JP2012140518A - Copolymer latex and paper coating composition - Google Patents
Copolymer latex and paper coating composition Download PDFInfo
- Publication number
- JP2012140518A JP2012140518A JP2010293236A JP2010293236A JP2012140518A JP 2012140518 A JP2012140518 A JP 2012140518A JP 2010293236 A JP2010293236 A JP 2010293236A JP 2010293236 A JP2010293236 A JP 2010293236A JP 2012140518 A JP2012140518 A JP 2012140518A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer latex
- polymerization
- latex
- weight
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004816 latex Substances 0.000 title claims abstract description 90
- 229920000126 latex Polymers 0.000 title claims abstract description 90
- 229920001577 copolymer Polymers 0.000 title claims abstract description 73
- 239000008199 coating composition Substances 0.000 title abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 81
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 239000004793 Polystyrene Substances 0.000 claims abstract description 7
- 229920002223 polystyrene Polymers 0.000 claims abstract description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 73
- 150000001875 compounds Chemical class 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 19
- -1 methyl α-methylstyrene Chemical compound 0.000 description 19
- 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 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000009835 boiling Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 150000004996 alkyl benzenes Chemical class 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FSWCCQWDVGZMRD-UHFFFAOYSA-N 4-methylcyclohexene Chemical compound CC1CCC=CC1 FSWCCQWDVGZMRD-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
- 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 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 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
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 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
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004090 dissolution 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
- 239000000839 emulsion Substances 0.000 description 2
- 239000004318 erythorbic acid Substances 0.000 description 2
- 235000010350 erythorbic acid Nutrition 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 229940026239 isoascorbic acid Drugs 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
- 239000007788 liquid Substances 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- BIRJAUKLRAMLEV-UHFFFAOYSA-N 1-phenylethenoxymethylbenzene Chemical compound C=1C=CC=CC=1C(=C)OCC1=CC=CC=C1 BIRJAUKLRAMLEV-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
- 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
- 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-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
- PMZVSHSZVKFXMZ-UHFFFAOYSA-N 2-phenylmethoxyprop-2-enamide Chemical compound NC(=O)C(=C)OCC1=CC=CC=C1 PMZVSHSZVKFXMZ-UHFFFAOYSA-N 0.000 description 1
- NYVPRWODADOGAO-UHFFFAOYSA-N 2-phenylmethoxyprop-2-enenitrile Chemical compound N#CC(=C)OCC1=CC=CC=C1 NYVPRWODADOGAO-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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-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
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-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
- 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
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
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Abstract
Description
本発明は、共重合体ラテックス及び紙塗工用組成物に関するものである。詳しくは、紙塗工用組成物にバインダーとして好適に使用される共重合体ラテックスであり、塗工紙製造工程での塗工操業性に優れ、かつ塗工紙のドライピック強度及び耐ブリスター性に優れた共重合体ラテックス及び該共重合体ラテックスを含有する紙塗工用組成物に関するものである。 The present invention relates to a copolymer latex and a paper coating composition. Specifically, it is a copolymer latex that is suitably used as a binder in a paper coating composition, is excellent in coating operability in the coated paper manufacturing process, and has dry pick strength and blister resistance of the coated paper. The present invention relates to an excellent copolymer latex and a paper coating composition containing the copolymer latex.
塗工紙は塗工原紙の表面に紙用塗被組成物を塗布、乾燥して製造される。塗工紙は印刷物に広く利用され、高品質の塗工紙を得るために顔料と水性バインダーとを主成分とした紙用塗被組成物の研究・改良が進められている。水性バインダーとしてはデンプンなどの天然バインダーやスチレン−ブタジエン系共重合体ラテックスの合成エマルションバインダーが広く用いられている。中でもスチレン−ブタジエン系共重合体ラテックスは、品質設計の自由度が大きく、今日では紙塗工用組成物に最も適したバインダーとして広く使用されており、スチレン−ブタジエン系共重合体ラテックスの性能が紙塗工用組成物の性能や塗工紙作成時の操業性あるいは最終的な塗工紙製品の表面強度、印刷光沢などの品質に影響することが知られている。
近年、紙加工分野において高速塗工化、高生産化が進められている中、スチレン−ブタジエン系共重合体ラテックスの品質設計や製造方法に関してはさまざまな検討がされ、技術改良が紹介されている。
The coated paper is produced by applying a paper coating composition to the surface of the coated base paper and drying it. Coated paper is widely used for printed materials, and research and improvement of paper coating compositions mainly composed of pigments and aqueous binders are being carried out in order to obtain high-quality coated paper. Natural binders such as starch and synthetic emulsion binders of styrene-butadiene copolymer latex are widely used as the aqueous binder. Among them, styrene-butadiene copolymer latex has a great degree of freedom in quality design, and is widely used as a binder most suitable for a paper coating composition today. It is known to affect the performance of the composition for paper coating, the operability at the time of preparing the coated paper, the quality of the final coated paper product, such as the surface strength and printing gloss.
In recent years, while high-speed coating and high production have been promoted in the paper processing field, various studies have been made on the quality design and manufacturing method of styrene-butadiene copolymer latex, and technical improvements have been introduced. .
上記諸物性の高バランス化を目指し、２段以上の多段重合法において１段目で得られる共重合体の溶媒可溶部の分子量をコントロールする方法を用いたラテックスが提案されている。例えば特開平７−３２４１１２号公報では、１段目の共重合体のテトラヒドロフラン溶解分のポリスチレン換算重量平均分子量を１０万以上とすることでさらなる塗工操業性と印刷適性の高バランス化が達成可能であると開示されている。また特開２００２−２４１４４３号公報において、１段目に得られる共重合体部分の分子量および分子量分布を特定の範囲にすることで塗工操業性と塗工紙のピック強度と耐ブリスター性に優れる共重合体ラテックスが提案されている。さらには特開２０００−１５４４９６号公報において、各特定組成の共重合体であってトルエン不溶分が８０重量％以上で、ゲルパーミエーションクロマトグラフィーの測定から得られる分子量分布において、ポリスチレン換算の分子量で１１０万に対応する溶出時間より早く検出される成分の割合が５０％以上である共重合体を含むことを特徴とする共重合ラテックスが提案されている。
しかし、これらのさまざまな改良技術は、紙塗工用共重合体ラテックスに要求される高レベルの品質を満足するに至っておらず、更なる改良が強く求められていた。
Aiming at achieving a high balance of the above physical properties, a latex using a method for controlling the molecular weight of the solvent-soluble part of the copolymer obtained in the first stage in a multistage polymerization process of two or more stages has been proposed. For example, in Japanese Patent Application Laid-Open No. 7-324112, a higher balance between coating operability and printability can be achieved by setting the weight average molecular weight in terms of polystyrene of the first-stage copolymer dissolved in tetrahydrofuran to 100,000 or more. It is disclosed that. In JP-A-2002-241443, coating operability, coated paper pick strength and blister resistance are excellent by setting the molecular weight and molecular weight distribution of the copolymer part obtained in the first stage to a specific range. Copolymer latex has been proposed. Furthermore, in JP-A No. 2000-15496, a copolymer having a specific composition and having a toluene insoluble content of 80% by weight or more, and a molecular weight distribution obtained from gel permeation chromatography measurement, There has been proposed a copolymer latex comprising a copolymer in which the proportion of components detected earlier than the elution time corresponding to 1.1 million is 50% or more.
However, these various improvements have not yet satisfied the high level of quality required for copolymer latexes for paper coating, and further improvements have been strongly demanded.
本発明は、紙塗工用組成物の再分散性に優れることにより塗工操業性に優れ、またドライピック強度及び耐ブリスター性が良好な塗工紙が得られる共重合体ラテックスを提供することを目的とするものである。 The present invention provides a copolymer latex that is excellent in coating operability by being excellent in redispersibility of a paper coating composition, and that provides a coated paper having good dry pick strength and blister resistance. It is intended.
本発明は、（ａ）脂肪族共役ジエン系単量体２０〜６９．５重量％、（ｂ）エチレン系不飽和カルボン酸単量体０．５〜２０重量％、並びに（ｃ）前記（ａ）成分および（ｂ）成分と共重合可能な他のビニル系単量体１０．５〜７９．５重量％を乳化重合して得られる共重合体ラテックスであり、得られた共重合体ラテックスのフィルムのテトラヒドラフラン溶解分のポリスチレン換算重量平均分子量（Ｍｗ）が２０００以上１０万未満であることを特徴とする共重合体ラテックスを提供する。また、該共重合体ラテックスを含有する紙塗工用組成物を提供するものである。 The present invention includes (a) 20 to 69.5% by weight of an aliphatic conjugated diene monomer, (b) 0.5 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer, and (c) the above (a ) Component and other vinyl monomers copolymerizable with component (b) are copolymer latex obtained by emulsion polymerization of 10.5 to 79.5% by weight of the copolymer latex obtained. Provided is a copolymer latex characterized by having a polystyrene-reduced weight average molecular weight (Mw) of a film dissolved in tetrahydrafuran of 2000 or more and less than 100,000. The present invention also provides a paper coating composition containing the copolymer latex.
本発明によれば、塗工紙作成時の塗工操業性に優れる紙塗工用組成物が得られ、また本発明の紙塗工用組成物を塗工することにより、ドライピック強度と耐ブリスター性に優れた塗工紙を提供することが可能である。 According to the present invention, a paper coating composition having excellent coating operability at the time of preparing coated paper can be obtained, and by applying the paper coating composition of the present invention, dry pick strength and resistance can be improved. It is possible to provide a coated paper excellent in blister properties.
本願発明の共重合体ラテックスは、脂肪族共役ジエン系単量体、エチレン系不飽和カルボン酸単量体およびこれらと共重合可能な他の単量体を乳化重合して得られる。
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、２，３−ジメチル−１，３−ブタジエン、２−クロル−１，３−ブタジエン、置換直鎖共役ペンタジエン類、置換および側鎖共役ヘキサジエン類などが挙げられ、これらを１種または２種以上使用することができる。特に１，３−ブタジエンの使用が好ましい。
The copolymer latex of the present invention is obtained by emulsion polymerization of an aliphatic conjugated diene monomer, an ethylenically unsaturated carboxylic acid monomer, and other monomers copolymerizable therewith.
Aliphatic conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted Examples thereof include linear conjugated pentadienes, substituted and side chain conjugated hexadienes and the like, and these can be used alone or in combination. In particular, the use of 1,3-butadiene is preferred.
エチレン系不飽和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、マレイン酸、フマール酸、イタコン酸などの１塩基酸または２塩基酸（無水物）を挙げられ、これらを１種または２種以上使用することができる。 Examples of the ethylenically unsaturated carboxylic acid monomer include monobasic acids or dibasic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Or 2 or more types can be used.
上記脂肪族共役ジエン系単量体およびエチレン系不飽和カルボン酸単量体と共重合可能な他の単量体としては、アルケニル芳香族単量体、シアン化ビニル単量体、不飽和カルボン酸アルキルエステル単量体、ヒドロキシアルキル基を含有する不飽和単量体、不飽和カルボン酸アミド単量体等が挙げられる。 Examples of other monomers copolymerizable with the aliphatic conjugated diene monomer and the ethylenically unsaturated carboxylic acid monomer include alkenyl aromatic monomers, vinyl cyanide monomers, and unsaturated carboxylic acids. Examples thereof include alkyl ester monomers, unsaturated monomers containing a hydroxyalkyl group, and unsaturated carboxylic acid amide monomers.
アルケニル芳香族単量体としては、スチレン、α−メチルスチレン、メチルα−メチルスチレン、ビニルトルエンおよびジビニルベンゼン等が挙げられ、これらを１種または２種以上使用することができる。特にスチレンの使用が好ましい。 Examples of the alkenyl aromatic monomer include styrene, α-methylstyrene, methyl α-methylstyrene, vinyltoluene and divinylbenzene, and these can be used alone or in combination. In particular, use of styrene is preferable.
シアン化ビニル単量体としては、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、α−エチルアクリロニトリルなどが挙げられ、これらを１種または２種以上使用することができる。特にアクリロニトリルまたはメタクリロニトリルの使用が好ましい。 Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, and the like, and one or more of these can be used. In particular, the use of acrylonitrile or methacrylonitrile is preferred.
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、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、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、２−エチルヘキシルアクリレート等が挙げられ、これらを１種または２種以上使用することができる。特にメチルメタクリレートの使用が好ましい。 Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate, Examples thereof include monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate, and the like can be used alone or in combination. In particular, the use of methyl methacrylate is preferred.
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、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３−クロロ−２−ヒドロキシプロピルメタクリレート、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などが挙げられ、これらを１種または２種以上使用することができる。特にβ−ヒドロキシエチルアクリレートの使用が好ましい。 Examples of unsaturated monomers containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and 3-chloro-2-hydroxypropyl. Methacrylate, di- (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, and the like. Or 2 or more types can be used. In particular, the use of β-hydroxyethyl acrylate is preferred.
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などが挙げられ、これらを１種または２種以上使用することができる。特にアクリルアミドまたはメタクリルアミドの使用が好ましい。 Examples of the unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylacrylamide, and the like, and one or more of these may be used. it can. Particularly preferred is the use of acrylamide or methacrylamide.
さらに、上記単量体の他に、エチレン、プロピレン、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン等、通常の乳化重合において使用される単量体は何れも使用可能である。 Further, in addition to the above monomers, any of the monomers used in ordinary emulsion polymerization such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride can be used.
上記の単量体組成は、脂肪族共役ジエン系単量体２０〜６９．５重量％、エチレン系不飽和カルボン酸単量体０．５〜２０重量％およびこれらと共重合可能な他の単量体１０．５〜７９．５重量％であることが必要である。 The above monomer composition includes 20 to 69.5% by weight of an aliphatic conjugated diene monomer, 0.5 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer, and other monomers copolymerizable therewith. It is necessary to be 10.5 to 79.5% by weight of the monomer.
脂肪族共役ジエン系単量体が２０重量％未満では塗工紙のドライピック強度が劣り、また６９．５重量％を超えると紙塗工用組成物の再分散性が劣り、塗工紙作成時の塗工操業性に悪影響を及ぼす。好ましくは３０〜６０重量％である。 When the aliphatic conjugated diene monomer is less than 20% by weight, the dry pick strength of the coated paper is inferior, and when it exceeds 69.5% by weight, the redispersibility of the paper coating composition is inferior, and the coated paper is produced. It adversely affects the coating operability at the time. Preferably it is 30 to 60% by weight.
エチレン系不飽和カルボン酸単量体が０．５重量％未満では共重合体ラテックスの機械的安定性および放置安定性が劣り、また２０重量％を超えるとラテックス自身の粘度が高くなりすぎ、送液ポンプによるラテックスの輸送搬送性が劣るなど、いずれも取り扱い性が悪化する。好ましくは１〜１５重量％である。 When the amount of the ethylenically unsaturated carboxylic acid monomer is less than 0.5% by weight, the mechanical stability and the standing stability of the copolymer latex are inferior. In all cases, handling properties are deteriorated, such as poor transport and transport of latex by a liquid pump. Preferably, it is 1 to 15% by weight.
共重合可能な他の単量体が１０．５〜７９．５重量％の範囲から外れると、塗工紙のドライピック強度が著しく低下する。 When the other copolymerizable monomer is out of the range of 10.5 to 79.5% by weight, the dry pick strength of the coated paper is remarkably lowered.
本発明の共重合体ラテックスの重合には、公知の乳化剤（界面活性剤）を使用することができる。例えば、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、アルキルジフェニルエーテルジスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、デヒドロアビエチン酸塩、ナフタレンスルホン酸のホルマリン縮合物、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、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挙げられ、これらを１種又は２種以上使用することができる。 A known emulsifier (surfactant) can be used for the polymerization of the copolymer latex of the present invention. For example, sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietic acid salts, formalin condensates of naphthalene sulfonic acid, nonionic surface activity Nonionic surfactants such as anionic surfactants such as sulfuric acid ester salts, polyethylene glycol alkyl ester type, alkylphenyl ether type, alkyl ether type, etc., and one or more of these should be used Can do.
本発明の共重合体ラテックスの重合には、公知の連鎖移動剤（分子量調整剤）を制限されることなく使用することができる。例えば、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等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、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物、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、四臭化炭素等のハロゲン化炭化水素化合物、α−ベンジルオキシスチレン、α−ベンジルオキシアクリロニトリル、α−ベンジルオキシアクリルアミド等のビニルエーテル、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、チオリンゴ酸、２−エチルヘキシルチオグリコレート、ターピノレン、α−メチルスチレンダイマー等が挙げられ、これらを１種または２種以上使用することができる。 For the polymerization of the copolymer latex of the present invention, a known chain transfer agent (molecular weight adjusting agent) can be used without limitation. For example, xanthogen compounds such as alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, dimethylxanthogen disulfide, diisopropylxanthogen disulfide, etc. Thiuram compounds such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, phenol compounds such as 2,6-di-t-butyl-4-methylphenol, styrenated phenol, and allyl compounds such as allyl alcohol , Halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon tetrabromide, α-benzyloxystyrene, α-benzyloxyacrylonitrile And vinyl ethers such as ril, α-benzyloxyacrylamide, triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexyl thioglycolate, terpinolene, α-methylstyrene dimer, etc. One or more of these can be used.
本発明の共重合体ラテックスの重合には、公知の重合開始剤として、過硫酸リチウム、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤、クメンハイドロパーオキサイド、過酸化ベンゾイル、t−ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤を適宜用いることができる。特に過硫酸カリウム、過硫酸ナトリウム、クメンハイドロパーオキサイド、t−ブチルハイドロパーオキサイドの使用が好ましい。重合開始剤の量は特に制限されないが、単量体組成、重合反応系のｐＨ、他の添加剤などの組み合わせを考慮して適宜調整される。 For the polymerization of the copolymer latex of the present invention, known polymerization initiators include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, Oil-soluble polymerization initiators such as t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide can be appropriately used. In particular, it is preferable to use potassium persulfate, sodium persulfate, cumene hydroperoxide, or t-butyl hydroperoxide. The amount of the polymerization initiator is not particularly limited, but is appropriately adjusted in consideration of a combination of the monomer composition, the pH of the polymerization reaction system, and other additives.
本発明において好ましく用いられる還元剤の具体例としては、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩、また、Ｌ−アスコルビン酸、エリソルビン酸、酒石酸、クエン酸などのカルボン酸類及びその塩、更にはデキストロース、サッカロースなどの還元糖類、更にはジメチルアニリン、トリエタノールアミンなどのアミン類が挙げられる。特にＬ−アスコルビン酸、エリソルビン酸の使用が好ましい。 Specific examples of the reducing agent preferably used in the present invention include sulfite, bisulfite, pyrosulfite, nitrite, nithionate, thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate, Examples thereof include carboxylic acids such as L-ascorbic acid, erythorbic acid, tartaric acid and citric acid and salts thereof, reducing sugars such as dextrose and saccharose, and amines such as dimethylaniline and triethanolamine. In particular, use of L-ascorbic acid and erythorbic acid is preferable.
本発明の共重合体ラテックスの重合には、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロヘプタン等の飽和炭化水素、ペンテン、ヘキセン、ヘプテン、シクロペンテン、シクロヘキセン、シクロヘプテン、４−メチルシクロヘキセン、１−メチルシクロヘキセン等の不飽和炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素などの炭化水素化合物を使用することができる。特に、沸点が適度に低く、重合終了後に水蒸気蒸留などによって回収、再利用しやすいシクロヘキセンやトルエンが、本発明の目的とは異なるものの、環境問題の観点から好適である。 For the polymerization of the copolymer latex of the present invention, saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, 1-methyl Hydrocarbon compounds such as unsaturated hydrocarbons such as cyclohexene and aromatic hydrocarbons such as benzene, toluene and xylene can be used. In particular, cyclohexene and toluene, which have a moderately low boiling point and can be easily recovered and reused by steam distillation after the completion of polymerization, are suitable from the viewpoint of environmental problems, although they are different from the object of the present invention.
本発明の共重合体ラテックスの粒子径にはなんら制限はないが、２００ｎｍ以下であることが好ましい。特に好ましくは５０〜１５０ｎｍである。 The particle size of the copolymer latex of the present invention is not limited at all, but is preferably 200 nm or less. Especially preferably, it is 50-150 nm.
本発明の共重合体ラテックスについて、ラテックスフィルムのテトラヒドラフラン溶解分のポリスチレン換算重量平均分子量（Ｍｗ）は、２０００以上１０万未満であることが必要である。Ｍｗが２０００未満であると、塗工紙のドライピック強度が低下する。また１０万以上であると共重合体の架橋密度が高く、塗工紙のドライピック強度と耐ブリスター性のバランスが低下する。また、ポリスチレン換算数平均分子量（Ｍｎ）が２０００以上８万未満であることが好ましい。さらには、ポリスチレン換算重量平均分子量（Ｍｗ）とポリスチレン換算数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）は、１．３〜４．５であることが、塗工紙のドライピック強度と耐ブリスター性のバランスを向上させるために、特に好ましい。 About the copolymer latex of this invention, the polystyrene conversion weight average molecular weight (Mw) of the tetrahydrafuran melt | dissolution part of a latex film needs to be 2000 or more and less than 100,000. If the Mw is less than 2000, the dry pick strength of the coated paper decreases. Moreover, when it is 100,000 or more, the crosslinking density of the copolymer is high, and the balance between dry pick strength and blister resistance of the coated paper is lowered. Moreover, it is preferable that polystyrene conversion number average molecular weight (Mn) is 2000 or more and less than 80,000. Furthermore, the ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) to the polystyrene-equivalent number average molecular weight (Mn) is 1.3 to 4.5. This is particularly preferable in order to improve the balance of blister properties.
共重合体ラテックスフィルムのテトラヒドラフラン溶解分のポリスチレン換算重量平均分子量（Ｍｗ）は、重合温度、単量体の添加速度、連鎖移動剤の量を適宜設定することでコントロール可能である。Ｍｗ／Ｍｎの比すなわち重合して得られる共重合体部分の分子量分布は、架橋密度が高くなると、大きくなる。Ｍｗ／Ｍｎの比は、上記同様に重合温度、単量体の添加速度及び連鎖移動剤の量や添加方法によって調整でき、また架橋反応を引き起こす共役ジエン系単量体の量によってもコントロール可能である。本発明の共重合体ラテックスにおいては、架橋密度が高くなりすぎないことが諸物性のバランスを保つために必要であることから、たとえば重合後期に重合転化率が９５％を超えてから連鎖移動剤を連続的に添加する方法、重合が進行するに従って全単量体中の共役ジエン系単量体の比率を少なくする方法、重合後期に炭化水素化合物を添加してラテックス粒子を膨潤させる方法などにより、過度の架橋体が生成しないようにすることが有効である。 The polystyrene-converted weight average molecular weight (Mw) of the copolymer latex film dissolved in tetrahydrafuran can be controlled by appropriately setting the polymerization temperature, the monomer addition rate, and the amount of chain transfer agent. The Mw / Mn ratio, that is, the molecular weight distribution of the copolymer portion obtained by polymerization, increases as the crosslink density increases. The Mw / Mn ratio can be adjusted by the polymerization temperature, the addition rate of the monomer, the amount of the chain transfer agent and the addition method as described above, and can also be controlled by the amount of the conjugated diene monomer causing the crosslinking reaction. is there. In the copolymer latex of the present invention, since it is necessary to maintain the balance of physical properties that the crosslinking density does not become too high, for example, the chain transfer agent after the polymerization conversion rate exceeds 95% in the latter stage of polymerization. By continuously adding, a method of decreasing the ratio of conjugated diene monomer in all monomers as polymerization proceeds, a method of adding a hydrocarbon compound in the late stage of polymerization and swelling latex particles, etc. It is effective to prevent the formation of an excessive cross-linked product.
本発明の共重合体ラテックスの重合には、必要に応じて酸素補足剤、キレート剤、分散剤等の公知の添加剤を用いることも差し支えなく、これらは種類、使用量ともに特に限定されず、適宜適量使用することが出来る。更には消泡剤、老化防止剤、防腐剤、抗菌剤、難燃剤、紫外線吸収剤などの公知の添加剤を用いることも差し支えなく、これらも種類、使用量ともに特に限定されず、適宜適量使用することが出来る。また、本発明の共重合体ラテックスは、その使用目的に応じて他のラテックスと適宜適量ブレンドすることもできる。 For the polymerization of the copolymer latex of the present invention, known additives such as oxygen scavengers, chelating agents, and dispersing agents may be used as necessary, and these are not particularly limited in both type and amount used. An appropriate amount can be used as appropriate. Furthermore, known additives such as antifoaming agents, anti-aging agents, antiseptics, antibacterial agents, flame retardants, and UV absorbers may be used. I can do it. Further, the copolymer latex of the present invention can be appropriately blended with other latexes depending on the purpose of use.
本発明の共重合体ラテックスの製造にあたって、単量体ならびにその他の成分の添加方法については特に制限されるものではなく、一括添加方法、分割添加方法、連続添加方法、パワーフィード方法の何れでも採用することができる。また、本発明においては、一段重合、二段重合又は多段階重合等何れも採用することができる。 In the production of the copolymer latex of the present invention, the method for adding the monomer and other components is not particularly limited, and any of batch addition method, divided addition method, continuous addition method, and power feed method is adopted. can do. In the present invention, any one of single-stage polymerization, two-stage polymerization, and multi-stage polymerization can be employed.
本発明の共重合体ラテックスを使用する紙塗工用組成物は、顔料として、例えば、カオリンクレー、炭酸カルシウム、タルク、硫酸バリウム、酸化チタン、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をそれぞれ単独または混合して使用することができる。
また、紙塗工用組成物中の共重合体ラテックスの含有量は顔料１００重量部（固形分）に対して２〜２０重量部（固形分）を使用することが好ましい。共重合体ラテックスの含有量が２重量部以下では顔料を充分に接着できず好ましくなく、２０重量部を超えると不透明度や白紙光沢が低下して好ましくない。
The composition for paper coating using the copolymer latex of the present invention is, for example, an inorganic pigment such as kaolin clay, calcium carbonate, talc, barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide, and satin white as a pigment. Alternatively, organic pigments such as polystyrene latex can be used alone or in combination.
The content of the copolymer latex in the paper coating composition is preferably 2 to 20 parts by weight (solid content) with respect to 100 parts by weight (solid content) of the pigment. If the content of the copolymer latex is 2 parts by weight or less, it is not preferable because the pigment cannot be sufficiently adhered, and if it exceeds 20 parts by weight, the opacity and white paper gloss are lowered.
また、必要に応じて澱粉、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、カルボキシメチルセルロースなどの水溶性合成バインダーなどを使用しても差し支えない。さらに、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等を本発明の共重合体ラテックスと併用してもよい。 If necessary, modified starches such as starch, oxidized starch and esterified starch, natural binders such as soybean protein and casein, or water-soluble synthetic binders such as polyvinyl alcohol and carboxymethyl cellulose may be used. Further, synthetic latex such as polyvinyl acetate latex and acrylic latex may be used in combination with the copolymer latex of the present invention.
本発明の共重合体ラテックスを用いて紙塗工用組成物を調整する際には、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、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（アルギン酸ナトリウムなど）を必要に応じて添加しても良い。 In preparing a paper coating composition using the copolymer latex of the present invention, other auxiliary agents such as a dispersant (sodium pyrophosphate, sodium polyacrylate, sodium hexametaphosphate, etc.), antifoaming Agent (polyglycol, fatty acid ester, phosphate ester, silicone oil, etc.), leveling agent (funnel oil, dicyandiamide, urea, etc.), preservative, mold release agent (calcium stearate, paraffin emulsion, etc.), fluorescent dye, color water retention An improver (such as sodium alginate) may be added as necessary.
さらに、紙塗工用組成物を塗工用紙へ塗布する方法には、公知の技術、例えばエアナイフコーター、カーテンコーター、ブレードコーター、ロールコーター、バーコーターなどのいずれの塗工機を使用しても差し支えない。また、塗工後、表面を乾燥し、カレンダーリングなどにより仕上げる。 Furthermore, as a method for applying the paper coating composition to the coated paper, any known technique such as an air knife coater, curtain coater, blade coater, roll coater, bar coater or the like may be used. There is no problem. Also, after coating, the surface is dried and finished by calendaring or the like.
以下、実施例を挙げて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％は特に断りのない限り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評価は次の方法に拠った。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples, unless the summary is exceeded. In the examples, parts and percentages indicating percentages are based on weight unless otherwise specified. In addition, various physical properties in the examples were evaluated by the following methods.
共重合体ラテックスフィルムのテトラヒドラフラン溶解分の重量平均分子量の測定
＜試料調整方法＞
ラテックスフィルムを作成し、テトラヒドラフラン（液クロ用）に溶解し、ラテックスフィルムの可溶部が、テトラヒドラフラン（液クロ用）１０ｍｌ中に約０．０２ｇとなるように調整した。
溶解後、ディスポーザブルフィルター（仕様：島津製作所、液クロ・非水系１３Ｎ 孔径０．４５μｍ）でろ過し、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。
＜ＧＰＣ条件＞
測定装置：島津製作所ＬＣ−１０ＡＶＰ
データ処理装置：クロマトパック Ｃ−Ｒ７Ａｐｌｕｓ
分析カラム
：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ―８０２．５
：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ―８０５
：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ―８０６
ガードカラム：島津製作所Ｓｈｉｍ-ｐａｃｋ ＧＰＣ-２０００Ｐ
カラムオーブン：５０℃
キャリアー液：テトラヒドロフラン（液クロ用）
流量：１ｍｌ/ｍｉｎ
検出器：ＵＶ（２５４ｎｍ）
サンプル注入量：１００μｌ
Measurement of weight average molecular weight of tetrahydrafuran dissolved in copolymer latex film <Sample preparation method>
A latex film was prepared and dissolved in tetrahydrafuran (for liquid chromatography), and the soluble part of the latex film was adjusted to be about 0.02 g in 10 ml of tetrahydrafuran (for liquid chromatography).
After dissolution, the solution was filtered with a disposable filter (specifications: Shimadzu Corporation, liquid chromatography / non-aqueous 13N pore size 0.45 μm) and measured by gel permeation chromatography (GPC).
<GPC conditions>
Measuring device: Shimadzu LC-10AVP
Data processing device: Chromatopack C-R7Aplus
Analytical column: Shodex GPC KF-802.5
: Shodex GPC KF-805
: Shodex GPC KF-806
Guard column: Shimadzu Shim-pack GPC-2000P
Column oven: 50 ° C
Carrier liquid: Tetrahydrofuran (for liquid chromatography)
Flow rate: 1 ml / min
Detector: UV (254 nm)
Sample injection volume: 100 μl
共重合体ラテックスの数平均粒子径の測定
共重合体ラテックスの数平均粒子径を動的光散乱法により測定した。尚、測定に際しては、ＦＰＡＲ−１０００（大塚電子製）を使用した。
Measurement of number average particle size of copolymer latex The number average particle size of the copolymer latex was measured by a dynamic light scattering method. In the measurement, FPAR-1000 (manufactured by Otsuka Electronics) was used.
共重合体ラテックス（ａ）の合成
耐圧製の重合反応器に、重合水１７７部、炭酸水素ナトリウム０．０１部、アルキルベンゼンスルホン酸ナトリウム１．３５部、アルキルジフェニルエーテルジスルホン酸ナトリウム０．１部を仕込み、十分攪拌した後、表１に示した各単量体および他の化合物を加えて７０℃にて重合を開始し、５時間反応させた。さらに２段目として表１に示した各単量体および他の化合物を４．５時間にわたって連続的に添加し重合を継続した。さらに３段目として表１に示した各単量体および他の化合物を１時間にわたって連続的に添加し重合を継続した。重合転化率が９８％を超えた時点で重合を終了した。次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去しラテックス（ａ）を得た。
Synthesis of copolymer latex (a) A polymerization reactor made of pressure resistant polymer was charged with 177 parts of polymerized water, 0.01 part of sodium hydrogencarbonate, 1.35 parts of sodium alkylbenzenesulfonate, and 0.1 part of sodium alkyldiphenyl ether disulfonate. After sufficiently stirring, each monomer and other compounds shown in Table 1 were added, polymerization was started at 70 ° C., and the reaction was allowed to proceed for 5 hours. Furthermore, each monomer and other compounds shown in Table 1 as the second stage were continuously added over 4.5 hours to continue the polymerization. Furthermore, each monomer and other compounds shown in Table 1 as the third stage were continuously added over 1 hour to continue the polymerization. The polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (a).
共重合体ラテックス（ｂ）の合成
耐圧製の重合反応器に、重合水２５０部、アルキルベンゼンスルホン酸ナトリウム１．５部を仕込み、十分攪拌した後、表１に示す１段目の各単量体および他の化合物を加えて６５℃にて重合を開始し５．５時間反応させた。次いで表１に示す２段目の各単量体および他の化合物を３．５時間にわたって連続的に添加し７５℃にて重合を継続した。さらに表１に示す３段目の各単量体および他の化合物を１時間にわたって連続的に添加し重合させた。重合転化率が９８％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留により未反応単量体および他の低沸点化合物を除去し、共重合体ラテックス（ｂ）を得た。
Synthesis of copolymer latex (b) A polymerization reactor made of pressure-resistant polymer was charged with 250 parts of polymerization water and 1.5 parts of sodium alkylbenzenesulfonate, and after sufficient stirring, each monomer in the first stage shown in Table 1 And other compounds were added and polymerization was started at 65 ° C. and reacted for 5.5 hours. Next, each monomer and other compounds in the second stage shown in Table 1 were continuously added over 3.5 hours, and polymerization was continued at 75 ° C. Furthermore, the monomers in the third stage shown in Table 1 and other compounds were continuously added over 1 hour for polymerization. The polymerization was terminated when the polymerization conversion rate exceeded 98%.
Next, the obtained copolymer latex is adjusted to pH 7 with sodium hydroxide, and unreacted monomers and other low-boiling compounds are removed by distillation under reduced pressure to obtain a copolymer latex (b). It was.
共重合体ラテックス（ｃ）の合成
耐圧製の重合反応器に、重合水１７５部、アルキルベンゼンスルホン酸ナトリウム１．０５部、アルキルジフェニルエーテルジスルホン酸ナトリウム０．７部、炭酸水素ナトリウム０．０１部を仕込み、十分攪拌した後、表１に示す各単量体および他の化合物を加えて７５℃にて重合を開始し、５時間反応させた。さらに表１に示す２段目の各単量体および他の化合物を３．５時間にわたって連続的に添加し７０℃で重合を継続した。さらに表１に示す３段目の各単量体および他の化合物を１時間にわたって連続的に添加し７２℃で重合を継続した。重合転化率が９８％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去しラテックス（ｃ）を得た。
Synthesis of copolymer latex (c) Charged polymerization reactor is charged with 175 parts of polymerized water, 1.05 parts of sodium alkylbenzene sulfonate, 0.7 parts of sodium alkyldiphenyl ether disulfonate, and 0.01 parts of sodium bicarbonate. After sufficiently stirring, each monomer and other compounds shown in Table 1 were added, polymerization was started at 75 ° C., and the reaction was allowed to proceed for 5 hours. Furthermore, each monomer and other compounds in the second stage shown in Table 1 were continuously added over 3.5 hours, and polymerization was continued at 70 ° C. Furthermore, the monomers and other compounds in the third stage shown in Table 1 were continuously added over 1 hour, and polymerization was continued at 72 ° C. The polymerization was terminated when the polymerization conversion rate exceeded 98%.
Next, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (c).
共重合体ラテックス（ｄ）の合成
耐圧製の重合反応器に、重合水１７５部、アルキルベンゼンスルホン酸ナトリウム１．０５部、アルキルジフェニルエーテルジスルホン酸ナトリウム０．７部を仕込み、十分攪拌した後、表１に示す各単量体および他の化合物を加えて、４２℃で６時間反応させた。さらに表１に示す２段目の各単量体および他の化合物を４時間で連続的に添加し、６５℃で重合を継続した。続いて表１に示す３段目の各単量体および他の化合物を１時間にわたって連続的に添加し７５℃で重合を継続した。重合転化率が９８％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去し、ラテックス（ｄ）を得た。
Synthesis of copolymer latex (d) A polymerization reactor made of pressure resistant polymer was charged with 175 parts of polymerized water, 1.05 part of sodium alkylbenzene sulfonate, and 0.7 part of sodium alkyldiphenyl ether disulfonate. Each monomer and other compounds shown in the above were added and reacted at 42 ° C. for 6 hours. Further, each monomer in the second stage shown in Table 1 and other compounds were continuously added in 4 hours, and polymerization was continued at 65 ° C. Subsequently, the monomers in the third stage shown in Table 1 and other compounds were continuously added over 1 hour, and polymerization was continued at 75 ° C. The polymerization was terminated when the polymerization conversion rate exceeded 98%.
Next, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (d).
共重合体ラテックス（ｅ）の合成
耐圧製の重合反応器に、重合水１３０部、アルキルベンゼンスルホン酸ナトリウム１．２６部を仕込み、十分攪拌した後、表１に示す各単量体および他の化合物を加えて、６５℃で重合を開始した。重合転化率が９５％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去し、ラテックス（ｅ）を得た。
Synthesis of copolymer latex (e) Into a pressure-resistant polymerization reactor, 130 parts of polymerized water and 1.26 parts of sodium alkylbenzene sulfonate were charged and stirred sufficiently, and then each monomer and other compounds shown in Table 1 were mixed. Was added to initiate polymerization at 65 ° C. The polymerization was terminated when the polymerization conversion rate exceeded 95%.
Subsequently, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (e).
共重合体ラテックス（ｆ）の合成
耐圧製の重合反応器に、重合水１８０部、アルキルベンゼンスルホン酸ナトリウム１．２０部、アルキルジフェニルエーテルジスルホン酸ナトリウム０．３部、炭酸水素ナトリウム０．０５部を仕込み、十分攪拌した後、表２に示す各単量体および他の化合物を加えて、５５℃で５時間反応させた。さらに表２に示す２段目の各単量体および他の化合物を０．５時間にわたって連続的に添加し７０℃にて重合を継続した。さらに表２に示す３段目の各単量体および他の化合物を０．５時間にわたって連続的に添加し８０℃で重合を継続した。重合転化率が９５％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去し、ラテックス（ｆ）を得た。
Synthesis of copolymer latex (f) Charged polymerization reactor was charged with 180 parts of polymerized water, 1.20 parts of sodium alkylbenzene sulfonate, 0.3 part of sodium alkyldiphenyl ether disulfonate, and 0.05 part of sodium bicarbonate. After sufficiently stirring, each monomer and other compounds shown in Table 2 were added and reacted at 55 ° C. for 5 hours. Furthermore, the monomers and other compounds in the second stage shown in Table 2 were continuously added over 0.5 hours, and polymerization was continued at 70 ° C. Furthermore, the monomers and other compounds in the third stage shown in Table 2 were continuously added over 0.5 hours, and polymerization was continued at 80 ° C. The polymerization was terminated when the polymerization conversion rate exceeded 95%.
Next, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (f).
共重合体ラテックス（ｇ）の合成
耐圧製の重合反応器に、重合水２３５部、アルキルベンゼンスルホン酸ナトリウム２．１０部を仕込み、十分攪拌した後、表２に示す各単量体および他の化合物を加えて６５℃で４時間反応させた。さらに表２に示す２段目の各単量体および他の化合物を４時間にわたって連続的に添加し６８℃で重合を継続した。さらに表２に示す３段目の各単量体および他の化合物を反応温度０．５時間にわたって連続的に添加し７０℃で重合を継続した。重合転化率が９７％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去し、ラテックス（ｇ）を得た。
Synthesis of copolymer latex (g) Into a polymerization reactor made of pressure-resistant polymer, 235 parts of polymerization water and 2.10 parts of sodium alkylbenzene sulfonate were charged and sufficiently stirred, and then each monomer and other compounds shown in Table 2 were mixed. And reacted at 65 ° C. for 4 hours. Furthermore, the monomers and other compounds in the second stage shown in Table 2 were continuously added over 4 hours, and polymerization was continued at 68 ° C. Furthermore, the monomers and other compounds in the third stage shown in Table 2 were continuously added over a reaction temperature of 0.5 hours, and polymerization was continued at 70 ° C. The polymerization was terminated when the polymerization conversion rate exceeded 97%.
Next, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (g).
共重合体ラテックス（ｈ）の合成
耐圧製の重合反応器に、重合水１００部、炭酸水素ナトリウム０．１５部、アルキルベンゼンスルホン酸ナトリウム０．７５部を仕込み、十分攪拌した後、表２に示す各単量体および他の化合物を加えて６５℃で４時間反応させた。さらに表２に示す２段目の各単量体および他の化合物を４時間にわたって連続的に添加し６８℃で重合を継続した。重合転化率が９８％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去し、ラテックス（ｈ）を得た。
Synthesis of copolymer latex (h) 100 parts of polymerization water, 0.15 part of sodium hydrogen carbonate, and 0.75 part of sodium alkylbenzene sulfonate were charged into a polymerization reactor made of pressure resistant, and after stirring sufficiently, the results are shown in Table 2. Each monomer and other compounds were added and reacted at 65 ° C. for 4 hours. Furthermore, the monomers and other compounds in the second stage shown in Table 2 were continuously added over 4 hours, and polymerization was continued at 68 ° C. The polymerization was terminated when the polymerization conversion rate exceeded 98%.
Next, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (h).
共重合体ラテックス（ｉ）の合成
耐圧製の重合反応器に、重合水１５０部、炭酸水素ナトリウム０．０５部、アルキルベンゼンスルホン酸ナトリウム１．2５部を仕込み、十分攪拌した後、表２に示す各単量体および他の化合物を加えて７０℃で４時間反応させた。さらに表２に示す２段目の各単量体および他の化合物を４時間にわたって連続的に添加し７０℃で重合を継続した。さらに表２に示す３段目の各単量体および他の化合物を反応温度０．５時間にわたって連続的に添加し７０℃で重合を継続した。重合転化率が９８％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去し、ラテックス（ｉ）を得た。
Synthesis of copolymer latex (i) A polymerization reactor made of pressure-resistant polymer was charged with 150 parts of polymerized water, 0.05 part of sodium hydrogen carbonate, and 1.25 parts of sodium alkylbenzene sulfonate, and after stirring sufficiently, the results are shown in Table 2. Each monomer and other compounds were added and reacted at 70 ° C. for 4 hours. Further, each monomer and other compounds in the second stage shown in Table 2 were continuously added over 4 hours, and polymerization was continued at 70 ° C. Furthermore, the monomers and other compounds in the third stage shown in Table 2 were continuously added over a reaction temperature of 0.5 hours, and polymerization was continued at 70 ° C. The polymerization was terminated when the polymerization conversion rate exceeded 98%.
Next, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (i).
共重合体ラテックス（ｊ）の合成
耐圧製の重合反応器に、重合水１2０部、炭酸水素ナトリウム０．０５部、アルキルベンゼンスルホン酸ナトリウム１．2５部を仕込み、十分攪拌した後、表２に示す各単量体および他の化合物を加えて６５℃で４時間反応させた。さらに表２に示す２段目の各単量体および他の化合物を５時間にわたって連続的に添加し７０℃で重合を継続した。さらに表２に示す３段目の各単量体および他の化合物を反応温度０．５時間にわたって連続的に添加し７０℃で重合を継続した。重合転化率が９８％を超えた時点で重合を終了した。
次いで、得られた共重合体ラテックスを、水酸化ナトリウムを用いてｐＨ７に調整し、加熱減圧蒸留で未反応単量体および他の低沸点化合物を除去し、ラテックス（ｊ）を得た。
Synthesis of copolymer latex (j) A polymerization reactor made of pressure-resistant polymer was charged with 120 parts of polymerization water, 0.05 part of sodium hydrogen carbonate, and 1.25 parts of sodium alkylbenzenesulfonate, and after stirring sufficiently, the results are shown in Table 2. Each monomer and other compounds were added and reacted at 65 ° C. for 4 hours. Furthermore, the monomers and other compounds in the second stage shown in Table 2 were continuously added over 5 hours, and polymerization was continued at 70 ° C. Furthermore, the monomers and other compounds in the third stage shown in Table 2 were continuously added over a reaction temperature of 0.5 hours, and polymerization was continued at 70 ° C. The polymerization was terminated when the polymerization conversion rate exceeded 98%.
Next, the obtained copolymer latex was adjusted to pH 7 using sodium hydroxide, and unreacted monomers and other low-boiling compounds were removed by heating under reduced pressure to obtain latex (j).
紙塗工用組成物の作製と評価
下記に示した配合処方に従って共重合体ラテックスａ〜ｈを用い、水酸化ナトリウム水溶液でｐＨ９.５に調整して紙塗工用組成物を作製した。
（紙塗工用組成物の配合処方）
配合処方
カオリンクレー ６０部
重質炭酸カルシウム ４０部
変性デンプン ４部
共重合体ラテックス １０部
・・・・・・・・・・・・・・・・・・・・・・・
固形分濃度 ６４％
Preparation and Evaluation of Paper Coating Composition According to the formulation shown below, copolymer latexes a to h were used and adjusted to pH 9.5 with an aqueous sodium hydroxide solution to prepare a paper coating composition.
(Formulation formulation of paper coating composition)
Formulated kaolin clay 60 parts Heavy calcium carbonate 40 parts Modified starch 4 parts Copolymer latex 10 parts ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・
Solid content concentration 64%
塗工紙の作製と評価
塗工原紙（坪量６７ｇ／ｍ２）に、上記の紙塗工用組成物を片面あたりの塗被量が１３g／ｍ２となるようにワイヤーバーを用いて塗工し乾燥した後、線圧６０ｋｇ／ｃｍ、温度５０℃の条件でカレンダー処理を行って塗工紙を得た。得られた塗工紙を各試験に供して評価し、その結果を表１および表２に示した。
Preparation and Evaluation of Coated Paper Coated paper (basis weight 67 g / m 2 ) is coated with the above-mentioned composition for paper coating using a wire bar so that the coating amount per side is 13 g / m 2. After being worked and dried, a calendar treatment was performed under conditions of a linear pressure of 60 kg / cm and a temperature of 50 ° C. to obtain a coated paper. The obtained coated paper was subjected to each test and evaluated, and the results are shown in Tables 1 and 2.
紙塗工用組成物の再分散性の評価
ＮＢＲ黒ゴム板上に各組成物サンプルを並べて＃６ワイヤーバーにて塗布し６０℃熱風循環式オーブンにて３分間乾燥させた後、３０℃の流水で１分間洗浄してＮＢＲ黒ゴム板上に残った組成物の皮膜を目視にて観察した。皮膜の付着の少ない再分散性に優れるものを◎、皮膜の付着の多い再分散性に劣るものを×とし、下記のとおり目視にて相対的に評価した。
（優）◎ ＞ ○ ＞ △ ＞ ×（劣）
Evaluation of Redispersibility of Composition for Paper Coating Each composition sample was placed on an NBR black rubber plate, applied with a # 6 wire bar, dried in a 60 ° C. hot air circulating oven for 3 minutes, and then heated at 30 ° C. The film of the composition which was washed with running water for 1 minute and remained on the NBR black rubber plate was visually observed. A film having excellent redispersibility with little adhesion of the film was evaluated as る も の, and a film having poor redispersibility with large adhesion of the film was evaluated as x.
(Excellent) ◎>○>△> × (poor)
塗工紙のドライピック強度の評価
ＲＩ印刷機で各塗工紙試料を同時に印刷した際のピッキングの程度を肉眼で判定し、５級（優）から１級（劣）まで相対的に目視評価した。
Evaluation of dry pick strength of coated paper The degree of picking when each coated paper sample is printed at the same time with an RI printing machine is judged with the naked eye, and relatively visually evaluated from grade 5 (excellent) to grade 1 (inferior). did.
塗工紙の耐ブリスター性の評価
２２℃×６５％ＲＨの恒温恒湿器中で調湿した各塗工紙試料の試験片（５ｃｍ×５ｃｍ）について、所定の温度に調節したオイルバスへ浸漬し、ブリスターが発生するか否かを観察した。オイルバスの温度を変化させて同様に試験を行い、ブリスターが発生する温度を測定した。発生温度が高いものほど耐ブリスター性に優れる。
Evaluation of blister resistance of coated paper Each test piece (5 cm x 5 cm) of each coated paper sample conditioned in a constant temperature and humidity chamber of 22 ° C x 65% RH is immersed in an oil bath adjusted to a predetermined temperature. Then, it was observed whether or not blisters were generated. The same test was performed while changing the temperature of the oil bath, and the temperature at which blisters were generated was measured. The higher the generation temperature, the better the blister resistance.
表１、２に示すとおり、本発明による共重合体ラテックスａ〜ｅを用いた紙塗工用組成物はいずれも再分散性が良好で、かつこれら紙塗工用組成物を塗工して得られた塗工紙は、いずれもドライピック強度及び耐ブリスター性が良好である。 As shown in Tables 1 and 2, the paper coating compositions using the copolymer latexes a to e according to the present invention all have good redispersibility, and these paper coating compositions are coated. All of the obtained coated papers have good dry pick strength and blister resistance.
比較例１は、ブタジエン量が２０重量％未満で、Ｍｗが１０以上であることから、塗工紙のドライピック強度が大きく劣り、さらに耐ブリスター性も劣る。
比較例２及び３では、Ｍｗが範囲外であることから、塗工紙のドライピック強度が劣る。
比較例４は、ブタジエン量が６９．５重量％を超えており、紙塗工用組成物の再分散性が劣る。
比較例５は、Ｍｗが２０００未満であることから、塗工紙のドライピック強度が劣る。
In Comparative Example 1, since the amount of butadiene is less than 20% by weight and the Mw is 10 or more, the dry pick strength of the coated paper is greatly inferior and the blister resistance is also inferior.
In Comparative Examples 2 and 3, since the Mw is out of the range, the dry pick strength of the coated paper is inferior.
In Comparative Example 4, the amount of butadiene exceeds 69.5% by weight, and the redispersibility of the paper coating composition is poor.
Since the comparative example 5 has Mw of less than 2000, the dry pick strength of the coated paper is inferior.
上記のとおり、本発明の共重合体ラテックスは、紙塗工用組成物に配合すると、再分散性に優れることにより、塗工操業性に優れる。また、本発明の紙塗工用組成物を塗工した塗工紙は、ドライピック強度にも耐ブリスター性にも優れ、極めて有用である。 As described above, the copolymer latex of the present invention is excellent in coating operability by being excellent in redispersibility when blended in a paper coating composition. Moreover, the coated paper coated with the paper coating composition of the present invention is excellent in dry pick strength and blister resistance, and is extremely useful.
Claims (4)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6454435B1 (en) * | 2017-07-25 | 2019-01-16 | 日本エイアンドエル株式会社 | Lubricant dispersion stability improving method and paper coating composition |
| JP2021195549A (en) * | 2020-06-10 | 2021-12-27 | 日本エイアンドエル株式会社 | Polymer latex |
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| JPH07173798A (en) * | 1993-12-17 | 1995-07-11 | Mitsui Toatsu Chem Inc | Composition for coated paper |
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| JPH09316131A (en) * | 1996-06-03 | 1997-12-09 | Mitsui Petrochem Ind Ltd | Copolymer latex and composition for coated paper |
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| JPH07173798A (en) * | 1993-12-17 | 1995-07-11 | Mitsui Toatsu Chem Inc | Composition for coated paper |
| JPH0949191A (en) * | 1995-08-01 | 1997-02-18 | Sanyo Chem Ind Ltd | Lustering coating agent for paper |
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| JP6454435B1 (en) * | 2017-07-25 | 2019-01-16 | 日本エイアンドエル株式会社 | Lubricant dispersion stability improving method and paper coating composition |
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