JPH02117981A - Emulsion-based adhesive composition - Google Patents
Emulsion-based adhesive compositionInfo
- Publication number
- JPH02117981A JPH02117981A JP26966788A JP26966788A JPH02117981A JP H02117981 A JPH02117981 A JP H02117981A JP 26966788 A JP26966788 A JP 26966788A JP 26966788 A JP26966788 A JP 26966788A JP H02117981 A JPH02117981 A JP H02117981A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- monomer
- vinyl resin
- resin emulsion
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 85
- 239000000853 adhesive Substances 0.000 title claims abstract description 31
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 7
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract 2
- 239000002904 solvent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 238000005187 foaming Methods 0.000 abstract description 4
- 239000005453 ketone based solvent Substances 0.000 abstract description 4
- 239000005456 alcohol based solvent Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- -1 alkylbenzene sulfonates Chemical class 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000012190 activator Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- LQZDDWKUQKQXGC-UHFFFAOYSA-N 2-(2-methylprop-2-enoxymethyl)oxirane Chemical compound CC(=C)COCC1CO1 LQZDDWKUQKQXGC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group 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
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LEQCYZPSDVXIJZ-UHFFFAOYSA-N cumene hydrochloride Chemical compound Cl.CC(C)C1=CC=CC=C1 LEQCYZPSDVXIJZ-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid 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
- 150000002689 maleic acids Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はエマルション系接着剤に関するもので、特定の
ソープフリーエマルションを用いることにより、塗工時
の発泡性を抑えると共に、接着力の良好な接着剤組成物
を与えることを目的とするものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an emulsion-based adhesive. By using a specific soap-free emulsion, it is possible to suppress foaming during coating and to achieve good adhesive strength. The object is to provide an adhesive composition.
従来、接着剤としては有機溶剤型のものが主流であった
が、近年では環境や人体に対する安全性の面より、溶媒
として水を使用するエマルション系接着剤が多用される
ようになってきた。Traditionally, organic solvent adhesives have been the mainstream, but in recent years, emulsion adhesives that use water as a solvent have come into widespread use due to environmental and human safety concerns.
かかる用途に使用されているエマルションとしては、酢
酸ビニル系エマルション、酢酸ビニル−エチレン共重合
体エマルション、アクリル酸エステル共重合体エマルシ
ョン、スチレン−ブタジェン共重合体ラテックス、イソ
プレンラテックス等が知られており、これらエマルショ
ンの製造法としては、安全性及び経済性の面より乳化重
合法が広く使用されている。As emulsions used for such purposes, vinyl acetate emulsions, vinyl acetate-ethylene copolymer emulsions, acrylic acid ester copolymer emulsions, styrene-butadiene copolymer latexes, isoprene latexes, etc. are known. As a method for producing these emulsions, emulsion polymerization is widely used from the viewpoint of safety and economy.
しかしながら、乳化重合法によりエマルションを製造す
る場合、重合の場を与えたり、生成したエマルションの
安定化のために、一般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ジスルホン酸塩、アルキ
ル硫酸エステル塩、高級脂肪酸塩等のアニオン界面活性
剤、ポリオキシエチレンアルキルフェニルエーテル等の
非イオン界面活性剤が単独あるいは混合物として原料モ
ノマーに対して０．５〜５重量％使用されている。However, when producing an emulsion by emulsion polymerization, alkylbenzene sulfonates, alkyldiphenyl ether disulfonates, alkyl sulfate ester salts, higher fatty acid salts, etc. are generally used to provide a polymerization site and to stabilize the produced emulsion. Nonionic surfactants such as anionic surfactants and polyoxyethylene alkylphenyl ethers are used singly or as a mixture in an amount of 0.5 to 5% by weight based on the raw material monomer.
このように乳化重合を行うに際しては、これら界面活性
剤は重要な役割を果たしているわけであるが、製造され
たエマルションを接着剤として用いる際には次のような
いくつかの問題が生じてくる。These surfactants play an important role in emulsion polymerization, but the following problems arise when using the produced emulsion as an adhesive: .
即ち、■発泡性が大きいため、エマルションに各種副資
材を配合撹拌の際、仕込容量が大となると共に混合状態
の観察が不十分となる、■エマルションを塗布する場合
泡がピンホールの原因となる、■更には該界面活性剤は
不揮発性であるため、エマルションより水分が蒸発した
後もポリマー中に残存することになり、特に界面活性剤
は親水基を有する低分子物質であるため、ポリマー皮膜
内部よりポリマーと被着体の界面に多く移行する傾向が
あり、接着剤として使用した場合、接着力を低下させる
と共に、耐水性、耐熱性、耐候性等の低下の原因にもな
ること等が指摘されている。Namely, ■Due to the high foaming property, when mixing various auxiliary materials with emulsions, the amount of preparation becomes large and the mixing state cannot be observed sufficiently.■When applying emulsions, bubbles may cause pinholes. Furthermore, since the surfactant is non-volatile, it will remain in the polymer even after the water has evaporated from the emulsion. It tends to migrate more to the interface between the polymer and the adherend than inside the film, and when used as an adhesive, it reduces adhesive strength and can also cause a decline in water resistance, heat resistance, weather resistance, etc. has been pointed out.
これら界面活性剤に起因する悪影響を改善するため各種
方法が検討されており、分子内にエチレン性不飽和結合
を有するいわゆる反応性活性剤、或いは液状ポリブタジ
ェンのマレイン酸付加体、末端にアルキルメルカプト基
を有するアクリル酸−アクリロニ） ｌ）ル共重合体等
の高分子型界面活性剤を使用する方法、並びに活性剤不
在下での乳化重合法等が知られている。Various methods have been studied to improve the adverse effects caused by these surfactants, such as so-called reactive surfactants with ethylenically unsaturated bonds in the molecule, maleic acid adducts of liquid polybutadiene, and alkyl mercapto groups at the terminals. A method using a polymer type surfactant such as an acrylic acid-acrylonyl copolymer having the following, and an emulsion polymerization method in the absence of an active agent are known.
しかしこれら反応型或いは高分子型活性剤を用いる方法
では、乳化重合において界面活性剤に要求される基本的
性能である重合の場を与えることに関しては、これら界
面活性剤の構造が複雑化しているためミセル形成能が抑
制され、乳化重合速度の低下が起こり、従って適度な重
合速度を得るには活性剤を多量に添加する必要が生じる
。そのため、これら活性剤を用いることによってたとえ
低泡性で高表面張力のエマルションを得ることができて
も、皮膜の接着性、耐熱性、耐水性等の低下を十分に改
善することができない。However, in methods using these reactive or polymeric surfactants, the structures of these surfactants are complicated in terms of providing a polymerization site, which is the basic performance required of surfactants in emulsion polymerization. As a result, the ability to form micelles is suppressed and the rate of emulsion polymerization is lowered. Therefore, in order to obtain a suitable polymerization rate, it is necessary to add a large amount of the activator. Therefore, even if it is possible to obtain an emulsion with low foaming properties and high surface tension by using these activators, it is not possible to sufficiently improve the deterioration of the adhesion, heat resistance, water resistance, etc. of the film.
さらに活性剤不在下での乳化重合についての重合法の詳
細は多くの文献に述べられているが、活性剤不在下の乳
化重合より得られた水性樹脂分散物は放置安定性と機械
的安定性が著しく悪いといった問題点があり、実用的で
ない。Furthermore, the details of the polymerization method for emulsion polymerization in the absence of an activator are described in many literatures, but the aqueous resin dispersion obtained by emulsion polymerization in the absence of an activator has poor storage stability and mechanical stability. There are problems such as extremely poor performance, making it impractical.
本発明者らは、かかる実情において優れた性能を有する
エマルンヨン系接着剤組成物を得るべく鋭意研究の結果
、下記ソープフリーエマルンヨン（Ａ）及び／又は（Ｂ
）を用いれば、本目的に対し極めて有効であることを見
出し、本発明を完成するに至った。As a result of intensive research to obtain an emulsion-based adhesive composition having excellent performance under these circumstances, the present inventors have found the following soap-free emulsion (A) and/or (B).
) was found to be extremely effective for this purpose, and the present invention was completed.
（Ａ＞塩生成基又はポリアルキレンオキサイド基を有す
る重合可能な二重結合を有する単量体０．５〜６０重世
％と、それと共重合し得る重合可能な二重結合を有する
単量体９９．５〜４０重量％とを、アルコール系及び／
又はケトン系溶剤中で溶液重合を行い均質な共重合体を
得、次にこの共重合体に、必要に応じ中和剤を加え塩生
成基をイオン化し、続いて水を加えた後、アルコール系
及び／又はケトン系溶剤を留去し水系に転相することに
より得られる粒径０．００１〜０．０５μｍの安定な自
己分散型水性ビニル樹脂エマルション。(A> 0.5 to 60% of a monomer having a polymerizable double bond having a salt-forming group or a polyalkylene oxide group, and a monomer having a polymerizable double bond that can be copolymerized with it) 99.5 to 40% by weight of alcohol and/or
Alternatively, solution polymerization is carried out in a ketone solvent to obtain a homogeneous copolymer, then a neutralizing agent is added to this copolymer as necessary to ionize the salt-forming groups, water is subsequently added, and then alcohol A stable, self-dispersing aqueous vinyl resin emulsion with a particle size of 0.001 to 0.05 μm obtained by distilling off the system and/or ketone solvent and inverting the phase to an aqueous system.
（Ｂ）上記（Ａ）の粒径０．００１〜０．０５ μｒｎ
の自己分散型水性ビニル樹脂エマルション０．５〜８０
重重％（固形分）の存在下に重合可能な不飽和結合を有
する単量体９９．５〜２０重量％をラジカル重合して得
られる水性ビニル樹脂エマルション。(B) Particle size of the above (A) 0.001 to 0.05 μrn
Self-dispersing aqueous vinyl resin emulsion of 0.5 to 80
An aqueous vinyl resin emulsion obtained by radical polymerizing 99.5 to 20% by weight of a monomer having a polymerizable unsaturated bond in the presence of 99.5% to 20% by weight (solid content).
以下に本発明の接着剤組成物の製造方法について詳細に
記す。The method for producing the adhesive composition of the present invention will be described in detail below.
上記（Ａ）で示される粒径０．００１〜０．０５ μｍ
の自己分散型水性ビニルエマルションは、転相法を特徴
とする製造方法を用いて得ることができ、より詳しくは
塩生成基又はポリアルキレンオキサイド基を有する重合
可能な二重結合を有する単量体０．５〜６０重量％と、
それと共重合し得る重合可能な二重結合を有する単量体
９９．５〜４０重量％とを、アルコール系及び／又はケ
トン系溶剤中で溶液重合を行い均質な共重合体を得、次
にこの共重合体に、必要に応じ中和剤を加え塩生成基を
イオン化し、続いて水を加えた後アルコール系及び／又
はケトン系溶剤を留去して得られる。Particle size shown in (A) above: 0.001 to 0.05 μm
The self-dispersed aqueous vinyl emulsion can be obtained using a production method characterized by a phase inversion method, more specifically a monomer having a polymerizable double bond having a salt-forming group or a polyalkylene oxide group. 0.5 to 60% by weight,
99.5 to 40% by weight of a monomer having a polymerizable double bond that can be copolymerized with it is subjected to solution polymerization in an alcoholic and/or ketone solvent to obtain a homogeneous copolymer, and then This copolymer is obtained by adding a neutralizing agent as necessary to ionize the salt-forming groups, then adding water, and then distilling off the alcohol and/or ketone solvent.
この様にして得られた自己分散型水性樹脂エマルション
は、粒子径０．００１〜０，０５μｍで、透明ないし半
透明のコロイド分散体で、レーザー光照射でチンダル現
象が認められる。The self-dispersing aqueous resin emulsion thus obtained is a transparent to semitransparent colloidal dispersion with a particle size of 0.001 to 0.05 μm, and Tyndall phenomenon is observed when irradiated with laser light.
塩生成基又はポリアルキレンオキサイド基を有し重合可
能な二重結合を有する単量体としては、アニオン性単量
体、カチオン性単量体、両性単量体、ノニオン性単量体
等があり、必要に応じて：れらを併用してもよい。更に
詳しくは、アニオン性単量体としてはアクリル酸、メタ
クリル酸、イタコン酸、マレイン酸等の不飽和カルボン
酸モノマー、スチレンスルホン酸、２−アクリルアミド
−２−メチルプロパンスルホン酸等の不飽和スルホン酸
モノマー及びその塩が挙げられ、カチオン性単量体とし
てはＮ、Ｎ−ジメチルアミノエチル（メタ）アクリレー
ト、Ｎ。Monomers having a salt-forming group or a polyalkylene oxide group and a polymerizable double bond include anionic monomers, cationic monomers, amphoteric monomers, nonionic monomers, etc. , if necessary: These may be used in combination. More specifically, the anionic monomers include unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid, and unsaturated sulfonic acids such as styrene sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. Monomers and salts thereof are mentioned, and examples of the cationic monomer include N,N-dimethylaminoethyl (meth)acrylate, N.
Ｎ−ジエチルアミンエチル（メタ）アクリレートの如き
アクリル酸又はメタクリル酸のジアルキルアミノ基を有
するエステル類、或いはこれらをハロゲン化アルキノベ
ハロゲン化ベンジル及び硫酸ジアルキルの如き公知の四
級化剤で四級化したもの等が挙げられる。ノニオン性単
量体としては、不飽和カルボン酸モノマーとポリオキシ
アルキレングリコール又は低級アルコールのポリオキシ
アルキレンオキサイド付加物とのエステル類、或いはア
リルグリシジルエーテル又は不飽和カルボン酸モノマー
のグリシジルエーテルとポリオキシアルキレングリコー
ル又は低級アルコールのポリオキシアルキレンオキサイ
ド付加物との反応物等かあ、る。両性単量体トシては、
Ｎ−（３−スルホプロピル） −Ｎ −メタクロリルオ
キシエチルーＮ、Ｎ−ジメチルアンモニウムベタイン等
がある。Acrylic acid or methacrylic acid esters having a dialkylamino group, such as N-diethylamine ethyl (meth)acrylate, or these are quaternized with known quaternizing agents such as halogenated alkinobenzyl halides and dialkyl sulfates. Examples include things. Examples of nonionic monomers include esters of unsaturated carboxylic acid monomers and polyoxyalkylene glycols or polyoxyalkylene oxide adducts of lower alcohols, or allyl glycidyl ether or glycidyl ethers of unsaturated carboxylic acid monomers and polyoxyalkylenes. Reactants of glycols or lower alcohols with polyoxyalkylene oxide adducts, etc. The amphoteric monomer is
Examples include N-(3-sulfopropyl)-N-methacryloxyethyl-N,N-dimethylammonium betaine.
本発明において、自己分散型永住樹脂エマルションの製
造に用いられる塩生成基又はポリオキシアルキレン基を
有する重合可能な二重結合を有する単量体の量は、共重
合性単量体中０．５重量％から６０重量％である。０．
５重量％未満では均一で安定な粒子径０．００１〜０．
０５μｍの自己分散型水性樹脂エマルションが得られな
い。−方、６０重量％を越えると耐水性等の物性の低下
が著しく、接着剤組成物として実用性のある樹脂が得ら
れない。In the present invention, the amount of the monomer having a polymerizable double bond having a salt-forming group or a polyoxyalkylene group used in the production of a self-dispersed permanent resin emulsion is 0.5 in the copolymerizable monomer. % to 60% by weight. 0.
If it is less than 5% by weight, the particle size is uniform and stable from 0.001 to 0.00%.
A self-dispersing aqueous resin emulsion with a diameter of 0.05 μm cannot be obtained. On the other hand, if it exceeds 60% by weight, the physical properties such as water resistance are significantly reduced, and a resin that is practical as an adhesive composition cannot be obtained.
本発明において、自己分散型水性樹脂エマルションの製
造に用いられる塩生成基又はポリオキンアルキレン基を
有する重合可能な二重結合を有する単量体以外の単量体
としては、アクリル酸メチル、アクリル酸エチル、アク
リル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、メ
タクリル酸メチル等の（メタ）アクリル酸エステル類、
エチレン等のモノオレフィン類、ブタジェン、イソプレ
ン等の共役ジオレフィン類、スチレン、ビニルトルエン
などのスチレン系モノマー、酢酸ビニル、アクリロニト
リル等ヲ始め、架橋性官能基を有する単量体としてアク
リル酸ヒドロキシエチル、アクリル酸ヒドロキシプロピ
ルなどのヒドロキシ基含有モノマー、Ｎ−メチロール（
メタ）アクリルアミド、Ｎ−ブトキンメチル（メタ）ア
クリルアミドなどのＮ−置換（メタ）アクリル糸上ツマ
−、アクリル酸グリシジル、メタクリル酸グリシジルな
どのエポキン基含有モノマーなどの１種又は２種以上か
ら選択することができる。In the present invention, monomers other than monomers having a polymerizable double bond having a salt-forming group or a polyoxine alkylene group used in the production of a self-dispersed aqueous resin emulsion include methyl acrylate, acrylic acid (Meth)acrylic acid esters such as ethyl, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,
Monoolefins such as ethylene, conjugated diolefins such as butadiene and isoprene, styrene monomers such as styrene and vinyltoluene, vinyl acetate, acrylonitrile, etc., as well as monomers with crosslinkable functional groups such as hydroxyethyl acrylate, Hydroxy group-containing monomers such as hydroxypropyl acrylate, N-methylol (
Select from one or more types of N-substituted (meth)acrylic yarns such as meth)acrylamide, N-butquine methyl(meth)acrylamide, and Epoquine group-containing monomers such as glycidyl acrylate and glycidyl methacrylate. Can be done.
このようにして得られる共重合体のＴｇは０〜５０℃が
好ましく、０℃以下では凝集力が不足し、５０℃以上で
は接着時に加熱が必要となる外、材質破壊が起こりやす
い。しかし、熱架橋性のモノマーの共重合や架橋性の各
種樹脂を配合する場合はこの限りではない。The Tg of the copolymer thus obtained is preferably 0 to 50°C; below 0°C, the cohesive force is insufficient, and above 50°C, heating is required during adhesion and material destruction is likely to occur. However, this is not the case when copolymerizing thermally crosslinkable monomers or blending various crosslinkable resins.
本発明において、自己分散型水性樹脂エマルションの製
造に用いられるアルコール系溶剤としては、例えばメタ
ノール、エタノール、ｎ−プロパツール、インプロパツ
ールが、ケトン系溶剤としてはアセトン、メチルエチル
ケトン等が挙げられ、これらは１種又は２種以上混合し
て用いても良く、又塩生成基又はポリアルキレンオキサ
イドを有する単量体のこれら溶剤に対する溶解度が低い
場合、必要に応じて水を加えることが望ましい場合もあ
る。In the present invention, alcoholic solvents used in the production of the self-dispersing aqueous resin emulsion include, for example, methanol, ethanol, n-propatool, and impropatool, and ketone solvents include acetone, methyl ethyl ketone, etc. may be used alone or in combination of two or more, and if the monomer having a salt-forming group or polyalkylene oxide has low solubility in these solvents, it may be desirable to add water as necessary. .
本発明において、自己分散型水性樹脂エマルションの製
造に用いられる開始剤としては、公知のラジカル開始剤
が用いられる。例えば、過酸化ペンゾイノペ過酢酸ｔ−
ブチル等の過酸化物類、及び２．２°−アゾビス（イン
ブチロニ） ＩＪル）、２．２“−アゾビス（２，４−
ジメチルワレロニトリル）等に代表されるアゾ重合開始
剤が挙げられる。In the present invention, a known radical initiator is used as the initiator for producing the self-dispersed aqueous resin emulsion. For example, peroxide penzoinope peracetic acid t-
peroxides such as butyl, and 2.2°-azobis(imbutyroni), 2.2″-azobis(2,4-
Examples include azo polymerization initiators such as dimethylvaleronitrile).
前記各原料を使用して均一で安定な自己分散型水性樹脂
エマルションを得るには、例えば、撹拌機、還流冷却器
、滴下ロート、温度計、チッ素ガス導入管のついた反応
器を準備し、塩生成基又はポリアルキレンオキサイド基
を有する重合可能な二重結合を有する単量体０．５〜６
０重量％と、それと共重合し得る重合可能な二重結合を
有する単量体９９．５〜４０重量％と、ラジカル開始剤
を全モノマーに対し０．１〜２．０重量％及び必要によ
っては連鎖移動剤を用い、アルコール系及びケトン系溶
剤の１種又は２種以上を用いチッ素ガス気流中で５０℃
〜溶剤還流下で均質な共重合体を得、次にこの共重合体
に、必要に応じて中和剤等を加え塩生成基をイオン化し
くすでにイオン化されている場合は不要）、続いて水を
加えた後、アルコール系及び／又ハケトン系溶剤を留去
し水系に転相することにより得られる。In order to obtain a uniform and stable self-dispersed aqueous resin emulsion using each of the above raw materials, for example, a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas introduction tube must be prepared. , a monomer having a polymerizable double bond having a salt-forming group or a polyalkylene oxide group, 0.5 to 6
0% by weight, 99.5-40% by weight of a monomer having a polymerizable double bond that can be copolymerized with it, and 0.1-2.0% by weight of a radical initiator based on the total monomers, and if necessary. using a chain transfer agent and one or more alcohol-based and ketone-based solvents at 50°C in a nitrogen gas stream.
~ Obtain a homogeneous copolymer under solvent reflux, then add a neutralizing agent to this copolymer as necessary to ionize the salt-forming groups (unnecessary if the salt-forming groups are already ionized), and then add water to the copolymer. is added, the alcoholic and/or haketonic solvent is distilled off, and the phase is inverted to an aqueous one.
上記の如き方法で得られる自己分散型水性ビニル樹脂の
数平均分子量は５．０００〜２００．０００が好適であ
る。この理由は５．０００未満では接着強度が劣り、ま
た２００．０００を越えると高粘度となり転相工程等で
支障をきたし、高濃度で安定な自己分散型水性ビニル樹
脂が得られない。The number average molecular weight of the self-dispersed aqueous vinyl resin obtained by the above method is preferably 5.000 to 200.000. The reason for this is that if it is less than 5.000, the adhesive strength will be poor, and if it exceeds 200.000, it will have a high viscosity, which will cause problems in the phase inversion step, etc., making it impossible to obtain a self-dispersed water-based vinyl resin that is stable at high concentrations.
このようにして得られたエマルションはソープフリーと
いう特徴の外に、粒径が０．００１〜０．０５μｍと小
さいという特徴も併せもっており、従って被着体の微細
な細孔にも浸透しやすく、接着力の増加に寄与する。又
粒径の小さいことから造膜性も良（、緻密な膜が得られ
ることより初期接着力も向上する。The emulsion obtained in this way is not only soap-free, but also has a small particle size of 0.001 to 0.05 μm, so it easily penetrates into the fine pores of the adherend. , which contributes to an increase in adhesive strength. In addition, since the particle size is small, the film forming property is good (and since a dense film can be obtained, the initial adhesion strength is also improved).
しかし、このような超微粒子エマルションは高粘度とな
りやすく、例えば固形分３０％で粘度が１万ｃｐ以上と
なるものが多く、一般に高濃度化が困難である。又、製
造上の制約より高分子量のものを得ることはできず、接
着剤として利用する場合、用途によっては凝集力が不足
する場合もある。However, such ultrafine particle emulsions tend to have a high viscosity, for example, many have a viscosity of 10,000 cp or more at a solid content of 30%, and it is generally difficult to increase the concentration. Furthermore, due to manufacturing constraints, it is not possible to obtain a product with a high molecular weight, and when used as an adhesive, the cohesive force may be insufficient depending on the application.
そのような場合上記（Ｂ）で示したように、（Ａ＞の自
己分散型水性ビニル樹脂エマルションの存在下に重合可
能な不飽和結合を有する単量体をラジカル重合して得ら
れる水性ビニル樹脂エマルションを利用するのが有効で
ある。In such a case, as shown in (B) above, an aqueous vinyl resin obtained by radical polymerizing a monomer having a polymerizable unsaturated bond in the presence of the self-dispersed aqueous vinyl resin emulsion of (A>). It is effective to use an emulsion.
（Ｂ）のエマルションを得る場合、いわゆるシード重合
反応が起るわけであるが、使用するシード、即ち（Ａ＞
の自己分散型水性ビニル樹脂エマルションの粒径が０．
００１〜０．０５μｍと非常に小さく、通常の界面活性
剤が形成するミセルの粒径とほぼ同等であることより、
通常の乳化重合とほぼ同等の速度で乳化重合が進み、短
時間で重合を完結することができる。又この場合、溶媒
としては主として水を使用するため、有機溶剤を多量に
使用する（Ａ）の自己分散型エマルションの製造量を極
力抑えたい場合にも有効な手段となる。When obtaining the emulsion (B), a so-called seed polymerization reaction occurs, and the seeds used, ie (A>
The particle size of the self-dispersed aqueous vinyl resin emulsion is 0.
Because it is very small at 0.001 to 0.05 μm and is almost the same as the particle size of micelles formed by ordinary surfactants,
Emulsion polymerization proceeds at approximately the same speed as normal emulsion polymerization, and can be completed in a short time. In this case, since water is mainly used as the solvent, it is also an effective means when it is desired to minimize the production amount of the self-dispersing emulsion (A), which uses a large amount of organic solvent.
サラニ（Ｂ）のエマルションでは（Ａ）エマルションの
ポリマーを殻とするいわゆる二層構造エマルションが生
成するため、芯ポリマーと酸ポリマーの種類を変えるこ
とにより、例えば酸ポリマーに強い接着力を有するポリ
マーを用い、芯ポリマーとして強い凝集力を有するポリ
マーを用いるという様に設計することにより、接着剤に
要求される粘着力、凝集力、接着力の３つをうまくバラ
ンスさせるのにも好都合である。In the Sarani (B) emulsion, a so-called two-layered emulsion with the polymer of the emulsion (A) as the shell is produced, so by changing the types of the core polymer and acid polymer, for example, a polymer with strong adhesive strength to the acid polymer can be used. By using a polymer having strong cohesive force as the core polymer, it is convenient to achieve a good balance between the three requirements of an adhesive: adhesive force, cohesive force, and adhesive force.
（Ｂ）のエマルションの製造に際して用いられる重合可
能な不飽和結合を有する単量体としては、例えば前記（
＾）エマルションの製造に使用された単量体がすべて使
用可能であり、共重合体のＴｇは前記と同じ理由で０〜
５０℃が好ましい。Examples of the monomer having a polymerizable unsaturated bond used in the production of the emulsion (B) include the above-mentioned (
^) All the monomers used in the production of the emulsion can be used, and the Tg of the copolymer is 0 to 0 for the same reason as above.
50°C is preferred.
その他にはジビニルベンゼン、エチレングリコールジア
クリレート等のジビニル化合物も使用可能で、内部架橋
を行わせると皮膜の凝集力が増し、特に耐熱接着性が向
上することになる。In addition, divinyl compounds such as divinylbenzene and ethylene glycol diacrylate can also be used, and internal crosslinking increases the cohesive force of the film and particularly improves heat-resistant adhesion.
又、（Ｂ）エマルションを得るたメ、（＾）エマルショ
ンをシードとして乳化重合を行う際に用いられる重合開
始剤としては、例えば過硫酸カリウム、過硫酸アンモニ
ウム、過酸化水素、過酸化ベンゾイル、クメンヒドロパ
ーオキサイド等の過酸化物、或いは２．２″−アゾビス
（２−アミジノプロパン）ハイドロクロリド等のアゾビ
ス系のものが使用でき、必要に応じて水溶性アミンやピ
ロ亜硫酸、重亜硫酸ソーダ、ナトリウムホルムアルデヒ
ドスルホキシレート等を賦活剤として重合触媒と組み合
わせて用いたり、また重合度調節剤として有機ハロゲン
化合物、アルキルメルカプタン類等を用いることもでき
る。(B) To obtain an emulsion, (^) Polymerization initiators used when performing emulsion polymerization using an emulsion as a seed include, for example, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, and cumene hydrochloride. Peroxides such as peroxide, or azobis-based products such as 2.2″-azobis(2-amidinopropane) hydrochloride can be used, and if necessary, water-soluble amines, pyrosulfite, sodium bisulfite, and sodium formaldehyde can be used. Sulfoxylates and the like can be used as activators in combination with polymerization catalysts, and organic halogen compounds, alkyl mercaptans, etc. can also be used as polymerization degree regulators.
（Ｂ） 、Ｔ−マルションを得るための乳化重合反応は
、本発明に係る粒子径０．００１〜０．０５μｍの高分
子エマルション（Ａ）の存在下、上記の重合性単量体、
触媒、触媒賦活剤及び重合調節剤等を適宜、適当に組み
合わせて、公知の方法で、特別の工夫を施すことな〈実
施される。(B), the emulsion polymerization reaction to obtain the T-mulsion is carried out in the presence of the polymer emulsion (A) having a particle size of 0.001 to 0.05 μm according to the present invention, the above polymerizable monomer,
It can be carried out by appropriately combining a catalyst, a catalyst activator, a polymerization regulator, etc., and using a known method without any special devising.
また、（Ｂ）エマルションを得る際、粒径０．００１〜
０．０５μｍのエマルション（Ａ）と重合性単量体との
混合比は、重合性単量体９９．８〜２０重里％に対して
、粒径０．００１〜０．０５μｍのエマルション（Ａ）
０．５〜８０重量％（固形分）である。(B) When obtaining the emulsion, the particle size is 0.001~
The mixing ratio of the emulsion (A) with a particle size of 0.05 μm and the polymerizable monomer is 99.8 to 20% of the polymerizable monomer to the emulsion (A) with a particle size of 0.001 to 0.05 μm.
It is 0.5 to 80% by weight (solid content).
粒子径０．００１〜０．０５ μｍのエマルション（Ａ
）の使用量が０．５重量％未満では適度の重合速度と乳
化分散安定性を保つことが難しく、また、８０重量％以
上であると操作が煩雑になるだけで、このシード重合物
を用いるメリットがなくなる。Emulsion with a particle size of 0.001 to 0.05 μm (A
) If the amount used is less than 0.5% by weight, it will be difficult to maintain a suitable polymerization rate and emulsion dispersion stability, and if it is more than 80% by weight, the operation will only become complicated, making it difficult to use this seed polymer. There will be no benefit.
なお、本発明に係るエマルション系接着剤組成物には、
用途に応じてトルエン、キシレン等の有機溶剤や、メラ
ミン樹脂、尿素樹脂、エポキシ樹脂、フェノール樹脂等
の熱硬化性樹脂をはじめ、炭酸カルシウム、タルク、ク
レー等の充填剤、チタン白等の色材、界面活性剤、増粘
剤、可塑剤、防腐剤、老化防止剤、紫外線吸収剤、さら
にはロジン樹脂、テルペン樹脂等の粘着付与剤を本発明
の接着剤の諸性能を低下させない範囲において適宜加え
てもよい。In addition, the emulsion adhesive composition according to the present invention includes:
Depending on the application, organic solvents such as toluene and xylene, thermosetting resins such as melamine resin, urea resin, epoxy resin, and phenol resin, fillers such as calcium carbonate, talc, and clay, and coloring materials such as titanium white. , surfactants, thickeners, plasticizers, preservatives, anti-aging agents, ultraviolet absorbers, and tackifiers such as rosin resins and terpene resins as appropriate within the range that does not reduce the various performances of the adhesive of the present invention. May be added.
さらに初期接着力を上げるため、反対のイオン性を有す
るエマルションを被着体の一方に塗布したり、アニオン
系のエマルションでは多価金・属イオン水溶液を、さら
にはブロック化インシアネートを利用する等の公知の方
法を併用することも可能である。Furthermore, in order to increase the initial adhesion strength, it is possible to apply an emulsion with the opposite ionicity to one side of the adherend, use an aqueous solution of polyvalent metal/metal ions in the case of anionic emulsions, or even use blocked incyanate. It is also possible to use these known methods in combination.
本発明に係る接着剤組成物はソープフリーエマルション
を用いることを基本としており、界面活性剤に起因する
各種悪影響を極力少なくすることができるため、各種基
材間、例えば各種合成識維、合成樹脂、紙、皮革、ゴム
、木材、金属、コンクリート、石膏、ガラス等の接着剤
として有効に利用できる。The adhesive composition according to the present invention is based on the use of a soap-free emulsion, and since it can minimize various adverse effects caused by surfactants, it can be used between various base materials, such as various synthetic fibers, synthetic resins, etc. It can be effectively used as an adhesive for paper, leather, rubber, wood, metal, concrete, plaster, glass, etc.
次に参考例、実施例を掲げて本発明を具体的に説明する
が、本発明がこれらに限定されないことは勿論である。Next, the present invention will be specifically explained with reference to reference examples and examples, but it goes without saying that the present invention is not limited thereto.
なお、例中の部及び％は特記しない限りすべて重量基準
である。In addition, all parts and percentages in the examples are based on weight unless otherwise specified.
実施例１
撹拌機、還流冷却器、滴下ロート、温度計、チッ素導入
管の付いた反応器にメチルエチルケトン１００部、メチ
ルメタクリレート４６部、２−エチルへキシルアクリレ
ート４６部及びアクリル酸８部からなるモノマー混合物
１００部中の１０部を仕込み、チッ素ガスを流し、溶存
酸素を除去する。Example 1 A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube was charged with 100 parts of methyl ethyl ketone, 46 parts of methyl methacrylate, 46 parts of 2-ethylhexyl acrylate, and 8 parts of acrylic acid. 10 parts out of 100 parts of the monomer mixture are charged and nitrogen gas is passed through to remove dissolved oxygen.
一方、滴下ロートに溶存酸素を除去した残りの９０部の
モノマー混合物溶液及びアゾビスイソブチロニトリル０
．０７部を仕込む。Meanwhile, 90 parts of the remaining monomer mixture solution from which dissolved oxygen was removed and 0 parts of azobisisobutyronitrile were added to the dropping funnel.
．． Prepare part 07.
反応器を８０℃に加熱後、アゾビスイソブチロニトリル
０゜１３部をメチルエチルケトン２部に溶解したものを
加え重合を開始し、次いで滴下ロートよりモノマーの消
費速度にあわせてモノマー溶液を滴下する。After heating the reactor to 80°C, 0°13 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added to start polymerization, and then the monomer solution is added dropwise from the dropping funnel in accordance with the monomer consumption rate. .
モノマーヲ？ｌｉ下終了後、アゾビスイソブチロニトリ
ル０．２部をメチルエチルケトン３部に溶解したものを
加え、更に２時間熟成し、均質な共重合体を得た。Monomer? After completion of the li condition, a solution of 0.2 parts of azobisisobutyronitrile dissolved in 3 parts of methyl ethyl ketone was added, and the mixture was further aged for 2 hours to obtain a homogeneous copolymer.
次にこの共重合体にトリエチルアミ７１１，５部を加え
中和し、続いてイオン交換水３００部を加えた後、減圧
下望ましくは５０℃以下でメチルエチルケトンを留去し
、自己分散型水性ビニル樹脂を得た。Next, 711.5 parts of triethylamine was added to this copolymer to neutralize it, and then 300 parts of ion-exchanged water was added, and the methyl ethyl ketone was distilled off under reduced pressure, preferably below 50°C, to form a self-dispersed water-based vinyl. Resin was obtained.
このＶ＝エマルションは透明でレーザー光線照射により
チンダル現象が認められ、粒径は０゜０２０μｍであっ
た。尚、粒径はＣ０ＵＬＴＥＲＥＬＥＣＴＲＯＮＩＣＳ
［ＮＣ製ＣＯ［ＪＬＴＥＲＭＵＤεＬ Ｎ４で測定し
た。This V=emulsion was transparent, a Tyndall phenomenon was observed when irradiated with a laser beam, and the particle size was 0.020 μm. In addition, the particle size is C0ULTERELECTRONICS
[Measured with CO [JLTERMUDεL N4 manufactured by NC].
実施例２．３及び参考例１
表１に示すモノマー組成混合物、溶媒を用いて重合を行
い、表１に記載量のトリエチルアミンで中和する他は実
施例１に従い重合を行い、安定なエマルションを得た。Example 2.3 and Reference Example 1 Polymerization was carried out using the monomer composition mixture and solvent shown in Table 1, and the polymerization was carried out according to Example 1 except for neutralization with triethylamine in the amount listed in Table 1, to obtain a stable emulsion. Obtained.
表 １ 略号は夫々次のものを示す。Table 1 The abbreviations indicate the following.
ＥＡ；エチルアクリレート
ＢＡ ； ｎ−ブチルアクリレート
２−ＨＥＭＡ ； ２−ヒドロキシエチルメタクリレー
トＡＡ；アクリル酸
２−εＨＡ；エチルへキシルアクリレートＥｔに ）リ
エチルアミン
ブレンマーＰＥ３５０ ；日本油脂製ノニオン系モノマ
ー実施例４
参考例１で得たエマルション２５部（固形分）をチッ素
導入管、撹拌機、温度計を備えた反応器にとり、イオン
交換水１９０部を加え、スチレン４８Ｌ ２−エチルへ
キシルアクリレート５０！、ジビニルベンゼン１部、グ
リシジルメタクリレート１部からなる単量体混合物１０
０部中の１０部を加え、７５℃に加熱後、２％過硫酸カ
リウム水溶液５部を加えて重合を開始し、さらに３時間
にわたって残りのモノマー混合物９０部を添加した。次
いで８０℃で１時間熟成して安定な固形分４０％のエマ
ルションを得た。EA; ethyl acrylate BA; n-butyl acrylate 2-HEMA; 2-hydroxyethyl methacrylate AA; acrylic acid 2-εHA; ethylhexyl acrylate Et) ethylamine Bremmer PE350; NOF nonionic monomer Example 4 Reference 25 parts (solid content) of the emulsion obtained in Example 1 was placed in a reactor equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 190 parts of ion-exchanged water was added, and 48 L of styrene and 50 L of 2-ethylhexyl acrylate were added. , 1 part of divinylbenzene, and 1 part of glycidyl methacrylate.
After heating to 75° C., 5 parts of a 2% aqueous potassium persulfate solution was added to initiate polymerization, and the remaining 90 parts of the monomer mixture was further added over 3 hours. The mixture was then aged at 80° C. for 1 hour to obtain a stable emulsion with a solid content of 40%.
実施例５
参考例１で得たエマルション２０部（固形分）をオート
クレーブ内に仕込み、イオン交換水１８０部、過硫酸ア
ンモニウム０．３部、ビロリン酸ソーダ０．２部を仕込
み、初期エチレン圧５０ｋｇ／ｃｍ’下、７０℃で酢酸
ビニル１００部を３時間にわたり圧入した。さらに８０
℃で１時間熟成してエチレン含１１８％のエマルション
を得た。Example 5 20 parts (solid content) of the emulsion obtained in Reference Example 1 was charged into an autoclave, 180 parts of ion-exchanged water, 0.3 parts of ammonium persulfate, and 0.2 parts of sodium birophosphate were charged, and the initial ethylene pressure was 50 kg/ 100 parts of vinyl acetate was injected under pressure at 70° C. over a period of 3 hours. 80 more
The emulsion was aged for 1 hour at ℃ to obtain an emulsion containing 118% ethylene.
比較例１
撹拌機、還流冷却機、滴下ロート、温度計、チッ素導入
管を備えた反応器に、イオン交換水１５０部、エマール
ＮＣ１部、エマルケン９３５２部、過硫酸カリウム０．
３部を仕込み、７５℃に加熱し、メチルメタクリレート
４８部、２−エチルへキシルアクリレート５０部、メタ
リルグリシジルエーテル１部、アクリル酸２部からなる
単量体混合物の１０％を添加して重合を開始し、次いで
残りの単量体混合物を３時間にわたって添加した。Comparative Example 1 In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube, 150 parts of ion-exchanged water, 1 part of Emar NC, 9352 parts of Emulken, and 0.0 parts of potassium persulfate were added.
3 parts were charged, heated to 75°C, and polymerized by adding 10% of a monomer mixture consisting of 48 parts of methyl methacrylate, 50 parts of 2-ethylhexyl acrylate, 1 part of methallyl glycidyl ether, and 2 parts of acrylic acid. was started and then the remaining monomer mixture was added over a period of 3 hours.
さらに８０℃で１時間熟成し、トリエチルアミンで中和
して固形分濃度３９％、粒径０．０８μｍのエマルショ
ンを得た。The mixture was further aged at 80° C. for 1 hour and neutralized with triethylamine to obtain an emulsion with a solid content concentration of 39% and a particle size of 0.08 μm.
比較例２
活性剤としてペレックス５Ｓ−Ｌ １部、エマルケン９
５０３部を用い、混合単量体としてスチレン４８ｍ１ブ
チルアクリレート５０部、アクリル酸２部の混合物を用
いる他は、比較例１と同様に重合を行い、固形分濃度４
０％、粒径０．１μｍのエマルションを得た。Comparative Example 2 Activator: 1 part of Perex 5S-L, Emulken 9
Polymerization was carried out in the same manner as in Comparative Example 1, except that a mixture of 48 ml of styrene, 50 parts of butyl acrylate, and 2 parts of acrylic acid was used as the mixed monomer, and the solid content concentration was 4.
An emulsion with a particle size of 0.1 μm and a particle size of 0.1 μm was obtained.
比較例３
活性剤としてエマール２Ｆ１０部を用い、混合単量体と
してメチルメタクリレート４５部、２−エチルへキシル
アクリレート５２部、アクリル酸３部を用いる他は比較
例１と同様に重合を行い、固形分濃度４０％、粒径０，
０３μｍのエマルションを得た。Comparative Example 3 Polymerization was carried out in the same manner as in Comparative Example 1, except that 10 parts of Emal 2F was used as the activator, and 45 parts of methyl methacrylate, 52 parts of 2-ethylhexyl acrylate, and 3 parts of acrylic acid were used as the mixed monomers. Minute concentration 40%, particle size 0,
An emulsion of 0.03 μm was obtained.
比較例４
シードエマルションとして参考例１で得たエマルション
を用いる替わりに、比較例３のエマルションを用いる以
外は、実施例４と同様にして固形分４０％、粒径０．０
５μｍのエマルションを得た。Comparative Example 4 The same procedure was used as in Example 4, except that instead of using the emulsion obtained in Reference Example 1 as a seed emulsion, the emulsion of Comparative Example 3 was used, with a solid content of 40% and a particle size of 0.0.
A 5 μm emulsion was obtained.
比較例５
シードエマルションとして参考例１で得たエマルション
を用いる替わりに、比較例３のエマルションを用いる以
外は、実施例５と同様にしてエチレン含量１５％のエマ
ルションを得た。Comparative Example 5 An emulsion with an ethylene content of 15% was obtained in the same manner as in Example 5, except that the emulsion of Comparative Example 3 was used instead of the emulsion obtained in Reference Example 1 as a seed emulsion.
比較例６
参考例１で得たエマルションの使用量を０．３部（固形
分）とする以外は、実施例４と同様に重合を行ったが、
最終重合率が低く、安定なエマルションが得られなかっ
た。Comparative Example 6 Polymerization was carried out in the same manner as in Example 4, except that the amount of the emulsion obtained in Reference Example 1 was 0.3 parts (solid content).
The final polymerization rate was low and a stable emulsion could not be obtained.
試験例
上記実施例及び比較例で得られたエマルション系接着剤
について、各種被接着体を用いて常態接着力、耐水接着
力を下記要領で測定した。６結果を表２に示す。Test Example The normal adhesive strength and water-resistant adhesive strength of the emulsion adhesives obtained in the above Examples and Comparative Examples were measured using various adherends in the following manner. 6 results are shown in Table 2.
常態接着カニ各種被着体（２０ｃｍ ｘ２．５ｃｍ）に
ロールでエマルションを塗布し、８０℃で１０分間乾燥
後、被着体を貼り合わせハンドローラーで圧着後、２０
℃、６５％ＲＨ恒温室で７日間放置した。この試料につ
いてオートグラフくクロスヘツドスピード１００ｍｍ／
分）で１８０℃ハクリ強度を測定した。Normally Adhesive Crab The emulsion was applied with a roll to various adherends (20 cm x 2.5 cm), and after drying at 80°C for 10 minutes, the adherends were bonded together and pressed with a hand roller, and then dried for 20 minutes.
It was left in a constant temperature room at 65% RH for 7 days. For this sample, autograph crosshead speed 100mm/
The peeling strength was measured at 180°C.
耐水接着力；同試料を２０℃で水中に８時間浸漬後、上
記方法に従いハクリ強度を測定した。Water-resistant adhesive strength: The same sample was immersed in water at 20° C. for 8 hours, and the peeling strength was measured according to the above method.
なお、比較例のエマルションの製造において使用した商
品名で示した活性剤は、いずれも花王■社製のもので、
内容は次の通りである。The activators shown by the trade names used in the production of the emulsions of comparative examples were all manufactured by Kao Corporation.
The contents are as follows.
エマールＮＣ；
ポリオキシエチレンノニルフェニルエーテル硫酸ナトリ
ウム
エマルケン９３５；
ポリオキシエチレンノニルフェニルエーテル
ペレックス５Ｓ−Ｌ ；
アルキルジフェニルエーテルジスルホン酸ジナトリウム
。Emal NC; polyoxyethylene nonylphenyl ether sodium sulfate Emalken 935; polyoxyethylene nonylphenyl ether Perex 5S-L; disodium alkyl diphenyl ether disulfonate.
エマルケン９５０； ポリオキシエチレンノニルフェニルエーテル エマール２Ｆ： アルキル硫酸エステルＮａ塩Emarken 950; Polyoxyethylene nonylphenyl ether Emar 2F: Alkyl sulfate ester sodium salt
Claims (1)
を含有することを特徴とするエマルション系接着剤組成
物。 （Ａ）塩生成基又はポリアルキレンオキサイド基を有す
る重合可能な二重結合を有する単量体０．５〜６０重量
％と、それと共重合し得る重合可能な二重結合を有する
単量体９９．５〜４０重量％とを、アルコール系及び／
又はケトン系溶剤中で溶液重合を行い均質な共重合体を
得、次にこの共重合体に、必要に応じ中和剤を加え塩生
成基をイオン化し、続いて水を加えた後、アルコール系
及び／又はケトン系溶剤を留去し水系に転相することに
より得られる粒径０．００１〜０．０５μｍの安定な自
己分散型水性ビニル樹脂エマルション。 （Ｂ）上記（Ａ）の粒径０．００１〜０．０５μｍの自
己分散型水性ビニル樹脂エマルション０．５〜８０重量
％（固形分）の存在下に重合可能な不飽和結合を有する
単量体９９．５〜２０重量％をラジカル重合して得られ
る水性ビニル樹脂エマルション。[Claims] The following soap-free emulsion (A) and/or (B)
An emulsion adhesive composition comprising: (A) 0.5 to 60% by weight of a monomer having a polymerizable double bond having a salt-forming group or a polyalkylene oxide group, and a monomer 99 having a polymerizable double bond that can be copolymerized therewith. .5 to 40% by weight, alcoholic and/or
Alternatively, solution polymerization is carried out in a ketone solvent to obtain a homogeneous copolymer, then a neutralizing agent is added to this copolymer as necessary to ionize the salt-forming groups, water is subsequently added, and then alcohol A stable, self-dispersing aqueous vinyl resin emulsion with a particle size of 0.001 to 0.05 μm obtained by distilling off the system and/or ketone solvent and inverting the phase to an aqueous system. (B) A monomer having an unsaturated bond that can be polymerized in the presence of 0.5 to 80% by weight (solid content) of the above (A) self-dispersed aqueous vinyl resin emulsion with a particle size of 0.001 to 0.05 μm. An aqueous vinyl resin emulsion obtained by radical polymerization of 99.5 to 20% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26966788A JPH02117981A (en) | 1988-10-26 | 1988-10-26 | Emulsion-based adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26966788A JPH02117981A (en) | 1988-10-26 | 1988-10-26 | Emulsion-based adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02117981A true JPH02117981A (en) | 1990-05-02 |
Family
ID=17475532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26966788A Pending JPH02117981A (en) | 1988-10-26 | 1988-10-26 | Emulsion-based adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02117981A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61152757A (en) * | 1984-12-26 | 1986-07-11 | Dainippon Toryo Co Ltd | Cationic aqueous dispersion and its production |
| JPS61264077A (en) * | 1985-05-17 | 1986-11-21 | Nitto Electric Ind Co Ltd | Water-dispersed type pressure-sensitive adhesive composition |
| JPS62241965A (en) * | 1986-04-14 | 1987-10-22 | Kao Corp | Emulsion composition |
| JPS63269668A (en) * | 1987-04-28 | 1988-11-07 | Fujitsu Ltd | Facsimile controlling system |
-
1988
- 1988-10-26 JP JP26966788A patent/JPH02117981A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61152757A (en) * | 1984-12-26 | 1986-07-11 | Dainippon Toryo Co Ltd | Cationic aqueous dispersion and its production |
| JPS61264077A (en) * | 1985-05-17 | 1986-11-21 | Nitto Electric Ind Co Ltd | Water-dispersed type pressure-sensitive adhesive composition |
| JPS62241965A (en) * | 1986-04-14 | 1987-10-22 | Kao Corp | Emulsion composition |
| JPS63269668A (en) * | 1987-04-28 | 1988-11-07 | Fujitsu Ltd | Facsimile controlling system |
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