, 3,3'-dichlorospirodinaphthopyra
3-benzylspirodinaphthopyran, 3-methylna
Futo- (3-methoxybenzo) spiropyran, 3-pro
Pilspirobenzopyran and the like. The above usually colorless or pale color dye precursor is
One kind or a mixture of two or more kinds may be used. The reversible thermosensitive recording layer is provided with a reversible thermosensitive recording layer.
As an additive to adjust color sensitivity and decoloration temperature, heat
A fusible substance can be contained in the reversible thermosensitive recording layer.
You. Those having a melting point of 60 ° C to 200 ° C are preferred,
Particularly, those having a melting point of 80 ° C to 180 ° C are preferable.
Use sensitizers used in general thermal recording paper.
You can also. These compounds include N-hydroxy
Methyl stearamide, stearamide, pal
Waxes such as mitamide, 2-benzyloxy
Naphthol derivatives such as naphthalene, p-benzylbiphe
Biphenyl derivatives such as nyl and 4-allyloxybiphenyl
Body, 1,2-bis (3-methylphenoxy) ethane,
2,2'-bis (4-methoxyphenoxy) diethyl
Of bis (4-methoxyphenyl) ether
Liether compounds, diphenyl carbonate, dibenzium oxalate
And bis (p-methylbenzyl) oxalate
Carbonic acid or oxalic acid diester derivatives;
More than one kind can be added in combination. The support of the reversible thermosensitive recording layer is transparent, translucent,
It may be opaque, paper, tracing paper
Par, various nonwoven fabrics, woven fabric, synthetic resin film, synthetic resin
Laminated paper, synthetic resin impregnated paper, synthetic paper, metal foil, glass
Or composite sheet combining these
Can be used arbitrarily, but is not limited to these.
It is not something to be done. According to the method for producing a reversible thermosensitive recording material of the present invention,
The layer structure of the reversible thermosensitive recording material
Only the recording layer may be used. Reversible thermal recording, if necessary
Providing a protective layer on the layer also supports the reversible thermosensitive recording layer.
Intermediate between the body and / or between the reversible thermosensitive recording layer and the protective layer
Layers can also be provided. In this case, the protective layer and / or
Indicates that the intermediate layer is composed of two or three or more layers.
It may be. Further, a layer between the reversible thermosensitive recording layer and the support
And / or the surface on which the reversible thermosensitive recording layer is provided or
Information can be recorded electrically, magnetically and optically on the opposite side
It may contain functional materials. In addition, a reversible thermosensitive recording layer is provided.
To prevent curl and antistatic on the surface opposite to the
A back coat layer may be provided as a target.
Engineering may be performed. The reversible thermosensitive recording layer has a different coloring hue.
Reversible thermosensitive recording layers may be laminated to form a multilayer structure. The reversible thermosensitive recording layer and / or the protective layer and / or
Alternatively, the intermediate layer may have a thickness that does not impair the transparency of these layers.
Each time, diatomaceous earth, talc, kaolin, calcined kaolin,
Calcium carbonate, magnesium carbonate, titanium oxide, oxidation
Zinc, silicon oxide, aluminum hydroxide, urea-former
Pigment such as phosphorus resin, etc.
Zinc stearate, stearin
Higher fatty acid metal salts such as calcium phosphate, paraffin, oxidation
Paraffin, polyethylene, polyethylene oxide, steer
Waxes such as phosphoric amide and caster wax
A dispersant such as sodium dioctyl sulfosuccinate;
It can also contain surfactants, fluorescent dyes, etc.
Wear. The protective layer and / or the reversible thermosensitive recording layer have
Antioxidants can be added to improve weatherability
You. Specific examples of antioxidants include hindered amine-based antioxidants.
Antioxidants, hindered phenolic antioxidants, sulf
Fide-based antioxidants, etc., are not particularly limited.
No. The protective layer and / or the reversible thermosensitive recording layer have
UV absorbers can be added to improve light properties.
Wear. Benzotriazo is a specific example of an ultraviolet absorber.
UV absorber, salicylic acid UV absorber, ben
Zophenone UV absorbers, zinc oxide, etc.
There is no particular limitation. The reversible thermosensitive recording produced by the production method of the present invention.
In the recording material, heating to form a color recording image
It is only necessary that rapid cooling occurs following the decolorization of the recorded image.
In order to perform the above, the cooling rate after heating should be slow. example
For example, after heating by an appropriate method,
Rapid cooling, such as pressing
Condition can be expressed. Also, thermal head,
When heating for a very short time using laser light, etc.,
Cools immediately after heating to maintain the color development
be able to. On the other hand, use a suitable heat source (thermal head, laser
Laser light, heat roll, heat stamp, high frequency heating, electric heating
Heaters and tungsten lamps and halogen lamps
Heating for a relatively long time with radiant heat from a light source, hot air, etc.)
Heats not only the recording layer but also the support
Even if is removed, the color is erased because the cooling speed is slow. Subordinate
Therefore, even when using the same heating temperature and / or the same heat source,
By controlling the cooling rate, the colored state and the decolored state can be changed.
It can be expressed arbitrarily. [0077] The present invention will be described in more detail with reference to the following examples.
I do. Embodiment 1 (A) Preparation of reversible thermosensitive coating liquid Carboxyl group-modified polyvinyl alcohol (Nippon Gohsei
Dissolve 20 parts of Gaku Kogyo Co., Ltd. T-350) in 840 parts of water.
I understand. This carboxyl group-modified polyvinyl alcohol
3-Diethylamino, an electron-donating dye precursor, is added to the solution.
-6-methyl-7-anilinofluoran 40 parts, N'-
(4-hydroxyphenyl) -N-octadecylurea
100 parts were mixed and pulverized with a sand mill for 30 minutes and reversible heat-sensitive
A coating liquid was prepared. (B) Preparation of reversible thermosensitive recording material The reversible heat-sensitive coating solution prepared in (A) is transparent to a thickness of 100 μm.
Solid on polyethylene terephthalate (PET) sheet
4g / m^TwoSmear so that it becomes
-Processed by calendar. Embodiment 2 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Instead of carboxyl group-modified polyvinyl alcohol
(T-330H, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Otherwise, a reversible thermosensitive recording material was obtained in the same manner as in Example 1.
Was. Embodiment 3 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Instead of carboxyl group-modified polyvinyl alcohol
Other than KL-318 (manufactured by Kuraray Co., Ltd.)
A reversible thermosensitive recording material was obtained in the same manner as in Example 1. Embodiment 4 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Instead of carboxyl group-modified polyvinyl alcohol
Other than KL-118 (manufactured by Kuraray Co., Ltd.)
A reversible thermosensitive recording material was obtained in the same manner as in Example 1. Embodiment 5 100 μm thick transparent polymer used in (B) of Example 1
Instead of Tylene terephthalate (PET) sheet,
188μm thick white poly with black characters printed on the surface
Others using ethylene terephthalate (PET) sheet
In the same manner as in Example 1, a reversible thermosensitive recording material was obtained. Comparative Example 1 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
0) instead of fully saponified polyvinyl alcohol (day
Other than using NM-11 manufactured by Synthetic Chemical Industry Co., Ltd.,
A reversible thermosensitive recording material was obtained in the same manner as in Example 1. Comparative Example 2 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
0) instead of partially saponified polyvinyl alcohol (day
Other than using Synthetic Chemical Industry Co., Ltd. KM-11),
A reversible thermosensitive recording material was obtained in the same manner as in Example 1. Comparative Example 3 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
0) instead of silane-modified polyvinyl alcohol (day
Others using the Synthetic Chemical Industry Co., Ltd. R-2105)
In the same manner as in Example 1, a reversible thermosensitive recording material was obtained. Comparative Example 4 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Oxidized starch (Nippon Shokuhin Kako Co., Ltd.)
  MS-8800), except that Example 1 was used.
Thus, a reversible thermosensitive recording material was obtained. Comparative Example 5 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
0) Instead of a solution of 20 parts dissolved in 840 parts of water, 5
3% vinyl acetate-ethylene-acrylic copolymer emulsion
(Sumika Flex 920, manufactured by Sumitomo Chemical Co., Ltd.) 3
Same as Example 1 except that 8 parts and 822 parts of water were mixed and used.
Thus, a reversible thermosensitive recording material was obtained. Comparative Example 6 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
0) Instead of a solution of 20 parts dissolved in 840 parts of water, 4
3% carboxyl group-modified styrene-butadiene emulsion
(LX-415A, manufactured by Zeon Corporation) with 44 parts
Same as Example 1 except that 816 parts of water were mixed and used.
Thus, a reversible thermosensitive recording material was obtained. Comparative Example 7 Carboxyl group-modified polyvinyl used in (A) of Example 1
Alcohol (T-35 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
0) instead of fully saponified polyvinyl alcohol (day
Example using NM-11 manufactured by Synthetic Chemical Industry Co., Ltd.
100 μm thick transparent polyethylene used in 1 (B)
Black on the surface instead of terephthalate (PET) sheet
188μm thick white polyethylene printed with colored letters
Other than using terephthalate (PET) sheet
A reversible thermosensitive recording material was obtained in the same manner as in Example 1. Test 1 (Coloring density) Reversible thermosensitive recording materials obtained in Examples 1 to 4 and Comparative Examples 1 to 6
Is heated in an oven controlled at 160 ° C. for 5 minutes
And quickly immerse it in liquid nitrogen to quench and develop color
State. The density of the obtained colored part and the density of the uncolored part
It measured using the transmission density meter Macbeth TD904. result
Are shown in Table 1. Test 2 (Coloring density) The reversible thermosensitive recording materials obtained in Example 5 and Comparative Example 7 were
Heat for 5 minutes in an oven controlled at
Quickly immerse in liquid nitrogen and cool quickly.
The unprinted part was colored. The resulting color
Densitometer Macbeth RD9
18 was used. The results are shown in Table 2. Test 3 (Erasability of Image) The reversible thermosensitive recording material having a colored portion obtained in Test 1
After heating in an oven controlled at 20 ° C for 5 minutes,
After cooling, the colored portion was erased. The density of this erased part is transparent.
The measurement was performed using Macbeth TD904. The result
The results are shown in Table 1. Test 4 (Erasability of Image) The colored part obtained in Test 2 was heated at 120 ° C
After heating in an oven for 5 minutes, the mixture was allowed to cool naturally and erased. this
Using the reflection densitometer Macbeth RD918 to determine the density of the erased part
It was measured. The results are shown in Table 2. Test 5 Reversible thermosensitive recording material obtained in Tests 1 and 3 and reversibility of uncolored color
Project thermal recording material with an overhead projector
And visually check the state of the colored part, erased part and uncolored part.
I thought. The results are shown in Table 1. Test 6 Reversible thermosensitive recording material obtained in Tests 2 and 4 and reversibility of uncolored color
The thermosensitive recording material is visually observed, and the colored portion, the erased portion,
Judgment of visibility of colored part and black character printed part
did. The results are shown in Table 2. [0097] [Table 1] In Table 1, .largecircle. Indicates a discrimination between an uncolored portion and an erased portion.
Is impossible at all, and the light transmission of the uncolored area and the erased area is not possible.
Good transience, the whole image is bright, and the printed image is clearly legible
X indicates that the light can be transmitted through the uncolored area and the erased area.
The image is too dark and the whole image is dark, making it difficult to determine the printed image.
Indicates difficulty. [0099] [Table 2] In Table 2, ○ indicates a colored portion, a non-colored portion, and a colored portion.
And erased part, black character printed part and uncolored part and black text
Good contrast between printed and erased characters
And there is almost no difference in visibility between the colored portion and the printed portion of black characters.
× indicates that the printed part of black characters is white and cloudy
Visibility, the visibility of the printed part of black characters is worse than that of the colored part
To indicate that [0101] As shown in Tables 1 and 2, a reversible developer,
Electron-donating dye precursor and carboxyl group-modified polyvinyl
Reversible heat by applying a coating solution containing alcohol on the support
A method for forming a recording layer, wherein the coating liquid comprises carboxy
Group-modified polyvinyl alcohol aqueous solution, reversible developer and
The electron-donating dye precursor is mixed, and the reversible microscope
The colorant and the electron-donating dye precursor are simultaneously wet-milled.
According to the method for producing a reversible thermosensitive recording material,
The reversible thermosensitive recording layer is transparent, and
Colored areas can be formed, and if a transparent support is used, transparency can be achieved.
A light-reversible thermosensitive recording material can be obtained, and an opaque support
When used, the color is clear and compatible with the support.
Characters and figures are formed between the reverse thermosensitive recording layer
In some cases, the visibility of this information is very good
A thermal recording material was obtained.

Claims (1)

(57) [Claim 1] A reversible thermosensitive recording layer on a support is usually provided with a colorless or pale-colored electron-donating dye precursor and a dye precursor depending on a difference in cooling rate after heating. A method for producing a color developing / decoloring type reversible thermosensitive recording material mainly containing a reversible developer which causes a reversible color tone change, comprising a reversible developer, an electron-donating dye precursor and a carboxyl group-modified polyvinyl alcohol. A method of forming a transparent reversible thermosensitive recording layer by coating a coating solution on a support, wherein the coating solution is obtained by mixing a carboxyl group-modified polyvinyl alcohol aqueous solution, a reversible developer and an electron-donating dye precursor. And a method for producing a reversible thermosensitive recording material obtained by simultaneously wet pulverizing a reversible developer and an electron-donating dye precursor in the mixture.