JP2006225527A - Copolymer latex and paper coating composition - Google Patents
Copolymer latex and paper coating composition Download PDFInfo
- Publication number
- JP2006225527A JP2006225527A JP2005041520A JP2005041520A JP2006225527A JP 2006225527 A JP2006225527 A JP 2006225527A JP 2005041520 A JP2005041520 A JP 2005041520A JP 2005041520 A JP2005041520 A JP 2005041520A JP 2006225527 A JP2006225527 A JP 2006225527A
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- JP
- Japan
- Prior art keywords
- mass
- copolymer latex
- monomer
- latex
- paper
- 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
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- 239000004816 latex Substances 0.000 title claims abstract description 129
- 229920000126 latex Polymers 0.000 title claims abstract description 129
- 229920001577 copolymer Polymers 0.000 title claims abstract description 120
- 239000008199 coating composition Substances 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 24
- 239000000049 pigment Substances 0.000 claims abstract description 23
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 23
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 19
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940126062 Compound A Drugs 0.000 claims abstract description 6
- 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 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 3
- 239000000123 paper Substances 0.000 abstract description 61
- 239000000853 adhesive Substances 0.000 abstract description 22
- 230000001070 adhesive effect Effects 0.000 abstract description 22
- 239000011230 binding agent Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000000835 fiber Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 description 28
- 238000000034 method Methods 0.000 description 26
- 239000002245 particle Substances 0.000 description 24
- -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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 238000007639 printing Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 229920000642 polymer Polymers 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
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 230000001965 increasing effect 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
- 239000003973 paint Substances 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 230000000704 physical effect Effects 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
- 229920002472 Starch Polymers 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 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
- 239000004372 Polyvinyl alcohol Substances 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
- 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
- XDIJWRHVEDUFGP-UHFFFAOYSA-N azanium;2-phenylethenesulfonate Chemical compound [NH4+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 XDIJWRHVEDUFGP-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 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
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical group NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 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
- 238000002360 preparation method Methods 0.000 description 2
- 239000005060 rubber Substances 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
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent 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
- 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
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- 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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-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
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 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
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 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
- 239000011668 ascorbic acid Substances 0.000 description 1
- 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
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
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- 239000003755 preservative agent Substances 0.000 description 1
- 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
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- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
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- 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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- 229920003048 styrene butadiene rubber Polymers 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
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 239000004408 titanium dioxide Substances 0.000 description 1
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- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
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に関する。更に詳しくは、高い化学的安定性と耐湿潤ベタツキ性、紙塗工における接着強度、塗工液の機械的安定性に優れた効果を発揮する共重合体ラテックスに関するものである。 The present invention relates to a conjugated diene copolymer latex used for pigment binders, carpet backing agents, adhesives, pressure-sensitive adhesives, fiber binders and paints in paper coating. More specifically, the present invention relates to a copolymer latex that exhibits excellent effects on high chemical stability and wet stickiness resistance, adhesive strength in paper coating, and mechanical stability of a coating solution.
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、各種粘着剤、繊維結合剤および塗料など広範囲な用途に用いられている。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 are used in a wide range of applications such as pigment binders, carpet backing agents, various adhesives, various pressure-sensitive adhesives, fiber binders and paints in paper coating. The copolymer latex used in these applications is required to have excellent adhesion to water and water resistance to the base material and the pigment to be blended.
塗工紙は、紙の印刷適性の向上および光沢などの光学特性の向上を目的として、抄造された原紙表面に、カオリンクレー、炭酸カルシウム、サチンホワイト、タルク、酸化チタンなどの顔料、それらのバインダーとしての共重合体ラテックスおよび粘度調整剤あるいは補助バインダーとしてのスターチ、ポリビニルアルコール、カルボキシメチルセルロースなどの水溶性高分子を主構成成分とする紙塗工用組成物が塗工されているものである。 Coated paper is used for the purpose of improving paper printability and optical properties such as gloss, and pigments such as kaolin clay, calcium carbonate, satin white, talc, titanium oxide, and binders on the surface of the base paper. A paper coating composition comprising a copolymer latex as a main component and a water-soluble polymer such as starch, polyvinyl alcohol or carboxymethyl cellulose as a viscosity modifier or an auxiliary binder is coated.
ここで、バインダーとしての共重合体ラテックスとしては、従来からスチレンとブタジエンを主要モノマー成分として乳化重合された、スチレン−ブタジエン系共重合体ラテックス、いわゆるＳＢ系ラテックスが汎用的に用いられており、ここで用いられる共重合体ラテックスの性質が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。 Here, as the copolymer latex as a binder, a styrene-butadiene copolymer latex, so-called SB latex, which has been conventionally emulsion-polymerized with styrene and butadiene as main monomer components, has been widely used. It is known that the properties of the copolymer latex used here have a great influence not only on the surface strength of the paper but also on the printability of the coated paper.
近年、カラー印刷された雑誌類やパンフレット、広告類の需要の拡大に伴って塗工紙の生産が著しく増大している。それに伴って印刷速度の高速化が進められており、塗工紙および顔料バインダーに対する要求水準はますます高度化している。その中でも、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（いわゆる湿潤ピック強度）の向上が以前にも増して要求されるようになっている。 In recent years, the production of coated paper has increased remarkably with the growing demand for color-printed magazines, brochures and advertisements. Along with this, the printing speed has been increased, and the required level of coated paper and pigment binder has become increasingly sophisticated. Among them, in particular, resistance to destruction of the surface of the paper due to ink tack (so-called pick strength) and improvement in pick strength when soaking water is applied (so-called wet pick strength) are required more than before. It is like that.
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（室井宗一著、高分子ラテックスの化学）などに示されるように、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よく知られている。 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. In order to produce normal latex with small particle size, increase the amount of initiator radicals and increase the amount of emulsifier in the initial stage of polymerization, as shown in ordinary literature (Muroichi Muroi, Polymer Latex Chemistry). It is well known that polymerization monomer micelles increase due to.
この他に粒子径の小さいラテックスを得る方法としては、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、これまで一般に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 to this, as a method for obtaining a latex having a small particle size, a method of using a large amount of an initiator 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 a latex having a small particle diameter is produced by a generally known method, there is a known disadvantage that the water resistance performance of a product obtained by application is significantly impaired.
また、小粒子径のラテックスの工業生産に関わる問題点としては固形分の問題がある。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％以上が必要であり、工業的生産に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高い固形分を維持しながら１００ｎｍ以下の共重合体ラテックスを製造することはこれまでは困難であった。 In addition, as a problem related to the industrial production of latex having a small particle size, there is a problem of solid content. The amount of solid content of the copolymer latex that meets the economic efficiency of normal operation is required to be about 30% by mass or more, and industrial production is high due to operational conditions and restrictions on the physical properties of the copolymer latex. It has been difficult to produce a copolymer latex of 100 nm or less while maintaining the solid content.
また、印刷用紙である塗工紙の生産においても、塗工紙の製造が高速化しており、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。そこで、塗工操業性の改良、特に主な障害であるバッキングロール汚れに対する特性、すなわち共重合体ラテックスの化学的安定性や塗工層の耐湿潤ベタツキ性、および塗工液の機械的安定性の向上も強く要求されている。 Also, in the production of coated paper, which is a printing paper, the production of coated paper is accelerated, and high solid differentiation is required in order to cope with the decrease in drying ability accompanying the increased coating speed. 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. Therefore, the improvement of coating operability, especially the properties against the backing roll stain, which is the main obstacle, that is, the chemical stability of the copolymer latex, the wet stickiness resistance of the coating layer, and the mechanical stability of the coating liquid There is also a strong demand for improvement.
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１（特公昭６２−５８３７１号公報）、特許文献２（特公昭６２−３１１１６号公報）、特許文献３（特公昭６４−２７１６号公報）、特許文献４（特公昭６０−１９９２７号公報）、特許文献５（特開平４−４１５０２号公報）、特許文献６（特開平５−２７２０９４号公報）、特許文献７（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, Patent Document 1 (Japanese Patent Publication No. 62-58371) and Patent Document 2 (Japanese Patent Publication No. 62-31116) have been proposed in which a number of improvements have been proposed for copolymer latexes in which polymerization is carried out in two or multiple stages with a specific monomer composition. No. 4), Japanese Patent Publication No. 64-27716, Japanese Patent Publication No. 60-19927, Japanese Patent Publication No. 4-41502, Japanese Patent No. 4-4502. No. -272094) and Patent Document 7 (Japanese Patent Laid-Open No. 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８（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９（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１０（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１１（特開２００３−１１９２０３号公報）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製造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、化学的安定性や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提供する事を目的とする。 From the above situation, the present invention is excellent in chemical stability and wet stickiness resistance, improves both pick strength and wet pick strength of coated paper, and further, fineness when a coating color is prepared. An object of the present invention is to provide a diene copolymer latex that reduces the generation of coagulum.
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、特定組成の単量体を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して得られる共重合体ラテックスであり、かつ得られた共重合体ラテックス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残存率を特定範囲に調整する事によって上記課題が解決できる事を見出し、本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a copolymer latex obtained by emulsion polymerization of a monomer having a specific composition in the presence of an alkali salt of an ethylenically unsaturated sulfonic acid. And it has been found that the above problem can be solved by adjusting the residual ratio of the alkali salt of ethylenically unsaturated carboxylic acid in the copolymer latex to a specific range, and the present invention has been achieved.
即ち本発明は、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、少なくとも一種類以上の化合物（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％
（ｄ）その他共重合可能な単量体０〜７６．５質量％
（ただし（ａ）＋（ｂ）＋（ｃ）＋（ｄ）＝１００質量％）を乳化重合して得られる共重合体ラテックスであって、該共重合体ラテックス中に残存する未反応の化合物Ａの量が、該共重合体ラテックスの不揮発成分に対して５質量％以下であることを特徴とする共重合体ラテックスに関するものである。
That is, the present invention provides the following monomer mixture (a) conjugated diene in the presence of at least one kind of compound (hereinafter abbreviated as Compound A) selected from alkali salts of ethylenically unsaturated sulfonic acids. 20-80% by mass of monomer
(B) 0.5-10 mass% of unsaturated carboxylic acid monomer
(C) 3 to 50% by mass of vinyl cyanide monomer
(D) Other copolymerizable monomers 0 to 76.5% by mass
A copolymer latex obtained by emulsion polymerization of (a) + (b) + (c) + (d) = 100 mass%), and an unreacted compound remaining in the copolymer latex The present invention relates to a copolymer latex characterized in that the amount of A is 5% by mass or less based on the nonvolatile component of the copolymer latex.
本発明の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、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等として、高い化学的安定性と耐湿潤ベタツキ性、紙塗工における接着強度、塗工液の機械的安定性に優れた効果を発揮する。 The copolymer latex of the present invention has high chemical stability as a conjugated diene copolymer latex used for pigment binders, carpet backing agents, adhesives, pressure-sensitive adhesives, fiber binders and paints in paper coating, etc. It exhibits excellent effects on wet stickiness resistance, adhesive strength in paper coating, and mechanical stability of the coating solution.
本発明は、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、後述する単量体混合物を乳化重合して得られる共重合体ラテックスであって、該共重合体ラテックス中に残存する未反応の化合物Ａの量が該共重合体ラテックスの不揮発成分に対して５質量％以下である共重合体ラテックスである。 The present invention is obtained by emulsion polymerization of a monomer mixture described later in the presence of at least one compound (hereinafter abbreviated as Compound A) selected from alkali salts of ethylenically unsaturated sulfonic acids. The copolymer latex is a copolymer latex in which the amount of the unreacted compound A remaining in the copolymer latex is 5% by mass or less with respect to the nonvolatile component of the copolymer latex.
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、アリル基、あるいはメタアリ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、アリル基、あるいはメタアリ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 vinyl group, allyl group, or methallyl group in the molecule, These 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 vinyl, allyl, or methallyl groups in the molecule, such as sodium styrene sulfonate, potassium styrene sulfonate, and ammonium styrene sulfonate. 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, meta Acrylic sulfonate sodium, potassium methacryl sulfonate, ammonium methacryl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, ammonium sulfonate Um, 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。
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。好ましくは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。
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 mentioned.
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。
工業的規模で本発明の共重合体ラテックスを製造するに際して、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。
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.
When producing the copolymer latex of the present invention on an industrial scale, it is preferable to use an alkali salt of ethylenically unsaturated sulfonic acid 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%. In order to prevent the alkali salt of ethylenically unsaturated sulfonic acid from being altered 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、得られた共重合体ラテックス中における、エチレン性不飽和スルホン酸のアルカリ塩の残存率を特定の範囲に調整する事が必須である。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、重合が完了した時点において、共重合体ラテックス中のエチレン性不飽和スルホン酸のアルカリ塩の残存率が共重合体ラテックスの揮発成分に対して５質量％以下である事が必要である。この範囲の残存率に抑える事により、得られた共重合体ラテックスの乳化重合時に発生する微細凝固物の量を抑えつつ、かつ良好な耐湿潤ベタツキ性、化学的安定性および塗工紙の湿潤ピック強度を発現させる事ができる。好ましい範囲は３質量％以下、より好ましくは１質量％以下である。
エチレン性不飽和スルホン酸のアルカリ塩の共重合体ラテックス中における残存率の制御は、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。
In order to express the desired effect in the present invention, it is essential to adjust the residual ratio of the alkali salt of ethylenically unsaturated sulfonic acid in a specific range in the obtained copolymer latex. That is, when adding a monomer mixture such as a conjugated diene monomer and performing emulsion polymerization, at the time when the polymerization is completed, the residual ratio of the alkali salt of ethylenically unsaturated sulfonic acid in the copolymer latex is shared. It must be 5% by mass or less based on the volatile components of the polymer latex. By controlling the residual rate within this range, the amount of fine coagulum generated during emulsion polymerization of the obtained copolymer latex is suppressed, and good wet-sticking resistance, chemical stability, and wetness of the coated paper are achieved. Pick strength can be expressed. A preferred range is 3% by mass or less, more preferably 1% by mass or less.
Control of the residual ratio of the ethylenically unsaturated sulfonic acid alkali salt in the copolymer latex depends on the polymerization temperature during the emulsion polymerization, the addition rate of the monomer mixture into the emulsion polymerization system, and the polymerization retarder used in combination. It can be adjusted to a desired range by controlling the amount, addition rate, pH of the emulsion polymerization system, and the like.
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。この範囲で用いる事により、得られた共重合体ラテックスは高い接着強度を持ち、かつ高い耐湿潤ベタツキ性を維持する事ができる。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 using in this range, the obtained copolymer latex has high adhesive strength and can maintain high 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。この範囲の単量体を用いる事により、顔料混和時および塗工工程において必要な分散安定性を維持する事ができる。この単量体の範囲を１０質量％以下にする事により、共重合体の粘度を抑え、かつ耐水性も維持する事ができる。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 using a monomer within this range, it is possible to maintain the dispersion stability required when mixing the pigment and in the coating process. By setting the range of this monomer to 10% by mass or less, the viscosity of the copolymer can be suppressed and the water resistance can be maintained. 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。この範囲の単量体を用いる事で、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を向上させつつ、かつ共重合体ラテックスの高い重合安定性を維持する事ができる。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 using a monomer within this range, it is possible to improve the wet stickiness resistance and wet pick strength, which are the objects of the present invention, and to maintain high polymerization stability of the copolymer latex. 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 other monomers capable of copolymerization. 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。この範囲で用いる事により、好ましい接着強度を発現させることができる。 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 in this range, preferable adhesive strength can be expressed.
本発明の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 of the present invention is not particularly limited. However, from the viewpoint of achieving both adhesive strength in application paper and wet-stickiness resistance of the latex, −50 ° C. to + 40 ° C. 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。粒子径を６０ｎｍ以上とする事でラテックスの粘度が必要以上に上昇する事を抑える事ができる。一方粒子径を１５０ｎｍ未満とする事で、接着強度を向上させ、塗料粘度を低く保つ事ができる。 The copolymer latex of the present invention has a particle size of 50 to 150 nm, preferably 60 to 110 nm. By setting the particle diameter to 60 nm or more, it is possible to suppress the viscosity of the latex from rising more than necessary. On the other hand, when the particle diameter is less than 150 nm, the adhesive strength can be improved and the paint viscosity can be kept low.
本発明の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。ゲル分率が低すぎる場合にはラテックスの耐湿潤ベタツキ性が劣り、逆に高すぎる場合は塗工紙の湿潤ピック強度が大きく低下する。 About the copolymer latex 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 is 85-93. It is in the range of mass%. When the gel fraction is too low, the wet stickiness resistance of the latex is poor. On the other hand, when the gel fraction is too high, the wet pick strength of the coated paper is greatly reduced.
本発明の共重合体ラテックスの製造法は、公知の乳化重合法の範疇で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公知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 in the category of known emulsion polymerization methods, and there is no particular limitation on the method, and in the presence of a surfactant in an aqueous medium, a radical initiator is used. A known method such as polymerization 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を製造する場合、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−メチルスチレンの二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 the copolymer latex of the present invention is produced, a known chain transfer agent that is usually used in radical polymerization can be used. Preferred examples of the chain transfer agent include α-methylstyrene dimer, n-butyl mercaptan, t-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, 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製造時の重合温度は、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。
本発明の共重合体ラテックス製造時の重合固形分は、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 temperature during production of the copolymer latex of the present invention is not particularly limited, but it is generally performed in the range of 40 to 100 ° C., but production efficiency and adhesive strength of the obtained copolymer latex are generally determined. From the viewpoint of quality, etc., the range of 55 to 95 ° C. is preferable.
The polymerization solid content during the production of 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 the suppression of fine coagulum during emulsion polymerization.
本発明の共重合体ラテックスを製造する場合、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。ここで、多段階重合とは二種類以上の異なる組成の単量体混合物を段階的に添加し、単量体混合物の極性値差や系中のモノマー組成（濃度）を制御する事によって、生成するポリマーのＴｇを制御し、粒子表面を硬質に、粒子内部を軟質にする事を目的とした重合方法である。
このような重合方法の例としては、例えば、重合の前半に供給するモノマー組成物については比較的ブタジエン配合量の多い組成として軟質な組成で粒子中心部を形成させ、その後比較的ブタジエン配合量の少ないモノマー組成物を重合の後半に供給し、前述の軟質な中心部を被覆するように粒子表層部を硬質な組成で構成させる方法、或いは重合の前半に比較的ブタジエン配合量の少ないモノマー組成物を供給して硬質層を形成させ、このモノマー組成物の重合反応率が適切な時点で、重合の後半成分として比較的ブタジエン配合量の多いモノマー組成物を供給して軟質成分を形成させ、前半／後半のポリマーの溶解度パラメーターの差を利用して、重合後半の成分を粒子中心部に、重合前半の成分を粒子表層部に配位させるように層反転を起こさせるやり方、などが挙げられる。
When the copolymer latex of the present invention is produced, there are no particular restrictions 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. Here, multistage polymerization is a process in which two or more types of monomer mixtures with different compositions are added stepwise to control the difference in polarity of the monomer mixture and the monomer composition (concentration) in the system. This polymerization method aims to control the Tg of the polymer to make the surface of the particle hard and the inside of the particle soft.
As an example of such a polymerization method, for example, for the monomer composition supplied in the first half of the polymerization, the particle center is formed with a soft composition as a composition having a relatively large amount of butadiene, and thereafter, the composition of the butadiene is relatively large. A method in which a small amount of the monomer composition is supplied in the latter half of the polymerization, and the particle surface layer is composed of a hard composition so as to cover the soft central portion, or a monomer composition having a relatively small amount of butadiene in the first half of the polymerization. When a polymerization reaction rate of this monomer composition is appropriate, a monomer composition having a relatively large amount of butadiene is supplied as a latter component of the polymerization to form a soft component. Using the difference in solubility parameter of the polymer in the latter half, layer inversion is performed so that the component in the latter half of the polymerization is coordinated with the particle center and the component in the first half of the polymerization is coordinated with the particle surface layer. Manner of causing, and the like.
本発明の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。 Various known polymerization regulators can be used in the copolymer latex of the present invention 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。
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。
There is no restriction | limiting in particular also about solid content as a final product of the copolymer latex obtained by this invention, Usually, solid content is prepared by diluting or concentrating in the range of 30-60 mass%.
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 can be added to the copolymer latex obtained in the present invention as needed, or other latexes can be mixed and used. For example, a dispersant, an antifoaming agent, anti-aging, etc. Additives, water resistance agents, bactericides, printability agents, etc., alkali-sensitive latexes, plastic pigments, and the like can also be mixed and used.
本発明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 using the copolymer latex obtained by this invention as a binder of the coating material for paper coating, it can carry out by the embodiment currently performed normally. 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 in the present invention is a particularly remarkable pick strength and wet pick strength when the pigment constituting the paint for paper coating is mainly used with a pigment having a small average particle diameter. Is expressed. 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、より好ましくは４〜１５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 in the present invention can be appropriately determined according to the purpose of use of the composition, but preferably 3 to 30 parts by mass of latex, more preferably 100 parts by mass of pigment. 4 to 15 parts by mass. 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。
更に本発明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。
The composition for paper coating using the copolymer latex obtained in the present invention includes various printing papers such as offset sheet-fed printing paper, offset rotary printing paper, gravure printing paper, letterpress printing paper, and paperboard. It is preferably used for corrugated cardboard paper, wrapping paper, etc., but is particularly preferably used for offset sheet-fed printing paper and offset rotary printing paper.
Furthermore, the copolymer latex obtained in 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＆Ｋ ＴＯＫＡ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＆Ｋ ＴＯＫＡ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 a RI printing tester (Meiji Seisakusho), 0.4 cc of printing ink (SD Super Deluxe 50 Crimson B; Tack 18 manufactured by T & K TOKA) was overprinted and picked 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.
(2) Wet pick strength: Water was applied to the coated paper surface with a sleeve roll using an RI printing tester (Meiji Seisakusho), and immediately after that, printing ink (SD Super Deluxe 50 Red B, manufactured by T & K TOKA; Tack 15) The printed state was printed once for 0.4 cc, and 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）共重合体ラテックス中のエチレン性不飽和スルホン酸のアルカリ塩の残存率：製品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１ｇ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、残存率（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（ｍｇ）を測定した。
(3) Residual rate of alkali salt of ethylenically unsaturated sulfonic acid in copolymer latex: It was determined by quantifying the alkali salt of ethylenically unsaturated sulfonic acid remaining in the product copolymer latex. That is, about 1 g of copolymer latex was collected and diluted with water 125 times. Subsequently, 1 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 residual rate (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 weight (mg 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。
（７）共重合体ラテックスの化学的安定性：得られた共重合体ラテックス １００ｇ（固形分４８質量％）を２００ｒｐｍの撹拌速度で撹拌し、そこに０．１Ｎ−塩化カルシウム５ｇを１分間で滴下し、その後２分間撹拌した後３２５メッシュ金網で濾過し、その時の凝固物量（ｍｇ）を求めた。値が小さいほど塩に対する化学的安定性が大きい事を示す。
(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) Chemical stability of the copolymer latex: 100 g of the obtained copolymer latex (solid content: 48% by mass) was stirred at a stirring speed of 200 rpm, and 5 g of 0.1 N calcium chloride was added thereto in 1 minute. After dropping, the mixture was stirred for 2 minutes and then filtered through a 325 mesh wire net, and the amount of coagulum (mg) at that time was determined. It shows that the chemical stability with respect to a salt is so large that a value is small.
（８）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。
（９）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。
（１０）塗工カラーの調製：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。
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）
(8) 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).
(9) Viscosity of copolymer latex: The obtained copolymer latex was prepared at a solid content of 50 mass%, a pH of 8.0, and a temperature of 23 ° C, and measured with a B-type viscometer.
(10) Preparation of coating color: First, a master color was prepared with the following constituent materials excluding the copolymer latex.
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。
（１１）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。
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.
(11) Preparation of coated paper: After coating each coated color on a coated base paper having a basis weight of 74 g / m 2 with a blade coater so that the coated amount is 13 g / m 2 on one side, and drying Then, a super calender treatment was performed at a roll 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.
実施例１〜５、７
耐圧反応容器に水８５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、および表１中に記載されたエチレン系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℃で十分に攪拌した。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。これと並行して、１段目の単量体混合物の添加開始から２０分後に、過硫酸ナトリウム０．５質量部を一括して添加して重合反応を開始させた。さらに水４０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０．３質量部、及び過硫酸ナトリウム０．９質量部からなる水溶液を、４時間かけて連続的に添加した。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を水酸化カリウムと水酸化ナトリウムを用いてｐＨ７．５とした後、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により濾過した後、各物性を測定した。その結果を表１に記す。また、得られた共重合体ラテックス中のエチレン性不飽和スルホン酸のアルカリ塩の残存率の測定結果も、表１中に併せて記す。
Examples 1-5, 7
A pressure-resistant reaction vessel is charged with 85 parts by mass of water, 0.2 parts by mass of sodium dodecylbenzenesulfonate, and an initial polymerization raw material containing an alkali salt of an ethylenically unsaturated sulfonic acid described in Table 1 at 75 ° C. With sufficient agitation. 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. In parallel with this, 20 minutes after the start of addition of the first-stage monomer mixture, 0.5 part by mass of sodium persulfate was added all at once to initiate the polymerization reaction. Further, an aqueous solution comprising 40 parts by mass of water, 0.1 part by mass of sodium hydroxide, 0.3 part by mass of sodium dodecylbenzenesulfonate, and 0.9 part by mass of sodium persulfate was continuously added over 4 hours. 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. After this copolymer latex was adjusted to pH 7.5 using potassium hydroxide and sodium hydroxide, unreacted monomers were removed by a steam stripping method, and 0.5 parts by mass of sodium polyacrylate was added. The pH was adjusted to 8.0 using sodium hydroxide, and 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. The measurement results of the residual ratio of the alkali salt of ethylenically unsaturated sulfonic acid in the obtained copolymer latex are also shown in Table 1.
実施例６
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２時間でｐ−スチレンスルホン酸ソーダ０．５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。
表1に記載内容から明らかな様に、本発明の構成要件に該当する共重合体ラテックスについては、製造時の微細凝固物の発生量が少なく、化学的安定性試験時の残渣量も少なく、得られた共重合体ラテックスの耐湿潤ベタツキ性も優れている。更に本発明の共重合体ラテックスを使用した場合、塗工紙のピック強度、湿潤ピック強度はいずれも高いレベルにあった。
Example 6
Except for adding 0.5 parts by weight of sodium p-styrenesulfonate as an aqueous solution in two hours after the start of addition of the first-stage monomer mixture, using the raw materials and monomer mixtures shown in Table 1, 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.
As is clear from the description in Table 1, for the copolymer latex corresponding to the constituent requirements of the present invention, the amount of fine coagulum generated during production is small, the amount of residue during chemical stability test is small, The resulting copolymer latex is also excellent in wet tack resistance. Further, when the copolymer latex of the present invention was used, the pick strength and wet pick strength of the coated paper were both at high levels.
比較例１〜３、５
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た。各物性評価結果を表２に記す。
Comparative Examples 1-3, 5
A copolymer latex was produced in the same manner as in Example 1 using the raw material and monomer mixture shown in Table 2. The physical property evaluation results are shown in Table 2.
比較例４
エチレン性不飽和スルホン酸のアルカリ塩を全く使用せずに、その他は表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た。各物性評価結果を表２に記す。
表２は、いずれも本発明の共重合体ラテックス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および２は得られた共重合体ラテックス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残存率が高く、共重合体ラテックス製造時の化学的安定性試験時の残渣量が多い。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３は使用した不飽和カルボン酸単量体の量が多い為に、湿潤ピック強度が劣る。比較例６は使用した共役ジエン系単量体の量が少なく、得られた共重合体ラテックスの粘度が高く、また、得られた共重合ラテックスの塗工紙のピック強度および湿潤ピック強度が低い。また、比較例４はエチレン系不飽和スルホン酸のアルカリ塩を全く用いていない為、化学的安定性試験時の残渣量が多く、塗工紙の接着強度が低く、更には共重合体ラテックス製造時の微細凝固物の発生量も多い。比較例５はエチレン系不飽和スルホン酸のアルカリ塩の使用量が多い為、共重合体ラテックスの粘度が著しく高い。
A copolymer latex was produced in the same manner as in Example 1 except that no alkali salt of ethylenically unsaturated sulfonic acid was used and the other ingredients and monomer mixtures listed in Table 2 were used. The physical property evaluation results are shown in Table 2.
Table 2 shows the results for all of the copolymer latexes of the present invention that were out of the range. In Comparative Examples 1 and 2, the residual ratio of the ethylenically unsaturated sulfonic acid alkali salt in the obtained copolymer latex is high, and the amount of residue in the chemical stability test during production of the copolymer latex is large. 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 3, since the amount of the unsaturated carboxylic acid monomer used is large, the wet pick strength is inferior. In Comparative Example 6, the amount of the conjugated diene monomer used was small, the viscosity of the obtained copolymer latex was high, and the pick strength and wet pick strength of the coated paper of the obtained copolymer latex were low. . In addition, since Comparative Example 4 does not use an alkali salt of ethylenically unsaturated sulfonic acid at all, the amount of residue during the chemical stability test is large, the adhesive strength of the coated paper is low, and further, a copolymer latex is produced. There is also a lot of fine coagulum generated at the time. In Comparative Example 5, since the amount of the alkali salt of ethylenically unsaturated sulfonic acid is large, the viscosity of the copolymer latex is extremely high.
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に関する。更に詳しくは、高い化学的安定性と耐湿潤ベタツキ性、紙塗工における接着強度、塗工液の機械的安定性に優れた効果を発揮する共重合体ラテックスに関するものである。 The present invention relates to a conjugated diene copolymer latex used for pigment binders, carpet backing agents, adhesives, pressure-sensitive adhesives, fiber binders and paints in paper coating. More specifically, the present invention relates to a copolymer latex that exhibits excellent effects on high chemical stability and wet stickiness resistance, adhesive strength in paper coating, and mechanical stability of a coating solution.
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％
（ｄ）その他共重合可能な単量体０〜７６．５質量％
（ただし（ａ）＋（ｂ）＋（ｃ）＋（ｄ）＝１００質量％）を乳化重合して得られる共重合体ラテックスであって、該共重合体ラテックス中に残存する、未反応の化合物Ａの量が、該共重合体ラテックスの不揮発成分に対して５質量％以下であることを特徴とする共重合体ラテックス。 In the presence of at least one compound (hereinafter abbreviated as Compound A) selected from alkali salts of ethylenically unsaturated sulfonic acids, the following monomer mixture (a) conjugated diene monomer 20 ~ 80% by mass
(B) 0.5-10 mass% of unsaturated carboxylic acid monomer
(C) 3 to 50% by mass of vinyl cyanide monomer
(D) Other copolymerizable monomers 0 to 76.5% by mass
(Wherein (a) + (b) + (c) + (d) = 100 mass%) is a copolymer latex obtained by emulsion polymerization, and remains in the copolymer latex and remains unreacted A copolymer latex, wherein the amount of compound A is 5% by mass or less based on the nonvolatile components of the copolymer latex.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012121135A1 (en) * | 2011-03-10 | 2012-09-13 | 電気化学工業株式会社 | Method for evaluating chemical stability of polychloroprene latex |
| JP2013067922A (en) * | 2011-09-26 | 2013-04-18 | Jsr Corp | Composition for paper coating and coated paper |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012121135A1 (en) * | 2011-03-10 | 2012-09-13 | 電気化学工業株式会社 | Method for evaluating chemical stability of polychloroprene latex |
| DE112012001176T5 (en) | 2011-03-10 | 2013-12-05 | Denki Kagaku Kogyo Kabushiki Kaisha | Method for evaluating the chemical stability of polychloroprene latex |
| US8883511B2 (en) | 2011-03-10 | 2014-11-11 | Denki Kagaku Kogyo Kabushiki Kaisha | Method for evaluating chemical stability of polychloroprene latex |
| JP5867748B2 (en) * | 2011-03-10 | 2016-02-24 | デンカ株式会社 | Evaluation method of chemical stability of polychloroprene latex |
| JP2013067922A (en) * | 2011-09-26 | 2013-04-18 | Jsr Corp | Composition for paper coating and coated paper |
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