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WO2013061994A1 - Heat-sensitive sublimation transfer image receiving sheet - Google Patents

Heat-sensitive sublimation transfer image receiving sheet Download PDF

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Publication number
WO2013061994A1
WO2013061994A1 PCT/JP2012/077448 JP2012077448W WO2013061994A1 WO 2013061994 A1 WO2013061994 A1 WO 2013061994A1 JP 2012077448 W JP2012077448 W JP 2012077448W WO 2013061994 A1 WO2013061994 A1 WO 2013061994A1
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WIPO (PCT)
Prior art keywords
weight
parts
vinyl chloride
heat
transfer image
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Ceased
Application number
PCT/JP2012/077448
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French (fr)
Japanese (ja)
Inventor
和徳 渡邉
佐藤　保
伊藤　信行
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Tosoh Corp
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Tosoh Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/32—Thermal receivers

Definitions

  • the present invention relates to a heat-sensitive sublimation transfer image-receiving sheet, and more particularly to a heat-sensitive sublimation transfer image-receiving sheet having a receiving layer containing a vinyl chloride copolymer and capable of forming an excellent image.
  • the thermal transfer method a thermal sublimation transfer method and a thermal fusion transfer method are widely used.
  • the heat-sensitive sublimation transfer method uses a sublimable dye as a colorant, and uses a heating device such as a thermal head or laser light whose heat is controlled in accordance with 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.
  • a heat-sensitive transfer image-receiving sheet has at least a heat insulating layer and a dye image-receiving layer (receiving layer) formed on a support.
  • the resin for forming the receiving layer vinyl chloride resin is used because it has excellent dye dyeing and releasability, and abnormal transfer such as fusion does not occur between the thermal transfer sheet and the thermal transfer image-receiving sheet during thermal transfer.
  • 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.
  • Patent Documents 1 and 2 a method of forming a receiving layer using vinyl chloride resin latex without using an organic solvent has been widely studied.
  • Patent Documents 1 and 2 the storage stability of the vinyl chloride resin latex used for forming the receiving layer is inferior, and satisfactory images cannot be obtained with the heat-sensitive sublimation transfer image receiving sheet using this vinyl chloride resin latex.
  • the present invention has been made in view of the above problems, and is to provide a heat-sensitive sublimation transfer image-receiving sheet having a receiving layer containing a novel vinyl chloride copolymer capable of forming an excellent image.
  • an organic compound having a sulfonate or sulfate ester salt of 0.20 to 100 parts by weight per 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer It was prepared using an organic compound having a sulfonate or sulfate ester salt during polymerization and a latex to which a higher fatty acid salt was added so as to be 10.0 parts by weight and 0.05 to 3.0 parts by weight of a higher fatty acid salt.
  • the heat-sensitive sublimation type transfer image-receiving sheet has been found to be capable of excellent image formation, leading to the present invention.
  • the present invention is a heat-sensitive sublimation type transfer image-receiving sheet comprising at least a support and a receiving layer, and the receiving layer is based on 100 parts by weight of a vinyl chloride-unsaturated carboxylic acid ester copolymer.
  • a thermosensitive material comprising a vinyl chloride copolymer containing 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 3.0 parts by weight of a higher fatty acid salt. It is a sublimation type transfer image receiving sheet.
  • the heat-sensitive sublimation transfer image-receiving sheet of the present invention has the advantage that printing is clearer than conventional heat-sensitive sublimation-type transfer image-receiving sheets and there is less bleeding.
  • 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).
  • a receiving layer is formed on the support, and 2) on the support.
  • Examples include a structure in which a heat insulating layer and a receiving layer are formed, and 3) an underlayer, a heat insulating layer, and a receiving layer are formed on a support.
  • the vinyl chloride copolymer contained in the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention (hereinafter sometimes simply referred to as vinyl chloride copolymer) is a vinyl chloride-unsaturated carboxylic acid ester copolymer. It contains 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 3.0 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of the combined body.
  • the vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention (hereinafter sometimes simply referred to as vinyl chloride copolymer latex) It contains 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 3.0 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of a saturated carboxylic acid ester copolymer. .
  • the vinyl chloride-unsaturated carboxylic acid ester copolymer is obtained by copolymerizing a vinyl chloride monomer and an unsaturated carboxylic acid ester monomer.
  • unsaturated carboxylic acid ester monomers include esters of acrylic acid such as methyl, ethyl, and butyl, esters of methyl methacrylate such as methyl, ethyl, and butyl, maleic acid esters, fumaric acid esters, and cinnamic acid esters. Two or more of these can be used.
  • Examples of the method for copolymerizing the vinyl chloride monomer and the unsaturated carboxylic acid ester monomer include emulsion polymerization, solution polymerization, and gas phase polymerization.
  • Examples of the organic compound having a sulfonate include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate; dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate; and alkylnaphthalenesulfonic acid.
  • Alkyl naphthalene sulfonates such as sodium
  • alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate and the like.
  • organic compounds having a sulfate ester salt examples include sodium lauryl sulfate and sodium myristyl sulfate.
  • the content of the organic compound having a sulfonate or sulfate ester salt is 0.20 to 10.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer.
  • the latex When the amount is less than 0.20 parts by weight, the latex is unstable due to inferior storage stability, and when it exceeds 10.0 parts by weight, it becomes an impurity of the vinyl chloride copolymer.
  • it is 1.0 to 5.0 parts by weight.
  • higher fatty acid salts include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and the like with alkalis.
  • a salt with potassium, sodium, ammonia, or triethanolamine is preferable because it is easily available.
  • the content of the higher fatty acid salt is 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. When it is less than 0.05 parts by weight, the pH of the vinyl chloride copolymer latex is lower than 3, and when it exceeds 3.0 parts by weight, the pH of the vinyl chloride copolymer latex is higher than 8.
  • the amount is preferably 0.1 to 1.0 part by weight.
  • the vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation type transfer image-receiving sheet of the present invention preferably has an average particle size of 0.14 ⁇ m or less in order to obtain good image quality.
  • the average particle diameter is more preferably 0.12 ⁇ m or less, particularly preferably 0.10 ⁇ m or less, and most preferably 0.05 to 0.10 ⁇ m.
  • the vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention has a pH of 3-8. If the pH deviates from 3 to 8, hydrolysis of the vinyl chloride-unsaturated carboxylic acid ester copolymer proceeds, the quality of the latex deteriorates, and there is a possibility that the heat-sensitive sublimation transfer image-receiving sheet may be affected by bleeding.
  • the vinyl chloride copolymer and the vinyl chloride copolymer latex may contain a chain transfer agent, a reducing agent, a buffering agent, an emulsifier other than the alkylbenzene sulfonate, and the like.
  • the vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention comprises a vinyl chloride monomer and an unsaturated carboxylic acid in the presence of a polymerization initiator using water as a dispersion medium.
  • a polymerization initiator using water as a dispersion medium.
  • the organic compound having a sulfonate salt or a sulfate ester salt is less than 0.05 parts by weight, the polymerization becomes unstable, and the average particle size of the obtained latex exceeds 0.14 ⁇ m. If it exceeds 3.0 parts by weight, foaming becomes a problem.
  • the higher fatty acid salt is less than 0.05 parts by weight, the pH during the polymerization is lowered, and even if added in excess of 1.0 part by weight, the effect is small.
  • the organic compound having a sulfonate salt or a sulfate ester salt is added as appropriate before, during or after the polymerization.
  • the higher fatty acid salt may be added before the start of polymerization, during the polymerization, or after the completion of the polymerization, and the higher fatty acid salt may be added sequentially or in divided additions during the polymerization. Among these, it is preferable to add the higher fatty acid salt sequentially or in divided additions, since the pH of the latex can be reduced to 3 to 8 with a small amount.
  • polymerization initiator examples include water-soluble initiators such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, lauroyl peroxide, Examples thereof include oil-soluble initiators such as t-butyl peroxypivalate, diacyl peroxide, peroxyester, and peroxydicarbonate.
  • 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 rate of the vinyl chloride monomer and the unsaturated carboxylic acid ester monomer is preferably 80 to 97% by weight based on the total monomers.
  • 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.
  • an alkylbenzenesulfonic acid sulfonate is added to the latex after completion of polymerization so that the latex contains 0.20 to 10.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. Additional additions can be made.
  • a higher fatty acid salt can be additionally added so as to contain 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer.
  • a chain transfer agent When producing a vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention, a chain transfer agent, a reducing agent for the purpose of stabilizing the polymerization and reducing the amount of scale generated, Buffering agents, emulsifiers other than alkylbenzene sulfonates, and the like can also be added.
  • a receiving layer of a heat-sensitive sublimation transfer image-receiving sheet can be formed by applying and drying vinyl chloride copolymer latex on the sheet. When applying and drying the vinyl chloride copolymer latex on the sheet, it may be performed only with the vinyl chloride copolymer latex or with other vinyl chloride copolymer latex.
  • ⁇ Method for producing heat-sensitive sublimation transfer image-receiving sheet> The vinyl chloride copolymer latex 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. Latex adjusted to a solid content of 30% by weight was poured onto the upper surface of the wallpaper backing paper, and coated with a bar coater to a thickness of about 20 ⁇ m. After coating, the wallpaper backing paper was dried for 24 hours at room temperature to prepare a heat-sensitive sublimation transfer image-receiving sheet.
  • ⁇ Storage stability of latex> The vinyl chloride copolymer latex was diluted with water to adjust the solid content to 30% by weight. 500 g of the adjusted vinyl chloride copolymer latex 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 was visually confirmed and evaluated as follows.
  • A There is no generation of sediment.
  • B Slight occurrence was observed.
  • C A large amount of sediment was observed.
  • ⁇ Average particle diameter of vinyl chloride copolymer latex> A sample for measurement in which the concentration of the vinyl chloride copolymer latex was adjusted by adding water so that the laser transmittance was 84 to 86% was measured using a laser diffraction / scattering particle size measuring device (trade name LA-920, Using a Horiba Seisakusho Co., Ltd.), the median diameter was measured and taken as the average particle diameter.
  • Synthesis example 1 In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C.
  • Synthesis example 2 A vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 except that 60 g of butyl acrylate monomer was added continuously over 300 minutes immediately after the start of emulsion polymerization (vinyl chloride-unsaturated carboxylic acid ester copolymer). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.56 parts by weight) with respect to 100 parts by weight of the polymer). It was in the range of pH 6.9 and pH 3 to 8, and the average particle diameter was measured and found to be 0.1 ⁇ m. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.
  • Synthesis example 3 In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 84 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and immediately after the start of polymerization, 24 g of a 5 wt% potassium laurate aqueous solution (0.20 parts by weight based on the monomer) was continuously added over 300 minutes. After the pressure in the autoclave at 66 ° C.
  • Synthesis example 4 A vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 3 except that 60 g of butyl acrylate monomer was added continuously over 300 minutes immediately after the start of emulsion polymerization (vinyl chloride-unsaturated carboxylic acid ester copolymer). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.56 parts by weight) with respect to 100 parts by weight of the polymer). It was in the range of pH 6.7 and pH 3 to 8, and the average particle diameter was measured and found to be 0.1 ⁇ m. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.
  • Synthesis example 5 The amount of 5 wt% potassium laurate aqueous solution added 60 minutes after the start of emulsion polymerization is reduced to 2.4 g (0.02 parts by weight based on the monomer), and finally 5 wt% potassium laurate aqueous solution is added. Except for this, a vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 (sodium dodecylbenzenesulfonate: 2.06 parts by weight, 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer, laurin) Acid potassium: 0.02 parts by weight). When the average particle diameter was measured, it was 0.1 ⁇ m, but it was a low pH of 2.2. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.
  • Synthesis Example 6 The amount of 5 wt% potassium laurate aqueous solution added 60 minutes after the start of emulsion polymerization was increased to 105.6 g (0.88 parts by weight with respect to the monomer), and finally added 5 wt% potassium laurate aqueous solution.
  • a vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 except that the amount of the polymer was increased to 184 g (1.53 parts by weight based on the monomer) (vinyl chloride-unsaturated carboxylic acid ester copolymer). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 3.41 parts by weight) with respect to 100 parts by weight of the polymer). When the average particle diameter was measured, it was 0.1 ⁇ m, but it was a high result of pH 8.4. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.
  • Synthesis example 7 The amount of 5% by weight sodium dodecylbenzenesulfonate aqueous solution added at the stage of preparation is reduced to 2.4 g (0.02 part by weight based on the monomer), and 5% by weight dodecylbenzenesulfonic acid 60 minutes after the start of polymerization.
  • a vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 except that an aqueous sodium solution was not added (sodium dodecylbenzenesulfonate per 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer: 0.02 Parts by weight, potassium laurate: 0.56 parts by weight). It was in the range of pH 6.7 and pH 3 to 8, and the average particle size was measured and found to be 0.15 ⁇ m. When the storage stability of the latex was evaluated, a large amount of sediment was generated (C), which was an inferior result.
  • Synthesis example 8 The amount of 5% by weight sodium dodecylbenzenesulfonate aqueous solution added at the stage of preparation was increased to 222 g (1.85 parts by weight with respect to the monomer), and 5% by weight sodium dodecylbenzenesulfonate aqueous solution 60 minutes after the start of polymerization. was added in an amount of 222 g (1.85 parts by weight with respect to the monomer). After recovering the unreacted vinyl chloride monomer and butyl acrylate monomer, the amount of the 15 wt% sodium dodecylbenzenesulfonate aqueous solution was 233.
  • a vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 except that the amount was increased to 0.2 g (5.83 parts by weight based on the monomer) (vinyl chloride-unsaturated carboxylic acid ester copolymer). 100 weight parts sodium dodecylbenzenesulfonate: 10.59 weight parts, potassium laurate: 0.56 weight parts). It was in the range of pH 6.7 and pH 3 to 8, and the average particle size was measured and found to be 0.10 ⁇ m. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.
  • Synthesis Example 9 In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 222.2 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.85 parts by weight with respect to the monomer) was continuously added over 240 minutes.
  • a vinyl chloride copolymer latex was obtained (sodium dodecylbenzenesulfonate: 2.61 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer).
  • sodium dodecylbenzenesulfonate 2.61 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer.
  • the average particle size was measured, it was 0.1 ⁇ m, but it was a low pH of 2.8.
  • no precipitate was generated (A), and the result was good.
  • Synthesis Example 10 In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight aqueous sodium alkyldiphenyl ether disulfonate The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 222.2 g of a 5 wt% sodium alkyldiphenyl ether disulfonate aqueous solution (1.85 parts by weight with respect to the monomer) was continuously added over 240 minutes.
  • a vinyl chloride copolymer latex was obtained (sodium alkyldiphenyl ether disulfonate: 2.61 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer).
  • the average particle diameter was measured, it was 0.1 ⁇ m, but the result was as low as pH 2.7.
  • no precipitate was generated (A), and the result was good.
  • Synthesis Example 11 In a 2.5 L autoclave, 670 g of deionized water, 600 g of vinyl chloride monomer, 5.4 g of 3% by weight potassium persulfate and 84 g of 5% by weight sodium alkyldiphenyl ether disulfonate aqueous solution (0.70 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and immediately after the start of polymerization, 24 g of a 5 wt% potassium laurate aqueous solution (0.20 parts by weight based on the monomer) was continuously added over 300 minutes.
  • Synthesis Example 12 In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3 wt% potassium persulfate and 2.4 g of 5 wt% sodium dodecylbenzenesulfonate aqueous solution (single amount) 0.02 part by weight with respect to the body), the temperature was raised to 66 ° C., and emulsion polymerization was started. The temperature was kept at 66 ° C.
  • Synthesis Example 13 Into a 2.5 L autoclave was charged 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate, and the temperature was raised to 66 ° C. to initiate emulsion polymerization. . Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 2.4 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (0.02 wt part relative to the monomer) and 38.4 g of a 5 wt% aqueous potassium laurate solution are added.
  • a vinyl chloride copolymer latex sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer: 0.56 parts by weight. It was in the range of pH 6.6 and pH 3 to 8, and the average particle size was measured to be 0.31 ⁇ m. When the storage stability of the latex was evaluated, a large amount of sediment was generated (C), which was an inferior result.
  • Example 1 When an image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 1, the printing was clear, no bleeding was observed, and good results (score 5) were obtained.
  • Example 2 When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 2, the printing was clear and no bleeding was observed, and the result was good (score 5).
  • Example 3 When an image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 3, the printing was clear, no bleeding was observed, and good results (score 5) were obtained.
  • Example 4 When the image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 4, the printing was clear, no bleeding was observed, and good results (score 5) were obtained.
  • Comparative Example 1 An image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 5. The result was that the color was thin and the printed content was not known (2 points). Comparative Example 2 When the image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 6, the result was a thin color and the printed content was not known (2 points). Comparative Example 3 When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 7, the color was thin and the printed content was not known (score 2). Comparative Example 4 When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 8, the color was thin and the printed contents were not known (score 2).
  • Comparative Example 5 When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 9, the color was thin and the printed content was not known (score 2). Comparative Example 6 An image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 10. The result was that the color was thin and the printed content was not known (2 points).
  • Reference example 1 When an image formation test was performed using the vinyl chloride latex prepared in Synthesis Example 11, a slight blur was observed (score 4).
  • Reference example 2 When the image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 12, slight bleeding was observed (score 4).
  • Reference example 3 When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 13, slight bleeding was observed (score 4).
  • the heat-sensitive sublimation transfer image-receiving sheet of the present invention has advantages that image printing becomes clearer and bleeding is less. Therefore, the industrial value of the present invention is remarkable.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

Provided is a heat-sensitive sublimation-type transfer image receiving sheet capable of forming outstanding images without smearing. The heat-sensitive sublimation-type transfer image receiving sheet is configured from at least a support and a receiving layer, and is characterized in that the receiving layer contains a vinyl chloride-based copolymer that includes between 0.20 and 10.0 parts by weight of an organic compound having either a sulfonate or a sulfuric acid ester salt and between 0.05 and 3.0 parts by weight of a high-grade fatty acid salt relative to 100 parts by weight of a vinyl chloride-unsaturated carboxylate copolymer.

Description

感熱昇華型転写受像シートThermal sublimation transfer image-receiving sheet

　本発明は、感熱昇華型転写受像シートに関するものであり、さらに詳しくは塩化ビニル系共重合体を含有する受容層を有する、優れた画像形成が可能な感熱昇華型転写受像シートに関するものである。 The present invention relates to a heat-sensitive sublimation transfer image-receiving sheet, and more particularly to a heat-sensitive sublimation transfer image-receiving sheet having a receiving layer containing a vinyl chloride copolymer and capable of forming an excellent image.

　従来から熱転写方式を用いて被転写体に文字や画像を形成することが行われている。熱転写方式としては、感熱昇華型転写方式と感熱溶融型転写方式が広く用いられている。このうち、感熱昇華型転写方式は昇華性染料を色材とし、それを画像情報に応じて発熱制御されたサーマルヘッドやレーザー光等の加熱デバイスを用いて、熱転写シート上の昇華性染料層中の染料を感熱転写受像シート等の被転写体に移行させて画像を形成させる方式である。この感熱昇華型転写方式は、極めて短時間の過熱によってドット単位で染料の移行量を制御できる。このように形成された画像は、使用する色材が染料であることから非常に鮮明であり、かつ透明性に優れているため、得られる画像は中間調の再現性や階調性に優れ、極めて高精細な画像を得ることができる。このため、フルカラー銀塩写真に匹敵する高品質の画像を得ることができる。しかも、銀塩写真に比べて、ドライであること、デジタルデータから直接可視像化できる、複製作りが簡単であるなどの利点を持っている。 Conventionally, characters and images are formed on a transfer medium using a thermal transfer method. As the thermal transfer method, a thermal sublimation transfer method and a thermal fusion transfer method are widely used. Of these, the heat-sensitive sublimation transfer method uses a sublimable dye as a colorant, and uses a heating device such as a thermal head or laser light whose heat is controlled in accordance with 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.

　一般的に感熱転写受像シートは少なくとも支持体上に断熱層及び染料受像層（受容層）が形成されている。受容層形成用樹脂としては、染料染着性、離型性に優れ、熱転写時に熱転写シートと感熱転写受像シートとの間において融着等の異常転写が起こらない点で、塩化ビニル系樹脂が使用されている。塩化ビニル系樹脂は受容層形成のために基材シートに塗工するに際し、従来、有機溶剤に溶解させて用いられてきた。 Generally, a heat-sensitive transfer image-receiving sheet has at least a heat insulating layer and a dye image-receiving layer (receiving layer) formed on a support. As the resin for forming the receiving layer, vinyl chloride resin is used because it has excellent dye dyeing and releasability, 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.

　しかしながら、有機溶剤使用により作業環境の悪化が懸念されている。
　そこで、塩化ビニル系樹脂ラテックスを使用して、有機溶剤を使用することなく受容層を形成する方法が広く検討されている（特許文献１、特許文献２）。
　ところが、受容層の形成に用いられる塩ビ系樹脂ラテックスの貯蔵安定性に劣ったり、この塩化ビニル系樹脂ラテックスを用いた感熱昇華型転写受像シートでは満足な画像が得られなかった。 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 Documents 1 and 2).
However, the storage stability of the vinyl chloride resin latex used for forming the receiving layer is inferior, and satisfactory images cannot be obtained with the heat-sensitive sublimation transfer image receiving sheet using this vinyl chloride resin latex.

日本国特開２００６－２６４０８７号公報Japanese Unexamined Patent Publication No. 2006-264087 日本国特開２００８－６７５２号公報Japanese Unexamined Patent Publication No. 2008-6752

　本発明は、上記課題に鑑みてなされたものであり、優れた画像形成が可能な新規な塩化ビニル系共重合体を含有する受容層を有する感熱昇華型転写受像シートを提供することである。 The present invention has been made in view of the above problems, and is to provide a heat-sensitive sublimation transfer image-receiving sheet having a receiving layer containing a novel vinyl chloride copolymer capable of forming an excellent image.

　本発明者らは、上記の課題について鋭意検討を重ねた結果、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０～１０．０重量部及び高級脂肪酸塩０．０５～３．０重量部となるように、重合中にスルホン酸塩又は硫酸エステル塩を有する有機化合物、高級脂肪酸塩を添加したラテックスを用いて作製した感熱昇華型転写受像シートは、優れた画像形成が可能であることを見出し、本発明に至った。すなわち、本発明は、少なくとも支持体及び受容層から構成されている感熱昇華型転写受像シートであって、当該受容層が、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０～１０．０重量部及び高級脂肪酸塩０．０５～３．０重量部を含む塩化ビニル系共重合体を含有することを特徴とする感熱昇華型転写受像シートである。 As a result of intensive studies on the above-mentioned problems, the present inventors have found that an organic compound having a sulfonate or sulfate ester salt of 0.20 to 100 parts by weight per 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. It was prepared using an organic compound having a sulfonate or sulfate ester salt during polymerization and a latex to which a higher fatty acid salt was added so as to be 10.0 parts by weight and 0.05 to 3.0 parts by weight of a higher fatty acid salt. The heat-sensitive sublimation type transfer image-receiving sheet has been found to be capable of excellent image formation, leading to the present invention. That is, the present invention is a heat-sensitive sublimation type transfer image-receiving sheet comprising at least a support and a receiving layer, and the receiving layer is based on 100 parts by weight of a vinyl chloride-unsaturated carboxylic acid ester copolymer. A thermosensitive material comprising a vinyl chloride copolymer containing 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 3.0 parts by weight of a higher fatty acid salt. It is a sublimation type transfer image receiving sheet.

　本発明の感熱昇華型転写受像シートは、印刷が従来の感熱昇華型転写受像シートよりも鮮明となり、滲みが少ない利点を有する。 The heat-sensitive sublimation transfer image-receiving sheet of the present invention has the advantage that printing is clearer than conventional heat-sensitive sublimation-type transfer image-receiving sheets and there is less bleeding.

　以下に本発明について詳細に説明する。
　本発明の感熱昇華型転写受像シートは、少なくとも支持体及び染料受像層（受容層）から構成されており、例えば、１）支持体上に受容層が形成されている、２）支持体上に断熱層と受容層が形成されている、３）支持体上に下地層、断熱層及び受容層が形成されている等の構成があげられる。
　本発明の感熱昇華型転写受像シートの受容層が含有する塩化ビニル系共重合体（以下、単に、塩化ビニル系共重合体と称する場合がある）は、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０～１０．０重量部及び高級脂肪酸塩０．０５～３．０重量部を含むものである。
　そして、本発明の感熱昇華型転写受像シートの受容層を形成するための塩化ビニル系共重合体ラテックス（以下、単に、塩化ビニル系共重合体ラテックスと称する場合がある）は、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０～１０．０重量部及び高級脂肪酸塩０．０５～３．０重量部を含むものである。 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). For example, 1) a receiving layer is formed on the support, and 2) on the support. Examples include a structure in which a heat insulating layer and a receiving layer are formed, and 3) an underlayer, a heat insulating layer, and a receiving layer are formed on a support.
The vinyl chloride copolymer contained in the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention (hereinafter sometimes simply referred to as vinyl chloride copolymer) is a vinyl chloride-unsaturated carboxylic acid ester copolymer. It contains 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 3.0 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of the combined body.
The vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention (hereinafter sometimes simply referred to as vinyl chloride copolymer latex) It contains 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 3.0 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of a saturated carboxylic acid ester copolymer. .

　塩化ビニル－不飽和カルボン酸エステル共重合体は、塩化ビニル単量体と不飽和カルボン酸エステル単量体を共重合させたものである。
　不飽和カルボン酸エステル単量体としては、例えば、アクリル酸のメチル，エチル，ブチル等のエステル、メタクリル酸のメチル，エチル，ブチル等のエステル類、マレイン酸エステル、フマル酸エステル、桂皮酸エステル等を挙げることができ、これらは２種類以上でも用いることができる。
　塩化ビニル単量体と不飽和カルボン酸エステル単量体を共重合させる方法としては、例えば、乳化重合、溶液重合、気相重合等が挙げられる。 The vinyl chloride-unsaturated carboxylic acid ester copolymer is obtained by copolymerizing a vinyl chloride monomer and an unsaturated carboxylic acid ester monomer.
Examples of unsaturated carboxylic acid ester monomers include esters of acrylic acid such as methyl, ethyl, and butyl, esters of methyl methacrylate such as methyl, ethyl, and butyl, maleic acid esters, fumaric acid esters, and cinnamic acid esters. Two or more of these can be used.
Examples of the method for copolymerizing the vinyl chloride monomer and the unsaturated carboxylic acid ester monomer include emulsion polymerization, solution polymerization, and gas phase polymerization.

　スルホン酸塩を有する有機化合物としては、例えば、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸アンモニウム等のアルキルベンゼンスルホン酸塩；ジオクチルスルホコハク酸ナトリウム、ジヘキシルスルホコハク酸ナトリウム等のジアルキルスルホコハク酸塩類；アルキルナフタレンスルフォン酸ナトリウム等のアルキルナフタレンスルフォン酸塩類；アルキルジフェニルエーテルジスルフォン酸ナトリウム等のアルキルジフェニルエーテルジスルフォン酸塩類等が挙げられ、硫酸エステル塩を有する有機化合物としては、例えば、ラウリル硫酸エステルナトリウム、ミリスチル硫酸エステルナトリウム等のアルキル硫酸エステル塩類；ポリオキシエチレンアルキル硫酸エステル塩類、ポリオキシエチレンアルキルアリール硫酸エステル塩類等が挙げられる。スルホン酸塩又は硫酸エステル塩を有する有機化合物の含有量としては、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、０．２０～１０．０重量部である。０．２０重量部未満の場合は、ラテックスが貯蔵安定性に劣って不安定となり、１０．０重量部を超える場合は、塩化ビニル系共重合体の不純物となる。好ましくは、１．０～５．０重量部である。 Examples of the organic compound having a sulfonate include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate; dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate; and alkylnaphthalenesulfonic acid. Alkyl naphthalene sulfonates such as sodium; alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate and the like. Examples of organic compounds having a sulfate ester salt include sodium lauryl sulfate and sodium myristyl sulfate. Alkyl sulfate ester salts; polyoxyethylene alkyl sulfate ester salts, polyoxyethylene alcohol Ruariru and the like sulfuric ester salts. The content of the organic compound having a sulfonate or sulfate ester salt is 0.20 to 10.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. When the amount is less than 0.20 parts by weight, the latex is unstable due to inferior storage stability, and when it exceeds 10.0 parts by weight, it becomes an impurity of the vinyl chloride copolymer. Preferably, it is 1.0 to 5.0 parts by weight.

　高級脂肪酸塩としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸等とアルカリとの塩が挙げられる。入手のしやすさから、カリウム、ナトリウム、アンモニア、トリエタノールアミンとの塩が好ましい。高級脂肪酸塩の含有量は、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、０．０５～３．０重量部である。０．０５重量部未満の場合は、塩化ビニル系共重合体ラテックスのｐＨが３より低くなり、３．０重量部を超える場合は、塩化ビニル系共重合体ラテックスのｐＨが８より高くなる。好ましくは、０．１～１．０重量部である。 Examples of higher fatty acid salts include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and the like with alkalis. A salt with potassium, sodium, ammonia, or triethanolamine is preferable because it is easily available. The content of the higher fatty acid salt is 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. When it is less than 0.05 parts by weight, the pH of the vinyl chloride copolymer latex is lower than 3, and when it exceeds 3.0 parts by weight, the pH of the vinyl chloride copolymer latex is higher than 8. The amount is preferably 0.1 to 1.0 part by weight.

　さらに、本発明の感熱昇華型転写受像シートの受容層を形成するための塩化ビニル系共重合体ラテックスは、良好な画質を得るためには、平均粒子径が０．１４μｍ以下であることが好ましい。平均粒子径が０．１４μｍを超えると長期貯蔵後に沈殿物が発生し、作製されたシートを用いた印刷でわずかに滲み、画質が低下するおそれがある。平均粒子径は、さらに好ましくは０．１２μｍ以下であり、特に好ましくは０．１０μｍ以下であり、最も好ましくは０．０５～０．１０μｍである。
　しかも、本発明の感熱昇華型転写受像シートの受容層を形成するための塩化ビニル系共重合体ラテックスは、ｐＨが３～８である。ｐＨが３～８を外れると、塩化ビニル－不飽和カルボン酸エステル共重合体の加水分解が進行し、ラテックスの品質が低下し、感熱昇華型転写受像シートに滲みの影響が生ずるおそれがある。
　塩化ビニル系共重合体、塩化ビニル系共重合体ラテックスは、連鎖移動剤、還元剤、緩衝剤、アルキルベンゼンスルホン酸塩以外の乳化剤等を含んでいてもよい。 Furthermore, the vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation type transfer image-receiving sheet of the present invention preferably has an average particle size of 0.14 μm or less in order to obtain good image quality. . When the average particle diameter exceeds 0.14 μm, precipitates are generated after long-term storage, and there is a possibility that image quality deteriorates due to slight bleeding when printed using the prepared sheet. The average particle diameter is more preferably 0.12 μm or less, particularly preferably 0.10 μm or less, and most preferably 0.05 to 0.10 μm.
Moreover, the vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention has a pH of 3-8. If the pH deviates from 3 to 8, hydrolysis of the vinyl chloride-unsaturated carboxylic acid ester copolymer proceeds, the quality of the latex deteriorates, and there is a possibility that the heat-sensitive sublimation transfer image-receiving sheet may be affected by bleeding.
The vinyl chloride copolymer and the vinyl chloride copolymer latex may contain a chain transfer agent, a reducing agent, a buffering agent, an emulsifier other than the alkylbenzene sulfonate, and the like.

　本発明の感熱昇華型転写受像シートの受容層を形成するための塩化ビニル系共重合体ラテックスは、水を分散媒とし、重合開始剤の存在下で、塩化ビニル単量体と不飽和カルボン酸エステル単量体を共重合する際に、塩化ビニル単量体及び不飽和カルボン酸エステル単量体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．０５～３．０重量部及び高級脂肪酸塩０．０５～１．０重量部を使用して、乳化重合することによって得られる。スルホン酸塩又は硫酸エステル塩を有する有機化合物が０．０５重量部未満の場合は、重合が不安定となり、得られるラテックスの平均粒子径が０．１４μｍを超える。３．０重量部を超える場合は、あわ立ちが問題となる。高級脂肪酸塩が０．０５重量部未満の場合は、重合中のｐＨが低くなり、１．０重量部を超えて添加しても効果が少ない。スルホン酸塩又は硫酸エステル塩を有する有機化合物は、重合開始前、重合中、重合終了後に適時添加する。高級脂肪酸塩は、重合の開始前、重合中、重合終了後のいずれでいれても問題なく、重合中に高級脂肪酸塩を逐次又は分割添加で添加することも可能である。このなかでも高級脂肪酸塩を逐次又は分割添加で添加することが、少ない量でラテックスのｐＨを３～８とすることが可能で好ましい。 The vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention comprises a vinyl chloride monomer and an unsaturated carboxylic acid in the presence of a polymerization initiator using water as a dispersion medium. When copolymerizing the ester monomer, an organic compound having a sulfonate or sulfate ester salt of 0.05 to 3.0 with respect to 100 parts by weight of the vinyl chloride monomer and the unsaturated carboxylic acid ester monomer. It is obtained by emulsion polymerization using parts by weight and 0.05 to 1.0 parts by weight of a higher fatty acid salt. When the organic compound having a sulfonate salt or a sulfate ester salt is less than 0.05 parts by weight, the polymerization becomes unstable, and the average particle size of the obtained latex exceeds 0.14 μm. If it exceeds 3.0 parts by weight, foaming becomes a problem. When the higher fatty acid salt is less than 0.05 parts by weight, the pH during the polymerization is lowered, and even if added in excess of 1.0 part by weight, the effect is small. The organic compound having a sulfonate salt or a sulfate ester salt is added as appropriate before, during or after the polymerization. The higher fatty acid salt may be added before the start of polymerization, during the polymerization, or after the completion of the polymerization, and the higher fatty acid salt may be added sequentially or in divided additions during the polymerization. Among these, it is preferable to add the higher fatty acid salt sequentially or in divided additions, since the pH of the latex can be reduced to 3 to 8 with a small amount.

　重合開始剤は、例えば、過硫酸カリウム、過硫酸アンモニウム等の水溶性開始剤、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス－２－メチルブチロニトリル、ラウロイルパーオキサイド、ｔ－ブチルペルオキシピバレート、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネート等の油溶性開始剤等を挙げることができる。
　重合温度は、特に限定するものではないが、３０～１００℃が好ましく、４０～８０℃がさらに好ましい。
　重合時間は、特に限定するものではないが、３～２４時間が好ましい。 Examples of the polymerization initiator include water-soluble initiators such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, lauroyl peroxide, Examples thereof include oil-soluble initiators such as t-butyl peroxypivalate, diacyl peroxide, peroxyester, and peroxydicarbonate.
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.

　塩化ビニル単量体と不飽和カルボン酸エステル単量体の重合率は、全単量体に対して８０～９７重量％であることが好ましい。
　重合の終了は、容器内の圧力を常圧、さらに減圧し、モノマーを回収することにより行う。重合禁止剤を添加して重合を終了させてもよい。
　必要に応じ、重合終了後のラテックスに、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して０．２０～１０．０重量部を含有するように、アルキルベンゼンスルホン酸スルホン酸塩を追加添加することができる。また、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、０．０５～３．０重量部を含有するように、高級脂肪酸塩を追加添加することができる。 The polymerization rate of the vinyl chloride monomer and the unsaturated carboxylic acid ester monomer is preferably 80 to 97% by weight based on the total monomers.
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, an alkylbenzenesulfonic acid sulfonate is added to the latex after completion of polymerization so that the latex contains 0.20 to 10.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. Additional additions can be made. Further, a higher fatty acid salt can be additionally added so as to contain 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer.

　本発明の感熱昇華型転写受像シートの受容層を形成するための塩化ビニル系共重合体ラテックスを製造する際に、重合の安定化やスケール発生量の低減を目的として連鎖移動剤、還元剤、緩衝剤、アルキルベンゼンスルホン酸塩以外の乳化剤等を添加することもできる。
　塩化ビニル系共重合体ラテックスをシート上に塗布乾燥することにより、感熱昇華型転写受像シートの受容層を形成することができる。塩化ビニル系共重合体ラテックスをシート上に塗布乾燥する場合は、塩化ビニル系共重合体ラテックスのみで行ってもよく、他の塩化ビニル系共重合体ラテックスとともに行ってもよい。 When producing a vinyl chloride copolymer latex for forming the receiving layer of the heat-sensitive sublimation transfer image-receiving sheet of the present invention, a chain transfer agent, a reducing agent for the purpose of stabilizing the polymerization and reducing the amount of scale generated, Buffering agents, emulsifiers other than alkylbenzene sulfonates, and the like can also be added.
A receiving layer of a heat-sensitive sublimation transfer image-receiving sheet can be formed by applying and drying vinyl chloride copolymer latex on the sheet. When applying and drying the vinyl chloride copolymer latex on the sheet, it may be performed only with the vinyl chloride copolymer latex or with other vinyl chloride copolymer latex.

　以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれらに限定されるものではない。
　感熱昇華型転写受像シートの作製方法、画像形成テスト方法、感熱昇華型転写受像シートの受容層を形成するための塩化ビニル系共重合体ラテックスの各種評価方法は、以下の通りである。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.
Various evaluation methods for the 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.

　＜感熱昇華型転写受像シートの作製方法＞
　塩化ビニル系共重合体ラテックスを水で希釈し、固形分を３０重量％に調整した。次に平らな金属板の上に壁紙用裏打ち紙（日本製紙株式会社製）を固定した。壁紙用裏打ち紙の上面に、固形分を３０重量％に調整したラテックスを流し、バーコーターで約２０μｍの厚みになるようにコーティングした。コーティング後、壁紙用裏打ち紙を２４時間室温で乾燥し、感熱昇華型転写受像シートを作製した。 <Method for producing heat-sensitive sublimation transfer image-receiving sheet>
The vinyl chloride copolymer latex 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. Latex adjusted to a solid content of 30% by weight was poured onto the upper surface of the wallpaper backing paper, and coated with a bar coater to a thickness of about 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.

　＜画像形成テスト方法＞
　壁紙用裏打ち紙を用いて作製した感熱昇華型転写受像シートが乾いたのを確認後、壁紙用裏打ち紙をペーパーＫＬ－３６１Ｐ（キヤノン株式会社製　カラーインク／ペーパーセット）と同サイズに切り、ＫＬ－３６１Ｐの印刷面上に、壁紙用裏打ち紙を両面テープで貼った。
　セルフィーＣＰ－８００（キヤノン株式会社製、昇華型熱転写プリンター）のペーパーカセットに、試験ラテックスがコーティングされた面が印刷面になるように、ペーパーをセッティングし、セルフィーＣＰ－８００で印刷した。印刷の鮮明さ、滲み具合で画像形成性を以下の通り判定した。 <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.). A wallpaper backing paper was affixed to the -361P printing surface 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：印刷が鮮明であり、滲みが全く見られない。
　　４：僅かに滲みが見られる。
　　３：印刷内容がわかるが色が薄い。
　　２：色が薄く印刷内容がわからない。
　　１：印刷されない。 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.

　＜ラテックスの貯蔵安定性＞
　塩化ビニル系共重合体ラテックスを水で希釈し、固形分を３０重量％に調整した。当該調整した塩化ビニル共重合体ラテックス５００ｇを透明なガラス瓶に入れ、室温下２週間静置し、ラテックス中の沈降物発生の有無を目視で確認し、以下の通り評価した。 <Storage stability of latex>
The vinyl chloride copolymer latex was diluted with water to adjust the solid content to 30% by weight. 500 g of the adjusted vinyl chloride copolymer latex 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 was visually confirmed and evaluated as follows.

　　Ａ：沈降物の発生が全く無い。
　　Ｂ：僅かに発生が見られた。
　　Ｃ：多量の沈降物発生が見られた。 A: There is no generation of sediment.
B: Slight occurrence was observed.
C: A large amount of sediment was observed.

　＜塩化ビニル系共重合体ラテックスの平均粒子径＞
　塩化ビニル共重合体ラテックスをレーザー透過率が８４～８６％となるように水を添加して濃度調整を行った測定用試料を、レーザー回折／散乱式粒径測定装置（商品名ＬＡ－９２０、堀場製作所（株）製）を用いて、メジアン径を測定し、平均粒子径とした。 <Average particle diameter of vinyl chloride copolymer latex>
A sample for measurement in which the concentration of the vinyl chloride copolymer latex was adjusted by adding water so that the laser transmittance was 84 to 86% was measured using a laser diffraction / scattering particle size measuring device (trade name LA-920, Using a Horiba Seisakusho Co., Ltd.), the median diameter was measured and taken as the average particle diameter.

　＜塩化ビニル系共重合体ラテックスのｐＨ＞
　ｐＨメーター（商品名Ｄ－１２、堀場製作所（株）製）を用いて、濃度調整をせず室温にて塩化ビニル系共重合体ラテックスのｐＨを測定した。 <PH of vinyl chloride copolymer latex>
Using a pH meter (trade name D-12, manufactured by Horiba, Ltd.), the pH of the vinyl chloride copolymer latex was measured at room temperature without adjusting the concentration.

　合成例１
　２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液１０５．６ｇ（単量体に対して０．８８重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム５６．４ｇ（単量体に対して０．４７重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ６．７とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis example 1
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 105.6 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution (0.88 parts by weight with respect to the monomer) and 38.4 g of 5% by weight potassium laurate aqueous solution. (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 56.4 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (0.47 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). It was in the range of pH 6.7 and pH 3 to 8, and the average particle diameter was measured and found to be 0.1 μm. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例２
　ブチルアクリレート単量体６０ｇを乳化重合開始直後に３００分間かけて連続添加した以外は合成例１と同様の方法で塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ６．９とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis example 2
A vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 except that 60 g of butyl acrylate monomer was added continuously over 300 minutes immediately after the start of emulsion polymerization (vinyl chloride-unsaturated carboxylic acid ester copolymer). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.56 parts by weight) with respect to 100 parts by weight of the polymer). It was in the range of pH 6.9 and pH 3 to 8, and the average particle diameter was measured and found to be 0.1 μm. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例３
　２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液８４ｇ（単量体に対して０．７０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後すぐに、５重量％ラウリン酸カリウム水溶液２４ｇ（単量体に対して０．２０重量部）を３００分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム１３８ｇ（単量体に対して１．１５重量部）、５重量％ラウリン酸カリウム水溶液３６ｇ（単量体に対して０．３０重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ６．７とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis example 3
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 84 g of 5% by weight aqueous sodium dodecylbenzenesulfonate solution The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and immediately after the start of polymerization, 24 g of a 5 wt% potassium laurate aqueous solution (0.20 parts by weight based on the monomer) was continuously added over 300 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this was added 138 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (1.15 parts by weight based on the monomer) and 36 g of a 5% by weight aqueous potassium laurate solution (0.30 parts by weight based on the monomer). To obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer). ). It was in the range of pH 6.7 and pH 3 to 8, and the average particle diameter was measured and found to be 0.1 μm. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例４
　ブチルアクリレート単量体６０ｇを乳化重合開始直後に３００分間かけて連続添加した以外は合成例３と同様の方法で塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ６．７とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis example 4
A vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 3 except that 60 g of butyl acrylate monomer was added continuously over 300 minutes immediately after the start of emulsion polymerization (vinyl chloride-unsaturated carboxylic acid ester copolymer). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 0.56 parts by weight) with respect to 100 parts by weight of the polymer). It was in the range of pH 6.7 and pH 3 to 8, and the average particle diameter was measured and found to be 0.1 μm. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例５
　乳化重合開始６０分後に添加する５重量％ラウリン酸カリウム水溶液の量を２．４ｇ（単量体に対して０．０２重量部）と少なくし、最後に５重量％ラウリン酸カリウム水溶液を追加添加しない以外は合成例１と同様の方法で塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．０６重量部、ラウリン酸カリウム：０．０２重量部）。平均粒子径を測定したところ０．１μｍであったが、ｐＨ２．２と低い結果であった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis example 5
The amount of 5 wt% potassium laurate aqueous solution added 60 minutes after the start of emulsion polymerization is reduced to 2.4 g (0.02 parts by weight based on the monomer), and finally 5 wt% potassium laurate aqueous solution is added. Except for this, a vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 (sodium dodecylbenzenesulfonate: 2.06 parts by weight, 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer, laurin) Acid potassium: 0.02 parts by weight). When the average particle diameter was measured, it was 0.1 μm, but it was a low pH of 2.2. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例６
　乳化重合開始６０分後に添加する５重量％ラウリン酸カリウム水溶液の量を１０５．６ｇ（単量体に対して０．８８重量部）と多くし、最後に追加添加する５重量％ラウリン酸カリウム水溶液の量を１８４ｇ(単量体に対して１.５３重量部)と多くした以外は合成例１と同様の方法で塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．０６重量部、ラウリン酸カリウム：３．４１重量部）。平均粒子径を測定したところ０．１μｍであったが、ｐＨ８．４と高い結果であった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis Example 6
The amount of 5 wt% potassium laurate aqueous solution added 60 minutes after the start of emulsion polymerization was increased to 105.6 g (0.88 parts by weight with respect to the monomer), and finally added 5 wt% potassium laurate aqueous solution. A vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 except that the amount of the polymer was increased to 184 g (1.53 parts by weight based on the monomer) (vinyl chloride-unsaturated carboxylic acid ester copolymer). (Sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 3.41 parts by weight) with respect to 100 parts by weight of the polymer). When the average particle diameter was measured, it was 0.1 μm, but it was a high result of pH 8.4. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例７
　仕込みの段階で添加する５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液の量を２．４ｇ（単量体に対して０．０２重量部）と少なくし、重合開始６０分後に５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液を添加しない以外は合成例１と同様の方法で塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：０．０２重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ６．７とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．１５μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物が大量に発生し(Ｃ)、劣った結果であった。 Synthesis example 7
The amount of 5% by weight sodium dodecylbenzenesulfonate aqueous solution added at the stage of preparation is reduced to 2.4 g (0.02 part by weight based on the monomer), and 5% by weight dodecylbenzenesulfonic acid 60 minutes after the start of polymerization. A vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 except that an aqueous sodium solution was not added (sodium dodecylbenzenesulfonate per 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer: 0.02 Parts by weight, potassium laurate: 0.56 parts by weight). It was in the range of pH 6.7 and pH 3 to 8, and the average particle size was measured and found to be 0.15 μm. When the storage stability of the latex was evaluated, a large amount of sediment was generated (C), which was an inferior result.

　合成例８
　仕込みの段階で添加する５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液の量を２２２ｇ（単量体に対して１．８５重量部）と多くし、重合開始６０分後に５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液の添加量も２２２ｇ（単量体に対して１．８５重量部）、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した後に１５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液の量を２３３．２ｇ（単量体に対して５．８３重量部）と多くした以外は合成例１と同様の方法で塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：１０．５９重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ６．７とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．１０μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis example 8
The amount of 5% by weight sodium dodecylbenzenesulfonate aqueous solution added at the stage of preparation was increased to 222 g (1.85 parts by weight with respect to the monomer), and 5% by weight sodium dodecylbenzenesulfonate aqueous solution 60 minutes after the start of polymerization. Was added in an amount of 222 g (1.85 parts by weight with respect to the monomer). After recovering the unreacted vinyl chloride monomer and butyl acrylate monomer, the amount of the 15 wt% sodium dodecylbenzenesulfonate aqueous solution was 233. A vinyl chloride copolymer latex was obtained in the same manner as in Synthesis Example 1 except that the amount was increased to 0.2 g (5.83 parts by weight based on the monomer) (vinyl chloride-unsaturated carboxylic acid ester copolymer). 100 weight parts sodium dodecylbenzenesulfonate: 10.59 weight parts, potassium laurate: 0.56 weight parts). It was in the range of pH 6.7 and pH 3 to 8, and the average particle size was measured and found to be 0.10 μm. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例９
　２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２２２．２ｇ（単量体に対して１．８５重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．６１重量部）。平均粒子径を測定したところ０．１μｍであったがｐＨ２．８と低い結果であった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis Example 9
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight sodium dodecylbenzenesulfonate aqueous solution The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 222.2 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (1.85 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. A vinyl chloride copolymer latex was obtained (sodium dodecylbenzenesulfonate: 2.61 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer). When the average particle size was measured, it was 0.1 μm, but it was a low pH of 2.8. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例１０
　２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％アルキルジフェニルエーテルジスルホン酸ナトリウム水溶液６０ｇ（単量体に対して０．５０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％アルキルジフェニルエーテルジスルホン酸ナトリウム水溶液２２２．２ｇ（単量体に対して１．８５重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対するアルキルジフェニルエーテルジスルホン酸ナトリウム：２．６１重量部）。平均粒子径を測定したところ０．１μｍであったがｐＨ２．７と低い結果であった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis Example 10
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate and 60 g of 5% by weight aqueous sodium alkyldiphenyl ether disulfonate The emulsion polymerization was started by raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 222.2 g of a 5 wt% sodium alkyldiphenyl ether disulfonate aqueous solution (1.85 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. A vinyl chloride copolymer latex was obtained (sodium alkyldiphenyl ether disulfonate: 2.61 parts by weight based on 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer). When the average particle diameter was measured, it was 0.1 μm, but the result was as low as pH 2.7. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例１１
　２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体６００ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％アルキルジフェニルエーテルジスルホン酸ナトリウム水溶液８４ｇ（単量体に対して０．７０重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始後すぐに、５重量％ラウリン酸カリウム水溶液２４ｇ（単量体に対して０．２０重量部）を３００分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体を回収した。これに５重量％濃度のアルキルジフェニルエーテルジスルホン酸ナトリウム１３８ｇ（単量体に対して１．１５重量部）、５重量％ラウリン酸カリウム水溶液３６ｇ（単量体に対して０．３０重量部）を追加添加し、塩化ビニルラテックスを得た（塩化ビニル重合体１００重量部に対するアルキルジフェニルエーテルジスルホン酸ナトリウム：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ７．９とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．１μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物の発生は全くなく（Ａ）、良好な結果であった。 Synthesis Example 11
In a 2.5 L autoclave, 670 g of deionized water, 600 g of vinyl chloride monomer, 5.4 g of 3% by weight potassium persulfate and 84 g of 5% by weight sodium alkyldiphenyl ether disulfonate aqueous solution (0.70 parts by weight based on the monomer) ) And the temperature was raised to 66 ° C. to initiate emulsion polymerization. The temperature was kept at 66 ° C., and immediately after the start of polymerization, 24 g of a 5 wt% potassium laurate aqueous solution (0.20 parts by weight based on the monomer) was continuously added over 300 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer was recovered. To this was added 138 g of sodium alkyldiphenyl ether disulfonate having a concentration of 5% by weight (1.15 parts by weight based on the monomer) and 36 g of a 5% by weight aqueous potassium laurate solution (0.30 parts by weight based on the monomer). By addition, a vinyl chloride latex was obtained (sodium alkyldiphenyl ether disulfonate: 2.06 parts by weight, potassium laurate: 0.56 parts by weight based on 100 parts by weight of the vinyl chloride polymer). It was in the range of pH 7.9 and pH 3 to 8, and the average particle diameter was measured to be 0.1 μm. When the storage stability of the latex was evaluated, no precipitate was generated (A), and the result was good.

　合成例１２
　２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇ及び５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２．４ｇ（単量体に対して０．０２重量部）を仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム２１９．６ｇ（単量体に対して１．８３重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ６．７とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．１５μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物が発生し(Ｃ)、劣った結果であった。 Synthesis Example 12
In a 2.5 L autoclave, 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3 wt% potassium persulfate and 2.4 g of 5 wt% sodium dodecylbenzenesulfonate aqueous solution (single amount) 0.02 part by weight with respect to the body), the temperature was raised to 66 ° C., and emulsion polymerization was started. The temperature was kept at 66 ° C. and 60 minutes after the start of polymerization, 38.4 g of a 5 wt% aqueous potassium laurate solution (0.32 parts by weight based on the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this, 219.6 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (1.83 parts by weight based on the monomer) and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer) Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). It was in the range of pH 6.7 and pH 3 to 8, and the average particle size was measured and found to be 0.15 μm. When the storage stability of the latex was evaluated, a precipitate was generated (C), which was an inferior result.

　合成例１３
　２．５Ｌオートクレーブ中に脱イオン水６７０ｇ、塩化ビニル単量体５４０ｇ、ブチルアクリレート単量体６０ｇ、３重量％過硫酸カリウム５．４ｇを仕込み、温度を６６℃に上げて、乳化重合を開始した。温度を６６℃に保ち、重合開始６０分後より、５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２．４ｇ（単量体に対して０．０２重量部）と５重量％ラウリン酸カリウム水溶液３８．４ｇ（単量体に対して０．３２重量部）を２４０分間かけて連続添加した。６６℃におけるオートクレーブ内の圧力が０．７０ＭＰａまで低下した後、未反応の塩化ビニル単量体およびブチルアクリレート単量体を回収した。これに５重量％濃度のドデシルベンゼンスルホン酸ナトリウム２１９．６ｇ（単量体に対して１．８３重量部）、５重量％濃度のラウリン酸カリウム２１．６ｇ（単量体に対して０．１８重量部）を追加添加し、塩化ビニル系共重合体ラテックスを得た（塩化ビニル－不飽和カルボン酸エステル共重合体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：２．０６重量部、ラウリン酸カリウム：０．５６重量部）。ｐＨ６．６とｐＨ３～８の範囲に入っており、平均粒子径を測定したところ０．３１μｍであった。ラテックスの貯蔵安定性を評価したところ、沈降物が大量に発生し(Ｃ)、劣った結果であった。 Synthesis Example 13
Into a 2.5 L autoclave was charged 670 g of deionized water, 540 g of vinyl chloride monomer, 60 g of butyl acrylate monomer, 5.4 g of 3% by weight potassium persulfate, and the temperature was raised to 66 ° C. to initiate emulsion polymerization. . Maintaining the temperature at 66 ° C., 60 minutes after the start of polymerization, 2.4 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution (0.02 wt part relative to the monomer) and 38.4 g of a 5 wt% aqueous potassium laurate solution are added. (0.32 parts by weight with respect to the monomer) was continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.70 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this was added 219.6 g of sodium dodecylbenzenesulfonate at a concentration of 5% by weight (1.83 parts by weight based on the monomer), and 21.6 g of potassium laurate at a concentration of 5% by weight (0.18% relative to the monomer). Parts by weight) were added to obtain a vinyl chloride copolymer latex (sodium dodecylbenzenesulfonate: 2.06 parts by weight, potassium laurate: 100 parts by weight of vinyl chloride-unsaturated carboxylic acid ester copolymer): 0.56 parts by weight). It was in the range of pH 6.6 and pH 3 to 8, and the average particle size was measured to be 0.31 μm. When the storage stability of the latex was evaluated, a large amount of sediment was generated (C), which was an inferior result.

　実施例１
　合成例１で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、印刷が鮮明であり、滲みが全く見られず、良好な結果（点数５）であった。
　実施例２
　合成例２で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、印刷が鮮明であり、滲みが全く見られず、良好な結果（点数５）であった。
　実施例３
　合成例３で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、印刷が鮮明であり、滲みが全く見られず、良好な結果（点数５）であった。
　実施例４
　合成例４で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、印刷が鮮明であり、滲みが全く見られず、良好な結果（点数５）であった。 Example 1
When an image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 1, the printing was clear, no bleeding was observed, and good results (score 5) were obtained.
Example 2
When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 2, the printing was clear and no bleeding was observed, and the result was good (score 5).
Example 3
When an image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 3, the printing was clear, no bleeding was observed, and good results (score 5) were obtained.
Example 4
When the image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 4, the printing was clear, no bleeding was observed, and good results (score 5) were obtained.

　比較例１
　合成例５で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、色が薄く印刷内容がわからない結果（点数２）であった。
　比較例２
　合成例６で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、色が薄く印刷内容がわからない結果（点数２）であった。
　比較例３
　合成例７で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、色が薄く印刷内容がわからない結果（点数２）であった。
　比較例４
　合成例８で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、色が薄く印刷内容がわからない結果（点数２）であった。
　比較例５
　合成例９で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、色が薄く印刷内容がわからない結果（点数２）であった。
　比較例６
　合成例１０で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、色が薄く印刷内容がわからない結果（点数２）であった。 Comparative Example 1
An image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 5. The result was that the color was thin and the printed content was not known (2 points).
Comparative Example 2
When the image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 6, the result was a thin color and the printed content was not known (2 points).
Comparative Example 3
When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 7, the color was thin and the printed content was not known (score 2).
Comparative Example 4
When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 8, the color was thin and the printed contents were not known (score 2).
Comparative Example 5
When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 9, the color was thin and the printed content was not known (score 2).
Comparative Example 6
An image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 10. The result was that the color was thin and the printed content was not known (2 points).

　参考例１
　合成例１１で調製した塩化ビニルラテックスを使用して画像形成テストを実施したところ、わずかに滲みが見られる結果（点数４）であった。
　参考例２
　合成例１２で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、わずかに滲みが見られる結果（点数４）であった。
　参考例３
　合成例１３で調製した塩化ビニル系共重合体ラテックスを使用して画像形成テストを実施したところ、わずかに滲みが見られる結果（点数４）であった。 Reference example 1
When an image formation test was performed using the vinyl chloride latex prepared in Synthesis Example 11, a slight blur was observed (score 4).
Reference example 2
When the image formation test was carried out using the vinyl chloride copolymer latex prepared in Synthesis Example 12, slight bleeding was observed (score 4).
Reference example 3
When an image formation test was conducted using the vinyl chloride copolymer latex prepared in Synthesis Example 13, slight bleeding was observed (score 4).

　本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
　なお、本出願は、２０１１年１０月２５日付で出願された日本特許出願（特願２０１１－２３４１５８）及び２０１２年４月２４日付で出願された日本特許出願（特願２０１２－９８８１６）に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2011-234158) filed on October 25, 2011 and a Japanese patent application (Japanese Patent Application No. 2012-98816) filed on April 24, 2012. Which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

　本発明の感熱昇華型転写受像シートは、画像印刷が更に鮮明となり、滲みが少ない利点を有するものである。よって、本発明の工業価値は顕著である。 The heat-sensitive sublimation transfer image-receiving sheet of the present invention has advantages that image printing becomes clearer and bleeding is less. Therefore, the industrial value of the present invention is remarkable.

Claims (7)

少なくとも支持体及び受容層から構成されている感熱昇華型転写受像シートであって、当該受容層が、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０～１０．０重量部及び高級脂肪酸塩０．０５～３．０重量部を含む塩化ビニル系共重合体を含有することを特徴とする感熱昇華型転写受像シート。 A heat-sensitive sublimation transfer image-receiving sheet comprising at least a support and a receiving layer, wherein the receiving layer is a sulfonate or a sulfate ester with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. A heat-sensitive sublimation transfer image-receiving sheet comprising a vinyl chloride copolymer containing 0.20 to 10.0 parts by weight of an organic compound having a salt and 0.05 to 3.0 parts by weight of a higher fatty acid salt. 受容層が、塩化ビニル－不飽和カルボン酸エステル共重合体１００重量部に対して、スルホン酸塩又は硫酸エステル塩を有する有機化合物０．２０～１０．０重量部及び高級脂肪酸塩０．０５～３．０重量部を含み、ｐＨ３～８である塩化ビニル系共重合体ラテックスを用いて形成されていることを特徴とする請求項１に記載の感熱昇華型転写受像シート。 The receiving layer is 0.20 to 10.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 0.05 to higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride-unsaturated carboxylic acid ester copolymer. 2. The heat-sensitive sublimation transfer image-receiving sheet according to claim 1, wherein the heat-sensitive sublimation transfer image-receiving sheet is formed using a vinyl chloride copolymer latex containing 3.0 parts by weight and having a pH of 3 to 8. 塩化ビニル系共重合体ラテックスが、平均粒子径が０．１４μｍ以下であることを特徴とする請求項２に記載の感熱昇華型転写受像シート。 The heat-sensitive sublimation transfer image-receiving sheet according to claim 2, wherein the vinyl chloride copolymer latex has an average particle size of 0.14 µm or less. スルホン酸塩又は硫酸エステル塩を有する有機化合物が、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩及びジアルキルスルホコハク酸塩から選ばれる少なくとも１種であることを特徴とする請求項１～請求項３のいずれかの項に記載の感熱昇華型転写受像シート。 4. The organic compound having a sulfonate or sulfate ester salt is at least one selected from alkyl sulfate ester salts, alkylbenzene sulfonate salts, and dialkyl sulfosuccinate salts. The heat-sensitive sublimation type transfer image-receiving sheet as described in the above item. スルホン酸塩又は硫酸エステル塩を有する有機化合物が、スルホン酸又は硫酸エステルを有する有機化合物と、カリウム、ナトリウム、アンモニア、トリエタノールアミンのいずれかとの塩であることを特徴とする請求項１～請求項４のいずれかの項に記載の感熱昇華型転写受像シート。 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 5. The heat-sensitive sublimation transfer image-receiving sheet according to any one of items 4 to 5. 高級脂肪酸塩が、高級脂肪酸のカリウム、ナトリウム、アンモニア、トリエタノールアミンのいずれかとの塩であることを特徴とする請求項１～請求項５のいずれかの項に記載の感熱昇華型転写受像シート。 6. The heat-sensitive sublimation transfer image-receiving sheet according to claim 1, wherein the higher fatty acid salt is a salt of higher fatty acid with any of potassium, sodium, ammonia and triethanolamine. . 不飽和カルボン酸が、メタクリル酸又はアクリル酸であることを特徴とする請求項１～請求項６のいずれかの項に記載の感熱昇華型転写受像シート。 The heat-sensitive sublimation transfer image-receiving sheet according to any one of claims 1 to 6, wherein the unsaturated carboxylic acid is methacrylic acid or acrylic acid.
PCT/JP2012/077448 2011-10-25 2012-10-24 Heat-sensitive sublimation transfer image receiving sheet Ceased WO2013061994A1 (en)

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