JPH04359001A - Production of copolymer latex and paper-coating composition produced by using the same - Google Patents
Production of copolymer latex and paper-coating composition produced by using the sameInfo
- Publication number
- JPH04359001A JPH04359001A JP15966691A JP15966691A JPH04359001A JP H04359001 A JPH04359001 A JP H04359001A JP 15966691 A JP15966691 A JP 15966691A JP 15966691 A JP15966691 A JP 15966691A JP H04359001 A JPH04359001 A JP H04359001A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- weight
- ethylenically unsaturated
- copolymer 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.)
- Granted
Links
- 239000004816 latex Substances 0.000 title claims abstract description 32
- 229920000126 latex Polymers 0.000 title claims abstract description 32
- 229920001577 copolymer Polymers 0.000 title claims abstract description 28
- 239000008199 coating composition Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 150000001993 dienes Chemical class 0.000 claims abstract description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 9
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 6
- 150000005673 monoalkenes Chemical class 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 239000011230 binding agent Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 abstract description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001530 fumaric acid Substances 0.000 abstract description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 150000002763 monocarboxylic acids Chemical class 0.000 abstract 1
- -1 methyl alpha methyl styrene Chemical compound 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000004899 motility Effects 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 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
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- ZRBSVVRDXNHVFE-UHFFFAOYSA-N (3-chloro-2-hydroxybutyl) 2-methylprop-2-enoate Chemical compound CC(Cl)C(O)COC(=O)C(C)=C ZRBSVVRDXNHVFE-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- MAIIXYUYRNFKPL-UPHRSURJSA-N (z)-4-(2-hydroxyethoxy)-4-oxobut-2-enoic acid Chemical compound OCCOC(=O)\C=C/C(O)=O MAIIXYUYRNFKPL-UPHRSURJSA-N 0.000 description 1
- ZUDLIFVTNPYZJH-UHFFFAOYSA-N 1,1,2,2-tetraphenylethylbenzene Chemical compound C1=CC=CC=C1C(C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 ZUDLIFVTNPYZJH-UHFFFAOYSA-N 0.000 description 1
- QIDUHGHFWAMMPV-UHFFFAOYSA-N 1,1-diphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C)C1=CC=CC=C1 QIDUHGHFWAMMPV-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 description 1
- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- 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 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 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
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- GCTWZXLKCMVCKS-NSCUHMNNSA-N 4-o-(2-hydroxyethyl) 1-o-methyl (e)-but-2-enedioate Chemical compound COC(=O)\C=C\C(=O)OCCO GCTWZXLKCMVCKS-NSCUHMNNSA-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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 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
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- SMPWDQQFZPIOGD-UPHRSURJSA-N bis(2-hydroxyethyl) (z)-but-2-enedioate Chemical compound OCCOC(=O)\C=C/C(=O)OCCO SMPWDQQFZPIOGD-UPHRSURJSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229940102838 methylmethacrylate Drugs 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 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
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Paper (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、微細凝固物の発生が少
なく、重合安定性に優れた共重合体ラテックスの製造方
法ならびに該共重合体ラテックスを用いてなる機械的安
定性、接着強度、インクモトリング、印刷光沢に優れた
紙被覆用組成物に関する。[Industrial Field of Application] The present invention relates to a method for producing a copolymer latex which is less likely to generate fine coagulates and has excellent polymerization stability, as well as a method for producing a copolymer latex that exhibits mechanical stability, adhesive strength, and This invention relates to a paper coating composition with excellent ink motility and printing gloss.
【0002】0002
【従来の技術】ブタジエンを主要成分とする、いわゆる
ブタジエン系共重合体ラテックスが紙加工分野または、
カーペットのバックサイジング等におけるバインダーと
して広く用いられていることはよく知られているところ
である。[Prior Art] So-called butadiene-based copolymer latex, which has butadiene as its main component, is used in the paper processing field and
It is well known that it is widely used as a binder in carpet backsizing and the like.
【0003】それぞれの用途においてバインダーに要求
される性能は多岐にわたっており、それに応じてブタジ
エン系共重合体ラテックスの組成や構造を変えているの
が一般的である。[0003] The performance required of the binder for each application is wide-ranging, and the composition and structure of the butadiene copolymer latex are generally changed accordingly.
【0004】これらの共重合体ラテックスは、一般に乳
化重合によって製造されるが、その際、共重合体ラテッ
クスを構成する単量体混合物の組成、各種添加剤の種類
や量により若干の差は見られるものの、共重合体ラテッ
クス中に微細凝固物が発生するという問題がある。[0004] These copolymer latexes are generally produced by emulsion polymerization, but at this time, slight differences may be observed depending on the composition of the monomer mixture constituting the copolymer latex and the types and amounts of various additives. However, there is a problem in that fine coagulation occurs in the copolymer latex.
【0005】この微細凝固物は、コーティングカラーの
機械的安定性を損なう要因ともなり、さらに、かかる凝
固物が多いとブレード塗工時のストリークトラブルやア
プリケーターの汚れ、キャレンダー処理時の汚れ、印刷
時のブランケットパイリング等の問題が生じる。[0005] These fine coagulates impair the mechanical stability of the coating color, and furthermore, if there are many such coagulates, streak problems during blade coating, stains on the applicator, stains during calendering, and printing problems may occur. Problems such as blanket piling occur.
【0006】また、近年、印刷物の視覚化、高級化とい
った嗜好に伴い、塗工紙の需要が増大しており、これら
塗工紙に求められる性能も多岐に亘っている。これらの
中でもより美麗な印刷仕上がりを得るべく、印刷光沢が
高く、かつインクモノトリングの良好なる塗工紙が要求
されている。[0006]Furthermore, in recent years, the demand for coated paper has been increasing with the preference for visualization and higher quality printed matter, and the performance required of these coated papers is also wide-ranging. Among these, in order to obtain a more beautiful print finish, there is a demand for coated paper that has high printing gloss and has good ink monotling.
【0007】ここでインクモトリングとは、多色印刷に
おいて、2色目以降のインクがその前に印刷されたイン
クの上に重ね刷りされたときに生じる印刷むらのことで
ある。これは2色目以降のインクが印刷されるとき、ロ
ールから塗工紙上に転移するインクの厚みが不均一にな
り、それが印刷むらとして観察されるものである。[0007] Ink mottle refers to printing unevenness that occurs when ink of a second or subsequent color is overprinted on previously printed ink in multicolor printing. This is because when the second and subsequent colors of ink are printed, the thickness of the ink transferred from the roll onto the coated paper becomes uneven, which is observed as printing unevenness.
【0008】通常、印刷光沢を高くするには、バインダ
ーとして用いられるブタジエン系共重合体ラテックス中
に、アクリロニトリル等の極性基を有するモノマーを共
重合体させることが知られているが、この方法では逆に
インクモトリングが低下してしまうという問題があった
。[0008] Normally, in order to increase the print gloss, it is known that a monomer having a polar group such as acrylonitrile is copolymerized into the butadiene copolymer latex used as a binder. On the contrary, there was a problem in that the ink motility decreased.
【0009】従って、この印刷光沢とインクモトリング
を同時に満足させる塗工紙を得ることは困難であった。[0009] Therefore, it has been difficult to obtain a coated paper that satisfies both printing gloss and ink mottle.
【0010】0010
【発明が解決しようとする問題点】本発明者らは、この
ような状況に鑑み、微細凝固物の発生を抑制し、重合安
定性に優れた共重合体ラテックス、さらには機械的安定
性、接着強度、インクモトリング、印刷光沢に優れた紙
被覆用組成物を得るべく鋭意検討の末、本発明を完成す
るに至った。[Problems to be Solved by the Invention] In view of the above circumstances, the present inventors have developed a copolymer latex that suppresses the generation of fine coagulums and has excellent polymerization stability, as well as mechanical stability and The present invention has been completed after extensive research in order to obtain a paper coating composition with excellent adhesive strength, ink motility, and printing gloss.
【0011】[0011]
【問題点を解決するための手段】すなわち、本発明は、
第1段目として、脂肪族共役ジエン系単量体20〜60
重量%、エチレン系不飽和ジカルボン酸単量体0.5〜
5重量%、エチレン系不飽和モノカルボン酸単量体0〜
5重量%およびこれらと共重合可能な他のモノオレフィ
ン系単量体20〜79.4重量%を乳化共重合し、重合
転化率90%以上になった時点で、第2段目として、エ
チレン系不飽和モノカルボン酸単量体 0.1〜10重
量%を添加しさらに乳化共重合を行い反応を完結させる
ことを特徴とする共重合体ラテックスの製造方法ならび
に該共重合体ラテックスと顔料を含有してなる紙被覆用
組成物を提供するものである。[Means for solving the problems] That is, the present invention has the following features:
As the first stage, aliphatic conjugated diene monomer 20 to 60
Weight%, ethylenically unsaturated dicarboxylic acid monomer 0.5~
5% by weight, ethylenically unsaturated monocarboxylic acid monomer 0~
5% by weight and 20 to 79.4% by weight of other monoolefin monomers copolymerizable with these are emulsion copolymerized, and when the polymerization conversion rate reaches 90% or more, ethylene is added as a second stage. A method for producing a copolymer latex, which is characterized by adding 0.1 to 10% by weight of an unsaturated monocarboxylic acid monomer and further emulsion copolymerization to complete the reaction, and a method for producing a copolymer latex and a pigment. The present invention provides a paper coating composition comprising:
【0012】以下に、本発明につき更に詳しく説明する
。本発明にて用いられる脂肪族共役ジエン系単量体とし
ては、1,3−ブタジエン、2−メチル−1,3−ブタ
ジエン、2−クロロ−1,3−メチルブタジエン等が挙
げられるが、特に1,3−ブタジエンが好ましい。The present invention will be explained in more detail below. Examples of the aliphatic conjugated diene monomer used in the present invention include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-methylbutadiene, etc. 1,3-butadiene is preferred.
【0013】肪族共役ジエン系単量体は、20〜60重
量%の範囲にて用いられるが、この使用量が20重量%
未満ではドライ・ピック強度が低下し、また60重量%
を越えるとウェット・ピック強度が低下するので好まし
くない。[0013] The aliphatic conjugated diene monomer is used in a range of 20 to 60% by weight;
If it is less than 60% by weight, the dry pick strength will decrease.
Exceeding this is not preferable because the wet pick strength decreases.
【0014】本発明にて用いられるエチレン系不飽和ジ
カルボン酸単量体としては、フマル酸、マイレン酸、イ
タコン酸等が挙げられる。エチレン系不飽和ジカルボン
酸単量体は1段目に必須である。エチレン系不飽和ジカ
ルボン酸単量体は 0.5〜5重量%の範囲で用いられ
るが、この使用量が 0.5重量%未満ではドライ・ピ
ック強度およびラテックスの機械的安定性が低下し、ま
た5重量%を越えるとラテックスの粘度が高くなりすぎ
るので好ましくない。なお、エチレン系不飽和ジカルボ
ン酸単量体を2段目において使用するとインクモトリン
グの良好な塗工紙が得られないばかりでなく、ドライ・
ピック強度およびウェット・ピック強度に劣り好ましく
ない。Examples of the ethylenically unsaturated dicarboxylic acid monomer used in the present invention include fumaric acid, maleic acid, and itaconic acid. The ethylenically unsaturated dicarboxylic acid monomer is essential in the first stage. The ethylenically unsaturated dicarboxylic acid monomer is used in the range of 0.5 to 5% by weight, but if the amount used is less than 0.5% by weight, the dry pick strength and mechanical stability of the latex will decrease; Moreover, if it exceeds 5% by weight, the viscosity of the latex becomes too high, which is not preferable. Note that if an ethylenically unsaturated dicarboxylic acid monomer is used in the second stage, not only will it not be possible to obtain a coated paper with good ink motility, but also dry and
Unfavorable due to poor pick strength and wet pick strength.
【0015】本発明にて用いられるエチレン系不飽和モ
ノカルボン酸単量体としては、アクリル酸、メタクリル
酸、クロトン酸等が挙げられる。エチレン系不飽和モノ
カルボン酸単量体は2段目に必須である。1段目におい
ては、エチレン系不飽和モノカルボン酸単量体は0〜5
重量%の範囲で用いられる。この使用量が5重量%を越
えるとラテックスの粘度が高くなりすぎるので好ましく
ない。2段目においては、エチレン系不飽和モノカルボ
ン酸単量体は 0.1〜10重量%の範囲で用いられ、
さらに好ましくは 0.5〜7重量%の範囲で用いられ
る。この使用量が 0.1重量%未満では本特許の目的
とするインクモトリング及び印刷光沢の良好な塗工紙を
得ることができない。また10重量%以上ではラテック
スの粘度が高くなりすぎるので好ましくない。[0015] Examples of the ethylenically unsaturated monocarboxylic acid monomer used in the present invention include acrylic acid, methacrylic acid, and crotonic acid. Ethylenically unsaturated monocarboxylic acid monomer is essential in the second stage. In the first stage, the ethylenically unsaturated monocarboxylic acid monomer is 0 to 5
It is used in a range of % by weight. If the amount used exceeds 5% by weight, the viscosity of the latex becomes too high, which is not preferable. In the second stage, the ethylenically unsaturated monocarboxylic acid monomer is used in a range of 0.1 to 10% by weight,
More preferably, it is used in a range of 0.5 to 7% by weight. If the amount used is less than 0.1% by weight, coated paper with good ink motility and printing gloss, which is the object of this patent, cannot be obtained. Moreover, if it exceeds 10% by weight, the viscosity of the latex becomes too high, which is not preferable.
【0016】本発明に用いられる共重合可能な他のモノ
オレフィン系単量体としては、アルケニル芳香族単量体
、不飽和カルボン酸アルキルエステル単量体、ヒドロキ
アルキル基を含有する不飽和単量体、シアン化ビニル単
量体およびエチレン系不飽和カルボン酸アミド系単量体
等が挙げられる。Other copolymerizable monoolefin monomers used in the present invention include alkenyl aromatic monomers, unsaturated carboxylic acid alkyl ester monomers, and unsaturated monomers containing hydroxyalkyl groups. Examples include vinyl cyanide monomers, ethylenically unsaturated carboxylic acid amide monomers, and the like.
【0017】アルケニル芳香族単量体としては、スチレ
ン、アルファメチルスチレン、メチルアルファメチルス
チレン、ビニルトルエン等が挙げられるが、特にスチレ
ンが好ましい。Examples of the alkenyl aromatic monomer include styrene, alpha methyl styrene, methyl alpha methyl styrene, vinyl toluene and the like, with styrene being particularly preferred.
【0018】不飽和カルボン酸アルキルエステル単量体
としては、メチルアクリレート、メチルメタクリレート
、エチルアクリレート、エチルメタクリレート、ブチル
アクリレート、2−エチルヘキシルアクリレート、グリ
シジルメタクリレート、ジメチルフマレート、ジメチル
マレエート、ジエチルマレエート、ジメチルイタコネー
ト、モノメチルフマレート、モノエチルフマレート等が
挙げられるが、特にメチルメタクリレートが好ましい。Examples of the unsaturated carboxylic acid alkyl ester monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate, dimethyl fumarate, dimethyl maleate, diethyl maleate, Examples include dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, and methyl methacrylate is particularly preferred.
【0019】ヒドロキシアルキル基を含有する不飽和単
量体としては、β−ヒドロキシエチルアクリレート、β
−ヒドロキシエチルメタクリレート、ヒドロキシプロピ
ルアクリレート、ヒドロキシブチルメタクリレート、3
−クロロ−2−ヒドロキシブチルメタクリレート、ジ−
(エチレングリコール)マレエート、ジ−(エチレング
リコール)イタコネート、2−ヒドロキシエチルマレエ
ート、ビス(2−ヒドロキシエチル)マレエート、2−
ヒドロキシエチルメチルフマレート等が挙げられるが、
特にβ−ヒドロキシエチルアクリレートが好ましい。Examples of the unsaturated monomer containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl acrylate, and β-hydroxyethyl acrylate.
-Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, 3
-chloro-2-hydroxybutyl methacrylate, di-
(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-
Examples include hydroxyethyl methyl fumarate,
Particularly preferred is β-hydroxyethyl acrylate.
【0020】シアン化ビニル単量体としては、アクリロ
ニトリル、アルファークロルアクリロニトリル、メタク
リロニトリル、アルファーエチルアクリロニトリル等が
挙げられるが、特にアクリロニトリルおよびメタクリロ
ニトリルが好ましい。[0020] Examples of the vinyl cyanide monomer include acrylonitrile, alpha chloroacrylonitrile, methacrylonitrile, alpha ethyl acrylonitrile and the like, with acrylonitrile and methacrylonitrile being particularly preferred.
【0021】エチレン系不飽和カルボン酸アミド単量体
としては、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−メチロールメタクリルア
ミド、N,N−ジメチルアクリルアミド等が挙げられる
が、特にアクリルアミドが好ましい。Examples of the ethylenically unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N,N-dimethylacrylamide, and acrylamide is particularly preferred.
【0022】これらのモノオレフィン系単量体は、一種
または二種以上の併用にて使用することができる。また
、モノオレフィン系単量体は、20〜79.4重量%の
範囲にて用いられるが、この使用量が20重量%未満で
はウェット・ピック強度が低下し、また79.4重量%
を越えるとドライ・ピック強度が低下するので好ましく
ない。These monoolefin monomers can be used singly or in combination of two or more. In addition, the monoolefin monomer is used in a range of 20 to 79.4% by weight, but if the amount used is less than 20% by weight, the wet pick strength decreases;
Exceeding this is not preferable because the dry pick strength decreases.
【0023】本発明においては、第1段目の乳化共重合
において重合転化率が90%以上になった時点で、第2
段目のエチレン系不飽和モノカルボン酸単量体を添加し
乳化共重合を行うものである。該重合転化率が90%未
満の時点で第2段目の単量体を転化した場合にはインク
モトリングの改良が十分でなく、またウェット・ピック
強度に劣り好ましくない。In the present invention, when the polymerization conversion rate reaches 90% or more in the first stage emulsion copolymerization, the second stage emulsion copolymerization is performed.
The ethylenically unsaturated monocarboxylic acid monomer in the first stage is added to carry out emulsion copolymerization. If the second-stage monomer is converted when the polymerization conversion rate is less than 90%, the improvement in ink motility is not sufficient and the wet pick strength is poor, which is not preferable.
【0024】本発明における各種成分の添加方法につい
ては特に制限するものではなく、一括添加方法、分割添
加方法、連続添加方法の何れでも採用することができる
。更に、乳化重合において、常用の乳化剤、連鎖移動剤
、重合開始剤、電解質、重合促進剤、キレート剤等を使
用することができる。[0024] The method of adding the various components in the present invention is not particularly limited, and any of a batch addition method, a divided addition method, and a continuous addition method can be employed. Furthermore, in emulsion polymerization, commonly used emulsifiers, chain transfer agents, polymerization initiators, electrolytes, polymerization promoters, chelating agents, etc. can be used.
【0025】乳化剤としては高級アルコールの硫酸エス
テル塩、アルキルベンゼンスルホン酸塩、脂肪族スルホ
ン酸塩、脂肪族カルボン酸塩、非イオン性界面活性剤の
硫酸エステル塩等のアニオン性界面活性剤あるいはポリ
エチレングリコールのアルキルエステル型、アルキルフ
ェニルエーテル型、アルキルエーテル型等のノニオン性
界面活性剤が1種又は2種以上で用いられる。Examples of emulsifiers include anionic surfactants such as sulfate ester salts of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, aliphatic carboxylates, sulfate ester salts of nonionic surfactants, or polyethylene glycol. Nonionic surfactants such as alkyl ester type, alkylphenyl ether type, and alkyl ether type are used alone or in combination of two or more.
【0026】本発明で使用される連鎖移動剤としては、
n−ヘキシルメルカプタン、n−オクチルメルカプタン
、t−オクチルメルカプタン、n−ドデシルメルカプタ
ン、t−ドデシルメルカプタン、n−ステアリルメルカ
プタンなどのアルキルメルカプタン、ジメチルキサント
ゲンジサルファイド、ジエチルキサントゲンジサルファ
イド、ジイソプロピルキサントゲンジサルファイドなど
のキサントゲン化合物、α−メチルスチレンダイマー、
ターピノーレンや、テトラメチルチウラムジスルフィド
、テトラエチルチウラムジスルフィド、テトラメチルチ
ウラムモノスルフィド等のチウラム系化合物、2,6−
ジ−t−ブチル−4−メチルフェノール、スチレン化フ
ェノール等のフェノール系化合物、アリルアルコール等
のアリル化合物、ジクロルメタン、ジブロモメタン、四
塩化炭素、四臭化炭素等のハロゲン化炭化水素化合物、
トリフェニルエタン、ペンタフェニルエタン、アクロレ
イン、メタアクロレイン、チオグリコール酸、2−エチ
ルヘキシルチオグリコレート等が挙げられ、1種又は2
種以上用いることができる。The chain transfer agent used in the present invention is as follows:
Alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, etc. xanthogen compound, α-methylstyrene dimer,
Terpinolene, thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, 2,6-
Phenolic compounds such as di-t-butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon tetrachloride, carbon tetrabromide,
Triphenylethane, pentaphenylethane, acrolein, metaacrolein, thioglycolic acid, 2-ethylhexylthioglycolate, etc., and one or two
More than one species can be used.
【0027】開始剤としては、過硫酸カリウム、過硫酸
アンモニウム、過硫酸ナトリウム等の水溶性開始剤、あ
るいはレドックス系開始剤あるいは、過酸化ベンゾイル
等の油溶性開始剤が使用できる。As the initiator, water-soluble initiators such as potassium persulfate, ammonium persulfate, and sodium persulfate, redox-based initiators, and oil-soluble initiators such as benzoyl peroxide can be used.
【0028】本発明の紙被覆用組成物は、かかる共重合
体ラテックスに、顔料、さらに必要に応じてその他の結
合剤とともに水性分散液として調整される。The paper coating composition of the present invention is prepared as an aqueous dispersion of the copolymer latex together with a pigment and, if necessary, other binders.
【0029】この際、固形分換算で顔料100重量部に
対し、本発明の共重合体ラテックスが2〜100重量部
、好ましくは5〜30重量部、その他の結合剤が0〜3
0重量部使用できる。At this time, the amount of the copolymer latex of the present invention is 2 to 100 parts by weight, preferably 5 to 30 parts by weight, and the other binder is 0 to 3 parts by weight, based on 100 parts by weight of the pigment in terms of solid content.
0 parts by weight can be used.
【0030】ここで、顔料としては、カオリンクレー、
タルク、硫酸バリウム、酸化チタン、炭酸カルシウム、
水酸化アルミニウム、酸化亜鉛、サチンホワイトなどの
無機顔料、あるいはポリスチレンラテックスのような有
機顔料が挙げられ、これらは単独または混合して使用さ
れる。[0030] Here, as the pigment, kaolin clay,
Talc, barium sulfate, titanium oxide, calcium carbonate,
Examples include inorganic pigments such as aluminum hydroxide, zinc oxide, and satin white, and organic pigments such as polystyrene latex, which may be used alone or in combination.
【0031】また、その他の結合剤としては、澱粉、酸
化澱粉、エステル化澱粉等の変性澱粉、大豆蛋白、カゼ
インなどの天然バインダー、あるいはポリビニルアルコ
ール、ポリ酢酸ビニルラテックス、アクリル系ラテック
スなどの合成ラテックスが使用される。Other binders include starch, modified starch such as oxidized starch and esterified starch, natural binders such as soybean protein and casein, or synthetic latex such as polyvinyl alcohol, polyvinyl acetate latex, and acrylic latex. is used.
【0032】本発明の紙被覆用組成物を調整するには、
さらにその他の助剤、例えば分散剤(ピロリン酸ナトリ
ウム、ポリアクリル酸ナトリウム、ヘキサメタリン酸ナ
トリウムなど)、消泡剤(ポリグリコール、脂肪酸エス
テル、リン酸エステル、シリコーンオイルなど)、レベ
リング剤(ロート油、ジシアンジアミド、尿素など)、
防腐剤、耐水化剤(ホルマリン、ヘキサミン、メラミン
樹脂、尿素樹脂、グリオキサルなど)、離型剤(ステア
リン酸カルシウム、パラフィンエマルジョンなど)、蛍
光染料、カラー保水性向上剤(カルボキシメチルセルロ
ース、アルギン酸ナトリウムなど)が必要に応じて添加
される。To prepare the paper coating composition of the present invention,
Furthermore, other auxiliary agents such as dispersants (sodium pyrophosphate, sodium polyacrylate, sodium hexametaphosphate, etc.), antifoaming agents (polyglycol, fatty acid ester, phosphate ester, silicone oil, etc.), leveling agents (funnel oil, dicyandiamide, urea, etc.),
Preservatives, water resistance agents (formalin, hexamine, melamine resin, urea resin, glyoxal, etc.), mold release agents (calcium stearate, paraffin emulsion, etc.), fluorescent dyes, color water retention improvers (carboxymethylcellulose, sodium alginate, etc.) Added as needed.
【0033】本発明の紙被覆用組成物を塗工用紙へ塗布
する方法は、公知の技術、例えばエアナイフコーター、
ブレードコーター、ロールコーター、バーコーターなど
の塗布機によって行なわれる。また、塗布後、表面を乾
燥し、カレンダーリングなどにより仕上げる。The paper coating composition of the present invention can be applied to coated paper using known techniques such as air knife coater,
This is done using a coating machine such as a blade coater, roll coater, or bar coater. After application, the surface is dried and finished by calendering, etc.
【0034】また、本発明の製造方法によって得られた
共重合体ラテックスは微細凝固物量が少ないので、他の
用途、例えばカーペット、タイヤコード、ロック繊維等
の繊維処理用途、木材用途や皮革用途における接着剤と
しても好適に使用することができるものである。Furthermore, since the copolymer latex obtained by the production method of the present invention has a small amount of fine coagulation, it can be used in other applications such as fiber processing applications such as carpets, tire cords, rock fibers, wood applications, and leather applications. It can also be suitably used as an adhesive.
【0035】〔実施例〕以下、実施例を挙げ本発明をさ
らに具体的に説明するが、本発明はその要旨を超えない
限り、これらの実施例に限定されるものではない。なお
実施例中、割合を示す部および%は重量基準によるもの
である。また実施例における諸物性の測定は次の方法に
拠った。[Examples] The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded. In the examples, parts and percentages are based on weight. In addition, measurements of various physical properties in Examples were based on the following methods.
【0036】・微細凝固物
顕微鏡により数μm〜50μmの微細凝固物を観察し、
○:非常に少ない
△:少ない
×:多い この3段階で行う。- Observing fine coagulates of several μm to 50 μm using a microcoagulate microscope,
○: very little △: little ×: much This is done in three stages.
【0037】・ゲル含有量
室温乾燥にて共重合体ラテックスのフィルムを作製し、
該フィルムを約200〜800倍のトルエン中に投入し
、48時間放置した後、No.2濾紙を用いて濾過する
。
濾液を70℃で減圧乾燥を行い、秤量し、共重合体ラテ
ックスフィルムのトルエン可溶分(%)を求める。10
0%から上記トルエン可溶分を減じた数値、すなわち、
トルエン不溶分(%)をゲル含有量として算出した。・Gel content A copolymer latex film was prepared by drying at room temperature,
The film was placed in toluene of about 200 to 800 times the concentration and left for 48 hours. 2. Filter using filter paper. The filtrate is dried under reduced pressure at 70°C and weighed to determine the toluene soluble content (%) of the copolymer latex film. 10
The value obtained by subtracting the above toluene soluble content from 0%, that is,
The toluene insoluble content (%) was calculated as the gel content.
【0038】・機械的安定性
コーティングカラーをパタスタビリティーを用いて金属
ロールとゴムロール間で練り、機械的剪断をかけ、ゴム
ロール上に凝固物が発生するまでの時間(分)を測定す
る。- Mechanical stability The coating color is kneaded between a metal roll and a rubber roll using patter stability, mechanical shear is applied, and the time (minutes) until a coagulum appears on the rubber roll is measured.
【0039】・RIウェット・ピック強度RI印刷機で
湿し水を用いて印刷した時のピッキングの程度を肉眼で
判定し、1級(最も良好なもの)から5級(最も悪いも
の)の5段階法で評価した。6回の平均値を示す。- RI Wet Pick Strength The degree of picking when printed using dampening water with an RI printing machine is visually judged and ranked from 1st grade (best) to 5th grade (worst). It was evaluated using a stepwise method. The average value of 6 times is shown.
【0040】・RIドライ・ピック強度湿し水を用いな
い以外は、上記RIウェット・ピック強度測定方法と同
様の方法で判定した。RI Dry Pick Strength Judgment was made in the same manner as the RI wet pick strength measurement method described above, except that no dampening water was used.
【0041】・印刷光沢
RI印刷機を用い、市販オフセット印刷用紅インクを一
定量使用して1回印刷を行ない、塗被紙の印刷面を村上
式光沢度計で入射角75°、反射角75°で測定する。
印刷光沢値は数字の大きい方が良好。- Printing gloss Using a RI printing machine, print once using a fixed amount of commercially available red ink for offset printing, and measure the printed surface of the coated paper with a Murakami gloss meter at an incident angle of 75° and a reflection angle. Measure at 75°. The higher the print gloss value, the better.
【0042】・インクモトリング
RI印刷機を用いて、イエローのプロセスインキを試験
片に印刷し、さらに10秒後にマゼンタのプロセスイン
キを重ねて印刷し、マゼンタのプロセスインキの印刷む
らを肉眼で判定して1級(一番良好なもの)から5級(
一番悪いもの)の5段階法で評価した。6回の平均値を
示す。-Using an Inkmotling RI printing machine, print yellow process ink on a test piece, and after 10 seconds, overprint magenta process ink, and judge the printing unevenness of magenta process ink with the naked eye. and grade 1 (best) to grade 5 (
Evaluation was made on a five-point scale, with the worst being the worst. The average value of 6 times is shown.
【0043】共重合体ラテックスの作製表−1に示す1
段目成分(単量体、連鎖移動剤、重合開始剤)及びドデ
シルベンゼンスルホン酸ソーダ 0.5部、炭酸水素ナ
トリウム 0.5部、水100部を100l オートク
レーブに仕込み、重合温度70℃にて重合を行った。重
合転化率が90%以上になった時点で、表−1に示す2
段目成分(単量体、連鎖移動剤、重合開始剤)及び水1
0部を追加添加して重合を継続し、重合を完了した。最
終重合転化率は98%であった。Preparation of copolymer latex 1 shown in Table-1
Charge stage components (monomer, chain transfer agent, polymerization initiator), 0.5 part of sodium dodecylbenzenesulfonate, 0.5 part of sodium hydrogen carbonate, and 100 parts of water into a 100 L autoclave, and polymerize at 70°C. Polymerization was performed. When the polymerization conversion rate reaches 90% or more, 2 shown in Table-1
Stage components (monomer, chain transfer agent, polymerization initiator) and water 1
The polymerization was continued by adding 0 part of the polymer to complete the polymerization. The final polymerization conversion rate was 98%.
【0044】これらのラテックスは、濃度5%のアンモ
ニア水を加えてpHを5.0に調整した後、未反応単量
体を水蒸気蒸留で除去し、共重合体ラテックス1〜10
を得た。After adjusting the pH of these latexes to 5.0 by adding aqueous ammonia at a concentration of 5%, unreacted monomers were removed by steam distillation, and copolymer latexes 1 to 10
I got it.
【0045】同様に、表−2に示す成分を使用する以外
は共重合体ラテックス1と同様の方法にて重合を行った
。なお、共重合体ラテックス16については、1段目の
重合転化率が70%になった時点で2段目の成分を添加
し、重合を行った。Similarly, polymerization was carried out in the same manner as for Copolymer Latex 1 except that the components shown in Table 2 were used. For copolymer latex 16, when the first stage polymerization conversion rate reached 70%, the second stage components were added and polymerization was carried out.
【0046】これらのラテックスも、共重合体ラテック
ス1と同様未反応単量体を除去し、共重合体ラテックス
11〜17を得た。From these latexes, unreacted monomers were removed in the same manner as Copolymer Latex 1 to obtain Copolymer Latexes 11 to 17.
【0047】紙被覆用組成物の調整及び塗工紙の評価共
重合体ラテックス1〜17を用いて下記の処方に基いて
紙被覆用組成物を作成し、機械的安定性を測定した。
更に、各組成物を市販の上質紙に塗工し、塗工紙を得た
。Preparation of Paper Coating Composition and Evaluation of Coated Paper Paper coating compositions were prepared using copolymer latexes 1 to 17 according to the following formulation, and their mechanical stability was measured. Furthermore, each composition was coated on commercially available high-quality paper to obtain coated paper.
【0048】得られた塗工紙についてRIウェット・ピ
ック強度、RIドライ・ピック強度、印刷光沢及びイン
クモトリングを測定した。結果を表−3及び表−4に示
す。(処方)
カオリンクレー 80部炭酸カ
ルシウム 20部変性デンプン
8部共重合体ラテッ
クス 12部(固形分)The obtained coated paper was measured for RI wet pick strength, RI dry pick strength, printing gloss and ink mottle. The results are shown in Table-3 and Table-4. (Formulation) Kaolin clay 80 parts Calcium carbonate 20 parts Modified starch 8 parts Copolymer latex 12 parts (solid content)
【0049】[0049]
【表1】[Table 1]
【0050】[0050]
【表2】[Table 2]
【0051】[0051]
【表3】[Table 3]
【0052】[0052]
【表4】[Table 4]
Claims (2)
単量体20〜60重量%、エチレン系不飽和ジカルボン
酸単量体 0.5〜5重量%、エチレン系不飽和モノカ
ルボン酸単量体0〜5重量%およびこれらと共重合可能
な他のモノオレフィン系単量体20〜79.4重量%を
乳化共重合し、重合転化率90%以上になった時点で、
第2段目として、エチレン系不飽和モノカルボン酸単量
体0.1〜10重量%を添加しさらに乳化共重合を行い
反応を完結させることを特徴とする共重合体ラテックス
の製造方法。Claim 1: As the first stage, 20 to 60% by weight of an aliphatic conjugated diene monomer, 0.5 to 5% by weight of an ethylenically unsaturated dicarboxylic acid monomer, and an ethylenically unsaturated monocarboxylic acid monomer. Emulsion copolymerization of 0 to 5% by weight of the polymer and 20 to 79.4% by weight of other monoolefin monomers copolymerizable with these, and when the polymerization conversion rate reaches 90% or more,
A method for producing a copolymer latex, which comprises, in the second stage, adding 0.1 to 10% by weight of an ethylenically unsaturated monocarboxylic acid monomer and further carrying out emulsion copolymerization to complete the reaction.
れた共重合体ラテックスと顔料を含有してなる紙被覆用
組成物。2. A paper coating composition comprising a copolymer latex obtained by the production method according to claim 1 and a pigment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15966691A JP2745253B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing copolymer latex and paper coating composition using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15966691A JP2745253B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing copolymer latex and paper coating composition using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04359001A true JPH04359001A (en) | 1992-12-11 |
JP2745253B2 JP2745253B2 (en) | 1998-04-28 |
Family
ID=15698691
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15966691A Expired - Fee Related JP2745253B2 (en) | 1991-06-03 | 1991-06-03 | Method for producing copolymer latex and paper coating composition using the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2745253B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1072685C (en) * | 1997-08-14 | 2001-10-10 | 中国石油化工集团公司 | Method for prepn. of latex for coating paper |
US7220797B2 (en) * | 2003-08-04 | 2007-05-22 | Nippon A&L Incorporated | Method of producing copolymer latex using for aqueous paint |
-
1991
- 1991-06-03 JP JP15966691A patent/JP2745253B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1072685C (en) * | 1997-08-14 | 2001-10-10 | 中国石油化工集团公司 | Method for prepn. of latex for coating paper |
US7220797B2 (en) * | 2003-08-04 | 2007-05-22 | Nippon A&L Incorporated | Method of producing copolymer latex using for aqueous paint |
Also Published As
Publication number | Publication date |
---|---|
JP2745253B2 (en) | 1998-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4613650A (en) | Copolymer latex | |
US7629410B2 (en) | Latex compositions | |
JP5288544B2 (en) | Multilayer coated paper | |
JPH04359001A (en) | Production of copolymer latex and paper-coating composition produced by using the same | |
JP5313088B2 (en) | Copolymer latex, composition for paper coating and coated paper | |
JP2844031B2 (en) | Gravure printing paper coating composition | |
JP3106292B2 (en) | Method for producing copolymer latex | |
JP3047144B2 (en) | Composition for paper coating | |
JP3404417B2 (en) | Method for producing copolymer latex for paper coating | |
JPH08259611A (en) | Production of resin latex | |
JPH04332701A (en) | Production of copolymer latex and composition for coating paper using the same latex | |
JP3172883B2 (en) | Latex for sheet-fed offset printing paper coating. | |
JP2009013541A (en) | Copolymer latex for coating paper | |
JPH0912647A (en) | Production of copolymer latex | |
JPH06101196A (en) | Copolymer latex for coating paper | |
JPH05279406A (en) | Production of copolymer latex and composition containing the same | |
JPH072911A (en) | Production of copolymer latex, and copolymer latex | |
JPH04240297A (en) | Production of copolymer latex for coating paper | |
JPH07119089A (en) | Copolymer latex for paper coating | |
JPH01280095A (en) | Copolymer latex for coating paper | |
JP5647394B2 (en) | Copolymer latex, paper coating composition and printing coated paper | |
JPH0577685B2 (en) | ||
JPH11507999A (en) | Use of paper coatings with high butadiene content in offset printing | |
JP3842311B2 (en) | Method for producing copolymer latex for paper coating | |
JPH09118841A (en) | Composition for coating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080213 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090213 Year of fee payment: 11 |
|
LAPS | Cancellation because of no payment of annual fees |