JP3403757B2 - Reversible thermosensitive recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a method for controlling heat energy.
Reversible thermosensitive recording material that can form and erase images
It is about fees. [0002] 2. Description of the Related Art Thermosensitive recording materials,Generally, the electron on the support
Donor, usually colorless or pale color dye precursor and electron acceptor
And 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,The recorded image is
What can be obtained, JP-B-43-4160, JP-B-45
It is disclosed in -14039 and the like. [0003] Generally,,Such a thermal recording material, once
When an image is formed, that part is erased and
It is impossible to return to the state, so record more information
If you do,Is it necessary to add to the part where the image is not formed
Was. When the area of the thermal recording part is limited
Has limited information that can be recorded,Enter all necessary information
There was a problem that it could not be recorded. In recent years, in order to deal with such a problem,,image
Reversible thermosensitive recording material capable of repeated formation and image erasure
For example, Japanese Patent Application Laid-Open No. 54-119377 has been proposed.
JP-A-63-39377, JP-A-63-39377
No. 41186 discloses a resin base material and a resin base material.
Describes a thermal recording material composed of dispersed organic small molecules
Have been. However,This method uses heat energy.
Is a material that reversibly changes the transparency of heat-sensitive recording materials.
The contrast between the image-formed area and the non-image-formed area is insufficient
It is. [0005] Also, Japanese Patent Application Laid-Open No. 50-81157,
In the method described in JP-A-50-105555
In other words, the image to be formed changes according to the ambient temperature.
Therefore, the temperature at which the image forming state and the erasing state are maintained is different.
At room temperature, these two states are maintained for an arbitrary period.
I can't hold it. Further, Japanese Patent Application Laid-Open No. 59-120492 is disclosed.
The recording material uses the hysteresis characteristics of the color components
Is maintained in the hysteresis temperature range.
A method for maintaining the erased state is described.
Requires a heating source and a cooling source for image formation and erasing.
The temperature range in which the image formation state and the erased state can be maintained
It has drawbacks limited to the temperature range of
It is still insufficient for use in living temperature environments. On the other hand, Japanese Patent Laid-Open Publication No.
JP-A-2-188294, International Publication No. WO90 /
No. 11898 includes leuco dyesas well asLeuco dyeing by heating
Reversibility composed of color-degrading agents that develop and decolorize dyes
Thermal recording materials are described. The color reducing agent is leuco dyeing
Decolorizes acidic groups that cause coloring and the leuco dye that has developed.
Amphoteric compound that has a basic group
Color by an acidic group or quenching by a basic group
One of the color effects is preferentially generated to perform color development and decoloration.
It is. However,In this way, the control of heat energy
It is not possible to completely switch between the coloring reaction and the
Possible, and both reactions occur at a certain rate
Color density was not obtained and decoloring could not be performed completely.
Me,Sufficient image contrast cannot be obtained. Also salt
Since the decolorizing action of the basic group also acts on the color-developed part at room temperature,
A phenomenon in which the density of the color-developed portion sometimes decreases is inevitable. As described above, in the conventional technology,,Good image
Contrast, capable of forming and erasing images,
Reversibility that can keep images stable over time in a living environment
No thermal recording material was present. However, the applicant,
In Japanese Patent Application No. 4-347032,New reversible color development
A reversible thermosensitive recording material using an agent was proposed. This
R,Form and erase images with good image contrast
To keep images stable over time in the environment of everyday life.
A reversible thermosensitive recording material has been proposed for the first time. Ma
In addition, this reversible thermosensitive recording material has one of the features of a color developing system.
In addition, recording in various hues is possible. [0009] The problem to be solved by the present invention is that blue to
Good contrast in density between color development and color erasure in purple hue
Good image formation and erasing is possible, and in the environment of everyday life
Keeps images stable over time, and has excellent repeated durability
To provide a reversible thermosensitive recording material. [0010] Means for Solving the Problems The present inventors have solved this problem.
As a result of research to solve the problem, usually colorless or pale color
Of the dye precursor and the cooling rate after heating
Reversible color developer causing reversible color change in precursor
Thermosensitive recording material provided with a reversible thermosensitive layer containing
Wherein the aza represented by the above formula 1 is used as the dye precursor
Use one or more phthalide compoundsthingBy
Image with good contrast in density between color development and color erasure
Can be formed and erased, and can be used over time in the environment of daily life
Reversibility with stable image retention and excellent repeated durability
A thermal recording material is obtainedthingFind,Complete the present invention
I came to. In Chemical Formula 1,Q¹, Q^TwoIs a hydrogen atom, halo
Gen atom, alkyl group, allyl group, hydroxyl group,
Represents a alkoxy group or a cycloalkyl group. Q¹, Q^Twoof
A divalent atom may be inserted in the carbon-carbon bond.
Q¹, Q^TwoIs an alkyl group or an alkoxy group,That one
The moiety may be cyclized. Also, Q¹, Q^TwoBinds to form a ring
You may not. Q^ThreeRepresents a hydrogen atom, a halogen atom,
Alkyl, nitro, allyl, hydroxyl, shear
Represents an amino group, an alkoxy group or a cycloalkyl group. Q
^ThreeA divalent atom is inserted into the carbon-carbon bond of
Is also good. Q^ThreeIs an alkyl group or an alkoxy group,So
May be cyclized. Q^FourIs hydrogen atom, halogen
Atom, alkyl group, alkoxy group or phenyl group,
Q^FiveIs hydrogen atom, halogen atom, alkyl group, alkoxy
Represents a silyl group or a phenyl group. Ring A represents a nitrogen-containing aromatic ring
The benzene nucleus B is unsubstituted,
Toro, alkyl, alkoxy or alkylamino
Represents a benzene nucleus substituted by a phenyl group. When a dye precursor satisfying the above conditions is used,
In this case, an image having a blue to purple hue is obtained, and
The contrast between the area and the decolored area is good, and
And the image storability is good. vice versa,Triphenyl meta
Naphthalide-based coloring dyes and asymmetric indolylphthalide-based dyes
Color pigments,In terms of the contrast between the color-developed part and the decolored part
Not preferred. These findings,Traditionally used
From the technology of general thermal paper and thermochromic materials
It was difficult to predict. The dye represented by the above formula 1 used in the present invention.
Specific examples of the material precursor include, for example,
However, the present invention is not limited to this.
No. 3- (1-ethyl-2-methylindoーLe
-3-yl) -3- (2-ethoxy-4-aminophenyi
) -4-azaphthalide, 3- (1-ethyl-2-methyl)
RuinーRu-3-yl) -3- (2-ethoxy-4-
Methylaminophenyl) -4-azaphthalide, 3- (1
-Ethyl-2-methylindiaーRu-3-yl) -3-
(2-ethoxy-4-ethylaminophenyl) -4-a
Zaphthalide, 3- (1-ethyl-2-methylindoーLe
-3-yl) -3- (2-ethoxy-4-dimethylamido
Nophenyl) -4-azaphthalide, 3- (1-ethyl-
2-methyl IndiaーRu-3-yl) -3- (2-ethoxy)
C-4-diethylaminophenyl) -4-azaphthali
Do, 3- (1-ethyl-2-methylindoーLe-3-a
) -3- (2-ethoxy-4-dipropylaminophen)
Nil) -4-azaphthalide, 3- (1-ethyl-2-me
Chill IndiaーRu-3-yl) -3- (2-ethoxy-4
-Dibutylaminophenyl) -4-azaphthalide, 3-
(1-ethyl-2-methylindiaーRu-3-yl) -3
-(2-ethoxy-4-dipentylaminophenyl)-
4-azaphthalide, 3- (1-ethyl-2-methylin
DoーRu-3-yl) -3- (2-ethoxy-4-dihexene
Silaminophenyl) -4-azaphthalide, 3- (1-
Ethyl-2-methylindol-3-yl) -3- (2
-Ethoxy-4-dihydroxyaminophenyl) -4-
Azaphthalide 3- (1-ethyl-2-methylindoーLe
-3-yl) -3- (2-ethoxy-4-dichloroamido
Nophenyl) -4-azaphthalide, 3- (1-ethyl-
2-methyl IndiaーRu-3-yl) -3- (2-ethoxy)
C-4-dibromoaminophenyl) -4-azaphthali
Do, 3- (1-ethyl-2-methylindoーLe-3-a
) -3- (2-ethoxy-4-diallylaminopheni)
) -4-azaphthalide, 3- (1-ethyl-2-methyl)
RuinーRu-3-yl) -3- (2-ethoxy-4-
Dihydroxyaminophenyl) -4-azaphthalide, 3
-(1-ethyl-2-methylindoーRu-3-yl)-
3- (2-ethoxy-4-dimethoxyaminophenyl)
-4-azaphthalide, 3- (1-ethyl-2-methyli
AndーRu-3-yl) -3- (2-ethoxy-4-die)
Toxiaminophenyl) -4-azaphthalide, 3- (1
-Ethyl-2-methylindiaーRu-3-yl) -3-
(2-ethoxy-4-dicyclohexylaminopheni
) -4-azaphthalide, 3- (1-ethyl-2-methyl)
RuinーRu-3-yl) -3- (2-ethoxy-4-
Dimethylethoxyaminophenyl) -4-azaphthali
Do, 3- (1-ethyl-2-methylindoーLe-3-a
) -3- (2-ethoxy-4-diethylethoxyamido)
Nophenyl) -4-azaphthalide, 3- (1-ethyl-
2-methyl IndiaーRu-3-yl) -3- (2-ethoxy)
C-4-diethylbutoxyaminophenyl) -4-aza
Phthalide, 3- (1-ethyl-2-methylindoーRoux
3-yl) -3- (2-ethoxy-4-dimethylcyclo
Hexaminophenyl) -4-azaphthalide, 3- (1
-Ethyl-2-methylindiaーRu-3-yl) -3-
(2-ethoxy-4-dimethoxycyclohexylamino
Phenyl) -4-azaphthalide, 3- (1-ethyl-2)
-Methyl IndiaーRu-3-yl) -3- (2-ethoxy)
-4-pyrrolidylaminophenyl) -4-azaphthalide 3- (1-ethyl-2-methylindoーLe
-3-yl) -3- (3-ethoxy-4-diethylamido
Nophenyl) -4-azaphthalide, 3- (1-ethyl-
2-methyl IndiaーRu-3-yl) -3- (2,3-di
Ethoxy-4-diethylaminophenyl) -4-azaph
Talide, 3- (1-ethyl-2-methylindoーLe-3
-Yl) -3- (4-diethylaminophenyl) -4-
Azaphthalide, 3- (1-ethyl-2-methylindoー
Ru-3-yl) -3- (2-chloro-4-diethylamido
Nophenyl) -4-azaphthalide, 3- (1-ethyl-
2-methyl IndiaーRu-3-yl) -3- (2-bromo
-4-diethylaminophenyl) -4-azaphthalide,
3- (1-ethyl-2-methylindoーRu-3-yl)
-3- (3-Chloro-4-diethylaminophenyl)-
4-azaphthalide, 3- (1-ethyl-2-methylin
DoーRu-3-yl) -3- (3-bromo-4-diethyl
Aminophenyl) -4-azaphthalide, 3- (1-ethyl
Ru-2-methyl-indiaーRu-3-yl) -3- (2-me
Tyl-4-diethylaminophenyl) -4-azaphthali
Do, 3- (1-ethyl-2-methylindoーLe-3-a
) -3- (2-Ethyl-4-diethylaminophenyl)
) -4-azaphthalide, 3- (1-ethyl-2-methyl)
RuinーRu-3-yl) -3- (2-propyl-4-
Diethylaminophenyl) -4-azaphthalide, 3-
(1-ethyl-2-methylindiaーRu-3-yl) -3
-(3-methyl-4-diethylaminophenyl) -4-
Azaphthalide, 3- (1-ethyl-2-methylindoー
Ru-3-yl) -3- (2-nitro-4-diethylamido
Nophenyl) -4-azaphthalide, 3- (1-ethyl-
2-methyl IndiaーRu-3-yl) -3- (2-allyl
-4-diethylaminophenyl) -4-azaphthalide,
3- (1-ethyl-2-methylindoーRu-3-yl)
-3- (2-hydroxy-4-diethylaminopheni
) -4-azaphthalide, 3- (1-ethyl-2-methyl)
RuinーRu-3-yl) -3- (2-cyano-4-di
Ethylaminophenyl) -4-azaphthalide, 3- (1
-Ethyl-2-methylindiaーRu-3-yl) -3-
(2-cyclohexylethoxy-4-diethylaminop
Enyl) -4-azaphthalide, 3- (1-ethyl-2-
Methyl IndiaーRu-3-yl) -3- (2-methylethy
(Xy-4-diethylaminophenyl) -4-azaphthalate
Do, 3- (1-ethyl-2-methylindoーLe-3-a
) -3- (2-Cyclohexylethyl-4-diethyl)
Aminophenyl) -4-azaphthalide, 3- (2-ethylindoーRu-3-yl)
-3- (2-ethoxy-4-diethylaminophenyl)
-4-azaphthalide, 3- (1-ethyl-2-chloroyi)
AndーRu-3-yl) -3- (2-ethoxy-4-die)
Tylaminophenyl) -4-azaphthalide, 3- (1-
Ethyl-2-bromoindoーRu-3-yl) -3- (2
-Ethoxy-4-diethylaminophenyl) -4-aza
Phthalide, 3- (1-ethyl-2-ethylindoーRoux
3-yl) -3- (2-ethoxy-4-diethylamino
Phenyl) -4-azaphthalide, 3- (1-ethyl-2)
-Propyl IndiaーRu-3-yl) -3- (2-ethoxy)
C-4-diethylaminophenyl) -4-azaphthali
, 3- (1-ethyl-2-methoxyindoーLe-3-
Yl) -3- (2-ethoxy-4-diethylaminophen
Nil) -4-azaphthalide, 3- (1-ethyl-2-e
Toxic IndiaーRu-3-yl) -3- (2-ethoxy-
4-diethylaminophenyl) -4-azaphthalide, 3
-(1-ethyl-2-phenylindoーRu-3-yl)
-3- (2-ethoxy-4-diethylaminophenyl)
-4-azaphthalide, 3- (2-methylindoーLe-3
-Yl) -3- (2-ethoxy-4-diethylaminophen)
Enyl) -4-azaphthalide, 3- (1-chloro-2-
Methyl IndiaーRu-3-yl) -3- (2-ethoxy-
4-diethylaminophenyl) -4-azaphthalide, 3
-(1-bromo-2-methylindoーRu-3-yl)-
3- (2-ethoxy-4-diethylaminophenyl)-
4-azaphthalide, 3- (1-methyl-2-methylin
DoーRu-3-yl) -3- (2-ethoxy-4-diethyl
L-aminophenyl) -4-azaphthalide, 3- (1-p)
Ropyl-2-methylindiaーRu-3-yl) -3- (2
-Ethoxy-4-diethylaminophenyl) -4-aza
Phthalide, 3- (1-butyl-2-methylindoーRoux
3-yl) -3- (2-ethoxy-4-diethylamino
Phenyl) -4-azaphthalide, 3- (1-pentyl-
2-methyl IndiaーRu-3-yl) -3- (2-ethoxy)
C-4-diethylaminophenyl) -4-azaphthali
De, 3- (1-hexyl-2-methylindoーLe-3-
Yl) -3- (2-ethoxy-4-diethylaminophen
Nyl) -4-azaphthalide, 3- (1-octyl-2-
Methyl IndiaーRu-3-yl) -3- (2-ethoxy-
4-diethylaminophenyl) -4-azaphthalide, 3
-(1-nonyl-2-methylindoーRu-3-yl)-
3- (2-ethoxy-4-diethylaminophenyl)-
4-azaphthalide, 3- (1-methoxy-2-methyli
AndーRu-3-yl) -3- (2-ethoxy-4-die)
Tylaminophenyl) -4-azaphthalide, 3- (1-
Ethoxy-2-methyl IndiaーRu-3-yl) -3-
(2-ethoxy-4-diethylaminophenyl) -4-
Azaphthalide, 3- (1-phenyl-2-methylindo
ーRu-3-yl) -3- (2-ethoxy-4-diethyl
Aminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindoーLe
-3-yl) -3- (2-ethoxy-4-diethylamido
Nophenyl) -7-azaphthalide, 3- (1-ethyl-
2-methyl IndiaーRu-3-yl) -3- (2-ethoxy)
C-4-diethylaminophenyl) -4,7-diazaf
Talide, 3- (1-methyl-2-methylindoーLe-3
-Yl) -3- (2-ethoxy-4-diethylaminophen)
Enyl) -7-azaphthalide, 3- (1-butyl-2-
IndiaーRu-3-yl) -3- (2-ethoxy-4-di
Ethylaminophenyl) -7-azaphthalide, 3- (1
-Pentyl-2-methylindiaーRu-3-yl) -3-
(2-ethoxy-4-diethylaminophenyl) -7-
Azaphthalide, 3- (1-hexyl-2-methylindo
ーRu-3-yl) -3- (2-ethoxy-4-diethyl
Aminophenyl) -7-azaphthalide, 3- (1-hepc
Cyl-2-methylindiaーRu-3-yl) -3- (2-
Ethoxy-4-diethylaminophenyl) -7-azaph
Talide, 3- (1-octyl-2-methylindoーRoux
3-yl) -3- (2-ethoxy-4-diethylamino
Phenyl) -7-azaphthalide, 3- (1-nonyl-2)
-Methyl IndiaーRu-3-yl) -3- (2-ethoxy)
-4-diethylaminophenyl) -7-azaphthalide,
3- (1-octyl-2-methylindoーLe-3-a
) -3- (2-ethoxy-4-diethylaminophenyl)
Le) -4,7-diazaphthalide, 3- (1-ethyl-4,5,6,7-tet)
Lachloro-2-methyl IndiaーRu-3-yl) -3-
(2-ethoxy-4-diethylaminophenyl) -4-
Azaphthalide, 3- (1-ethyl-4-nitro-2-me
Chill IndiaーRu-3-yl) -3- (2-ethoxy-4
-Diethylaminophenyl) -4-azaphthalide, 3-
(1-ethyl-4-methoxy-2-methylindoーRoux
3-yl) -3- (2-ethoxy-4-diethylamino
Phenyl) -4-azaphthalide, 3- (1-ethyl-4)
-Methylamino-2-methylindoーRu-3-yl)-
3- (2-ethoxy-4-diethylaminophenyl)-
4-azaphthalide, 3- (1-ethyl-4-methyl-2)
-Methyl IndiaーRu-3-yl) -3- (2-ethoxy)
-4-diethylaminophenyl) -4-azaphthalide. The above-mentioned dye precursors are each one kind or two kinds.
A mixture of more than one species may be used. Also,Emits in other hues
By mixing the dye precursor to color,I also do toning
Can be. [0021]AlsoUsed in the reversible thermosensitive layer according to the present invention.
As a reversible developer, in the presence of the above dye precursor,
Reversible color that can be retained due to the difference in cooling rate after heating
If it produces a tonal change,Used without any particular restrictions
I can do it. Preferred compounds in terms of color density and decolorability
As Japanese Patent Application No. 4-34732 filed by the present applicant,
The compounds described are preferably used. With these compounds
And the following general formula3Are represented. [0022]Embedded image [0023]However, in the chemical formula 3, n is an integer of 1 or more and 3 or less.
Represents a number, and l1 and l2 each represent an integer of 0 or 1.
R ¹ , R ^Two Is an aliphatic hydrocarbon group, alkoxy group, halogen
Represents a substituent or a hydrogen atom selected from atoms,
They may be the same or different. R ^Three Has 22 or more carbon atoms
It represents the following aliphatic hydrocarbon group. Also, X ¹ , X ^Two Is few
Represents a divalent group having at least one heteroatom,
May be the same or different, but when l1 is 0,
X ¹ Is -NRCO-, -NRSO _Two -, -NHCONH-
Represents a divalent group selected from the group consisting of
Represents a group hydrocarbon group. Ar is an aromatic which may have a substituent
Represents a group. In addition,3In the compound represented by^Threeof
It is preferable that the number of carbon atoms is large.^ThreeHas 5 or less carbon atoms
Some do not have sufficient decoloring effect. Also, R^ThreeCarbon number of
Is 23 or more because the production cost is high.^ThreeIs
Those having an aliphatic hydrocarbon group having 6 to 22 carbon atoms
Particularly preferred. General formula3The compound represented by is electron-accepting
It is a compound that has the ability to develop a dye precursor
HeelNot a specific decoloring effect,In other words, it also has a reversible effect
I'm cooperating. In addition, it is not used for ordinary thermal recording materials.
Electron accepting compound,Ie2,2-bis (4-hyd
Roxyphenyl) propane, bis (4-hydroxyphen)
Nyl) sulfone, benzyl 4-hydroxybenzoate, etc.
Is,No such reversible effect is seen. Next,
Electron-accepting compounds as reversible developers used in light
Specific examples of preferred examples are given below.
However, the present invention is not limited to this.[0026] 4'-hydroxyheptaneanilide, 4 '
-Hydroxy-3-methyloctaneanilide, 4'-h
Droxytridecaneanilide, 4'-hydroxyhepta
Decaneanilide, 4'-hydroxynonadecaneanili
, 3'-hydroxynonadecaneanilide, 4'-hydr
Roxy-10-octadeceneanilide, 4'-hydroxy
Seedocasan anilide, 15-cyclohexyl-4'-
Hydroxypentadecaneanilide, 4'-hydroxy-
5-tetradeceneanilide, 4'-hydroxy-3'-
Methylnonaneanilide, 3'-cyclohexyl-4'-
Hydroxyheptadecaneanilide, 3'-allyl-4 '
-Hydroxypentadecaneanilide, 4'-hydroxy
-3'-methoxyoctadecaneanilide, 3'-chloro
-4'-hydroxyoctadecaneanilide, 3'-hydr
Roxide decaneanilide, 2 ', 4'-dihydroxy
Putadecaneanilide,[0027] 4'-hydroxy-4-hexylbenzur
Nilide, 4'-hydroxy-4-dodecylbenzanili
4,4'-hydroxy-4-tetradecylbenzanili
4,4'-hydroxy-4-octadecylbenzanili
4,4'-hydroxy-4-pentadecylaminocarbo
Nilbenzanilide, 4'-hydroxy-4-hexyl
Carbonylaminobenzanilide, 4'-hydroxy-
4- (heptylthio) benzanilide, 4'-hydroxy
4-octadecyloxybenzanilide, 4'-h
Droxy-4-dodecylsulfonylbenzanilide,
4'-hydroxy-4-nonylsulfonyloxybenz
Anilide, 4'-hydroxy-4-dodecyloxysul
Honylbenzanilide, 4'-hydroxy-4-pentane
Decylaminosulfonylbenzanilide, 4'-hydro
Xy-4- (N-pentadecylideneamino) benzani
Lido, 4'-hydroxy-4- (N-heptadecylidene
Amino) benzanilide,[0028] 4'-hydroxy-3,4-dioctylio
Xibenzanilide, 4'-hydroxy-3,4,5-
Trioctadecyloxybenzanilide, 4'-hydro
Xy-3-octyl-4- (octylthio) benzani
Lido, 4'-hydroxy-3- (heptadecylthio)-
5-pentadecyloxybenzanilide, 4'-hydro
Xy-3-heptadecylcarbonylamino-5-dodeci
Rubenzanilide, 4'-hydroxy-3-octadecy
L-aminocarbonyl-5-tetradecylaminocarboni
Rubenzanilide, 4'-hydroxy-3-octadecy
Rusulfonylamino-5-octadecyloxybenzure
Nilide, 4'-hydroxy-3-heptadecyloxys
Ruphonyl-5-tetradecyloxysulfonylbenzure
Nilide, 4'-hydroxy-3,5-bis (N-dokoshi
Ridenamino) benzanilide,[0029] 4'-hydroxy-4-octadecylcal
Bonylaminobenzanilide, 4'-hydroxy-3-
Octadecylcarbonylamino-5-octadecyloxy
Sivenzanilide, 4'-hydroxy-3'-methyl-
4-nonylbenzanilide, 3'-allyl-4'-hydr
Roxy-4-pentadecylbenzanilide, 4'-hydr
Roxy-3'-methoxy-4-octadecylbenzani
Lido, 4'-hydroxy-3'-methyl-4-nonylo
Xibenzanilide, 4'-hydroxy-3'-propyl
Ru-4-nonadecylcarbonyloxybenzanilide,
3'-butyl-4'-hydroxy-4-octadecylo
Xycarbonyl benzanilide, 3'-hydroxy-4
-Pentadecylcarbonyloxybenzanilide, 3 '
-Hydroxy-4-nonadecylsulfonylbenzanili
3,3 ', 4'-dihydroxy-4-heptadecyl sulf
Honyloxybenzanilide, 3 ', 4', 5'-tri
Hydroxy-4-tetracosylaminosulfonylbenz
Anilide, 3 ', 5'-dihydroxy-4-pentakoshi
Luminocarbonyl benzanilide, 3'-hydroxy
-4- (N-dodecylideneamino) benzanilide, N
-[4- (3-hydroxyphenylaminocarbonyl)
Benzylidene] pentadecylamine,[0030] 4-hydroxy-4'-dodecylbenzure
Nilide, 4-hydroxy-4'-tetradecylbenza
Nilide, N-methyl-4-hydroxy-4'-octade
Silbenzanilide, 4-hydroxy-4'-octyl
Oxybenzanilide, 4-hydroxy-4'-octa
Decyloxybenzanilide, 4-hydroxy-4'-
(Octadecylthio) benzanilide, 4-hydroxy
-4'-pentylcarbonylbenzanilide, 4-hydrido
Roxy-4'-hexadecylcarbonylbenzanili
De, 4-hydroxy-4'-heptadecyloxycarbo
Nyloxybenzanilide, 4-hydroxy-4'-do
Decyloxycarbonylbenzanilide, 4-hydroxy
C-4'-docosyloxycarbonylbenzanilide,
4-hydroxy-4'-heptadecylcarbonyloxy
Benzanilide, 4-hydroxy-4'-cyclohexyl
Luminobenzanilide, 4-hydroxy-4'-oct
Tylaminobenzanilide, 4-hydroxy-4'-o
Kutadecylaminobenzanilide,[0031] 4-hydroxy-4'-heptylcarboni
Luminobenzanilide, 4-hydroxy-4'-hep
Tadecylcarbonylaminobenzanilide, 4-hydro
Xy-4'-octadecylaminocarbonylbenzani
Lido, 4-hydroxy-4 '-(8-octadecenyl)
Aminocarbonyl benzanilide, 4-hydroxy-
4'-dodecyl sulfENilbenzanilide, 4-hydro
Xy-4'-octyloxysulENilbensanili
Do, 4-hydroxy-4'-octadecyloxysulE
Nilbenzanilide, 4-hydroxy-4'-dodecyl
SurENyloxybenzanilide, N-4-hydroxy
Benzoyl-N'-octadecylidene-1,4-phenyl
Diamine, N-4- (4-hydroxyphenylcar
Bonylamino) benzylidenedecylamine, 4-hydrido
Roxy-4'-octyloxycarbonylaminobenz
Anilide, 4-hydroxy-4'-tetradecyloxy
Carbonylaminobenzanilide, 4-hydroxy-
4'-octadecylureylenebenzanilide,[0032] 3-hydroxy-4'-dodecyloxybe
Nsanilide, N-methyl-4-hydroxy-3'-o
Kutadecyloxybenzanilide, 3-hydroxy-
4'-octylbenzanilide, 3-hydroxy-4 '
-Tetradecylbenzanilide, N-methyl-3-hydrido
Roxy-4'-octadecylbenzanilide, 3-meth
Xy-4-hydroxy-4'-octadecyloxyben
Zuanilide, 3-allyl-4-hydroxy-4'-oct
Tadecyloxybenzanilide, 3-chloro-4-hydride
Roxy-4'-octadecylbenzanilide, 4-hydr
Roxy-4'-octyloxy-3'-methylbenzure
Nilide, 4-hydroxy-4'-octadecyloxy-
3'-chlorobenzanilide, 4-hydroxy-3 ',
4'-didecyloxybenzanilide, 4-hydroxy
-3'-octadecylamino-4'-octadecyloxy
Sivenzanilide, 4-hydroxy-2'-chloro-
3 ', 5'-didecyloxybenzanilide, 4-hydrido
Roxy-3 ', 4'-dioctadecyloxybenzani
Lido, 4-hydroxy-4'-octyl-3'-methyl
Benzanilide, 3-hydroxy-4-methyl-4'-
Tetradecylbenzanilide, N-methyl-4-hydro
Xy-3'-octadecylbenzanilide,[0033] 4- (N-octylsulfonylamino) phenyl
Enol, 4- (N-dodecylsulfonylamino) fe
Nol, 4- (N-octadecylsulfonylamino) phenyl
Enol, 4- (N-methyl-N-octadecylsulfo
Nylamino) phenol, 4- (N-3-methylhexyl)
Rusulfonylamino) phenol, 4'-hydroxy-
4-cyclohexylbenzenesulfonanilide, 4'-
Hydroxy-4-octylbenzenesulfoneanilide,
4'-hydroxy-4-dodecylbenzenesulfoneani
Lido, 4'-hydroxy-4-dodecyloxybenzene
Sulfonanilide, 4'-hydroxy-4-octadecy
Luoxybenzenesulfonanilide, 4'-hydroxy
-4- (dodecylthio) benzenesulfonanilide,
4'-hydroxy-4-hexylcarbonylbenzenes
Rufonanilide, 4'-hydroxy-4-hexadecyl
Carbonylbenzenesulfonanilide, 4'-hydroxy
C-4- (8-heptadecenyl) carbonylbenzenes
Rufonanilide, 4'-hydroxy-4-octyloxy
Cycarbonyloxybenzenesulfonanilide, 4'-
Hydroxy-4-dodecyloxycarbonylbenzenes
Rufonanilide, '-hydroxy-4-octacosylo
Xycarbonylbenzenesulfonanilide, 4'-hydr
Roxy-4-dodecylcarbonyloxybenzenesulfo
Anilide, 4'-hydroxy-4-hexylaminobe
Nzensulfoneanilide, 4'-hydroxy-4-oct
Tadecylaminobenzenesulfonanilide,[0034] 4'-hydroxy-4-heptadecylcal
Bonylaminobenzenesulfonanilide, 4'-hydro
Xy-4-dodecylaminocarbonylbenzenesulfone
Anilide, 4'-hydroxy-4-dodecylsulfonyl
Benzenesulfonanilide, 4'-hydroxy-4-o
Octyloxysulfonylbenzenesulfonanilide,
4'-hydroxy-4-octadecyloxysulfonyl
Benzenesulfonanilide, 4'-hydroxy-4-do
Decylsulfonyloxybenzenesulfoneanilide, N
-Octylidene-4- (4-hydroxyphenyl) amido
Nosulfonylaniline, N-dodecylidene-4- (4-
(Hydroxyphenyl) aminosulfonylaniline, N-
4- (4-hydroxyphenylaminosulfonyl) ben
Dylideneoctadecylamine, 4'-hydroxy-4-
Octyloxycarbonylaminobenzenesulfoneani
Lido, 4'-hydroxy-4-octadecyloxycal
Bonylaminobenzenesulfonanilide, 4'-hydro
Xy-4-octadecylureylenebenzenesulfone
Nilide,[0035] 3- (N-dodecylsulfonylamino) phenyl
Enol, 4- (N-octadecylsulfonamino) ca
Techol, 4- (N-octadecylsulfonamino)
Zorcinol, 4- (N-octadecylsulfonylamido
No) Pyrogallol, 4'-hydroxy-3-octylio
Xybenzenesulfonanilide, 3'-hydroxy-4
-Dodecyloxybenzenesulfonanilide, N-methyl
4'-Hydroxy-3-octadecyloxybenze
Sulphoneanilide, 3'-hydroxy-4-dodecyl
Benzenesulfoneanilide, 3-methyl-4- (N-do
(Decylsulfonamino) phenol, 4-methyl-3-
(N-tetradecylsulfonamino) phenol, 3 '
-Methoxy-4'-hydroxy-4-octadecyloxy
Sibenzenesulfonanilide, 3'-chloro-4'-hi
Droxy-4-octadecylbenzenesulfoneanily
4,4'-hydroxy-2,5-dimethyl-4-octa
Decylbenzenesulfonanilide, 3-methyl-4-
(N-octadecylsulfonamino) phenol, 4 '
-Hydroxy-3,4-dioctadecyloxybenzene
Sulfoneanilide,[0036] 4'-hydroxy-4-hexyldiphenyl
Rusulfide, 4'-hydroxy-4-dodecyldife
Nyl sulfide, 4'-hydroxy-4-tetradecyl
Diphenyl sulfide, 4'-hydroxy-4-octa
Decyl diphenyl sulfide, 4'-hydroxy-4-
Octadecylcarbonylaminodiphenyl sulfide,
4'-hydroxy-4-dodecyloxydiphenylsul
Fido, 4'-hydroxy-4-octadecyloxydi
Phenyl sulfide, 4'-hydroxy-4-dodecyl
Sulfonyldiphenyl sulfide, 4'-hydroxy-
4-octadecyloxysulfonyldiphenylsulfi
4,4'-hydroxy-4-octadecylsulfonylua
Minodiphenyl sulfide, 4'-hydroxy-4-to
Ridecylcarbonyl diphenyl sulfide, 4'-hydr
Roxy-4- (N-heptadecylideneamino) diphenyl
Rusulfide,[0037] 4'-hydroxy-3,4-didecyloxy
Sidiphenyl sulfide, 4'-hydroxy-3,4-
Dioctadecyloxydiphenyl sulfide, 4'-h
Droxy-3-octyl-4- (octylthio) dife
Nylsulfide, 4'-hydroxy-3-octadecyl
-5-tridecylsulfonyldiphenyl sulfide,
4'-hydroxy-3- (heptadecylthio) -5-pe
Pentadecyloxydiphenyl sulfide, 4'-hydro
Xy-3-heptadecylcarbonylamino-5-dodeci
Rudiphenyl sulfide, 4'-hydroxy-3-oct
Tadecylcarbonylamino-5-octadecyloxydi
Phenyl sulfide, 4'-hydroxy-3-heptade
Siloxysulfonyl-5-tetradecyloxysulfo
Nyldiphenyl sulfide, 4'-hydroxy-3,5
-Bis (N-docosylideneamino) diphenyl sulphie
Do, 4- (15-cyclohexylpentadecyl) -4 '
-Hydroxydiphenyl sulfide, 4'-hydroxy
-4- (5-tetradecenyl) diphenyl sulfide,
4'-hydroxy-4- (10-octadecenyloxy
Carbonyl) diphenyl sulfide, 4'-hydroxy
-3'-methyl-4-nonyldiphenyl sulfide[0038] 3'-allyl-4'-hydroxy-4-pe
Antadecyl diphenyl sulfide, 3'-chloro-4 '
-Hydroxy-4-octadecyldiphenyl sulfy
3,3'-chloro-4'-hydroxy-4-octadec
Ru-5-pentadecyloxydiphenyl sulfide,
4'-hydroxy-3'-methyl-4-nonyloxydi
Phenyl sulfide, 4'-hydroxy-3 '-(1-
Methylethyl) -4-pentacosylsulfonylaminodi
Phenyl sulfide, 4'-hydroxy-3 '-(2-
Methylpropyl) -4-nonadecyloxysulfonyldi
Phenyl sulfide, 3'-hydroxy-4-dodecyl
Diphenyl sulfide, 3'-hydroxy-4-octa
Decyl diphenyl sulfide, 2 ', 4'-dihydroxy
C-4-heptadecyldiphenyl sulfide, 3 ',
4'-dihydroxy-4-heptadecyldiphenylsul
Fido, 3'-hydroxy-4-dodecyloxycarbo
Nildiphenyl sulfide,[0039] N- (4-hydroxyphenyl) -N'-
Hexylurea, N- (4-hydroxyphenyl) -N '
-Octylurea, N- (4-hydroxyphenyl)-
N'-dodecyl urea, N- (4-hydroxyphenyl)
-N'-octadecyl urea, N- (4-hydroxy
Nyl) -N'-docosylurea, N- (4-hydroxy
Enyl) -N '-(2-heptyloctyl) urea, N-
(4-hydroxyphenyl) -N '-(14-cyclo
Xyltetradecyl) urea, N- (3-methyl-4-hi)
(Droxyphenyl) -N'-octadecylurea, N-
(4-hydroxyphenyl) -N '-(9-octadece
Nyl) urea, N- (3-allyl-4-hydroxyphenyl)
L) -N'-octadecyl urea, N- [3- (1,1-
Dimethylethyl) -4-hydroxyphenyl] -N'-
Octadecyl urea, N- (3,5-dimethyl-4-hydride
Roxyphenyl) -N'-octadecyl urea, N- (2
-Hydroxyphenyl) -N'-octylurea, N-
(3-hydroxyphenyl) -N'-octadecyl urine
Element, N- (3,4-dihydroxyphenyl) -N'-O
Kutadecyl urea, N- (3,4,5-trihydroxy
Enyl) -N'-tricosylurea, N- (4-hydroxy
(Ciphenyl) -N '-(4-tetradecylphenyl) urine
Element, N- (4-hydroxyphenyl) -N '-(4-
Xylphenyl) urea, N- (4-hydroxyphenyl)
) -N '-(3,4-dioctadecylphenyl) urea
And the like.[0040] Each of these reversible developers is one kind or
May be used as a mixture of two or more kinds.
The amount of the reversible developer used is 5 to 5000% by weight,
More preferably, it is 10 to 3000% by weight.[0041] Reversible dye precursor and reversible developer
As a method to be contained in the heat-sensitive layer,
A method of dispersing and containing is included. As a way to disperse
Is,Dissolve each compound alone in a solvent or in a dispersion medium
Dispersion method, mix each compound and then into solvent
Dissolving or dispersing in a dispersion medium, adding each compound
Dissolve or disperse in solvent after cooling by heating and homogenizing
There is a method of dispersing in a medium, etc.,What is specified
There is no. When dispersing,If necessary, a dispersant may be used.
As a dispersant when water is the dispersion medium,,Polyvinyl alcohol
Water-soluble polymers and various surfactants.
You. When dispersing aqueous systems,Water-soluble organic solvents such as ethanol
May be mixed. Besides this,Represented by hydrocarbons
When the organic solvent is the dispersion medium,Lecithin and phosphates
And the like may be used as the dispersant.[0042] Also, such as improving the strength of the reversible thermosensitive layer
With purpose,Binder can be added to reversible thermosensitive layer
Noh. Specific examples of the binder include starches,
Hydroxyethyl cellulose, methyl cellulose, cal
Boxymethylcellulose, gelatin, casein, polyvinyl chloride
Nyl alcohol, modified polyvinyl alcohol, polyacyl
Sodium acrylate, acrylamide / acrylate
Copolymer, acrylamide / acrylate / me
Tacrylic acid terpolymer, styrene / maleic anhydride copolymer
Polymer alkali salt, ethylene / maleic anhydride copolymerization
Water-soluble polymers such as alkali salts of the body, polyvinyl acetate,
Urethane, polyacrylate, styrene / pig
Diene copolymer, acrylonitrile / butadiene copolymer
Body, methyl acrylate / butadiene copolymer, ethylene
/ Vinyl acetate copolymer, ethylene / vinyl chloride copolymer
Body, polyvinyl chloride, ethylene / vinylidene chloride copolymer
And latexes such as polyvinylidene chloride
But,It is not limited to these.[0043] In addition, the coloring sensitivity and decolorization temperature of the reversible thermosensitive layer
Reversible thermo-fusible material as additive to control the degree
It can be contained in the heat-sensitive layer. 60 ° C ~ 200
C. It is preferred to have a melting point of 80.degree.
Those having a melting point of ° C. are preferred. For general thermal recording paper
The sensitizers used can also be used. these
As a compound of the formula, N-hydroxymethylstearic acid
Amide, stearic acid amide, palmitic acid amide, etc.
Waxes, naphthenes such as 2-benzyloxynaphthalene
Toll derivatives, p-benzylbiphenyl, 4-allyluo
Biphenyl derivatives such as xibiphenyl, 1,2-bis
(3-methylphenoxy) ethane, 2,2'-bis (4
-Methoxyphenoxy) diethyl ether, bis (4-
Polyether compounds such as methoxyphenyl) ether,
Diphenyl carbonate, dibenzyl oxalate, bis oxalate
Carbonic acid such as (p-methylbenzyl) ester
Acid diester derivatives and the like.
Can be added.[0044] Layer structure of the reversible thermosensitive recording material of the present invention,
If necessary, underlay between the support and the reversible thermosensitive layer.
Provide a protective layer on the coat layer and / or the reversible thermosensitive layer
You can also. In this case, the undercoat layer and / or
Alternatively, the protective layer is composed of a plurality of layers of two or three or more layers.
May be implemented. Undercoat layer and reversible thermosensitive layer
And / or an intermediate layer is provided between the protective layer and the reversible thermosensitive layer.
It may be. Reversible thermosensitive layer also contains each component one by one
2 layers or more by adding
The upper layer may be used. Further, in the reversible thermosensitive layer and / or
Or another layer and / or a reversible thermosensitive layer
Information is electrically, optically, and magnetically
A recordable material may be included. Also, the reversible thermosensitive layer
Anti-blocking and cover on the side opposite to the
A back coat layer is provided for the purpose of preventing
You can also.[0045] Protective layerPassingAnd / or the undercoat layer,
For the binder of the reversible thermosensitive layer, such as polyvinyl alcohol
Among the water-soluble polymers and latexes mentioned in the explanation,
It is formed with a material capable of forming a film as a main component. On the spot
Compound such as a compound having an epoxy group or zirconium salts
Hardening agents and crosslinking agents can be added. In addition, a protective layer
as,Apply light or electron beam curable resin or thermosetting resin.
It may be cured to form a protective layer. By plasma polymerization
A thin film may be formed and used as a protective layer.Also, Synthetic resin
A film may be laminated to form a protective layer. example
For example, films such as polystyrene and polypropylene
Used for nates. In any of the above cases,Writing
, RunnabilityAlsoHas improved repetition durability
Me,You may mix the pigment etc. which are mentioned later. Face used for protective layer
The average particle size of the material,0.4μmThe following are ways to increase image density
Preferred.[0046] Protective layerPassingAnd / or undercoat layer
IsDiatomaceous earth, talc, kaolin, calcined kaolin, charcoal
Calcium acid, magnesium carbonate, basic magnesium carbonate
, Titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide
Minium, urea-formalin resin, benzoguanamine tree
Fats, containing inorganic and organic pigments such as polyethylene resin
Is also good. In addition, in each layer, zinc stearate, stearate
Higher fatty acids such as calcium phosphate and barium stearate
Metal salts, paraffin, oxidized paraffin, polyethylene,
Polyethylene oxide, stearamide, caster wax
Waxes such as wax and dioctyl sulfoAmber
Dispersants such as sodium acid, surfactants, fluorescent dye
And coloring dyes and pigments.[0047] The reversible thermosensitive recording material of the present inventionPerson in chargeSupport
Paper, various nonwoven fabrics, woven fabrics, polyethylene
Synthetic resin film such as tarate or polypropylene, poly
Laminate synthetic resin such as ethylene and polypropylene
Paper, synthetic paper, metal foil, glass, etc.
Optional use of combined sheets according to purpose
However, the present invention is not limited to these. these
Is,Any of opaque, transparent, and translucent may be used.Ma
Was, To make the background look white or other specific colors,White
Pigments, colored dyes and bubbles in the supportAlsoIs contained on the surface
You may let it. Especially when aqueous coating is performed on films etc.
so,Low hydrophilicity of support,Undercoat layer
When it is difficult to apply the reversible thermosensitive recording layer,Corona discharge or
Supports hydrophilic treatment of the surface with razma and various polymers
An easy adhesion treatment such as application to the body surface may be performed. other
A treatment for antistatic treatment, curl correction, and the like may be performed.[0048] next,Specific examples of the reversible thermosensitive recording material of the present invention
However, the present invention is not limited to this.
Not something. Method for producing reversible thermosensitive recording material of the present invention
As a specific example of the method,If necessaryA provided
On the undercoat layer,Mainly composed of dye precursor and reversible developer
The reversible thermosensitive coating solution containing the reversible thermosensitive layer components
Dry,A method of forming a reversible thermosensitive layer is exemplified.
The method of smearing is not particularly limited, and may be replaced by a conventional method.
Can be formed. For example, air knife coat
Coater, blade coater, bar coater, curtain coater
Coating equipment such as lithography, letterpress, letterpress, intaglio, flexo,
Various marks by via, screen, hot melt, etc.
A printing press or the like can be used. In the hot melt method,Dissolution
MediumAlsoDoes not use a dispersion medium,Mix the ingredients,Can be heated
Melt the melt,Apply when hot.[0049] Next, the color development of the reversible thermosensitive recording material of the present invention
And a decoloring method will be described. To form a colored image
It is only necessary that rapid cooling occurs following heating.
Possible by heating with a thermal head, laser light, etc.
It is. Also, in order to erase the recorded image, after heating,
It is sufficient to cool it down.
, Heat stamp, high frequency heating, hot air, electric heater and
From light sources such as tungsten lamps and halogen lamps
It can be performed by using radiant heat, hot air or the like.[0050] The present invention will be described in more detail with reference to the following examples.
I do. Parts and percentages in the examples are on a weight basis.[0051] Example 1 (A) Preparation of reversible thermosensitive coating liquidMade Is a dye precursor 3- (1-ethyl-2-methylindo
Yl-3-yl) -3- (2-ethoxy-4-diethyl
Aminophenyl) -4-azaphthalide 40 parts 2.5%
Ball mill with 90 parts of polyvinyl alcohol aqueous solution
The mixture was pulverized to obtain a dye precursor dispersion. Then, Reversible color development
AgentN- (4-hydroxyphenyl) -N'-n-
100 parts of hexadecyl urea in 2.5% polyvinyl alcohol
Milled with a ball mill together with 400 parts,Reversibility
A developer dispersion was obtained. After mixing the two dispersions,
200 parts of 10% polyvinyl alcohol aqueous solution, water 400
Add partdo itMix well to form a reversible heat-sensitive coating liquid.Madedid.[0052] (B) Production of reversible thermosensitive recording materialMade The reversible heat-sensitive coating solution prepared in (A) is
2.5 g / solids smear on tarate (PET) sheet
m^TwoAfter smearing and drying, 5% polyvinyl alcohol
Aqueous solution of rucol 1.0g / m^TwoLike
Smeared and dried, treated with a super calender and reversible heat
A recording material was obtained.[0053] Example 2 3- (1-ethyl-2-methylindo used in Example 1
Yl-3-yl) -3- (2-ethoxy-4-diethyl
Instead of 40 parts of aminophenyl) -4-azaphthalide
3- (1-ethyl-2-methylindole-3-i
) -3- (2-ethoxy-4-diethylaminophenyl)
G) Except using 40 parts of -7-azaphthalide
A reversible thermosensitive recording material was obtained in the same manner as in Example 1.[0054] Example 3 3- (1-ethyl-2-methylindo used in Example 1
Yl-3-yl) -3- (2-ethoxy-4-diethyl
Instead of 40 parts of aminophenyl) -4-azaphthalide
3- (1-octyl-2-methylindole-3-
Yl) -3- (2-ethoxy-4-diethylaminophen
Nyl) -7-azaphthalide except that 40 parts were used.
A reversible thermosensitive recording material was obtained in the same manner as in Example 1.[0055] Comparative Example 1 3- (1-ethyl-2-methylindo used in Example 1
Yl-3-yl) -3- (2-ethoxy-4-diethyl
Instead of 40 parts of aminophenyl) -4-azaphthalide
3- (1-ethyl-indol-3-yl) -3-
Using 40 parts of (4-diethylaminophenyl) -phthalide
A reversible thermosensitive recording material was prepared in the same manner as in Example 1 except that the recording material was used.
I got the fee.[0056] Comparative Example 2 3- (1-ethyl-2-methylindo used in Example 1
Yl-3-yl) -3- (2-ethoxy-4-diethyl
Instead of 40 parts of aminophenyl) -4-azaphthalide
3,3-bis (4-dimethylaminophenyl) -6
-Dimethylaminophthalide (Crystal Violet La)
(Kuton) Except that 40 parts were used.
Thus, a reversible thermosensitive recording material was obtained.[0057] Test 1 (color density = thermal response) Reversible thermosensitive recordings obtained in Examples 1-3 and Comparative Examples 1-2
The material is Kyocera's print head KJT-256-8MGF.
1 with Okura Electric Thermal Facsimile Printing Tester TH-P
Using an MD, an applied pulse of 1.1 milliseconds and an applied voltage of 26
Print under the default conditions and measure the density of the resulting color image
It was measured using Macbeth RD918. Used for measurement
The spectral characteristics of the densitometer are the same as those of the densitometer Macbeth RD918.
This is a spectral characteristic when using a visual filter. Example 1
And the hue of the color images of Comparative Examples 1 and 2 were all blue.
~ Purple,The background, that is, the uncolored portion was white.[0058] Test 2 (image erasability) Colored images of Examples 1 to 3 and Comparative Examples 1 and 2 obtained in Test 1
And by passing the background through a hot roll at 110-120 ° C.
After erasing the image, the density was measured in the same manner as in Test 1.
Was. The results are shown in Table 1. Also, the image portion is calculated by the following equation 1.
And the contrast ratio of the density of the decolored part was calculated. Table 1 shows the results
It was shown to. If it is 10 or more, the contrast ratio is good.[0059] (Equation 1) A = B / C A: Contrast ratio B: Image density of color forming part C: Image density of decolored area[0060] Test 3 (repeated durability) Reversible thermosensitive recording materials obtained in Examples 1-3 and Comparative Examples 1-2
The fee for printing in test 1 and erasing the image in test 2 was 30.
Repeat the number of times to change the image density,
And the appearance of the sheets were tested.[0061] Initial marks of Examples 1-3 and Comparative Examples 1-2
Compare the image density of the character part with the image density of the print part after 30 times.
As a result, the image density of the printed portion after 30 times is
90% or more of the image density of
was there. Also, the density of the decolored area and the appearance of the sheet itself
Was good after the repetition.[0062] [Table 1] [0063] According to the present invention, the colorless or pale color represented by the general formula (1)
Difference between electron donor dye precursor of color and cooling rate after heating
Causes a reversible color change in the dye precursor
For reversible thermosensitive recording materials containing electron-accepting compounds
Image with good density contrast between color development and color erasure
Image formation / deletion can be repeated, under the environment of daily life
A reversible thermosensitive recording material that can maintain a stable image over time
I got it.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B41M 5/28-5/34 C09K 9/00

Claims (1)

(57) [Claims 1] A colorless or pale-colored dye precursor on a support, and a reversible color tone of the dye precursor caused by a difference in cooling rate after heating. A reversible thermosensitive recording material provided with a reversible thermosensitive layer containing a color developing agent, wherein one or more of the azaphthalide compounds represented by the following formula 1 are used as the dye precursor , and Agent
As one or more compounds represented by the following formula
Reversible thermosensitive recording material characterized Rukoto used. Embedded image (However, of Q ¹ in 1, Q ² represents a hydrogen atom, a halogen atom, an alkyl group, an allyl group, a hydroxyl group, a .Q ^1, Q ² which represents an alkoxy group or a cycloalkyl group having a carbon -
A divalent atom may be inserted into a carbon bond. Q ¹ ,
Q ² is an alkyl group, in the case of alkoxy groups, a part thereof may be cyclized. Further, Q ¹ and Q ² may combine to form a ring. Q ³ represents a hydrogen atom, a halogen atom, an alkyl group, a nitro group, an allyl group, a hydroxyl group, a cyano group, an alkoxy group or a cycloalkyl group. Q ³
May have a divalent atom inserted into the carbon-carbon bond. When Q ³ is an alkyl group or an alkoxy group, a part thereof may be cyclized. Q ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a phenyl group, Q ⁵
Represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a phenyl group. Ring A represents a nitrogen-containing aromatic ring,
The benzene nucleus B represents a benzene nucleus which is unsubstituted or substituted by a halogen atom, a nitro group, an alkyl group, an alkoxy group or an alkylamino group. ) ## STR2 ## (However, in Chemical formula 2, n represents an integer of 1 or more and 3 or less,
l1 and l2 each represent an integer of 0 or 1. R ¹ and R ² are
Select from aliphatic hydrocarbon groups, alkoxy groups, and halogen atoms
Represents a substituent or a hydrogen atom.
It may be. R ³ is a fat having 6 to 22 carbon atoms
Represents a group hydrocarbon group. X ¹ and X ² are at least one
Represents a divalent group having a hetero atom of
It may be different, but when l1 is 0, X ¹ is -N
_{RCO -, - NRSO 2 -,} - NHCONH -, - CR
= N-, -N = CR- represents a divalent group,
Represents a hydrogen atom or an aliphatic hydrocarbon group. Ar is substituted
Represents an aromatic group which may have a group. )