JPH0699674A - Thermal-transfer image receiving material - Google Patents

Abstract

PURPOSE:To provide heat transfer image receiving material, no fusion bonding of which occurs during transferring, for recording sharp and high density image developing no bleeding during storage. CONSTITUTION:A thermal-transfer image receiving material comprises a base carrying a dyestuff acceptance layer which contains a dienophile compound and a releasing agent, and it receives dye transferred from a coloring material, which has a thermally transferable dyestuff layer having a diene group on a base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer image receiving material used for thermal transfer image recording, and more specifically, a thermal transfer containing a dienophile compound for receiving a heat transferable dye having a diene group and a releasing agent. The present invention relates to a thermal transfer image receiving material provided with a dye receiving layer on a support.

[0002]

2. Description of the Related Art In recent years, thermal transfer systems have been developed for obtaining prints from images electronically formed by color video cameras. According to one method of obtaining such prints, an electronic image is first color separated with color filters. Next, the color-separated images are exchanged for electrical signals. Subsequently, these signals are manipulated to generate yellow, magenta and cyan electrical signals. These signals are then transmitted to the thermal printer. To obtain a print, a yellow, magenta or cyan dye-donor element is placed face-to-face with a dye-image receiving element. Subsequently, the both are inserted between the thermal head and the platen roller. A line type thermal head is used to heat from the back of the dye-donor element. The thermal head has multiple heating elements and is heated up sequentially in response to the yellow, magenta and cyan signals. This process is then repeated for the other two colors. In this way a color hard copy corresponding to the original image viewed on the screen is obtained.

An alternative method of obtaining a thermal print using the aforementioned electrical signal is to use a laser instead of a thermal head. In this system, the dye-donor element contains a material that strongly absorbs the laser beam. When a dye-donor material is irradiated with a laser beam, the absorbing material converts light energy into heat energy and immediately transfers the heat to a nearby dye, heating it to a heat transfer temperature for transferring the dye to the image-receiving material. To do. The absorbent material is present in layers under 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 dye-donor material to reconstitute the original target color and heat transfer.

The dye used in the above heat transfer transfer method is preferably a dye that is easily transferred to heat in order to reduce the load on the thermal head and to increase the recording speed. However, a dye that is easily transferred to heat is stored for a long time. In medium, high temperature, and high humidity environment, there is a problem in the storage stability of the record after transfer because it moves in the image receiving layer to reduce the sharpness of the image or transfers to a contact object to be contaminated. , There was a long-awaited way to satisfy them.

In order to solve these problems, an application has been made for the purpose of stabilizing the storage of the dye in the image receiving layer by a thermal reaction. Among them, JP-A-60-26006.
No. 0, No. 60-260381 and No. 60-2603.
No. 91 is excellent. However, even with these, the storage stability of the dye in the image-receiving layer is not sufficient, the transfer density is difficult to obtain, the storage stability in the dye-donor layer is not sufficient,
The white background of the image-receiving layer had defects such that it was likely to be oxidized and colored over time, and there was a problem in material stability.

The above-mentioned defects are caused by a thermal transfer dye-donor material having a dye-donor layer containing a heat-transferable dye on a support,
Using a thermal transfer image receiving material provided with a dye receiving layer for forming an image by receiving a dye transferred from the thermal transfer dye donating material by heating, the heat transferable dye has a diene group, It has been found that the dye receiving layer can be solved by using a material containing a dienophile compound. The details are described in Japanese Patent Application No. 4-184768.

[0007]

However, the dye receiving layer containing the above dienophile compound has a defect of being fused with the dye donating layer during thermal transfer recording. The object of the present invention is to find a thermal transfer image receiving material which is free of these defects.

[0008]

It has been found that the above-mentioned defects can be solved by the thermal transfer image-receiving material of the present invention shown below. A support is provided with a dye-receiving layer which is combined with a thermal transfer dye-providing material having a dye-donating layer containing a heat-transferable dye on a support and receives a dye transferred from the dye-donating material by heating to form an image. A thermal transfer image receiving material provided on the above, wherein the heat transferable dye has a diene group, and the dye receiving layer contains a dienophile compound and a releasing agent.

The dye-donor element and the image-receiving element will be described below. Any conventionally known support can be used as the support of the thermal transfer dye-providing material. 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.

A thermal transfer dye-donor element using a heat-transferable dye basically has a dye-donor layer containing a dye and a binder which are movable by heat on a support. This thermal transfer dye-donating material is prepared by dissolving or dispersing a conventionally well-known dye that becomes sublimable or becomes mobile and a binder resin in an appropriate solvent to prepare a coating solution, which is prepared by a conventionally known thermal transfer dye-donor. On one side of the support for the material, for example about 0.2-5 μm, preferably 0.4-2 μm.
It can be obtained by coating and drying at a coating amount that results in a dry film thickness of m to form a dye-donor layer. The dye-donor layer may be formed of one layer, but may be formed of two or more layers for use in a method in which the dye-donating layer is repeatedly used many times.
In this case, the dye content and dye / binder ratio in each layer may be different. Dye application amount is 0.03 ~
1 g / m ^2, preferably from 0.1 to 0.6 g / m ^2.

The dye useful for forming such a dye-donor layer is a dye having a diene group. The dye having a diene group is preferably represented by the following general formula (I). General formula (I) A-[(B) _n1- (X) _n2 ] _n3 Here, A represents a dye main body, B represents a linking group composed of a non-metal atom or an atomic group, and X represents CR ¹ ( R ² ) = C
R ³ -CR ⁴ = represents a diene group represented by CR ⁵ (R ⁶ ). R ^{1 to} R ⁶ represent a hydrogen atom or a non-metal atomic group.
R ¹ and R ⁵ and / or R ³ and R ⁴ and / or R ¹ and R ²
And / or R ⁵ and R ⁶ and / or R ¹ and R ³ and / or R ⁴ and R ⁵ may be taken together to form a carbocycle or a heterocycle. The diene group may be bonded to A or B via any of R ^{1 to} R ⁶ , or if the diene skeleton is directly bonded to A or B instead of any of R ^{1 to} R ^6. Good. n1 represents 0, 1 or 2, n2 represents 1 or 2 and n3 represents 1 or 2.

In the general formula (I), B is a divalent amino group, an ether bond, a thioether bond or an alkylene group [preferably-(CH ₂ ) _n4 -,-(CH (R ²¹ )).
_n5 - or ^{- (CR 22 (R 23)} ) n6 - represents what alone or in combination of. Here, R ^{21 to} R ²³ have 1 carbon atom
~ 3 represents an alkyl group, n4 ~ n6 represents an integer of 1 ~ 6. Particularly preferred are methylene group, ethylene group and propylene group. ], A vinylene bond, an imino bond, a sulfonyl group, a carbonyl group, an arylene group (preferably a phenylene group), a divalent heterocyclic group, etc. are shown, and a group in which a plurality of these are combined may be further substituted. May have.

In the general formula (I), the diene group is R ¹ to
It may be bonded to A or B via either R ⁶ , or a diene skeleton may be directly bonded to A or B instead of any of R ^{1 to} R ⁶ . n2 represents 1 or 2, and n3 represents 1 or 2. When n3 is 2, it means that two [(B) _n1- (X) _n2 ] are bonded to the dye main body A. The bonding position may be any position as long as it can be bonded to the dye body A. In this case, the two diene groups X may be the same or different, and the respective linking groups B may be the same or different, or may have no linking group (n1 = 0). Good. Specific examples of the diene group represented by X in the general formula (I) include the following.

[0014]

[Chemical 1]

Specific examples of the dye having a diene group represented by the general formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0016]

[Chemical 2]

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

The method for synthesizing the dye having a diene group represented by the general formula (I) used in the present invention includes, for example,
The method described in Japanese Patent Application No. 4-184768 can be referred to.

It is preferable to introduce the fading-preventing group described in JP-A-3-205189 into the dye of the general formula (I) since the light fastness is improved.

As the binder resin used together with the above-mentioned dye, any of the binder resins known in the prior art for such purpose can be used, which usually has high heat resistance and migration of the dye when heated. The one that does not interfere with 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 Partially saponified polyvinyl alcohol) such as butyral, petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g. polyethylene, polypropylene) and the like.

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

The dye-donor element may have an intermediate layer provided between the support and the dye-donor layer. Preferred specific examples include (acrylonitrile / vinylidene chloride / acrylic acid) copolymer, (butyl acrylate / methacrylic acid-2).
-Aminoethyl / 2-hydroxyethyl methacrylate) copolymers, linear / saturated polyesters, or chlorinated high density poly (ethylene-trichloroethylene) resins. The coating amount of the intermediate layer is not particularly limited, but it is usually used in an amount of 0.1 to 2.0 g / m ² .

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, a reaction product of polyvinyl butyral resin and isocyanate,
It is preferable to provide a heat-resistant slip layer mainly composed of an alkali metal salt or alkaline earth metal salt of phosphoric acid ester and a filler. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80 to 110.
C. and from the viewpoint of many reaction sites with isocyanate, the weight% of vinyl butyral portion is 15 to 40.
% Is good. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafac RD720 manufactured by Toho Kagaku Co., Ltd. is used, which is 1 to 50% by weight, preferably 10 to 40% by weight based on the polyvinyl butyral resin.
Good to use. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

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

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

In the present invention, the support used for the thermal transfer image-receiving material can withstand the transfer temperature and satisfies the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, dent after transfer and the like. Anything that can be used can be used. For example, synthetic paper (synthetic paper such as polyolefin and polystyrene), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper support such as paper, paperboard, cellulose fiber paper, polyolefin coated paper (paper coated with polyethylene on both sides), 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.

The thermal transfer image receiving material is provided with a dye receiving layer. This receiving layer contains a dienophile compound and a release agent,
Preferably, a substance capable of receiving the heat-transferable dye that migrates from the heat-transfer dye-providing material during printing and capable of receiving the heat-transferable dye having a function of dyeing the heat-transferable dye alone, or It is preferably a coating having a thickness of about 0.5 to 50 μm, which is contained together with other binder substances. The following resins are examples of polymers that are typical examples of substances that can receive heat transferable dyes.

(A) 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 or polymethacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate : Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 can be mentioned. As commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-14 are used.
0, Byron GK-130, ATR-200 made by Kao
9, ATR-2010, etc. can be used.

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

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

The dienophile compound used in the dye receiving layer of the present invention is represented by the following general formula (II) or (III). Formula ^{(II) CR 7 (R 8} ) = CR 9 (R 10) where R ⁷ to R ¹⁰ represents a hydrogen atom or a nonmetallic atom group. However, not all of R ^{7 to} R ¹⁰ are hydrogen atoms. R ⁷ and R ⁹ and / or R ⁷ and R ⁸ and / or R ⁹
And R ¹⁰ and / or R ⁸ and R ⁹ may together form a carbocycle or a heterocycle. General formula (III) CR ¹¹ ≡CR ¹² Here, R ¹¹ and R ¹² represent a hydrogen atom or a non-metal atomic group. However, neither R ¹¹ nor R ¹² is a hydrogen atom. R ¹¹ and R ¹² may be joined together to form a carbocycle or a heterocycle.

Specific examples of the dienophile compound represented by the general formula (II) used in the present invention are shown below.

[0037]

[Chemical 8]

[0038]

[Chemical 9]

[0039]

[Chemical 10]

[0040]

[Chemical 11]

Specific examples of the dienophile compound represented by the general formula (III) used in the present invention are shown below.

[0042]

[Chemical 12]

General formula (II) or (I
The amount of the dienophile compound represented by II) is generally 0.1 g / m ^{2 to} 10 g / m ² , preferably 0.5.
^{g / m 2 ~10g / m 2} , particularly preferably 0.5 g / m
^{2 to 5} g / m ² .

In the present invention, a releasing agent is contained in the dye receiving layer in order to improve the releasing property between the thermal transfer dye-donating material and the thermal transfer image-receiving material. As the release agent, solid or wax-like substances such as polyethylene wax, amide wax, fine powder of silicone resin, fine powder of fluorine resin; surfactants such as fluorine and phosphate ester; paraffin and silicone Any conventionally known release agent such as system oil and fluorine oil can be used, but silicone oil is particularly preferable.

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

Examples of the silicone compound used in the present invention include unmodified or modified silicone oil, solid silicone polymers soluble in organic solvents such as toluene, and silicone fine particles insoluble in the solvent used. Examples of the modified silicone oil (including solid silicone oil) include those having the following skeleton structure and examples of compounds thereof. (1) Epoxy-modified silicone oil

[0047]

[Chemical 13]

Here, R _a is a bonding group [eg, —CH _{2
-, - C 3 H 6 -O} -CH 2 - represents the like (hereinafter the same)]. (2) Alkyl-modified silicone oil

[0049]

[Chemical 14]

Here, R represents an alkyl group or an alkyl group / aralkyl group (copolymer of a monomer which is an alkyl group and a monomer which is an aralkyl group). (3) Polyether-modified silicone oil

[0051]

[Chemical 15]

Here, R _a represents the above-mentioned linking group, and POA
Is a polyoxyalkylene group [eg oxyethylene /
Oxypropylene (the same applies hereinafter)]. (4) Alcohol-modified silicone oil

[0053]

[Chemical 16]

Here, R _a represents the above-mentioned bonding group. (5) Amino-modified silicone oil

[0055]

[Chemical 17]

Here, R _a represents the above-mentioned bonding group, and R represents C
Represents H ₃ or OCH ₃ . (6) Carboxyl-modified silicone oil

[0057]

[Chemical 18]

Here, R _a represents the above-mentioned bonding group. (7) Fluorine-modified silicone oil

[0059]

[Chemical 19]

(8) Higher fatty acid-modified silicone oil

[0061]

[Chemical 20]

Here, R _a represents the above-mentioned bonding group, and R represents an aliphatic hydrocarbon group. (9) Epoxy / polyether modified silicone oil

[0063]

[Chemical 21]

Here, R _a represents the above-mentioned linking group, and POA
Represents the polyoxyalkylene group. (10) Alkyl / polyether modified silicone oil

[0065]

[Chemical formula 22]

Here, R _a represents the above-mentioned linking group, and POA
Represents the polyoxyalkylene group, and R represents an alkyl group.

The silicone-based fine particles used in the present invention are three-dimensionally cross-linked silicone rubber or silicone resin indefinite or true spherical particles.
Trefill (registered trademark) R-90 manufactured by Silicone Co., Ltd.
2, R-925, R-930, E-500, E-50
1, E-600, E-601, E-602, E-60
3, Toshiba Silicone Tospearl (registered trademark) 12
0, 130, 145, 240 and the like. The average particle size of the silicone-based fine particles used in the present invention is 0.01 to 20.
The one having a thickness of 0.1 μm, preferably 0.1 to 10 μm is used.

The silicone compounds used in the present invention may be used in combination of two or more kinds. In particular, it is preferable to use unmodified or modified silicone oil in combination with silicone-based solid fine particles. The amount of the unmodified or modified silicone oil used in the present invention and the silicone compound soluble in the solvent is 0.001 to 20%, preferably 0.01 to 20% of the total weight of the binder in the layer to which the silicone compound is added. 10%, particularly preferably 0.1 to 1%. The coating amount of the silicone-based fine particles used in the present invention is usually 0.001 to 3 g / m ² , preferably 0.00
5 to 1 g / m ² , particularly preferably 0.01 to 0.5 g / m ² .
m ² .

The unmodified or modified silicone oil used in the present invention is added to the coating solution as follows. Dilute the silicone oil as it is with an organic solvent,
Add to the binder and solvent of the dienophile compound. When the organic solvent solution of the dienophile compound and the binder is emulsified and dispersed in the hydrophilic polymer, the silicone oil is diluted with the organic solvent as it is and emulsified and dispersed together. The silicone polymer (solid) used in the present invention is dissolved in an organic solvent such as toluene and added to the coating solution in the same manner as the silicone oil. The silicone-based fine particles used in the present invention are dispersed in an organic solvent solution of a dienophile compound and a binder with a homogenizer or the like and added. Further, these releasing agents can also be used in the dye-providing material.

In the present invention, the receiving layer of the thermal transfer image receiving material may have a structure in which a substance capable of receiving the heat transferable dye is dispersed and carried in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but water-soluble polymers having a group capable of undergoing a crosslinking reaction by a hardening agent are preferable, and gelatins are particularly preferable. The receiving layer may be composed of two or more layers. In that case, it is preferable to use the dienophile compound of the present invention in the layer closer to the support and to use the release agent of the present invention in the layer closer to the surface. Further, in this 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 outermost layer is formed. Use a synthetic resin with a higher glass transition point, or reduce the amount of high-boiling organic solvent or thermal solvent to the required minimum amount, or sticky the surface, adhere to other substances, transfer to other substances It is desirable to have a structure that prevents troubles such as retransfer of the toner, blocking with the thermal transfer dye-donor material, and the like. The total thickness of the receiving layer is preferably 0.5 to 50 μm, particularly preferably 3 to 30 μm. In the case of a two-layer structure, the outermost layer has a thickness of 0.1 to 2 μm, and especially has a thickness of 0.1.
It is preferably in the range of 2 to 1 μm.

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

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

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

The layers constituting the thermal transfer dye-donating material and the thermal transfer image-receiving material used in the present invention may be cured with a hardener. In the case of curing an organic solvent-based polymer, JP-A Nos. 61-199997 and 58-21539.
The hardeners described in No. 8 and the like can be used. 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 hardener (dimethylolurea, etc.), or polymer hardener (Japanese Patent Laid-Open Publication No. Sho 6-62).
2-234157 etc. are mentioned.

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

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

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

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

When a substance capable of receiving a heat transferable dye, a dienophile compound, a release agent, an anti-fading agent, an ultraviolet absorber, an optical brightening agent, and other hydrophobic compounds are dispersed in a water-soluble binder. It is preferable to use a surfactant as a dispersion aid. For this purpose, in addition to the above-mentioned surfactant, 37 to 3 of JP-A-59-157636.
The surfactants described on page 8 are particularly preferably used.

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

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

In a preferred embodiment of the present invention, the dye-donor element comprises a polyethylene terephthalate support coated in successive repeating regions of a cyan dye, a magenta dye and a yellow dye, the steps being carried out sequentially for each color to give a triple dye. Form a color transfer image. Of course, when this process is performed in a single color, a monochrome transfer image is obtained.
For thermal transfer of a dye from a dye-donor material to an image-receiving material, energization corresponding to an electric signal to a thermal head, or an ion gas laser such as argon or krypton, a metal vapor laser such as copper, gold and cadmium, ruby or YAG
Heating with several lasers can be used, such as solid state lasers such as, or semiconductor lasers such as gallium-arsenide, which emits in the infrared region of 750 to 870 nm.

[0083]

The following are detailed examples of the present invention. However,
The thermal transfer image receiving material of the present invention is not limited to the examples shown below. Example 1 (Preparation of Thermal Transfer Dye Donor 1) A 6 μm thick polyethylene terephthalate film having a heat resistant slipping layer provided on one side was used as a support, and the support was provided on the side opposite to the side provided with the heat resistant slipping layer. A dye-donor layer coating composition having the following composition was gravure-coated to form a thermal transfer dye-donor material 1 having a thickness after drying of 0.7 μm.

Dye-donor layer coating composition (1) Dye I-1 4 g Polyvinyl butyral resin (5000A: manufactured by Electrochemical) 4 g Silicone oil (KF-96: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 mg Polyisocyanate (takenate) D110N: Takeda Yakuhin) 0.2 ml Methyl ethyl ketone 60 ml Toluene 20 ml

(Preparation of thermal transfer image receiving material 1) 30 μ on both sides
Using a 140 μm resin-coated paper laminated with polyethylene to a thickness of m as a support, a dye receiving layer coating composition having the following composition was applied so that the thickness after drying would be 6 μm,
Thermal transfer image receiving material 1 was obtained.

Dye Receptor Layer Coating Composition (1) Polyester resin (Vylon 200: manufactured by Toyobo) 15 g Polyether-modified silicone oil (SH-3771: manufactured by Toray Dow Corning) 0.5 g Polyisocyanate (KP-90: large) Nippon Ink Chemical Co., Ltd.) 2 g Compound II-1 3 g Methyl ethyl ketone 80 ml Toluene 20 ml

Example 2 The compound II-1 of Example 1 was replaced with the following dienophile compounds to obtain thermal transfer image receiving materials 2 to 6.

Example 3 The silicone oil of Example 1 was replaced with the following release agent,
Thermal transfer image receiving materials 7 to 10 were obtained.

Example 4 Dye I-1 of Example 1 was replaced with the following dyes to obtain thermal transfer dye donating materials 2 to 6.

Comparative Example 1 Comparative image receiving materials a to f were obtained with the composition except that the silicone oil (SH-3771) was removed from the image receiving materials 1 to 6 of Examples 1 and 2.

Comparative Example 2 Comparative image receiving materials g to k were obtained by removing the dienophile compound from the image receiving materials 1 and 7 to 10 of Examples 1 and 3.

The thermal transfer dye-donor material and the thermal transfer image-receiving material obtained as described above are superposed so that the dye-donor layer and the image-receiving layer are in contact with each other, and a thermal head is used from the support side of the thermal transfer dye-donating material to conduct thermal transfer. Heat was applied under the conditions of a head output of 0.25 W / dot, a pulse width of 0.15 to 15 msec, and a dot density of 6 dots / mm, and dye was dyed imagewise on the image-receiving layer of the thermal transfer image-receiving material.

The portion (Dmax) where the density was saturated in the obtained recorded thermal transfer image-receiving material was measured by a reflection density measuring device (X Rit
e. Status A filter) was used to measure the reflection density of the color image. Further, the obtained image was stored in an oven at 80 ° C. for 1 week, and the bleeding of the color image after storage was visually determined. The evaluation criteria were as follows: the image was almost unchanged from that before storage, the image was slightly blurred, and the image was very blurred. In addition, the degree of fusion of the dye-donor layer to the dye-receiving layer during transfer is evaluated as ○, little adhered, △, slightly adhered, depending on the area of the dye-donor layer adhered to the receptor layer. The terrible thing was expressed by x. The results of the above tests are shown in Table-A and Table-B.

[0094]

[Table 1]

[0095]

[Table 2]

As shown in Table-A and Table-B, when the thermal transfer image-receiving material of the present invention was used, the transfer density was high,
There is no bleeding of images during storage or fusion during transfer. However, in the case of the comparative example, the transfer density was low, and bleeding of images during storage and fusion during transfer occurred.

[0097]

INDUSTRIAL APPLICABILITY According to the present invention, thermal transfer recording was carried out using a dye-donor material containing a dye having a diene group and an image-receiving material containing a dienophile compound and a release agent. However, a clear image recording with high transfer density was obtained. This image was found to not bleed during storage.

Claims (1)

[Claims] 1. A dye which is combined with a thermal transfer dye-donating material having a dye-donating layer containing a heat-transferable dye on a support and which receives a dye transferred from the dye-donating material by heating to form an image. A thermal transfer image receiving material having a receiving layer provided on a support, wherein the heat transferable dye has a diene group, and the dye receiving layer contains a dienophile compound and a releasing agent. .