WO2010140647A1 - 塩化ビニル系樹脂エマルジョン、水性インキ及び記録用紙 - Google Patents
塩化ビニル系樹脂エマルジョン、水性インキ及び記録用紙 Download PDFInfo
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- WO2010140647A1 WO2010140647A1 PCT/JP2010/059418 JP2010059418W WO2010140647A1 WO 2010140647 A1 WO2010140647 A1 WO 2010140647A1 JP 2010059418 W JP2010059418 W JP 2010059418W WO 2010140647 A1 WO2010140647 A1 WO 2010140647A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl chloride
- water
- mass
- resin emulsion
- chloride resin
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 54
- 229920005989 resin Polymers 0.000 title claims abstract description 54
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000839 emulsion Substances 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 56
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 7
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 10
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000976 ink Substances 0.000 description 49
- 238000007639 printing Methods 0.000 description 24
- -1 acrylate ester Chemical class 0.000 description 21
- 239000011230 binding agent Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000012546 transfer Methods 0.000 description 10
- 229920005692 JONCRYL® Polymers 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000740 bleeding effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- WYDMEZZKAWHQFP-UHFFFAOYSA-N 1,1,6-trichloro-3-methylhex-1-ene Chemical compound ClC(Cl)=CC(C)CCCCl WYDMEZZKAWHQFP-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 238000000149 argon plasma sintering Methods 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
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- 230000000903 blocking effect Effects 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- CXAFSGPCNGYTOZ-UHFFFAOYSA-N chloroethene hydrate Chemical compound O.ClC=C CXAFSGPCNGYTOZ-UHFFFAOYSA-N 0.000 description 1
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- 239000006103 coloring component Substances 0.000 description 1
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
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- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 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 1
- 239000011254 layer-forming composition Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
Definitions
- the present invention relates to a vinyl chloride resin emulsion that can be effectively used as a binder for ink, paint, inorganic substance dispersion, a receiving layer for recording paper, a fiber treating agent, and the like.
- a vinyl chloride resin emulsion that can be effectively used as a binder for ink, paint, inorganic substance dispersion, a receiving layer for recording paper, a fiber treating agent, and the like.
- a vinyl chloride resin emulsion that can be effectively used as a binder for ink, paint, inorganic substance dispersion, a receiving layer for recording paper, a fiber treating agent, and the like.
- it when used in water-based inks, it exhibits excellent water resistance, moisture resistance, high gloss, and alcohol resistance.
- recording paper it exhibits excellent color development, moisture resistance, and color visibility.
- a vinyl chloride resin emulsion exhibiting high gloss.
- the gravure printing ink in general printing, its quality is determined by the printability and printing effect of the printing ink.
- Printability is a property related to the behavior of the ink from when the ink on the printing press is transferred to the substrate to form the printing surface.
- the main properties include ink fluidity, interface suitability, and drying properties.
- the printing effect is the quality of printing exhibited by the ink on which the printing surface is formed, and the characteristics include color tone, gloss, water resistance, blocking resistance and the like.
- the basic composition of ink is composed of colorants (dyes, pigments), vehicles, and auxiliary agents (fluidity adjusting agents, drying property adjusting agents, etc.). Of these, the vehicle has a great influence on printability and printing effect. .
- the basic composition of the vehicle is a binder, wax, solvent, etc. Therefore, the properties of the vehicle greatly change depending on the choice of the binder, and this greatly affects the printability and the quality of the printing effect.
- Binders are roughly classified into solvent-type binders and aqueous binders.
- the solvent-type binder include urethane resins proposed in Japanese Patent Laid-Open No. 9-12956 (Patent Document 1).
- Patent Document 1 Japanese Patent Laid-Open No. 9-12956
- an aqueous binder that does not use an organic solvent has been attracting attention in consideration of air pollution, fire hazard, occupational health, and the like.
- aqueous binder examples include alkali-soluble resins typified by styrene / acrylic resins, water-soluble resins typified by polyvinyl alcohol and urethane emulsions (Patent Document 2: JP-A-2-238015), and acrylic emulsions. And water-dispersed resin.
- the ink when printing with water-based ink with a water-dispersible resin as a binder, the ink is applied to the printing surface at room temperature on a printing press, and then dried to finish above the glass transition temperature of the water-dispersible resin. It is done. Thus, if it heats more than a glass transition temperature, resin particles will cause the whole to fuse
- the drying property on the printing press among the printability it is necessary for the printing ink to maintain fluidity without drying for as long as possible on the printing press.
- Patent Document 3 selects from vinyl chloride, (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms and monoalkenylbenzenes.
- a binder for water-based inks comprising a monomer selected from an ethylenically unsaturated monomer having a functional group, an ethylenically unsaturated monomer having a functional group, and other ethylenically unsaturated monomers.
- a binder for water-based inks comprising a monomer selected from an ethylenically unsaturated monomer having a functional group, an ethylenically unsaturated monomer having a functional group, and other ethylenically unsaturated monomers.
- Patent Document 4 Japanese Patent Application Laid-Open No. 11-35866. Fluoropolymers are excellent in various aspects such as weather resistance and corrosion resistance, but cost problems still remain.
- the ink jet recording method is excellent in quietness, recording speed, printing quality, and running cost, and is generally widely used.
- the ink used in this method is water-based ink from the viewpoints of ink physical properties, safety, ease of handling, and the like.
- an ink obtained by dissolving a water-soluble dye such as an acid dye, a direct dye, or a basic dye in a glycol solvent and water (Patent Documents 5 to 7: JP-A-53-61412 and JP-A-2003-61412).
- Patent Documents 5 to 7 JP-A-53-61412 and JP-A-2003-61412
- Japanese Laid-Open Patent Publication No. 54-89811 and Japanese Laid-Open Patent Publication No. 55-65269 are known, but have a drawback of poor water resistance.
- Patent Document 8 JP-A 61-61.
- Patent Document 9 JP-A-8-253716.
- improvement in water resistance and weather resistance was observed, there was room for improvement in terms of pigment dispersibility (change over time).
- the receiving layer of the recording paper particularly the ink jet recording paper
- the ratio of recording methods using water-based inks has been increasing in printers for OA equipment such as personal computers, and the demand for recording materials has been increasing accordingly.
- a recording material having higher properties has been demanded.
- the required properties such as water resistance and color developability are becoming stricter.
- a recording sheet Patent Document 10: Japanese Patent Application Laid-Open No. 55-51583 in which amorphous binder and a polymer binder such as polyvinyl alcohol are mixed and applied to a base paper or a base paper is used.
- Patent Document 11 Japanese Patent Laid-Open No. 56-144854
- an ink receiving layer containing porous pigment particles is provided on both sides.
- Patent Document 12 Japanese Patent Laid-Open No. 62-2880766
- a water-insoluble resin obtained by reacting polyvinyl alcohol, acrylic acid and methyl methacrylate.
- the water-insoluble resin is anionic, the fixability of the same anionic water-based ink is poor, and no solution has been reached to improve ink bleeding or water resistance.
- a recording sheet containing a polycation polymer electrolyte (Patent Document 13: Japanese Patent Laid-Open No. 56-84992) and an ink receiving layer mainly composed of a cationic polymer binder having ink adsorption properties were provided.
- Recording sheets (Patent Document 14: Japanese Patent Laid-Open No. 58-24493) and recording sheets containing a cationic acrylic resin emulsion (Patent Documents 15 and 16: Japanese Patent Laid-Open Nos. 11-123867 and 2001-199152) Publication) has also been proposed, but it is not always satisfactory in terms of color development and water resistance.
- the present invention has been made in view of the above circumstances, and when used in water-based ink, exhibits excellent water resistance, moisture resistance, high gloss, and alcohol resistance, and when used in recording paper, it is excellent.
- Vinyl chloride that can be used effectively in inks, paints, binders for dispersing inorganic substances, recording paper receiving layers, fiber treating agents, etc., with excellent color development, water resistance, moisture resistance, color visibility, and high gloss. It is an object to provide a resin emulsion.
- (A) a styrene / acrylate ester oligomer and / or an acrylate ester oligomer having a number average molecular weight of 5000 to 50000 is (B) chloride 40 to 500 parts by mass with respect to 100 parts by mass of the monomer composition containing the vinyl monomer or (B) vinyl chloride monomer and (C) an ethylenically unsaturated group-containing monomer copolymerizable therewith. It has been found that a vinyl chloride resin emulsion obtained by emulsion polymerization in the presence of a part can overcome the above-mentioned problems, and has led to the present invention.
- Claim 1 (A) Styrene / acrylic acid ester oligomer and / or acrylic acid ester oligomer having a number average molecular weight of 5000 to 50000 can be copolymerized with (B) vinyl chloride monomer or (B) vinyl chloride monomer. (C) A vinyl chloride resin emulsion obtained by emulsion polymerization in the presence of 40 to 500 parts by mass with respect to 100 parts by mass of a monomer composition containing an ethylenically unsaturated group-containing monomer.
- Claim 2 The vinyl chloride resin emulsion according to claim 1, wherein the ratio of the component (B) to the component (C) is 50 to 50 in terms of mass ratio.
- Claim 3 A water-based ink containing the vinyl chloride resin emulsion according to claim 1 or 2.
- Claim 4 The content of the vinyl chloride resin emulsion is 2 to 30% by mass as a solid content, further contains 3 to 40% by mass of a colorant, 0 to 60% by mass of a water-soluble organic solvent, and 5 to 95% by mass of water.
- Claim 5 A recording paper having a coating film of the vinyl chloride resin emulsion according to claim 1.
- Claim 6 The recording paper according to claim 5, wherein the coating film forms a receiving layer.
- the coating film is formed of a composition containing 2 to 30% by mass of a solid content of a vinyl chloride resin emulsion, further containing 0 to 30% by mass of a pigment, and the balance containing water or a water-soluble organic solvent. 5. Recording paper according to 5 or 6.
- the vinyl chloride resin emulsion of the present invention exhibits excellent water resistance, moisture resistance, high gloss and alcohol resistance when used in water-based inks, and excellent color developability when used in recording paper. It can be effectively used as a binder for inks, paints, inorganic substance dispersions, recording paper receiving layers, fiber treating agents, and the like, exhibiting water resistance, moisture resistance, color visibility, and high gloss.
- the binder for vinyl chloride water-based ink of the present invention comprises (A) a styrene / acrylate ester oligomer and / or an acrylate ester oligomer having a number average molecular weight of 5000 to 50000, (B) a vinyl chloride monomer or (B ) Emulsion polymerization in the presence of 40 to 500 parts by mass with respect to 100 parts by mass of a monomer composition containing a vinyl chloride monomer and a copolymerizable monomer containing (C) an ethylenically unsaturated group. It is a vinyl chloride resin emulsion obtained by making it.
- Examples of the acrylate monomer used in the styrene / acrylate oligomer and the acrylate oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
- (meth) acryl is a general term for acrylic and methacrylic. Examples of commercially available products include JONCRYL JDX-6500, JONCRYL JDX-6102B, JONCRYL HPD-96J, JONCRYL 52J (all manufactured by BASF), etc., but are not limited thereto. Two or more are used.
- the amount used is 100 mass of monomer composition containing (B) vinyl chloride monomer or (B) vinyl chloride monomer and (C) ethylenically unsaturated group-containing monomer copolymerizable therewith.
- the amount is preferably 40 to 500 parts by mass, more preferably 100 to 300 parts by mass. If the amount is less than 40 parts by mass, there may be a problem that aggregates are generated. If the amount exceeds 500 parts by mass, the reaction may be inactivated and stable production may not be possible.
- the number average molecular weight of the styrene / acrylic acid ester oligomer and acrylic acid ester oligomer is preferably 5000 to 50000, and more preferably 8000 to 20000. If the molecular weight is less than 5000, there may be a disadvantage that aggregates are generated, and if it exceeds 50000, a large amount of aggregates are generated, and in the worst case, problems such as gelation may occur.
- the number average molecular weight is a polystyrene conversion value measured by GPC, and in the present invention, those having 50000 or less are called oligomers.
- the ethylenically unsaturated group-containing monomer copolymerizable with the vinyl chloride monomer (C) includes vinyl acetate, ethylene, propylene, vinylidene chloride, and vinyl carboxylates such as vinyl propionate.
- Aromatic vinyl monomers such as styrene and ⁇ -methylstyrene, conjugated diene monomers such as 1,3-butadiene and 2-methyl-1,3-butadiene, methyl acrylate, acrylic acid Ethylenic unsaturated monocarboxylic esters such as ethyl, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethylenic dimethyl itaconate, diethyl maleate, monobutyl maleate, monoethyl fumarate, dibutyl fumarate, etc.
- Ethylenic unsaturation such as unsaturated polycarboxylic acid esters, acrylic acid, methacrylic acid, crotonic acid Nocarboxylic acids, itaconic acid, maleic acid, fumaric acid and other ethylenically unsaturated dicarboxylic acids, glycidyl methacrylate and other epoxy group-containing monomers, 2-hydroxyethyl methacrylate and other alcoholic hydroxyl group-containing monomers, methoxyethyl Alkoxy group-containing monomers such as acrylate, nitrile group-containing monomers such as acrylonitrile, amide group-containing monomers such as acrylamide, amino group-containing monomers such as dimethylaminoethyl methacrylate, divinylbenzene, Examples include monomers having two or more ethylenically unsaturated groups in one molecule, such as allyl methacrylate, and one or more of these are selected. Vinyl acetate, ethylenically uns
- the ratio of (B) the vinyl chloride monomer and the (C) ethylenically unsaturated group-containing monomer copolymerizable therewith is 50:50 to 100: 0, particularly 70:30 as a mass ratio. Preferably it is ⁇ 100: 0. If the amount of vinyl chloride is too small, there may be a disadvantage that aggregates are generated.
- emulsion polymerization method can be employed for the emulsion polymerization.
- Monomers and other polymerization aids for example, emulsifiers such as alkyl sulfate esters, polymerization initiators such as ammonium persulfate, chain transfer agents such as mercaptans, pH adjusters such as sodium carbonate, various antifoaming agents, etc.
- emulsifiers such as alkyl sulfate esters
- polymerization initiators such as ammonium persulfate
- chain transfer agents such as mercaptans
- pH adjusters such as sodium carbonate
- various antifoaming agents etc.
- nonionic surfactants and anionic emulsifiers can be used in combination as long as the effects of the present invention are not impaired.
- Examples of the polymerization initiator used in the emulsion polymerization include persulfates such as ammonium persulfate and potassium persulfate, azo compounds such as 2,2′-diamidino-2,2′-azopropane dihydrochloride and azobisisobutyronitrile. , Cumene hydroperoxide, benzoyl peroxide, peroxides such as hydrogen peroxide, tartaric acid and the like. Moreover, a well-known redox-type initiator, for example, potassium persulfate, sodium hydrogensulfite, etc. are mentioned.
- the amount of the polymerization initiator used is usually 0.1 to 2.0% by mass, preferably 0.2 to 1.0% by mass, based on the monomer.
- the polymerization temperature for carrying out the above emulsion polymerization is usually 40 to 80 ° C., preferably 50 to 70 ° C.
- the polymerization time may be set appropriately, but is preferably 10 to 15 hours. This polymerization is desirably performed in an atmosphere of an inert gas such as nitrogen gas.
- the evaporation residue is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. If it is less than 10% by mass, aggregates may be generated, and if it exceeds 50% by mass, a large amount of aggregates may be generated.
- a plasticizer, an inorganic or organic filler, a thickener, etc. can also be added after the completion of the polymerization within a range that does not impair the performance of the binder for water-based ink of the present invention.
- the average particle size of the emulsion is 10 to 1000 nm, preferably 20 to 800 nm, and the viscosity is 5 to 1800 mPa ⁇ s.
- the resin emulsion according to the present invention can be used for various applications, but particularly when used for recording paper, it exhibits excellent color development, water resistance, moisture resistance, high gloss, and when used for water-based ink. Gives water resistance, moisture resistance, color visibility, high gloss, and excellent alcohol resistance.
- the vinyl chloride resin emulsion of the present invention when used in water-based ink, a colorant, a water-soluble organic solvent, various additives, water, etc. are blended in this vinyl chloride resin emulsion, and a known disperser, mixing It can be produced by dispersing and mixing with a machine, a kneader or the like.
- the content of the vinyl chloride resin emulsion in the water-based ink is preferably 2 to 30% by mass, particularly 5 to 20% by mass as a solid content.
- the colorant, dyes, pigments and the like can be used, and it is preferable to contain 3 to 40% by mass, particularly 5 to 30% by mass in the aqueous ink.
- water-soluble organic solvents examples include ethylene glycol monoether, diethylene glycol monoether, propylene glycol monoether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, propylene glycol, glycerin, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl cellosolve, Ethyl cellosolve, acetone, ethyl acetate, diacetone alcohol and the like can be used, and the content is preferably 0 to 60% by mass, particularly 0 to 50% by mass in the aqueous ink.
- Water is preferably contained in the water-based ink in an amount of 5 to 95% by mass, preferably 5 to 93% by mass, particularly 10 to 90% by mass.
- the additive include a pigment dispersant, a leveling agent, an antifoaming agent, and the like, and these additives can be used at a normal dose in water-based ink.
- the vinyl chloride resin emulsion of the present invention when used for recording paper, it can be suitably used particularly for forming a receiving layer of recording paper.
- a pigment, a water-soluble organic solvent, various additives, water, and the like can be blended with this vinyl chloride resin emulsion, and dispersed and mixed by a known disperser, mixer, kneader, or the like.
- the composition for forming the receiving layer containing the vinyl chloride resin emulsion used for forming the receiving layer contains 2 to 30% by mass, particularly 5 to 20% by mass, of the solid content of the vinyl chloride resin emulsion. preferable.
- amorphous synthetic silica, aluminum silicate, magnesium silicate, precipitated calcium carbonate, heavy calcium carbonate, calcium silicate, aluminum hydroxide, zeolite, calcined clay, kaolin clay, talc, white carbon, etc. are blended. be able to.
- the blending amount of these components is preferably 0 to 30% by mass, particularly preferably 0 to 20% by mass.
- water-soluble organic solvents examples include ethylene glycol monoether, diethylene glycol monoether, propylene glycol monoether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, propylene glycol, glycerin, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl cellosolve, Ethyl cellosolve, acetone, ethyl acetate, diacetone alcohol and the like can be used, and the content is preferably 0 to 60% by mass, more preferably 0 to 50% by mass in the aqueous ink.
- Water is preferably contained in the water-based ink in an amount of 5 to 98% by mass, particularly 10 to 90% by mass.
- a pigment dispersant, an antifoaming agent, a colorant, an antioxidant, an ultraviolet absorber, a viscosity modifier, a release agent, and the like can be blended.
- the receiving layer-forming composition is applied to a support such as commercially available paper by a coating method such as a brush coater, an air knife coater, a curtain coater, a Meyer bar coater, a gravure coater, or a roll coater. It can be produced by coating and drying to a concentration of ⁇ 25 g / m 2 (dry polymerization solid content), preferably 1 to 10 g / m 2 .
- Example 1 In a polymerization vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet, after replacement with nitrogen, 33 parts of deionized water, 15 parts of vinyl chloride, 50 parts by weight of JONCRYL JDX-6500 (BASF acrylate oligomer) 30% active ingredient) was added and heated to 60 ° C. with stirring. Further, 0.1 part of ammonium persulfate (initiator) was dissolved in 1 part of deionized water and added to cause a polymerization reaction. When the polymerization internal pressure reached 0 MPa, the residual monomer was removed to 1000 ppm in a vacuum, and then cooled to 40 ° C.
- JONCRYL JDX-6500 BASF acrylate oligomer 30% active ingredient
- the solid content was 30%, pH 7.5, and the viscosity of a B-type viscometer (23 ° C.) was 10 mPa ⁇ s. Table 1 shows the results. In addition, it was measured by GPC that the obtained emulsion was a vinyl chloride resin.
- Examples 2 to 7, Comparative Examples 1 to 7 Polymerization similar to that of Example 1 was carried out with the compositions shown in Tables 1 and 2 to obtain a vinyl chloride resin emulsion.
- ⁇ PH measurement method> The vinyl chloride resin emulsion was measured as it was using a pH meter according to JIS Z8802 (pH measurement method).
- ⁇ B type viscometer viscosity measurement method The temperature of the vinyl chloride resin emulsion was maintained at 23 ⁇ 0.5 ° C. and measured with a BM viscometer (No. 1 rotor, 6 rpm).
- Glossy The printed part was measured with a gloss meter PG-1M (manufactured by Nippon Denshoku Industries Co., Ltd.), a value of 60 ° was read and judged according to the following criteria. ⁇ : Gloss value is 90 or more ⁇ : Gloss value is 70 or more and less than 90 ⁇ : Gloss value is less than 70
- JONCRYL JDX-6500 BASF acrylic oligomer, number average molecular weight 10,000 JONCRYL JDX-6102B: BASF acrylic oligomer, number average molecular weight 60000 JONCRYL HPD-96J: BASF styrene acrylic oligomer, number average molecular weight 16500 JONCRYL 52J: Styrene acrylic oligomer manufactured by BASF, number average molecular weight 1700 PVA-117: manufactured by Kuraray Co., Ltd., saponification degree 98.5, polymerization degree 1700 PVA-617: manufactured by Kuraray Co., Ltd., saponification degree 95.0, polymerization degree 1700 Neugen XL-6190: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., nonionic emulsifier Perex SS-L: manufactured by Kao Corporation, anionic emulsifier
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Abstract
Description
請求項1:
(A)数平均分子量が5000~50000であるスチレン・アクリル酸エステルオリゴマー及び/又はアクリル酸エステルオリゴマーを、(B)塩化ビニル単量体又は(B)塩化ビニル単量体とこれと共重合可能な(C)エチレン性不飽和基含有単量体を含む単量体組成物100質量部に対して、40~500質量部の存在下で乳化重合させることによって得られる塩化ビニル系樹脂エマルジョン。
請求項2:
(B)成分と(C)成分の割合が質量比として50以上:50以下である請求項1記載の塩化ビニル系樹脂エマルジョン。
請求項3:
請求項1又は2記載の塩化ビニル系樹脂エマルジョンを含有する水性インキ。
請求項4:
塩化ビニル系樹脂エマルジョンの含有量が固形分として2~30質量%であり、更に着色剤を3~40質量%、水可溶性有機溶剤を0~60質量%、水を5~95質量%含有してなる請求項3記載の水性インキ。
請求項5:
請求項1又は2記載の塩化ビニル系樹脂エマルジョンの塗膜を有する記録用紙。
請求項6:
上記塗膜が受容層を形成する請求項5記載の記録用紙。
請求項7:
上記塗膜が、塩化ビニル系樹脂エマルジョンの固形分2~30質量%を含み、更に顔料を0~30質量%含み、残部が水又は水可溶性有機溶剤を含有する組成物で形成される請求項5又は6記載の記録用紙。
攪拌機、コンデンサー、温度計及び窒素ガス導入口を備えた重合容器に、窒素置換後、脱イオン水33部、塩化ビニル15部、JONCRYL JDX-6500(BASF社製アクリル酸エステルオリゴマー)50質量部(有効成分30%)を仕込み、攪拌しながら60℃に加温した。更に過硫酸アンモニウム(開始剤)0.1部を脱イオン水1部に溶解させて添加して重合反応させた。
重合内圧が0MPaになった時点で、残存モノマーを真空にて1000ppmまで除去し、その後40℃以下まで冷却して重合体を得た。固形分30%、pH7.5、B型粘度計粘度(23℃)10mPa・sであった。表1に結果を示す。なお、得られたエマルジョンが塩化ビニル樹脂であることはGPCにより測定した。
表1,2に示すような組成で、実施例1と同様の重合を実施して、塩化ビニル系樹脂エマルジョンを得た。
<固形分測定方法>
塩化ビニル系樹脂エマルジョン約1gをアルミ箔製の皿にはかり取り、105~110℃に保った乾燥器に入れて1時間加熱した後、乾燥器より取り出して、デシケーターの中にて放冷した。試料の乾燥後の重さをはかり、次の式により固形分を算出した。
塩化ビニル系樹脂エマルジョンをそのまま、JIS Z8802(pH測定方法)によりpHメーターを用いて測定した。
塩化ビニル系樹脂エマルジョン液温を23±0.5℃に保持し、BM型粘度計(No.1ローター、6rpm)にて測定した。
光散乱型粒子径測定装置を用いて測定した。
サンプル調製
1.ディスカップにサンプルを採取し、25℃純水にて希釈した。
2.希釈したサンプルを300メッシュ濾布にてろ過した。
測定液温 25℃
積算回数 100回
測定回数 1回
測定
適正濃度であることを確認し、上記測定条件にて測定した。
測定結果が良好であることを確認した。
塩化ビニル系樹脂エマルジョンを6ミルのドクターナイフでガラス板に塗布し、凝集物発生の有無を目視にて確認した。
○:凝集物は確認できなかった
×:凝集物が発生した
塩化ビニル系樹脂エマルジョンの含有量を固形分として20%とし、市販顔料DISPERS RED SD-1011(DIC社製)を5%、水を75%混合し、これを試料Aとした。
卓上印刷機(GRAVO-PROOF CM、日商グラビア社製)に試料Aをセットし、印刷ロールを1回転させ、市販の紙に印刷した。
印刷した紙を学振形染色摩擦堅ろう度試験機(安田精機製作所製)にセットし、水で湿らせたガーゼを用いて25回摩擦試験を実施し、下記の基準に従って判定した。
○:ガーゼへの色移り無し
△:色移りが見られる
×:完全に色移りし、印刷面の色が落ちる
印刷した紙を50℃、湿度90%で1日静置し、下記の基準に従って判定した。
○:印刷部位に滲みが無い
△:印刷部位から少し滲みが見られる
×:完全に滲む
印刷した部位をグロスメーターPG-1M(日本電色工業社製)で測定し、60°の値を読み取り、下記の基準に従って判定した。
○:グロス値が90以上
△:グロス値が70以上90未満
×:グロス値が70未満
印刷した紙を学振形染色摩擦堅ろう度試験機(安田精機製作所製)にセットし、エタノールで湿らせたガーゼを用いて25回摩擦試験を実施し、下記の基準に従って判定した。
○:ガーゼへの色移り無し
△:色移りが見られる
×:完全に色移りし、印刷面の色が落ちる
[インクの調製]
塩化ビニル系樹脂エマルジョンの含有量を固形分として20%とし、カーボンブラックMA100(三菱製紙社製)を20%、水を60%混合し、これを試料Bとした。
調製した試料Bを、市販の紙にバーコーターNo.4にて乾燥重量で4g/m2になるように塗工し、40℃で30秒乾燥した。得られた塗工紙と調製した試料の外観を下記の基準で目視により判定した。
○:色調が同等
△:黒色濃度が不足する
×:色見が変化している
調製した試料Bを、軟質塩ビフィルム・スーパーフィルムノンタックE(オカモト社製)にバーコーターNo.4にて乾燥重量で4g/m2になるように塗工し、40℃で30秒乾燥した。得られた塗工品に、セロテープ(ニチバン社製、登録商標)を貼り付けた後剥離し、下記の基準で判定した。
○:剥離無し
△:一部剥離有り
×:完全剥離
調製した試料Bを常温で1週間放置し、経時沈降を下記の基準で目視により判定した。
○:沈降無し
△:沈降するが再撹拌可能
×:沈降し復元せず
[受容層の調製]
市販の紙に、各塩化ビニル系樹脂エマルジョンをバーコーターNo.4にて塗工し、40℃で30秒乾燥し試料Cとした。
h.発色性
EPSON PM-800Cで、試料Cにイエロー、シアン、マゼンダの3色を印刷し、各色の色濃度を下記の基準で目視により判定した。
○:色抜けが無く鮮明に印刷されている
△:一部に色抜けがある
×:色抜けがあり、色褪せている
前記印刷した紙を学振形染色摩擦堅ろう度試験機(安田精機製作所製)にセットし、水で湿らせたガーゼを用いて25回摩擦試験を実施し、下記の基準に従って判定した。
○:ガーゼへの色移り無し
△:色移りが見られる
×:完全に色移りし、印刷面の色が落ちる
前記印刷した紙を50℃、湿度90%で1日静置し、下記の基準に従って目視により判定した。
○:印刷部位に滲みが無い
△:印刷部位から少し滲みが見られる
×:完全に滲む
JONCRYL JDX-6102B:BASF社製アクリルオリゴマー、数平均分子量60000
JONCRYL HPD-96J:BASF社製スチレンアクリルオリゴマー、数平均分子量16500
JONCRYL 52J:BASF社製スチレンアクリルオリゴマー、数平均分子量1700
PVA-117:(株)クラレ製、ケン化度98.5、重合度1700
PVA-617:(株)クラレ製、ケン化度95.0、重合度1700
ノイゲンXL-6190:第一工業製薬(株)製、ノニオン系乳化剤
ペレックスSS-L:花王(株)製、アニオン系乳化剤
Claims (7)
- (A)数平均分子量が5000~50000であるスチレン・アクリル酸エステルオリゴマー及び/又はアクリル酸エステルオリゴマーを、(B)塩化ビニル単量体又は(B)塩化ビニル単量体とこれと共重合可能な(C)エチレン性不飽和基含有単量体を含む単量体組成物100質量部に対して、40~500質量部の存在下で乳化重合させることによって得られる塩化ビニル系樹脂エマルジョン。
- (B)成分と(C)成分の割合が質量比として50以上:50以下である請求項1記載の塩化ビニル系樹脂エマルジョン。
- 請求項1又は2記載の塩化ビニル系樹脂エマルジョンを含有する水性インキ。
- 塩化ビニル系樹脂エマルジョンの含有量が固形分として2~30質量%であり、更に着色剤を3~40質量%、水可溶性有機溶剤を0~60質量%、水を5~95質量%含有してなる請求項3記載の水性インキ。
- 請求項1又は2記載の塩化ビニル系樹脂エマルジョンの塗膜を有する記録用紙。
- 上記塗膜が受容層を形成する請求項5記載の記録用紙。
- 上記塗膜が、塩化ビニル系樹脂エマルジョンの固形分2~30質量%を含み、更に顔料を0~30質量%含み、残部が水又は水可溶性有機溶剤を含有する組成物で形成される請求項5又は6記載の記録用紙。
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KR1020157012728A KR101643554B1 (ko) | 2009-06-04 | 2010-06-03 | 염화비닐계 수지 에멀션, 수성 잉크 및 기록용지 |
EP10783429.3A EP2439217B1 (en) | 2009-06-04 | 2010-06-03 | Vinyl chloride-based resin emulsion, water-based ink and recording paper |
KR1020157024317A KR101658119B1 (ko) | 2009-06-04 | 2010-06-03 | 염화비닐계 수지 에멀션, 수성 잉크 및 기록용지 |
CN201080020374.XA CN102421811B (zh) | 2009-06-04 | 2010-06-03 | 氯乙烯基树脂乳液、水性油墨及记录用纸 |
JP2011518484A JP5644762B2 (ja) | 2009-06-04 | 2010-06-03 | 水性インキ及び記録用紙 |
US12/933,277 US8691888B2 (en) | 2009-06-04 | 2010-06-03 | Vinyl chloride resin emulsion, aqueous ink, and recording sheet |
KR1020147033348A KR101548361B1 (ko) | 2009-06-04 | 2010-06-03 | 염화비닐계 수지 에멀션, 수성 잉크 및 기록용지 |
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Also Published As
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JP5796617B2 (ja) | 2015-10-21 |
EP2439217A4 (en) | 2012-10-24 |
KR20140146667A (ko) | 2014-12-26 |
TW201111397A (en) | 2011-04-01 |
EP2439217B1 (en) | 2015-09-16 |
KR101643554B1 (ko) | 2016-07-29 |
US20110124801A1 (en) | 2011-05-26 |
CN102421811B (zh) | 2016-05-18 |
KR20150063580A (ko) | 2015-06-09 |
EP2439217A1 (en) | 2012-04-11 |
CN104892844B (zh) | 2017-07-28 |
TWI477516B (zh) | 2015-03-21 |
US8691888B2 (en) | 2014-04-08 |
JP5644762B2 (ja) | 2014-12-24 |
KR20120022856A (ko) | 2012-03-12 |
KR20150111368A (ko) | 2015-10-05 |
CN102421811A (zh) | 2012-04-18 |
KR101548361B1 (ko) | 2015-08-31 |
CN104892844A (zh) | 2015-09-09 |
JPWO2010140647A1 (ja) | 2012-11-22 |
JP2014043585A (ja) | 2014-03-13 |
KR101658119B1 (ko) | 2016-09-20 |
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