JP4832242B2 - Thermal transfer image-receiving sheet, image forming method using thermal transfer system, and method for producing thermal transfer image-receiving sheet - Google Patents

Description

  The present invention relates to a thermal transfer image receiving sheet, an image forming method using a thermal transfer system, and a method for producing a thermal transfer image receiving sheet.

  Conventionally, various thermal transfer recording methods are known, and among them, the dye diffusion transfer recording method 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 addition, it has the advantages of being dry, being able to visualize directly from digital data, and being easy to duplicate, compared to silver salt photography.

  In this dye diffusion transfer recording system, a thermal transfer sheet containing a pigment (hereinafter also referred to as an ink sheet) 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. In the dye diffusion transfer recording system, as described above, the thermal transfer image-receiving sheet and the ink sheet are in direct contact with each other, so the surface properties of the thermal transfer image-receiving sheet (meaning releasability, friction, unevenness, etc.) are important. It is.

In recent years, as the dye diffusion transfer recording system has become widespread, the printing speed has been increasing, and even if the conventional thermal transfer image-receiving sheet is printed with conventional thermal energy, a sufficient transfer density cannot be obtained. Has arisen. Furthermore, there is a demand for a higher density and clearer image printed by thermal transfer, and attempts have been made to improve transfer sensitivity. One of them is an improvement means for increasing the thermal energy during printing to obtain a clearer transfer density. However, in this method, the thermal damage to the heat-sensitive transfer image-receiving sheet is large, and (1) the ink ribbon dye layer and the dye-receiving layer of the heat-sensitive transfer image-receiving sheet of the material to be transferred are thermally fused, or (2 ) Not only the dye of the ink ribbon dye layer but also the dye layer is transferred to the heat-sensitive transfer image-receiving sheet of the material to be transferred. In designing a thermal transfer image-receiving sheet used in these high-speed printers, consideration must be given to surface properties, particularly releasability, different from those of conventional thermal transfer image-receiving sheets when the printing speed is low.
Further, since the ink sheet is conveyed relative to the image receiving sheet, a force generated by friction between the image receiving sheet surface and the ink sheet tends to contribute. Therefore, if the frictional force between the ink sheet and the image receiving sheet is not within an appropriate range, the ink sheet and the image receiving sheet will be transported misaligned, various irregularities due to transfer misalignment, ink sheet wrinkles, etc., and the ink sheet will be cut during transport. May cause a transport failure such as

Conventionally, attempts have been made to devise and improve the surface properties (releasing properties, friction, unevenness, etc.) of the thermal transfer image-receiving sheet (for example, Patent Documents 1 to 7).
Patent Documents 1, 2, and 3 describe that waxes such as polyethylene wax, amide wax, Teflon (registered trademark), and urethane-modified wax are added as a release agent to the receiving layer of the thermal transfer image-receiving sheet. . Although it is disclosed that the release property is improved by adding these release agents, there is no description about the friction between the ink sheet and the image receiving sheet, that is, the influence on the transportability.
Patent Documents 4 and 5 describe that the receiving layer of the thermal transfer image-receiving sheet contains a styrene resin, a urea-formalin condensation polymer resin, or the like as an organic filler. However, the purpose here is to increase the density of the thermal transfer image. At this time, the above-mentioned problems caused by the speeding up of the printer were not noticeable. As a result, Patent Documents 4 and 5 clearly specify the influence on the releasability of the transfer material and the transfer material and the transportability due to friction. Absent.
In Patent Document 6, an inorganic filler is used as a surface property modifying means. However, this is a viewpoint of imparting writing property, and there is no function of imparting releasability by adding an inorganic filler.
On the other hand, in the silver salt photography industry, from the viewpoint of glossiness control, studies have been made to add irregularities to the surface by adding fine particles, and such fine particles having a function of imparting irregularities to the surface are widely referred to as matting agents. ing. In addition to gloss control, surface unevenness control has been studied from the viewpoint of surface adhesion, friction control, etc., using matting agents. Specifically, adhesion between films, scratches, heat development Deformation and peeling off of the matting agent are problems, and various studies on the matting agent have been conducted (for example, Patent Document 7).
However, such a silver halide photographic light-sensitive material does not form an image by transfer of a dye, and it is not necessary to consider releasability between the transfer sheet and the image receiving sheet. Moreover, there is no need to consider transfer inhibition and transfer unevenness at the time of transfer from the transfer sheet to the image receiving sheet.
Note that the use of a matting agent has also been proposed for a transfer material such as a color filter (Patent Document 8), but it is used for a back layer, not a transfer layer.

Japanese Patent No. 2572769 Japanese Patent No. 2854319 JP 2005-238748 A JP 59-214696 A JP 62-105689 A Japanese Patent No. 2872781 Japanese Patent Laid-Open No. 2005-70251 JP 2006-48024 A “New development of information recording (hard copy) and its materials”, published by Toray Research Center, Inc., 1993, p. 241-285 “Development of Printer Materials”, issued by CMC Co., Ltd., 1995, p. 180

  An object of the present invention is to provide a thermal transfer image-receiving sheet imparted with high-speed printer suitability, an image forming method using a thermal transfer system, and a method for producing a thermal transfer image-receiving sheet. In particular, thermal transfer image-receiving sheet with excellent image releasability and transportability, high image graininess, no transfer unevenness, etc., image forming method using thermal transfer system, and production of thermal transfer image-receiving sheet It is to provide a method.

As a result of intensive studies, the present inventors have achieved the above-described problem by the following means.
(1) The support has at least one receiving layer containing a melamine-silica resin fine particle matting agent, and the average particle size of the matting agent is 50% to 200% of the thickness of the layer containing the matting agent. %, And the layer containing the matting agent contains a release agent.
( 2 ) The thermal transfer image-receiving sheet as described in ( 1 ), wherein the release agent is at least one compound selected from a wax, a silicone-based compound and a fluorine-based surfactant.
( 3 ) The heat-sensitive transfer image-receiving sheet as described in (1) or (2) , which contains at least one heat-insulating layer containing at least one hollow polymer.
( 4 ) At least one heat-insulating layer containing a non-foaming hollow polymer formed of polystyrene resin, acrylic resin or styrene-acrylic resin having an average particle size of 0.1 to 2 μm. The heat-sensitive transfer image-receiving sheet as described in (1) or (2) .
( 5 ) At least one heat insulating layer containing at least one average particle size of 0.1 to 2 [mu] m and containing a non-foaming hollow polymer formed of polystyrene resin, acrylic resin or styrene-acrylic resin, and gelatin. The heat-sensitive transfer image-receiving sheet according to (1) or (2), which is contained.
( 6 ) The heat-sensitive transfer image-receiving sheet according to any one of (1) to ( 5 ), wherein the receiving layer contains a polymer latex containing at least a repeating unit obtained from vinyl chloride.
( 7 ) The heat-sensitive transfer image-receiving sheet as described in any one of (1) to ( 5 ), wherein the receiving layer contains at least one polymer latex of a vinyl chloride acrylic copolymer.
( 8 ) The heat-sensitive transfer image-receiving sheet according to any one of (1) to ( 5 ), wherein the receiving layer contains at least two polymer latexes containing at least a repeating unit obtained from vinyl chloride. .
( 9 ) The said receiving layer contains the polymer latex of the at least 2 sorts of vinyl chloride acrylic copolymer from which the chemical structure of an acryl part differs, Any one of (1)-( 5 ) characterized by the above-mentioned. Thermal transfer image-receiving sheet.
( 10 ) The heat-sensitive transfer image-receiving sheet has a heat-insulating layer, further has an undercoat layer in contact with the heat-insulating layer, and all the layers above the undercoat layer contain latex (1) The thermal transfer image-receiving sheet according to any one of ( 9 ) to ( 9 ).
( 11 ) A heat-sensitive transfer image-receiving sheet that is used by being overlapped with a heat-sensitive transfer sheet on which ink layers of at least two colors or more are sequentially formed, and an ink surface that is first transferred during image formation; The thermal transfer image-receiving sheet according to any one of (1) to ( 10 ), wherein the coefficient of static friction with the receiving layer surface of the thermal transfer image-receiving sheet is 0.280 or more.
( 12 ) The coefficient of static friction between the second and subsequent ink surfaces during image formation and the receiving layer surface of the thermal transfer image-receiving sheet to which the ink before the ink surface is transferred is transferred at the highest density is 0.280 or more. ( 11 ) The thermal transfer image-receiving sheet as described in ( 11 ) above.
( 13 ) The heat-sensitive transfer image-receiving sheet according to any one of (1) to ( 12 ), wherein the receptor layer is formed by an aqueous coating method.
( 14 ) The heat-sensitive transfer image-receiving sheet as described in ( 13 ), wherein the receptor layer and the heat insulating layer are formed by simultaneous multilayer coating.
( 15 ) An image forming method using a thermal transfer sheet in which ink layers of at least two colors or more are sequentially formed, and the thermal transfer image receiving sheet according to any one of (1) to ( 14 ), When an image is formed by superimposing the thermal transfer sheet on the thermal transfer image-receiving sheet, the coefficient of static friction between the ink surface of the thermal transfer sheet to be transferred first and the receiving layer surface of the untransferred thermal transfer image-receiving sheet is 0. . An image forming method comprising using a heat-sensitive image-receiving sheet of 280 or more.
( 16 ) The coefficient of static friction between the ink surface of the thermal transfer sheet to be transferred after the second time and the receiving layer surface of the thermal transfer image receiving sheet to which the ink before the ink surface is transferred is transferred at the highest density is 0.280 or more. ( 15 ) The image forming method as described in ( 15 ) above.
( 17 ) In the manufacturing process of the thermal transfer image-receiving sheet according to any one of (1) to ( 14 ), the receiving layer is applied by an aqueous coating method. .
( 18 ) The method for producing a heat-sensitive transfer image-receiving sheet as described in ( 17 ), wherein the heat-sensitive transfer image-receiving sheet has a heat-insulating layer, and the receiving layer and the heat-insulating layer are simultaneously applied.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a heat-sensitive transfer image-receiving sheet with excellent releasability and a high-quality image, an image forming method using a heat-sensitive transfer method, and a method for producing a heat-sensitive transfer image-receiving sheet. In particular, thermal transfer image-receiving sheet with excellent image releasability and transportability, high image graininess, no transfer unevenness, etc., image forming method using thermal transfer system, and production of thermal transfer image-receiving sheet A method can be provided.

First, the thermal transfer image receiving sheet of the present invention will be described.
In the heat-sensitive transfer image-receiving sheet of the present invention, a dye receiving layer (receiving layer) is formed on at least a support, and particularly preferably a heat insulating layer (preferably formed between the receiving layer and the support) is formed. Has been. A base layer is preferably formed between the receptor layer and the support. For example, a white background adjustment layer, a charge adjustment layer, an adhesive layer, and a primer layer are formed. Moreover, it is preferable that the heat insulation layer is formed between the base layer and the support body. Furthermore, a curl adjusting layer, a writing layer, and a charge adjusting layer are preferably formed on the back side of the support. Each layer is applied by a general method such as roll coat, bar coat, gravure coat, gravure reverse coat, die coat, slide coat, curtain coat, etc., but multiple layers such as slide coat, curtain coat etc. are applied simultaneously in multiple layers. A method that can be used is preferred.

(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 receptor layer may be formed by dissolving a receptor polymer and other functional compounds in a solvent and applying and drying by so-called solvent coating. The receptor polymer is dispersed in a water-soluble dispersion medium as a polymer latex. Further, a compound having other functions may be dissolved or dispersed and applied and dried by so-called aqueous coating.
In general, a receiving layer formed by solvent coating can be used preferably in order to obtain a coating film having a uniform receiving polymer composition and exhibit a uniform thermal response.
On the other hand, the receiving layer formed by water-based coating uses the non-uniform receiving polymer composition to reduce the change in sharpness of the image over time after transfer, and to use latex with different properties in combination. It is preferably used because it enables functional design that is characteristic such as control of the mechanical properties of the receptor layer. In addition, since the receiving layer formed by water-based coating does not use a solvent, it has a low environmental load and can be reduced in cost by high-speed coating or multi-layer coating.
The receiving layer contains a release agent in order to control the releasability with the ink sheet. Furthermore, the receiving layer in the present invention contains a matting agent in the receiving layer.
In addition, the receiving layer can contain various functional materials such as a surfactant, a thickener, a set agent, and a charge control agent for improving the coating property.
In the present invention, the thickness of the receptor layer is not particularly limited, but is preferably 2 to 10 μm, more preferably 2.5 to 8 μm.

<Receiving polymer>
The thermoplastic polymer that can be used as the receiving polymer is not particularly limited as long as it can accept the dye transferred from the transfer material, but vinyl chlorides, acrylates, polyesters (including polycarbonate structure), rubbers (for example, SBR) Resin), polyurethanes, polyvinyl chlorides, polyvinyl acetates, polyvinylidene chlorides, polyolefins and the like can be preferably used.
More preferred are vinyl chlorides, polyesters (including a polycarbonate structure), acrylates, rubbers (for example, SBRs), and polyvinyl acetates, and even more preferred are vinyl chlorides.
There are no particular limitations on the form of the acceptor polymer, such as a solvent-coated polymer used by dissolving in a solvent, or a polymer latex used by dispersing in a water-soluble dispersion medium.
The polymer latex type receiving polymer preferably used for water-based coating, which is one of the preferred embodiments of the present invention, will be described below. The solvent-coated receiving polymer can also be used in accordance with this property. .
<Polymer latex>
A polymer latex that is preferably used in a receiving layer formed by aqueous coating, which is one of the preferred embodiments of the present invention, will be described.
The polymer latex that can be used in the receiving layer in the heat-sensitive transfer image-receiving sheet of the present invention is obtained by dispersing a water-insoluble hydrophobic polymer as fine particles in a water-soluble dispersion medium. The polymer latex is not particularly limited as long as at least one thermoplastic polymer that can accept the dye transferred from the transfer material is used. A polymer latex having a specific structure may be used alone, or several different types of polymer latex may be used in combination.
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 Publishing Society (1993), Soichi Muroi, “Synthetic Latex Chemistry”, published by Polymer Publishing Society (1970), supervised by Yoshiaki Mitsuzawa, “Development and Application of Aqueous Coating Materials”, CMC Publishing ( 2004) and Japanese Patent Application Laid-Open No. 64-538. The average particle size of the dispersed particles is preferably 1 to 50000 nm, more preferably 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 of the polymer latex used in the present invention is preferably −30 ° C. to 100 ° C., more preferably 0 ° C. to 80 ° C., further preferably 10 ° C. to 70 ° C., and particularly preferably 15 ° C. to 60 ° C.

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. The homopolymer glass transition temperature (Tgi) of each monomer can be the value of “Polymer Handbook (3rd Edition)” (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).

  As a polymer latex used for the receiving layer in the present invention, a polymer latex containing a repeating unit obtained from vinyl chloride (vinyl chloride latex) is one preferred embodiment. As the vinyl chloride latex, polyvinyl chlorides and copolymers containing vinyl chloride as monomer units, such as vinyl chloride vinyl acetate copolymers and vinyl chloride acrylic copolymer polymers, can be preferably used. In this case, the ratio of the vinyl chloride monomer is preferably 50% or more and 95% or less. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. 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 100,000, preferably 10,000 to 500,000. If the molecular weight is too small, the mechanical strength of the layer containing the latex is insufficient, and if it is too large, the film formability is poor and this is not preferred. A crosslinkable polymer latex is also preferably used.

  The vinyl chloride latex that can be used in the present invention is also commercially available, and the following polymers can be used. Examples include G351 and G576 manufactured by Nippon Zeon Co., Ltd., Vinibrand 240, 270, 277, 375, 386, 609, 550, 601, 602, 630, 660, 671, 683, 680 manufactured by Nissin Chemical Industry Co., Ltd. 680S, 681N, 685R, 277, 380, 381, 410, 430, 432, 860, 863, 865, 867, 900, 900GT, 938, 950, etc. (all are trade names).

  In addition to PVC-based latex, latex of hydrophobic polymers such as acrylic polymers, polyesters, rubbers (eg SBR resin), polyurethanes, polyvinyl chlorides, polyvinyl acetates, polyvinylidene chlorides, polyolefins, etc. It can be preferably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. 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. If the molecular weight is too small, the mechanical strength of the layer containing the latex is insufficient, and if it is too large, the film formability is poor and this is not preferred. A crosslinkable polymer latex is also preferably used.

  The monomer used in combination with the synthesis of the polymer latex used in the present invention is not particularly limited, and monomers that can be polymerized by a normal radical polymerization or ionic polymerization method include the following monomer groups (a) to (j): It can be used suitably. 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, tetrahydrofurfurylme Chryrate, 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 (eg, monobutyl maleate, dimethyl maleate, monomethyl itaconate, dibutyl itaconate, etc.), polyfunctional esters (eg, ethylene glycol diacrylate) , Ethylene glycol dimethacrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, dipentaerythritol pentamethacrylate, pentaerythritol hexaacrylate, 1,2 , 4-cyclohexanetetramethacrylate, etc.).

(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-methylpropanesulfonic acid, methylenebisacrylamide, dimethacryloylpiperazine, etc. (e) Unsaturated nitriles: acrylonitrile, methacrylonitrile, etc.
(F) Styrene and derivatives thereof: 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.

Such polymer latex is also commercially available, and the following polymers can be used in combination.
Examples of the acrylic polymer include Sebian A-4635, 4718, 4601 manufactured by Daicel Chemical Industries, Ltd., Nipol Lx811, 814, 821, 820, 855 manufactured by Nippon Zeon Co., Ltd. (P-17: Tg 36 ° C.), 857 × 2 (P-18: Tg 43 ° C.), Voncoat R3370 (P-19: Tg 25 ° C.), 4280 (P-20: Tg 15 ° C.) manufactured by Dainippon Ink & Chemicals, Jurimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) P-21: Tg44 ° C), AE116 (P-22: Tg50 ° C) manufactured by JSR Corporation, 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: Tg 60 ° C.), Toagosei Co., Ltd. Aron A-104 (P-30: Tg 45 ° C.), Takamatsu Yushi Co., Ltd. NS-600X, NS-620X, Nissin Chemical Industry Co., Ltd. ) Vinibrand 2580, 2583, 2641, 2770, 2770H, 2635, 2886, 5202C, 2706, etc. (all are trade names).

  Examples of polyesters include: FINETENX 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-121, 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-244L NS-140L, NS-141LX, NS-282LX, Aronmelt 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, Sephorjon ES manufactured by Sumitomo Seika Co., Ltd. (all are trade names).

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

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

  Examples of polyolefins include Chemipearl S120, SA100, V300 (P-40: Tg 80 ° 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 Nibsin Chemical Industry Co., Ltd., Vinibrand 1080, 1082, 1085W, 1108W, 1108S, 1563M, 1566, 1570, 1588C, A22J7-F2, 1128C, 1137, 1138, A20J2, A23J1, A23J1, A23K1, A23P2E, A68J1N, 1086A, 1086D, 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, 107L, 1225,1245L, GV-6170, GV-6181,4468W, such as 4468S, and the like (all trade names).

These polymer latexes may be used alone or in combination of two or more as required.
In the receiving layer in the present invention, the polymer latex containing vinyl chloride as a monomer unit is preferably 50% or more in terms of the total solid content in the layer.

  The polymer latex used in the present invention preferably has a glass transition temperature (Tg) in the range of −30 ° C. to 70 ° C., more preferably in the range of −10 ° C. to 50 ° C. in terms of processing brittleness and image storage stability. More preferably, it is the range of 0 degreeC-40 degreeC. 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.

The minimum film-forming temperature (MFT) of the polymer latex is preferably −30 ° C. to 90 ° C., more preferably about 0 ° C. to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. A film-forming aid, also called a temporary plasticizer, is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of a polymer latex. )It is described in. Preferred film-forming aids are the following compounds, but the compounds that can be used in the present invention are not limited to the following specific examples.
Z-1: benzyl alcohol Z-2: 2,2,4-trimethylpentanediol-1,3-monoisobutyrate Z-3: 2-dimethylaminoethanol Z-4: diethylene glycol

  The polymer latex used in the present invention can be easily obtained by a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, an anionic polymerization method, a cationic polymerization or the like. Most preferred. 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 radical generating ability, such as inorganic peroxides such as persulfate and hydrogen peroxide, peroxides described in Nippon Oil & Fats Co., Ltd. organic peroxide catalog, and Wako Pure Chemical Industries, Ltd. The azo compounds described in the azo polymerization initiator catalog can be used. Among these, water-soluble peroxides such as persulfate and water-soluble azo compounds described in the Wako Pure Chemical Industries, Ltd. Azo Polymerization Initiator Catalog 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, peroxidation such as ammonium persulfate, sodium persulfate, potassium persulfate and the like. The product is preferable from the viewpoint of image preservability, 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 iron ion or an alkaline earth metal ion such as calcium ion. Japanese Patent Publication No. 6-8956, US Pat. JP-A-73645, JP-A-4-127145, JP-A-4-47073, JP-A-4-305572, JP-A-6-11805, JP-A-5-1773312, 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, JP-A-7-114154 JP, 7-120894, JP 7-199433, JP 7-306504, JP 9-43792, JP 8-314090, JP 10-182571, JP 10-182570. The compounds described in JP-A-11-190892 or the specification can be used.

  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, 55-65955, 55-65956, 57-17943, 54-61125, and West German Patent No. 1045373, and the like, polyphenol-based chelating agents, Polyamine chelation Preferably such things, aminopolycarboxylic 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-diamino Butane-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-propanedia -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, triethylenetetramine-N, N, N', N '', N '' ', N' ''- Hexaacetic acid, 1,2,3-triaminopropane-N, N, N ′, N ″, N ′ ″, N ′ ″-hexaacetic acid, and some of the carboxyl groups of these compounds are Examples include substituted 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.

The polymer latex used in the present invention is preferably prepared by applying an aqueous coating solution and then drying it. 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.
In addition, the polymer latex in the image-receiving sheet used in the present invention includes a gel or a dried film formed by drying a part of the solvent after coating.

<Water-soluble polymer>
The water-soluble polymer used for the receiving layer formed by aqueous coating, which is one preferred embodiment of the present invention, will be described below.
Here, the water-soluble polymer may be dissolved in an amount of 0.05 g or more with respect to 100 g of water at 20 ° C., more preferably 0.1 g or more, still more preferably 0.5 g or more, and particularly preferably 1 g or more.
When the receptor layer is formed by aqueous coating, the receptor 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 polysaccharides include gum arabic, κ-carrageenan, ι-carrageenan, λ-carrageenan, guar gum (Squalon Supercol, etc.), locust bean gum, pectin, tragacanth, corn starch (Purity- from National Starch & Chemical Co.) 21), 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 animal natural polymers include gelatin (such as Crodyne B419 from Croda), casein, sodium chondroitin sulfate (such as Cromoist CS from Croda), and the like (all are trade names). 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). Other starches such as phosphorylated starch (National 78-1898 from National Starch & Chemical) and sodium alginate (Keltone from Kelco), propylene glycol alginate, etc. are classified as cationized guar gum (Alcolac). Hi-care1000, etc.) and sodium hyaluronate (Hyalure, etc. from Lifecare Biomedial) are included (all are trade names).
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 ⁻ , 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. include polyethylene glycol, polypropylene glycol, polyisopropyl acrylamide, polymethyl vinyl ether, polyethylene imine, 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 acryloylme Propane sulfonic acid or its copolymer, etc.), polydimethyldiallylammonium chloride or its copolymer, polyamidine or its copolymer, polyimidazoline, dicyanciamide condensate, epichlorohydrin-dimethylamine condensate, polyacrylamide Hoffman Decomposed product, water-soluble polyester (Plus coat Z-221, Z-446, Z-561, Z-450, Z-565, Z-850, Z-3308, RZ-105, RZ-570, manufactured by Kyodo Chemical Co., Ltd.) , Z-730, RZ-142 (both 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% by mass, viscosity (4% by mass, 20 ° C.) 39.5 ± 4.5 CPS], PVA-124 [PVA content 94.0% by 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 mass%, saponification degree 97.5 ± 0.5 mol%, sodium acetate content 1.0 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 mass%, 20 ℃) 25.0 ± 3.5CPS] (trade names, available from Kuraray Co.), etc.,

  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% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile content 5. 0% by mass, viscosity (4% by mass, 20 ° C.) 22.5 ± 2.0 CPS], PVA-220 [PVA content 94.0% by 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% by mass, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0% by 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 mass%, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0 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, degree of saponification 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.

  Suitable binders are transparent or translucent, generally colorless, and are natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other film-forming media such as rubbers, polyvinyl alcohols, hydroxyethyl celluloses, cellulose Acetates, cellulose acetate butyrate, polyvinylpyrrolidone, starch, polyacrylic acid, polymethylmethacrylic 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, cellulose esters, and polyamides such water-soluble.

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.

<Hardener>
In the present invention, it is preferable to use a crosslinking agent.
The hardener preferably 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) 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) at the lower right of JP-A-2-214852, page 8, 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 61-18942. And the hardening agent described in JP-A-4-218444 or the specification thereof. 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) n-L
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.

  Specific examples of the vinyl sulfone hardener include the following (VS-1) to (VS-27), but are not limited to these in the present invention.

These hardeners can be obtained by referring to the method described in US Pat. No. 4,173,481.
As the chlorotriazine hardener, a 1,3,5-triazine compound in which at least one chloro atom is substituted at the 2-position, 4-position or 6-position is preferable.
More preferably, the chlorine atom is substituted at the 2nd, 4th or 6th position by 2 or 3 groups. At least one chlorine atom may be substituted at the 2-position, 4-position or 6-position, and a group other than a chlorine atom may be substituted at the remaining positions. Examples of these groups include a hydrogen atom, a bromine atom, Fluorine atom, iodine atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, hydroxy group, nitro group, cyano group, amino group, hydroxylamino group, alkylamino group, Arylamino group, heterocyclic amino group, acylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, alkoxy group, alkenoxy group, aryloxy group, heterocyclic oxy group, acyl group, acyloxy group, alkyl Or arylsulfonyl group, alkyl or arylsulfinyl group, alkyl Ku is arylsulfonyloxy group, a mercapto group, an alkylthio group, an alkenylthio group, an arylthio group, a heterocyclic thio group, such as alkyloxy or aryloxy carbonyl group.
Specific examples of chlorotriazine hardeners include 4,6-dichloro-2-hydroxy-1,3,5-triazine or its Na salt, 2-chloro-4,6-diphenoxytriazine, 2-chloro. -4,6-bis [2,4,6-trimethylphenoxy] triazine, 2-chloro-4,6-diglycidoxy-1,3,5-triazine, 2-chloro-4- (n-butoxy) -6 Glycidoxy-1,3,5-triazine, 2-chloro-4- (2,4,6-trimethylphenoxy) -6-glycidoxy-1,3,5-triazine, 2-chloro-4- (2-chloroethoxy ) -6- (2,4,6-trimethylphenoxy) 1,3,5-triazine, 2-chloro-4- (2-bromoethoxy) -6- (2,4,6-trimethylphenoxy) -1, 3,5-tri 2-chloro-4- (2-di-n-butylphosphatoethoxy) -6- (2,4,6-trimethylphenoxy) -1,3,5-triazine, 2-chloro-4- (2 -Di-n-butylphosphatoethoxy) -6- (2,6-xylenoxy) -1,3,5-triazine and the like, but not limited thereto.
Such a compound can be easily produced by reacting cyanuric chloride (that is, 2,4,6-trichlorotriazine) with a hydroxy compound, a thio compound or an amino compound corresponding to a substituent on the heterocyclic ring.

  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.

<Emulsions>
As a preferred embodiment of the present invention, an emulsion used for forming a receiving layer by aqueous coating will be described below.
As a preferred embodiment of the present invention, when the receptor layer is formed by aqueous coating, the receptor layer of the thermal transfer image-receiving sheet preferably contains an emulsion.

The emulsion preferably used in the present invention will be described below.
Hydrophobic additives such as mold release agents and antioxidants can be prepared by a known method such as the method described in U.S. Pat. Layer) and the like. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476 No. 4,599,296, JP-B-3-62256, or a high boiling point organic solvent described in the specification or the like, if necessary, in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C. Can be used. These release agents, antioxidants, high-boiling organic solvents and the like can be used in combination of two or more.

  As the antioxidant (hereinafter also referred to as a radical scavenger), a compound represented by any one of the following general formulas (E-1) to (E-3) is preferably used.

R ₄₁ is an aliphatic group, aryl group, heterocyclic group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, aliphatic sulfonyl group, arylsulfonyl group, phosphoryl group, or —Si (R ₄₇ ) (R ₄₈ ). (R ₄₉ ) is represented. Here, R ₄₇ , R ₄₈ and R ₄₉ each independently represents an aliphatic group, an aryl group, an aliphatic oxy group or an aryloxy group. R _{42 to} R ₄₆ represent a hydrogen atom or a substituent. Examples of the substituent include halogen atoms, aliphatic groups (including alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups), aryl groups, heterocyclic groups, hydroxy groups, mercapto groups, aliphatic oxy groups. Group, aryloxy group, heterocyclic oxy group, aliphatic thio group, arylthio group, heterocyclic thio group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, acylamino group, sulfonamide group, cyano group Nitro group, carbamoyl group, sulfamoyl group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group and the like. R _{a1 to} R _a4 each independently represents a hydrogen atom or an aliphatic group (for example, methyl, ethyl).
With respect to the compound represented by any one of the general formulas (E-1) to (E-3), preferred substituents in terms of the effects of the present invention will be described.
In the general formulas (E-1) to (E-3), R ₄₁ is an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or a phosphoryl group, and R ₄₂ , R ₄₃ , R ₄₅ And R ₄₆ are each independently preferably a hydrogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group, R ₄₁ is an aliphatic group, and R ₄₂ , R ₄₃ , R ₄₅ and R ₄₆ are It is more preferable that each independently represents a hydrogen atom or an aliphatic group.
Although the preferable specific example represented by either of general formula (E-1)-(E-3) below is shown below, this invention is not limited to these.

  The content of the antioxidant is preferably 1.0 to 7.0% by mass, more preferably 2.5 to 5.0% by mass, based on the solid content in the polymer latex.

  Examples of the release agent include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder; silicone oil, phosphate ester compound, fluorine surfactant, silicone surfactant, and other related technologies A mold release agent known in the field can be used, and a silicone compound such as a fluorine compound represented by a fluorine surfactant, a silicone surfactant, silicone oil and / or a cured product thereof is preferably used. It is done. The content of the release agent is preferably 1.0 to 10.0% by mass, more preferably 1.5 to 2.5% by mass, based on the solid content in the polymer latex.

  As the silicone oil as the release agent, straight silicone oil, modified silicone oil and its cured product can be used. Straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of dimethyl silicone oil include KF96-10, KF96-100, KF96-1000, KF96H-10000, KF96H-12500, and KF96H. -100,000 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and as dimethyl silicone oil, KF50-100, KF54, KF56 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned.

The modified silicone oil can be classified into a reactive silicone oil and a non-reactive silicone oil. The reactive silicone oil includes amino modification, epoxy modification, carboxyl modification, hydroxy modification, methacryl modification, mercapto modification, phenol modification, one-terminal reactivity and heterofunctional modification. As amino-modified silicone oil, KF-393, KF-857, KF-858, X-22-3680, X-22-3801C, KF-8010, X-22-161A, KF-8012 (all trade names, Shin-Etsu Chemical Co., Ltd.) and the like, and epoxy-modified silicone oils include KF-100T, KF-101, KF-60-164, KF-103, X-22-343, X-22-3000T ( All of them are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the carboxyl-modified silicone oil include X-22-162C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxy-modified silicone oil include X-22-160AS, KF-6001, KF-6002, KF-6003, X-22-170DX, X-22-176DX, X-22-176D, X-22-176DF (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) X-22-164A, X-22-164C, X-24-8201, X-22-174D, X-22-2426 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. .

  The reactive silicone oil can be used after being cured, and can be classified into a reaction curable type, a photo curable type, a catalyst curable type, and the like. Of these, reaction-curable silicone oils are particularly preferable. As the reaction-curable silicone oils, those obtained by reaction-curing amino-modified silicone oil and epoxy-modified silicone oil are preferable. Further, as the catalyst curable type or photo curable type silicone oil, KS-705F-PS, KS-705F-PS-1, KS-770-PL-3 [catalyst curable type silicone oil: all trade names, Shin-Etsu Chemical Co., Ltd. Co., Ltd.], KS-720, KS-774-PL-3 [photocured silicone oil: trade names, manufactured by Shin-Etsu Chemical Co., Ltd.], and the like. The addition amount of these curable silicone oils is preferably 0.5 to 30% by mass of the resin constituting the receiving layer. The release agent is used in an amount of 2 to 4% by mass, preferably about 2 to 3% by mass, based on 100 parts by mass of the polyester resin. If the amount is too small, the releasability cannot be ensured, and if the amount is too large, the protective layer will not be transferred to the image receiving sheet.

  Non-reactive silicone oils include polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, fluorine modification and the like. Examples include polyether-modified silicone (KF-6012, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and methylstil-modified silicone silicone oils (24-510, KF41-410, both trade names, Shin-Etsu Chemical ( Etc.). Moreover, the modified silicone represented by either of the following general formulas 1-3 can also be used.

  In General Formula 1, R represents a hydrogen atom, an aryl group, or a linear or branched alkyl group that may be substituted with a cycloalkyl group. m and n represent an integer of 2000 or less, and a and b represent an integer of 30 or less.

  In General Formula 2, R represents a hydrogen atom, an aryl group, or a linear or branched alkyl group which may be substituted with a cycloalkyl group. m represents an integer of 2000 or less, and a and b represent an integer of 30 or less.

In General Formula 3, R represents a hydrogen atom, an aryl group, or a linear or branched alkyl group which may be substituted with a cycloalkyl group. m and n represent an integer of 2000 or less, and a and b represent an integer of 30 or less. R ¹ represents a single bond or a divalent linking group, E represents an ethylene group which may have a substituent, and P represents a propylene group which may have a substituent.

  Silicone oils such as those described above are described in “Silicone Handbook” (published by Nikkan Kogyo Shimbun Co., Ltd.), and are described in JP-A-8-108636 and JP-A-2002-264543 as curing technologies for curable silicone oils. The technique can be preferably used.

High boiling point organic solvents include phthalates (dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, etc.), phosphoric acid or phosphonic esters (triphenyl phosphate, tricresyl phosphate, triphosphate phosphate) 2-ethylhexyl, etc.), fatty acid esters (di-2-ethylhexyl succinate, tributyl citrate, etc.), benzoates (2-ethylhexyl benzoate, dodecyl benzoate, etc.), amides (N, N-diethyl, etc.) Dodecanamide, N, N-dimethyloleamide, etc.), alcohol or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), anilines (N, N-dibutyl-2-butoxy-5-) tert-octylaniline, etc.), chlorinated paraffins, hydrocarbons (dode) Rubenzen, diisopropyl naphthalene), carboxylic acids (2- (2,4-di -tert- amylphenoxy) butyric acid, and the like.
The following compounds are preferably used.

  Further, an organic solvent (such as ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, or methyl cellosolve acetate) having a boiling point of 30 ° C. or higher and 160 ° C. or lower may be used in combination as an auxiliary solvent. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g based on 1 g of the hydrophobic additive used. In addition, 1 milliliter or less, further 0.5 milliliter or less, particularly 0.3 milliliter or less is appropriate for 1 g of binder.

A dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943, or a fine particle dispersion described in JP-A-62-22422, etc. Can also be used. In the case of a compound that is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder other than the above method.
In dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants described in JP-A No. 59-157636, pages 37 to 38 can be used. Further, phosphate ester type surfactants described in JP-A-7-56267, JP-A-7-228589 and West German Patent No. 1,932,299A or the specification can also be used.

<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 UV absorber can be fixed to the receiving layer by increasing the molecular weight, and can be prevented from being diffused into the ink sheet or sublimation / transpiration due to heating.
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 added to the receiving layer to form a thermal transfer image-receiving sheet, 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 weight average molecular weight of 10,000 or more, and more preferably a weight 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 added 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>
A release agent is blended in the receiving layer in order to prevent thermal fusion with the thermal transfer sheet during image formation. As the release agent, silicone oil, phosphate ester release agent, fluorine compound, and various wax dispersions can be used. In particular, silicone oil, wax, and fluorine compounds are preferably used.
The amount of release agent added depends on the releasability when the ink sheet and the image receiving sheet are peeled off after transfer, the relationship between the ink sheet and the image receiving sheet that affects the transportability, and the release agent has other properties. Determined in consideration of the impact on
These release agents are used by dissolving or dispersing in accordance with the coating solvent for the receiving layer.
These release agents may be used alone or in combination, but in general, the combined use often works advantageously from the viewpoint of adjusting the release properties and other performances.

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. As described above, the addition amount of the release agent should be adjusted together with other performances, but a preferable range is about 0.2 to 30 parts by mass with respect to the receiving polymer.
As one of the preferred embodiments of the present invention, when the receiving layer is formed by aqueous coating, the silicone oil is preferably emulsified and dispersed. In this case, the introduction method was explained in the above-mentioned emulsion section.

A well-known thing can be used as a wax. 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 derivatives, 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 preferred, and kaunauba wax, mondan wax and derivatives thereof, microcrystalline wax. Stearamide is more preferable, and paraffin wax and derivatives thereof, 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.
In one preferred embodiment of the present invention, when the receptor layer is formed by aqueous coating, the wax is preferably an aqueous dispersion, and more preferably finely divided. The water dispersion method and the micronization method can be achieved by the methods described in “Revised Wax Properties and Applications” (Sachibo, 1989).
As described above, the addition amount of the wax should be adjusted in accordance with other performances, but a preferable range is 0.5 mass% to 30 mass% of the total solid content of the receiving layer. %, More preferably 20% by mass to 20% by mass, and still more preferably 1.5% by mass to 15% by mass.

  As a fluorine-type mold release agent, the compound which shows well-known mold release property can be used. Surfactants having fluorinated alkyl ends are widely known as mold release agents. It is known that surfactants having alkyl fluoride ends are also used as coating aids.

<Matting agent>
In the present invention, a matting agent is added to control surface irregularities.
This is because the addition of a matting agent and the combination of a release agent can both control the frictional force between the ink sheet and the image receiving sheet and improve the releasability of the ink sheet and the image receiving sheet during peeling after thermal transfer. The invention has been achieved.
In the present invention, the matting agent is preferably contained in the outermost surface layer, the layer functioning as the outermost surface layer of the image forming surface 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 receiving layer located in the outermost layer. The matting agent can also be added to the back surface.

Matting agent contained in acceptance layer may be an organic matting agent in an inorganic matting agent. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (eg, sulfates and carbonates, specifically barium sulfate, calcium carbonate). , Magnesium sulfate, strontium sulfate, calcium carbonate, etc.), silver halide grains and glass that do not form an image. U.S. Pat. Nos. 3,053,662, 3,062,649, 3,257,206, 3,322,555, 3,353,958, and 3,370,951 3,411,907, 3,437,484, 3,523,022, 3,615,554, 3,635,714, 3,769,020, Inorganic matting agents described in each specification of 4,021,245 and 4,029,504 can also be used. Among these inorganic matting agents, silicon dioxide, strontium barium sulfate, titanium oxide, alumina, silver halide and the like are preferable, and spherical or amorphous silicon dioxide is particularly preferable.
Examples of the organic matting agent include starch, cellulose ester (such as cellulose acetate propionate), cellulose ether (such as ethyl cellulose), gelatin, and synthetic resin. Examples of synthetic resins are synthetic polymers that are insoluble or sparingly soluble in solvents such as alkyl acrylates, alkyl methacrylates, alkoxyalkyl acrylates, alkoxyalkyl methacrylates, glycidyl acrylates, glycidyl methacrylates, acrylamide methacrylates, vinyl esters, acrylonitriles. , Olefin, styrene, benzoguanamine / formaldehyde condensate alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, sulfoethyl acrylate, sulfoethyl methacrylate A polymer having a combination of acrylate, styrenesulfonic acid and the like as a monomer component can be used. In addition, epoxy resin, nylon, polycarbonate, phenol resin, polyvinyl carbazole, polyvinylidene chloride, and the like can also be used. In addition, U.S. Pat. Nos. 1,055,713, 1,939,213, 2,221,873, 4,268,662, 2,322,037, 2,376, Organic matting agents described in the specifications of Nos. 005 and 2,391,181 can be used.

Also, a matting agent having a narrow particle size distribution described in JP-A-63-8736 and JP-A-61-230141 can be used, and JP-A-62-14647, JP-A-62-17744, and JP-A-62-17743. It is also possible to use particles having fluorine atoms or silicon atoms as described in each publication. Among these organic matting agents, water such as a homopolymer of an acrylate ester such as methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, or a copolymer of these acrylate esters alone with other vinyl monomers is preferable. Dispersible vinyl polymer matting agent, styrene, benzoguanamine / formaldehyde condensate alone or in combination, melamine resin is preferable, and particularly preferable is a copolymer of methyl methacrylate / methacrylic acid = 95/5 to 40/60 Polymer, methyl methacrylate / acrylic acid = 95/5 to 40/60 copolymer, methyl methacrylate, melamine resin, and styrene polymer.
Organic / inorganic hybrid fine particles can also be preferably used. In the present invention, melamine-silica resin fine particles, which are organic / inorganic hybrid fine particles , are used.

Matting agents having different average particle size, size distribution, and shape can be mixed and used as necessary.
The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In practicing the present invention, it is preferable to use a particle having a particle size of 50% to 200% of the thickness of the receiving layer. More preferably, it is 60% to 150%.
Further, the particle size distribution of the matting agent may be narrow or wide. The variation coefficient of the size distribution is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less. Here, the coefficient of variation is a value represented by (standard deviation of particle size) / (average value of particle size) × 100. It is also preferable to use two types of matting agents having a small variation coefficient and having an average particle size ratio larger than 3.
On the other hand, the matting agent greatly affects the haze and surface gloss of the coating film. It is preferable to do.
In the present invention, a preferable matting agent is made of a polymer such as the organic compounds listed above, and is particularly preferably a polymer having a glass transition temperature of 60 ° C. or higher and 150 ° C. or lower. More preferably, it is a polymer having a glass transition temperature of 80 ° C. or higher and 130 ° C. or lower.

It shows an example of Ma Tsu preparative agents in the following, of which matting agent of the present invention is M-23~M-27, the remaining M-1~M-22, M- 28, M-29 is reference It is an example. However, the present invention is not limited to the following compounds M-23 to M-27 .

M-1: Polyethylene particles (Flow beads LE-1080, manufactured by Sumitomo Seika Co., Ltd.)
M-2: Polyethylene particles (Flow beads EA-209, manufactured by Sumitomo Seika Co., Ltd.)
M-3: Polyethylene particles (Flow beads HE-3040, manufactured by Sumitomo Seika Co., Ltd.)
M-4: Silicone particles M-5: Silicone particles (E701 manufactured by Toray Dow Silicone Co., Ltd.)
M-6: Silicone particles M-7: Polystyrene particles (SB-6 manufactured by Sekisui Plastics Co., Ltd.)
M-8: Poly (St / MAA = 97/3) copolymer particles M-9: Poly (St / MAA = 90/10) copolymer particles M-10: Poly (St / MMA / MAA = 50 / 40/10) Copolymer particles M-11: Cross-linked polyethylene particles M-12: Cross-linked polyethylene particles M-13: Cross-linked polyethylene particles M-14: Cross-linked silicone particles M-15: Cross-linked silicone particles M-16: Cross-linked silicone particles M-17: Poly (St / DVB = 90/10) particles (SX-713, manufactured by Soken Chemical Co., Ltd.)
M-18: Poly (St / DVB = 80/20) particles (SX-713, manufactured by Soken Chemical Co., Ltd.)
M-19: Poly (St / DVB = 70/30) particles (SX-713, manufactured by Soken Chemical Co., Ltd.)
M-20: Poly (St / MAA / DVB = 87/3/10) copolymer particles
(SX-713A manufactured by Soken Chemical Co., Ltd.)
M-21: Poly (St / MAA / DVB = 80/10/10) copolymer particles
(SX-713B Soken Chemical Co., Ltd.)
M-22: Poly (St / MMA / MAA / DVB = 40/40/10/10) copolymer particles M-23: Melamine-silica resin (Opto Beads 500s, manufactured by Nissan Chemical Industries, Ltd.)
M-24: Melamine-silica resin (Optobead 2000M manufactured by Nissan Chemical Industries, Ltd.)
M-25: Melamine-silica resin (Opto beads 3500M, manufactured by Nissan Chemical Industries, Ltd.)
M-26: Melamine-silica resin (Opto beads 6500s, manufactured by Nissan Chemical Industries, Ltd.)
M-27: Melamine-silica resin (Opto beads 10500s, manufactured by Nissan Chemical Industries, Ltd.)
M-28: Cross-linked PMMA particles (MX series, manufactured by Soken Chemical Co., Ltd.)
M-29: Crosslinked PMMA particles (MR series, manufactured by Soken Chemical Co., Ltd.)
Here, St represents styrene, DVB represents divinylbenzene, MAA represents methacrylic acid, MMA represents methyl methacrylate, and PMMA represents poly (methyl methacrylate).

The content of the matting agent affects the releasability and transportability and other performances as well as the release agent, and should be adjusted together with the release agent. Within the range not excessively hindering its original function. Matting agents, if indicated by the coating amount per receiving layer 1 m ^2, preferably from ^{1mg / m 2 ~400mg / m 2} , more preferably ^{5mg / m 2 ~300mg / m 2} .
When the matting agent is contained on the image forming layer surface side, the matting agent content is generally adjusted so as not to cause stardust failure, and preferably the Beck smoothness is 500 seconds or more and 10,000 seconds or less. And more preferably 500 seconds or more and 2,000 seconds or less. When the back layer contains a matting agent, it is preferable that the Beck smoothness is 2000 seconds or less and 10 seconds or more, and more preferably 1500 seconds or less and 50 seconds or more. The Beck smoothness in this specification is JIS
It is obtained from P8119 and TAPPI T479.

  The matting agent contained in the outermost layer on the image forming layer surface side and the outermost layer adjacent layer is preferably dispersed in advance with a binder and used as a matting agent particle dispersion. The matting agent is obtained by removing the low-boiling organic solvent from the emulsion by obtaining a polymer droplet by emulsifying and dispersing the polymer to be used as an agent in a solution (for example, dissolved in a low-boiling organic solvent) in an aqueous medium. There are two methods: a method of preparing a dispersion of (b), a method of preparing fine particles such as a polymer to be a matting agent in advance, and preparing a dispersion so as not to cause lumps in an aqueous medium. is there. 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.

In the method of dispersing the matting agent, an aqueous medium containing a binder is previously present as a dispersion aid in an aqueous solvent, and known high-speed stirring means (for example, a disperser emulsifier, a homomixer, a turbine mixer, a homogenizer) Or using an ultrasonic emulsifier or the like. In dispersing, in order to suppress foaming, means for dispersing in a reduced pressure state rather than atmospheric pressure can be used in combination. The dispersion aid to be used is generally dissolved in an aqueous medium in advance, and then the matting agent is generally added, but the matting agent remains in an aqueous dispersion obtained by polymerization (drying step). (Without going through). The dispersion aid can also be added to the dispersion during dispersion. Moreover, it can also add to a dispersion liquid for stabilization of the physical property after dispersion | distribution. In either case, it is common that a solvent (for example, water / alcohol) coexists. You may control pH by a suitable pH adjuster before and after dispersion | distribution or during dispersion | distribution.
In addition to the mechanical dispersion means, the stability of the dispersed matting agent may be increased by controlling the pH. In addition, a very small amount of a low-boiling organic solvent may be used for dispersion, and the organic solvent is usually removed after the formation of fine particles.
The prepared dispersion is stored with stirring for the purpose of suppressing the settling of the matting agent during storage, or stored in a highly viscous state (for example, using gelatin to make a jelly state) with a hydrophilic colloid. You can also Moreover, it is preferable to add a preservative for the purpose of preventing the propagation of various germs during storage.
The binder is preferably added and dispersed so as to be 5% by mass to 300% by mass with respect to the matting agent. More preferably, it adds so that it may become 10 mass% or more and 200 mass or less.

  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. The surfactant used here is not particularly limited, but is preferably a surfactant having at least one fluorine atom.

The coating amount of the receiving layer is preferably 0.5 to 10 g / m ² (in terms of solid content, hereinafter the coating amount in the present invention is a numerical value in terms of solid content unless otherwise specified), and more preferably 1 to 1. 8 g / m ^2, more preferably the coating weight of 2~7g / m ² is preferred. The thickness of the receiving layer is preferably 1 to 20 μm.

<Releasability at the time of peeling after transfer between the ink sheet and the image receiving sheet, and adjustment of the friction between the ink sheet and the image receiving sheet affecting the transportability>
The releasability when the ink sheet and the image receiving sheet are peeled off after transfer depends on the addition amount of the release agent, and is improved by increasing the addition amount. However, if the amount of the release agent added is increased, the friction between the ink sheet and the image receiving sheet decreases, which may adversely affect the transportability of the ink sheet.
According to the study by the present inventors, in order not to adversely affect the transportability of the ink sheet, the static friction coefficient of the surface that contacts the ink sheet and the image receiving sheet when transporting the ink sheet is adjusted to 0.280 or more. Was found to be necessary.
That is, when an image is formed by superimposing a thermal transfer sheet and a thermal transfer image receiving sheet on which ink layers of at least two colors are sequentially formed, an ink surface to be transferred at the beginning of image formation, and an untransferred thermal transfer It is preferable to adjust the thermal image-receiving sheet so that the coefficient of static friction with the receiving layer surface of the image-receiving sheet is 0.280 or more. Furthermore, the static friction coefficient between the ink surface to be transferred second and later in the image formation and the receiving layer surface of the thermal transfer image receiving sheet to which the ink before the ink surface is transferred at the highest density is 0.280 or more. It is more preferable to adjust the heat-sensitive image receiving sheet.
Due to the restriction of adjusting the surface of the image-receiving sheet within this range, the amount of the release agent that can be added to the receiving layer is limited, and sufficient releasability may not be obtained, but by adding a matting agent, It was found that the friction between the ink sheet and the image receiving sheet becomes less dependent on the amount of the release agent added.
In other words, by adding a certain amount of the matting agent to the receiving layer, the amount of the release agent is increased, and it is a condition for not adversely affecting the transportability of the ink sheet while maintaining sufficient release properties. It is possible to achieve both a static friction coefficient of 0.280 or more on the surface of the ink sheet and the image receiving sheet that are in contact with each other when the ink sheet is conveyed.
Since the addition of the matting agent to the receiving layer reduces the friction between the ink sheet and the image receiving sheet, it is necessary to adjust the addition amount within a range satisfying the above relationship.
The static friction coefficient of the surface of the ink sheet and the image receiving sheet that are in contact with each other when the ink sheet is conveyed can be measured with a commercially available static friction meter (for example, a static friction coefficient measuring machine TYPE: 10 manufactured by Shinto Kagaku Co., Ltd.) Coefficient of static friction between the image-forming surface of the untransferred image-receiving sheet and the ink surface to be transferred first of the ink sheet, and the static friction between the image-forming surface of the image-receiving sheet where transfer has occurred and the ink surface to be transferred next Each coefficient is measured and determined.
The releasability when the ink sheet and the image receiving sheet are peeled off after transfer is actually determined by loading the ink sheet and the image receiving sheet into a sublimation printer and outputting them, and the peeling sound during printing, print uniformity, and the state of peeling within the printer. Although it is possible by observing, etc., it can be evaluated as a model experiment by measuring the load when the ink sheet and the image receiving sheet are overlapped and heat-bonded and then peeled.

(Insulation layer)
In the present invention, it is particularly preferable to have a heat insulating layer, and the heat insulating layer plays a role of protecting 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 substrate. 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 image receiving sheet used in the present invention, the heat insulating layer particularly preferably contains a hollow polymer.
The hollow polymer in the present invention is a polymer particle having independent pores inside the particle. For example, [1] a dispersion medium such as water enters a partition formed by polystyrene, acrylic resin, styrene-acrylic resin or the like. After coating and drying, non-foamed hollow particles in which the dispersion medium in the particles evaporates outside the particles and the inside of the particles becomes hollow, [2] low boiling point liquids such as butane and pentane, polyvinylidene chloride, polyacrylonitrile Foam that is covered with a resin made of polyacrylic acid, polyacrylic acid ester, or a mixture or polymer thereof, and the inside of which is hollowed by the expansion of the low-boiling liquid inside the particles by heating after coating. Type microballoons, and [3] microballoons obtained by heating and foaming the above [2] in advance to form a hollow polymer.

  The particle size of these hollow polymers is preferably 0.1 to 20 μm, more preferably 0.1 to 2 μm, still more preferably 0.1 to 1 μm, and particularly preferably 0.2 to 0.8 μm. If the 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 particle diameter of the hollow polymer is too large for the film thickness of the heat insulating layer to obtain a smooth surface. This is because it becomes difficult to cause coating failure due to coarse particles.

  The hollow ratio of the hollow polymer in the present invention is determined by measuring the equivalent circle diameter of the internal voids of at least 300 hollow polymers and the particle diameter of the hollow polymer from transmission electron micrographs. The hollow ratio (%) of the hollow polymer is averaged by calculating the individual hollow ratio (%) obtained by

Individual hollow ratio (%) = (circle equivalent diameter of voids) ³ / (particle diameter of hollow polymer) ³ × 100

  The glass transition temperature (Tg) of the hollow polymer 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.

  Such hollow polymers are commercially available, and specific examples of the above [1] include Law and Haas Ropaque 1055, Dainippon Ink Boncoat PP-1000, JSR SX866 (B), Nippon Zeon Nippon MH5055 (both are trade names). 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., EXPANSELL 461DE, 551DE, and 551DE20 (all trade names) manufactured by Nippon Ferrite Co., Ltd. Among these, the hollow polymer of the series [1] can be used more preferably.

  The heat insulating layer containing the hollow polymer preferably contains a water-dispersed resin or a water-soluble resin as a binder resin as a binder resin. 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 butadiene copolymers, polyvinylidene chloride resins, cellulose derivatives, casein, starch, and gelatin can be used. 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, and preferably between 5 and 1000 parts by mass when the solid content of the binder resin is 100 parts by mass. More preferably, it is more preferably between 5 and 400 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 is lowered, sufficient film strength cannot be obtained, and scratch resistance is obtained. Getting worse.

The image-receiving sheet used in the present invention does not contain a resin having no resistance to organic solvents in addition to the hollow polymer in the heat insulating layer. It is not preferable to include a resin (dye dyeing resin) that is not resistant to an organic solvent in the heat insulating layer because blurring of an image after image transfer increases. This is because the dye-stainable resin and the hollow polymer exist in the heat insulating layer, so that the dye dyed on the receiving layer after the transfer moves over time through the adjacent heat-insulating layer. it is conceivable that.
Here, “not resistant to organic solvent” means that the solubility in an organic solvent (methyl ethyl ketone, ethyl acetate, benzene, toluene, xylene, etc.) is 1% by mass or less, preferably 0.5% by mass or less. Say. For example, the polymer latex is included in “resin not resistant to organic solvent”.

Moreover, it is preferable that a heat insulation layer contains the said water-soluble polymer. The compounds that can be preferably used are the same as described above.
The amount of the water-soluble polymer added to the heat insulating layer is preferably 1 to 75% by mass and more preferably 1 to 50% by mass with respect to the entire heat insulating layer.

The heat insulating layer preferably contains gelatin. The amount of the heat insulating layer in the gelatin coating solution is preferably 0.5 to 14% by mass, particularly preferably 1 to 6% by mass. 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.

Moreover, it is preferable that the water-soluble polymer contained in the heat insulation layer is crosslinked by a crosslinking agent. The preferred range of the crosslinking agent that can be preferably used and the amount of use thereof is the same as described above.
Although the water-soluble polymer in the heat insulating layer varies depending on the type of the crosslinking agent, it is preferably 0.1 to 20% by mass crosslinked with respect to the water-soluble polymer, and 1 to 10% by mass crosslinked. 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.

The porosity of the heat insulating layer calculated from the thickness of the heat insulating layer containing the hollow polymer and the solid coating amount of the heat insulating layer containing the hollow polymer is preferably 10 to 70%, and more preferably 15 to 60%. When the porosity of the heat insulating layer is less than 10%, sufficient heat insulating properties cannot be obtained.
In the present invention, the porosity of the heat insulating layer is a value V calculated by the following equation (b).

  In the above formula (b), L represents the film thickness of the heat insulating layer, gi represents the solid coating amount of the specific material i constituting the heat insulating layer, and di represents the specific gravity of the specific material i. Here, when di represents the specific gravity of the hollow polymer, di represents the specific gravity of the wall material of the hollow polymer.

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

(Support)
In the present invention, any conventionally known support can be used, but the use of a water-resistant support prevents moisture from being absorbed into the support, and the performance of the receptor layer over time. Changes can be prevented. As the water-resistant support, for example, coated paper or laminated paper can be used.

-Coated paper-
The coated paper is a paper obtained by coating various sheets of resin, rubber latex, or polymer material on one side 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, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate and other polyacrylic acid ester resins or polymethacrylic acid ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, 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 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 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.

  The thickness of the support is preferably 25 μm to 300 μm, more preferably 50 μm to 260 μm, and still more preferably 75 μm to 220 μm. Various stiffnesses can be used according to the purpose, and the support for a photographic image receiving sheet for electrophotography is close to a support for color silver halide photography. Those 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 can be formed by simultaneously applying at least one receiving layer, intermediate layer and heat insulating layer on a support.
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, Kaisho 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, specification or Edgar B. Gutoff et al., “Coating and Drying Defects: Troubleshooting Operating Problems”, John Wiley & Sons, 1995. , 101-103, etc., so-called slide coating (slide coating method) and curtain coating (curtain coating method) are known.
In the present invention, the simultaneous multi-layer coating is used for manufacturing a multi-layer image-receiving sheet, whereby productivity can be greatly improved and image defects can be greatly reduced.

In the present invention, the plurality of layers are composed mainly of a resin. The coating solution for forming each layer is preferably water-dispersed latex. The solid content weight 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 water-dispersed latex is 5 μm or less and particularly preferably 1 μm or less. The water-dispersed latex may contain a known additive such as a surfactant, a dispersant, and a binder resin as necessary.
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 quickly solidify. 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.
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 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 at the time of thermal transfer, any conventionally known means for applying can be used. For example, recording is performed by a recording device such as a thermal printer (for example, product name, video printer VY-100, manufactured by Hitachi, Ltd.). By controlling the time, the intended purpose can be sufficiently achieved by applying thermal energy of about 5 to 100 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.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these. In Examples, “part” or “%” is based on mass unless otherwise specified.

Example 1
(Ink sheet)
A dedicated ink ribbon for sublimation printer ASK-2000 manufactured by Fuji Photo Film Co., Ltd. was used.

(Preparation of layer-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 NSC Japan, Inc.) 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 at a setting of 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 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-t-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 obtained by blending in a proportion of, and coated to a thickness of 21g / m ^2, thereby forming a thermoplastic resin layer having a matte surface (hereinafter, "rear surface of the thermoplastic resin layer surface The thermoplastic resin layer on the back 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 silicon dioxide (Nissan Chemical). A dispersion obtained by dispersing “Snowtex O” manufactured by Kogyo Co., Ltd. in water at a mass ratio of 1: 2 was applied so that the dry mass was 0.2 g / m ² . treated MFR 4.0 g / 10 min with 10 wt% of titanium oxide, by using a melt extruder so that the low-density polyethylene having a density of 0.93 g / m ² to 27 g / m ² was coated, made of mirror A thermoplastic resin layer was formed.

(Preparation of thermal transfer image-receiving sheet 101)
On the support prepared as described above, a multi-layer coating composition composed of an undercoat layer, a heat insulating layer, and a receiving layer was applied simultaneously from the lower layer. The composition and coating amount of the coating solution are shown below.

Undercoat layer coating liquid (composition)
93 parts by mass of styrene-butadiene latex (SR103 manufactured by Nippon A & L Co., Ltd.)
PVA 8.7% aqueous solution 57 parts by mass Adjust pH to 8 with NaOH (application amount) 21 ml / m ²

Heat insulation layer coating liquid (composition)
38 parts by mass of hollow polymer latex (MH5055 manufactured by Nippon Zeon Co., Ltd.)
16% aqueous gelatin solution 26 parts by weight Water 4 parts by weight Adjust pH to 8 with NaOH (coating amount) 45 ml / m ²

Receptive layer coating solution (composition)
44 parts by weight of vinyl chloride acrylic latex (Nishin Chemical Co., Ltd. Vinibrand 900)
27 parts by weight of vinyl chloride acrylic latex (Vinyl Blanc 276 manufactured by Nissin Chemical Co., Ltd.)
16% gelatin aqueous solution 3.5 parts by weight Release agent Microcrystalline wax 6 parts by weight (EMUSTAR-42X manufactured by Nippon Wax Co., Ltd.)
Matting agent PMMA particles 3.5 μm 1.5 parts by weight Water 30 parts by weight The following compound A 0.05 part by weight The pH is adjusted to 8 with NaOH (coating amount) 10 ml / m ²
Compound A

Compound B (crosslinking material) was added to the receiving layer coating solution immediately before coating. The amount of Compound B added was 3% by mass with respect to the total mass of gelatin in the heat insulating layer and the receiving layer. The thickness of the receiving layer is 5.8 μm.
Compound B

(Preparation of thermal transfer image-receiving sheets 102 to 118)
The release agent and matting agent of the thermal transfer image receiving sheet 101 were changed according to Table 1 to prepare thermal transfer image receiving sheets 102 to 118.
Each addition amount was changed according to Table 1, but was adjusted by changing the amount of water so that the application amount of materials other than water did not change. In any of the thermal transfer image receiving sheets 102 to 118, the thickness of the receiving layer was 5.8 μm.

(Image formation)
The ink sheet and the thermal transfer image receiving sheets 101 to 118 are processed so that they can be loaded, and using a sublimation thermal transfer printer ASK2000 (manufactured by Fuji Photo Film Co., Ltd.), in an environment of 35 ° C. and 70% in a high-speed print mode. Output below. The heat-sensitive transfer image-receiving sheet was conditioned for 2 hours in an environment of 35 ° C. and 70%, and then loaded into a printer. The following two types of images were used as output images.
1) Full-scale black image with high density (solid black image)
2) Test patterns in which gradation images of various single colors and grays ranging from white to the highest density are arranged. Each of these two types of images was continuously output as 30 images.
In the high-speed print mode, the time from when the first sheet is discharged to when the second sheet is discharged is 8 seconds.

(Evaluation of releasability)
After the yellow (Y) ink surface of the ink sheet and the heat-sensitive transfer image receiving sheets 101 to 118 are each processed into a 5 cm square, the surfaces that can be transferred are bonded to each other, and are adhered to each other at 90 ° C. under a load of 2 kg weight. The ink sheet and the image receiving sheet were peeled off at 90 ° C., and the load applied to the peeling was measured. The peeling angle was 180 °, the peeling speed was 5 cm / s, the load when peeling occurred with a substantially uniform load was measured, and the average value was evaluated as the peeling force.
Furthermore, the release state was evaluated by observing the output state of the output image described in the above image formation.

(Evaluation of transportability)
The ASK-2000 is loaded with the static friction coefficient of the Y surface of the ink sheet, the image forming surface of the thermal image receiving sheets 101 to 118, the magenta (M) surface of the ink sheet, the thermal image receiving sheets 101 to 118, and the ink sheet. Measures the static friction coefficient of the surface on which the Y solid was formed by image formation (created by stopping the image formation immediately after the transfer of Y occurred) (Static friction coefficient measuring machine manufactured by Shinto Kagaku Co., Ltd. TYPE: 10 It was used. When this value is 0.28 or less, the transportability becomes poor.

  Each evaluation result is shown in Table 2 below.

From the results in Table 2 above, the addition of a matting agent having a particle size of 50 to 200% of the thickness of the receiving layer can maintain a good transportability range even when the amount of release agent added is increased. Recognize. Furthermore, in this case, it was found that a good release property was exhibited by increasing the amount of the release agent added.
In addition, the coefficient of static friction between the image receiving sheet and the ink sheet is 0.28 or more, and in a sample to which a matting agent and a release agent are added, both releasability and transportability can be achieved.
The sample 114 in which the particle size of the matting agent exceeds 200% of the film thickness of the image receiving layer has insufficient releasability and insufficient transportability, and some JAM (cannot be transported and processed when the image is output). A phenomenon that stopped halfway) occurred, but when the surface of this sample was observed, it was found that a part of the matting agent had fallen off. For this reason, it is presumed that the releasability is unstable and the transportability is not constant. In Table 2 above, sticking is a phenomenon in which linear unevenness occurs in an image due to peeling abnormality.

Reference example 1
(Preparation of emulsion A)
Emulsified dispersion A was prepared by the following procedure.
12 g of antioxidant (EB-9) and amino-modified silicone oil KF-857 are dissolved in 30 g of high boiling point solvent (Solv-5) and 20 ml of ethyl acetate, and this solution contains 1 g of sodium dodecylbenzenesulfonate. 280 g of Emulsion A was prepared by emulsifying and dispersing in 250 g of 20% by weight gelatin aqueous solution with a high-speed stirring emulsifier (dissolver), and adding water. The amount of antioxidant (EB-9) added was 30 mmol in Emulsion A.

(Preparation of thermal transfer image receiving sheets 201-203)
The same procedure except that 4.2 parts by mass of Emulsion A was added in place of the 16% gelatin aqueous solution used in the receiving layers of the thermal transfer image-receiving sheets 101 to 103, and the amount of water added was reduced by 0.7 parts by mass. Thus, thermal transfer image receiving sheets 201 to 203 were prepared.
The prepared thermal transfer image-receiving sheets 201 to 203 were added to each thermal transfer image-receiving sheet by emulsifying and dispersing the participation inhibitor (EB-9), a high boiling point solvent, and an amino-modified silicone oil as a release agent. It is a thing.

In the same manner as in Example 1, evaluation of releasability and transportability and image formation were performed to evaluate the performance as a thermal transfer image receiving sheet.
The results are shown in Table 3 below.

  As is clear from Table 3 above, even when an emulsion is introduced into the receiving layer and silicone oil is added by emulsifying and dispersing as a release agent, both releasability and transportability are achieved as in the case of Example 1. I found out that I can do it.

Claims (18)

The support has at least one receiving layer containing a melamine-silica resin fine particle matting agent, and the average particle size of the matting agent is 50% to 200% of the thickness of the layer containing the matting agent. And a layer containing the matting agent contains a release agent. 2. The heat-sensitive transfer image-receiving sheet according to claim 1 , wherein the release agent is at least one compound selected from a wax, a silicone-based compound, and a fluorine-based surfactant. The heat-sensitive transfer image-receiving sheet according to claim 1 or 2 , comprising at least one heat-insulating layer containing at least one hollow polymer. It is characterized by containing at least one heat-insulating layer containing a non-foaming hollow polymer formed of polystyrene resin, acrylic resin or styrene-acrylic resin having an average particle size of 0.1 to 2 μm. The heat-sensitive transfer image-receiving sheet according to claim 1 or 2 . At least one heat-insulating layer containing at least one average particle size of 0.1 to 2 μm and containing a non-foaming hollow polymer made of polystyrene resin, acrylic resin or styrene-acrylic resin, and gelatin. The heat-sensitive transfer image-receiving sheet according to claim 1 or 2 . The thermal transfer image-receiving sheet according to any one of claims 1 to 5 , wherein the receptor layer contains a polymer latex containing at least a repeating unit obtained from vinyl chloride. The thermal transfer image-receiving sheet according to any one of claims 1 to 5 , wherein the receiving layer contains at least one polymer latex of a vinyl chloride acrylic copolymer. The thermal transfer image-receiving sheet according to any one of claims 1 to 5 , wherein the receiving layer contains at least two polymer latexes containing at least repeating units obtained from vinyl chloride. The heat-sensitive transfer image-receiving sheet according to any one of claims 1 to 5 , wherein the receiving layer contains a polymer latex of at least two kinds of vinyl chloride acrylic copolymers having different acrylic structures. . The thermal transfer image-receiving sheet has a heat-insulating layer, further comprising an undercoat layer in contact with the heat insulating layer, according to claim 1-9 where the undercoat layer or more layers, characterized in that it contains a latex none The thermal transfer image-receiving sheet according to any one of the above. A thermal transfer image-receiving sheet that is used while being superimposed on a thermal transfer sheet in which at least two or more color ink layers are sequentially formed, and an ink surface that is first transferred during image formation, and an untransferred thermal transfer The thermal transfer image receiving sheet according to any one of claims 1 to 10 , wherein a coefficient of static friction with the receiving layer surface of the image receiving sheet is 0.280 or more. The coefficient of static friction between the ink surface to be transferred after image formation and the receiving layer surface of the thermal transfer image receiving sheet to which the ink before the ink surface was transferred at the highest density is 0.280 or more. The heat-sensitive transfer image-receiving sheet according to claim 11 . The heat-sensitive transfer image-receiving sheet according to any one of claims 1 to 12, characterized in that the receiving layer is formed by coating method of the water-based. The heat-sensitive transfer image-receiving sheet according to claim 13 , wherein the receiving layer and the heat insulating layer are formed by simultaneous multilayer coating. An image forming method using a thermal transfer sheet in which at least two or more ink layers are sequentially formed and the thermal transfer image-receiving sheet according to any one of claims 1 to 14 , wherein the thermal transfer sheet is When an image is formed by overlapping with the thermal transfer image-receiving sheet, the coefficient of static friction between the ink surface of the thermal transfer sheet to be transferred first and the receiving layer surface of the untransferred thermal transfer image-receiving sheet is 0.280 or more. An image forming method using a heat-sensitive image-receiving sheet. The coefficient of static friction between the ink surface of the thermal transfer sheet to be transferred after the second time and the receiving layer surface of the thermal transfer image receiving sheet to which the ink before the ink surface was transferred at the highest density is 0.280 or more. The image forming method according to claim 15 . The method for producing a thermal transfer image-receiving sheet according to any one of claims 1 to 14 , wherein the receiving layer is applied by an aqueous coating method in the production process of the thermal transfer image-receiving sheet according to any one of claims 1 to 14 . The method for producing a heat-sensitive transfer image receiving sheet according to claim 17 , wherein the heat-sensitive transfer image-receiving sheet has a heat insulating layer, and the receiving layer and the heat insulating layer are coated simultaneously.