JP5834703B2 - Thermal transfer image receiving sheet - Google Patents

Description

  The present invention relates to a thermal transfer image receiving sheet, and more particularly to a thermal transfer image receiving sheet comprising a base material, and a hollow layer and a receiving layer on the base material in this order.

  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 sublimation transfer printing materials, for example, when 100 or more prints are continuously printed, the thermal transfer image-receiving sheet is peeled off from the front and back, peeled off from the ink ribbon, and friction between the printer and the conveying member in the printer system. As a result, there is a problem of deterioration in the handleability (hereinafter referred to as “separation”) of printed matter printed by static electricity. Therefore, in order to improve antistatic properties, it has been proposed to provide a conductive layer in at least one layer between the base sheet and the receiving layer of the thermal transfer image-receiving sheet (see Patent Document 1).

JP 2004-299108 A

  As a result of examining the above-described background art, the inventors of the present invention have sufficient dispersibility in a method in which a conductive layer is sequentially applied to at least one layer between a base sheet and a receiving layer of a thermal transfer image receiving sheet. I found a problem that I could not obtain.

  The present invention has been made in view of the above-described background art and newly discovered problems, and an object of the present invention is to provide a thermal transfer image-receiving sheet having improved separation characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by including a binder resin and a layered silicate in the receiving layer in the thermal transfer image-receiving sheet having a specific layer structure. I found out that I can do it. 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, a hollow layer, and a receiving layer in this order on the substrate,
There is provided a thermal transfer image-receiving sheet, wherein the receiving layer comprises a binder resin and a layered silicate.

  In the embodiment of the present invention, the binder resin is preferably a vinyl acetate resin.

  In the embodiment of the present invention, it is preferable that the receiving layer further comprises a wax additive.

  In the aspect of the present invention, the content of the layered silicate is preferably 0.5 to 10% by mass with respect to the total solid mass of the receptor layer.

  In the embodiment of the present invention, it is preferable that a primer layer is further included between the hollow layer and the receiving layer.

  In the aspect of the present invention, it is preferable that all the layers constituting the surface side having the receiving layer of the base material are formed by aqueous coating.

  In the aspect of the present invention, it is preferable that a back layer is further provided on the surface of the substrate opposite to the receiving layer.

  According to the thermal transfer image receiving sheet of the present invention, it is possible to improve the spreading property.

1 is a schematic cross-sectional view showing an embodiment of a thermal transfer image receiving sheet according to the present invention.

Thermal transfer image-receiving sheet The thermal transfer image-receiving sheet of the present invention comprises a substrate, a hollow layer, and a receiving layer in this order on the substrate, and the receiving layer contains a binder resin and a layered silicate. It will be. In a preferred embodiment, the thermal transfer image-receiving sheet may further have a primer layer or an intermediate layer between the hollow layer and the receiving layer, and may further have a back layer on the surface opposite to the receiving layer. 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, on one surface of the substrate, two hollow layers, a primer layer, and a receiving layer are provided in this order, and the surface of the substrate opposite to the receiving layer. There is provided a thermal transfer image-receiving sheet having a back layer thereon. Specifically, a schematic cross-sectional view of one embodiment of the thermal transfer image receiving sheet according to the present invention is shown in FIG. A thermal transfer image receiving sheet 10 shown in FIG. 1 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 surface on one surface of the base material 11. The layer 15 is provided in this order, and the back layer 16 is provided on the surface of the substrate opposite to the receiving layer. 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 or a porous 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 cellulose fiber paper and plastic film, or a combination of plastic film and synthetic paper. Furthermore, resin-coated paper (RC paper) in which the front and back surfaces of cellulose fiber paper are coated with polyethylene or polypropylene resin can be used. In the present invention, a commercially available base material can be used, and for example, RC paper for photography manufactured by Mitsubishi Paper Industries Co., Ltd. is 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 receiving layer contains a binder resin and a layered silicate, and may further contain a wax additive. According to a preferred embodiment, the receiving layer may contain a release agent, a surfactant or the like according to various purposes. Note that the receiving layer is preferably formed by an aqueous coating method. Further, the receiving layer may be composed of two or more layers.

  The layered silicate contained in the receiving layer is a composite obtained by reacting sodium, magnesium, and lithium salts with sodium silicate under appropriate conditions. By containing the layered silicate in the receiving layer, the chargeability of the surface of the thermal transfer image-receiving sheet can be controlled and the spreading property can be improved. Further, the content of the layered silicate is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the total solid mass of the receiving layer. If the content of the layered silicate is within the above range, the stability of the receiving layer coating solution to which the layered silicate is added can be maintained without impairing the original functions of the receiving layer such as coloring properties and releasability. . Moreover, it is preferable that the average particle diameter of a layered silicate is 30 nm or less. Within the above range, the gloss and print roughness of the printed material are not impaired. In the present invention, a commercially available layered silicate can be used, and for example, Laponite JS, Laponite S (manufactured by Wilber Ellis Co., Ltd.) and the like are preferable.

  The binder resin contained in the receiving layer includes acrylic resins, vinyl chloride resins, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride / acrylic copolymers, vinyl chloride / vinyl acetate copolymers (vinyl chloride vinyl chloride). Resins), halogenated polymers such as polyvinylidene chloride, vinyl polymers such as polyvinyl acetate and polyacrylate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, ethylene and propylene, etc. Examples of such resins include copolymer resins of olefins with other vinyl monomers, cellulose resins such as ionomers and cellulose diacetates, polycarbonates, and mixtures of these resins, with vinyl acetate resins being particularly preferred. .

  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.

  As the wax additive, an emulsion type in which carnauba wax and paraffin wax are emulsified with an emulsifier may be used, and a known method can be used as an emulsification method. In the present invention, it is preferable to use a mixture of carnauba wax and paraffin wax as the wax additive, which can improve the stability of the receiving layer coating solution and improve the productivity in the production process. The mixing ratio of carnauba wax and paraffin wax is preferably 1: 0.1 to 1: 5, more preferably 1: 0.5 to 1: 2. When the mixing ratio is in the above range, the stability of the receiving layer forming coating solution can be further improved. Further, the total content of carnauba wax and paraffin wax in the receiving layer is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and further preferably 5 to 20% by mass with respect to the solid content mass of the resin. %. When the total content of carnauba wax and paraffin wax is in the above range, the stability of the receiving layer-forming coating solution can be further improved. In the present invention, a commercially available wax additive may be used, and for example, Q526 (a 1: 1 mixture of carnauba wax and paraffin wax, manufactured by Chukyo Yushi Co., Ltd.) is preferable.

  Examples of the release agent contained in the receiving layer include silicone oil (including reaction-curable silicone), phosphate ester plasticizers, and fluorine compounds, and silicone oil is particularly preferable. Various silicones such as dimethyl silicone can be used as the silicone oil. Specifically, amino-modified silicone, epoxy-modified silicone, alcohol-modified silicone, vinyl-modified silicone, urethane-modified silicone, polyester-modified silicone, polyether-modified silicone, polyester-modified silicone oil, acrylic-modified silicone, amide-modified silicone, etc. These may be mixed or polymerized using various reactions. Two or more release agents may be mixed and used. By using such a 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 a polyether-modified silicone type release agent. Two or more polyether-modified silicone mold release agents may be used, or other mold release agents may be used in combination. In the present invention, a commercially available release agent may be appropriately dispersed in water. Examples of commercially available mold release agents include X-22-3000T, KF-343, KF-1001, X-24-510, and KF410 (manufactured by Shin-Etsu Chemical Co., Ltd.). It is preferable to use the epoxy-modified silicone alone or in combination with other silicone from the viewpoint of the combination with the binder resin.

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. This is because if the average particle size is too small, the amount of hollow particles used increases and the cost increases, and if the average particle size is too large, it becomes difficult to form a smooth hollow layer. 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.

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

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, G1236K (manufactured by Nitta Gelatin Co., Ltd.) and the like 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.

Release layer In the present invention, the release agent may not be added to the receiving layer, but may be provided as a separate release layer on the receiving layer.

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 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 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, commercially available binder resins can also be used. Lucidene 375CI, Lucidene 606APEF, Primal ASR PlUS S25, Primal I-2183N (above, manufactured by Rohm and Haas), Jonkrill 60J, 61J, 62J, 63J, 354J, PDX7700, PDX7641, PDX7643 (above, manufactured by BASF), Vironal MD-1500, MD-2000 (made by Toyobo), Polyester WR-905S20WO, WR-961 (above, manufactured by Nippon Synthetic Chemical Co., Ltd.), Plus Coat Z-690, Z-687 (above, manufactured by Kyoyo Chemical Industry Co., Ltd.), Pateracol IJ-150R, RSI-001, RSI-017 (above, manufactured by DIC Corporation), Superflex 130 (above, Daiichi Kogyo Seiyaku Co., Ltd.) And the like 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.

Manufacturing Method of Thermal Transfer Image Receiving Sheet A known manufacturing method can be used for manufacturing the thermal transfer image receiving sheet of the present invention. For applying 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. In the present invention, on the surface side having the receiving layer, it is preferable to form all the layers constituting the receiving layer from the hollow layer by aqueous coating.

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. Those that do not are preferred. For example, 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), Samalon Red F3BS (manufactured by Mitsubishi Chemical), etc. are yellow. Examples of the dye include Holon Brilliant Yellow 6GL (manufactured by Clariant), PTY-52 (manufactured by Mitsubishi Kasei Co., Ltd.), Macrolex Yellow 6G (manufactured by Bayer), etc., and examples of the blue dye include Kayaset Blue 714 (Nippon Kayaku Co., Ltd.). Manufactured), Waxoline Blue AP-FW (manufactured by ICI), Holon Brilliant Blue SR (manufactured by Sand), MS Blue 100 (manufactured by Mitsui Toatsu Chemicals) and the like.

  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 above dyes and binder resin, if necessary, dissolved in an appropriate organic solvent such as toluene or methyl ethyl ketone, or dispersed 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, 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 include a sublimation thermal transfer printer (manufactured by ALTECH ADS, model: MEGAPIXEL III).

  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
RC paper (manufactured by Mitsubishi Paper Industries Co., Ltd.) is used as a base material for producing the thermal transfer image-receiving sheet 1. It was applied so as to be 0.8 g / m ² and dried at 120 ° C. for 30 seconds.
Composition of backside layer coating solution 1 Binder resin (styrene / acrylic resin, manufactured by Rohm and Haas Co., Ltd., trade name: Luciden 606APEF) 28.6 parts by mass Binder resin (styrene / acrylic resin, Rohm and Haas) 28.6 parts by mass of alumina (average particle size 1 μm (laser diffraction method), manufactured by Sumitomo Chemical Co., Ltd., trade name: AM-27) 42.8 parts by mass Part

Subsequently, the coating liquid 1 for the hollow layer A having the following composition is heated to 40 ° C., and the coating amount after drying is 2.0 g / m ^{2 on} the other surface of the substrate using the gravure reverse method. The coating liquid 1 for hollow layer A was apply | coated, and it dried at 50 degreeC for 2 minute (s), and formed the hollow layer A on the base material. Then, using the coating solution 1 for the hollow layer B, the coating solution 1 for the primer layer, and the coating solution 1 for the receiving layer having the following composition, the coating amounts after drying were 3.0 g / m ² and 3.0 g, respectively, in order. / ^m 2, sequentially applied to each coating solution so that 3.5 g / ^{m 2} by a gravure reverse method, and dried (each 50 ° C. 2 min), the hollow layer B, a primer layer, and by forming a receiving layer Thermal transfer image-receiving sheet 1 (layer constitution: back layer / base material / hollow layer A / hollow layer B / primer layer / receptive layer) was obtained. This thermal transfer image-receiving sheet had a layer structure as shown in FIG.
Composition of coating liquid 1 for hollow layer A (for lower layer) Hollow particles (average particle size: 0.5 μm, average hollowness: 45%, manufactured by Rohm and Haas Co., Ltd., trade name: Ropeke Ultra) 61 .2 parts by weight Gelatin (made by Nitta Gelatin Co., Ltd., trade name: G1236K) 18.3 parts by weight, binder resin (styrene / acrylic resin, Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B- 13) 10.2 parts by mass Binder resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., trade name: Jonkrill 62J) 10.2 parts by mass
Composition of hollow layer B coating solution 1 (for upper layer) Hollow particles (average particle size: 0.5 μm, average hollowness: 45%, manufactured by Rohm and Haas Co., Ltd., trade name: Ropeke Ultra) 67 0.0 parts by weight gelatin (Nitta Gelatin Co., Ltd., trade name: G1236) 20.0 parts by weight binder resin (styrene / acrylic resin, Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B- 13) 5.0 parts by mass Binder resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., trade name: Joncrill 62J) 8.0 parts by mass
Composition of primer layer coating solution 1 • Hollow particles (average particle size: 0.1 μm, average hollowness: 30%, manufactured by JSR Corporation, trade name: SX866) 72.8 parts by mass of gelatin (Nitta Gelatin ( Product name: G1236) 18.7 parts by mass Binder resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., product name: Jonkrill 62J) 3.1 parts by mass Binder resin (modified rubber, ( Product name MG-67, manufactured by Resitex Co., Ltd.
5.2 parts by mass / surfactant (sodium dioctyl sulfosuccinate) 0.2 parts by mass
Composition of coating solution 1 for receiving layer / vinyl acetate emulsion (vinyl chloride / vinyl acetate = 97.5 / 2.5) 74.0 parts by mass, aqueous dispersion of release agent 8.1 parts by mass, wax additive (Carnauba wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass / epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass / layered silicate (Wilver Product made by Ellis Co., Ltd., trade name: Laponite JS) 3.0 parts by mass

Preparation of vinyl chloride-based emulsion The vinyl chloride- based resin latex used in the receiving layer coating solution 1 was prepared as follows. 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 (2% with respect to all charged monomers) .5 mass%) and 2.25 g of potassium persulfate were 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. When the pressure dropped from 0.6 MPa to 0.6 MPa, the polymerization was stopped, and the remaining monomer was recovered to obtain a vinyl chloride resin latex.

Preparation of Release Agent Aqueous Dispersion The release agent aqueous dispersion used in the receiving layer coating solution 1 was prepared as follows. In 85 g of ethyl acetate, 16 g of epoxy-modified silicone (trade name X-22-3000T, manufactured by Shin-Etsu Chemical Co., Ltd.) and 8 g of aralkyl-modified silicone (trade name: KF-410, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in a solvent. A system solution was prepared. Next, 14 g of triisopropyl naphthalene sulfonic acid sodium salt (solid content: 10%) was dissolved in 110 g of pure water to prepare an aqueous solution. Subsequently, the solvent-based solution and the aqueous solution 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.

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 liquid 2 for receiving layer / vinyl acetate emulsion (vinyl chloride / vinyl acetate = 97.5 / 2.5) 74.0 parts by mass, aqueous dispersion of release agent 8.1 parts by mass, wax additive (Carnauba wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass / epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass / layered silicate (Wilver Ellis Co., Ltd., trade name: Laponite JS) 0.5 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 coating solution 3 for receiving layer / vinyl acetate emulsion (vinyl chloride / vinyl acetate = 97.5 / 2.5) 74.0 parts by mass, aqueous dispersion of release agent 8.1 parts by mass, wax additive (Carnauba wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass / epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass / layered silicate (Wilver 10.0 parts by mass, manufactured by Ellis Co., Ltd., trade name: LAPONITE JS)

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 coating solution 4 for receiving layer: Binder resin (vinyl chloride emulsion, manufactured by Nissin Chemical Industry Co., Ltd., trade name: Vinibrand 985) 66.6 parts by mass Binder resin (vinyl acetate emulsion, Nissin Chemical Industry) 7.4 parts by weight, release agent (polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF6004) 8.1 parts by weight, wax additive (Carnava) Wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass, epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass / layered silicate (Wilver Product made by Ellis Co., Ltd., trade name: Laponite JS) 3.0 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, manufactured by Nissin Chemical Industry Co., Ltd., trade name: Viniblanc 985) 37.0 parts by mass Binder resin (vinyl acetate emulsion, Nissin Chemical Industry) Product name: Vinyblan 603) 37.0 parts by weight release agent (polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF6004) 8.1 parts by weight wax additive (Carnava Wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass, epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass / layered silicate (Wilver Product made by Ellis Co., Ltd., trade name: Laponite JS) 3.0 parts by mass

Comparative Example 1
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 / vinyl chloride emulsion (vinyl chloride / vinyl acetate = 97.5 / 2.5) 74.0 parts by weight, aqueous dispersion of release agent 8.1 parts by weight, wax additive (Carnauba wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass / epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass

Comparative Example 2
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 primer layer coating solution and the receiving layer coating solution was as follows.
Composition of coating liquid 2 for primer layer : Hollow particles (average particle size: 0.1 μm, average hollow ratio: 30%, manufactured by JSR Corporation, product name: SX866) 72.8 parts by mass of gelatin (Nitta Gelatin ( Product name: G1236) 18.7 parts by mass Binder resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., product name: Jonkrill 62J) 3.1 parts by mass Binder resin (modified rubber, ( Product name MG-67, manufactured by Resitex Co., Ltd.
5.2 parts by mass / surfactant (sodium dioctylsulfosuccinate) 0.2 parts by mass / layered silicate (manufactured by Wilber Ellis Co., Ltd., trade name: Laponite JS) 3.0 parts by mass
Composition of coating solution 7 for receiving layer / vinyl acetate emulsion (vinyl chloride / vinyl acetate = 97.5 / 2.5) 74.0 parts by mass, aqueous dispersion of release agent 8.1 parts by mass, wax additive (Carnauba wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass / epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass

Comparative Example 3
Preparation of Thermal Transfer Image Receiving Sheet 8 A thermal transfer image receiving sheet 8 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the hollow layer B and the coating solution for the receiving layer was as follows.
Composition of coating liquid 2 for hollow layer B (for upper layer) Hollow particles (average particle size: 0.5 μm, average hollowness: 45%, manufactured by Rohm and Haas Co., Ltd., trade name: Ropeke Ultra) 67 0.0 parts by weight gelatin (Nitta Gelatin Co., Ltd., trade name: G1236) 20.0 parts by weight binder resin (styrene / acrylic resin, Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B- 13) 5.0 parts by mass / binder resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., trade name: Joncrill 62J) 8.0 parts by mass / layered silicate (made by Wilber Ellis Co., Ltd., trade name) : Laponite JS) 3.0 parts by mass
Composition of coating solution 8 for receiving layer / vinyl acetate emulsion (vinyl chloride / vinyl acetate = 97.5 / 2.5) 74.0 parts by mass, aqueous dispersion of release agent 8.1 parts by mass, wax additive (Carnauba wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass / epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass

Comparative Example 4
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 hollow layer A and the coating solution for receiving layer was as follows.
Composition of coating liquid 2 for hollow layer A (for lower layer) Hollow particles (average particle size: 0.5 μm, average hollowness: 45%, manufactured by Rohm and Haas Co., Ltd., trade name: Ropeke Ultra) 61 .2 parts by weight Gelatin (made by Nitta Gelatin Co., Ltd., trade name: G1236K) 18.3 parts by weight, binder resin (styrene / acrylic resin, Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B- 13) 10.2 parts by mass / binder resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., trade name: Jonkrill 62J) 10.2 parts by mass / layered silicate (made by Wilber Ellis Co., Ltd., trade name) : Laponite JS) 3.0 parts by mass
Composition of coating solution 9 for receiving layer / vinyl acetate emulsion (vinyl chloride / vinyl acetate = 97.5 / 2.5) 74.0 parts by mass, aqueous dispersion of release agent 8.1 parts by mass, wax additive (Carnauba wax / paraffin wax dispersion, manufactured by Chukyo Yushi Co., Ltd., trade name: Q-526) 5.2 parts by mass / epoxy-based crosslinking agent (produced by Nagase ChemteX Corporation, trade name: EX-512)
3.7 parts by mass / surfactant (sodium dioctyl succinate) 2.3 parts by mass / thickening agent (manufactured by ADEKA, trade name: UH-526) 6.7 parts by mass

Evaluation of Coating Solution and Thermal Transfer Image Receiving Sheet The coating solution and thermal transfer image receiving sheet prepared above were subjected to (1) coating solution stability evaluation and (2) evaluation of dispersibility.

(1) Evaluation of coating solution stability The coating solution to which the layered silicate used in the above Examples and Comparative Examples was added was allowed to stand at room temperature in a dark place for 1 day, and then the coating solution was evaluated according to the following criteria. In addition, when there was no coating liquid which added layered silicate, it was set as "-".
-Evaluation criteria A : The coating solution thickened somewhat, but there was no practical problem.
(Triangle | delta): The coating liquid was thickened and there existed trouble in application | coating.
X: Aggregates were generated in the coating solution and could not be applied.

(2) Evaluation of judgment property Using the thermal transfer image-receiving sheet produced as described above, 100 natural images were printed with a sublimation transfer printing system “Print Center (DNP Photo Lucio Co., Ltd.)”, and the prints were prepared. The ease was sensory evaluated.
-Evaluation criteria ( circle): It was able to arrange easily and the judgment property was favorable.
(Triangle | delta): It can arrange, and the judgment property was normal.
X: It was not able to arrange, and the judgment property was unsatisfactory.

The results of the above evaluations are shown in Table 1. It can be seen that the thermal transfer image-receiving sheets of Examples 1 to 5 satisfying the composition of the present invention are superior in the spreadability as compared with the thermal transfer image-receiving sheets of Comparative Examples 1 to 4.

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 16 Back layer

Claims (5)

A thermal transfer image receiving material comprising a base material, a hollow layer and a receiving layer in this order on the base material, and further comprising a back layer on the surface of the base material opposite to the receiving layer. A sheet,
The receptor layer comprises a binder resin and a layered silicate;
The back layer comprises a styrene-acrylic resins, and colloidal alumina, a thermal transfer image-receiving sheet.   The thermal transfer image receiving sheet according to claim 1, wherein the binder resin is a vinyl acetate resin.   The thermal transfer image receiving sheet according to claim 1 or 2, wherein the receiving layer further comprises a wax additive.   The thermal transfer image-receiving sheet according to any one of claims 1 to 3, wherein a content of the layered silicate is 0.5 to 10% by mass based on a total solid mass of the receiving layer.   The thermal transfer image receiving sheet according to any one of claims 1 to 4, further comprising a primer layer between the hollow layer and the receiving layer.

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