JP5901707B2 - Water-based adhesive - Google Patents
Water-based adhesive Download PDFInfo
- Publication number
- JP5901707B2 JP5901707B2 JP2014153226A JP2014153226A JP5901707B2 JP 5901707 B2 JP5901707 B2 JP 5901707B2 JP 2014153226 A JP2014153226 A JP 2014153226A JP 2014153226 A JP2014153226 A JP 2014153226A JP 5901707 B2 JP5901707 B2 JP 5901707B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- chain transfer
- monomer
- transfer agent
- polymerization
- 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.)
- Expired - Fee Related
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- 239000000853 adhesive Substances 0.000 title claims description 37
- 230000001070 adhesive effect Effects 0.000 title claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims description 117
- 238000006116 polymerization reaction Methods 0.000 claims description 107
- 239000004816 latex Substances 0.000 claims description 59
- 229920000126 latex Polymers 0.000 claims description 59
- 229920001577 copolymer Polymers 0.000 claims description 56
- 239000012986 chain transfer agent Substances 0.000 claims description 52
- 150000001993 dienes Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 38
- -1 vinyl benzyl Chemical group 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 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
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 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
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000002270 dispersing agent Substances 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
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentadiol Natural products OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- GYHZLNKMZPYTFB-UHFFFAOYSA-N 2-(oxiran-2-yl)acetamide Chemical compound NC(=O)CC1CO1 GYHZLNKMZPYTFB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- UYXQLQUXXCIFQM-UHFFFAOYSA-N 2-hydroxy-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound OP1(=O)OCCO1 UYXQLQUXXCIFQM-UHFFFAOYSA-N 0.000 description 1
- RYRDKOIZZRUCMC-UHFFFAOYSA-N 2-hydroxy-4-methyl-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound CC1COP(O)(=O)O1 RYRDKOIZZRUCMC-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 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
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N cinnamyl alcohol Chemical compound OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- HWEQKSVYKBUIIK-UHFFFAOYSA-N cyclobuta-1,3-diene Chemical compound C1=CC=C1 HWEQKSVYKBUIIK-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
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- 239000011120 plywood Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
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- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、住宅の建材、木工家具等の工業分野、建築現場で使用される建築内装用等の分野、及び一般家庭において広く使用されている溶剤型接着剤の適用分野において使用でき、有害な有機溶剤を含まないため環境汚染や健康を害することがなく、火災等の危険性もなく、しかも貼り合わせ直後のコンタクト接着性に優れ、且つ耐熱クリープ性及び養生後の接着強度に優れる水性接着剤用共重合体ラテックスに関する。 INDUSTRIAL APPLICABILITY The present invention can be used in industrial fields such as residential building materials, woodworking furniture, fields for architectural interiors used at construction sites, and application fields for solvent-based adhesives widely used in general households. A water-based adhesive that does not harm the environment and health because it does not contain organic solvents, has no danger of fire, etc., has excellent contact adhesion immediately after bonding, and has excellent heat creep resistance and adhesive strength after curing. Copolymer latex for use.
溶剤を多く含む溶剤型接着剤は、接着性の良さ、乾燥速度の速さ、作業の容易さ等の理由から広い分野で使用されている。しかしながら、これらの接着剤に多く含まれる溶剤の多くは、毒性があり、環境を汚染する危険性があるため、溶剤を含まない水性接着剤の開発が進められており、その中でも溶剤系クロロプレン接着剤の代替が積極的に行われている。この溶剤系クロロプレン接着剤は、乾燥して張り合わせた直後の接着力(コンタクト接着性)が良好であり、養生後の接着強度が強く、耐熱クリープ性も良好である等の特徴を有している。この溶剤系クロロプレン接着剤の水系化として、例えばクロロプレンゴムのエマルジョン化等が行われており、数多くの先行技術が開示されている。例えばビニルアルコール系共重合体を分散剤とし、クロロプレンとエチレン性不飽和カルボン酸を乳化重合する方法(特許文献1)が提案されている。またジエン系共重合体ラテックスについては、コンタクト接着性や耐熱クリープに関する記述は見られないものの、接着強度に優れるラテックスとして、連鎖移動剤の使用方法を規定した先行技術が提案されている。例えば重合系への単量体添加終了後も連鎖移動剤の添加を継続する方法(特許文献2)、単量体添加終了後に連鎖移動剤を別添加する方法(特許文献3)が提案されている。また共役ジエン系単量体全量を第一重合段に配合する2段重合において、第一重合段と第二重合段に使用する連鎖移動剤量を規定する方法(特許文献4)が提案されている。
しかしながら、コンタクト接着性、耐熱クリープ性、養生後接着強度をバランスよく両立させる水性接着剤を実現するという観点からは、まだ十分に満足できるものが得られていないのが実情である。また、多くのジエン系ラテックスの連鎖移動剤添加方法に関する提案についても、コンタクト接着性、耐熱クリープ性の改良については、何ら言及されていない。 However, from the viewpoint of realizing a water-based adhesive that balances contact adhesiveness, heat-resistant creep resistance, and post-curing adhesive strength in a balanced manner, the actual situation is that a sufficiently satisfactory one has not yet been obtained. In addition, no proposals have been made regarding the improvement of contact adhesiveness and heat-resistant creep resistance with respect to proposals for adding chain transfer agents to many diene latexes.
本発明は、貼り合わせ直後のコンタクト接着性に優れ、且つ耐熱クリープ性及び養生後の接着強度に優れる水性接着剤用共重合体ラテックスを提供することを課題とする。 An object of the present invention is to provide a copolymer latex for an aqueous adhesive that is excellent in contact adhesiveness immediately after bonding and excellent in heat-resistant creep resistance and adhesive strength after curing.
本発明者らは、上述の課題を解決するために鋭意検討した結果、乳化重合により共重合体ラテックスを製造するにあたり、共役ジエン系単量体を必須成分とした単量体を二段に分けて乳化重合させ、且つ第一重合段単量体を特定量の連鎖移動剤を用いて特定の重合転化率に達するまで重合させた後、第二重合段単量体と特定量の連鎖移動剤を添加して重合させることにより、その目的を達成しうることを見出し、この知見に基づいて本発明を完成するに至った。 As a result of diligent studies to solve the above-mentioned problems, the present inventors have divided the monomer containing a conjugated diene monomer as an essential component into two stages when producing a copolymer latex by emulsion polymerization. The first polymerization stage monomer is polymerized using a specific amount of chain transfer agent until a specific polymerization conversion is reached, and then the second polymerization stage monomer and a specific amount of chain transfer agent are used. It was found that the object can be achieved by adding and polymerizing, and the present invention has been completed based on this finding.
即ち、本発明は、以下の水性接着剤用共重合体ラテックス製造方法及び水性接着剤用共重合体ラテックスを提供する。 That is, the present invention provides the following method for producing a copolymer latex for aqueous adhesive and a copolymer latex for aqueous adhesive.
(1) 共役ジエン系単量体30〜70質量%、エチレン系不飽和カルボン酸単量体0.1〜15質量%、及びこれらと共重合可能な他の単量体15〜69.9質量%を乳化重合させることを含む水性接着剤用共重合体ラテックスの製造方法であって、
共役ジエン系単量体1〜69質量%を含む全単量体の30〜90質量%を、第一の連鎖移動剤を添加して重合させ、重合転化率を75%以上とする第一重合段、及び
共役ジエン系単量体1〜69質量%を含む全単量体の10〜70質量%及び第二の連鎖移動剤を添加して重合を継続する第二重合段、
を含み、且つ
第一の連鎖移動剤の、第一重合段における単量体100質量に対する質量部をa、第二の連鎖移動剤の、第二重合段における単量体100質量部に対する質量部をbとしたとき、a及びbが次式(I):
0.1≦a≦5
0.2≦b≦10 (I)
b>a
を満たすことを特徴とする、上記方法。
(1) 30 to 70% by mass of conjugated diene monomer, 0.1 to 15% by mass of ethylenically unsaturated carboxylic acid monomer, and 15 to 69.9% of other monomers copolymerizable therewith %, A method for producing a copolymer latex for an aqueous adhesive comprising emulsion polymerization of
First polymerization in which 30 to 90% by mass of all monomers including 1 to 69% by mass of the conjugated diene monomer is polymerized by adding the first chain transfer agent, and the polymerization conversion rate is 75% or more. A second polymerization stage in which the polymerization is continued by adding 10 to 70% by mass of the total monomer including 1 to 69% by mass of the conjugated diene monomer and a second chain transfer agent;
A part by mass of the first chain transfer agent relative to 100 parts by mass of the monomer in the first polymerization stage, and a part by mass of the second chain transfer agent relative to 100 parts by mass of the monomer in the second polymerization stage. Is b, a and b are represented by the following formula (I):
0.1 ≦ a ≦ 5
0.2 ≦ b ≦ 10 (I)
b> a
The method as described above, characterized in that:
(2) 前記連鎖移動剤が、メルカプタン類から選ばれる連鎖移動剤又はメルカプタン類から選ばれる連鎖移動剤とそれ以外の連鎖移動剤との組合せであり、前記第一重合段で使用される連鎖移動剤に含まれるメルカプタン類から選ばれる連鎖移動剤の第一重合段における単量体100質量部に対する質量部xと、前記第二重合段で使用される連鎖移動剤に含まれるメルカプタン類から選ばれる連鎖移動剤の第二重合段における単量体100質量部に対する質量部yが、次式(II):
0.1≦x≦5
0.2≦y≦10 (II)
y>x
を満たす、(1)記載の方法。
(2) The chain transfer agent is a chain transfer agent selected from mercaptans or a combination of a chain transfer agent selected from mercaptans and other chain transfer agents, and used in the first polymerization stage. Selected from mercaptans contained in the chain transfer agent used in the second polymerization stage, and a mass part x of 100 parts by mass of the monomer in the first polymerization stage of the chain transfer agent selected from mercaptans contained in the agent. Mass part y with respect to 100 parts by mass of the monomer in the second polymerization stage of the chain transfer agent is represented by the following formula (II):
0.1 ≦ x ≦ 5
0.2 ≦ y ≦ 10 (II)
y> x
The method according to (1), wherein
(3) 前記第二重合段において、第二重合段における単量体及び第二の連鎖移動剤の添加を開始する時点における、第一重合段における共重合物のゲル分率(m)が35〜80%である、(1)又は(2)記載の方法。 (3) In the second polymerization stage, the gel fraction (m) of the copolymer in the first polymerization stage at the start of addition of the monomer and the second chain transfer agent in the second polymerization stage is 35. The method according to (1) or (2), which is -80%.
(4) 最終的に得られた共重合体ラテックスのゲル分率(n)が40〜90%であり、かつ第一重合段における共重合物のゲル分率(m)が、次式
0.8≦(n)/(m)≦1.25
を満たす、(3)記載の方法。
(4) The gel fraction (n) of the finally obtained copolymer latex is 40 to 90%, and the gel fraction (m) of the copolymer in the first polymerization stage is
0.8 ≦ (n) / (m) ≦ 1.25
The method according to (3), wherein
(5) (1)〜(4)のいずれか一項に記載の方法で製造され得る水性接着剤用共重合体ラテックス。 (5) A copolymer latex for aqueous adhesive that can be produced by the method according to any one of (1) to (4).
本発明の共重合体ラテックスを用いることにより、貼り合わせ直後のコンタクト接着性に優れ、且つ耐熱クリープ性及び接着強度に優れる水性接着剤を実現できる。溶剤型接着剤を本発明の共重合体ラテックスで代替することが可能となり、有機溶剤に起因して発生する環境汚染等の問題を回避することができる。 By using the copolymer latex of the present invention, it is possible to realize an aqueous adhesive that is excellent in contact adhesion immediately after bonding, and excellent in heat-resistant creep resistance and adhesive strength. The solvent-type adhesive can be replaced with the copolymer latex of the present invention, and problems such as environmental pollution caused by organic solvents can be avoided.
以下、本発明を実施するための最良の形態(以下、発明の実施の形態)について詳細に説明する。なお、本発明は以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
本発明の実施の形態において、共重合体ラテックスを構成する単量体の組成は、共役ジエン系単量体30〜70質量%、エチレン系不飽和カルボン酸単量体0.1〜15質量%、及びこれらと共重合可能な他の単量体15〜69.9質量%である。 In the embodiment of the present invention, the composition of the monomer constituting the copolymer latex is 30 to 70% by mass of the conjugated diene monomer and 0.1 to 15% by mass of the ethylenically unsaturated carboxylic acid monomer. And 15 to 69.9% by mass of other monomers copolymerizable therewith.
これらの単量体を二段に分けて添加し乳化重合させて共重合体ラテックスを製造するにあたり、第一重合段における単量体(以下、第一重合段単量体とも言う)として、共役ジエン系単量体1〜69質量%及び適宜選択される他の単量体で構成され、且つ全単量体の30〜90質量%である単量体を、第一の連鎖移動剤a質量部(aは第一重合段単量体100質量部に対する質量部)を添加して重合させ、重合転化率が75%以上になってから、第二重合段における単量体(以下、第二重合段単量体とも言う)として共役ジエン系単量体1〜69質量%と適宜選択される他の単量体で構成され、且つ全単量体の10〜70質量%と第二の連鎖移動剤b質量部(bは第二重合段単量体100質量部に対する質量部)を添加して重合させる。 When these monomers are added in two stages and emulsion polymerization is carried out to produce a copolymer latex, the monomer in the first polymerization stage (hereinafter also referred to as the first polymerization stage monomer) is conjugated. A monomer composed of 1 to 69% by mass of a diene monomer and another monomer appropriately selected, and 30 to 90% by mass of the total monomer, a first chain transfer agent a mass Part (a is a mass part with respect to 100 parts by mass of the first polymerization stage monomer) and polymerized, and after the polymerization conversion rate becomes 75% or more, the monomer in the second polymerization stage (hereinafter referred to as the second polymerization stage). It is also composed of 1 to 69% by mass of a conjugated diene monomer as the polymerization stage monomer) and 10 to 70% by mass of the total monomer and the second chain. A transfer agent b parts by mass (b is a part by mass with respect to 100 parts by mass of the second polymerization stage monomer) is added for polymerization.
第一重合段単量体及び第二重合段単量体における、共役ジエン系以外の単量体は特に限定されるものではなく、1種又は複数種を適宜選択すればよい。 The monomers other than the conjugated diene system in the first polymerization stage monomer and the second polymerization stage monomer are not particularly limited, and one or more kinds may be appropriately selected.
第一重合段単量体及び第二重合段単量体の重合系への添加方法は、一括添加法、連続的に又は断続的に添加する方法、これらの方法を組み合わせた方法(例えば、単量体の一部を添加した後に、残りの単量体を重合の進行に従って連続的又は断続的に添加する方法)などいずれでもよい。 The addition method of the first polymerization stage monomer and the second polymerization stage monomer to the polymerization system may be a batch addition method, a method of adding continuously or intermittently, or a method combining these methods (for example, a simple method). Any method may be used in which a part of the monomer is added and then the remaining monomer is added continuously or intermittently as the polymerization proceeds.
第二重合段における第二重合段単量体及び第二の連鎖移動剤の添加開始は、第一重合段単量体の重合転化率が通常75%以上、好ましくは80%以上に達してからであることが必要である。75%未満では本発明の目的である、貼り合わせ直後のコンタクト接着性に優れ、且つ耐熱クリープ性に優れる共重合体ラテックスを得ることができない。 The start of addition of the second polymerization stage monomer and the second chain transfer agent in the second polymerization stage is after the polymerization conversion rate of the first polymerization stage monomer reaches usually 75% or more, preferably 80% or more. It is necessary to be. If it is less than 75%, it is not possible to obtain a copolymer latex which is the object of the present invention and has excellent contact adhesion immediately after bonding and excellent heat-resistant creep resistance.
本発明において用いられる共役ジエン系単量体としては、例えば1,3−ブタジエン、イソプレン、2,3−ジメチル−1,3−ブタジエン、2−エチル−1,3−ブタジエン、2−メチル−1,3−ブタジエン、1,3−ペンタジエン、クロロプレン、2−クロロ−1,3−ブタジエン、シクロブタジエンなどを挙げることができ、これらは1種を単独で、又は2種以上を組み合わせて使用できる。これらの中でも1,3−ブタジエンが好適に使用できる。 Examples of the conjugated diene monomer used in the present invention include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, and 2-methyl-1. , 3-butadiene, 1,3-pentadiene, chloroprene, 2-chloro-1,3-butadiene, cyclobutadiene and the like, and these can be used alone or in combination of two or more. Among these, 1,3-butadiene can be preferably used.
共役ジエン系単量体が全単量体、即ち第一及び第二重合段単量体の合計量に占める割合としては、通常30〜70質量%、好ましくは35〜65質量%である。また、第一重合段単量体及び第二重合段単量体に含まれる共役ジエン系単量体は、全重合単量体に占める割合として通常1〜69質量%、好ましくは5〜60質量%である。共役ジエン系単量体を上記範囲に設定することにより、共重合体ラテックスに適度の柔軟性と強靭性を付与して、耐熱クリープ性及び接着強度を向上させることができる。 The ratio of the conjugated diene monomer to the total amount of all monomers, that is, the first and second polymerization stage monomers, is usually 30 to 70% by mass, preferably 35 to 65% by mass. Further, the conjugated diene monomer contained in the first polymerization stage monomer and the second polymerization stage monomer is usually 1 to 69% by mass, preferably 5 to 60% by mass as a proportion of the total polymerization monomers. %. By setting the conjugated diene monomer within the above range, the copolymer latex can be imparted with appropriate flexibility and toughness, and heat resistant creep resistance and adhesive strength can be improved.
本発明における連鎖移動剤は、第一重合段単量体の重合に際して、第一の連鎖移動剤a質量部(第一重合段単量体100質量部に対する質量部)を添加し、重合率が75%以上になってから、第二重合段単量体と第二の連鎖移動剤b質量部(第二重合段単量体100質量部に対する質量部)を添加するが、その添加量はb>aで表される範囲内である必要がある。また質量部aは、通常0.1≦a≦5、好ましくは0.3≦a≦4、更に好ましくは0.5≦a≦3であり、質量部bは、通常0.2≦b≦10、好ましくは1≦b≦7、更に好ましくは2≦b≦6である。 In the polymerization of the first polymerization stage monomer, the chain transfer agent in the present invention is added with 1 part by mass of the first chain transfer agent (part by mass with respect to 100 parts by mass of the first polymerization stage monomer), and the polymerization rate is After 75% or more, the second polymerization stage monomer and b parts by mass of the second chain transfer agent (parts by mass with respect to 100 parts by mass of the second polymerization stage monomer) are added. It must be within the range represented by> a. The mass part a is usually 0.1 ≦ a ≦ 5, preferably 0.3 ≦ a ≦ 4, more preferably 0.5 ≦ a ≦ 3, and the mass part b is usually 0.2 ≦ b ≦ 3. 10, preferably 1 ≦ b ≦ 7, more preferably 2 ≦ b ≦ 6.
第一の連鎖移動剤の質量部a及び第二の連鎖移動剤の質量部bがこの範囲を満足しなければ、貼り合わせ直後のコンタクト接着性に優れ、且つ耐熱クリープ性に優れる共重合体ラテックスを得ることができない。特に、bがaよりも大きいことが重要であり、第二重合段における第二の連鎖移動剤の添加量を増して、ゲル分率を低下させることにより、貼り合わせ直後のコンタクト接着性に優れ、且つ耐熱クリープ性に優れる水性接着剤を実現できる。 If the mass part a of the first chain transfer agent and the mass part b of the second chain transfer agent do not satisfy this range, the copolymer latex is excellent in contact adhesion immediately after bonding and excellent in heat-resistant creep resistance. Can't get. In particular, it is important that b is larger than a, and by increasing the amount of the second chain transfer agent added in the second polymerization stage and reducing the gel fraction, the contact adhesion immediately after bonding is excellent. In addition, it is possible to realize a water-based adhesive having excellent heat resistance creep resistance.
連鎖移動剤の添加方法としては、例えば単量体と混合して添加する方法、連鎖移動剤を単独で添加する方法、連鎖移動剤を連続的又は断続的に添加する方法、連鎖移動剤を一括添加する方法などが挙げられるが、上記のa及びbが規定する範囲を満足していれば、その添加方法に制限はない。 As a method for adding a chain transfer agent, for example, a method of adding a mixture with a monomer, a method of adding a chain transfer agent alone, a method of adding a chain transfer agent continuously or intermittently, a batch of chain transfer agents Although the method of adding etc. is mentioned, if the range which said a and b prescribe is satisfied, there will be no restriction | limiting in the addition method.
本発明において使用される連鎖移動剤としては、例えばα−メチルスチレンダイマーなどの核置換α−メチルスチレンの二量体、n−ブチルメルカプタン、n−オクチルメルカプタン、n−ラウリルメルカプタン、n−ドデシルメルカプタン、及びt−ドデシルメルカプタンなどのメルカプタン類、テトラメチルチウラムジスルフィド、及びテトラエチルチウラムジスルフィドなどのジスルフィド類、2−エチルヘキシルチオグリコレート、ターピノーレン、シクロペンテン、シクロヘキセンなど公知の全てのものを単独又は2種以上組み合わせて使用することができる。これらの中でもメルカプタン類が好適に使用できる。 Examples of the chain transfer agent used in the present invention include dimers of nucleus-substituted α-methylstyrene such as α-methylstyrene dimer, n-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, and n-dodecyl mercaptan. , And mercaptans such as t-dodecyl mercaptan, disulfides such as tetramethylthiuram disulfide and tetraethylthiuram disulfide, 2-ethylhexyl thioglycolate, terpinolene, cyclopentene, cyclohexene alone or in combination of two or more Can be used. Among these, mercaptans can be preferably used.
第一の連鎖移動剤及び第二の連鎖移動剤は同じであっても異なっていてもよい。 The first chain transfer agent and the second chain transfer agent may be the same or different.
本発明において使用されるエチレン系不飽和カルボン酸単量体としては、例えば、アクリル酸、メタクリル酸等の一塩基性エチレン系不飽和カルボン酸単量体、イタコン酸、マレイン酸、フマル酸等の二塩基性エチレン系不飽和カルボン酸単量体等が挙げられる。これらは1種を単独で、又は2種以上を組み合わせて使用することができる。 Examples of the ethylenically unsaturated carboxylic acid monomer used in the present invention include monobasic ethylenically unsaturated carboxylic acid monomers such as acrylic acid and methacrylic acid, itaconic acid, maleic acid, and fumaric acid. And dibasic ethylenically unsaturated carboxylic acid monomers. These can be used alone or in combination of two or more.
エチレン系不飽和カルボン酸単量体の使用割合は、通常0.1〜15質量%、好ましくは0.3〜10質量%である。エチレン系不飽和カルボン酸単量体の使用量を上記範囲に設定することにより、得られる共重合体ラテックスの分散安定性を良好に保つことができる。また、共重合体ラテックスの粘度を取り扱いに支障がない適度な範囲に調整することができる。 The use ratio of the ethylenically unsaturated carboxylic acid monomer is usually 0.1 to 15% by mass, preferably 0.3 to 10% by mass. By setting the amount of the ethylenically unsaturated carboxylic acid monomer used within the above range, the dispersion stability of the resulting copolymer latex can be kept good. In addition, the viscosity of the copolymer latex can be adjusted to an appropriate range that does not hinder handling.
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と共重合可能な他の単量体としては、芳香族ビニル系単量体、(メタ)アルキルエステル単量体、シアン化ビニル系単量体、(メタ)アクリルアミド系単量体、水酸基含有エチレン系不飽和単量体などを挙げることができる。 Other monomers copolymerizable with conjugated diene monomers and ethylenically unsaturated carboxylic acid monomers include aromatic vinyl monomers, (meth) alkyl ester monomers, and vinyl cyanide monomers. Examples thereof include monomers, (meth) acrylamide monomers, and hydroxyl group-containing ethylenically unsaturated monomers.
芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、ビニルトルエン、p−メチルスチレン、o−メチルスチレン、m−メチルスチレン、エチルスチレン、ヒドロキシメチルスチレン、ビニルキシレン、ブロモスチレン、ビニルベンジルクロリド、クロロスチレン、ジビニルベンゼン、トリビニルベンゼンなどが挙げられる。これらは1種を単独で、又は2種以上を組み合わせて使用できる Aromatic vinyl monomers include styrene, α-methyl styrene, vinyl toluene, p-methyl styrene, o-methyl styrene, m-methyl styrene, ethyl styrene, hydroxymethyl styrene, vinyl xylene, bromostyrene, vinyl benzyl. Examples include chloride, chlorostyrene, divinylbenzene, and trivinylbenzene. These can be used alone or in combination of two or more.
(メタ)アルキルエステル単量体としては、例えばメチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、t−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、n−アミル(メタ)アクリレート、イソアミルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ドデシル(メタ)アクリレート、オクタデシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、グリシジル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、1−3−ブチレングリコールジ(メタ)アクリレート、1,4−ブチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,5−ペンタジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、アリル(メタ)アクリレート、ビス(4−アクリロキシポリエトキシフェニル)プロパン、フェノキシエチル(メタ)アクリレート、2,2−ビス[4−((メタ)アクリロキシエトキシ)フェニル]プロパン、2,2−ビス[4−((メタ)アクリロキシ・ジエトキシ)フェニル]プロパン、2,2−ビス[4−((メタ)アクリロキシ・ポリエトキシ)フェニル]プロパン、イソボルニル(メタ)アクリレートなどを挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用できる。 Examples of the (meth) alkyl ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl (meth). Acrylate, n-amyl (meth) acrylate, isoamylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meta) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1-3 Butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,5-pentadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate , Tetramethylolmethane tetra (meth) acrylate, allyl (meth) acrylate, bis (4-acryloxypolyethoxyphenyl) propane, phenoxyethyl (meth) Acrylate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloxy-diethoxy) phenyl] propane, 2,2-bis [4- ((Meth) acryloxy / polyethoxy) phenyl] propane, isobornyl (meth) acrylate and the like. These can be used alone or in combination of two or more.
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などを挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用できる Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like. These can be used alone or in combination of two or more.
(メタ)アクリルアミド系単量体としては、例えば(メタ)アクリルアミド、N−メチロール(メタ)アクリルアミドやN−メチル(メタ)アクリルアミドなどのN−モノアルキル(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミドなどのN,N−ジアルキル(メタ)アクリルアミド、グリシジルメタアクリルアミド、N−アルコキシ(メタ)アクリルアミド、2−アクリルアミド−2−メチルプロパンスルホン酸などをあげることができる。これらは1種を単独で、又は2種以上を組み合わせて使用できる。 Examples of (meth) acrylamide monomers include N-monoalkyl (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide and N-methyl (meth) acrylamide, N, N-dimethyl (meth) ) N, N-dialkyl (meth) acrylamide such as acrylamide, glycidylmethacrylamide, N-alkoxy (meth) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the like. These can be used alone or in combination of two or more.
水酸基含有エチレン系不飽和単量体としては、ヒドロキシエチルアクリレート、ヒドロキシメチルアクリレート、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、アリルアルコール、多価アルコールのモノアリルエーテルなどを挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用できる。 Examples of the hydroxyl group-containing ethylenically unsaturated monomer include hydroxyethyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, allyl alcohol, and monoallyl ether of polyhydric alcohol. These can be used alone or in combination of two or more.
他の単量体としては、例えばアミノエチル(メタ)アクリレートやジメチルアミノエチル(メタ)アクリレート、及び2−ビニルピリジンなどのアミノ基含有エチレン性単量体、酢酸ビニルなどのカルボン酸ビニルエステル類、塩化ビニルや塩化ビニリデンなどのハロゲン化ビニル、スチレンスルホン酸塩や2−(メタ)アクリロイルオキシエチルスルホン酸、及び(メタ)アリルスルホン酸塩などのスルホン酸基含有単量体、燐酸エチレン(メタ)アクリレートや燐酸プロピレン(メタ)アクリレート、及び2−(メタ)アクリロイルオキシエチルアシッドホスフェートなどの燐酸基含有単量体などを挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用できる。 Other monomers include, for example, aminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate, amino group-containing ethylenic monomers such as 2-vinylpyridine, and vinyl carboxylates such as vinyl acetate, Vinyl halides such as vinyl chloride and vinylidene chloride, sulfonic acid group-containing monomers such as styrene sulfonate, 2- (meth) acryloyloxyethyl sulfonic acid, and (meth) allyl sulfonate, ethylene phosphate (meth) Examples thereof include phosphate group-containing monomers such as acrylate, propylene phosphate (meth) acrylate, and 2- (meth) acryloyloxyethyl acid phosphate. These can be used alone or in combination of two or more.
本発明の実施の形態において、第二重合段単量体及び第二の連鎖移動剤の添加を開始する時点における、第一重合段共重合物のゲル分率(m)の範囲は、通常35〜80%、好ましくは40〜75%である。この範囲にゲル分率を調整することにより、耐熱クリープ性と接着強度を向上させることができる。 In the embodiment of the present invention, the range of the gel fraction (m) of the first polymerization stage copolymer at the start of addition of the second polymerization stage monomer and the second chain transfer agent is usually 35. -80%, preferably 40-75%. By adjusting the gel fraction within this range, the heat resistant creep resistance and the adhesive strength can be improved.
また、本発明の実施の形態において、最終的に得られる共重合体ラテックス中のゲル分率(n)の範囲は、通常40〜90%、好ましくは45〜85%であり、且つ第一重合段共重合物のゲル分率(m)との関係が、次式で表される範囲内であることが好ましい。
0.8≦(n)/(m)≦1.25
In the embodiment of the present invention, the range of the gel fraction (n) in the finally obtained copolymer latex is usually 40 to 90%, preferably 45 to 85%, and the first polymerization. The relationship with the gel fraction (m) of the step copolymer is preferably within the range represented by the following formula.
0.8 ≦ (n) / (m) ≦ 1.25
この範囲にゲル分率を調整することにより、貼り合わせ直後のコンタクト接着性に優れ、且つ耐熱クリープ性に優れる共重合体ラテックスを得ることができる。 By adjusting the gel fraction within this range, it is possible to obtain a copolymer latex excellent in contact adhesion immediately after bonding and excellent in heat-resistant creep resistance.
ゲル分率は公知の方法で制御できるが、連鎖移動剤の添加量により調整するのが好ましい。 The gel fraction can be controlled by a known method, but is preferably adjusted by the amount of chain transfer agent added.
本発明の実施の形態において、共重合体ラテックスの平均粒子径は、特に限定されないが、好ましくは80〜500nm、より好ましくは100〜400nmである。 In the embodiment of the present invention, the average particle diameter of the copolymer latex is not particularly limited, but is preferably 80 to 500 nm, more preferably 100 to 400 nm.
平均粒子径は、乳化重合により製造する際の、乳化剤の使用量を調節する方法や公知のシード重合法を用いることで調整することが可能である。シード用ラテックスの組成は特に限定されず、共重合体ラテックスの組成と同じであっても異なってもよい。また、シード用ラテックスは、同一反応容器で製造したものを用いても、異なる他の反応容器で製造したものを用いてもよく、その粒子径や粒子径分布、及びその使用量も特に限定されない。 The average particle diameter can be adjusted by using a method for adjusting the amount of emulsifier used in the production by emulsion polymerization or a known seed polymerization method. The composition of the latex for seed is not particularly limited, and may be the same as or different from the composition of the copolymer latex. Further, the latex for seed may be produced in the same reaction vessel or may be produced in a different other reaction vessel, and its particle size, particle size distribution, and amount used are not particularly limited. .
本発明の実施の形態において、共重合体ラテックスの製造法については、例えば、水性媒体中で乳化剤の存在下、ラジカル開始剤により重合を行う等の方法を採用することができる。 In the embodiment of the present invention, as a method for producing the copolymer latex, for example, a method of performing polymerization with a radical initiator in the presence of an emulsifier in an aqueous medium can be employed.
ここで使用する乳化剤としては、従来公知のアニオン、カチオン、両性および非イオン性の乳化剤を用いることができる。好ましい乳化剤の例としては、例えば、脂肪族セッケン、ロジン酸セッケン、アルキルスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、アルキルスルホコハク酸塩、ポリオキシエチレンアルキル硫酸塩などのアニオン性乳化剤;ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオキシプロピレンブロックコポリマーなどのノニオン性乳化剤が挙げられる。これらは1種を単独で、または2種以上を組み合わせて用いることができる。使用される乳化剤の量としては、単量体100質量部に対して、好ましくは0.1質量部〜2.0質量部である。 As the emulsifier used here, conventionally known anionic, cationic, amphoteric and nonionic emulsifiers can be used. Examples of preferred emulsifiers include, for example, anionic emulsifiers such as aliphatic soap, rosin acid soap, alkyl sulfonate, alkyl diphenyl ether disulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate; polyoxyethylene alkyl ether Nonionic emulsifiers such as polyoxyethylene alkyl allyl ether and polyoxyethylene oxypropylene block copolymer. These can be used alone or in combination of two or more. The amount of the emulsifier used is preferably 0.1 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the monomer.
また、分子中にビニル基、アクリロイル基、メタクリロイル基などのラジカル重合性の二重結合を有する反応性乳化剤を用いることも何ら差し支えない。 In addition, it is possible to use a reactive emulsifier having a radical polymerizable double bond such as a vinyl group, an acryloyl group or a methacryloyl group in the molecule.
ラジカル開始剤としては、熱又は還元剤の存在下でラジカル分解して単量体の付加重合を開始させるものであり、無機系開始剤、有機系開始剤のいずれも使用することが可能である。好ましい開始剤の例としては、例えば、ペルオキソ二硫酸塩、過酸化物、アゾビス化合物などを挙げることができる。 The radical initiator is one that initiates addition polymerization of a monomer by radical decomposition in the presence of heat or a reducing agent, and both inorganic and organic initiators can be used. . Examples of preferred initiators include peroxodisulfate, peroxide, azobis compound and the like.
このような開始剤としてより具体的には、例えば、ペルオキソ二硫酸カリウム、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸アンモニウム、過酸化水素、t−ブチルヒドロペルオキシド、過酸化ベンゾイル、2,2−アゾビスブチロニトリル、クメンヒドロペルオキシド等が挙げられる。これらは1種を単独で、または2種以上を組み合わせて用いることができる。 More specific examples of such initiators include, for example, potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, 2,2-azobisbutyro Nitrile, cumene hydroperoxide and the like can be mentioned. These can be used alone or in combination of two or more.
また、酸性亜硫酸ナトリウム、アスコルビン酸やその塩、エリソルビン酸やその塩、ロンガリットなどの還元剤を上述の重合開始剤と組み合わせて用いる、いわゆるレドックス重合法を用いることもできる。 In addition, a so-called redox polymerization method in which a reducing agent such as acidic sodium sulfite, ascorbic acid or a salt thereof, erythorbic acid or a salt thereof or Rongalite is used in combination with the above-described polymerization initiator can also be used.
共重合体ラテックスを製造する場合の重合温度としては、例えば、40〜100℃であるが、特に制限されるものではない。 The polymerization temperature for producing the copolymer latex is, for example, 40 to 100 ° C., but is not particularly limited.
また、全単量体を重合系内に添加終了後に、各単量体の重合転化率を引き上げるために重合温度を上げる方法(いわゆるクッキング工程)を採用することも可能である。このような工程における重合温度は、通常80〜100℃である。 It is also possible to employ a method of raising the polymerization temperature (so-called cooking step) in order to increase the polymerization conversion rate of each monomer after the addition of all the monomers in the polymerization system. The polymerization temperature in such a process is usually 80 to 100 ° C.
共重合体ラテックスを製造する場合の重合固形分濃度(重合が完結した際の固形分濃度。乾燥により得られた固形分質量の、元の共重合体ラテックス(水等を含む)質量に対する割合を言う。)としては、生産効率と、乳化重合時の粒子径制御の観点から、好ましくは35〜65質量%、より好ましくは40〜60質量%である。 Polymerization solid content concentration in the case of producing a copolymer latex (solid content concentration when polymerization is completed. The ratio of the solid content mass obtained by drying to the mass of the original copolymer latex (including water) ) Is preferably 35 to 65% by mass, more preferably 40 to 60% by mass, from the viewpoint of production efficiency and particle size control during emulsion polymerization.
前記共重合体ラテックスの製造に際しては、必要に応じて公知の各種重合調整剤を乳化重合時又は乳化重合終了時に用いることができる。例えばpH調整剤、キレート化剤などを使用することができる。 In the production of the copolymer latex, various known polymerization regulators can be used at the time of emulsion polymerization or at the end of emulsion polymerization, if necessary. For example, a pH adjuster, a chelating agent, etc. can be used.
pH調整剤の好ましい例としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム、炭酸水素ナトリウム、リン酸水素二ナトリウム、モノエタノールアミンやトリエタノールアミンなどのアミン類等が挙げられる。また、キレート化剤としては、例えば、エチレンジアミン四酢酸ナトリウム等が挙げられる。 Preferable examples of the pH adjuster include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium hydrogen carbonate, disodium hydrogen phosphate, amines such as monoethanolamine and triethanolamine, and the like. Examples of the chelating agent include sodium ethylenediaminetetraacetate.
ここで、本発明実施の形態の共重合体ラテックスには、その効果を損ねない限り、必要に応じて各種添加剤を添加したり、あるいは他のラテックスを混合して用いたりすることができる。例えば分散剤、消泡剤、老化防止剤、耐水化剤、殺菌剤、増粘剤、保水剤、架橋剤などを添加することができる。また、ウレタン樹脂ラテックス、アクリル樹脂ラテックスなどを混合して用いることもできる。なお、実用物性上問題のない範囲で、他の(ジエン系)共重合体ラテックスを併用してもよい。 Here, various additives may be added to the copolymer latex of the embodiment of the present invention as needed, or other latexes may be mixed and used as long as the effect is not impaired. For example, a dispersant, an antifoaming agent, an anti-aging agent, a water resistant agent, a bactericidal agent, a thickener, a water retention agent, a crosslinking agent, and the like can be added. Moreover, urethane resin latex, acrylic resin latex, etc. can also be mixed and used. In addition, other (diene) copolymer latex may be used in combination as long as there is no problem in practical properties.
次に、実施例及び比較例を挙げて本実施の形態をより具体的に説明するが、本実施の形態はその要旨を越えない限り、以下の実施例に限定されるものではない。なお、各物性の評価は以下の通りの方法で行った。 Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist. Each physical property was evaluated by the following method.
(1)ゲル分率
水酸化ナトリウムでpH8に調整した共重合体ラテックスを130℃で30分間乾燥し、ラテックスフィルムを得た。このラテックスフィルム約0.5gを精秤した。これをトルエン30mlと混合して3時間振とうした後、目開き32μmの金属網にてろ過し、残留物を130℃で1時間乾燥して乾燥質量を秤量した。もとのラテックスフィルム質量に対する残留物の乾燥質量の割合をゲル分率(%)とした。
ゲル分率(%)=(残留物乾燥質量/ラテックスフィルム質量)×100
(1) Gel fraction The copolymer latex adjusted to pH 8 with sodium hydroxide was dried at 130 ° C. for 30 minutes to obtain a latex film. About 0.5 g of this latex film was precisely weighed. This was mixed with 30 ml of toluene and shaken for 3 hours, followed by filtration through a metal net having an opening of 32 μm, and the residue was dried at 130 ° C. for 1 hour, and the dry mass was weighed. The ratio of the dry mass of the residue to the original latex film mass was defined as the gel fraction (%).
Gel fraction (%) = (residue dry mass / latex film mass) × 100
(2)重合転化率
抜き取った反応液を約1g精秤し、130℃で1時間乾燥して乾燥質量を秤量した。乾燥前質量に対する乾燥後質量の割合から固形分(質量%)を計算した。
固形分(質量%)=(乾燥後質量/乾燥前質量)×100
また、抜き取った時点での仕込み総質量に対する不揮発成分の質量及び仕込み揮発性単量体の割合から、仕込み固形分を計算した。
仕込み固形分(質量%)=
(不揮発成分質量及び仕込み揮発性単量体質量/仕込み総質量)×100
仕込み固形分に対する反応液固形分の割合から重合転化率を計算した。
重合転化率(%)=(反応液固形分/仕込み固形分)×100
(2) Polymerization conversion rate About 1 g of the extracted reaction solution was precisely weighed and dried at 130 ° C. for 1 hour to weigh the dry mass. The solid content (% by mass) was calculated from the ratio of the mass after drying to the mass before drying.
Solid content (mass%) = (mass after drying / mass before drying) × 100
Further, the charged solid content was calculated from the mass of the nonvolatile component and the ratio of the charged volatile monomer with respect to the charged total mass at the time of extraction.
Charged solid content (mass%) =
(Nonvolatile component mass and charged volatile monomer mass / total charged mass) × 100
The polymerization conversion rate was calculated from the ratio of the solid content of the reaction solution to the charged solid content.
Polymerization conversion rate (%) = (reaction liquid solid content / charged solid content) × 100
(3)ラテックスの粒子径
動的光散乱法により、光散乱光度計(シーエヌウッド社製、モデル6000)を用いて、初期角度45度−測定角度135度で測定し、数平均粒子径を求めた。
(3) Particle size of latex Measured by dynamic light scattering method using a light scattering photometer (Model 6000, manufactured by CNN Wood) at an initial angle of 45 degrees and a measurement angle of 135 degrees, and the number average particle diameter was determined. Asked.
(4)コンタクト接着性
塩化ビニル板2枚にラテックスを塗布し、50℃で5分間乾燥した。塗布した面同士を貼り合わせ、2kgのロールを2回往復させてから1分後に手で剥がし、剥離抵抗の強さと接着剤の破壊状態からコンタクト接着性の良否を判定した。判定に際しては、以下の基準に従って行った。
◎(優):剥離抵抗がかなり強く、基材両面の接着剤が凝集破壊している状態
○(良):剥離抵抗が強く、基材両面の接着剤が凝集破壊している状態
△(可):剥離抵抗が弱く、基材両面の接着剤界面付近で剥離している状態
×(不可):剥離抵抗が非常に弱く、基材両面の接着剤界面付近で剥離している状態
(4) Contact adhesion Latex was applied to two vinyl chloride plates and dried at 50 ° C. for 5 minutes. The coated surfaces were bonded to each other and peeled by hand 1 minute after reciprocating a 2 kg roll twice, and the contact adhesiveness was judged from the strength of the peeling resistance and the state of destruction of the adhesive. The determination was made according to the following criteria.
◎ (excellent): The peel resistance is quite strong and the adhesive on both sides of the base material is agglomerated and broken ○ (Good): The peel resistance is strong and the adhesive on both sides of the base material is agglomerated and broken △ (possible ): Peeling resistance is weak and the state is peeling near the adhesive interface on both sides of the substrate. × (Not possible): Peeling resistance is very weak and the state is peeling near the adhesive interface on both sides of the substrate.
(5)耐熱クリープ性
アルミ板2枚にラテックスを25mm幅で塗布し、50℃で5分間乾燥した後、塗布した面同士を長さ12mmで重ねて貼り合わせ、4.5kgのロールを2回往復させてから3日間養生した。この貼り合わせ試験片に1kgの錘を吊るして80℃の熱風循環乾燥機に入れ、クリープ破壊試験を行った。張り合わせたアルミ板が剥がれ落ちるまでの時間を測定した。
(5) Heat resistance creep resistance After applying latex to 25 mm width on two aluminum plates and drying at 50 ° C. for 5 minutes, the coated surfaces are laminated with a length of 12 mm and bonded together, and a 4.5 kg roll is applied twice. After reciprocating, it was cured for 3 days. A 1 kg weight was hung on the bonded test piece and placed in a hot air circulating dryer at 80 ° C. to conduct a creep rupture test. The time until the bonded aluminum plate peeled off was measured.
(6)接着強度
シナ合板(3プライ、厚み5.5mm)及びキャンバス(9号)生地にラテックスを25mm幅で塗布し、50℃で5分乾燥した後、塗布した面同士を貼り合わせ、4.5kgのロールを2回往復させてから3日間養生した。この貼り合わせ試験片について、剥離強度を引張り試験機で測定した。引張り速度100mm/分で180度の剥離強度を室温で測定した。
(6) Adhesive strength Latex was applied to China plywood (3 ply, thickness 5.5 mm) and canvas (No. 9) fabric in a width of 25 mm, dried at 50 ° C. for 5 minutes, and then the applied surfaces were bonded together. A 5 kg roll was reciprocated twice and then cured for 3 days. The peel strength of this bonded test piece was measured with a tensile tester. A peel strength of 180 degrees was measured at room temperature at a pulling rate of 100 mm / min.
実施例A1
攪拌装置と温度調節用ジャケットを備えた耐圧反応容器に、重合初期の原料としてイオン交換水72質量部、ドデシルベンゼンスルホン酸ナトリウム0.1質量部、平均粒子径40nmのポリスチレン製シードラテックス0.9質量部、及び第一重合段単量体中のイタコン酸を一括して仕込み、75℃にて十分に攪拌した。
Example A1
In a pressure-resistant reaction vessel equipped with a stirrer and a temperature control jacket, as a raw material for the initial stage of polymerization, 72 parts by mass of ion-exchanged water, 0.1 part by mass of sodium dodecylbenzenesulfonate, and a polystyrene seed latex of 0.9 nm in average particle size of 0.9 Itaconic acid in the mass part and the first polymerization stage monomer was charged all at once and sufficiently stirred at 75 ° C.
次いで、イタコン酸を除く表1−1記載の第一重合段単量体と第一の連鎖移動剤を、この耐圧容器内に連続的に添加した。一方、この添加開始から10分後より、水22質量部、水酸化ナトリウム0.15質量部、ドデシルベンゼンスルホン酸ナトリウム0.3質量部、及びペルオキソ二硫酸ナトリウム1.0質量部からなる水系混合物の添加を開始し、重合反応を開始させた。 Next, the first polymerization stage monomer described in Table 1-1 excluding itaconic acid and the first chain transfer agent were continuously added into the pressure vessel. On the other hand, an aqueous mixture comprising 22 parts by mass of water, 0.15 parts by mass of sodium hydroxide, 0.3 parts by mass of sodium dodecylbenzenesulfonate, and 1.0 parts by mass of sodium peroxodisulfate from 10 minutes after the start of the addition. Was started to initiate the polymerization reaction.
第一重合段単量体と第一の連鎖移動剤の添加が終了し、第一重合段単量体の重合転化率が90%になった時点で、第二重合段単量体と第二の連鎖移動剤を連続的にこの耐圧容器内に添加し、重合反応を継続させた。 When the addition of the first polymerization stage monomer and the first chain transfer agent is completed and the polymerization conversion rate of the first polymerization stage monomer reaches 90%, the second polymerization stage monomer and the second polymerization stage monomer The chain transfer agent was continuously added into the pressure vessel, and the polymerization reaction was continued.
第二重合段単量体と第二の連鎖移動剤の添加が終了してから30分後に、耐圧容器内の温度を95℃に昇温させ、95℃で1時間30分維持し重合を終了した。次いで、水酸化ナトリウムを添加してpHを8.0に調整し、スチームストリッピング法で未反応の単量体を除去した後、固形分濃度を50質量%に調整した。この共重合体ラテックスを325メッシュのフィルターを通過させて濾過し、共重合体ラテックスA1を得た。共重合体ラテックスA1の各物性の評価結果を表1−1及び表2−1に示す。 30 minutes after the addition of the second polymerization stage monomer and the second chain transfer agent is completed, the temperature in the pressure vessel is raised to 95 ° C. and maintained at 95 ° C. for 1 hour 30 minutes to complete the polymerization. did. Next, sodium hydroxide was added to adjust the pH to 8.0, and unreacted monomers were removed by a steam stripping method, and then the solid content concentration was adjusted to 50% by mass. This copolymer latex was filtered through a 325 mesh filter to obtain a copolymer latex A1. The evaluation results of the physical properties of the copolymer latex A1 are shown in Table 1-1 and Table 2-1.
実施例A2及びA3
第一重合段単量体及び第二重合段単量体の質量%を、表1−1に示した通りに変更したこと以外は、全て実施例A1と同じ手順で共重合体ラテックスA2及びA3を製造した。これら共重合体ラテックスの各物性の評価結果を表1−1及び表2−1に示す。
Examples A2 and A3
The copolymer latexes A2 and A3 were all the same procedure as in Example A1, except that the mass% of the first polymerization stage monomer and the second polymerization stage monomer were changed as shown in Table 1-1. Manufactured. The evaluation results of the physical properties of these copolymer latexes are shown in Table 1-1 and Table 2-1.
実施例A4
第一及び第二の連鎖移動剤の添加量である質量部a及びbを、表1−1に示す通りに変更したこと以外は、全て実施例A1と同じ手順で共重合体ラテックスA4を製造した。これら共重合体ラテックスの各物性の評価結果を表1−1及び表2−1に示す。
Example A4
A copolymer latex A4 is produced by the same procedure as in Example A1, except that the mass parts a and b, which are the addition amounts of the first and second chain transfer agents, are changed as shown in Table 1-1. did. The evaluation results of the physical properties of these copolymer latexes are shown in Table 1-1 and Table 2-1.
実施例A5
第一重合段単量体の組成、第二重合段単量体の組成、第一及び第二の連鎖移動剤の添加量である質量部a及びbを表1−1に示す通りに変更したこと以外は、全て実施例A1と同じ手順で共重合体ラテックスA5を製造した。これらの各物性の評価結果を表1−1及び表2−1に示す。
Example A5
The composition of the first polymerization stage monomer, the composition of the second polymerization stage monomer, and the mass parts a and b, which are the addition amounts of the first and second chain transfer agents, were changed as shown in Table 1-1. Except for this, copolymer latex A5 was produced by the same procedure as in Example A1. The evaluation results of these physical properties are shown in Table 1-1 and Table 2-1.
実施例A6
第一重合段の重合転化率を表1−1に示す通りに変更したこと以外は、全て実施例A1と同じ手順で共重合体ラテックスA6を製造した。これらの各物性の評価結果を表1−1及び表2−1に示す。
Example A6
A copolymer latex A6 was produced in the same procedure as in Example A1, except that the polymerization conversion rate in the first polymerization stage was changed as shown in Table 1-1. The evaluation results of these physical properties are shown in Table 1-1 and Table 2-1.
実施例A7
重合初期に仕込むポリスチレン製シードラテックスを1.3質量部に変更し、第一及び第二の連鎖移動剤の添加量である質量部a及びbを、表1−1に示す通りに変更したこと以外は、全て実施例A1と同じ手順で共重合体ラテックスA7を製造した。これら共重合体ラテックスの各物性の評価結果を表1−1及び表2−1に示す。
Example A7
The polystyrene seed latex charged in the initial stage of polymerization was changed to 1.3 parts by mass, and the parts a and b, which are the addition amounts of the first and second chain transfer agents, were changed as shown in Table 1-1. Except for the above, copolymer latex A7 was produced by the same procedure as in Example A1. The evaluation results of the physical properties of these copolymer latexes are shown in Table 1-1 and Table 2-1.
比較例B1及びB2
第一及び第二の連鎖移動剤の添加量である質量部a及びbを表1−2に示す通りに変更したこと以外は、全て実施例A1と同じ手順で共重合体ラテックスB1及びB2を製造した。これらの各物性の評価結果を表1−2及び表2−2に示す。
Comparative examples B1 and B2
Except that the mass parts a and b, which are the addition amounts of the first and second chain transfer agents, were changed as shown in Table 1-2, the copolymer latexes B1 and B2 were all prepared in the same procedure as in Example A1. Manufactured. The evaluation results of these physical properties are shown in Table 1-2 and Table 2-2.
比較例B3
第一重合段単量体の組成、第二重合段単量体の組成を表1−2に示す通りに変更したこと以外は、全て実施例A5と同じ手順で共重合体ラテックスB3を製造した。これらの各物性の評価結果を表1−2及び表2−2に示す。
Comparative Example B3
A copolymer latex B3 was produced by the same procedure as in Example A5 except that the composition of the first polymerization stage monomer and the composition of the second polymerization stage monomer were changed as shown in Table 1-2. . The evaluation results of these physical properties are shown in Table 1-2 and Table 2-2.
比較例B4
第一重合段の重合転化率を表1−2に示す通りに変更したこと以外は、全て実施例A1と同じ手順で共重合体ラテックスB4製造した。これらの各物性の評価結果を表1−2及び表2−2に示す。
Comparative Example B4
A copolymer latex B4 was produced in the same procedure as in Example A1, except that the polymerization conversion rate in the first polymerization stage was changed as shown in Table 1-2. The evaluation results of these physical properties are shown in Table 1-2 and Table 2-2.
比較例5
第二の連鎖移動剤の添加量である質量部bについて、表1−2に示す通りに変更し、更に第二重合段単量体及び第二の連鎖移動剤の添加終了後に、t−ドデシルメルカプタンを2.8質量部(第二重合段単量体100質量部に対して)を30分かけて添加したこと以外は、全て実施例A1と同じ手順で共重合体ラテックスB5を製造した。これらの各物性の評価結果を表1−2及び表2−2に示す。
About the mass part b which is the addition amount of a 2nd chain transfer agent, it changes as shown in Table 1-2, and also after completion | finish of addition of a 2nd polymerization stage monomer and a 2nd chain transfer agent, t-dodecyl A copolymer latex B5 was produced by the same procedure as in Example A1, except that 2.8 parts by mass of mercaptan (based on 100 parts by mass of the second polymerization stage monomer) was added over 30 minutes. The evaluation results of these physical properties are shown in Table 1-2 and Table 2-2.
本発明の形態の共重合体ラテックスは、水性接着剤用途の他、カーペットバッキング剤、各種塗料、塗工紙用バインダー、各種コーティング剤などにも用いることができる。 The copolymer latex in the form of the present invention can be used for carpet backing agents, various paints, binders for coated paper, various coating agents and the like in addition to water-based adhesive applications.
Claims (4)
該水性接着剤用共重合体ラテックスの製造方法が
共役ジエン系単量体30〜70質量%、エチレン系不飽和カルボン酸単量体0.1〜15質量%、及びこれらと共重合可能な他の単量体15〜69.9質量%を乳化重合させることを含み、該乳化重合工程が
共役ジエン系単量体1〜69質量%を含む全単量体の30〜90質量%を、第一の連鎖移動剤を添加して重合させ、重合転化率を75%以上とする第一重合段、及び
共役ジエン系単量体1〜69質量%を含む全単量体の10〜70質量%及び第二の連鎖移動剤を添加して重合を継続する第二重合段、
からなり、且つ
第一の連鎖移動剤の、第一重合段における単量体100質量に対する質量部をa、第二の連鎖移動剤の、第二重合段における単量体100質量部に対する質量部をbとしたとき、a及びbが次式(I):
0.1≦a≦5
0.2≦b≦10 (I)
b>a
を満たすことを特徴とする、
上記コンタクト接着用水性接着剤の製造方法。 A method for producing an aqueous adhesive for contact adhesion comprising a copolymer latex for aqueous adhesive ,
The method for producing the copolymer latex for aqueous adhesive is 30 to 70% by mass of a conjugated diene monomer, 0.1 to 15% by mass of an ethylenically unsaturated carboxylic acid monomer, and other copolymerizable with these. monomer from 15 to 69.9 saw including that to the mass% emulsion polymerization, 30 to 90% by weight of the total monomers emulsifying polymerization process comprises 1 to 69 wt% conjugated diene monomer, The first chain transfer agent is polymerized by adding a first chain transfer agent, and the polymerization conversion rate is 75% or more, and 10 to 70 mass of all monomers including 1 to 69 mass% of conjugated diene monomer. % And a second polymerization stage in which the second chain transfer agent is added to continue the polymerization,
And a part by mass of the first chain transfer agent with respect to 100 parts by mass of the monomer in the first polymerization stage, and a part by mass of the second chain transfer agent with respect to 100 parts by mass of the monomer in the second polymerization stage. Is b, a and b are represented by the following formula (I):
0.1 ≦ a ≦ 5
0.2 ≦ b ≦ 10 (I)
b> a
It is characterized by satisfying,
The manufacturing method of the said water-based adhesive for contact adhesion | attachment .
0.1≦x≦5
0.2≦y≦10 (II)
y>x
を満たす、請求項1記載の製造方法。 The chain transfer agent is a chain transfer agent selected from mercaptans or a combination of a chain transfer agent selected from mercaptans and other chain transfer agents, and is included in the chain transfer agent used in the first polymerization stage. The chain transfer agent selected from the mercaptans contained in the chain transfer agent used in the second polymerization stage and the mass transfer part x selected from 100 parts by mass of the monomer in the first polymerization stage of the chain transfer agent selected from the mercaptans selected The mass part y with respect to 100 parts by mass of the monomer in the second polymerization stage of the following formula (II):
0.1 ≦ x ≦ 5
0.2 ≦ y ≦ 10 (II)
y> x
The manufacturing method of Claim 1 which satisfy | fills.
0.8≦(n)/(m)≦1.25
を満たす、請求項3記載の製造方法。 The gel fraction (n) of the finally obtained copolymer latex is 40 to 90%, and the gel fraction (m) of the copolymer in the first polymerization stage is
0.8 ≦ (n) / (m) ≦ 1.25
The manufacturing method of Claim 3 which satisfy | fills.
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JP3203122B2 (en) * | 1994-03-23 | 2001-08-27 | 旭化成株式会社 | Conjugated diene copolymer latex, process for producing the same, and coating composition for paper using the same |
JPH1121414A (en) * | 1997-07-04 | 1999-01-26 | Sumika A B S Latex Kk | Copolymer latex for adhesive used for adhering rubber to fiber |
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