JP6146033B2 - Thermal sublimation transfer image-receiving sheet - Google Patents

Description

  The present invention relates to a heat-sensitive sublimation transfer image-receiving sheet, and more specifically, a heat-sublimation transfer image-receiving sheet capable of forming an excellent image.

  2. Description of the Related Art Conventionally, characters and images are formed on a transfer object using a thermal transfer method. As the thermal transfer method, a thermal sublimation transfer method and a thermal fusion transfer method are widely used. Among these, the heat-sensitive sublimation transfer method uses a sublimation dye as a color material, and uses a heating device such as a thermal head or laser light whose heat is controlled according to image information, in the sublimation dye layer on the thermal transfer sheet. This dye is transferred to a transfer medium such as a thermal transfer image-receiving sheet to form an image. This heat-sensitive sublimation transfer method can control the amount of dye transfer in dot units by overheating for a very short time. The image formed in this way is very clear because the colorant used is a dye and is excellent in transparency, so the resulting image is excellent in halftone reproducibility and gradation, An extremely high-definition image can be obtained. For this reason, a high quality image comparable to a full-color silver salt photograph can be obtained. 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 general, a thermal transfer image-receiving sheet has a dye image-receiving layer (receiving layer) formed on at least a support. As the resin for forming the receiving layer, vinyl chloride resin is used because it is excellent in dyeing and releasing properties, and abnormal transfer such as fusion does not occur between the thermal transfer sheet and the thermal transfer image-receiving sheet during thermal transfer. Has been. A vinyl chloride resin has been conventionally used by being dissolved in an organic solvent when applied to a base sheet for forming a receiving layer.

  However, there is a concern about the deterioration of the working environment due to the use of organic solvents.

  Therefore, a method of forming a receiving layer using vinyl chloride resin latex without using an organic solvent has been widely studied (Patent Document 1).

  However, the PVC resin latex used for forming the receiving layer is inferior in storage stability, the stability of the coating film is deteriorated, and the image quality is deteriorated. Thus, the heat-sensitive sublimation transfer image using the vinyl chloride resin latex is used. A satisfactory image was not obtained with the sheet.

  Thus, there was no vinyl chloride resin latex from which a heat-sensitive sublimation transfer image-receiving sheet capable of excellent image formation was obtained.

JP 2006-264087 A

  The present invention has been made in view of the above problems, and the object of the present invention is to provide a vinyl chloride polymer that is excellent in storage stability of latex and capable of forming an excellent image with which a uniform coating film can be obtained. It is intended to provide a heat-sensitive sublimation type transfer image-receiving sheet.

As a result of intensive studies on the above problems, the present inventors have found that a heat-sensitive sublimation transfer image-receiving sheet obtained by applying and drying a vinyl chloride polymer latex composition described below on a support is excellent. It has been found that image formation and a uniform coating film can be obtained, and the present invention has been completed. That is, the present invention is a heat-sensitive sublimation transfer image-receiving sheet comprising at least a support and a receiving layer containing a vinyl chloride polymer, wherein the vinyl chloride polymer comprises a core portion and the core A core portion is a vinyl chloride polymer having an average particle size of 0.12 μm or less and an average degree of polymerization of 400 to 2000, and the shell portion is Polymer 1 having at least one repeating unit represented by a predetermined general formula (1), (2), (3), (4), (5) and (6) with respect to 100 parts by weight of vinyl polymer To 300 parts by weight, and further, 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 2 parts of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer. Contains 5 parts by weight And 10 parts by weight or less of an emulsifier with respect to 100 parts by weight of the vinyl chloride polymer, the average particle size of the vinyl chloride polymer is 0.30 μm or less, and the chloride of the vinyl chloride polymer is A heat-sensitive sublimation transfer image-receiving sheet in which a receiving layer is formed using a vinyl polymer latex composition .

  The present invention is described in detail below.

  The heat-sensitive sublimation transfer image-receiving sheet of the present invention comprises at least a support and a dye image-receiving layer (receiving layer). The heat-sensitive sublimation transfer image-receiving sheet of the present invention has, for example, 1) a receiving layer formed on a support, 2) a heat insulating layer and a receiving layer formed on the support, and 3) a support. For example, an underlayer, a heat insulating layer, and a receiving layer are formed thereon.

  The receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention contains a vinyl chloride polymer. The vinyl chloride polymer is obtained by using a vinyl chloride polymer latex composition.

  The vinyl chloride polymer latex composition for forming the receiving layer of the heat-sensitive sublimation type transfer image-receiving sheet of the present invention has a core part and a shell part that forms an outer layer of the core part.

  The core portion of the vinyl chloride polymer latex composition is a vinyl chloride polymer having an average particle size of 0.12 μm or less and an average degree of polymerization of 400 to 2000.

  The average particle diameter of the vinyl chloride polymer constituting the core part of the vinyl chloride polymer latex composition is 0.12 μm or less, preferably 0.10 μm or less. When the average particle diameter exceeds 0.12 μm, the coating film of the vinyl chloride polymer latex composition is not uniform, which is not preferable.

  The average degree of polymerization of the vinyl chloride polymer constituting the core part is 400 to 2000. When the average degree of polymerization exceeds 2000, foreign matter is generated in the coating film of the vinyl chloride polymer latex composition and it is not uniform, and even when the average degree of polymerization is less than 400, the coating of the vinyl chloride polymer latex composition is not possible. Foreign matter is generated on the film and does not become uniform.

  The vinyl chloride polymer constituting the core part can be obtained by using a vinyl chloride polymer latex obtained by the method described below, and adding a predetermined monomer described later to perform polymerization. .

  Specifically, this vinyl chloride polymer latex is composed of a vinyl chloride monomer alone, or 100 parts by weight of a vinyl chloride monomer and a monomer copolymerizable therewith, and an organic compound having a sulfonate salt or a sulfate ester salt of 1.0 to It can be obtained by emulsion polymerization in the presence of 5.0 parts by weight, preferably 1.5 to 4.5 parts by weight, and 0.05 to 2.5 parts by weight of a higher fatty acid salt. In the emulsion polymerization, water is used as a dispersion medium, 10 to 140% by weight of vinyl chloride monomer alone, or a vinyl chloride monomer and a copolymerized monomer, an organic compound having a predetermined amount of sulfonate or sulfate ester salt, and The polymerization is carried out with stirring using a polymerization initiator in the presence of a higher fatty acid salt.

  Examples of the organic compound having a sulfonate include alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate, dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate, and alkyls. Examples thereof include alkyl naphthalene sulfonates such as sodium naphthalene sulfonate, alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate, and organic compounds having a sulfate ester salt include, for example, sodium lauryl sulfate, myristyl sulfate. Examples thereof include alkyl sulfates such as sodium and polyoxyethylene alkylaryl sulfates. When the amount of the organic compound having a sulfonate or sulfate ester salt is less than 1.0 part by weight based on 100 parts by weight of the monomer, the amount of precipitates increases during the production of the vinyl chloride polymer latex, which is preferable. Absent. If the amount exceeds 5.0 parts by weight, the amount of impurities increases and a good image formation cannot be obtained.

  Examples of the higher fatty acid salt include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like with an alkali. From the viewpoint of availability, a salt with sodium, potassium, ammonia, or triethanolamine is preferable. When the amount of the higher fatty acid salt used is less than 0.05 parts by weight based on 100 parts by weight of the monomer, there are many precipitates at the time of producing the vinyl chloride polymer latex, and the image quality deteriorates. When the amount exceeds 2.5 parts by weight, the amount of impurities increases and the image quality deteriorates, which is not preferable.

  Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl oleate, vinyl benzoate, acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, etc. Unsaturated carboxylic acids or anhydrides thereof, esters of acrylic acid such as methyl, ethyl, butyl, octyl, benzyl, etc., esters of maleic acid such as methyl, ethyl, butyl, octyl, benzyl, maleic acid esters, fumaric acid esters, cinnamon Unsaturated carboxylic acid esters such as acid esters, vinyl ethers such as vinyl methyl ether, vinyl amyl ether, vinyl phenyl ether, monoolefins such as ethylene, ethylene, propylene, butene, pentene, vinylidene chloride, styrene or derivatives thereof, acrylic Nitrile, one or more methacrylonitrile conventional vinyl compounds vinyl chloride and may radical copolymerization such as nitriles.

  Examples of the polymerization initiator used include water-soluble initiators such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, lauroyl. Examples thereof include oil-soluble initiators such as peroxide, t-butylperoxypivalate, diacyl peroxide, peroxyester, and peroxydicarbonate. The addition method of the polymerization initiator used at this time is usually one of batch addition, intermittent addition, continuous addition, or a combination thereof. The polymerization rate of the vinyl chloride monomer is preferably 80 to 97% by weight based on the total monomers.

  The polymerization temperature is 10 to 85 ° C, preferably 30 to 80 ° C, and more preferably 40 to 80 ° C. When the polymerization temperature is less than 10 ° C., the average degree of polymerization of the vinyl chloride polymer increases, and when it exceeds 85 ° C., the average degree of polymerization of the vinyl chloride polymer decreases.

  The polymerization time is not particularly limited, but is preferably 3 to 24 hours.

  The polymerization is terminated by recovering the monomer by reducing the pressure in the vessel to normal pressure and further reducing the pressure. A polymerization inhibitor may be added to terminate the polymerization.

  If necessary, in the latex after completion of the polymerization, 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 100 to 2 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer. These emulsifiers can be additionally added to contain 5 parts by weight.

  In addition, when producing this vinyl chloride polymer latex, other than organic compounds having chain transfer agents, reducing agents, buffering agents, sulfonates or sulfates for the purpose of stabilizing polymerization and reducing the amount of scale generated. An emulsifier or the like can also be added.

  The vinyl chloride polymer latex produced in this manner has an amount of 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and a higher fatty acid salt of 0 to 100 parts by weight of the vinyl chloride polymer. 0.05 to 2.5 parts by weight, the average particle size of the vinyl chloride polymer is 0.12 μm or less, and the average degree of polymerization is 400 to 2000. When the organic compound having a sulfonate salt or a sulfate ester salt is less than 1.0 part by weight, the amount of precipitates increases during the production of the vinyl chloride polymer latex composition, leading to deterioration in image quality. If it exceeds 5.0 parts by weight, the amount of impurities increases and the image quality deteriorates. When the higher fatty acid salt is less than 0.05 parts by weight, a large amount of precipitates are produced during the production of the vinyl chloride polymer latex composition, leading to deterioration in image quality. If it exceeds 2.5 parts by weight, the amount of impurities increases and the image quality deteriorates. When the average particle diameter exceeds 0.12 μm, coarse particles are generated when the monomer that becomes the shell portion is polymerized, and the amount of precipitates increases to deteriorate the image quality. When the average degree of polymerization is out of 400 to 2000, scale is generated during synthesis of the vinyl chloride polymer latex composition, and the image quality is deteriorated.

  The shell portion of the vinyl chloride polymer latex composition for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention has the following general formula with respect to 100 parts by weight of the vinyl chloride polymer constituting the core portion. It comprises 1 to 300 parts by weight of a polymer having at least one repeating unit represented by (1), (2), (3), (4), (5) and (6).

（式中、Ｒ_１は炭素数２〜８のアルキル基を表し、Ｒ_２は水素またはメチル基を表す。）

(In the formula, R ₁ represents an alkyl group having 2 to 8 carbon atoms, and R ₂ represents hydrogen or a methyl group.)

（式中、Ｒ_３は炭素数１〜４のアルキレン基を表し、Ｒ_４は炭素数１〜４のアルキル基もしくはアルコキシルアルキル基、または水素を表し、Ｒ_５は水素またはメチル基を表す。）

(In the formula, R ₃ represents an alkylene group having 1 to ₄ carbon atoms, R ₄ represents an alkyl group or alkoxylalkyl group having 1 to ₄ carbon atoms, or hydrogen, and R ₅ represents hydrogen or a methyl group.)

（式中、Ｒ_６はメチル基またはエチル基を表す。）

(In the formula, R ₆ represents a methyl group or an ethyl group.)

（式中、Ｒ_７は水素またはメチル基を表す。）

(Wherein R ₇ represents hydrogen or a methyl group.)

（式中、Ｒ_８は水素またはメチル基を表す。）

(In the formula, R ₈ represents hydrogen or a methyl group.)

（式中、Ｒ_９は水素またはメチル基を表す。）
一般式（１）で表される繰返し単位をもつポリマーとしては、例えば、ポリ（メタ）アクリル酸エチル、ポリ（メタ）アクリル酸ｎ−プロピル、ポリ（メタ）アクリル酸イソプロピル、ポリ（メタ）アクリル酸ｎ−ブチル、ポリ（メタ）アクリル酸イソブチル、ポリ（メタ）アクリル酸ｎ−ヘキシル、ポリ（メタ）アクリル酸２−エチルヘキシル、ポリ（メタ）アクリル酸ｎ−オクチル等が挙げられる。

(In the formula, R ₉ represents hydrogen or a methyl group.)
Examples of the polymer having the repeating unit represented by the general formula (1) include poly (meth) acrylate ethyl, poly (meth) acrylate n-propyl, poly (meth) acrylate isopropyl, and poly (meth) acrylic. Examples include n-butyl acid, isobutyl poly (meth) acrylate, n-hexyl poly (meth) acrylate, 2-ethylhexyl poly (meth) acrylate, and n-octyl poly (meth) acrylate.

  Examples of the polymer having a repeating unit represented by the general formula (2) include methoxyethyl poly (meth) acrylate, ethoxyethyl poly (meth) acrylate, propoxyethyl poly (meth) acrylate, and poly (meth) acrylic acid. n-butoxyethyl, poly (meth) acrylic acid methoxypropyl, poly (meth) acrylic acid ethoxypropyl, poly (meth) acrylic acid n-propoxypropyl, poly (meth) acrylic acid n-butoxypropyl, poly (meth) acrylic Examples include hydroxyethyl acid and hydroxypropyl poly (meth) acrylate, and one or more copolymers of these repeating units may be used.

  Examples of the polymer having a repeating unit represented by the general formula (3) include polyvinyl acetate and polyvinyl propionate, and one or more kinds of copolymers of these repeating units may be used.

  Examples of the polymer having a repeating unit represented by the general formula (4) include polyglycidyl methacrylate and polyglycidyl acrylate, and one or more kinds of copolymers of these repeating units may be used.

  Examples of the polymer having a repeating unit represented by the general formula (5) include polyallyl glycidyl ether.

  Examples of the polymer having a repeating unit represented by the general formula (6) include polyacrylic acid and polymethacrylic acid. One or more types of copolymers of these repeating units may be used.

  The vinyl chloride polymer latex composition for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention is an organic compound 1 having a sulfonate salt or a sulfate ester salt with respect to 100 parts by weight of the vinyl chloride polymer. 0.05 to 5.0 parts by weight and 0.05 to 2.5 parts by weight of a higher fatty acid salt, and 10 parts by weight or less of an emulsifier with respect to 100 parts by weight of the vinyl chloride polymer.

  When the organic compound having a sulfonate or sulfate ester salt is less than 1.0 part by weight with respect to 100 parts by weight of the vinyl chloride polymer, the coating film obtained from the composition is not uniform, and the image quality is deteriorated. Invite. If it exceeds 5.0 parts by weight, the amount of impurities increases and the image quality deteriorates.

  If the higher fatty acid salt is less than 0.05 parts by weight based on 100 parts by weight of the vinyl chloride polymer, the amount of precipitates will deteriorate the image quality, and if it exceeds 2.5 parts by weight, the impurities will increase and the image quality will deteriorate. To do.

  If the emulsifier exceeds 10 parts by weight, the amount of impurities increases and the image quality deteriorates. Here, the emulsifier refers to an emulsifier used in the polymerization of the shell portion described later, in addition to the organic compound having a sulfonate or sulfate ester salt and a higher fatty acid salt.

  The average particle size of the vinyl chloride polymer in the vinyl chloride polymer latex composition for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention is 0.30 μm or less. When the average particle diameter exceeds 0.30 μm, the coating film stability is lowered and the image quality is deteriorated.

  The vinyl chloride polymer latex composition for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention is a chain transfer agent, a reducing agent, a buffering agent, as long as the object of the present invention is not impaired. Thickeners, condensed phosphates, surfactants, dispersants, tackifiers, pH adjusters, antifoaming agents, preservatives, film-forming aids, anti-aging agents, anti-freezing agents, etc. .

  Examples of the thickener include methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylate, polyacrylamide, polyvinyl pyrrolidone and the like, and examples of the condensed phosphate include tripolyphosphate and hexametaphosphate. Examples of the dispersant include a styrene-maleic acid monoester salt copolymer.

  The vinyl chloride polymer latex composition for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention is an organic compound 1 having a sulfonate salt or a sulfate ester salt with respect to 100 parts by weight of the vinyl chloride polymer. A chlorinated salt containing 0.0 to 5.0 parts by weight and 0.05 to 2.5 parts by weight of a higher fatty acid salt, the vinyl chloride polymer having an average particle size of 0.12 μm or less and an average degree of polymerization of 400 to 2000 A single amount represented by the following general formulas (7), (8), (9), (10) and (11) with respect to 100 parts by weight of the vinyl chloride polymer in the latex in the presence of the vinyl polymer latex. And 1 to 300 parts by weight of at least one monomer selected from methacrylic acid and acrylic acid, and 10 parts by weight or less of an emulsifier are added and polymerized. When the amount of the monomer is less than 1 part by weight or when it exceeds 300 parts by weight, the image quality deteriorates, which is not preferable.

（式中、Ｒ_９は炭素数２〜８のアルキル基を表し、Ｒ_１０は水素またはメチル基を表す。）

(In the formula, R ₉ represents an alkyl group having 2 to 8 carbon atoms, and R ₁₀ represents hydrogen or a methyl group.)

（式中、Ｒ_１１は炭素数１〜４のアルキレン基を表し、Ｒ_１２は炭素数１〜４のアルキル基もしくはアルコキシルアルキル基、または水素を表し、Ｒ_１３は水素またはメチル基を表す。）

(In the formula, R ₁₁ represents an alkylene group having 1 to 4 carbon atoms, R ₁₂ represents an alkyl group or alkoxylalkyl group having 1 to 4 carbon atoms, or hydrogen, and R ₁₃ represents hydrogen or a methyl group.)

（式中、Ｒ_１４はメチル基またはエチル基を表す。）

(In the formula, R ₁₄ represents a methyl group or an ethyl group.)

（式中、Ｒ_１５は水素またはメチル基を表す。）

(In the formula, R ₁₅ represents hydrogen or a methyl group.)

（式中、Ｒ_１６は水素またはメチル基を表す。）
一般式（７）で表される（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｎ−ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル等が挙げられる。

(In the formula, R ₁₆ represents hydrogen or a methyl group.)
Examples of the (meth) acrylic acid ester represented by the general formula (7) include, for example, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate. Examples include butyl, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate.

  Examples of the (meth) acrylic acid ester represented by the general formula (8) include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, and (meth) acrylic acid n. -Butoxyethyl, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, n-propoxypropyl (meth) acrylate, n-butoxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth ) Hydroxypropyl acrylate and the like.

  Examples of the monomer represented by the general formula (9) include vinyl acetate and vinyl propionate.

  Examples of the monomer represented by the general formula (10) include glycidyl methacrylate and glycidyl acrylate.

  Examples of the monomer represented by the general formula (11) include allyl glycidyl ether.

  If methyl methacrylate is used during the synthesis of the vinyl chloride polymer latex composition, the cause is unknown, but a precipitate is generated during the synthesis of the vinyl chloride polymer latex composition, which is not preferable.

  Other than the monomers represented by the general formulas (7) to (11), examples of vinyl monomers copolymerizable with these include methyl acrylate, n-pentyl methacrylate, and (meth). N-decyl acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, cyanomethyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, ( 1-cyanopropyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, 4-cyanobutyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, (meth ) 2-ethyl-6-cyanohexyl acrylate, 8-cyanooctyl (meth) acrylate, methoxymethyl (meth) acrylate, (meth) ) Can be exemplified acrylic acid ethoxymethyl, methacrylic acid n- propoxy-propyl, methacrylic acid n- butoxy propyl, vinyl acetate, vinyl propionate and the like.

  Further, 1,1-dihydroperfluoroethyl (meth) acrylate, 1,1-dihydroperfluoropropyl (meth) acrylate, 1,1,5-trihydroperfluorohexyl (meth) acrylate, (meth) acrylic acid 1 , 1,2,2-tetrahydroperfluoropropyl, 1,1,7-trihydroperfluoroheptyl (meth) acrylate, 1,1-dihydroperfluorooctyl (meth) acrylate, 1,1-dihydro (meth) acrylate Perfluorodecyl, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, (meth ) As ingredients other than acrylic esters, Alkyl vinyl ketone compounds such as ru vinyl ketone, alkyl vinyl ether compounds such as vinyl ethyl ether, allyl ether compounds such as allyl methyl ether, styrene, α-methyl styrene, chlorostyrene, vinyl toluene, p-chloromethyl styrene, p-acetoxy styrene, p-acetoxystyrene, p-butoxystyrene, 4-vinylbenzoic acid, 2-vinylpyridine, 4-vinylpyridine, vinyl aromatic compounds such as vinylnaphthalene, vinylnitrile compounds such as acrylonitrile and methacrylonitrile, acrylamide, budadiene, 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, 2- (N-piperidimethyl) -1,3-butadiene, 2-triethoxy Methyl 1,3-butadiene compounds such as -1,3-butadiene, 2- (N, N-dimethylamino) -1,3-butadiene, N- (2-methylene-3-butenoyl) morpholine, isoprene, pentadiene, chloride Vinyl, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl propionate, maleic anhydride, citraconic anhydride, itaconic anhydride, maleic acid, maleic acid ester, fumaric acid ester, crotonic acid, itaconic acid, fumaric acid, methacrylate Roxyxypropyltrimethoxysilane, acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, diacetone methacrylate, vinyl sulfonic acid, 2-acrylamido-1-methyl sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid Etc. Can be, for obtaining a uniform coating, with respect to 100 parts by weight of vinyl chloride polymer, preferably 1 to 200 parts by weight as required, and more preferably may be added at a ratio of 5 to 150 parts by weight.

  As a method for adding the monomer represented by the general formulas (7), (8), (9), (10) and (11) and at least one monomer selected from methacrylic acid and acrylic acid Is usually performed by any one method of batch addition, intermittent addition, continuous addition, or a combination thereof. Further, the monomer can be added by emulsifying all or part of the monomer.

  To polymerize the monomer represented by the general formulas (7), (8), (9), (10) and (11) and at least one monomer selected from methacrylic acid and acrylic acid. Examples of the polymerization initiator used include water-soluble initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, and t-butyl hydroperoxide, 2,2′-azobisisobutyronitrile, 2, 2′-azobis-2-methylbutyronitrile, lauroyl peroxide, t-butyl peroxypivalate, diacyl peroxide, peroxy ester, peroxydicarbonate, and other oil-soluble initiators, and the like. In some cases, a polymerization is initiated by adding a reducing agent such as ferrous salt such as ferrous sulfate, sodium hydrosulfite, or L-alcorbic acid. . The addition method of the polymerization initiator used at this time is usually one of batch addition, intermittent addition, continuous addition, or a combination thereof. In the production method of the present invention, a mixture of the above monomer and, if necessary, a molecular weight regulator can be used. As the molecular weight regulator, alkyl mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan are usually used.

  The emulsifier used when polymerizing the monomer is not particularly limited, and examples thereof include alkyl benzene sulfonic acids such as sodium dodecyl benzene sulfonate, potassium dodecyl benzene sulfonate, ammonium dodecyl benzene sulfonate, and sodium lauryl sulfate. Anionic surfactants such as alkyl sulfates such as sodium myristyl sulfate, sodium dioctyl sulfosuccinate, sulfosuccinates such as sodium dihexyl sulfosuccinate, polyoxyethylene alkyl sulfates, polyoxyethylene alkylaryl sulfates, Sorbitan esters such as sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene alkylphenyl ethers, polyoxyethylene Nonions such as ethylene alkyl esters, polyoxyethylene alkyl ethers such as polyoxyethylene alkyl ether, polyalkylene glycols, polyvinyl alcohol, partially saponified polyvinyl alcohol, partially saponified polymethyl methacrylate, polyacrylic acid and salts thereof And surface active agents. These may be used alone or in combination of two or more. As the addition method, it is usually performed by any one of batch addition, intermittent addition, continuous addition, or a combination thereof.

  The polymerization temperature is not particularly limited, but is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.

  The polymerization time is not particularly limited, but is preferably 3 to 24 hours.

  The polymerization is completed by cooling the reaction solution. In some cases, a polymerization inhibitor may be added to terminate the polymerization.

  When producing a vinyl chloride polymer latex composition, chain transfer agents, reducing agents, buffering agents, thickeners, condensed phosphates, dispersants, adhesives are used to stabilize the polymerization and reduce the amount of scale generated. An imparting agent, a pH adjusting agent, an antifoaming agent, a preservative, a film-forming aid, an anti-aging agent, an antifreezing agent and the like can also be added.

  The receiving layer of the heat-sensitive sublimation type transfer image-receiving sheet of the present invention can be formed by applying and drying the vinyl chloride polymer latex composition on the sheet. When the vinyl chloride polymer latex composition is applied and dried on a sheet, it may be performed only with the vinyl chloride polymer latex composition or with other vinyl chloride polymer latex compositions.

  The receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention formed using a vinyl chloride polymer latex composition contains a vinyl chloride polymer. The vinyl chloride polymer contains a vinyl chloride polymer having an average degree of polymerization of 400 to 2000, and the general formulas (1) and (2) with respect to 100 parts by weight of the vinyl chloride polymer. 1 to 300 parts by weight of a polymer having at least one repeating unit represented by any one of (3), (4), (5) and (6), and an organic compound having a sulfonate or sulfate ester salt of 1.0 to 5 0.05 part by weight, 0.05 to 2.5 parts by weight of higher fatty acid salt and 10 parts by weight or less of emulsifier. The explanation regarding these is the same as described above.

  The heat-sensitive sublimation transfer image-receiving sheet of the present invention has the advantage that printing is clearer than conventional heat-sublimation transfer image-receiving sheets and there is less bleeding.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.

  Various methods for evaluating a vinyl chloride copolymer latex for forming a heat-sensitive sublimation transfer image-receiving sheet, an image formation test method, and a receptor layer of the heat-sublimation transfer image-receiving sheet are as follows.

<Method for producing heat-sensitive sublimation transfer image-receiving sheet>
The vinyl chloride polymer latex composition was diluted with water to adjust the solid content to 30% by weight. Next, wallpaper backing paper (manufactured by Nippon Paper Industries Co., Ltd.) was fixed on a flat metal plate. A latex composition having a solid content adjusted to 30% by weight was poured on the upper surface of the backing paper for wallpaper, and coated with a bar coater to a thickness of 20 μm. After coating, the wallpaper backing paper was dried for 24 hours at room temperature to prepare a heat-sensitive sublimation transfer image-receiving sheet.

<Image formation test method>
After confirming that the heat-sensitive sublimation transfer image-receiving sheet prepared using the wallpaper backing paper was dry, cut the wallpaper backing paper to the same size as the paper KL-361P (color ink / paper set manufactured by Canon Inc.). The backing paper for wallpaper was pasted on the printed surface of -361P with double-sided tape.

  The paper was set in a paper cassette of SELPHY CP-800 (manufactured by Canon Inc., sublimation type thermal transfer printer) so that the surface coated with the test latex became the printing surface, and printing was performed with SELPHY CP-800. The image formability was determined as follows based on the sharpness of printing and the degree of bleeding.

    5: Printing is clear and no bleeding is observed.

    4: Slight bleeding is observed.

    3: The print contents can be understood but the color is light.

    2: The color is thin and the printed content is unknown.

    1: Not printed.

<Cracks during image formation>
Whether or not there was a crack in the image printed by the image formation test method was visually observed and judged as follows.

    5: There is no crack in the entire image.

    4: There is no crack more than 2/3 of the printed area.

    3: There is a crack of 1/2 or more of the printed area.

    2: There is a crack of 2/3 or more of the printed area.

    1: There is a crack in the entire image.

<Storage stability>
The vinyl chloride polymer latex composition was diluted with water to adjust the solid content to 30% by weight. 500 g of this vinyl chloride polymer latex composition was placed in a transparent glass bottle and allowed to stand at room temperature for 2 weeks. The presence or absence of precipitates in the latex composition was visually confirmed and evaluated as follows.

    ○: No sediment is generated.

    Δ: Slightly generated sediment was observed.

    X: Generation of a large amount of sediment was observed.

<Average particle size>
The average particle size was determined by measuring the particle size distribution using a particle size distribution measuring machine (Microtrac UPA150, manufactured by Nikkiso Co., Ltd.) to obtain the median particle size.

<Average polymerization degree>
After drying the vinyl chloride polymer latex, 5 times the amount of methanol is stirred and added to the THF solution to precipitate the vinyl chloride polymer, and after filtration and drying, the K value is measured according to JIS K7367-2. The average degree of polymerization was calculated.

<Production stability (foaming property)>
The foaming property of the reaction liquid during the production of the vinyl chloride polymer latex composition was visually confirmed and evaluated as follows.

    ○: Slightly foamed.

    Δ: Foaming occurs, but the liquid level can be visually confirmed.

    X: Foaming is severe and the liquid level cannot be visually confirmed.

<Manufacturing stability (scale generation rate)>
The scale generation rate was used as an evaluation of the amount of precipitate produced during the production of the vinyl chloride polymer latex composition.

<Film stability>
The vinyl chloride polymer latex composition was coated on a PET film to a thickness of 20 μm with a bar coater. Furthermore, it dried at 110 degreeC * 30 second, and the state of the obtained coating film was confirmed visually.

○: No coating unevenness Δ: Some coating unevenness ×: Coating unevenness <Amount of sodium dodecylbenzenesulfonate and potassium laurate in vinyl chloride polymer latex>
The vinyl chloride polymer latex after completion of the polymerization is collected from the polymerization vessel, the polymerization conversion rate of the vinyl monomer is obtained by measuring the solid content after vacuum drying at 40 ° C. for 24 hours, and the amount of sodium dodecylbenzenesulfonate in the polymer from the charged composition And the amount of potassium laurate was calculated | required.

<Amount of polymer in shell portion in vinyl chloride polymer latex composition>
For butyl acrylate, glycidyl acrylate, 2-hydroxyethyl methacrylate, and ethyl acrylate, DB-5 (manufactured by Agilent Technologies) is used as a column in gas chromatography GC-14A (Shimadzu Corporation). Used and determined from the monomer conversion. About acrylic acid, it calculated | required from the monomer conversion rate using Inertsil ODS-3 for the column with the liquid chromatography.

<Amount of emulsifier in the vinyl chloride polymer latex composition>
After obtaining the monomer conversion rate by gas chromatography and liquid chromatography, the solid content obtained by the same operation as the measurement of sodium dodecylbenzenesulfonate amount and potassium laurate amount in the vinyl chloride polymer latex Obtained from measurement.

Synthesis example 1
As shown in Table 1, 830.0 g of deionized water, 750.0 g of vinyl chloride monomer, 6.8 g of 3 wt% potassium persulfate and 75.0 g of 5 wt% aqueous sodium dodecylbenzenesulfonate in a 2.5 L autoclave (monomer The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and emulsion polymerization proceeded. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, the polymerization was stopped, unreacted vinyl chloride monomer was recovered, and 270.0 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 to the monomer). Parts by weight) and 46.0 g of a 5% by weight aqueous potassium laurate solution (0.34 parts by weight with respect to the monomer) were added to obtain a vinyl chloride polymer latex (dodecylbenzenesulfonic acid with respect to 100 parts by weight of the vinyl chloride polymer). Amount of sodium: 2.56 parts by weight, amount of potassium laurate: 0.34 parts by weight, average particle size: 0.08 μm, average degree of polymerization: 750).

合成例２〜３
表１に示す通り、ドデシルベンゼンスルホン酸ナトリウム量を変えた以外は合成例１と同様の操作で、塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量及びラウリン酸カリウムの量、平均粒子径、平均重合度を表１に示す）。

Synthesis Examples 2-3
As shown in Table 1, a vinyl chloride polymer latex was obtained in the same manner as in Synthesis Example 1 except that the amount of sodium dodecylbenzenesulfonate was changed (the amount of sodium dodecylbenzenesulfonate relative to 100 parts by weight of the vinyl chloride polymer). And the amount of potassium laurate, the average particle diameter, and the average degree of polymerization are shown in Table 1).

Synthesis Examples 4-5
As shown in Table 1, a vinyl chloride polymer latex was obtained in the same manner as in Synthesis Example 1 except that the amount of potassium laurate was changed (the amount of sodium dodecylbenzenesulfonate and laurin relative to 100 parts by weight of the vinyl chloride polymer). The amount of potassium acid, the average particle diameter, and the average degree of polymerization are shown in Table 1).

合成例６
表２に示す通り、重合温度を７０℃に変更し、ドデシルメルカプタンを０．７５ｇ仕込んだ以外は合成例１と同様の操作で、塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量及びラウリン酸カリウムの量、平均粒子径、平均重合度を表２に示す）。

Synthesis Example 6
As shown in Table 2, a vinyl chloride polymer latex was obtained in the same manner as in Synthesis Example 1 except that the polymerization temperature was changed to 70 ° C. and 0.75 g of dodecyl mercaptan was added (100 parts by weight of vinyl chloride polymer). Table 2 shows the amount of sodium dodecylbenzenesulfonate and the amount of potassium laurate, the average particle diameter, and the average degree of polymerization with respect to the above).

Synthesis example 7
As shown in Table 2, a vinyl chloride polymer latex was obtained in the same manner as in Synthesis Example 1 except that the polymerization temperature was changed to 45 ° C (the amount of sodium dodecylbenzenesulfonate relative to 100 parts by weight of the vinyl chloride polymer and The amount of potassium laurate, the average particle size, and the average degree of polymerization are shown in Table 2).

Comparative Synthesis Example 1
<Preparation of vinyl chloride polymer latex by fine suspension polymerization method>
A 1 m ³ autoclave was charged with 360.0 kg of deionized water, 300.0 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide, and 30.0 kg of a 15 wt% sodium dodecylbenzenesulfonate aqueous solution, and this polymerization solution was used for 3 hours using a homogenizer. After the homogenization treatment, the temperature was raised to 45 ° C. to proceed the polymerization. After the pressure has dropped, the polymerization is stopped, the unreacted vinyl chloride monomer is recovered, the solid content 35% by weight particles have an average particle size of 0.55 μm, and the polymer has an excess of 2% by weight. A seed latex 1 containing lauroyl oxide was obtained.

In a 2.5 L autoclave, 500 g of deionized water, 500.0 g of vinyl chloride monomer, 16.0 g of 5 wt% sodium lauryl sulfate aqueous solution, 95.0 g of seed latex 1 and 4.0 g of 0.1 wt% copper sulfate aqueous solution The temperature of the charged reaction mixture was raised to 48 ° C., and 150.0 g of 0.05 wt% aqueous ascorbic acid solution was continuously added throughout the entire polymerization time. Further, 0.7 parts by weight of sodium lauryl sulfate was continuously added to 100 parts by weight of the vinyl chloride monomer from the start of the polymerization to a polymerization conversion rate of 85%. The polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of vinyl chloride at 48 ° C. by 2 kg / cm ² , and the unreacted vinyl chloride monomer was recovered, and 46.0 g of 5 wt% aqueous potassium laurate solution (0% relative to the monomer). .46 parts by weight) was added to obtain a vinyl chloride polymer latex (amount of sodium dodecylbenzenesulfonate with respect to 100 parts by weight of vinyl chloride polymer: 0.12 parts by weight, amount of potassium laurate: 0.50 parts by weight). Part, average particle size: 1.52 μm, average degree of polymerization: 1400).

Comparative Synthesis Examples 2-6
As shown in Table 3, a vinyl chloride polymer latex was obtained in the same manner as in Synthesis Example 1 except that the amount of sodium dodecylbenzenesulfonate and the amount of potassium laurate were changed (dodecylbenzene with respect to 100 parts by weight of the vinyl chloride polymer). The amount of sodium sulfonate, the amount of potassium laurate, the average particle size, and the average degree of polymerization are shown in Table 3).

比較合成例７
表４に示す通り、重合温度を９０℃に変更し、ドデシルメルカプタンを７．５０ｇ仕込んだ以外は合成例１と同様の操作で、塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量及びラウリン酸カリウムの量、平均粒子径、平均重合度を表４に示す）。

Comparative Synthesis Example 7
As shown in Table 4, a vinyl chloride polymer latex was obtained in the same manner as in Synthesis Example 1 except that the polymerization temperature was changed to 90 ° C. and 7.50 g of dodecyl mercaptan was added (100 parts by weight of vinyl chloride polymer). Table 4 shows the amount of sodium dodecylbenzenesulfonate and the amount of potassium laurate, the average particle size, and the average degree of polymerization with respect to the above).

比較合成例８
表４に示す通り、重合温度を５℃に変更し、重合中にピロ亜硫酸カリウムの１０重量％水溶液３．５８ｇを連続添加した以外は、合成例１と同様の操作で、塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量及びラウリン酸カリウムの量、平均粒子径、平均重合度を表４に示す）。

Comparative Synthesis Example 8
As shown in Table 4, the polymerization temperature was changed to 5 ° C., and a vinyl chloride polymer latex was prepared in the same manner as in Synthesis Example 1 except that 3.58 g of a 10% by weight aqueous solution of potassium pyrosulfite was continuously added during the polymerization. (The amount of sodium dodecylbenzenesulfonate, the amount of potassium laurate, the average particle size, and the average degree of polymerization are shown in Table 4 with respect to 100 parts by weight of the vinyl chloride polymer).

Production Example 1
As shown in Table 5, 67.6 g of vinyl chloride polymer latex and 164.1 g of deionized water were added to a 0.5 L separable flask in a nitrogen atmosphere using the vinyl chloride polymer latex obtained in Synthesis Example 1. First, the internal temperature was raised to 60 ° C., followed by continuous addition of a mixture of 12.5 g of butyl acrylate and 0.125 g of dodecyl mercaptan (continuous addition during polymerization-1), and simultaneously 0.14 g of ammonium persulfate as an emulsifier 0.1 g of sodium lauryl sulfate and 20.0 g of deionized water were continuously added (continuous addition during polymerization-2), and after the reaction for 6 hours, the reaction solution was cooled to obtain a vinyl chloride polymer latex composition. (Average particle diameter: 0.09 μm). Table 5 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. Foamability during the reaction was good, almost no scale was generated, and storage stability and coating film stability were also good.

製造例２〜５
表５に示す通り、合成例１で得られた塩化ビニル系ポリマーラテックスを合成例２〜合成例５で得られた塩化ビニル系ポリマーラテックスに変えた以外は製造例１と同様の操作で、塩化ビニル系重合体ラテックス組成物を得た。得られた塩化ビニル系重合体ラテックス組成物の平均粒子径、製造安定性、製造後の状態、貯蔵安定性、塗膜安定性を表５に示す。表５の結果から、本発明での塩化ビニル系重合体ラテックス組成物は製造後に沈殿物が生成せず、泡立ち性に優れ、均一な塗膜が得られ、貯蔵安定性、塗膜安定性に優れていた。

Production Examples 2-5
As shown in Table 5, the vinyl chloride polymer latex obtained in Synthesis Example 1 was replaced with the vinyl chloride polymer latex obtained in Synthesis Examples 2 to 5, and the same procedure as in Production Example 1 was followed. A vinyl polymer latex composition was obtained. Table 5 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results of Table 5, the vinyl chloride polymer latex composition according to the present invention does not produce a precipitate after production, has excellent foaming properties, a uniform coating film is obtained, and has storage stability and coating film stability. It was excellent.

Production Example 6
A vinyl chloride polymer latex composition was obtained in the same manner as in Production Example 1, except that the changes were made as shown in Table 5. Table 5 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results of Table 5, the vinyl chloride polymer latex composition according to the present invention does not produce a precipitate after production, has excellent foaming properties, a uniform coating film is obtained, and has storage stability and coating film stability. It was excellent.

Production Examples 7 to 11
A vinyl chloride polymer latex composition was obtained in the same manner as in Production Example 1, except that the changes were made as shown in Table 6. Table 6 shows the average particle diameter, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results of Table 6, the vinyl chloride polymer latex composition according to the present invention does not produce a precipitate after production, has excellent foaming properties, and a uniform coating film is obtained. Storage stability, coating film stability, It was excellent.

製造例１２〜１４
表７に示す通りに変更した以外は製造例１と同様の操作で、塩化ビニル系重合体ラテックス組成物を得た。得られた塩化ビニル系重合体ラテックス組成物の平均粒子径、製造安定性、製造後の状態、貯蔵安定性、塗膜安定性を表７に示す。表７の結果から、本発明での塩化ビニル系重合体ラテックス組成物は製造後に沈殿物が生成せず、泡立ち性に優れ、均一な塗膜が得られ、貯蔵安定性、塗膜安定性に優れていた。

Production Examples 12-14
A vinyl chloride polymer latex composition was obtained in the same manner as in Production Example 1, except that the changes were made as shown in Table 7. Table 7 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results of Table 7, the vinyl chloride polymer latex composition of the present invention does not produce a precipitate after production, has excellent foaming properties, and a uniform coating film is obtained, with storage stability and coating film stability. It was excellent.

製造例１５
表７に示す通りに変更し、ラウリル硫酸ナトリウムの代わりに乳化剤としてポリオキシエチレンアルキルエーテル（花王製、エマルゲン１１０８）を用いた以外は製造例１と同様の操作で、塩化ビニル系重合体ラテックス組成物を得た。得られた塩化ビニル系重合体ラテックス組成物の平均粒子径、製造安定性、製造後の状態、貯蔵安定性、塗膜安定性を表７に示す。表７の結果から、本発明での塩化ビニル系重合体ラテックス組成物は製造後に沈殿物が生成せず、泡立ち性に優れ、均一な塗膜が得られ、貯蔵安定性、塗膜安定性に優れていた。

Production Example 15
The vinyl chloride polymer latex composition was changed in the same manner as in Production Example 1 except that polyoxyethylene alkyl ether (Kao, Emulgen 1108) was used as an emulsifier instead of sodium lauryl sulfate. I got a thing. Table 7 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results of Table 7, the vinyl chloride polymer latex composition of the present invention does not produce a precipitate after production, has excellent foaming properties, and a uniform coating film is obtained, with storage stability and coating film stability. It was excellent.

Comparative production example 1
As shown in Table 8, 67.6 g of vinyl chloride polymer latex and 164.1 g of deionized water were placed in a 0.5 L separable flask in a nitrogen atmosphere using the vinyl chloride polymer latex obtained in Comparative Synthesis Example 1. The internal temperature was raised to 60 ° C., followed by continuous addition of a mixture of 12.5 g of butyl acrylate and 0.125 g of dodecyl mercaptan, and at the same time 0.14 g of ammonium persulfate, 0.1 g of sodium lauryl sulfate, deionized water 20.0 g was continuously added (continuous addition during polymerization-2), and after the reaction for 6 hours, the reaction solution was cooled to obtain a vinyl chloride polymer latex composition (average particle size: 1.53 μm). Table 8 shows the average particle diameter, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. Although the foaming property during the reaction was good, a large amount of scale was generated, and there were many precipitates, so the coating film stability could not be measured. A large amount of sediment was observed (storage stability).

比較製造例２
表８に示す通り、比較合成例２で得られた塩化ビニル系ポリマーラテックスを用いた以外は比較製造例１と同様の操作で、塩化ビニル系重合体ラテックス組成物を得た（平均粒子径：０．１８μｍ）。得られた塩化ビニル系重合体ラテックス組成物の平均粒子径、製造安定性、製造後の状態、貯蔵安定性、塗膜安定性を表８に示す。反応中の発泡が多く、スケールが発生し、沈殿物が多く、得られた塩化ビニル系重合体ラテックス組成物の塗膜安定性は実施例に対し劣り、多量の沈降物の発生が見られた（貯蔵安定性）。

Comparative production example 2
As shown in Table 8, a vinyl chloride polymer latex composition was obtained in the same manner as in Comparative Production Example 1 except that the vinyl chloride polymer latex obtained in Comparative Synthesis Example 2 was used (average particle size: 0.18 μm). Table 8 shows the average particle diameter, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. There was much foaming during the reaction, scale was generated, there were many precipitates, and the coating stability of the obtained vinyl chloride polymer latex composition was inferior to that of the examples, and a large amount of precipitates was observed. (Storage stability).

Comparative production example 3
As shown in Table 8, a vinyl chloride polymer latex composition was obtained in the same manner as in Comparative Production Example 1 except that the vinyl chloride polymer latex obtained in Comparative Synthesis Example 3 was used (average particle size: 0.08 μm). Table 8 shows the average particle diameter, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. There was much foaming during the reaction. Although the coating stability of the obtained vinyl chloride polymer latex composition was good, slight precipitation was observed (storage stability).

Comparative production example 4
As shown in Table 8, a vinyl chloride polymer latex composition was obtained in the same manner as in Comparative Production Example 1 except that the vinyl chloride polymer latex obtained in Comparative Synthesis Example 4 was used (average particle size: 0.10 μm). Table 8 shows the average particle diameter, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. The foaming property during the reaction was good, but scale was generated and there were many precipitates. Although the coating stability of the obtained vinyl chloride polymer latex composition was good, a large amount of precipitate was observed (storage stability).

Comparative Production Example 5
As shown in Table 8, a vinyl chloride polymer latex composition was obtained in the same manner as in Comparative Production Example 1 except that the vinyl chloride polymer latex obtained in Comparative Synthesis Example 5 was used (average particle size: 0.09 μm). Table 8 shows the average particle diameter, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. Some bubbling occurred during the reaction. Although the coating stability of the obtained vinyl chloride polymer latex composition was good, slight precipitation was observed (storage stability).

Comparative Production Example 6
As shown in Table 9, a vinyl chloride polymer latex composition was obtained in the same manner as in Comparative Production Example 1 except that the vinyl chloride polymer latex obtained in Comparative Synthesis Example 6 was used (average particle size: 0.33 μm). Table 9 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. There was much foaming during the reaction, scale was generated, and there were many precipitates. The film stability of the obtained vinyl chloride polymer latex composition was inferior, and a large amount of precipitate was observed (storage stability).

比較製造例７
表９に示す通り、合成例１で得られた塩化ビニル系ポリマーラテックスを用いて、アクリル酸ブチルをメタクリル酸メチルに変更した以外は比較製造例１と同様の操作で、塩化ビニル系重合体ラテックス組成物を得た（平均粒子径：０．０９μｍ）。得られた塩化ビニル系重合体ラテックス組成物の平均粒子径、製造安定性、製造後の状態、貯蔵安定性、塗膜安定性を表９に示す。反応中の泡立ち性は良好であったが、沈殿物が多かった。得られた塩化ビニル系重合体ラテックス組成物の塗膜安定性は実施例に対し劣り、多量の沈降物の発生が見られた（貯蔵安定性）。

Comparative Production Example 7
As shown in Table 9, a vinyl chloride polymer latex was prepared in the same manner as in Comparative Production Example 1, except that the vinyl chloride polymer latex obtained in Synthesis Example 1 was used and the butyl acrylate was changed to methyl methacrylate. A composition was obtained (average particle size: 0.09 μm). Table 9 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. The foaming property during the reaction was good, but there were many precipitates. The film stability of the obtained vinyl chloride polymer latex composition was inferior to that of the Examples, and a large amount of precipitate was observed (storage stability).

Comparative Production Example 8
As shown in Table 9, a vinyl chloride polymer latex composition was obtained in the same manner as in Comparative Production Example 1 except that the vinyl chloride polymer latex obtained in Comparative Synthesis Example 7 was used (average particle size: 0.09 μm). Table 9 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. The foaming property during the reaction was good, but there were many precipitates. The obtained vinyl chloride polymer latex composition was inferior in coating film stability, and a large amount of precipitate was observed (storage stability).

Comparative production example 9
As shown in Table 9, a vinyl chloride polymer latex composition was obtained in the same manner as in Comparative Production Example 1 except that the vinyl chloride polymer latex obtained in Comparative Synthesis Example 8 was used (average particle size: 0.12 μm). Table 9 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. The foaming property during the reaction was good, but there were many precipitates. The film stability of the obtained vinyl chloride polymer latex composition was inferior, and a large amount of precipitate was observed (storage stability).

Comparative production example 10
As shown in Table 10, a vinyl chloride polymer latex composition was prepared in the same manner as in Comparative Production Example 1, except that the amount of butyl acrylate was further changed using the vinyl chloride polymer latex obtained in Synthesis Example 1. A product was obtained (average particle size: 0.13 μm). Table 10 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. The production stability during the reaction was good. Although the coating stability of the obtained vinyl chloride polymer latex composition was good, slight precipitation was observed (storage stability).

比較製造例１１
表１０に示す通り、合成例１で得られた塩化ビニル系ポリマーラテックスを用いて、さらにアクリル酸ブチルの量を変更した以外は比較製造例１と同様の操作で、塩化ビニル系重合体ラテックス組成物を得た（平均粒子径：０．０８μｍ）。得られた塩化ビニル系重合体ラテックス組成物の平均粒子径、製造安定性、製造後の状態、貯蔵安定性、塗膜安定性を表１０に示す。得られた塩化ビニル系重合体ラテックス組成物の塗膜安定性は良好であり、沈降物の発生が全く無かった（貯蔵安定性）。

Comparative Production Example 11
As shown in Table 10, a vinyl chloride polymer latex composition was prepared in the same manner as in Comparative Production Example 1, except that the amount of butyl acrylate was further changed using the vinyl chloride polymer latex obtained in Synthesis Example 1. A product was obtained (average particle size: 0.08 μm). Table 10 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. The obtained vinyl chloride polymer latex composition had good coating film stability, and no precipitate was generated (storage stability).

Comparative Production Example 12
As shown in Table 10, a vinyl chloride polymer latex composition was prepared in the same manner as in Comparative Production Example 1 except that the amount of sodium lauryl sulfate was changed using the vinyl chloride polymer latex obtained in Synthesis Example 1. A product was obtained (average particle size: 0.09 μm). Table 10 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. There was much foaming during the reaction. Although the coating stability of the obtained vinyl chloride polymer latex composition was good, slight precipitation was observed (storage stability).

Example 1
Using the vinyl chloride polymer latex composition prepared in Production Example 1, a heat-sensitive sublimation type transfer image-receiving sheet was prepared, and when the image formation was judged by the sharpness of printing and the degree of bleeding, the printing was clear. No bleeding was observed, and the result was good (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 2
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 2, and an image formation test was performed. The printing was clear and no bleeding was observed at all. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 3
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 3 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 4
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 4 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed at all. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 5
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 5, and an image formation test was conducted. The printing was clear and no bleeding was observed at all. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 6
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 6 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 7
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 7, and an image formation test was performed. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 8
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 8 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 9
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 9 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 10
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 10 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 11
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 11 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed at all. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 12
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 12 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 13
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 13 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 14
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 14 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Example 15
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Production Example 15 and subjected to an image formation test. As a result, printing was clear and no bleeding was observed. Result (score 5). Further, when cracks were confirmed during image formation, no cracks were found (score 5).

Comparative Example 1
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 1 and an image formation test was conducted. there were. Further, when cracks were confirmed during image formation, no cracks were found that were more than ½ of the printed area (score 3).

Comparative Example 2
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 2 and an image formation test was conducted. Met. Further, when cracks were confirmed during image formation, cracks were found in 2/3 or more of the printed area (2 points).

Comparative Example 3
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 3, and an image formation test was performed. Further, when cracks during image formation were confirmed, there were cracks in the entire image (score 1).

Comparative Example 4
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 4 and subjected to an image formation test. Met. Further, when cracks were confirmed during image formation, cracks were found in 2/3 or more of the printed area (2 points).

Comparative Example 5
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 5, and an image formation test was conducted. there were. Further, when cracks were confirmed during image formation, cracks were found in 2/3 or more of the printed area (2 points).

Comparative Example 6
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 6, and an image formation test was conducted. there were. Further, when cracks were confirmed during image formation, cracks were found in 2/3 or more of the printed area (2 points).

Comparative Example 7
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 7, and an image formation test was conducted. Further, when cracks were confirmed during image formation, cracks were found in half or more of the printed area (score 3).

Comparative Example 8
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 8, and an image formation test was conducted. Further, when cracks during image formation were confirmed, there were cracks in the entire image (score 1).

Comparative Example 9
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 9, and an image formation test was performed. Further, when cracks during image formation were confirmed, there were cracks in the entire image (score 1).

Comparative Example 10
A heat-sensitive sublimation transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 10, and an image formation test was conducted. Met. Further, when cracks were confirmed during image formation, cracks were found in 2/3 or more of the printed area (2 points).

Comparative Example 11
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 11, and an image formation test was performed. there were. Further, when cracks were confirmed during image formation, cracks were found in 2/3 or more of the printed area (2 points).

Comparative Example 12
A heat-sensitive sublimation type transfer image-receiving sheet was prepared using the vinyl chloride polymer latex composition prepared in Comparative Production Example 12, and an image formation test was performed. there were. Further, when cracks were confirmed during image formation, cracks were found in 2/3 or more of the printed area (2 points).

Claims (4)

A heat-sensitive sublimation type transfer image-receiving sheet comprising at least a support and a receiving layer containing a vinyl chloride polymer, wherein the vinyl chloride polymer forms a core portion and an outer layer of the core portion. A shell portion, the core portion is a vinyl chloride polymer having an average particle size of 0.12 μm or less and an average degree of polymerization of 400 to 2000, and the shell portion is 100 parts by weight of the vinyl chloride polymer. On the other hand, 1 to 300 parts by weight of a polymer having at least one repeating unit represented by the following general formulas (1), (2), (3), (4), (5) and (6), Furthermore, it contains 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 2.5 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer. And the vinyl chloride 10 parts by weight or less of an emulsifier with respect to 100 parts by weight of the polymer, the average particle size of the vinyl chloride polymer is 0.30 μm or less, and the vinyl chloride polymer latex composition of the vinyl chloride polymer A heat-sensitive sublimation type transfer image-receiving sheet , wherein a receptor layer is formed using

(In the formula, R ₁ represents an alkyl group having 2 to 8 carbon atoms, and R ₂ represents hydrogen or a methyl group.)

(In the formula, R ₃ represents an alkylene group having 1 to ₄ carbon atoms, R ₄ represents an alkyl group or alkoxylalkyl group having 1 to ₄ carbon atoms, or hydrogen, and R ₅ represents hydrogen or a methyl group.)

(In the formula, R ₆ represents a methyl group or an ethyl group.)

(Wherein R ₇ represents hydrogen or a methyl group.)

(In the formula, R ₈ represents hydrogen or a methyl group.)

(In the formula, R ₉ represents hydrogen or a methyl group.) The vinyl chloride polymer latex composition comprises 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 2 parts of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer. 100 parts by weight of a vinyl chloride polymer in the latex in the presence of a vinyl chloride polymer latex having an average particle size of 0.12 μm or less and an average degree of polymerization of 400 to 2000. In contrast, the monomer represented by the following general formulas (7), (8), (9), (10) and (11), and at least one monomer selected from methacrylic acid and acrylic acid The heat-sensitive sublimation transfer image-receiving sheet according to claim 1 , which is obtained by adding 1 to 300 parts by weight of a body and 10 parts by weight or less of an emulsifier and polymerizing the same .

(In the formula, R ₉ represents an alkyl group having 2 to 8 carbon atoms, and R ₁₀ represents hydrogen or a methyl group.)

(In the formula, R ₁₁ represents an alkylene group having 1 to 4 carbon atoms, R ₁₂ represents an alkyl group or alkoxylalkyl group having 1 to 4 carbon atoms, or hydrogen, and R ₁₃ represents hydrogen or a methyl group.)

(In the formula, R ₁₄ represents a methyl group or an ethyl group.)

(In the formula, R ₁₅ represents hydrogen or a methyl group.)

(In the formula, R ₁₆ represents hydrogen or a methyl group.) The organic compound having a sulfonate or sulfate ester salt is a salt of an organic compound having a sulfonic acid or sulfate ester and any of potassium, sodium, ammonia, and triethanolamine. Item 3. The heat-sensitive sublimation transfer image-receiving sheet according to Item 2 . The heat-sensitive sublimation transfer image-receiving sheet according to any one of claims 1 to 3 , wherein the higher fatty acid salt is a salt of higher fatty acid with any of potassium, sodium, ammonia, and triethanolamine. .