JPH06135169A - Thermal transfer recording material - Google Patents

Abstract

PURPOSE:To provide a thermal transfer recording material for obtaining an image which can obtain high density clear thermal transfer image recording, is free from generation of welding in transfer and decrease of image quality owing to bleeding preservation of the recording image. CONSTITUTION:A thermal transfer recording material is composed of a thermal transfer pigment donative material wherein a pigment donative layer which contains a heat transferable pigment containing a dissociative substituent is provided onto a base material, and a thermal transfer image receiving material wherein an acceptive layer containing a pigment fixing agent is provided onto the base material, and contains a self condensable compound in the pigment donative layer and/or the image receiving layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording material for recording an image by a thermal transfer system by heating corresponding to image information.

[0002]

2. Description of the Related Art In recent years, thermal transfer systems have been developed for obtaining prints from images electronically formed by color video cameras. According to the method for obtaining such a print, the color-separated image is converted into an electric signal, and this signal is transmitted to the printer. To obtain the print, the dye-donor element is placed face-to-face with the image-receiving element and inserted between the thermal head and the platen roller. The thermal head is energized and heated according to the transmitted signal. The dye-donor element is heated from the back side by a thermal head. The dye in the dye-donor element migrates to the image-receiving element and is recorded as an image. In the case of a color image, this operation is followed by heating using yellow, magenta, cyan and optionally black dye-donor elements to record the image. An alternative method of obtaining a thermal print using the aforementioned electrical signal is to use a laser instead of a thermal head. In this method, the dye-donor element contains a substance that strongly absorbs laser light. When the dye-donor material is irradiated with laser light, the light-absorbing substance converts light energy into heat energy, heats the dye-donor material, and the dye transfers to the image-receiving material. This light absorbing substance is contained in the dye-donor layer or in contact therewith. Laser light is modulated with an electrical signal to heat the dye-donor element.

[0003]

In order to reduce the load on the thermal head and to increase the recording speed, the dye-donor material used in the above-mentioned thermal transfer recording system should use a dye that is liable to transfer heat as much as possible. desirable. But,
Therefore, there arises a problem that the dye moves in the recorded image-receiving material to reduce the sharpness of the image, or it transfers to a contact object to be contaminated. In addition, the binder of the dye-donor layer is limited for high-speed recording, or the dye-fixing agent contained in the image-receiving layer of the image-receiving material causes wrinkles during transport of the dye-donor material in the printer, and The fusion of the dye-donor layer or the slip between the dye-donor element and the image-receiving element reduces the image quality.

[0004]

The above problems of the present invention are as follows.
A thermal transfer recording material comprising a thermal transfer dye-donating material having a dye-donating layer containing a heat-transferable dye on a support and a thermal transfer image-receiving material having a receiving layer containing a dye-receiving compound on the support. The heat transferable dye has a dissociative substituent, the dye receiving compound is a dye fixing agent, and the dye donating layer and / or the image receiving layer contains a self-condensing compound. It was found that a thermal transfer recording material characterized in that can be solved.

The thermal transfer recording material of the present invention uses a dye having a dissociative substituent in the dye-donor layer and a dye-fixing agent in the image-receiving layer to obtain a stable dye image during storage of the transfer record. You can Therefore, a heat transferable dye having a structure that allows easy transfer can be used. However, many of the dye fixing agents contained in the image-receiving layer have low heat resistance, and when the dye-donor layer and the image-receiving layer are closely contacted and heated during transfer, they may be fused to each other. The self-condensation type compound contained in the dye-donor layer and / or the image-receiving layer of the present invention is for solving the above problems. As a result, thermal transfer recording having a high transfer density, no trouble during transfer, and no deterioration in image quality during storage can be obtained.

The structures of the dye-donor element and the image-receiving element will be described below. Any conventionally known support can be used as the support of the thermal transfer dye-providing material. For example, polyethylene terephthalate, polyamide, polycarbonate,
Examples thereof include glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-donor element is generally 2
˜30 μm. An undercoat layer may be provided if necessary.

A thermal transfer dye-donor material using a heat-transferable dye basically has a dye-donor layer containing a dye and a binder which are movable by heat on a support. This thermal transfer dye-providing material is prepared by dissolving or dispersing a dye that becomes mobile by heat and a binder resin in an appropriate solvent to prepare a coating solution, which is used as a support for a conventionally known thermal transfer dye-providing material. On one side, for example, about 0.2-
It can be obtained by coating and drying at a coating amount of 5 μm, preferably 0.4 to 2 μm, to form a dye-donor layer. The dye-donor layer may be formed as a single layer, but it may be used in a case where it is used in a method in which it is repeatedly used many times.
You may form with a structure more than a layer. In this case, the dye content and dye / binder ratio in each layer may be different. The coating amount of the dye is 0.03 to 5 g / m ² , preferably 0.1 to ² g / m ² .

The heat transferable dye used in the present invention has a dissociative substituent. The dissociative substituent is preferably a substituted dye having a pka of 12 or less, particularly p
It is preferable that ka is 7 or less. As the dissociative substituent, known substituents can be used as long as they have the above properties,
Specifically, a phenolic hydroxyl group, carboxylic acid group, a sulfonic acid group, enolic hydroxyl group, a sulfonylamino group, active methylene group, -CONHCO -, - SO ₂ NHCO
And a heterocycle containing a structure of —SO ₂ NHSO ₂ — or —NH—. As the dissociative substituent of the present invention, a phenolic hydroxyl group is particularly preferable, and the dye having the phenolic hydroxyl group is a dye having a structure represented by the following general formula (I).

[0009]

[Chemical 1]

In the formula (I), R ¹ , R ² , R ³ and R ⁴ are
Each independently represents a hydrogen atom or an organic group capable of substituting for a benzene ring. Q is an atomic group necessary for the dye having the structure represented by the formula (I) to have absorption in the visible region and / or the near infrared region. R ¹ and R ² and / or R ³ and R ⁴ may be bonded to each other to form a ring structure. As the ring structure, for example, a benzene ring (condensed to a naphthyl ring), a pyridine ring (condensed to a quinoline ring), or a structure of the following general formula (Ia) is preferable.

[0011]

[Chemical 2]

In the formula (Ia), d ¹ , d ² , d ³ and d ⁴ are alkyl groups (which may be substituted and have 1 to 10 carbon atoms),
Hydrogen atom, aryl group (6 carbon atoms which may be substituted)
10 to 10), and R ¹ , R ² and Q have the same meanings as described above.
The general formula (I) will be described in detail below. R ¹ ,
R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent capable of substituting on the benzene ring, and the substituent includes a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, Hydroxy group, nitro group, amino group (including substituted amino group), alkoxy group, aryloxy group, acylamino group, aminocarbonylamino group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino Group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl Groups, acyl groups, carboxylic acid groups (and their salts ), Sulfonic acid groups (including salts thereof), and the like.

Specific examples of the substituent include a hydrogen atom,
Alkyl group (preferably having 1 to 30 carbon atoms such as methyl, cyclopropyl, vinyl, allyl, octyl, methoxyethyl, cyanoethyl, ethyl, propyl and butyl), alkoxy group (preferably having 1 to 30 carbon atoms such as methoxy and ethoxy) , Methoxyethoxy, isopropoxy), halogen atoms (eg bromine, fluorine, chlorine),
Acylamino group (preferably an alkylcarbonylamino group having 1 to 30 carbon atoms (eg formylamino, acetylamino, propionylamino, cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 30 carbon atoms (eg benzoylamino, p- Toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino)], an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl), a cyano group, a sulfonylamino group (preferably having 1 to 30 carbon atoms). , Methanesulfonylamino, ethanesulfonylamino, N-methylmethanesulfonylamino), a carbamoyl group [preferably an alkylcarbamoyl group having 2 to 30 carbon atoms (for example, methylcarbamoyl,
Dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl, t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl, ethylcyanoethylcarbamoyl, benzylcarbamoyl, ethoxycarbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl, Phenoxymethylcarbamoyl, allylcarbamoyl, crotylcarbamoyl, prenylcarbamoyl, 2,3-dimethyl-2-butenylcarbamoyl, homoallylcarbamoyl, homocrotylcarbamoyl, homoprenylcarbamoyl), preferably arylcarbamoyl group having 7 to 30 carbon atoms ( For example phenylcarb Yl, p- toluylene carbamoyl, m- methoxyphenylcarbamoyl, 4,5-dichloro-phenylcarbamoyl, p- cyanophenylcarbamoyl, p- acetylamino phenylcarbamoyl, p
-Methoxycarbonylphenylcarbamoyl, m-trifluoromethylphenylcarbamoyl, o-fluorophenylcarbamoyl, 1-naphthylcarbamoyl), preferably a C4-30 phthalylcarbamoyl group (eg 2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4 -Pyridylcarbamoyl, 2-thiazolylcarbamoyl, 2-benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl, 2- (4-methylphenyl) 1,3,4-thiadiazolylcarbamoyl)],
Sulfamoyl group (preferably having 0 to 30 carbon atoms, for example, methylsulfamoyl, dimethylsulfamoyl), aminocarbonylamino group (preferably having 1 to 30 carbon atoms,
For example, methylaminocarbonylamino, dimethylaminocarbonylamino), an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino), a hydroxy group, an amino group (preferably having 0 to 30 carbon atoms,

For example, amino, methylamino, dimethylamino, anilino), an aryl group (preferably having 6 to 6 carbon atoms)
30, for example, phenyl, m-acetylphenyl, p-methoxyphenyl), a heterocyclic group (preferably having 3 to 10 carbon atoms).
30, such as 2-pyridyl, 2-furyl, 2-tetrahydrofuryl), nitro group, aryloxy group (preferably having 6 to 30 carbon atoms such as phenoxy, p-methoxyphenoxy, o-chlorophenoxy), sulfamoylamino. A group (preferably having 0 to 30 carbon atoms, for example, methylsulfamoylamino, dimethylsulfamoylamino),
Alkylthio group (preferably having 1 to 30 carbon atoms, for example, methylthio, ethylthio), arylthio group (preferably having 6 to 30 carbon atoms, such as phenylthio, p-methoxyphenylthio, o-chlorophenylthio), sulfonyl group (preferably having carbon number) 1-30, for example, methanesulfonyl, p-toluenesulfonyl), an acyl group (preferably having 1-30 carbon atoms, for example, formyl, acetyl, benzoyl, p-toluyl), a heterocyclic oxy group (preferably having 3-30 carbon atoms). , An azo group (preferably having a carbon number of 3 to 30,
For example, p-nitrophenylazo), an acyloxy group (preferably having a carbon number of 1 to 30, such as acetyloxy, benzoyloxy), a carbamoyloxy group (preferably having a carbon number of 1 to 30, such as methylcarbamoyloxy), a silyloxy group (preferably C3-30, such as trimethylsiloxy, an aryloxycarbonyl group (preferably C7-30, such as phenoxycarbonyl), an imide group (preferably C4-30, such as phthalimide), a heterocyclic thio group (preferably Has 3 to 3 carbon atoms
30), a sulfinyl group (preferably having 1 to 30 carbon atoms,
For example, diethylaminosulfinyl), phosphoryl group (preferably having 0 to 30 carbon atoms, for example, diaminophosphoryl), carboxylic acid group (including its sodium salt, potassium salt, etc.), sulfonic acid group (including its sodium salt, potassium salt, etc.) , And so on.

The structure of Q is preferably the following general formula (I
I) to (XIX).

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

In the formula (II), R ⁵ represents a 5- or 6-membered ring containing at least one of oxygen, nitrogen or sulfur as an alkyl group, an aryl group or a hetero atom. R ⁶ is R
It has the same meaning as ^1, and specific examples thereof include those described for R ¹ . X is, -N = or, -C (R ¹⁰⁰⁾ =
Represents R ¹⁰⁰ represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group or an aminocarbonyl group. All X's in formulas (III) to (XVII) have the same meaning as described above. R ⁵ is an alkyl group (having a carbon number of 1 to
6) and an aryl group (having 6 to 10 carbon atoms) are preferable. R ⁶
Are preferably an alkyl group (having 1 to 6 carbon atoms), an aryl group (having 10 carbon atoms), and an amino group (having 1 to 7 carbon atoms, particularly an anilino group). X is preferably -N =.

In the formula (III), R ⁷ has the same meaning as R ¹ .
The same specific examples can be given. X ¹ is 5-6
Represents the atomic group necessary to form a nitrogen-containing heterocycle of the member. R ⁷ is preferably an alkyl group (having 1 to 6 carbon atoms) or an aryl group (having 6 to 10 carbon atoms). Particularly preferably, X ¹ forms a triazole ring.

In the formula (IV), R ⁸ , R ⁹ and R ¹⁰ each independently have the same meaning as R ¹ . Specific examples thereof include those mentioned for R ¹ . R ⁸ is preferably an acylamino group (having 1 to 6 carbon atoms). R ⁹ is preferably a halogen atom or a hydrogen atom. R ¹⁰ is preferably an acylamino group (having 1 to 6 carbon atoms) or an alkyl group (having 1 to 4 carbon atoms).

In the formula (V), R ¹¹ and R ¹² are each independently R.
Synonymous with ¹ . Specific examples thereof include those described for R ¹ . R ¹¹ is an alkyl group (having a carbon number of 1 to
6), an aryl group (having 6 to 10 carbon atoms) and a heterocyclic group (having 2 to 6 carbon atoms) are preferable. R ¹² is preferably an aryl group (having 6 to 10 carbon atoms), an acylamino group (having 1 to 6 carbon atoms), and a heterocyclic group (having 2 to 6 carbon atoms).

In the formulas (VI), (VII) and (VIII), R ¹³ and R
¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ are each independently R ¹
Is synonymous with. Specific examples thereof include those described for R ¹ . X ² and X ³ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. R ¹³ , R ¹⁴ , R
¹⁵ and R ¹⁶ are each independently a cyano group, an alkoxycarbonyl group (having 2 to 10 carbon atoms), an aryloxycarbonyl group (having 7 to 10 carbon atoms), an aminocarbonyl group (having 1 carbon atom).
To 6) and aryl groups (having 6 to 10 carbon atoms) are preferable. R
Each of ¹⁷ , R ¹⁸ and R ¹⁹ is preferably a substituent determined such that the sum of Hammett's substituent constants σp values is 0.60 or more. It is preferable that X ² and X ³ each independently form a triazole ring.

In the formula (IX), R ²⁰ , R ²¹ and R ²² each independently have the same meaning as R ¹ . Specific examples thereof include those described for R ¹ . Z ¹ is -N = or -C (R
¹⁰¹ ) = represents. R ¹⁰¹ has the same ^meaning as R ¹⁰⁰ , R ²⁰ ,
R ²¹ is independently a cyano group, an alkoxycarbonyl group (having 2 to 10 carbon atoms), an aryloxycarbonyl group (having 7 to 10 carbon atoms), an aminocarbonyl group (having 1 to 1 carbon atoms).
6) and an acyl group (having 2 to 6 carbon atoms) are preferable. R ²² is
Preferred as R ²⁰ is a halogenated alkyl group (having 1 carbon atom).
To 6) and halogenated aryl groups (having 6 to 10 carbon atoms) are preferable. Z ¹ is preferably -C (CN) =.

In the formulas (X), (XI) and (XII), R ²³ ,
R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , and R ³² each independently have the same meaning as R ¹ . Specific examples thereof include those described for R ¹ . R ²⁸ and R ²⁹ may combine with each other to form a naphthalene ring or a condensed heterocycle. The condensed heterocycle represents a 5- or 6-membered ring containing at least one of oxygen, nitrogen and sulfur as a hetero atom. Preferably, a pyridine ring (condensed to form a quinoline ring).
Alternatively, it is the following chemical formula 7.

[0027]

[Chemical 7]

In the above formula, d ¹ , d ² , d ³ and d ⁴ are
It is the same as the one explained in. R ²⁶ , R ²⁷ and X are as defined above. n and m each independently represent an integer of 0 to 4. R ²⁴ , R ²⁵ , R ³⁰ , and R ³¹ each independently represent a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an aminocarbonyl group. Z ² is -S-,
-SO -, - SO ₂ - represent. Both R ²³ and R ³² are preferably hydrogen atoms. Both R ²⁴ and R ²⁵ are preferably a cyano group. R ²⁶ is preferably an acylamino group (having 1 to 6 carbon atoms). R ²⁷ is preferably a hydrogen atom. R ²⁸ is a halogen atom,
A hydrogen atom is preferred. R ²⁹ is preferably an acylamino group (having 1 to 6 carbon atoms) or an alkyl group (having 1 to 6 carbon atoms). R
Both of ³⁰ and R ³¹ are preferably a cyano group. Z ² is -SO ₂
− Is preferable.

In the formulas (XIII), (XIV) and (XV), Z ³ is ═C (R ³³ ) — or ═N—. R ³³ , R ³⁴ , R
³⁵ has the same meaning as R ¹ each independently. The concrete example is also R
^The ones mentioned in ¹ can be mentioned. R ³⁴ and R ³⁵ may combine with each other to form a ring structure. The ring structure is
Specific examples include rings of furan, thiophene, pyrrole, pyrazole, imidazole, thiazole, isothiazole, oxazole, isoxazole, and pyridine. R ³⁶ , R ³⁷ , and R ³⁹ are each independently an alkyl group,
It represents an aryl group, a heterocyclic group, or an amino group (including an anilino group). Here, the heterocyclic group contains at least one of oxygen, nitrogen and sulfur as a hetero atom.
~ Represents a 6-membered ring. Specific examples thereof include those described for R ¹ . R ³⁸ represents an electron-withdrawing group having a Hammett substituent constant of 0.3 or more. Z ³ is = CR ³³ - is preferable. Both R ³³ and R ³⁴ are preferably a cyano group. R ³⁵ is an aryl group (having 6 to 10 carbon atoms) or a heterocyclic group (having 2 to 2 carbon atoms).
6) is preferred. R ³⁶ is an anilino group (having 6 to 1 carbon atoms)
0) is preferred. R ³⁷ is an alkyl group (having 1 to 6 carbon atoms),
Aryl group (C6-10), heterocyclic group (C6)
10 to 10) are preferable. R ³⁸ is preferably a cyano group. R
³⁹ is preferably an aryl group (having 6 to 10 carbon atoms) or a heterocyclic group (having 2 to 6 carbon atoms).

In the formula (XVI), R ⁴⁰ and R ⁴¹ are each independently
Synonymous with R ²⁴ . Specific examples thereof include those mentioned for R ²⁴ . Both R ⁴⁰ and R ⁴¹ are preferably a cyano group.

In formula (XVII), R ⁴³ and R ⁴⁴ each independently have the same meaning as R ⁵ . Specific examples thereof include those mentioned for R ⁵ . R ⁴³ and R ⁴⁴ are each independently an alkyl group (having 1 to 6 carbon atoms) or an aryl group (having 6 to 1 carbon atoms).
0) is preferred.

In formula (XVIII), R ⁴⁵ and R ⁴⁶ each independently have the same meaning as R ²⁵ . Specific examples thereof include those mentioned for R ²⁵ . R ⁴⁷ has the same meaning as R ¹ . Specific examples thereof include those described for R ¹ . R
Both ⁴⁵ and R ⁴⁶ are preferably a cyano group. R ⁴⁷ is preferably an aryl group (having 6 to 10 carbon atoms) or a heterocyclic group (having 2 to 6 carbon atoms).

In formula (XIX), A represents an aryl group or a heteroaromatic ring group. Preferred as A is an aryl group [having 6 to 10 carbon atoms. It may be substituted with a substituent, and as the substituent, an alkyl group, an alkoxy group,
Aryloxy group, acyloxy group, aryl group, halogen atom, aryloxycarbonyl group, alkyloxycarbonyl group, cyano group, nitro group, carbamoyl group, acyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, amino A carbonylamino group, a sulfonyl group, a sulfamoyl group, a sulfonylamino group, an amino group (including a substituted amino group), a hydroxy group, and a heterocyclic group]. Further, a heteroaromatic ring group (having 2 to 30 carbon atoms) is also preferable. Preferred heterocyclic groups include imidazolyl group, pyridyl group, pyrazolyl group, thiazolyl group, benzimidazolyl group, quinolyl group, benzopyrazolyl group, benzothiazolyl group, isothiazolyl group. , A benzoisothiazolyl group, a pyridoisothiazolyl group, and a thiadiazolyl group.

Preferred examples of A include 6 to 6 carbon atoms.
30 aryl groups, for example p-methoxyphenyl, m
-Methoxyphenyl, o-methoxyphenyl, p-chlorophenyl, m-chlorophenyl, o-chlorophenyl, p-nitrophenyl, p-cyanophenyl, p-
(N, N-diethyl) phenyl, 2,4-dichlorophenyl, m-fluorophenyl, p-tolyl, p-mesylphenyl, 3,4-dicyanophenyl, 4-methoxycarbonylphenyl, 2,4,6-trichlorophenyl ),
Examples thereof include a heterocyclic group having 2 to 30 carbon atoms, for example, a group represented by the following chemical formula.

[0035]

[Chemical 8]

Among the dyes used in the present invention, particularly preferable ones are those in which Q is represented by the general formula (VI), (VII) or (VIII). Specific examples of the dye used in the present invention are shown below, but the present invention is not limited thereto.

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

[0051]

[Chemical formula 23]

As a method for synthesizing the above-mentioned dyes used in the present invention, a conventional synthesizing method can be used. For example, oxidative coupling of the coupler compound and the p-hydroxyaniline compound for each dye (X is -N = Or when a coupler compound and p-hydroxyaryl aldehyde are dehydrated and condensed [when X is —C (R ¹⁰⁰ ) =]. In the dye-donor layer, as the binder for fixing the dye used together with the above-mentioned dye, any binder resin known in the related art for such purpose can be used. That is, a material having high heat resistance, which prevents the dye from migrating and precipitating during transfer of the dye-donor material or migrating to another, and which does not hinder the migration of the dye when heated is selected. It For example, polyamide resin,
Polyester resin, epoxy resin, polyurethane resin, polyacrylic resin (for example, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resin such as polyvinylpyrrolidone, polyvinyl chloride resin (for example, chloride Vinyl-vinyl acetate copolymer), polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose). Partial saponification of triacetate) and polyvinyl alcohol resins (eg polyvinyl alcohol, polyvinyl butyral, etc.) Polyvinyl alcohol), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g. polyethylene,
Polypropylene) is used.

Such a binder resin is preferably used in a proportion of, for example, about 20 to 600 parts by weight per 100 parts by weight of the dye. In the present invention, a conventionally known ink solvent can be freely used as an ink solvent for dissolving or dispersing the above dye and binder resin.

Further, a slipping layer may be provided to prevent the thermal head from sticking to the dye-donor element. The slipping layer is composed of a lubricating material, with or without a polymeric binder, such as a surfactant, a solid or liquid lubricant or mixtures thereof. In order to prevent sticking due to the heat of the thermal head and improve slippage when printing from the back side of the dye-donor material, it is preferable to perform sticking prevention treatment on the side of the support on which the dye-donor layer is not provided. For example, a reaction product of polyvinyl butyral resin and isocyanate,
It is preferable to provide a heat-resistant slip layer mainly composed of an alkali metal salt or alkaline earth metal salt of phosphoric acid ester and a filler. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80 to 11
The weight percentage of the vinyl butyral portion is from 15 to 4 from the viewpoint that there are many reaction sites with isocyanate at 0 ° C.
0% is good. As the alkali metal salt or alkaline earth metal salt of the phosphoric acid ester, Gafac RD720 manufactured by Toho Kagaku Co., Ltd. is used, and it may be used in an amount of 1 to 50% by weight, preferably 10 to 40% by weight, based on the polyvinyl butyral resin. . The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

The dye-donor element may be provided with a hydrophilic barrier layer for preventing the dye from diffusing toward the support. The hydrophilic dye barrier layer contains hydrophilic materials useful for the intended purpose. Generally good results are gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate grafted gelatin,
Ethyl methacrylate graft gelatin, cellulose monoacetate, methyl cellulose, poly (vinyl alcohol),
Poly (ethyleneimine), poly (acrylic acid), a mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) ). Especially preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The dye-donor layer is formed by selecting a dye so that a desired hue can be transferred when printed, and by arranging two or more dye-donor layers having different hues side by side with one thermal transfer dye-donor material, if necessary. May be. For example, when an image such as a color photograph is formed by repeatedly printing each color according to the color separation signal, it is desirable that the hue when printed is cyan, magenta, and yellow, and such a hue is given. Line up the three dye-donor layers containing the dye. Alternatively, in addition to cyan, magenta, and yellow, a dye-donor layer containing a dye that imparts a black hue may be added. It is preferable to provide a mark for position detection at the same time when any one of the dye-donor layers is formed during the formation of these dye-donor layers, because an ink or printing step different from the dye-donor layer formation is not required.

The dye-donor elements of the invention are used in sheet form or as a continuous roll or ribbon. If a continuous roll or ribbon is used, it may have only one type of dye, or may have areas of different dyes such as heat transfer cyan and / or magenta and / or yellow and / or black and other dyes. Have separately. That is, one-color, two-color, three-color, or four-color materials (or even multi-color materials) are included within the scope of the present invention.

In the present invention, the support used for the thermal transfer image-receiving material can withstand the transfer temperature and satisfies the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, dents after transfer and the like. Anything that can be used can be used. For example, synthetic paper (synthetic paper such as polyolefin and polystyrene), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper support such as paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, polycarbonate, etc. Films or sheets treated to impart white reflectivity to the plastic, and laminates of any combination of the above may also be used.

As the support of the image receiving material for transmission observation, a generally known support is used as long as it has heat resistance enough to withstand thermal transfer processing and transparency enough to allow the transferred image to be observed. . Specifically, polyethylene, polypropylene, polyvinylidene chloride, polyvinyl alcohol, polyester, polycarbonate, polyamide, polystyrene, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ionomer, acetyl cellulose, cellulose ester, polyvinyl acetal. Resin films of polyvinyl chloride, polyphenylene sulfone, polyether sulfone, polyether ketone, polyetherimide, polyacrylate, polymethylmethacrylate, etc. are used. In consideration of transparency, flexibility, heat resistance, etc., films of polyester, polycarbonate, polyamide, etc. are preferable, and polyethylene terephthalate and polyethylene naphthalate films are particularly preferable. These resin films may be used alone or in the form of a laminated film. The thickness of these supports is usually 25 μm to 500 μm.
m, preferably about 75 μm to 200 μm.

The thermal transfer image receiving material is provided with a dye receiving layer. This receiving layer contains a substance capable of receiving the heat transferable dye which has a function of receiving the heat transferable dye transferred from the heat transfer dye-providing material during printing and dyeing the heat transferable dye. Or with other binder substances, it is preferable that the film has a thickness of about 0.5 to 50 μm. In the present invention, a dye fixing agent is used as the substance capable of receiving the heat transferable dye.

In the above case, the dye fixing agent can be arbitrarily selected from the commonly used dye fixing agents, and among them, polymer dye fixing agents are particularly preferable. Here, the polymer dye fixing agent includes a polymer containing a repeating unit represented by the following general formula (XX).

[0062]

[Chemical formula 24]

In the formula (XX), a ¹ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 4 carbon atoms.
D ¹ represents a divalent group connecting a carbon atom and D ² . D
² represents a tertiary amino group, a nitrogen-containing heterocyclic group, or a quaternary cation group.

Specific examples of a ¹ are hydrogen atom, halogen atom (eg chlorine atom, bromine atom), cyano group or alkyl group having 1 to 4 carbon atoms (eg methyl, ethyl, propyl, butyl etc.). Represents a ¹ preferably represents a hydrogen atom or a methyl group. Specifically as D ¹ , -O
CO -, - COO -, - (CH 2) V -, - SO 2 -,
_{-COO- (CH 2) V -,} - OCO- (CH 2) V -
(V represents an integer of 1 to 3), -O-, -CONH-,
^{-CON (R 1) -, -} SO 2 N (R 1) -, - CON
HCONH -, - CONHCOO- or -C ₆ H ₄ -
(Wherein R ¹ has the same meaning as that of formula (I)) alone or in combination. D
¹ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl,
Ethyl, propyl, butyl, chloromethyl, methoxymethyl, etc.), alkoxy groups (eg methoxy, ethoxy,
Propoxy, butoxy, etc.) and the like. D ¹ is
Preferably _{-OCO -, - OCO- (CH 2} ) V -, -
_{COO- (CH 2) V -,} - CH 2 - or -C ₆ H ₄ -
CH ₂ - represent.

When D ² represents a tertiary amino group, the tertiary amino group is represented by —N (D ⁴ ) D ⁵ , and D ⁴ and D ⁵ each independently have the same meaning as R ¹ . D ⁴ and D ⁵ may form a ring structure, and the ring structure represents a 5- or 6-membered ring which may contain oxygen, nitrogen or sulfur. D ⁴ and D ⁵ preferably independently represent an alkyl group having 1 to 6 carbon atoms or a benzyl group. When D ² represents a nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic group is preferably an imidazole group or a pyridyl group, which may be substituted. Examples of the substituent include the above R ¹ . When D ² represents a quaternary cation group, the quaternary cation group is preferably a quaternary ammonium group or a quaternary imidazole group. The quaternary ammonium group is represented by the following general formula (XXI).

[0066]

[Chemical 25]

In the formula (XXI), D ⁶ , D ⁷ and D ⁸ each independently have the same meaning as R ¹ . D ⁶ and D ⁷ or D ⁷ and D ⁸ or D ⁶ and D ⁸ may form a ring structure, and the ring structure is D ⁴
And D ⁵ are synonymous with each other. M represents an anion that neutralizes the cation charge in the substituent. The anion may be either an inorganic anion or an organic anion, preferably a perchlorate ion, an iodine ion,
Bromide ion, substituted aryl sulfonate ion (for example,
p-toluenesulfonate ion). D ⁶ ,
D ⁷ and D ⁸ preferably independently represent an alkyl group having 1 to 6 carbon atoms or a benzyl group. Examples of the quaternary imidazole group include the following general formula (XXII).

[0068]

[Chemical formula 26]

In the formula (XXII), D ⁹ has the same meaning as R ¹ . M has the same meaning as above. R ⁹ is preferably a substituted or unsubstituted alkyl group. The repeating unit represented by the formula (XX) is 10 mol% to 100 mol% in the polymer.
included. Further, as a polymer component that can be contained in the polymer together with the polymer component represented by the formula (XX), a monomer corresponding to another repeating unit that can be copolymerized with the polymer component of the formula (XX). Any of them can be used. Preferred are vinyl compounds, and more specifically, methacrylic acid esters, acrylic acid esters, styrenes,
Heterocyclic vinyls and the like can be mentioned. These other monomers are used within the range of not more than 90 mol% in the total polymer components of the polymer dye fixing agent. The repeating unit represented by the formula (XX) and the other polymer component may be present in the polymer in a random form or a block form. Specific representative examples of the dye fixing agent used in the present invention are shown below, but the present invention is not limited to these. Specific examples of the polymer dye fixing agent having a tertiary amino group include the following polymers. (Numbers represent mol%)

[0070]

[Chemical 27]

The nitrogen-containing heterocyclic group is preferably an imidazole group or a pyridyl group, and specific examples of the polymer dye fixing agent having the group include the following polymers.

[0072]

[Chemical 28]

[0073]

[Chemical 29]

Specific examples of the polymeric dye fixing agent having a quaternary ammonium group include the following polymers.

[0075]

[Chemical 30]

[0076]

[Chemical 31]

[0077]

[Chemical 32]

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include US Pat. Nos. 4,282,305 and 4,11.
5,124, 3,148,061, JP-A-60.
-118834, 60-122941, JP-A-6-6
Examples of the dye fixing agent include those described in JP-A No. 2-244043 and JP-A No. 62-244036.

[0079]

[Chemical 33]

[0080]

[Chemical 34]

[0081]

[Chemical 35]

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, and 1,594. , 961, U.S. Pat. Nos. 4,124,386, 4,115,12.
No. 4, No. 4,273,853, No. 4,450,2
No. 24, and the followings including dye fixing agents described in JP-A-48-28325.

[0083]

[Chemical 36]

[0084]

[Chemical 37]

Other preferable specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary ammonium salt include US Pat. No. 3,709,690.
No. 3,898,088, No. 3,958,99
5, JP-A-60-57836, and JP-A-60-60643.
Issue No. 60-122940, Issue No. 60-122942
And dye fixing agents described in JP-A No. 60-235134 and the like.

[0086]

[Chemical 38]

[0087]

[Chemical Formula 39]

[0088]

[Chemical 40]

[0089]

[Chemical 41]

Of the above polymers, P-51 to P-61 are particularly preferable. The molecular weight of the polymer dye fixing agent of the present invention is appropriately 1 × 10 ³ to 1 × 10 ⁶ ,
Particularly, 1 × 10 ^{4 to} 2 × 10 ⁵ is preferable. The above-mentioned polymer dye fixing agent can also form the receiving layer by itself.
It can also be used as a mixture with the synthetic resin described below. The amount of the dye fixing agent applied is suitably 0.2 to 30 g / m ² , and preferably 0.5 to 15 g / m ² . The dye fixing agent used in the present invention can be synthesized by radical polymerization of a monomer having a vinyl group and a basic site. After polymerizing, if necessary, a basic site may be introduced through an alkylation reaction using amines. Or through a quaternary amination reaction,
A quaternary amino group may be introduced. When used in combination with a synthetic resin, it can be easily determined by those skilled in the art according to the type and composition of the dye fixing agent and the image forming process used, but the fixing agent / synthetic resin ratio is preferable. Is 1
It is preferably used at 0/90 to 100/0.

As the synthetic resin, an ordinary synthetic resin can be used as long as it can accept the dye transferred from the transfer sheet. Specifically, the following synthetic resins are used. (A) Those having an ester bond Dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group or a carboxyl group), ethylene glycol, diethylene glycol Polyester resin obtained by condensation of propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic acid ester resin or polymethacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate: polycarbonate resin : Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 can be mentioned. As commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-14 are used.
0, Byron GK-130, ATR-200 made by Kao
9, ATR-2010, etc. can be used.

(B) Those having a urethane bond Polyurethane resin and the like. (C) Those having an amide bond Polyamide resin and the like. (D) Those having a urea bond, such as urea resin. (E) Those having a sulfone bond Polysulfone resin, etc. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the above synthetic resins, mixtures or copolymers of these can also be used.

In the thermal transfer image-receiving material, particularly in the receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a substance capable of receiving the heat-transferable dye or as a diffusion aid of the dye. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A Nos. 62-174754 and 62-24525.
No. 3, No. 61-209444, No. 61-200538
No. 6, No. 62-8145, No. 62-9348, No. 62
The compounds described in Nos. -30247 and 62-136646 can be mentioned.

In the present invention, the receiving layer of the thermal transfer image receiving material may have a structure in which a substance capable of receiving the heat transferable dye is dispersed and carried in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but water-soluble polymers having a group capable of undergoing a crosslinking reaction by a hardening agent are preferable, and gelatins are particularly preferable. The receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a dye having a high boiling point organic solvent or thermal solvent is used to enhance the dyeing property, and the outermost layer has a glass transition point. Use a synthetic resin with a higher point, reduce the amount of high-boiling organic solvent or thermal solvent to the required minimum amount or do not use it, and make the surface sticky, adhere to other substances, re-transfer to other substances after transfer. It is desirable to have a structure that prevents failures such as transfer and blocking with a thermal transfer dye-donating material. The total thickness of the receiving layer is 0.5 to 50 μm, especially 3 to
The range of 30 μm is preferable. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm.

In the present invention, the thermal transfer image-receiving material may have an intermediate layer between the support and the receiving layer. The intermediate layer is any one of a cushion layer, a porous layer, and a dye diffusion preventing layer or a layer having two or more functions depending on the constituent material, and also serves as an adhesive in some cases. The dye diffusion-preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable, and examples thereof include the water-soluble binders mentioned above as the binder for the image-receiving layer, particularly gelatin. The porous layer is
This layer serves to prevent the heat applied during thermal transfer from diffusing from the image receiving layer to the support and to effectively utilize the applied heat.

In the present invention, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, a receptive layer, a cushion layer, a porous layer, a diffusion preventing layer, an adhesive layer, etc., which constitute the thermal transfer image receiving material, Fine powders of aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina and the like may be contained.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. As an example, K. Veenkatarama
n edition "The Chemistry of Synth
"tic Dyes", Volume V, Chapter 8, JP-A-61-1
The compound described in No. 43752 can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

The self-condensable compound contained in the dye-donor layer and / or the image-receiving layer used in the present invention reacts between the compounds to form a polymer structure. The polymer structure referred to here is one that forms a three-dimensional network structure. This improves the heat resistance of the dye-donor layer and / or the receptor layer, and prevents problems such as fusion. Examples of the self-condensable compound include polyisocyanate compounds, polysilane compounds, polyol compounds, polyamine compounds and the like. Preferred as the self-condensable compound is a polyisocyanate compound. The molecular weight of the polyisocyanate compound is 200 to 2
000 is preferable. The polyisocyanate compound is a reaction of forming a urea bond by a reaction between the isocyanate compound and water in each layer, and a reaction of further reacting the urea bond with the isocyanate compound to form a burette bond,
Further, it was found that the reaction for forming the uretidinedione ring or the isocyanurate ring by the condensation reaction between the isocyanate compounds proceeds in the dye-donor layer and / or the image-receiving layer is particularly effective for preventing heat fusion.

As the isocyanate compound which forms a urea bond, a burette bond, a uretidinedione ring or an isocyanurate ring by a reaction in the dye-donor layer and / or the image-receiving layer, a triisocyanate compound is preferable to a diisocyanate compound. Specific examples of the triisocyanate compound include trimethylolpropane-modified tolylene diisocyanate, trimethylolpropane-modified hexamethylene diisocyanate, isocyanurate-bonded tolylene diisocyanate, isocyanurate-bonded hexamethylene diisocyanate, buretet-bonded hexamethylene diisocyanate, trimethylolisophorone diisocyanate. , Isocyanurate-bonded isophorone diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, and the like.

As a method for synthesizing the polyisocyanate compound which is the self-condensable compound, there may be mentioned a conventionally known method, for example, a reaction between amines and phosgene, a reaction between diazonium salts and isocyanate, and the like. A synthetic method can be mentioned. As a method of forming a condensation compound of an isocyanate compound and water in a coating layer, a method of adding water to a coating film-forming composition containing a thermoplastic resin and an isocyanate compound, a drying step at the time of coating layer formation There is a method in which it is performed in an atmosphere that absorbs water. It is also possible to form a condensation compound with water in a solvent that dissolves the resin without adding water as described above. The self-condensable compound of the present invention is preferably contained in an amount of 1 to 50 wt% of the coating amount of the binder in the dye-donating layer and / or the synthetic resin in the receiving layer.

In the present invention, in order to improve the releasability of the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, particularly preferably the surface of both materials in contact with each other. It is preferable to include a release agent in the outermost layer corresponding to the above. As the release agent, polyethylene wax, amide wax, fine powder of silicone resin,
Solid or wax-like substance such as fine powder of fluororesin: Fluorine-based, phosphate-based surfactants: Paraffin-based, silicone-based, fluorine-based oils, etc. However, silicone oil is particularly preferable.

As the silicone oil, in addition to non-modified one, carboxy-modified, amino-modified, epoxy-modified, polyether-modified, alkyl-modified and other modified silicone oils can be used alone or in combination of two or more kinds. Examples thereof include various modified silicone oils described on pages 6 to 18B of "Modified Silicone Oil" technical data issued by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with an isocyanate) is also emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, manufactured by Shin-Etsu Silicone Co., Ltd .: trade name X-22-3710) or an epoxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd.).
Made by: Product name KF-100T) is effective.

The layers constituting the thermal transfer dye-donating material and the thermal transfer image-receiving material used in the present invention contain a binder in the dye-donating layer and a curing agent when the synthetic resin in the image-receiving layer is cured by a hardener. You can When curing an organic solvent-based polymer, JP-A-61-19999 is used.
The hardeners described in No. 7, No. 58-215398 and the like can be used. For curing water-soluble polymers, U.S. Pat. No. 4,678,739, column 41, JP-A-59-116.
No. 655, No. 62-245261, No. 61-1894.
The hardeners described in No. 2 and the like are suitable for use. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylolurea, etc.), or polymer hardeners (compounds described in JP-A-62-234157). It is desirable that the curing agent reacts sufficiently quickly with the binder and the synthetic resin, and it is not preferable that it interferes with the reaction of the self-condensable compound of the present invention.

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
The compounds described in JP-A-61-159644 are also effective.

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (US Pat. No. 3,352,68
No. 1), benzophenone compounds (JP-A-56-2)
No. 784, etc.), Japanese Patent Laid-Open No. 54-48535,
There are compounds described in JP-A-62-136641, JP-A-61-188256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,2.
45,018, columns 3 to 36, ibid., 4,254,195.
Nos. 3-8, JP-A-62-174741, 61-
88256, pages (27) to (29), JP-A-1-755.
68, compounds described in JP-A No. 63-199248 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). An anti-fading agent for preventing discoloration of the dye transferred to the image-receiving material may be contained in the image-receiving material in advance, or may be supplied to the image-receiving material from the outside by a method such as transferring from the dye-providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination.

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Nonionic surfactants, anionic surfactants, amphoteric surfactants and cationic surfactants can be used. Specific examples of these are disclosed in JP-A-62-1734.
63, 62-183457 and the like.

When a substance capable of accepting a heat-transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent and other hydrophobic compounds are dispersed in a water-soluble binder, they are dispersed. It is preferable to use a surfactant as an auxiliary agent.
For this purpose, in addition to the above-mentioned surfactants, the surfactants described on pages 37 to 38 of JP-A-59-157636 are particularly preferably used.

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the matting agent, in addition to the compounds described in JP-A No. 61-88256, page 29, such as silicon dioxide, polyolefin or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-27.
There are compounds described in 4944 and 63-274952.

The constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving releasability and the like. As typical examples of the organic fluoro compound, JP-B-57-9053, columns 8 to 17, JP-A-61-20944 and JP-A-62-13.
5826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as tetrafluoroethylene resin.

In the present invention, the thermal transfer dye-providing material is superposed on the thermal transfer image-receiving material, and heat is applied according to the image information from either side, preferably from the back side of the thermal transfer dye-providing material, by heating means such as a thermal head. By applying energy, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material according to the amount of heating energy, and a color image with excellent sharpness and resolution can be obtained. Further, an anti-fading agent can be similarly transferred. The heating means is not limited to the thermal head, and known ones such as laser light (for example, semiconductor laser), infrared flash, and hot pen can be used. In laser-based systems, the thermal transfer dye-donor material preferably contains a material that strongly absorbs laser light. When a thermal transfer dye-donor material is irradiated with laser light, the absorbing material converts light energy into heat energy, transfers the heat to the dye in the immediate vicinity, and the dye is transferred to the heat transfer image-receiving material at a temperature (heat transfer temperature). ) Is heated up to. The absorbent material is layered below the dye and / or is mixed with the dye. The laser beam is modulated with an electrical signal that represents the shape and color of the original image, heating only the areas of the dye that need to be present on the thermal transfer dye-donor material to reconstitute the original target color and heat transfer.

In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to form an image by printing using various printers of thermal printing system, facsimile, or magnetic recording system, magneto-optical recording system, optical recording system and the like. It can be used to create prints, prints from a television or CRT screen. For details of the thermal transfer recording method, the description in JP-A-60-34895 can be referred to.

In a preferred embodiment of the present invention, the thermal transfer dye-donor element comprises a polyethylene terephthalate support coated in successive repeating regions of a cyan dye, a magenta dye and a yellow dye, wherein the thermal transfer step is performed sequentially for each dye. Perform to form a three color transfer image. Of course,
When this thermal transfer process is performed in a single color, a monochrome transfer image is obtained. For thermal transfer of dyes from a thermal transfer dye-donor material to a thermal transfer image-receiving material, an ion gas laser such as argon or krypton, a metal vapor laser such as copper, gold and cadmium, a solid state laser such as ruby or YAG, or 750-870 nm. Heating with several lasers can be used, such as semiconductor lasers such as gallium-arsenide, which emits in the infrared. However, in reality,
A semiconductor laser is advantageous in terms of low cost, stability, reliability, durability, and ease of modulation.

[0114]

EXAMPLES The following are detailed examples of the present invention. However, the thermal transfer recording material of the present invention is not limited to the examples shown below.

Example 1 Preparation of thermal transfer dye-donor material (1) A polyethylene terephthalate film having a thickness of 5 μm and having a heat resistant slipping layer provided on one side was used as a support.
A composition (1) for coating a dye-donor layer having the following composition was applied to the side opposite to the side provided with the heat resistant slipping layer using a gravure coater so that the thickness after drying would be 0.6 μm. ,
It was dried and left in an oven at 40 ° C. and 50% RH for 1 day to obtain a thermal transfer dye-providing material (1) (hereinafter, also simply referred to as dye-providing material). Dye Donor Layer Coating Composition (1) Dye 22 10 g Polyvinyl butyral (Denka Butyral 5000A: manufactured by Electrochemical) 10 g Silicone oil (KF-96: manufactured by Shin-Etsu Chemical) 0.2 g Polyisocyanate (Takenate D110N: manufactured by Takeda Yakuhin) 0 0.5g Methyl ethyl ketone 100ml Toluene 80ml

Preparation of Thermal Transfer Image Receiving Material (1) A laminated type synthetic paper having a thickness of 150 μm was used as a support,
The composition (1) for applying a receptive layer having the following composition was applied to the surface using a wire bar coater so that the thickness when dried was 5 μm, and the thermal transfer image receiving material (1) (hereinafter, also simply referred to as an image receiving material) was used. Was produced. Drying was performed in an oven at 90 ° C. for 1 hour. Then, it was left in an oven at 40 ° C. and 50% RH for 1 day. Receptor layer coating composition (1) Dye fixing agent P-4 15 g Synthetic resin (Vylon 200: Toyobo) 25 g Polyisocyanate (KP-90: Dainippon Ink and Chemicals) 4 g Methyl ethyl ketone 100 ml Toluene 50 ml

Example 2 Preparation of Dye-donor Materials (2) to (12) The dye-donor material (1) was replaced with the dyes, binders and self-condensable compounds shown in Table A below, and other examples were used. 1
Dye-providing materials (2) to (12) were prepared in the same manner as in.

[0118]

[Table 1]

Preparation of Image-Receiving Material (2) Resin-coated paper having a thickness of 30 μm laminated on both sides of a high-quality paper having a thickness of 140 μm was used as a support, and a composition (2) for coating a receiving layer having the following composition The image receiving material (2) was produced in the same manner as in Example (1) except that. Receptor layer coating composition (2) Dye fixing agent P-59 10 g Synthetic resin (Polyester TP-220: manufactured by Nippon Synthetic Chemical Industry) 25 g Polyisocyanate (Coronate L: manufactured by Nippon Polyurethane) 5 g Methyl ethyl ketone 100 ml Toluene 80 ml Example 3 Image receiving Preparation of Materials (3) to (10) In the same manner as in Example 1 except that the dye fixing agent, the self-condensable compound and the synthetic resin of the image receiving material (2) were replaced with those shown in Table B below. The image receiving materials (3) to (10) were produced.

[0120]

[Table 2]

Example 4 Preparation of Thermal Transfer Image-Receiving Material (11) An organic solvent solution of the dye-receptive polymer having the composition (B) was emulsified and dispersed in an aqueous gelatin solution (A) having the following composition to give a dye-receptive substance. A gelatin dispersion of was prepared. Aqueous gelatin solution (A) Gelatin 2.5 g Sodium dodecylbenzenesulfonate (5% aqueous solution) 20 ml Water 80 ml Dye receptive polymer solution (B) Dye fixing agent P-58 7 g Binder resin (Vylon 300: Toyobo) 7 g Polyisocyanate ( KP-90: manufactured by Dainippon Ink and Chemicals, Inc. 0.7 g Silicone oil (X-22-3710: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 g Triphenyl phosphate 2 g Methyl ethyl ketone 20 ml Toluene 20 ml This gelatin dispersion was treated with the resin coat of Example 2. On paper, in the same manner as in Example 1, the thickness after drying was 7 μm,
An image receiving material (11) was produced.

Comparative Example Dye-providing materials (A) and (B) for comparison were prepared by replacing the dye of the dye-providing material (1) of Example 1 with the following dye A or dye B.

[0123]

[Chemical 42]

Comparative dye-providing materials (C) and (D) were prepared by removing the self-condensable compounds from the dye-providing materials (1) and (2). An image receiving material (A) for comparison was prepared using the composition having the composition obtained by removing the dye fixing agent from the image receiving material (2) of Example 2. Further, a comparative image-receiving material (B) obtained by removing the self-condensable compound from the image-receiving material (2) and a comparative image-receiving material (C) obtained by removing the dye fixing agent and the self-condensable compound from the image-receiving material (2). It was made.

The thermal transfer dye-donor material and the thermal transfer image-receiving material obtained as described above are superposed such that the dye-donor layer and the receptor layer are in contact with each other, and a thermal head is used from the support side of the thermal-transfer dye-donor material. Thermal head output 0.25W / dot, pulse width 0.1-10msec,
Heating was performed under the condition that the dot density was 6 dots / mm, and the dye was dyed imagewise on the receiving layer of the image receiving material. The portion where the density of the recorded image-receiving material obtained at this time is saturated (D
The _max), the reflection type densitometer (X Rite Inc. Co., was measured reflection density of the image using a Status A filter built). Further, the degree of image bleeding was observed after fusing the dye-donor layer to the image-receiving material during thermal transfer and leaving the recorded image-receiving material in an oven at 60 ° C. for 2 weeks. The criteria for fusion are indicated by ◯ when there was no fusion and by x when fusion was performed. The criterion for the degree of bleeding is
Images with almost no change from those before storage were marked with ◯, slightly blurred images were marked with Δ, and very blurred images were marked with x. The results are shown in Table-C below.

[0126]

[Table 3]

[0127]

[Table 4]

As shown in Table C, when the dye-donor element and the image-receiving element of the present invention were used, the image transfer density was high,
No fusing of the dye-donor layer to the image receiving material was observed during thermal transfer, and no image bleeding during storage of the recorded image receiving material was observed. However, none of the comparative examples showed good results in terms of transfer density, fusing and image bleeding.

[0129]

By using the thermal transfer recording material of the present invention, it is possible to obtain an image recording which has a high transfer density, is not fused at the time of transfer, and the recorded image does not bleed during storage and deteriorate in image quality.

Claims (1)

[Claims] 1. A thermal transfer dye-donating material having a dye-donating layer containing a heat-transferable dye on a support and a thermal transfer image-receiving material having a receiving layer containing a dye-receiving compound on the support. A heat transfer recording material, wherein the heat transferable dye has a dissociative substituent, the dye receptive compound is a dye fixing agent, and self-condensation property in the dye donating layer and / or the image receiving layer. A thermal transfer recording material comprising the compound of