JP2005029679A - Ecofriendly copolymer latex excellent in long-term storage stability - Google Patents
Ecofriendly copolymer latex excellent in long-term storage stability Download PDFInfo
- Publication number
- JP2005029679A JP2005029679A JP2003195898A JP2003195898A JP2005029679A JP 2005029679 A JP2005029679 A JP 2005029679A JP 2003195898 A JP2003195898 A JP 2003195898A JP 2003195898 A JP2003195898 A JP 2003195898A JP 2005029679 A JP2005029679 A JP 2005029679A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer latex
- parts
- polymerization
- copolymer
- 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.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 85
- 229920000126 latex Polymers 0.000 title claims abstract description 76
- 239000004816 latex Substances 0.000 title claims abstract description 76
- 238000003860 storage Methods 0.000 title abstract description 15
- 230000007774 longterm Effects 0.000 title abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 239000007787 solid Substances 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 claims abstract 2
- -1 methylol group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- UEFCKYIRXORTFI-UHFFFAOYSA-N 1,2-thiazolidin-3-one Chemical compound O=C1CCSN1 UEFCKYIRXORTFI-UHFFFAOYSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 35
- 239000000203 mixture Substances 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 8
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 abstract description 4
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 2
- 238000003915 air pollution Methods 0.000 abstract 1
- 208000008842 sick building syndrome Diseases 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 73
- 238000006243 chemical reaction Methods 0.000 description 38
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- 239000003995 emulsifying agent Substances 0.000 description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 20
- 239000003755 preservative agent Substances 0.000 description 16
- 239000002211 L-ascorbic acid Substances 0.000 description 15
- 235000000069 L-ascorbic acid Nutrition 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229960005070 ascorbic acid Drugs 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 14
- 238000001256 steam distillation Methods 0.000 description 14
- 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 13
- 238000009835 boiling Methods 0.000 description 13
- 230000002335 preservative effect Effects 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 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 11
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 10
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 10
- 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 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 230000002421 anti-septic effect Effects 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 235000011118 potassium hydroxide Nutrition 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material 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
- 238000000576 coating method Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000009408 flooring Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000003905 indoor air pollution Methods 0.000 description 3
- 239000011120 plywood Substances 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
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 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
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 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
- 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
- BIRJAUKLRAMLEV-UHFFFAOYSA-N 1-phenylethenoxymethylbenzene Chemical compound C=1C=CC=CC=1C(=C)OCC1=CC=CC=C1 BIRJAUKLRAMLEV-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
- 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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- 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
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 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
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000894006 Bacteria Species 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- FVCPXLWAKNJIKK-UHFFFAOYSA-N Dimexano Chemical compound COC(=S)SSC(=S)OC FVCPXLWAKNJIKK-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- VOOVDZMAQQVAEW-PFONDFGASA-N [(z)-2-methyl-4-phenylpent-3-en-2-yl]benzene Chemical compound C=1C=CC=CC=1C(/C)=C\C(C)(C)C1=CC=CC=C1 VOOVDZMAQQVAEW-PFONDFGASA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N benzocyclopentane Natural products C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000003792 electrolyte Substances 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
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- CNFQJGLKUZBUBD-TXHUMJEOSA-N hexa-1,5-diene;(3e)-hexa-1,3-diene;(4e)-hexa-1,4-diene Chemical class CC\C=C\C=C.C\C=C\CC=C.C=CCCC=C CNFQJGLKUZBUBD-TXHUMJEOSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- 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
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N pentadiene group Chemical class C=CC=CC PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229960002447 thiram Drugs 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、長期保存安定性に優れる環境対応型共重合体ラテックスに関する。更には、腐敗しにくく長期保存安定性に優れ、かつ、ホルムアルデヒド、スチレンなどの室内空気汚染の原因物質を含有しない接着剤組成物や塗料に用いられる共重合体ラテックスに関する。
【０００２】
【従来の技術】ＳＢＲ、ＮＢＲ、ＭＢＲ等の合成ゴムラテックスやスチレン−アクリル等のアクリル系エマルション（以下、広義に共重合体ラテックスと総称する）は、従来から一般塗料組成物、紙塗工用組成物、各種接着剤組成物に広く利用されてきている。これら共重合体ラテックスは水性であるために製造後の貯槽タンクでの保存、海上コンテナ、コンテナ、ドラム缶、一兎缶に充填出荷された後の保存中に菌類が繁殖して異臭を発生させるなどの問題があり、これらを解決する目的で防腐剤が製品の有り姿重量に対して数十ｐｐｍから数千ｐｐｍ配合されることが知られている。
【０００３】
一方、室内空気汚染（シックハウス）の問題から室内用塗料組成物や室内用建材であるフローリング材料、突き板、化粧合板、家具用化粧版、壁紙用接着剤組成物や自動車の内装材料から室内空気汚染の原因物質であるホルムアルデヒド、スチレンなどが放散しないことが強く求められるようになり、そのため、これら用途においては水系接着剤が使用されると共にこれら用途に使用できる防腐剤についても制限されてきている。つまり、安価で防腐効果の優れたホルムアルデヒド系防腐剤であるホルマリンやトリアジンが使用できなくなってきている。
【０００４】
そこで、例えば特公昭６０−５４２８１号公報（特許文献１）のごとく２−メチル−４−イソチアゾリン−３−オン（以下Ｈ−ＭＩＴと称する）、及びその塩素付加物（以下Ｃ−ＭＩＴと称する）、あるいは臭素付加物の混合物を防腐剤として添加する技術が開示されている。しかし、これらを単独で使用しても防腐効果が低く長期保存安定性に劣る。
また、特開２００１−３０３４８０号公報（特許文献２）や特開２００１−３０３４８２号公報（特許文献３）には前記の一般式（１）で表わされるベンゾイソチアゾリン系化合物（以下ＢＩＴと称する）を含有することを特徴とする紙塗工用ラテックスが紹介されているが、ＢＩＴ単独では防腐効果が低く長期保存安定性は未だ十分とは言い難い。
更に、特開２００１−３０３４８１号公報（特許文献４）にＢＩＴと下記の一般式（２）で表わされるハロゲン化脂肪族ニトロアルコールとを併用する技術、特開２００２−８８６８１号公報（特許文献５）にＨ−ＭＩＴと一般式（２）で表わされるハロゲン化脂肪族ニトロアルコールを併用する技術などが開示されている。
【０００５】
【化２】ハロゲン化脂肪族ニトロアルコール
（式中、Ｒ１は水素原子、ハロゲン原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表わし、Ｒ２は水素原子又は炭素数１〜４のアルキル基を、Ｘはハロゲン原子を表わす）
【０００７】
しかし、機構は不明であるが、このようなハロゲン化脂肪族ニトロアルコールは、使用条件によっては分解すると極微量のホルムアルデヒドを発生させる可能性があり、その使用条件が制限される場合がある。
また、特開２００１−１８１１１３号公報（特許文献６）や特表２００１ −５１５０１６号（特許文献７）には、防腐効果に対するＢＩＴとＨ−ＭＩＴの相乗効果に関する技術開示があるが、それらを特定組成の共重合体エマルジョンに適用することに関し何ら開示されておらず、特に本発明にて規定する酸化還元電位との関係についての技術開示はない。
【０００８】
【特許文献１】特公昭６０−５４２８１号公報
【特許文献２】特開２００１−３０３４８０号公報
【特許文献３】特開２００１−３０３４８１号公報
【特許文献４】特開２００１−３０３４８２号公報
【特許文献５】特開２００２−８８６８１号公報
【特許文献６】特開２００１−１８１１１３号公報
【特許文献７】特表２００１ −５１５０１６号公報
【０００９】
【発明が解決しようとする課題】
本発明者らは、上記課題を解決すべく長期保存安定性に優れる環境対応型共重合体ラテックスについて検討を重ねた結果、特定の酸化還元電位にコントロールされた特定単量体組成の共重合体ラテックスにＨ−ＭＩＴとＢＩＴの特定量を併用して配合することで、室内空気汚染（シックハウス）の原因物質を放散せず、かつ長期保存安定性に優れた環境対応型共重合体ラテックスを提供できることを見出し、本発明を完成するに至った。
【００１０】
【課題を解決するための手段】
すなわち本発明は、
不飽和カルボン酸アルキルエステル系単量体および、これらと共重合可能な他のビニル系単量体（ただし、芳香族ビニル系単量体とメチロール基含有単量体を除く）からなる単量体を乳化重合して得られる共重合体ラテックス１００重量部（固形分換算）に対し、ＢＩＴを０．００１重量部以上および２−メチル−４−イソチアゾリン−３−オンを０．００１重量部以上含有し、かつ酸化還元電位が−１００ｍＶ〜＋３００ｍＶであることを特徴とする環境対応型共重合体ラテックスを提供するものである。
【００１１】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明における共重合体ラテックスは、不飽和カルボン酸アルキルエステル系単量体およびその他の共重合可能なビニル系単量体（ただし、芳香族ビニル系単量体とメチロール基含有単量体を除く）により構成される。
【００１２】
不飽和カルボン酸アルキルエステル系単量体としては、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、２−エチルヘキシルアクリレート等が挙げられ、１種または２種以上用いることができる。これらのうち、特にメチルメタクリレートを３０重量％以上用いることが好ましい。
【００１３】
不飽和カルボン酸アルキルエステル系単量体と共重合可能な他の単量体としては、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系単量体、エチレン系不飽和カルボン酸アミド系単量体、シアン化ビニル系単量体などが挙げられる。
【００１４】
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、１種または２種以上用いることができる。特に１，３−ブタジエンが好ましい。
エチレン系不飽和カルボン酸系単量体としては、アクリル酸、メタクリル酸、クロトン酸、フマール酸、イタコン酸、マレイン酸などが挙げられ、１種または２種以上用いることができる。特にアクリル酸、メタクリル酸、フマール酸、イタコン酸が好ましい。
不飽和カルボン酸アミド系単量体としては、例えばアクリルアミド、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、１種または２種以上用いることができる。特にアクリルアミドが好ましい。
シアン化ビニル系単量体としては、例えばアクリロニトリル、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、１種または２種以上用いることができる。特にアクリロニトリル、メタクリロニトリルが好ましい。
さらに、アミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）クリレート、ジエチルアミノエチル（メタ）アクリレート、２−ビニルピリジン、４−ビニルピリジン、塩化ビニル、塩化ビニリデンなどが挙げられ、各種用途に必要な接着性能などを付与する目的で、適時適量使用することができる。
【００１５】
上記の単量体組成については特に限定されないが、各用途でそれに必要な接着性能を満足できるよう適宜調節される。例えば、耐水性を要求される用途の場合には不飽和カルボン酸アルキルエステル系単量体としてメチルメタクリレート、脂肪族共役ジエン系単量体として１，３−ブタジエンを主な単量体組成として使用し、共重合体のガラス転移温度が−５０℃〜５０℃の範囲になるよう調節した共重合体ラテックスを使用することが望ましい。
【００１６】
また、耐候性が必要とされる用途の場合には不飽和カルボン酸アルキルエステル系単量体としてメチルメタクリレート、ブチルアクリレート、メチルメタクリレート、エチルアクリレートなどの組み合わせを主な単量体組成として、共重合体のガラス転移温度が−５０℃〜５０℃の範囲になるよう調節した共重合体ラテックスを使用することが望ましい。
【００１７】
本発明にて使用される共重合体ラテックスは、その酸化還元電位が−１００ｍＶ〜＋３００ｍＶに調整されていることが必要である。この範囲を外れると、たとえＨ−ＭＩＴとＢＩＴを共重合体成分１００重量部（固形分換算）に対し、それぞれ０．００１重量部以上存在させたとしても本発明の目的とする防腐効果が得られないため好ましくない。
【００１８】
上記共重合体ラテックスの酸化還元電位を調節する方法は特に限定されないが、通常の重合に用いられる反応開始剤としての酸化触媒、その酸化触媒の分解を促進するための還元剤、または酸化還元触媒の使用量および反応停止剤の使用量をコントロールしたり、残存する酸化剤を加熱操作や水蒸気蒸留操作によって低減したりする方法などが挙げられる。
【００１９】
本発明の共重合体ラテックスの乳化重合においては、常用の乳化剤、重合開始剤、還元剤、酸化還元触媒、炭化水素系溶剤、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。
【００２０】
重合開始剤としては、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、過硫酸アンモニウムの水溶性重合開始剤、クメンハイドロパーオキサイドの油溶性重合開始剤の使用が好ましい。
【００２１】
また、反応系内に重合開始剤とともに還元剤を存在させると、反応速度が適度に促進されるとともに残留する重合開始剤の分解を助けるので好ましく、その使用量は反応終了時点で酸化還元電位が−１００ｍＶ〜＋３００ｍＶとなるよう調節しておいたほうがよい。ただし、反応終了時点で酸化還元電位が−１００ｍＶ〜＋３００ｍＶの範囲を逸脱していても、その後の工程で酸化剤や還元剤の微量添加、加熱操作や水蒸気蒸留操作によって、最終的にＨ−ＭＩＴとＢＩＴを添加する時点で、酸化還元電位が−１００ｍＶ〜＋３００ｍＶとなっていれば本発明の効果を妨げるものではない。
【００２２】
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、また、Ｌ−アスコルビン酸、酒石酸、クエン酸などのカルボン酸類、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−アスコルビン酸が好ましい。
なお、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などの還元性スルホン酸塩は製品にホルムアルデヒドを含有させる結果となるので、本発明においては使用するものではない。
【００２３】
本発明の共重合体ラテックスの製造に使用できる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、アルキルジフェニルエーテルスルホン酸塩、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。特に、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スルホン酸塩が好ましい。
【００２４】
本発明の共重合体ラテックスの製造に使用でき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、ターピノレンや、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、ｎ−オクチルメルカプタンやｔ−ドデシルメルカプタンが好ましい。これら連鎖移動剤の量は特に限定されないが、通常、単量体１００重量部に対して０〜５重量部にて使用される。
【００２５】
また、本発明においては連鎖移動剤としてα−メチルスチレンダイマーも使用することが可能である。α−メチルスチレンダイマーには、異性体として２，４−ジフェニル−４−メチル−１−ペンテン、２，４−ジフェニル−４−メチル−２−ペンテンおよび１，１，３−トリメチル−３−フェニルインダンがあるが、本発明に使用されるα−メチルスチレンダイマーとしては、２，４−ジフェニル−４−メチル−１−ペンテンの含有量が６０重量％以上、特に８０重量％以上であることが好ましい。なお、α−メチルスチレンダイマーは沸点が高く、共重合体ラテックスの製造後もラテックス粒子中に残留するため、本発明の目的とは別の環境問題から、その使用量は単量体１００重量部に対して２重量部未満とすることが好ましい。
【００２６】
また、重合に際してペンテン、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を使用しても良い。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が、本発明の目的とは異なるもの、環境問題の観点から好適である。
【００２７】
本発明における重合方法は、一段重合、二段重合、多段階重合、シード重合、パワーフィード重合法等何れを採用してもよい。また、本発明の重合方法における各種成分の添加方法についても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、連続添加方法の何れも採用することができる。
【００２８】
本発明における環境対応型共重合体ラテックスは、その共重合体ラテックス１００重量部（固形分換算）に対し、ＢＩＴを０．００１重量部以上および２−メチル−４−イソチアゾリン−３−オンを０．００１重量部以上含有することが必要であり、その何れの含有量が０．００１重量未満でも本発明の目的とする防腐効果が得られないため好ましくない。なお、これら防腐剤を必要以上に多量に添加してもそれ以上の防腐効果は望めず却ってコストアップに繋がるため、その上限値は合計で１重量部程度である。
【００２９】
本発明における環境対応型共重合体ラテックスは、腐敗しにくく長期保存安定性に優れ、かつ、ホルムアルデヒド、スチレンなどの室内空気汚染の原因物質を含有しないため、室内用塗料組成物や室内用建材であるフローリング材料、突き板、化粧合板、家具用化粧版、壁紙用等の接着剤組成物に使用される水系接着剤として好適に使用することができるものである。
【００３０】
【実施例】
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。
【００３１】
共重合体ラテックスの粒子径の測定
数平均粒子径を動的光散乱法により測定した。測定に際しては、大塚電子製ＬＰＡ−３０００／３１００を使用した。
【００３２】
共重合体ラテックスのゲル含有量の測定
室温雰囲気にて２４時間乾燥させ、共重合体ラテックスのフィルムを作成する。そのフィルムを約１ｇ秤量し、これを４００ｃｃのトルエンに入れ４８時間膨張溶解させる。その後、これを３００メッシュの金網で濾過し、金網に捕捉されたトルエン不溶部を乾燥後秤量し、この重量のはじめのフィルム重量に占める割合をゲル含有量として重量％で算出した。
【００３３】
共重合体ラテックスのガラス転移温度の測定
室温雰囲気にて２４時間乾燥させて共重合体ラテックスのフィルムを作成し、セイコーインスツルメンツ社製示差走査熱量計（ＤＳＣ６２００）を用い、昇温速度１０℃／分の条件にてガラス転移温度を測定した。
【００３４】
共重合体ラテックスの酸化還元電位の測定
堀場製作所製 ｐＨメーターに白金（ＯＲＰ）電極を装着し、電極を２５℃に温度調節したラテックスに浸漬し安定した時の電位を測定した。
【００３５】
共重合体ラテックスのホルムアルデヒド放散量とスチレン放散量の測定
ホルムアルデヒド放散量とスチレン放散量はＪＩＳ Ａ１９０１（２００３）に準じた。共重合体ラテックス１〜１１各々２．４ｇを塗布面積０．００８ｍ２のガラス板の表面に塗布して（塗布量３００ｇ／ｍ２）、２３℃で６０分放置した。これを２０リットルの小型チャンバー内に入れ、２４時間後の放散速度をＪＩＳ Ａ１９０１（２００３）に準じて測定し、測定結果によって下記の通り評価した。
ホルムアルデヒド放散量
○・・・５（μｇ／ｍ２・ｈ）以下
△・・・５（μｇ／ｍ２・ｈ）を越えて２０（μｇ／ｍ２・ｈ）以下
×・・・２０（μｇ／ｍ２・ｈ）を越える
スチレン放散量
○・・・２０（μｇ／ｍ２・ｈ）以下
△・・・２０（μｇ／ｍ２・ｈ）を越えて１００（μｇ／ｍ２・ｈ）以下
×・・・１００（μｇ／ｍ２・ｈ）を越える
【００３６】
共重合体ラテックスの長期保存安定性の評価
▲１▼試験する各共重合体ラテックス１００ｇに対して腐敗した共重合体ラテックス（菌数１０６以上）５ｇを加え、３０℃で１０時間放置し、さらに４５℃に昇温して２４時間保った後、３０℃に戻し２４時間保管する。
▲２▼これをＴＧＣ寒天平板混釈法にて、３０℃、４８時間培養後のコロニーの数を測定する。以上が１回目の試験になる。
２回目の試験は、腐敗したラテックスを更に５ｇ加えて、▲１▼の温度条件で保管、管理し、▲２▼の方法でコロニーの数を数える。同様に、コロニーが確認されるまで（菌数１０６以上で終了）腐敗ラテックスの摂取、測定を繰り返す。コロニーが確認されるまでの繰り返しの回数で長期保存安定性を下記の通り判定した。回数の多い方が防腐効果がよい。
○・・・コロニーが確認されるまでの繰り返しの回数が１６回以上
△・・・コロニーが確認されるまでの繰り返しの回数が７回以上１５回以下
×・・・コロニーが確認されるまでの繰り返しの回数が６回以下
【００３７】
共重合体ラテックス１の作製（本発明例）
耐圧性の重合反応機に、窒素雰囲気下で純水１２０部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム（花王製ネオペレックスＮｏ２５）０．３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（日本乳化剤製ニューコール２７１Ａ）２．０部、表１に示す１段目の各単量体およびシクロヘキセン２部、ｎ−オクチルメルカプタン０．６部、Ｌ−アスコルビン酸０．１部を加えて十分攪拌した後、過硫酸カリウム０．７部を仕込み、６５℃で重合を開始した。重合転化率が９７％に達した後、重合停止剤として硫酸ヒドロキシルアミン０．２０部を添加して重合を終了した。次いで、共重合体ラテックスを苛性カリ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＨ−ＭＩＴを０．０１３部とＢＩＴ０．０４０部を添加し、これら防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス１を得た。
【００３８】
共重合体ラテックス２の作製（本発明例）
耐圧性の重合反応機に、窒素雰囲気下で純水１０５部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）１．５部、表１に示す１段目の各単量体およびα−メチルスチレンダイマー０．５部、ｔ−ドデシルメルカプタン０．３部、Ｌ−アスコルビン酸０．０５部を加えて十分攪拌した後、過硫酸カリウム１．０部を仕込み、５５℃で重合を開始した。重合転化率が７５％に達した後、表１に示す２段目の各単量体およびα−メチルスチレンダイマー０．２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（日本乳化剤製ニューコール２７１Ａ）０．３部、Ｌ−アスコルビン酸０．０５部、過硫酸カリウム０．３部、純水２０部を仕込み、反応温度を６５℃に上げて更に反応を継続した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．１０部を添加して重合を終了した。次いで共重合体ラテックスを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＨ−ＭＩＴを０．０１０部とＢＩＴ０．０５０部を添加し、これら防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス２を得た。
【００３９】
共重合体ラテックス３の作製（本発明例）
耐圧性の重合反応機に、窒素雰囲気下で純水９５部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム（花王製ネオペレックスＮｏ２５）１．０部、表１に示す１段目の各単量体およびα−メチルスチレンダイマー０．３部、シクロヘキセン２．０部、ｔ−ドデシルメルカプタン０．３部、Ｌ−アスコルビン酸０．０５部を加えて十分攪拌した後、過硫酸カリウム０．９部を仕込み、６５℃で重合を開始した。重合転化率が６５％に達した後、表１に示す２段目の各単量体およびｎ−オクチルメルカプタン０．２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（日本乳化剤製ニューコール２７１Ａ）１．０部、Ｌ−アスコルビン酸０．０３部、過硫酸カリウム０．３部、純水１０部を仕込み、反応温度を６５℃に保って更に反応を継続した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．１０部を添加して重合を終了した。次いで、共重合体ラテックスを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、苛性ソーダでｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＨ−ＭＩＴを０．０６０部とＢＩＴ０．０１０部を添加し、これら防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス３を得た。
【００４０】
共重合体ラテックス４の作製（比較例）
耐圧性の重合反応機に、窒素雰囲気下で純水１００部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）１．８部、表１に示す１段目の各単量体およびシクロヘキセン２．０部、ｎ−オクチルメルカプタン０．８部を加えて十分攪拌した後、過硫酸カリウム０．５部を仕込み、６０℃で重合を開始した。重合転化率が８０％に達した後、表１に示す２段目の各単量体およびｔ−ドデシルメルカプタン０．１部、ドデシルベンゼンスルホン酸ナトリウム（花王製ネオペレックスＮｏ２５）０．３部、過硫酸カリウム１．２部、純水２５部を仕込み、反応温度を６５℃に上げて更に反応を継続した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．０１部を添加して重合を終了した。次いで、共重合体ラテックスを苛性カリ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＨ−ＭＩＴを０．０２０部とＢＩＴ０．０５０部を添加し、これら防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス４を得た。
【００４１】
共重合体ラテックス５の作製（比較例）
耐圧性の重合反応機に、窒素雰囲気下で純水１２０部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）２．０部、ドデシルベンゼンスルホン酸ナトリウム（花王製ネオペレックスＮｏ２５）０．３部、表１に示す１段目の各単量体およびα−メチルスチレンダイマー０．３部、ｔ−ドデシルメルカプタン０．３部、Ｌ−アスコルビン酸０．２０部を加えて十分攪拌した後、過硫酸カリウム０．５部を仕込み、６５℃で重合を開始した。重合転化率が７０％に達した後、表１に示す２段目の各単量体およびα−メチルスチレンダイマー０．２部、過硫酸カリウム０．１部、Ｌ−アスコルビン酸０．３０部、純水１０部を仕込み、反応温度を６５℃に保って更に反応を継続した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．２５部を添加して重合を終了した。次いで、共重合体ラテックスを苛性カリ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＨ−ＭＩＴを０．０５０部とＢＩＴ０．０１５部を添加し、これら防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス５を得た。
【００４２】
共重合体ラテックス６の作製（比較例）
耐圧性の重合反応機に、窒素雰囲気下で純水１２０部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）１．５部、表１に示す１段目の各単量体およびシクロヘキセン３．０部、ｔ−ドデシルメルカプタン０．３部、Ｌ−アスコルビン酸０．１０部を加えて十分攪拌した後、過硫酸カリウム０．８部を仕込み、６５℃で重合を開始した。重合転化率が８０％に達した後、表１に示す２段目の各単量体およびｔ−ドデシルメルカプタン０．２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（日本乳化剤製ニューコール２７１Ａ）０．４０部、純水１０部を仕込み、反応温度を６５℃に保って更に反応を継続した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．１０部を添加して重合を終了した。次いで、共重合体ラテックスを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、苛性ソーダ水溶液でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＨ−ＭＩＴを０．０２０部とＢＩＴ０．０２５部を添加し、これら防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス６を得た。
【００４３】
共重合体ラテックス７の作製（比較例）
耐圧性の重合反応機に、窒素雰囲気下で純水１２５部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）２．８部、表２に示す１段目の各単量体およびα−メチルスチレンダイマー０．２部、ｎ−オクチルメルカプタン０．６部、Ｌ−アスコルビン酸０．３０部を加えて十分攪拌した後、過硫酸カリウム０．６部を仕込み、６０℃で重合を開始した。重合転化率が７０％に達した後、表２に示す２段目の各単量体およびα−メチルスチレンダイマー０．１部、純水５部を仕込み、反応温度を６５℃に上げて更に反応を継続した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．２０部を添加して重合を終了した。次いで、共重合体ラテックスを苛性カリ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＨ−ＭＩＴを０．０７０部添加し、防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス７を得た。
【００４４】
共重合体ラテックス８の作製（比較例）
耐圧性の重合反応機に、窒素雰囲気下で純水１２０部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）２．３部、ドデシルベンゼンスルホン酸ナトリウム（花王製ネオペレックスＮｏ２５）０．１部、表２に示す１段目の各単量体およびシクロヘキセン４．０部、ｎ−オクチルメルカプタン０．８部、Ｌ−アスコルビン酸０．１０部を加えて十分攪拌した後、過硫酸カリウム１．２部を仕込み、６５℃で重合を開始した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．０５部を添加して重合を終了した。次いで、共重合体ラテックスを苛性カリ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＢＩＴを０．０７０部添加し、防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス８を得た。
【００４５】
共重合体ラテックス９の作製（比較例）
耐圧性の重合反応機に、窒素雰囲気下で純水１２５部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）２．０部、表２に示す１段目の各単量体およびα−メチルスチレンダイマー０．５部、シクロヘキセン２．０部、ｔ−ドデシルメルカプタン０．４部、ｎ−オクチルメルカプタン０．６部、Ｌ−アスコルビン酸０．２５部を加えて十分攪拌した後、過硫酸カリウム０．７部を仕込み、６０℃で重合を開始した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．２５部を添加して重合を終了した。次いで、共重合体ラテックスを苛性カリ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＨ−ＭＩＴを０．０６０部と２−ブロモ−２−ニトロ−１，３−プロパンジオール（以下ＢＮＰＡと称する）０．０１０部を添加し、防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス９を得た。
【００４６】
共重合体ラテックス１０の作製（比較例）
耐圧性の重合反応機に、窒素雰囲気下で純水１３５部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）１．９部、ドデシルベンゼンスルホン酸ナトリウム（花王製ネオペレックスＮｏ２５）０．１５部、表２に示す１段目の各単量体シクロヘキセン２．０部、ｎ−オクチルメルカプタン０．６部、Ｌ−アスコルビン酸０．０５部を加えて十分攪拌した後、過硫酸カリウム１．１０部を仕込み、６５℃で重合を開始した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．０７部を添加して重合を終了した。次いで、共重合体ラテックスを苛性カリ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＢＩＴを０．０５０部とＢＮＰＡ０．０１０部を添加し、防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス１０を得た。
【００４７】
共重合体ラテックス１１の作製（比較例）
耐圧性の重合反応機に、窒素雰囲気下で純水１２０部、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム（日本乳化剤製ニューコール２７１Ａ）２．０部、ドデシルベンゼンスルホン酸ナトリウム（花王製ネオペレックスＮｏ２５）０．３部、表２に示す１段目の各単量体およびシクロヘキセン２．０部、ｎ−オクチルメルカプタン０．６部、Ｌ−アスコルビン酸０．１０部を加えて十分攪拌した後、過硫酸カリウム０．８部を仕込み、５５℃で重合を開始した。重合転化率が８５％に達した後、表２に示す２段目の各単量体および純水１０部を仕込み、反応温度を６５℃に上げて更に反応を継続した。重合転化率が９７％に達した後、重合停止剤としてジエチルヒドロキシルアミン０．１０部を添加して重合を終了した。次いで、共重合体ラテックスを苛性カリ水溶液でｐＨを約７に調整した後、水蒸気蒸留（７０〜９０℃で３〜５時間）により未反応単量体および他の低沸点化合物を除去したのち３０℃まで降温し、アンモニア水でｐＨを約８に調整した。その後、直ちに共重合体の固形分１００部に対してＢＩＴを０．０３０とトリアジン０．１００部を添加し、防腐剤成分が均一に分散されるよう３０分間撹拌して共重合体ラテックス１１を得た。
【００４８】
各共重合体ラテックスの組成および、粒子径、ゲル含有量、酸化還元電位、ガラス転移温度、長期保存安定性評価結果、ホルムアルデヒド放散量測定結果、スチレン放散量測定結果を表１および表２にまとめた。
【００４９】
【表１】
【表２】
【発明の効果】
上記の通り、本発明によって得られる環境対応型共重合体ラテックスは、室内空気汚染（シックハウス）の原因物質を放散せず、優れた長期保存安定性を示し、一般塗料組成物、紙塗工用組成物、各種接着剤組成物はもちろん、特に室内用塗料組成物や室内用建材であるフローリング材料、突き板、化粧合板、家具用化粧版、壁紙用接着剤組成物、自動車の内装材料などに好適に用いられる構成材料を提供するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an environmentally friendly copolymer latex having excellent long-term storage stability. Further, the present invention relates to a copolymer latex used for an adhesive composition or a paint which is not easily spoiled and has excellent long-term storage stability and does not contain a substance causing indoor air contamination such as formaldehyde and styrene.
[0002]
2. Description of the Related Art Synthetic rubber latexes such as SBR, NBR, MBR, and acrylic emulsions such as styrene-acrylic (hereinafter collectively referred to as copolymer latex) are conventionally used for general coating compositions and paper coatings. It has been widely used in compositions and various adhesive compositions. Since these copolymer latexes are aqueous, they can be stored in storage tanks after production, and fungi can propagate during storage after being filled and shipped in marine containers, containers, drums, and cans. In order to solve these problems, it is known that a preservative is blended from several tens of ppm to several thousand ppm with respect to the actual weight of the product.
[0003]
On the other hand, because of the problem of indoor air pollution (sick house), indoor air from indoor paint compositions and flooring materials that are indoor building materials, veneer, decorative plywood, decorative veneer for furniture, adhesive composition for wallpaper and automotive interior materials It has been strongly demanded that formaldehyde, styrene and the like that cause contamination are not diffused. For this reason, water-based adhesives are used in these applications, and preservatives that can be used in these applications are also limited. . That is, formalin and triazine, which are formaldehyde preservatives that are inexpensive and have excellent antiseptic effects, cannot be used.
[0004]
Therefore, for example, as disclosed in Japanese Patent Publication No. 60-54281 (Patent Document 1), 2-methyl-4-isothiazolin-3-one (hereinafter referred to as H-MIT) and its chlorine adduct (hereinafter referred to as C-MIT). Alternatively, a technique of adding a mixture of bromine adducts as a preservative is disclosed. However, even if these are used alone, the antiseptic effect is low and the long-term storage stability is poor.
JP-A-2001-303480 (Patent Document 2) and JP-A-2001-303482 (Patent Document 3) describe a benzoisothiazoline compound (hereinafter referred to as BIT) represented by the general formula (1). Although latex for paper coating, which is characterized by containing it, has been introduced, BIT alone has a low antiseptic effect, and long-term storage stability is still insufficient.
Furthermore, Japanese Patent Application Laid-Open No. 2001-303481 (Patent Document 4) uses a technique in which BIT and a halogenated aliphatic nitroalcohol represented by the following general formula (2) are used in combination, Japanese Patent Application Laid-Open No. 2002-88681 (Patent Document 5). ) Discloses a technique in which H-MIT and a halogenated aliphatic nitroalcohol represented by the general formula (2) are used in combination.
[0005]
Embedded image Halogenated aliphatic nitroalcohol
(Wherein R1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom) Represents an atom)
[0007]
However, although the mechanism is unknown, such a halogenated aliphatic nitroalcohol may generate a trace amount of formaldehyde when decomposed depending on the use conditions, and the use conditions may be limited.
Japanese Patent Laid-Open No. 2001-181113 (Patent Document 6) and Special Table 2001-515016 (Patent Document 7) have technical disclosures regarding the synergistic effect of BIT and H-MIT for the antiseptic effect. There is no disclosure regarding application to a copolymer emulsion of composition, and there is no technical disclosure regarding the relationship with the oxidation-reduction potential defined in the present invention.
[0008]
[Patent Document 1] Japanese Patent Publication No. 60-54281
[Patent Document 2] Japanese Patent Laid-Open No. 2001-303480
[Patent Document 3] Japanese Patent Laid-Open No. 2001-303481
[Patent Document 4] Japanese Patent Laid-Open No. 2001-303482
[Patent Document 5] Japanese Patent Application Laid-Open No. 2002-88681
[Patent Document 6] Japanese Patent Laid-Open No. 2001-181113
[Patent Document 7] JP-T-2001-515016
[0009]
[Problems to be solved by the invention]
In order to solve the above-mentioned problems, the present inventors have repeatedly studied about an environmentally friendly copolymer latex excellent in long-term storage stability. As a result, a copolymer having a specific monomer composition controlled to a specific oxidation-reduction potential. Providing environment-friendly copolymer latex that does not dissipate the cause of indoor air pollution (sick house) and has excellent long-term storage stability by blending latex with specific amounts of H-MIT and BIT The present inventors have found that this can be done and have completed the present invention.
[0010]
[Means for Solving the Problems]
That is, the present invention
Monomers composed of unsaturated carboxylic acid alkyl ester monomers and other vinyl monomers copolymerizable therewith (excluding aromatic vinyl monomers and methylol group-containing monomers) Containing 100 parts by weight (in terms of solid content) of copolymer latex obtained by emulsion polymerization of BIT in an amount of 0.001 part by weight or more and 0.001 part by weight or more of 2-methyl-4-isothiazolin-3-one In addition, the present invention provides an environmentally friendly copolymer latex characterized by having an oxidation-reduction potential of -100 mV to +300 mV.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The copolymer latex in the present invention is an unsaturated carboxylic acid alkyl ester monomer and other copolymerizable vinyl monomers (excluding aromatic vinyl monomers and methylol group-containing monomers). ).
[0012]
Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, 2-ethylhexyl acrylate, and the like, and one or more of them can be used. . Of these, it is particularly preferable to use 30% by weight or more of methyl methacrylate.
[0013]
Other monomers that can be copolymerized with unsaturated carboxylic acid alkyl ester monomers include aliphatic conjugated diene monomers, ethylenically unsaturated carboxylic acid monomers, and ethylenically unsaturated carboxylic acid amides. And monomer based on vinyl cyanide.
[0014]
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 one or more kinds can be used. 1,3-butadiene is particularly preferable.
Examples of the ethylenically unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, and the like, and one or more can be used. Acrylic acid, methacrylic acid, fumaric acid and itaconic acid are particularly preferable.
Examples of the unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N, N-dimethylacrylamide, and the like, and one or more of them can be used. Particularly preferred is acrylamide.
Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like, and one or more can be used. In particular, acrylonitrile and methacrylonitrile are preferable.
Furthermore, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, vinyl chloride, vinylidene chloride, and the like are required for various applications. It can be used in a timely and appropriate amount for the purpose of imparting performance and the like.
[0015]
Although it does not specifically limit about said monomer composition, It adjusts suitably so that the adhesive performance required for it may be satisfied by each use. For example, in applications requiring water resistance, methyl methacrylate is used as the unsaturated carboxylic acid alkyl ester monomer, and 1,3-butadiene is used as the main monomer composition as the aliphatic conjugated diene monomer. It is desirable to use a copolymer latex adjusted so that the glass transition temperature of the copolymer is in the range of -50 ° C to 50 ° C.
[0016]
For applications that require weather resistance, combinations of methyl methacrylate, butyl acrylate, methyl methacrylate, ethyl acrylate, etc. as unsaturated carboxylic acid alkyl ester monomers are used as the main monomer composition. It is desirable to use a copolymer latex adjusted so that the glass transition temperature of the coalescence is in the range of -50 ° C to 50 ° C.
[0017]
The copolymer latex used in the present invention needs to have an oxidation-reduction potential adjusted to −100 mV to +300 mV. Outside this range, even if H-MIT and BIT are present in an amount of 0.001 part by weight or more with respect to 100 parts by weight of the copolymer component (in terms of solid content), the antiseptic effect targeted by the present invention is obtained. Since it is not possible, it is not preferable.
[0018]
The method for adjusting the oxidation-reduction potential of the copolymer latex is not particularly limited, but an oxidation catalyst as a reaction initiator used in normal polymerization, a reducing agent for promoting the decomposition of the oxidation catalyst, or a redox catalyst And the amount of the reaction terminator used may be controlled, or the remaining oxidizing agent may be reduced by a heating operation or a steam distillation operation.
[0019]
In the emulsion polymerization of the copolymer latex of the present invention, conventional emulsifiers, polymerization initiators, reducing agents, redox catalysts, hydrocarbon solvents, electrolytes, polymerization accelerators, chelating agents, and the like can be used.
[0020]
As the polymerization initiator, water-soluble polymerization initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, An oil-soluble polymerization initiator such as 1,1,3,3-tetramethylbutyl hydroperoxide can be appropriately used. In particular, water-soluble polymerization initiators such as potassium persulfate, sodium persulfate and ammonium persulfate and oil-soluble polymerization initiators of cumene hydroperoxide are preferred.
[0021]
In addition, the presence of a reducing agent together with the polymerization initiator in the reaction system is preferable because the reaction rate is moderately accelerated and the decomposition of the remaining polymerization initiator is facilitated, and the amount used thereof has a redox potential at the end of the reaction. It is better to adjust to -100 mV to +300 mV. However, even if the oxidation-reduction potential deviates from the range of −100 mV to +300 mV at the end of the reaction, the H-MIT is finally obtained by adding a small amount of an oxidizing agent or a reducing agent, heating operation, or steam distillation operation in the subsequent steps. If the oxidation-reduction potential is -100 mV to +300 mV at the time of adding BIT and BIT, the effect of the present invention is not hindered.
[0022]
Specific examples of the reducing agent preferably used in the present invention include sulfite, bisulfite, pyrosulfite, nitrite, nithionate, thiosulfate, L-ascorbic acid, tartaric acid, citric acid and the like. Carboxylic acids of the above, further reducing sugars such as dextrose and saccharose, and amines such as dimethylaniline and triethanolamine. L-ascorbic acid is particularly preferable.
Note that reducing sulfonates such as formaldehyde sulfonate and benzaldehyde sulfonate are not used in the present invention because they result in the product containing formaldehyde.
[0023]
Examples of emulsifiers that can be used in the production of the copolymer latex of the present invention include sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether sulfonates, aliphatic sulfonates, aliphatic carboxylates, and nonionic surfactants. Nonionic surfactants such as anionic surfactants such as sulfuric acid ester salts of polyethylene or alkyl ester type, alkyl phenyl ether type, alkyl ether type of polyethylene glycol, and the like, and one or more of these should be used Can do. In particular, alkylbenzene sulfonate and alkyl diphenyl ether sulfonate are preferable.
[0024]
Examples of the chain transfer agent that can be used for the production of the copolymer latex of the present invention include alkyls such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-stearyl mercaptan. Xanthogen compounds such as mercaptan, dimethylxanthogen disulfide, diisopropylxanthogen disulfide, terpinolene, thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, 2,6-di-t-butyl-4 -Halogenation of phenolic compounds such as methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, dichloromethane, dibromomethane, carbon tetrabromide, etc. Hydrogenated compounds, α-benzyloxystyrene, α-benzyloxyacrylonitrile, vinyl ethers such as α-benzyloxyacrylamide, triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglyco A rate etc. are mentioned, These can be used 1 type or 2 or more types. In particular, n-octyl mercaptan and t-dodecyl mercaptan are preferable. The amount of these chain transfer agents is not particularly limited, but is usually 0 to 5 parts by weight with respect to 100 parts by weight of the monomer.
[0025]
In the present invention, α-methylstyrene dimer can also be used as a chain transfer agent. α-Methylstyrene dimer includes 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4-methyl-2-pentene and 1,1,3-trimethyl-3-phenyl as isomers. Although there is indane, the α-methylstyrene dimer used in the present invention has a content of 2,4-diphenyl-4-methyl-1-pentene of 60% by weight or more, particularly 80% by weight or more. preferable. Since α-methylstyrene dimer has a high boiling point and remains in the latex particles even after the production of the copolymer latex, the amount used is 100 parts by weight of the monomer due to environmental problems different from the object of the present invention. The amount is preferably less than 2 parts by weight.
[0026]
In the polymerization, unsaturated hydrocarbons such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, and 1-methylcyclohexene may be used. In particular, cyclohexene, which has a moderately low boiling point and can be easily recovered and reused by steam distillation or the like after the completion of polymerization, is preferable from the viewpoint of environmental problems, which is different from the object of the present invention.
[0027]
As the polymerization method in the present invention, any one of single-stage polymerization, two-stage polymerization, multi-stage polymerization, seed polymerization, power feed polymerization and the like may be adopted. Further, the addition method of various components in the polymerization method of 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.
[0028]
The environmentally friendly copolymer latex in the present invention has a BIT of 0.001 part by weight or more and 2-methyl-4-isothiazolin-3-one of 0 with respect to 100 parts by weight of the copolymer latex (in terms of solid content). It is necessary to contain 0.001 part by weight or more, and any content of less than 0.001 weight is not preferable because the desired antiseptic effect of the present invention cannot be obtained. Even if these preservatives are added in a larger amount than necessary, no further antiseptic effect can be expected, leading to an increase in cost, so the upper limit is about 1 part by weight in total.
[0029]
The environmentally friendly copolymer latex in the present invention is resistant to spoilage and has excellent long-term storage stability and does not contain indoor air pollution-causing substances such as formaldehyde and styrene. Therefore, it is suitable for indoor paint compositions and indoor building materials. It can be suitably used as a water-based adhesive used in an adhesive composition such as a certain flooring material, veneer, decorative plywood, decorative plate for furniture, and wallpaper.
[0030]
【Example】
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.
[0031]
Measurement of particle size of copolymer latex
The number average particle size was measured by a dynamic light scattering method. In the measurement, LPA-3000 / 3100 manufactured by Otsuka Electronics was used.
[0032]
Measurement of gel content of copolymer latex
Dry in a room temperature atmosphere for 24 hours to make a film of copolymer latex. About 1 g of the film is weighed, put in 400 cc of toluene, and allowed to expand and dissolve for 48 hours. Thereafter, this was filtered through a 300-mesh wire mesh, and the toluene insoluble portion captured by the wire mesh was dried and weighed, and the ratio of the weight to the initial film weight was calculated as a gel content in wt%.
[0033]
Measurement of glass transition temperature of copolymer latex.
A film of copolymer latex was prepared by drying in a room temperature atmosphere for 24 hours, and the glass transition temperature was measured using a differential scanning calorimeter (DSC6200) manufactured by Seiko Instruments Inc. at a temperature increase rate of 10 ° C./min. .
[0034]
Measurement of redox potential of copolymer latex.
A platinum (ORP) electrode was attached to a pH meter manufactured by HORIBA, Ltd., and the potential was measured when the electrode was immersed and stabilized in latex whose temperature was adjusted to 25 ° C.
[0035]
Measurement of formaldehyde emission and styrene emission of copolymer latex.
Formaldehyde emission and styrene emission were in accordance with JIS A1901 (2003). Coated latex 1-11 each 2.4g each coated area 0.008m2(Applied amount 300 g / m)2) And left at 23 ° C. for 60 minutes. This was put in a 20-liter small chamber, and the emission rate after 24 hours was measured according to JIS A1901 (2003), and evaluated as follows according to the measurement results.
Formaldehyde emission
○ 5 (μg / m2・ H) Below
Δ ... 5 (μg / m2-H) over 20 (μg / m2・ H) Below
× 20 (μg / m2・ Over h)
Styrene emissions
○ 20 (μg / m2・ H) Below
Δ ... 20 (μg / m2-H) over 100 (μg / m2・ H) Below
× ... 100 (μg / m2・ Over h)
[0036]
Evaluation of long-term storage stability of copolymer latex
(1) Corrupted copolymer latex (bacterial count 10) for 100 g of each copolymer latex to be tested6Add 5 g above, leave at 30 ° C. for 10 hours, further raise the temperature to 45 ° C. and keep it for 24 hours, then return to 30 ° C. and store for 24 hours.
(2) The number of colonies after culturing at 30 ° C. for 48 hours is measured by the TGC agar plate pour method. This is the first test.
In the second test, an additional 5 g of spoiled latex is added, stored and managed under the temperature condition (1), and the number of colonies is counted by the method (2). Similarly, until colonies are confirmed (bacteria count 106End of above) Repeat intake and measurement of spoiled latex. The long-term storage stability was determined by the number of repetitions until colonies were confirmed as follows. The higher the number of times, the better the antiseptic effect.
○ ... 16 times or more until colony is confirmed
Δ: The number of repetitions until the colony is confirmed is 7 times or more and 15 times or less.
X: Number of repetitions until colony is confirmed is 6 or less
[0037]
Preparation of copolymer latex 1 (example of the present invention)
In a pressure-resistant polymerization reactor, 120 parts of pure water in a nitrogen atmosphere, 0.3 parts of sodium dodecylbenzenesulfonate (Naoperex No25 manufactured by Kao) as an emulsifier, sodium alkyldiphenyl ether disulfonate (Newcol 271A manufactured by Nippon Emulsifier) 2 0.0 part, each monomer in the first stage shown in Table 1 and 2 parts of cyclohexene, 0.6 part of n-octyl mercaptan and 0.1 part of L-ascorbic acid were added and stirred well. 7 parts were charged and polymerization was started at 65 ° C. After the polymerization conversion rate reached 97%, 0.20 part of hydroxylamine sulfate was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic potash solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.) and then 30 ° C. The pH was adjusted to about 8 with aqueous ammonia. Immediately thereafter, 0.013 part of H-MIT and 0.040 part of BIT were added to 100 parts of the solid content of the copolymer, and the copolymer was stirred for 30 minutes so that these preservative components were uniformly dispersed. Latex 1 was obtained.
[0038]
Preparation of copolymer latex 2 (example of the present invention)
In a pressure-resistant polymerization reactor, in a nitrogen atmosphere, 105 parts of pure water, 1.5 parts of sodium alkyldiphenyl ether disulfonate (Nippon Emulsifier 271A) as an emulsifier, each monomer in the first stage shown in Table 1, and After adding 0.5 part of α-methylstyrene dimer, 0.3 part of t-dodecyl mercaptan and 0.05 part of L-ascorbic acid and stirring sufficiently, 1.0 part of potassium persulfate was added and polymerization was conducted at 55 ° C. Started. After reaching a polymerization conversion rate of 75%, each monomer in the second stage shown in Table 1 and 0.2 part of α-methylstyrene dimer, sodium alkyldiphenyl ether disulfonate (Nippon Emulsifier Newcor 271A) 0.3 Part, 0.05 part of L-ascorbic acid, 0.3 part of potassium persulfate and 20 parts of pure water were added, the reaction temperature was raised to 65 ° C., and the reaction was further continued. After the polymerization conversion reached 97%, 0.10 parts of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic soda solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.), and then up to 30 ° C. The temperature was lowered, and the pH was adjusted to about 8 with aqueous ammonia. Immediately thereafter, 0.010 part of H-MIT and 0.050 part of BIT are added to 100 parts of the solid content of the copolymer, and the copolymer is stirred for 30 minutes so that these preservative components are uniformly dispersed. Latex 2 was obtained.
[0039]
Preparation of copolymer latex 3 (example of the present invention)
In a pressure resistant polymerization reactor, in a nitrogen atmosphere, 95 parts of pure water, 1.0 part of sodium dodecylbenzenesulfonate (Naoperex No25 manufactured by Kao) as an emulsifier, each monomer in the first stage shown in Table 1 and α -0.3 parts of methylstyrene dimer, 2.0 parts of cyclohexene, 0.3 part of t-dodecyl mercaptan and 0.05 part of L-ascorbic acid were added and stirred sufficiently, and then 0.9 part of potassium persulfate was charged. Polymerization was started at 65 ° C. After the polymerization conversion reached 65%, each of the second-stage monomers shown in Table 1 and 0.2 part of n-octyl mercaptan, sodium alkyldiphenyl ether disulfonate (Nippon Emulsifier Newcor 271A) 1.0 part Then, 0.03 part of L-ascorbic acid, 0.3 part of potassium persulfate and 10 parts of pure water were charged, and the reaction was continued at a reaction temperature of 65 ° C. After the polymerization conversion reached 97%, 0.10 parts of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic soda solution, the unreacted monomer and other low-boiling compounds were removed by steam distillation (3 to 5 hours at 70 to 90 ° C.), and then 30 ° C. The pH was adjusted to about 8 with caustic soda. Immediately thereafter, 0.060 part of H-MIT and 0.010 part of BIT are added to 100 parts of the solid content of the copolymer, and the copolymer is stirred for 30 minutes so that these preservative components are uniformly dispersed. Latex 3 was obtained.
[0040]
Preparation of copolymer latex 4 (comparative example)
In a pressure-resistant polymerization reactor, 100 parts of pure water under a nitrogen atmosphere, 1.8 parts of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Japan Emulsifier) as an emulsifier, each monomer in the first stage shown in Table 1, and After adding 2.0 parts of cyclohexene and 0.8 part of n-octyl mercaptan and stirring sufficiently, 0.5 part of potassium persulfate was charged and polymerization was started at 60 ° C. After the polymerization conversion rate reached 80%, each of the second-stage monomers shown in Table 1 and 0.1 part of t-dodecyl mercaptan, 0.3 part of sodium dodecylbenzenesulfonate (Naoperex No25 manufactured by Kao), 1.2 parts of potassium persulfate and 25 parts of pure water were added, the reaction temperature was raised to 65 ° C., and the reaction was further continued. After the polymerization conversion rate reached 97%, 0.01 part of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic potash solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.) and then 30 ° C. The pH was adjusted to about 8 with aqueous ammonia. Immediately thereafter, 0.020 part of H-MIT and 0.050 part of BIT are added to 100 parts of the solid content of the copolymer, and the copolymer is stirred for 30 minutes so that these preservative components are uniformly dispersed. Latex 4 was obtained.
[0041]
Preparation of copolymer latex 5 (comparative example)
In a pressure-resistant polymerization reactor, 120 parts of pure water under a nitrogen atmosphere, 2.0 parts of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Nippon Emulsifier) as an emulsifier, sodium dodecylbenzenesulfonate (Neopelex No25 manufactured by Kao) 0 .3 parts, each monomer in the first stage shown in Table 1, 0.3 part of α-methylstyrene dimer, 0.3 part of t-dodecyl mercaptan and 0.20 part of L-ascorbic acid were added and sufficiently stirred. Thereafter, 0.5 part of potassium persulfate was charged, and polymerization was started at 65 ° C. After reaching a polymerization conversion rate of 70%, each monomer in the second stage shown in Table 1 and 0.2 part of α-methylstyrene dimer, 0.1 part of potassium persulfate, 0.30 part of L-ascorbic acid Then, 10 parts of pure water was charged, and the reaction was further continued while maintaining the reaction temperature at 65 ° C. After the polymerization conversion reached 97%, 0.25 part of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic potash solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.) and then 30 ° C. The pH was adjusted to about 8 with aqueous ammonia. Immediately thereafter, 0.050 part of H-MIT and 0.015 part of BIT are added to 100 parts of the solid content of the copolymer, and the copolymer is stirred for 30 minutes so that these preservative components are uniformly dispersed. Latex 5 was obtained.
[0042]
Preparation of copolymer latex 6 (comparative example)
In a pressure-resistant polymerization reactor, 120 parts of pure water under a nitrogen atmosphere, 1.5 parts of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Japan Emulsifier) as an emulsifier, each monomer in the first stage shown in Table 1, and After adding 3.0 parts of cyclohexene, 0.3 part of t-dodecyl mercaptan and 0.10 part of L-ascorbic acid and stirring sufficiently, 0.8 part of potassium persulfate was charged and polymerization was started at 65 ° C. After the polymerization conversion rate reached 80%, each second-stage monomer shown in Table 1 and 0.2 part of t-dodecyl mercaptan, sodium alkyldiphenyl ether disulfonate (Nippon Emulsifier Newcor 271A) 0.40 part Then, 10 parts of pure water was charged, and the reaction was further continued while maintaining the reaction temperature at 65 ° C. After the polymerization conversion reached 97%, 0.10 parts of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic soda solution, the unreacted monomer and other low-boiling compounds were removed by steam distillation (3 to 5 hours at 70 to 90 ° C.), and then 30 ° C. The pH was adjusted to about 8 with an aqueous caustic soda solution. Immediately thereafter, 0.020 part of H-MIT and 0.025 part of BIT are added to 100 parts of the solid content of the copolymer, and the copolymer is stirred for 30 minutes so that these preservative components are uniformly dispersed. Latex 6 was obtained.
[0043]
Preparation of copolymer latex 7 (comparative example)
In a pressure-resistant polymerization reactor, 125 parts of pure water in a nitrogen atmosphere, 2.8 parts of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Japan Emulsifier) as an emulsifier, each monomer in the first stage shown in Table 2, and After adding 0.2 part of α-methylstyrene dimer, 0.6 part of n-octyl mercaptan and 0.30 part of L-ascorbic acid and sufficiently stirring, 0.6 part of potassium persulfate was added and polymerization was conducted at 60 ° C. Started. After the polymerization conversion rate reached 70%, each monomer in the second stage shown in Table 2, 0.1 part of α-methylstyrene dimer and 5 parts of pure water were charged, and the reaction temperature was raised to 65 ° C. The reaction was continued. After the polymerization conversion rate reached 97%, 0.20 part of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic potash solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.) and then 30 ° C. The pH was adjusted to about 8 with aqueous ammonia. Thereafter, 0.070 part of H-MIT was immediately added to 100 parts of the solid content of the copolymer, and stirred for 30 minutes so that the preservative component was uniformly dispersed to obtain a copolymer latex 7.
[0044]
Preparation of copolymer latex 8 (comparative example)
In a pressure-resistant polymerization reactor, 120 parts of pure water in a nitrogen atmosphere, 2.3 parts of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Japan Emulsifier) as an emulsifier, sodium dodecylbenzenesulfonate (Neopelex No25 manufactured by Kao) 0 1 part, each monomer in the first stage shown in Table 2, and 4.0 parts of cyclohexene, 0.8 part of n-octyl mercaptan and 0.10 part of L-ascorbic acid were added, and the mixture was sufficiently stirred. 1.2 parts of potassium was charged, and polymerization was started at 65 ° C. After the polymerization conversion reached 97%, 0.05 part of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic potash solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.) and then 30 ° C. The pH was adjusted to about 8 with aqueous ammonia. Thereafter, 0.070 part of BIT was immediately added to 100 parts of the solid content of the copolymer, and stirred for 30 minutes so that the preservative component was uniformly dispersed to obtain a copolymer latex 8.
[0045]
Preparation of copolymer latex 9 (comparative example)
In a pressure-resistant polymerization reactor, 125 parts of pure water in a nitrogen atmosphere, 2.0 parts of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Japan Emulsifier) as an emulsifier, each monomer in the first stage shown in Table 2, and After adding 0.5 part of α-methylstyrene dimer, 2.0 parts of cyclohexene, 0.4 part of t-dodecyl mercaptan, 0.6 part of n-octyl mercaptan, 0.25 part of L-ascorbic acid, 0.7 parts of potassium persulfate was charged, and polymerization was started at 60 ° C. After the polymerization conversion reached 97%, 0.25 part of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic potash solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.) and then 30 ° C. The pH was adjusted to about 8 with aqueous ammonia. Immediately thereafter, 0.060 part of H-MIT and 0.010 part of 2-bromo-2-nitro-1,3-propanediol (hereinafter referred to as BNPA) were added to 100 parts of the solid content of the copolymer. The mixture was stirred for 30 minutes so that the preservative component was uniformly dispersed to obtain a copolymer latex 9.
[0046]
Preparation of copolymer latex 10 (comparative example)
In a pressure-resistant polymerization reactor, 135 parts of pure water in a nitrogen atmosphere, 1.9 parts of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Japan Emulsifier) as an emulsifier, sodium dodecylbenzenesulfonate (Neopelex No25 manufactured by Kao) 0 After adding 15 parts, 2.0 parts of each first-stage monomer cyclohexene shown in Table 2, 0.6 part of n-octyl mercaptan, 0.05 part of L-ascorbic acid, and sufficiently stirring, potassium persulfate 1.10 parts were charged and polymerization was started at 65 ° C. After the polymerization conversion reached 97%, 0.07 part of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic potash solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.) and then 30 ° C. The pH was adjusted to about 8 with aqueous ammonia. Immediately thereafter, 0.050 part of BIT and 0.010 part of BNPA are added to 100 parts of the solid content of the copolymer, and stirred for 30 minutes so that the preservative component is uniformly dispersed. Obtained.
[0047]
Preparation of copolymer latex 11 (comparative example)
In a pressure-resistant polymerization reactor, 120 parts of pure water under a nitrogen atmosphere, 2.0 parts of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Nippon Emulsifier) as an emulsifier, sodium dodecylbenzenesulfonate (Neopelex No25 manufactured by Kao) 0 .3 parts, each monomer in the first stage shown in Table 2, 2.0 parts of cyclohexene, 0.6 parts of n-octyl mercaptan, and 0.10 parts of L-ascorbic acid were added and sufficiently stirred, and then persulfuric acid was added. 0.8 parts of potassium was charged and polymerization was started at 55 ° C. After the polymerization conversion rate reached 85%, each monomer in the second stage shown in Table 2 and 10 parts of pure water were charged, the reaction temperature was raised to 65 ° C., and the reaction was further continued. After the polymerization conversion reached 97%, 0.10 parts of diethylhydroxylamine was added as a polymerization terminator to complete the polymerization. Next, after adjusting the pH of the copolymer latex to about 7 with an aqueous caustic potash solution, the unreacted monomer and other low-boiling compounds are removed by steam distillation (3 to 5 hours at 70 to 90 ° C.) and then 30 ° C. The pH was adjusted to about 8 with aqueous ammonia. Immediately thereafter, 0.030 of BIT and 0.100 part of triazine were added to 100 parts of the solid content of the copolymer, and stirred for 30 minutes so that the preservative component was uniformly dispersed. Obtained.
[0048]
Tables 1 and 2 summarize the composition, particle size, gel content, redox potential, glass transition temperature, long-term storage stability evaluation results, formaldehyde emission measurement results, and styrene emission measurement results of each copolymer latex. It was.
[0049]
[Table 1]
[Table 2]
【The invention's effect】
As described above, the environmentally friendly copolymer latex obtained by the present invention does not dissipate the substances causing indoor air pollution (sick house), exhibits excellent long-term storage stability, and is used for general coating compositions and paper coatings. Not only compositions and various adhesive compositions, but also flooring materials that are indoor paint compositions and indoor building materials, veneer, decorative plywood, decorative sheets for furniture, adhesive compositions for wallpaper, automotive interior materials, etc. The constituent material used suitably is provided.
Claims (1)
【化１】ベンゾイソチアゾリン系化合物
Benzisothiazoline compounds
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003195898A JP4282393B2 (en) | 2003-07-11 | 2003-07-11 | Environmentally friendly copolymer latex with excellent long-term storage stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003195898A JP4282393B2 (en) | 2003-07-11 | 2003-07-11 | Environmentally friendly copolymer latex with excellent long-term storage stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005029679A true JP2005029679A (en) | 2005-02-03 |
| JP4282393B2 JP4282393B2 (en) | 2009-06-17 |
Family
ID=34206596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003195898A Expired - Fee Related JP4282393B2 (en) | 2003-07-11 | 2003-07-11 | Environmentally friendly copolymer latex with excellent long-term storage stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4282393B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012201855A (en) * | 2011-03-28 | 2012-10-22 | Nippon Zeon Co Ltd | METHOD OF ADJUSTING pH OF POLYMER LATEX |
| WO2017164078A1 (en) * | 2016-03-23 | 2017-09-28 | 日本ゼオン株式会社 | Method for producing latex composition |
| WO2017164077A1 (en) * | 2016-03-23 | 2017-09-28 | 日本ゼオン株式会社 | Latex composition and friction material |
| JPWO2019176921A1 (en) * | 2018-03-12 | 2021-02-25 | 日本ゼオン株式会社 | Latex and complex |
-
2003
- 2003-07-11 JP JP2003195898A patent/JP4282393B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012201855A (en) * | 2011-03-28 | 2012-10-22 | Nippon Zeon Co Ltd | METHOD OF ADJUSTING pH OF POLYMER LATEX |
| WO2017164078A1 (en) * | 2016-03-23 | 2017-09-28 | 日本ゼオン株式会社 | Method for producing latex composition |
| WO2017164077A1 (en) * | 2016-03-23 | 2017-09-28 | 日本ゼオン株式会社 | Latex composition and friction material |
| CN108884232A (en) * | 2016-03-23 | 2018-11-23 | 日本瑞翁株式会社 | The manufacturing method of latex composition |
| JPWO2017164077A1 (en) * | 2016-03-23 | 2019-01-31 | 日本ゼオン株式会社 | Latex composition and friction material |
| JPWO2017164078A1 (en) * | 2016-03-23 | 2019-02-07 | 日本ゼオン株式会社 | Method for producing latex composition |
| US20190093724A1 (en) | 2016-03-23 | 2019-03-28 | Zeon Corporation | Method for producing latex composition |
| US11067145B2 (en) | 2016-03-23 | 2021-07-20 | Zeon Corporation | Method for producing latex composition |
| JP7036003B2 (en) | 2016-03-23 | 2022-03-15 | 日本ゼオン株式会社 | Method for manufacturing latex composition |
| JPWO2019176921A1 (en) * | 2018-03-12 | 2021-02-25 | 日本ゼオン株式会社 | Latex and complex |
| JP7207397B2 (en) | 2018-03-12 | 2023-01-18 | 日本ゼオン株式会社 | latex and composites |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4282393B2 (en) | 2009-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20100076149A1 (en) | Polychloroprene latex composition and its production method | |
| JP2009293048A (en) | Polychloroprene dispersion | |
| JP4503261B2 (en) | Copolymer latex with excellent long-term storage stability | |
| JP6841827B2 (en) | A one-component water-based adhesive comprising a latex composition and the latex composition | |
| JP4282393B2 (en) | Environmentally friendly copolymer latex with excellent long-term storage stability | |
| JP2014152183A (en) | Polychloroprene latex composition and adhesive | |
| JP5603356B2 (en) | Latex composition, method for producing the composition, and aqueous adhesive composition | |
| JP2002053703A (en) | Polychloroprene latex composition, manufacturing method therefor and adhesive composition using this latex composition | |
| JP4368646B2 (en) | Copolymer latex with excellent long-term storage stability | |
| EP3778676A1 (en) | Method for producing conjugated-diene-based copolymer latex | |
| JP2013177504A (en) | Chloroprene polymer composition, and method for producing the same | |
| JP2010106073A (en) | Chloroprene latex and method of manufacturing the same | |
| JP5238454B2 (en) | Copolymer latex for rubber and polyester fiber adhesives | |
| JP3426481B2 (en) | Chloroprene rubber composition and adhesive using the same | |
| JP6380048B2 (en) | Monomer composition for emulsion polymerization | |
| JP2016166293A (en) | Aqueous adhesive | |
| JP2021008574A (en) | Copolymer latex for adhesive and adhesive composition | |
| JPH05311128A (en) | Emulsion composition for foam | |
| JP5302251B2 (en) | Copolymer latex | |
| JP2005008859A (en) | Polychloroprene latex composition, adhesive, coating material and production method for the same composition | |
| JP7122351B2 (en) | Copolymer latex and composition | |
| JP2011195974A (en) | Composition for coating paper, and coated paper | |
| JP2000351886A (en) | Aqueous resin dispersion and coating composition prepared by using same | |
| JP4957062B2 (en) | Anti-slip finishing agent | |
| JPWO2020144955A1 (en) | Isoprene-based polymer latex composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060710 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090205 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090303 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090317 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4282393 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120327 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120327 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130327 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140327 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |