JP6107329B2 - Thermal transfer image-receiving sheet and method for producing the same - Google Patents

Description

  The present invention relates to a thermal transfer image receiving sheet and a method for producing the same, and more particularly to a thermal transfer image receiving sheet comprising a substrate and a receiving layer on the substrate and a method for producing the same.

  Conventionally, various printing methods are known. Among them, the thermal diffusion type transfer method (sublimation type thermal transfer method) uses a sublimation dye as a color material, so that density gradation can be freely adjusted, and intermediate colors and gradations can be adjusted. It has excellent tone reproducibility and can form high-quality images comparable to silver halide photographs.

  This thermal diffusion transfer system is a method in which a thermal transfer ink sheet containing a dye (sublimation dye) and a thermal transfer image receiving sheet are superposed, and then the ink sheet is heated by a thermal head whose heat generation is controlled by an electrical signal. The dye in the ink sheet is transferred to the image receiving sheet to record image information. As such thermal diffusion transfer systems become widespread, the printing speed has been increased, and sufficient color density can be obtained even if the conventional thermal energy is printed using the conventional thermal transfer ink sheet and thermal transfer image receiving sheet. There are problems such as inability to obtain.

  Furthermore, there are various other problems in the thermal diffusion transfer system. For example, due to insufficient releasability of the image receiving sheet, the ink sheet sticks to the receiving layer surface of the image receiving sheet at the time of printing, and when the ink sheet is peeled off from the image receiving layer after printing, generation of peeling sound, Problems such as poor running and occurrence of peeling lines on the image have occurred.

  In general, in order to improve releasability, there are methods such as increasing the glass transition temperature (Tg) of the resin, but there is also a problem that the concentration and / or light resistance is lowered. Therefore, it has been proposed to use a thermal transfer image-receiving sheet having a receiving layer containing at least one paraffin wax dispersion and vinyl chloride latex. However, in printing in a high-temperature and high-humidity environment, the peeling sound is intense. However, depending on the composition change, there is a problem that a peeling line is generated (for example, see Patent Document 1).

  In the hard copy including the thermal transfer method, at least one paraffin wax dispersion and a vinyl chloride latex are contained in order to increase the image density of the shadow area as high as possible, and conversely to increase the image density of the highlight area. It has been proposed to use a thermal transfer image-receiving sheet having a receptive layer (see, for example, Patent Document 2). However, simply adding paraffin wax to vinyl chloride latex increases the image density in the highlight area. It was not possible to finish a soft natural image.

  In order to improve glossiness and prevent bleeding, an ink jet recording medium in which silica fine particles having a primary particle diameter of 20 nm or less are contained in the outermost surface layer has been proposed (for example, see Patent Document 3). However, the hue of the printed material is not adjusted by adjusting the components of the receiving layer. Therefore, the development of a thermal transfer image-receiving sheet that can control the hue of printed matter while controlling the hue of the printed matter while maintaining the releasability at the time of printing in high temperature and high humidity environment and the density of the printed matter produced. Longed for.

JP 2008-6789 A JP 2011-073340 A Japanese Patent No. 4357403

  As a result of examining the above-mentioned background art, the inventors of the present invention have to increase the glass transition temperature of the resin from the viewpoint of heat resistance, particularly in the development of a thermal transfer image-receiving sheet using an aqueous coating solution. It was found that the film formation of the receiving layer was hindered. Since the receiving layer does not form a film, the releasability, adhesion and the like are deteriorated. On the other hand, in general, a material having a low glass transition temperature is added to assist film formation. However, in a thermal transfer image receiving sheet, fusion occurs when the thermal transfer image receiving sheet and the thermal transfer ink sheet are peeled off due to high heat. I learned the problem of being easy to do.

  The present invention has been made in view of the above-mentioned background art and newly discovered problems, and its purpose is to maintain the releasability at the time of printing in a high-temperature and high-humidity environment and the concentration of the produced printed matter while maintaining abnormalities. Another object of the present invention is to provide a thermal transfer image-receiving sheet and a method for producing the same, which can suppress the occurrence of transfer and adjust the hue of a printed material.

  As a result of intensive studies to solve the above problems, the present inventors have combined a specific vinyl acetate resin and a specific polyester resin in a receiving layer in a thermal transfer image-receiving sheet having a specific layer configuration. It discovered that the said subject could be solved by making it contain. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention,
A thermal transfer image receiving sheet comprising a substrate and a receiving layer on the substrate,
There is provided a thermal transfer image-receiving sheet, wherein the receptor layer comprises a vinyl acetate resin having a glass transition temperature of 50 to 90 ° C and a polyester resin having a glass transition temperature of 35 to 120 ° C.

  In the embodiment of the present invention, the polyester resin is preferably a water-soluble polyester resin.

  In the embodiment of the present invention, it is preferable that the receiving layer further comprises a silicone release agent.

  In the embodiment of the present invention, it is preferable that a hollow layer having hollow particles is further provided between the base material and the receiving layer.

According to another aspect of the invention,
A method for producing a thermal transfer image-receiving sheet, comprising a substrate and a receiving layer on the substrate,
Including a step of forming a receiving layer using an aqueous dispersion coating liquid comprising a vinyl chloride resin having a glass transition temperature of 50 to 90 ° C. and a polyester resin having a glass transition temperature of 35 to 120 ° C. A method for producing a thermal transfer image receiving sheet is provided.

  In another aspect of the present invention, the aqueous dispersion coating solution preferably does not contain an organic solvent.

  According to the thermal transfer image-receiving sheet of the present invention, while maintaining the releasability at the time of printing in a high-temperature and high-humidity environment and the density of the produced printed material, the occurrence of abnormal transfer is suppressed and the hue of the printed material is adjusted to adjust the blue color. Can be seasoned.

1 is a schematic cross-sectional view showing an embodiment of a thermal transfer image receiving sheet according to the present invention. It is the schematic cross section which showed other embodiment of the thermal transfer image receiving sheet by this invention.

Thermal transfer image-receiving sheet The thermal transfer image-receiving sheet of the present invention has a base material and a receiving layer on the base material, and the receiving layer contains a specific vinyl acetate resin and a specific polyester resin. Is. In a preferred embodiment, the thermal transfer image-receiving sheet may further have a hollow layer between the substrate and the receiving layer, and may further have a primer layer or an intermediate layer between the hollow layer and the receiving layer. You may further have a back layer on the surface on the opposite side. Hereinafter, the structure of the thermal transfer image receiving sheet of the present invention will be described with reference to the drawings.

  According to one aspect of the present invention, there is provided a thermal transfer image receiving sheet having a receiving layer on a substrate. According to another aspect of the present invention, there is provided a thermal transfer image receiving sheet comprising, on a base material, two hollow layers, a primer layer, and a receiving layer in this order. Specifically, schematic sectional views of one embodiment of the thermal transfer image receiving sheet according to the present invention are shown in FIGS. A thermal transfer image receiving sheet 1 shown in FIG. 1 has a base material 2 and a receiving layer 3 formed on the base material 2. A thermal transfer image receiving sheet 10 shown in FIG. 2 includes a base material 11, a hollow layer A (lower layer) 12, a hollow layer B (upper layer) 13, a primer layer 14, and a receiving layer 15 on the base material 11. In this order. Hereinafter, each layer constituting the thermal transfer image receiving sheet of the present invention will be described.

Base material The base material in the present invention has a role of holding the hollow layer and the receiving layer, and heat is applied at the time of thermal transfer, so that it has mechanical strength that does not hinder handling even in a heated state. A material is preferred.

  Examples of the base material include condenser paper, glassine paper, sulfuric acid paper, high-size paper, synthetic paper (polyolefin-based, polystyrene-based), high-quality paper, art paper, coated paper, and resin-coated paper. , Cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, or polyester, polyacrylate, polycarbonate, polyurethane, polyimide, polyether Imide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, Examples include polyethersulfone, tetrafluoroethylene, perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene / ethylene, tetrafluoroethylene / hexafluoropropylene, polychlorotrifluoroethylene, and polyvinylidene fluoride. A white opaque film formed by adding a white pigment or a filler to these synthetic resins can also be used, and is not particularly limited. Moreover, the laminated body by the arbitrary combinations of the said base material can also be used. Examples of typical laminates include cellulose fiber paper and synthetic paper, or synthetic paper of cellulose synthetic paper and a plastic film. In this invention, a commercially available base material can also be used, for example, RC paper (Mitsubishi Paper Co., Ltd. make, brand name) etc. are preferable. The base material thickness can be appropriately changed according to the strength and heat resistance required for the thermal transfer image-receiving sheet and the material of the material employed as the base material. Specifically, the base material thickness is 50 μm. It is preferable to be within a range of ˜1000 μm, and it is more preferable to be within a range of 100 μm to 300 μm.

Receiving layer The receiving layer in the present invention receives the sublimation dye transferred from the thermal transfer ink sheet during image formation by thermal transfer, and holds the received sublimation dye in the receiving layer, whereby an image is formed on the surface of the receiving layer. Can be formed and maintained. The receptor layer contains a vinyl acetate resin (vinyl chloride-vinyl acetate copolymer) having a glass transition temperature of 50 to 90 ° C. as a binder resin and a polyester resin having a glass transition temperature of 35 to 120 ° C. . By combining a vinyl chloride-based resin having a specific glass transition temperature and a polyester resin into a receiving layer, the hue can be adjusted and bluish. A silicone release agent, a urethane associative thickener, a wax additive, and an epoxy crosslinking agent may be further included. According to a preferred embodiment, the receiving layer may further contain a surfactant or the like according to various purposes.

  The glass transition temperature (Tg) of the vinyl chloride-based resin contained in the receiving layer is 50 to 90 ° C, preferably 55 to 88 ° C, and more preferably 60 to 85 ° C. If the glass transition temperature of the vinyl chloride-based resin is in the above range, the heat resistance of the resin forming the receptor layer is increased, and thus the mold releasability can be improved. The glass transition temperature (Tg) can be measured in accordance with JIS K7121. In the present invention, a commercially available vinyl chloride resin can be used. For example, Viniblanc 900, 985, and 603 (manufactured by Nisshin Chemical Co., Ltd.) are preferable.

  The glass transition temperature (Tg) of the polyester resin contained in the receiving layer is 35 to 120 ° C, preferably 35 to 90 ° C, more preferably 40 to 65 ° C, and still more preferably 50 to 65 ° C. It is. If the glass transition temperature of the polyester resin is in the above range, the hue can be adjusted to make it more bluish. Tg can be measured according to JIS K7121.

  The present invention is not limited to any theory, but it is presumed that the mechanism that can adjust the bluish color of the printed matter with the polyester resin is as follows. However, it goes without saying that the present invention should not be limited by the following description. The present inventors can moderately suppress the dyeing of the yellow dye to the receiving layer by adding a polyester resin to the receiving layer of the thermal transfer image-receiving sheet in low to medium density gray printing. I found the amazing effect. In addition, in medium to high density gray prints, the surprising effect that the dyeing of the cyan dye to the receptor layer can be improved moderately by adding a polyester resin to the receptor layer of the thermal transfer image receptor sheet. Also found out. By using the thermal transfer image receiving sheet of the present invention, it is possible to make gray bluish preferable in all density regions.

  Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate. The polyester resin is preferably a water-soluble polyester resin, and more preferably a water-soluble polyester resin dispersed in an aqueous solvent. The aqueous solvent may contain 1% or less of an alcohol solvent and an ether solvent. Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, and hexanol. Examples of ether solvents include alkyl ethers such as dimethyl ether, diethyl ether, and ethylene glycol monobutyl ether, and tetrahydrofuran. The polyester resin is more preferably a water-soluble polyester resin that does not contain an organic solvent.

  The content of the polyester resin is preferably 1 to 100% by mass, more preferably 10 to 50% by mass, based on the solid content of the binder resin (vinyl chloride resin) in the receiving layer. If the content of the polyester resin is in the above range, the hue can be adjusted to make it more bluish. In the present invention, a commercially available polyester resin can be used, and for example, Pluscoat Z-561, Z-565, Z-221, Z-687 and Z-730 (above, manufactured by Kyodo Chemical Co., Ltd.) are preferable. .

  As the silicone release agent contained in the receiving layer, amino-modified silicone, alcohol-modified silicone, vinyl-modified silicone, urethane-modified silicone, epoxy-modified silicone, polyester-modified silicone, polyether-modified silicone, polyester-modified silicone, acrylic-modified silicone, Examples include silicone oils such as aralkyl-modified silicones and amide-modified silicones. In the present invention, these may be mixed or polymerized using various reactions. By using such a silicone release agent, problems such as fusion between the thermal transfer ink sheet and the receiving layer of the thermal transfer image receiving sheet and a decrease in printing sensitivity during printing can be improved. In the present invention, it is particularly preferable to use epoxy-modified silicone or polyether-modified silicone.

Epoxy-modified silicone used in the present invention, the viscosity is preferably 100~10000mm ² / s, more preferably 300~9000mm ² / s, more preferably 500~6000mm ² / s, even more preferably, 1000～3000Mm ² / s. The epoxy-modified silicone has an epoxy equivalent of preferably 50 to 2000, more preferably 80 to 1800, and still more preferably 100 to 1000. The viscosity can be measured by various methods of JIS Z 8803: Viscosity of liquid-Measurement method. The epoxy equivalent (g / eq) is the molecular weight value of the epoxy crosslinking agent per functional group. By using an epoxy-modified silicone having a viscosity within the above range and / or an epoxy equivalent within the above range, the releasability at the time of printing and the heat resistance / humidity resistance of the printed material can be further improved.

  The content of the silicone release agent is preferably 1 to 20% by mass, more preferably 5 to 15% by mass with respect to the solid mass of the binder resin (vinyl chloride resin) in the receiving layer. When the content of the silicone release agent is within the above range, it is possible to further improve the releasability at the time of printing and the heat resistance and moisture resistance of the printed matter. In the present invention, a commercially available release agent may be used, and examples thereof include X22-3000T and KF410 (manufactured by Shin-Etsu Chemical Co., Ltd.). Use of such an epoxy-modified silicone is preferable from the viewpoint of combination with the binder resin. Examples of commercially available polyether-modified silicones that can be used include KF351, KF352, KF354, KF615, X-22-6008, KF-6004 (Shin-Etsu Chemical).

The urethane associative thickener contained in the receiving layer has a viscosity when measured at a liquid temperature of 25 ° C. according to JIS Z8803 using a B-type viscometer when the solid concentration is 30%. , Preferably it is 1000-100000 mPa * s, More preferably, it is 2000-60000 mPa * s. Furthermore, the viscosity ratio is the following formula (1):
Viscosity ratio = V _30,6 / V _30,60 (1)
_{(Wherein, V 30,6} by using a B-type viscometer, in conformity with JIS Z8803, a viscosity (mPa.s) when the rotational speed 6rpm at a liquid temperature 25 ° _{C., V 30, 60} is B Using a viscometer, the viscosity (mPa.s) at a liquid temperature of 25 ° C. and a rotational speed of 60 rpm is shown in accordance with JIS Z8803)
And is preferably 2.0 to 5.0, more preferably 2.0 to 4.5. This viscosity ratio is generally called a thixotropy index (TI) and is an index that correlates with sagging difficulty. By using a urethane associative thickener with a viscosity and a viscosity ratio in the above range, it gives leveling viscosity to the coating solution for the receiving layer, improves surface quality, and exists in the form of particles. Binders are bound together to form a film, and heat fusion during image printing can be suppressed.

  The content of the urethane associative thickener is preferably 1 to 10% by mass, more preferably 2 to 5% by mass, based on the solid content of the binder resin (vinyl acetate resin) in the receiving layer. When the content of the urethane associative thickener is within the above range, the receptor layer can be sufficiently formed, and heat fusion during image printing can be suppressed. In the present invention, a commercially available urethane associative thickener can also be used. For example, UH-450, UH-526, UH-530, UH-540, UH-550 (above, manufactured by ADEKA Corporation), SN thickener A812 (manufactured by San Nopco) is preferable.

  Examples of the wax additive contained in the receiving layer include carnauba wax and paraffin wax, and these may be used alone or in combination. In the present invention, the carnauba wax includes natural carnauba wax and purified products and derivatives thereof, including those modified with additives and the like. According to a preferred embodiment, the melting point of carnauba wax is 80 to 90 ° C., the acid value is 10 mg · KOH / g or less, and the saponification value is 78 to 88 mg · KOH / g. The paraffin wax includes natural paraffin wax and purified products and derivatives thereof, and those modified with additives and the like. The melting point of the paraffin wax is preferably 40 to 105 ° C, more preferably 40 to 90 ° C, and further preferably 40 to 75 ° C.

  The epoxy crosslinking agent contained in the receiving layer preferably has an epoxy equivalent of 300 or less, more preferably 100 or more and 200 or less, and the number of functional groups is preferably 2 or more, more preferably 4 or more and 10 or less. Is used. By using such an epoxy crosslinking agent, the releasability and bleeding resistance of the thermal transfer image receiving sheet are further improved, and the hue of the printed material can be more easily adjusted.

  It is also preferable to use two or more epoxy crosslinking agents in combination. As such, for example, an epoxy crosslinking agent having a functional group number of 4 or more and 10 or less and an epoxy crosslinking agent having a functional group number of 2 or more and less than 4 can be used in combination. For example, an epoxy crosslinking agent having an epoxy equivalent of 100 or more and 200 or less and an epoxy crosslinking agent having an epoxy equivalent of 200 or more and 300 or less can be used in combination. By using these epoxy crosslinking agents in combination, the releasability and bleeding resistance of the thermal transfer image receiving sheet can be further improved.

  In addition, an epoxy equivalent (g / eq) is a value of the molecular weight of the epoxy crosslinking agent per functional group. Moreover, the functional group number is the number of epoxy groups in one molecule of the epoxy crosslinking agent. That is, it can be said that the smaller the epoxy equivalent and the greater the number of functional groups, the higher the crosslinking effect as a crosslinking agent.

  The content of the epoxy crosslinking agent crosslinking agent is preferably 1 to 30% by mass, more preferably 1 to 15% by mass, and even more preferably 1 to 10% by mass, based on the solid content mass of the binder resin in the receiving layer. %. When the content of the crosslinking agent is in the above range, the release property and bleeding resistance of the thermal transfer image-receiving sheet are further improved, and the hue of the printed material can be more easily adjusted. In the present invention, a commercially available epoxy crosslinking agent can also be used, and examples thereof include EX512, EX521, EX851, EX832 (above, Nagase ChemteX Corporation), CR5L (DIC Corporation), and the like.

Other Layers The thermal transfer image-receiving sheet of the present invention may further have other layers other than the receiving layer. In a preferred embodiment, the thermal transfer image-receiving sheet may further have other layers such as a hollow layer, a primer layer, and an intermediate layer on the receiving layer side. Moreover, it can have a back surface layer on the opposite side to a receiving layer.

Hollow layer The hollow layer in the present invention has a heat insulating property that can prevent heat applied during image formation by thermal transfer from being lost due to heat transfer to a substrate or the like. In a preferred embodiment, the hollow layer contains hollow particles and may further contain a hydrophilic binder and other additives. According to a preferred embodiment, the hollow layer may be composed of two or more layers. A hollow layer is provided with cushioning properties by including hollow particles. Here, the degree of cushioning property of the hollow layer can be appropriately adjusted according to the application of the thermal transfer image receiving sheet. The degree of cushioning property of the hollow layer can also be adjusted to an arbitrary range by changing the thickness of the hollow layer, for example. The thickness of the hollow layer is not particularly limited as long as the heat insulating property, cushioning property and the like can be adjusted to a desired level, but preferably in the range of 10 μm to 100 μm, and in the range of 10 μm to 50 μm. More preferably, it is within. The density of the hollow layer, for example in the range of ^{0.1g / cm 3 ~0.8g / cm 3} , preferably in the range of inter alia ^{0.2g / cm 3 ~0.7g / cm 3} .

  The average particle diameter of the hollow particles used in the present invention is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm. If the average particle diameter of the hollow particles is in the above range, heat insulation and cushioning properties can be imparted to the hollow layer. In the present invention, the volume average particle diameter of the hollow particles can be measured by a conventionally known method such as the Coulter method (Sysmex FPIA-3000 by Malvern). The average hollowness of the hollow particles is preferably 20% or more, more preferably 30 to 80%. If the average hollowness of the hollow particles is in the above range, heat insulation and cushioning properties can be imparted to the hollow layer. Furthermore, the organic hollow particle comprised from resin etc. may be sufficient, and the inorganic hollow particle comprised from glass etc. may be sufficient. The hollow particles may be cross-linked hollow particles. In the present invention, commercially available hollow particles can also be used. For example, Ropeke HP-1055, Ropeke HP-91, Ropeke OP-84J, Ropeke Ultra and Ropeke SE (manufactured by Rohm and Haas Co., Ltd.), Nipol MH-5055 (Nippon Zeon Corporation), SX8782 and SX866 (JSR Corporation) are preferred.

Primer layer The primer layer in the present invention has a role of satisfactorily adhering the hollow layer and the receiving layer, and prevents image migration to the hollow layer side in a high-temperature and high-humidity environment, thereby improving image storage stability. It has a function. In a preferred embodiment, the primer layer contains hollow particles, a resin, and a hydrophilic binder, and the resin preferably contains an acrylic resin. Although it does not specifically limit as thickness of a primer layer, For example, it is preferable that they are 1 micrometer-40 micrometers, 1 micrometer-20 micrometers are more preferable, and 1 micrometer-10 micrometers are more preferable.

  In the present invention, the acrylic resin refers to a polymer of acrylic acid or methacrylic acid monomer or derivative thereof, a polymer of acrylic acid ester or methacrylic acid ester monomer or derivative thereof, acrylic acid or methacrylic acid monomer and other derivatives. It includes a copolymer with a monomer or a derivative thereof, and a copolymer of a monomer of an acrylate ester or a methacrylate ester with another monomer or a derivative thereof.

  According to a preferred embodiment of the present invention, the acrylic resin is preferably a copolymer of an acrylic ester or methacrylic ester monomer and another monomer or a derivative thereof. Examples of the acrylic acid ester or methacrylic acid ester monomer include alkyl acrylate and alkyl methacrylate, preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, lauryl acrylate, and lauryl methacrylate. Can be mentioned. Examples of other monomers include aromatic hydrocarbons, aryl group-containing compounds, amide group-containing compounds, and vinyl chloride, preferably styrene, benzylstyrene, phenoxyethyl methacrylate, acrylamide, and methacrylamide. it can. In the present invention, a copolymer of an alkyl acrylate or an alkyl methacrylate and at least one other monomer selected from the group consisting of an aromatic hydrocarbon, an aryl group-containing compound, and an amide group-containing compound, or a derivative thereof. It is particularly preferable to use it. By copolymerizing the monomers as described above, the concentration and releasability can be improved. Two or more acrylic resins may be mixed and used.

  According to a preferred embodiment of the present invention, the hydrophilic binder contained in the hollow layer or primer layer described above includes gelatin and derivatives thereof, polyvinyl alcohol, polyethylene oxyside, polyvinyl pyrrolidone, pullulan, carboxymethyl cellulose, hydroxyethyl cellulose, Examples include dextran, dextrin, polyacrylic acid and salts thereof, agar, κ-carrageenan, λ-carrageenan, ι-carrageenan, casein, xanthene gum, locust bean gum, alginic acid, and gum arabic, with gelatin being particularly preferred. By using such a hydrophilic binder, interlayer adhesion of each layer can be improved. In particular, when each layer is formed by an aqueous coating method and a simultaneous multilayer coating method, by using gelatin, the viscosity of each coating solution can be adjusted to a desired range, and a desired film thickness can be obtained. In the present invention, commercially available gelatin can also be used. For example, RR, R, CLV, and N1236 (manufactured by Nitta Gelatin Co., Ltd.) are preferable.

Intermediate Layer In the present invention, at least one intermediate layer may be provided between the hollow layer and the primer layer or between the primer layer and the receiving layer. By providing an intermediate layer, functions such as solvent resistance, dye diffusion barrier during image storage under high temperature / high humidity, interlayer adhesion, white color imparting, glare / unevenness of the substrate, and antistatic functions are added. Can do. As a method for forming the intermediate layer, known means can be used. For example, an optical brightener, inorganic fine particles, hollow fine particles, and an organic conductive material such as a conductive filler or polyaniline sulfonic acid are added to the intermediate layer. The method of doing is mentioned.

Back layer The back layer in the present invention has the fixability of ink used in an ink jet method, a dot impact method, a writing instrument, and the like, and enables a back print excellent in quick-drying with less bleeding of the recording portion ( To improve the backprint suitability). Furthermore, it also has the basic characteristics as the image receiving paper back side described below.
1. When superposed on the receiving layer surface, no sticking (blocking) occurs even if it is stored under a temperature or load.
2. Even when the paper is mistakenly mounted on the printer with the front and back sides reversed, and the thermal transfer sheet is superposed on the thermal transfer sheet, it will stick to the thermal transfer sheet and will not clog in the printer, and the printed matter will be discharged. (Has back surface releasability).
3. Even if it rubs against the receiving layer surface, the receiving layer surface is not damaged, and the particle component does not fall off (powder off) from the back layer.
The back layer preferably contains a binder resin and inorganic fine particles, and other additives such as an antifoaming agent and an antistatic agent can be appropriately added to the back layer. In recent years, a water-based coating method is preferred from the viewpoint of environmental considerations, but the back layer of the present invention can be particularly suitably used as the back surface of an image receiving paper on which a receiving layer is formed by a water-based coating method.

  The binder resin contained in the back layer is preferably at least one selected from the group consisting of styrene / acrylic resins, polyester resins, polyurethane resins, and acrylic resins. By using such a binder resin, it is possible to have good adhesion to the base material and good backprint suitability. In the present invention, a commercially available binder resin can also be used, such as Bironal MD 1500 (manufactured by Toyobo Co., Ltd.), Plus Coat Z690 (manufactured by Kyoyo Chemical Co., Ltd.), Superflex 130 (Daiichi Kogyo Seiyaku ( Etc.) are preferable.

  The inorganic fine particles contained in the back layer are at least one selected from the group consisting of colloidal alumina, colloidal silica, and silica particles. By using such inorganic fine particles, it is possible to improve the backprint suitability and prevent blocking.

In the present invention, but are not coating amount of the back layer is particularly limited, it is preferable that the coating amount is in the range of drying after ^{0.1g / m 2 ~3.0g / m 2} , 0.3g / More preferably, it is in the range of m ^{2 to} 1.5 g / m ² . If the coating amount is in the above range, sufficient back print suitability can be obtained.

Method for Producing Thermal Transfer Image-Receiving Sheet A method for producing a thermal transfer image-receiving sheet according to the present invention is a method for producing a thermal transfer image-receiving sheet comprising a base material and a receiving layer on the base material, and glass having a temperature of 50 to 90 ° C. The method includes a step of forming a receiving layer using an aqueous dispersion coating liquid containing a binder resin having a transition temperature and a polyester resin having a glass transition temperature of 35 to 120 ° C. The polyester resin is preferably a water-soluble polyester resin. Moreover, it is more preferable that the aqueous dispersion coating liquid does not contain an organic solvent. By not containing an organic solvent, the stability of the aqueous dispersion coating liquid can be improved. In addition, an organic solvent is not specifically limited, A conventionally well-known organic solvent, for example, alcohols and ethers, is mentioned.

  In the present invention, it is preferable that all layers constituting the surface side having the receiving layer are formed by aqueous coating, preferably by aqueous coating and simultaneous multilayer coating. For the application of each layer of the thermal transfer image-receiving sheet, known methods such as roll coating, bar coating, gravure coating, gravure reverse coating, die coating, slide coating, and curtain coating can be used. A method in which a plurality of layers such as a slide coat and a curtain coat can be applied simultaneously in multiple layers is preferred. By such a manufacturing method, effects such as improvement in interlayer adhesion of each layer of the thermal transfer image-receiving sheet and cost improvement can be obtained.

Aqueous dispersion coating liquid The aqueous dispersion coating liquid used for forming the receiving layer in the present invention can be obtained by dispersing (emulsifying) a binder resin, a polyester resin, and a silicone release agent in water by a known method. . For example, the aqueous dispersion coating liquid can be prepared by mixing a wax additive in the state of an aqueous dispersion and another aqueous dispersion. First, an aqueous dispersion and a solvent-based solution are prepared separately. The aqueous solution is obtained by mixing the above emulsifier and water. On the other hand, the solvent-based solution is obtained by mixing a wax additive and a known organic solvent (solvent). The solvent-based solution can also be obtained by heating and melting wax. From the viewpoint that it is not necessary to remove the organic solvent when preparing the wax additive, it is preferable to heat and melt the wax to obtain an organic solution. In terms of being able to prepare an organic solution at a lower temperature, it is preferable to use a (small amount) of an organic solvent. The aqueous solution and the solvent solution are mixed and stirred, and then dispersed using a homogenizer to prepare a dispersion. Thereafter, the solvent is removed under reduced pressure while heating the dispersion to 30 to 60 ° C., the volume change of the solvent is corrected by adding pure water, and the solid content is prepared to obtain an aqueous dispersion. It is done.

  In the present invention, the “aqueous solution” is a solution using water as a medium, and the “solvent solution” is a solution using an organic solvent as a medium. The organic solvent used for the preparation of the solvent-based solution is not particularly limited as long as it can dissolve the dye. Ethyl acetate, aromatic hydrocarbon solvents such as toluene and benzene, ketone solvents such as acetone and methyl ethyl ketone, and mixtures thereof Those selected from the group consisting of: By using such an organic solvent, it is possible to increase dispersibility and maintain an appropriate dispersion state with water. Thereby, an aqueous dispersion coating solution for the receiving layer can be obtained. In this invention, you may put the process of removing an organic solvent by means, such as a heating and / or pressure reduction, after dispersion | distribution or simultaneously with dispersion | distribution.

Thermal transfer ink sheet The thermal transfer ink sheet used together with the thermal transfer image-receiving sheet of the present invention is provided with a heat transferable color material layer on one side of the base sheet and a heat resistant slipping layer on the other side of the base sheet. It is preferable to have a layer structure. Hereinafter, each layer constituting the thermal transfer ink sheet will be described.

As the material of the base sheet constituting the thermal transfer ink sheet used in the present invention, a conventionally known material can be used, and even if it is other than that, it has a certain degree of heat resistance and strength. Can be used. For example, polyethylene terephthalate, polyester, polypropylene, polycarbonate, polyethylene, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyimide, nylon, cellulose acetate, ionomer and other resin films, condenser paper, paraffin paper, and other non-woven fabrics Etc. These may be used alone, or a laminate in which these are arbitrarily combined may be used. Among these, polyethylene terephthalate which is a versatile plastic that can be thinned and is inexpensive is preferable.

  The thickness of the base sheet can be appropriately selected according to the material so that the strength, heat resistance and the like are appropriate, but is usually preferably about 0.5 to 50 μm, more preferably 1 to 20 μm, and further Preferably it is 1-10 micrometers.

  The base sheet may be subjected to a surface treatment in order to improve adhesion with an adjacent layer. As the surface treatment, known resin surface modification techniques such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, and grafting treatment are applied. can do. Only one type of the surface treatment may be applied, or two or more types may be applied.

  Furthermore, it is also possible to apply and form an adhesive layer on the base sheet as an adhesive treatment of the base sheet. An adhesion layer can be formed from the following organic materials and inorganic materials, for example. Examples of the organic material include polyester resins, polyacrylate resins, polyvinyl acetate resins, polyurethane resins, styrene acrylate resins, polyacrylamide resins, polyamide resins, polyether resins, polystyrene resins, Examples thereof include polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyvinyl pyrrolidone and vinyl resins such as modified products thereof, and polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral. Examples of the inorganic material include silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate, suspicion bakumaite, etc.), aluminum silicate, magnesium silicate, magnesium carbonate, oxidation Examples thereof include ultrafine particles of colloidal inorganic pigments such as magnesium and titanium oxide.

  Moreover, when manufacturing a plastic film by extending | stretching as said surface treatment, a primer liquid can be apply | coated to an unstretched film and it can also carry out by extending | stretching after that (primer process).

Thermal transferable color material layer The thermal transfer ink sheet used in the present invention is provided with a thermal transferable color material layer on one surface of a substrate sheet. When the thermal transfer ink sheet is a sublimation type thermal transfer ink sheet, a layer containing a sublimation dye is formed as the thermal transferable color material layer, and when the thermal transfer type thermal transfer ink sheet is a hot melt composition containing a colorant A layer containing a heat-meltable ink is formed. A layer region containing a sublimable dye and a layer region containing a heat-meltable ink composed of a heat-melting composition containing a colorant are provided in a surface sequence on a continuous base sheet. Also good.

  As the material of the heat transferable color material layer, conventionally known dyes can be used, but those having good characteristics as a printing material, for example, having a sufficient coloring density and changing color due to light, heat, temperature, etc. Preferred are diarylmethane dyes, triarylmethane dyes, thiazole dyes, merocyanine dyes, pyrazolone dyes, methine dyes, indoaniline dyes, acetophenone azomethine, pyrazoloazomethine, imidazolazomethine, imidazoazomethine, pyridone Azomethine dyes such as azomethine, xanthene dyes, oxazine dyes, cyanostyrene dyes such as dicyanostyrene and tricyanostyrene, thiazine dyes, azine dyes, acridine dyes, benzeneazo dyes, pyridoneazo, thiophenazo, iso Thiazoleazo, pyro Azo dyes such as ruazo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo, and disazo, spiropyran dyes, indolinospiropyran dyes, fluorane dyes, rhodamine lactam dyes, naphthoquinone dyes, anthraquinone dyes, quinophthalone dyes And dyes. Specifically, as a red dye, MS Red G (manufactured by Mitsui Toatsu Chemical Co., Ltd.), Macrolex Red Violet R (manufactured by Bayer), CeresRed 7B (manufactured by Bayer), Samaron Red F3BS (manufactured by Mitsubishi Chemical), etc. Is mentioned. Examples of yellow dyes include Holon Brilliant Yellow 6GL (manufactured by Clariant), PTY-52 (manufactured by Mitsubishi Kasei), Macrolex Yellow 6G (manufactured by Bayer), and the like. As blue dyes, Kayaset Blue 714 (manufactured by Nippon Kayaku Co., Ltd.), Waxoline Blue AP-FW (manufactured by ICI), Holon Brilliant Blue SR (manufactured by Sand Corporation), MS Blue 100 (Mitsui Toatsu Chemical Co., Ltd.) Manufactured), C.I. I. Solvent Blue 22 etc. are mentioned. In addition, the dye contained in the ribbon used by the sublimation type thermal transfer system marketed can also be used.

  Examples of the binder resin for supporting the dye include cellulose resins such as ethyl cellulose resin, hydroxyethyl cellulose resin, ethyl hydroxy cellulose resin, methyl cellulose resin, and cellulose acetate resin, polyvinyl alcohol resin, polyvinyl acetate resin, and polyvinyl butyral resin. And vinyl resins such as polyvinyl acetal resin and polyvinyl pyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, and polyester resins. Among these, cellulose-based, vinyl-based, acrylic-based, polyurethane-based, and polyester-based resins are preferable from the viewpoints of heat resistance, dye transferability, and the like.

  Examples of the method for forming the heat transferable color material layer include the following methods. For the heat-transferable colorant layer obtained by adding additives such as a release agent to the dye and binder resin as necessary, dissolving in an appropriate organic solvent such as toluene and methyl ethyl ketone, or dispersing in water. A coating solution (dissolved solution or dispersion) is applied to one surface of a substrate sheet by, for example, a gravure printing method, a reverse roll coating method using a gravure plate, a roll coater, a bar coater, etc., and dried. Can be formed. The heat transferable color material layer has a thickness of about 0.2 to 5.0 μm, and the content of the sublimable dye in the heat transferable color material layer is 5 to 90% by mass, preferably 5 to 70% by mass. It is preferable that

Protective layer The thermal transfer ink sheet used in the present invention may be provided with a protective layer in the surface order on the same side as the thermal transferable color material layer. After the color material is transferred to the thermal transfer image-receiving sheet, the protective layer is transferred to cover the image, whereby the image can be protected from light, gas, liquid, abrasion and the like. Other layers such as an adhesive layer, a release layer, or an undercoat layer may be provided as a protective layer.

Heat-resistant slip layer The heat-resistant slip layer is mainly composed of a heat-resistant resin. The heat resistant resin is not particularly limited. For example, polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, polyether resin, polybutadiene resin, styrene-butadiene copolymer resin, Acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, cellulose acetate-hydrodiene Phthalate resin, cellulose acetate resin, aromatic polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, Fine chlorinated polyolefin resins.

  The heat resistant slipping layer may be formed by blending additives such as a slipperiness imparting agent, a crosslinking agent, a release agent, an organic powder, and an inorganic powder in addition to the above heat resistant resin.

  In general, the heat-resistant slipping layer is prepared by adding the above-mentioned heat-resistant resin and the above-mentioned slipperiness-imparting agent and additives that are optionally added to the solvent, and dissolving or dispersing each component to form a heat-resistant slipping layer coating solution. After the preparation, the heat resistant slipping layer coating solution can be applied on a substrate and dried. As the solvent in the heat resistant slipping layer coating solution, the same solvents as those in the dye ink can be used.

Examples of the coating method of the heat resistant slipping layer coating liquid include wire bar coating, gravure printing, screen printing, reverse roll coating using a gravure plate, and gravure coating is particularly preferable. Heat-resistant slip layer coating solution, dry coating amount is preferably 0.1 to 3 g / ^{m 2,} more preferably may be applied so as to be 1.5 g / ^{m 2} or less.

Image Forming Method In the image forming method using the thermal transfer image receiving sheet of the present invention, the thermal transfer image receiving sheet and the thermal transfer ink sheet containing a heat diffusible dye are overlaid and heated in accordance with a recording signal, thereby transferring the thermal transfer image. An image can be formed by transferring the thermal diffusible dye contained in the ink sheet to the thermal transfer image-receiving sheet.

  As a thermal transfer recording apparatus that can be used in such an image forming method, a known apparatus can be used and is not particularly limited. In the present invention, a commercially available thermal transfer recording apparatus can be used, and examples thereof include a sublimation thermal transfer printer (manufactured by ALTECH ADS (model: MEGAPICEL III), manufactured by DNP Photo Lucio (model: DS40)).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In addition, the mass part of description described was described by solid content, and it diluted with the pure water as needed.

Example 1
Using RC paper (manufactured by Mitsubishi Paper Industries Co., Ltd.) as a base material for producing the thermal transfer image-receiving sheet 1, the coating liquid for the hollow layer A, the coating liquid for the hollow layer B, the coating liquid for the primer layer, and the coating for the receiving layer having the following composition Liquid 1 was heated to 40 ° C., and using slide coating, the coating amounts after drying were 2.0 g / m ² , 3.0 g / m ² , 3.0 g / m ² , 3.0 g / m ^{2, respectively.} After coating at the same time, cooling at 5 ° C. for 30 seconds, drying at 50 ° C. for 2 minutes, and thermal transfer image-receiving sheet 1 (layer constitution: substrate / hollow layer A / hollow layer B / primer layer / Receptor layer) was obtained. The coating speed was 20 m / min. This thermal transfer image-receiving sheet had a layer structure as shown in FIG.
Composition of coating liquid for hollow layer A (for lower layer) Hollow particles (volume average particle size: 0.5 μm, average hollow ratio: 45%, manufactured by Rohm and Haas Co., Ltd., trade name: Ropeke ST) 55 parts by mass Gelatin (made by Nitta Gelatin Co., Ltd., trade name: N1236) 26 parts by mass / binder resin (styrene / acrylic resin, made by Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B-13) 8 parts by mass / binder Resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., trade name: Jonkrill 62J) 8 parts by mass
Composition of hollow layer B coating liquid (for upper layer) Hollow particles (volume average particle size: 0.5 μm, average hollow ratio: 45%, manufactured by Rohm and Haas Co., Ltd., trade name: Ropeke ST) 59 parts by mass Gelatin (made by Nitta Gelatin Co., Ltd., trade name: N1236) 28 parts by mass / binder resin (styrene / acrylic resin, made by Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B-13) 5 parts by mass / binder Resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., trade name: Jonkrill 62J) 8 parts by mass
Composition of coating liquid for primer layer : Hollow particles (crosslinked hollow particles, volume average particle size: 0.4 μm, average hollow ratio: 39%, manufactured by Rohm and Haas Co., Ltd., trade name: OA-39) 70 parts by mass Gelatin (manufactured by Nitta Gelatin Co., Ltd., trade name: N1236) 16 parts by mass / fluorescent brightener (manufactured by Showa Chemical Industry Co., Ltd., trade name: WN-1) 4 parts by mass / binder resin (styrene / acrylic resin) New Nakamura Chemical Co., Ltd., trade name: New Coat B-13) 2 parts by mass Binder resin (styrene / acrylic resin, BASF Japan Ltd., trade name: Jonkrill 62J) 2 parts by mass
Composition of coating solution 1 for receiving layer / binder resin (vinyl chloride emulsion: PVC / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.)
70 parts by mass / polyester resin (Tg = 64 ° C., manufactured by Kyoyo Chemical Industry Co., Ltd., trade name: Pluscoat Z-561, not including organic solvent) 30 parts by mass / urethane associative thickener (viscosity: 2000, viscosity) Ratio: 3.0, manufactured by ADEKA Corporation, trade name: UH-526) 3.8 parts by weight, aqueous dispersion of release agent (silicone dispersion) 11 parts by weight, wax dispersant (Cerosol 524 Chukyo Yushi ( Ltd.) 7 parts by mass / epoxy crosslinking agent (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass The coating solution for the receiving layer is an aqueous dispersion in which the above components are dispersed in water by a known method. It is a coating solution.

Preparation of a vinyl chloride-based emulsion In a 2.5 L autoclave, 600 g of deionized water, 438.8 g of vinyl chloride monomer (97.5% by mass with respect to all charged monomers) and 11.2 g of vinyl acetate (all charged) A monomer mixture of 2.5% by mass with respect to the monomer, 2.25 g of potassium persulfate was charged. The reaction mixture was stirred with a stirring blade so as to maintain a rotation speed of 120 rpm, and the temperature of the reaction mixture was raised to 60 ° C. to initiate polymerization. 180 g of a 5% by mass aqueous sodium dodecylbenzenesulfonate solution (2% by mass with respect to all charged monomers) was continuously added until after the start of polymerization until 4 hours, and the saturated vapor pressure of the vinyl chloride monomer at a polymerization pressure of 60 ° C. Then, the polymerization was stopped when the pressure dropped from 0.6 MPa, and the remaining monomer was recovered to obtain a vinyl acetate emulsion.

Preparation of aqueous dispersion of release agent 85 g of ethyl acetate, 16 g of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-3000T) and aralkyl-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X) -24-510) 8 g was dissolved. Next, 14 g of sodium triisopropyl naphthalene sulfonate (solid content: 10%) was dissolved in 110 g of pure water. The two liquids were mixed and stirred, and then dispersed using a homogenizer to prepare a dispersion. Thereafter, ethyl acetate was removed under reduced pressure while heating the dispersion to 30 to 60 ° C. to obtain an aqueous dispersion of silicone.

Preparation of thermal transfer ink sheet 1 A 4.5 μm-thick polyethylene terephthalate film with an easy adhesion treatment was used as a base sheet, and a coating solution for a heat-resistant slipping layer having the following composition was added to 0.8 g / m ² upon drying. This was applied to form a heat-resistant slipping layer.
Composition of coating solution 1 for heat resistant slipping layer / polyvinyl acetal (Sekisui Chemical Co., Ltd., trade name: ESREC KS-1)
60.6 parts by mass / polyisocyanate (Dainippon Ink Chemical Co., Ltd., trade name: Barnock D750)
8.4 parts by mass. Silicone resin fine particles (Momentive Performance Materials Japan G.K., trade name: Tospearl 240, average particle size: 4 μm, polygonal shape) 1 part by mass. Zinc stearyl phosphate (LBT-1830 purification, Sakai Chemical Industry Co., Ltd.) 10 parts by mass, zinc stearate (SZ-PF Sakai Chemical Industry Co., Ltd.) 10 parts by mass, polyethylene wax (Polywax 3000, manufactured by Toyo Petrolite Co., Ltd.) 3 parts by mass Ethoxylated alcohol-modified wax (manufactured by Toyo Adre Co., Ltd., trade name: Unitox 750) 7 parts by mass, 200 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene

Next, a primer layer coating liquid having the following composition is applied to a part of the surface opposite to the side on which the heat-resistant slip layer of the substrate is provided, so that the dry coating amount is 0.10 g / m ² . The primer layer was formed by drying. Subsequently, a yellow color material layer coating solution, a magenta color material layer coating solution, and a cyan color material layer coating solution having the following composition are dried on the primer layer so that the amount is 0.6 g / m ² when dried. The yellow color material layer, the magenta color material layer, and the cyan color material layer were formed by coating and drying repeatedly in order.
Coating liquid for primer layer / Colloidal silica (particle diameter 4-6 nm, solid content 10%, manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex OXS) 30 parts by mass / binder resin (polyvinylpyrrolidone resin, K-90, (Made by ISP) 3 parts by weight, 50 parts by weight of water, 17 parts by weight of isopropyl alcohol

Composition of coating solution for yellow color material layer: 2.5 parts by weight of disperse dye (dispersed yellow 201) 2.5 parts by weight of disperse dye (yellow dye represented by the following chemical formula)
・ Binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
4.5 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass
Composition of coating solution for magenta color material layer / Dye represented by the following chemical formula: 2.0 parts by mass
・ Binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
4.5 parts by mass, alkyl-modified silicone oil (KF-412, manufactured by Shin-Etsu Silicone Co., Ltd.)
0.1 part by mass, polyethylene wax 0.1 part by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass
Composition of the coating solution for the cyan color material layer 2.0 parts by mass of the dye represented by the following chemical formula
・ Binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
4.5 parts by mass, alkyl-modified silicone oil (KF-412, manufactured by Shin-Etsu Silicone Co., Ltd.)
0.1 part by mass, polyethylene wax 0.1 part by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass

In addition, a protective layer coating solution having the following composition is applied to the other part of the other side of the base sheet on which the heat-resistant slipping layer is provided, so that the amount is 1.5 g / m ² when dried. Dried to form. Thereby, a heat-resistant slipping layer is provided on one surface of the base material, and a primer layer and a heat transferable color material layer (Y, M, C) are laminated in this order on a part of the other surface of the base material, A thermal transfer ink sheet 1 was obtained in which a protective layer was provided on another part of the other surface of the substrate.
Composition of coating liquid for protective layer / Acrylic resin (Mitsubishi Rayon Co., Ltd., trade name: Dianar BR-83)
69.6 parts by mass-Acrylic copolymer reactively bonded with a reactive ultraviolet absorber (trade name: UVA635L, manufactured by BASF Japan) 17.4 parts by mass-silica (manufactured by Fuji Silysia Co., Ltd., trade name: Silicia 310) 25 parts by mass, 100 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene

Example 2
Preparation of thermal transfer image-receiving sheet 2 A thermal transfer image-receiving sheet 2 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of coating solution 2 for receiving layer / Binder resin (vinyl chloride emulsion: PVC / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.) 90 parts by mass / polyester resin (Tg = 64 ° C., compatible chemistry) Kogyo Co., Ltd., trade name: Pluscoat Z-561, organic solvent not included) 10 parts by mass / urethane associative thickener (viscosity: 2000, viscosity ratio: 3.0, manufactured by ADEKA Corporation, trade name) : UH-526) 3.8 parts by weight, aqueous dispersion of release agent (silicone dispersion) 11 parts by weight, wax dispersant (Cerosol 524 Chukyo Yushi Co., Ltd.) 7 parts by weight, epoxy cross-linking agent (Nagase ChemteX) (Product name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Example 3
Preparation of thermal transfer image-receiving sheet 3 A thermal transfer image-receiving sheet 3 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of Receptive Layer Coating Liquid 3 Binder resin (vinyl chloride emulsion: PVC / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.) 70 parts by mass Polyester resin (Tg = 64 ° C., interactive chemistry Manufactured by Kogyo Co., Ltd., trade name: Pluscoat Z-565, 30 parts by mass of ethylene glycol mono-t-butyl ether as an organic solvent, urethane associative thickener (viscosity: 2000, viscosity ratio: 3.0, ADEKA) Product name: UH-526) 3.8 parts by weight, aqueous release agent dispersion (silicone dispersion) 11 parts by weight, wax dispersant (Cerosol 524 Chukyo Yushi Co., Ltd.) 7 parts by weight Epoxy crosslinking agent (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Example 4
Preparation of thermal transfer image-receiving sheet 4 A thermal transfer image-receiving sheet 4 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of Receptive Layer Coating Solution 4 Binder resin (vinyl chloride emulsion: PVC / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.) 70 parts by mass Polyester resin (Tg = 47 ° C., compatible chemistry) Manufactured by Kogyo Co., Ltd., trade name: Pluscoat Z-221, organic solvent not included) 30 parts by mass, urethane associative thickener (viscosity: 2000, viscosity ratio: 3.0, manufactured by ADEKA Corporation, trade name) : UH-526) 3.8 parts by weight, aqueous dispersion of release agent (silicone dispersion) 11 parts by weight, wax dispersant (Cerosol 524 Chukyo Yushi Co., Ltd.) 7 parts by weight, epoxy cross-linking agent (Nagase ChemteX) (Product name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Example 5
Preparation of thermal transfer image-receiving sheet 5 A thermal transfer image-receiving sheet 5 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of coating solution 5 for receiving layer / binder resin (vinyl chloride emulsion: PVC / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.) 70 parts by mass / polyester resin (Tg = 46 ° C., interactive chemistry) Manufactured by Kogyo Co., Ltd., trade name: Pluscoat Z-730, organic solvent not included) 30 parts by mass / urethane associative thickener (viscosity: 2000, viscosity ratio: 3.0, manufactured by ADEKA Corporation, trade name) : UH-526) 3.8 parts by weight, aqueous dispersion of release agent (silicone dispersion) 11 parts by weight, wax dispersant (Cerosol 524 Chukyo Yushi Co., Ltd.) 7 parts by weight, epoxy cross-linking agent (Nagase ChemteX) (Product name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Example 6
Preparation of Thermal Transfer Image Receiving Sheet 6 A thermal transfer image receiving sheet 6 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of coating solution 6 for receiving layer: Binder resin (vinyl acetate emulsion, manufactured by Nissin Chemical Industry Co., Ltd., trade name: VINYBRAN 603, Tg = 60 ° C.) 70 parts by mass / polyester resin (Tg = 64 ° C., Product name: Plus Coat Z-561, organic solvent not included) 30 parts by mass / urethane associative thickener (viscosity: 2000, viscosity ratio: 3.0, manufactured by ADEKA Corporation) Product name: UH-526) 3.8 parts by weight, water dispersion of release agent (silicone dispersion) 11 parts by weight, wax dispersant (Cerosol 524 Chukyo Yushi Co., Ltd.) 7 parts by weight, epoxy cross-linking agent (Nagase) Product name: Denacol EX512, manufactured by Chemtex Co., Ltd.
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Example 7
Preparation of thermal transfer image-receiving sheet 7 A thermal transfer image-receiving sheet 7 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of coating solution 7 for receiving layer : Binder resin (vinyl chloride emulsion: PVC / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.) 70 parts by mass Polyester resin (Tg = 110 ° C., compatible chemistry) Kogyo Co., Ltd., trade name: Plus Coat Z-687, organic solvent not included) 30 parts by mass / urethane associative thickener (viscosity: 2000, viscosity ratio: 3.0, manufactured by ADEKA Corporation, trade name) : UH-526) 3.8 parts by weight, aqueous dispersion of release agent (silicone dispersion) 11 parts by weight, wax dispersant (Cerosol 524 Chukyo Yushi Co., Ltd.) 7 parts by weight, epoxy cross-linking agent (Nagase ChemteX) (Product name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Example 8
Using RC paper (manufactured by Mitsubishi Paper Industries Co., Ltd.) as a base material for producing the thermal transfer image-receiving sheet 8, the hollow layer coating solution having the following composition and the above receiving layer coating solution 1 were heated to 40 ° C., respectively, and slide coating was performed. using the coating amount after drying respectively 10.0 g ^/ m 2, and simultaneously coated so that 3.0 g / ^{m 2,} was cooled for 30 seconds at 5 ° C., dried for 2 minutes at 50 ° C. As a result, a thermal transfer image-receiving sheet 8 (layer structure: substrate / hollow layer / receiving layer) was obtained. The coating speed was 20 m / min.
Composition of coating liquid for hollow layer : Hollow particles (volume average particle diameter: 0.5 μm, average hollowness: 45%, manufactured by Rohm and Haas Co., Ltd., trade name: Ropeke ST) 59 parts by mass gelatin (Nitta gelatin) Product name: N1236) 28 parts by mass binder resin (styrene / acrylic resin, Shin-Nakamura Chemical Co., Ltd., product name: New Coat B-13) 5 parts by mass binder resin (styrene / acrylic) Resin, manufactured by BASF Japan Ltd., trade name: Jonkrill 62J) 8 parts by mass

Comparative Example 1
Preparation of thermal transfer image receiving sheet 9 A thermal transfer image receiving sheet 9 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of coating liquid 8 for receiving layer / binder resin (vinyl chloride emulsion: vinyl chloride / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.) 100 parts by mass / urethane associative thickener (viscosity: 2000 , Viscosity ratio: 3.0, manufactured by ADEKA Corporation, trade name: UH-526) 3.8 parts by weight, aqueous dispersion of release agent (silicone dispersion) 10 parts by weight, epoxy cross-linking agent (Nagase ChemteX) (Product name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Comparative Example 2
Preparation of thermal transfer image-receiving sheet 10 A thermal transfer image-receiving sheet 10 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of coating solution 9 for receiving layer : Binder resin (vinyl chloride emulsion: PVC / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.) 100 parts by mass Polyester resin (Tg = 20 ° C., interactive chemistry) Manufactured by Kogyo Co., Ltd., trade name: Pluscoat Z-880, including ethylene glycol mono-t-butyl ether as an organic solvent, 3 parts by mass, urethane-associated thickener (viscosity: 2000, viscosity ratio: 3.0, ADEKA Product name: UH-526) 3.8 parts by weight, aqueous release agent dispersion (silicone dispersion) 10 parts by weight, epoxy cross-linking agent (manufactured by Nagase ChemteX Corporation, trade name: Denacol) EX512)
5 parts by mass / surfactant (dioctylsulfosuccinate Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Comparative Example 3
Preparation of thermal transfer image receiving sheet 11 A thermal transfer image receiving sheet 11 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the receiving layer was as follows.
Composition of coating solution 10 for receiving layer / binder resin (manufactured by Nissin Chemical Industry Co., Ltd., trade name: VINYBRAN 278, Tg = 20 ° C.)
100 parts by mass / polyester resin (Tg = 64 ° C., manufactured by Kyoyo Chemical Industry Co., Ltd., trade name: Pluscoat Z-561, without organic solvent) 3 parts by mass / urethane associative thickener (viscosity: 2000, viscosity) Ratio: 3.0, manufactured by ADEKA Corporation, trade name: UH-526) 3.8 parts by mass, aqueous dispersion of release agent (silicone dispersion) 10 parts by mass, epoxy crosslinking agent (Nagase ChemteX Corporation ) Product name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass

Evaluation of Thermal Transfer Image Receiving Sheet The thermal transfer image receiving sheets 1 to 11 produced above were subjected to (1) image density evaluation, (2) releasability evaluation, (3) abnormal transfer evaluation, and (4) hue evaluation.

(1) Image Density Evaluation Using the thermal transfer image-receiving sheet prepared above, the thermal transfer ink sheet 1 prepared above, and a sublimation thermal transfer printer (manufactured by DNP Photolcio, model: DS40), an RGB value of 15 X n (n = 0 to 17) 18 gradation gradation image is printed, and the value at which the optical reflection density is maximized by an optical densitometer (spectrino manufactured by Gretag Macbeth) (Ansi-A, D65) is measured, The OD value (optical density) of black was shown.
Evaluation criteria 5: OD value was 1.95 or more 4: OD value was 1.90 or more and less than 1.95 3: OD value was 1.85 or more and less than 1.90 2: OD The value was 1.80 or more and less than 1.85 1: The OD value was less than 1.80

(2) Evaluation of releasability Black solid image using the thermal transfer image-receiving sheet prepared above, the thermal transfer ink sheet 1 prepared above, and a sublimation thermal transfer printer (manufactured by DNP Photolcio, model: DS40) (RGB value is 0) was printed, and the peeling sound generated at that time was subjected to sensory evaluation. Similarly, after leaving for 3 hours in a high-temperature and high-humidity environment at 40 ° C. and 85% RH), a solid black image was printed in that environment, and the peeling sound generated at that time was subjected to sensory evaluation.
Evaluation criteria 5: No peeling sound was heard.
4: A slight peeling sound was heard at the time of printing the third color, but there was no practical problem.
3: A large peeling sound was heard at the time of printing the third color, and there was a problem in practical use.
2: A peeling sound was heard at the time of printing the 2nd color.
1: Could not print.

(3) Abnormal transfer evaluation Using the thermal transfer image receiving sheet prepared above, the thermal transfer ink sheet 1 prepared above, and a sublimation thermal transfer printer (manufactured by DNP Photolcio, model: DS40), a solid black image ( The RGB value was 0), and abnormal transfer was evaluated (visually according to the following criteria).
・Evaluation criteria 3: Abnormal transfer did not occur. 2: Abnormal transfer occurred only slightly, but there was no problem in actual use. 1: Abnormal transfer occurred at first glance.

(4) Hue evaluation Using the thermal transfer image receiving sheet prepared above, the thermal transfer ink sheet 1 prepared above, and a sublimation thermal transfer printer (manufactured by DNP Photolcio, model: DS40), the RGB value is 15 ×. 18 gradation gradation images of n (n = 0 to 17) were printed, and the hue was visually evaluated.
Evaluation criteria 3: The hue of the printed material was bluish.
2: The hue of the printed material was slightly bluish.
1: The hue of the printed material was not bluish.

The results of the above evaluations are shown in Table 1. Each evaluation result shows that it is so favorable that a numerical value is large. The thermal transfer image-receiving sheet of the example satisfying the composition of the present invention is compared with the thermal transfer image-receiving sheet of the comparative example, while maintaining the releasability at the time of printing in a high-temperature and high-humidity environment and the density of the produced printed matter, It was possible to control the hue of the printed matter and to make it bluish.

DESCRIPTION OF SYMBOLS 1 Thermal transfer image receiving sheet 2 Base material 3 Receiving layer 10 Thermal transfer image receiving sheet 11 Base material 12 Hollow layer A (lower layer)
13 Hollow layer B (upper layer)
14 Primer layer 15 Receptor layer

Claims (5)

A thermal transfer image receiving sheet comprising a substrate and a receiving layer on the substrate,
A thermal transfer image-receiving sheet, wherein the receptor layer comprises a vinyl acetate resin having a glass transition temperature of 50 to 90 ° C and a water-soluble polyester resin having a glass transition temperature of 35 to 120 ° C. The thermal transfer image-receiving sheet according to claim 1, wherein the receiving layer further comprises a silicone release agent. The thermal transfer image-receiving sheet according to claim 1 or 2 , further comprising a hollow layer having hollow particles between the substrate and the receiving layer. A method for producing a thermal transfer image-receiving sheet comprising a base material and a receiving layer on the base material, wherein the vinyl chloride resin having a glass transition temperature of 50 to 90 ° C and 35 to 120 ° C A method for producing a thermal transfer image-receiving sheet, comprising a step of forming a receptor layer using an aqueous dispersion coating liquid comprising a water-soluble polyester resin having a glass transition temperature. The method for producing a thermal transfer image receiving sheet according to claim 4 , wherein the aqueous dispersion coating liquid does not contain an organic solvent.