JP2008246927A - Manufacturing method of thermal transfer image accepting sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal transfer image accepting sheet which has an improved state of a surface and enables attainment of an excellent printing finish. <P>SOLUTION: In this manufacturing method of the thermal transfer image accepting sheet which has at least one accepting layer containing at least one kind of polymeric latex on a substrate and has at least one heat insulating layer containing hollow particles between the accepting layer and the substrate, at least two layers including the accepting layer and the heat insulating layer are formed by simultaneous multilayered coating at a coating speed of 50 m/min or more by using water-based coating solutions. The concentration of any volatile organic solvent in the water-based coating solutions used for the simultaneous multilayered coating is 2 mass% or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a thermal transfer image-receiving sheet, and more particularly to a method for producing a thermal transfer image-receiving sheet with improved uniformity of a printed image.

Conventionally, various thermal transfer recording systems are known, and among them, the dye diffusion transfer recording system is attracting attention as a process capable of producing a color hard copy closest to the image quality of a silver salt photograph (for example, Non-Patent Document 1 and 2). In this dye diffusion transfer recording system, a thermal head in which a heat-sensitive transfer sheet (hereinafter also referred to as an ink sheet) containing a dye is superimposed on a thermal transfer image-receiving sheet (hereinafter also referred to as an image-receiving sheet), and then heat generation is controlled by an electrical signal. The ink sheet is heated to transfer the dye in the ink sheet to the image receiving sheet to record image information. By recording three colors of cyan, magenta, and yellow in succession, the color density is continuous. A color image having a specific change can be transferred and recorded. Therefore, the obtained image is excellent in halftone reproducibility and gradation expression, and an extremely high-definition image can be obtained.
In addition, it has advantages such as being dry, being able to visualize directly from digital data, and being easy to duplicate, and is expanding its market as a full-color hard copy system.
In this dye diffusion transfer recording system, a thermal transfer sheet (hereinafter also referred to as an ink sheet) containing a pigment and a thermal transfer image-receiving sheet (hereinafter also referred to as an image-receiving sheet) are superposed, and then heat is generated by an electrical signal. By heating the ink sheet with a controlled thermal head, the dye in the ink sheet is transferred to the image receiving sheet to record image information. By recording three colors of cyan, magenta, and yellow in an overlapping manner, A color image having a continuous change in color shading can be transferred and recorded.

Conventionally, as a method for producing the image receiving sheet, a composite support using a biaxially stretched polyolefin film containing microvoids is used (for example, Patent Documents 1 and 2), and a receiving polymer is dissolved in an organic solvent and coated thereon. Although a method for producing a receiving layer is known, it is preferable to produce an image receiving sheet in an aqueous system in consideration of reduction of the amount of organic solvent released to the environment, influence of the organic solvent on the human body during production, etc. .
However, when an image receiving sheet is produced by a water-based coating method, a load is imposed on drying as compared with an organic solvent system, and there is a problem that productivity is lowered due to an increase in energy consumption and an increase in coating time. Therefore, in order to reduce the coating time as much as possible, a manufacturing method in which a demand layer and a heat insulating layer are simultaneously coated has been studied. However, when a coating solution containing an aqueous dispersion of organic polymer particles such as latex or hollow polymer is applied simultaneously in a multilayer, a new and unexpected problem has occurred. When the heat-sensitive transfer image-receiving sheet is to be produced in an aqueous system, it is necessary to emulsify and add these in order to introduce oil-soluble additives such as anti-fading agents and ultraviolet absorbers. However, it has been found that the uniformity of the print image obtained from the heat-sensitive transfer image-receiving sheet obtained when these emulsions are added to an aqueous coating solution and further subjected to simultaneous multilayer coating is lowered. In addition, when a surfactant or the like is added to lower the surface tension of the coating solution, it has been found that the image uniformity is lowered when the surfactant is added as a solution of a volatile organic solvent such as methanol.
The problem became more serious when high-speed coating was studied to improve productivity. From the viewpoint of productivity, the coating speed is preferably 50 m / min, and more preferably 100 m / min or more. However, it has also been found that the deterioration of image uniformity due to the addition of the above-mentioned emulsion becomes more remarkable when the coating speed is increased. .
As a result of investigations to overcome the above problems, the above problems occur when the concentration of the volatile organic solvent in the coating solution of the receiving layer and the heat insulating layer becomes high, and can be improved by reducing this. I understand. That is, it has been found that the volatile organic solvent in the above emulsion, for example, ethyl acetate, can be improved by removing under reduced pressure in advance or changing the surfactant solvent from methanol to a water / methanol mixed solvent. It was. It has also been found that the effect is particularly great in high-speed coating. The cause is not clear, but when the above-mentioned latex or hollow polymer-containing aqueous coating solution is applied simultaneously in multiple layers, the volatile organic solvent evaporates faster than water, resulting in local concentration changes that cause the interlayer. It is presumed that it depends on the fact that the balance of physical properties such as the viscosity and interfacial tension of the coating solution is lost, and that the agglomeration of latex and hollow polymer occurs due to local concentration change.
Patent Document 3 describes an image-receiving sheet in which a layer constituting an image-receiving layer from a heat-insulating layer is manufactured by water-based simultaneous multilayer coating, but is specifically deteriorated when the latex and hollow particles of the present invention are used. There is no description of a method for solving the problem, or a method for solving the problem that occurs specifically when the coating speed is increased by controlling the concentration of the volatile organic solvent in the coating solution.
US Pat. No. 866,282 JP-A-3-268998 JP-A-2005-335115 “New development of information recording (hard copy) and its materials”, published by Toray Research Center, Inc., 1993, p. 241-285 "Development of printer materials", published by CMC, 1995, p.180

  Accordingly, the present inventors have provided an object of the present invention to provide a heat-sensitive image-receiving sheet having an improved surface shape and capable of achieving a good print finish in order to solve the above-described problems of the prior art. Set.

As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following means.
(1) In a method for producing a thermal transfer image-receiving sheet, comprising at least one receiving layer containing at least one polymer latex on a support and at least one heat insulating layer containing hollow particles between the receiving layer and the support. The volatile organic solvent concentration in the aqueous coating solution in which at least two layers including the receiving layer and the heat-insulating layer are simultaneously coated in water at a coating speed of 50 m / min or more and both are simultaneously coated is 2% by mass or less. 2. The method for producing a thermal transfer image-receiving sheet according to claim 1, wherein the concentration of the volatile organic solvent in the aqueous coating solution is 1% by mass or less. (3) The method for producing a thermal transfer image-receiving sheet according to claim 1 or 2, wherein the coating speed is 100 m / min or more. (4) An anti-fading agent is added to at least one of the receiving layer or the heat insulating layer. Method for producing a thermal transfer image-receiving sheet according to claims 1 to 3, characterized in that it contains an emulsion containing the ultraviolet absorbent

  By the production method of the present invention, it is possible to produce a thermal transfer image-receiving sheet that can form a recorded image with improved print image uniformity and improved image quality.

Below, the manufacturing method of the thermal transfer image receiving sheet of this invention is demonstrated in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
The volatile organic solvent used in the present invention generally indicates an organic solvent that easily volatilizes in the atmosphere at normal temperature and normal pressure. In the present invention, the volatile organic solvent is defined as an organic solvent having a boiling point of 90 ° C. or lower at normal temperature and normal pressure. These chemical substances are widely used as solvents or cleaning agents for paints, adhesives, etc., taking advantage of their characteristics such as being easy to volatilize (easy to dry) and having lipophilicity (easy to remove oil stains). Yes.
Examples of the volatile organic solvent defined in the present invention include ethyl acetate, methyl acetate, hexane, ethanol, methanol, isopropyl alcohol, benzene, methyl ethyl ketone, acetone, acetaldehyde, dichloromethane, dichloroethane, trichloroethylene, and chloroform.
In the present invention, the concentration of the volatile organic solvent in the aqueous coating solution is required to be 2% by mass or less, and preferably 1% by mass or less in all the aqueous coating solutions to be coated simultaneously.

The heat-sensitive transfer image-receiving sheet of the present invention has at least one receiving layer (dye-receiving layer) on a support, and has at least one heat insulating layer (porous layer) between the support and the receiving layer. . Further, an intermediate layer such as a white background adjusting layer, a charge adjusting layer, an adhesive layer, a primer layer, or an undercoat layer may be formed between the support and the receiving layer.
In the present invention, at least one receiving layer and at least one heat insulating layer are coated by aqueous coating. These layers are preferably formed by simultaneous multilayer coating. When the intermediate layer is included, the receiving layer, the heat insulating layer and the intermediate layer can be formed by simultaneous multilayer coating.
It is preferable that a curl adjusting layer, a writing layer, and a charge adjusting layer are formed on the back side of the support. Each layer on the back side of the support can be applied by a general method such as roll coating, bar coating, gravure coating, or gravure reverse coating.

(Receptive layer)
The receiving layer serves to receive the dye transferred from the ink sheet and maintain the formed image. The image-receiving sheet used in the present invention has at least one receiving layer having a thermoplastic receiving polymer capable of receiving at least a dye.
The accepting polymer is preferably used as a polymer latex dispersed in a water-soluble dispersion medium. Further, the receiving layer preferably contains a water-soluble polymer in addition to the polymer latex. By containing a polymer latex and a water-soluble polymer, a water-soluble polymer that is difficult to be dyed on the dye can be present between the polymer latexes, and the dye dyed on the polymer latex can be prevented from diffusing. Thus, it is possible to reduce a change in sharpness of the receiving layer with time and to form a recorded image with a small change in transfer image with time.
For the receiving layer, in addition to the polymer latex of the receiving polymer, for example, a polymer latex having other functions can be used in combination for the purpose of adjusting the elastic modulus of the film.
The receiving layer can contain an ultraviolet absorber, a release agent, a lubricant, an antioxidant, a preservative, a surfactant, and other additives.

<Polymer latex>
The polymer latex used in the present invention will be described. In the heat-sensitive transfer image-receiving sheet of the present invention, the polymer latex that can be used in the receptor layer is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, the emulsion is polymerized, the micelle is dispersed, or the polymer molecule has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Anything may be used. For polymer latex, Tadashi Okuda, Hiroshi Inagaki, “Synthetic Resin Emulsion”, published by Kobunshi Publishing (1978), Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, “Application of Synthetic Latex”, Takashi Published by Molecular Press (1993), Soichi Muroi, “Synthetic Latex Chemistry”, published by High Polymer Press (1970), supervised by Yoshiaki Mitsuzawa, “Development and application of water-based coating materials”, CM Publishing ( 2004) and JP-A-64-538. The average particle size of the dispersed particles is preferably from 1 to 50000 nm, more preferably from about 5 to 1000 nm.
The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

  The polymer latex may be a so-called core / shell type latex in addition to a normal uniform polymer latex. In this case, it may be preferable to change the glass transition temperature between the core and the shell. The glass transition temperature (Tg) of the polymer latex of the present invention is preferably -30 ° C to 130 ° C, more preferably 0 ° C to 120 ° C. Among these, the glass transition temperature is preferably 40 ° C or higher (preferably 40 to 120 ° C), and more preferably 70 ° C or higher (70 to 100 ° C).

  Preferred embodiments of the polymer latex of the present invention include polymer latexes such as acrylic polymers, polyesters, rubbers (for example, SBR resin), polyurethanes, polyvinyl chlorides, polyvinyl acetates, polyvinylidene chlorides, and polyolefins. Can be preferably used. The polymer latex may be a linear polymer, a branched polymer, a crosslinked polymer, a so-called homopolymer obtained by polymerizing a single monomer, or a copolymer obtained by polymerizing two or more monomers. Good. In the case of a copolymer, it may be a random copolymer or a block copolymer. These polymers have a number average molecular weight of 5,000 to 1,000,000, preferably 10,000 to 500,000. When the molecular weight is too small, the mechanical strength of the latex-containing layer is insufficient, and when the molecular weight is too large, the film formability is poor and is not preferable. A crosslinkable polymer latex is also preferably used.

  The monomer used for the synthesis of the polymer latex used in the present invention is not particularly limited, and monomers that can be polymerized by ordinary radical polymerization or ionic polymerization method are preferably the following monomer groups (a) to (j). Can be used. Polymer monomers can be synthesized by selecting these monomers independently and freely in combination.

-Monomer group (a)-(j)-
(A) Conjugated dienes: 1,3-pentadiene, isoprene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, cyclo Pentadiene and the like.
(B) Olefins: ethylene, propylene, vinyl chloride, vinylidene chloride, 6-hydroxy-1-hexene, 4-pentenoic acid, methyl 8-nonenoate, vinylsulfonic acid, trimethylvinylsilane, trimethoxyvinylsilane, 1,4- Divinylcyclohexane, 1,2,5-trivinylcyclohexane, etc.

  (C) α, β-unsaturated carboxylic acid esters: alkyl acrylate (eg, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc.), substituted alkyl acrylate (eg, 2-chloro Ethyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, etc.), alkyl methacrylate (eg, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, etc.), substituted alkyl methacrylate (eg, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycerin) Monomethacrylate, 2-acetoxyethyl methacrylate, tetrahydrofurfuryl meta Relate, 2-methoxyethyl methacrylate, polypropylene glycol monomethacrylate (polyoxypropylene added mole number = 2 to 100), 3-N, N-dimethylaminopropyl methacrylate, chloro-3-N, N, N-trimethyl Ammoniopropyl methacrylate, 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate, 4-oxysulfobutyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc.), unsaturated dicarboxylic acid derivatives (For example, monobutyl maleate, dimethyl maleate, monomethyl itaconate, dibutyl itaconate, etc.), polyfunctional esters (for example, ethylene glycol diacrylate, Tylene glycol dimethacrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, dipentaerythritol pentamethacrylate, pentaerythritol hexaacrylate, 1,2, 4-cyclohexanetetramethacrylate and the like.

(D) Amides of α, β-unsaturated carboxylic acid: for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylmethacrylamide, N-tert-butylacrylamide N-tert-octylmethacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetone acrylamide, itaconic acid diamide, N-methylmaleimide, 2 -Acrylamide-methylpropane sulfonic acid, methylene bisacrylamide, dimethacryloyl piperazine and the like.
(E) Unsaturated nitriles: acrylonitrile, methacrylonitrile and the like.
(F) Styrene and its derivatives: styrene, vinyl toluene, p-tert-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, α-methyl styrene, p-chloromethyl styrene, vinyl naphthalene, p-hydroxymethyl styrene, p -Styrene sulfonic acid sodium salt, p-styrene sulfinic acid potassium salt, p-aminomethylstyrene, 1,4-divinylbenzene and the like.
(G) Vinyl ethers: methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether, and the like.
(H) Vinyl esters: vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, and the like.
(I) α, β-unsaturated carboxylic acid and salts thereof: acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, ammonium methacrylate, potassium itaconate and the like.
(J) Other polymerizable monomers: N-vinylimidazole, 4-vinylpyridine, N-vinylpyrrolidone, 2-vinyloxazoline, 2-isopropenyloxazoline, divinylsulfone, and the like.

  The polymer latex that can be used in the present invention is commercially available, and the following polymers can be used. Examples of acrylic polymers include Sebian A-4635, 4718, 4601 manufactured by Daicel Chemical Industries, Ltd., Nipol Lx811, 814, 821, 820, 855 (P-17: Tg36 ° C.) manufactured by Zeon Corporation, 857x2. (P-18: Tg43 ° C), Dainippon Ink Chemical Co., Ltd. Voncoat R3370 (P-19: Tg25 ° C), 4280 (P-20: Tg15 ° C), Nippon Pure Chemical Co., Ltd. Jurimer ET-410 ( P-21: Tg44 ° C), JSR AE116 (P-22: Tg50 ° C), AE119 (P-23: Tg55 ° C), AE121 (P-24: Tg58 ° C), AE125 (P-25: Tg60) ° C), AE134 (P-26: Tg48 ° C), AE137 (P-27: Tg48 ° C), AE140 (P-28: Tg53 ° C), AE173 (P-29: Tg60 ° C), Aron from Toagosei Co., Ltd. A-104 (P-30: Tg45 ° C), NS-600X, NS-620X, manufactured by Takamatsu Yushi Co., Ltd., Vinibrand 2580, 2583, 2641, 2770, 2770H, 2635, 2886, 5202C, manufactured by Nissin Chemical Industry Co., Ltd. , 2706, etc. (all are trade names).

  Examples of polyesters include FINETEX ES650, 611, 675, 850 manufactured by Dainippon Ink Chemical Co., Ltd., WD-size, WMS manufactured by Eastman Chemical, A-110, A-115GE manufactured by Takamatsu Yushi Co., Ltd., A- 120, A-21, A-124GP, A-124S, A-160P, A-210, A-215GE, A-510, A-513E, A-515GE, A-520, A-610, A-613, A-615GE, A-620, WAC-10, WAC-15, WAC-17XC, WAC-20, S-110, S-110EA, S-111SL, S-120, S-140, S-140A, S- 250, S-252G, S-250S, S-320, S-680, DNS-63P, NS-122L, NS-122LX, NS-244LX, NS-140L, NS-141LX, NS-282LX, Toagosei Co., Ltd. ) Aron Melt PES-1000 series, PES-2000 series, Toyobo Co., Ltd. Bironal MD-1100, MD-1200, MD-1220, MD-1245, MD-1250, MD-1335, MD-1400, MD-1480 , MD-1500, MD-1930, MD-1985, Sepuljon ES manufactured by Sumitomo Seika Co., Ltd. (all are trade names).

  Examples of polyurethanes include Dainippon Ink Chemical Co., Ltd.HYDRAN AP10, AP20, AP30, AP40, 101H, Vondic 1320NS, 1610NS, Dainichi Seika Co., Ltd.D-1000, D-2000, D-6000, D-4000, D-9000, Takamatsu Yushi Co., Ltd. NS-155X, NS-310A, NS-310X, NS-311X, Daiichi Kogyo Seiyaku Co., Ltd. Elastron etc. (all are trade names).

  Examples of rubbers include LACSTAR 7310K, 3307B, 4700H, 7132C (above, manufactured by Dainippon Ink and Chemicals), Nipol Lx416, LX410, LX430, LX435, LX110, LX415A, LX438C, 2507H, LX303A, LX407BP series, V1004, MH5055 (made by Nippon Zeon Co., Ltd.), etc. (all are trade names).

  Examples of polyvinyl chlorides include: Z351, G351, G576, Nissin Chemical Industry Co., Ltd., Vinibrand 240, 270, 277, 375, 386, 609, 550, 601, 602, 630, 660, 671, 683, 680, 680S, 681N, 685R, 277, 380, 381, 410, 430, 432, 860, 863, 865, 867, 900, 900GT, 938, 950, etc. (all are trade names). Examples of polyvinylidene chlorides include L502 and L513 manufactured by Asahi Kasei Kogyo Co., Ltd., and D-5071 manufactured by Dainippon Ink & Chemicals, Inc. (all are trade names). Examples of polyolefins include Chemipearl S120, SA100, V300 (P-40: Tg80 ° C) manufactured by Mitsui Petrochemical Co., Ltd., Voncoat 2830, 2210, 2960 manufactured by Dainippon Ink Chemical Co., Ltd., Sumitomo Seika Co., Ltd. Examples of Zyxen, Sepoljon G, and copolymerized nylons include Sepoljon PA manufactured by Sumitomo Seika Co., Ltd. (all are trade names).

  Examples of polyvinyl acetates include Nishin Chemical Industry Co., Ltd.ViniBran 1080, 1082, 1085W, 1108W, 1108S, 1563M, 1566, 1570, 1588C, A22J7-F2, 1128C, 1137, 1138, A20J2, A23J1, A23J1, A23K1, A23P2E, A68J1N, 1086A, 1086, 1086D, 1108S, 1187, 1241LT, 1580N, 1083, 1571, 1572, 1581, 4465, 4466, 4468W, 4468S, 4470, 4485LL, 4495LL, 1023, 1042, 1060, 1060S, 1080M, 1084W, 1084S, 1096, 1570K, 1050, 1050S, 3290, 1017AD, 1002, 1006, 1008, 1107L, 1225, 1245L, GV-6170, GV-6181, 4468W, 4468S, etc. Product name).

  These polymer latexes may be used alone or in combination of two or more as required.

  In the present invention, at least one of the receiving layers is coated with an aqueous coating solution. When the receiving layer has a plurality of receiving layers, it is more preferable to prepare all of these receiving layers by drying after applying the aqueous coating solution. . However, “aqueous” as used herein means that 60% by mass or more of the solvent (dispersion medium) of the coating solution is water. Components other than water in the coating solution include methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate, diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, oxyethyl phenyl ether A water miscible organic solvent such as can be used.

  Preferable examples of the polymer latex used in the present invention include polylactic acid esters, polyurethanes, polycarbonates, polyesters, polyacetals, SBRs, and polyvinyl chlorides. Among these, polyesters, polycarbonates Most preferably, polyvinyl chlorides are included.

In the present invention, among the above polymer latexes, polyvinyl chlorides are preferred in the present invention. Among the polyvinyl chlorides, that is, the polymer latex containing at least a repeating unit obtained from vinyl chloride, a polymer latex containing 50 mol% or more of a repeating unit obtained from the vinyl chloride is preferable, and a copolymerized polymer latex is more preferable. It is. As such a copolymer latex, a monomer copolymerized with vinyl chloride is preferably acrylic or methacrylic acid or an ester thereof, vinyl acetate or ethylene, more preferably acrylic or methacrylic acid or an ester thereof, and an acrylic ester. Is more preferable. The alcohol part of the ester part of the acrylate ester preferably has 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms.
Examples of such polyvinyl chlorides include those mentioned above, among others, ViniBran 240, ViniBran 270, ViniBran 276, ViniBran 277, ViniBran 375, ViniBran 380, ViniBran 386, ViniBran 410, ViniBran 430, ViniBran 432, VINYBRAN 550, VINYBRAN 601, VINYBRAN 602, VINYBRAN 609, VINYBRAN 619, VINYBRAN 680, VINYBRAN 680S, VINYBRAN 681N, VINYBRAN 683, VINYBRAN 685R, VINYBRAN 690, VINYBRAN 860, VINYBRAN 863, VINYBRAN 685, VINYBRAN 867, VINYBRAN 900, , ViniBran 950 (all are Nissin Chemical Industry Co., Ltd., SE1320, S-830 (all are Sumitomo Chemtech ( )) Is preferable.

The polymer latex used in the present invention is used for receiving the dye that migrates from the ink sheet, but any polymer may be used in combination with the polymer latex.
The polymer that can be used in combination may be used for receiving a dye, but may also be used as a binder for holding the polymer latex.
Such a polymer is preferably transparent or translucent and colorless, and natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other media forming films such as gelatins, polyvinyl alcohols, hydroxy Ethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinyl pyrrolidone, casein, starch, polyacrylic acid, polymethyl methacrylic acid, polyvinyl chloride, polymethacrylic acid, styrene-maleic anhydride copolymers, styrene -Acrylonitrile copolymers, styrene-butadiene copolymers, polyvinyl acetals (eg, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy resins Polyvinylidene chlorides, polyepoxides, polycarbonates, polyvinyl acetates, polyolefins, and polyamides. The binder may be coated from water or an organic solvent or emulsion.

  In addition to the polymer latex used for the purpose of accepting the dye migrating from the ink sheet, when using a polymer latex mainly used as the binder, the polymer latex has processing brittleness and image storage stability. The glass transition temperature (Tg) is preferably in the range of -30 ° C to 70 ° C, more preferably in the range of -10 ° C to 50 ° C, still more preferably in the range of 0 ° C to 40 ° C. It is also possible to use a blend of two or more polymers as the binder, and in this case, it is preferable that the weighted average Tg in consideration of the composition falls within the above range. Moreover, when phase-separating or having a core-shell structure, the weighted average Tg is preferably within the above range.

This glass transition temperature (Tg) can be calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. Xi is the mass fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. In addition, the value of the homopolymer glass transition temperature (Tgi) of each monomer can adopt the value of “Polymer Handbook (3rd Edition)” (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).
In addition, although the glass transition temperature of the said polymer latex for receiving the dye in this invention and the hollow polymer mentioned later is prescribed | regulated by a measured value, it is also possible to estimate with said calculation method.

<Water-soluble polymer>
The receiving layer preferably contains a water-soluble polymer. Water-soluble polymers that can be used in the present invention include natural polymers (polysaccharides, microorganisms, animals), semi-synthetic polymers (cellulose, starch, alginic acid), and synthetic polymers (vinyl, Others), synthetic polymers such as polyvinyl alcohol described below, and natural or semi-synthetic polymers made from plant-derived cellulose or the like correspond to water-soluble polymers that can be used in the present invention. The water-soluble polymer in the present invention does not include the polymer latex.
In the present invention, a water-soluble polymer may be labeled as a binder to distinguish it from the polymer latex.

Of the water-soluble polymers that can be used in the present invention, natural polymers and semi-synthetic polymers will be described in detail. Plant-based polysaccharides include gum arabic, κ-carrageenan, ι-carrageenan, λ-carrageenan, guar gum (Squalon Supercol, etc.), locust bean gum, pectin, tragacanth, corn starch (National Starch & Chemical Co. Purity-21, etc.) ), Phosphorylated starch (National Starch & Chemical Co. National 78-1898, etc.) and other microbial polysaccharides such as xanthan gum (Kelco Keltrol T), dextrin (National Starch & Chemical Co. Nadex360, etc.) Examples of the polymer include gelatin (such as Crodyne B419 manufactured by Croda), casein, sodium chondroitin sulfate (such as Crodaist CS manufactured by Croda), and the like. Cellulose systems include ethyl cellulose (ICI Cellofas WLD, etc.), carboxymethyl cellulose (Daicel CMC, etc.), hydroxyethyl cellulose (Daicel HEC, etc.), hydroxypropyl cellulose (Aqualon Klucel, etc.), methyl cellulose (Henkel Viscontran, etc.), Examples include nitrocellulose (such as Isopropyl Wet from Hercules) and cationized cellulose (such as Crodacel QM from Croda). As starch systems, phosphorylated starch (such as National Starch &Chemical's National 78-1898), alginic acid systems such as sodium alginate (such as Kelco's Keltone), propylene glycol alginate, etc. -care1000), and sodium hyaluronate (such as Hyalure from Lifecare Biomedial).
In the present invention, gelatin is one of the preferred embodiments. The gelatin used in the present invention may have a molecular weight of 10,000 to 1,000,000. Gelatin used in the present invention may contain anions such as Cl- and SO ₄ ^2- and cations such as Fe ²⁺ , Ca ²⁺ , Mg ²⁺ , Sn ²⁺ and Zn ^2+. It may be included. It is preferable to add gelatin dissolved in water.

  Of the water-soluble polymers that can be used in the present invention, synthetic polymers will be described in detail. Examples of the acrylic system include sodium polyacrylate, polyacrylic acid copolymer, polyacrylamide, polyacrylamide copolymer, polydiethylaminoethyl (meth) acrylate quaternary salt or a copolymer thereof, and the vinyl system includes polyvinylpyrrolidone, Polyvinyl pyrrolidone copolymer, polyvinyl alcohol, etc., including polyethylene glycol, polypropylene glycol, polyisopropylacrylamide, polymethyl vinyl ether, polyethyleneimine, polystyrene sulfonic acid or copolymer thereof, naphthalene sulfonic acid condensate salt, polyvinyl sulfonic acid Or a copolymer thereof, polyacrylic acid or a copolymer thereof, acrylic acid or a copolymer thereof, a maleic acid copolymer, a maleic acid monoester copolymer, an acrylic acid Ylmethylpropane sulfonic acid or its copolymer, etc.), polydimethyldiallylammonium chloride or its copolymer, polyamidine or its copolymer, polyimidazoline, dicyanciamide condensate, epichlorohydrin-dimethylamine condensate, polyacrylamide Hoffman degradation product, water-soluble polyester (Plus Coat Z-221, Z-446, Z-561, Z-450, Z-565, Z-850, Z-3308, RZ-105, RZ- 570, Z-730, RZ-142 (all are trade names)).

Further, it has a superabsorbent polymer described in US Pat. No. 4,960,681, JP-A-62-245260, etc., that is, —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal). A homopolymer of vinyl monomers or a copolymer of these vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H (trade name) manufactured by Sumitomo Chemical Co., Ltd.) should also be used. Can do.

Of the water-soluble synthetic polymers that can be used in the present invention, polyvinyl alcohols are preferred.
Hereinafter, polyvinyl alcohol will be described in more detail.
As a complete saponified product, PVA-105 [polyvinyl alcohol (PVA) content 94.0% by mass or more, saponification degree 98.5 ± 0.5 mol%, sodium acetate content 1.5% by mass or less, volatile content 5 0.0 mass% or less, viscosity (4 mass%, 20 ° C.) 5.6 ± 0.4 CPS], PVA-110 [PVA content 94.0 mass%, saponification degree 98.5 ± 0.5 mol%, acetic acid Sodium content 1.5% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20 ° C.) 11.0 ± 0.8 CPS], PVA-117 [PVA content 94.0% by mass, saponification degree 98.5 ± 0.5 mol%, sodium acetate content 1.0 mass%, volatile content 5.0 mass%, viscosity (4 mass%, 20 ° C.) 28.0 ± 3.0 CPS],

PVA-117H [PVA content 93.5% by mass, saponification degree 99.6 ± 0.3 mol%, sodium acetate content 1.85% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 29.0 ± 3.0 CPS], PVA-120 [PVA content 94.0 mass%, saponification degree 98.5 ± 0.5 mol%, sodium acetate content 1.0 mass%, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 39.5 ± 4.5 CPS], PVA-124 [PVA content 94.0 mass%, saponification degree 98.5 ± 0.5 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 60.0 ± 6.0 CPS],

PVA-124H [PVA content 93.5% by mass, saponification degree 99.6 ± 0.3 mol%, sodium acetate content 1.85% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 61.0 ± 6.0 CPS], PVA-CS [PVA content 94.0% by mass, saponification degree 97.5 ± 0.5 mol%, sodium acetate content 1.0% by mass, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 27.5 ± 3.0 CPS], PVA-CST [PVA content 94.0 mass%, saponification degree 96.0 ± 0.5 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 27.0 ± 3.0 CPS], PVA-HC [PVA content 90.0 mass%, saponification degree 99. 85 mol% or more, sodium acetate content 2.5 mass%, volatile content 8.5 mass%, viscosity (4 quality %, 20 ℃) 25.0 ± 3.5CPS] (or more, both of Kuraray Co., Ltd., trade name of) such as,

As a partially saponified product, PVA-203 [PVA content 94.0% by mass, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4 mass%, 20 ° C.) 3.4 ± 0.2 CPS], PVA-204 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0 mass %, Volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 3.9 ± 0.3 CPS], PVA-205 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.5 Mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20 ° C.) 5.0 ± 0.4 CPS],

PVA-210 [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 9.0 ± 1.0 CPS], PVA-217 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0 mass%, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 22.5 ± 2.0 CPS], PVA-220 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.0 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 30.0 ± 3.0 CPS],

PVA-224 [PVA content 94.0% by mass, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 44.0 ± 4.0 CPS], PVA-228 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0 mass%, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 65.0 ± 5.0 CPS], PVA-235 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.5 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 95.0 ± 15.0 CPS],

PVA-217EE [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 23.0 ± 3.0 CPS], PVA-217E [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 23.0 ± 3.0 CPS], PVA-220E [PVA content 94.0 mass%, saponification degree 88.0 ± 1.0 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 31.0 ± 4.0 CPS],

PVA-224E [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 45.0 ± 5.0 CPS], PVA-403 [PVA content 94.0 mass%, saponification degree 80.0 ± 1.5 mol%, sodium acetate content 1.0 mass%, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 3.1 ± 0.3 CPS], PVA-405 [PVA content 94.0 mass%, saponification degree 81.5 ± 1.5 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 4.8 ± 0.4 CPS],

PVA-420 [PVA content 94.0% by mass, saponification degree 79.5 ± 1.5 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass], PVA-613 [PVA-containing Rate 94.0% by mass, saponification degree 93.5 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20 ° C.) 16.5 ± 2.0 CPS], L-8 [PVA content 96.0 mass%, saponification degree 71.0 ± 1.5 mol%, sodium acetate content 1.0 mass% (ash content), volatile content 3.0 mass% Viscosity (4% by mass, 20 ° C.) 5.4 ± 0.4 CPS] (all are trade names manufactured by Kuraray Co., Ltd.).

  In addition, said measured value is calculated | required according to JISK-6726-1977.

  As for the modified polyvinyl alcohol, those described in Koichi Nagano et al., “Poval” (published by Kobunshi Shuppankai) are used. There is modification by cation, anion, -SH compound, alkylthio compound, silanol.

  As such modified polyvinyl alcohol (modified PVA), C-118, C-318, C-318-2A, C-506 (all are trade names manufactured by Kuraray Co., Ltd.), HL polymer as C polymer. HL-12E, HL-1203 (all are trade names manufactured by Kuraray Co., Ltd.), HM polymer is HM-03, HM-N-03 (all are trade names manufactured by Kuraray Co., Ltd.), KL-118, KL-318, KL-506, KM-118T, KM-618 (all are trade names manufactured by Kuraray Co., Ltd.) as the K polymer, and M-115 (manufactured by Kuraray Co., Ltd.) as the M polymer. (Trade name), MP-102, MP-202, MP-203 (all are trade names manufactured by Kuraray Co., Ltd.) as MP polymers, MPK-1, MPK-2, MPK-3, PK-4, MPK-5, MPK-6 (all are trade names manufactured by Kuraray Co., Ltd.), R polymer as R-1130, R-2105, R-2130 (all are manufactured by Kuraray Co., Ltd.) And V-2250 (trade name, manufactured by Kuraray Co., Ltd.).

  Polyvinyl alcohol can be adjusted in viscosity or stabilized by a small amount of solvent or inorganic salt added to the aqueous solution. For details, refer to the above document, Koichi Nagano et al., “Poval”, Polymer Issued by the publisher, pages 144 to 154 can be used. As a typical example, it is possible to improve the coating surface quality by containing boric acid, which is preferable. The addition amount of boric acid is preferably 0.01 to 40% by mass with respect to polyvinyl alcohol.

The polymer latex used in the present invention is used for receiving the dye that migrates from the ink sheet, but any polymer may be used in combination with the polymer latex.
The polymer that can be used in combination may be used for receiving a dye, but may also be used as a binder for holding the polymer latex. Such a polymer is preferably transparent or translucent, and generally colorless. Natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other media forming films such as rubbers, polyvinyl alcohols, Hydroxyethylcelluloses, cellulose acetates, cellulose acetate butyrate, polyvinylpyrrolidones, starch, polyacrylic acids, polymethylmethacrylic acids, polyvinylchlorides, polymethacrylic acids, styrene-maleic anhydride copolymers, styrene- Acrylonitrile copolymers, styrene-butadiene copolymers, polyvinyl acetals (eg, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy resins, poly salts Vinylidene, polyepoxides, polycarbonates, polyvinyl acetates, polyolefins, cellulose esters, and polyamides. The binder may be coated from water or an organic solvent or emulsion.

In the present invention, the water-soluble polymer is preferably polyvinyl alcohol or gelatin, and most preferably gelatin.
The addition amount of the water-soluble polymer in the receiving layer is preferably 1 to 25% by mass, and more preferably 1 to 10% by mass with respect to the entire receiving layer. Moreover, it is also one of the preferable aspects that a water-soluble polymer is not used.

  Polymers other than water-soluble polymers used as binders in the present invention can be easily obtained by solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, anionic polymerization, cationic polymerization, etc. The emulsion polymerization method obtained as is most preferable. Also preferred is a method of preparing a polymer in a solution and neutralizing or adding an emulsifier and then adding water and forcibly stirring to prepare an aqueous dispersion. In the emulsion polymerization method, for example, water or a mixed solvent of water and an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.) is used as a dispersion medium, and the monomer is 5 to 150% by mass with respect to the dispersion medium. Using the mixture and the total amount of monomers, an emulsifier and a polymerization initiator are used, and polymerization is carried out with stirring at about 30 to 100 ° C., preferably 60 to 90 ° C. for 3 to 24 hours. Various conditions such as the dispersion medium, the monomer concentration, the initiator amount, the emulsifier amount, the dispersant amount, the reaction temperature, and the monomer addition method are appropriately set in consideration of the type of monomer used. Moreover, it is preferable to use a dispersing agent as needed.

  The emulsion polymerization method can be generally performed according to the following literature. Tadashi Okuda, Hiroshi Inagaki, "Synthetic Resin Emulsion", published by Polymer Publishing Association (1978), Takaaki Sugimura, Akio Kataoka, Junichi Suzuki, Keiji Kasahara, "Application of Synthetic Latex", Published by Polymer Publishing Society (1993) 1), Soichi Muroi, “Chemistry of Synthetic Latex”, published by Kobunshi Shuppankai (1970). In the emulsion polymerization method for synthesizing the polymer latex used in the present invention, a batch polymerization method, a monomer (continuous / divided) addition method, an emulsion addition method, a seed polymerization method, etc. can be selected from the viewpoint of latex productivity. A batch polymerization method, a monomer (continuous / divided) addition method, and an emulsion addition method are preferred.

  The polymerization initiator only needs to have a radical generating ability, such as inorganic peroxides such as persulfate and hydrogen peroxide, and peroxides described in Nippon Oil & Fats Co., Ltd. “Organic Peroxide Catalog”, etc. The azo compounds described in Yaku Kogyo Co., Ltd. “Azo Polymerization Initiator Catalog” can be used. Among them, water-soluble peroxides such as persulfate and water-soluble azo compounds described in Wako Pure Chemical Industries, Ltd., `` Azo polymerization initiator catalog '' and the like are preferable, ammonium persulfate, sodium persulfate, potassium persulfate, Azobis (2-methylpropionamidine) hydrochloride, azobis (2-methyl-N- (2-hydroxyethyl) propionamide), azobiscyanovaleric acid is more preferable, and in particular, ammonium persulfate, sodium persulfate, potassium persulfate, etc. Peroxides are preferred from the viewpoints of image storage stability, solubility, and cost.

  As the addition amount of the polymerization initiator, the polymerization initiator is preferably 0.3% by mass to 2.0% by mass, and 0.4% by mass to 1.75% by mass with respect to the total amount of monomers. Is more preferable, and 0.5% by mass to 1.5% by mass is particularly preferable.

  As the polymerization emulsifier, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, but the anionic surfactant has dispersibility and image storability. From the viewpoint, it is preferable to use a sulfonic acid type anionic surfactant because polymerization stability can be secured in a small amount and resistance to hydrolysis, and a long chain represented by Perex SS-H (trade name, Kao Corp.). Alkyl diphenyl ether disulfonate is more preferable, and a low electrolyte type such as Pionine A-43-S (trade name, Takemoto Yushi Co., Ltd.) is particularly preferable.

  As the polymerization emulsifier, a sulfonic acid type anionic surfactant is preferably used in an amount of 0.1% by mass to 10.0% by mass with respect to the total amount of monomers, and 0.2% by mass to 7.5% by mass is used. It is more preferable that 0.3% by mass to 5.0% by mass is used.

  In the synthesis of the polymer latex used in the present invention, it is preferable to use a chelating agent. A chelating agent is a compound capable of coordinating (chelating) a multivalent ion such as a metal ion such as an iron ion or an alkaline earth metal ion such as a calcium ion. Japanese Patent Publication No. 6-8956, US Pat. JP-A-4-73645, JP-A-4-127145, JP-A-4-247703, JP-A-4-305572, JP-A-6-11805, JP-A-5-173712, JP-A-5-66527, JP-A-5-158195, JP-A-6-118580, JP-A-6-110168, JP-A-6-161054, JP-A-6-175299, JP-A-6-214352, JP-A-7-114161, Special Kaihei 7-114154, JP-A-7-120894, JP-A-7-199433, JP-A-7-306504, JP-A-9 No. 43792, JP-A-8-314090, JP-A-10-182571, JP-A-10-182570, can be employed compounds described in JP-like JP 11-190892.

  Examples of the chelating agent include inorganic chelate compounds (sodium tripolyphosphate, sodium hexametaphosphate, sodium tetrapolyphosphate, etc.), aminopolycarboxylic acid chelate compounds (nitrilotritriacetic acid, ethylenediaminetetraacetic acid, etc.), organic phosphonic acid chelate compounds ( Research Disclosure 18170, JP-A-52-102726, 53-42730, 56-97347, 54-121127, 55-4024, 55-4025, 55-29883, 55 -126241, 55-65555, 55-65956, 57-17943, 54-61125, West German Patent No. 1045373, and the like), polyphenol-based chelating agents, polyamines Chelate compounds Etc. Preferably, amino acid derivatives being particularly preferred.

  Preferable examples of the aminopolycarboxylic acid derivatives include the compounds listed in the appendix of “EDTA (-Complexane Chemistry)” (Nanedo, 1977), and some of the carboxyl groups of these compounds are sodium or potassium. Alkali metal salts and ammonium salts such as may be substituted. Particularly preferred aminocarboxylic acid derivatives include iminodiacetic acid, N-methyliminodiacetic acid, N- (2-aminoethyl) iminodiacetic acid, N- (carbamoylmethyl) iminodiacetic acid, nitrilotriacetic acid, ethylenediamine-N, N '-Diacetic acid, ethylenediamine-N, N'-di-α-propionic acid, ethylenediamine-N, N'-di-β-propionic acid, N, N'-ethylene-bis (α-o-hydroxyphenyl) glycine N, N′-di (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-diacetic acid-N, N′-diacethydroxamic acid, N-hydroxyethylethylenediamine-N , N ′, N′-triacetic acid, ethylenediamine-N, N, N ′, N′-tetraacetic acid, 1,2-propylenediamine-N, N, N ′, N′-tetraacetic acid, d l-2,3-diaminobutane-N, N, N ′, N′-tetraacetic acid, meso-2,3-diaminobutane-N, N, N ′, N′-tetraacetic acid, 1-phenylethylenediamine-N , N, N ′, N′-tetraacetic acid, d, l-1,2-diphenylethylenediamine-N, N, N ′, N′-tetraacetic acid, 1,4-diaminobutane-N, N, N ′, N'-tetraacetic acid, trans-cyclobutane-1,2-diamine-N, N, N ', N'-tetraacetic acid, trans-cyclopentane-1,2-diamine-N, N, N', N'- Tetraacetic acid, trans-cyclohexane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, cis-cyclohexane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, cyclohexane -1,3-diamine-N, N, N ′, N′-tetraacetic acid, cyclohexane-1,4-diamine-N, N N ′, N′-tetraacetic acid, o-phenylenediamine-N, N, N ′, N′-tetraacetic acid, cis-1,4-diaminobutene-N, N, N ′, N′-tetraacetic acid, trans -1,4-diaminobutene-N, N, N ′, N′-tetraacetic acid, α, α′-diamino-o-xylene-N, N, N ′, N′-tetraacetic acid, 2-hydroxy-1 , 3-propanediamine-N, N, N ′, N′-tetraacetic acid, 2,2′-oxy-bis (ethyliminodiacetic acid), 2,2′-ethylenedioxy-bis (ethyliminodiacetic acid), ethylenediamine -N, N'-diacetic acid-N, N'-di-α-propionic acid, ethylenediamine-N, N'-diacetic acid-N, N'-di-β-propionic acid, ethylenediamine-N, N, N ', N'-tetrapropionic acid, diethylenetriamine-N, N, N ′, N ″, N ″ -pentaacetic acid, triethylenetetra -N, N, N ′, N ″, N ′ ″, N ′ ″-hexaacetic acid, 1,2,3-triaminopropane-N, N, N ′, N ″, N ″ Examples include ', N' ''-hexaacetic acid, and those in which a part of the carboxyl group of these compounds is substituted with alkali metal salts such as sodium and potassium, and ammonium salts.

  The addition amount of the chelating agent is preferably 0.01% by mass to 0.4% by mass, more preferably 0.02% by mass to 0.3% by mass with respect to the total amount of monomers. It is especially preferable that it is 03 mass%-0.15 mass%. When the amount of the chelating agent is less than 0.01% by mass, capture of metal ions mixed in the production process of the polymer latex becomes insufficient, stability against aggregation of the latex is lowered, and applicability is deteriorated. On the other hand, if it exceeds 0.4%, the viscosity of the latex increases and the coatability is lowered.

  A chain transfer agent is preferably used for the synthesis of the polymer latex used in the present invention. As the chain transfer agent, those described in “Polymer Handbook, 3rd edition” (Wiley-Interscience, 1989) are preferable. Sulfur compounds are more preferred because they have high chain transfer ability and can be used in small amounts. Hydrophobic mercaptan-based chain transfer agents such as tert-dodecyl mercaptan and n-dodecyl mercaptan are particularly preferred.

  The amount of the chain transfer agent is preferably 0.2% by mass to 2.0% by mass, more preferably 0.3% by mass to 1.8% by mass, and 0.4% by mass to 1.6% by mass with respect to the total amount of monomers. Mass% is particularly preferred.

  In emulsion polymerization, in addition to the above compounds, electrolytes, stabilizers, thickeners, antifoaming agents, antioxidants, vulcanizing agents, antifreezing agents, gelling agents, vulcanization accelerators, etc. are described in synthetic rubber handbooks, etc. These additives may be used.

  In the polymer latex used in the present invention, an aqueous solvent can be used as a solvent in the coating solution, but a water-miscible organic solvent may be used in combination. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide. The amount of these organic solvents added is preferably 40% or less, more preferably 30% or less of the solvent.

The polymer latex used in the present invention preferably has a polymer concentration of 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 55% by mass with respect to the latex liquid.
The addition amount of the polymer latex is preferably 50 to 95% by mass, more preferably 70 to 90% by mass, based on the total polymer content in the receptor layer.
The polymer latex in the heat-sensitive transfer image-receiving sheet of the present invention includes a gel or dried film formed by drying a part of the solvent after coating.

<Ultraviolet absorber>
In the present invention, an ultraviolet absorber may be added to the receiving layer in order to improve light resistance. At this time, the ultraviolet absorber can be dissolved in a high-boiling organic solvent to give an emulsion, or it can be fixed to the receiving layer by increasing the molecular weight, preventing sublimation / transpiration due to diffusion to the ink sheet or heating. it can.
As the ultraviolet absorber, compounds having various ultraviolet absorber skeletons widely known in the field of information recording can be used. Specific examples include 2-hydroxybenzotriazole type ultraviolet absorbers, 2-hydroxybenzotriazine type ultraviolet absorbers, and compounds having a 2-hydroxybenzophenone type ultraviolet absorber skeleton. A compound having a benzotriazole type or triazine skeleton is preferable from the viewpoint of ultraviolet absorption ability (absorption coefficient) / stability, and a compound having a benzotriazole type or benzophenone type skeleton is preferable from the viewpoint of increasing the molecular weight or forming a latex. Specifically, an ultraviolet absorber described in JP 2004-361936 A can be used.

  The ultraviolet absorber preferably has absorption in the ultraviolet region and does not have an absorption edge in the visible region. Specifically, when a thermal transfer image-receiving sheet is formed by adding to the receiving layer, the reflection density at 370 nm is preferably Abs 0.5 or more, and the reflection density at 380 nm is more preferably Abs 0.5 or more. . The reflection density at 400 nm is preferably Abs 0.1 or less. A high reflection density in the range exceeding 400 nm is not preferable because the image is yellowed.

  In the present invention, the ultraviolet absorber has a high molecular weight, preferably a mass average molecular weight of 10,000 or more, and more preferably a mass average molecular weight of 100,000 or more. As a means for increasing the molecular weight, it is preferable to graft an ultraviolet absorber onto the polymer. The polymer that becomes the main chain preferably has a polymer skeleton that is inferior in dyeability to the dye used in combination. Moreover, it is preferable to have sufficient film strength when the film is formed. The graft ratio of the ultraviolet absorber to the polymer main chain is preferably 5 to 20% by mass, and more preferably 8 to 15% by mass.

Moreover, it is more preferable that the polymer grafted with the ultraviolet absorber is made into a latex. The receptor layer can be formed by forming an aqueous dispersion type coating solution into a latex to form a latex, and the manufacturing cost can be reduced. For example, the method described in Japanese Patent No. 3450339 can be used as a method for forming a latex. Examples of the latex-made ultraviolet absorber include ULS-700, ULS-1700, ULS-1383MA, ULS-1635MH, XL-7016, ULS-933LP, ULS-935LH, Shin-Nakamura Chemical Co., Ltd. Commercially available ultraviolet absorbers such as New Coat UVA-1025W, New Coat UVA-204W, and New Coat UVA-4512M (both are trade names) can also be used.
When the polymer to which the ultraviolet absorber is grafted is made into a latex, it is possible to form a receiving layer in which the ultraviolet absorber is uniformly dispersed by mixing with the latex of the above-mentioned dyeable receiving polymer and applying it.

  The addition amount of the polymer grafted with the ultraviolet absorber or the latex thereof is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to the dyeable accepting polymer latex forming the receptor layer.

<Release agent>
In addition, a release agent may be added to the receiving layer in order to prevent thermal fusion with the thermal transfer sheet during image formation. As the mold release agent, silicone oil, phosphate ester plasticizer fluorine compound, and various wax dispersions can be used. In particular, silicone oil and wax dispersion are preferably used.

  As the silicone oil, modified silicone oils such as epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy / polyether modification, and polyether modification are preferably used. A reaction product of vinyl-modified silicone oil and hydrogen-modified silicone oil is preferable. The addition amount of the release agent is preferably 0.2 to 30 parts by mass with respect to the receiving polymer.

  A known dispersion can be used as the wax dispersion. In the present invention, “wax is treated as an organic substance having a solid or semi-solid alkyl chain at normal temperature” (according to the definition of “Revised properties and application of wax” (Shoshobo, 1989)). Examples of preferred compounds include candelilla wax, carnauba wax, rice wax, wood wax, montan wax, ozokerite, paraffin wax, microcrystalline wax, petrolactam, Fischer-Tropsch wax, polyethylene wax, montan wax derivative, paraffin wax. Derivatives, microcrystalline wax derivatives, hardened castor oil, hardened castor oil derivatives, 12-hydroxystearic acid, stearamide, phthalic anhydride, chlorinated hydrocarbons, and other blended waxes. Of these, carnauba wax, montan wax and derivatives thereof, paraffin wax and derivatives thereof, microcrystalline wax and derivatives thereof, polyethylene wax and stearamide are preferable, and kaunauba wax, mondan wax and derivatives thereof, microcrystalline wax. Stearamide is more preferable, and montan wax and derivatives thereof, and microcrystalline wax are more preferable.

This wax is selected from those having a melting point of 25 ° C to 120 ° C, preferably 40 ° C to 100 ° C, more preferably 60 ° C to 90 ° C.
<Emulsions>
Hydrophobic additives such as anti-fading agents, ultraviolet absorbers, antioxidants, and lubricants can be applied to image receiving sheet layers (for example, receiving layers) by known methods such as those described in US Pat. No. 2,322,027. , Heat insulation layer, intermediate layer, subbing layer, etc.). In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, and 4,555,476 No. 4,599,296, etc., Japanese Patent Publication No. 3-62256, etc., a high boiling point organic solvent, if necessary, a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C. It can be used in combination. These lubricants, antioxidants, high-boiling organic solvents and the like can be used in combination of two or more.
Examples of the lubricant include solid waxes such as polyethylene wax, amide wax, and Teflon powder (Teflon: registered trademark); silicone oil, phosphate ester compounds, fluorine surfactants, silicone surfactants, and other related technologies. Any release agent known in the art can be used. Silicone compounds such as various waxes, fluorine compounds represented by fluorine surfactants, silicone surfactants, silicone oils and / or cured products thereof are preferably used.
Examples of the anti-fading agent include A-6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92, described in European Patent Publication No. EP298321A 94,164 (pages 69-118), US Pat. No. 5,122,444, columns 25-38, II-1 to III-23, in particular III-10, European Patent Publication No. EP471347A, 8-12. I-1 to III-4 described in the page, in particular II-2, A-1 to 48 described in columns 32 to 40 of US Pat. No. 5,139,931, in particular A-39,42, Europe The formulas (I) to (III), particularly I-47, 72, III-1, 27 (pages 24 to 48) described on page 4, lines 30 to 33 of Patent Publication EP298321A can be used.

<Surfactant>
In the heat-sensitive transfer image-receiving sheet of the present invention, a surfactant can be contained in the above arbitrary layer. Among these, it is preferable to make it contain in a receiving layer and an intermediate | middle layer.
The addition amount of the surfactant is preferably 0.01 to 5% by mass, more preferably 0.01 to 1% by mass, and 0.02 to 0.2% by mass with respect to the total solid content. It is particularly preferred that
Various surfactants such as anionic, nonionic, and cationic surfactants are known. As the surfactant that can be used in the present invention, known ones can be used. For example, those introduced in “Supervision of Functional Surfactant / Mitsuo Tsunoda, Issued / August 2000, Chapter 6” Among them, an anionic fluorine-containing surfactant is preferable.
Application is possible even when no surfactant is contained, but since the surface tension of the application liquid is high, the application surface may be uneven and uneven. By containing a surfactant in the coating solution, the surface tension can be lowered, unevenness during coating can be eliminated, the coated surface can be made uniform, and coating can be performed stably.

  Although the specific example of a fluorine compound is illustrated below, the fluorine compound which can be used by this invention is not restrict | limited at all by the following specific examples. Unless otherwise specified, the alkyl group and perfluoroalkyl group in the structure notation of the following exemplified compounds means a group having a linear structure.

  These fluorine compounds are used as a surfactant in a coating composition for forming a layer constituting a heat-sensitive transfer image-receiving sheet (in particular, a receiving layer, a heat insulating layer, an intermediate layer, an undercoat layer, a back layer, etc.). Although used, in the present invention, it can be preferably contained in the receiving layer and the intermediate layer.

<Hardener>
The hardening agent used in the present invention as a crosslinking agent can be added to a coating layer (for example, a receiving layer, a heat insulating layer, a subbing layer, etc.) of the image receiving sheet.
Examples of the hardening agent that can be used in the present invention include H-1,4,6,8,14 on page 17 of JP-A-1-214845, column 13 to U.S. Pat. No. 4,618,573. 23 compounds (H-1 to 54) represented by formulas (VII) to (XII), compounds (H-1 to 76) represented by formula (6) on page 8, lower right of JP-A-2-214852, In particular, H-14 and the compounds described in claim 1 of US Pat. No. 3,325,287 are preferably used. Examples of hardeners are US Pat. No. 4,678,739, column 41, US Pat. No. 4,791,042, JP-A Nos. 59-116655, 62-245261, and 61. No. 18942, Japanese Patent Laid-Open No. 4-218044, and the like. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N′-ethylene-bis (vinylsulfonylacetamide) Ethane), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid, or polymer hardeners (compounds described in JP-A-62-234157).
Preferably, a vinyl sulfone type hardener and chlorotriazines are used.
More preferable hardeners in the present invention are compounds represented by the following general formula (B) or (C).
General formula (B)
_{(CH 2 = CH-SO 2} ) n-L
General formula (C)
(X—CH ₂ —CH ² —SO ₂ ) nL
In general formulas (B) and (C), X represents a halogen atom, and L represents an n-valent organic linking group. When the compound represented by formula (B) or (C) is a low molecular compound, n represents an integer of 1 to 4. In the case of a polymer compound, L is an organic linking group containing a polymer chain, and n is in the range of 10 to 1000.

  In the general formulas (B) and (C), X is preferably a chlorine atom or a bromine atom, more preferably a bromine atom. n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably an integer of 2 to 3, and most preferably 2.

  L represents an n-valent organic group, preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, and these groups are ether bond, ester bond, amide bond, sulfonamide bond, urea bond, It may be further connected with a urethane bond or the like. These groups may have a substituent, such as a halogen atom, alkyl group, aryl group, heterocyclic group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, alkoxycarbonyl. Groups, carbamoyloxy groups, acyl groups, acyloxy groups, acylamino groups, sulfonamido groups, carbamoyl groups, sulfamoyl groups, sulfonyl groups, phosphoryl groups, carboxyl groups, sulfo groups, etc., halogen atoms, alkyl groups, hydroxy groups, Alkoxy groups, aryloxy groups and acyloxy groups are preferred.

  These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of water-soluble polymer.

<Preservative>
If the coating solution, the image receiving sheet, the print image, and the like are stored, microorganisms (particularly bacteria, mold, yeast, etc.) adhere to these materials during storage, and their performance is often lowered. In order to prevent this, a preservative can be contained in a range that does not affect other performances.
The preservative referred to in the present invention is a compound used to suppress the compound used in the image-receiving sheet from undergoing a decomposition reaction due to the growth of the microorganism, and the definition and specific compound by the general formula are Handbook, Gihodo Publishing (1986), Hiroshi Horiguchi, Antibacterial and Funeral Chemistry, Sankyo Publishing (1986), Antibacterial and Antifungal Encyclopedia, Japanese Antibacterial and Antifungal Society (1986).
The preservative contained in the heat-sensitive transfer image-receiving sheet of the present invention is not particularly limited, but phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzoisothiazoline-3-one , Benzotriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, derivatives of pyrozine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives, 2-mercaptopyridine-N-oxide or salts thereof, formaldehyde donor antibacterial agents Etc. Among these, phenol or a derivative thereof, 4-isothiazolin-3-one derivative, benzoisothiazolin-3-one, and the like are preferable.

  Besides these, compounds represented by any one of the following general formulas [I] to [IV] can be used as preservatives.

一般式〔Ｉ〕中、Ｒ¹、Ｒ²は同じでも異なっていてもよく、水素原子、ヒドロキシ基、または低級アルキル基を表す。Ｘは水素原子、ハロゲン原子、ニトロ基、シアノ基、アリール基、低級アルキル基、低級アルケニル基、アラルキル基、アルコキシ基、−ＣＯＲ³、−ＳＯ₂Ｒ⁴、またはＮ（Ｒ⁵）Ｒ⁶を表し、Ｒ³、Ｒ⁴は同じでも異なっていてもよく、水素原子、−ＯＭ、低級アルキル基、低級アルコキシ基、またはＮ（Ｒ⁷）Ｒ⁸を表す。
Ｒ⁵、Ｒ⁶は同じでも異なっていてもよく、水素原子、低級アルキル基、−ＣＯＲ⁹、またはＳＯ₂Ｒ¹⁰を表わす。Ｒ⁹、Ｒ¹⁰は同じでも異なっていてもよく、低級アルキル基、またはＮ（Ｒ¹¹）Ｒ¹²を表し、Ｒ⁷、Ｒ⁸、Ｒ¹¹、Ｒ¹²は同じであっても異なっていてもよく、水素原子または低級アルキル基を表す。
Ｍは、水素原子、アルカリ金属原子、または１価のカチオンを形成するに必要な原子群を表わし、ｌは２〜６の整数を表し、ｍは１〜４の整数を表し、ｎは６−ｍを表す。ただし、Ｒ¹、Ｒ²、Ｘが複数存在する時はそれぞれが互いに異なっていてもよい。

In the general formula [I], R ¹ and R ² may be the same or different and each represents a hydrogen atom, a hydroxy group, or a lower alkyl group. X represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aryl group, a lower alkyl group, a lower alkenyl group, an aralkyl group, an alkoxy group, —COR ³ , —SO ₂ R ⁴ , or N (R ⁵ ) R ⁶ . R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, —OM, a lower alkyl group, a lower alkoxy group, or N (R ⁷ ) R ⁸ .
R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom, a lower alkyl group, —COR ⁹ , or SO ₂ R ¹⁰ . R ⁹ and R ¹⁰ may be the same or different and each represents a lower alkyl group or N (R ¹¹ ) R ¹² , and R ⁷ , R ⁸ , R ¹¹ and R ¹² may be the same or different. Often represents a hydrogen atom or a lower alkyl group.
M represents a hydrogen atom, an alkali metal atom, or an atomic group necessary for forming a monovalent cation, l represents an integer of 2 to 6, m represents an integer of 1 to 4, and n represents 6- represents m. However, when there are a plurality of R ¹ , R ² , and X, each may be different from each other.

一般式〔II〕中、Ｒ¹³は水素原子、アルキル基、アルケニル基、アラルキル基、アリール基、複素環基、

In the general formula [II], R ¹³ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group,

を表し、Ｒ¹⁴、Ｒ¹⁵は同じでも異なっていてもよく、水素原子、アルキル基、アリール基、シアノ基、複素環基、アルキルチオ基、アルキルスルホキシ基、またはアルキルスルホニル基を表し、Ｒ¹⁴とＲ¹⁵は互いに結合して芳香環を形成していても良い。
Ｒ¹⁶、Ｒ¹⁷は同じでも異なっていてもよく、水素原子、アルキル基、アリール基、またはアラルキル基を表す。
これらの中でも、Ｒ¹⁴、Ｒ¹⁵が水素原子であり、Ｒ¹³がメチル基であるもの（以下、化合物II−ａと称する）が好ましい。また、Ｒ¹⁴とＲ¹⁵が互いに結合して芳香環を形成しＲ¹³が水素原子であるものと化合物II−ａとの組み合わせ、および、Ｒ¹⁴が塩素原子、Ｒ¹⁵が水素原子、Ｒ¹³がメチル基であるものと化合物II−ａとの組み合わせはさらに好ましい。

R ¹⁴ and R ¹⁵ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkylsulfoxy group, or an alkylsulfonyl group, and R ¹⁴ And R ¹⁵ may combine with each other to form an aromatic ring.
R ¹⁶ and R ¹⁷ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
Among these, those in which R ¹⁴ and R ¹⁵ are hydrogen atoms and R ¹³ is a methyl group (hereinafter referred to as compound II-a) are preferable. In addition, R ¹⁴ and R ¹⁵ are bonded to each other to form an aromatic ring and R ¹³ is a hydrogen atom in combination with Compound II-a, R ¹⁴ is a chlorine atom, R ¹⁵ is a hydrogen atom, R ¹³ The combination of the compound in which is a methyl group and the compound II-a is further preferred.

一般式〔III〕中、Ｒ¹⁸は水素原子、アルキル基、ヒドロキシメチル基を表わし、Ｒ¹⁹は水素原子、アルキル基を表す。

In the general formula [III], R ¹⁸ represents a hydrogen atom, an alkyl group or a hydroxymethyl group, and R ¹⁹ represents a hydrogen atom or an alkyl group.

一般式〔IV〕式中、Ｒ²⁰は低級アルキレン基を表し、Ｘは水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、シアノ基、低級アルキル基、低級アルコキシ基、−ＣＯＲ²¹、−Ｎ（Ｒ²²）Ｒ²³、または−ＳＯ₃Ｍを表し、Ｒ²¹は水素原子、−ＯＭ、低級アルキル基、アリール基、アラルキル基、低級アルコキシ基、アリールオキシ基、アラルキルオキシ基、または−Ｎ（Ｒ²⁴）Ｒ²⁵を表す。
Ｒ²²、Ｒ²³は同じでも異なっていてもよく、水素原子、低級アルキル基、アリール基、アラルキル基、-ＣＯＲ²⁶、または−ＳＯ₂Ｒ²⁶を表し、互に同じであっても異なっていてもよく、Ｒ²⁴、Ｒ²⁵は同じでも異なっていてもよく、水素原子、低級アルキル基、アリール基、またはアラルキル基を表わし、Ｒ²⁶は低級アルキル基、アリール基、またはアラルキル基を表わし、Ｍは水素原子、アルカリ金属原子、または１価のカチオンを形成するに必要な原子群を表し、ｐは０または１を表わし、ｑは０〜５の整数を表わす。

In the general formula [IV], R ²⁰ represents a lower alkylene group, X represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, —COR ²¹ , —N (R ²²⁾ R ²³ or represents -SO ₃ M, R ²¹ is a hydrogen atom, -OM, a lower alkyl group, an aryl group, an aralkyl group, a lower alkoxy group, an aryloxy group, an aralkyloxy group or -N (R ^24,, ) Represents R ²⁵ .
R ²² and R ²³ may be the same or different and each represents a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, —COR ²⁶ , or —SO ₂ R ^{26, and} may be the same or different from each other. R ²⁴ and R ²⁵ may be the same or different and each represents a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group; R ²⁶ represents a lower alkyl group, an aryl group, or an aralkyl group; Represents a hydrogen atom, an alkali metal atom, or an atomic group necessary to form a monovalent cation, p represents 0 or 1, and q represents an integer of 0 to 5.

  Any one of the preservatives may be used alone, or two or more arbitrary compounds may be selected and used in combination. The preservative may be added as it is, but it may be dissolved in water or an organic solvent such as methanol, ethanol, isopropyl alcohol, acetone, ethylene, ethylene glycol, and added as a solution to the image-receiving sheet coating solution. Or you may add in latex. Alternatively, it may be dissolved in a high boiling point solvent, a low boiling point solvent, or a mixed solvent of both, and then emulsified and dispersed in the presence of a surfactant and added to the latex.

<Matting agent>
In the present invention, it is preferable to add a matting agent for imparting releasability. The matting agent is preferably contained in the outermost surface layer, the layer functioning as the outermost surface layer of the heat-sensitive transfer image-receiving sheet, or a layer close to the outer surface. The outermost surface layer can be made into two layers as required. Most preferably, it is added to the outermost receiving layer. The matting agent can be added to both the outermost layer on the image forming layer surface and the outermost layer on the back surface, and can also be added to both layers. In particular, it is preferable to include a matting agent on the side of the support containing the slip agent.

  The matting agent is preferably dispersed in advance with a binder and used as a matting agent particle dispersion.

  Examples of the matting agent generally include fine particles of an organic compound insoluble in water and fine particles of an inorganic compound. In the present invention, fine particles containing an organic compound are preferable from the viewpoint of dispersibility. As long as it contains an organic compound, it may be an organic compound fine particle composed of an organic compound alone, or an organic / inorganic composite fine particle containing not only an organic compound but also an inorganic compound. Examples of the matting agent include, for example, U.S. Pat. Nos. 1,939,213, 2,701,245, 2,322,037, 3,262,782, 3,539,344, Those well known in the silver salt sensitive material industry such as the organic matting agent described in each specification such as US Pat. No. 3,767,448 can be used.

Since the temperature of the receiving layer surface becomes high during image printing, the matting agent preferably has heat resistance.
In particular, a polymer having a thermal decomposition temperature of 200 ° C. or higher is preferable. More preferably, it is a polymer having a thermal decomposition temperature of 240 ° C. or higher.
In addition, when the image is printed, not only heat but also pressure is applied to the surface of the receiving layer.

  The matting agent contained in the outermost layer on the image forming layer side and the outermost layer adjacent layer is dispersed in advance with a binder and used as a matting agent particle dispersion. The dispersion method is (a) a matting agent. The dispersion of the matting agent by removing the low boiling point organic solvent from the emulsion by emulsifying and dispersing the polymer to be dissolved in an aqueous medium as a solution (for example, dissolved in a low boiling point organic solvent) to obtain polymer droplets There are two methods: (b) a method in which fine particles such as a polymer to be a matting agent are prepared in advance, and a dispersion is prepared so as not to cause lumps in an aqueous medium. In the present invention, in consideration of the environment, the method (b) in which a low-boiling organic solvent is not discharged to the environment is preferable.

  Since the dispersion state of the mat particle dispersion in the present invention is stabilized when it contains a surfactant, it is preferable to add a surfactant.

(Insulation layer)
The heat insulating layer serves to protect the support from heat during heat transfer using a thermal head or the like. Moreover, since it has high cushioning properties, a thermal transfer image-receiving sheet with high printing sensitivity can be obtained even when paper is used as the support. The heat insulating layer may be one layer or two or more layers. The heat insulating layer is provided on the support side from the receptor layer.

In the heat-sensitive transfer image-receiving sheet of the present invention, the heat insulating layer is preferably produced by aqueous coating, and more preferably contains a hollow polymer.
The hollow polymer in the present invention is a polymer particle having independent pores inside the particle, preferably a polymer latex. For example, 1) water is contained in a partition wall formed of polystyrene, acrylic resin, styrene-acrylic resin, or the like. Non-foamed hollow polymer particles in which the water inside the particles evaporates outside the particles after coating and drying, and the inside of the particles becomes hollow. 2) Low-boiling liquids such as butane and pentane are added to polyvinylidene chloride, poly It is covered with a resin made of acrylonitrile, polyacrylic acid, polyacrylic acid ester, or a mixture or polymer thereof, and after coating, the low-boiling liquid inside the particles expands by heating to make the interior hollow. Foaming type microballoons, 3) Microbubbles obtained by heating and foaming the above 2) in advance to form a hollow polymer Such as over emissions and the like.

The average particle size of these hollow polymers is preferably 0.3 to 1.0 μm. If this size is too small, the hollowness tends to decrease and the desired heat insulating property cannot be obtained. If the size is too large, the frequency of occurrence of planar failures other than coarse particles in the heat insulating layer increases.
The hollow polymer preferably has a hollow ratio of about 20 to 70%, particularly preferably 20 to 50%. If the hollow ratio is too small, the desired heat insulating property cannot be obtained, and if it is too large, the ratio of hollow polymer particles and incomplete hollow particles that are easily broken increases, resulting in printing defects and insufficient film strength. .
Two or more types of hollow polymers can be mixed and used as necessary. Specific examples of 1) include Ropaque 1055 manufactured by Law & Haas Co., Ltd., Bon Coat PP-1000 manufactured by Dainippon Ink, Inc. . Specific examples of 2) include F-30 and F-50 (both trade names) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Specific examples of 3) include F-30E manufactured by Matsumoto Yushi Seiyaku Co., Ltd., EXPANSEL 461DE, 551DE, and 551DE20 (all trade names) manufactured by Nippon Ferrite Co., Ltd. The hollow polymer used for the heat insulating layer may be made into a latex.

  The glass transition temperature (Tg) of the hollow polymer is not particularly limited, but is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher. Two or more types of hollow polymers can be mixed and used as necessary.

  The heat insulating layer containing the hollow polymer preferably contains a water-dispersed resin or a water-soluble resin as a binder in addition to the hollow polymer. Examples of the binder resin used in the present invention include acrylic resins, styrene-acrylic copolymers, polystyrene resins, polyvinyl alcohol resins, vinyl acetate resins, ethylene-vinyl acetate copolymers, vinyl chloride vinyl acetate copolymers, and styrene. Known resins such as a butadiene copolymer, a urethane resin, a polyvinylidene chloride resin, a cellulose derivative, casein, starch, and gelatin can be used. These are preferably water-soluble polymers described in the receiving layer. Among these binder resins, gelatin, polyvinyl alcohol, styrene-butadiene copolymer and urethane resin are preferable, and gelatin and polyvinyl alcohol are more preferable. These resins can be used alone or in combination.

The solid content of the hollow polymer in the heat insulating layer is preferably between 5 and 2000 parts by mass when the solids content of the binder resin is 100 parts by mass. Moreover, 1-70 mass% is preferable, and, as for the mass ratio which occupies with respect to the coating liquid of the solid content of a hollow polymer, 10-40 mass% is more preferable. If the ratio of the hollow polymer is too small, sufficient heat insulation cannot be obtained, and if the ratio of the hollow polymer is too large, the binding force between the hollow polymers decreases, causing problems such as powder falling off during processing or film peeling. Arise.
The particle size of the hollow polymer particles is preferably 0.1 to 20 μm, more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1 μm.

0.5-14 mass% is preferable, and, as for the quantity which occupies for the coating liquid of the said binder of a heat insulation layer, 1-6 mass% is especially preferable. The coating amount of the hollow polymer in the heat insulation layer is preferably ^{1~100g / m 2, 5~20g / m} 2 is more preferable.
The thickness of the heat insulating layer containing the hollow polymer is preferably 5 to 50 μm, and more preferably 5 to 40 μm.

(Middle layer)
An intermediate layer may be formed between the receptor layer and the support. For example, a white background adjusting layer, a charge adjusting layer, an adhesive layer, a primer layer, and an undercoat layer are formed. About these layers, it can be set as the structure similar to what was described, for example in patent 3585599 specification, patent 2925244 specification.

(Support)
In the present invention, it is preferable to use a water-resistant support as the support. By using a water-resistant support, it is possible to prevent moisture from being absorbed into the support, and to prevent a change in performance of the receiving layer over time. As the water-resistant support, for example, coated paper or laminated paper can be used. Of these, laminated paper is preferable in terms of surface smoothness. Similar to polyethylene laminated paper (sometimes abbreviated as WP paper) used for photographic paper in the field of silver salt photography, that is, a support mainly composed of cellulose, and at least a receiving layer is applied. A support having a surface coated with a polyolefin resin can be suitably used.

-Coated paper-
The coated paper is a paper obtained by coating various sheets of resin, rubber latex or polymer material on one or both sides of a sheet such as a base paper, and the coating amount varies depending on the application. Examples of such coated paper include art paper, cast coated paper, Yankee paper, and the like.

  As the resin applied to the surface of the base paper or the like, it is appropriate to use a thermoplastic resin. Examples of such a thermoplastic resin include the following thermoplastic resins (a) to (h).

(A) Polyolefin resins such as polyethylene resins and polypropylene resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, acrylic resins, and the like.
(B) A thermoplastic resin having an ester bond. For example, a dicarboxylic acid component (these dicarboxylic acid components may be substituted with a sulfonic acid group, a carboxyl group, etc.) and an alcohol component (these alcohol components may be substituted with a hydroxyl group, etc.) Polyester resin obtained by condensation of poly (methyl methacrylate), polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate, etc. or polymethacrylate resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, styrene -Methacrylic acid ester copolymer resin, vinyl toluene acrylate resin, etc. are mentioned.
Specific examples include those described in JP-A Nos. 59-101395, 63-7971, 63-7972, 63-7773, and 60-294862. it can.
Commercially available products include Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130 manufactured by Toyobo Co., Ltd., Tufton NE-382, Tufton manufactured by Kao Corporation U-5, ATR-2009, ATR-2010; Elitel UE3500, UE3210, XA-8153, KZA-7049, KZA-1449 manufactured by Unitika Ltd. Polyester TP-220, R manufactured by Nippon Synthetic Chemical Co., Ltd. -188; various types of thermoplastic resins of the Hiros series manufactured by Seiko Chemical Industry Co., Ltd. (all trade names).

(C) Polyurethane resin etc. are mentioned.
(D) Polyamide resin, urea resin, etc. are mentioned.
(E) Polysulfone resin and the like.
(F) Polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin, and the like.
(G) Cellulose resins, such as polyol resin, ethyl cellulose resin, cellulose acetate resin, etc., such as polyvinyl butyral.
(H) Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, epoxy resin, phenol resin and the like.
In addition, the said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

  Further, the thermoplastic resin may contain pigments or dyes such as brighteners, conductive agents, fillers, titanium oxide, ultramarine blue, and carbon black as required.

-Laminated paper-
The laminated paper is a paper obtained by laminating various resins, rubber or polymer sheets or films on a sheet such as a base paper. Examples of the laminate material include polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, polyimide, triacetyl cellulose, and the like. These resins may be used alone or in combination of two or more.

  In general, the polyolefin is often formed using low density polyethylene, but in order to improve the heat resistance of the support, polypropylene, a blend of polypropylene and polyethylene, high density polyethylene, high density polyethylene and low density polyethylene, It is preferable to use a blend of In particular, it is most preferable to use a blend of high-density polyethylene and low-density polyethylene from the viewpoint of cost, suitability for lamination, and the like.

The blend of the high density polyethylene and the low density polyethylene is used, for example, in a blend ratio (mass ratio) of 1/9 to 9/1. The blend ratio is preferably 2/8 to 8/2, and more preferably 3/7 to 7/3. When forming a thermoplastic resin layer on both surfaces of the support, the back surface of the support is preferably formed using, for example, high-density polyethylene or a blend of high-density polyethylene and low-density polyethylene. The molecular weight of the polyethylene is not particularly limited, but the melt index is 1.0 to 40 g / 10 min for both high-density polyethylene and low-density polyethylene, and has an extrudability. preferable.
In addition, you may perform the process which gives white reflectivity to these sheets or films. Examples of such a treatment method include a method of blending a pigment such as titanium oxide in these sheets or films. This is generally used as a support for photographic paper in the field of silver salt photography (sometimes abbreviated as WP paper).

  The thickness of the support is preferably 25 μm to 300 μm, more preferably 50 μm to 260 μm, and further preferably 75 μm to 220 μm. Various stiffnesses can be used according to the purpose of the support. As a support for a thermal transfer image-receiving sheet of photographic quality, a support for color silver salt photographic paper is used. Close ones are preferred.

(Curl adjustment layer)
If the support is exposed as it is, the heat-sensitive transfer image-receiving sheet may be curled due to the humidity and temperature in the environment. Therefore, it is preferable to form a curl adjusting layer on the back side of the support. The curl adjusting layer not only prevents the image receiving sheet from curling but also serves as a waterproof. For the curl adjusting layer, polyethylene laminate, polypropylene laminate, or the like is used. Specifically, it can be formed in the same manner as described in, for example, JP-A-61-110135 and JP-A-6-202295.

(Writing layer / Charge adjustment layer)
An inorganic oxide colloid, an ionic polymer, or the like can be used for the writing layer and the charge adjusting layer. As the antistatic agent, for example, a cationic antistatic agent such as a quaternary ammonium salt or a polyamine derivative, an anionic antistatic agent such as an alkyl phosphate, or a nonionic antistatic agent such as a fatty acid ester can be used. . Specifically, it can be formed in the same manner as that described in, for example, Japanese Patent No. 3585585.

The method for producing the thermal transfer image receiving sheet of the present invention will be described below.
The heat-sensitive transfer image-receiving sheet of the present invention is produced by applying at least one receptor layer and at least one heat-insulating layer on a support by aqueous coating. The coating method can be appropriately selected from known methods.
The receiving layer and the heat-insulating layer are each preferably two or more layers, or one of them is a two-layer or more. However, if at least the adjacent constituent layers are both water-based, these layers can be applied simultaneously. preferable.
When producing a multi-layer image receiving sheet comprising a plurality of layers having different functions (such as a bubble layer, a heat insulating layer, an intermediate layer, and a receiving layer) on a support, JP-A Nos. 2004-106283 and 2004-181888 are disclosed. In addition, it is known that each layer is sequentially coated as disclosed in each publication such as JP-A 2004-345267, or the layers are previously applied on a support and bonded together. On the other hand, it is known in the photographic industry that productivity is greatly improved, for example, by applying a plurality of layers simultaneously. For example, JP-A Nos. 2,761,791, 2,681,234, 3,508,947, 4,457,256, 3,993,019, etc. Each specification, JP-A 63-54975, JP-A 61-278848, 55-86557, 52-31727, 55-142565, 50-43140, 63-80872, 54-54020, JP-A-5-104061, JP-A-5-127305, JP-B-49-7050, Edgar B. Gutoff et al., “Coating and Drying Defects: Troubleshooting Operating Problems”, John Wiley & Sons 1995, pages 101 to 103, etc., so-called slide coating (slide coating method) and curtain coating (curtain coating method) are known. In these coating methods, a plurality of coating liquids are simultaneously supplied to a coating apparatus to form a plurality of different layers.
In the present invention, the simultaneous multi-layer coating is used for the production of a multi-layer image-receiving sheet, so that the effect of the present invention is effectively exhibited, and at the same time, the runnability when superposed on the ink sheet is excellent. A heat-sensitive transfer image-receiving sheet can be obtained. In addition, it is possible to obtain a heat-sensitive transfer image-receiving sheet that has excellent adhesion between coating layers and is unlikely to peel off even when the display with an adhesive tape is repeated. Furthermore, productivity can be significantly improved.
In simultaneous multi-layer coating, it is necessary to adjust the viscosity and surface tension of the coating solution constituting each layer from the viewpoints of forming a uniform coating film and good coating properties. The viscosity of the coating solution can be easily adjusted by using a known thickener or thickener within a range that does not affect other performances. Further, the surface tension of the coating solution can be adjusted by various surfactants.

In the present invention, the plurality of layers are composed mainly of a resin. The coating solution for forming each layer is preferably a polymer latex. The solid content mass of the latex resin in the coating solution of each layer is preferably in the range of 5 to 80%, particularly preferably in the range of 20 to 60%. The average particle size of the resin contained in the polymer latex is 5 μm or less, and particularly preferably 1 μm or less. The polymer latex may contain a known additive such as a surfactant, a dispersant, and a binder resin as necessary.
These coating solution temperatures are preferably 25 ° C. to 60 ° C., and more preferably 30 ° C. to 50 ° C.
In the present invention, it is preferable to form a laminate of a plurality of layers on a support by the method described in US Pat. No. 2,761,791 and then solidify immediately. As an example, in the case of a multilayer structure solidified by a resin, it is preferable to quickly raise the temperature after forming a plurality of layers on the support. When a binder that gels at a low temperature such as gelatin is included, it may be preferable to quickly lower the temperature after forming a plurality of layers on the support, cool and solidify the coating, and then raise the temperature and dry it. .
As an example of a method for lowering the temperature, there is a method of applying cold air or the like to the coating film. The temperature of the cold air is preferably 25 ° C. or less, more preferably 15 ° C. or less, and particularly preferably 10 ° C. or less. Further, the time for which the coating film is exposed to cold air is preferably 15 seconds or longer, although it depends on the coating conveyance speed. In order to promote gelation, a known gelling agent may be used in addition to increasing the binder mass ratio.
The coating amount of a coating solution per one layer constituting the multilayer in the present invention in the range of 1g / m ² ~500g / m ² is preferred. The number of layers in the multilayer configuration can be arbitrarily selected as 2 or more. The receiving layer is preferably provided as the layer furthest away from the support.

The heat-sensitive transfer image-receiving sheet of the present invention is coated by the above-described method, and preferably dried after simultaneous multi-layer coating. However, in the present invention, since latex constitutes the main coating solution, the film shrinks due to drying when dried rapidly. Since it occurs unevenly and cracks occur in the coated film after drying, it is preferable to dry slowly.
In order to satisfy such requirements, the drying process needs to be dried while adjusting the drying speed, adjusting the drying temperature, the amount of drying air, and the dew point of the drying air.

The thermal transfer sheet (ink sheet) used in combination with the above-described thermal transfer image-receiving sheet of the present invention at the time of thermal transfer image formation is provided with a dye layer containing a diffusion transfer dye on a support. Ink sheets can be used. As the means for applying thermal energy during thermal transfer, any conventionally known means for applying can be used. For example, the recording time is controlled by a recording device such as a thermal printer (for example, ASK-2000 manufactured by FUJIFILM Corporation). By doing so, the intended purpose can be sufficiently achieved by applying thermal energy of about 0 to 50 mJ / mm ² .
The heat-sensitive transfer image-receiving sheet of the present invention can be applied to various uses such as a sheet- or roll-shaped heat-sensitive transfer image-receiving sheet, cards, and transmission-type manuscript preparation sheets capable of thermal transfer recording by appropriately selecting a support. You can also

  The present invention can be used in printers, copiers and the like using a thermal transfer recording system.

  Hereinafter, the features of the present invention will be described more specifically with reference to Examples and Comparative Examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. In Examples, “part” or “%” is based on mass unless otherwise specified.

(1) Production of thermal transfer image-receiving sheet (production of support)
50 parts by mass of LBKP (hardwood bleached kraft pulp) made of acacia and 50 parts by mass of LBKP made of aspen were each beaten to 300 ml of Canadian freeness by a disc refiner to prepare a pulp slurry.
Next, to the pulp slurry obtained above, cation-modified starch (CAT0304L manufactured by Nippon NSC Co., Ltd.) 1.3%, anionic polyacrylamide (DA4104 manufactured by Seiko PMC Co., Ltd.) 0.15% per pulp, Alkyl ketene dimer (size Pine K manufactured by Arakawa Chemical Co., Ltd.) 29%, 0.29% epoxidized behenamide, 0.32% polyamide polyamine epichlorohydrin (Arakawa Chemical Co., Ltd .: Arafix 100) were added, and then 0.12% of an antifoaming agent was added.
In the process of making the pulp slurry prepared as described above with a long paper machine and pressing the felt surface of the web against the drum dryer cylinder through the dryer canvas for drying, the tensile force of the dryer canvas is 1.6 kg / After drying by setting to cm, 1 g / m ² of polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: KL-118) was applied on both sides of the base paper with a size press and dried, and then calendar treatment was performed. The base paper was made with a basis weight of 157 g / m ² to obtain a base paper (base paper) having a thickness of 160 μm.
After performing corona discharge treatment on the wire surface (back surface) side of the obtained base paper, MFR (melt flow rate; hereinafter the same) 16.0 g / 10 min, density 0.96 g / cm using a melt extruder. ³ high density polyethylene (hydrotalcite (trade name DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) 250 ppm, secondary antioxidant (tris (2,4-di-tert-butylphenyl) phosphite, product) Name: Irgaphos 168, manufactured by Ciba Specialty Chemicals Co., Ltd., containing 200 ppm) and MFR 4.0 g / 10 min, low density polyethylene having a density of 0.93 g / cm ³ , 75/25 (mass ratio) The resin composition blended at a ratio of 1 to ² was coated to a thickness of 21 g / m ² to form a thermoplastic resin layer comprising a mat surface (hereinafter, this thermoplastic resin layer). The surface is referred to as “rear surface.”) The thermoplastic resin layer on the rear surface side is further subjected to corona discharge treatment, and then, as an antistatic agent, aluminum oxide (“Alumina Sol 100” manufactured by Nissan Chemical Industries, Ltd.) and A dispersion in which silicon dioxide (“Snowtex O” manufactured by Nissan Chemical Industries, Ltd.) was dispersed in water at a mass ratio of 1: 2 was applied so that the dry mass was 0.2 g / m ² . followed by a corona treatment on the surface MFR 4.0 g / 10 min with 10 wt% of titanium oxide, coated with a melt extruder so that the low-density polyethylene having a density of 0.93 g / m ² to 27 g / m ² Then, a thermoplastic resin layer having a mirror surface was formed.

(Production of image receiving sheet)
On the support prepared as described above, an image receiving sheet sample having a constitution of an undercoat layer, a heat insulating layer and a receiving layer was prepared in order from the lower layer. The composition and coating amount of the coating solution are shown below.
All the following layers were applied simultaneously at a coating speed of 50 m / min. The application was performed by the slide coating described above, and after passing through a zone of 8 ° C., drying was performed by blowing dry air of 28 ° C. and relative humidity of 40%.

Undercoat layer coating liquid (composition)
55 parts by mass of styrene butadiene latex (SR103 manufactured by Nippon A & L Co., Ltd.)
Polyvinyl alcohol (PVA) 6% aqueous solution 45 parts by weight Surfactant 1% aqueous solution (BFS-1) 2 parts by weight Adjust pH to 8 with NaOH (coating amount) 14 ml / m ²
(Volatile organic solvent concentration) 0% by mass

Heat insulation layer coating liquid (composition)
Emulsion A and Emulsion B with mixing ratios shown in Table 1 30 parts by mass Hollow polymer 42 parts by mass (MH5055 hollow particle content concentration: 30% by mass, manufactured by Nippon Zeon Co., Ltd.)
10% aqueous gelatin solution 25 parts by weight Water 3 parts by weight Preservative (compound represented by formula n) 0.2 parts by weight Adjust pH to 8 with NaOH (coating amount) 55 ml / m ²
(Volatile organic solvent concentration) 2.70% by mass

Receiving layer coating liquid (composition)
Emulsion A and Emulsion B having a mixing ratio shown in Table 1 4 parts by weight Vinyl chloride polymer latex 45 parts by weight (Vinyl Blanc 900 manufactured by Nissin Chemical Co., Ltd.)
18 parts by weight of vinyl chloride polymer latex (Nishin Chemical Co., Ltd. BiniBran 276)
6 parts by weight of microcrystalline wax (EMUSTAR-42X manufactured by Nippon Wax Co., Ltd.)
Water 26 parts by weight Surfactant 1% aqueous solution (BFS-1) 4 parts by weight Matting agent 1 part by weight Preservative (1,2-benzisothiazol-3 (2H) -one) 0.1 part by weight NaOH with pH Adjust to 8 (application amount) 16ml / m ²
(Volatile organic solvent concentration) 0.4% by mass

(Preparation of anti-fading emulsion)
Emulsified dispersion A was prepared by the following procedure. The anti-fading agent EB-9 was dissolved in 42 g of a high boiling point solvent (Solv-5) and 40 ml of ethyl acetate, and this solution was dissolved in 250 g of a 20% by weight gelatin aqueous solution containing 1 g of sodium dodecylbenzenesulfonate in a high-speed stirring emulsifier (dissolver). ), And 380 g of Emulsion A was prepared by adding water. Here, the amount of Compound EB-9 added was adjusted to 30 mmol in Emulsion A.
Emulsion A of the heat insulating layer was treated at 6700 Pa under reduced pressure at 40 ° C. for 20 minutes to remove ethyl acetate, and the mass loss was corrected with water to prepare Emulsion B. The concentration of ethyl acetate in Emulsion A and Emulsion B was determined by gas chromatography. As a result, it was 9.0% by mass for Emulsion A and 1.8% by mass for Emulsion B.

(2) Production of Ink Sheet A polyester film having a thickness of 6.0 μm (Lumirror, trade name, manufactured by Toray Industries, Inc.) was used as a base film. A heat-resistant slip layer (thickness 1 μm) was formed on the back side of the film, and yellow, magenta and cyan compositions having the following compositions were applied to the surface side in a single color (coating amount 1 g / m ² during dry film formation).

Yellow composition Dye (Macrolex Yellow 6G, trade name, manufactured by Bayer) 5.5 parts by weight Polyvinyl butyral resin 4.5 parts by weight (ESREC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass Magenta composition Magenta dye (Disperse Red 60) 5.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (ESREC BX-1, trade name, Sekisui Chemical Co., Ltd.) Made by Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass Cyan composition Cyan dye (Solvent Blue 63) 5.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (ESREC BX-1, trade name, Sekisui Chemical Co., Ltd.) ) Made)
90 parts by mass of methyl ethyl ketone / toluene (mass ratio 1/1)

(3) Preparation of protective layer sheet A protective layer and an adhesive layer having the following composition were applied to the same polyester film used for the preparation of the ink sheet. The coating amount during dry film is 1 g / m ^{2 for the} protective layer and 0.7 g / m for the adhesive layer.
m ² ). The adhesive layer was applied on the protective layer after coating and drying.
Protective layer Acrylic resin 20 parts by mass (Dianar BR-80, trade name, manufactured by Mitsubishi Rayon Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 80 parts by mass adhesive layer polyester resin 30 parts by mass (Byron 220, trade name, manufactured by Toyobo Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 70 parts by mass

(4) Image formation and evaluation (image formation)
Using the ink sheet, the protective layer sheet, and the image receiving sheet, a 152 mm × 102 mm size image was output by a thermal transfer printer (manufactured by ASK2000 FUJIFILM Corporation). The conveyance speed was 73 mm / second.

(Image disturbance evaluation)
Five continuous black solid images were output, and the printed prints were visually evaluated. This evaluation was performed for 50 evaluators, and the average value was obtained.
1: Image distortion is strong on the print.
2: Image distortion is a problem that causes problems in printing 3: Image distortion is recognized in printing, but there is no problem in practical use 4: Image distortion is almost undetectable in prints 5: Image distortion is not observed in printing I can not confirm at all

(Fading evaluation)
The optical density (Dmax) of the black solid portion of the image sample immediately after the image formation and xenon light (96000 lux) are irradiated for 9 days, and the yellow density after the irradiation is measured with a reflection densitometer. The concentration residual ratio was calculated with the concentration of 100% being 100%.

  The results are shown in Table 1 below.

  From Table 1, it can be seen that Samples 105 to 111, 115 and 117 of the present invention having a volatile organic solvent concentration of 2% by mass or less are preferable to Comparative Examples 101 to 104, 112 to 114 and 116 with little image disturbance. In addition, it can be seen that the effect of the sample 115 with respect to the sample 114 is greater than the effect of 106 with respect to the sample 102, and the effect of the present invention becomes remarkable when the coating speed is high. The sample 117 without the emulsion A or B is preferable because the image distortion is improved, but is slightly inferior to the sample 115 in terms of fading.

Claims (4)

  In the method for producing a thermal transfer image-receiving sheet, the support layer has at least one receiving layer containing at least one polymer latex on the support and at least one heat insulating layer containing hollow particles between the receiving layer and the support. And at least two layers including the heat insulating layer are simultaneously coated with an aqueous coating solution at a coating speed of 50 m / min or more, and the concentration of the volatile organic solvent in the aqueous coating solution to be coated simultaneously is 2% by mass or less. A method for producing a heat-sensitive transfer image-receiving sheet.   2. The method for producing a thermal transfer image-receiving sheet according to claim 1, wherein the concentration of the volatile organic solvent in the aqueous coating solution is 1% by mass or less.   The method for producing a thermal transfer image-receiving sheet according to claim 1 or 2, wherein the coating speed is 100 m / min or more.   The thermal transfer image-receiving sheet according to any one of claims 1 to 3, wherein an emulsion containing an anti-fading agent or an ultraviolet absorber is contained in at least one of the receiving layer or the heat insulating layer. Method.