JP4621608B2 - Image forming method using thermal transfer system - Google Patents

Description

  The present invention relates to an image forming method using a thermal transfer method, and more particularly to an image forming method using a thermal transfer sheet and a thermal transfer image receiving sheet that are suitable for rapid processing.

  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 recent years, the demand for higher speed thermal transfer printers has been increasing, and various studies have been made to cope with it. For example, improvement of the transfer speed at the time of printing has been studied by making the thermal transfer sheet thinner, but the degree of speed-up has been insufficient. Patent Document 1 proposes to provide a metal foil film layer between the base material and the dye layer, but further improvement has been desired.
JP-A-2005-280253 “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 sheet suitable for rapid processing and an image forming method using the same.

  As a result of intensive studies, the present inventors have found a thermal transfer sheet having a high transfer density even when processed at a high speed, and an image forming method using the thermal transfer sheet.

The problems of the present invention have been solved by the following means.
(1) A dye having a heat transfer layer containing a heat transferable colorant and a binder component on a plastic film substrate, wherein the heat transfer layer containing a magenta dye is represented by the following general formula (9), Each of the dye represented by the general formula (10) and the dye represented by the following general formula (11) contains a cyan dye and the thermal transfer layer containing the dye represented by the following general formula (12) A thermal transfer sheet containing a pigment represented by formula (13) and having a base material composed of the plastic film and having a thickness of 5 μm or less, and at least 2 having different chemical structures of alkyl acrylate constituent components on the support At least one receiving layer comprising a polymer latex of a copolymer of vinyl chloride and alkyl acrylate, a polystyrene having a particle size of 0.1 to 2.0 μm An image is formed by a combination of a heat-sensitive transfer image-receiving sheet having at least one heat insulating layer containing a hollow polymer having non-foamed hollow particles formed of a resin, an acrylic resin or a styrene-acrylic resin. Thermal transfer image forming method.
In the general formula (9), R ⁷¹ and R ⁷³ each independently represent a hydrogen atom or a substituent, and R ⁷² and R ⁷⁴ each independently represent a substituent. n11 represents an integer of 0 to 4. n12 represents the integer of 0-2. R ⁷² and R ⁷⁴ each independently represents a substituent. n11 represents an integer of 0 to 4.
In the general formula (10), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represents a substituent. n13 represents an integer of 0 to 4, and n14 represents an integer of 0 to 2.
In the general formula (11), R ⁹¹ represents a hydrogen atom or a substituent. R ⁹³ and R ⁹⁴ each independently represents a hydrogen atom or a substituent. R ⁹² represents a substituent. n15 represents an integer of 0 to 2. One of Z ¹ and Z ² represents ═N—, and the other represents ═C (R ⁹⁵ ) —. Z ³ and Z ⁴ each independently represent ═N— or ═C (R ⁹⁵ ) —. R ⁹⁵ represents a hydrogen atom or a substituent.
In general formula (12), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or a substituent. n16 and n17 each independently represents an integer of 0 to 4.
In general formula (13), R ¹¹¹ and R ¹¹³ each independently represents a hydrogen atom or a substituent. R ¹¹² and R ¹¹⁴ each independently represent a substituent. n18 represents an integer of 0 to 4, and n19 represents an integer of 0 to 2.
(2) The thermal transfer image forming method as described in (1) above, wherein the thickness of the receptor layer is 4 μm or less.
(3) In the item (1) or (2), the image forming method records information with a thermal head, and the scanning speed of the thermal head with respect to the thermal transfer sheet is 40 mm / second or more. Thermal transfer image forming method.
(4) The thermal transfer image forming method according to any one of (1) to (3), wherein the heat insulating layer contains a water-soluble resin as a binder resin.
(5) The thermal transfer image forming method according to any one of (1) to (3), wherein the heat insulating layer contains gelatin as a binder resin.
(6) The thermal transfer image forming method according to any one of (1) to (4), wherein the heat insulating layer contains only a water-soluble resin as a binder resin.
(7) The thermal transfer image forming method according to any one of (1) to (5), wherein the heat insulating layer contains only a water-soluble resin as a binder resin and contains gelatin.
(8) The thermal transfer image forming method according to any one of (1) to (3) and (5), wherein the heat insulating layer contains only gelatin as a binder resin.
(9) The thermal transfer image forming method according to any one of (1) to (8), wherein the receiving layer contains a water-soluble polymer.
(10) The thermal transfer image forming method according to any one of (1) to (8), wherein the receiving layer contains gelatin.
(11) The support is a double-sided laminated paper in which polyethylene is laminated on both sides of the base paper, and the receiving layer side polyethylene contains titanium oxide and has a charge adjusting layer on the polyethylene on the side opposite to the receiving layer side. The thermal transfer image forming method according to any one of claims 1 to 10.
(12) The thermal transfer image forming method as described in (11), wherein the polyethylene on the surface opposite to the receiving layer side is a mixed resin of low density polyethylene and high density polyethylene.
(13) The thermal transfer image forming method as described in (11) or (12), wherein the polyethylene on the receiving layer side is a mixed resin of low density polyethylene and high density polyethylene.
(14) The thermal transfer sheet contains the dye represented by the following general formula (7) or the dye represented by the following general formula (8) in the yellow dye layer (1) to ( 13 ) any heat-sensitive transfer image forming method according to one of).
In the general formula (7), R ⁵¹ and R ⁵² each independently represent a substituent. n8 represents an integer of 0 to 5. n9 represents an integer of 0 to 4.
In the general formula (8), R ⁶¹ represents a substituent, and R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. n10 represents an integer of 0 to 4.
(15) The receiving layer contains a compound represented by any one of the following general formulas (E-1) to (E-3), according to any one of (1) to ( 14) , The thermal transfer image forming method described.
In the formula, 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 ). 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. R _{a1 to} R _a4 each independently represents a hydrogen atom or an aliphatic group.

  The image forming method of the present invention can realize a high transfer density even in high-speed printing.

Hereinafter, the present invention will be described in detail.
The heat-sensitive transfer image-receiving sheet used in the present invention has a dye-receiving layer (receiving layer) formed on a support. 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 coating, bar coating, gravure coating, or gravure reverse coating.

(Receptive layer)
The receiving layer functions to receive the dye transferred from the ink sheet and maintain the formed image.
In the present invention, the thickness of the receiving layer is preferably 6 μm or less. Especially preferably, it is the range of 2.5 micrometers or more and 4 micrometers or less.
At least one layer of the receiving layer of the present invention, the at least two different kinds of chemical structures of the alkyl acrylate component, contains a polymer latex copolymers of vinyl chloride and alkyl acrylates. Moreover, it is preferable that a receiving layer contains a water-soluble polymer with a polymer latex. By including a polymer latex and a water-soluble polymer, a water-soluble polymer that is difficult to be dyed to the dye can be present between the polymer latexes, and the dye dyed to the polymer latex can be prevented from diffusing. Therefore, it is possible to reduce a change in sharpness of the receiving layer with time and to form a recorded image with a small change in transfer image with time.

<Polymer latex>
The polymer latex used in the present invention will be described. In the heat-sensitive transfer image-receiving sheet used in the present invention, the polymer latex that can be used in the receptor layer is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, the emulsion is polymerized, the micelle is dispersed, or the polymer molecule has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Anything may be used. For polymer latex, Tadashi Okuda, Hiroshi Inagaki, “Synthetic Resin Emulsion”, published by Kobunshi Publishing (1978), Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, “Application of Synthetic Latex”, Takashi Published by Molecular Publications (1993), Soichi Muroi, “Chemistry of Synthetic Latex”, published by High Polymers Publications (1970), supervised by Yoshiaki Mitsuzawa, “Development and Application of Water-Based 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 130 ° C., more preferably 0 ° C. to 100 ° C., and further preferably 10 ° C. to 80 ° C.

Preferred embodiments of the polymer latex used in the present invention include acrylic polymers, polyesters, rubbers (for example, SBR resin), polyurethanes, polyvinyl chlorides, polyvinyl acetates, polyvinylidene chlorides, polyolefins, co-polymers. A hydrophobic polymer such as polymerized nylon 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 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.
However, in the present invention, different at least two chemical structures alkyl acrylate components, the use of polymer latex of a copolymer of vinyl chloride and alkyl acrylate is essential.

The monomer used to synthesize the port Rimmer latex is not particularly limited, is as it can be polymerized in the usual radical polymerization or ion polymerization method, it is possible to use the following monomer groups of (a) ~ (j) preferably . Polymer monomers can be synthesized by selecting these monomers independently and freely in combination.
Here, in the present invention, vinyl chloride and acrylic acrylate monomers are used as monomers in the polymer latex of the essential copolymer of vinyl chloride and alkyl acrylate.

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

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

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

  The polymer latex that can be used in the present invention is commercially available, and the following polymers can be used. Examples of acrylic polymers include Sebian A-4635, 4718, 4601 (all trade names) manufactured by Daicel Chemical Industries, Ltd., and Nipol Lx811, 814, 821, 820, 855 (P-17) manufactured by Nippon Zeon Co., Ltd. : Tg36 ° C), 857x2 (P-18: Tg43 ° C) (all trade names), Voncoat R3370 (P-19: Tg25 ° C), 4280 (P-20: Tg15 ° C) (Dainippon Ink Chemical Co., Ltd.) All are trade names), Jurimer ET-410 (P-21: Tg44 ° C) manufactured by Nippon Pure Chemicals Co., Ltd. (trade name), 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: Tg60 ° C) (all trade names), Aron A-104 (P-30: Tg45 ° C) manufactured by Toagosei Co., Ltd. (trade name), Takamatsu Yushi Co., Ltd. NS-600X, NS-620X (both are trade names), Nishin Chemical Industry Co., Ltd. Vinibrand 2580, 2583, 2641, 2770, 2770H, 2635, 2886, 5202C, 2706 ( Shift trade names), and the like.

  Examples of polyesters include: Dainippon Ink Chemical Co., Ltd. FINETEX ES650, 611, 675, 850 (all trade names), Eastman Chemical WD-size, WMS (all trade names), Takamatsu Oil ( A-110, A-115GE, 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-244LX, NS-140L NS-141LX, NS-282LX (all are trade names), Aronmelt PES-1000 series, PES-2000 series (all trade names) manufactured by Toagosei Co., Ltd., Baironal MD-1100, MD- manufactured by Toyobo Co., Ltd. 1200, MD-1220, MD-1245, MD-1250, MD-1335, MD-1400, MD-1480, MD-1500, MD-1930, MD-1985 (all trade names), Sumitomo Seika Co., Ltd. Sephorjon ES (trade name) and so on.

  Examples of polyurethanes include HYDRAN AP10, AP20, AP30, AP40, 101H (all trade names), Vondic 1320NS, 1610NS (all trade names), manufactured by Dainippon Ink Chemical Co., Ltd. D-1000, D-2000, D-6000, D-4000, D-9000 (all trade names), NS-155X, NS-310A, NS-310X, NS-311X (all manufactured by Takamatsu Yushi Co., Ltd.) Trade name), Elastolon (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.

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

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

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

These polymer latexes may be used alone or in combination of two or more as required.
However, in the present invention, a polymer latex of a copolymer of vinyl chloride and alkyl acrylate is used for at least two types having different chemical structures of the alkyl acrylate constituent components .

  In the present invention, the receptor layer 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.

  Although there is no restriction | limiting in particular regarding drying time, The shorter one is preferable on manufacture. Specifically, it is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes.

MFT is the minimum film forming temperature of the polymer latex, and is the minimum temperature required for the emulsion to form a smooth and transparent continuous coating film. The MFT 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. Film-forming aids, also called temporary plasticizers, are organic compounds (usually organic solvents) that lower the minimum film-forming temperature of polymer latex. For example, Soichi Muroi, “Synthetic Latex Chemistry”, published by Kobunshi Publishing Co. (1970) )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

Preferable examples of the polymer latex include polylactic acid esters, polyurethanes, polycarbonates, polyesters, polyacetals, SBRs, and polyvinyl chlorides. Among these, polyesters, polycarbonates, and polyvinyl chlorides In the present invention, at least two polymer latexes of vinyl chloride and alkyl acrylate copolymers , which differ in the chemical structure of the alkyl acrylate component, are used.

  As the polymer latex used in the present invention, any polymer may be used in combination with the polymer latex. The polymer that can be used in combination is preferably transparent or translucent and colorless. Natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other media for forming films such as gelatins and polyvinyl alcohol , Hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinylchloride, polymethacrylic acid, styrene-maleic anhydride copolymer , Styrene-acrylonitrile copolymers, styrene-butadiene copolymers, polyvinyl acetals (eg, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy Fat, polyvinylidene chlorides, polyepoxides, polycarbonates, polyvinyl acetates, polyolefins, and polyamides. The binder may be coated from water or an organic solvent or emulsion.

  The binder that can be 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.

This glass transition temperature (Tg) can be calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. Xi is the mass fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. In addition, the value of the homopolymer glass transition temperature (Tgi) of each monomer can adopt the value of “Polymer Handbook (3rd Edition)” (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).

  The polymer used in the binder that can be used in the present invention can be easily obtained by solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, anion polymerization, cation polymerization, etc. The emulsion polymerization method is 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 a mixture, an emulsifier and a polymerization initiator, polymerization is carried out under stirring at about 30 to 100 ° C., preferably 60 to 90 ° C. for 3 to 24 hours. Various conditions such as the dispersion medium, the monomer concentration, the initiator amount, the emulsifier amount, the dispersant amount, the reaction temperature, and the monomer addition method are appropriately set in consideration of the type of monomer used. Moreover, it is preferable to use a dispersing agent as needed.

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

  The polymerization initiator only needs to have a radical generating ability, such as inorganic peroxides such as persulfate and hydrogen peroxide, and peroxides described in Nippon Oil & Fats Co., Ltd. “Organic Peroxide Catalog”, etc. The azo compounds described in Yaku Kogyo Co., Ltd. “Azo Polymerization Initiator Catalog” can be used. Among them, water-soluble peroxides such as persulfate and water-soluble azo compounds described in Wako Pure Chemical Industries, Ltd., `` Azo polymerization initiator catalog '' and the like are preferable, ammonium persulfate, sodium persulfate, potassium persulfate, Azobis (2-methylpropionamidine) hydrochloride, azobis (2-methyl-N- (2-hydroxyethyl) propionamide), azobiscyanovaleric acid is more preferable, and in particular, ammonium persulfate, sodium persulfate, potassium persulfate, etc. Peroxides are preferred from the viewpoints of image storability, 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) multivalent ions such as metal ions such as iron ions and alkaline earth metal ions such as calcium ions. Japanese Patent Publication No. 6-8956, US Pat. No. 5,053,322 JP-A-4-73645, JP-A-4-127145, JP-A-4-47073, JP-A-4-305572, JP-A-6-11805, JP-A-5-173312, 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-A-7-120894, JP-A-7-199433, JP-A-7-306504, JP-A-9-43792, JP-A-8-314090, JP-A-10-182571, Special The compounds described in Kaihei 10-182570 and JP-A-11-190892 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-diaminobuta -N, N, N ', N'-tetraacetic acid, 1-phenylethylenediamine-N, N, N', N'-tetraacetic acid, d, l-1,2-diphenylethylenediamine-N, N, N ' , N′-tetraacetic acid, 1,4-diaminobutane-N, N, N ′, N′-tetraacetic acid, trans-cyclobutane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, trans-cyclopentane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, trans-cyclohexane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, cis-cyclohexane -1,2-diamine-N, N, N ′, N′-tetraacetic acid, cyclohexane-1,3-diamine-N, N, N ′, N′-tetraacetic acid, cyclohexane-1,4-diamine-N , N, N ′, N′-tetraacetic acid, o-phenylenediamine-N, N, N ′, N′-tetraacetic acid, cis-1,4-diaminobutene-N, N, N ′, N′-tetra Acetic 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-p Lopandiamine-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. Moreover, when it exceeds 0.4 mass%, the viscosity of latex will rise and coatability will fall.

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

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

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

  In the polymer latex used in the present invention, an aqueous solvent can be used as a solvent in the coating solution, but a water-miscible organic solvent may be used in combination. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide. The amount of these organic solvents added is preferably 50% by mass or less, more preferably 30% by mass or less of the solvent.

The polymer latex used in the present invention preferably has a polymer concentration of 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 55% by mass with respect to the latex liquid.
The addition amount of the polymer latex is preferably 50 to 95% by mass, more preferably 70 to 90% by mass, based on the total polymer content in the receptor layer.
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>
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.

  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 (trade name), etc.), locust bean gum, pectin, tragacanth, corn starch (National Starch & Chemical Co Purity-21 (trade name, etc.), phosphorylated starch (National Starch & Chemical Co., National 78-1898 (trade name, etc.) and other microbial polysaccharides include xanthan gum (Kelco's Keltrol T (product) Name), dextrin (Nadex360 (trade name) manufactured by National Starch & Chemical Co.), and other natural animal polymers such as gelatin (Crodyne B419 (trade name) manufactured by Croda), casein, chondroitin sulfate sodium ( Croda's Cromoist CS (trade name), etc.). Celluloses include ethyl cellulose (ICI Cellofas WLD (trade name), etc.), carboxymethyl cellulose (Daicel CMC (trade name), etc.), hydroxyethyl cellulose (Daicel HEC (trade name), etc.), hydroxypropyl cellulose (Aqualon, etc.) Klucel (trade name, etc.), methylcellulose (Henkel Viscontran (trade name), etc.), nitrocellulose (Hercules Isopropyl Wet (trade name, etc.), cationized cellulose (Croda Crodacel QM (trade name, etc.)) Can be mentioned. As starch system, phosphorylated starch (National Starch & Chemical National 78-1898 (trade name) etc.), as alginic acid system, sodium alginate (Kelco Keltone (trade name) etc.), propylene glycol alginate, etc. Examples of the classification include cationized guar gum (such as Hi-care1000 (trade name) manufactured by Alcolac) and sodium hyaluronate (such as Hyalure (trade name) manufactured by Lifecare Biomedial).

  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 (manufactured by Kyodo Chemical Co., Ltd .: Pluscoat Z-221, Z-446, Z-561, Z-450, Z-565, Z-850, Z-3308, RZ-105, RZ- 570, Z-730, RZ-142 (all are trade names)).

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

  Of the water-soluble synthetic polymers that can be used in the present invention, polyvinyl 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 is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 0.005 to 10% by mass, based on the total polymer in the receiving layer. ˜5% by weight is particularly preferred.

<Release agent>
In addition, a release agent may be added to the receiving layer in order to prevent thermal fusion with the thermal transfer sheet during image formation. As the release agent, silicone oil and phosphoric ester plasticizer fluorine compound can be used, and silicone oil is particularly preferably used. As the silicone oil, modified silicone oils such as epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy / polyether modification, and polyether modification are preferably used. The reaction product of vinyl modified silicone oil and hydrogen modified silicone oil is good. The amount of the release agent added is preferably 0.2 to 30 parts by mass with respect to 100 parts by mass of the polymer (polymer latex or the like) that accepts the dye in the receptor layer.

<Emulsions>
Hydrophobic additives such as lubricants and antioxidants can be introduced into the layers of the image receiving sheet by known methods such as those described in US Pat. No. 2,322,027. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, and 4,555,476 In addition, a high boiling point organic solvent as described in the publications and specifications of JP 4,599,296 and JP-B-3-62256 is used in combination with a low boiling point organic solvent having a boiling point of 50 ° C to 160 ° C as necessary. Can be used. These lubricants, 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. Here, examples of the substituent include the substituents exemplified for R ⁵¹ in the general formula (7) described later. 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 lubricant include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder; silicone oil, phosphate ester compounds, fluorine surfactants, silicone surfactants, and other in the technical field. A known release agent can be used, and a fluorine-based compound represented by a fluorine-based surfactant, a silicone-based surfactant, a silicone oil such as a silicone oil and / or a cured product thereof is preferably used.
The content of the lubricant 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, straight silicone oil, modified silicone oil or a cured product thereof can be used. Straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen 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 reactive / different functional group 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.), etc., 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.) and the like, methacryl-modified silicone oil 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.) KK-720), KS-720, KS-774-PL-3 (photo-curing 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.

  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. R ¹ represents a single bond or a divalent linking group, E represents a substituted or unsubstituted ethylene group, and P represents a substituted or unsubstituted propylene group. m and n represent an integer of 2000 or less, and a and b represent an integer of 30 or less.

  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.
In addition, a high boiling point organic solvent is preferably used when using an emulsified dispersion.

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.

(Underlayer)
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. These layers can be formed in the same manner as described in, for example, Japanese Patent No. 3585599 and Japanese Patent No. 2925244.

(Insulation layer)
The heat insulating layer (foamed layer) plays a role of protecting the support from heat during heat transfer using a thermal head. 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 is formed from a resin and a foaming agent. As the resin for the heat insulating layer, a known resin such as urethane resin, acrylic resin, methacrylic resin, modified olefin resin, or a blend thereof can be used. A heat insulating layer is formed by coating a resin obtained by dissolving and / or dispersing these resins in an organic solvent or water. The heat insulating layer coating liquid is an aqueous coating liquid that does not affect the foaming agent. For example, water-soluble, water-dispersible, or SBR latex, urethane emulsion, polyester emulsion, emulsion of vinyl acetate and its copolymer, emulsion of acrylic copolymer such as acrylic and acrylic styrene, vinyl chloride Emulsions such as emulsions, or dispersions thereof can be used. However, in the case where microspheres described later are used as the foaming agent, an emulsion of vinyl acetate and its copolymer, acrylic and Emulsion of acrylic copolymer such as acrylic styrene It is preferable to use.

  Since these resins can easily control the glass transition point, flexibility, and film-forming property by changing the type of monomer to be copolymerized and their blending ratio, plasticizers and film-forming aids are added. Even if it is not, it is suitable in that the desired physical properties can be obtained, the color change is small during storage in various environments after film formation, and the physical properties change little over time. Of the above-mentioned resins, SBR latex is not preferred because it generally has a low glass transition point and is likely to cause blocking, and yellowing is likely to occur after film formation or during storage. Many urethane-based emulsions contain solvents such as NMP and DMF, and are not preferable because they easily affect the foaming agent. Polyester emulsions, dispersions, and vinyl chloride emulsions are generally not preferred because of their high glass transition points and poor microsphere foaming properties. Although some of them are soft, they are preferably not used because they are given flexibility by adding a plasticizer.

  The foaming performance of the foaming agent is greatly influenced by the hardness of the resin. In order for the foaming agent to expand to a desirable expansion ratio, a glass transition point of −30 to 20 ° C. or a film forming temperature of 20 ° C. or lower is desirable. When the glass transition point is 20 ° C. or higher, the flexibility is insufficient and the foaming performance of the foaming agent is reduced. In addition, those having a glass transition point of −30 ° C. or lower may cause blocking (generated at the foam layer and the back surface of the base material when the base material after the foam layer is wound) or thermal transfer. When the image receiving sheet is cut, a defect (such as when the image receiving sheet is cut, the resin of the foam layer is stuck to the blade of the cutter, the appearance is deteriorated, and the size of the cutting is caused, for example) occurs. Sometimes. Moreover, when the minimum film-forming temperature is 20 ° C. or higher, film-forming defects occur during coating and drying, and defects such as surface cracks occur.

  Defoaming agents such as dinitropentamethylenetetramene, diazoaminobenzene, azobisisobutyronitrile, azodicarboxamide, etc. that decompose when heated to generate gases such as oxygen, carbon dioxide, and nitrogen Examples thereof include known foaming agents such as microspheres in which a low boiling point liquid such as butane or pentane is covered with a resin such as polyvinylidene chloride or polyacrylonitrile to form microcapsules. Among these, microspheres in which a low-boiling liquid such as butane and pentane is covered with a resin such as polyvinylidene chloride and polyacrylonitrile to form microcapsules are preferably used. These foaming agents are foamed by heating after forming the foamed layer, and have high cushioning properties and heat insulation properties after foaming. The amount of the foaming agent used is preferably in the range of 0.5 to 100 parts by mass per 100 parts by mass of the resin forming the foamed layer. If it is 0.5 parts by mass or less, the cushioning property of the foam layer is low, and the effect of forming the foam layer cannot be obtained. If it is 100 parts by mass or more, the hollow ratio after foaming becomes too large, the mechanical strength of the foamed layer is lowered, and it becomes impossible to withstand normal handling. In addition, the foam layer surface loses smoothness and adversely affects the appearance and print quality. The total thickness of the foam layer is preferably 30 to 100 μm. When it is 30 μm or less, cushioning properties and heat insulation are insufficient, and when it is 100 μm or more, the effect of the foamed layer is not improved and the strength is lowered. Moreover, as a particle size of a foaming agent, that whose volume average particle diameter before foaming is about 5-15 micrometers and whose particle diameter after foaming is 20-50 micrometers is preferable. When the volume average particle size before foaming is 5 μm or less and the particle size after foaming is 20 μm or less, the cushion effect is low, the volume average particle size before foaming is 15 μm or more, and the particle size after foaming is 20 to 50 μm or more. In this case, the surface of the foam layer is made uneven, which adversely affects the image quality of the formed image.

  Particularly preferred among the foaming agents are low-temperature foaming type microspheres having a partition wall softening temperature and foaming start temperature of 100 ° C. or lower and an optimal foaming temperature (the temperature at which the foaming ratio becomes the highest with a heating time of 1 minute) of 140 ° C. or lower. It is preferable that the heating conditions during foaming be as low as possible. By using microspheres having a low foaming temperature, thermal wrinkles and curling of the base material during foaming can be prevented. The microsphere having a low foaming temperature can be obtained by adjusting the blending amount of a thermoplastic resin such as polyvinylidene chloride or polyacrylonitrile that forms the partition walls. The volume average particle diameter is 5 to 15 μm. The foam layer using this microsphere is such that the bubbles obtained by foaming are closed cells, foamed by a simple process of heating alone, the thickness of the foam layer can be easily controlled by the amount of microspheres, etc. There are advantages.

  However, this microsphere is weak against an organic solvent, and when a coating solution using an organic solvent is used as the foam layer, the partition walls of the microsphere are eroded and the foamability is lowered. Therefore, when microspheres such as those described above are used, organic solvents that attack the partition walls, for example, ketones such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, and organic solvents such as lower alcohols such as methanol and ethanol It is better to use a water-based coating solution that does not contain water. Accordingly, an aqueous coating solution, specifically, a resin using a water-soluble or water-dispersible resin, or a resin emulsion, preferably an acrylic styrene emulsion or a modified vinyl acetate emulsion may be used. In addition, even if the foamed layer is formed with an aqueous coating solution, the addition of high-boiling and highly polar solvents such as NMP, DMF, and cellosolve as co-solvents, film-forming aids, and plasticizers will affect the microspheres. Therefore, it is necessary to pay attention to the composition of the aqueous resin to be used, the amount of the high-boiling solvent added, and to confirm whether the microcapsules are adversely affected.

In the image receiving sheet used in the present invention, the heat insulating layer preferably contains a hollow polymer.
Here, the hollow polymer is a polymer particle having independent pores inside the particle. For example, 1) Water is contained in a partition wall made of polystyrene resin , acrylic resin, styrene-acrylic resin, etc., and is coated and dried. After that, non-foamed hollow particles in which the water in the particles evaporates outside the particles and the inside of the particles becomes hollow. 2) A low boiling point liquid such as butane or pentane is added to polyvinylidene chloride, polyacrylonitrile, polyacrylic acid, poly Foamed microballoons that are covered with a resin composed of any one of acrylate esters, a mixture thereof, or a polymer, and after coating, the low-boiling liquid inside the particles expands by heating, so that the inside becomes hollow 3) Examples include microballoons obtained by heating and foaming the above 2) in advance to form a hollow polymer.
In the present invention, the hollow polymer having non-foamed hollow particles formed of polystyrene resin, acrylic resin or styrene-acrylic resin of 1) above is used.

  These hollow polymers preferably have a hollow ratio of about 20 to 70%, and can be used by mixing two or more kinds as necessary. Specific examples of 1) include Low and Haas Ropaque 1055, Dainippon Ink Boncoat PP-1000, JSR SX866 (B), Nippon Zeon Nipol MH5055 (all trade names), and the like. . Specific examples of 2) include F-30 and F-50 (both trade names) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Specific examples of 3) include F-30E manufactured by Matsumoto Yushi Seiyaku Co., Ltd., EXPANSEL 461DE, 551DE, and 551DE20 (all trade names) manufactured by Nippon Ferrite Co., Ltd. The hollow polymer used for the heat insulating layer may be made into a latex.

  The 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. In the present invention, gelatin is particularly preferred.

The solid content of the hollow polymer in the heat insulating layer is preferably between 5 and 2000 parts by mass when the solids content of the binder resin is 100 parts by mass. Moreover, 1-70 mass% is preferable, and, as for the mass ratio which occupies with respect to the coating liquid of the solid content of a hollow polymer, 10-40 mass% is more preferable. If the ratio of the hollow polymer is too small, sufficient heat insulation cannot be obtained, and if the ratio of the hollow polymer is too large, the binding force between the hollow polymers decreases, causing problems such as powder falling off during processing or film peeling. Arise.
Particle size is preferably 0.1~20μm of hollow polymer, and more preferably 0.1-2 .mu.m, 0.1 to 1 [mu] m is rather particular preferred, in the present invention, to use those 0.1-2 .mu.m. Further, the glass transition temperature (Tg) of the hollow polymer is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher.

(Support)
In the present invention, a water-resistant support is used as the support. By using a water-resistant support, it is possible to prevent moisture from being absorbed into the support, and to prevent a change in performance of the receiving layer over time. As the water-resistant support, for example, coated paper or laminated paper can be used.

-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 (all trade names) manufactured by Toyobo Co., Ltd .; manufactured by Kao Corporation Tufton NE-382, Tufton U-5, ATR-2009, ATR-2010 (all trade names); Elitel UE3500, UE3210, XA-8153, KZA-7449, KZA-1449 (all products) manufactured by Unitika Ltd. Name); Polyester TP-220, R-188 manufactured by Nippon Synthetic Chemical Co., Ltd. (both are trade names); Various types of high-loss series thermoplastic resins manufactured by Seiko Chemical Industry Co., Ltd. (all are trade names), etc. Is mentioned.

(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.

Next, the thermal transfer sheet (ink sheet) used in the present invention will be described.
In the thermal transfer image formation, the ink sheet used in combination with the above-described thermal transfer image receiving sheet is provided with a thermal transfer layer (pigment layer) containing a diffusion transfer dye on a support. The thermal transfer layer is applied by a general method such as roll coating, bar coating, gravure coating, or gravure reverse coating.
The thermal transfer layer of the ink sheet used in the present invention, have preferably comprise at least one dye represented by the following general formula as a yellow dye (7) or (8).
In the present invention, under following general formula as magenta dye (9), (10) or includes a respective at least one dye represented by (11), under following general formula as a cyan dye (12) or (13 including at least one dye each represented by).
As the material of the ink sheet base material, a plastic film such as a polyester film, a polystyrene film, a polysulfone film, a polyimide film, a polyvinyl alcohol film, or a cellophane is suitable. In the present invention, the plastic substrate has a thickness of 5 μm or less. Preferably it is the range of 3.5 micrometers or more and 4.5 micrometers or less. In a preferred embodiment of the present invention, the thermal transfer dye-donating material comprises a cyan terephthalate support or a polyester support coated with a cyan dye, a magenta dye and a yellow dye in successive repeating regions, and the thermal transfer process is performed for each dye. Are sequentially performed to form a three-color transfer image. Of course, when this thermal transfer process is carried out in a single color, a monochrome transfer image can be obtained.
A polyvinyl butyral resin or a polyester resin is preferably used as the main part of the binder resin. More preferable polyester resin is that terephthalic acid is more than one-half of the acid component, more preferably more than two-thirds of the acid component is terephthalic acid, and most preferably more than three-quarters of the acid component is terephthalic acid. It is an acid. Thereby, fusion with a heat-sensitive transfer image-receiving sheet can be prevented. The polyester that can be used in the present invention can be obtained by the method described in JP-A-9-295389.

  Below, the pigment | dye represented by General formula (7) preferably used by this invention is demonstrated in detail.

In the general formula (7), R ⁵¹ and R ⁵² each independently represent a substituent, and examples of the substituent include those described below. n8 represents an integer of 0 to 5, and n9 represents an integer of 0 to 4.
In the general formula (7), R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a substituent.
Here, the substituent will be described in more detail. Examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group (any number of rings)), an alkenyl group (including a cycloalkenyl group (any number of rings)), an alkynyl group, and an aryl group. , Heterocyclic group, cyano group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonyl Amino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, Sill group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl- or heterocyclic azo group, and a imide group, each group may further have a substituent.

Hereinafter, R ⁵¹ and R ⁵² will be described in more detail.
Examples of the halogen atom represented by R ⁵¹ and R ⁵² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable.

The alkyl group represented by R ⁵¹ and R ⁵² includes a cycloalkyl group and a bicycloalkyl group. The alkyl group includes a straight-chain, branched substituted or unsubstituted alkyl group. The linear, branched substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, or 2-ethylhexyl. The cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms. Examples include cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl. The bicycloalkyl group is a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Examples include bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl). Further, it includes a tricyclo structure having many ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group.
The alkenyl group represented by R ⁵¹ and R ⁵² includes a cycloalkenyl group and a bicycloalkenyl group. The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. As the alkenyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms is preferable. Examples include vinyl, allyl, prenyl, geranyl, oleyl. The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms. Examples include 2-cyclopenten-1-yl and 2-cyclohexen-1-yl. The bicycloalkenyl group includes a substituted or unsubstituted bicycloalkenyl group. The bicycloalkenyl group is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Examples include bicyclo [2,2,1] hept-2-en-1-yl and bicyclo [2,2,2] oct-2-en-4-yl.

The alkynyl group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

The aryl group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl. Is mentioned.

The heterocyclic group represented by R ⁵¹ and R ⁵² is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, May be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the heterocyclic group include, but are not limited to, substitution positions (ie, exemplified as a ring): pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, Furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, Examples include imidazolidine and thiazoline.

The alkoxy group represented by R ⁵¹ and R ⁵² includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

The acyloxy group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of carbamoyloxy groups include N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy and the like. Can be mentioned.

The alkoxycarbonyloxy group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

The aryloxycarbonyloxy group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group represented by R ⁵¹ and R ⁵² includes an alkylamino group and an arylamino group. The amino group is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of amino groups include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino, etc. Can be mentioned.

The acylamino group represented by R ⁵¹ and R ⁵² is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. . Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino and the like.

The aminocarbonylamino group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

The aryloxycarbonylamino group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkyl or arylsulfonylamino group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms. . Examples of the alkylsulfonylamino group and arylsulfonylamino group include methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like.

The alkylthio group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The sulfamoyl group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of sulfamoyl groups include N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl) and the like.

The alkyl or arylsulfinyl group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms. Examples of the alkyl or arylsulfinyl group include, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

The alkyl or arylsulfonyl group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms. Examples of the alkyl or arylsulfonyl group include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by R ⁵¹ and R ⁵² is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or 4 to 4 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group with 30 substituted or unsubstituted carbon atoms is preferred. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

The aryloxycarbonyl group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl and the like.

The alkoxycarbonyl group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group represented by R ⁵¹ and R ⁵² is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

Examples of the aryl or heterocyclic azo group represented by R ⁵¹ and R ⁵² include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. Can do.

Examples of the imide group represented by R ⁵¹ and R ⁵² include N-succinimide and N-phthalimide.
When R ⁵¹ and R ⁵² represent a substituent and the substituent further has a substituent, examples of such a substituent include the groups listed as the substituents for R ⁵¹ and R ⁵² described above.

R ⁵¹ and R ⁵² are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. And more preferably a hydrogen atom or a substituted or unsubstituted alkyl group.

R ⁵¹ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a hydrogen atom. , A substituted or unsubstituted alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Most preferably, it is a C1-C6 alkyl group.

Examples of R ⁵² are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably Is a hydrogen atom, a substituted or unsubstituted alkyl group, more preferably an aryloxycarbonyl group having 6 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted carbamoyl group, most preferably Is a substituted carbamoyl group.

  As for the preferable combination of substituents of the dye represented by the general formula (7), a compound in which at least one of various substituents is the above-mentioned preferable group is preferable, and a compound in which more various substituents are the above-mentioned preferable groups More preferred are compounds in which all substituents are the preferred groups.

  The dye represented by the general formula (8) will be described in detail.

In the general formula (8), R ⁶¹ represents a substituent. R ⁶² , R ⁶³ and R ⁶⁴ each independently represents a hydrogen atom or a substituent. Examples of the substituent in R ^{61 to} R ⁶⁴ include those described above for R ⁵¹ and R ⁵² . n10 represents an integer of 0 to 4.

Examples of R ⁶¹ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably Is a hydrogen atom or a substituted or unsubstituted alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Most preferably, it is a C1-C6 alkyl group.
Examples of R ⁶² and R ⁶³ are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group It is a heterocyclic group. A hydrogen atom or a substituted or unsubstituted alkyl group is more preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms is more preferable.
Examples of R ⁶⁴ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably Is a hydrogen atom or a substituted or unsubstituted alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom.

  As for the preferred combination of substituents of the dye represented by the general formula (8), a compound in which at least one of various substituents is the preferred group is preferred, and a compound in which more various substituents are the preferred groups More preferred are compounds in which all substituents are the preferred groups.

  The dye represented by the general formula (9) or (10) will be described in detail.

In the general formula (9), R ⁷¹ and R ⁷³ each independently represent a hydrogen atom or a substituent, and R ⁷² and R ⁷⁴ each independently represent a substituent. n11 represents an integer of 0 to 4. n12 represents the integer of 0-2. Examples of the substituent in R ^{71 to} R ⁷⁴ include those described for R ⁵¹ and R ⁵² described above.

Examples of R ⁷¹ and R ⁷³ include substituents as described for R ⁵¹ in formula (7), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted C1-C6 alkyl group, More preferably, it is a hydrogen atom.

Examples of R ⁷² and R ⁷⁴ include substituents as described for R ⁵¹ in formula (7). An alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy are preferable, and an alkoxy group and an aryloxy group are more preferable. Each group may further have a substituent.

In the general formula (10), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represents a substituent. n13 represents an integer of 0 to 4, and n14 represents an integer of 0 to 2. ^Examples of the substituent for R ⁸¹ , R ⁸² , and R ⁸⁴ include those described for R ⁵¹ and R ⁵² described above.

Examples of R ⁸¹ include substituents as described for R ⁵¹ and R ⁵² , and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted C1-C6 alkyl group, More preferably, it is a hydrogen atom.

Examples of R ⁸² and R ⁸⁴ include substituents as described for R ⁵¹ in formula (7). An alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, and an aryloxycarbonyloxy are preferable, and an alkoxy group and an aryloxy group are more preferable. Each group may further have a substituent.

  Regarding the preferred combination of substituents of the dye represented by the general formula (9) or (10), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  The dye represented by the general formula (11) will be described in detail.

In the general formula (11), R ⁹¹ represents a hydrogen atom or a substituent. R ⁹³ and R ⁹⁴ each independently represents a hydrogen atom or a substituent. R ⁹² represents a substituent. n15 represents an integer of 0 to 2. Z ^1, Z ² is either one of = the N-, the other is = C (R ⁹⁵⁾ - represents a. Z ³ and Z ⁴ each independently represent ═N— or ═C (R ⁹⁵ ) —. R ⁹⁵ represents a hydrogen atom or a substituent. Examples of the substituent in R ^{91 to} R ⁹⁵ include those described for R ⁵¹ and R ⁵² described above.

R ⁹¹ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted amino. And more preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Examples of R ⁹² include substituents as described for R ⁵¹ in formula (7), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted alkyl group.

Examples of R ⁹³ and R ⁹⁴ include substituents as described for R ⁵¹ and R ⁵² , and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted C1-C6 alkyl group, More preferably, they are a substituted or unsubstituted C1-C6 alkyl group.

Examples of R ⁹⁵ include substituents as described for R ⁵¹ in formula (7), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted alkyl group.

  As for the preferred combination of substituents of the dye represented by the general formula (11), a compound in which at least one of various substituents is the above preferred group is preferred, and a compound in which more various substituents are the above preferred groups More preferred are compounds in which all substituents are the preferred groups.

  The dye represented by the general formula (12) or (13) will be described in detail.

R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent in R ^{101 to} R ¹⁰⁴ include those described above for R ⁵¹ and R ⁵² . n16 and n17 each independently represents an integer of 0 to 4.

Examples of R ¹⁰¹ include substituents as described for R ⁵¹ in formula (7), and preferred ranges are also the same. More preferably an amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, More preferably, it is an acylamino group.
Examples of ^R102 include substituents as described for ^R51 in formula (7), and the preferred ranges are also the same. More preferably, they are a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkoxy group.
Examples of R ¹⁰³ and R ¹⁰⁴ include substituents as described for R ⁵¹ and R ⁵² , and preferred ranges are also the same. A substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is more preferred, and a substituted or unsubstituted alkyl group is more preferred.

In general formula (13), R ¹¹¹ and R ¹¹³ each independently represents a hydrogen atom or a substituent. R ¹¹² and R ¹¹⁴ each independently represent a substituent. n18 represents an integer of 0 to 4, and n19 represents an integer of 0 to 2. Examples of the substituent in R ^{111 to} R ¹¹⁴ include those described for R ⁵¹ and R ⁵² described above.

Examples of R ¹¹¹ and R ¹¹³ include substituents as described for R ⁵¹ and R ⁵² , and preferred ranges are also the same. More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group.

Examples of R ¹¹² and R ¹¹⁴ include a hydrogen atom and a substituent as described for R ⁵¹ in the general formula (7), and preferred ranges are also the same. More preferably, it is a hydrogen atom.

  Regarding the preferred combination of substituents of the dye represented by the general formula (12) or (13), a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are preferable. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  Specific examples of the dyes represented by the general formulas (7) to (13) are shown below, but the dyes that can be used in the present invention are not limited to the following examples.

Each of these dyes is preferably contained in the thermal transfer layer (dye layer) in an amount of 10 to 90% by mass, and more preferably 20 to 80% by mass.
The coating amount of the thermal transfer layer is preferably 0.1 to 1.0 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). Is 0.15 to 0.60 g / m ² . The film thickness of the thermal transfer layer is preferably from 0.1 to 2.0 μm, more preferably from 0.1 to 1.0 μm.

The image forming method of the present invention is preferably a method in which an image is formed by superimposing the thermal transfer layer of the thermal transfer sheet and the receiving layer of the thermal transfer image-receiving sheet in contact with each other and applying thermal energy corresponding to the image signal from the thermal head. .
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 image forming method can be performed in the same manner as described in, for example, JP-A-2005-88545. In the present invention, from the viewpoint of shortening the time until the printed matter is provided to the consumer, the scanning speed of the thermal head with respect to the thermal transfer sheet is preferably 40 mm / second or more, more preferably 40 mm / second or more and 500 mm / second or less, More preferably, it is 50 mm / second or more and 400 mm / second or less. The present invention is particularly effective for such a high scanning speed.
The present invention can be used in printers, copiers, and the like that use a thermal transfer recording system.
In addition, the thermal transfer image-receiving sheet used in the present invention can be used in various applications such as a sheet- or roll-shaped thermal transfer image-receiving sheet, cards, and a transmissive original document sheet that can be thermally transferred and recorded by appropriately selecting a support. It can also be applied to.

  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.

(Preparation of ink sheet D1)
A polyester film having a thickness of 7.0 μm (TOYOBO thin film polyester film, trade name, manufactured by Toyobo Co., Ltd.) was used as a base film.
A heat resistant slip layer was formed on the back side of the film with a coating solution having the following composition so that the dry film thickness was 1 μm.

13.6 parts by mass of a heat-resistant slip layer coating liquid polyvinyl butyral resin (ESREC BX-1 (trade name), manufactured by Sekisui Chemical Co., Ltd.)
0.6 parts by mass of polyisocyanate curing agent (Takenate D218 (trade name), manufactured by Takeda Pharmaceutical Co., Ltd.)
0.8 parts by mass of phosphate ester (Pricesurf A208S (trade name), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Methyl ethyl ketone 42.5 parts by mass Toluene 42.5 parts by mass

A yellow, magenta and cyan composition having the following composition was applied to the surface side in a single color (coating amount 1 g / m ² when dry film).

Yellow Ink Dye (7) -1 2.5 parts by mass Dye (8) -1 2.0 parts by mass Polyvinyl butyral resin 4.5 parts by mass (Denka Butyral (trade name), manufactured by Electrochemical Co., Ltd.)
90 parts by mass of methyl ethyl ketone / toluene (1/1)

Magenta ink dye (9) -1 1.0 part by weight dye (10) -1 1.0 part by weight dye (11) -1 2.5 parts by weight polyvinyl butyral resin 4.5 parts by weight (Denkabutyral (trade name) Manufactured by Electrochemical Co., Ltd.)
90 parts by mass of methyl ethyl ketone / toluene (1/1)

Cyan ink dye (12) -1 2.0 parts by mass Dye (13) -1 2.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (Denkabutyral (trade name), manufactured by Electrochemical Co., Ltd.)
90 parts by mass of methyl ethyl ketone / toluene (1/1)

(Preparation of ink sheet D2)
An ink sheet D2 was produced in the same configuration as D1 except that the base material was changed to a 5.9 μm thick polyester film (TOYOBO thin film polyester film, trade name, manufactured by Toyobo).

(Preparation of ink sheet D3)
An ink sheet D3 was produced in the same configuration as D1 except that the base material was changed to a polyester film having a thickness of 4.5 μm (TOYOBO thin film polyester film, trade name, manufactured by Toyobo).

(Preparation of ink sheet D4)
An ink sheet D4 was produced in the same configuration as D1 except that the base material was changed to a 4.0 μm thick polyester film (TOYOBO thin film polyester film, trade name, manufactured by Toyobo).

Creation of image-receiving sheet (production of support)
50 parts by mass of LBKP (hardwood bleached kraft pulp) made of acacia and 50 parts by mass of LBKP made of aspen were each beaten to 300 ml of Canadian freeness by a disc refiner to prepare a pulp slurry.
Next, to the pulp slurry obtained above, cation-modified starch (CAT0304L (trade name) manufactured by NSC Japan) 1.3%, anionic polyacrylamide (DA4104 (trade name) manufactured by Seiko PMC) 0.15 per pulp. %, Alkyl ketene dimer (Arakawa Chemical Size Pine K) 29%, 0.29% epoxidized behenamide, 0.32% polyamide polyamine epichlorohydrin (Arakawa Chemical Co., Ltd .: Arafix 100 (trade name)) and 0.12% defoamer were added. It was.

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 performing the dry set to cm, size polyvinyl alcohol to both surfaces of the base paper by a press (manufactured by Kuraray Co., Ltd.: KL-118 (trade name)) and dried to 1 g / m ² coated, calendered went. 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 blended at a ratio of 1 to ² was coated to a thickness of 21 g / m ² to form a thermoplastic resin layer composed of a mat surface (hereinafter, this thermoplastic resin layer surface is referred to as “ This back side thermoplastic resin layer is further subjected to corona discharge treatment, and then, as an antistatic agent, aluminum oxide (“Alumina Zil 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide ( A dispersion obtained by dispersing “Snowtex O” manufactured by Nissan Chemical Industries, Ltd. in water at a mass ratio of 1: 2 was applied so that the dry mass was 0.2 g / m ² . And coated with a melt extruder to a low density polyethylene of MFR 4.0 g / 10 min, density 0.93 g / m ² having a titanium oxide of 10% by mass, and having a density of 27 g / m ^2. A thermoplastic resin layer was formed.

(Emulsion creation)
Emulsified dispersion A was prepared by the following procedure. Compound EB-9 was dissolved in 42 g of a high boiling point solvent (Solv-5) and 20 ml of ethyl acetate, and this liquid was dissolved in 250 g of a 20% by weight gelatin aqueous solution containing 1 g of sodium dodecylbenzenesulfonate by a high-speed stirring emulsifier (dissolver). Emulsified and dispersed, and water was added to prepare 380 g of Emulsion A.
The amount of compound EB-9 added was adjusted to 30 mol in Emulsion A.

(Creation of image receiving sheet)
Image receiving sheet 1
On the support prepared as described above, a multi-layer coating product having a configuration of an undercoat layer 1, an undercoat layer 2, a heat insulating layer, and an image receiving layer was prepared in order from the lower layer. The composition and coating amount of the coating solution are shown below.

Undercoat layer 1 coating liquid (composition)
Adjusted to 8 with p H gelatin 3% aqueous solution of NaOH (coated amount) 11 ml / ^{m 2}

Undercoat layer 2 coating liquid (composition)
60 parts by mass of styrene butadiene latex (manufactured by Nippon A & L, SR103 (trade name))
PVA 6% aqueous solution 40 parts by mass NaOH to adjust pH to 8 (coating amount) 11 ml / m ²

Heat insulation layer coating liquid (composition)
Hollow polymer latex 60 parts by mass (manufactured by Nippon Zeon, MH5055 (trade name))
10% aqueous gelatin solution 20 parts by weight Emulsion A prepared earlier 20 parts by weight Adjust pH to 8 with NaOH (coating amount) 45 ml / m ²

Receiving layer coating solution (composition)
50 parts by weight of vinyl chloride polymer latex (manufactured by Nissin Chemical Co., Ltd., Vinyblan 900 (trade name))
20 parts by mass of a vinyl chloride polymer latex (manufactured by Nissin Chemical Co., Ltd., Vinyblan 270 (trade name))
10% aqueous gelatin solution 10 parts by weight Emulsion A 10 parts by weight Microcrystalline wax 5 parts by weight (EMUSTAR-042X, trade name, Nippon Seiki Co., Ltd.)
Water 5 parts by weight NaOH to adjust pH to 8 (coating amount) 18 ml / m ²

  It was 5.2 micrometers when the dry film thickness of the receiving layer of the image receiving sheet 1 was calculated | required from the microscope cross-sectional photograph.

Image receiving sheet 2, 3, 4, 5
Samples with a receiving layer having a dry film thickness of 3.5 μm, 2.5 μm, and 1.5 μm were prepared by adjusting the coating amount of the receiving layer coating solution of the image receiving sheet 1 to obtain image receiving sheets 2, 3, and 4 in order.

Image receiving sheet 5
An image-receiving sheet 5 having an undercoat layer 1, an undercoat layer 2, and an image-receiving layer was prepared in this order from the support side, with the image-receiving sheet 1 except for the heat-insulating layer.

(Image formation)
Images were formed by combining the prepared ink sheet and image receiving sheet in 11 combinations as shown in Table 1 below. It was processed so that it could be loaded into a high-speed thermal transfer printer UP-DR150 / 2 manufactured by Sony Corporation, and a gradation image was output. The time from the start of yellow printing to the discharge of the print sample was 8 seconds. The scanning speed was about 80 mm / second.
In the obtained image, the highest density portion (black portion) Dmax was measured with a reflection optical density system.
The results are shown in Table 1 below.

  No. From the comparison of 1-4, the effect of the thickness of the polyester support of the ink sheet is small when there is no heat insulating layer. On the other hand, no. From the comparison of 5 to 8, when a hollow polymer heat insulating layer is present, the effect of increasing Dmax by thinning the polyester support of the ink sheet is large. Further, if the dry film thickness of the receiving layer is lowered, the Dmax increases, and an unexpected Dmax concentration is achieved in the absence of the heat insulating layer.

Claims (15)

A thermal transfer layer containing a heat transferable colorant and a binder component on a plastic film substrate, wherein the thermal transfer layer containing a magenta dye is represented by the following general formula (9): 10) and a dye represented by the following general formula (11), respectively, and a cyan dye-containing thermal transfer layer is represented by the following general formula (12) and the following general formula (13) ) And a thermal transfer sheet having a thickness of 5 μm or less of the substrate made of the plastic film, and at least two kinds of alkyl acrylate constituent components having different chemical structures on the support , At least one receiving layer comprising a polymer latex of a copolymer of vinyl chloride and alkyl acrylate, a polystyrene resin with a particle size of 0.1-2.0 μm, Thermal transfer characterized in that an image is formed by a combination of a thermal transfer image-receiving sheet having at least one heat insulating layer containing a hollow polymer having non-foamed hollow particles formed of acrylic resin or styrene-acrylic resin Image forming method.
In the general formula (9), R ⁷¹ and R ⁷³ each independently represent a hydrogen atom or a substituent, and R ⁷² and R ⁷⁴ each independently represent a substituent. n11 represents an integer of 0 to 4. n12 represents the integer of 0-2. R ⁷² and R ⁷⁴ each independently represents a substituent. n11 represents an integer of 0 to 4.
In the general formula (10), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represents a substituent. n13 represents an integer of 0 to 4, and n14 represents an integer of 0 to 2.
In the general formula (11), R ⁹¹ represents a hydrogen atom or a substituent. R ⁹³ and R ⁹⁴ each independently represents a hydrogen atom or a substituent. R ⁹² represents a substituent. n15 represents an integer of 0 to 2. One of Z ¹ and Z ² represents ═N—, and the other represents ═C (R ⁹⁵ ) —. Z ³ and Z ⁴ each independently represent ═N— or ═C (R ⁹⁵ ) —. R ⁹⁵ represents a hydrogen atom or a substituent.
In general formula (12), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or a substituent. n16 and n17 each independently represents an integer of 0 to 4.
In general formula (13), R ¹¹¹ and R ¹¹³ each independently represents a hydrogen atom or a substituent. R ¹¹² and R ¹¹⁴ each independently represent a substituent. n18 represents an integer of 0 to 4, and n19 represents an integer of 0 to 2. 2. The thermal transfer image forming method according to claim 1, wherein the receiving layer has a thickness of 4 [mu] m or less. 3. The thermal transfer image forming method according to claim 1, wherein the image forming method records information with a thermal head, and a scanning speed of the thermal head with respect to the thermal transfer sheet is 40 mm / second or more. The thermal transfer image forming method according to claim 1, wherein the heat insulating layer contains a water-soluble resin as a binder resin. The thermal transfer image forming method according to claim 1, wherein the heat insulating layer contains gelatin as a binder resin. The thermal transfer image forming method according to claim 1, wherein the heat insulating layer contains only a water-soluble resin as a binder resin. 6. The thermal transfer image forming method according to claim 1, wherein the heat insulating layer contains only a water-soluble resin as a binder resin and contains gelatin. 6. The thermal transfer image forming method according to claim 1, wherein the heat insulating layer contains only gelatin as a binder resin. The thermal transfer image forming method according to claim 1, wherein the receiving layer contains a water-soluble polymer. The thermal transfer image forming method according to claim 1, wherein the receiving layer contains gelatin. The support is a double-sided laminated paper laminated with polyethylene on both sides of the base paper, and the polyethylene on the receiving layer side contains titanium oxide and has a charge adjusting layer on the polyethylene on the opposite side to the receiving layer side. The thermal transfer image forming method according to any one of claims 1 to 10. 12. The thermal transfer image forming method according to claim 11, wherein the polyethylene on the surface opposite to the receiving layer side is a mixed resin of low density polyethylene and high density polyethylene. 13. The thermal transfer image forming method according to claim 11, wherein the polyethylene on the receiving layer side is a mixed resin of low density polyethylene and high density polyethylene. The thermal transfer sheet, the yellow dye layer, claim 1-13, characterized by containing the dye represented by the dye or the following general formula represented by (8) the following general formula (7) 1 The thermal transfer image forming method according to Item.
In the general formula (7), R ⁵¹ and R ⁵² each independently represent a substituent. n8 represents an integer of 0 to 5. n9 represents an integer of 0 to 4.
In the general formula (8), R ⁶¹ represents a substituent, and R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. n10 represents an integer of 0 to 4. The thermal transfer image according to any one of claims 1 to 14 , wherein the receptor layer contains a compound represented by any one of the following general formulas (E-1) to (E-3). Forming method.
In the formula, 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 ). 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. R _{a1 to} R _a4 each independently represents a hydrogen atom or an aliphatic group.