JP2007230030A - Image forming method using thermal transfer method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method using a thermal transfer method, which enables attainment of a print being free from welding of an ink sheet and an image accepting sheet and having a uniform and excellent image quality, even in the case of high-speed printing. <P>SOLUTION: A thermal transfer sheet has a thermal transfer layer containing a thermally transferable coloring material and at least one kind of polyester as a binder component, 1/2 or more of an acid constituent of the polyester being a terephthalic acid. The thermal transfer image accepting sheet has on a substrate at least one accepting layer containing a polymeric latex and at least one heat insulating layer containing a hollow polymer, and this layer does not contain a resin having no resistance to an organic solvent, other than the hollow polymer. In the image forming method, an image is formed by a process wherein the thermal transfer sheet and the thermal transfer image accepting sheet are laid on each other so that the thermal transfer layer of the thermal transfer sheet and the accepting layer of the thermal transfer image accepting sheet come into contact with each other, and thermal energy conforming to an image signal is given thereto from a thermal head. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an image forming method using a thermal transfer method, and in particular, an image forming method in which a high-quality print having no unevenness is obtained even when high-speed printing is performed, with no fusion between an ink sheet and an image receiving sheet. Regarding the method.

  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.

One of the fields of use pioneered as a new application of this method is, for example, a thermal transfer recording label or a thermal transfer recording tag for a POS (Point Of Sales) system. Conventional food labels and apparel tags are relatively rarely used under harsh conditions for a long period of time, but the opportunities for use in distribution management applications such as shipping labels and air baggage tags have increased. Therefore, precise recording such as barcodes is required and high image quality is desired. Further, the recording medium may be exposed to harsh conditions, and there is a demand for improvement in the paper strength of the image receiving paper for thermal transfer recording.
On the other hand, for example, Patent Document 1 discloses the use of crepe paper or kulpack paper as a support. However, when crepe paper or curl wrap paper is used as a support, moisture is absorbed in the paper between application and drying, and moisture remains in the paper even after drying, depending on the aging of the receiving layer. There was a problem of causing a reduction in sharpness.
Japanese Patent Laid-Open No. 9-220863 “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

  SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method using a thermal transfer method in which a good image quality without unevenness can be obtained without fusing an ink sheet and an image receiving sheet even when high speed printing is performed. And

  As a result of intensive studies, the present inventors have found that high-speed printing can be achieved without causing fusion of the ink sheet and the image-receiving sheet even when processed at high speed. The present invention has been made based on such findings.

The above problems have been achieved by the following means.
(1) It has a thermal transfer layer containing a color material capable of thermal transfer, contains at least one polyester as a binder component of the thermal transfer layer, and at least one half of the acid component of the polyester is terephthalic acid. A thermal transfer sheet characterized by
A heat-sensitive transfer image-receiving sheet having, on a support, at least one receptor layer containing a polymer latex and at least one heat-insulating layer containing a hollow polymer, wherein the heat-insulating layer contains an organic solvent in addition to the hollow polymer. A thermal transfer image-receiving sheet characterized by not containing a non-resistant resin,
An image forming method for forming an image by superimposing the thermal transfer layer of the thermal transfer sheet and the receiving layer of the thermal transfer image receiving sheet so as to contact each other and applying thermal energy corresponding to an image signal from a thermal head.
(2) The image forming method as described in (1), wherein the receptor layer and / or the heat insulating layer of the heat-sensitive transfer image-receiving sheet contains a water-soluble polymer.
(3) The heat-sensitive transfer image-receiving sheet contains a compound capable of crosslinking the water-soluble polymer in the receiving layer and / or heat insulating layer containing the water-soluble polymer, and a part or all of the water-soluble polymer is crosslinked. The image forming method according to (1) or (2), wherein
(4) Image formation according to any one of (1) to (3), wherein the polyester of the thermal transfer layer in the thermal transfer sheet is terephthalic acid in which two thirds or more of the acid component is terephthalic acid. Method.
(5) Image formation according to any one of (1) to (4), wherein the polyester of the thermal transfer layer in the thermal transfer sheet is terephthalic acid in which at least three quarters of the acid component is terephthalic acid. Method.
(6) The image forming method as described in any one of (1) to (5), wherein the receiving layer of the heat-sensitive transfer image-receiving sheet contains at least one vinyl chloride polymer.
(7) The heat-sensitive transfer sheet contains at least one dye represented by the following general formula (7) or (8), (1) to (6), Image forming method.

(In 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, R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. N10 represents an integer of 0 to 4)
(8) The heat-sensitive transfer sheet contains at least one dye represented by any one of the following general formulas (9), (10), or (11): (1) to (7) The image forming method according to any one of the above.

(In General Formula (9), R ⁷¹ and R ⁷³ each independently represent a hydrogen atom or a substituent. R ⁷² and R ⁷⁴ each independently represent a substituent. N11 represents an integer of 0 to 4. n12 Represents an integer of 0 to 2.)

(In General Formula (10), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represent a substituent. N13 represents an integer of 0 to 4. n14 represents an integer of 0 to 2. Represents.)

(In the general formula (11), R ⁹¹ represents a hydrogen atom or a substituent. R ⁹² represents a substituent. R ⁹³ and R ⁹⁴ each independently represents a hydrogen atom or a substituent. Z ¹ and Z ² each represents ═N—, and the other represents ═C (R ⁹⁵ ) —, and Z ³ and Z ⁴ each independently represent ═N— or ═C (R ⁹⁵ )-, Wherein R ⁹⁵ represents a hydrogen atom or a substituent.)
(9) The heat-sensitive transfer sheet contains at least one dye represented by the following general formula (12) or (13), according to any one of (1) to (8), Image forming method.

(In General Formula (12), R ¹⁰¹ and R ¹⁰² each independently represent a substituent. R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or a substituent. N16 and n17 each independently represent 0 to 4; Represents an integer.)

(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. n19 Represents an integer of 0 to 2.)
(10) having a thermal transfer layer containing a color material capable of thermal transfer, including at least one polyester as a binder component of the thermal transfer layer, and at least one-half of the acid component of the polyester being terephthalic acid A thermal transfer sheet characterized by
A heat-sensitive transfer image-receiving sheet having, on a support, at least one receptor layer containing a polymer latex and at least one heat-insulating layer containing a hollow polymer, wherein the heat-insulating layer contains an organic solvent in addition to the hollow polymer. A thermal transfer image-receiving sheet characterized by not containing a non-resistant resin,
A system for forming an image by superimposing the thermal transfer layer of the thermal transfer sheet and the receiving layer of the thermal transfer image receiving sheet so as to contact each other and applying thermal energy corresponding to an image signal from a thermal head.

  According to the image forming method of the present invention, even when high-speed printing is performed, there is no fusion between the ink sheet and the image receiving sheet, and a good quality print without unevenness can be obtained.

The present invention will be described in detail below.
In the heat-sensitive transfer image-receiving sheet of the present invention, a dye-receiving layer (receiving layer) is 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 serves to receive the dye transferred from the ink sheet and maintain the formed image. The image-receiving sheet of the present invention has at least one receptor layer containing a polymer latex and a water-soluble polymer. 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 of the present invention, the polymer latex that can be used in the receptor layer is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, the emulsion is polymerized, the micelle is dispersed, or the polymer molecule has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Anything may be used. For polymer latex, Tadashi Okuda, Hiroshi Inagaki, “Synthetic Resin Emulsion”, published by Kobunshi Publishing (1978), Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, “Application of Synthetic Latex”, Takashi Published by Molecular Press (1993), Soichi Muroi, “Synthetic Latex Chemistry”, published by High Polymer Press (1970), supervised by Yoshiaki Mitsuzawa, “Development and application of water-based coating materials”, CM Publishing ( 2004) and JP-A-64-538. The average particle size of the dispersed particles is preferably 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 of 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 of the present invention include hydrophobic polymers such as acrylic polymers, polyesters, rubbers (for example, SBR resin), polyurethanes, polyvinyl chlorides, polyvinyl acetates, polyvinylidene chlorides, polyolefins, etc. A polymer can be preferably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. In the case of a copolymer, it may be a random copolymer or a block copolymer. These polymers have a number average molecular weight of 5,000 to 1,000,000, preferably 10,000 to 500,000. If the molecular weight is too small, the mechanical strength of the layer containing the latex is insufficient, and if it is too large, the film formability is poor and this is not preferred. A crosslinkable polymer latex is also preferably used.

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

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

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

(D) Amides of β-unsaturated carboxylic acid: for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylmethacrylamide, N-tert-butylacrylamide, N -Tert-octylmethacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetoneacrylamide, itaconic acid diamide, N-methylmaleimide, 2-acrylamide -Methylpropanesulfonic acid, methylenebisacrylamide, dimethacryloylpiperazine 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 the acrylic polymer include Sebian A-4635, 4718, 4601 manufactured by Daicel Chemical Industries, Ltd., Nipol Lx811, 814, 821, 820, 855 manufactured by Nippon Zeon Co., Ltd. (P-17: Tg 36 ° C.), 857 × 2 (P-18: Tg 43 ° C.), Voncoat R3370 (P-19: Tg 25 ° C.), 4280 (P-20: Tg 15 ° C.) manufactured by Dainippon Ink & Chemicals, Jurimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) P-21: Tg44 ° C), AE116 (P-22: Tg50 ° C) manufactured by JSR Corporation, AE119 (P-23: Tg55 ° C), AE121 (P-24: Tg58 ° C), AE125 (P-25: Tg60) ° C), AE134 (P-26: Tg48 ° C), AE137 (P-27: Tg48 ° C), AE140 (P-28: Tg53 ° C) ), AE173 (P-29: Tg 60 ° C.), Toagosei Co., Ltd. Aron A-104 (P-30: Tg 45 ° C.), Takamatsu Yushi Co., Ltd. NS-600X, NS-620X, Nissin Chemical Industry ( Vinibrand 2580, 2583, 2641, 2770, 2770H, 2635, 2886, 5202C, 2706, etc. manufactured by Co., Ltd. (all are trade names).

  Examples of polyesters include: Finetex ES650, 611, 675, 850 manufactured by Dainippon Ink Chemical Co., Ltd., WD-size, WMS manufactured by Eastman Chemical Co., Ltd., A-110, A-115GE manufactured by Takamatsu Yushi Co., Ltd., A -120, A-121, A-124GP, A-124S, A-160P, A-210, A-215GE, A-510, A-513E, A-515GE, A-520, A-610, A-613 A-615GE, A-620, WAC-10, WAC-15, WAC-17XC, WAC-20, S-110, S-110EA, S-111SL, S-120, S-140, S-140A, S -250, S-252G, S-250S, S-320, S-680, DNS-63P, NS-122L, NS-122LX, NS-244 X, NS-140L, NS-141LX, NS-282LX, Aronmelt PES-1000 series, PES-2000 series, manufactured by Toagosei Co., Ltd. Bironal MD-1100, MD-1200, MD-1220, MD manufactured by Toyobo Co., Ltd. -1245, MD-1250, MD-1335, MD-1400, MD-1480, MD-1500, MD-1930, MD-1985, and Sephorjon ES manufactured by Sumitomo Seika Co., Ltd. (all are trade names). .

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

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

As an example of polyvinyl chloride, Nippon Zeon Co., Ltd. G351, G576, Nissin Chemical Industry Co., Ltd. Vinibrand 240, 270, 277, 375, 386, 609, 550, 601, 602, 630, 660, 671, 683, 680, 680S, 681N, 685R, 277, 380, 381, 410, 430, 432, 860, 863, 865, 867, 900, 900GT, 938, 950, etc. (all are trade names).
Examples of polyvinylidene chlorides include L502 and L513 manufactured by Asahi Kasei Kogyo Co., Ltd., D-5071 manufactured by Dainippon Ink and Chemicals, Inc. (all are trade names).
Examples of polyolefins include Chemipearl S120, SA100, V300 (P-40: Tg 80 ° C.) manufactured by Mitsui Petrochemical Co., Ltd., Voncoat 2830, 2210, 2960 manufactured by Dainippon Ink Chemical Co., Ltd., Sumitomo Seika Co., Ltd. Examples of Zyxen, Sepoljon G, and copolymerized nylons include Sepoljon PA manufactured by Sumitomo Seika Co., Ltd. (all are trade names).

  Examples of the polyvinyl acetates include Nibsin Chemical Industry Co., Ltd. Vinibrand 1080, 1082, 1085W, 1108W, 1108S, 1563M, 1566, 1570, 1588C, A22J7-F2, 1128C, 1137, 1138, A20J2, A23J1, A23J1, A23K1, A23P2E, A68J1N, 1086A, 1086A, 1086D, 1108S, 1187, 1241LT, 1580N, 1083, 1571, 1572, 1581, 4465, 4466, 4468W, 4468S, 4470, 4485LL, 4495LL, 1023, 1042, 1060, 1060S, 1080M, 1084W, 1084S, 1096, 1570K, 1050, 1050S, 3290, 1017AD, 1002, 1006, 1008, 107L, 1225,1245L, GV-6170, GV-6181,4468W, such as 4468S, and the like (all trade names).

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

  In the 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. A film-forming aid, also called a temporary plasticizer, is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of polymer latex. For example, Soichi Muroi, “Chemistry of Synthetic Latex”, published by Kobunshi Shuppankai (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 used in the present invention include polylactic acid esters, polyurethanes, polycarbonates, polyesters, polyacetals, SBRs, and polyvinyl chlorides. Among these, polyesters, polycarbonates Most preferably, polyvinyl chlorides are included.

  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 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 view of processing brittleness and image storage stability. 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. The homopolymer glass transition temperature value (Tgi) of each monomer may be the value of “Polymer Handbook (3rd Edition)” (J. Brandrup, EH Immergut (Wiley-Interscience, 1989)).

  The polymer used for the binder used in the present invention can be easily obtained by solution polymerization method, suspension polymerization method, emulsion polymerization method, dispersion polymerization method, anionic polymerization method, cationic polymerization, etc., but the emulsion obtained as latex A 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 Press (1978), Takaaki Sugimura, Akio Kataoka, Junichi Suzuki, Keiji Kasahara, “Application of Synthetic Latex”, Published by Polymer Press (1993) 1), Soichi Muroi, “Chemistry of Synthetic Latex”, published by Kobunshi Shuppankai (1970). In the emulsion polymerization method for synthesizing the polymer latex used in the present invention, a batch polymerization method, a monomer (continuous / divided) addition method, an emulsion addition method, a seed polymerization method, etc. can be selected from the viewpoint of latex productivity. A batch polymerization method, a monomer (continuous / divided) addition method, and an emulsion addition method are preferred.

  The polymerization initiator only needs to have radical generating ability, and may be an inorganic peroxide such as persulfate or hydrogen peroxide, a peroxide described in “Oil peroxide catalog” of Nippon Oil & Fats, and Wako Jun. 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” 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 ensured in a small amount and resistance to hydrolysis, and a long chain represented by Perex SS-H (trade name, Kao Corporation). Alkyl diphenyl ether disulfonate is more preferable, and a low electrolyte type such as Pionein 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. The 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. JP-A-73645, JP-A-4-127145, JP-A-4-247703, JP-A-4-305572, JP-A-6-11805, JP-A-5-173712, JP-A-5-66527, JP-A-5-66527. 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, JP-A-10-182570, can be employed compounds described in JP-A-11-190892.

  Examples of the chelating agent include inorganic chelate compounds (sodium tripolyphosphate, sodium hexametaphosphate, sodium tetrapolyphosphate, etc.), aminopolycarboxylic acid chelate compounds (nitrilotritriacetic acid, ethylenediaminetetraacetic acid, etc.), organic phosphonic acid chelate compounds ( Research Disclosure 18170, JP-A-52-102726, 53-42730, 56-97347, 54-121127, 55-4024, 55-4025, 55-29883, 55 -126241, 55-65955, 55-65956, 57-17943, 54-61125, and West German Patent No. 1045373), polyphenol-based chelating agents, polyamine-based chelates Preferably such DOO compounds, with aminopolycarboxylic acid derivatives being particularly preferred.

  Preferable examples of the aminopolycarboxylic acid derivatives include the compounds listed in the appendix of “EDTA (-Complexane Chemistry)” (Nanedo, 1977), and some of the carboxyl groups of these compounds are sodium or potassium. Alkali metal salts and ammonium salts such as may be substituted. Particularly preferred aminocarboxylic acid derivatives include iminodiacetic acid, N-methyliminodiacetic acid, N- (2-aminoethyl) iminodiacetic acid, N- (carbamoylmethyl) iminodiacetic acid, nitrilotriacetic acid, ethylenediamine-N, N '-Diacetic acid, ethylenediamine-N, N'-di-α-propionic acid, ethylenediamine-N, N'-di-β-propionic acid, N, N'-ethylene-bis (α-o-hydroxyphenyl) glycine N, N′-di (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-diacetic acid-N, N′-diacethydroxamic acid, N-hydroxyethylethylenediamine-N , N ′, N′-triacetic acid, ethylenediamine-N, N, N ′, N′-tetraacetic acid, 1,2-propylenediamine-N, N, N ′ N′-tetraacetic acid, d, l-2,3-diaminobutane-N, N, N ′, N′-tetraacetic acid, meso-2,3-diaminobutane-N, N, N ′, N′-four Acetic 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′-four Acid, cyclohexane-1,4-diamine-N, N, N ′, N′-tetraacetic acid, o-phenylenediamine-N, N, N ′, N′-tetraacetic acid, cis-1,4-diaminobutene- N, N, N ′, N′-tetraacetic acid, trans-1,4-diaminobutene-N, N, N ′, N′-tetraacetic acid, α, α′-diamino-o-xylene-N, N, N ′, N′-tetraacetic acid, 2-hydroxy-1,3-propanediamine-N, N, N ′, N′-tetraacetic acid, 2,2′-oxy-bis (ethyliminodiacetic acid), 2,2 '-Ethylenedioxy-bis (ethyliminodiacetic acid), ethylenediamine-N, N'-diacetic acid-N, N'-di-α-propionic acid, ethylenediamine-N, N'-diacetic acid-N, N'- Di-β-propionic acid, ethylenediamine-N, N, N ′, N′-tetrapropionic acid Diethylenetriamine-N, N, N ′, N ″, N ″ -pentaacetic acid, 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 sodium or potassium Substituted ones such as alkali metal salts and ammonium salts can also be mentioned.

  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 of the present invention includes a gel or a dried film state 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. Examples of plant polysaccharides include gum arabic, κ-carrageenan, ι-carrageenan, λ-carrageenan, guar gum (such as Supercol from Squalon), locust bean gum, pectin, tragacanth, and corn starch (Purity- from National Starch & Chemical Co.). 21), phosphorylated starch (National Star & Chemical Co., National 78-1898, etc.) and the like, and microbial polysaccharides such as xanthan gum (Kelco, Keltrol T), dextrin (National Star & Chemical Co., Ndex 360, etc.) ) And other animal natural polymers such as gelatin (Crodine B419 manufactured by Croda) Casein, such as sodium chondroitin sulfate (such as Croda made Cromoist CS), and the like (all trade names). Cellulose-based materials include ethyl cellulose (ICF Cellofas WLD, etc.), carboxymethyl cellulose (Daicel CMC, etc.), hydroxyethyl cellulose (Daicel HEC, etc.), hydroxypropyl cellulose (Aqualon Klucel, etc.), and methyl cellulose (Henkel). Viscontran, etc.), nitrocellulose (Isopropyl Wet, etc. from Hercules), cationized cellulose (Crodacel QM, etc. from Croda), etc. (all are trade names). Examples of starch systems include phosphorylated starch (such as National Starch & Chemical's National 78-1898), alginic acid systems such as sodium alginate (such as Kelco's Keltone), propylene glycol alginate, and other classifications such as cationized guar gum (Alcolac). Hi-care 1000, etc.) and sodium hyaluronate (Hyalure, etc. from Lifecare Biomedical) (all are trade names).

  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 Kyoyo 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.) is also 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 mass%, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0 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 was 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 polymer as C-118, C-318, C-318-2A, C-506 (all are trade names manufactured by Kuraray Co., Ltd.), HL polymer HL-12E, HL-1203 (all are trade names made by Kuraray Co., Ltd.), HM polymer is HM-03, HM-N-03 (all are trade names made 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 made by Kuraray Co., Ltd.) as MP polymers, and MPK-1, MPK- as MPK polymers. , MPK-3, MPK-4, MPK-5, MPK-6 (all are trade names manufactured by Kuraray Co., Ltd.), R-1130, R-2105, R-2130 (all are all as R polymers) Kuraray Co., Ltd. product name), V polymer V-2250 (Kuraray Co., Ltd. product name) and the like.

  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 Publications published 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.

<Crosslinking agent>
It is preferable that part or all of the water-soluble polymer contained in the receiving layer is crosslinked with a crosslinking agent.
As the cross-linking agent, a plurality of groups capable of reacting with amino groups, carboxyl groups, hydroxyl groups, etc. may be contained in the molecule, and it may be appropriately selected and used depending on the type of water-soluble polymer. It is not limited. T.A. H. Each method described in James, "THE THEORY OF THE PHOTOGRAPHIC PROCESS FOURTH EDITION" (published by Macmillan Publishing Co., Inc., published in 1977), pages 77 to 87, and US Patent No. 4,678,739 The crosslinking agents described in column 41, JP-A-59-116655, JP-A-62-245261, JP-A-61-18942 and the like are suitable for use. Inorganic compound crosslinking agents (for example, chromium alum, boric acid and salts thereof) and organic compound crosslinking agents are preferred. Moreover, you may use the crosslinking agent which consists of mixed aqueous solution containing the chelating agent and the zirconium compound which are 1-7 of pH of Unexamined-Japanese-Patent No. 2003-231775.

  Specific examples of the crosslinking agent include epoxy compounds (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl-4- Glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, compounds described in JP-A-6-329877 and JP-A-7-309954, or Dick Fine EM-60 (trade name, Dainippon Ink & Chemicals, Inc.) Aldehyde compounds (formaldehyde, glyoxal, glutaraldehyde, etc.); active halogen compounds (2,4-dichloro-4-hydroxy-1,3,5-s-triazine, US Pat. No. 3, 325,287 Compounds described herein, etc.);

Active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, N, N′-ethylene-bis (vinylsulfonylacetamide) ethane, Japanese Patent Publication No. 53-41220, Compounds described in JP-A-53-57257, JP-A-59-162546, JP-A-60-80846, etc.); mucohalic acid compounds (such as mucochloric acid); N-carbamoylpyridinium salt compounds ((1-morpholinocarbonyl-3) -Pyridinio) methanesulfonate, etc.); haloamidinium salt compounds (1- (1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate, etc.); N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.) );

Carbodiimide compounds (polycarbodiimides derived from isophorone diisocyanate described in JP-A-59-187029 and JP-B-5-27450, carbodiimide compounds derived from tetramethylxylylene diisocyanate described in JP-A-7-330849, No. 10-30024, a multi-branched carbodiimide compound, and a carbodiimide compound derived from dicyclohexylmethane diisocyanate described in JP-A-2000-7642, or carbodilite V-02, V-02-L2, V-04, V-06. , E-01, E-02 (both trade names, Nisshinbo Co., Ltd.)); oxazoline compounds (oxazoline compounds described in JP-A No. 2001-215653, or Epocross K-1010E, K-1020E, K 1030E, K-2010E, K-2020E, K-2030E, WS-500, WS-700 (trade names, manufactured by Nippon Shokubai Co., Ltd.), and the like);

Isocyanate compounds (JP-A-7-304841, JP-A-8-277315, JP-A-10-45866, JP-A-9-71720, JP-A-9-328654, JP-A-9-104814 , JP-A-2000-194045, JP-A-2000-194237, and JP-A-2003-64149, dispersible isocyanate compounds, or Duranate WB40-100, WB40-80D, WT20-100, WT30-100 ( All are trade names, Asahi Kasei Co., Ltd., CR-60N (trade name, Dainippon Ink & Chemicals), etc.); polymer hardeners (compounds described in JP-A-62-2234157, etc.); boric acid And salts thereof; borax; aluminum alum and the like.

  Preferred compounds as the crosslinking agent include epoxy compounds, aldehyde compounds, active halogen compounds, active vinyl compounds, N-carbamoylpyridinium salt compounds, N-methylol compounds (such as dimethylol urea and methylol dimethyl hydantoin), and carbodiimide compounds. Oxazoline compounds, isocyanate compounds, polymer hardeners (compounds described in JP-A-62-234157, etc.), boric acid and salts thereof, borax, aluminum alum and the like. More preferably, an epoxy compound, an active halogen compound, an active vinyl compound, an N-carbamoylpyridinium salt compound, an N-methylol compound (such as dimethylol urea and methylol dimethyl hydantoin), and a polymer hardener (Japanese Patent Laid-Open No. Sho) Compounds described in JP-A-62-234157), boric acid and the like. These crosslinking agents may be used alone or in combination of two or more.

  The cross-linking agent used in the present invention may be added in a state of being premixed in a water-soluble polymer solution, may be added at the end of the preparation process of the coating solution, or may be added immediately before coating. .

The water-soluble polymer in the receiving layer varies depending on the type of the crosslinking agent, but 0.1 to 20% by mass of the total amount of the water-soluble polymer is preferably crosslinked, and 1 to 10% by mass is crosslinked. Is more preferable.
The amount of the crosslinking agent used in the present invention varies depending on the type of the water-soluble binder and the crosslinking agent, but is generally 0.1 to 50 parts by mass with respect to 100 parts by mass of the water-soluble polymer in the constituent layer. It is preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass.
<Release agent>
In addition, a release agent can be added to the receiving layer in order to prevent thermal fusion with the heat-sensitive 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, 4,555,476 No. 4,599,296, JP-B-3-62256, or a high boiling point organic solvent described in the specification or the like, if necessary, in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C. Can be used. These 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.

  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.

  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 trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and examples of dimethyl silicone oil include KF50-100, KF54, KF56 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned.

  The modified silicone oil can be classified into a reactive silicone oil and a non-reactive silicone oil. The reactive silicone oil includes amino modification, epoxy modification, carboxyl modification, hydroxy modification, methacryl modification, mercapto modification, phenol modification, one-terminal reactivity and heterofunctional modification. As amino-modified silicone oil, KF-393, KF-857, KF-858, X-22-3680, X-22-3801C, KF-8010, X-22-161A, KF-8012 (all trade names, Shin-Etsu Chemical Co., Ltd.) and the like, and epoxy-modified silicone oils include KF-100T, KF-101, KF-60-164, KF-103, X-22-343, X-22-3000T ( All of them are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the carboxyl-modified silicone oil include X-22-162C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxy-modified silicone oil include X-22-160AS, KF-6001, KF-6002, KF-6003, X-22-170DX, X-22-176DX, X-22-176D, X-22-176DF (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) 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. KS-720, KS-774-PL-3 [photocured silicone oil: trade names, manufactured by Shin-Etsu Chemical Co., Ltd.], and the like. The addition amount of these curable silicone oils is preferably 0.5 to 30% by mass of the resin constituting the receiving layer.

  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. Polyether-modified silicone (KF-6012, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned, and methylstil-modified silicone silicone oils (24-510, KF41-410, both trade names, Shin-Etsu Chemical ( Etc.). Moreover, the modified silicone represented by either of the following general formulas 1-3 can also be used.

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

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

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

  Silicone oils as 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 oil. The technique can be preferably used.

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

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

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

(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 serves to protect 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 may be one layer or two or more layers. The heat insulating layer is provided on the support side from the receptor layer.
In the image receiving sheet of the present invention, the heat insulating layer contains a hollow polymer.
The hollow polymer in the present invention is a polymer particle having independent pores inside the particle. For example, 1) Water is contained inside a partition formed by polystyrene, acrylic resin, styrene-acrylic resin, etc., and after coating and drying Non-foamed hollow particles in which the water inside the particles evaporates outside the particles and the inside of the particles becomes hollow. 2) Low boiling point liquids such as butane and pentane, polyvinylidene chloride, polyacrylonitrile, polyacrylic acid, polyacrylic Foamed microballoons that are covered with a resin made of any of acid esters, a mixture or a polymer thereof, and become hollow when the low-boiling liquid inside the particles expands by heating after coating, 3) above (2) can be heated and foamed in advance to form a hollow polymer.

  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 Ropaque 1055 manufactured by Law & Haas Co., Ltd., Bon Coat PP-1000 manufactured by Dainippon Ink Co., Ltd., SX866 (B) manufactured by JSR Co., Ltd. and Nippon MH MH5055 manufactured by Nippon Zeon Co., Ltd. (all trade names). . Specific examples of 2) include F-30 and F-50 (both trade names) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Specific examples of 3) include F-30E manufactured by Matsumoto Yushi Seiyaku Co., Ltd., 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, styrene. Known resins such as butadiene copolymers, polyvinylidene chloride resins, cellulose derivatives, casein, starch, and gelatin can be used. These resins can be used alone or in combination.

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

In the heat-receiving layer, the image-receiving sheet of the present invention does not contain an aqueous dispersion of a resin that is not resistant to organic solvents, in addition to the hollow polymer. It is not preferable to include a resin (dye dyeing resin) that is not resistant to an organic solvent in the heat insulating layer because blurring of an image after image transfer increases. This is because the dye-stainable resin and the hollow polymer exist in the heat insulating layer, so that the dye dyed on the receiving layer after the transfer moves over time through the adjacent heat-insulating layer. it is conceivable that.
Here, “not resistant to organic solvent” means that the solubility in an organic solvent (methyl ethyl ketone, ethyl acetate, benzene, toluene, xylene, etc.) is 1% by mass or less, preferably 0.5% by mass or less. Say. For example, the polymer latex is included in “resin not resistant to organic solvent”.

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

The heat insulating layer preferably contains gelatin. The amount of the heat insulating layer in the gelatin coating solution is preferably 0.5 to 14% by mass, particularly preferably 1 to 6% by mass. The coating amount of the hollow polymer in the heat insulation layer is preferably ^{1~100g / m 2, 5~20g / m} 2 is more preferable.

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

  The thickness of the heat insulating layer containing the hollow polymer is preferably 5 to 50 μm, and more preferably 5 to 40 μm.

(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 manufactured by Toyobo Co., Ltd., Tufton NE-382, Tufton manufactured by Kao Corporation U-5, ATR-2009, ATR-2010; Elitel UE3500, UE3210, XA-8153, KZA-7049, KZA-1449 manufactured by Unitika Ltd. Polyester TP-220, R manufactured by Nippon Synthetic Chemical Co., Ltd. -188; various types of thermoplastic resins (all are trade names) of the high loss series manufactured by Seiko Chemical Industry Co., Ltd.

(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 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.
A polyvinyl butyral resin or a polyester resin is preferably used as the binder of the thermal transfer layer. In the present invention, at least one polyester is included, and at least one-half of the acid component of the polyester is terephthalic acid, more preferably at least two-thirds of the acid component is terephthalic acid, most preferably More than three quarters of the acid component is terephthalic acid.
Thereby, fusion with a heat-sensitive transfer image-receiving sheet can be prevented. The polyester of the present invention can be obtained by the method described in JP-A-9-295389.

Details of the heat-sensitive transfer sheet are described in, for example, Japanese Patent Application Laid-Open No. 11-105437, and descriptions of paragraph numbers 0017 to 0078 are preferably incorporated in the specification of the present application.
The thermal transfer layer of the ink sheet used in the present invention preferably contains at least one dye represented by the general formula (7) or (8) as a yellow dye, and the general formula (9) as a magenta dye. It is preferable that at least one dye represented by (10) or (11) is contained, and at least one dye represented by the general formula (12) or (13) is preferably contained as a cyan dye. .
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. The thickness of the support is preferably 1 to 10 μm, and more preferably 2 to 10 μm.
In a preferred embodiment of the present invention, the thermal transfer dye-donating material comprises a polyethylene terephthalate support coated with a cyan dye, a magenta dye and a yellow dye in successive repeating regions, and the thermal transfer step is carried out sequentially for each dye. A three-color transfer image is formed. Of course, when this thermal transfer process is carried out in a single color, a monochrome transfer image can be obtained.

The preferred dyes will be described below.
First, the dye represented by the general formula (7) will be described in detail.

In 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 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 or 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, or a substituted or unsubstituted heterocyclic group, 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 for R ⁵¹ and R ⁵² described above. 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, or a substituted or unsubstituted heterocyclic group, 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 heterocycle It is a 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 most 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 in 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. 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. 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, a substituted or unsubstituted amino group. 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 for R ⁵¹ and R ⁵² described above. 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 R ¹⁰² include substituents as described for R ⁵¹ 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 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 superimposes 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 applies the thermal energy corresponding to the image signal from the thermal head to form an image to form an image. Form.
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 required for providing the printed matter to the consumer, the printing time for one sheet is preferably less than 15 seconds, and more preferably 5 to 12 seconds.
The present invention can be used in printers, copiers and the like using a thermal transfer recording system.
The heat-sensitive transfer image-receiving sheet of the present invention can be applied to various uses such as a sheet- or roll-shaped heat-sensitive transfer image-receiving sheet, cards, and transmission-type manuscript preparation sheets capable of thermal transfer recording by appropriately selecting a support. You can also

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

Example 1

Comparative thermal transfer sheet (ink sheet)

(Preparation of ink sheet D1)
A polyester film having a thickness of 6.0 μm (Lumirror, trade name, manufactured by Toray Industries, Inc.) was used as a base film. A heat resistant slip layer (thickness 1 μm) was formed on the back side of the film, and yellow, magenta and cyan compositions having the following compositions were applied to the surface side in a single color (coating amount 1 g / m ² during dry film formation).
Yellow ink Dye (7) -1 2.5 parts by mass Dye (8) -1 2.0 parts by mass Polyvinyl butyral resin (Denka Butyral, manufactured by Electrochemical Co., Ltd.) 4.5 parts by mass Methyl ethyl ketone / toluene (1/1 ) 90 parts by mass 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 (Denkabutyral, Electrochemical Co., Ltd.) )) 4.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by weight cyan ink Dye (12) -1 2.0 parts by weight Dye (13) -1 2.5 parts by weight Polyvinyl butyral resin (Denkabutyral, 4.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass

(Preparation of ink sheet D2)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -1 2.5 parts by weight Dye (8) -1 2.0 parts by weight Polyvinyl butyral resin (Denka Butyral, manufactured by Denki Kagaku) 3.0 parts by weight Polyester 4 1.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by mass 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 (Denkabutyral, manufactured by Electrochemical Co., Ltd.) 3.0 Part by mass Polyester 4 1.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass Cyan ink Dye (12) -1 2.0 parts by mass Dye (13) -1 2.5 parts by mass Polyvinyl butyral resin (Denkabutyral) 3.0 parts by mass Polyester 4 1.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass

Thermal transfer sheet (ink sheet) of the present invention

(Preparation of ink sheet D3)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -1 2.5 parts by mass Dye (8) -1 2.0 parts by mass Polyvinyl butyral resin (Denka Butyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by mass Polyester 1 1.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass 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 ( Denkabutyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by weight Polyester 1 1.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by weight Cyan ink Dye (12) -1 2.0 parts by weight Dye (13) -1 2.5 parts by mass Polyvinyl butyral resin (Denkabutyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by mass Polyester 1 1.5 parts by mass Methyl ethyl keto / Toluene (1/1) 90 parts by weight

(Preparation of ink sheet D4)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -1 2.5 parts by weight Dye (8) -1 2.0 parts by weight Polyvinyl butyral resin (Denka Butyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by weight Polyester 2 1.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by mass 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 ( Denkabutyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by mass Polyester 2 1.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass Cyan ink Dye (12) -1 2.0 parts by mass Dye (13) -1 2.5 parts by mass Polyvinyl butyral resin (Denkabutyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by mass Polyester 2 1.5 parts by mass Methyl ethyl keto / Toluene (1/1) 90 parts by weight

(Preparation of ink sheet D5)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -1 2.5 parts by weight Dye (8) -1 2.0 parts by weight Polyvinyl butyral resin (Denka Butyral, manufactured by Electrochemical Co., Ltd.) 2.0 parts by weight Polyester 2 2.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by mass 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 ( Denkabutyral, manufactured by Electrochemical Co., Ltd.) 2.0 parts by mass Polyester 2 2.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass Cyan ink Dye (12) -1 2.0 parts by mass Polyvinyl butyral resin ( Denkabutyral, manufactured by Electrochemical Co., Ltd.) 2.0 parts by mass Polyester 2 2.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 quality Part

(Preparation of ink sheet D6)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -1 2.5 parts by weight Dye (8) -1 2.0 parts by weight Polyvinyl butyral resin (Denka Butyral, manufactured by Electrochemical Co., Ltd.) 2.0 parts by weight Polyester 3 2.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by mass 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 ( Denkabutyral, manufactured by Electrochemical Co., Ltd.) 2.0 parts by mass Polyester 3 2.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass Cyan ink Dye (12) -1 2.0 parts by mass Dye (13) -1 2.5 parts by mass Polyvinyl butyral resin (Denkabutyral, manufactured by Electrochemical Co., Ltd.) 2.0 parts by mass Polyester 3 2.5 parts by mass Methyl ethyl keto / Toluene (1/1) 90 parts by weight

(Preparation of ink sheet D7)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -1 2.5 parts by mass Dye (8) -1 2.0 parts by mass Polyvinyl butyral resin (Denkabutyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by mass Polyester 3 1.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass 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 ( Denkabutyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by weight Polyester 3 1.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by weight Cyan ink Dye (12) -1 2.0 parts by weight Dye (13) -1 2.5 parts by mass Polyvinyl butyral resin (Denkabutyral, manufactured by Electrochemical Co., Ltd.) 3.0 parts by mass Polyester 3 1.5 parts by mass Methyl ethyl keto / Toluene (1/1) 90 parts by weight

(Preparation of ink sheet D8)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -2 2.5 parts by mass Dye (8) -2 2.0 parts by mass Polyvinyl butyral resin (S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.) 1.5 parts by mass Polyester 3 3.0 Mass parts Methyl ethyl ketone / toluene (1/1) 90 parts by mass Magenta ink Dye (9) -2 1.0 parts by mass Dye (10) -2 1.0 parts by mass Dye (11) -2 2.5 parts by mass Polyvinyl butyral Resin (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) 1.5 parts by weight Polyester 3 3.0 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by weight Cyan ink Dye (12) -2 2.0 parts by weight Dye (13) -2 2.5 parts by mass Polyvinyl butyral resin (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) 1.5 parts by mass Polyester 3 3.0 parts by mass Methyl ethyl Ton / toluene (1/1) 90 parts by weight

(Preparation of ink sheet D9)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -1 2.5 parts by weight Dye (8) -1 2.0 parts by weight Polyester 3 4.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by weight Magenta ink Dye (9) -1 1.0 part by mass Dye (10) -1 1.0 part by mass Dye (11) -1 2.5 parts by mass Polyester 3 4.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass Cyan ink Dye (12 ) -1 2.0 parts by mass Dye (13) -1 2.5 parts by mass Polyester 3 4.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass

(Preparation of ink sheet D10)
Only the monochromatic ink layer had the following composition, and the others were produced in the same manner as Sample D1.
Yellow ink Dye (7) -2 2.5 parts by weight Dye (8) -2 2.0 parts by weight Polyester 3 4.5 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by weight Magenta ink Dye (9) -2 1.0 part by mass Dye (10) -2 1.0 part by mass Dye (11) -2 2.5 parts by mass Polyester 3 4.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass Cyan ink Dye (12 ) -2 2.0 parts by mass Dye (13) -2 2.5 parts by mass Polyester 3 4.5 parts by mass Methyl ethyl ketone / toluene (1/1) 90 parts by mass

Said polyesters 1-4 are as follows.
Polyester 1
A polyester having a number average molecular weight of 3000 obtained by polymerizing the following acid component and diol component in the following molar ratio.
Isophthalic acid 25 parts by mass Terephthalic acid 25 parts by mass Ethylene glycol 5 parts by mass Diethylene glycol 45 parts by mass

Polyester 2
A polyester having a number average molecular weight of 2000 obtained by polymerizing the following acid component and diol component in the following molar ratio.
Isophthalic acid 10 parts by mass Terephthalic acid 40 parts by mass Ethylene glycol 5 parts by mass Diethylene glycol 45 parts by mass

Polyester 3
A polyester having a number average molecular weight of 2000 obtained by polymerizing the following acid component and diol component in the following molar ratio.
Isophthalic acid 5 parts by mass Terephthalic acid 45 parts by mass Ethylene glycol 5 parts by mass Diethylene glycol 45 parts by mass

Polyester 4
A number average molecular weight 2000 polyester obtained by polymerizing the following acid component and diol component in the following molar ratio.
Isophthalic acid 45 parts by mass Terephthalic acid 5 parts by mass Ethylene glycol 5 parts by mass Diethylene glycol 45 parts by mass

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

In the process of making the pulp slurry prepared as described above with a long paper machine and pressing the felt surface of the web against the drum dryer cylinder through the dryer canvas for drying, the tensile force of the dryer canvas is 1.6 kg / After drying by setting to cm, 1 g / m ² of polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: KL-118 (trade name)) is applied on both sides of the base paper with a size press and dried to perform calendar treatment. 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: Irgafos 168, manufactured by Ciba Specialty Chemicals Co., Ltd., containing 200 ppm) and MFR 4.0 g / 10 min, low density polyethylene having a density of 0.93 g / cm ³ , 75/25 (mass ratio) The resin composition blended at a ratio of 1 to ² was coated to a thickness of 21 g / m ² to form a thermoplastic resin layer comprising a mat surface (hereinafter, this thermoplastic resin layer surface). The thermoplastic resin layer on the back side is further subjected to corona discharge treatment, and then, as an antistatic agent, aluminum oxide (“Alumina Zil 100” manufactured by Nissan Chemical Industries, Ltd.) and dioxide dioxide are used. A dispersion in which silicon (“Snowtex O” manufactured by Nissan Chemical Industries, Ltd.) was dispersed in water at a mass ratio of 1: 2 was applied so that the dry mass was 0.2 g / m ² . corona treated MFR 4.0 g / 10 min with 10 wt% of titanium oxide, by using a melt extruder so that the low-density polyethylene having a density of 0.93 g / ^{m 2} to 27 g / ^{m 2} was applied to the surface Te A thermoplastic resin layer having a mirror surface 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 30 mmol in Emulsion A.

(Creation of image receiving sheet)

Image receiving sheet 1 (Comparative image receiving sheet)
On the support prepared as described above, a multi-layer coating composition having a configuration of an undercoat layer 1, an undercoat layer 2, a heat insulating layer, and a receiving layer 1 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)
Gelatin 3% aqueous solution Adjust pH to 8 with NaOH (coating amount) 11 ml / m ²

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

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

Receiving layer 1 coating liquid (composition)
100 parts by mass of vinyl chloride / vinyl acetate copolymer (# 1000D, manufactured by Denki Kagaku Kogyo Co., Ltd.)
Amino-modified silicone 3 parts by mass (Shin-Etsu Chemical Co., Ltd. X-22-343)
Epoxy-modified silicone 3 parts by mass (Shin-Etsu Chemical Co., Ltd. KF-393)
Toluene / methyl ethyl ketone (1 part / 1 part) 500 parts by mass (coating amount) 20 ml / m ²

Image receiving sheet 2
It was prepared in the same manner as the image receiving sheet 1 except that the receiving layer coating solution was changed to the following receiving layer 2.

Receiving layer 2 coating liquid (composition)
50 parts by weight of vinyl chloride polymer latex (Nippon Chemical Co., Ltd., Vinyl Blanc 900)
20 parts by mass of a vinyl chloride polymer latex (Nishin Chemical Co., Ltd., Vinyl Blanc 270)
10% gelatin aqueous solution 10 parts by weight Emulsion A prepared earlier 10 parts by weight Microcrystalline wax 5 parts by weight Hardener (VS-7) 0.2 parts by weight Water 5 parts by weight Adjust pH to 8 with NaOH (coating amount) 18ml / m ²

Here, the hardening agent (VS-7) is the following compound.
_{CH 2 = CHSO 2 CH 2 C} (= O) -NHCH 2 CH 2 NHC (= O) -SO 2 CH = CH 2

(Image formation)
Using these ink sheet and image receiving sheet, thermal transfer type printer A (DPB1500 (trade name), manufactured by Nidec Copal) or thermal transfer type printer B (JP-A-5-278247, as shown in FIG. 6) 10 continuous black images were output by the printer. In the thermal transfer type printer A, the time from the start of yellow printing to the discharge of one print sample was 12 seconds. In the thermal transfer printer B, the time from the start of yellow printing to the discharge of one print sample was set to 9 seconds, and Dmax printing was performed. At this time, the amount of heat generated by the thermal head was adjusted so that the reflection density was the same as that printed by the thermal transfer type printer A.
The output image was evaluated for fusing and ink peeling based on the following rank.

5 Fusing and ink peeling are not seen and there is almost no unevenness 4 Slight unevenness is seen, but no fusing or ink peeling is seen and no problem in practical use 3 Fusing or ink peeling is not seen, but obviously The image receiving sheet is ejected from the printer, but the ink sheet and the image receiving sheet are fused, and are not ejected from the printer.

As is apparent from Table 1 above, it can be seen that the combination of the ink sheet of the present invention and the image receiving sheet of the present invention is superior to the other combinations without causing fusion or ink peeling in the output image. This effect is more remarkable as the print discharge time is faster than 12 seconds to 9 seconds.

Claims (10)

It has a thermal transfer layer containing a color material capable of thermal transfer, contains at least one kind of polyester as a binder component of the thermal transfer layer, and more than half of the acid component of the polyester is terephthalic acid Thermal transfer sheet to
A heat-sensitive transfer image-receiving sheet having, on a support, at least one receptor layer containing a polymer latex and at least one heat-insulating layer containing a hollow polymer, wherein the heat-insulating layer contains an organic solvent in addition to the hollow polymer. A thermal transfer image-receiving sheet characterized by not containing a non-resistant resin,
An image forming method for forming an image by superimposing the thermal transfer layer of the thermal transfer sheet and the receiving layer of the thermal transfer image receiving sheet so as to contact each other and applying thermal energy corresponding to an image signal from a thermal head.   The image forming method according to claim 1, wherein a water-soluble polymer is contained in the receiving layer and / or the heat insulating layer of the heat-sensitive transfer image-receiving sheet.   The heat-sensitive transfer image-receiving sheet contains a water-soluble polymer-containing receptor layer and / or heat insulating layer containing a compound capable of crosslinking the water-soluble polymer, and a part or all of the water-soluble polymer is crosslinked. The image forming method according to claim 1, wherein:   The image forming method according to any one of claims 1 to 3, wherein in the polyester of the thermal transfer layer in the thermal transfer sheet, two or more of the acid components are terephthalic acid.   5. The image forming method according to claim 1, wherein in the polyester of the thermal transfer layer in the thermal transfer sheet, three or more quarters of the acid component is terephthalic acid.   6. The image forming method according to claim 1, wherein the receiving layer of the heat-sensitive transfer image-receiving sheet contains at least one vinyl chloride polymer. The image forming method according to claim 1, wherein the heat-sensitive transfer sheet contains at least one dye represented by the following general formula (7) or (8).

(In 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, 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 heat-sensitive transfer sheet contains at least one kind of dye represented by any one of the following general formulas (9), (10), and (11). The image forming method described.

(In General Formula (9), R ⁷¹ and R ⁷³ each independently represent a hydrogen atom or a substituent. R ⁷² and R ⁷⁴ each independently represent a substituent. N11 represents an integer of 0 to 4. n12 Represents an integer of 0 to 2.)

(In General Formula (10), R ⁸¹ represents a hydrogen atom or a substituent. R ⁸² and R ⁸⁴ each independently represent a substituent. N13 represents an integer of 0 to 4. n14 represents an integer of 0 to 2. Represents.)

(In the general formula (11), R ⁹¹ represents a hydrogen atom or a substituent. R ⁹² represents a substituent. R ⁹³ and R ⁹⁴ each independently represents a hydrogen atom or a substituent. Z ¹ and Z ² each represents ═N—, and the other represents ═C (R ⁹⁵ ) —, and Z ³ and Z ⁴ each independently represent ═N— or ═C (R ⁹⁵ )-, Wherein R ⁹⁵ represents a hydrogen atom or a substituent.) The image forming method according to claim 1, wherein the heat-sensitive transfer sheet contains at least one dye represented by the following general formula (12) or (13).

(In General Formula (12), R ¹⁰¹ and R ¹⁰² each independently represent a substituent. R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or a substituent. N16 and n17 each independently represent 0 to 4; Represents an integer.)

(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. n19 Represents an integer of 0 to 2.) It has a thermal transfer layer containing a color material capable of thermal transfer, contains at least one kind of polyester as a binder component of the thermal transfer layer, and more than half of the acid component of the polyester is terephthalic acid Thermal transfer sheet to
A heat-sensitive transfer image-receiving sheet having, on a support, at least one receptor layer containing a polymer latex and at least one heat-insulating layer containing a hollow polymer, wherein the heat-insulating layer contains an organic solvent in addition to the hollow polymer. A thermal transfer image-receiving sheet characterized by not containing a non-resistant resin,
A system for forming an image by superimposing the thermal transfer layer of the thermal transfer sheet and the receiving layer of the thermal transfer image receiving sheet so as to contact each other and applying thermal energy corresponding to an image signal from a thermal head.