JPH04275192A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer image receiving material used in a thermal transfer method by a thermal transfer dye, easy to prepare, easy adjust void volume, reduced in the thermal deformation at the of transfer possible to obtain a high quality image, particularly uniform and high transfer density and provided with porous layer enhanced in the adhesiveness to a support and having sufficient film strength. CONSTITUTION:A porous layer consisting of at least cellulose acetate, an inorg. filler, polyhydric alcohol and a crossling agent is provided between the support and image receiving layer of a thermal transfer image receiving material.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a thermal transfer image-receiving material used in a thermal transfer method using a heat-transferable dye.
In particular, the present invention relates to a thermal transfer image-receiving material that has excellent manufacturing suitability and can provide images of high quality, particularly high transfer density.

0002

2. Description of the Related 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. . There are two main types of thermal transfer recording methods: thermal melting type and 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.

[0003] Various methods have been used to obtain high transfer density and high density in this thermal transfer type thermal transfer recording method, and one method is to increase the temperature of the transfer surface by preventing thermal diffusion during thermal transfer. Therefore, a method is known in which a porous layer containing porous particles or the like is provided as a low thermal conductivity layer. The porous layer is a layer that prevents the heat applied during thermal transfer from diffusing from the image-receiving layer to the support and effectively utilizes the applied heat. Furthermore, since the porous layer serves as a cushion layer, it has the effect of improving the adhesion with the dye-providing material during printing, and therefore has the effect of providing a uniform image without white spots or unevenness.

[0004] When using a water-soluble polymer as a binder for a porous layer, there are two methods: (1) dispersing porous fine particles in a water-soluble polymer and coating and drying; (2) dispersing the water-soluble polymer in which air bubbles are generated by mechanical stirring; (2) Apply a water-soluble polymer solution with a foaming agent added to it by foaming it before application or foaming it during the coating drying process; (2) Adding an organic solvent (preferably) to the water-soluble polymer solution or latex dispersion. A solvent with a boiling point higher than that of water) is emulsified and dispersed, and microvoids are formed in the process of coating and drying (Japanese Patent Laid-Open No. 63-15
3187), ■ Coating microcapsules with a low boiling point organic solvent as the core and a thermoplastic resin as the walls and heating and foaming them (
Methods such as JP-A-2-60790) are known.

[0005] When using an organic solvent-soluble binder as the porous layer, (1) a liquid obtained by mechanically stirring a synthetic resin emulsion such as polyurethane or a synthetic rubber latex such as methyl methacrylate-butadiene to generate air bubbles; (1) Coat the above synthetic resin emulsion or synthetic rubber latex mixed with a foaming agent on the support and dry it (2) Apply synthetic resin such as PVC plastisol, polyurethane, or styrene-butadiene-based resin to the support and dry it. A liquid mixture of a synthetic rubber such as a foaming agent and a foaming agent is applied onto a support and foamed by heating.
45192), (1) formation using a W/O type emulsion consisting of a thermoplastic resin, an organic solvent with limited mutual solubility with water, and water (Japanese Patent Application Laid-open No. 122593/1983). There is. Furthermore, a method is also known in which a porous support is produced by stretching a film made of a thermoplastic resin containing an inorganic filler and used.

[0006]

[Problems to be Solved by the Invention] However, conventionally known porous layers are not easy to manufacture, there is a limit to the porosity that can be obtained, and it is difficult to adjust the porosity, making it difficult to obtain stable performance. The problem was particularly pronounced when mechanical stirring was used. In addition, in the method of obtaining porous materials by foaming, the foaming agent used contains many harmful substances, and the resulting images tend to fade over time.Also, since foaming requires relatively high temperatures, a heat-resistant support is required. There were problems such as having to choose. Attempts were made to form a porous layer using polyester resin, etc., taking advantage of the solubility of the solvent used, but a satisfactory porous layer could not be formed. Unable to obtain concentration. Furthermore, in the method of forming a porous layer using a W/O emulsion, control of the size of the W/O emulsion and stability over time are poor, and it is difficult to obtain an image receiving material having a porous layer with a certain level of performance. It was difficult to obtain an image-receiving material that gave a sufficiently high transfer density. Furthermore, a porous support obtained using a stretching technique has the problem that it is highly deformed by heat and curls significantly during transfer.

As a result of research into a method for forming a porous layer that solves these problems, the present inventor dissolved cellulose acetate in a good solvent, added a plasticizer and a crosslinking agent, and further added a poor solvent for cellulose acetate. We discovered that the above-mentioned problems could be solved by applying a solution containing a non-solvent and/or a non-solvent onto a support and drying it, and filed a patent application.
No. 6287).

However, as a result of further research,
It was found that the porous layer formed by this method had insufficient adhesion to the support and the strength of the porous layer itself. Therefore, an object of the present invention is to provide a method that is easy to manufacture, easy to adjust the porosity, has little thermal deformation during transfer, can obtain high image quality, especially uniform and high transfer density, and furthermore, The object of the present invention is to obtain a thermal transfer image-receiving material using a heat-transferable dye, which has high adhesion and sufficient film strength.

[0009]

[Means for Solving the Problems] The above object is to provide at least one image-receiving layer on a support for receiving the dye transferred from the thermal transfer dye-providing material when heated to form an image. This was achieved using a thermal transfer image-receiving material characterized by having a porous layer consisting of at least cellulose acetate, an inorganic filler, a polyhydric alcohol, and a crosslinking agent. Furthermore, the above object is more preferably achieved by a thermal transfer image-receiving material characterized in that the porous layer is formed using a parent solvent for cellulose acetate and a poor solvent and/or non-solvent for cellulose acetate. .

[0010] The cellulose acetate referred to herein can be of any type as long as it is produced by known techniques, but among these, those having an average degree of acetylation of 55 to 62 are particularly advantageous. Here, the degree of acetylation is as follows: degree of acetylation=(weight of acetic acid obtained by saponifying cellulose acetate)/(weight of cellulose acetate)×100.

[0011] A porous layer containing cellulose acetate can be produced by dissolving cellulose acetate in a good solvent and applying a mixed solution containing a poor solvent and/or a non-solvent, followed by drying. The mixed solution is preferably applied and dried under controlled temperature and humidity conditions. The porous layer obtained in this way can be provided on the support by adhering it to the support, but for ease of production, it is possible to apply the mixed solution containing cellulose acetate on the support and dry it. A one-step method is preferred. After coating a solution containing cellulose acetate on a support, it is maintained at a temperature below the boiling point of the parent solvent, preferably at a temperature at which cellulose acetate tends to undergo phase separation (35°C or below) to form micropores, and then heated at 50°C to 120°C. Heat to dry at ℃. The amount of parent solvent is 30 to 200 parts by weight per 10 parts of cellulose acetate.
6 to 40 parts for non-solvents and 0 to 40 parts for poor solvents.
140 copies is appropriate.

[0012] The affinity solvent herein refers to a solvent that can dissolve cellulose acetate well, and includes halogenated hydrocarbons such as methylene chloride and chloroform, esters such as methyl acetate and methyl glycol acetate, and acetone and methyl ethyl ketone. There are ketones, etc. The term "poor solvent" as used herein refers to a solvent that only swells cellulose acetate but does not substantially dissolve it, is miscible with the above-mentioned parent solvent, and has a boiling point higher than that of the parent solvent. Specific examples of poor solvents include alcohols such as methanol, ethanol and butanol, and ethers such as isopropyl ether, with methanol being particularly preferred. The term "non-solvent" as used herein refers to a solvent that does not dissolve or swell cellulose acetate, is miscible with the above-mentioned pro-solvent or poor solvent, and has a boiling point higher than that of the pro-solvent. Specific examples of the non-solvent include hydrocarbons such as heptane, decane and toluene, polyhydric alcohols such as ethylene glycol and ethylene glycol monoethyl ether, ethers of these polyhydric alcohols, and water, with water being particularly preferred.

Since the porous layer according to the present invention is obtained by mixing cellulose acetate with a good solvent and a poor solvent (and/or a non-solvent) and drying the mixture, it can be easily produced at a relatively low temperature. In this case, cellulose acetate may be added to a mixture of a good solvent and a poor solvent (and/or a non-solvent), or a poor solvent (and/or a non-solvent) may be added to a solution of a good solvent of cellulose acetate. . Further, there is no particular restriction on the timing of addition of the inorganic filler, polyhydric alcohol, and crosslinking agent, and the porous layer of the present invention can be obtained by applying a solution obtained by adding these. Further, since the porosity of the porous layer can be easily adjusted by appropriately setting the type and amount of the solvent used and the drying temperature and humidity, a thermal transfer image-receiving material with stable performance can be obtained. Generally, when creating a porous layer using phase separation, increasing the proportion of non-solvent and/or poor solvent promotes phase separation and increases the porosity.
Since the porous layer-forming resin cannot be dissolved, there is a limit to its proportion, and therefore it is difficult to obtain a sufficient porosity. However, since the system using cellulose acetate of the present invention has the property of absorbing water, which is a poor solvent, during coating and drying, it is possible to produce a porous layer having a large porosity. Furthermore, it became possible to adjust the porosity by controlling the humidity and temperature during coating and drying. According to the present invention, the porosity can be set relatively freely, for example, 10 to 90%.
, preferably 20 to 70%. A larger porosity is more advantageous in terms of heat insulation effect, but if the porosity is too large, the porous layer tends to become brittle.

By incorporating an inorganic filler, a polyhydric alcohol, and a crosslinking agent into a porous layer mainly composed of cellulose acetate, the membrane strength and adhesion of the porous layer to the support and/or image-receiving layer can be practically improved. It has now become possible to make significant improvements to a level where there are no problems.

Inorganic fillers used in the present invention include fine particles of silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina, etc. is used, but the smaller the particle size, the better, usually an average of 0.5 μm or less, more preferably 0.2 μm or less. Colloidal silica can be particularly preferably used.

Examples of the polyhydric alcohol used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, glycerin, pentaerythryl, etc. Those having a molecular weight of 1000 or less are preferred, and ethylene glycol, propylene glycol, etc. are particularly preferably used.

[0017] As the crosslinking agent used in the present invention, OH
Any compound having two or more groups capable of reacting with the group may be used, but isocyanate-based and epoxy-based crosslinking agents are preferably used. Especially as polyisocyanate,
Compounds commercially available as diisocyanates such as diphenylmethane diisocyanate or tolylene diisocyanate, triisocyanates such as triphenylmethane triisocyanate, or polyisocyanates can be used.

In addition to the above-mentioned polyhydric alcohol, the porous layer of the present invention contains phthalate esters (for example, dibutyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, etc.) and phosphoric acid esters (for example, triphenyl phosphate, trichloride, etc.) as plasticizers. dil phosphate, etc.),
Oil-soluble polymers, oligomers, etc. having a low glass transition point (Tg) can also be contained.

Further, if necessary, a higher carboxylic acid salt, a higher alcohol sulfate ester salt, a polyethylene glycol sulfate ester salt, an alkylaryl sulfonate, a phosphate ester salt, etc. may be added to the mixture of cellulose acetate and the above-mentioned solvent. Anionic surfactants, amine salts, cationic surfactants such as quaternary ammonium salts, amphoteric surfactants such as dodecylaminoethylglycine sulfate, alkyl ethers, alkyl allyl ethers, sorbitan monoalkyl esters, polyoxyethylene alkyl Amine, polyoxyethylene alkylamide, polyethyleneimine, polyoxyethylene, polyoxypropylene,
Nonionic surfactants such as glycol esters, saccharose esters, fatty acid ethanolamides, methylolamides, and glucosides, particularly surfactants such as stearic acid monoglyceride, polyoxyethylene sorbitan monostearate, polyoxyethylene octylphenol ether, non-ionic additives added to foods such as propylene glycol monooleate; foaming aids such as inorganic salts such as calcium chloride, sodium chloride, magnesium chloride, and sodium sulfate; pore size control agents such as starch; and cellulose ethers. Various additives can be added. Specific examples of these additives are also described in Japanese Patent Publications Nos. 46-40426 and 48-40050.

The amount of the inorganic filler used in the present invention is generally 1 to 60% by weight, preferably 5 to 50% by weight based on cellulose acetate. The amount of plasticizer (including polyhydric alcohol) used in the present invention is usually 1 to 60% by weight, preferably 3 to 30% by weight based on cellulose acetate. The amount of the crosslinking agent used in the present invention is usually 1 to 30% by weight based on cellulose acetate.
It is preferably used in a range of 5 to 20% by weight.

In the thermal transfer image-receiving material according to the present invention, the porous layer may be used as an image-receiving layer, but usually the porous layer is provided between the image-receiving layer and the support.

[0022] The support used in the thermal transfer image-receiving material of the present invention can withstand the transfer temperature and satisfies 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), 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 supports such as paperboard, paperboard, cellulose fiber paper, polyolefin-coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, etc. A film or sheet treated to give the plastic a white reflective property, and a laminate made of any combination of the above may also be used. In particular, polyolefin-coated paper in which both sides of a paper support are laminated with films has excellent image quality and is excellent in gloss processing suitability, whiteness improvement, curling prevention, etc., and is preferably used in the present invention. In particular, polyethylene coated paper laminated with polyethylene film is most preferred. Furthermore, in order to strengthen the adhesion between the support and the porous layer, it is preferable to coat the support with an anchor coat of gelatin, PVA, or the like.

The thermal transfer image-receiving material is provided with an image-receiving layer. This image-receiving layer accepts the heat-transferable dye that migrates from the thermal transfer dye-providing material during printing, and contains a single substance capable of receiving the heat-transferable dye that has the function of dyeing the heat-transferable dye. It is preferable that the film is about 0.5 to 50 μm thick and contains the binder material or other binder substances. Typical examples of polymers that can accept heat-transferable dyes include the following resins.

(a) Those having an ester bond Dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components may be substituted with sulfonic acid groups, carboxyl groups, etc.) and ethylene Polyester resins obtained by condensation of glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc.; polyacrylic acid ester resins or polymethacrylic acid ester resins such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate, etc. ;
Polycarbonate resin; polyvinyl acetate resin; styrene acrylate resin; vinyltoluene acrylate resin, etc. Specifically, JP-A-59-101395 and JP-A No. 63-
Examples include those described in No. 7971, No. 63-7972, No. 63-7973, and No. 60-294862. In addition, as a commercially available product, Byron 29 manufactured by Toyobo
0, Byron 200, Byron 280, Byron 300
, Byron 103, Byron GK-140, Byron G
K-130, Kao ATR-2009, ATR-20
10. Elitel UE3500, UE32 made by Unitika
10, XA-8153, Nippon Gosei Kagaku's polyester TP-220, R-188, etc. can be used.

(b) Those having urethane bonds, such as polyurethane resins. (c) Polyamide resins having amide bonds, etc. (d) Things with urea bonds, such as urea resins. (e) Things with sulfone bonds, such as polysulfone resins. (f) Others having highly polar bonds, such as 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 thermal transfer image-receiving material, particularly the image-receiving layer, may contain a high-boiling organic solvent or a thermal solvent as a substance capable of receiving heat-transferable dyes or as a dye diffusion aid. Specific examples of high boiling point organic solvents and thermal solvents include JP-A-62-174754 and JP-A-62-24525.
No. 3, No. 61-209444, No. 61-200538
No. 62-8145, No. 62-9348, No. 62
Examples include compounds described in No. 30247 and No. 62-136646. Further, the above-mentioned high-boiling organic solvents and thermal solvents may be used for the purpose of improving slipperiness, peelability, curl balance, and the like.

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which (1) a substance capable of receiving a heat-transferable dye is provided alone on a support, or (2) a substance capable of receiving a heat-transferable dye is provided on a support. It is also possible to have a configuration in which the particles are dispersed and supported in a water-soluble binder. As the water-soluble binder used in case (2), various known water-soluble polymers may be used, but water-soluble polymers having groups capable of crosslinking with a hardening agent are preferred. The water-soluble polymer used in the present invention includes:
Vinyl polymers such as polyvinyl alcohol, polyvinylpyridinium, cationic modified polyvinyl alcohol, and derivatives thereof (JP-A-60-145879, JP-A-60-145879,
-220750, 61-143177, 61-
No. 235182, No. 61-245183, No. 61-2
37681, 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or its salt, acrylic acid-methacrylic acid copolymer or its salt, polymethacrylic acid or its salt, acrylic Polymers containing acrylic groups such as acid-vinyl alcohol copolymers or salts thereof (JP-A-60-168651, JP-A-62-9988)
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, hydroxypropyl Natural polymers such as cellulose or derivatives thereof (JP-A No. 59-174382, No. 60-262685, No. 6
No. 1-143177, No. 61-181679, No. 61
-193879, 61-287782), polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, maleic acid-vinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer, maleic acid-alkyl vinyl ether copolymer , synthetic polymers such as polyethyleneimine (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. Also, SO3
Various copolymers made water-solubilized by monomer components containing - groups, COO- groups, SO2 - groups, etc. can also be used.

It is particularly preferable to use gelatin as the water-soluble binder since it can be dried in a set manner and the drying load is much lower. 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.
．． Photo. Japan, No. 16, P3 (1966
) Enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products can be mentioned. These water-soluble polymers may be used alone or in combination of two or more. The water-soluble binder and the receptive substance have a weight ratio of receptive substance/water-soluble binder=1 to 20, preferably 2 to 10, particularly preferably 2.
Use in the range of 5 to 7.

When a water-soluble binder is used, a receiving layer can be obtained by coating and drying an aqueous solution containing a dye-receiving substance. As a method for dispersing a receptive substance in a water-soluble binder, any known dispersion method for dispersing a hydrophobic substance in a water-soluble polymer can be used. Typical methods include emulsifying and dispersing a receptive substance dissolved in an organic solvent that is immiscible with water and mixing it with an aqueous solution of a water-soluble binder; There are ways to mix it with.

The aqueous solution may be an aqueous solution of a water-soluble dye-receiving resin or a blended solution of the water-soluble dye-receiving resin with a water-soluble polymer having low dye-receptivity, a dye-receptive fine particle dispersion, or a mixture of the dispersion and the dye-receiving resin. It may also be a blended solution with a low water-soluble polymer. Also receptive substance (polymer)
water-soluble groups (e.g. COOM, SO3M, -O-SO3
M, -(OCH2CH2)n-, where M is an alkali metal ion and n is an integer) may be introduced to form a water-soluble polymer, which may be used alone or in combination with the above-mentioned water-soluble binder. A specific example of a receptive polymer latex or a receptive water-soluble polymer is Plus Coat Z- manufactured by Gooi Kagaku.
466, Z-448, Z-455, Z-461, Z-7
61, Z-771, Pesresin A-124 manufactured by Takamatsu Yushi Co., Ltd.
3. A-2141, A-2151, Dainippon Ink Finetex ES-611, ES-650, ES-6
70, ES-675, ES-850, etc.

On the other hand, in the case of (2) above, since the polymer used in the receiving layer for the heat-transferable dye is soluble in organic solvents,
The coating liquid for the receiving layer is organic solvent based. Therefore, since an organic solvent-based coating liquid is applied to the porous layer according to the present invention as an image-receiving layer, there is a disadvantage that the porous layer, which is mainly made of cellulose acetate, partially dissolves in the organic solvent, reducing the heat insulation effect. . Furthermore, it is necessary to clean the equipment, containers, etc. used for manufacturing with an organic solvent. Therefore, explosion-proof equipment is required for coating liquid preparation equipment, coating equipment, etc., and organic solvents are more expensive than water, which not only increases production costs, but also poses health problems for workers. There's a problem. Furthermore, in order to obtain a high-density image, a polymer that softens or becomes rubbery during thermal transfer is used as a binder in the receiving layer, or a plasticizer is used. However, when such means are used, unevenness occurs on the transfer surface at the highest density portion, and gloss is also lost. Furthermore, when the thermal transfer image-receiving material after transfer is stored for a long period of time, blurring of the image is likely to occur.

However, in the case of (2) above, the dye-receiving substance is not dissolved in an organic solvent and applied as in the case of (2), but the dye-receptive substance is dispersed in a water-soluble binder and applied. It can be applied using a solvent, there is no risk of explosion, the manufacturing cost is significantly reduced, and the negative impact on the health of workers is also extremely low. In addition, the layer in which the dye-receiving substance is dispersed in the water-soluble binder sufficiently receives the heat-transferable dye, and an image with high transfer density can be obtained.
The obtained image has the advantage that there is very little blurring of the image even if it is stored for a long period of time. Therefore, the image-receiving layer used in the present invention preferably has a structure in which a substance capable of receiving a heat-transferable dye is dispersed and supported in a water-soluble binder, as in the case (2) above.

[0033] In addition, when applying a material capable of receiving an image of a heat-transferable dye using an organic solvent as in the case (2), a crosslinking agent such as polyisocyanate and epoxy resin is added to the porous layer of the present invention. It is preferable to include it in order to maintain the heat insulating effect. Furthermore, by including the crosslinking agent, the film strength and adhesion to the support and image-receiving layer are improved. In addition, even in a system using a water-based binder such as in case (2), if the crosslinking agent is included, the coating film will be prevented from dissolving even if the surface of the image-receiving material is accidentally wetted with an organic solvent.
Deterioration in performance is less likely to occur.

The image receiving layer may be composed of two or more layers. In that case, the layer closer to the support may be made of a synthetic resin with a low glass transition point, contain a fluorine-containing compound or a silicone compound, or use a high boiling point organic solvent or hot solvent to improve dyeing properties. By using a synthetic resin with a higher glass transition point in the outermost layer, containing fluorine-containing compounds and silicone compounds, and minimizing the amount of high-boiling point organic solvents and thermal solvents used. It is desirable to have a structure that prevents failures such as surface stickiness, adhesion with other substances, retransfer to other substances after transfer, and blocking with the thermal transfer dye-providing material by not using the dye. 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 preferably in the range of ~2 μm, particularly 0.2 to 1 μm.

The thermal transfer image-receiving material of the present invention may have an intermediate layer other than the porous layer between the support and the image-receiving layer, such as an anti-blur layer or an adhesive layer. The binder constituting this layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferred, and examples thereof include the water-soluble binders mentioned above as the binder for the image-receiving layer, particularly gelatin.

The image receiving layer, anti-blur layer, adhesive layer and back layer constituting the thermal transfer image receiving material of the present invention include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic Fine powders of zeolite, zinc oxide, lithopone, titanium oxide, alumina, etc. may be included.

A fluorescent brightener may be used in the thermal transfer image-receiving material. An example is K. Veenkatarama
Volume n “The Chemistry of Sy”
``Nthetic Dyes'' Volume 5 Chapter 8, Japanese Patent Publication No. 6
Examples include compounds described in No. 1-143752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyril compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned. Optical brighteners can be used in combination with antifade agents.

The thermal transfer dye-providing material is a thermal transfer dye-providing material having a layer containing a heat-transferable dye on a support. It is for recording.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. Examples include polyethylene terephthalate, polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, cellophane, and the like. The thickness of the support of the thermal transfer dye-providing material is generally 2 to 3 mm.
It is 0 μm. An undercoat layer may be provided if necessary. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye-donating layer. This further improves the transfer density. 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.

For the dye-donating layer, a dye is selected so that the desired hue can be transferred when printed, and if necessary, two or more dye-donating layers with different dyes are formed side by side on one thermal transfer dye-donating material. may have been done. For example, when forming an image such as a color photograph by repeatedly printing each color according to the color separation signal, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers containing the dye to be provided are arranged. Alternatively, a dye-donating layer containing a dye that provides a black 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 forming any of the dye-donating layers, since this eliminates the need for an ink or printing process separate from the formation of the dye-donating 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 about 0.2 to 5 μm, preferably 0.
It is obtained by applying the coating amount to give a dry film thickness of 4 to 2 μm and drying to form a thermal transfer layer.

As the dye useful for forming such a thermal transfer layer, any dye conventionally used in thermal transfer dye-providing materials can be used, but in the present invention, particularly preferred dyes are about 150 to 800. It has a small molecular weight and is selected in consideration of transfer temperature, hue, light resistance, solubility in ink and binder resin, dispersibility, etc. Specifically, examples include disperse dyes, basic dyes, oil-soluble dyes, and in particular, Sumikalon Yellow E4GL, Dianix Yellow H2G-FS, Miketon Polyeltel Yellow 3GSL, Kayaset Yellow 937, and Sumikalon. Red EFBL, Dianic Red ACE, Miketon Polyeltel Red FB, Kayaset Red 126, Miketon Fast Brilliant Blue B, Kayaset Blue 136, etc. are preferably used. Further, it is preferable to use a yellow dye represented by the following general formula (Y).

[0044]

[Chemical formula 1]

In the formula, D1 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group, D2 represents a hydrogen atom, an alkyl group, or an aryl group, and D3 represents an aryl group or an aryl group. It represents a heteryl group, and D4 and D5 represent a hydrogen atom or an alkyl group. The above groups may be further substituted. Specific compound examples are shown below.

[0046]

[Case 2]

[0047]

[Chemical formula 3]

[0048]

[C4]

[0049]

[C5]

As the magenta dye, a dye represented by the following general formula (M) is preferable.

[0051]

[C6]

In the formula, D6 to D10 are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, cyano groups, acylamino groups, sulfonylamino groups, ureido groups, alkoxycarbonylamino groups, alkylthio groups, represents an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, or an amino group, D11, D1
2 represents a hydrogen atom, an alkyl group or an aryl group. D11 and D12 may be combined with each other to form a ring,
Further, D8 and D11 or/and D9 and D12 may be combined to form a ring. X, Y and Z are =C(D
13)- or represents a nitrogen atom (D13 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group). Also, X and Y are =C(
D13)- or when Y and Z are =C(D13)
- In the case of -, two D13s may be bonded to each other to form a saturated or unsaturated carbon ring. The above groups may be further substituted. Specific compound examples are shown below.

[0053]

[C7]

[0054]

[Chemical formula 8]

[0055]

[Chemical formula 9]

[0056]

[Chemical formula 10]

Further, as a cyan dye, the following general formula (C)
dyes are preferred.

[0058]

[Chemical formula 11]

In the formula, D14 to D21 are the same as D6 to D10, and D22 and D23 are the same as D11 and D12. Specific compound examples are shown below.

[0060]

[Chemical formula 12]

[0061]

[Chemical formula 13]

[0062]

[Chemical formula 14]

It is preferable to introduce the anti-fading group described in Japanese Patent Application No. 1-271078 into the compounds of the above general formulas (Y), (M) and (C) because the light fastness is improved.

[0064] As the binder resin used together with the above dye, any binder resin conventionally known for this purpose can be used, and usually has high heat resistance and does not cause migration of the dye when heated. The one that does not interfere with this is selected. For example, polyamide resins, polyester resins, epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polychlorinated resins, etc. Vinyl resins (e.g. vinyl chloride-vinyl acetate copolymer), polycarbonate resins, polystyrene, polyphenylene oxide, cellulose resins (e.g. methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, Cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resins (e.g. polyvinyl alcohol, partially saponified polyvinyl alcohols such as polyvinyl butyral), petroleum resins, rosin derivatives, coumaron-indene resins, terpene resins, polyolefin resins (e.g. Polyethylene, polypropylene), etc. are used. Such binder resin is
For example, it is preferably used in a proportion of 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.

[0065] In the present invention, in order to improve the releasability of the thermal transfer dye-providing material and the thermal transfer image-receiving material, in the layers constituting the dye-providing material and/or the image-receiving material, particularly preferably the surface where both materials come into contact is It is preferable to contain a mold release agent in the outermost layer. As a mold release agent, any of the conventionally known mold release agents can be used, such as waxy substances such as polyethylene wax and amide wax; surfactants such as fluorine-based and phosphate esters; and paraffin-based and fluorine-based oils. can.

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be hardened with a hardening agent. When curing organic solvent-based polymers, JP-A-61-199997 and JP-A-58-21539 are used.
Hardeners described in No. 8 etc. can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners. For curing water-soluble polymers, see U.S. Pat. No. 4,678,739, column 41;
No. 55, No. 62-245261, No. 61-18942
The hardening agents described in No. 1, etc. are suitable for use. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners (such as compounds represented by the following chemical formula 15), vinyl sulfone hardeners (N,
N'-ethylene-bis(vinylsulfonylacetamide)
ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-62-23
4157, etc.).

[0067]

[Chemical formula 15]

An anti-fading agent 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 (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as U.S. Pat. No. 3,352,681), and benzophenone compounds (Japanese Patent Laid-Open No. 1983-1999). 278
No. 4, etc.), and other Japanese Patent Application Laid-open Nos. 54-48535 and 62
There are compounds described in No.-136641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective. As metal complexes, U.S. Pat. Nos. 4,241,155 and 4,245,0
No. 18, columns 3 to 36, No. 4,254,195, columns 3 to 8
Column, JP-A-62-174741, JP-A No. 61-88256
There are compounds described in pages (27) to (29) of No. 63-199248, JP-A-1-75568, and JP-A-1-74272. Examples of useful antifading agents are described in JP-A-62-215272, pages 125-137. The 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 supplied to the image-receiving material from the outside by a method such as transfer from a dye-donating material. It's okay. 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 releasability, improving slipperiness, preventing electrification, and the like. Nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants can be used. Specific examples of these are described in JP-A-62-173463 and JP-A-62-183457. 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 water-soluble binders, they can be used as dispersion aids. Preference is given to using surfactants. For this purpose, in addition to the above-mentioned surfactants,
The surfactants described on pages 7 to 38 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 slipperiness, preventing static electricity, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B No. 57-9053, columns 8 to 17, JP-A No. 61-20944, JP-A No. 62-13.
Fluorine surfactants described in No. 5826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, and water dispersions thereof. Can be mentioned. Specific examples include Daifree ME-313, ME-413, ME-414 manufactured by Daikin Industries, Ltd.
ME-810, MES-443, MS-743, MS-
043, MS-843, Asahi Guard AG-530, AG-533(S), AG-550, A manufactured by Asahi Glass Co., Ltd.
G-650, AG-710, AG-730, AG-74
0, AG-780, AG-800, Daiichi Kogyo Seiyaku Co., Ltd.
For example, Erasgund 100 manufactured by Co., Ltd.

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

[0072] 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 sticking caused by the heat of the thermal head and improve slippage. . For example, ■
It is preferable to provide a heat-resistant slip layer mainly consisting of a reaction product of a polyvinyl butyral resin and an isocyanate, (1) an alkali metal salt or alkaline earth metal salt of a phosphoric acid ester, and (2) a filler. Polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80.
~110℃, and from the viewpoint of having many reaction sites with isocyanate, the weight% of the vinyl butyral portion is 1.
5 to 40% is preferable. 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 1 to 50% by weight, preferably 10 to 4% by weight, based on the polyvinyl butyral resin.
It is preferable to use about 0% by weight. The heat-resistant slip layer preferably has a heat-resistant lower layer, and is made of 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 applied by coating.

The dye-donor element may also be provided with a hydrophilic barrier layer to prevent diffusion of the dye towards the support. Hydrophilic dye barrier layers contain hydrophilic materials useful for their intended purpose. Generally excellent results have been obtained using gelatin, poly(acrylamide), poly(isopropylacrylamide), butyl methacrylate grafted gelatin, ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, 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 a mixture of cellulose monoacetate and poly(acrylic acid). can get. Particularly preferred are poly(acrylic acid), cellulose monoacetate or poly(vinyl alcohol).

The dye-providing material may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has the desired effect, but a preferred specific example is an (acrylonitrile/vinylidene chloride/acrylic acid) copolymer (weight ratio: 1).
4:80:6), (butyl acrylate/methacrylic acid-
2-aminoethyl/2-hydroxyethyl methacrylate) copolymers (weight ratio 30:20:50), linear/saturated polyesters such as Bostik 7650 (Emhart, Bostik Chemical Group) or highly chlorinated Density poly(ethylene-trichloroethylene) resins may be mentioned. There are no special restrictions on the amount of undercoat layer applied, but
It is usually used in an amount of 0.1 to 2.0 g/m2.

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

[0076] The heating means is not limited to a thermal head, but also a laser beam (for example, a semiconductor laser), an infrared flash,
A known device such as a thermal pen can be used.

In the present invention, by combining the thermal transfer dye-providing material with the thermal transfer image-receiving material, images can be printed using various thermal printing printers, facsimiles, or images by magnetic recording, magneto-optical recording, optical recording, etc. It can be used to create prints from TV, CRT screens, etc. For details of the thermal transfer recording method, reference can be made to the description in JP-A-60-34895.

[0078]

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

<Example 1> (Preparation of thermal transfer dye-providing material (A)) A 4.5 μm thick polyethylene terephthalate film (Lumirror: manufactured by Toray Industries) with a heat-resistant slipping layer made of a thermosetting acrylic resin on one side. was used as a support, and a coating composition (A) for forming a thermal transfer dye-providing layer having the following composition was coated with a wire bar on the side opposite to the side on which the heat-resistant slipping layer was provided, so that the thickness after drying was 2 μm. A slipping layer containing 0.45 g/m2 of polyvinyl butyral (Butvar 76: manufactured by Monsanto) and 0.3 g/m2 of poly(vinyl stearate) was formed on the back side of the support from a tetrahydrofuran solution. Coated with thermal transfer dye-providing material (A)
I got it. Coating composition for forming thermal transfer dye-donating layer (A) Dye (said dye M-4)
2.5 parts
Polyvinyl butyral resin (S-LEX BX-1:
Sekisui Chemical) 2.5 parts Polyisocyanate (KP-
90: Dainippon Ink Chemical Co., Ltd.) 0.1 part Silicone oil (KF-857: Shin-Etsu Silicone Co., Ltd.) 0.004 part Methyl ethyl ketone
70 parts toluene

30 copies

(Preparation of porous layer coating composition) Cellulose acetate A (degree of acetylation 60%)
25.9g
Cellulose acetate B (〃 57%)
17.3g
methylene chloride

653 g methanol

125 g water


28 g polyhydric alcohol 1)

x g crosslinking agent 2)

y g Inorganic filler 3)

Add the above ingredients in order while stirring well. Polyhydric alcohol 1), crosslinking agent 2), and inorganic filler 3) are shown in Table-1.

(Preparation of dye-receiving polymer emulsion A) Liquid I composition;
Gelatin (10% aqueous solution)
100g
Sodium dodecylbenzenesulfonate (5% aqueous solution) 50ml water

50ml II liquid composition; Polyester resin (1) *

30g toluene

60g
Methyl ethyl ketone

60g hot solvent (1)*

After preparing 12g II solution,
Solution II was added to Solution I while stirring, and emulsified and dispersed using a homogenizer at 15,000 rpm for 9 minutes to prepare a dye-receiving polymer emulsion A. In the above, polyester resin (1) *: Vylon 290 (manufactured by Toyobo Co., Ltd.) Heat solvent (1) *: diphenyl phthalate/dicyclohexyl phthalate = 1/1

(Preparation of dye-receiving polymer emulsion B) Liquid I composition;
Gelatin (10% aqueous solution)
100g
Sodium dodecylbenzenesulfonate (5% aqueous solution) 50ml water

50ml
II liquid composition; polyester resin (2)*
3
0g toluene

60g
Methyl ethyl ketone
60g
Heat solvent (1) *

9g Epoxy modified silicone oil (KF100T; 4.5g
Shin-Etsu Silicone) I liquid, I
After sufficiently dissolving the I solution, add the II solution into the I solution while stirring, and mix it at 15000 rpm using a homogenizer.
The emulsion was emulsified and dispersed for 9 minutes to prepare a dye-receptive polymer emulsion B.

(Preparation of coating solution for thermal transfer image-receiving material) First layer: Gelatin (10% by weight aqueous solution)
10
0g water

40ml Hardener [1,
2-bis(vinylsulfonylacetamide)etha
60ml of 4% by weight aqueous solution]
2nd layer: Dye-receiving polymer emulsion A
1
00g water

50ml third layer (outermost layer): Dye-receptive polymer emulsion B
1
00g water

50ml Fluorine-containing surfactant (1)* (5% solution)
5ml
Fluorine-containing solid fine particles (1)* Dispersion (solid content 20%)
7g In the above, fluorine-containing surfactant (1) *; C8 F17SO2
N(C3H7)CH2COOK Fluorine-containing solid fine particles (1)* Dispersion (20%): Trade name Lubron L-2 (manufactured by Daikin Industries, Ltd.)

0084
(Preparation of thermal transfer image-receiving material) The above porous layer coating composition was applied to a dry film thickness of 50 g/m2 on a support made of paper with a thickness of 180 g/m2 laminated on both sides with polyethylene in which titanium oxide was dispersed.
g/m2 and immediately dried at 30°C and 60% RH for 5 minutes, and further dried at 60°C for 5 minutes to form a porous layer. Furthermore, the above-mentioned first to third layers were applied to wet coating amounts of 20, 60, and 15 ml/m2, respectively, and dried to form thermal transfer image-receiving materials 101 to 10 as shown in Table 1.
110 was produced. In the image receiving material 110, a porous layer to which polyhydric alcohol, inorganic filler, and crosslinking agent were not added was applied. Comparative image-receiving material 111 was produced in the same manner as above except that no porous layer was applied.

The thermal transfer dye-providing material and the thermal transfer image-receiving material obtained as described above are superimposed so that the dye-providing layer and the image-receiving layer are in contact with each other, and using a thermal head from the support side of the thermal transfer dye-providing material, Thermal head output 0.25W/dot, pulse width 0.15~15msec
, printing was carried out under the conditions of a dot density of 6 dots/mm, and the magenta dye was imagewise dyed on the image receiving layer of the thermal transfer image receiving material.

(Performance evaluation) Membrane strength (adhesion strength) of porous layer
Scratches are made on the surface of the recorded image-receiving sheet with a cutter knife at intervals of 2 cm in both length and width, adhesive tape is applied to the entire surface, and it is peeled off as quickly as possible. At that time, the degree of peeling of the coating film on the image-receiving sheet was evaluated as follows. A: No peeling at all (good adhesion) B: Approximately 25% peeling C: Approximately half peeling D: Whole surface peeling (poor adhesion) Solid printing is performed with a transfer unevenness pulse width of 7 msec to produce a half-tone color on the entire surface. Transfer unevenness was evaluated. A: No unevenness at all B: Some visible unevenness C: Some unevenness The transfer density at transfer density pulse widths of 7 msec and 15 msec was measured using a Macbeth reflection densitometer, and Dhal was measured, respectively.
f, expressed as Dmax. Table 1 shows these results.
It was shown to.

[0087]

[Table 1]

[0088] Crosslinking agent *1

[0089]

[Chemical formula 16]

As is clear from Table 1, image-receiving materials 101 to 110 provided with porous layers can provide uniform and high-density images with no transfer unevenness, but none of the inorganic filler, crosslinking agent, and polyhydric alcohol Image-receiving materials 101 to 103 having a porous layer containing all three of the above, although the adhesion of the image-receiving layer is not necessarily sufficient in an image-receiving material in which even one of the three is chipped;
No. 108 showed excellent adhesion. In particular, a combination of colloidal silica/polyisocyanate/ethylene glycol is excellent.

<Example 2> Using the support (1) described later, image-receiving material coating solutions having the following compositions A, B, and C were prepared on the surface, and when the dry film thickness was composition A by wire bar coating, The first layer is 1 μm, the second layer is 6 μm, and in the case of composition B, the first layer is 1 μm, the second layer is 3 μm, and the third layer is 3 μm.
In the case of composition C, thermal transfer image-receiving materials 201 to 203 were prepared by coating to a thickness of 8 μm. Also, support (1)
After coating a porous layer thereon in the same manner as image-receiving material 103 of Example-1, image-receiving material coating liquids having the above compositions A, B, and C were prepared and applied in the same manner as above to obtain a thermal transfer image-receiving material. 2
04-206 were produced. Drying was performed at 100°C for 10 minutes.

<Image-receiving material coating liquid composition A> First layer: Gelatin (10% by weight aqueous solution)
100g
water

40ml Hardener (4% by weight aqueous solution) (same as the first layer of Example-1) 6
0ml 2nd layer: Dye-receptive polymer emulsion E
10
0g water

50ml
Fluorine-containing surfactant (1)* (5% aqueous solution, Example-1 5ml
) Fluorine-containing solid fine particles (1)*
Dispersion (solid content 20%, fruit 1g)

Same as Example 1) In the above, dye-receiving polymer emulsion E was prepared as follows. Example-1
In preparing the dye-receiving polymer emulsion A, the composition of liquid II was as follows: Polyester (Polyester TP-220; manufactured by Nippon Gosei Kagaku) 4.5 g Polyester (Chemit R-188; manufactured by Toray Industries)
4.5g polyester (Kemit K-
1294; manufactured by Toray) 4.
5g Polyester (S-LEC BLS; manufactured by Sekisui Chemical) 4.5g
toluene

60g methyl ethyl ketone

60g dicyclohexyl phthalate
1.8g dimethyl phthalate
0.9g
Carboxy-modified silicone oil (X-22-37
10; 1.8 g (manufactured by Shin-Etsu Silicone) Fatty acid ester (Unistar H476; manufactured by Daihachi Chemical) Dye-receiving polymer emulsion E was prepared in the same manner except that the amount was reduced to 1.8 g.

<Image-receiving material coating liquid composition B> First layer: Same as the first layer of image-receiving material coating liquid composition A
2nd layer: Dye-receiving substance dispersion W-1
500g
water

85ml Fluorine surfactant (1)* (5% aqueous solution, Example-
25ml Same as 1) 3rd layer: Dye-receiving substance dispersion W-2
80g
Fluorine surfactant (1)* (5
% aqueous solution, Example - 6ml
Same as 1) Fluorine-based fine particles (1)* Dispersion (solid content 20%, actual 0.8g
Same as Example-1)
water

34ml Dye-receiving substance dispersion W-
1 and W-2 were prepared as follows. (Preparation of dye-receiving substance dispersion W-1) Liquid I composition Gelatin (10 wt% aqueous solution)
20
0g PES Resin SH-2101 (solid content 30w
t%, manufactured by Takamatsu Yushi) 200g Sodium dodecylbenzenesulfonate (5wt% aqueous solution)
50ml water

80ml II
Liquid composition dicyclohexyl phthalate
1
6.5g diphenyl phthalate

6g ethyl acetate

73g silicone oil (SF8421; manufactured by Toray Silicone)
Mix liquid II into 7.5g liquid I, and add 1500 g
Emulsification and dispersion was carried out for 6 minutes at 0 rpm. (Preparation of dye-receiving substance dispersion W-2) Liquid I composition Gelatin (10 wt% aqueous solution)
80
g Water-soluble polyester (Z-455; manufactured by Goyo Kagaku) 80g Sodium dodecylbenzenesulfonate
20ml water


40ml II liquid composition dicyclohexyl phthalate
2
．． 5g C12H25OOCCH2 CH2C
OOC12H25
2.5g ethyl acetate

30g silicone oil (SF8421; manufactured by Toray Silicone)
Solution II was mixed into 1 g of solution I, and emulsified and dispersed at 15,000 rpm for 6 minutes.

<Image receiving material coating liquid composition C> Polyester resin (Vylon-280; manufactured by Toyobo Co., Ltd.)
20g methyl ethyl ketone
95ml
toluene

95ml methoxypropylene glycol
10ml polyisocyanate (
KP-90; Dainippon Ink Chemical Co., Ltd.) 1
g Fluorine-containing solid fine particles (1)* (Luburon L-
2; manufactured by Daikin) 0.4 g Silicone oil (KF-857; manufactured by Shin-Etsu Silicone)
1.0g

The structure of the support (1) is shown in Table 2 below.

[0096]

[Table 2]

(Preparation of thermal transfer dye-providing material) A heat-resistant, slippery layer made of thermosetting acrylic resin was provided on one side, and the thickness was 6 μm.
m polyester film (manufactured by Teijin) was used as a support, and on the side of this support opposite to the side on which the heat-resistant slipping layer was provided, an ink for forming a dye-donating layer having the following composition was applied in an amount of 1.2 after drying.
A dye-providing material was obtained by sequentially applying the coating in order to obtain a dye-providing material. Cyan ink composition for forming dye-donating layer Dye (said dye C-2)

3 parts polyvinyl butyral resin (Denka Butyral 5000A; 2.5 parts
Polyisocyanate (Takenate D110N; Takeda Pharmaceutical Co., Ltd.) 0.1 part Amino-modified silicone oil (KF-857; Shin-Etsu Silico Co., Ltd. 0.1 part)
004 parts) Methyl ethyl ketone

50 parts toluene

50 parts Magenta ink composition for forming a dye-donating layer Dye (the above-mentioned dye M-4)

2.5 parts polyvinyl butyral resin (S-LEX BX-1; Sekisui Chemical 2
．． Polyisocyanate (KP-90; manufactured by Dainippon Ink Chemical Co., Ltd.) 0.1 part Amino-modified silicone oil (KF-857)
0.004 parts methyl ethyl ketone

70 parts toluene

3
0 parts Yellow ink composition for forming dye-donating layer Dye (
Said dye Y-8)
5th part
ethyl cellulose

Part 3 Methyl ethyl ketone

50 parts toluene

50 copies

009
8] This dye-providing material and the previously prepared image-receiving material 201~
Thermal transfer was performed in the same manner as described in Example 1 using No. 206, and the performance was evaluated. The results are shown in Table-3.

[0099]

[Table 3]

As is clear from Table 3, whether the dye-receiving polymer, which is the composition of the image-receiving layer, is applied directly in a solvent system, emulsified and dispersed in a water-soluble binder, or even in a latex form, When a porous layer was provided, an excellent transferred image with high density and no transfer unevenness was obtained.

[0101]

According to the present invention, it is possible to obtain an image having excellent manufacturing suitability, improved adhesion to a support, and uniform high transfer density without transfer unevenness.

Claims (2)

[Claims] Claim 1. A thermal transfer image-receiving material comprising, on a support, at least one image-receiving layer for receiving a dye that migrates from a thermal transfer dye-providing material when heated to form an image, the thermal transfer image-receiving material comprising at least cellulose acetate. A thermal transfer image-receiving material characterized by having a porous layer comprising an inorganic filler, a polyhydric alcohol, and a crosslinking agent. 2. The thermal transfer image-receiving material according to claim 1, wherein the porous layer is formed using a parent solvent of cellulose acetate and a poor solvent and/or non-solvent of cellulose acetate.