JPH06219063A - Heat transfer material - Google Patents

Abstract

PURPOSE:To provide a heat transfer coloring matter giving material capable of forming a coloring matter image which is clear and superior in photofastness properties. CONSTITUTION:In a heat transfer coloring matter giving material which is comprised by possessing a coloring matter giving layer containing a heat shifting coloring matter on a substrate, the coloring matter giving layer contains an azomethine coloring matter possessing diphenylamino group and/or an azo coloring matter possessing the diphenylamino group or a methine coloring matter possessing a diphenylaminophenyl group as the heat shifting coloring matter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer dye-donor element using a heat transferable dye.

[0002]

2. Description of the Related Art At present, a thermal transfer method, an electrophotographic method, an ink jet method and the like are vigorously studied as a technology relating to a color hard copy. The thermal transfer method has many advantages over other methods because the apparatus is easy to maintain and operate and the apparatus and consumables are inexpensive. The thermal transfer method is a method in which a thermal transfer dye-donating material having a heat-fusible ink layer formed on a base film is heated by a thermal head to melt the ink and record on the thermal transfer image-receiving material, and heat transfer to the base film. There is a method of heating a thermal transfer dye-donating material having a dye-donating layer containing a functional dye by a thermal head to transfer the dye to a thermal transfer image-receiving material by heat transfer. The amount of dye transfer can be changed by changing the applied energy, which facilitates gradation recording and is particularly advantageous for high-quality full-color recording. However, the heat transferable dye used in this method has various restrictions, and very few satisfy all the required performances. The required performance is, for example,
It has favorable spectral characteristics for color reproduction, it is easy to transfer heat, it is resistant to light and heat, it is resistant to various chemicals, the sharpness is not easily reduced, retransfer of the image is difficult to occur, and a thermal transfer dye It is easy to make donation materials.

Azomethine dyes, azo dyes, and methine dyes are typical dyes for thermal transfer use, and most of these dyes have an amino group or an aminophenyl group. For example, as an azomethine dye having an amino group, JP-A-64-1591 and JP-A-1-17665 are available.
No. 91, No. 1-176589, No. 1-176590 and the like disclose yellow dyes. In addition, JP-A-64
-48862, 64-48863, 64-63
194, JP-A-2-178088 and JP-A-2-1751.
No. 90, No. 2-208094, No. 2-265791.
No. 2-310087, No. 3-7386, No. 3-
Nos. 51188 and 1-176592 disclose pyrazoloazole azomethine dyes and azomethine dyes similar thereto. Further, JP-A-2-155693,
International patent WO 91/01890 discloses imidazole azomethine dyes. Further, infrared absorbing dyes are disclosed in JP-A-3-81192, JP-A-3-81193 and JP-A-3-81193.
No. 81194, azomethine dyes derived from aminothiazole are disclosed in JP-A-3-93862, and other azomethine dyes are disclosed in JP-A-2-84391 and 2-671.
No. 87, No. 2-172792, No. 2-172793.
No. 3,16,792, and No. 3,17,163.

Azo dyes having an amino group are disclosed in JP-A-57-46714, JP-A-60-31565 and JP-A-62-62.
-99195, 60-30392, 60-30
No. 394, No. 60-239291, No. 61-1239.
No. 2, No. 61-227091, No. 62-33688.
No. 62-55194, No. 62-294593,
An aniline-based azo dye, for example, in No. 63-5992,
U.S. Pat. No. 5,158,928 discloses aminothiazole azo dyes.

Further, methine dyes having an aminophenyl group are disclosed in JP-A-59-78895 and JP-A-60-2.
No. 8451, No. 60-53564, No. 60-2392.
No. 90, No. 253594, No. 60-253596 and the like, dicyanostyryl dyes are disclosed in JP-A-59-78896.
No. 60, No. 60-28452, No. 60-31563, No. 6
0-31564, 60-223862, 61-1
Nos. 63895 and 63-203393 disclose tricyanostyryl dyes. Other methine dyes having an aminophenyl group are disclosed in JP-A-63-14.
1799, JP-A-2-217290, and JP-A-3-309.
93, 4-4190, JP-A-60-156790.
No. 62-273265, JP-A-2-69292.
No. 2-67187, 3-499993, 2-
No. 6559, No. 2-208093, No. 2-3450
And No. 4-8589. However, azomethine dyes and azo dyes having an N, N-diphenylamino group as an amino group, or methine dyes having an N, N-diphenylaminophenyl group as an aminophenyl group are not known at all.

[0006]

Conventionally known azomethine dyes having an amino group, and azo dyes, or methine dyes having an aminophenyl group do not satisfy all the performances required as a thermal transfer dye. In particular, the fastness to light and heat was insufficient. In order to solve the above problems, the present inventors have developed an azomethine dye having an N, N-diphenylamino group and an azo dye, or N, N.
As a result of intensive studies on methine dyes having a -diphenylaminophenyl group, it was found that these dyes have higher fastness to light and heat than conventional dyes. Accordingly, it is an object of the present invention to provide a thermal transfer dye-donor element using a novel dye that sufficiently satisfies the required performance. In particular, it is to provide a thermal transfer dye-donor material using a novel dye that is resistant to light and heat.

[0007]

The above objects of the present invention are as follows.
It was achieved by the following configuration. (1) In a thermal transfer dye-donor material having a dye-donor layer containing a heat-transfer dye on a support, the dye-donor layer contains a heat-migrator dye having an N, N-diphenylamino group. A characteristic thermal transfer dye-donor material. (2) A thermal transfer dye-donating material as described in (1), wherein the heat transferable dye is an azomen dye having an N, N-diphenylamino group. (3) A thermal transfer dye-donating material as described in (1), wherein the heat transferable dye is an azo dye having an N, N-diphenylamino group. (4) A thermal transfer dye-donating material as described in (1) above, wherein the heat transferable dye is a methine dye having an N, N-diphenylaminophenyl group.

The present invention will be described in detail below. The azomethine dye having an N, N-diphenylamino group and / or the azo dye having an N, N-diphenylamino group and / or the methine dye having an N, N-diphenylaminophenyl group used in the present invention are in the visible range. , And / or has an absorption in the infrared region, and each is preferably represented by the following general formulas (I) to (III).

[0009]

[Chemical 1]

[0010]

[Chemical 2]

[0011]

[Chemical 3]

In formula (I), Q is derived from a coupler compound which forms an azomethine dye by an oxidative coupling reaction with p-phenylenediamines. Examples of the coupler compound include phenols and naphtho
Or 5-pyrazolones, 1H-pyrazolo [1,
5-a] benzimidazoles, 1H-pyrazolo [5,5]
1-c] -1,2,4-triazoles, 1H-pyrazolo [2,3-b] -1,2,4-triazoles, 2,
Heterocycles having active hydrogen, such as 4-diphenylimidazoles, pyrrolotriazoles, pyrazolopyrimidin-5-ones, pyrazolopyrimidin-7-ones,
Further, active methylene compounds such as acylacetonitriles, acylacetanilides, diacylmethanes, malononitrile, malondianilides and phenylacetonitriles can be mentioned.

A represents an arylene group or a divalent unsaturated heterocycle, which may have a substituent. More preferably, A is a phenylene group or a divalent 5- or 6-membered unsaturated heterocycle (eg, thiazole ring, pyridine ring, thiophene ring), and the substituent is a halogen atom or carbon number. 1 to 12 alkyl groups (eg methyl,
Ethyl, butyl), a C1-C12 alkoxy group (for example, methoxy, ethoxy, i-propoxy), a C1-C12 alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl), a C1-C12 Acylamino group (eg, acylamino, pivaloylamino), carbamoyl group having 1 to 12 carbon atoms (eg, methylcarbamoyl, phenylcarbamoyl), carbon number 1
To 12 sulfonamide groups (for example, methanesulfonamide, ethanesulfonamide) groups, cyano groups, nitro groups, phenyl groups and the like. Of these, an unsubstituted phenylene group is most preferable. R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms (methyl, ethyl, butyl), an alkoxy group having 1 to 12 carbon atoms (methoxy, ethoxy), 1 to 1 carbon atoms. 12 alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl), C1-12 acylamino groups (eg, acylamino, pivaloylamino), total carbon numbers 2-24
Represents a dialkylamino group (eg, dimethylamino, diethylamino), a cyano group, a nitro group, or a phenyl group. m and n represent an integer of 1 to 5, and when m and n are 2 or more, R ₁ and R ₂ may be the same or different.
More preferably, both R ₁ and R ₂ are hydrogen atoms.

In the formula (II), B is a coupler component residue of the azo dye, has the same meaning as A in the formula (I), and the substituents are also the same. More preferably, B is a phenylene group or a divalent 5- or 6-membered unsaturated heterocycle (for example,
Thiazole ring, pyridine ring, thiophene ring). Among them, B is most preferably a phenylene group, and as a substituent, an alkyl group (for example, methyl, ethyl, butyl) substituted at the 2-position with respect to an azo group, an alkoxy group having 1 to 6 carbon atoms (for example, methoxy). , Ethoxy, i-propoxy), an acylamino group having 1 to 6 carbon atoms (acylamino,
Pivaloylamino) and a sulfonamide group having 1 to 6 carbon atoms (methanesulfonamide, ethanesulfonamide) group are preferable. R _1, R _2, m, and n have the same meanings as R _1, R _2, m, and n in formula (I). D is a diazo component residue and represents an aryl group or an unsaturated heterocyclic group.
More preferably, an optionally substituted phenyl group (eg, phenyl, 2,6-dichloro-4-nitrophenyl, 2,6-dicyano-4-chlorophenyl, p-nitrophenyl), optionally substituted , Isothiazole residue, thiazole residue, thiophene residue, triazole residue, thiadiazole residue, imidazole residue and the like. A specific example is shown below.

[0015]

[Chemical 4]

In the formula (III), R ₃ and R ₄ are each independently a cyano group, an alkoxycarbonyl group having 2 to 12 carbon atoms (eg, methoxycarbonyl, phenoxycarbonyl), a carbamoyl group having 2 to 12 carbon atoms ( For example, butylcarbamoyl, dimethylcarbamoyl), having 2 to 2 carbon atoms
12 acyl groups (eg benzoyl, furanoyl, thienoyl), aryl groups having 6 to 24 carbon atoms (eg p
-Nitrophenyl, naphthyl), optionally fused 5
To a 6-membered heterocyclic group (for example, benzothiazolyl) and an alkyl group having 1 to 12 carbon atoms (for example, ethyl, t-butyl). Alternatively, it may combine with R ₃ and R ₄ to form a 5- or 6-membered ring (eg, pyrazolone ring, pyrazolo-3,5-dione ring). More preferably, a cyano group, an alkoxycarbonyl group having 2 to 8 carbon atoms, or 2 carbon atoms.
~ 8 carbamoyl groups, most preferably R ₃
And R ₄ are both cyano groups. R ₅ is a hydrogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms (for example, methyl,
Ethyl) and an aryl group having 6 to 24 carbon atoms (eg, phenyl). Preferably, it is a hydrogen atom or a cyano group.

R ₆ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl, butyl), an alkoxy group having 1 to 12 carbon atoms (eg, methoxy, ethoxy, i-propoxy). , An alkoxycarbonyl group having 1 to 12 carbon atoms (for example, methoxycarbonyl,
Ethoxycarbonyl), an acylamino group having 1 to 12 carbon atoms (eg, acylamino, pivaloylamino), a carbamoyl group having 1 to 12 carbon atoms (eg, methylcarbamoyl, phenylcarbamoyl), a sulfonamide group having 1 to 12 carbon atoms (eg, Methanesulfonamide, ethanesulfonamide) group, cyano group, nitro group, phenyl group and the like. l represents an integer of 1 to 5, and when l is 2 or more, R ₆ may be the same or different. The most preferable R ₆ is a hydrogen atom. R _1, R _2, m, and n have the same meanings as R _1, R _2, m, and n in formula (I).
Specific examples of the dyes represented by formulas (I) to (III) used in the present invention are shown below, but the present invention is not limited thereto.

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

Next, a method for synthesizing the dye used in the present invention will be described. The azomethine dye represented by the general formula (I) of the present invention is obtained by dehydration condensation of the corresponding coupler compound and the nitroso compound represented by the following general formula (IV), or by the corresponding coupler compound and the following general formula: It is synthesized by oxidative coupling with an amino compound represented by the formula (V).

[0026]

[Chemical 12]

For example, dye 1. Is synthesized by the following reaction formula.

[0028]

[Chemical 13]

The azo dye represented by the general formula (II) of the present invention comprises a coupler component represented by the following general formula (VI) and DN.
It is synthesized by diazo coupling with a diazo component represented by H ₂ .

[0030]

[Chemical 14]

For example, dye 35. Is synthesized by the following reaction formula.

[0032]

[Chemical 15]

The methine dye represented by the general formula (III) of the present invention can be synthesized by various methods. For example, dye 47.
And dye 49. Are each synthesized by the following reaction formulas.

[0034]

[Chemical 16]

[0035]

[Chemical 17]

(A, B, R ₁ , R ₂ , m, n are general formulas
It has the same meaning as described in (I) and (II). )

The heat transferable dye of the present invention is contained in the color material layer on the support to serve as a thermal transfer dye-providing material, which is used for image formation by the 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 below. To compose a normal full-color image,
Yellow, magenta and cyan dyes are required.
Therefore, three colors can be appropriately selected from the dyes of the present invention. Alternatively, one of the yellow, magenta, and cyan colors can be selected from the dyes of the present invention, and the other two colors can be selected from conventionally known dyes. Alternatively, 2 of the yellow, magenta, and cyan colors among the dyes of the present invention can be used.
A color can be selected and another one can be selected from conventionally known dyes. 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 in the same color.

Next, a method of using the heat transferable dye of the present invention will be described. The thermal transfer dye-providing material can be used in the form of a sheet or a continuous roll or ribbon. yellow,
The magenta and cyan dyes are usually arranged on the 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 frame-sequential or line-sequential manner. Further, it is also possible to prepare three types of thermal transfer dye-donor materials in which the above-mentioned yellow dye, magenta dye, and cyan dye are provided on separate supports, and from these, the thermal transfer of dyes to one thermal transfer image-receiving material can be carried out sequentially. . The dye of the present invention can be dissolved or dispersed in a suitable solvent together with a binder resin and applied 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 to 5 in terms of dry film thickness.
It is preferable to set in the range of μm, particularly 0.4 to 2 μm. The coating amount of the dye is 0.03 to 1 g / m ² , preferably 0.1 to 0.6 g / m ² .

As the binder resin to be used with the above-mentioned dye, any of the conventionally known binder resins for such purpose can be used, and usually has high heat resistance,
Moreover, one that does not interfere with the migration of the dye when heated is 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 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 in a ratio of about 20 to 600 parts by weight, for example, per 100 parts by weight of the dye. In the present invention, any conventionally known ink solvent can be used as the ink solvent for dissolving or dispersing the dye and the binder resin.

Any conventionally known support can be used as the support of the thermal transfer dye-providing material. Examples thereof include polyethylene terephthalate, polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-donor element is generally 2 to
It is 30 μm. An undercoat layer may be provided if necessary. 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. 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 heat of the thermal head and to improve slippage when printing from the back side of the dye-donor material, it is preferable to perform 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 containing a reaction product of polyvinyl butyral resin and isocyanate, an alkali metal salt or an alkaline earth metal salt of phosphoric acid ester, and a filler. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000, 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 a phosphoric acid ester, Gafac RD720 manufactured by Toho Kagaku Co., Ltd. is used, which is 1 to 50% by weight, preferably 1
It is recommended to use about 0 to 40% by weight. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

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

The dye-donor element may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has a desired function, but 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, for example, Bostic 7650 (M Heart Company, Bostic 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 it 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 superposed on the thermal transfer image-receiving material, and heat is applied according to the image information from either side, preferably from the back side of the thermal transfer dye-providing material, by 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. For a more detailed description of this process, see British Patent 2,
083,726A. British Patent 2,0
The absorbing material disclosed in the 83,726A for its laser system is carbon.

In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to form an image by printing using various printers of thermal printing system, facsimile, or magnetic recording system, magneto-optical recording system, optical recording system and the like. It can be used to create prints, prints from a television or CRT screen. For details of the thermal transfer recording method, the description in JP-A-60-34895 can be referred to. In a preferred embodiment of the invention, the thermal transfer dye-donor element comprises a polyethylene terephthalate support coated with cyan dye, magenta dye and yellow dye in successive repeating regions, wherein the thermal transfer step is performed sequentially for each dye. A transfer image of three colors is formed. Of course, when the thermal transfer process is performed in a single color, a monochrome transfer image is obtained. Thermal transfer of dyes from a thermal transfer dye-donor material to a thermal transfer image-receiving material is accomplished by ion gas lasers such as argon or krypton, metal vapor lasers such as copper, gold and cadmium, solid state lasers such as ruby or YAG, or 7
Several lasers can be used, such as semiconductor lasers such as gallium-arsenide, which emit in the infrared range from 50 to 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 support and an image-receiving layer for receiving the dye transferred from the dye-providing material. This image-receiving layer contains a substance capable of receiving a heat-transferable dye having a function of dyeing the heat-transferable dye, which receives the heat-transferable dye transferred from the heat-transfer dye-providing material during printing. Or with other binder substances, it is preferable that the film has a thickness of about 0.5 to 50 μm. The following resins are examples of polymers that are typical examples of substances that can receive heat transferable dyes.

(A) Those having an ester bond: dicarboxylic acid components such as terephthalic acid, isophthalic acid and succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group or a carboxyl group) and ethylene. Polyester resin obtained by condensation of 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 polymethacrylic acid ester resin : Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 may be mentioned. As commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-14 are used.
0, Byron GK-130, ATR-200 made by Kao
9, ATR-2010, etc. can be used. (B) Those having a urethane bond, such as polyurethane resin. (C) Those having an amide bond Polyamide resin and the like. (D) Those having a urea bond, such as urea resin. (E) Those having a sulfone bond Polysulfone resin, etc. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the above synthetic resins, mixtures or copolymers of these can also be used. In addition, JP-A 1-188
The basic compounds and / or mordants described in No. 391 and No. 3-83685 can also be used.

In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a substance capable of receiving the heat-transferable dye or as a diffusion aid of the dye. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A Nos. 62-174754 and 62-24525.
No. 3, No. 61-209444, No. 61-200538
No. 6, No. 62-8145, No. 62-9348, No. 62
The compounds described in Nos. -30247 and 62-136646 can be mentioned. The image receiving layer of the thermal transfer image receiving material is
A substance capable of receiving the heat transferable dye may be 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 a water-soluble polymer having a group capable of undergoing a crosslinking reaction by a hardening agent is preferable. The image 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 composition having enhanced dyeing property to a dye by using a high-boiling organic solvent or a thermal solvent, and the glass transition layer is used for the outermost layer. Using a synthetic resin with a higher point, sticking to the surface, adhering to other substances, or sticking to other substances after transfer, with or without using the minimum amount of high boiling organic solvents or heat solvents It is desirable to have a structure that prevents troubles such as retransfer and blocking with a thermal transfer dye-donor material. The total thickness of the image receiving layer is 0.5 to 50.
μm, particularly 3 to 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.

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 either a cushion layer, a porous layer, a dye diffusion preventing layer, or a layer having two or more functions 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 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 a layer which prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support and effectively utilizes the applied heat. An image receiving layer, a cushion layer, which constitutes the thermal transfer image receiving material,
For the porous layer, the diffusion preventing layer, the adhesive layer, etc., silica, clay,
Fine powders of talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina and the like may be contained. What kind of support can be used for the thermal transfer image-receiving material as long as it can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, and dents after transfer? Anything 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.

A fluorescent whitening agent may be used in the thermal transfer image receiving material. For example, see “The Chem” by K. Veenkataraman.
istry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples thereof include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, carbostyryl-based compounds, and 2,5-dibenzoxazolethiophene-based compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent. In the present invention, in order to improve the releasability of the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, particularly preferably the outermost layer which is the surface in contact with both materials. It is preferable to include a release agent in the. As release agents, solid or wax-like substances such as polyethylene wax, amide wax, Teflon powder: Surfactants such as fluorine-based and phosphoric ester-based: paraffin-based, silicone-based, fluorine-based oils, etc. Although any of the above releasing agents can be used, silicone oil is particularly preferable. As the silicone oil, in addition to unmodified ones, carboxy-modified, amino-modified,
Modified silicone oil such as epoxy modified can be used. Examples thereof include various modified silicone oils described on pages 6 to 18B of "Modified Silicone Oil" technical data issued by Shin-Etsu Silicone Co., Ltd.
When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with an isocyanate) is also emulsified and dispersed in a water-soluble binder. Is effectively a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd .: trade name X-22-3710).

The layers constituting the thermal transfer dye-providing 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. It is particularly preferable to use an isocyanate type hardener for the polyester resin. For curing water-soluble polymers, U.S. Pat. No. 4,678,739, column 41, JP-A-59-1166.
55, 62-245261 and 61-18942.
The hardeners described in the publications are suitable for use. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of anti-fading agents include antioxidants, ultraviolet absorbers, and certain metal complexes. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, 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), 4-
Thiazolidone compounds (US Pat. No. 3,352,681
No.), benzophenone compounds (JP-A-56-27)
84, etc., and other Japanese Patent Laid-Open Nos. 54-48535 and 6
There are compounds described in Nos. 2-136641 and 61-88256. 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 4,24.
No. 5,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A Nos. 62-174741 and 61-8.
8256, pages (27) to (29), JP-A-1-7556
8 and the compounds described in JP-A-63-199248. Examples of useful anti-fading agents are disclosed in JP-A-62-2.
15272 (125)-(137). 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 may be supplied to the image-receiving material from the outside by a method such as transferring from the dye-providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination.

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, prevention of electrostatic charge, acceleration of development and the like. For example, saponin (steroidal), alkylene oxide derivative (eg, polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone Polyethylene oxide adducts), glycidol derivatives (for example, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars and the like: alkylcarboxylic acid salts, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates N-acyl-N-alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphoric acid esters and other carboxy groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups Anionic surfactants containing acidic groups such as:
Amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium Heterocyclic fourth such as
Cationic surfactants such as primary ammonium salts and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring can be used. Specific examples of these are disclosed in JP-A Nos. 62-173463 and 62-18345.
No. 7, etc. Further, when dispersing a substance capable of receiving a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent and other hydrophobic compounds in a water-soluble binder, an interface as a dispersion aid is obtained. Preference is given to using activators. 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.

The constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. As typical examples of the organic fluoro compound, JP-B-57-9053, columns 8 to 17, JP-A-61-20944 and JP-A-62-13.
5826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as tetrafluoroethylene resin. A matting agent can be used in the thermal transfer dye-donating material and the thermal transfer image-receiving material. Matting agents such as silicon dioxide, polyolefins and polymethacrylates are disclosed in JP-A-61-88256.
JP-A-63-274944 and JP-A-63-274, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads, in addition to the compounds described on page (29).
There are compounds described in No. 952.

[0054]

EXAMPLES In the following Examples and Comparative Examples, production of a thermal transfer dye-donor material and a thermal transfer image-receiving material, printing using both materials, and a test of the thermal transfer image-receiving material will be described.

Example 1 (Preparation of thermal transfer dye-providing material (1-1)) A polyethylene terephthalate film having a thickness of 6 μm, the back surface of which was subjected to a heat-resistant lubrication treatment, was used as a support, and The coating composition for the thermal transfer dye-donating layer of composition has a thickness of 1.5 μm when dried by wire bar coating.
The thermal transfer dye-donor material (1-
1) was created. Coating composition for thermal transfer dye-donor layer Dye 1. 10 mmol Polyvinyl butyral resin (manufactured by Denki Kagaku; Denka butyral 5000-A) 3 g Toluene 40 ml Methyl ethyl ketone 40 ml Polyisocyanate (manufactured by Takeda Yakuhin; Takenate D110N) 0.2 ml Next, the above dye 1 is changed to another dye described in Table 1. The thermal transfer dye-donor materials of the present invention and the comparative thermal transfer dye-donor materials (1-2) to (1-23) were prepared in the same manner as described above except for the above.

(Preparation of Thermal Transfer Image Receiving Material A) As a base material, a synthetic paper having a thickness of 150 μm (manufactured by Oji Yuka, YUPO-FPG)
-150) and a coating composition for an image receiving layer having the following composition on the surface by wire bar coating to a dry thickness of 8
A thermal transfer image-receiving material was formed by coating so as to have a thickness of μm.
Drying was carried out for 30 minutes in an oven at a temperature of 100 ° C. after temporary drying with a dryer. Coating composition A for image receiving layer Polyester resin (Vylon-280 manufactured by Toyobo) 22 g Polyisocyanate (KP-90: manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KP-857 manufactured by Shin-Etsu Silicone) 0.5 g Methyl ethyl ketone 85 ml Toluene 85 ml Cyclohexanone 15 ml

The thermal transfer dye-donor materials (1-1) to (1-23) obtained as described above and the thermal transfer image-receiving material are
The thermal transfer dye-donor layer and the image-receiving layer are superposed so that they are in contact with each other, and a thermal head is used from the support side of the thermal transfer donor layer. Thermal head output 0.25 W / dot, pulse width 0.15 to 15 m Sec, dot density 6 dots /
Printing was performed under the condition of mm, and dyes of respective colors (cyan, magenta, yellow) were dyed imagewise on the image-receiving layer of the image-receiving material, and clear image recording without transfer unevenness was obtained. Next, each recorded thermal transfer material obtained as described above was irradiated with a fluorescent lamp of 17,000 lux for 7 days, and the stability of the color image was examined. The Status A reflection density was measured before and after irradiation, and the stability was evaluated by the ratio. The results are shown in Table 1.

Table 1 No. Chromium Maximum density Light fastness Remarks 1-1 1 ○ ○ Present invention 1-2 3 ○ ◎ "1-3 5 ○ ○" 1-4 9 ○ ○ "1-5 13 ○ ○" 1-6 15 ○ ◎ "1-7 17 ○ ◎" 1-8 24 ○ △ "1-9 27 ○ ○" 1-10 29 ○ ○ "1-11 31 ○ ◎" 1-12 34 ○ ○ "1-13 35 ○ ○" 1-14 38 ○ ◎ "1-15 47 ○ ○" 1-16 49 ○ ○ "1-17 a ○ △ (1-1) Comparative Example 1-18 b ○ ○ (1-6)" 1-19 c ○ × (1-8) "1-20 d ○ △ (1-9)" 1-21 e ○ △ (1-13) "1-22 f ○ △ (1-15)" 1-23 g ○ × (1-16) ”

In the above table, the maximum value of reflection density is 1.5.
In the above cases, ○; in the case of 1.0 to less than 1.5, Δ;
The value less than 0 was defined as x. In addition, the light fastness is 9 when the dye residual ratio is 9
◎ for 0% or more, ○ for 70 to less than 90%, 5
When it was less than 0 to 70%, it was evaluated as Δ, and when less than 50%, it was evaluated as x. The following dyes a to g were used as comparative dyes.

[0060]

[Chemical 18]

From the above table, the dye of the present invention is excellent in transferability,
It can be seen that a high density image is provided, and the light fastness of the obtained image is one rank higher than that when the comparative dye is used due to the effect of the diphenylamino group. Although no comparative example is described, all other dyes also showed satisfactory light fastness.

Example 2 In place of the polyvinyl butyral resin and the dye in the thermal transfer dye-donor layer coating composition of Example 1, the resins and dyes shown in Table 2 were used, and the thermal transfer dye-donor materials (2-1), ( 2-
2) and (2-3) were created. The same image-receiving material as in Example 1 was used for printing, and evaluation was performed in the same manner as in Example 1. As shown in Table 2, clear image recording without transfer unevenness was obtained, and light fastness was excellent. (The evaluation method is the same as in Example 1)

Table 2 Dye donating material Resin Maximum concentration of dye Residual rate (%) 2-1 Ethyl cellulose 2 ○ ○ 2-2 Cellulose acetate butyrate 3 ○ ◎ 2-3 Polysulfone 15 ○ ○

The following are examples of combinations of other thermal transfer image-receiving materials with the thermal transfer dye-donor element of the present invention. Example 3 (Preparation of thermal transfer image receiving material) 150 μm thick as a support
Of synthetic paper (YUPO-FPG-150 manufactured by Oji Oil Chemical Co., Ltd.) is applied to the surface by wire bar coating so as to have a dry thickness of 10 μm, and a thermal transfer image is received. Created the material. Drying is done temporarily with a dryer and then in an oven at a temperature of 100 ° C for 30
I went for a minute.

Coating composition B for image receiving layer Polyester resin No. 1 * 2.0 g Amino-modified silicone oil (KF-857: manufactured by Shin-Etsu Silicone) 0.5 g Epoxy-modified silicone oil (KF-100T: manufactured by Shin-Etsu Silicone) 0. 5g Methyl ethyl ketone 85ml Toluene 85ml Cyclohexanone 30ml * Polyester resin No. 1

[0066]

[Chemical 19]

When printing was carried out in combination with the thermal transfer dye-donor materials of Examples 1 and 2, clear image recording was obtained. Also, the light fastness was excellent.

Example 4 (Preparation of Thermal Transfer Image Receiving Material) Resin coated paper prepared by laminating polyethylene having a thickness of 15 μm and 25 μm on both sides of 200 μm paper was prepared, and an image receiving layer having the following composition was formed on the laminated surface having a thickness of 15 μm. The coating composition for coating was applied by wire bar coating to a dry thickness of 10 μm and dried to prepare a thermal transfer image receiving material. Coating composition for image-receiving layer Polyester resin No. 1 25 g Amino-modified silicone oil (KF-857: manufactured by Shin-Etsu Silicone) 0.8 g Polyisocyanate (KP-90: manufactured by Dainippon Ink) 4 g Methyl ethyl ketone 100 ml Toluene 100 ml Same as Example 3. When printed with, a clear and high-density image record was obtained. Also, the light fastness was excellent.

Example 5 (Preparation of Thermal Transfer Image Receiving Material) An organic solvent solution of the dye-receptive polymer having the composition (B ′) was emulsified and dispersed in an aqueous gelatin solution having the composition (A ′) shown below by a homogenizer. A gelatin dispersion of was prepared. (A ') Gelatin aqueous solution 2.3 g Sodium dodecylbenzenesulfonate (5% aqueous solution) 20 ml Water 80 ml (B') Dye receptive polymer solution Polyester resin (Toyobo: Byron 300) 7.0 g Carboxy-modified silicone oil (Shin-Etsu) Silicone: X-22-3710) 0.7 g Methyl ethyl ketone 20 ml Toluene 10 ml Triphenyl phosphate 1.5 g To the dispersion thus prepared, a fluorosurfactant is added.
(a) A solution prepared by dissolving 0.5 g of C ₃ F ₇ SO ₂ N (C ₃ F ₇ ) CH ₂ COOK in 10 ml of a mixed solvent of water / methanol (1: 1) was added,
This was used as a coating composition for an image receiving layer. The surface of this coating composition was corona-discharged, and a synthetic paper having a thickness of 150 μm (manufactured by Oji Yuka:
YUPO-SGG-150) was coated by a wire bar coating method so as to have a wet film thickness of 75 μm and dried to obtain a thermal transfer image receiving material. Images were recorded in the same manner as in Example 1 by using the thermal transfer dye-donor materials and the thermal transfer image-receiving materials obtained in Examples 1 and 2. The obtained image had high density, was clear, and had high fastness.

[0070]

When the thermal transfer dye-donor material of the present invention is used for transfer to an image-receiving material, a clear color image having high density and excellent light fastness can be obtained.

Claims (4)

[Claims] 1. A thermal transfer dye-donating material comprising a dye-donor layer containing a heat-migrating dye on a support, the dye-donor layer containing a heat-migrating dye having an N, N-diphenylamino group. A thermal transfer dye-providing material, characterized in that 2. The thermal transfer dye-donor element according to claim 1, wherein the heat transferable dye is an azomene dye having an N, N-diphenylamino group. 3. The thermal transfer dye-donor element according to claim 1, wherein the heat transferable dye is an azo dye having an N, N-diphenylamino group. 4. The thermal transfer dye-donor element according to claim 1, wherein the heat transferable dye is a methine dye having an N, N-diphenylaminophenyl group.