JPH06183163A - Thermal transfer recording material - Google Patents

Abstract

PURPOSE:To provide a thermal transfer recording material obtaining a high density sharp image recording not generating the lowering of image quality due to a slip during transfer or coating irregularity and forming a recording image generating no lowering in image quality due to blotting during preservation. CONSTITUTION:A thermal transfer recording material consists of a thermal transfer dye donating material wherein a dye donating layer containing a thermal transfer dye having a releasable substituent is provided on a support and a thermal transfer image receiving material wherein a receiving layer containing a dye fixing agent is provided on a support and a fluorine compd. is added to the dye donating 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. Further, when the above materials are manufactured, it is difficult to obtain a uniform material because the binder of the dye-donor layer is limited for high-speed recording or because of the dye-fixing agent contained in the image-receiving layer of the image-receiving material. . Further, in the printer, slippage occurs between the dye-donor element and the image-receiving element and the image quality deteriorates. It is an object of the present invention to provide a novel thermal transfer recording material that solves the above problems.

[0004]

The above objects 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. Wherein 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 fluorine compound. It was found that this can be achieved by the thermal transfer recording material. That is, by using a dye having a dissociative substituent and a dye fixing agent in the thermal transfer recording material of the present invention, it is possible to obtain a stable dye image which does not cause deterioration such as image bleeding during storage of transfer records. .
Therefore, a heat transferable dye having a structure that allows easy transfer can be used. However, it is difficult to produce a uniform material for the dye-donor material containing the dye or the image-receiving material containing the dye fixing agent. Further, during transfer, the image quality is likely to deteriorate due to slippage between the dye-donor material and the image-receiving material. The fluorine compound contained in the dye-donor layer and / or the receptor layer of the present invention is for solving the above problems, whereby the transfer speed is high and the transfer density is high.
It is possible to manufacture a material that does not deteriorate in image quality during storage of recorded images and has no unevenness, and it is possible to obtain thermal transfer recording without deterioration in image quality due to problems such as slips during transfer.

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, polyethylene naphthalate, polyamide, polycarbonate, glassine paper, condenser paper,
Examples thereof include 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 to 200 μm. When used for recording with a thermal head, the thickness is preferably 2 to 30 μm. An undercoat layer may be provided if necessary.

A thermal transfer dye-donor element 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 is obtained by coating and drying at a coating amount of 20 μm, preferably 0.4 to 5 μm to give a dry film thickness, to form a dye-donor layer. The dye-donor layer may be formed of a single layer,
For cases such as when used in a method of repeatedly using many times,
It may be formed of two or more layers. 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 20 g / m ² , preferably 0.1 to 5 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).

[0008]

[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) and a structure of the following general formula (Ia) are preferable.

[0010]

[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. The structure of Q is preferably
It is represented by the following general formulas (II) to (XIX).

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

In the formula (II), R ⁵ represents an alkyl group, an aryl group, or a 5- or 6-membered ring containing at least one of oxygen, nitrogen and sulfur as a hetero atom. R ⁶ is R ¹
Is synonymous with. X represents a -N = or -C (R ¹⁰⁰⁾ =. 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. In formula (III), R ⁷ has the same meaning as R ¹ . X ¹ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle.

Formulas (IV), (V), (VI), (VII), (VI
During II), R ⁸ ~R ¹⁹ is independently the same meaning as R ^1. In formulas (VI), (VII) and (VIII), X ² and X ³ are 5 to each other.
It represents a group of atoms necessary for forming a 6-membered nitrogen-containing heterocycle. In formula (IX), R ²⁰ , R ²¹ and R ²² are each independently R
Synonymous with ¹ . Z ¹ is -N = or -C (R ¹⁰¹ ).
Represents =. R ¹⁰¹ has the same ^meaning as R ^{100. In} 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 .
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 (which is condensed to form a quinoline ring) or the following chemical formula 7
Is.

[0018]

[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.

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. R ³⁴ and R ³⁵ may combine with each other to form a ring structure. R ³⁶ , R ³⁷ , R
³⁹ each independently represents an alkyl group, an aryl group, a heterocyclic group, or an amino group (including an anilino group). R ³⁸ is
It represents an electron-withdrawing group having a Hammett substituent constant of 0.3 or more. In formula (XVI), R ⁴⁰ and R ⁴¹ each independently have the same meaning as R ²⁴ . In formula (XVII), R ⁴³ and R ⁴⁴ are each independently
Synonymous with R ⁵ . In formula (XVIII), R ⁴⁵ and R ⁴⁶ each independently have the same meaning as R ²⁵ . R ⁴⁷ has the same meaning as R ¹ .

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.

A preferred example of A is 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.

[0023]

[Chemical 8]

Among the dyes used in the present invention, Q is particularly preferably one represented by the general formulas (VI), (VII) and (VIII). Specific examples of the dye used in the present invention are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

[Chemical 14]

[0031]

[Chemical 15]

[0032]

[Chemical 16]

[0033]

[Chemical 17]

[0034]

[Chemical 18]

[0035]

[Chemical 19]

[0036]

[Chemical 20]

[0037]

[Chemical 21]

[0038]

[Chemical formula 22]

[0039]

[Chemical formula 23]

As a method for synthesizing the above-mentioned dyes used in the present invention, a conventional synthesizing method is used. For example, oxidative coupling (X is -N = X) of a coupler compound and a p-hydroxyaniline compound for each dye is used. Or when a coupler compound and p-hydroxyaryl aldehyde are dehydrated and condensed [when X is —C (R ¹⁰⁰ ) =]. Further, as the binder resin used together with the above-mentioned dye, any of conventionally known binder resins can be used for such purpose, and usually has high heat resistance and does not prevent migration of the dye when heated. Things are selected. For example, polyamide-based resin, polyester-based resin, epoxy-based resin, polyurethane-based resin, polyacrylic-based resin (eg, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl-based resin such as polyvinylpyrrolidone, polychlorinated Vinyl resin (for example, vinyl chloride-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 triacetate), polyvinyl alcohol resin (eg polyvinyl alcohol, polyvinyl Partially saponified polyvinyl alcohols such as butyral or polyvinyl acetal), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g. polyethylene, polypropylene) and the like.

Such a binder resin is preferably used in a ratio of about 20 to 600 parts by weight, for example, per 100 parts by weight of the dye. The above binder resins may be used alone, or may be the same type but different in composition and molecular weight or different types may be mixed and used. 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.

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 containing an alkali metal salt or alkaline earth metal salt of a phosphoric acid ester, a filler, and a release agent such as a silicone resin. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000, a glass transition point of 80 to 110 ° C., and a vinyl butyral portion having a weight percentage of 15 to 40% from the viewpoint of many reaction sites with isocyanate. 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 is 1 to 50 with respect to the polyvinyl butyral resin.
It may be used in an amount of about 10% by weight, preferably about 10% by weight. The filler is 0.01 to 5 g / m ² , and the release agent is 0.1 to 5
It is preferable to use it in the range of g / m ² . 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 diffusion of the dye 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 element of the invention is 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.

Further, these dye-providing materials can be provided with a dye layer and the like by various known coaters. For example, a gravure coater, a rod coater, a blade coater, an air knife coater, a roll coater or the like is used. In the case of the above-mentioned material having a plurality of dyes, a method such as gravure printing or microgravure printing is preferable. These coaters can also be used for the production of image receiving materials.

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 property, dent 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. . In consideration of transparency, flexibility, heat resistance and the like, films of polyester, polycarbonate, polyamide and the like 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, 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 dye fixing agents which are usually used, and among them, the polymer dye fixing agent is particularly preferable. Here, the polymer dye fixing agent includes a polymer containing a repeating unit represented by the following general formula (XX).

[0050]

[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).

[0054]

[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).

[0056]

[Chemical formula 26]

In the formula (XXII), D ⁹ has the same meaning as R ¹ above. 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%)

[0058]

[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.

[0060]

[Chemical 28]

[0061]

[Chemical 29]

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

[0063]

[Chemical 30]

[0064]

[Chemical 31]

[0065]

[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.

[0067]

[Chemical 33]

[0068]

[Chemical 34]

[0069]

[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.

[0071]

[Chemical 36]

[0072]

[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.

[0074]

[Chemical 38]

[0075]

[Chemical Formula 39]

[0076]

[Chemical 40]

[0077]

[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 polymer 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. Alternatively, a quaternary amino group may be introduced through a quaternary amination reaction. When used in combination with a synthetic resin, the type and composition of the dye fixing agent,
Further, it can be easily determined by those skilled in the art depending on the image forming process used, but it is preferable to use the fixing agent / synthetic resin ratio of 10/90 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, sebacic acid, sidipic acid, succinic acid (these dicarboxylic acid components may be substituted with sulfonic acid groups, carboxyl groups, etc.) And a polyester resin obtained by condensation of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate or polymethacryl Acid ester resin: polycarbonate resin: polyarylate resin, polyvinyl acetate resin: styrene acrylate resin: vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395 and 6
3-7971, 63-7792, 63-797.
No. 3 and No. 60-294862 can be mentioned. As commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 3
00, Byron 103, Byron GK-140, Byron GK-130, Kao ATR-2009, ATR-
Chemit K1089 manufactured by Toray Industries, Inc., Polyester TP220 manufactured by Nippon Synthetic Chemical Industry, and the like can be used.

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

A high-boiling organic solvent or a thermal solvent can be contained in the thermal transfer image-receiving material, particularly in the receiving layer, 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, aluminum silicate are used for the cushion layer, the porous layer, the diffusion preventing layer, the adhesive layer and the like which constitute the thermal transfer image receiving material. Fine pigment powders such as synthetic zeolite, zinc oxide, lithopone, titanium oxide and alumina 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.

In the present invention, in order to improve the releasability between 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 surfaces where both materials contact each other. It is preferable to include a release agent in the outermost layer corresponding to the above. Solid release agents such as polyethylene wax, amide wax, fine powder of silicone resin or wax-like substances: Phosphate ester-based surfactants: Paraffin-based, silicone-based, fluorine-based oils, etc. Any known release agent can be used,
Silicone oil is particularly preferable.

As the silicone oil, in addition to non-modified silicone oil, modified silicone oil such as carboxy-modified, amino-modified, epoxy-modified, polyether-modified and alkyl-modified 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, an amino-modified silicone oil having a non-modified one and a group capable of reacting with a cross-linking agent of this binder (for example, a group capable of reacting with isocyanate) is also emulsified in a water-soluble binder. When dispersed and used, a carboxy-modified silicone oil (for example, manufactured by Shin-Etsu Silicone Co., Ltd .: trade name X-22-371)
0) or an epoxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd .: trade name KF-100T) is effective. Polyether-modified silicone oil and isocyanate-modified silicone oil are also effective.

The layers constituting the thermal transfer dye-donating material and the thermal transfer image-receiving material used in the present invention may be cured with a hardener. In the case of curing an organic solvent-based polymer, JP-A Nos. 61-199997 and 58-21539.
The hardeners described in No. 8 and the like can be used. OH group,
Resins having amino groups, carboxyl groups, etc. For polyester resins, polyvinyl butyral resins, ethyl cellulose resins, etc., it is particularly preferable to use an isocyanate hardener. For curing water-soluble polymers, U.S. Pat. No. 4,678,739, column 41, JP-A-59-11.
No. 6655, No. 62-245261, No. 61-189.
The hardeners described in No. 42 and the like are suitable for use. More specifically, aldehyde type hardeners (formaldehyde etc.),
Aziridine hardener, epoxy hardener, vinyl sulfone hardener (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N-methylol hardener (dimethylol urea, etc.) Alternatively, polymer hardeners (compounds described in JP-A-62-234157) can be used.

An anti-fading agent may be used in the thermal transfer dye-donating 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 may be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, prevention of electrostatic charge, 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 may be contained in the dye-donor layer and / or the image-receiving layer. There are various matting agents, which may be inorganic or organic. Further, it is desirable that it is less likely to be deformed by heat. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, zinc oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (eg, sulfates and carbonates, Examples include barium sulfate, calcium carbonate, magnesium sulfate, etc.) and glass. Further, it is desirable that the organic matting agent does not soften by heat at 60 ° C. or lower. Examples thereof include cellulose ester (for example, cellulose acetate propionate and the like), cellulose ether (for example, ethyl cellulose and the like), synthetic resin and the like. Examples of synthetic resins include, for example, alkyl methacrylate, alkoxyalkyl methacrylate,
Glycidyl methacrylate, acrylamide, methacrylamide, styrene and the like, alone or in combination, or with these, acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl-acrylate or-
A polymer having a monomer component of a combination of methacrylate, sulfone alkyl-acrylate or -methacrylate, styrene sulfonic acid and the like can be used. Among them, polymethylmethacrylate is preferable. Also, vinyl synthetic resins such as polyethylene, benzoguanamine resin,
Polycarbonate resin, AS resin and the like can also be used. The amount of the matting agent used is 0.5 to 10 wt% of the coating amount of the binder in the dye-donating layer and / or the synthetic resin in the image-receiving layer.
%, Preferably 1 to 5 wt%.

The fluorine compound used in the present invention may be a fluorine polymer compound or a fluorine surfactant. Fluorine polymer compounds used in the present invention are disclosed in U.S. Patent Nos. 4,175,969 and 4,087,
394, 4,016,125, 3,676,1
No. 23, No. 3,676, 411, No. 4,304,85
No. 2, JP-A Nos. 52-129520 and 54-1582.
No. 22, No. 55-57842, No. 57-13422.
No. 57-19735, No. 57-179837,
The compounds described in Chemistry Review, No. 27, "New Fluorine Chemistry" (edited by the Chemical Society of Japan, 1980), "Functional Fluorine-Containing Polymers" (edited by Nikkan Kogyo Shimbun, 1982) and the like can be mentioned. . These fluorine compounds can be produced by the methods described in the above-mentioned patent publications and documents, and more generally, can be synthesized by fluorinating corresponding hydrocarbons. Regarding the fluorination of hydrocarbons, "New Experimental Chemistry Course" vol.14 [I] (Maruzen,
1982), pp. 308-331.
In the present invention, the fluorine compound is 0.001 g / m ^{2 to} 3
g / m ² , preferably 0.002 g / m ^{2 to} 1.5 g / m ² ,
Particularly preferably, 0.005 g / m ^{2 to} 1.0 g / m ² is added to either or both of the dye-donor layer of the dye-donor element and the dye-receptive layer of the color image-receiving element. Specific examples of the fluorine compound used in the present invention are shown below, but the present invention is not limited thereto.

[0096]

[Chemical 42]

[0097]

[Chemical 43]

The fluorosurfactant used in the present invention is a surfactant containing a fluorinated hydrocarbon as a partial structure and may be any of anionic, cationic, nonionic and betaine type surfactants. Good. Specific examples of the fluorosurfactant will be shown, but the present invention is not limited thereto.

[0099]

[Chemical 44]

[0100]

[Chemical formula 45]

[0101]

[Chemical formula 46]

[0102]

[Chemical 47]

[0103]

[Chemical 48]

[0104]

[Chemical 49]

In addition, Megafac F-131 to 133 and F-141 to 144 manufactured by Dainippon Ink and Chemicals, Inc.
F-170 to 173, F-180 to 184, F-190
~ 195, F-522; Surflon S manufactured by Asahi Glass Co., Ltd.
-111 to 113, S-131 to 133, S-141,
S-101, S-105, S-381, S-382, S
-383 and Asahi Guard AG650, AG660,
LS520, LS540; foot gradient 400S manufactured by Neos Co., Ltd., and the like. The particle shape and particle diameter of the matting agent are not particularly limited, but usually 0.5 to 10 μm.
Particles having an average particle size of m, especially 1 to 5 μm are preferred. The inorganic material and the organic material may be used alone or in combination. As a method for synthesizing the matting agent used in the present invention, a conventional method can be mentioned. For example, the particle size is made uniform by mechanically treating it into fine particles and, if necessary, screening. In the case of a resin, a resin dispersed by emulsion polymerization or the like can be dried to obtain a resin having the same shape.

In the present invention, the thermal transfer dye-providing material is superposed on the thermal transfer image-receiving material and heat is applied in accordance with the image information from either side, preferably the back side of the thermal transfer dye-providing material, by means of 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-donor 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, reference can be made to the description in JP-A-60-34898.

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 repeated 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. Thermal transfer To transfer a dye from a dye-donor material to a thermal transfer image-receiving material, current is supplied to the thermal head in response to an electric signal, or an ion gas laser such as argon or krypton, a metal vapor laser such as copper, gold and cadmium, or a ruby. Heating with several lasers can be used, such as solid state lasers like YAG or YAG or semiconductor lasers like gallium-arsenide emitting in the infrared range from 750 to 870 nm. However, in practice, semiconductor lasers are advantageous in terms of small size, low cost, stability, reliability, durability, and ease of modulation.

[0109]

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 heat-resistant slipping layer provided on one side and having a thickness of 5 μm 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. ,
A thermal transfer dye-providing material (1) (hereinafter, also simply referred to as a dye-donating material) was obtained. Dye Donor Layer Coating Composition (1) Dye 1 10 g Polyvinyl butyral (Denka Butyral 5000A: manufactured by Denki Kagaku) 7 g Polyvinyl acetal (S-Rex K; manufactured by Sekisui Chemical) 3 g Fluorine compound F11 0.1 g Polyisocyanate (Takenate D110N: Takeda) Chemical) 0.5 g Methyl ethyl ketone 100 ml Toluene 80 ml

Preparation of Thermal Transfer Image Receiving Material (1) A laminated 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. Produced). Drying was performed temporarily with a dryer and then in an oven at 80 ° C. for 1 hour. Receptor layer coating composition (1) Dye fixing agent P-4 10 g Binder resin (Vylon 300: manufactured by Toyobo) 25 g Silicone oil (KF857: manufactured by Shin-Etsu Chemical) 0.4 g Fluorine compound (Asahi Card LS540; manufactured by Asahi Glass) 0 .2 g Methyl ethyl ketone 100 ml Toluene 50 ml

Example 2 Preparation of Dye-donor Materials (2) to (6) The dye-donor material (1) was replaced with the dye, binder resin and fluorine compound shown in Table A below, and other examples were used. Dye-providing materials (2) to (6) were prepared in the same manner as in 1.

[0113]

[Table 1]

Preparation of Image-Receiving Material (2) Resin-coated paper having a thickness of 20 μm laminated on both sides of high-quality paper having a thickness of 160 μm was used as a support, and a receiving layer coating composition (2) having the following composition In the same manner as in Example 1 except that, an image receiving material (2) was produced. Receptor layer coating composition (2) Dye fixing agent P-58 10 g Binder resin (Vylon 200: manufactured by Toyobo) 20 g Polyisocyanate (KP-90: manufactured by Dainippon Ink and Chemicals) 5 g Fluorine compound F-11 0.4 g Methyl ethyl ketone 100 ml Toluene 80 ml Example 3 Preparation of Image Receiving Materials (3) to (6) In place of the dye fixing agent, the fluorine compound and the binder resin of the image receiving material (2) shown in Table B below, the other examples were obtained. In the same manner, image receiving materials (3) to (6) were produced.

[0115]

[Table 2]

Example 4 Preparation of thermal transfer image-receiving material (7) 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 103: Toyobo) 7 g Silicone oil ( X-22-3710: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 g Fluorine compound SA-1 0.3 g Triphenyl phosphate 2 g Methyl ethyl ketone 20 ml Toluene 20 ml This gelatin dispersion was applied onto the resin-coated paper of Example 2 in the same manner as in Example 1. And the thickness after drying is 7 μm,
An image receiving material (7) was produced.

Comparative Example The dye of the dye-donor element (3) of Example 2 was replaced by the following dye A
A dye-providing material (A) for comparison was prepared instead of the above, and a dye-providing material (B) was prepared except for the fluorine compound.

[0118]

[Chemical 50]

Further, a comparative image-receiving material (A) was prepared by using the composition having the composition obtained by removing the dye fixing agent from the image-receiving material (2) of Example 2, and the image-receiving material (B) was prepared by removing the fluorine compound. An image receiving material (C) was prepared except for the dye fixing agent and the fluorine compound.

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 0.15W / dot, pulse width 1-12msec, dot density line direction 12dots / mm scanning direction 10dots / mm are heated, and the dye is dyed imagewise on the receiving layer of the image receiving material. Dressed The reflection density of the image of the portion (D _max ) where the density of the recorded image-receiving material obtained was saturated was measured using a reflection densitometer (X Rite Inc., built-in status A filter). . Also,
The degree of image bleeding was observed after the recorded image receiving material was left in an oven at 60 ° C. for 4 weeks. The judgment criteria are shown by ◯ when the image hardly changes from before storage, Δ when slightly bleeding, and x when extremely blurred.
In addition, it was judged by the degree of deterioration of the image quality due to the slip between the dye-donor element and the image-receiving element and the difference between the length of the transferred image and the length of the input image in the scanning direction. The criteria for judgment are indicated by ◯ when there is almost no difference, by Δ when slightly deviated, and by x when the deviation is severe. The results are shown in Table-C below.

[0121]

[Table 3]

The degree of coating unevenness between the dye-donor material and the image-receiving material was judged by the transfer unevenness of the transferred image. Those with almost no unevenness were indicated by ◯, and those with severe unevenness were indicated by ×. The results are shown in Table-D below.

[0123]

[Table 4]

As shown in Table-C and Table-D, when the dye-donor element and the image-receiving element of the present invention are used, the image transfer density is high and there is no slip between the dye-donor element and the image-receiving element during thermal transfer. No bleeding of the image during storage of the recorded image receiving material was observed. Also, there was almost no uneven coating of the material. However, using the comparative example,
Regarding the transfer density, slip, image bleeding during storage of recorded images, and coating unevenness, all did not show good results.

[0125]

By using the thermal transfer recording material of the present invention, the transfer density is high, the dye-donor layer and the image-receiving layer do not slip during transfer, and the image quality of the transferred image does not deteriorate. It is possible to obtain an image record that does not deteriorate in image quality due to bleeding. Further, a material having no coating unevenness can be obtained.

Claims (1)

[Claims] 1. A thermal transfer dye-donating material having a dye-donor layer containing a heat-transferable dye on a support and a thermal transfer image-receiving material having a receiving layer containing a dye-receptive compound on the support. The heat transfer recording material according to claim 1, wherein the heat transferable dye has a dissociative substituent, the dye receiving compound is a dye fixing agent, and the fluorine compound is contained in the dye donating layer and / or the image receiving layer. A thermal transfer recording material characterized by containing.