JP2006131654A - Manufacturing method of copolymer latex - Google Patents
Manufacturing method of copolymer latex Download PDFInfo
- Publication number
- JP2006131654A JP2006131654A JP2004318761A JP2004318761A JP2006131654A JP 2006131654 A JP2006131654 A JP 2006131654A JP 2004318761 A JP2004318761 A JP 2004318761A JP 2004318761 A JP2004318761 A JP 2004318761A JP 2006131654 A JP2006131654 A JP 2006131654A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- copolymer latex
- monomer
- compound
- monomer mixture
- 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.)
- Pending
Links
- 239000004816 latex Substances 0.000 title claims abstract description 113
- 229920000126 latex Polymers 0.000 title claims abstract description 113
- 229920001577 copolymer Polymers 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 25
- 229940126062 Compound A Drugs 0.000 claims abstract description 11
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 208000012839 conversion disease Diseases 0.000 claims abstract description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 28
- 238000000576 coating method Methods 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 29
- 239000011248 coating agent Substances 0.000 abstract description 28
- 239000000123 paper Substances 0.000 description 57
- 239000002245 particle Substances 0.000 description 21
- 239000000049 pigment Substances 0.000 description 21
- -1 satin white Substances 0.000 description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 12
- 238000007639 printing Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 7
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 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 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-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
- 241000243251 Hydra Species 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- 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 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical group NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- QIFCIFLDTQJGHQ-UHFFFAOYSA-M potassium;2-phenylethenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 QIFCIFLDTQJGHQ-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 230000007704 transition Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GYHZLNKMZPYTFB-UHFFFAOYSA-N 2-(oxiran-2-yl)acetamide Chemical compound NC(=O)CC1CO1 GYHZLNKMZPYTFB-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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
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- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- 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
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
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- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
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- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
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- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
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- 230000003712 anti-aging effect Effects 0.000 description 1
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- 239000012736 aqueous medium Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
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- 229960005070 ascorbic acid Drugs 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- ZNCWVPSAFCGZPH-UHFFFAOYSA-N azanium;2-methyl-1-oxoprop-2-ene-1-sulfonate Chemical compound [NH4+].CC(=C)C(=O)S([O-])(=O)=O ZNCWVPSAFCGZPH-UHFFFAOYSA-N 0.000 description 1
- XDIJWRHVEDUFGP-UHFFFAOYSA-N azanium;2-phenylethenesulfonate Chemical compound [NH4+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 XDIJWRHVEDUFGP-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
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- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- VRAHSRHQTRYBJV-UHFFFAOYSA-M sodium;2-methyl-1-oxoprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)C(=O)S([O-])(=O)=O VRAHSRHQTRYBJV-UHFFFAOYSA-M 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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- 150000003457 sulfones Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
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- 239000002023 wood Substances 0.000 description 1
Abstract
Description
本発明は、紙塗工における顔料バインダー、カーペットバッキング剤、接着剤、粘着剤、繊維結合剤および塗料などに用いられる共役ジエン系共重合体ラテックスの製造方法に関するものである。更に詳しくは、高い化学的安定性と耐湿潤ベタツキ性を有し、紙塗工における接着強度及び耐水性に特に優れた効果を発揮する共重合体ラテックスを効率的に製造する方法に関するものである。 The present invention relates to a method for producing a conjugated diene copolymer latex used for pigment binders, carpet backing agents, adhesives, pressure-sensitive adhesives, fiber binders and paints in paper coating. More particularly, the present invention relates to a method for efficiently producing a copolymer latex having high chemical stability and wet stickiness resistance, and exhibiting particularly excellent effects in adhesive strength and water resistance in paper coating. .
共役ジエン系共重合体ラテックスは、紙塗工における顔料バインダー、カーペットバッキング剤、各種接着剤および粘着剤、繊維結合剤ならびに塗料など広範な用途に用いられてきた。これらの用途に用いられる共重合体ラテックスには、基材や配合される顔料などに対する優れた接着力、耐水性などが要求される。 Conjugated diene copolymer latexes have been used in a wide range of applications such as pigment binders in paper coating, carpet backing agents, various adhesives and tackifiers, fiber binders and paints. The copolymer latex used for these uses is required to have excellent adhesion to water and water resistance with respect to the substrate and the pigment to be blended.
塗工紙は、抄造された紙の表面の平滑性を高め、光沢や印刷適性を向上させる目的で、原紙にカオリンクレー、炭酸カルシウム、サチンホワイト、タルク、酸化チタンなどの無機顔料およびプラスチック顔料などの有機顔料を塗布したものであり、これらの顔料のバインダーとしてジエン系共重合体ラテックスが一般的に用いられている。顔料バインダーとして用いられる共重合体ラテックスの性質は、紙の表面強度はもとより、塗工紙の印刷適性にも大きな影響を及ぼすことが知られている。 Coated paper is used to improve the smoothness of the surface of the paper and improve gloss and printability. The base paper contains inorganic pigments such as kaolin clay, calcium carbonate, satin white, talc, and titanium oxide, and plastic pigments. These organic pigments are applied, and diene copolymer latex is generally used as a binder for these pigments. It is known that the properties of copolymer latex used as a pigment binder have a great influence not only on the surface strength of paper but also on the printability of coated paper.
近年、カラー印刷された雑誌類やパンフレット、広告等の需要の増大に伴い、印刷速度の高速化が進められており、特にインクのタックによる紙の表面の破壊に対する抵抗性（いわゆるピック強度）や湿し水が塗布された際のピック強度（湿潤ピック強度）の向上が以前にも増して要求されるようになった。また塗工紙の品質向上ニーズも高まり、特に白紙光沢を向上させる要求が強い。これに対し、塗工に用いる顔料を小粒子径化させる傾向が進んでいるが、この結果バインダーとして用いられる共重合体ラテックスに対しては、更なるピック強度や湿潤ピック強度の向上が求められている。 In recent years, with increasing demand for color-printed magazines, pamphlets, advertisements, etc., the printing speed has been increased, especially resistance to the destruction of the paper surface due to ink tack (so-called pick strength) Improvement in pick strength (wet pick strength) when fountain solution is applied has been required more than before. There is also a growing need to improve the quality of coated paper, and there is a strong demand for improving the gloss of white paper. On the other hand, there is a tendency to reduce the particle size of the pigment used for coating. As a result, further improvement in pick strength and wet pick strength is required for copolymer latex used as a binder. ing.
ピック強度や湿潤ピック強度を向上させる為には、共重合体ラテックスの粒子径をより小さくする事が有効である事が知られている。通常ラテックスを小粒子径で生産するためには通常の文献（非特許文献１ 室井宗一著、高分子ラテックスの化学）等に示されるように、重合初期における開始剤ラジカルの発生量の増加や、乳化剤の増量による重合単量体ミセルの増加が良く知られている。 In order to improve pick strength and wet pick strength, it is known that it is effective to make the particle diameter of the copolymer latex smaller. Usually, in order to produce latex with a small particle size, as shown in ordinary literature (Non-Patent Document 1, Soichi Muroi, Chemistry of Polymer Latex), etc. It is well known that polymerization monomer micelles are increased by increasing the amount of emulsifier.
この他、同様な効果の期待できる方法としては、重合に用いる開始剤を単量体添加開始前に大量に用いる方法等も良く用いられる。また、このような手法に関してはスミス−エバートのエマルジョンの重合理論として一般に良く知られていることである。しかし、このように一般に良く知られている方法で小粒子径のラテックスを生産した場合、応用して得られた製品の耐水性能を著しく損なうという短所も知られている。 In addition, as a method that can be expected to have the same effect, a method in which an initiator used for polymerization is used in a large amount before the start of monomer addition is often used. Such a technique is generally well known as the theory of polymerization of Smith-Evert emulsions. However, when the latex having a small particle diameter is produced by a generally well-known method as described above, there is also a disadvantage that the water resistance performance of a product obtained by application is significantly impaired.
さらに、工業的生産に対しては操業的条件や共重合体ラテックスの物性への制限等があるため１００ｎｍ以下の共重合体ラテックスを製造することは事実上困難であった。これら、工業生産にかかわる問題点でもっとも重要な点は共重合体の固形分に関わる問題である。通常の操業上の経済性に見合う共重合体ラテックスの固形分量は約３０質量％以上が確実に必要である。しかし、１００ｎｍ以下の共重合体ラテックスの固形分の設定を３０質量％以上にした場合、重合時の微細凝固物の発生や重合中の２次粒子への成長などにより重合に使用する乳化剤の量が、さらに過剰に必要であった。 Furthermore, for industrial production, it is practically difficult to produce a copolymer latex of 100 nm or less due to operational conditions and restrictions on the physical properties of the copolymer latex. Of these problems related to industrial production, the most important point is a problem related to the solid content of the copolymer. The solid content of the copolymer latex that meets the economic efficiency of normal operation must surely be about 30% by mass or more. However, when the solid content of the copolymer latex of 100 nm or less is set to 30% by mass or more, the amount of the emulsifier used for the polymerization due to the generation of fine coagulum during polymerization or the growth to secondary particles during the polymerization. However, it was necessary in excess.
これに対し、特許文献１（特開平６−２１１９１１号公報）や特許文献２（特許第３１０６２９２号公報）にある乳化剤の併用や添加方法による考案も提出されている。一方、非特許文献２「重合性界面活性剤・高分子活性剤」（長井勝利、日本接着学会誌Vol.33N0.6(1997),p233-239）に総説されているように、いわゆる反応性基を有する界面活性剤である反応性乳化剤を用いた乳化重合の技術が従来より良く知られている。このような反応性乳化剤を用いて製造された共重合体ラテックスは乳化剤自身が共重合体の粒子に化学結合を行うため、通常の乳化剤を用いた場合に比べ飛躍的に塗膜の耐水性や湿潤時の接着強度が増大することが多くの文献によって提出されている。 On the other hand, the idea by the combined use and the addition method of the emulsifier in patent document 1 (Unexamined-Japanese-Patent No. 6-2111911) and patent document 2 (patent 3106292) is also submitted. On the other hand, as described in Non-Patent Document 2 “Polymerizing Surfactant / Polymer Activator” (Katsu Nagai, Journal of Adhesion Society of Japan Vol.33N0.6 (1997), p233-239), so-called reactivity A technique of emulsion polymerization using a reactive emulsifier which is a surfactant having a group is well known. The copolymer latex produced using such a reactive emulsifier is chemically bonded to the copolymer particles by the emulsifier itself. Many publications have suggested that the adhesive strength when wet is increased.
たとえば特許文献３（特開平１１−２０９４１３号公報）、特許文献４（特開平５−１７１５９８号公報）、特許文献５（特開２０００−２３４２９３）等には表面強度等に優れる紙塗工用バインダーとしての考案が提出されている。 For example, Patent Document 3 (Japanese Patent Laid-Open No. 11-209413), Patent Document 4 (Japanese Patent Laid-Open No. 5-171598), Patent Document 5 (Japanese Patent Laid-Open No. 2000-234293) and the like are binders for paper coating that have excellent surface strength and the like. As a device has been submitted.
いずれの技術においても、ある程度の小粒子径化を達成することは可能であるが、工業的規模で共重合体ラテックスを生産するに際しては、微細凝固物の発生を充分に抑制する事は不可能であり、更なる改良が求められている。また、小粒子径化されたラテックスは、一般的に化学的安定性が劣り、紙塗工用カラーのバインダとして調製された場合にも、カラー中で微細凝固物の発生を起こし、塗工紙表面へのキズ（ストリーク、スクラッチなど）を起こすという課題を有している。 In any technique, it is possible to achieve a certain small particle size, but it is impossible to sufficiently suppress the generation of fine coagulum when producing a copolymer latex on an industrial scale. There is a need for further improvements. In addition, latex with a reduced particle size generally has poor chemical stability, and even when it is prepared as a binder for paper coating colors, it causes the generation of fine coagulates in the collar, resulting in coated paper. It has a problem of causing scratches (streaks, scratches, etc.) on the surface.
一方、印刷用紙である塗工紙の生産においても、生産能力および生産性の向上のため、塗工速度の高速化が進められている。顔料、共重合体ラテックスおよびスターチ、カゼインなどの水溶性高分子を主成分とする塗工液においては、塗工の高速化に伴う乾燥能力の低下に対応するため、高固形分化が求められている。塗工液の高固形分化による流動性の低下を改良するため、炭酸カルシウムの配合比率を増加するといった顔料配合面からの検討や、スターチなどの増粘性の大きい水溶性バインダーを減らし、共重合体ラテックスを増加する等のバインダー面からの検討が行われている。しかし炭酸カルシウムの配合比率を高めると塗工紙の光沢が低下するという問題があり、また共重合体ラテックスの配合量を増加すると、塗工紙表面のベタツキ性が増大し、バッキングロールやカレンダーロールの汚れといった操業上の問題を発生しやすくなる。 On the other hand, in the production of coated paper, which is printing paper, the coating speed has been increased in order to improve production capacity and productivity. In coating liquids mainly composed of pigments, copolymer latex, and water-soluble polymers such as starch and casein, high solid differentiation is required in order to cope with the decrease in drying capacity accompanying higher speed coating. Yes. In order to improve the decrease in fluidity due to high solidification of the coating liquid, it is possible to study from the pigment formulation side, such as increasing the blending ratio of calcium carbonate, reduce the water-soluble binder with high viscosity such as starch, and copolymer Investigations from the binder side, such as increasing latex, are being conducted. However, there is a problem that the gloss of the coated paper decreases when the blending ratio of calcium carbonate is increased, and when the blending amount of the copolymer latex is increased, the stickiness of the coated paper surface increases, and a backing roll or calendar roll It becomes easy to generate operational problems such as dirt.
以上のような塗工紙の品質や塗工紙の生産に関わる問題のため、共重合体ラテックスについても様々な改良がなされてきた。例えば特定の単量体組成で二段もしくは多段で重合を行う共重合体ラテックスの改良が多数提案されている（特許文献６ 特公昭６２−５８３７１号公報、特許文献７ 特公昭６２−３１１１６号公報、特許文献８ 特公昭６４−２７１６号公報、特許文献９ 特公昭６０−１９９２７号公報、特許文献１０ 特開平４−４１５０２号公報、特許文献１１ 特開平５−２７２０９４号公報、特許文献１２ 特開平７−２４７３２７号公報）。しかしながらこれらの発明では、塗工紙のドライピック強度、湿潤ピック強度、および紙塗工における耐ロール汚れ特性の向上手段としていずれも不十分なものであった。 Due to the problems relating to the quality of coated paper and the production of coated paper as described above, various improvements have been made to copolymer latex. For example, many improvements of copolymer latexes in which polymerization is carried out in a two-stage or multi-stage with a specific monomer composition have been proposed (Japanese Patent Publication No. 62-58371, Japanese Patent Publication No. 62-31116). Patent Document 8 Japanese Patent Publication No. 64-27716, Patent Document 9 Japanese Patent Publication No. 60-19927, Patent Document 10 Japanese Patent Laid-Open No. 4-41502, Patent Document 11 Japanese Patent Laid-open No. Hei 5-272904, Patent Document 12 7-247327). However, these inventions are insufficient as means for improving dry pick strength, wet pick strength of coated paper, and anti-roll dirt property in paper coating.
ところで、特許文献１３（特開平４−１２６８９６号公報）にはスチレンスルホン酸系化合物を共重合したジエン系共重合体ラテックスが、特許文献１４（特開昭６１−２６６６９６号公報）にはエチレン系不飽和スルホン酸単量体及び／又はそのアルカリ塩を共重合したジエン系共重合体ラテックスが、更には特許文献１５（特開平７−１６６４９４号公報）には水溶性アリール化合物を共重合したジエン系共重合体ラテックスが、更には特許文献１６（特開２００３−１１９２０３）には特定の反応性乳化剤を用いて粒子径とゲル分率が特定の範囲に入るジエン系共重合体ラテックスが開示されているが、いずれの発明においても、上記に記した課題である塗工紙のピック強度、湿潤ピック強度、共重合体ラテックス生産時の微細凝固物の抑制、共重合体ラテックスの化学的安定性と耐湿潤ベタツキ性を全て解決できるものではなかった。
本発明は、以上のような状況から、耐湿潤ベタツキ性に優れ、塗工紙のピック強度と湿潤ピック強度の両者を向上させ、更には塗工カラーを調製した際の微細凝固物の発生を低減させるジエン系共重合体ラテックスを、工業的規模で効率よく製造する技術を提供する事を目的とする。 From the above situation, the present invention has excellent wet stickiness resistance, improves both pick strength and wet pick strength of coated paper, and further generates fine solidified products when a coating color is prepared. The object is to provide a technique for efficiently producing diene copolymer latex to be reduced on an industrial scale.
本発明者らは、上述の問題点を解決するために鋭意検討した結果、共重合体ラテックスを製造するに際し、出発原料である単量体組成を特定範囲に限定し、かつエチレン系不飽和スルホン酸のアルカリ塩の存在下に乳化重合を行うと共に、乳化重合途中におけるエチレン性不飽和カルボン酸のアルカリ塩の反応転化率を特定範囲に定めることによって、上記目的を達成できる事を見出し、本発明に至った。 As a result of intensive investigations to solve the above-mentioned problems, the inventors of the present invention limited the monomer composition as a starting material to a specific range and produced an ethylenically unsaturated sulfone when producing a copolymer latex. It was found that the above-mentioned object can be achieved by carrying out emulsion polymerization in the presence of an alkali salt of an acid and by setting the reaction conversion rate of the alkali salt of ethylenically unsaturated carboxylic acid in the middle of the emulsion polymerization within a specific range. It came to.
即ち本発明は、
［１］エチレン系不飽和スルホン酸のアルカリ塩の中から選ばれる、少なくとも一種以上の化合物（以下、化合物Ａと略する）の存在下に、下記単量体混合物
（ａ）共役ジエン系単量体２０〜８０質量％、
（ｂ）不飽和カルボン酸単量体０．５〜１０質量％、
（ｃ）シアン化ビニル単量体３〜５０質量％、および
（ｄ）その他共重合可能な単量体０〜７６．５質量％
（但し（ａ）＋（ｂ）＋（ｃ）＋（ｄ）＝１００質量％）を乳化重合して共重合体ラテックスを製造するに当たり、全単量体混合物の添加が終了した時点において、重合系内に添加された化合物Ａの反応転化率が７０質量％以上である事を特徴とする共重合体ラテックスの製造方法。
［２］上記化合物Ａの存在下、単量体混合物を少なくとも2段階以上の多段階に分けて乳化重合し共重合体ラテックスを製造するに当たり、最終段階の単量体混合物の添加を開始する時点において、重合系内に添加された化合物Ａの反応転化率が６０質量％以上である事を特徴とする、［１］記載の共重合体ラテックスの製造方法、に関する。
That is, the present invention
[1] In the presence of at least one compound selected from alkali salts of ethylenically unsaturated sulfonic acid (hereinafter abbreviated as Compound A), the following monomer mixture (a) conjugated diene monomer Body 20-80 mass%,
(B) 0.5 to 10% by mass of an unsaturated carboxylic acid monomer,
(C) 3 to 50% by mass of vinyl cyanide monomer, and (d) 0 to 76.5% by mass of other copolymerizable monomers.
(However, (a) + (b) + (c) + (d) = 100% by mass) is produced by emulsion polymerization to produce a copolymer latex. A method for producing a copolymer latex, wherein the reaction conversion rate of compound A added to the system is 70% by mass or more.
[2] When the monomer mixture is emulsion-polymerized in at least two or more stages in the presence of the compound A to produce a copolymer latex, the addition of the monomer mixture at the final stage is started. The method for producing a copolymer latex according to [1], wherein the reaction conversion rate of the compound A added in the polymerization system is 60% by mass or more.
本発明の製造方法によれば、塗工紙のピック強度、湿潤ピック強度、耐ベタツキ性、塗工カラーに対する安定性などに優れる共重合体ラテックスを、乳化重合時の微細凝固物の発生を低減させて、安定に重合することができる。 According to the production method of the present invention, a copolymer latex excellent in pick strength, wet pick strength, stickiness resistance, coating color stability, etc. of coated paper is reduced, and the occurrence of fine coagulum during emulsion polymerization is reduced. And can be stably polymerized.
本発明は、エチレン系不飽和カルボン酸のアルカリ塩の中から選ばれる、少なくとも一種以上の化合物（化合物A）の存在下に、後述する単量体混合物を乳化重合して共重合体ラテックスを製造する方法である。 The present invention produces a copolymer latex by emulsion polymerization of a monomer mixture described below in the presence of at least one compound (compound A) selected from alkali salts of ethylenically unsaturated carboxylic acids. It is a method to do.
本発明について、以下に具体的に説明する。
本発明で用いる、エチレン系不飽和スルホン酸のアルカリ塩とは、その分子中にビニル基、アクリロレイル基、あるいはメタアクリロレイル基等のラジカル重合性の二重結合を有したスルホン酸のアルカリ塩であり、１種単独で、又は２種以上併用して使用可能である。具体例としては、分子中にビニル基、アクロレイル基、あるいはメタアクロレイル基を有するスルホン酸化合物のナトリウム塩、カリウム塩、あるいはアンモニウム塩であり、例えばスチレンスルホン酸ソーダ、スチレンスルホン酸カリウム、スチレンスルホン酸アンモニウム、アリルスルホン酸ソーダ、アリルスルホン酸カリウム、アリルスルホン酸アンモニウム、メタアリルスルホン酸ソーダ、メタアリルスルホン酸カリウム、メタアリルスルホン酸アンモニウム、アクリルスルホン酸ソーダ、アクリルスルホン酸カリウム、アクリルスルホン酸アンモニウム、メタアクリルスルホン酸ソーダ、メタアクリルスルホン酸カリウム、メタアクリルスルホン酸アンモニウム、ビニルスルホン酸ソーダ、ビニルスルホン酸カリウム、ビニルスルホン酸アンモニウム、２−アクリルアミド−２−メチルプロパンソーダ、２−アクリルアミド−２−メチルプロパンカリウム、２−アクリルアミド−２−メチルプロパンアンモニウム等があげられる。
The present invention will be specifically described below.
The alkali salt of an ethylenically unsaturated sulfonic acid used in the present invention is an alkali salt of a sulfonic acid having a radical polymerizable double bond such as a vinyl group, an acryloyl group, or a methacryloyl group in the molecule. It can be used alone or in combination of two or more. Specific examples include sodium salts, potassium salts, and ammonium salts of sulfonic acid compounds having a vinyl group, an acroleyl group, or a metaacroleyl group in the molecule, such as sodium styrene sulfonate, potassium styrene sulfonate, and styrene sulfone. Ammonium acid, sodium allyl sulfonate, potassium allyl sulfonate, ammonium allyl sulfonate, sodium methallyl sulfonate, potassium methallyl sulfonate, ammonium methallyl sulfonate, sodium acrylate sulfonate, potassium acryl sulfonate, ammonium acrylate sulfonate , Sodium methacryl sulfonate, potassium methacryl sulfonate, ammonium methacryl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, vinyl sulfate Ammonium phosphate, 2-acrylamido-2-methylpropane sodium 2-acrylamido-2-methylpropane potassium 2-acrylamido-2-methylpropane ammonium and the like.
更には分子中にラジカル重合性の二重結合、硫酸基、ポリオキシアルキレン基を有する、所謂、反応性乳化剤も使用可能であり、このような反応性乳化剤の例としては下記一般式（Ｉ）〜（ＶＩＩ）で示されるものが例としてあげられる。 Furthermore, so-called reactive emulsifiers having radically polymerizable double bonds, sulfuric acid groups and polyoxyalkylene groups in the molecule can be used. Examples of such reactive emulsifiers include the following general formula (I) Examples shown by-(VII) are listed.
これらのエチレン性不飽和スルホン酸のアルカリ塩は、通常単量体混合物１００質量部当たり、０．０１〜５質量部の範囲で用いられる。この範囲で用いる事により、得られた共重合体ラテックスは取り扱いに支障を及ぼさない粘度を維持し、かつ塗工紙の良好な接着強度を発現させる。このましくは０．１〜３質量部、更に好ましくは０．３〜２質量部の範囲である。 These alkali salts of ethylenically unsaturated sulfonic acids are usually used in the range of 0.01 to 5 parts by mass per 100 parts by mass of the monomer mixture. By using in this range, the obtained copolymer latex maintains a viscosity that does not hinder handling, and exhibits good adhesive strength of the coated paper. Preferably, it is 0.1-3 mass parts, More preferably, it is the range of 0.3-2 mass parts.
次に乳化重合に際しての、エチレン性不飽和スルホン酸のアルカリ塩の使用方法であるが、これは特に制約はなく、乳化重合を行う系内に予め一括で全量を仕込んでおいてもよく、また、乳化重合開始後に追添しても良い。しかし得られる共重合体ラテックスの化学的安定性、微細凝固物抑制効果の観点から判断すると、使用するエチレン性不飽和スルホン酸のアルカリ塩の全量の内、５０質量％以上については予め系内に仕込んでおいてから乳化重合を開始する事が好ましく、より好ましくは７０質量％以上である。 Next, it is a method of using an alkali salt of ethylenically unsaturated sulfonic acid at the time of emulsion polymerization, but this is not particularly limited, and the whole amount may be charged all at once in the system for emulsion polymerization. Further, it may be added after the start of emulsion polymerization. However, judging from the viewpoint of the chemical stability of the obtained copolymer latex and the effect of suppressing the fine coagulation, about 50% by mass or more of the total amount of the alkali salt of ethylenically unsaturated sulfonic acid to be used is already in the system. It is preferable to start emulsion polymerization after charging, and more preferably 70% by mass or more.
工業的規模で本発明の共重合体ラテックスの製造方法を適用するには、エチレン性不飽和スルホン酸のアルカリ塩については、水溶液として使用する事が取り扱い上好ましい。水溶液の濃度については特に規定はないが、５〜５０質量％の範囲で使用される。またエチレン性不飽和スルホン酸のアルカリ塩が、乳化重合に供する前の段階で、変質をしてしまう事を防ぐ為に、水溶液のＰＨは７〜１４、好ましくは９〜１３．５、最も好ましくは１０〜１３に調製する事が望ましい。水溶液のＰＨ調整は、水溶液に公知の塩基性物質を添加する事によって可能となる。 In order to apply the method for producing the copolymer latex of the present invention on an industrial scale, it is preferable in terms of handling that the alkali salt of ethylenically unsaturated sulfonic acid is used as an aqueous solution. Although there is no restriction | limiting in particular about the density | concentration of aqueous solution, It uses in the range of 5-50 mass%. Further, in order to prevent the alkali salt of ethylenically unsaturated sulfonic acid from being deteriorated before being subjected to emulsion polymerization, the pH of the aqueous solution is 7 to 14, preferably 9 to 13.5, most preferably. Is preferably adjusted to 10-13. The pH of the aqueous solution can be adjusted by adding a known basic substance to the aqueous solution.
本発明において目的の効果を発現させる為には、乳化重合途中における、エチレン性不飽和スルホン酸のアルカリ塩の反応転化率が特定の範囲に入る事が必須である。すなわち、共役ジエン系単量体等の単量体混合物を添加して乳化重合するに当たり、全単量体混合物の添加が完了した時点において、その時点までに乳化重合系内に添加されたエチレン性不飽和スルホン酸のアルカリ塩の反応転化率が７０質量％以上である事が必要である。この反応転化率を７０質量％以上にさせる事によって、得られた共重合体ラテックスの湿潤ピック強度、耐湿潤ベタツキ性、及び化学的安定性を良好にさせる事が可能となり、乳化重合時に発生する微細凝固物の量を著しく低減させる事ができる。更に好ましい範囲は８０％質量以上、より好ましくは９０質量％以上である。 In order to express the target effect in the present invention, it is essential that the reaction conversion rate of the alkali salt of ethylenically unsaturated sulfonic acid during the emulsion polymerization falls within a specific range. That is, in the emulsion polymerization by adding a monomer mixture such as a conjugated diene monomer, when the addition of the whole monomer mixture is completed, the ethylenic acid added in the emulsion polymerization system up to that point is added. It is necessary that the reaction conversion rate of the alkali salt of unsaturated sulfonic acid is 70% by mass or more. By making this reaction conversion rate 70% by mass or more, it becomes possible to improve the wet pick strength, wet stickiness resistance, and chemical stability of the obtained copolymer latex, which occurs during emulsion polymerization. The amount of fine solidified material can be remarkably reduced. A more preferable range is 80% by mass or more, more preferably 90% by mass or more.
また、単量体混合物を2段以上の複数の段階に分けて乳化重合の系内に添加し、共重合体ラテックスを製造する場合には、最終段階の単量体混合物の添加を開始する時点において、その時点までに乳化重合系内に添加されたエチレン性不飽和スルホン酸のアルカリ塩の反応添加率が６０質量％以上である事が好ましい。この反応添加率を６０質量％以上にさせる事によって、得られた共重合体ラテックスの湿潤ピック強度、耐湿潤ベタツキ性、及び化学的安定性を良好にさせる事ができ、更には、乳化重合時に発生する微細凝固物の量を低減せしめることができる。更に好ましい範囲は７０質量％以上、最も好ましくは８０質量％以上である。 In addition, when the monomer mixture is added to the emulsion polymerization system in two or more stages and a copolymer latex is produced, when the addition of the monomer mixture at the final stage is started In the above, it is preferable that the reaction addition rate of the alkali salt of ethylenically unsaturated sulfonic acid added to the emulsion polymerization system up to that point is 60% by mass or more. By making this reaction addition rate 60 mass% or more, the resulting copolymer latex can be improved in wet pick strength, wet stickiness resistance, and chemical stability, and at the time of emulsion polymerization. It is possible to reduce the amount of fine solidified matter generated. A more preferred range is 70% by mass or more, and most preferred is 80% by mass or more.
エチレン性不飽和スルホン酸のアルカリ塩の反応転化率の制御は、乳化重合時の重合温度や、乳化重合系内への単量体混合物の添加速度、併用する重合遅延剤の量や添加速度、乳化重合系のＰＨ等のコントロールで所望の範囲に調整可能である。 Control of the reaction conversion rate of the alkali salt of ethylenically unsaturated sulfonic acid is the polymerization temperature during emulsion polymerization, the addition rate of the monomer mixture into the emulsion polymerization system, the amount and addition rate of the polymerization retarder used together, It can be adjusted to a desired range by controlling the pH of the emulsion polymerization system.
本発明における単量体混合物を構成する（ａ）共役ジエン系単量体は、共重合体に柔軟性を与え、接着力、衝撃吸収性を与えるために必須の成分であり、該共重合体を構成する全単量体を１００質量％とした場合、２０〜８０質量％、好ましくは３０〜７０質量％、最も好ましくは３５〜５５質量％の割合で用いられる。この単量体の使用量を上記範囲に設定する事により、共重合体に適度の柔軟性と弾性を付与して接着力を向上させ、更には耐湿潤ベタツキ性を向上させる事ができる。使用される共役ジエン系単量体の好ましい例としては、１，３−ブタジエン、イソプレン、２−クロロ−１，３−ブタジエンなどがあげられ、これらは１種または２種以上が組み合わせて用いられる。 The (a) conjugated diene monomer constituting the monomer mixture in the present invention is an essential component for imparting flexibility to the copolymer and providing adhesive strength and impact absorption. In the case where the total amount of monomers constituting 100 is 100% by mass, it is used in a proportion of 20 to 80% by mass, preferably 30 to 70% by mass, and most preferably 35 to 55% by mass. By setting the use amount of this monomer within the above range, it is possible to impart appropriate flexibility and elasticity to the copolymer to improve the adhesive force and to further improve the wet stickiness resistance. Preferable examples of the conjugated diene monomer used include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and the like, and these are used alone or in combination of two or more. .
本発明における（ｂ）不飽和カルボン酸単量体は、共重合体ラテックスに必要な分散安定性を与え、接着力を高めるための必須成分であり、該共重合体を構成する全単量体を１００質量％とした場合、全単量体に対し０．５〜１０質量％、好ましくは０．８〜８質量％、更に好ましくは１〜５質量％の割合で用いられる。この単量体の使用量を上記範囲に設定する事により、共重合体ラテックスに必要な分散安定性を与えることが可能となり顔料混和時および塗工工程におけるさまざまな問題発生を回避する事ができる。また共重合体の粘度を取り扱いに支障をきたさない適度な範囲に調整する事が可能であり、かつ耐水性も良好なレベルを実現する。不飽和カルボン酸単量体の好ましい例としては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、スチレンスルホン酸などのエチレン系不飽和カルボン酸などがあげられ、これらは１種または２種以上が組み合わせて用いられる。 The (b) unsaturated carboxylic acid monomer in the present invention is an essential component for imparting the necessary dispersion stability to the copolymer latex and enhancing the adhesive force, and all monomers constituting the copolymer Is 100 to 10% by mass, it is used in a proportion of 0.5 to 10% by mass, preferably 0.8 to 8% by mass, and more preferably 1 to 5% by mass with respect to all monomers. By setting the amount of this monomer used within the above range, it is possible to give the necessary dispersion stability to the copolymer latex, and avoid various problems during pigment mixing and coating processes. . In addition, the viscosity of the copolymer can be adjusted to an appropriate range that does not hinder handling, and the water resistance is also good. Preferable examples of the unsaturated carboxylic acid monomer include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and styrene sulfonic acid. More than one species are used in combination.
本発明における（ｃ）シアン化ビニル単量体は、耐湿潤ベタツキ性および湿潤ピック強度の向上に必須の成分であり、該共重合体を構成する全単量体を１００質量％とした場合、全単量体に対し３〜５０質量％、好ましくは５〜４０質量％、更に好ましくは７〜３０質量％の割合で用いられる。この単量体の使用量を上記範囲に設定する事により、本発明の目的である耐湿潤ベタツキ性や湿潤ピック強度の向上効果が得られ、かつ共重合体ラテックスの重合安定性を低下させる事がない。シアン化ビニル単量体の好ましい例としては、アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリルなどがあげられ、これらは１種または２種以上が組み合わせて用いられる。 (C) vinyl cyanide monomer in the present invention is an essential component for improving wet tack resistance and wet pick strength, and when the total monomer constituting the copolymer is 100% by mass, It is used in a proportion of 3 to 50% by mass, preferably 5 to 40% by mass, more preferably 7 to 30% by mass with respect to the total monomers. By setting the use amount of this monomer within the above range, the effect of improving wet stickiness and wet pick strength, which are the objects of the present invention, can be obtained, and the polymerization stability of the copolymer latex can be reduced. There is no. Preferable examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and these are used alone or in combination of two or more.
本発明においては（ｄ）共重合可能な他の単量体を併用して含む事が好ましい。この共重合可能な他の単量体の出発物質となる単量体を適宜選択することにより、共重合体ラテックスにさまざまな特性を付与できる。共重合可能な他の単量体の好ましい例としては、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−メチルスチレンなどの芳香族ビニル単量体、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシルなどのアクリル酸アルキルエステル類、メタクリル酸メチル、メタクリル酸ブチルなどのメタクリル酸アルキルエステル類、アクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシエチルなどのヒドロキシアルキルエステル類、アクリル酸アミノエチル、アクリル酸ジメチルアミノエチル、アクリル酸ジエチルアミノエチルなどのアミノアルキルエステル類、２−ビニルピリジン、４−ビニルピリジンなどのピリジン類、アクリル酸グリシジル、メタクリル酸グリシジルなどのグリシジルエステル類、アクリルアミド、メタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−メチルメタクリルアミド、グリシジルメタクリルアミド、Ｎ，Ｎ−ブトキシメチルアクリルアミドなどのアミド類、酢酸ビニルなどのカルボン酸ビニルエステル類、塩化ビニルなどのハロゲン化ビニル類などがあげられ、これらは１種または２種以上が組み合わせて用いられる。 In the present invention, it is preferable to use (d) another copolymerizable monomer in combination. Various properties can be imparted to the copolymer latex by appropriately selecting a monomer that is a starting material for the other copolymerizable monomer. Preferred examples of other copolymerizable monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, hydroxyalkyl esters such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, acrylic acid Aminoalkyl esters such as aminoethyl, dimethylaminoethyl acrylate and diethylaminoethyl acrylate; pyridines such as 2-vinylpyridine and 4-vinylpyridine; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate Amides such as acrylamide, acrylamide, methacrylamide, N-methylol acrylamide, N-methyl acrylamide, N-methyl methacrylamide, glycidyl methacrylamide, N, N-butoxymethyl acrylamide, vinyl acetates such as vinyl acetate, Examples thereof include vinyl halides such as vinyl chloride, and these are used alone or in combination of two or more.
この（ｄ）共重合可能な単量体は、該共重合体を構成する全単量体を１００質量％とした場合、全単量体に対し０〜７６．５質量％、好ましくは２５〜６６質量％の割合で用いられる。この単量体を上記範囲で使用する事で、好適な接着強度が発現させる事が可能となる。 The monomer (d) capable of copolymerization is 0 to 76.5% by mass, preferably 25 to 25%, based on 100% by mass of all monomers constituting the copolymer. It is used at a ratio of 66% by mass. By using this monomer in the above range, it is possible to develop suitable adhesive strength.
本発明の製法で製造される共重合体ラテックスのガラス転移温度（Ｔｇ）は、特に限定されるものではないが、塗工紙用途における接着強度とラテックスの耐湿潤ベタツキ性を両立させる観点から、−５０℃〜＋４０℃、好ましくは−４０℃〜＋４５℃、よりこのましくは−３０〜＋４０℃の範囲にあることである。Ｔｇは１種類の共重合体ラテックスおいて１点だけでなく、複数のＴｇを有していても良い。 The glass transition temperature (Tg) of the copolymer latex produced by the production method of the present invention is not particularly limited, but from the viewpoint of achieving both the adhesive strength in coated paper applications and the wet stickiness resistance of the latex. It is in the range of −50 ° C. to + 40 ° C., preferably −40 ° C. to + 45 ° C., more preferably −30 to + 40 ° C. Tg may have not only one point but also a plurality of Tg in one type of copolymer latex.
本発明の製造法で製造される共重合体ラテックスにおいては、その粒子径は５０〜１５０ｎｍ、好ましくは６０〜１１０ｎｍにあることが好適である。この範囲の粒子径に設定する事により、ラテックスの粘度を好適な範囲に調整する事が可能であり、作業性を低下せしめない。更には、接着強度の低下や塗料粘度の上昇が発生を抑制させる事ができる。 The copolymer latex produced by the production method of the present invention has a particle size of 50 to 150 nm, preferably 60 to 110 nm. By setting the particle diameter within this range, the viscosity of the latex can be adjusted to a suitable range, and workability is not lowered. Furthermore, the occurrence of a decrease in adhesive strength and an increase in paint viscosity can be suppressed.
本発明の製造法で製造される共重合体ラテックスについては、共重合体中のゲル分率（トルエン不溶分）が６０〜９８質量％に有ることが好ましく、更に好ましくは７０〜９５質量％、最も好ましくは８５〜９３質量％の範囲にあることである。この範囲にゲル分率を調整する事によって、ラテックスの耐湿潤ベタツキ性と塗工紙の湿潤ピック強度を同時に向上させる事ができる。 About the copolymer latex manufactured by the manufacturing method of this invention, it is preferable that the gel fraction (toluene insoluble content) in a copolymer exists in 60-98 mass%, More preferably, it is 70-95 mass%, Most preferably, it exists in the range of 85-93 mass%. By adjusting the gel fraction within this range, the wet stickiness resistance of the latex and the wet pick strength of the coated paper can be improved at the same time.
本発明の共重合体ラテックスの製造法は、従来商業的に用いられている乳化重合法の装置を使用して行われるものであり、その方法については特に制限はなく、水性媒体中で界面活性剤の存在下、ラジカル開始剤により重合を行うなどの方法を用いることができる。 The method for producing the copolymer latex of the present invention is carried out using an emulsion polymerization method apparatus which is conventionally used commercially. There is no particular limitation on the method, and the surface active in an aqueous medium. A method of performing polymerization with a radical initiator in the presence of an agent can be used.
使用する乳化剤についても特に制限はなく、従来公知のアニオン、カチオン、両性および非イオン性の界面活性剤を用いることができる。好ましい界面活性剤の例としては、脂肪族セッケン、ロジン酸セッケン、アルキルスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキル硫酸塩などのアニオン性界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオキシプロピレンブロックコポリマーなどのノニオン性界面活性剤があげられ、これらは単独または２種以上を組み合わせて用いられる。反応性乳化剤を除いて、使用する乳化剤の合計量は、単量体１００質量部当たり、０．１〜０．４質量部である事が好ましい。 There is no restriction | limiting in particular also about the emulsifier to use, A conventionally well-known anion, a cation, an amphoteric, and a nonionic surfactant can be used. Examples of preferred surfactants include anionic surfactants such as aliphatic soaps, rosin acid soaps, alkyl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl ethers, polyoxyethylenes Nonionic surfactants such as alkyl allyl ether and polyoxyethylene oxypropylene block copolymer are listed, and these are used alone or in combination of two or more. Except for the reactive emulsifier, the total amount of the emulsifier used is preferably 0.1 to 0.4 parts by mass per 100 parts by mass of the monomer.
ラジカル開始剤は、熱または還元剤の存在下でラジカル分解して単量体の付加重合を開始させるものであり、無機系開始剤、有機系開始剤のいずれも使用することが可能である。好ましい例としてはペルオキソニ硫酸塩、過酸化物、アゾビス化合物などがあり、具体的にはペルオキソニ硫酸カリウム、ペルオキソニ硫酸ナトリウム、ペルオキソニ硫酸アンモニウム、過酸化水素、ｔ−ブチルヒドロペルオキシド、過酸化ベンゾイル、２，２−アゾビスブチロニトリル、クメンハイドロパーオキサイドなどがあげられ、これらは単独または２種以上を組み合わせて用いることができる。また酸性亜硫酸ナトリウム、アスコルビン酸やその塩、エリソルビン酸やその塩、ロンガリットなどの還元剤を重合開始剤と組み合わせて用いる、いわゆるレドックス重合法を用いることもできる。 The radical initiator initiates addition polymerization of the monomer by radical decomposition in the presence of heat or a reducing agent, and either an inorganic initiator or an organic initiator can be used. Preferred examples include peroxodisulfates, peroxides, azobis compounds, and the like. Specifically, potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, 2,2 -Azobisbutyronitrile, cumene hydroperoxide, etc. are mention | raise | lifted and these can be used individually or in combination of 2 or more types. Further, a so-called redox polymerization method in which a reducing agent such as acidic sodium sulfite, ascorbic acid or a salt thereof, erythorbic acid or a salt thereof or Rongalite is used in combination with a polymerization initiator can also be used.
本発明の共重合体ラテックスの製造法を適用する場合、ラジカル重合において通常用いられる公知の連鎖移動剤を用いることが可能である。連鎖移動剤の好ましい例としては、核置換α−メチルスチレンのニ量体のひとつであるα−メチルスチレンダイマー、ｎ−ブチルメルカプタン、ｔ−ブチルメルカプタン、ｎ−オクチルメルカプタン、ｎ−ラウリルメルカプタンなどのメルカプタン類、テトラメチルチウラジウムジスルフィド、テトラエチルチウラジウムジスルフィドなどのジスルフィド類、四塩化炭素、四臭化炭素などのハロゲン化誘導体、２−エチルヘキシルチオグリコレートなどがあげられ、これらは単独または２種以上を組み合わせて用いることができる。連鎖移動剤の添加方法にも特に制限はなく、一括添加、回分添加、連続添加など公知の添加方法が用いられる。 When applying the method for producing a copolymer latex of the present invention, it is possible to use a known chain transfer agent usually used in radical polymerization. Preferred examples of the chain transfer agent include α-methylstyrene dimer, n-butyl mercaptan, t-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, etc., which is one of dimers of nucleus-substituted α-methylstyrene. Examples include mercaptans, disulfides such as tetramethylthiudium disulfide and tetraethylthuradium disulfide, halogenated derivatives such as carbon tetrachloride and carbon tetrabromide, and 2-ethylhexyl thioglycolate. These may be used alone or in combination. Can be used in combination. The addition method of the chain transfer agent is not particularly limited, and known addition methods such as batch addition, batch addition, and continuous addition are used.
本発明の共重合体ラテックスの製造法を適用する場合の重合温度は、特に制約はないが、通常４０〜１００℃の範囲で行う事が一般的であるが、生産効率と、得られる共重合体ラテックスの接着強度等の品質の観点からは、５５〜９５℃の範囲が好ましい。 The polymerization temperature in the case of applying the method for producing the copolymer latex of the present invention is not particularly limited, but it is generally carried out in the range of 40 to 100 ° C. From the viewpoint of quality such as the adhesive strength of the combined latex, a range of 55 to 95 ° C is preferable.
本発明の共重合体ラテックスの製造法を適用する場合の重合固形分は、生産効率と乳化重合時の微細凝固物抑制の観点から、３５〜６０質量％、更に好ましくは３８〜５２質量％である。 The polymerization solid content in the case of applying the method for producing the copolymer latex of the present invention is 35 to 60% by mass, more preferably 38 to 52% by mass, from the viewpoint of production efficiency and suppression of fine coagulum during emulsion polymerization. is there.
本発明の共重合体ラテックスの製造法においては、乳化重合の系内に単量体混合物を添加する手段については特に制約はない。単量体混合物の一部を一括して予め乳化重合系内に仕込み重合した後、残りの単量体混合物を連続的もしくは間欠的に仕込む方法、あるいは単量体混合物を重合最初から連続的または間欠的に仕込む方法を採りうるものであり、これらの重合方法を組み合わせて重合してもよいが、得られる共重合体ラテックスの耐湿潤ベタツキ性を高め、かつ優れた接着強度を発現させる為には、単量体混合物を複数の段階に分け、各段階で単量体混合物の組成を変えて仕込む、多段階重合法が好ましい。この場合、全単量体を合計した混合組成が請求項１記載の内容に該当している範囲においては特に制約はないが、得られる共重合体ラテックスのポリマーについては、粒子中心部が比較的軟質な組成であり、かつ粒子表層部が比較的硬質な組成となるべく、各段階の単量体組成を設定する事が、耐湿潤ベタツキ性と接着強度を発現させるために好ましい。 In the method for producing the copolymer latex of the present invention, there is no particular limitation on the means for adding the monomer mixture into the emulsion polymerization system. A method in which a part of the monomer mixture is charged into the emulsion polymerization system in advance and polymerized, and then the remaining monomer mixture is charged continuously or intermittently, or the monomer mixture is continuously or continuously from the beginning of the polymerization. In order to improve the wet stickiness resistance of the copolymer latex obtained and to develop excellent adhesive strength, it is possible to adopt a method of charging intermittently and to polymerize by combining these polymerization methods. Is preferably a multi-stage polymerization method in which the monomer mixture is divided into a plurality of stages and the composition of the monomer mixture is changed at each stage. In this case, there is no particular limitation in the range in which the total composition of all monomers corresponds to the content of claim 1, but the polymer latex of the copolymer latex obtained has a relatively small particle center. It is preferable to set the monomer composition at each stage so that the composition has a soft composition and the particle surface layer portion has a relatively hard composition in order to develop wet tack resistance and adhesive strength.
本発明の製造法で得られた共重合体ラテックスには、必要に応じて公知の各種重合調整剤を用いることができる。これらはたとえばｐＨ調整剤、キレート剤などであり、ｐＨ調整剤の好ましい例としては水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム、炭酸水素ナトリウム、リン酸水素二ナトリウムなどがあげられ、キレート剤の好ましい例としてはエチレンジアミン四酢酸ナトリウムなどがあげられる。 For the copolymer latex obtained by the production method of the present invention, various known polymerization regulators can be used as necessary. These are, for example, pH adjusters, chelating agents, etc. Preferred examples of pH adjusting agents include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, disodium hydrogen phosphate, and the like. Preferable examples include sodium ethylenediaminetetraacetate.
本発明の製造法で得られた共重合体ラテックスの、最終製品としての固形分についても特に制限はなく、通常固形分は３０〜６０質量％の範囲に希釈もしくは濃縮して調製される。 There is no restriction | limiting in particular also about solid content as a final product of the copolymer latex obtained by the manufacturing method of this invention, Usually solid content is prepared by diluting or concentrating in the range of 30-60 mass%.
本発明の共重合体ラテックスの製造に際しては、粒子径の調整のため公知のシード重合法を用いることも可能であり、シードを作製後同一反応系内で共重合体ラテックスの重合を行うインターナルシード法、別途作製したシードを用いるエクスターナルシード法などの方法を適宜選択して用いることができる。 In the production of the copolymer latex of the present invention, it is possible to use a known seed polymerization method for adjusting the particle diameter, and after the seed is prepared, the internal seed is polymerized in the same reaction system. A method such as an external seed method using a seed or a separately prepared seed can be appropriately selected and used.
本発明の製造法で得られた共重合体ラテックスには、必要に応じて各種添加剤を添加すること、あるいは他のラテックスを混合して用いることが可能であり、例えば分散剤、消泡剤、老化防止剤、耐水化剤、殺菌剤、印刷適性剤などを添加すること、アルカリ感応型ラテックス、プラスチック顔料などを混合して用いることもできる。 Various additives may be added to the copolymer latex obtained by the production method of the present invention as necessary, or other latexes may be mixed and used, for example, a dispersant, an antifoaming agent. Anti-aging agents, water-resistant agents, bactericides, printability agents and the like, alkali-sensitive latexes, plastic pigments and the like can also be mixed and used.
本発明の製造法で得られた共重合体ラテックスを紙塗工用塗料のバインダーとして用いる場合には、通常行われている実施態様で行うことができる。すなわち、分散剤を溶解させた水中に、カオリンクレー、炭酸カルシウム、二酸化チタン、水酸化アルミニウム、サチンホワイト、タルク等の無機顔料、プラスチックピグメントやバインダーピグメントとして知られる有機顔料、澱粉、カゼイン、ポリビニルアルコール、カルボキシメチルセルロース等の水溶性高分子、増粘剤、染料、消泡剤、防腐剤、耐水化剤、滑剤、印刷適性向上剤、保水剤等の各種添加剤とともに共重合体ラテックスを添加して混合し、均一な分散液とする態様である。ここで、本発明の製造法で得られた共重合体ラテックスは、紙塗工用塗料を構成する顔料については、その平均粒子径が小さいものを主として用いた場合に、特に顕著なピック強度、湿潤ピック強度を発現する。即ち、カオリンクレーについては、２μｍ以下の粒子が８４質量％以上であるもの、炭酸カルシウムについては２μｍ以下の粒子が９０質量％以上である顔料を用いる場合に有効である。 When the copolymer latex obtained by the production method of the present invention is used as a binder for a paint for paper coating, it can be carried out in a usual manner. That is, inorganic water such as kaolin clay, calcium carbonate, titanium dioxide, aluminum hydroxide, satin white, and talc, organic pigments known as plastic pigment and binder pigment, starch, casein, and polyvinyl alcohol in water in which the dispersant is dissolved Add copolymer latex together with various additives such as water-soluble polymers such as carboxymethyl cellulose, thickeners, dyes, antifoaming agents, preservatives, water resistance agents, lubricants, printability improvers, water retention agents, etc. It is an aspect which mixes and makes it a uniform dispersion liquid. Here, the copolymer latex obtained by the production method of the present invention is a particularly remarkable pick strength when the pigment constituting the coating material for paper coating is mainly one having a small average particle diameter. Expresses wet pick strength. That is, kaolin clay is effective when a pigment having 2 μm or less particles is 84% by mass or more, and calcium carbonate is effective when a pigment having 2 μm or less particles is 90% by mass or more.
顔料と本発明の製造法で得られた共重合体ラテックスの使用割合は、組成物の使用目的によって適宜決定することが出来るが、好ましくは顔料１００質量部に対してラテックス３〜３０質量部である。そして、この紙塗工液は、各種ブレードコーター、ロールコーター、エアーナイフコーター、バーコーターなどを用いる通常の方法によって原紙に塗工することができる。塗工形態も原紙に対し片面、又は表裏の両面に塗工されうるものであり、また片面当たりの塗工回数についても１回であるシングル塗工の他、２回の塗工工程を行ういわゆるダブル塗工に供する事もできる。この場合、本発明の共重合体ラテックスはその下塗り用顔料組成物、及び上塗り用顔料組成物のいずれにも用いる事ができる。 The proportion of the pigment and the copolymer latex obtained by the production method of the present invention can be appropriately determined depending on the purpose of use of the composition, but preferably 3 to 30 parts by mass of latex with respect to 100 parts by mass of pigment. is there. The paper coating solution can be applied to the base paper by a usual method using various blade coaters, roll coaters, air knife coaters, bar coaters and the like. The coating form can be applied to one side of the base paper, or both sides of the front and back sides, and the number of times of coating per side is one so that the coating process is performed twice, in addition to single coating. It can also be used for double coating. In this case, the copolymer latex of the present invention can be used for both the undercoat pigment composition and the overcoat pigment composition.
本発明の製造法で得られた共重合体ラテックスを使用した紙塗工用組成物は、オフセット枚葉式印刷用紙、オフセット輪転式印刷用紙、グラビア式印刷用紙、凸版式印刷用紙等の各種印刷用紙及び板紙、ダンボール用紙、包装紙等に好的に用いられるが、特にオフセット枚葉式印刷用紙及びオフセット輪転印刷用紙に用いられる事が望ましい。 The composition for paper coating using the copolymer latex obtained by the production method of the present invention is various printing such as offset sheet-fed printing paper, offset rotary printing paper, gravure printing paper, letterpress printing paper, etc. It is preferably used for paper and paperboard, cardboard paper, wrapping paper, etc., but is particularly preferably used for offset sheet-fed printing paper and offset rotary printing paper.
更に本発明の製造法で得られた共重合体ラテックスは、紙のコーティング剤、カーペットバッキング剤、その他接着剤、各種塗料にも用いる事ができる。 Furthermore, the copolymer latex obtained by the production method of the present invention can be used for paper coating agents, carpet backing agents, other adhesives, and various paints.
本発明を実施例に基づいて説明するが、本発明はこれらの実施例によって制約を受けるものではない。 The present invention will be described based on examples, but the present invention is not limited by these examples.
各物性は、以下の方法で評価した。
（１）ピック強度：ＲＩ印刷試験機（明製作所製）を用いて、印刷インク（Ｔ＆ＫＴＯＫＡ社製ＳＤスーパーデラックス５０紅Ｂ；タック１８）０．４ｃｃを重ね刷りし、ゴムロールに現れたピッキング状態を別の台紙に裏取りし、その状態を観察した。評価は１０点評価法とし、ピッキング現象の少ないものほど高得点とした。
（２）湿潤ピック強度：ＲＩ印刷試験機（明製作所製）を用いてスリーブロールで塗工紙表面に給水し、その直後に印刷インク（Ｔ＆ＫＴＯＫＡ社製ＳＤスーパーデラックス５０紅Ｂ；タック１５）０．４ｃｃ１回刷りし、ゴムロールに現れたピッキング状態を別の台紙に裏取りし、その状態を観察した。評価は１０点評価法とし、ピッキング現象の少ないものほど高得点とした。
Each physical property was evaluated by the following methods.
(1) Pick strength: Using an RI printing tester (manufactured by Meisei Seisakusho), 0.4 cc of printing ink (SD Super Deluxe 50 Red B; Tack 18 manufactured by T & KTOKA) was overprinted, and the picking state appeared on the rubber roll It was backed on another mount and the state was observed. The evaluation was based on a 10-point evaluation method, and the smaller the picking phenomenon, the higher the score.
(2) Wet pick strength: Water was applied to the coated paper surface with a sleeve roll using an RI printing tester (manufactured by Meisei Seisakusho). Immediately after that, printing ink (SD Super Deluxe 50 Red B; Tack 15 manufactured by T & KTOKA) 0 .4cc was printed once, the picking state appearing on the rubber roll was backed on another mount, and the state was observed. The evaluation was based on a 10-point evaluation method, and the smaller the picking phenomenon, the higher the score.
（３）エチレン性不飽和スルホン酸のアルカリ塩の反応添加率：反応途中の共重合体ラテックス中に残存する、エチレン性不飽和スルホン酸のアルカリ塩を定量する事により求めた。即ち共重合体ラテックスを約１ｇ採取し、１２５倍に水で希釈した。次いで１０質量％の硫酸アルミニウム水溶液０．５ｇを添加して、共重合体ラテックスのポリマー分を沈殿させた。上澄み液を０．２μｍ孔径の濾紙を通して濾過し、続いてイオンクロマトグラフィー（東ソー株式会社製 ＩＣ−２００１型）を使用して、上澄み液中のエチレン性不飽和スルホン酸のアルカリ塩量を測定し、反応添加率（質量％）を算出した。
（４）共重合体ラテックスの粒子径：動的光散乱法により、光散乱光度計（シーエヌウッド社製、モデル６０００）を用いて、初期角度４５度−測定角度１３５度で測定した。
（５）共重合体ラテックス中の微細凝固物生成量：５００ｇのポリマー分を含有する共重合体ラテックスを秤量し、＃２００の金網で濾過したときに金網上に残る残渣物の乾燥質量（ｇ）を測定した。
(3) Reaction addition rate of alkali salt of ethylenically unsaturated sulfonic acid: It was determined by quantifying the alkali salt of ethylenically unsaturated sulfonic acid remaining in the copolymer latex during the reaction. That is, about 1 g of copolymer latex was collected and diluted with water 125 times. Subsequently, 0.5 g of 10 mass% aluminum sulfate aqueous solution was added, and the polymer part of copolymer latex was precipitated. The supernatant liquid is filtered through a 0.2 μm pore size filter paper, and then ion chromatography (IC-2001, manufactured by Tosoh Corporation) is used to measure the amount of ethylenically unsaturated sulfonic acid alkali salt in the supernatant liquid. The reaction addition rate (% by mass) was calculated.
(4) Particle diameter of copolymer latex: Measured by a dynamic light scattering method using a light scattering photometer (model 6000, manufactured by CNN Wood) at an initial angle of 45 degrees and a measurement angle of 135 degrees.
(5) Production amount of fine coagulum in copolymer latex: Dry mass (g of residue remaining on wire mesh when weighed copolymer latex containing 500 g of polymer and filtered through # 200 wire mesh ) Was measured.
（６）共重合体ラテックスの耐湿潤ベタツキ性
マイラーフィルムに得られた共重合体ラテックスをＮｏ．１２のワイヤーバーで塗布して１３０℃で３０秒乾燥した。このフィルムを３０℃の水中に５秒間浸漬させた後、黒ラシャ紙と重ね合わせ、温度６０℃、線圧１９６００Ｎ／ｍのスーパーカレンダーを通過させた後、黒ラシャ紙を剥離する。この黒ラシャ紙繊維のラテックスフィルムのベタツキによる転移状態を目視評価した。評価は１０点評価法で行ない、転移の少ないものほど高得点とした。
(6) Wet and stickiness resistance of copolymer latex The copolymer latex obtained in the Mylar film was No. It was coated with 12 wire bars and dried at 130 ° C. for 30 seconds. This film is immersed in water at 30 ° C. for 5 seconds, then superimposed on black lasha paper, passed through a super calendar at a temperature of 60 ° C. and a linear pressure of 19600 N / m, and then the black lasha paper is peeled off. The state of transition of the black lasha paper fiber latex film due to stickiness was visually evaluated. The evaluation was performed by a 10-point evaluation method, and the smaller the transition, the higher the score.
（７）共重合体ラテックスのゲル分率：約２倍に希釈したラテックスを１３０℃で３０分間乾燥しラテックスフィルムを得る。このラテックスフィルムを約０．５ｇとり秤量する。これをトルエン３０ｍｌと混合して３時間浸透したのち、目開き３２μｍの金属網にてろ過した場合の残留物の乾燥質量を秤量する。もとのラテックスフィルム質量に対する残留物の乾燥質量の割合をゲル分率（質量％）とする。
（８）共重合体ラテックスの粘度：得られた共重合体ラテックスを、固形分５０質量％、ＰＨ８．０、温度２３℃の状態に調製し、Ｂ型粘度計で測定した。
（９）塗工カラーの調製と微細凝固物の発生量測定：始めに、共重合体ラテックスを除く以下の構成材料でマスターカラーを調製した。
(7) Gel fraction of copolymer latex: Latex diluted approximately twice is dried at 130 ° C. for 30 minutes to obtain a latex film. About 0.5 g of this latex film is taken and weighed. This is mixed with 30 ml of toluene and infiltrated for 3 hours, and then the dry mass of the residue is weighed when filtered through a metal net having an opening of 32 μm. The ratio of the dry mass of the residue to the original latex film mass is defined as the gel fraction (% by mass).
(8) Viscosity of copolymer latex: The obtained copolymer latex was prepared at a solid content of 50% by mass, a pH of 8.0, and a temperature of 23 ° C., and measured with a B-type viscometer.
(9) Preparation of coating color and measurement of generation amount of fine coagulum: First, a master color was prepared with the following constituent materials excluding copolymer latex.
微粒カオリンクレー ５０ 質量部
粗粒カオリンクレー ２０ 質量部
重質炭酸カルシウム（微粒） ２０ 質量部
重質炭酸カルシウム（粗粒） １０ 質量部
ポリアクリル酸ナトリウム ０．２質量部
水酸化ナトリウム ０．１質量部
リン酸エステル化でんぷん ２．５質量部
水（塗工液の全固形分が６８質量％となるように添加）
Fine kaolin clay 50 parts by weight Coarse grain kaolin clay 20 parts by weight Heavy calcium carbonate (fine particles) 20 parts by weight Heavy calcium carbonate (coarse grains) 10 parts by weight Sodium polyacrylate 0.2 parts by weight Sodium hydroxide 0.1 parts by weight Part phosphoric acid esterified starch 2.5 parts by weight water (added so that the total solid content of the coating solution is 68% by weight)
なお、微粒カオリンクレーとしては、ハイドラグロス９０（米国、Ｊ．Ｍ．ＨＵＢＥＲ社製；粒子径２μｍ以下の割合＝９６質量％以上）、粗粒カオリンクレーとしては、ハイドラスパース（米国、Ｊ．Ｍ．ＨＵＢＥＲ社製；粒子径２μｍ以下の割合＝８０〜８２質量％）、微粒重質炭酸カルシウムとしてはカービタル９５（ＥＣＣ社製；粒子径２μｍ以下の割合＝９５質量％以上）、粗粒重質炭酸カルシウムとしてはカービタル７５（ＥＣＣ社製；粒子径２μｍ以下の割合＝７５〜８０質量％）、ポリアクリル酸ナトリウムとしてはアロンＴ−４０（東亞合成社製）およびリン酸エステル化でんぷんとしてはＭＳ−４６００（日本食品加工社製）をそれぞれ使用した。 The fine kaolin clay is Hydra Gloss 90 (US, manufactured by JM HUBER; the ratio of particle diameter is 2 μm or less = 96 mass% or more), and the coarse kaolin clay is Hydra Sparse (US, JM). Manufactured by HUBER; ratio of particle diameter of 2 μm or less = 80 to 82% by mass), and fine heavy calcium carbonate, Carbital 95 (manufactured by ECC; ratio of particle diameter of 2 μm or less = 95% by mass or more), coarse heavy particle Carbital 75 as calcium carbonate (ECC; ratio of particle size of 2 μm or less = 75 to 80% by mass), Aron T-40 (manufactured by Toagosei Co., Ltd.) as sodium polyacrylate and MS as phosphated starch -4600 (Nippon Food Processing Co., Ltd.) was used.
このマスターカラーを２００メッシュのフィルターを通過させて濾過した後、小分けし、各々のマスターカラーに、顔料１００質量部当たり１２質量部の割合で共重合体ラテックスを、及び最終固形分が６４質量％になるよう、水をそれぞれ添加し、混合した。その後再び２００メッシュのフィルターを通過させ、フィルター上に残留した微細固形物の乾燥質量を測定し、カラー質量に対する濃度（ｐｐｍ）を算出した。この値が小さいもの程、効果が大きい事を示す。
（１０）塗工紙の調製：各々の塗工カラーを、塗工量が片面１３ｇ／ｍ２になるように坪量７４ｇ／ｍ２の塗工原紙にブレードコーターで塗工し、乾燥した後、ロール温度５０℃、線圧１５０ｋｇ／ｃｍでスーパーカレンダー処理を行い塗工紙を得た。得られた塗工紙を印刷試験に用いた。
実施例１〜４
The master color is filtered through a 200-mesh filter and then subdivided into each master color with a copolymer latex at a ratio of 12 parts by mass per 100 parts by mass of pigment and a final solid content of 64% by mass. Then, water was added and mixed. Thereafter, the filter was again passed through a 200-mesh filter, the dry mass of the fine solid remaining on the filter was measured, and the concentration (ppm) relative to the color mass was calculated. A smaller value indicates a greater effect.
(10) Preparation of coated paper: Each coated color is coated on a coated base paper having a basis weight of 74 g / m2 with a blade coater so that the coated amount is 13 g / m2 on one side, dried, and then rolled. Super calendering was performed at a temperature of 50 ° C. and a linear pressure of 150 kg / cm to obtain a coated paper. The obtained coated paper was used for a printing test.
Examples 1-4
耐圧反応容器に水８０質量部、ドデシルベンゼンスルホン酸ナトリウム０．１質量部、および表１中に記載された、エチレン性不飽和スルホン酸のアルカリ塩を含む重合初期原料を一括して仕込み、７５℃にて十分に攪拌した。尚、この時用いたエチレン性不飽和スルホン酸のアルカリ塩は、３０質量％に調整された水溶液であり、この水溶液のＰＨは１１であった。次いで表１中に記載した１段目の単量体混合物を、４時間かけて連続的に添加し、次いで表２中に記載した２段目の単量体混合物を、２時間かけて連続的に添加した。一方これと並行して、１段目の単量体混合物の添加開始１５分後に、過硫酸ナトリウム０．５質量部を容器内に一括して添加し、重合反応を開始させた。さらに水２０質量部、水酸化ナトリウム０．１質量部、ドデシルベンゼンスルホン酸ナトリウム０．２質量部、及び過硫酸ナトリウム０．９質量部からなる水系混合物を、３時間かけて連続的に添加し、重合反応を加速させた。最終段階の単量体混合物の添加が完了した時点で、容器の内温を９５℃に昇温し、さらに１時間反応させた後冷却して共重合体ラテックスを得た。この時点で、前述の方法により乳化重合中に発生した微細凝固物の量を測定した。この共重合体ラテックスには、スチームストリッピング法で未反応の単量体を除去した後、ポリアクリル酸ソーダ０，５質量部を添加し、水酸化ナトリウムを用いてＰＨを８，０に調整し、最後に固形分を５０質量％に調整した。この共重合体ラテックスを３２５メッシュのフィルターを通過させて濾過した後、各物性を測定した。その結果を表１に記す。また、乳化重合途中での、エチレン性不飽和スルホン酸のアルカリ塩の反応添加率の測定結果も、表１中に併せて記す。 75 parts by weight of water, 0.1 part by weight of sodium dodecylbenzenesulfonate, and an initial polymerization raw material containing an alkali salt of ethylenically unsaturated sulfonic acid described in Table 1 are charged in a pressure-resistant reaction vessel. Stir well at ℃. The alkali salt of ethylenically unsaturated sulfonic acid used at this time was an aqueous solution adjusted to 30% by mass, and the pH of this aqueous solution was 11. Next, the first stage monomer mixture described in Table 1 was continuously added over 4 hours, and then the second stage monomer mixture described in Table 2 was continuously added over 2 hours. Added to. On the other hand, in parallel with this, 15 parts after the start of addition of the first-stage monomer mixture, 0.5 part by mass of sodium persulfate was added all at once in the container to initiate the polymerization reaction. Further, an aqueous mixture composed of 20 parts by mass of water, 0.1 part by mass of sodium hydroxide, 0.2 part by mass of sodium dodecylbenzenesulfonate, and 0.9 part by mass of sodium persulfate was continuously added over 3 hours. Accelerated the polymerization reaction. When the addition of the monomer mixture at the final stage was completed, the internal temperature of the container was raised to 95 ° C., reacted for another hour, and then cooled to obtain a copolymer latex. At this point, the amount of fine coagulum generated during emulsion polymerization was measured by the method described above. To this copolymer latex, unreacted monomers are removed by a steam stripping method, 0.5 parts by mass of sodium polyacrylate is added, and the pH is adjusted to 8,0 using sodium hydroxide. Finally, the solid content was adjusted to 50% by mass. The copolymer latex was filtered through a 325 mesh filter, and each physical property was measured. The results are shown in Table 1. Moreover, the measurement result of the reaction addition rate of the alkali salt of ethylenically unsaturated sulfonic acid during the emulsion polymerization is also shown in Table 1.
実施例５
Example 5
表１に記した原料、単量体混合物を用い、１段目の単量体混合物の添加開始後３時間の段階で、ｐ−スチレンスルホン酸ソーダ０．３質量部を水溶液として一括添加した事以外は、実施例１と同様の方法で共重合体ラテックスを製造し、物性評価に供した。結果を表１に記す。 Using the raw materials and monomer mixture shown in Table 1, 0.3 parts by mass of sodium p-styrenesulfonate was added as an aqueous solution at the stage of 3 hours after the start of addition of the first monomer mixture. Except for the above, a copolymer latex was produced in the same manner as in Example 1 and subjected to physical property evaluation. The results are shown in Table 1.
表１から明らかなように、エチレン性不飽和スルホン酸のアルカリ塩の一部を、重合反応開始前でなく、開始後に添加した場合でも、本発明の製造法の範囲を適用したものについては、実施例１〜４と同じく、高い効果を発現した。
比較例１〜６
As is apparent from Table 1, even when a part of the alkali salt of ethylenically unsaturated sulfonic acid was added after the start of the polymerization reaction, but not after the start of the polymerization reaction, The high effect was expressed like Examples 1-4.
Comparative Examples 1-6
表２に記した原料、単量体混合物を用いで実施例１と同様の方法で共重合体ラテックスを製造し、物性評価に供した。尚、比較例６は、エチレン性不飽和スルホン酸のアルカリ塩を全く用いないで共重合体ラテックスを製造した。各物性評価結果を表２に記す。 A copolymer latex was produced in the same manner as in Example 1 using the raw material and monomer mixture shown in Table 2, and subjected to physical property evaluation. In Comparative Example 6, a copolymer latex was produced without using any alkali salt of ethylenically unsaturated sulfonic acid. The physical property evaluation results are shown in Table 2.
表２は、いずれも本発明の共重合体ラテックスの製造法の範囲を外れたものの結果を記したものである。比較例１、４および５は共重合体ラテックス製造途中における、エチレン性不飽和スルホン酸のアルカリ塩の反応添加率が低く、共重合体ラテックス製造時、および該共重合体ラテックスを使用した塗工カラー調製時の微細凝固物の発生量が多い。また、共重合体ラテックスの耐湿潤ベタツキ性は劣り、得られた塗工紙のピック強度、湿潤ピック強度も低い。比較例２は使用したシアン化ビニル単量体の量が少なく、得られた共重合体ラテックスの耐湿潤ベタツキ性が劣ると共に、塗工紙の湿潤ピック強度が低い。比較例３は使用した共役ジエン系単量体の量が多い為に、耐湿潤ベタツキ性および塗工紙の湿潤ピック強度が劣る。比較例６はエチレン性不飽和スルホン酸のアルカリ塩を使用せずに共重合体ラテックスを製造した為、耐湿潤ベタツキ性、微細凝固物発生量、塗工紙のピック強度および湿潤ピック強度がいずれも大きく劣る結果となった。 Table 2 shows the results of those that are outside the scope of the method for producing the copolymer latex of the present invention. Comparative Examples 1, 4 and 5 had a low reaction addition rate of the alkali salt of ethylenically unsaturated sulfonic acid during the production of the copolymer latex, and at the time of production of the copolymer latex, and coating using the copolymer latex A large amount of fine coagulum is generated during color preparation. Further, the wet-sticking resistance of the copolymer latex is inferior, and the obtained coated paper has low pick strength and wet pick strength. In Comparative Example 2, the amount of the vinyl cyanide monomer used is small, the resulting copolymer latex is inferior in wet stickiness resistance, and the wet pick strength of the coated paper is low. In Comparative Example 3, since the amount of the conjugated diene monomer used is large, the wet stickiness resistance and the wet pick strength of the coated paper are inferior . Since Comparative Example 6 produced a copolymer latex without using an alkali salt of an ethylenically unsaturated sulfonic acid, the wet stickiness resistance, the amount of fine coagulum generated, the pick strength of the coated paper, and the wet pick strength The result was greatly inferior.
Claims (2)
（ａ）共役ジエン系単量体２０〜８０質量％、
（ｂ）不飽和カルボン酸単量体０．５〜１０質量％、
（ｃ）シアン化ビニル単量体３〜５０質量％、および
（ｄ）その他共重合可能な単量体０〜７６．５質量％
（但し（ａ）＋（ｂ）＋（ｃ）＋（ｄ）＝１００質量％）を乳化重合して共重合体ラテックスを製造するに当たり、全単量体混合物の添加が終了した時点において、重合系内に添加された化合物Ａの反応転化率が７０質量％以上である事を特徴とする共重合体ラテックスの製造方法。 In the presence of at least one compound selected from alkali salts of ethylenically unsaturated sulfonic acid (hereinafter abbreviated as Compound A), the following monomer mixture (a) conjugated diene monomer 20 to 80% by mass,
(B) 0.5 to 10% by mass of an unsaturated carboxylic acid monomer,
(C) 3 to 50% by mass of vinyl cyanide monomer, and (d) 0 to 76.5% by mass of other copolymerizable monomers.
(However, (a) + (b) + (c) + (d) = 100% by mass) is produced by emulsion polymerization to produce a copolymer latex. A method for producing a copolymer latex, wherein the reaction conversion rate of compound A added to the system is 70% by mass or more.
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| KR101666260B1 (en) * | 2013-05-08 | 2016-10-14 | 주식회사 엘지화학 | Latex for coating paper and paper coating liquid composition |
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