JP2021075041A - Transfer printing sheet - Google Patents
Transfer printing sheet Download PDFInfo
- Publication number
- JP2021075041A JP2021075041A JP2020142671A JP2020142671A JP2021075041A JP 2021075041 A JP2021075041 A JP 2021075041A JP 2020142671 A JP2020142671 A JP 2020142671A JP 2020142671 A JP2020142671 A JP 2020142671A JP 2021075041 A JP2021075041 A JP 2021075041A
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- JP
- Japan
- Prior art keywords
- transfer printing
- less
- air permeability
- printing paper
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000010023 transfer printing Methods 0.000 title claims abstract description 131
- 239000010410 layer Substances 0.000 claims abstract description 107
- 239000011247 coating layer Substances 0.000 claims abstract description 86
- 230000035699 permeability Effects 0.000 claims abstract description 69
- 229920002472 Starch Polymers 0.000 claims abstract description 66
- 235000019698 starch Nutrition 0.000 claims abstract description 66
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 49
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 49
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 49
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000000859 sublimation Methods 0.000 claims abstract description 27
- 230000008022 sublimation Effects 0.000 claims abstract description 27
- 150000004676 glycans Chemical class 0.000 claims abstract description 18
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- 239000008107 starch Substances 0.000 claims description 42
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 claims description 28
- 239000000049 pigment Substances 0.000 claims description 23
- 239000004202 carbamide Substances 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 4
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- 230000006866 deterioration Effects 0.000 abstract description 22
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- 239000000976 ink Substances 0.000 description 44
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 22
- 238000007639 printing Methods 0.000 description 22
- 238000012546 transfer Methods 0.000 description 19
- 239000000975 dye Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
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- 238000013461 design Methods 0.000 description 6
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- 239000000945 filler Substances 0.000 description 5
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical class [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
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- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
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- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
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- 125000002270 phosphoric acid ester group Chemical group 0.000 description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
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- 239000000454 talc Substances 0.000 description 2
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- 239000004753 textile Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 229920001453 Arcel Polymers 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 240000001058 Sterculia urens Species 0.000 description 1
- 235000015125 Sterculia urens Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Coloring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、繊維材料等の被印刷物へ図柄を形成する転写捺染法において、図柄を転写するために使用する転写捺染用紙に関する。特に、インクに昇華型染料インクを使用する転写捺染法に好適な転写捺染用紙に関する。 The present invention relates to a transfer printing paper used for transferring a pattern in a transfer printing method for forming a pattern on a printed matter such as a textile material. In particular, the present invention relates to a transfer printing paper suitable for a transfer printing method using a sublimation type dye ink as an ink.
繊維材料等の被印刷物に図柄を形成させる方法として、昇華型染料インクを用いて転写捺染用紙に図柄を印刷して転写捺染紙を作製し、転写捺染紙を被印刷物に密着させて、昇華型染料インクを被印刷物に転写させる転写捺染法が公知である（例えば、特許文献１及び特許文献２参照）。 As a method of forming a pattern on a printed matter such as a textile material, a sublimation dye ink is used to print the pattern on a transfer printing paper to produce a transfer printing paper, and the transfer printing paper is brought into close contact with the printed matter to form a sublimation mold. A transfer printing method for transferring a dye ink to a printed matter is known (see, for example, Patent Document 1 and Patent Document 2).
既に、転写捺染法に用いる転写捺染用紙は公知である。
例えば、古紙パルプとして再利用された場合で色斑点の発生を抑制することが可能であり、転写性に優れた昇華型捺染用転写紙として、木材パルプを主成分とする基紙と、顔料と水溶性バインダーを含有するインク受容層とを有し、前記インク受容層の全固形分に対して前記顔料を５〜４０質量％含有することを特徴とする昇華型捺染用転写紙が公知である（例えば、特許文献３参照）。また、転写濃度及び残留印字濃度に優れ、インク乾燥性も良好な昇華型インクジェット捺染転写紙として、基紙の一方面に昇華型捺染インク受容層が形成されており、前記昇華型捺染インク受容層は、少なくとも１種類のバインダーと無機粒子とを含有したインク受容層塗料からなり、前記無機粒子が軽質炭酸カルシウムであり、前記バインダーは少なくともエチレン酢酸ビニル共重合体を含み、前記エチレン酢酸ビニル共重合体は無機粒子の合計１００質量部に対して５．０〜１５．０質量部の割合で含有されており、表面・サイズ度テスターで測定した、前記基紙の初期吸水特性の超音波が１００％に達するまでの時間が、０．０１〜３．００秒であることを特徴とする、昇華型インクジェット捺染転写紙が公知である（例えば、特許文献４参照）。
The transfer printing paper used for the transfer printing method is already known.
For example, when recycled as used paper pulp, it is possible to suppress the occurrence of color spots, and as a transfer paper for sublimation printing with excellent transferability, base paper containing wood pulp as the main component and pigments A transfer paper for sublimation printing, which has an ink receiving layer containing a water-soluble binder and contains 5 to 40% by mass of the pigment with respect to the total solid content of the ink receiving layer, is known. (See, for example, Patent Document 3). Further, as a sublimation type inkjet printing transfer paper having excellent transfer density and residual printing density and good ink drying property, a sublimation type printing ink receiving layer is formed on one side of a base paper, and the sublimation type printing ink receiving layer is formed. Consists of an ink receiving layer coating material containing at least one kind of binder and inorganic particles, the inorganic particles being light calcium carbonate, the binder containing at least an ethylene vinyl acetate copolymer, and the ethylene vinyl acetate common weight. The coalescence is contained in a ratio of 5.0 to 15.0 parts by mass with respect to 100 parts by mass of the total of the inorganic particles, and the ultrasonic wave of the initial water absorption characteristic of the base paper measured by the surface / size degree tester is 100. A sublimation type inkjet printing transfer paper characterized in that the time required to reach% is 0.01 to 3.00 seconds is known (see, for example, Patent Document 4).
昇華型捺染インクを用いて転写捺染用紙に図柄を印刷して転写捺染紙を作製する方法では、特許文献３及び特許文献４に記載されるように、インクジェット印刷方式がよく用いられる。 In a method for producing a transfer printing paper by printing a pattern on a transfer printing paper using a sublimation type printing ink, an inkjet printing method is often used as described in Patent Documents 3 and 4.
図柄が印刷される前の白紙である転写捺染用紙と、転写捺染用紙に転写用の図柄を印刷した転写捺染紙との間では、相反する２つの特性を有する必要がある。すなわち、インクを受容する能力とインクを転写する能力である。転写捺染用紙には、昇華型染料インク等のインクを上手く受容する能力が必要である。転写捺染紙には、昇華型染料インク等が含む色材を被印刷物に上手く転写する能力が必要である。一般に、前記受容する能力を高めると、前記転写する能力が低下する。その結果、被印刷物に転写した図柄の色濃度は、低下する場合がある。 It is necessary to have two contradictory characteristics between the transfer printing paper, which is a blank sheet before the pattern is printed, and the transfer printing paper, which is the transfer printing paper on which the pattern for transfer is printed. That is, the ability to receive ink and the ability to transfer ink. The transfer printing paper needs to have the ability to receive ink such as sublimation dye ink well. The transfer printing paper needs to have the ability to successfully transfer the color material contained in the sublimation type dye ink or the like to the printed matter. In general, increasing the ability to accept decreases the ability to transcribe. As a result, the color density of the pattern transferred to the printed matter may decrease.
また、転写捺染用紙に印刷した図柄の画質を超えて、転写捺染紙から被印刷物に転写した図柄の画質は得られない。よって、転写捺染用紙は、転写捺染用紙に印刷した図柄の画質に対して転写捺染紙から被印刷物に転写した図柄の画質が劣化しない又は画質の劣化を抑制する能力が必要である。 Further, the image quality of the pattern transferred from the transfer printing paper to the printed matter cannot be obtained beyond the image quality of the pattern printed on the transfer printing paper. Therefore, the transfer printing paper needs to have the ability to suppress the deterioration of the image quality of the pattern transferred from the transfer printing paper to the printed matter with respect to the image quality of the pattern printed on the transfer printing paper.
また、転写捺染紙から被印刷物へ効率良く転写するために、転写捺染用紙と昇華型染料インク等のインクとは、親和性が低いことが望まれる。転写捺染用紙と昇華型染料インク等のインクとの親和性が低くなければ、転写捺染紙から被印刷物へのインクが含む色材の転写に、相対的に大きいエネルギーを要することになる。例えば、同じ温度条件で転写する場合では、相対的に長い時間を要して、転写捺染紙から被印刷物へ昇華型染料インク等が含む色材が転写することになる。 Further, in order to efficiently transfer from the transfer printing paper to the printed matter, it is desired that the transfer printing paper and the ink such as the sublimation type dye ink have low affinity. If the affinity between the transfer printing paper and the ink such as the sublimation dye ink is not low, a relatively large amount of energy is required to transfer the color material contained in the ink from the transfer printing paper to the printed matter. For example, when transferring under the same temperature conditions, it takes a relatively long time to transfer the color material containing the sublimation dye ink or the like from the transfer printing paper to the printed matter.
インクジェット用紙には、最大含有量成分が白色顔料である塗工液を原紙に塗工した顔料系インクジェット用紙と、最大含有量成分が樹脂である塗工液を原紙に塗工した樹脂系インクジェット用紙とがある。顔料系インクジェット用紙の特徴は、一般に、インクの吸収速度が速いもののインクの吸収容量に劣る。樹脂系インクジェット用紙の特徴は、一般に、インクの吸収速度が遅いもののインクの吸収容量に優れる。インクの吸収速度が遅くなると、用紙上でインクが拡散するために、インクジェット用紙に印刷した図柄の画質が劣化する。インクの吸収容量が不足すると、インクの溶媒によってインクジェット用紙に皺が発生する。 Inkjet paper includes pigment-based inkjet paper in which a coating liquid having a maximum content component of white pigment is applied to the base paper, and resin-based inkjet paper in which a coating liquid having a maximum content component of resin is applied to the base paper. There is. The characteristics of pigment-based inkjet paper are generally that the ink absorption rate is high, but the ink absorption capacity is inferior. A feature of resin-based inkjet paper is that it generally has a slow ink absorption rate but an excellent ink absorption capacity. When the ink absorption rate is slowed down, the ink is diffused on the paper, so that the image quality of the pattern printed on the inkjet paper is deteriorated. When the ink absorption capacity is insufficient, the ink solvent causes wrinkles on the inkjet paper.
特許文献３の昇華型捺染用転写紙及び特許文献４の昇華型インクジェット捺染転写紙の品質は必ずしも十分とはいえない。 The quality of the sublimation type printing transfer paper of Patent Document 3 and the sublimation type inkjet printing transfer paper of Patent Document 4 cannot always be said to be sufficient.
上記を鑑みて、本発明の目的は、後記項目の品質を有する転写捺染用紙を提供することである。
（１）転写捺染紙において皺の発生が抑制できること（耐皺発生性）
（２）転写捺染紙において転写効率が良好であること（転写性）
（３）被印刷物において画質の劣化が抑制できること（耐画質劣化性）
（４）被印刷物において色濃度の低下が抑制できること（発色性）
In view of the above, an object of the present invention is to provide a transfer printing paper having the quality described below.
(1) The generation of wrinkles can be suppressed in the transfer printing paper (wrinkle resistance).
(2) Good transfer efficiency in transfer printing paper (transferability)
(3) Deterioration of image quality can be suppressed in the printed matter (image resistance deterioration resistance)
(4) The decrease in color density can be suppressed in the printed matter (color development).
本発明者らは、上記の課題を解決するために鋭意研究を重ねた。その結果、本発明の目的は、以下により達成される。
［１］原紙層と、前記原紙層の片面に対して多糖類を主成分とする塗工層とを有し、前記多糖類が、カルボキシメチルセルロース及び澱粉類を少なくとも含有し、ＩＳＯ５６３６−５：２００３に準拠して測定される透気度であって、前記原紙層の透気度が３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１０倍以上である、昇華型染料インクを用いる転写捺染法に使用する転写捺染用紙。
The present inventors have conducted extensive research to solve the above problems. As a result, the object of the present invention is achieved by the following.
[1] A base paper layer and a coating layer containing a polysaccharide as a main component are provided on one side of the base paper layer, and the polysaccharide contains at least carboxymethyl cellulose and starches, and ISO5636-5: 2003. The air permeability of the transfer printing paper having the air permeability of the base paper layer of 30 sec or less and having a coating layer on one side of the base paper layer is the air permeability of the base paper layer. A transfer printing paper used in a transfer printing method using a sublimation type dye ink, which is 10 times or more the amount of the above.
［２］多糖類を主成分とする塗工層の付与量が、乾燥固形分量で片面あたり４ｇ／ｍ２以下である上記［１］に記載の転写捺染用紙。 [2] The transfer printing paper according to the above [1], wherein the amount of the coating layer containing a polysaccharide as a main component is 4 g / m 2 or less per side in terms of dry solid content.
［３］多糖類を主成分とする前記塗工層が、実質的に顔料を含有しない上記［１］又は上記［２］に記載の転写捺染用紙。 [3] The transfer printing paper according to the above [1] or the above [2], wherein the coating layer containing a polysaccharide as a main component does not substantially contain a pigment.
［４］上記澱粉類の少なくとも一種が、尿素燐酸エステル化澱粉である上記［１］乃至上記［３］のいずれかに記載の転写捺染用紙。 [4] The transfer printing paper according to any one of the above [1] to the above [3], wherein at least one of the starches is a urea phosphate esterified starch.
［５］上記カルボキシメチルセルロースが、低分子量タイプである上記［１］乃至上記［４］のいずれかに記載の転写捺染用紙。 [5] The transfer printing paper according to any one of the above [1] to the above [4], wherein the carboxymethyl cellulose is a low molecular weight type.
［６］ＩＳＯ５６３６−５：２００３に準拠して測定される透気度であって、上記原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１２倍以上５４５０倍以下である、上記［１］乃至上記［５］のいずれかに記載の転写捺染用紙。 [6] A transfer printing paper having an air permeability measured in accordance with ISO 5636-5: 2003, wherein the air permeability of the base paper layer is 12 sec or more and 30 sec or less and a coating layer is provided on one side of the base paper layer. The transfer printing paper according to any one of the above [1] to [5], wherein the air permeability is 12 times or more and 5450 times or less the air permeability of the base paper layer.
［７］上記尿素燐酸エステル化澱粉が、尿素置換度平均値０．００５以上０．０５以下である上記［４］に記載の転写捺染用紙。 [7] The transfer printing paper according to the above [4], wherein the urea phosphoric acid esterified starch has an average urea substitution degree of 0.005 or more and 0.05 or less.
［８］上記カルボキシメチルセルロースにおいて、ゲルパーミエーションクロマトグラフィーにより得られるポリエチレングリコール換算の重量平均分子量が２７，０００以上７７０，０００以下である上記［１］乃至上記［７］のいずれかに記載の転写捺染用紙。 [8] The transfer according to any one of the above [1] to the above [7], wherein the weight average molecular weight of the carboxymethyl cellulose in terms of polyethylene glycol obtained by gel permeation chromatography is 27,000 or more and 770,000 or less. Printing paper.
［９］上記カルボキシメチルセルロースにおいて、エーテル化度が０．６以上１．２７以下である上記［１］乃至上記［７］のいずれかに記載の転写捺染用紙。 [9] The transfer printing paper according to any one of the above [1] to the above [7], wherein the degree of etherification of the carboxymethyl cellulose is 0.6 or more and 1.27 or less.
［１０］上記カルボキシメチルセルロースにおいて、ゲルパーミエーションクロマトグラフィーにより得られるポリエチレングリコール換算の重量平均分子量が２７，０００以上７７０，０００以下かつエーテル化度が０．６以上１．２７以下である上記［１］乃至上記［７］のいずれかに記載の転写捺染用紙。 [10] In the above-mentioned carboxymethyl cellulose, the weight average molecular weight in terms of polyethylene glycol obtained by gel permeation chromatography is 27,000 or more and 770,000 or less, and the degree of etherification is 0.6 or more and 1.27 or less. ] To the transfer printing paper according to any one of the above [7].
［１１］ＩＳＯ５６３６−５：２００３に準拠して測定される透気度であって、上記原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１２倍以上５４５０倍以下であり、上記尿素燐酸エステル化澱粉が尿素置換度平均値０．００５以上０．０５以下である上記［４］に記載の転写捺染用紙。 [11] An air permeability measured in accordance with ISO 5636-5: 2003, which is a transfer printing paper having an air permeability of the base paper layer of 12 sec or more and 30 sec or less and having a coating layer on one side of the base paper layer. The transfer according to the above [4], wherein the air permeability is 12 times or more and 5450 times or less of the air permeability of the base paper layer, and the urea phosphoric acid esterified starch has an average urea substitution degree of 0.005 or more and 0.05 or less. Printing paper.
［１２］ＩＳＯ５６３６−５：２００３に準拠して測定される透気度であって、上記原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１２倍以上５４５０倍以下であり、上記尿素燐酸エステル化澱粉が尿素置換度平均値０．００５以上０．０５以下であり、上記カルボキシメチルセルロースにおいてゲルパーミエーションクロマトグラフィーにより得られるポリエチレングリコール換算の重量平均分子量が２７，０００以上７７０，０００以下かつエーテル化度が０．６以上１．２７以下である上記［４］に記載の転写捺染用紙。 [12] A transfer printing paper having an air permeability measured in accordance with ISO 5636-5: 2003, wherein the air permeability of the base paper layer is 12 sec or more and 30 sec or less and a coating layer is provided on one side of the base paper layer. The air permeability is 12 times or more and 5450 times or less of the air permeability of the base paper layer, the urea phosphoric acid esterified starch has an average urea substitution degree of 0.005 or more and 0.05 or less, and gel permeation in the carboxymethyl cellulose. The transfer printing paper according to the above [4], wherein the polyethylene glycol-equivalent weight average molecular weight obtained by chromatography is 27,000 or more and 770,000 or less and the degree of etherification is 0.6 or more and 1.27 or less.
本発明により、耐皺発生性、転写性、耐画質劣化性及び発色性を有する転写捺染用紙を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a transfer printing paper having wrinkle resistance, transferability, image quality deterioration resistance and color development.
以下に本発明を詳細に説明する。
本発明において、「転写捺染用紙」とは、転写する図柄が印刷される前の白紙状態にある用紙を指す。「転写捺染紙」とは、転写捺染用紙に対して転写する図柄が印刷された状態にある用紙を指す。
The present invention will be described in detail below.
In the present invention, the "transfer printing paper" refers to a paper that is in a blank state before the pattern to be transferred is printed. The "transfer printing paper" refers to a paper in which a pattern to be transferred is printed on the transfer printing paper.
転写捺染用紙は、原紙層と、前記原紙層の片面に対して塗工層とを有する。
原紙層は、ＬＢＫＰ（Leaf Bleached Kraft Pulp）、ＮＢＫＰ（Needle Bleached Kraft Pulp）等の化学パルプ、ＧＰ（Groundwood Pulp）、ＰＧＷ（Pressure GroundWood pulp）、ＲＭＰ（Refiner Mechanical Pulp）、ＴＭＰ（ThermoMechanical Pulp）、ＣＴＭＰ（ChemiThermoMechanical Pulp）、ＣＭＰ（ChemiMechanical Pulp）、ＣＧＰ（ChemiGroundwood Pulp）等の機械パルプ、及びＤＩＰ（DeInked Pulp）等の古紙パルプから選ばれる少なくとも一種のパルプに、炭酸カルシウム、タルク、クレー、カオリン等の各種填料、さらに、バインダー、サイズ剤、定着剤、歩留まり剤、カチオン化剤、紙力剤、顔料分散剤、増粘剤、流動性改良剤、消泡剤、抑泡剤、離型剤、発泡剤、浸透剤、着色染料、着色顔料、蛍光増白剤、紫外線吸収剤、酸化防止剤、防腐剤、防バイ剤、耐水化剤等の各種添加剤を必要に応じて配合した紙料を抄造して得られる抄造紙からなる。さらに、原紙層には、前記抄造紙に従来公知のカレンダー処理を施したカレンダー処理抄造紙が含まれる。カレンダー処理には、従来公知のカレンダー処理装置を用いることができる。カレンダー処理装置の例としては、マシンカレンダー、ソフトニップカレンダー、スーパーカレンダー、多段カレンダー、マルチニップカレンダー等を挙げることができる。
The transfer printing paper has a base paper layer and a coating layer on one side of the base paper layer.
The base paper layer is chemical pulp such as LBKP (Leaf Bleached Kraft Pulp) and NBKP (Needle Bleached Kraft Pulp), GP (Groundwood Pulp), PGW (Pressure GroundWood pulp), RMP (Refiner Mechanical Pulp), TMP (ThermoMechanical Pulp), At least one type of pulp selected from mechanical pulps such as CTMP (ChemiThermoMechanical Pulp), CMP (ChemiMechanical Pulp), CGP (ChemiGroundwood Pulp), and waste paper pulps such as DIP (DeInked Pulp) includes calcium carbonate, talc, clay, kaolin, etc. Various fillers, binders, sizing agents, fixing agents, yield agents, cationizing agents, pulp strength agents, pigment dispersants, thickeners, fluidity improvers, defoaming agents, defoaming agents, mold release agents, Pulp materials containing various additives such as foaming agents, penetrants, coloring dyes, coloring pigments, fluorescent whitening agents, ultraviolet absorbers, antioxidants, preservatives, antibacterial agents, and water resistant agents as needed. It consists of made paper obtained by making. Further, the base paper layer includes a calendar-processed paper made by subjecting the paper-made paper to a conventionally known calendar-processed paper. A conventionally known calendar processing device can be used for the calendar processing. Examples of the calendar processing device include a machine calendar, a soft nip calendar, a super calendar, a multi-stage calendar, a multi-nip calendar, and the like.
抄造は、紙料を酸性、中性又はアルカリ性に調整して、従来公知の抄紙機を用いて行うことができる。抄紙機の例としては、長網抄紙機、ツインワイヤー抄紙機、コンビネーション抄紙機、円網抄紙機、ヤンキー抄紙機等を挙げることができる。 Paper making can be performed using a conventionally known paper machine by adjusting the paper material to acidic, neutral or alkaline. Examples of the paper machine include a long net paper machine, a twin wire paper machine, a combination paper machine, a circular net paper machine, a Yankee paper machine, and the like.
塗工層は、上記原紙層に対して、従来公知の塗工装置及び乾燥装置を用いて塗工層用塗工液を原紙層に付与することによって得ることができる。実施態様として、塗工層は、塗工層用塗工液の成分が抄造紙表面に塗工層領域として存在する状態及び／又は抄造紙の内部に塗工層用塗工液の成分が浸透した拡散層領域として存在する状態を含む。すなわち、塗工層は、原紙層に対して、塗工層領域として存在する状態、拡散層領域として存在する状態、並びに塗工層領域及び拡散層領域の両状態として存在する状態のいずれかである。塗工層の前記状態は、エネルギー分散形Ｘ線分光器等の元素分析機能付の電子顕微鏡で用紙の断面を観察し、元素分布を解析することによって確認することができる。
塗工層領域として存在する状態及び／又は拡散層領域として存在する状態は、原紙層のバインダーの種類及び含有量、原紙層のサイズ剤の種類及び含有量、原紙層の紙力剤の種類及び含有量、並びにカレンダー処理条件によって制御できる。
The coating layer can be obtained by applying a coating liquid for a coating layer to the base paper layer using a conventionally known coating device and a drying device. In an embodiment, the coating layer has a state in which the component of the coating liquid for the coating layer exists as a coating layer region on the surface of the paper and / or the component of the coating liquid for the coating layer penetrates into the inside of the paper. Includes a state that exists as a diffused layer region. That is, the coating layer is either in a state of existing as a coating layer region, a state of existing as a diffusion layer region, or a state of existing as both a coating layer region and a diffusion layer region with respect to the base paper layer. is there. The state of the coating layer can be confirmed by observing the cross section of the paper with an electron microscope having an elemental analysis function such as an energy dispersive X-ray spectroscope and analyzing the elemental distribution.
The state existing as the coating layer region and / or the state existing as the diffusion layer region includes the type and content of the binder of the base paper layer, the type and content of the sizing agent of the base paper layer, the type of the paper strength agent of the base paper layer, and the state. It can be controlled by the content and the calendar processing conditions.
塗工層は、多糖類を主成分として有する。多糖類は、カルボキシメチルセルロースと澱粉類とを少なくとも含有する。ここで、「主成分として有する」とは、塗工層を構成する乾燥固形分に対して５０質量％超を占める状態を指す。この様な塗工層は、カルボキシメチルセルロースと澱粉類とを少なくとも含有する塗工層塗工液を、従来公知の塗工装置及び乾燥装置を用いて、原紙層に対して塗工及び乾燥することによって得ることができる。従来公知の塗工装置の例としては、サイズプレス、ゲートロールコーター、フィルムトランスファーコーター、ブレードコーター、ロッドコーター、エアナイフコーター、グラビアコーター、バーコーター、Ｅバーコーター、カーテンコーター等を挙げることができる。従来公知の乾燥装置の例としては、直線トンネル乾燥機、アーチドライヤー、エアループドライヤー、サインカーブエアフロートドライヤー等の熱風乾燥機、赤外線加熱ドライヤー、マイクロ波等を利用した乾燥機等の各種乾燥装置を挙げることができる。
塗工層塗工液を塗工及び乾燥後に、塗工層には、従来公知のカレンダー処理を施すことができる。
The coating layer has a polysaccharide as a main component. The polysaccharide contains at least carboxymethyl cellulose and starches. Here, "having as a main component" refers to a state in which more than 50% by mass is occupied with respect to the dry solid content constituting the coating layer. In such a coating layer, a coating layer coating liquid containing at least carboxymethyl cellulose and starch is coated and dried on the base paper layer using a conventionally known coating device and drying device. Can be obtained by. Examples of conventionally known coating devices include size presses, gate roll coaters, film transfer coaters, blade coaters, rod coaters, air knife coaters, gravure coaters, bar coaters, E bar coaters, curtain coaters and the like. Examples of conventionally known drying devices include hot air dryers such as straight tunnel dryers, arch dryers, air loop dryers, and sine curve air float dryers, infrared heating dryers, and various drying devices such as dryers using microwaves. Can be mentioned.
Coating layer After coating and drying the coating liquid, the coating layer can be subjected to a conventionally known calendar treatment.
転写捺染用紙の実施形態として、原紙層に対して塗工層は、原紙層の片面に存在する。転写捺染用紙は、原紙層の塗工層を有する側の反対側に、従来公知のバックコート層を有することができる。 As an embodiment of the transfer printing paper, the coating layer exists on one side of the base paper layer with respect to the base paper layer. The transfer printing paper may have a conventionally known backcoat layer on the opposite side of the base paper layer to the side having the coating layer.
いくつかの実施態様として、原紙層に対する塗工層の付与量は、乾燥固形分量で原紙層の片面あたり４ｇ／ｍ２以下である。また、いくつかの実施態様として、原紙層に対する塗工層の付与量は、乾燥固形分量で原紙層の片面あたり１．５ｇ／ｍ２以上である。また、いくつかの実施態様として、原紙層に対する塗工層の付与量は、乾燥固形分量で原紙層の片面あたり２．４ｇ／ｍ２以上である。さらに、少なくとも一つの実施態様として、原紙層に対する塗工層の付与量は、乾燥固形分量で原紙層の片面あたり１．５ｇ／ｍ２以上４ｇ／ｍ２以下である。原紙層に対する塗工層の付与量がこの範囲であると、耐画質劣化性が良化する。 In some embodiments, the amount of the coating layer applied to the base paper layer is 4 g / m 2 or less per side of the base paper layer in terms of dry solid content. Further, in some embodiments, the amount of the coating layer applied to the base paper layer is 1.5 g / m 2 or more per side of the base paper layer in terms of dry solid content. Further, in some embodiments, the amount of the coating layer applied to the base paper layer is 2.4 g / m 2 or more per side of the base paper layer in terms of dry solid content. Further, in at least one embodiment, the amount of the coating layer applied to the base paper layer is 1.5 g / m 2 or more and 4 g / m 2 or less per one side of the base paper layer in terms of dry solid content. When the amount of the coating layer applied to the base paper layer is within this range, the image quality deterioration resistance is improved.
カルボキシメチルセルロースは、セルロースエーテルの一種であり、従来公知のものであって特に限定されない。カルボキシメチルセルロースには、カルボキシメチルセルロースアルカリ金属塩が含まれる。カルボキシメチルセルロースは、例えば、パルプを原料としてモノクロル酢酸ナトリウム及び水酸化ナトリウムを反応させて得ることができる（直接法）。また、直接法以外にアルセル法及び溶媒法によって得ることができる。カルボキシメチルセルロースは、使用するパルプの性状及び製造方法により様々な分子量又は重合度のものが製造可能である。一般的に、カルボキシメチルセルロースは、カルボキシメチルセルロースアルカリ金属塩として工業的に生産及び販売される。カルボキシメチルセルロースアルカリ金属塩は、多くは、カルボキシメチルセルロースナトリウム塩又はカルボキシメチルセルロースカリウム塩である。慣用的に、ナトリウム塩やカリウム塩の記載は省略する場合が多い。少なくとも一つの実施態様として、カルボキシメチルセルロースアルカリ金属塩はカルボキシメチルセルロースナトリウム塩である。この理由は、カルボキシメチルセルロースナトリウム塩が商業的に入手し易いからである。カルボキシメチルセルロースは、例えば、シグマアルドリッチ社、ダイセルミライズ社、第一工業製薬社、ＣＰＫｅｌｃｏ社、日本製紙社、及びＡｓｈｌａｎｄ社等から市販される。 Carboxymethyl cellulose is a kind of cellulose ether, which is conventionally known and is not particularly limited. Carboxymethyl cellulose includes alkali metal salts of carboxymethyl cellulose. Carboxymethyl cellulose can be obtained, for example, by reacting sodium monochloroacetate and sodium hydroxide using pulp as a raw material (direct method). In addition to the direct method, it can be obtained by the Arcel method and the solvent method. Carboxymethyl cellulose can be produced with various molecular weights or degrees of polymerization depending on the properties of the pulp used and the production method. Generally, carboxymethyl cellulose is industrially produced and sold as a carboxymethyl cellulose alkali metal salt. Most of the carboxymethyl cellulose alkali metal salts are sodium carboxymethyl cellulose salts or potassium carboxymethyl cellulose salts. Conventionally, the description of sodium salt and potassium salt is often omitted. In at least one embodiment, the carboxymethyl cellulose alkali metal salt is a sodium carboxymethyl cellulose salt. The reason for this is that sodium carboxymethyl cellulose salts are commercially available. Carboxymethyl cellulose is commercially available from, for example, Sigma-Aldrich, Daicel FineChem, Dai-ichi Kogyo Seiyaku, CPKelco, Nippon Paper Industries, Ashland and others.
いくつかの実施態様として、カルボキシメチルセルロースは、ゲルパーミエーションクロマトグラフィーにより得られるポリエチレングリコール換算の重量平均分子量が１００万未満の低分子量タイプである。いくつかの実施態様として、カルボキシメチルセルロースは同換算の重量平均分子量が７７０，０００以下である。また、いくつかの実施態様として、カルボキシメチルセルロースは同換算の重量平均分子量が２７，０００以上である。また、少なくとも一つの実施形態として、カルボキシメチルセルロースは同換算の重量平均分子量が２７，０００以上７７０，０００以下である。カルボキシメチルセルロースの重量平均分子量がこの範囲であると、転写性及び／又は耐画質劣化性が良化する。また、少なくとも一つの実施形態として、カルボキシメチルセルロースは同換算の重量平均分子量が２７，０００以上３６０，０００以下である。カルボキシメチルセルロースの重量平均分子量がこの範囲であると、塗工層塗工液の製造が容易となる。
いくつかの実施態様として、カルボキシメチルセルロースのエーテル化度は０．６以上１．２７以下である。カルボキシメチルセルロースのエーテル化度がこの範囲であると、耐画質劣化性が良化する。エーテル化度は、セルロースを構成するグルコース環上にある３つの水酸基のうちカルボキシメチル基で置換された水酸基の数（平均値）を指す。エーテル化度は、理論的に０から３の間の値を有することができ、一般的に置換度が高いほど親水性となる。
少なくとも一つの実施態様として、カルボキシメチルセルロースは、ゲルパーミエーションクロマトグラフィーにより得られるポリエチレングリコール換算の重量平均分子量が２７，０００以上７７０，０００以下であり、かつエーテル化度が０．６以上１．２７以下である。
In some embodiments, carboxymethyl cellulose is a low molecular weight type obtained by gel permeation chromatography with a polyethylene glycol equivalent weight average molecular weight of less than 1 million. In some embodiments, carboxymethyl cellulose has a weight average molecular weight of 770,000 or less in the same equivalent. Further, in some embodiments, carboxymethyl cellulose has a weight average molecular weight of 27,000 or more in the same equivalent. Further, in at least one embodiment, carboxymethyl cellulose has a weight average molecular weight of 27,000 or more and 770,000 or less in the same equivalent. When the weight average molecular weight of carboxymethyl cellulose is in this range, the transferability and / or the image quality deterioration resistance is improved. Further, in at least one embodiment, carboxymethyl cellulose has a weight average molecular weight of 27,000 or more and 360,000 or less in the same equivalent. When the weight average molecular weight of carboxymethyl cellulose is in this range, the coating layer coating liquid can be easily produced.
In some embodiments, the degree of etherification of carboxymethyl cellulose is 0.6 or more and 1.27 or less. When the degree of etherification of carboxymethyl cellulose is within this range, the image quality deterioration resistance is improved. The degree of etherification refers to the number (average value) of the hydroxyl groups substituted with carboxymethyl groups among the three hydroxyl groups on the glucose ring constituting cellulose. The degree of etherification can theoretically have a value between 0 and 3, and generally, the higher the degree of substitution, the more hydrophilic the material.
In at least one embodiment, carboxymethyl cellulose has a polyethylene glycol-equivalent weight average molecular weight obtained by gel permeation chromatography of 27,000 or more and 770,000 or less, and an etherification degree of 0.6 or more and 1.27. It is as follows.
いくつかの実施態様として、塗工層におけるカルボキシメチルセルロースの含有量は、０．７５ｇ／ｍ２以上３．５ｇ／ｍ２以下である。また、少なくとも一つの実施態様として、塗工層におけるカルボキシメチルセルロースの含有量は、１ｇ／ｍ２以上３．４ｇ／ｍ２以下である。カルボキシメチルセルロースの含有量がこの範囲であると、耐皺発生性、転写性及び／又は耐画質劣化性が良化する。 In some embodiments, the content of carboxymethyl cellulose in the coating layer is 0.75 g / m 2 or more and 3.5 g / m 2 or less. Further, in at least one embodiment, the content of carboxymethyl cellulose in the coating layer is 1 g / m 2 or more and 3.4 g / m 2 or less. When the content of carboxymethyl cellulose is in this range, wrinkle resistance, transferability and / or image quality deterioration resistance are improved.
澱粉類は、グルコースがグリコシド結合によって重合した従来公知の多糖類又はグルコースがグリコシド結合によって重合した多糖類においてグルコースが有する水酸基を種々置換基によって変性した従来公知の多糖類であって、特に限定されない。澱粉類の例としては、澱粉、酸化澱粉、酵素変性澱粉、エーテル化澱粉、カチオン性澱粉、両性澱粉、ジアルデヒド澱粉、燐酸エステル化澱粉及び尿素燐酸エステル化澱粉等のエステル化澱粉、ヒドロキシエチル化澱粉、並びにヒドロキシブチル化澱粉等を挙げることができる。 The starches are conventionally known polysaccharides in which glucose is polymerized by a glycosidic bond or conventionally known polysaccharides in which the hydroxyl group of glucose is modified by various substituents in a polysaccharide obtained by polymerizing glucose by a glycosidic bond, and the present invention is not particularly limited. .. Examples of starches include esterified starches such as starches, oxidized starches, enzyme-modified starches, etherified starches, cationic starches, amphoteric starches, dialdehyde starches, phosphoric acid esterified starches and urea phosphoric acid esterified starches, hydroxyethylated starches. Examples thereof include starch and hydroxybutylated starch.
少なくとも一つの実施態様として、澱粉類の少なくとも一種は尿素燐酸エステル化澱粉である。澱粉類が尿素燐酸エステル化澱粉であると、転写性、耐画質劣化性及び／又は発色性が良化する。尿素燐酸エステル化澱粉は、燐酸エステル基とカルバミン酸エステル基とをグルコースに有する澱粉である。燐酸エステル基を導入する方法の例としては、トリポリ燐酸ナトリウム等の燐酸塩を単独で添加して焙焼反応させる方法、燐酸エステル基とカルバミン酸エステル基とを導入する方法の例としては、無機燐酸類と共に尿素を添加して焙焼反応させる方法を挙げることができる。尿素燐酸エステル化澱粉は、主に、後者の無機燐酸類と尿素を焙焼反応させる方法によって各種尿素置換度のものを得ることができる。尿素燐酸エステル化澱粉は、王子コーンスターチ社、日本食品化工社、ジー・エス・エル・ジャパン社等から市販される。 In at least one embodiment, at least one of the starches is urea phosphate esterified starch. When the starches are urea phosphate esterified starches, the transferability, image quality deterioration property and / or color development property are improved. The urea phosphate esterified starch is a starch having a phosphate ester group and a carbamic acid ester group in glucose. Examples of the method for introducing a phosphoric acid ester group include a method in which a phosphate such as sodium tripolyphosphate is added alone for a roasting reaction, and an example of a method for introducing a phosphoric acid ester group and a carbamate group is inorganic. Examples thereof include a method in which urea is added together with phosphoric acids to cause a roasting reaction. Urea phosphoric acid esterified starch can be obtained with various degrees of urea substitution mainly by the latter method of roasting inorganic phosphoric acids and urea. Urea-phosphate esterified starch is commercially available from Oji Cornstarch, Nihon Shokuhin Kako, GSL Japan, and others.
いくつかの実施態様において、尿素燐酸エステル化澱粉は尿素置換度平均値が０．００５以上０．０９以下である。少なくとも一つの実施態様として、尿素燐酸エステル化澱粉は尿素置換度平均値が０．００５以上０．０５以下である。尿素燐酸エステル化澱粉の尿素置換度平均値がこの範囲であると、転写性及び／又は発色性が良化する。「尿素置換度」とは、澱粉を構成するグルコース単位が有する水酸基におけるカルバミン酸エステル基の置換度である。例えば、尿素置換度＝０．０２は、澱粉を構成するグルコース単位１００個当たり置換基が２個有することを意味する。尿素置換度は、澱粉において従来から知られた値であって公知の方法で求められる。例えば、熱分解ＧＣ法又はＣＨＮ元素分析計を用いた窒素含有量から求めることができる。また、「澱粉科学実験法」鈴木繁男・中村道徳編集、１９７９年第１刷発行、朝倉書店発行を参考にすることができる。 In some embodiments, the urea phosphate esterified starch has an average urea substitution of 0.005 or more and 0.09 or less. In at least one embodiment, the urea phosphate esterified starch has an average urea substitution degree of 0.005 or more and 0.05 or less. When the average urea substitution degree of the urea phosphate esterified starch is in this range, the transferability and / or the color development property is improved. The "urea substitution degree" is the degree of substitution of the carbamic acid ester group in the hydroxyl group of the glucose unit constituting the starch. For example, the degree of urea substitution = 0.02 means that there are two substituents per 100 glucose units constituting the starch. The degree of urea substitution is a value conventionally known for starch and is determined by a known method. For example, it can be determined from the nitrogen content using a pyrolysis GC method or a CHN elemental analyzer. You can also refer to "Starch Science Experimental Method" edited by Shigeo Suzuki and Michinori Nakamura, published in the first printing in 1979, and published by Asakura Shoten.
いくつかの実施態様として、塗工層における澱粉類の含有量は、０．５ｇ／ｍ２以上３ｇ／ｍ２以下である。また、少なくとも一つの実施態様として、塗工層における尿素燐酸エステル化澱粉の含有量は、０．５ｇ／ｍ２以上２．７ｇ／ｍ２以下である。尿素燐酸エステル化澱粉の含有量がこの範囲であると、耐皺発生性及び／又は耐画質劣化性が良化する。 In some embodiments, the starch content in the coating layer is 0.5 g / m 2 or more and 3 g / m 2 or less. Further, in at least one embodiment, the content of the urea phosphate esterified starch in the coating layer is 0.5 g / m 2 or more and 2.7 g / m 2 or less. When the content of the urea phosphate esterified starch is in this range, the wrinkle resistance and / or the image quality deterioration resistance is improved.
いくつかの実施態様として、塗工層におけるカルボキシメチルセルロースの含有量が０．７５ｇ／ｍ２以上３．５ｇ／ｍ２以下かつ塗工層における澱粉類の含有量が０．５ｇ／ｍ２以上３ｇ／ｍ２以下である。また、少なくとも一つの実施態様として、塗工層におけるカルボキシメチルセルロースの含有量が１ｇ／ｍ２以上３．４ｇ／ｍ２以下かつ塗工層における尿素燐酸エステル化澱粉の含有量が０．５ｇ／ｍ２以上２．７ｇ／ｍ２以下である。 In some embodiments, the carboxymethyl cellulose content in the coating layer is 0.75 g / m 2 or more and 3.5 g / m 2 or less and the starch content in the coating layer is 0.5 g / m 2 or more and 3 g. It is less than / m 2. Further, in at least one embodiment, the content of carboxymethyl cellulose in the coating layer is 1 g / m 2 or more and 3.4 g / m 2 or less, and the content of urea phosphate esterified starch in the coating layer is 0.5 g / m. 2 or more and 2.7 g / m 2 or less.
少なくとも一つの実施態様として、カルボキシメチルセルロースは、ゲルパーミエーションクロマトグラフィーにより得られるポリエチレングリコール換算の重量平均分子量が２７，０００以上７７０，０００以下であり、かつエーテル化度が０．６以上１．２７以下であって、並びに澱粉類の少なくとも一種は、尿素燐酸エステル化澱粉であって、尿素燐酸エステル化澱粉が尿素置換度平均値０．００５以上０．０５以下である。 In at least one embodiment, carboxymethyl cellulose has a polyethylene glycol equivalent weight average molecular weight of 27,000 or more and 770,000 or less and an esterification degree of 0.6 or more and 1.27 obtained by gel permeation chromatography. And at least one of the starches is urea phosphate esterified starch, and the urea phosphate esterified starch has an average degree of urea substitution of 0.005 or more and 0.05 or less.
塗工層は、カルボキシメチルセルロース及び澱粉類以外に従来公知のバインダーを含有することができる。従来公知のバインダーの例としては、カルボキシメチルセルロースを除くヒドロキシエチルセルロース等のセルロース誘導体、カゼイン、ゼラチン、大豆蛋白、プルラン、アラビアゴム、カラヤゴム及びアルブミン等の天然由来の樹脂又はその誘導体、ポリビニルピロリドン、ポリビニルアルコール及び各種変性ポリビニルアルコール、ポリアクリルアミド、ポリエチレンイミン、ポリプロピレングリコール、ポリエチレングリコール、無水マレイン酸樹脂、（メタ）アクリル酸系樹脂、（メタ）アクリル酸エステル系樹脂、（メタ）アクリル酸エステル−ブタジエン共重合体、スチレン−ブタジエン共重合体及びエチレン−酢酸ビニル共重合体等の共重合体並びにこれらの各種共重合体のカルボキシ基等の官能基含有単量体による官能基変性共重合体、メラミン樹脂及び尿素樹脂等の熱硬化合成樹脂、ポリウレタン樹脂、不飽和ポリエステル樹脂、ポリビニルブチラール、並びにアルキッド樹脂ラテックス等を挙げることができる。 The coating layer can contain a conventionally known binder in addition to carboxymethyl cellulose and starches. Examples of conventionally known binders include cellulose derivatives such as hydroxyethyl cellulose excluding carboxymethyl cellulose, naturally derived resins such as casein, gelatin, soybean protein, purulan, arabic rubber, Karaya rubber and albumin or derivatives thereof, polyvinylpyrrolidone and polyvinyl alcohol. And various modified polyvinyl alcohols, polyacrylamides, polyethyleneimines, polypropylene glycols, polyethylene glycols, maleic anhydride resins, (meth) acrylic acid-based resins, (meth) acrylic acid ester-based resins, (meth) acrylic acid esters-butadiene copolymers. Copolymers such as coalescing, styrene-butadiene copolymers and ethylene-vinyl acetate copolymers, and functional group-modified copolymers with functional group-containing monomers such as carboxy groups of these various copolymers, melamine resins and Examples thereof include a heat-curable synthetic resin such as a urea resin, a polyurethane resin, an unsaturated polyester resin, a polyvinyl butyral, and an alkyd resin latex.
いくつかの実施態様として、塗工層は、従来公知の顔料を含有する。顔料の例としては、カオリン、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、サチンホワイト、リトポン、酸化チタン、酸化亜鉛、シリカ、アルミナ、水酸化アルミニウム、酸化亜鉛、活性白土及び珪藻土等の無機顔料、並びにプラスチック顔料等の有機顔料を挙げることができる。塗工層が顔料を含有する場合、顔料は、前記顔料から成る群から選ばれる一種又は二種以上である。
少なくとも一つの実施態様として、塗工層は、実質的に顔料を含有しない。塗工層が実質的に顔料を含有しないことによって、耐皺発生性が良化する。ここで、「実質的に顔料を含有しない」とは、エネルギー分散形Ｘ線分光器等の元素分析機能付の電子顕微鏡で用紙の断面を観察したときに、原紙層を覆う顔料から成る層が認められないことを指す。例えば、原紙層の片面あたりの塗工層の付与量に対して、顔料が１０質量％未満であれば原紙層を顔料で十分に覆うことができないために顔料から成る層が認められない。
In some embodiments, the coating layer contains a conventionally known pigment. Examples of pigments include inorganic pigments such as kaolin, heavy calcium carbonate, light calcium carbonate, talc, satin white, lithopone, titanium oxide, zinc oxide, silica, alumina, aluminum hydroxide, zinc oxide, active white clay and diatomaceous clay. In addition, organic pigments such as plastic pigments can be mentioned. When the coating layer contains a pigment, the pigment is one or more selected from the group consisting of the pigments.
In at least one embodiment, the coating layer is substantially free of pigment. Since the coating layer contains substantially no pigment, the wrinkle resistance is improved. Here, "substantially free of pigment" means that when the cross section of the paper is observed with an electron microscope having an elemental analysis function such as an energy dispersive X-ray spectroscope, the layer made of the pigment covering the base paper layer is formed. It means that it is not recognized. For example, if the amount of the pigment is less than 10% by mass with respect to the amount of the coating layer applied to one side of the base paper layer, the base paper layer cannot be sufficiently covered with the pigment, so that the layer made of the pigment is not recognized.
透気度はＩＳＯ５６３６−５：２００３に準拠して測定される数値であって、原紙層の透気度が３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１０倍以上である。いくつかの実施態様として、原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１１倍以上である。また、いくつかの実施態様として、原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１２倍以上６０００倍以下である。６０００倍以下であると耐皺発生性及び耐画質劣化性が良化する。少なくとも一つの実施態様として、原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１２倍以上５４５０倍以下である。
転写捺染用紙から原紙層の透気度は、例えば、用紙の断面を観察しながら塗工層をスライスして除去し、露出した原紙層として測定できる。
The air permeability is a numerical value measured in accordance with ISO 5636-5: 2003, and the air permeability of the transfer printing paper having the air permeability of the base paper layer of 30 sec or less and the coating layer on one side of the base paper layer is high. It is 10 times or more the air permeability of the base paper layer. In some embodiments, the air permeability of the base paper layer is 12 sec or more and 30 sec or less, and the air permeability of the transfer printing paper having the coating layer on one side of the base paper layer is 11 times or more the air permeability of the base paper layer. .. Further, in some embodiments, the air permeability of the base paper layer is 12 sec or more and 30 sec or less, and the air permeability of the transfer printing paper having the coating layer on one side of the base paper layer is 12 times or more the air permeability of the base paper layer. It is 6000 times or less. When it is 6000 times or less, the wrinkle resistance and the image quality deterioration resistance are improved. In at least one embodiment, the air permeability of the base paper layer is 12 sec or more and 30 sec or less, and the air permeability of the transfer printing paper having the coating layer on one side of the base paper layer is 12 times or more and 5450 times the air permeability of the base paper layer. It is as follows.
The air permeability of the base paper layer from the transfer printing paper can be measured as an exposed base paper layer by slicing and removing the coating layer while observing the cross section of the paper, for example.
カルボキシメチルセルロース及び澱粉類を少なくとも含有する塗工層と上記の様な透気度の構成とを採用することによって、昇華型染料インク等のインク中のインク溶媒と色材とを効率良く分離及びインク溶媒の吸収ができ、同時に塗工層に色材を保持できる。結果として、転写捺染用紙は、耐皺発生性、転写性、耐画質劣化性及び発色性を有することができる。原紙層の透気度が３０ｓｅｃ超であると、転写捺染用紙は、耐皺発生性及び耐画質劣化性を有することができない。原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１０倍未満であると、転写捺染用紙は、転写性及び耐画質劣化性を有することができない。 By adopting the coating layer containing at least carboxymethyl cellulose and starch and the above-mentioned air permeability configuration, the ink solvent and the coloring material in the ink such as the sublimation dye ink can be efficiently separated and the ink. The solvent can be absorbed, and at the same time, the coloring material can be retained in the coating layer. As a result, the transfer printing paper can have wrinkle resistance, transferability, image quality deterioration resistance, and color development. If the air permeability of the base paper layer exceeds 30 sec, the transfer printing paper cannot have wrinkle resistance and image quality deterioration resistance. If the air permeability of the transfer printing paper having the coating layer on one side of the base paper layer is less than 10 times the air permeability of the base paper layer, the transfer printing paper cannot have transferability and image quality deterioration resistance. ..
透気度を調整する方法は、塗工紙分野で従来公知の方法である。原紙層の透気度は、抄造紙の密度及び厚さ、パルプの叩解度、填料の種類及び含有量、バインダーの種類及び含有量、カレンダー処理条件によって調整できる。原紙層の透気度の値を下げる方法は、例えば、密度を小さくする、厚さを小さくする、パルプの叩解を抑える、非平板状填料の使用量及び填料量を減少する、低分子量バインダーの使用量及びバインダー量を減少する、並びにカレンダー圧を抑える等を挙げることができる。ただし、過度に厚さを小さくすると、吸収容量の低下又は皺の発生をもたらす。原紙層の片面に塗工層を有した転写捺染用紙の透気度は、塗工層塗工液の乾燥固形分量としての付与量、塗工層塗工液の塗工方法、塗工層塗工液の乾燥方法及び乾燥時間、並びにカレンダー処理条件等によって調整できる。原紙層の片面に塗工層を有した転写捺染用紙の透気度の値を上げる方法は、例えば、付与量を増す、エアナイフコーター等の非接触型の塗工方式を使用して塗工層塗工液の乾燥時間を短くする、カレンダー圧を増す等を挙げることができる。ただし、過度に付与量を増すと、吸収速度の低下をもたらす。 The method for adjusting the air permeability is a method conventionally known in the field of coated paper. The air permeability of the base paper layer can be adjusted by adjusting the density and thickness of the papermaking paper, the beating degree of pulp, the type and content of the filler, the type and content of the binder, and the calendar processing conditions. Methods of reducing the air permeability of the base paper layer include, for example, reducing the density, reducing the thickness, suppressing pulp beating, reducing the amount of non-flat filler used and the amount of filler, and for low molecular weight binders. Examples include reducing the amount used and the amount of binder, and suppressing the calendar pressure. However, if the thickness is excessively reduced, the absorption capacity is reduced or wrinkles are generated. The air permeability of the transfer printing paper having a coating layer on one side of the base paper layer is the amount given as the amount of dry solid content of the coating layer coating liquid, the coating method of the coating layer coating liquid, and the coating layer coating. It can be adjusted according to the drying method and drying time of the working liquid, the calendar processing conditions, and the like. The method of increasing the air permeability value of the transfer printing paper having a coating layer on one side of the base paper layer is, for example, a coating layer using a non-contact coating method such as an air knife coater that increases the amount of application. Examples include shortening the drying time of the coating liquid and increasing the calendar pressure. However, if the amount applied is excessively increased, the absorption rate will decrease.
少なくとも一つの実施態様として、転写捺染用紙は、ＩＳＯ５６３６−５：２００３に準拠して測定される透気度であって、原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１２倍以上５４５０倍以下であり、及び塗工層の多糖類において澱粉類の少なくとも一種が尿素燐酸エステル化澱粉であって、尿素燐酸エステル化澱粉が尿素置換度平均値０．００５以上０．０５以下である。 In at least one embodiment, the transfer printing paper has an air permeability measured in accordance with ISO 5636-5: 2003, in which the air permeability of the base paper layer is 12 sec or more and 30 sec or less and one side of the base paper layer is coated. The air permeability of the transfer printing paper having a layer is 12 times or more and 5450 times or less of the air permeability of the base paper layer, and at least one of the starches in the polysaccharide of the coating layer is urea phosphate esterified starch. , Urea-phosphate esterified starch has an average urea substitution degree of 0.005 or more and 0.05 or less.
少なくとも一つの実施態様として、転写捺染用紙は、ＩＳＯ５６３６−５：２００３に準拠して測定される透気度であって、原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１２倍以上５４５０倍以下であり、塗工層の多糖類において澱粉類の少なくとも一種が尿素燐酸エステル化澱粉であって、尿素燐酸エステル化澱粉が尿素置換度平均値０．００５以上０．０５以下であり、及びカルボキシメチルセルロースにおいてゲルパーミエーションクロマトグラフィーにより得られるポリエチレングリコール換算の重量平均分子量が２７，０００以上７７０，０００以下かつエーテル化度が０．６以上１．２７以下である。 In at least one embodiment, the transfer printing paper has an air permeability measured in accordance with ISO 5636-5: 2003, in which the air permeability of the base paper layer is 12 sec or more and 30 sec or less and one side of the base paper layer is coated. The air permeability of the transfer printing paper having a layer is 12 times or more and 5450 times or less of the air permeability of the base paper layer, and at least one of the starches in the polysaccharide of the coating layer is urea phosphate esterified starch. The average value of urea phosphate esterified starch is 0.005 or more and 0.05 or less, and the weight average molecular weight of carboxymethyl cellulose obtained by gel permeation chromatography in terms of polyethylene glycol is 27,000 or more and 770,000 or less. And the degree of etherification is 0.6 or more and 1.27 or less.
塗工層は、必要に応じて塗工紙分野で従来公知の各種添加剤を含有することができる。添加剤の例としては、分散剤、定着剤、増粘剤、流動性改良剤、消泡剤、離型剤、発泡剤、浸透剤、着色顔料、着色染料、蛍光増白剤、紫外線吸収剤、酸化防止剤、防腐剤、防バイ剤等を挙げることができる。
また、塗工層は、転写捺染法で従来公知の各種助剤を含有することができる。助剤は、塗工層塗工液の各種物性を最適化する、又は昇華型染料インク等のインクが含む色材の染着性を向上させるため等に加えられるものである。助剤は、例えば、各種界面活性剤、保湿剤、湿潤剤、ｐＨ調整剤、アルカリ剤、濃染化剤、脱気剤及び還元防止剤等を挙げることができる。
The coating layer can contain various additives conventionally known in the field of coated paper, if necessary. Examples of additives include dispersants, fixers, thickeners, fluidity improvers, antiseptics, mold release agents, foaming agents, penetrants, color pigments, color dyes, optical brighteners, UV absorbers. , Antioxidants, preservatives, antibacterial agents and the like.
In addition, the coating layer can contain various conventionally known auxiliaries by the transfer printing method. Auxiliary agents are added to optimize various physical properties of the coating layer coating liquid, or to improve the dyeability of color materials contained in inks such as sublimation dye inks. Examples of the auxiliary agent include various surfactants, moisturizers, wetting agents, pH adjusting agents, alkaline agents, darkening agents, deaeration agents, reduction inhibitors and the like.
転写捺染紙は、昇華型染料インク等を備える従来公知の各種印刷方法を用いて、転写捺染用紙の塗工層を有する面側に図柄を印刷することによって得ることができる。
転写捺染用紙に図柄を印刷する従来公知の各種印刷方法は、特に限定されない。印刷方法は、例えば、グラビア印刷方式、インクジェット印刷方式、電子写真印刷方式及びスクリーン印刷方式などを挙げることができる。少なくとも一つの実施態様として、転写捺染用紙に図柄を印刷する印刷方法はインクジェット印刷方式である。
The transfer printing paper can be obtained by printing a pattern on the surface side of the transfer printing paper having a coating layer by using various conventionally known printing methods including a sublimation type dye ink and the like.
Various conventionally known printing methods for printing a pattern on transfer printing paper are not particularly limited. Examples of the printing method include a gravure printing method, an inkjet printing method, an electrophotographic printing method, and a screen printing method. In at least one embodiment, the printing method for printing a pattern on transfer printing paper is an inkjet printing method.
転写捺染法は、転写捺染用紙に図柄を印刷して転写捺染紙を得る工程と、転写捺染紙の図柄を印刷した面と被印刷物とを対向して密着させる工程とを有する方法である。密着させる工程には、必要に応じて、加熱及び／又は加圧が含まれる。密着させる工程における加熱及び加圧のそれぞれの条件は、転写捺染法で従来公知の条件である。密着させる工程は、例えば、プレス機又は加熱ドラム等により転写捺染紙を被印刷物に密着させ加熱及び／又は加圧する方法を挙げることができる。
少なくとも一つの実施態様として、転写捺染法のインクは昇華型染料インクである。
The transfer printing method is a method including a step of printing a pattern on a transfer printing paper to obtain a transfer printing paper and a step of bringing the printed surface of the transfer printing paper and the printed matter to face each other and adhere to each other. The step of bringing them into close contact includes heating and / or pressurization, if necessary. Each of the heating and pressurizing conditions in the step of bringing them into close contact is a condition conventionally known in the transfer printing method. Examples of the step of bringing the transfer-printed paper into close contact with the printed matter by a press machine, a heating drum, or the like can be mentioned as a method of heating and / or pressing the printed matter.
In at least one embodiment, the transfer printing ink is a sublimation dye ink.
被印刷物は、繊維材料であって、特に限定されない。繊維材料は、天然素材由来の繊維材料及び合成樹脂由来の繊維材料のいずれでも構わない。天然素材由来の繊維材料は、例えば、綿、麻、リヨセル、レーヨン、アセテート等のセルロース系繊維材料、絹、羊毛、獣毛等の蛋白質系繊維材料等を挙げることができる。合成樹脂由来の繊維材料は、例えば、ポリアミド繊維（ナイロン）、ビニロン、ポリエスエル、ポリアクリル等を挙げることができる。少なくとも一つの実施態様として、昇華型染料インクを用いる場合、繊維材料はポリエステルである。繊維材料の構成としては、織物、編物、不織布等の単独、混紡、混繊又は交織等を挙げることができる。さらに、これらの構成が複合化してよい。また、必要に応じて、染着促進に効果のある薬剤などで被印刷物を前処理してよい。 The printed matter is a fiber material and is not particularly limited. The fiber material may be either a fiber material derived from a natural material or a fiber material derived from a synthetic resin. Examples of the fiber material derived from the natural material include cellulosic fiber materials such as cotton, hemp, lyocell, rayon and acetate, and protein fiber materials such as silk, wool and animal hair. Examples of the fiber material derived from the synthetic resin include polyamide fiber (nylon), vinylon, polysell, and polyacrylic. In at least one embodiment, when a sublimation dye ink is used, the fiber material is polyester. Examples of the composition of the fiber material include woven fabrics, knitted fabrics, non-woven fabrics and the like alone, blended fabrics, mixed fibers or mixed weaves. Further, these configurations may be compounded. Further, if necessary, the printed matter may be pretreated with a chemical or the like effective in promoting dyeing.
以下、実施例によって本発明をさらに詳細に説明する。なお、本発明は、これらの実施例に限定されない。ここで「質量部」及び「質量％」は、乾燥固形分量あるいは実質成分量の各々「質量部」及び「質量％」を表す。塗工層の付与量は乾燥固形分量を表す。 Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to these examples. Here, "parts by mass" and "% by mass" represent "parts by mass" and "% by mass" of the amount of dry solids or the amount of substantial components, respectively. The amount of the coating layer applied represents the amount of dry solids.
（原紙層）
叩解の程度として濾水度３８０ｍｌｃｓｆ〜４８０ｍｌｃｓｆの間に調整したＬＢＫＰ１００質量部からなるパルプスラリーに、填料として軽質炭酸カルシウム２０質量部、両性澱粉１〜２質量部、硫酸バンド０．８質量部、アルキルケテンダイマー型サイズ剤０．１質量部を添加して、長網抄紙機で抄造し、得られた抄造紙に対してマシンカレンダー処理をして原紙層を得た。ここで、叩解度、両性澱粉の添加量、及びカレンダー条件を調整して表１及び表２に記載した透気度を有する原紙層を作製した。
(Base paper layer)
A pulp slurry consisting of 100 parts by mass of LBKP adjusted to a degree of beating between 380 mlcsf and 480 mlcsf, as a filler, 20 parts by mass of light calcium carbonate, 1 to 2 parts by mass of amphoteric starch, 0.8 parts by mass of sulfate band, alkyl 0.1 part by mass of a keten dimer type sizing agent was added to make a paper with a long net paper machine, and the obtained paper was subjected to machine calendar treatment to obtain a base paper layer. Here, the degree of beating, the amount of amphoteric starch added, and the calendar conditions were adjusted to prepare a base paper layer having the air permeability shown in Tables 1 and 2.
（塗工層塗工液）
塗工層塗工液は、下記の内容により調製した。
セルロース類 種類及び質量部は表１及び表２に記載
澱粉類 種類及び質量部は表１及び表２に記載
重質炭酸カルシウム 質量部は表１及び表２に記載
上記の内容で配合し、水で混合・分散して、濃度８〜１０質量％に調整した。
(Coating layer coating liquid)
The coating layer coating liquid was prepared according to the following contents.
Cellulose types and parts by mass are listed in Tables 1 and 2. Starch types and parts by mass are listed in Tables 1 and 2. Heavy calcium carbonate Mass parts are listed in Tables 1 and 2. The concentration was adjusted to 8 to 10% by mass.
（転写捺染用紙）
転写捺染用紙を以下の手順にて作製した。
原紙層の片面に対して、塗工層塗工液をエアナイフコーターにて塗工及び熱風乾燥機にて乾燥して塗工層を設けた。乾燥後に、カレンダー処理を施して転写捺染用紙を得た。付与量は、表１及び表２に記載する。塗工液の付与量、乾燥温度及び時間、並びにカレンダー処理条件を調整して、原紙層の片面に塗工層を有する、表１及び２に記載した透気度の転写捺染用紙を作製した。
(Transfer printing paper)
The transfer printing paper was prepared by the following procedure.
A coating layer was provided on one side of the base paper layer by coating with an air knife coater and drying with a hot air dryer. After drying, a calendering process was performed to obtain a transfer printing paper. The amount to be granted is shown in Tables 1 and 2. The transfer printing paper having the air permeability shown in Tables 1 and 2 having a coating layer on one side of the base paper layer was prepared by adjusting the amount of the coating liquid applied, the drying temperature and time, and the calendar processing conditions.
（転写捺染紙）
得られた転写捺染用紙に、昇華型染料インクを使用したインクジェットプリンター（ＪＶ２−１３０ＩＩ、ミマキエンジニアリング社製）を用いて、昇華型染料インク（シアン、マゼンタ、イエロー、ブラック）の各インク単色、並びにイエローとシアンとの混色であるグリーン、イエローとマゼンタとの混色であるレッド、シアンとマゼンタとの混色であるブルー、及びイエローとシアンとマゼンタとの混色であるブラックから成る評価用図柄を印刷し、転写捺染紙を得た。
(Transfer printing paper)
Using an inkjet printer (JV2-130II, manufactured by Mimaki Engineering Co., Ltd.) using sublimation dye ink on the obtained transfer printing paper, each ink single color of sublimation dye ink (cyan, magenta, yellow, black), and Print an evaluation pattern consisting of green, which is a mixture of yellow and cyan, red, which is a mixture of yellow and magenta, blue, which is a mixture of cyan and magenta, and black, which is a mixture of yellow, cyan, and magenta. , Obtained transfer printing paper.
（耐皺発生性）
インクジェットプリンターで混色であるグリーン、レッド、ブルー及びブラックとから成る４ｃｍ×４ｃｍ各ベタ画像を含む評価用図柄を転写捺染用紙の塗工層を有する側の面に印刷し、転写捺染紙を得た。得られた転写捺染紙の印刷部において、ベタ画像に発生する皺について観察し、下記の基準で評価した。本発明において、転写捺染用紙は、評価３〜５であれば耐皺発生性を有するものとする。
５：図柄に、皺が認められない。
４：図柄に、印刷直後で極僅かに皺が認められるが、間もなく消失する。
３：図柄に、皺が僅かに認められる。しかしながら、実用可能である。
２：図柄に、皺が少し認められる。商品の図柄によっては実用できない。
１：図柄に、明らかに転写不良になる皺が認められる。
(Wrinkle resistance)
An evaluation pattern including 4 cm × 4 cm solid images consisting of green, red, blue, and black, which are mixed colors, was printed on the surface of the transfer printing paper having a coating layer to obtain a transfer printing paper. .. In the printing section of the obtained transfer printing paper, wrinkles generated in the solid image were observed and evaluated according to the following criteria. In the present invention, the transfer printing paper shall have wrinkle resistance if the evaluation is 3 to 5.
5: No wrinkles are found on the design.
4: Very slight wrinkles are observed on the design immediately after printing, but they disappear soon.
3: Slight wrinkles are observed on the design. However, it is practical.
2: There are some wrinkles on the design. It cannot be put into practical use depending on the design of the product.
1: Wrinkles that clearly cause transfer defects are observed in the design.
（転写捺染）
被印刷物として、白色ポリエステル布を使用した。転写捺染紙の塗工層を有する側の面と白色ポリエステル布とを対向させて密着した。白色ポリエステル布が密着した状態の転写捺染紙を、熱転写用プレス機（米国ＩＮＳＴＡ社、ヒートプレス機モデル２０４）を用いて、温度１４０℃、１０〜１４分間加熱した。
(Transfer printing)
A white polyester cloth was used as the printed matter. The surface of the transfer printing paper having the coating layer and the white polyester cloth were brought into close contact with each other so as to face each other. The transfer printing paper in which the white polyester cloth was in close contact was heated at a temperature of 140 ° C. for 10 to 14 minutes using a thermal transfer press (INSTA, USA, heat press model 204).
（転写性）
転写捺染時の加熱時間を変化させて、図柄を形成した白色ポリエステルにおける図柄の色濃度を観察し、下記の基準で評価した。加熱時間は、１０分間、１２分間及び１４分間とした。本発明において、転写捺染用紙は、評価が３〜５であれば転写性を有するものとする。
５：１０分、１２分及び１４分で色濃度に変化が無い。
４：１０分と１２分との間では色濃度の変化が極僅かに認められる。
１２分と１４分との間では色濃度の変化が認められない。
３：１０分と１２分との間では色濃度の変化が僅かに認められる。
１２分と１４分との間では色濃度の変化が認められない。
２：１２分と１４分との間では色濃度の変化が僅かに認められる。
１：１２分と１４分との間で色濃度の変化が認められる。
(Transcribability)
The heating time at the time of transfer printing was changed, and the color density of the pattern in the white polyester on which the pattern was formed was observed and evaluated according to the following criteria. The heating time was 10 minutes, 12 minutes and 14 minutes. In the present invention, the transfer printing paper is considered to have transferability if the evaluation is 3 to 5.
There was no change in color density at 5:10, 12 and 14 minutes.
A slight change in color density is observed between 4:10 and 12 minutes.
No change in color density was observed between 12 minutes and 14 minutes.
A slight change in color density is observed between 3:10 and 12 minutes.
No change in color density was observed between 12 minutes and 14 minutes.
A slight change in color density is observed between 2:12 and 14 minutes.
A change in color density is observed between 1:12 and 14 minutes.
（耐画質劣化性）
転写捺染時の加熱時間を１０分とした。図柄が形成された白色ポリエステル布について、図柄の鮮鋭性の観点から観察し、下記の基準で評価した。本発明において、転写捺染用紙は、評価が２〜４であれば耐画質劣化性を有するものとする。
４：画質の劣化が認められず、良好なレベル。
３：画質の劣化がほとんど認められず、概ね良好なレベル。
２：画質の劣化が僅かに認められるが、実用可能なレベル。
１：画質の劣化が認められ、実用できないレベル。
(Image quality deterioration resistance)
The heating time at the time of transfer printing was set to 10 minutes. The white polyester cloth on which the pattern was formed was observed from the viewpoint of the sharpness of the pattern and evaluated according to the following criteria. In the present invention, the transfer printing paper is considered to have image quality deterioration resistance if the evaluation is 2 to 4.
4: Good level with no deterioration in image quality.
3: Almost no deterioration in image quality is observed, and the level is generally good.
2: There is a slight deterioration in image quality, but it is a practical level.
1: Deterioration of image quality is observed, and it is a level that cannot be put into practical use.
（発色性）
白色ポリエステル布に形成した図柄において、シアン、マゼンタ、イエローの各ベタ画像を光学濃度計（Ｘ−ＲＩＴＥ（登録商標）５３０、エックス−ライト・インコーポレーテッド社）を用いて光学色濃度を測定し、３色の色濃度の値を合計した。発色性は、色濃度の値から下記の基準により評価した。本発明において、転写捺染用紙は、評価が３〜５であれば発色性を有するものとする。
５：合計の値が４．８以上。
４：合計の値が４．６以上４．８未満。
３：合計の値が４．４以上４．６未満。
２：合計の値が４．２以上４．４未満。
１：合計の値が４．２未満。
(Color development)
In the pattern formed on the white polyester cloth, the optical color density of each solid image of cyan, magenta, and yellow was measured using an optical densitometer (X-RITE (registered trademark) 530, X-Rite Incorporated). The values of the color densities of the three colors were totaled. The color development property was evaluated from the value of the color density according to the following criteria. In the present invention, the transfer printing paper is considered to have color-developing property if the evaluation is 3 to 5.
5: The total value is 4.8 or more.
4: The total value is 4.6 or more and less than 4.8.
3: The total value is 4.4 or more and less than 4.6.
2: The total value is 4.2 or more and less than 4.4.
1: The total value is less than 4.2.
各評価結果を表３及び４に記載する。 The evaluation results are shown in Tables 3 and 4.
表３及び４の評価結果から、本発明に該当する実施例１〜３３の転写捺染用紙は、耐皺発生性、転写性、耐画質劣化性及び発色性を有する、と分かる。しかしながら、本発明の構成を満足しない比較例１〜５の転写捺染用紙は、これらの効果の少なくとも一つを得ることができない、と分かる。
主に、実施例２、８、及び１０の間の対比から、転写捺染用紙は、塗工層の付与量が４ｇ／ｍ２以下であることが好ましい、と分かる。
主に、実施例８、１２〜１４の間の対比から、転写捺染用紙は、塗工層が実質的に顔料を含有しないことが好ましい、と分かる。
主に、実施例２と１９との対比及び実施例１０と３３との対比から、転写捺染用紙は、澱粉類が尿素燐酸エステル化澱粉であることが好ましい、と分かる。
主に、実施例２、実施例１５〜１８及び実施例３３の間の対比から、尿素燐酸エステル化澱粉の尿素置換度は０．００５以上０．０５以下が好ましい、と分かる。
主に、実施例２及び実施例２０〜２３、実施例２７、実施例２９及び実施例３１の間の対比から、転写捺染用紙は、カルボキシメチルセルロースが低分子量タイプであることが好ましい、と分かる。
主に、実施例１〜６、実施例１１及び実施例３２との間の対比から、転写捺染用紙は、原紙層の透気度が１２ｓｅｃ以上３０ｓｅｃ以下かつ原紙層の片面に塗工層を有した転写捺染用紙の透気度が原紙層の透気度の１２倍以上５４５０倍以下であることが好ましい、と分かる。
主に、実施例２及び実施例１５〜１８並びに実施例３３の間の対比から、転写捺染用紙は、多糖類が尿素燐酸エステル化澱粉であって、尿素燐酸エステル化澱粉が尿素置換度平均値０．００５以上０．０５以下であることが好ましい、と分かる。
主に、実施例２、実施例２０〜２３及び実施例２５〜２７、実施例２９及び実施例３１の間の対比から、転写捺染用紙は、カルボキシメチルセルロースにおいてゲルパーミエーションクロマトグラフィーにより得られるポリエチレングリコール換算の重量平均分子量が２７，０００以上７７０，０００以下であることが好ましい、と分かる。
主に、実施例２、実施例２１〜３０の間の対比から、転写捺染用紙は、カルボキシメチルセルロースにおいてエーテル化度が０．６以上１．２７以下であることが好ましい、と分かる。
From the evaluation results in Tables 3 and 4, it can be seen that the transfer printing papers of Examples 1 to 33 corresponding to the present invention have wrinkle resistance, transferability, image quality deterioration resistance and color development. However, it can be seen that the transfer printing papers of Comparative Examples 1 to 5 that do not satisfy the configuration of the present invention cannot obtain at least one of these effects.
Mainly, from the comparison between Examples 2, 8 and 10, it can be seen that the transfer printing paper preferably has a coating layer of 4 g / m 2 or less.
Mainly, from the comparison between Examples 8 and 12 to 14, it can be seen that it is preferable that the coating layer of the transfer printing paper contains substantially no pigment.
Mainly, from the comparison between Examples 2 and 19 and the comparison between Examples 10 and 33, it can be seen that the starches of the transfer printing paper are preferably urea phosphate esterified starch.
Mainly, from the comparison between Examples 2, 15 to 18 and 33, it can be seen that the degree of urea substitution of the urea phosphate esterified starch is preferably 0.005 or more and 0.05 or less.
Mainly, from the comparison between Example 2 and Examples 20 to 23, Example 27, Example 29 and Example 31, it can be seen that the transfer printing paper preferably has carboxymethyl cellulose of a low molecular weight type.
Mainly, from the comparison between Examples 1 to 6, Examples 11 and 32, the transfer printing paper has the air permeability of the base paper layer of 12 sec or more and 30 sec or less and has a coating layer on one side of the base paper layer. It can be seen that it is preferable that the air permeability of the transferred transfer printing paper is 12 times or more and 5450 times or less of the air permeability of the base paper layer.
Mainly, from the comparison between Examples 2 and 15 to 18 and Example 33, in the transfer printing paper, the polysaccharide is urea phosphate-esterified starch, and the urea phosphate-esterified starch is the average value of urea substitution degree. It can be seen that it is preferably 0.005 or more and 0.05 or less.
Mainly from the comparison between Examples 2, Examples 20-23 and 25-27, 29 and 31, the transfer printing paper is polyethylene glycol obtained by gel permeation chromatography on carboxymethyl cellulose. It can be seen that the converted weight average molecular weight is preferably 27,000 or more and 770,000 or less.
Mainly, from the comparison between Examples 2 and 21 to 30, it can be seen that the transfer printing paper preferably has an etherification degree of 0.6 or more and 1.27 or less in carboxymethyl cellulose.
Claims (12)
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