JP2007229991A - 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 is excellent in a blur resistance of an image. <P>SOLUTION: In the image forming method, the thermal transfer image is formed by a process wherein a thermal transfer image accepting sheet having on a substrate at least one accepting layer containing a polymeric latex and at least one heat insulating layer containing a hollow polymer and not containing a resin having no resistance to an organic solvent, other than the hollow polymer, and a thermal transfer sheet having on a substrate a thermal transfer layer containing one kind of compound of pyrazolone coloring matter expressed by a specific general formula are laid on each other so that the accepting layer and the thermal transfer layer come into contact with each other, and thermal energy is given thereto in conformity with an image signal. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an image forming method using a thermal transfer method, which has excellent image bleeding resistance.

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.
Conventionally, it has been proposed to use molecules having various structures such as polyester whose structure is defined for the ink sheet and the image receiving sheet in this method (see, for example, Patent Document 1). In this case, the formed image may bleed for a long period of time after printing, particularly when stored under high temperature and high humidity conditions, and improvement of the bleed resistance of the image has been demanded.
JP 2004-255880 A “New development of information recording (hard copy) and its materials”, published by Toray Research Center, Inc., 1993, p. 241-285 “Development of Printer Materials”, issued by CMC Co., Ltd., 1995, p. 180

  SUMMARY An advantage of some aspects of the invention is that it provides an image forming method using a thermal transfer method that is excellent in image bleeding resistance.

The problems of the present invention have been solved by the following means.
(1) 1) Containing at least one receiving layer containing a polymer latex and at least one heat insulating layer containing a hollow polymer and not containing a resin that is not resistant to organic solvents other than the hollow polymer on the support. And 2) a thermal transfer layer containing at least one compound represented by the following general formula (1), (3), (4), (5) or (6) on the support. The thermal transfer sheet is overlaid so that the receiving layer of the thermal transfer image-receiving sheet of 1) and the thermal transfer layer of the thermal transfer sheet of 2) are in contact with each other, and thermal energy is applied according to the image signal to form a thermal transfer image. Image forming method.

(In the general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. A ¹ represents an atomic group which forms a heterocycle with carbon atoms bonded to each other. B ¹ represents an atomic group that forms a heterocycle together with the carbon and nitrogen atoms at both ends to which it is bonded.

(In the general formula (3), R ¹¹ , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹² represents a substituent. A ² is a heterocycle together with carbon atoms at both ends to which it is bonded. N3 represents an integer of 0 to 4. Here, when n3 represents an integer of 2 to 4, a plurality of R ¹² may be the same or different.

(In the general formula (4), D represents an aromatic ring group or an aromatic heterocyclic group derived from a diazonium salt. R ¹⁵ represents a substituent, and R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. N4 represents an integer of 0 to 4. Here, when n4 represents an integer of 2 to 4, a plurality of R ¹⁵ may be the same or different.

(In General Formula (5), A ³ represents an atomic group that forms a heterocycle with carbon atoms bonded to both ends. EWG ¹ represents an electron-withdrawing group, R ¹⁸ represents a substituent, R ¹⁹ and R ²⁰ are each .n5 represents a hydrogen atom or a substituent independently represents an integer of 0 to 4. here, the plurality of R ¹⁸ when n5 represents an integer of 2 to 4 may be the same or different. )

(In General Formula (6), EWG ² represents an electron-withdrawing group. R ²¹ and R ²⁴ each independently represent a substituent, and R ²² , R ^23, and R ²⁵ each independently represent a hydrogen atom or a substituent. N6 and n7 each independently represents an integer of 0 to 4. Here, when n6 represents an integer of 2 to 4 or when n7 represents an integer of 2 to 4, a plurality of R ²¹ or a plurality of R ²⁴ May be the same or different.)
(2) The yellow component of the image formed on the image receiving sheet by the image forming method is a dye of the compound represented by the general formula (1) or (3), and the magenta component is the general formula (4) or The image forming method according to item (1), wherein the dye is a dye derived from the compound represented by (5) and the cyan component is a dye derived from the compound represented by the general formula (6).
(3) The image forming method as described in (1) or (2), wherein the resin having no resistance to the organic solvent used in the thermal transfer image-receiving sheet of 1) is an aqueous dispersion.
(4) Any one of (1) to (3), wherein a compound capable of crosslinking an aqueous polymer is contained in at least one of the receiving layer and the heat insulating layer of the thermal transfer image-receiving sheet of 1). The image forming method according to item.
(5) The image forming method according to any one of (1) to (4), wherein an emulsion is contained in the receiving layer of the heat-sensitive transfer image-receiving sheet of 1).
(6) The image forming method according to any one of (1) to (5), wherein the thermal energy is applied by a thermal head.
(7) 1) Containing at least one receiving layer containing a polymer latex and at least one heat insulating layer containing a hollow polymer and not containing a resin that is not resistant to organic solvents other than the hollow polymer on the support. And 2) a thermal transfer layer containing at least one compound represented by the above general formula (1), (3), (4), (5) or (6) on the support. The thermal transfer sheet is overlaid so that the receiving layer of the thermal transfer image-receiving sheet of 1) and the thermal transfer layer of the thermal transfer sheet of 2) are in contact with each other, and thermal energy is applied according to the image signal to form a thermal transfer image. Image forming system.

  According to the present invention, it is possible to provide an image forming method using a thermal transfer method, which has superior resistance to image bleeding during storage over a long period of time after printing, particularly under high-temperature and high-humidity conditions.

The present invention will be described in detail below.
1) Thermal transfer image-receiving sheet First, a thermal transfer image-receiving sheet (image-receiving sheet) will be described.
The heat-sensitive transfer image-receiving sheet used in the present invention has at least one dye-receiving layer (receiving layer) on a support, and at least one heat-insulating layer (porous layer) between the support and the receiving layer. Have In addition, an underlayer such as a white background adjusting layer, a charge adjusting layer, an adhesive layer, or a primer layer may be formed between the receiving layer and the heat insulating layer.
The receiving layer and the heat insulating layer are preferably formed by simultaneous multilayer coating. When the underlayer is included, the receiving layer, the underlayer and the heat insulating layer can be formed by simultaneous multilayer coating.
It is preferable that a curl adjusting layer, a writing layer, and a charge adjusting layer are formed on the back side of the support. Each layer on the back side of the support can be applied by a general method such as roll coating, bar coating, gravure coating, or gravure reverse coating.

(Receptive layer)
The receiving layer serves to receive the dye transferred from the ink sheet and maintain the formed image. In the image receiving sheet of the present invention, the receiving layer contains a polymer latex. The receiving layer may be one layer or two or more layers. Moreover, it is preferable that a receiving layer contains the water-soluble polymer mentioned later.

<Polymer latex>
The polymer latex used in the present invention will be described.
In the heat-sensitive transfer image-receiving sheet used in the present invention, the polymer latex that can be used in the receiving layer is a polymer in which a hydrophobic polymer containing water-insoluble vinyl chloride as a monomer unit is dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, the emulsion is polymerized, the micelle is dispersed, or the polymer molecule has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Anything may be used. For polymer latex, Tadashi Okuda, Hiroshi Inagaki, “Synthetic Resin Emulsion”, published by Kobunshi Publishing (1978), Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, “Application of Synthetic Latex”, Takashi Published by Molecular Publications (1993), Soichi Muroi, “Chemistry of Synthetic Latex”, published by High Polymers Publications (1970), supervised by Yoshiaki Mitsuzawa, “Development and Application of Water-Based Coating Materials”, CMC Publishing ( 2004) and Japanese Patent Application Laid-Open No. 64-538. The average particle size of the dispersed particles is preferably 1 to 50000 nm, more preferably about 5 to 1000 nm.
The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

  The polymer latex may be a so-called core / shell type latex in addition to a normal uniform polymer latex. In this case, it may be preferable to change the glass transition temperature between the core and the shell. The glass transition temperature of the polymer latex of the present invention is preferably -30 ° C to 100 ° C, more preferably 0 ° C to 80 ° C, further preferably 10 ° C to 70 ° C, and particularly preferably 15 ° C to 60 ° C.

  Preferred embodiments of the polymer latex used in the receiving layer in the present invention are preferably polyvinyl chlorides, copolymers containing vinyl chloride as monomer units, such as vinyl chloride vinyl acetate copolymers and vinyl chloride acrylic copolymer polymers. Can be used. In this case, the ratio of the vinyl chloride monomer is preferably 50% or more and 95% or less. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. In the case of a copolymer, it may be a random copolymer or a block copolymer. These polymers have a number average molecular weight of 5,000 to 100,000, preferably 10,000 to 500,000. If the molecular weight is too small, the mechanical strength of the layer containing the latex is insufficient, and if it is too large, the film formability is poor and this is not preferred. A crosslinkable polymer latex is also preferably used.

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

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

  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.

The minimum film-forming temperature (MFT) of the polymer latex is preferably −30 ° C. to 90 ° C., more preferably about 0 ° C. to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. A film-forming aid, also called a temporary plasticizer, is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of polymer latex. For example, Soichi Muroi, “Synthetic Latex Chemistry”, 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

  The polymer latex used in the present invention may be used in combination (blend) with other polymer latex, and preferred examples of such polymer latex include polylactic acid esters, polyurethanes, polycarbonates, polyesters, and polyacetals. SBRs can be mentioned, and among these, polyesters and polycarbonates are preferable.

  Furthermore, the polymer latex used in the present invention may be used in combination with any polymer together with the above 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. In addition, the value of the homopolymer glass transition temperature (Tgi) of each monomer can adopt the value of “Polymer Handbook (3rd Edition)” (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).

  The polymer used 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 the mixture and the total amount of monomers, an emulsifier and a polymerization initiator are used, and polymerization is carried out with stirring at about 30 to 100 ° C., preferably 60 to 90 ° C. for 3 to 24 hours. Various conditions such as the dispersion medium, the monomer concentration, the initiator amount, the emulsifier amount, the dispersant amount, the reaction temperature, and the monomer addition method are appropriately set in consideration of the type of monomer used. Moreover, it is preferable to use a dispersing agent as needed.

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

  The polymerization initiator only needs to have radical generating ability, such as inorganic peroxides such as persulfate and hydrogen peroxide, peroxides described in Nippon Oil & Fats Co., Ltd. organic peroxide catalog, and Wako Pure Chemical Industries, Ltd. The azo compounds described in the azo polymerization initiator catalog can be used. Among these, water-soluble peroxides such as persulfate and water-soluble azo compounds described in the Wako Pure Chemical Industries, Ltd. Azo Polymerization Initiator Catalog are preferable. Ammonium persulfate, sodium persulfate, potassium persulfate, azobis ( 2-methylpropionamidine) hydrochloride, azobis (2-methyl-N- (2-hydroxyethyl) propionamide), azobiscyanovaleric acid is more preferable, and in particular, peroxidation such as ammonium persulfate, sodium persulfate, potassium persulfate and the like. The product is preferable from the viewpoint of image preservability, solubility, and cost.

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

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

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

  In the synthesis of the polymer latex used in the present invention, it is preferable to use a chelating agent. A chelating agent is a compound capable of coordinating (chelating) a multivalent ion such as a metal ion such as iron ion or an alkaline earth metal ion such as calcium ion. Japanese Patent Publication No. 6-8956, US Pat. JP-A-73645, JP-A-4-127145, JP-A-4-47073, JP-A-4-305572, JP-A-6-11805, JP-A-5-1773312, JP-A-5-66527, JP-A-5- 158195, JP-A-6-118580, JP-A-6-110168, JP-A-6-161054, JP-A-6-175299, JP-A-6-214352, JP-A-7-114161, JP-A-7-114154 JP, 7-120894, JP 7-199433, JP 7-306504, JP 9-43792, JP 8-314090, JP 10-182571, JP 10-182570. The compounds described in JP-A-11-190892 or the specification can be used.

  Examples of the chelating agent include inorganic chelate compounds (sodium tripolyphosphate, sodium hexametaphosphate, sodium tetrapolyphosphate, etc.), aminopolycarboxylic acid chelate compounds (nitrilotritriacetic acid, ethylenediaminetetraacetic acid, etc.), organic phosphonic acid chelate compounds ( Research Disclosure 18170, JP-A-52-102726, 53-42730, 56-97347, 54-121127, 55-4024, 55-4025, 55-29883, 55 -126241, 55-65955, 55-65956, 57-179743, 54-61125, and West German Patent No. 1045373, or the like), a polyphenol chelating agent, Polyamine chelation Preferably such things, aminopolycarboxylic acid derivatives being particularly preferred.

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

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

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

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

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

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

Of the water-soluble polymers that can be used in the present invention, natural polymers and semi-synthetic polymers will be described in detail. Plant polysaccharides include gum arabic, κ-carrageenan, ι-carrageenan, λ-carrageenan, guar gum (such as Supercol from Squall), locust bean gum, pectin, tragacanth, corn starch (Purity- from National Starch & Chemical Co.) 21), phosphorylated starch (National Starch & Chemical Co. National 78-1898, etc.) and other microbial polysaccharides such as xanthan gum (Kelco Keltrol T), dextrin (National Starch & Chemical Co. Nadex360, etc.) Examples of animal natural polymers include gelatin (such as Crodyne B419 from Croda), casein, sodium chondroitin sulfate (such as Cromoist CS from Croda), and the like (all are trade names). Cellulose systems include ethyl cellulose (ICI Cellofas WLD, etc.), carboxymethyl cellulose (Daicel CMC, etc.), hydroxyethyl cellulose (Daicel HEC, etc.), hydroxypropyl cellulose (Aqualon Klucel, etc.), methyl cellulose (Henkel Viscontran, etc.), Examples include nitrocellulose (such as Isopropyl Wet from Hercules) and cationized cellulose (such as Crodacel QM from Croda). Other starches such as phosphorylated starch (National 78-1898 from National Starch & Chemical) and sodium alginate (Keltone from Kelco), propylene glycol alginate, etc. are classified as cationized guar gum (Alcolac). Hi-care1000, etc.) and sodium hyaluronate (Hyalure, etc. from Lifecare Biomedial) are included (all are trade names).
In the present invention, gelatin is one of the preferred embodiments. The gelatin used in the present invention can have a molecular weight of 10,000 to 1,000,000. The gelatin of the present invention may contain anions such as Cl ⁻ and SO ₄ ²⁻ , and may contain cations such as Fe ²⁺ , Ca ²⁺ , Mg ²⁺ , Sn ²⁺ and Zn ²⁺ . It is preferable to add gelatin dissolved in water.

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

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

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

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

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

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

PVA-210 [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 9.0 ± 1.0 CPS], PVA-217 [PVA content 94.0 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-118, C-318, C-318-2A, C-506 (all are trade names manufactured by Kuraray Co., Ltd.), HL polymer as C polymer. HL-12E, HL-1203 (all are trade names manufactured by Kuraray Co., Ltd.), HM polymer is HM-03, HM-N-03 (all are trade names manufactured by Kuraray Co., Ltd.), KL-118, KL-318, KL-506, KM-118T, KM-618 (all are trade names manufactured by Kuraray Co., Ltd.) as the K polymer, and M-115 (manufactured by Kuraray Co., Ltd.) as the M polymer. (Trade name), MP-102, MP-202, MP-203 (all are trade names manufactured by Kuraray Co., Ltd.) as MP polymers, MPK-1, MPK-2, MPK-3, PK-4, MPK-5, MPK-6 (all are trade names manufactured by Kuraray Co., Ltd.), R polymer as R-1130, R-2105, R-2130 (all are manufactured by Kuraray Co., Ltd.) And V-2250 (trade name, manufactured by Kuraray Co., Ltd.).

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

  Suitable binders are transparent or translucent, generally colorless, and are natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other film-forming media such as rubbers, polyvinyl alcohols, hydroxyethyl celluloses, cellulose Acetates, cellulose acetate butyrate, polyvinylpyrrolidone, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinyl chloride, polymethacrylic acid, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers , Styrene-butadiene copolymers, polyvinyl acetals (eg, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy resins, polyvinylidene chlorides, polyepoxides , Polycarbonates, polyvinyl acetates, polyolefins, cellulose esters, and polyamides such water-soluble.

In the present invention, the water-soluble polymer is preferably polyvinyl alcohol or gelatin, and most preferably gelatin.
The addition amount of the water-soluble polymer in the receiving layer is preferably 1 to 25% by mass, and more preferably 1 to 10% by mass with respect to the entire receiving layer.

<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. THJames, “THE THEORY OF THE PHOTOGRAPHIC PROCESS FOURTH EDITION” (Macmillan Publishing Co., Inc., published in 1977), pages 77-87, US Pat. 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 A compound according to Saisho 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, Other branched carbodiimide compounds described in JP-A-10-30024, and carbodiimide compounds 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.), etc .; Oxazoline compounds (oxazoline compounds described in JP-A No. 2001-215653, or Epocros K-1010E, K-1020E, K- 030E, 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 and 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. .

Although the water-soluble polymer in the receiving layer varies depending on the type of the crosslinking agent, it is preferably 0.1 to 20% by mass crosslinked with respect to the water-soluble polymer, and 1 to 10% by mass crosslinked. Is more preferable.
The 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.

<Hardener>
The hardening agent used in the present invention as a crosslinking agent can be added to a coating layer (for example, a receiving layer, a heat insulating layer, a subbing layer) of the image receiving sheet. The hardening agent that can be used in the present invention is disclosed in JP-A-1-214845, page 17, H-1,4,6,8,14, U.S. Pat. No. 4,618,573, columns 13-23. Compounds represented by formulas (VII) to (XII) (H-1 to 54), compounds represented by formula (6) at the lower right of JP-A-2-214852, page 8, H-14, compounds described in claim 1 of US Pat. No. 3,325,287, and the like are preferably used. Examples of hardeners are US Pat. No. 4,678,739, column 41, US Pat. No. 4,791,042, JP-A-59-116655, JP-A-62-245261, and JP-A-61-18942. And the hardening agent described in JP-A-4-218444 or the specification thereof. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N′-ethylene-bis (vinylsulfonylacetamide) Ethane), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid, or polymer hardeners (compounds described in JP-A-62-234157).
Preferably, a vinyl sulfone type hardener and chlorotriazines are used.
More preferable hardeners in the present invention are compounds represented by the following general formula (B) or (C).
General formula (B)
_{(CH 2 = CH-SO 2} ) n -L
General formula (C)
_{(X-CH 2 -CH 2 -SO} 2) n -L
In general formulas (B) and (C), X represents a halogen atom, and L represents an n-valent organic linking group. When the compound represented by formula (B) or (C) is a low molecular compound, n represents an integer of 1 to 4. In the case of a polymer compound, L is an organic linking group containing a polymer chain, and n is in the range of 10 to 1000.

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

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

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

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

  These hardeners are used in an amount of 0.001-1 g, preferably 0.005-0.5 g, per 1 g of hydrophilic binder.

<Emulsions>
The receiving layer of the heat-sensitive transfer image-receiving sheet used in the present invention preferably contains an emulsion. The emulsion preferably used in the present invention will be described below.
Hydrophobic additives such as lubricants and antioxidants can be obtained by a known method such as the method described in US Pat. No. 2,322,027 (for example, a receiving layer, a heat insulating layer, an undercoat layer, etc.). ) Can be introduced in. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, and 4,555,476 In addition, a high boiling point organic solvent as described in the publications and specifications of JP 4,599,296 and JP-B-3-62256 is used in combination with a low boiling point organic solvent having a boiling point of 50 ° C to 160 ° C as necessary. Can be used. These lubricants, antioxidants, high-boiling organic solvents and the like can be used in combination of two or more.

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

R ₄₁ is an aliphatic group, aryl group, heterocyclic group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, aliphatic sulfonyl group, arylsulfonyl group, phosphoryl group, or —Si (R ₄₇ ) (R ₄₈ ). (R ₄₉ ) is represented. Here, R ₄₇ , R ₄₈ and R ₄₉ each independently represents an aliphatic group, an aryl group, an aliphatic oxy group or an aryloxy group. R _{42 to} R ₄₆ represent a hydrogen atom or a substituent. R _{a1 to} R _a4 each independently represents a hydrogen atom or an aliphatic group (for example, methyl, ethyl).
With respect to the compound represented by any one of the general formulas (E-1) to (E-3), preferred substituents in terms of the effects of the present invention will be described.
In the general formulas (E-1) to (E-3), R ₄₁ is an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or a phosphoryl group, and R ₄₂ , R ₄₃ , R ₄₅ And R ₄₆ are each independently preferably a hydrogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group, R ₄₁ is an aliphatic group, and R ₄₂ , R ₄₃ , R ₄₅ and R ₄₆ are It is more preferable that each independently represents a hydrogen atom or an aliphatic group.
Although the preferable specific example represented by either of general formula (E-1)-(E-3) below is shown below, this invention is not limited to these.

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

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

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

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

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

  Non-reactive silicone oils include polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, fluorine modification and the like. Examples include polyether-modified silicone (KF-6012, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and methylstil-modified silicone silicone oils (24-510, KF41-410, both trade names, Shin-Etsu Chemical ( Etc.). Moreover, the modified silicone represented by either of the following general formulas 11-13 can also be used.

  In general formula 11, 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 12, R represents a hydrogen atom, an aryl group, or a linear or branched alkyl group that may be substituted with an cycloalkyl group. m represents an integer of 2000 or less, and a and b represent an integer of 30 or less.

In General Formula 13, R represents a hydrogen atom, an aryl group, or a linear or branched alkyl group that may be substituted with an 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 hydrogen atom, an aryl group, or a linear or branched alkyl group that may be substituted with an cycloalkyl 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 point organic solvents include phthalates (dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, etc.), phosphoric acid or phosphonic esters (triphenyl phosphate, tricresyl phosphate, triphosphate phosphate) -2-ethylhexyl, etc.), fatty acid esters 塁 (di-2-ethylhexyl succinate, tributyl citrate, etc.), benzoates (2-ethylhexyl benzoate, dodecyl benzoate, etc.), amides (N, N-diethyl, etc.) Dodecanamide, N, N-dimethyloleamide, etc.), alcohol or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), anilines (N, N-dibutyl-2-butoxy-5-) tert-octylaniline, etc.), chlorinated paraffins, hydrocarbons (dode) Rubenzen, diisopropyl naphthalene), carboxylic acids (2- (2,4-di -tert- amylphenoxy) butyric acid, and the like.
The following compounds are preferably used.

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

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

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

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

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

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

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

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

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

(Insulation layer)
The heat insulating layer serves to protect the support from heat during heat transfer using a thermal head or the like. Moreover, since it has high cushioning properties, a thermal transfer image-receiving sheet with high printing sensitivity can be obtained even when paper is used as the 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 in the partition formed by polystyrene, acrylic resin, styrene-acrylic resin, etc., and the coating is dried. Thereafter, non-foamed hollow particles in which the water in the particles evaporates out of 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, Foaming type microballoons, which are covered with a resin made of any one of polyacrylic acid esters or a mixture or polymer thereof, and the inside of which becomes hollow as a result of the low-boiling liquid inside the particles expanding by heating, [ 3] The microballoon etc. which heated and foamed said [2] previously and made the hollow polymer are mentioned.

  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 the above [1] include Low and Haas Ropaque 1055, Dainippon Ink Boncoat PP-1000, JSR SX866 (B), Nippon Zeon Nipol MH5055 (all trade names), and the like. It is done. Specific examples of [2] include F-30 and F-50 (both trade names) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Specific examples of [3] include F-30E manufactured by Matsumoto Yushi Seiyaku Co., Ltd., EXPANSELL 461DE, 551DE, and 551DE20 (all trade names) manufactured by Nippon Ferrite Co., Ltd. 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The thickness of the support is preferably 25 μm to 300 μm, more preferably 50 μm to 260 μm, and still more preferably 75 μm to 220 μm. Various stiffnesses can be used according to the purpose, and the support for a photographic image receiving sheet for electrophotography is close to a support for color silver halide photography. Those are preferred.

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

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

  In the present invention, the resin having no resistance to the organic solvent used in the image receiving sheet is preferably an aqueous dispersion.

The method for producing the thermal transfer image receiving sheet of the present invention will be described below.
The heat-sensitive transfer image-receiving sheet of the present invention can be produced by applying each layer by a general method such as roll coating, bar coating, gravure coating, and gravure reverse coating, and drying them.
The heat-sensitive transfer image-receiving sheet of the present invention can also be formed by simultaneously applying a receiving layer and a heat insulating layer on a support.
When producing a multi-layer image receiving sheet comprising a plurality of layers having different functions (such as a bubble layer, a heat insulating layer, an intermediate layer, and a receiving layer) on a support, JP-A Nos. 2004-106283 and 2004-181888 are disclosed. In addition, it is known that each layer is sequentially coated as shown in each publication such as JP-A-2004-345267 or the like, in which each layer is applied on a support in advance. On the other hand, it is known in the photographic industry that productivity is greatly improved, for example, by applying a plurality of layers simultaneously. For example, U.S. Pat. Nos. 2,761,791, 2,681,234, 3,508,947, 4,457,256, 3,993,019, JP 63-54975, JP-A-61-278848, 55-86557, 52-31727, 55-142565, 50-43140, 63-80872, 54-54020, Special Publications and specifications of Kaihei 5-104061, 5-127305, JP-B 49-7050, and Edgar B. Gutoff et al., "Coating and Drying Defects: Troubleshooting Operating Problems", John Wiley & Sons, 1995, 101. Methods known as slide coating (slide coating method) and curtain coating (curtain coating method) described in pp. 103 and the like are known.
In the present invention, the simultaneous multi-layer coating is used for manufacturing a multi-layer image-receiving sheet, whereby productivity can be greatly improved and image defects can be greatly reduced.

In the present invention, the plurality of layers are composed mainly of a resin. The coating solution for forming each layer is preferably water-dispersed latex. The solid content mass of the latex resin in the coating solution of each layer is preferably in the range of 5 to 80%, particularly preferably in the range of 20 to 60%. The average particle size of the resin contained in the water-dispersed latex is 5 μm or less and particularly preferably 1 μm or less. The water-dispersed latex may contain a known additive such as a surfactant, a dispersant, and a binder resin as necessary.
In the present invention, it is preferable to form a laminate of a plurality of layers on a support by the method described in US Pat. No. 2,761,791 and then solidify immediately. As an example, in the case of a multilayer structure solidified by a resin, it is preferable to quickly raise the temperature after forming a plurality of layers on the support. When a binder that gels at a low temperature such as gelatin is included, it may be preferable to quickly lower the temperature after forming a plurality of layers on the support.
The coating amount of a coating solution per one layer constituting the multilayer in the present invention in the range of 1g / m ² ~500g / m ² is preferred. The number of layers in the multilayer configuration can be arbitrarily selected as 2 or more. The receiving layer is preferably provided as the layer furthest away from the support.

The image forming method of the present invention forms a thermal transfer image by superimposing a thermal transfer layer of a thermal transfer sheet, which will be described later, and a receiving layer of the thermal transfer image-receiving sheet, and applying thermal energy in accordance with an image signal. To do. Any conventionally known heating means can be used as the heating means for applying thermal energy during thermal transfer. For example, an image is formed by applying thermal energy according to an image signal using a normal thermal head. be able to. As a device using a thermal head, for example, the recording time is controlled by a recording device such as a thermal printer (trade name, video printer VY-100, manufactured by Hitachi, Ltd.), so that it is about 5 to 100 mJ / mm ² . By applying thermal energy, the intended purpose can be sufficiently achieved.
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

2) Thermal transfer sheet 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 (hereinafter also referred to as a dye layer) containing a diffusion transfer dye on a support. The dye layer is applied by a general method such as roll coating, bar coating, gravure coating, or gravure reverse coating.
The ink sheet used in the present invention contains a thermal transfer layer containing at least one compound represented by the general formula (1), (3), (4), (5) or (6) on a support.
First, the pigment | dye represented by General formula (1) is demonstrated in detail.

In general formula (1), R ¹ , R ² and R ³ each independently represents 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 ¹ , R ² and R ³ will be described in more detail.
Examples of the halogen atom represented by R ¹ , R ² and R ³ 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ 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 ^1, R ² or R ³ is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, e.g., phenyl, p- tolyl, naphthyl, m- chlorophenyl, o- hexadeca Noylaminophenyl is mentioned.

The heterocyclic group represented by R ¹ , R ² or R ³ is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. Preferably, they 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ 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.

R ^1, R ² or a formyloxy group represented by R ^3, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms preferably. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group represented by R ^1, R ² or R ³ 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Groups are preferred. 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ 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.

Aryloxycarbonylamino group represented by R ^1, R ² or R ³ 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ is 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. Groups are preferred. Examples of the alkylsulfonylamino group and arylsulfonylamino group include methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like.

Alkylthio group represented by R ^1, R ² or R ³ 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 ^1, R ² or R ³ 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.

R ^1, an alkyl or arylsulfinyl group represented by R ² or R ³ is a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 substituted or unsubstituted arylsulfinyl group. Examples of the alkyl or arylsulfinyl group include, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

R ^1, an alkyl or arylsulfonyl group represented by R ² or R ³ is a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, 6 to 30 or a substituted or unsubstituted arylsulfonyl group is preferable. Examples of the alkyl or arylsulfonyl group include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by R ¹ , R ² or R ³ 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, carbon A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom of several 4 to 30 is preferred. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

Aryloxycarbonyl group represented by R ^1, R ² or R ³ 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ 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 ¹ , R ² or R ³ include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. Can be mentioned.

Examples of the imide group represented by R ¹ , R ² or R ³ include N-succinimide and N-phthalimide.

R ¹ and R ² 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 heterocyclic group, substituted Or an unsubstituted acylamino group, a substituted or unsubstituted aminocarbonylamino group, a substituted or unsubstituted alkoxycarbonylamino group, or a substituted or unsubstituted amino group, more preferably a hydrogen atom, substituted or unsubstituted alkyl It is a group.

R ³ is preferably a hydrogen atom, or 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 hydrogen atom or a substituted or unsubstituted alkyl group is more preferable.

A ¹ represents an atomic group that forms a heterocycle with carbon atoms at both ends to which A ¹ is bonded. A ¹ is particularly preferably an atomic group that forms an acidic nucleus. James, The Theory of the Photographic Process, 4th edition, Macmillan, 1977, p. 198; M.M. Defined by Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964. Preferably, A ¹ represents a 5- or 6-membered nitrogen-containing heterocycle. These may be further condensed with a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring or the like. Specific examples of the ring (nucleus) formed by A ¹ include 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2 -Iminooxazolidin-4-one, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one -1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3, 4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4- ON, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone, 3-dicyanomethylidenyl-3-phenylpropionitrile, Meldrum A nucleus such as an acid is exemplified, and 2-pyrazolin-5-one is preferable. These may further have a substituent.

B ¹ represents an atomic group that forms a heterocycle together with carbon atoms and nitrogen atoms at both ends. B ¹ is preferably an atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring. These may be further condensed with a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring or the like. B ¹ includes an oxazole nucleus having 3 to 25 carbon atoms (for example, 3-methyloxazol-2-yl), a thiazole nucleus having 3 to 25 carbon atoms (for example, 3-methylthiazol-2-yl), 25 imidazole nucleus (eg, 1,3-diethylimidazol-2-yl), C10-30 indolenine nucleus (eg, 3,3-dimethylindolenine), C9-25 quinoline nucleus (eg, 1-methylquinolin-2-yl), a C 3-25 selenazole nucleus (eg, 3-methylbenzoselenazol-2-yl), a C 5-25 pyridine nucleus (eg, 2-pyridyl), Thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quinoxaline] , It can be exemplified oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, an atomic group necessary for forming a pyrimidine nucleus. These may further have a substituent.

  Of the dyes represented by the general formula (1), a dye represented by the following general formula (2) is preferable. Hereinafter, the dye represented by the following general formula (2) will be described in detail.

In the general formula (2), R ^1, R ² and R ³ have the same meanings as R ^1, R ² and R ³ in the general formula (1), and the preferred range is also the same. R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent. Examples of the substituent include those described above for R ¹ , R ² and R ³ . n1 represents an integer of 0 to 4, and n2 represents an integer of 0 to 5. Here, when n1 represents an integer of 2 to 4 or n2 represents an integer of 2 to 5, a plurality of R ⁴ or a plurality of R ⁸ may be the same or different.

R ⁴ and R ⁸ are preferably each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxy group Carbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, sulfamoyl group An alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group, more preferably a hydrogen atom, Logen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino Group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, more preferably a halogen atom, a substituted or unsubstituted alkyl group, substituted or An unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a substituted or unsubstituted alkyl group.

R ⁵ and R ⁶ are preferably the same as R ¹ and R ² in the general formula (1), and more 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 heterocyclic group, and more preferably a hydrogen atom or a substituted or unsubstituted alkyl group.

R ⁷ 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 A substituted or unsubstituted acylamino group, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acylamino group.

  Regarding the preferred combination of substituents of the dye represented by the general formula (2), 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.

Specific examples of preferred combinations are as follows: R ¹ is a hydrogen atom, R ² is a hydrogen atom, R ³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁴ is a substituted or unsubstituted carbon number 1 to 1. 6 alkyl groups, R ⁵ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁷ is a substituted or unsubstituted carbon number 1 A combination of ˜12 dialkylamino group, R ⁸ is a substituted or unsubstituted alkoxycarbonyl group having 1 to 6 carbon atoms or a chlorine atom, n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3. More preferable examples of the combination are as follows: R ¹ is a hydrogen atom, R ² is a hydrogen atom, R ³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁵ is a substituted or unsubstituted carbon atom having 1 to 6 carbon atoms. A combination in which R ⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁷ is a substituted or unsubstituted dialkylamino group having 1 to 12 carbon atoms, and n1 and n2 are both 0.

The dye represented by the general formula (3) will be described in detail.

In the general formula (3), R ¹¹ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, and R ¹² represents a substituent. Examples of the substituent in R ^{11 to} R ¹⁴ include those described for R ¹ , R ² and R ³ described above. A ² represents an atomic group that forms a heterocycle with carbon atoms at both ends to which A ² is bonded. n3 represents an integer of 0 to 4. Here, when n3 represents an integer of 2 to 4, a plurality of R ¹² may be the same or different.

R ¹¹ is preferably the same as R ^{1 in the} general formula (1). More preferably, they are a hydrogen atom, a C1-C6 substituted or unsubstituted alkyl group. Most preferably, it is a hydrogen atom.

R ¹² is preferably the same as R ⁴ and R ^{8 in} the general formula (2). More preferably, they are a C1-C6 substituted or unsubstituted alkyl group, a C1-C6 alkoxy group, and a halogen atom.

R ¹³ and R ¹⁴ are preferably the same as those described for R ³ in the general formula (1), and the preferred range is also the same as R ³ . More preferably, they are a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

Specific examples of A ² include those described for A ¹ in formula (1), and preferred substituents are also the same.

  As for the preferred combination of substituents of the dye represented by the general formula (3), 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.

Specific examples of preferred combinations include 2-pyrazolin-5-one having a substituent as A ² , R ¹¹ is a hydrogen atom, R ¹² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted group. A substituted alkoxy group having 1 to 6 carbon atoms, R ¹³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and n3 is 0 to 2 It is a combination that is an integer. More preferable examples of the combination include A ² is 2-pyrazolin-5-one having a substituent, R ¹¹ is a hydrogen atom, R ¹² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted group. An alkoxy group having 1 to 6 carbon atoms, R ¹³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and n3 is 0 or 1 It is a combination.

  The dye represented by the general formula (4) will be described in detail.

In General Formula (4), D represents an aromatic ring group derived from a diazonium salt or an aromatic heterocyclic group. R ¹⁵ represents a substituent, and R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. Examples of the substituent in R ^{15 to} R ¹⁷ include those described for R ¹ , R ² , and R ³ described above. n4 represents an integer of 0 to 4. Here, a plurality of R ¹⁵ when n4 represents an integer of 2 to 4 may be the same or different.

  Here, the azo dye will be described in detail. An azo dye is a dye synthesized by reacting an aryl or heteroaryl diazonium salt (diazo component) with a compound (coupler component) having an acidic hydrogen atom that forms an azo coupling reaction with the diazonium salt. It is.

  D is an aromatic ring group or an aromatic heterocyclic group that can be derived from a diazonium salt, and the aromatic ring group or the aromatic heterocyclic group may have a substituent. That is, D is a diazo component. The diazo component is a partial structure that can be introduced by converting a heterocyclic compound having an amino group as a substituent or a benzene derivative into a diazo compound (diazonium salt) and diazo coupling reaction with a coupler. It is a frequently used concept in the field. In other words, it is an amino-substituted aromatic heterocyclic compound capable of diazotization reaction or a substituent that is a monovalent group by removing the amino group of the aromatic compound.

Examples of the aromatic heterocyclic group include, but are not limited to, substitution positions (that is, exemplified as a ring). A pyrrole ring, a pyrazole ring, a triazole ring, a thiazole ring, an isothiazole ring, a benzothiazole ring, 1, 3, 4-thiadiazole ring, 1,2,4-thiadiazole ring, oxazole ring, benzoxazole ring, imidazole ring, benzoisothiazole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, indole ring Quinoline ring, purine ring, carbazole ring and acridine ring. An isothiazole ring, a 1,3,4-thiadiazole ring and a 1,2,4-thiadiazole ring are preferred. Each heterocyclic ring may further have a substituent and may be further condensed.
Examples of the aromatic group include a phenyl group and a naphthyl group, which may have a substituent and may be further condensed.

R ¹⁵ is preferably the same as R ^{1 in the} general formula (1). More preferred are amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group.

R ¹⁶ and R ¹⁷ are preferably those mentioned for R ³ in the general formula (1), and the preferred range is also the same as R ³ . More preferably, it is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

  Regarding preferred combinations of substituents of the dye represented by the general formula (4), compounds in which at least one of various substituents is the above preferred group are preferred, and compounds in which more various substituents are the above preferred groups More preferred are compounds in which all substituents are the preferred groups.

Examples of particularly preferred combinations include a monovalent group derived from a substituted isothiazole ring or a monovalent group derived from a 1,3,4-thiadiazole ring having a substituent, R ¹⁵ Is an acylamino group, R ¹⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁷ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and n4 is a combination of 0 to 4 . Examples of more preferred combinations are those in which D is a monovalent group derived from a substituted isothiazole ring or a monovalent group derived from a 1,3,4-thiadiazole ring having a substituent, and R ¹⁵ is an acylamino group. group, R ¹⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ¹⁷ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, with respect to substituted positions azo group n4 is 1, R ¹⁵ It is a combination that is in the o-position.

  The dye represented by the general formula (5) will be described in detail.

In the general formula (5), A ³ represents an atomic group that forms a heterocycle together with carbon atoms at both ends to which it is bonded. EWG ¹ represents an electron withdrawing group, R ¹⁸ represents a substituent, R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, and the substituents in R ^{18 to} R ²⁰ are the above-described R Examples described in ¹ , R ² and R ³ can be given. n5 represents an integer of 0 to 4. Here, when n5 represents an integer of 2 to 4, a plurality of R ¹⁸ may be the same or different.

Specific examples of A ³ include those described for A ¹ in formula (1), and preferred substituents are also the same.

In EWG ¹ , an electron withdrawing group having a Hammett's substituent constant σ _p value of 0 or more represents substitution. EWG ¹ is preferably an electron-withdrawing group having a σ _p value of 0.30 or more, more preferably an electron-withdrawing group of 0.45 or more, and particularly preferably an electron-withdrawing group of 0.60 or more. Examples of electron withdrawing groups having a σ _p value of 0.60 or more include nitro group, cyano group, methanesulfonyl group, trifluoromethanesulfonyl group, trifluoroacetyl group, dimethylaminosulfonyl group, sulfamoyl group, and the like. Examples of electron withdrawing groups having a σ _p value of 0.45 or more include alkoxycarbonyl groups, acyl groups, and carboxy groups, and examples of electron withdrawing groups having a σ _p value of 0.30 or more are sulfo groups. And a carbamoyl group. More preferred are a cyano group, a carboxyl group, an alkoxycarbonyl group, and a carbamoyl group, still more preferred are a cyano group, an alkoxycarbonyl group, and a carbamoyl group, and most preferred are a cyano group and a carbamoyl group.

Here, Hammett's substituent constant σ _p value will be described briefly. Hammett's rule is described in 1935 by L.L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by the Hammett rule include a σ _p value and a σ _m value, and these values can be found in many general books. A. Dean's “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemical Fields” No. 122, 96-103, 1979 (Nankodo). In the present specification, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is limited only to a substituent having a known value that can be found in the above-mentioned book. Needless to say, even if the value is unknown, it also includes a substituent that would be included in the range when measured based on the Hammett rule. The general formula includes those that are not benzene derivatives, but the σ _p value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In this specification, the σ _p value is used in this sense.

Preferable examples of R ¹⁸ include substituents as described for R ⁴ and R ⁸ in the general formula (2). More preferably, they are a hydrogen atom, a C1-C6 alkyl group, and a C1-C6 alkoxy group.

Preferred examples of R ¹⁹ and R ²⁰ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferably, each independently is a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a hydrogen atom or a substituted Or it is an unsubstituted alkyl group.

  Regarding the preferred combination of substituents of the dye represented by the general formula (5), 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.

Specific examples of preferred combinations include a group in which A ³ forms a substituted 2-pyrazolin-5-one ring, EWG ¹ is a cyano group, R ¹⁸ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. A group or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, R ¹⁹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²⁰ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, A combination in which n5 is an integer of 0 to 4. Examples of more preferable combinations include a group in which A ³ forms a substituted 2-pyrazolin-5-one ring, EWG ¹ is a cyano group, R ¹⁹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, A combination in which R ²⁰ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and n5 is 0.

  The dye represented by the general formula (6) will be described in detail.

In General Formula (6), EWG ² represents an electron-withdrawing group, R ²¹ and R ²⁴ each independently represent a substituent, R ²² , R ²³ and R ²⁵ each independently represent a substituent, R Examples of the substituent in ^{21 to} R ²⁵ include those described for R ¹ , R ² and R ³ described above. n6 and n7 each independently represents an integer of 0 to 4. Here, when n6 represents an integer of 2 to 4 or n7 represents an integer of 2 to 4, the plurality of R ²¹ or the plurality of R ²⁴ may be the same or different.

Specific examples of EWG ² include those described in EWG ¹ of the general formula (5), and preferred ranges are also the same. EWG ² is preferably an electron-withdrawing group having a σ _p value of 0.30 or more, more preferably 0.45 or more. Specifically, a cyano group and a substituted or unsubstituted carbamoyl group having 1 to 6 carbon atoms are more preferable, and an unsubstituted carbamoyl group is more preferable.

Examples of R ²¹ , R ²⁴ and R ²⁵ include substituents as described for R ⁴ and R ⁸ in the general formula (2), and preferred ranges are also the same. More preferably, there are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, and an acylamino group, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, Acylamino group. Most preferably, it is a hydrogen atom.

Examples of R ²² and R ²³ include substituents as described for R ³ in the general formula (1), and preferred ranges are also the same. More preferably, they are a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

  Regarding the preferred combination of substituents of the dye represented by the general formula (6), 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.

Specific examples of preferred combinations are as follows: EWG ² is a substituted carbamoyl group, R ²¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²⁵ is a hydrogen atom, n6 is an integer of 0 to 4, and n7 is A combination that is an integer of 0 to 4. More preferable examples of the combination are as follows: EWG ² is a substituted carbamoyl group, R ²² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²³ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ²⁵ Is a hydrogen atom, and n6 and n7 are both 0.

  Specific examples of the dyes represented by the general formulas (1) to (6) are shown below, but the dyes used in the present invention are not limited to the following examples.

  The compound represented by the general formula (1), (3), (4), (5) or (6) is preferably contained in the thermal transfer layer (dye layer) in an amount of 10 to 90% by mass, It is more preferable to contain 20-80 mass%.

The coating amount of the thermal transfer layer of the thermal transfer sheet (ink sheet) is 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. .), Preferably 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 support for the heat-sensitive transfer sheet can be the same as the support for the heat-sensitive transfer image-receiving sheet, and polyethylene terephthalate or the like can be used.
The thickness of the support is preferably 1 to 10 μm, and more preferably 2 to 10 μm.
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 image formed on the receiving layer of the heat-sensitive transfer image-receiving sheet by the heat-sensitive transfer sheet by the method of the present invention is a magenta dye containing a compound represented by the general formula (1) or (3). It is preferable that the component is a dye of a compound represented by the general formula (4) or (5) and the cyan component is a dye of a compound represented by the general formula (6).
Specifically, preferably, a thermal transfer layer containing dyes of different colors is coated on the thermal transfer sheet in the longitudinal direction of the sheet in the order of the surface. In this thermal transfer layer, the corresponding dye compound (compound represented by the general formula (1), (3), (4), (5) or (6)) is contained.

  The image forming method of the present invention can be carried out in the same manner as described in, for example, JP-A-2005-88545. In the present invention, the printing time is preferably less than 15 seconds, and more preferably 5 to 12 seconds, from the viewpoint of shortening the time until the printed matter is provided to the consumer.

  In addition, the image forming system of the present invention forms a thermal transfer image by superimposing the receiving layer of the thermal transfer image-receiving sheet and the thermal transfer layer of the thermal transfer sheet in contact with each other and applying thermal energy in accordance with an image signal. To do. The system of the present invention can be in the form of, for example, a printer or a copying machine using a thermal transfer recording system.

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

[Preparation of 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 (1) -1 2.2 parts Dye (3) -1 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts Magenta ink Dye (4) -1 2.2 parts Dye (5) -1 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts cyan ink Dye (6) -1 2.2 parts Dye (6) -4 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, Sekisui Chemical Co., Ltd.)
90 parts of methyl ethyl ketone / toluene (mass ratio 1/1)

(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 (1) -2 2.2 parts Dye (3) -2 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts Magenta ink Dye (4) -2 2.2 parts Dye (5) -2 2.3 parts Polyvinyl butyral resin 4.5 parts (S-REC BX-1, trade name, Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts cyan ink Dye (6) -2 2.2 parts Dye (6) -5 2.3 parts Polyvinyl butyral resin 4.5 parts (Esreck BX-1, trade name, Sekisui Chemical Co., Ltd.)
90 parts of methyl ethyl ketone / toluene (mass ratio 1/1)

(1-1) Preparation of Sample 101 (Comparative Example)
Synthetic paper (YUPO FPG200, thickness 200 μm, trade name, manufactured by YUPO Corporation) was used as a support, and coating was performed on this one surface by a bar coater in the order of a white intermediate layer having the following composition and a receiving layer. The coating amount at the time of each drying was coated as a white intermediate layer 1.0 g / m ^2, the receiving layer 4.0 g / m ^2, drying each layer 110 ° C., it was carried out for 30 seconds.
(Production of image receiving sheet)
White intermediate layer Polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.) 10 parts by weight Optical brightener (Uvitex OB, trade name, manufactured by Ciba Geigy) 1 part by weight Titanium oxide 30 parts by weight Methyl ethyl ketone / toluene (mass) 1/1) 90 parts by mass Receptor layer 30 parts by mass of polycarbonate resin (LEXAN-141, trade name, General Electric)
70 parts by mass of polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3050C)
5 parts by mass of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-300E)
400 parts by mass of methylene chloride

(1-2) Preparation of sample 102 (comparative example)
The receiving layer was changed to one having the following composition, and the others were produced in the same manner as the image receiving sheet 101.
Receptor layer 100 parts by weight of vinyl chloride-vinyl acetate resin (Solvine A, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Amino-modified silicone 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-3050C)
5 parts by mass of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, X22-300E)
Methyl ethyl ketone / toluene (mass ratio 1/1) 400 parts by mass

(1-3) Preparation of sample 103 (comparative example)
The receiving layer was changed to one having the following composition, and the rest was prepared in the same manner as Sample 101.
Receptive layer A
48 parts by weight of vinyl chloride latex (Vinibrand 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
3 parts by weight of gelatin

(1-4) Preparation of Sample 104 (Invention Example) The receiving layer was prepared in the same manner as the sample 103, and the heat insulating layer A shown below was provided.
Thermal insulation layer A
Hollow polymer latex 563 parts by mass (MH5055, trade name, manufactured by ZEON CORPORATION)
120 parts by mass of gelatin Here, the hollow polymer latex is an aqueous dispersion of a hollow structure polymer having an outer diameter of 0.5 μm. In the state in which the heat insulating layer A and the receiving layer A having the above composition are laminated in this order from the support side, multilayer coating is performed by the method illustrated in FIG. 9 described in US Pat. No. 2,761,791. It was. Immediately after application, the film was dried at 50 ° C. for 16 hours. Coating was performed such that the coating amount at the time of drying was a heat insulating layer: 15 g / m ² and a receiving layer A: 4.0 g / m ² .

(1-5) Production of Sample 105 (Invention Example) A gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided on the surface of a paper support laminated on both sides with polyethylene after corona discharge treatment. On top of this, the heat insulating layer A and the receiving layer A having the above composition were applied and dried in the same manner as the sample 104. Coating was performed such that the coating amount at the time of drying was a heat insulating layer: 10 g / m ² and a receiving layer A: 4.0 g / m ² .

(1-6) Preparation of Sample 106 (Invention Example) Coating was performed in the same manner as in Sample 105, and the coating amount at the time of drying was as follows: heat insulating layer: 15 g / m ² , receiving layer A: 4.0 g / m ² The coating was performed so that

(1-7) Preparation of Sample 107 (Invention Example) The receiving layer A was changed to the receiving layer B having the following composition, and the rest was prepared in the same manner as the sample 105.
Receptive layer B
48 parts by weight of vinyl chloride latex (Vinibrand 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
3 parts by weight of gelatin 1 part by weight of wax (EMUSTAR-042X, trade name, manufactured by Nippon Seiki Co., Ltd.)
Hardener (VS-7) 0.2 parts by mass

(1-7) Preparation of Sample 108 (Invention Example) Preparation of Emulsion Dispersion A An outline of the preparation formulation of the emulsion dispersion A is shown below.
To a 20% gelatin solution, a solution obtained by dissolving the following compound (EB-9) in ethyl acetate, a high-boiling organic solvent (SOLV-5), and a surfactant (KF41-410) were added and mixed. The product was emulsified using Nippon Seiki Co., Ltd. to obtain an emulsion. The composition of the emulsifying dispersant A is shown below.
20% gelatin solution 250 parts by mass EB-9 30 parts by mass KF41-410 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts by mass SOLV-5 9 parts by mass Ethyl acetate 20 parts by mass

The receiving layer A of the sample 105 was changed to the receiving layer C having the following composition, and the rest was produced in the same manner as the sample 105.
Receptive layer C
48 parts by weight of vinyl chloride latex (Vinibrand 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
3 parts by weight of gelatin 1 part by weight of wax (EMUSTAR-042X, trade name, manufactured by Nippon Seiki Co., Ltd.)
Hardener (VS-7) 0.2 parts by weight Emulsified dispersion A 8 parts by weight

(1-9) Preparation of Sample 109 (Example of the Invention) The receiving layer A of the sample 105 was changed to the receiving layer D having the following composition, and the rest was manufactured in the same manner as the sample 105.
Receptive layer C
32 parts by mass of vinyl chloride latex (Vinibrand 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
16 parts by weight of vinyl chloride latex (Viniblanc 609, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
3 parts by weight of gelatin 1 part by weight of wax (EMUSTAR-042X, trade name, manufactured by Nippon Seiki Co., Ltd.)
Hardener (VS-7) 0.2 parts by weight Emulsified dispersion A 8 parts by weight

(1-10) Preparation of Sample 110 (Invention Example) The receiving layer A of the sample 105 was changed to the receiving layer E having the following composition, and the rest was manufactured in the same manner as the sample 105.
Receptive layer E
32 parts by mass of vinyl chloride latex (Vinibrand 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
16 parts by weight of vinyl chloride latex (Vinibrand 276, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
3 parts by weight of gelatin 1 part by weight of wax (EMUSTAR-042X, trade name, manufactured by Nippon Seiki Co., Ltd.)
Hardener (VS-7) 0.2 parts by weight Emulsified dispersion A 8 parts by weight

(Image formation)
Ink sheets (denoted as “ink” in the following table) D1 and D2 and receiving sheets of the samples 101 to 110 (denoted as “image receiving paper” in the following table) are sublimated printers manufactured by Nidec Copal. It was processed so that it could be loaded into DPB 1500 (trade name), and output was performed in a high-speed print mode.

(Evaluation test)
The evaluation was performed using 30 images of 5 general scenes, each of which was aged for 2 weeks at 70 ° C. and 70%. Each image was blotted by the observation of five observers and evaluated as follows.
◎: Almost no blurring ○: Slight blurring is observed, but there is virtually no change Δ: Slight blurring is observed, and the difference can be confirmed ×: Clearly blurring

As is clear from Table 1 above, the samples of the comparative examples are clearly blurred or a difference in bleeding can be confirmed, whereas the samples of the present invention were all excellent in bleeding resistance.

Claims (7)

1) Thermal transfer containing at least one receiving layer containing a polymer latex and at least one heat insulating layer containing a hollow polymer and not containing a resin that is not resistant to an organic solvent other than the hollow polymer on a support. A heat-sensitive transfer sheet comprising an image-receiving sheet and 2) a thermal transfer layer containing at least one compound represented by the following general formula (1), (3), (4), (5) or (6) on a support Is formed so that the receiving layer of the thermal transfer image-receiving sheet of 1) and the thermal transfer layer of the thermal transfer sheet of 2) are in contact with each other, and a thermal transfer image is formed by applying thermal energy in accordance with an image signal. .

(In the general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. A ¹ represents an atomic group which forms a heterocycle with carbon atoms bonded to each other. B ¹ represents an atomic group that forms a heterocycle together with the carbon and nitrogen atoms at both ends to which it is bonded.

(In the general formula (3), R ¹¹ , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹² represents a substituent. A ² is a heterocycle together with carbon atoms at both ends to which it is bonded. N3 represents an integer of 0 to 4. Here, when n3 represents an integer of 2 to 4, a plurality of R ¹² may be the same or different.

(In the general formula (4), D represents an aromatic ring group or an aromatic heterocyclic group derived from a diazonium salt. R ¹⁵ represents a substituent, and R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. N4 represents an integer of 0 to 4. Here, when n4 represents an integer of 2 to 4, a plurality of R ¹⁵ may be the same or different.

(In General Formula (5), A ³ represents an atomic group that forms a heterocycle with carbon atoms bonded to both ends. EWG ¹ represents an electron-withdrawing group, R ¹⁸ represents a substituent, R ¹⁹ and R ²⁰ are each .n5 represents a hydrogen atom or a substituent independently represents an integer of 0 to 4. here, the plurality of R ¹⁸ when n5 represents an integer of 2 to 4 may be the same or different. )

(In General Formula (6), EWG ² represents an electron-withdrawing group. R ²¹ and R ²⁴ each independently represent a substituent, and R ²² , R ^23, and R ²⁵ each independently represent a hydrogen atom or a substituent. N6 and n7 each independently represents an integer of 0 to 4. Here, when n6 represents an integer of 2 to 4 or when n7 represents an integer of 2 to 4, a plurality of R ²¹ or a plurality of R ²⁴ May be the same or different.)   The yellow component of the image formed on the image-receiving sheet by the image forming method is a dye of a compound represented by the general formula (1) or (3), and the magenta component is the general formula (4) or (5). 2. The image forming method according to claim 1, wherein the cyan component is a pigment derived from the compound represented by the general formula (6).   3. The image forming method according to claim 1, wherein the resin having no resistance to the organic solvent used in the thermal transfer image-receiving sheet of 1) is an aqueous dispersion.   The image according to any one of claims 1 to 3, wherein a compound capable of crosslinking an aqueous polymer is contained in at least one of the receiving layer and the heat insulating layer of the thermal transfer image-receiving sheet of (1). Forming method.   5. The image forming method according to claim 1, wherein an emulsion is contained in the receiving layer of the thermal transfer image receiving sheet of 1) above.   6. The image forming method according to claim 1, wherein the thermal energy is applied by a thermal head. 1) Thermal transfer containing at least one receiving layer containing a polymer latex and at least one heat insulating layer containing a hollow polymer and not containing a resin that is not resistant to an organic solvent other than the hollow polymer on a support. A heat-sensitive transfer sheet comprising an image-receiving sheet and 2) a thermal transfer layer containing at least one compound represented by the following general formula (1), (3), (4), (5) or (6) on a support Is formed so that the receiving layer of the thermal transfer image receiving sheet of 1) and the thermal transfer layer of the thermal transfer sheet of 2) are in contact with each other, and a thermal transfer image is formed by applying thermal energy in accordance with an image signal. .

(In the general formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent. A ¹ represents an atomic group which forms a heterocycle with carbon atoms bonded to each other. B ¹ represents an atomic group that forms a heterocycle together with the carbon and nitrogen atoms at both ends to which it is bonded.

(In the general formula (3), R ¹¹ , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹² represents a substituent. A ² is a heterocycle together with carbon atoms at both ends to which it is bonded. N3 represents an integer of 0 to 4. Here, when n3 represents an integer of 2 to 4, a plurality of R ¹² may be the same or different.

(In the general formula (4), D represents an aromatic ring group or an aromatic heterocyclic group derived from a diazonium salt. R ¹⁵ represents a substituent, and R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. N4 represents an integer of 0 to 4. Here, when n4 represents an integer of 2 to 4, a plurality of R ¹⁵ may be the same or different.

(In General Formula (5), A ³ represents an atomic group that forms a heterocycle with carbon atoms bonded to both ends. EWG ¹ represents an electron-withdrawing group, R ¹⁸ represents a substituent, R ¹⁹ and R ²⁰ are each .n5 represents a hydrogen atom or a substituent independently represents an integer of 0 to 4. here, the plurality of R ¹⁸ when n5 represents an integer of 2 to 4 may be the same or different. )

(In General Formula (6), EWG ² represents an electron-withdrawing group. R ²¹ and R ²⁴ each independently represent a substituent, and R ²² , R ^23, and R ²⁵ each independently represent a hydrogen atom or a substituent. N6 and n7 each independently represents an integer of 0 to 4. Here, when n6 represents an integer of 2 to 4 or when n7 represents an integer of 2 to 4, a plurality of R ²¹ or a plurality of R ²⁴ May be the same or different.)