JPH10330609A - Resin composition for thermal imprint recording and receiving image body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a clear recording image having a high coloration concentration by a dye receiving layer of a receiving image body for thermal imprint recording. SOLUTION: A dye receiving layer comprises a resin composition composed of a phenoxy resin or a resin composition composed of the phenoxy resin and at least one of a vinyl-based resin and a polyester based resin. Examples of the vinyl-based resin include an acrylic resin. In this resin composition, the phenoxy resin may be dispersed in a particular state in the resin. The resin composition may be a polymer aqueous emulsion containing polymer particles having a core/shell structure or a microdomain structure constituted of the phenoxy resin and at least one of the vinyl-based resin and the polyester based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for thermal transfer recording which is useful for forming a clear recorded image on a dye receiving layer by thermal transfer, an image receiving body for thermal transfer recording using the resin composition, and the same. It relates to a manufacturing method.

[0002]

2. Description of the Related Art As a thermal transfer method, various methods have conventionally been used.
For example, a thermal transfer sheet in which a recording material such as a sublimable dye is carried on a base sheet (eg, a polyester film), and a dye receiving member capable of dyeing a material to be transferred (eg, paper or a plastic film) with a sublimable dye. There has been proposed a method in which a full-color image is formed on an image receiving sheet by heating by bringing the layer into contact with an image receiving sheet having a layer formed thereon.
In this method, a thermal head of a printer is used as a heating means, and three colors or four colors can be obtained by heating for a very short time.
A large number of color dots are transferred to an image receiving sheet to reproduce a full-color image corresponding to the original. The image formed in this manner is very clear because the coloring material is a dye, and is excellent in transparency, so that the obtained image has excellent intermediate color reproducibility and gradation, and is a full-color photographic image. It is possible to form a high quality image comparable to the above.

In the thermal transfer method, not only the configuration of the thermal transfer sheet but also the configuration of an image receiving sheet for forming an image is important. As the thermal transfer recording image receiving sheet, for example, polyester resin, halogen-containing vinyl resin such as polyvinyl chloride resin, polycarbonate resin, polyvinyl butyral resin, acrylic resin, cellulose resin, olefin resin, styrene resin, etc. A sheet having a dye receiving layer formed thereon is known. In such a thermal transfer recording image-receiving sheet, a dye-receiving layer is formed using a resin having good dyeability in order to improve the dyeability of the sublimable dye to be transferred. JP-A-62-211195 proposes an image-receiving sheet for thermal transfer recording, in which an image-receiving layer having a high surface smoothness is formed from a mixture containing an easily dyeable resin such as polyester and polystyrene and a pigment. This document describes that the easily dyeable resin may be a water-soluble resin or an emulsion resin. JP-A-62-18
No. 9195 discloses a heat transfer sheet in which an image receiving layer carried on a substrate is formed of a styrene resin. However, when these resins are used, it is difficult to greatly improve the color density and sharpness of an image. In addition, when a resin having a low softening point is used to enhance dye dyeing properties, the heat of the thermal head during image formation causes
The dye receiving layer and the thermal transfer sheet are fused, and a large peeling sound is generated at the time of peeling, or a problem of transferring the entire dye layer of the thermal transfer sheet to the image receiving sheet (so-called abnormal transfer) occurs.

Japanese Patent Application Laid-Open No. 62-222895 discloses that a dyeing layer of a sublimation type thermal recording image receiver contains an acrylic polymer and a surface modifier having a fluorine or silicone graft or block structure. Is disclosed. JP-A-2-81674 discloses that a sublimable dye-receiving layer comprises a resin (for example, a main dye such as polyester, vinyl chloride resin, acrylic resin and nylon resin) which is easily dyed, and a room temperature curing. There is disclosed an image receiving medium composed of an acrylic urethane silicone resin (a mold release aid) and containing an acrylic urethane silicone resin at least in a surface layer portion. JP-A-3-23990 discloses that
A graft copolymer in which a releasable segment such as a polysiloxane segment, a fluorocarbon segment and a long-chain alkyl segment is grafted on the main chain of an acrylic, vinyl, polyester, polyurethane, polyamide or cellulose resin. It has been proposed to use them to form a dye receiving layer. JP-A-6-24152 discloses a composite polymer in which a dye-receiving layer of a sublimation transfer recording image-receiving body has a core-shell structure formed of a polymer of a polyester resin having at least one polar group and a polymerizable unsaturated compound. It has been proposed to form with an aqueous dispersion. These image receivers have high releasability from the thermal transfer sheet, but it is difficult to improve the color density and sharpness while maintaining the releasability at a high level. In addition, the room temperature-curable acrylic urethane silicone resin cures at room temperature, so that it is difficult to handle. As described above, when the dyeing property of the dye is improved, the releasability is reduced. When the releasability is improved, the dyeing property of the dye is reduced, and a high-density and high-clarity image cannot be formed. .

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resin composition for thermal transfer recording capable of forming a recorded image having high color density and excellent clarity, and a thermal transfer recording composition using this resin composition. An object of the present invention is to provide an image receiving body and a manufacturing method thereof. Another object of the present invention is to provide a thermal transfer method using a sublimable dye, which is excellent in releasability (release property) from a thermal transfer sheet in an image forming process or thermal transfer and is capable of forming a high quality recorded image. An object of the present invention is to provide a resin composition, an image receiving body for thermal transfer recording using the resin composition, and a method for producing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the dye receiving layer of the image receiving body for thermal transfer recording has (a) a phenoxy resin (that is, a high molecular weight Bisphenol-type epoxy resin), or (b) a resin composition composed of a phenoxy resin and at least one of a vinyl-based resin and a polyester-based resin, the coloration density is high and the sharpness is excellent. The present inventors have found that a recorded image can be formed, and that the releasability from a thermal transfer sheet during thermal transfer can be maintained at a high level, and the present invention has been completed. That is, the resin composition of the present invention is used for forming a dye receiving layer of an image receiving body for thermal transfer recording, and is composed of a phenoxy resin (1). The resin composition may be composed of a phenoxy resin (1) and at least one resin (2) selected from a vinyl resin and a polyester resin. In the resin (2), a phenoxy resin ( 1) may be dispersed in the form of particles. The resin composition comprises a phenoxy resin (1) and the resin (2) (especially an acrylic resin or a styrene resin) and contains polymer particles having a core-shell structure or a microdomain structure. It may be a molecular water-based emulsion. The present invention also includes a thermal transfer recording image receiver in which the dye receiving layer is constituted by the phenoxy resin (1). The present invention also includes a method for producing a thermal transfer recording image-receiving body, in which the resin composition is applied to at least one surface of a substrate to form a dye-receiving layer. In the present specification, the sublimable dye refers to a dye that sublimates by heat. The “thermal transfer recording image receiver” may be simply referred to as “image receiver”, and the “dye receiving layer” may be simply referred to as “receiving layer”. "Acrylic" monomer and "methacrylic"
Monomers are collectively referred to as “(meth) acrylic” monomers.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

[Phenoxy resin (1)] A feature of the present invention resides in that the dye receiving layer is composed of the phenoxy resin (1). This phenoxy resin is composed of bisphenol A, bisphenol F,
It has a bisphenol skeleton such as bisphenol AD, and is useful not only for dyeing properties but also for forming images with high color density and sharpness. Preferred phenoxy resins are bisphenol A phenoxy resins.

The weight average molecular weight of the phenoxy resin is, for example, 5,000 to 100,000, preferably 7000 to 5
0000, more preferably about 8,000 to 40,000, and usually about 10,000 to 35,000.

The resin composition for forming the receiving layer may be composed of the phenoxy resin (1) alone, but may be composed of various resins, for example, thermoplastic resins (eg, vinyl resins such as acrylic resins and polyvinyl acetate). Vinyl resins such as ester resins, vinyl chloride resins, olefin resins, styrene resins, polyester resins, polyamide resins, thermoplastic urethane resins, polycarbonate resins, polyvinyl butyral resins, cellulose resins, etc.) And a thermosetting resin (e.g., an epoxy resin having a weight average molecular weight of less than 5,000, a vinyl ester resin, a diallyl phthalate resin, a polyurethane resin, a silicone resin). These resins can be used alone or in combination of two or more. Preferred resins include vinyl resins such as acrylic resins, vinyl ester resins, vinyl chloride resins and styrene resins, thermoplastic resins such as polyester resins, polyamide resins, thermoplastic urethane resins, and cellulose resins. , Epoxy resins, and other thermosetting resins, and combinations thereof. In particular, it is advantageous to use the phenoxy resin (1) in combination with at least one resin (2) selected from a vinyl resin (2a) and a polyester resin (2b).

[Vinyl resin (2a)] Vinyl resin (2a)
Vinyl monomers for forming a) include, for example,
(Meth) acrylic monomers, aromatic vinyls, unsaturated carboxylic acids, vinyl esters, halogen-containing vinyls, vinyl ethers (eg, vinyl ethyl ether, vinyl isobutyl ether, etc.), vinyl ketones (eg, methyl vinyl Ketones), vinyl heterocyclic compounds (eg, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylimidazole, vinylpyridine, etc.), olefin monomers (eg, ethylene, propylene, etc.), allyl compounds (eg, And allyl esters such as allyl alcohol, allyl ether and allyl acetate), and monomers having a hydrolyzable silyl group. The vinyl monomers can be used alone or in combination of two or more.

(Meth) acrylic monomers include, for example,
(Meth) acrylates, (meth) acrylamides,
(Meth) acrylonitrile and the like are included. (Meth) acrylate includes, for example, alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate. ) Acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, _C1-18 alkyl (meth) acrylate such as lauryl (meth) acrylate, etc.),
Cycloalkyl (meth) acrylate [eg, cyclohexyl (meth) acrylate, etc.], aryl (meth) acrylate [eg, phenyl (meth) acrylate, etc.], aralkyl (meth) acrylate [eg, benzyl (meth) acrylate, etc.], hydroxy Alkyl (meth) acrylate [for example, hydroxy- _C2-4 alkyl (meth) acrylate such as 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate], glycidyl (meth) acrylate, dialkylamino-alkyl (meth) Acrylate [for example,
2- (dimethylamino) ethyl (meth) acrylate,
Di C _1-4 alkylamino-C _2-4 alkyl (meth) such as 2- (diethylamino) ethyl (meth) acrylate
Acrylate, etc.].

(Meth) acrylamides include, for example,
(Meth) acrylamide, hydroxyalkyl (meth)
Acrylamide [for example, N-hydroxy-C _1-4 alkyl (meth) acrylamide such as N-methylol (meth) acrylamide], alkoxyalkyl (meth) acrylamide [for example N-methoxymethyl (meth) acrylamide or other N- C _1-4 alkoxy-C
_1-4 alkyl (meth) acrylamide, etc.], diacetone (meth) acrylamide, etc. Preferred (meth) acrylic monomers include, for example, (meth) acrylates [eg, C _1-18 alkyl (meth) acrylate, hydroxy-C _2-4 alkyl (meth) acrylate, glycidyl (meth) acrylate, C _1-4 alkylamino-C _2-4 alkyl (meth) acrylate), (meth) acrylamides and the like. More preferably, C _2-10 alkyl acrylate, C _1-6 alkyl methacrylate, hydroxy-C _2-3 alkyl (meth) acrylate, glycidyl (meth) acrylate,
Di C _1-3 alkylamino-C _2-3 alkyl (meth) acrylates are included.

The monomers having a hydrolyzable silyl group include:
(Meth) acrylic monomers and monomers having a vinyl group or an alkenyl group are included. Examples of the (meth) acrylic monomer having a hydrolyzable silyl group include, for example, 2- (meth) acrylic monomer.
(Meth) acryloxyethyltrichlorosilane, 3-
(Meth) acryloxypropyltrichlorosilane, 2-
(Meth) acryloxyethylmethyldichlorosilane, 2
-(Meth) acryloxyethyldimethylchlorosilane,
2- (meth) acryloxyethyltrimethoxysilane,
2- (meth) acryloxyethyltriethoxysilane,
3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltris (2-
(Methoxyethoxy) silane and the like.

Examples of the monomer having a hydrolyzable silyl group and a vinyl or alkenyl group include vinyltrichlorosilane, vinylmethyldichlorosilane, isopropenyltrichlorosilane and isopropenyldimethylchlorosilane; vinyltrimethoxysilane, vinyl Triethoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, isopropenyltrimethoxysilane, isopropenyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, etc .; allyltrichlorosilane, allylmethyldichlorosilane, etc .; allyltrimethoxy Silane, vinylphenyltrimethoxysilane, isopropenylphenyltrimethoxysilane and the like;
3- [2- (allyloxycarbonyl) phenylcarbonyloxy] propyltrimethoxysilane, 3- [2-
(Isopropenylmethyloxycarbonyl) phenylcarbonyloxy] propyltrimethoxysilane and the like; 3
-(Vinylphenylamino) propyltrimethoxysilane, 3- (vinylphenylamino) propyltriethoxysilane and the like; 3- [2- (N-vinylphenylmethylamino) ethylamino] propyltrimethoxysilane,
3- [2- (N-isopropenylphenylmethylamino) ethylamino] propyltriethoxysilane and the like;
2- (vinyloxy) ethyltrimethoxysilane, 3-
(Vinyloxy) propyltrimethoxysilane, 4-
(Vinyloxy) butyltriethoxysilane, 2- (isopropenyloxy) ethyltrimethoxysilane and the like;
3- (allyloxy) propyltrimethoxysilane, 1
0- (allyloxycarbonyl) decyltrimethoxysilane, 3- (isopropenylmethoxy) propyltrimethoxysilane and the like; 3-[(meth) acryloxyethoxy] propyltrimethoxysilane, 3-[(meth) acryloxyethoxy] Propyldimethoxymethylsilane, etc.]; divinyldimethoxysilane, divinyldiethoxysilane, divinyldi (β-methoxyethoxy) silane and the like.

The unsaturated carboxylic acids include, for example, unsaturated monocarboxylic acids [eg, ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid], and unsaturated polycarboxylic acids [eg, maleic acid]. Acid, fumaric acid,
Ethylenically unsaturated polycarboxylic acids such as itaconic acid and its anhydrides (such as maleic anhydride) or esters (for example, monoalkyl esters of divalent carboxylic acids such as monomethyl maleate and monobutyl maleate)] And so on. Preferred unsaturated carboxylic acids include, for example, monocarboxylic acids such as (meth) acrylic acid, polycarboxylic acids such as maleic acid, and acid anhydrides or esters thereof.

The aromatic vinyls include, for example, styrene,
α-methylstyrene, α-halostyrene, alkyl-substituted styrenes (vinyltoluene, p-ethylstyrene, etc.), halogen-substituted styrenes (chlorostyrene, etc.)
And so on. Preferred aromatic vinyls include styrene, α-methylstyrene, vinyltoluene (especially styrene). Vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl versatate (such as VeoVa), and the like. Halogen-containing vinyls include, for example, vinyl chloride, vinylidene chloride, and the like.

Examples of the vinyl resin (2a) formed by polymerization of such a vinyl monomer include (meth) acrylic monomers (such as (meth) acrylate) and aromatic vinyls (styrene). Etc.), unsaturated carboxylic acids ((meth) acrylic acid, maleic acid, etc.), vinyl esters (vinyl acetate, etc.), halogen-containing vinyls (vinyl chloride, etc.), and monomers having a hydrolyzable silyl group. Preferred is a homo- or copolymer of at least one of the above-mentioned monomers. In particular, as the vinyl resin (2a),
Acrylic resin using (meth) acrylic monomer (homologous or copolymer of (meth) acrylic monomer), styrene resin using aromatic vinyls (styrene and (meth) acrylic monomer) Such as copolymers with monomers) are preferred,
Among them, acrylic resins are preferred.

[Polyester Resin (2b)] The polyester resin can be obtained by reacting a polyhydric alcohol with a polyhydric carboxylic acid or its lower alkyl ester or acid anhydride, and is a polyester derived from lactone. There may be.

The polyhydric alcohol of the polyester resin includes, for example, aliphatic polyhydric alcohols (eg, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, tetramethylene glycol, hexamethylene glycol, neopentyl) _C2-10 alkylene diols such as glycol, polyoxy- such as diethylene glycol, triethylene glycol, etc.
Polyols such as C _2-4 alkylene glycol, trimethylolpropane, pentaerythritol, etc.), alicyclic polyhydric alcohols (eg, alicyclic diol such as 1,4-cyclohexane dimethylol, hydrogenated bisphenol A, etc.), aromatic Polyhydric alcohol [for example, 2,2
-Bis (2-hydroxyethylphenyl) propane, etc.]. Polyhydric alcohols can be used alone or in combination of two or more. The polyhydric alcohol is usually an aliphatic diol. As the polyhydric alcohol, a diol containing an alkylene glycol such as ethylene glycol or butanediol is usually used.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids (eg, saturated aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and unsaturated acids such as maleic acid). Aliphatic dicarboxylic acid, etc.), alicyclic polycarboxylic acid (e.g., alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid), aromatic polycarboxylic acid (e.g.,
Examples thereof include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and 1,5-naphthalenedicarboxylic acid, and aromatic polycarboxylic acids such as trimellitic acid. Polycarboxylic acids can be used alone or in combination of two or more. As the polycarboxylic acid, a dicarboxylic acid containing an aromatic dicarboxylic acid such as phthalic acid, terephthalic acid, or isophthalic acid is often used. Lactones include, for example, butyrolactone, valerolactone, caprolactone, and the like, and may be used alone or in combination of two or more.

The polyester resin (2b) may be a homopolyester such as polyalkylene terephthalate, but a part of terephthalic acid and / or alkylene glycol may be replaced with another dicarboxylic acid (phthalic acid, isophthalic acid, etc.) or diol. ((Poly) such as diethylene glycol
A copolyester substituted with an alicyclic diol such as oxyalkylene glycol or cyclohexanedimethanol may be used. The polyester resin (2b) is preferably an organic solvent-soluble or solvent-dispersible polyester resin, and may be a crystalline or non-crystalline polyester resin.

In the present invention, the phenoxy resin (1)
May be used as an organic solvent solution or an aqueous emulsion. Such an aqueous emulsion may be prepared by dissolving or emulsifying and dispersing the phenoxy resin (1) using an emulsifier.

The vinyl resin (2a) and the polyester resin (2b) can be used as an organic solvent solution, an aqueous solution, or an aqueous emulsion. The aqueous solution or aqueous emulsion of resin (2) introduces free ionic functional groups such as carboxyl group, sulfonic acid group and tertiary amino group into the resin molecule, and dissolves or dissolves the resin using alkali or acid. It may be prepared by dispersing. Such a resin having a free carboxyl group, a sulfonic acid group or a tertiary amino group introduced into a molecule thereof is a resin having a free carboxyl group, a sulfonic acid group or a tertiary amino (for example, (meth) acrylic). Acid, styrenesulfonic acid or a salt thereof, polycarboxylic acid such as pyromellitic anhydride, dihydroxycarboxylic acid such as dimethylolpropionic acid, N-alkyldialkanolamine such as N-methyldiethanolamine or an alkylene oxide adduct thereof) Is obtained by using

The ratio of the phenoxy resin (1) to the resin (2) is in a range that does not impair the releasability, color density, and sharpness, for example, phenoxy resin (1) / resin (2) = 99.5 / 0.
5-20 / 80 (% by weight) [for example, 99.5 / 0.5
４０40/60 (% by weight)], and the former / latter = 99/1 to 50/50 (% by weight), especially 98
/ 2 to 60/40 (% by weight).

The resin composition can be used as a mixture of the phenoxy resin (1) and the resin (2) (particularly, an organic solvent solution or dispersion that can be applied). Examples of the organic solvent include solvents generally used as coating agents, for example, aliphatic hydrocarbons (such as hexane), alicyclic hydrocarbons (such as cyclohexane), aromatic hydrocarbons (such as toluene and xylene), and halogens. Hydrocarbons (such as dichloroethane), alcohols (such as ethanol and isopropanol), esters (such as ethyl acetate), ketones (such as acetone and methyl ethyl ketone), ethers (such as diethyl ether and tetrahydrofuran), and cellosolves (such as ethyl cellosolve) Or a mixed solvent thereof.

The resin composition has a form in which one of the phenoxy resin (1) and the resin (2) constitutes a matrix, and the other component is dispersed in the matrix in a particulate form, in particular, the resin ( It is preferable that the phenoxy resin (1) is dispersed in the form of particles in 2). The average particle size of the dispersed particles (eg, polymer (2)) is, for example, 0.001 to 5 μm (for example, 0.001 to 5 μm).
5 to 2 μm), preferably 0.01 to 2 μm (for example,
0.01 to 1.5 μm), more preferably 0.01 to 1.5 μm.
It can be selected from a range of about 1 μm.

In a resin composition in which one component (for example, phenoxy resin (1)) is dispersed in a particle state, one component (for example, phenoxy resin (1)) is maintained in a particulate form while the other component is kept in a particulate form. It may be prepared by mixing with a component (for example, resin (2)). As a preferred preparation method, for example, an emulsion of phenoxy resin (1) and resin (2)
And a method of emulsion-polymerizing a vinyl monomer corresponding to the resin (2) in the presence of an emulsion containing polymer particles composed of the phenoxy resin (1). The emulsion polymerization may be a seed polymerization using polymer particles containing the phenoxy resin (1) as seeds. Further, the polymer particles containing the resin (2) may be composed of not only the resin (2) alone but also the phenoxy resin (1) and the resin (2).

The emulsion polymerization is carried out by a conventional emulsion polymerization method, for example,
(A) a method of emulsion polymerization of a mixed solution of a phenoxy resin (1) and a vinyl monomer, (b) a vinyl monomer alone or in the presence of a polymer particle composed of a phenoxy resin (1), or Emulsion polymerization of a mixed solution of a vinyl monomer and a phenoxy resin (1) can be performed. The mixed solution of the phenoxy resin (1) and the vinyl monomer or the vinyl monomer may be used as a pre-emulsified emulsion. The mixed solution and the vinyl monomer may be charged at once and polymerized, or partially charged,
The remaining portion may be added for polymerization. The mixed solution and the vinyl monomer may be continuously added to the emulsion polymerization system by dropping or the like, or may be added intermittently. In the emulsion polymerization, a method combining these methods may be employed.

In the emulsion polymerization, a conventional method such as a multistage polymerization method can be employed. Multi-stage polymerization is performed, for example, continuously or intermittently in the presence of polymer particles containing at least a phenoxy resin (1), or polymer particles formed by emulsion polymerization of a mixed solution of a phenoxy resin (1) and a vinyl monomer. Specifically, the polymerization can be performed by a method of adding a vinyl-based monomer or a mixed solution of the phenoxy resin (1) and the vinyl-based monomer in multiple stages and performing emulsion polymerization. In this method, the composition of the vinyl monomer or the mixed solution to be added may be different between the initial stage and the late stage of the emulsion polymerization step. For example, the ratio of the vinyl monomer in the mixed solution to be added may be increased at a later stage than the initial stage, and the vinyl monomer may be used at a later stage. In the emulsion polymerization system, a phenoxy resin (1) and an unsaturated carboxylic acid among vinyl monomers, a compound having an amino group may coexist,
In order to suppress the reaction, it is advantageous not to allow both to coexist.

The emulsion polymerization can be carried out using a polymerization initiator, for example, a water-soluble polymerization initiator such as persulfate such as potassium persulfate, sodium persulfate and ammonium persulfate, and hydrogen peroxide. May constitute a water-soluble resin-type polymerization initiator system. In order to adjust the molecular weight of the resin (2), a chain transfer agent such as alcohols such as catechol, thiols, and mercaptans may be used. The polymerization temperature depends on the type of polymerization initiator,
For example, it is about 40 to 100 ° C, preferably about 50 to 90 ° C, and more preferably about 60 to 85 ° C.

The polymer particles in the resin composition (water-based emulsion) obtained by emulsion polymerization may have a homogeneous structure or a hetero-phase structure (for example, a core-shell structure, a micro-domain structure, etc.). Good. core·
In the shell structure, the core layer may be composed of the phenoxy resin (1) or the resin (2), and the shell layer may be composed of the resin (2) or the phenoxy resin (1). Examples of the resin (2) that forms such a heterophase structure include a vinyl resin (2a), particularly an acrylic resin or a styrene resin.

The average particle size of the polymer particles is within a range that does not impair the dispersion stability, adhesion, etc., for example, 0.01 to 0.01.
5 μm (for example, 0.01 to 1 μm), preferably 0.1 μm.
It can be selected from the range of about 01 to 2 μm, more preferably about 0.01 to 1 μm.

An emulsifier can be used for preparing an emulsion (for example, an emulsion of phenoxy resin (1) and the like) and emulsion polymerization. Examples of the emulsifier include anionic surfactants (for example, sodium dodecylbenzenesulfonate, alkyl Sodium diphenyl ether disulfonate, sodium alkylnaphthalene sulfonate, sodium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium dialkyl sulfosuccinate, etc., nonionic surfactants (for example, polyoxyethylene Lauryl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, oxyethylene / oxypropylene block copolymer And the like, and a protective colloid such as polyvinyl alcohol and a water-soluble polymer. The amount of the emulsifier used is, for example, 0.1 to 10% by weight, preferably 0.1 to 10% by weight, based on the total amount of the emulsified components such as the phenoxy resin (1) and the vinyl monomer.
5-8% by weight. More preferably, it is about 1 to 8% by weight.

The pH of the emulsion may be adjusted. The pH of the emulsion is, for example, 5 or more (for example,
5 to 10), preferably about 6 to 9 in a neutral to weakly alkaline region. The glass transition temperature (Tg) of the resin (2) is, for example, -20 ° C to 50 ° C, preferably-
It is about 10 ° C to 40 ° C. The minimum film formation temperature (MFT) of the aqueous emulsion is, for example, 0 to 40 ° C, preferably about 0 to 35 ° C.

The resin composition may be, for example, a fluororesin, a silicone resin, an organic sulfonate compound, an organic phosphate compound, or an organic carboxylic acid in order to improve the releasability during thermal transfer and the weather resistance of a recorded image. Additives such as lubricants such as salt compounds, stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, radical scavengers, quenchers, antistatic agents, plasticizers, thickeners and defoamers. It may be added.

[0036] The resin composition of the present invention is a simple composition comprising a phenoxy resin (1) (or this phenoxy resin (1) and resin (2)) without using a special resin such as acrylic urethane silicone resin. Even when the composition is applied to the receiving layer of the image receiving body, a high quality image having high color density and excellent sharpness can be formed. In addition, it has excellent releasability at the time of thermal transfer, and can form a high-quality image smoothly.

[Receiver for Thermal Transfer Recording] As the base material of the receptor, for example, natural paper, synthetic paper (for example, polypropylene-based, polystyrene-based, polyester-based synthetic paper, etc.),
A plastic film (for example, a polyester film such as polyalkylene terephthalate (eg, polyethylene terephthalate, polybutylene terephthalate), an olefin-based film such as polypropylene, a polyamide film such as nylon, or a laminate thereof) can be used. Preferred substrates include heat-resistant substrates, such as synthetic paper, plastic films. The thickness of the substrate is, for example, 5 to 500, depending on the application.
μm, preferably from 10 to 300 μm, more preferably from about 50 to 200 μm. If necessary, additives such as antioxidants, ultraviolet absorbers, stabilizers such as heat stabilizers, lubricants, antistatic agents, fillers, and pigments may be added to the base material.

The image receiving body of the present invention has a receiving layer composed of the resin composition on at least one surface of the substrate. This receiving layer can be formed by applying a coating solution containing a resin composition to a base material and drying the coating solution. This coating solution is
The resin composition can be prepared using an appropriate solvent (for example, water, an aqueous or non-aqueous organic solvent, or a mixed solvent thereof). When the resin composition is an aqueous emulsion, the coating solution is aqueous. As a method for applying the coating solution, a conventional method, for example, a roll coating method such as gravure or reverse, a doctor knife method, a knife coating method, a nozzle coating method, and the like can be adopted.

The layer structure of the receiving layer of the image receiving body may be either a single layer or a plurality of layers, and is usually a single layer. The thickness of the receiving layer is, for example, 0.1 μm
(For example, 0.1 to 50 μm), preferably 0.5
μm or more (for example, 0.5 to 40 μm), and more preferably a range of about 1 to 30 μm.

The image receiving body of the present invention is used in combination with a thermal transfer sheet containing a sublimable dye. The image receiving body of the present invention is a thermal transfer method, for example, by contacting the dye receiving layer of the image receiving body with a thermal transfer sheet containing a sublimable dye, and heating using a thermal head or the like to receive the dye of the thermal transfer sheet. It is useful for transferring to a body and forming an image on a receiver.

[0041]

The resin composition of the present invention is composed of the phenoxy resin (1) (or the phenoxy resin (1) and the resin (2)). And a high-quality image excellent in sharpness can be formed. In addition, it has high releasability from a thermal transfer sheet during an image forming process or thermal transfer. Therefore, a high quality image can be formed while maintaining the releasability from the thermal transfer sheet at a high level.

[0042]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 Deionized water 360 was placed in a 1-liter reaction vessel equipped with a stirrer, a condenser (reflux condenser), a dropping funnel, and a thermometer.
g, surfactant (Emulgen 935, manufactured by Kao Corporation)
20% by weight of a mixture of 7 g, 223 g of butyl acrylate (BA), 214 g of methyl methacrylate (MMA) and 45 g of phenoxy resin (PKMJ, manufactured by Union Carbide Co.) was charged and heated to 70 ° C. with stirring. The remaining 80% by weight of the mixture and an aqueous solution containing 2.8 g of potassium persulfate were added dropwise to the reaction system over 2 hours. After further reacting for 2 hours, the mixture was cooled to room temperature to obtain an aqueous composite resin emulsion (solid content: 56%, pH: 4.7, viscosity: 10 cps (30 ° C.)).

Example 2 1 equipped with a stirrer, a condenser, a dropping funnel and a thermometer
In a liter reactor, 140 g of the aqueous composite resin emulsion obtained in Example 1 above, 266 g of ion-exchanged water, and a surfactant (Emulgen 931 manufactured by Kao Corporation)
5 g was charged and heated to 70 ° C. while stirring. BA
A mixture of 26 g, 38 g of styrene, 1.5 g of diethylaminoethyl methacrylate and 1 g of acrylic acid, and an aqueous solution containing 0.5 g of potassium persulfate were added dropwise to the reaction system over 2 hours. After further reacting for 2 hours, the mixture was cooled to room temperature to obtain an aqueous composite resin emulsion (solid content 30% by weight, pH 4.7, viscosity 5.8 cps (30 ° C.)). Ammonia was added to this aqueous composite resin emulsion to adjust the pH to 8.0.

Example 3 60 parts by weight of polycaprolactone (Placcel H7, manufactured by Daicel Chemical Industries, Ltd.) and 40 parts by weight of a phenoxy resin (PKHC, manufactured by Union Carbide Co., Ltd.) were dissolved in methyl ethyl ketone to obtain a resin of 30% by weight. A solution was prepared.

Example 4 Thermoplastic polyester (Vittel Vi, manufactured by Goodyear)
50 parts by weight of tel PE-5545) and 50 parts by weight of a phenoxy resin (PKHH, manufactured by Union Carbide) were dissolved in methyl ethyl ketone to prepare a 30% by weight resin solution.

Example 5 50 parts by weight of coumarone-indene resin (manufactured by Nippon Steel Chemical Co., Ltd.) and phenoxy resin (manufactured by Union Carbide Co., Ltd., PK
HH) is dissolved in methyl ethyl ketone,
A 30% by weight resin solution was prepared.

Comparative Example 1 An aqueous resin emulsion was prepared in the same manner as in Example 1 without using a phenoxy resin.

Comparative Examples 2 to 4 A 30% by weight solution of polycaprolactone (Placcel H7, manufactured by Daicel Chemical Industries, Ltd.) used in Example 3 in methyl ethyl ketone (Comparative Example 2), and the thermoplastic polyester used in Example 4 ( Goodyear Vitel PE PE
-5545) in 30% by weight methyl ethyl ketone (Comparative Example 3), and a 30% by weight solution of coumarone-indene resin (manufactured by Nippon Steel Chemical Co., Ltd.) used in Example 5 (Comparative Example 4).

(Preparation of Thermal Transfer Recording Image Receiver) The aqueous resin emulsion or the resin solution was coated with a 150 μm thick polypropylene synthetic paper (Yopo F manufactured by Oji Oil Chemicals, Inc.).
PG-150), using a wire bar, 10 μm
And dried at 110 ° C. for 10 minutes to obtain a heat-sensitive transfer recording image receiver having a dye-receiving layer.

(Evaluation of Printed Image Density) A sublimation type digital color printer DPP-M1 was mounted on an image receiving body (image receiving sheet).
The image was printed using (manufactured by Sony Corporation) and the color density was measured with a reflection type Macbeth densitometer RD-1255 (manufactured by Sakata Inx). The ink ribbon used was a print pack VPM-P50STA dedicated to DPP-M1. The printing conditions were set to the standard settings of a printer driver (manufactured by Sony Corporation) for Macintosh (manufactured by Apple Inc.). Then, the color density was evaluated as the sum of the maximum values of the reflection densities of cyan, magenta, yellow, and black.

(Evaluation of Releasability) The releasability of the ink ribbon and the image receiving sheet during printing was visually observed and evaluated according to the following criteria. ：: Smooth printing without abnormal transfer such as heat fusion. △: Loud peeling sound ×: Abnormal transfer occurs. The evaluation results are shown in the table.

[0052]

[Table 1] As is clear from the table, in the resin compositions of Examples, high color developability was obtained, and high releasability without fusion was obtained.

Claims (7)

[Claims] 1. A resin composition for forming a dye receiving layer of a thermal transfer recording image-receiving body, which comprises at least a phenoxy resin. 2. The thermal transfer recording resin composition according to claim 1, comprising a phenoxy resin and at least one resin selected from a vinyl resin and a polyester resin. 3. The thermal transfer recording resin composition according to claim 2, wherein the vinyl resin is an acrylic resin or a styrene resin. 4. The thermal transfer recording resin composition according to claim 2, wherein the phenoxy resin is dispersed in at least one resin selected from a vinyl resin and a polyester resin. 5. The resin composition for thermal transfer recording according to claim 1, wherein the resin composition is an aqueous emulsion comprising a phenoxy resin and a vinyl resin and containing polymer particles having a core-shell structure or a microdomain structure. Stuff. 6. An image receiving body for thermal transfer recording, wherein the dye receiving layer comprises at least a phenoxy resin. 7. A method for producing a thermal transfer recording image receiving body, wherein the resin composition according to claim 1 is applied to at least one surface of a substrate to form a dye receiving layer.