JP2000280630A - Thermal transfer recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a thermal transfer recording material forming a color image provided with superior color reproducibility and light fastness, free from blur and bleeding and not fouling a contact material. SOLUTION: A thermal transfer recording material is formed of a thermal transfer coloring matter donative material containing thermally transferable coloring matters donating hydrogen atoms to turn into anion, and at least one kind of heat transfer coloring matters is an azo coloring matter represented by a formula. In the formula, R1, R2, R3 and R4 represent respectively and independently a hydrogen atom or a non-metallic atom group. R3 and R4 can be bonded together to form a cyclic structure. W represents atom groups required for forming 5-6 member rings.

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 performing image recording by a thermal transfer system in which a dye is transferred from a dye-donating material to a dye-receiving material by heating corresponding to image information and recorded.

[0002]

2. Description of the Related Art It is desirable to use a dye which transfers heat as much as possible as a dye-providing material for use in a thermal transfer recording system in order to reduce the load on a thermal head and increase the recording speed. However, the dye is deposited during storage or in a high-temperature, high-humidity environment, and the dye moves in the recorded image-receiving material to reduce the sharpness of the image. Problem.
In order to solve this problem, JP-A-1-18839 and JP-A-8-282133 disclose a method in which a mordant is contained in an image receiving layer to thermally transfer a dye having a mordant group such as a phenolic hydroxyl group. According to this method, the transferred dye is mordanted and hardly moves in the image receiving material, so that the sharpness of the image does not decrease, and the problem that the dye migrates to a contact object and is contaminated hardly occurs.

[0003]

However, the heat transfer dyes used in these systems have various restrictions, and very few satisfy all the required performances. The required performance includes, for example, easy heat transfer, dissociation into anions by a basic substance and / or mordant contained in the image receiving layer to have favorable spectral characteristics for color reproduction, and resistance to light and heat. That is, it is resistant to various chemicals, the image is not blurred and the sharpness is not reduced, the image is not retransferred, and a thermal transfer dye-providing material is easily produced. Although the dyes described in JP-A-8-282133 satisfy the required performance considerably, further improvements have been desired.

Accordingly, an object of the present invention is to provide an azo dye having a high heat transfer property, exhibiting excellent spectral characteristics upon dissociation, a high spectral absorption coefficient, and having excellent light and wet heat fastness, and a basic substance and / or a basic substance. Another object of the present invention is to provide a thermal transfer recording material which, when combined with a mordant, has high transferability, is excellent in hue and fastness, and gives an image free from a decrease in sharpness (image blur) and color fading (retransfer). .

[0005]

These objects of the present invention have been achieved by the following constitutions. In a thermal transfer recording material comprising a thermal transfer dye-providing material containing a thermal transfer dye capable of providing a hydrogen atom to become an anion and a thermal transfer image receiving material, at least one of the thermal transfer dyes is represented by the general formula (1). Transfer recording material characterized by being an azo dye:

[0006]

Embedded image

In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a nonmetallic atomic group. R ³ and R ⁴ may combine to form a ring structure. W
Represents an atom group necessary for forming a 5- to 6-membered ring.

Hereinafter, the present invention will be described in detail. In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an amino group. Group, alkoxy group, aryloxy group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl Group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group, carboxylic acid Represents a sulfonic acid group. R ³ and R ⁴ may combine to form a ring structure.

More specifically, R ¹ , R ² , R ³ , R ⁴
Is a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine); an alkyl group (having 1 to 18 carbon atoms, a substituent linked by an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl group,
Alternatively, it may be substituted with an aryl group, an alkenyl group, an alkynyl group, a hydroxy group, an amino group, a nitro group, a carboxy group, a cyano group, or a halogen atom. For example, a methyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a methoxyethoxy group, a 2-methanesulfonylethyl group, a 2-methanesulfonamidoethyl group,
An aryl group (for example, having 6 to 18 carbon atoms, such as a phenyl group, a 4-t-butylphenyl group, a 2-chlorophenyl group, or a 2-methoxyphenyl group); a heterocyclic group (for example, a carbon number of 6 to 18 carbon atoms). 1-18, 2-pyridyl group, 2-tetrahydrofuryl group, etc.); cyano group; hydroxy group; nitro group;
18, for example, a methylamino group, a diethylamino group, etc.);

An alkoxy group (having 1 to 18 carbon atoms, for example,
A methoxy group, an ethoxy group, a 2-phenoxyethoxy group,
2-methoxyethoxy group, 2-methanesulfonylethoxy group, etc.); aryloxy group (C6-18, for example, phenoxy group, 2-methoxyphenoxy group, etc.); acylamino group (C2-18, for example, acetamide) Group, benzamide group, etc.); anilino group (carbon number 6-1)
8, for example, a phenylamino group, a 2-chloroanilino group and the like; a ureido group (for example, having 1 to 18 carbon atoms, for example, a phenylureido group and a methylureido group); and a sulfamoylamino group (for having 0 to 18 carbon atoms, for example, N, N-dipropylsulfamoylamino group, etc.); alkylthio group (C1-18, for example, methylthio group, 2-phenoxythio group, etc.); arylthio group (C6-18, for example, phenylthio group, etc.) An alkoxycarbonylamino group (2 to 18 carbon atoms, for example, methoxycarbonylamino group); a sulfonamide group (1 to 18 carbon atoms, for example, methanesulfonamide group, benzenesulfonamide group, etc.); 1-18, for example, N-
Ethylcarbamoyl group, N-phenylcarbamoyl group, etc.); sulfamoyl group (having 0 to 18 carbon atoms, e.g., N
-Ethylsulfamoyl group, N, N-diethylsulfamoyl group, etc.); sulfonyl group (1 to 18 carbon atoms, for example, methanesulfonyl group, toluenesulfonyl group, etc.);

An alkoxycarbonyl group (containing 2 to 1 carbon atoms)
8, for example, a methoxycarbonyl group or a butoxycarbonyl group); a heterocyclic oxy group (for example, having 1 to 18 carbon atoms, for example, 2-tetrahydropyranyloxy group); an azo group (for having 3 to 18 carbon atoms, for example, p- Nitrophenylazo group and the like); acyloxy group (2 to 18 carbon atoms, for example, acetoxy group and the like); carbamoyloxy group (1 to 1 carbon atoms)
8, for example, N-methylcarbamoyloxy group); silyloxy group (3 to 18 carbon atoms, for example, trimethylsilyloxy group); aryloxycarbonylamino group (7 to 18 carbon atoms, for example, phenoxycarbonylamino group). An imide group (having 4 to 18 carbon atoms, such as an N-phthalimido group, an N-succinimido group); a heterocyclic thio group (having a carbon number of 1 to 18, such as a 2-pyridylthio group); a phosphonyl group (having 0 carbon atoms). To 18, for example, phenoxyphosphonyl group, phenylphosphonyl group, etc .; acyl group (1 to 18 carbon atoms, for example, acetyl group, benzoyl group, etc.); carboxylic acid group (sodium salt, potassium salt, etc., inorganic salt thereof). , And salts with organic bases such as tetramethylguanidine, etc.); sulfonates (sodium salt, potassium salt, etc.) Inorganic salts, and also includes salts with organic bases such as tetramethylguanidine salt) represents a.

Of these, preferred are a hydrogen atom, a halogen atom (fluorine, chlorine, bromine), an alkyl group (1-8 carbon atoms), a cyano group, and an alkoxy group (1-6 carbon atoms).
8), an acylamino group (2 to 8 carbon atoms), a ureido group (1 to 12 carbon atoms), an alkoxycarbonylamino group (2 to 12 carbon atoms), a sulfamoyl group (0 to 1 carbon atoms)
2) a carbamoyl group (1 to 12 carbon atoms) and an alkoxycarbonyl group (2 to 12 carbon atoms). More preferably, at least the 2-position of phenol is an acylamino group (1-8 carbon atoms).

W represents an atomic group necessary for forming a 5- to 6-membered ring. Specifically, when the phenolic hydroxyl group of the dye represented by the general formula (1) is dissociated, W
Is a group of atoms necessary to form a benzene ring, a thiophene ring, an isothiazole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring. Of these, a benzene ring is most preferred. These groups may have the substituents described for R ¹ , R ² , R ³ and R ⁴ . The dye in which R ³ and R ⁴ are bonded to each other to form a ring structure is represented by the following general formula (2) or (3).

[0014]

Embedded image

Where R¹ , R^Two , W are determined by the general formula (1)
Is synonymous with^Five, R ⁶, R⁷, R⁸Haichi
R in general formula (1)¹ Is synonymous with the definition of⁹Is hydrogen field
Or an alkyl group (1 to 12 carbon atoms). Q is
It is an atomic group necessary to form a 5- to 7-membered ring. General formula
The dye of (2) is preferably as follows. R¹ 
Represents a hydrogen atom, an acylamino group (2 to 12 carbon atoms),
Famoyl group (C1-12), carbamoyl group (charcoal
Prime number 2-12), sulfonamide group (carbon number 1-12)
And R^Two Is a hydrogen atom, and R^Five, R⁸Is a hydrogen source
, Sulfonamide group (1 to 12 carbon atoms), acylamido
Group (C2-12), alkoxycarbonylamino
Group (C 2-12)⁶, R⁷Is a hydrogen atom
is there.

The dye of the general formula (3) is preferably as follows. R ¹ is a hydrogen atom, an acylamino group (having 2 to 12 carbon atoms), R ² is a hydrogen atom, R ⁹ is a hydrogen atom, and Q is —CR ¹⁰ R ¹¹ — or —CR ¹² R
¹³ -CR ¹⁴ R ¹⁵ - a ^{and, R 10, R 11, R} 12, R 13 are each independently a hydrogen atom or an alkyl group (1-6 carbon atoms). The dye must have a low pKa in order to dissociate and mordant in the image receiving layer, and preferably has a low pKa.
Is preferably 8 or less, more preferably 6 to 1. Hereinafter, specific examples of the dye represented by Formula (1) used in the present invention are shown, but the present invention is not limited thereto.

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

Next, a method for synthesizing the image forming compound used in the present invention will be described. The compound of the present invention can be easily synthesized by a diazo coupling reaction between a naphthol or phenol as a coupler component and an amino compound of a fused isothiazole as a diazo component. The synthesis of amino compounds of fused isothiazoles is carried out by Dyesand Pigments 3,
81-121 (1982) and references cited therein.

The heat transferable dye of the present invention is contained in a colorant layer on a support, and is used as a thermal transfer dye-providing material for image formation of a thermal transfer system. Next, the case where the heat transferable dye of the present invention is used for image formation of a thermal transfer system will be described in detail below. Usually, in order to form a full-color image, dyes of three colors, yellow, magenta and cyan, are required. Therefore, a full-color image can be formed by using the dye represented by the general formula (1) of the present invention as a magenta dye or a cyan dye, and selecting other colors from conventionally known dyes. The other colors are preferably dissociable dyes like the dyes used in the present invention. For example, an azomethine dye having a phenolic hydroxyl group and a methine dye are exemplified. Further, for the same color, the dye of the present invention and a conventionally known dye may be mixed and used. Further, two or more kinds of the dyes of the present invention may be mixed and used as the same color.

The thermal transfer dye-providing material can be used in the form of a sheet, a continuous roll, or a ribbon. The yellow, magenta, and cyan dyes are usually arranged on a support so as to form independent regions. For example, a yellow dye area, a magenta dye area, and a cyan dye area are arranged on one support in a plane-sequential or line-sequential manner. Alternatively, three types of thermal transfer dye-providing materials in which the above-described yellow dye, magenta dye, and cyan dye are respectively provided on separate supports are prepared, and thermal transfer of the dye to one thermal transfer image-receiving material can be sequentially performed from these materials. . The dye of the present invention can be dissolved or dispersed in a suitable solvent together with a binder resin and coated on a support, or can be printed on the support by a printing method such as a gravure method. The thickness of the dye-donor layer containing these dyes is usually about 0.2 in dry film thickness.
It is preferably set to a range of from 5 to 5 μm, particularly from 0.4 to 2 μm. The coating amount of the dye is 0.03 to 1 g / m ² , and more preferably 0.1 to 0.6 g / m ² .

As the binder resin to be used together with the above-mentioned dye, any of the binder resins conventionally known for such a purpose can be used.
In addition, one that does not hinder the transfer of the dye when heated is selected. For example, polyamide resins, polyester resins, epoxy resins, polyurethane resins, polyacrylic resins (for example, polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resins such as polyvinylpyrrolidone, and polychlorinated resins 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-based resin (eg, polyvinyl alcohol, polyvinyl Acetal, partially saponified polyvinyl alcohol such as polyvinyl butyral), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g., polyethylene, polypropylene) and the like. In the present invention, such a binder resin is preferably used, for example, at a ratio of about 20 to 600 parts by weight per 100 parts by weight of the dye. In the present invention, any of conventionally known ink solvents can be used as the ink solvent for dissolving or dispersing the dye and the binder resin.

As the support of the thermal transfer dye-providing material, any of conventionally known supports can be used. For example, polyethylene terephthalate; polyamide; polycarbonate; glassine paper; condenser paper; cellulose ester; fluoropolymer; polyether; polyacetal; polyolefin; polyimide; polyphenylene sulfide; polypropylene; polysulfone; The thickness of the support of the thermal transfer dye-providing material is generally from 2 to
30 μm. An undercoat layer may be provided as needed. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye donating layer. This further improves the transfer density. As the hydrophilic polymer, the above-mentioned water-soluble polymer can be used. A slipping layer may be provided to prevent the thermal head from sticking to the dye-providing material. The slipping layer is composed of a lubricating material with or without a polymer binder, such as a surfactant, a solid or liquid lubricant or a mixture thereof.

In order to prevent sticking due to the heat of the thermal head when printing from the back side and to improve the slip, the dye-donor material is preferably subjected to anti-sticking treatment on the side of the support on which the dye-donor layer is not provided. . For example,
It is preferable to provide a heat-resistant slip layer mainly composed of a reaction product of a polyvinyl butyral resin and an isocyanate, an alkali metal salt or an alkaline earth metal salt of a phosphoric acid ester, and a filler. Polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80
To 110 ° C., and from the viewpoint that there are many reaction sites with isocyanate, the weight% of the vinyl butyral portion is 1
5% to 40% is preferred. As the alkali metal salt or alkaline earth metal salt of phosphate ester, Gaffa RD720 (trade name) manufactured by Toho Chemical Co., Ltd. is used, and 1 to 50% by weight, preferably about 10 to 40% by weight based on the polyvinyl butyral resin. Good to use. The heat-resistant slip layer is desirably accompanied by heat resistance in the lower layer, and a combination of a synthetic resin curable by heating and a curing agent thereof, for example, 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-providing material may be provided with a hydrophilic barrier layer for preventing the diffusion of the dye toward the support. The hydrophilic dye barrier layer contains a hydrophilic substance useful for the intended purpose. Excellent results are generally achieved with gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate-grafted gelatin,
Ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly (vinyl alcohol),
Poly (ethylene imine), poly (acrylic acid), mixture of poly (vinyl alcohol) and poly (vinyl acetate), mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) )). Particularly preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The dye-providing material may be provided with an undercoat layer. In the present invention, any undercoating layer may be used as long as it has a desired effect. Preferred specific examples include (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (weight ratio 14: 80: 6), (butyl acrylate) -2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear / saturated polyester such as Bostick 7650 (Emhart Corp., Bostick Chemical Group) Alternatively, a chlorinated high-density poly (ethylene-trichloroethylene) resin may be used. The coating amount of the undercoat layer is not particularly limited, but is usually used in an amount of 0.1 to 2.0 g / m ² .

In the present invention, the thermal transfer dye-providing material is superimposed on the thermal transfer image-receiving material, and from either side, preferably from the back side of the thermal transfer dye-providing material, heat is applied according to image information by a 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 in accordance with the magnitude of the heating energy, and a color image with excellent sharpness and resolution can be obtained. Further, an anti-fading agent can be transferred in the same manner. The heating means is not limited to a thermal head, and a known means such as a laser beam (for example, a semiconductor laser), an infrared flash, and a hot pen can be used. In systems using a laser, the dye-donor material contains a material that strongly absorbs the laser beam. When the dye-donor material is irradiated with a laser beam,
The absorbing material converts the light energy to thermal energy and immediately transfers the heat to nearby dyes, which heats them up to their heat transfer temperature for transfer to the image receiving material. The absorbent material is present in a layer below the dye and / or is mixed with the dye. The laser beam is modulated with electrical signals representing the shape and color of the original image, and only those areas of the dye that need to be present on the dye-donor to reconstruct the original color of interest are heated and thermally transferred. A more detailed description of the process is given in GB 2,083,726A. In British Patent 2,083,726A,
The absorbent material disclosed for the laser system is carbon. In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material, so that printing using various printers of a thermal printing system, facsimile, or magnetic recording system, printing of an image by an optical recording system, and the like,
It can be used to create prints from television and CRT screens. For details of the thermal transfer recording method, see
Reference can be made to the record of JP-A-34895.

In a preferred embodiment of the present invention, the dye-providing material comprises a polyethylene terephthalate support coated on a cyan dye, a magenta dye and a yellow dye in a successively repeated area. A color transfer image is formed. Of course, when this process is performed in a single color, a monochrome transfer image is obtained.
Ion gas lasers such as argon and krypton, metal vapor lasers such as copper, gold and cadmium, ruby and YA for thermal transfer of dye from dye-donor to image-receiving material.
Several types of lasers can be used, such as a solid state laser such as G, or a semiconductor laser such as gallium-arsenic that emits in the infrared region of 750-870 nm. However, in practice,
Semiconductor lasers are advantageous in terms of small size, low cost, stability, reliability, durability and ease of modulation.

The thermal transfer image-receiving material used in combination with the thermal transfer dye-providing material of the present invention comprises a basic substance having a function of receiving a dye transferred from the dye-providing material onto a support and dissociating the received dye. It is preferable to provide an image receiving layer containing a mordant alone or together with a binder substance. (Hereinafter, the basic substance and the mordant will be referred to as a dye fixing agent.) The dye fixing agent has a compound having a primary to tertiary, more preferably a tertiary amino group, and a nitrogen-containing heterocyclic group. Compounds and compounds having a quaternary cation group. Among them, a polymer dye fixing agent is particularly preferable. Typical examples of the polymer dye fixing agent include JP-A-60-260.
Nos. 060 and 60-260381, Japanese Patent Application No. 61
Japanese Patent Application Laid-Open Nos. 5-52995, 1-188391 and 3-83885, and Japanese Patent Application No. 5-137463. Among these polymer dye fixing agents, those having a tertiary amino group as a pendant are most preferred.

The molecular weight of the polymer dye fixing agent of the present invention is 1
× 10 ³ to 1 × 10 ⁶ is suitable, and especially 1 × 10 ⁴ to
2 × 10 ⁵ is preferred. The dye fixing agent may constitute the receiving layer alone, or may be used by being dispersed or mixed in another binder. In particular, those having a molecular weight of 1 × 10 ³ or less are preferably used by being dispersed or mixed in another binder. 0.2-30 g of dye fixative applied
/ M ² is suitable, and it is preferably used at 0.5 to 15 g / m ² . The Tg of the polymer dye fixing agent is 0
~ 120 ° C. Among them, Tg is preferably about 30 to 70 ° C.

When a synthetic resin is mixed and used as a binder, 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 to be used. Agent / synthetic resin ratio is 10
It is preferably used at a ratio of / 90 to 100/0. Any synthetic resin may be used as long as it accepts the dye migrating from the transfer sheet.
(F) is 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 sulfo group or a carboxyl group) and ethylene glycol; Polyester resin obtained by condensation of propylene glycol, neopentyl glycol, bisphenol A, etc .: Polyacrylate resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate or polymethacrylate resin: Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin:
Vinyl toluene acrylate resin, etc. Specifically, JP-A Nos. 59-101395, 63-7971, 63
No. -7972, No. 63-7973, No. 60-2948
No. 62 publications. Also,
As commercially available products, Byron 290 and Byron 2 manufactured by Toyobo
00, Byron 280, Byron 300, Byron 10
3, Byron GK-140, Byron GK-130, Kao ATR-2009, ATR-2010 (all of which are trade names) and the like can be used. (B) Those having a urethane bond Polyurethane resin and the like. (C) Those having an amide bond, such as polyamide resin. (D) Those having a urea bond, such as a urea resin. (E) Those having a sulfone bond, such as polysulfone resin. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin and the like.

In addition to the above synthetic resins, mixtures or copolymers thereof can also be used. In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling organic solvent or a hot solvent can be contained as a substance capable of accepting a heat transferable dye or as a dye diffusing agent. Specific examples of high boiling organic solvents and hot solvents are described in JP-A-62-1747.
No. 54, No. 62-245253, No. 61-20944
No. 4, No. 61-200538, No. 62-8145,
No. 62-9348, No. 62-30247, No. 62-
Compounds described in JP-B-136646 can be exemplified. The image receiving layer of the thermal transfer image receiving material of the present invention may have a structure in which a substance capable of accepting a heat transferable dye is dispersed in a water-soluble binder and supported. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of undergoing a cross-linking reaction with a hardener is preferable. The image receiving layer may be composed of two or more layers. In this case, use a synthetic resin with a low glass transition point for the layer closer to the support, or use a high-boiling organic solvent or a heat solvent to enhance the dyeing properties of the dye. Use a synthetic resin with a higher point, minimize the amount of high-boiling organic solvent or thermal solvent used or minimize the amount of stickiness on the surface, adhesion with other substances, transfer to other substances after transfer. It is desirable to adopt a configuration that prevents failures such as retransfer and blocking with the thermal transfer dye donating material. The total thickness of the image receiving layer is preferably in the range of 0.5 to 50 μm, particularly preferably 3 to 30 μm. 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.

The thermal transfer image-receiving material of the present invention may have an intermediate layer between the support and the image-receiving layer. The intermediate layer is a layer having one or more functions of any of a cushion layer, a porous layer, and a dye diffusion preventing layer, depending on the constituent material,
In some cases, it also serves as an adhesive. 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 is preferably a water-soluble binder, and examples thereof include the water-soluble binder described above as the binder for the image receiving layer, particularly gelatin. The porous layer is a layer that prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support, and plays a role of effectively using the applied heat. The image receiving layer, the cushion layer, the porous layer, the diffusion preventing layer, the adhesive layer, and the like constituting the thermal transfer image receiving material of the present invention include silica,
Fine powders such as clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithobon, titanium oxide, and alumina may be contained. The support used in the thermal transfer image-receiving material of the present invention can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, dents after transfer, and the like. Anything can be used. For example, synthetic paper (polyolefin-based, polystyrene-based synthetic paper), high-quality 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 base paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), and various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, and polycarbonate. And a film or sheet treated to give white reflectivity to this plastic or a laminate of any combination of the above.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. For example, K. Vevnkataraman ed., “The Chem
istry of Synthetic Dyes ", Vol. 5, Chapter 8, JP-A-61
And compounds described in JP-A-143752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyril compounds, 2,5-dibenzoxazole thiophene compounds, and the like. No. The fluorescent whitening agent can be used in combination with the anti-fading agent. In the present invention, in order to improve the releasability between the thermal transfer dye-providing material and the thermal transfer image-receiving material, the outermost layer which contacts the surface of the dye-providing material and / or the image-receiving material, particularly preferably the surface where both materials are in contact with each other It is preferable to include a releasability in the resin. Examples of the release agent include solid or wax-like substances such as polyethylene wax, amide wax, and Teflon powder: surfactants such as fluorine-based and phosphate-based agents: paraffin-based, silicone-based, and fluorine-based oils. Any release agent can be used, but silicone oil is particularly preferred. As the silicone oil, a modified silicone oil such as carboxy-modified, amino-modified, or epoxy-modified can be used in addition to the unmodified silicone oil. An example is Shin-Etsu Silicone Co., Ltd.
6-18B of "modified silicone oil" technical data issued
Various modified silicone oils described on the page can be mentioned. 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 isocyanate) is emulsified and dispersed in a water-soluble binder. Is effective to use a carboxy-modified silicone oil (for example, product name: X-22-3710 manufactured by Shin-Etsu Silicone Co., Ltd.).

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be hardened by a hardener. In the case of curing an organic solvent-based polymer, JP-A-61-199997 and JP-A-58-21439.
Hardening agents described in JP-A No. 8 and the like can be used. It is particularly preferable to use an isocyanate-based hardening agent for the polyester resin. For curing of the water-soluble polymer, US Pat. No. 4,678,739, column 41, JP-A-59-5959
-116655, 62-245261, 61-
Hardening agents described in JP-A-18942 are suitable for use. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-
Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157) can be mentioned.

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Further, Japanese Patent Application Laid-Open No. 61-159644
The compounds described in Japanese Patent Application Laid-Open Publication No. H11-163, 1993 are also effective. Benzotriazole compounds (U.S. Pat. No. 3,533)
3,794, etc.), 4-thiazolidone-based compounds (US Pat. No. 3,352,681, etc.), benzophenone-based compounds (JP-A-56-2784, etc.), and other JP-A-54-284. No. 48535, 62-13
There are compounds described in JP-A-6641 and JP-A-61-88256. Further, an 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 4,245,018, columns 3-36 and 4,2.
No. 54,195, columns 3-8, JP-A-62-174.
Nos. 741 and 61-88256 (27)-
(29), Japanese Patent Application No. 62-234103, 62-3
There are compounds described in the specifications of Japanese Patent Application No. 11096 and Japanese Patent Application No. 62-230596. Examples of useful anti-fading agents are described in JP-A-62-215272 (125) to (13).
7) It is described on page. An anti-fading agent for preventing fading of the dye transferred to the image receiving material may be contained in the image receiving material in advance, or supplied from the outside to the image receiving material by a method such as transferring from a dye donating material. You may. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

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 static charge, and improving releasability. Representative examples of the organic fluoro compound include columns 8 to 17 of JP-B-57-9053, JP-A-61-20944, and JP-A-62-297.
Examples include fluorine-based surfactants described in JP-B-135826 and hydrophobic fluorine-containing compounds such as oily fluorine-based compounds such as fluorine oil or solid fluorine-containing resins such as ethylene tetrafluoride resin. A matting agent can be used for the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
In addition to the compounds described in No. 8256 (page 29), benzoguanamine resin beads, polycarbonate resin beads,
There are compounds such as AS resin beads described in JP-A-63-274944 and JP-A-63-274952.

[0041]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the following specific examples as long as the gist of the invention is not exceeded. Representative synthesis examples are shown below. (Synthesis Example) Synthesis of Dye 3

[0042]

Embedded image

115 g of benzoisothiazole (H) was added to water 1
After adding 250 ml of concentrated hydrochloric acid, an aqueous solution in which 52 g of sodium nitrite was dissolved in 160 ml of water was added dropwise at 5 ° C. or lower, and the mixture was stirred for 30 minutes to prepare a diazo liquid. Compound (I) 104 g, acetonitrile 700 ml, water 230 m
l, The above diazo solution was slowly added to a mixture of 360 ml of triethylamine at 10 ° C or lower. After stirring for 1 hour, 1000 ml of 20% saline, 430 ml of hydrochloric acid and 1000 ml of isopropyl alcohol were sequentially added, and the precipitated crystals were collected by filtration to obtain 177 g of azo dye (J).

50 g of the dye (J) was added to dimethylacetamide 2
00 ml and a solution of 30 ml of triethylamine, 13.2 ml of methanesulfonyl chloride was added dropwise at room temperature, and after stirring for 30 minutes, 600 ml of acetonitrile was added.
The precipitated crystals were collected by filtration to obtain 57 g of compound (K).

Dye (K) 57 g was added to dimethylacetamide 6
To a solution of 0 ml and 400 ml of acetonitrile, 76.3 ml of phosphorus oxychloride was added dropwise under ice cooling. After reacting at 60 ° C. for 1 hour, the reaction solution was poured into ice water, and the precipitated crystals were collected by filtration to obtain 38 g of Compound (L).

12 g of the compound (L) was dissolved in 50 ml of dimethylacetamide, and 10 ml of diethylamine was added dropwise under ice-cooling, and the mixture was further stirred for 1 hour. Then, the reaction mixture was poured into aqueous hydrochloric acid, and the precipitated crystals were collected by filtration to obtain 10 g of crude crystals. Washing by heating with 60 ml of methanol, the exemplary compound (33)
8.5 g were obtained.

Example 1 Preparation of Thermal Transfer Dye Donor Material (D-1) A 5 μm thick polyethylene terephthalate film provided with a heat-resistant lubricating layer on one side was used as a support.
On the side opposite to the side provided with the heat-resistant lubricating layer, a dye-donating layer coating composition (1) having the following composition was applied using a gravure coater so that the thickness after drying was 0.6 μm. ,
A thermal transfer dye-providing material (D-1) (hereinafter, also simply referred to as a dye-providing material) was obtained. Dye donating layer coating composition (1) Dye 1 10 g Polyvinyl butyral (Denka butyral 5000A: trade name, manufactured by Denki Kagaku) 10 g Silicone oil (KF-96: trade name, manufactured by Shin-Etsu Chemical) 0.2 g Polyisocyanate (Takenate D110N: Takeda) 0.5 g of methyl ethyl ketone 100 ml toluene 80 ml

Preparation of Thermal Transfer Image-Receiving Material (P-1) A laminated synthetic paper having a thickness of 150 μm was used as a support.
A receiving layer coating composition (1) having the following composition is applied to the surface using a wire bar coater so that the thickness when dried becomes 5 μm, and the thermal transfer image-receiving material (1) (hereinafter simply referred to as the image-receiving material) ) Was produced. Drying was carried out in an oven at 80 ° C. for 1 hour after temporary drying with a dryer. Receptive layer coating composition (1) Dye fixative; A-9 (trade name: AEA, manufactured by Sankyo Co., Ltd.) 26 g Polyisocyanate (KP-90: trade name, manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil ( Shin-Etsu Silicone product name: KP-857) 0.5 g methyl ethyl ketone 100 ml toluene 50 ml cyclohexanone 10 ml

[0049]

Embedded image

Dye-donor materials (D-2) to (D-10),
And Preparation of (A) to (C) Dye donating materials (D-2) to (D-2) to (D-2) D-10) and comparative dye-donor materials (A) to (C) were prepared.

[0051]

Embedded image

[0052]

[Table 1]

Transfer Experiment Using the thermal transfer dye-providing material obtained as described above, the dye-providing layer and the receiving layer of the thermal transfer image-receiving material (1) are overlapped so as to be in contact with each other, and from the support side of the thermal transfer dye-providing material. Using a thermal head, heating is performed under the conditions of an output of the thermal head of 0.25 W / dot, a pulse width of 0.1 to 10 msec, and a dot density of 6 dots / mm, and dyes are dye-imaged on the receiving layer of the image receiving material. Upon application, clear image recording without transfer unevenness was obtained. The portion where the density of the recorded image receiving material obtained at this time was saturated (Dmax portion) was measured using a reflection densitometer (manufactured by X Rite Inc., built-in status A filter), and the maximum transfer density of the image was measured. Was measured. Next, the recorded image receiving material was used for 17 days at 17,000.
The image was irradiated with a Lux fluorescent lamp, and the light fastness of the image was examined. The reflection density after the test of the portion showing the reflection density of 1.0 was measured,
The stability was evaluated by the residual ratio (%) with respect to the reflection density of 1.0 before the test. Further, the image was stored in an oven at 60 ° C. for one week, and the thermal stability of the image was examined. The combined material of the present invention was stable with almost no decrease in density and no discoloration. Further, the recorded image receiving material is placed in a 60 ° C. oven for 2 hours.
The degree of bleeding of the image after storage for a week was observed. The criterion is indicated by ○ when the image has hardly changed from that before storage, Δ when the image is slightly blurred, and X when extremely blurred and blurred. The results are shown in Table 2. It can be seen that when the dye of the present invention is used, a clear image having a high transfer density, excellent light and heat fastness is obtained, and the image is not blurred with time. In addition, there was no color transfer (contamination due to transfer of dye from the transfer image surface due to contact between the front surface with the transfer image and the front or back surface of the image receiving paper without the transfer image). On the other hand, when the dye-providing material for comparison was used, there was no blur in (A) and (B), but the hue and light fastness were slightly inferior to those using the dye of the present invention.
When the non-dissociable dye (c) was used as shown in (C), blurring of the image was observed by the bleeding test.

[0054]

[Table 2]

Example 2 Preparation of Thermal Transfer Image-Receiving Material (P-2) to (P-5) Dye Fixing Agent of Receptive Layer Coating Composition (1) of Thermal Transfer Image-Receiving Material (P-1) of Example 1 Image receiving materials (P-2) to (P-5) were prepared in the same manner except that dye fixing agents and binder resins shown in Table 3 were used instead of A-9.

[0056]

Embedded image

[0057]

[Table 3]

Transfer Experiment Example 1 was performed using the thermal transfer dye-providing material obtained in Example 1 and the thermal transfer dye image-receiving materials (P-2) to (P-5).
As a result of conducting a transfer experiment according to the above method, clear high-density full-color image recording without transfer unevenness was obtained. Further, it was excellent in light and heat fastness, and no image blur was observed.

[0059]

By using the thermal transfer recording material of the present invention, an image having a high transfer density and excellent color reproducibility can be obtained. In addition, it is possible to obtain an image having excellent preservability and without a decrease in sharpness over time.

Claims (1)

[Claims] 1. A thermal transfer recording material comprising a thermal transfer dye-providing material and a thermal transfer image-receiving material containing a thermal transfer dye capable of forming a negative atom by donating a hydrogen atom, wherein at least one of the thermal transfer dyes has the following general formula: Thermal transfer recording material characterized by being an azo dye represented by (1); General formula (1) In the formula, R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a nonmetallic atomic group. R ³ and R ⁴ may combine to form a ring structure. W represents an atom group necessary for forming a 5- to 6-membered ring.