JPH0345388A - Preparation of thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To enhance film strength without lowering dyeing density by applying a liquid composition containing a dye acceptive polymer, a curing agent and a liquid medium to a support and applying drying and heat treatment thereto at respective specific temps. CONSTITUTION:A coating solution is prepared by dissolving or dispersing a mixture of a dye acceptive polymer, a curing agent and other necessary additives in proper liquid media and applied to a support, for example, by a roll coating method or a spray coating method to be successively subjected to drying and heat treatment. Drying is performed at temp. 85% of the mean b.p. of the liquid media or less, pref., at temp. of room temp. +5 deg.C to 80% of the mean b.p. The mean b.p. is shown as the sum calculated by multiplying the volumetric ratios of the used liquid media by the boiling points of the individual liquid media. The image receiving layer becoming a dry film is subsequently heat-treated at temp. of 100 - 150% of the mean b.p. of the liquid media, pref., 100 - 130%.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a thermal transfer image-receiving material for thermal transfer recording.
The present invention relates to a method for producing a thermal transfer image-receiving material having heat-resistant fusion bonding properties.

(Background Art) In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and devices suitable for each information processing system have also been developed and adopted. The thermal transfer recording method is one of these recording methods, and has recently become widely used because the equipment used is lightweight, compact, noiseless, has excellent operability and maintainability, and can be easily converted to color. . This thermal transfer recording method can be roughly divided into two types: a thermal melting type and a thermal transfer type. In the latter method, a thermal transfer dye-providing material having a dye-providing layer containing a binder and a heat-transferable dye on a support is superimposed on a thermal transfer image-receiving material, and heat is applied from the support side of the dye-providing material to create a pattern formed by the thermal application. This is a method of obtaining a transferred image by transferring a heat-transferable dye onto a recording medium (thermal transfer image-receiving material). Note that the term "thermally transferable dye" as used herein refers to a dye that can be transferred from a thermal transfer dye-providing material to a thermal transfer image-receiving material by sublimation or diffusion in a medium.

(Problems to be Solved by the Invention) However, conventional thermal transfer image-receiving materials tend to thermally fuse with the thermal transfer dye-providing material during transfer, have insufficient solvent resistance, and have weak film strength. There was a problem that the image-receiving layer of the material could be scratched.

For this reason, efforts have been made to improve the film properties of the image-receiving layer by adding a hardening agent to the image-receiving layer of the thermal transfer image-receiving material. However, an image-receiving sheet to which sufficient hardening agent is added to prevent thermal adhesion with the ink sheet presents a new problem in that the dye density decreases.

A thermal transfer image-receiving material that has both high dye density and good film properties cannot be obtained by using conventional techniques such as selecting the type and amount of hardener and adjusting the degree of heat treatment of the applied dry film. There wasn't.

(Means for Solving the Problems) An object of the present invention is to provide a method for producing a thermal transfer image-receiving feed having an image-receiving layer with improved film properties without reducing dye density. This purpose includes at least a dye-receiving polymer, a curing agent and a liquid medium. When forming an image-receiving layer by coating tJi Kaimono on a support, 85% of the average boiling point of the liquid medium is applied.
Forms a dry film at a temperature below 100% of the average boiling point.
This was achieved by a method for producing a thermal transfer image-receiving material, which is characterized by heat treatment at a temperature of ~150%.

The dye-receiving polymer that can be used in the image-receiving layer of the present invention is a polymer that has the function of receiving and dyeing the heat-transferable dye transferred from the heat-transfer dye-providing material during printing, Examples of resins include:

(a) Dicarboxylic acid components having ester bonds such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components contain sulfonic groups,
Polyester resins obtained by condensation of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc. with carboxyl groups (which may be substituted with carboxyl groups, etc.): polymethyl methacrylate, polybutyl acrylate, polymethyl acrylate, polybutyl Polyacrylic acid ester resin such as acrylate or polymethacrylic acid ester resin: Polycarbonate-1 resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101.395,
No. 63-7971, No. 63-7972, No. 63-7
Examples include those described in No. 973 and No. 60-294862. In addition, commercially available products include Toyobo's Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK140, Byron GK-1, 30, Kao's ATR-2009, AT
R-2010 etc. can be used.

(b) Urethane, those with bonds polyurethane resin, etc.

(c) Those with an amide bond polyamide resin, etc.

(d) Those with urea bonds urea resin etc.

(e) Those with a sulfone bond.

polysulfone resin, etc.

(v) Others having highly polar bonds=5 Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

In addition to the synthetic resins mentioned above, mixtures or copolymers thereof can also be used.

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which a substance capable of receiving a 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 may be used, but a water-soluble polymer having a group capable of crosslinking with a hardening agent is preferred.

Examples of water-soluble polymers used in the present invention include vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridinium, cationic modified polyvinyl alcohol, and derivatives thereof (Japanese Patent Laid-Open No. 60-1458
No. 79, No. 60-220750, No. 61-14317
7, No. 61235182, No. 61-245183, No. 61-237681, No. 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or its salt, acrylic acid- Polymers containing acrylic groups such as methacrylic acid copolymers or salts thereof, polymethacrylic acid or salts thereof, acrylic acid-vinyl alcohol copolymers or salts thereof (JP-A-60-168651, JP-A-62-9)
988), starch, oxidized starch, starch acetate, amine starch, carboxyl starch, dialdehyde starch, cationic starch, dextrin, sodium alginate, gelatin, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, hydro Natural polymers such as sikiethylcellulose and hydroxypropylcellulose or their derivatives (JP-A-59-174382, JP-A-60-2)
62685, 6m-143177, 6m-18
No. 1689, No. 61-193879, No. 61-287
782), polyethylene glycol, polypropylene glycol,
Base polymers such as polyvinyl methyl ether, maleic acid-hinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer, maleic acid-alkyl vinyl ether copolymer, polyethyleneimine, etc. (JP-A-61-3278
No. 7, No. 61-237680, No. 61-277483
Examples include water-soluble polymers described in JP-A No. 56-58869) and JP-A No. 56-58869.

Furthermore, various copolymers made water-soluble by monomer components containing SO,- groups, COO- groups, 5O2- groups, etc. can also be used.

The use of gelatin as a water-soluble binder is
It is particularly preferable because it can be dried and the drying load is much smaller. Specifically, gelatin and its derivatives such as lime-treated gelatin, decalcified lime-treated gelatin, acid-treated gelatin, phthalated gelatin, acetylated gelatin, and succinated gelatin, Bull, Soc, Ph
ot, Japan, No. 16. p30 (196
Examples include enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products as described in 6).

Only one type of these water-soluble polymers may be used,
Two or more types may be used in combination.

The water-soluble binder and the receiving material are used in a weight ratio of receiving material/water-soluble binder of 1 to 20, preferably 2 to 10, particularly preferably 2.5 to 7.

Any known dispersion method for dispersing a hydrophobic substance in a water-soluble polymer can be used to disperse the receiving substance in the water-soluble binder.

Typical methods include emulsifying and dispersing a solution of a receptor material dissolved in an organic solvent that is immiscible with water and mixing it with an aqueous solution of a water-soluble binder, and mixing a latex of the receptor material (polymer) with an aqueous solution of a water-soluble binder. There are ways to do this.

The hardening agent used in the present invention may be any hardening agent as long as it can harden the polymer of the image-receiving layer.
Hardeners described in No. 7, No. 5B-215398, etc. can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners.

For curing water-soluble polymers, U.S. Patent No. 4.678.7
No. 39, column 41, JP-A-59-116655, JP-A No. 62
Hardeners described in Japanese Patent Nos. 245261 and 61-18942 are suitable for use.

More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene bis(
(vinylsulfonylacetamido)ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), and polymer hardeners (compounds described in JP-A-62-234157, etc.).

The amount of hardener used is preferably 0.5 to 30% by weight, particularly preferably 1 to 2% by weight, based on the hardenable polymer.
It is 5% by weight.

The liquid medium used in the present invention may be any liquid capable of dissolving or dispersing the dye-receiving polymer, such as water, methanol, ethanol, isopropyl alcohol, butanol, etc.
Isobutanol, etc. Ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Aromatics include toluene, xylene, etc. Halogens include dichloromethane, trichloroethane, dioxane, tetrahydrofuran, etc. Glycol ethers include ethylene glycol monomethypheter, Ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, propylene glycol diacetate-1, methoxypropylene Examples of esters such as glycols include ethyl acetate, amyl acetate, phenyl dimethyl acetate, diethyl malonate, and dimethyl adipate. These liquid media may be used by appropriately mixing two or more liquid media as a mixed solvent.

The support used in the thermal transfer image-receiving material of the present invention can withstand the transfer temperature and satisfies the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, denting after transfer, etc. You can use anything. For example, synthetic paper (polyolefin-based, polystyrene-based, etc. synthetic paper), high-quality paper, art paper, coated paper, cast coat paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin-coated paper, paperboard,
Paper supports such as cellulose fiber paper, polyolefin-coated paper (particularly paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, etc., and white color on this plastic. Films or sheets treated to provide reflective properties, as well as laminates in any combination of the above, can also be used.

As a method for forming an image-receiving layer on the above-mentioned support, a coating solution is prepared by dissolving or dispersing a mixture of a dye-receiving polymer, a hardening agent, and other necessary additives in a suitable liquid medium, and this coating solution is For example, it is coated on a support by a known method such as a roll coating method, a wire bar coating method, an air knife coating method, a spray coating method, etc., and dried.
After that, heat treatment may be performed. Drying is carried out at a temperature below 85% of the average boiling point of the liquid medium, preferably at a temperature of room temperature +5° C. to 80% of the average boiling point.

Note that the average boiling point here is expressed as the sum of the volume fraction of the liquid medium used, multiplied by the boiling point of each liquid medium. For example, when using 10 ml of liquid medium with a boiling point of 100°C and 40 ml of a liquid medium with a boiling point of 125°C,
The average boiling point is determined below.

q 10 40 50 50 The end of drying can be considered as the point when the temperature of the membrane surface becomes almost equal to the temperature of the drying air, but it can be easily judged by touching the membrane surface and feeling the stickiness of the membrane surface. You may.

The image-receiving layer, which has become a dry film, is then heated to a temperature of 10% of the average boiling point of the liquid medium.
The heat treatment is carried out at a temperature of 0 to 150%, preferably 100 to 130%. It is preferable to carry out the heat treatment immediately after drying, but the heat treatment may be carried out by leaving it at room temperature for several hours and then heating it again. The leaving time at this time is preferably within 24 hours.

Humidity conditions during drying and heat treatment are 1%RH to 90%R
H, preferably 2% RH to 85% RH. The heat treatment time is usually set between 1 minute and 6 hours.

The image receiving layer may be composed of two or more layers. In that case, a synthetic resin with low glass transition is used for the layer closer to the support, or a high-boiling organic solvent or thermal solvent 4 is used to increase the dyeability of the dye, and the outermost layer is Avoid surface stickiness, contact with other substances, etc. by using synthetic resins with higher glass transition points, or minimizing or not using high-boiling point organic solvents or thermal solvents.
It is desirable to have a structure that prevents failures such as rearrangement to other substances after rearrangement and blocking with the thermal transfer dye-providing material.

The total thickness of the image-receiving layer is 0.5 to 50 μm, particularly 3 to 30 μm.
A range of μm is preferred. In the case of a two-layer configuration, the outermost layer is 0.1
It is preferable to set the thickness in the range of 1 to 2 μm, particularly 0.231 μm.

5. In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high boiling point organic solvent or thermal solvent can be contained as a substance capable of receiving a heat-transferable dye or as a dye diffusion aid.

Specific examples of high boiling point organic solvents and thermal solvents include JP-A No. 6
No. 2-174754, No. 62-245253, No. 61
-209444, 61-200538, 62-
No. 8145, No. 62-9348, No. 62-30247
No. 62-136646.

The thermal transfer image-receiving material of the present invention may have an intermediate layer between the support and the image-receiving layer.

Depending on the material it is made of, the intermediate layer may be a Kunjeong layer, a porous layer, or a porous layer.
This layer has the function of either one of the dye diffusion prevention layers or two or more of these functions, and in some cases also serves as an adhesive.

The D-major ILlj stop of the dye serves, in particular, to prevent migratory dyes from diffusing into the support. The binder forming this stop layer may be either water-soluble or 4T4m solvent-soluble, but a water-soluble binder is preferable, and an example thereof is the water-soluble binder mentioned above as the binder for the image-receiving layer. , particularly gelatin.

The porous layer is a layer that 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.

The image receiving layer, cushion layer, porous layer, diffusion prevention layer, adhesive layer, etc. that constitute the thermal transfer image receiving material of the present invention include silica, clay, talc, diatomite, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, Fine powders of synthetic zeolite, zinc oxide, lithopone, titane oxide, aldansu, etc. may be included.

A fluorescent brightener may be used in the thermal transfer image-receiving material.

Examples include K, Veenkat8ramaniJ
idThc Chemistry of 5ynthe
tic Dyesl Volume 5 Chapter 8, JP-A-61-163
Examples include compounds that are listed in 3 publications such as No. 752. More specifically, stilhen compounds, coumarin compounds, biphenyl compounds, henzoxazolyl compounds, naphthalimide compounds, birapurin compounds, carbostyril compounds, 2,5-dihenzooxazolthiophene compounds, etc. can be mentioned.

Optical brighteners can be used in combination with antifade agents.

The thermal transfer dye-providing material used in the present invention is a thermal transfer dye-providing material having a layer containing a heat-transferable dye on a support, in which the dye is applied in a pattern to the image-receiving layer of the thermal transfer image-receiving material. A thermal transfer dye-providing material having a heat-melting ink layer on a support and recording by transferring the ink to a heat-melted thermal transfer image-receiving material in the form of a heat-applied pattern. There are two things to do.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. For example, polyethylene terephthalate; polyamide; polycarbonate; glassine paper; capacitor; cellulose ester; fluoropolymer; polyether; polyacetal; polyolefin;
polyphenylene sulfide; polypropylene; polysulfone; cellophane and the like.

The thickness of the support of the thermal transfer dye-providing material is -fIn from 2 to
It is 30μ. 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. As the hydrophilic polymer, the water-soluble polymers described above can be used.

A slipping layer may also be provided to prevent the thermal head from sticking to the dye-donating material. This slipping layer is composed of lubricating substances, such as surfactants, solid or liquid lubricants or mixtures thereof, with or without polymeric binders.

The dye-donor layer is formed by selecting a dye so that the desired hue can be transferred when printed, and if necessary, arranging two or more dye-donating layers with different dyes on one thermal transfer dye-donating material. Also, 1: Yes. For example, when printing each color repeatedly according to color separation signals to form an image such as a 9-color photograph, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers containing dyes that give .

Alternatively, a dye-donor layer containing a dye that provides a blank hue in addition to cyan, magenta, and yellow may be added. It is preferable to provide a mark for position detection at the same time as the formation of any of the dye donor layers, since this eliminates the need for ink or printing process separate from the formation of the dye donor layer.

A thermal transfer dye-providing material using a thermally transferable dye basically has a thermal transfer layer on a support containing a dye that sublimes or becomes mobile by heat and a binder.

This thermal transfer dye-providing material is prepared by preparing a coating solution by dissolving or dispersing a dye that sublimes or becomes mobile by heat and a binder resin in a suitable solvent, and then applying this coating solution to the thermal transfer dye-providing material. On one side of the support for the material,
For example, it can be obtained by coating and drying at a coating amount of about 0.2 to 5 μm, preferably 0.4 to 2 μm, to give a dry film thickness of 0.0 μm to form a thermal transfer layer.

Dyes useful for forming such a thermal transfer layer include:
Although any dye conventionally used in thermal transfer dye-providing materials can be used, particularly preferred in the present invention are dyes of about 15
It has a small molecular weight of about 0 to 800, and is selected in consideration of transfer temperature, hue, light resistance, solubility in ink and binder resin, dispersibility, etc.

Specifically, for example, disperse dyes, basic dyes, oil-soluble dyes, etc. can be mentioned, but in particular, Scalon Yellow E
4GL, Dianix Yellow H2G-FS, Miketone Polyeltel Yellow 30S L, Kayasoseto Yellow 937, Sumikalon Red E F B L, Dianix Lent ACEXξKetone Polyeltel Red FB
, Kayanset Red 126, Miketon Fast Brilliant Blue 8, Kayanset Blue 136, etc. are preferably used.

Other known heat-transferable dyes can also be used.

Furthermore, as the binder resin used with the above dye, any binder resin conventionally known for this purpose can be used, and usually has high heat resistance and does not hinder the transfer of the dye when heated. things are selected. For example, polyamide resin, polyester resin,
Epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polyvinyl chloride resins (e.g. vinyl chloride-vinyl acetate) copolymer), polycarbonate phase sequence, polystyrene, polyphenylene oxide, cellulose resin (e.g. methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate-1 hydrogen phthalate, cellulose acetate [
1-su, cell 11-su acetate 1:1 bionate,
Cellulose acetate butyrate, cellulose triacetyl), polyvinylalnylene-based resin 11H (e.g. partially saponified polyvinyl alcohol such as bovinyl alcohol, polyvinyl butyral), stone yuzu-based resin, rosin resin
A coumaron-indene resin, a terpene resin, a polyolefin resin (eg, polyethylene, polypropylene), etc. are used.

Such a binder resin is preferably used in a proportion of, for example, about 80 to 600 parts by weight per 100 parts by weight of the dye.

In the present invention, any conventionally known ink solvent can be freely used as the ink solvent for dissolving or dispersing the above pigment and binder resin.

When printing from the back side of the dye-donating material, it is preferable to apply an anti-sticking treatment to the side of the support on which the dye-donating layer is not provided, in order to prevent stinking due to the heat of the thermal hend and improve slippage.

For example, it is possible to set up a ml thermal slime lff1 mainly consisting of ■ a reaction product of polyvinyl butyral resin and an isocyanate, ■ an alkali metal salt or alkaline earth metal salt of a phosphoric acid ester, and ■ a filler agent. good. 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 having many reaction sites with isocyanate, the weight percentage of the vinyl butyral portion is 15 to 40%. Things are good. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafac RD720 manufactured by Toho Chemical Co., Ltd. is used, and it is preferably used in an amount of about 1 to 50% by weight, preferably about 10 to 40% by weight, based on the polyvinyl butyral resin.

It is desirable that the heat-resistant slip layer has heat resistance as the lower layer.
A combination of a synthetic resin that can be cured by heating and its curing agent,
For example, polyvinyl butyral and polyvalent isocyanate 1-,
A combination of an acrylic polyol and a polyvalent isocyanate, a cellulose acetate and a titanium chelating agent, or a polyester and an organic titanium compound may be provided by coating.

The dye-donor material may be provided with a hydrophilic barrier layer to prevent IL from diffusing the dye toward the support. The hydrophilic dye barrier layer contains a hydrophilic material that is useful for the intended purpose. Generally excellent results are obtained with gelatin, poly(
acrylamide), poly(isopropylacrylamide), butyl methacrylate grafted gelatin, butyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly(vinyl alcohol), poly(ethyleneimine), poly(acrylic acid), poly(vinyl alcohol) and poly(vinyl acetate), a mixture of poly(vinyl alcohol) and poly(acrylic acid), or a mixture of cellulose monoacetate and poly(acrylic acid). Particularly preferred are poly(acrylic acid), cellulose monoacetate or poly(vinyl alcohol).

The dye-providing material may be provided with a subbing layer. In the present invention, any undercoat layer may be used as long as it has the desired effect, but a preferred specific example is (acrylonitrile-vinylidene chloride-acrylic M) copolymer (weight ratio 1410:6).
, (butyl acrylate-2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (
weight ratio 30:20:50), linear/saturated polyesters such as Bostik 7650 (Emhart, Bostik Chemical Group) or chlorinated high density polyesters (
Examples include ethylene-trichloroethylene) resin. There is no particular limit to the amount of undercoat layer applied, but it is usually 0.1~
It is used in an amount of 2.0 g/m2.

A second embodiment of the thermal transfer dye-providing material is an embodiment in which the thermal transfer layer is a thermal melt transfer layer composed of an ink for forming a thermal transfer layer consisting of a wax containing a coloring agent such as a dye or a pigment. This ink is made by distributing and dispersing colorants such as carbon blank and various colorants and pigments using waxes with appropriate melting points, such as paraffin wax, microcrystalline wax, carnauba wax, and urethane wax, as a binder. It is what it is. The ratio of the colorant and wax used is preferably such that the colorant accounts for about 10 to 65% by weight in the heat-melting transfer layer to be formed, and the thickness of the layer to be formed is about 1.5 to 6.0 μm. A range is preferred. The production of the ink and its application onto the support can be carried out according to known techniques.

In the present invention, in order to improve the releasability of the thermal transfer dye-providing material and the thermal transfer image-receiving material, the dye-providing material and/or
Alternatively, it is preferable to include a release agent in the layers constituting the image-receiving material, particularly preferably in the outermost layer corresponding to the surface where both materials come into contact.

As a mold release agent, solid or wax-like substances such as polyethylene wax, amide wax, fine powder of silicone resin, fine powder of fluorine resin, difluorine type, phosphate ester type surfactant: paraffin type, Any conventionally known mold release agent such as silicone-based or fluorine-based oils can be used, but silicone oil is particularly preferred. In addition to unmodified silicone oils, modified silicone oils such as carboxy-modified, acno-modified, epoxy-modified, polyether-modified, and alkyl-modified silicone oils may be used alone or in combination.
More than one species can be used in combination. For example,
"Modified silicone oil" issued by Shin-Etsu Silicone Co., Ltd.
Various modified silicone oils are listed on pages 6 to 18B of the technical data. When used in a solvent-based binder, an amino-modified silicone oil containing a group that can react with the crosslinking agent of the binder (for example, a group that can react with isocyanate) is also emulsified and dispersed in a water-soluble binder. In this case, carboxy-modified silicone oil (for example, manufactured by Shin-Etsu Silicone Co., Ltd., trade name: X=22-3710) or epoxy-modified silicone oil (for example, manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KF-100T) is effective.

Antifading agents may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (eg, pintate phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-1596448 are also effective.

Benzotriazole compounds (
U.S. Pat. No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Pat. No. 3,352,081, etc.),
Benzophenone compounds (JP-A-56-2784, etc.), other JP-A-54-48535, JP-A-62-136
There are compounds described in No. 641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

Examples of metal complexes include U.S. Patent No. 4.24LL55, U.S. Pat.
．． No. 195, columns 3 to 8, JP-A-62174741, JP-A No. 61-88256, pages (27) to (29), Japanese Patent Application No. 1982
-2341.03, 6231096, patent application 1982
There are compounds described in No.-230596 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

An anti-fading agent for preventing fading of the dye transferred to the image-receiving material may be included in the image-receiving material in advance, or it may be added to the image-receiving material from the outside by transferring it from the dye-providing material. You may also do so.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

Various surfactants can be used in the constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, accelerating development, and the like.

Nonionic surfactants, anionic surfactants.

Amphoteric surfactants and cationic surfactants can be used. Specific examples of these are JP-A-62-173463,
It is described in No. 62-183457 and the like.

In addition, when dispersing substances that can accept heat-transferable dyes, mold release agents, anti-fading agents, ultraviolet absorbers, optical brighteners, and other hydrophobic compounds in a water-soluble binder, the interface is used as a dispersion aid. Preferably, an activator is used. For this purpose, in addition to the above-mentioned surfactants, JP-A-59-15763
The surfactants described on pages 37-38 of No. 6 are particularly preferably used.

The constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving shearing properties, preventing 41 shingles, improving elision properties, and the like. Representative examples of i-1-fluoro compounds include Japanese Patent Publication No. 579053 No. 8 to
17 pity, 4. 'l Kaisho 61-20944, 62-1
．． Examples include fluorine-based surfactants described in Japanese Patent No. 35826, oil-like fluorine-based compounds such as fluorine-containing compounds, and powders of fluorine-based resins such as tetrafluoroethylene resin. It is also effective to include silicone oil containing polynylene oil for the above purpose.

Furthermore, it is also effective to use the polyether-modified silicone oil in combination with fine powder of fluororesin.

Mano-1 agents can be used in thermal transfer dye-providing materials and thermal transfer image-receiving materials. Silicon dioxide as a mantle agent,
In addition to compounds such as polyolefins or polymethacrylates described in JP-A-6188256 (page 29), compounds described in JP-A-62-110064 and JP-A-62110065 such as Henzoguanamine resin beads, polycarbonate resin beads, and AS resin beads. There is.

In the present invention, a thermal transfer dye-providing material is superimposed on a thermal transfer image-receiving material, and thermal energy corresponding to image information is applied from either side, preferably from the back side of the thermal transfer dye-providing material, by a heating means such as a thermal generator. As a result, the dye in the dye-donating layer can be transferred to the thermal transfer image-receiving material in accordance with the magnitude of heating energy, and a color image with excellent clarity and resolution and gradation can be obtained.

The heating means is not limited to the Thermalchen 1-, but any known means such as a laser beam (for example, a semiconductor laser), an infrared flash, a thermal pen, etc. can be used.

In the present invention, by combining the thermal transfer dye-providing material with the thermal transfer image-receiving material, printing using various thermal printing printers, fujigori, or A1 recording method,
Image printing using magneto-optical recording method, optical recording method, etc. 1-
It can be used to create prints from TV, RT screens, etc.

For details on the thermal transfer recording method, see Japanese Patent Application Laid-Open No. 634895.
You can refer to the description in the issue.

EXAMPLES The present invention will be explained in more detail by showing examples below.

Example 1 (Preparation of thermal transfer dye-providing material (A)) A 5.5 μm thick polyethylene terephthalate film (Lumirror: manufactured by Toshi) having a heat-resistant slipping layer made of a thermosetting acrylic resin on one side was used as a support, A coating composition (A) for forming a thermal transfer dye-providing layer having the following composition is coated with a wire bar on the side opposite to the side on which the heat-resistant slipping layer is provided, so that the coated amount after drying is Ig/rrr. A thermal transfer dye-providing material (A) was obtained by coating as follows.

Disperse dye (MS Red G: manufactured by Mitsui Toatsu) (Disperse Red 60) 3.6 moiety dye (Ma
crolex Violet R: manufactured by Bayer) (Disverse Rerad 26) 2.6 parts Polyvinyl butyral resin (Nisresoku BX-1: manufactured by Shimizu Chemical) 4.3 parts 4 Methyl ethyl ketone 45 parts Toluene 45 parts (thermal transfer image receiving material (
Preparation of B)) Synthetic paper with a thickness of 150μ as a support (manufactured by Tamago Yuka Co., Ltd.: Y
UPO-FPG-150), a coating composition for an image-receiving layer having the following composition was coated on the surface by wire bar coating so that the dry thickness was IOμ, and then dried under the conditions shown in Table 1. After heat treatment, sample (B1) ~
(B6) was obtained. The average boiling point of the liquid medium of this coating composition was 95°C.

gJIJLM41 plated polyester resin (Byron 290 manufactured by Toyobo) 20g amino-modified silicone oil (KF 875: manufactured by Shin-Etsu Silicone) 0.5g epoxy-modified silicone oil (KF looT: manufactured by Shin-Etsu Silicone) 0.5g isocyanate hardener (KP- 90 (manufactured by Dainippon Ink) 3 g Memethiethyl Ketone 100 ml Toluene 100 ra Table The thermal transfer dye-providing material and the thermal transfer image-receiving material obtained as above were superimposed so that the dye-providing layer and the image-receiving layer were in contact with each other. Using a thermal head from the support side of the thermal transfer dye-providing material, the output of the thermal spatula 1' is 0.25 W/ton 1-, and the pulse is 0. Printing was carried out under the conditions of 15 to 15 m5ec and a driver 1-density of 6 dots/mm. The image-receiving layer of the thermal transfer image-receiving material was dyed with magenta dye in an imagewise manner.

The portion where the density of the obtained recorded thermal transfer image-receiving material was saturated (at Dma) was measured using status A reflection density, and the results are shown in Table 2.

The surface thermal adhesion rating is 5. Over 60% of the image surface undergoes thermal adhesion 4.
30% or more and less than 60% 3 5% or more and less than 30% 2 Less than 5% 1 No heat fusion occurs. 1 is an acceptable level, and 2 to 5 is an unacceptable level.

As is clear from Table 2, it was found that the image-receiving sheet produced according to the present invention did not cause a decrease in density and maintained good thermal adhesion.

(Example 2) As the thermal transfer dye-providing material, the thermal transfer dye-providing material (A) used in Example 1 was used as it was.

(Preparation of thermal transfer image-receiving material (C)) 240 μm photographic polyethylene coated as a support (175 μm base paper, 33 μm on the front side, 32 μm on the back side)
Using polyethylene of 300 mL (100 mL) and gelatin undercoat (on the front side), paint for the image-receiving layer with the following composition is applied to the surface.
The amount of polyester is reduced by log /
The materials were coated in an amount of 0.3 m, and dried and heat treated under the conditions shown in Table 3 to form thermal transfer image-receiving materials (C1 to C6). The average boiling point of the liquid medium of this coating & [l acid is 96.5°C.
Met.

Coating composition for image-receiving layer (C) Polyester Jugetsuji (C) 20 g
Amino-modified silicone oil 0.5g (Shin-Etsu Silicone K F-857) Isocyanate hardener 3g (Inuhiki Ink KP-90) R Fluorine resin matte agent (Daikin Industries Lubron L Methyl ethyl ketone toluene methoxypropylene glycol 5mE 5mk 10m Composition (mol%) of polyester resin (D) Molecular weight approximately 20,000 In addition, in "2", the numerical value indicates the composition (mol%) of the polyester, TPA, IPA, 5IPA, BTS
-A-ED and EG each have the following meanings.

TPA Terephthalic acid IPA Isophthalic acid TPA IS ED EG Ethylene glycol The resulting thermal transfer image-receiving material was dyed with a magenta dye imagewise in the same manner as in Example 1, and the density was measured. The results are summarized in Table 3.

1 "Scratchability" is determined by placing a needle on the surface of the image-receiving layer of a thermal transfer image-receiving material and moving the needle at a constant speed while continuously applying a load. The product was rated on a 5-point scale, with 5 being resistant to scratches and 5 being extremely difficult to scratch.

1 and 2 are acceptable levels, and 3 to 5 are unacceptable levels.

As is clear from Table 3, the samples of the present invention provide good film properties without decreasing transfer density.

Claims (1)

[Claims] In a method for producing a thermal transfer image-receiving material having an image-receiving layer on a support that receives a dye transferred from a thermal transfer dye-providing material, the image-receiving layer contains a liquid composition containing at least a dye-receiving polymer, a hardening agent, and a liquid medium. It is formed by coating on a support, and when forming the image-receiving layer, a dry film is formed at a temperature of 85% or less of the average boiling point of the liquid medium, and then the average boiling point of the liquid medium is 1. A method for producing a thermal transfer image-receiving material, which comprises performing heat treatment at a temperature of 100 to 150% of the temperature.