JPH0699675A - Thermal-transfer coloring material - Google Patents

Abstract

PURPOSE:To make it possible to obtain thermal-transfer recording, the transferring density of which is high, in which no bleeding occurs in recorded image during storage, no fusion bonding of which occurs during transferring and no offset of dyestuff develops during the storage of ribbon. CONSTITUTION:A thermal-transfer coloring material having a thermally transferable dyestuff layer on a base is combined with a thermal-transfer image accepting material, which is prepared by providing dyestuff acceptance layer for accepting thermally transferable dyestuff. When the dyestuff has diene, the acceptance layer contains dienophile compound. Or when the dyestuff has dienophile, the acceptance layer contains diene compound. At the same time, the coloring layer contains matting agent.

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 material used for recording a thermal transfer image by heating corresponding to image information.

[0002]

2. Description of the Related Art In recent years, thermal transfer systems have been developed for obtaining prints from images electronically formed by color video cameras. According to 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.

[0004]

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, but it is easily transferred to heat. The dye may be stored in the recording layer after transfer because it may move in the image-receiving layer to reduce the sharpness of the image during storage for a long period of time or in an environment of high temperature and high humidity, or it may transfer to a contact substance and contaminate it. There was a problem with stability and 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, and among them, JP-A-60-260060.
No. 60, No. 60-260381 and No. 60-26039.
No. 1 is excellent. However, even in these cases, 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, and the white background of the image receiving layer is easily oxidized and colored over time. However, there were defects such as problems with material stability.

The above-mentioned defect is a thermal transfer dye-donating material in which a dye-donor layer containing a heat-migrating dye is provided on a support, and the dye transferred from the dye-donating layer on the support by heating. A thermal transfer dye-donor material used in combination with a thermal transfer image-receiving material provided with a dye-receiving layer for receiving to obtain an image record by heating corresponding to image information,
A combination containing a dye having a diene in the dye-providing layer and containing a dienophile compound in the receiving layer, or a combination containing a dye having a dienophile in the dye-providing layer and containing a diene compound in the receiving layer. It has been found that this can be solved by using a thermal transfer dye-donor element to obtain an image record. This content is Japanese Patent Application No. 4-1847
68. However, the dye-donor layer containing a dye having a diene or a dye having a dienophile adheres to the receptor layer during thermal transfer image recording by heating, and the dye-donor layer is peeled off and attached to the image-receiving material.
The problem of so-called heat fusion tends to occur. The dye-donor material is usually processed into a ribbon shape, wound on a bobbin and supplied, and set in a recording device for use. When wound on a bobbin and stored, there is a problem in that the dye-donor layer of the dye-donor element and the opposite side of the support come into contact with each other, causing blocking, or migration of the dye from the dye-donor layer to the opposite side of the support. Occurs.

[0007]

The various defects and problems described above are caused by a thermal transfer image-receiving material provided with a dye-receiving layer for receiving a dye transferred from a dye-donor layer by heating on the support of the present invention. A combined thermal transfer dye-providing material having a dye-donor layer containing a heat-transferable dye on a support, which contains a dye having a diene in the dye-donating layer,
A combination containing a dienophile compound in the receptor layer,
Alternatively, it is a combination of a dye-donating layer containing a dye having a dienophile and a receiving layer containing a diene compound, and a matting agent is contained in the dye-donating layer. I found that I could do it.

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 material using a heat-transferable dye basically has a dye-donor layer containing a dye and a binder which are movable by heat on a support. This thermal transfer dye-providing material is prepared by dissolving or dispersing a dye that becomes mobile by heat and a binder resin in an appropriate solvent to prepare a coating solution, which is used as a support for a conventionally known thermal transfer dye-providing material. On one side, for example, about 0.2-
It can be obtained by coating and drying at a coating amount of 5 μm, preferably 0.4 to 2 μm, to form a dye-donor layer. The dye-donor layer may be formed as a single layer, but it may be used in a case where it is used in a method in which it is repeatedly used many times.
You may form with a structure more than a layer. In this case, the dye content and dye / binder ratio in each layer may be different. The dye coating amount is 0.03 to 1 g / m ² , preferably 0.1 to 0.6 g / m ² .

The dye having a diene used in the present invention is represented by the 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 together form a carbon atom. A ring or a heterocycle may be formed. The diene group may be bonded to A or B via any of R ^{1 to} R ⁶ , or R ¹
Instead of any of R ⁶ to R ⁶ , it may be directly bonded to the diene skeleton. n1 represents 0, 1 or 2, n2 represents 1 or 2, and n3 represents 1 or 2. If n3 is 2, then 2
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,
It may also have no linking group (n1 = 0).

Specific examples of the linking group represented by B in the general formula (I) include a divalent amino group, an ether bond, a thioether bond and an alkylene group (preferably-(C
H _{2) n4} -, - [CH (R ^31)] _n5 - or - [CR
³² (R ³³ )] _n6 − represents a single or a combination of plural. Here, R < ³¹ > -R < ³³ > represents a C1-C3 alkyl group, n4-n6 represents the 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, and the like, which may be a group in which a plurality of them are combined, and these are further substituents. May have. Specific examples of the diene group represented by X in the general formula (I) include the following.

[0012]

[Chemical 1]

In the above specific examples, the free bond represents a position at which the free bond is bonded to the linking group B or the dye main body A. Specific examples of the dye represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 2]

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

The dye represented by the general formula (I) is, for example,
It can be synthesized using the method described in Japanese Patent Application No. 4-184768. The dye having a dienophile used in the present invention is represented by the general formula (II). General formula (II) A-[(B) _n1- (Y) _n2 ] _n3 where A, B, n1, n2 and n3 are the same as those in the general formula (I).
I agree with that. Y is CR ⁷ (R ⁸ ) = CR ⁹ (R
¹⁰ ) or a dienophile group represented by CR ¹¹ ≡CR ¹² . R ^{7 to} R ¹² represent a hydrogen atom or a non-metal atomic group.
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 ¹⁰ and / or R ¹¹ and R ¹² together form a carbocycle or heterocycle. May be. The dienophile group may be bonded to A or B via any of R ^{7 to} R ¹² , or may be directly bonded to the dienophile skeleton in place of any of R ^{7 to} R ¹² . n
When 3 is 2, it means that two [(B) _n1- (Y) _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 dienophile groups Y may be the same or different, the respective linking groups B may be the same or different, and may have no linking group (n1 = 0). Good. Specific examples of B in the general formula (II) include those described in the general formula (I). Specific examples of the dienophile group represented by Y in the general formula (II) are shown below.

[0021]

[Chemical 8]

In the above specific examples, the free bond represents a position at which the free bond is bonded to the linking group B or the dye main body A. next,
Specific examples of the dye represented by formula (II) used in the present invention are shown below, but the present invention is not limited thereto.

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

The dye represented by the general formula (II) is, for example,
It can be synthesized using the method described in Japanese Patent Application No. 4-184768. It is preferable to introduce the anti-fading group described in Japanese Patent Application No. 1-271078 into the dyes represented by the general formulas (I) and (II) because 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 about 20 to 600 parts by weight, for example, 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.

There are various matting agents used in the present invention, and either an inorganic material or an organic material may be used. Further, it is desirable that it is less deformed by heat. Examples of inorganic matting agents include oxides (eg, silicon dioxide,
Titanium oxide, zinc oxide, magnesium oxide, aluminum oxide, etc., alkaline earth metal salts (for example, sulfates and carbonates, specifically barium sulfate, calcium carbonate, magnesium sulfate, etc.), glass, etc. . Further, it is desirable that the organic matting agent does not soften by heat at 60 ° C. or lower. Examples thereof include cellulose ester (for example, cellulose acetate propionate and the like), cellulose ether (for example, ethyl cellulose and the like), synthetic resin and the like. Examples of synthetic resins include, for example, alkylmethacrylate, alkoxyalkylmethacrylate, glycidylmethacrylate, acrylamide, methacrylamide, styrene alone or in combination, or with acrylic acid, methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl-acrylate or -methacrylate, sulfone alkyl-acrylate or -methacrylate, and styrenesulfonic acid as a monomer component can be used. Among them, polymethylmethacrylate is preferable. Further, a vinyl synthetic resin such as polyethylene, a fluorine synthetic resin such as Teflon, a benzoguanamine resin, a polycarbonate resin, an AS resin or the like can also be used.

The amount of the matting agent used is 0.5 to 10 vol% of the amount of the binder resin in the dye-providing layer, preferably 1 to 5 v.
ol% is added. The particle shape and particle diameter of the matting agent are not particularly limited, but usually 0.1 to 10 μm, especially 1
Particles having an average particle size of ˜5 μm are preferred. The inorganic material and the organic material may be used alone or in combination. In addition, if necessary, these matting agents
It can also be used as an image receiving material. 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 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 phosphoric acid ester, Gafac RD720 manufactured by Toho Kagaku Co., Ltd. is used, and it may be used in an amount of 1 to 50% by weight, preferably 10 to 40% by weight, based on the polyvinyl butyral resin. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

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

The dye-donor 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 effect, but preferred specific examples include (acrylonitrile / vinylidene chloride / acrylic acid) copolymers, (butyl acrylate / -2-aminoethyl methacrylate / 2-hydroxyethyl methacrylate) copolymers, linear / saturated polyesters or chlorinated high density poly (ethylene-trichloroethylene) resins. 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 . The dye-donor layer may be formed by selecting dyes so that a desired hue can be transferred when printed, and if necessary, two or more dye-donor layers having different hues may be formed side by side on one thermal transfer dye-donor material. Good. For example, when repeatedly printing each color according to the color separation signal to form an image such as a color photograph, it is desirable that the hue at the time of printing is each color of cyan, magenta, and yellow.
Three dye-donor layers containing dyes that give such hues are lined up. 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 substance capable of receiving the heat transferable dye which has a function of receiving the heat transferable dye transferred from the heat transfer dye-providing material during printing and dyeing the heat transferable dye. Or with other binder substances, it is preferable that the film has a thickness of about 0.5 to 50 μm. The following resins are examples of polymers that are typical examples of substances that can receive heat transferable dyes.

(A) having an ester bond: a dicarboxylic acid component such as terephthalic acid, isophthalic acid, 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 receiving layer of the present invention is represented by the general formula (III) or (IV). General formula
(III) CR ¹³ (R ¹⁴ ) = CR ¹⁵ (R ¹⁶ ) Here, R ^{13 to} R ¹⁶ represent a hydrogen atom or a non-metal atomic group. However, not all of R ^{13 to} R ¹⁶ are hydrogen atoms. R ¹³ and R ¹⁵ and / or R ¹³ and R ¹⁴ and / or R ¹⁵ and R ¹⁶ and / or R ¹⁴ and R ¹⁵ may be taken together to form a carbocycle or a heterocycle. Formula (IV) CR ¹⁷ ≡CR ¹⁸ where R ^17, R ¹⁸ represents a hydrogen atom or a nonmetallic atom group. However, neither R ¹⁷ nor R ¹⁸ is a hydrogen atom. R ¹⁷ and R ¹⁸ may be joined together to form a carbocycle or a heterocycle. The diene compound used in the receiving layer of the present invention is represented by the general formula (V). Formula ^{(V) CR 19 (R 20} ) = CR 21 -CR 22 = CR 23 (R 24) wherein R ¹⁹ to R ²⁴ represents a hydrogen atom or a nonmetallic atom group. However, not all of R ^{19 to} R ²⁴ are hydrogen atoms. R ¹⁹ and R ²³ and / or R ²¹ and R ²² and / or R
¹⁹ and R ²⁰ and / or R ²³ and R ²⁴ and / or R ²⁰ and R
²⁴ may together form a carbocycle or a heterocycle. Specific examples of the dienophile compound represented by the general formula (III) used in the present invention are shown below.

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

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

[0046]

[Chemical 18]

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

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

The content of the dienophile compound or the diene compound contained in the image receiving layer is preferably 0.1.
^{g / m 2 ~10g / m 2} , more preferably 0.5 g / m
^{2 to 5} g / m ² . In the present invention, the receiving layer of the thermal transfer image receiving material may have a structure in which a substance capable of receiving the heat transferable dye is dispersed and carried in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but water-soluble polymers having a group capable of undergoing a crosslinking reaction by a hardening agent are preferable, and gelatins are particularly preferable. The receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a dye having a high boiling point organic solvent or thermal solvent is used to enhance the dyeing property, and the outermost layer has a glass transition point. Use a synthetic resin with a higher point, reduce the amount of high-boiling organic solvent or thermal solvent to the required minimum amount or do not use it, and make the surface sticky, adhere to other substances, re-transfer to other substances after transfer. It is desirable to have a structure that prevents failures such as transfer and blocking with a thermal transfer dye-donating material. The total thickness of the receiving layer is 0.5 to 50μ.
m, 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.

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, etc. are used for the receiving layer, cushion layer, porous layer, diffusion preventing layer, adhesive layer and the like constituting 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.

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

As the silicone oil, in addition to non-modified 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, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with an isocyanate) is also emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, manufactured by Shin-Etsu Silicone Co., Ltd .: trade name X-22-3710) or an epoxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd.).
Made by: Product name KF-100T) is effective.

The layers constituting the thermal transfer dye-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 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, prevention of electrostatic charge, acceleration of development and the like. Nonionic surfactants, anionic surfactants, amphoteric surfactants and cationic surfactants can be used. Specific examples of these are disclosed in JP-A-62-1734.
63, 62-183457 and the like.

Further, a substance capable of accepting a heat transferable dye, a dienophile compound, a diene 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. In doing so, it is preferable to use a surfactant as a dispersion aid. For this purpose, in addition to the above-mentioned surfactants, JP-A-59-15763
The surfactants described on pages 37 to 38 of No. 6 are particularly preferably used. In the present invention, a dye-donor element is superposed on an image-receiving element, and heat energy corresponding to image information is applied from either side, preferably the back side of the thermal transfer dye-donor element, by a heating means such as a thermal head. 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 having excellent sharpness and resolution gradation can be obtained. Further, an anti-fading agent can be similarly transferred. The heating means is not limited to the thermal head, and known ones such as laser light (for example, semiconductor laser), infrared flash, and hot pen can be used. In laser-based systems, the thermal transfer dye-donor material preferably contains a material that strongly absorbs laser light. When a thermal transfer dye-donor material is irradiated with laser light, the absorbing material converts light energy into heat energy, transfers the heat to the dye in the immediate vicinity, and the dye is transferred to the heat transfer image-receiving material at a temperature (heat transfer temperature). ) Is heated up to. The absorbent material is layered below the dye and / or is mixed with the dye. The laser beam is modulated with an electrical signal that represents the shape and color of the original image, heating only the areas of the dye that need to be present on the thermal transfer dye-donor material to reconstitute the original target color and heat transfer.

In the present invention, the thermal transfer dye-donating 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 a cyan dye, a magenta dye and a 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.

[0064]

EXAMPLES The following are detailed examples of the present invention. However, the thermal transfer dye-providing material of the present invention is not limited to the examples shown below. Example 1 (Preparation of Thermal Transfer Dye-donor Material) A polyethylene terephthalate film having a thickness of 5 μm having a heat-resistant slip layer provided on one side was used as a support, and the side of the support opposite to the side provided with the heat-resistant slip layer had The composition for coating a dye-donating layer having the composition was applied by gravure coating so that the thickness after drying was 0.8 μm, to obtain a thermal transfer dye-donating material.

(Dye Donor Layer Coating Composition) Dye I-1 10 g Polyvinyl butyral (Denka Butyral 5000A, manufactured by Electrochemical) 10 g Silicone oil (KF96, manufactured by Shin-Etsu Chemical) 0.2 g Polyisocyanate (Takenate D110N, Takeda Pharmaceutical Co., Ltd. 0.5 g Matting agent (Eposter MS, Nippon Shokubai Chemical Co., Ltd.) 0.4 g Methyl ethyl ketone 150 ml Toluene 50 ml

(Preparation of Thermal Transfer Image Receiving Material) A laminated synthetic paper having a thickness of 150 μm was used as a support, and a coating composition for a receptor layer having the following composition was applied on the surface by wire bar coating so that the thickness when dried was 8 μm. A thermal transfer image receiving material was formed by coating. After temporary drying with a dryer,
It was carried out in an oven at a temperature of 50 ° C. for 15 hours.

(Receptor layer coating composition) Polyester resin (Vylon-200 Toyobo) 22 g Polyisocyanate (KP-90 manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone Co.) 0. 3 g compound III-14 g methyl ethyl ketone 85 cc toluene 85 cc

Example 2 Thermal transfer dye-donating materials ~ were prepared in the same manner as in Example 1 except that the dye I-1 and the matting agent of the thermal transfer dye-donating material of Example 1 were replaced with those described below. Thermal transfer dye donating material Dye matting agent I-4 Lubron L-2 (Teflon resin manufactured by Daikin Industries) I-21 Flow beads CL1080 (Polyethylene resin manufactured by Sumitomo Seika) II-1 Colloidal silica II-18 Eposter S (Alkyd resin Nippon Shokubai) (Chemical Industry) Thermal transfer image receiving materials ~ were prepared in the same manner as in Example 1 except that the compound III-1 of the thermal transfer image receiving material was replaced with the following.

Example 3 Thermal transfer dye-donating materials ~ were prepared in the same manner as in Example 1 except that the binder resin of the thermal transfer dye-donating material of Example 1 was changed to the following. (Preparation of Thermal Transfer Image Receiving Material) Resin-coated paper having a thickness of 150 μm and polyethylene laminated to a thickness of 25 μm on each side is prepared, and a coating composition for a receiving layer having the following composition is dried by wire bar coating to a thickness of 10
It was coated so as to have a thickness of μm and dried to prepare a thermal transfer image receiving material.

Coating composition for receiving layer Polyester resin (Byron 280 Toyobo) 25 g Silicone oil (SH-3771 Toray Dow Corning) 0.3 g Polyisocyanate (KP-90 manufactured by Dainippon Ink and Chemicals) 4 g Compound III- 10 5 g Methyl ethyl ketone 100 cc Toluene 100 cc Example 4 (Preparation of thermal transfer image-receiving material) An organic solvent solution of a dye-accepting polymer of composition (B) was emulsified and dispersed in a gelatin aqueous solution of composition (A) below. A gelatin dispersion of the dye-receptive substance was prepared.

(A) Gelatin aqueous solution Gelatin 2.3 g Sodium dodecylbenzene sulfonate (5% aqueous solution) 20 cc Water 80 cc (B) Dye receptive polymer solution Polyester resin (Vylon 300 manufactured by Toyobo) 7.0 g Carboxy modified silicone oil (X-22-3710 manufactured by Shin-Etsu Silicone) 0.4 g Compound V-12 2 g Methyl ethyl ketone 20 cc Toluene 10 cc Triphenyl phosphate 1.5 g

In the dispersion thus prepared, 0.5 g of the following fluorine-based surfactant (a) C ₃ F ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK was added to water / methanol (1: 1). ) Mixed solvent 10
The solution dissolved in cc was added to obtain a receiving layer coating composition. This coating composition was applied onto the resin-coated paper of Example 3 by a wire bar coating method to obtain a wet film thickness of 75 μm.
To obtain a thermal transfer image-receiving material. Comparative Example 1 Comparative transfer dye-providing materials (a), (b) and (c) were prepared by removing the matting agent from the thermal transfer dye-providing material.
Further, the dye of the thermal transfer dye-providing material was replaced with the following dye A to prepare comparative dye-providing materials (d) and (e).

[0073]

[Chemical formula 22]

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-donor material to conduct thermal transfer. Head output 0.25W / dot, pulse width 0.15-15mse
Heat was applied under the conditions of c and dot density of 6 dots / mm to dye the image-wise dye on the image-receiving layer of the thermal transfer image-receiving material. The portion (Dmax) where the density was saturated of the recorded thermal transfer image-receiving material obtained at this time was measured by a reflection density measuring device,
(X Rite / Status A filter, X-Rit
e, Inc. Manufactured) was used to measure the reflection density of the color image.
The obtained image was stored in an oven at 80 ° C for 1 week,
Image bleeding after storage was visually determined. The criteria for judgment were as follows: ○: images with little change from before storage, △: slightly blurred, ×: very blurred. The degree of fusion of the dye-donor layer to the image-receiving material during transfer depends on the size of the area of the dye-donor layer attached to the image-receiving material. Bad adhesion was marked with x. Also, processed into a ribbon,
The dye-donor element wound on a bobbin was stored in an oven at 60 ° C. for one week, and the degree of the dye attached to the opposite side of the dye-donor layer after storage was similarly represented by ◯, Δ, and x. The results are shown in Table 1 below.

[0075]

[Table 1]

As shown in Table 1, when the thermal transfer dye-donating material of the present invention was used, bleeding of the recorded image during storage, thermal fusion during transfer, and back-transfer of the dye during ribbon storage were almost eliminated. A recorded image having no high transfer density was obtained. However, in the case of the thermal transfer dye-providing material of Comparative Example, although the image density was good, bleeding of the image during storage or heat fusion during transfer and back-transfer of the dye during ribbon storage appeared.

[0077]

INDUSTRIAL APPLICABILITY According to the present invention, a donor element containing a dye having a diene and an image receiving material containing a dienophile compound, or a combination of a donor element containing a dye having a dienophile and an image receiving material containing a diene compound is used. When thermal transfer recording is performed, by containing a matting agent in the dye-donor layer, it is possible to obtain a high-concentration image without bleeding of the image during storage, and further, the image is not fused during transfer and the ink ribbon is preserved. It was possible to obtain a thermal transfer donor material without dye settling in it.

Claims (1)

[Claims] 1. A heat transferable dye is contained on a support, which is combined with a thermal transfer image receiving material provided with a dye receiving layer for receiving a dye transferred from a dye donating layer by heating on the support. Which is a thermal transfer dye-donor material provided with a dye-donor layer, which contains a dye having a diene in the dye-donor layer,
A combination containing a dienophile compound in the receptor layer,
Alternatively, a thermal transfer dye-donating material comprising a combination of a dye-providing layer containing a dye having a dienophile and a receiving layer containing a diene compound, and a dye-donating layer containing a matting agent.