JPH02311583A - Adhesive composition and its manufacture - Google Patents
Adhesive composition and its manufactureInfo
- Publication number
- JPH02311583A JPH02311583A JP13126789A JP13126789A JPH02311583A JP H02311583 A JPH02311583 A JP H02311583A JP 13126789 A JP13126789 A JP 13126789A JP 13126789 A JP13126789 A JP 13126789A JP H02311583 A JPH02311583 A JP H02311583A
- Authority
- JP
- Japan
- Prior art keywords
- cyanoacrylate
- fine particles
- adhesive composition
- acrylate
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 239000000853 adhesive Substances 0.000 title claims abstract description 33
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 60
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000010419 fine particle Substances 0.000 claims description 47
- 229920006037 cross link polymer Polymers 0.000 claims description 39
- 239000004830 Super Glue Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 239000002612 dispersion medium Substances 0.000 abstract description 5
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000010985 leather Substances 0.000 abstract description 3
- 239000000123 paper Substances 0.000 abstract description 3
- 239000002023 wood Substances 0.000 abstract description 3
- 239000003505 polymerization initiator Substances 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 32
- -1 n-hebutane Chemical compound 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229920001651 Cyanoacrylate Polymers 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000009974 thixotropic effect Effects 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- 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
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- YYJIYUNJTKCRHL-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC(=O)C=C YYJIYUNJTKCRHL-UHFFFAOYSA-N 0.000 description 1
- STGNLGBPLOVYMA-KDTZGSNLSA-N (z)-but-2-enedioic acid;(e)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-KDTZGSNLSA-N 0.000 description 1
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 1
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- LUYHWJKHJNFYGV-UHFFFAOYSA-N 1,2-diisocyanato-3-phenylbenzene Chemical compound O=C=NC1=CC=CC(C=2C=CC=CC=2)=C1N=C=O LUYHWJKHJNFYGV-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CPWPSURCBKTNJX-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butan-2-yl 3-oxobutanoate Chemical compound CC(=C)C(=O)OCC(CC)OC(=O)CC(C)=O CPWPSURCBKTNJX-UHFFFAOYSA-N 0.000 description 1
- IOOZKHMFNNJCMG-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)propan-2-yl 3-oxobutanoate Chemical compound CC(=C)C(=O)OCC(C)OC(=O)CC(C)=O IOOZKHMFNNJCMG-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- NGZDFOYYIXAAPC-UHFFFAOYSA-N 1-prop-2-enoyloxypropan-2-yl 3-oxobutanoate Chemical compound C=CC(=O)OCC(C)OC(=O)CC(C)=O NGZDFOYYIXAAPC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-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
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- FHPDNLOSEWLERE-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCCOC(=O)C(C)=C FHPDNLOSEWLERE-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- VHNJXLWRTQNIPD-UHFFFAOYSA-N 3-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(O)CCOC(=O)C(C)=C VHNJXLWRTQNIPD-UHFFFAOYSA-N 0.000 description 1
- JRCGLALFKDKSAN-UHFFFAOYSA-N 3-hydroxybutyl prop-2-enoate Chemical compound CC(O)CCOC(=O)C=C JRCGLALFKDKSAN-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-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
- ZGLJYJVYUYQOHR-UHFFFAOYSA-N 3-oxobutanoyl 4-hydroxy-2-methylidenebutanoate Chemical compound CC(=O)CC(=O)OC(=O)C(=C)CCO ZGLJYJVYUYQOHR-UHFFFAOYSA-N 0.000 description 1
- FJKZPONBPMKPLO-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCCOC(=O)C=C FJKZPONBPMKPLO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- GZFANJYDVVSIMZ-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCCCOC(=O)C(C)=C GZFANJYDVVSIMZ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XWUNIDGEMNBBAQ-UHFFFAOYSA-N Bisphenol A ethoxylate diacrylate Chemical compound C=1C=C(OCCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCCOC(=O)C=C)C=C1 XWUNIDGEMNBBAQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 241001115903 Raphus cucullatus Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- OQHMGFSAURFQAF-UHFFFAOYSA-N [2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C(C)=C OQHMGFSAURFQAF-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AFVLVVWMAFSXCK-VMPITWQZSA-N alpha-cyano-4-hydroxycinnamic acid Chemical group OC(=O)C(\C#N)=C\C1=CC=C(O)C=C1 AFVLVVWMAFSXCK-VMPITWQZSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 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
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VBIAXKVXACZQFW-OWOJBTEDSA-N bis(2-isocyanatoethyl) (e)-but-2-enedioate Chemical compound O=C=NCCOC(=O)\C=C\C(=O)OCCN=C=O VBIAXKVXACZQFW-OWOJBTEDSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JYLMUNQVGJUCNX-UHFFFAOYSA-N butane-1,4-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCCCO JYLMUNQVGJUCNX-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- NPERTKSDHFSDLC-UHFFFAOYSA-N ethenol;prop-2-enoic acid Chemical compound OC=C.OC(=O)C=C NPERTKSDHFSDLC-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 1
- AEAQZOCLSSZDGQ-UHFFFAOYSA-N ethylbenzene;methyl acetate Chemical compound COC(C)=O.CCC1=CC=CC=C1 AEAQZOCLSSZDGQ-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 238000005191 phase separation Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Chemical class 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、α−シアノアクリレート系接着剤組成物とそ
の製造方法に関し、更に詳しくはα−シアノアクリレー
トに対し膨潤性を示す架橋高分子微粒子を含有し１作業
性、耐衝撃性及び耐水性等に優れたα−シアノアクリレ
ート系の接着剤組成物及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an α-cyanoacrylate adhesive composition and a method for producing the same, and more specifically to crosslinked polymer fine particles exhibiting swelling property with respect to α-cyanoacrylate. The present invention relates to an α-cyanoacrylate adhesive composition containing the following properties and having excellent workability, impact resistance, water resistance, etc., and a method for producing the same.
〈従来の技術〉
従来チキントロピー性を有するα−シアノアクリレート
系接着剤としては、例えば硅素化合物で表面処理された
疎水性微分シリカを含む接着剤（米国特許第４４７７６
０７号明細書）、アセチル化ヒドロキシプロピルセルロ
ーズを含む接着剤（特開昭６３−２４８８８０号公報）
、疎水性シリカ、ポリアルキレンオキサイドの誘導体及
びこれらの混合物から成る群より選択される成分を含む
接着剤（特開昭６３−２７５６０９号公報）が提案され
ている。<Prior art> Conventional α-cyanoacrylate adhesives having chicken-tropic properties include, for example, an adhesive containing hydrophobic differential silica surface-treated with a silicon compound (U.S. Pat. No. 44,776).
07 specification), an adhesive containing acetylated hydroxypropyl cellulose (Japanese Patent Application Laid-open No. 1983-248880)
, hydrophobic silica, polyalkylene oxide derivatives, and mixtures thereof (Japanese Unexamined Patent Publication No. 63-275609) has been proposed.
しかしながら、前記各接着剤はα−シアノアクリレート
単独からなる接着剤に比べて、高い粘度とチクソトロピ
ー性を有するものの、疎水性微粉シリカ等の無機フィラ
ーを配合した場合には、ポリ−α−シアノアクリレ−１
−の高極性、高ガラス転移温度に由来する脆弱とあいま
って耐衝撃性を低下させるという欠点を有している。ま
た前記セルロースあるいはポリアルキレン誘導体を配合
した場合には、耐水性を著るしく低下させると４ｑ’１
欠点がある。However, although each of the above-mentioned adhesives has higher viscosity and thixotropy than adhesives made of α-cyanoacrylate alone, when an inorganic filler such as hydrophobic fine powder silica is blended, poly-α-cyanoacrylate 1
- It has the disadvantage of lowering impact resistance together with the fragility resulting from high polarity and high glass transition temperature. In addition, when the cellulose or polyalkylene derivative is blended, water resistance may be significantly reduced.
There are drawbacks.
従って、垂直面あるいは天井等さらには多孔質の物質の
接着が可能な優れた作業性を有し、かつ耐？ｉｊ撃性、
耐水性に優れたα−シアノアクリレート系接着剤は今だ
開発されていないのが現状である。Therefore, it has excellent workability and is capable of bonding porous materials such as vertical surfaces or ceilings, and is highly durable. ij attack,
At present, an α-cyanoacrylate adhesive with excellent water resistance has not yet been developed.
〈発明が解決しようとする課題〉
本発明の主目的は、貯蔵安定性、硬化性及び接着性能等
が良好なα−シアノアクリレート系の接着剤組成物及び
その製造方法を提供することにある。<Problems to be Solved by the Invention> The main object of the present invention is to provide an α-cyanoacrylate adhesive composition having good storage stability, curability, adhesive performance, etc., and a method for producing the same.
本発明の別の目的は、木材、皮革、紙等の多孔質材にお
いても、作業性に優れた接着剤組成物及びその製造方法
を提供することにある。Another object of the present invention is to provide an adhesive composition that has excellent workability even on porous materials such as wood, leather, and paper, and a method for producing the same.
〈課題を解決するための手段〉
本発明によれば、非水系ディスパージョン法により合成
された架橋高分子微粒子０．１〜５０，０重量％とα−
シアノアクリレート５０．０〜９９．９重量％とを含む
ことを特徴とする接着剤組成物が提供される。<Means for Solving the Problems> According to the present invention, 0.1 to 50.0% by weight of crosslinked polymer fine particles synthesized by a non-aqueous dispersion method and α-
An adhesive composition comprising 50.0 to 99.9% by weight of cyanoacrylate is provided.
また本発明によれば、α−シアノアクリレート系接着剤
組成物を製造するにあたり、（Ａ）非水系ディスパージ
ョン法により架橋高分子微粒子を製造し、非水系ディス
パージョン中の微量水分を除去する工程と、（Ｂ）該架
橋高分子微粒子を含む非水系ディスパージョンとα−シ
アノアクリレートとを混合し架橋高分子微粒子を膨潤さ
せる工程と、（Ｃ）前記（Ｂ）工程により得られる非水
系ディスパージョンとα−シアノアクリレートとの混合
物から非水系ディスパージョンの分散溶媒を除去する工
程とを含むことを特徴とする接着剤組成物の製造方法が
提供される。Further, according to the present invention, in producing the α-cyanoacrylate adhesive composition, (A) producing crosslinked polymer fine particles by a non-aqueous dispersion method and removing trace amounts of water in the non-aqueous dispersion; and (B) a step of mixing a non-aqueous dispersion containing the cross-linked polymer fine particles with α-cyanoacrylate to swell the cross-linked polymer fine particles, and (C) a non-aqueous dispersion obtained by the above step (B). and a step of removing a dispersion solvent of a non-aqueous dispersion from a mixture of .alpha.-cyanoacrylate and .alpha.-cyanoacrylate.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明の接着剤組成物は、特定の架橋高分子微粒子と、
α−シアノアクリレートとを特定量含むことを特徴とす
る。The adhesive composition of the present invention comprises specific crosslinked polymer fine particles,
It is characterized by containing a specific amount of α-cyanoacrylate.
本発明において、架橋高分子微粒子は、非水系ディスパ
ージョン法により合成されるものであって、三次元高分
子網目構造を有する架橋型の高分子微粒子である。前記
非水系ディスパージョンの製造方法に関しては、多くの
総説が発表されており、例えば松阪らの総説（色材、５
１ （１９７８）ｐ、３６）および同総説中の引用文献
に詳しく記載されている。具体的には、非水系ディスパ
ージョンは、分散媒の有機溶剤、分散相の高分子微粒子
、分散安定性を主要な構成成分とするもので、製造方法
の概要は次のとおりである。In the present invention, the crosslinked polymer fine particles are synthesized by a non-aqueous dispersion method, and are crosslinked polymer fine particles having a three-dimensional polymer network structure. Many reviews have been published regarding the manufacturing method of non-aqueous dispersions, such as the review by Matsusaka et al.
1 (1978) p. 36) and the cited references in the same review. Specifically, the non-aqueous dispersion has an organic solvent as a dispersion medium, polymer fine particles as a dispersed phase, and dispersion stability as the main components, and the outline of the manufacturing method is as follows.
まず１粒子となる高分子に対して相対的に溶解力を制限
した組成の有機溶剤を選び、この中に、分子中に分散媒
に可溶な部分と分散媒に不溶で高分子微粒子との親和性
に富む部分を合わせ持つ両親媒性安定剤（Ａｍｐｈｉｐ
ａｔｈｉｃ ５ｔａｂｉｌｉｚｅｓ）と呼ばれる分散安
定剤を溶解する。この溶液を撹拌しながら加熱して所定
の温度に保ち、次いで架橋高分子微粒子の原料となる主
にアクリルモノマー等を重合開始剤と共に添加して重合
させる。モノマーの添加が終った後も反応を続け、所定
の重合転化率に達するのを待って合成することができる
。First, select an organic solvent whose composition has a relatively limited dissolving power for the polymer particles, and add a portion of the molecule that is soluble in the dispersion medium and a portion of the molecule that is insoluble in the dispersion medium to the fine polymer particles. Amphipathic stabilizer (Amphip
A dispersion stabilizer called athic 5 tabilizes) is dissolved. This solution is heated while being stirred and maintained at a predetermined temperature, and then acrylic monomers and the like, which are the raw materials for crosslinked polymer fine particles, are added together with a polymerization initiator and polymerized. The reaction can be continued even after the addition of monomers is completed, and synthesis can be carried out after waiting until a predetermined polymerization conversion rate is reached.
一般的に非水系ディスパージョンの製造に用いられる有
機溶剤としては、脂肪族炭化水素類、芳香族炭化水素類
、アルコール類、エステル類、ケトン類等があげられる
が、本発明のα−シアノアクリレート系接着剤組成物を
製造するに当っては、α−シアノアクリレートと反応し
ない溶剤であるので好ましく、具体的には例えばｎ−ヘ
キサン。Organic solvents generally used in the production of nonaqueous dispersions include aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, esters, ketones, etc., but the α-cyanoacrylate of the present invention In producing the adhesive composition, a solvent that does not react with α-cyanoacrylate is preferred, and specifically, n-hexane is preferred.
シクロヘキサン、メチルシクロヘキサン、エチルシクロ
ヘキサン、ｎ−へブタン、ｎ−オクタン、ミネラルスピ
リット等の脂肪族炭化水素；ベンゼン、トルエン、キシ
レン、エチルベンゼン等の芳香族炭化水素；酢酸メチル
、酢酸エチル、酢酸ｎ−プロビル、酢酸１ｓｏ−プロピ
ル、酢酸ｎ−ブチル、酢酸イソブチル、エチレングリコ
ールモノエチルエーテルアセテート類；アセトン、メチ
ルエチルケトン、メチル１ｓｏ−ブチルケトン、メチル
アミルケトン、シクロヘキサノン、イソホロン等のケト
ン類を好ましく挙げることができるが。Aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, n-hebutane, n-octane, mineral spirit; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene; Methyl acetate, ethyl acetate, n-propylacetate , 1so-propyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate; preferred examples include ketones such as acetone, methyl ethyl ketone, methyl 1so-butyl ketone, methyl amyl ketone, cyclohexanone, and isophorone.
前記分散安定剤を溶解し、高分子微粒子に不溶性を示し
、α−シアノアクリレートに対し不活性なものであれば
、いかなるものでも適時選択することができ、使用に際
しては、単独若しくは混合物として用いることができる
。したがって前記架橋高分子微粒子を構成する成分は、
粒子表面に吸着あるいはグラフトして粒子を分−散安定
化する分散安定剤（以下Ａ成分と略す）と、エチレン性
不飽和単量体（以下Ｂ成分と略す）と５粒子に架橋構造
を形成する多官能反応性単量体、（以下Ｃ成分と略す）
とを含有するのが望ましい。Any dispersion stabilizer can be appropriately selected as long as it dissolves the dispersion stabilizer, shows insolubility in polymer fine particles, and is inert to α-cyanoacrylate. When used, it can be used alone or as a mixture. I can do it. Therefore, the components constituting the crosslinked polymer fine particles are:
A dispersion stabilizer (hereinafter referred to as component A) that stabilizes the dispersion of particles by adsorption or grafting to the particle surface and an ethylenically unsaturated monomer (hereinafter referred to as component B) form a crosslinked structure in the 5 particles. (hereinafter abbreviated as component C)
It is desirable to contain the following.
また前記架橋高分子微粒子の平均粒径は、好ましくは０
．０１〜１００μｍであり、且っα−シアノアクリレー
トによる膨潤度は後述するように１０重量％以上である
のが好ましい。Further, the average particle size of the crosslinked polymer fine particles is preferably 0.
．． 01 to 100 μm, and the degree of swelling by α-cyanoacrylate is preferably 10% by weight or more, as described below.
前記Ａ成分は分子中に前記分散有機溶剤に可溶な部分と
１分散有機溶剤に不溶で高分子微粒子との親和性に富む
部分とを有する両親媒性の成分であって具体的には以下
の（１）〜（５）に示す化合物を好ましく挙げることが
できる。The component A is an amphiphilic component having in its molecule a part that is soluble in the dispersion organic solvent and a part that is insoluble in the dispersion organic solvent and has high affinity with the polymer fine particles. Preferable examples include the compounds shown in (1) to (5).
（１）１２−ヒドロキシステアリン酸などの水酸基を含
有する脂肪酸の自己縮合ポリエステルと、アクリル酸グ
リシジル、又はメタクリル酸グリシジルとの付加反応物
を、他の（メタ）アクリレートもしくはエチレン性不飽
和単量体等、具体的には例えばメチル（メタ）アクリレ
ート、エチル（メタ）アクリレート、ｎ−プロピル（メ
タ）アクリレート、イソプロピル（メタ）アクリレート
、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ
）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ
−ヘキシル（メタ）アクリレート、シクロヘキシル（メ
タ）アクリレート、ベンジル（メタ）アクリレート、グ
リシジル（メタ）アクリレート、オクチル（メタ）アク
リレート、２−エチルヘキシル（メタ）アクリレート、
ラウリル（メタ）アクリレート、ステアリル（メタ）ア
クリレート、（メタ）アクリル酸、（メタ）アクリルア
ミド、酢酸ビニル、プロピオン酸ビニル、酢酸ビニル、
カプロン酸ビニル、スチレン、ビニルトルエン、イタコ
ン酸、クロトン酸、フマル酸マレイン酸、ブタジェン、
塩化ビニル、塩化ビニリデン、（メタ）アクリロニトリ
ル、フマル酸ジブチル、無水マレイン酸、ドデシル無水
コハク酸、アリルグリシジルアクリレート、２−ヒドロ
キシエチル（メタ）アクリレート、２−ヒドロキシプロ
ピル（メタ）アクリレート、３−ヒドロキシプロピル（
メタ）アクリレート、２−ヒドロキシブチル（メタ）ア
クリレート、３−ヒドロキシブチル（メタ）アクリレー
ト、４−ヒドロキシブチル（メタ）アクリレート、およ
びこれら水酸基含有（メタ）アクリレートにε−カプロ
ラクトンを開環付加させた重合性化合物等から成る群よ
り選択される１種または２種以上の化合物とを共重合し
て得られるグラフト共重合体。(1) The addition reaction product of a self-condensed polyester of a fatty acid containing a hydroxyl group such as 12-hydroxystearic acid and glycidyl acrylate or glycidyl methacrylate is added to another (meth)acrylate or ethylenically unsaturated monomer. etc., specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n
-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid, (meth)acrylamide, vinyl acetate, vinyl propionate, vinyl acetate,
Vinyl caproate, styrene, vinyltoluene, itaconic acid, crotonic acid, maleic acid fumarate, butadiene,
Vinyl chloride, vinylidene chloride, (meth)acrylonitrile, dibutyl fumarate, maleic anhydride, dodecyl succinic anhydride, allyl glycidyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (
Polymerization of meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, and ring-opening addition of ε-caprolactone to these hydroxyl group-containing (meth)acrylates. A graft copolymer obtained by copolymerizing one or more compounds selected from the group consisting of chemical compounds and the like.
（２）炭素数８以上のアルキル基をエステル側鎖とする
（メタ）アクリレート、具体的にはオクチル（メタ）ア
クリレート、２−エチルヘキシル（メタ）アクリレート
、ラウリル（メタ）アクリレート、ステアリル（メタ）
アクリレートなどの長鎖を有する単量体を含むアクリル
共重合体。(2) (Meth)acrylates with an alkyl group having 8 or more carbon atoms as an ester side chain, specifically octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate
Acrylic copolymers containing monomers with long chains such as acrylates.
（３）前記長鎖を有する（メタ）アクリレートと（メタ
）アクリル酸とを共重合した後、得られる共重合体のカ
ルボキシル基に（メタ）アクリル酸グリシジルを反応さ
せて、側鎖二重結合を有する重合体を得、該重合体に前
記（１）で用いた（メタ）アクリレートもしくはエチレ
ン性不飽和単量体を共重合して得られるグラフト共重合
体。(3) After copolymerizing the long-chain (meth)acrylate and (meth)acrylic acid, the carboxyl groups of the resulting copolymer are reacted with glycidyl (meth)acrylate to form side chain double bonds. A graft copolymer obtained by obtaining a polymer having the following and copolymerizing the (meth)acrylate or ethylenically unsaturated monomer used in the above (1) with the polymer.
（４）ミネラルスプリット許容率の高いアルキル化メラ
ミン重合体。(4) Alkylated melamine polymer with high mineral split tolerance.
（５）ポリブタジェン、ポリイソプレンなどに前記（１
）で用いた（メタ）アクリレートもしくはエチレン性不
飽和単量体をグラフト重合して得られるグラフト共重合
体。(5) The above (1) polybutadiene, polyisoprene, etc.
A graft copolymer obtained by graft polymerizing the (meth)acrylate or ethylenically unsaturated monomer used in ).
また非水系ディスパージョン中の架橋高分子微粒子の構
成成分である前記Ｂ成分としては、例えば下記一般式（
１）で表わされる（メタ）アクリレート類を挙げること
ができる。In addition, as the component B, which is a constituent component of the crosslinked polymer fine particles in the non-aqueous dispersion, for example, the following general formula (
Examples include (meth)acrylates represented by 1).
（式中Ｒ工は水素原子又はメチル基を示し、Ｒ５は水素
原子、炭素数１〜１６のアルキル基又はヒドロキシアル
キル基を示す。）前記一般式（１）で表わされる（メタ
）アクリレート類としては、例えばメチルアクリレート
、エチルアクリレート、ｎ−プロピルアクリレート、イ
ソプロピルアクリレート、ｎ−ブチルアクリレート、イ
ソブチルアクリレート、ｔ−ブチルアクリレート、ｎ−
へキシルアクリレート、シクロへキシルアクリレート、
ベンジルアクリレート、メチルメタクリレート、エチル
メタクリレート、ｎ−プロピルメタクリレート、イソプ
ロピルメタクリレート、ｎ−ブチルメタクリレート、イ
ンブチルメタクリレート、を−ブチルメタクリレート、
ｎ−へキシルメタクリレート、シクロへキシルメタクリ
レート、ベンジルメタクリレート、２−ヒドロキシエチ
ルアクリレート、２−ヒドロキシエチルメタクリレート
、２−ヒドロキシプロピルアクリレート、２−ヒドロキ
シプロピルメタクリレート、３−ヒドロキシプロピルア
クリレート、３−ヒドロキシプロピルメタクリレート、
２−ヒドロキシブチルアクリレート、２−ヒドロキシブ
チルメタクリレート、３−ヒドロキシブチルアクリレー
ト、３−ヒドロキシブチルメタクリレート、４−ヒドロ
キシブチルアクリレート、４−ヒドロキシブチルメタク
リレート、アクリル酸、メタクリル酸等を挙げることが
でき、使用に際しては単独若しくは混合物として用いる
ことができる。(In the formula, R represents a hydrogen atom or a methyl group, and R5 represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a hydroxyalkyl group.) As (meth)acrylates represented by the general formula (1), is, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-
hexyl acrylate, cyclohexyl acrylate,
Benzyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, inbutyl methacrylate, -butyl methacrylate,
n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate,
Examples include 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, acrylic acid, methacrylic acid, etc. can be used alone or as a mixture.
更に非水系ディスパージョン中の架橋高分子微粒子の構
成成分である前記Ｃ成分は、該非水系ディスパージョン
中の高分子微粒子に架橋構造を導入する方法により異な
るので、以下に該方法に沿って説明する。Furthermore, the component C, which is a component of the crosslinked polymer fine particles in the nonaqueous dispersion, differs depending on the method of introducing the crosslinked structure into the polymer fine particles in the nonaqueous dispersion, so it will be explained below according to the method. .
■分子内にラジカル重合可能なエチレン性不飽和結合を
２個以上含有する多官能反応性化合物であるＣ成分を、
Ｂ成分に混合しておき、ラジカル共重合、させることに
より架橋構造を形成させる方法である場合のＣ成分とし
ては、例えばジビニルベンゼン、ジアリルフタレート、
ジアリルテレフタレート、エチレングリコールジアクリ
レート、エチレングリコール、ジメタクリレート、ジエ
チレングリコールジアクリレート、ジエチレングリコー
ルジメタクリレート、トリエチレングリコールジアクリ
レート、トリエチレンジメタクリレート、ポリエチレン
グリコールジアクリレート、ポリエチレングリコールジ
メタクリレート、１，４−ブタンジオールジアクリレー
ト、１，４−ブタンジオールジメタクリレート、１，３
−ブチレンゲリコールジアクリレート、１，３−ブチレ
ングリコールジメタクリレート、１，６−ヘキサンジオ
ールジアクリレート、１，６−ヘキサンジオールジアク
リレート、ネオペンチルグリコールジアクリレート、ネ
オペンチルグリコールジメタクリレート、２−ヒドロキ
シ−１，３−ジアクリロキシプロパン、２−ヒドロキシ
−１，３−ジメタクリロキシプロパン、２，２−ビス〔
４−（アクリロキシエトキシ）フェニル〕プロパン、２
，２−ビス（４−＜メタクリロキシエトキシ）フェニル
〕プロパン、トリメチロールプロパントリアクリレート
、トリメチロールプロパントリメタクリレート、テトラ
メチロールメタントリアクリレート、テトラメチロール
メタントリメタクリレート。■ Component C, which is a polyfunctional reactive compound containing two or more radically polymerizable ethylenically unsaturated bonds in the molecule,
In the case of a method of forming a crosslinked structure by mixing with component B and carrying out radical copolymerization, examples of component C include divinylbenzene, diallyl phthalate,
Diallyl terephthalate, ethylene glycol diacrylate, ethylene glycol, dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,4-butane diol diacrylate Acrylate, 1,4-butanediol dimethacrylate, 1,3
-Butylene gelicol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2-hydroxy- 1,3-diacryloxypropane, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis[
4-(acryloxyethoxy)phenyl]propane, 2
, 2-bis(4-<methacryloxyethoxy)phenyl]propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate.
ペンタエリスリトールトリアクリレート、ペンタエリス
リトールトリメタクリレート、ジペンタエリスリトール
トリアクリレート、ジペンタエリスリトールトリメタク
リレート、ペンタエリスリトールテトラアクリレート、
ペンタエリスリトールテトラメタクリレート、ジペンタ
エリスリトールペンタアクリレート、ジペンタエリスリ
トールペンタメタクリレート、ジペンタエリスリトール
へキサアクリレート、ジペンタエリスリトールへキサメ
タクリレート、テトラメチロールメタンテトラアクリレ
ート、テトラメチロールメタンテトラメタクリレート等
を挙げることができ、使用に際しては、単独若しくは混
合物として用いることができる。Pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, pentaerythritol tetraacrylate,
Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, etc. can be mentioned and used. In this case, they can be used alone or as a mixture.
■相互に反応し架橋構造を形成し得る官能基を含有する
２種類以上のエチレン性不飽和単量体の多官能反応性化
合物であるＣ成分を、Ｂ成分に混合しておき、Ｂ成分の
ラジカル重合と同時か、あるいはＢ成分のラジカル重合
が終了した後に、架橋構造を形成し得る前記Ｃ成分の官
能基同士を反応させることにより架橋構造を形成させる
方法である場合のＣ成分は、前記架橋構造を形成し得る
官能基の組み合わせ、即ちエポキシ基とカルボキシル基
、エポキシ基とアセトアセトキシ基の組合せにより分け
ることができる。■ Component C, which is a polyfunctionally reactive compound of two or more types of ethylenically unsaturated monomers containing functional groups that can react with each other to form a crosslinked structure, is mixed with component B. In the case where the method is to form a crosslinked structure by reacting the functional groups of the C component that can form a crosslinked structure with each other simultaneously with the radical polymerization or after the radical polymerization of the B component is completed, the C component is the above-mentioned component C. They can be classified according to the combination of functional groups that can form a crosslinked structure, ie, the combination of an epoxy group and a carboxyl group, or a combination of an epoxy group and an acetoacetoxy group.
前記エポキシ基を含有するエチレン性不飽和単量体とし
ては、例えばグリシジルアクリレート、グリシジルメタ
アクリレート、アリルグリシジルエーテル等を、またカ
ルボキシル基を有するエチレン性不飽和単量体としては
、例えばアクリル酸、メタクリル酸、イタコン酸、クロ
トン酸、フマル酸、マレインを、アセトアセトキシ基を
有するエチレン性不飽和単量体としては、例えば２−ア
セトアセトキシエチルアクリレート、２−アセトアセト
キシエチルメタクリレート、２−アセトアセトキシプロ
ピルアクリレート、２−アセトアセトキシプロピルメタ
クリレート、３−アセトアセトキシプロピルアクリレー
ト、３−アセトアセトキシプロピルメタクリレート、２
−アセトアセトキシブチルアクリレート、２−アセトア
セトキシブチルメタクリレート、３−アセトアセトキシ
ブチルアクリレート、３−アセトアセトキシブチルメタ
クリレート、４−７セトアセトキシブチルアクリレート
、４−アセトアセトキシブチルメタクリレート、アリル
アセトアセテート等を挙げることができ、使用に際して
は、夫々単独若しくは混合物として用いることができる
。これらの官能基を有するエチレン性不飽和単量体をＣ
成分として用いることにより、エポキシ基とカルボキシ
基のエステル化反応およびアセトアセトキシ基とエポキ
シ基間の炭素−炭素結合生成反応により１粒子内部に架
橋構造を導入することができる。Examples of the ethylenically unsaturated monomer containing an epoxy group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc., and examples of the ethylenically unsaturated monomer containing a carboxyl group include acrylic acid, methacrylate, etc. Examples of ethylenically unsaturated monomers having an acetoacetoxy group include 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, and 2-acetoacetoxypropyl acrylate. , 2-acetoacetoxypropyl methacrylate, 3-acetoacetoxypropyl acrylate, 3-acetoacetoxypropyl methacrylate, 2
-acetoacetoxybutyl acrylate, 2-acetoacetoxybutyl methacrylate, 3-acetoacetoxybutyl acrylate, 3-acetoacetoxybutyl methacrylate, 4-7cetoacetoxybutyl acrylate, 4-acetoacetoxybutyl methacrylate, allyl acetoacetate, etc. They can be used individually or as a mixture. Ethylenically unsaturated monomers having these functional groups are
By using it as a component, a crosslinked structure can be introduced into one particle through the esterification reaction between an epoxy group and a carboxy group and the carbon-carbon bond formation reaction between an acetoacetoxy group and an epoxy group.
■Ｂ酸成分有するヒドロキシ基と反応し、架橋構造を形
成し得る多官能反応性化合物であるＣ成分をＢ成分に混
合するか、あるいは別途反応系中に加えるかして、Ｂ成
分の重合と同時か、あるいはＢ成分の重合が終了した後
に、Ｂ成分のヒドロキシ基と、Ｃ成分の官能基とを反応
させることにより架橋構造を形成させる方法である場合
のＣ成分、更に具体的には、Ｂ成分中のヒドロキシ基を
利用し、多価イソシアネート化合物とのウレタン化反応
、あるいは多価アルコキシメチル化メラミンとのエーテ
ル化反応により架橋させる場合のＣ成分である多価イソ
シアネート化合物としては、例えばｐ−フェニレンジイ
ソシアネート、ビフェニルジイソシアネート、トルエン
ジイソシアネート、３，３′−ジメチル−４，４′−ビ
フェニレンジイソシアネート、１，４−テトラメチレン
ジイソシアネート、ヘキサメチレンジイソシアネート、
２，２．４−トリメチルヘキサン−１，６−ジイソシア
ネート、メチレンビス（フェニルイソシアネート）、リ
ジンメチルエステルジイソシアネート、ビス（イソシア
ナートエチル）フマレート、イソホロンジイソシアネー
ト、メチルシクロへキシルジイソシアネート等を用いる
ことができ、また、メラミン樹脂とのエーテル交換反応
による架橋を行なう場合には、Ｃ成分として多価アルコ
キシメチル化メラミン、例えば市販品の［サイヌル２３
５Ｊ、ｒ同３００Ｊ、ｒ同３０３Ｊ （商品名、三井
東圧化学（株） ｍｌ）、「ニカラックＭＷ−３０ＭＪ
、ｒ同ＭＷ−３０Ｊ 、ｒ同ＭＸ−４０Ｊｔ「同ＭＸ−
４８５４、ｒ同ＭＷ−２２Ｊ （商品名。■ Component C, which is a polyfunctional reactive compound that can react with the hydroxyl group of the B acid component and form a crosslinked structure, is mixed with the B component or added separately to the reaction system, and the polymerization of the B component is carried out. Component C, more specifically, when the method is to form a crosslinked structure by reacting the hydroxyl group of component B and the functional group of component C, either simultaneously or after the polymerization of component B is completed, The polyvalent isocyanate compound which is the C component when crosslinking is carried out by a urethanization reaction with a polyvalent isocyanate compound or an etherification reaction with a polyvalent alkoxymethylated melamine using the hydroxy group in the B component, for example, p -phenylene diisocyanate, biphenyl diisocyanate, toluene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate,
2,2.4-trimethylhexane-1,6-diisocyanate, methylene bis(phenylisocyanate), lysine methyl ester diisocyanate, bis(isocyanatoethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, etc. can be used, and When crosslinking is carried out by an ether exchange reaction with a melamine resin, polyhydric alkoxymethylated melamine is used as the C component, such as the commercially available [Synul 23].
5J, r-300J, r-303J (product name, Mitsui Toatsu Chemical Co., Ltd. ml), "Nikalac MW-30MJ
, r the same MW-30J, r the same MX-40Jt "the same MX-
4854, r MW-22J (product name.
、三相ケミカル（株）製）、「スミマールＭ１００−〇
、「同Ｍ−５５」、ｒ同Ｍ−４０ＳＪ（商品名、住友化
学工業（株）Ｉ） 、ｒレジミン７４５Ｊ。, manufactured by Sanso Chemical Co., Ltd.), ``Sumimar M100-0'', ``Sumimar M-55'', ``Sumimar M-40SJ'' (trade name, Sumitomo Chemical Co., Ltd. I), ``Resumimar 745J''.
「同７４７Ｊ、ｒ同７５３」、ｒ同７５５Ｊ （商品
名、モンサンド（株）製）等を挙げることができ、使用
に際しては、夫々単独若しくは混合物として用いること
ができる。Examples include "Dodo747J, rDo753" and rDo755J (trade name, manufactured by Monsando Co., Ltd.), and when used, each can be used alone or as a mixture.
前記架橋高分子微粒子を構成する原料成分であるＡ成分
、Ｂ成分及びＣ成分の配合割合は、Ａ成分０．１〜４９
．９重量％、Ｂ成分５０〜９９．８重量％、Ｃ成分０．
１〜４０重量％であるのが好ましく、特にＣ成分として
相互に反応し架橋構造を形成し得る官能基を有する２種
以上のエチレン性不飽和単量体を用いる場合には、前記
の範囲内で、反応する官能基のモル数を等しくするのが
望ましい。この際前記Ｃ成分が、０．１重量％未満では
、本発明のα−シアノアクリレート系接着剤組成物は、
著しい曳糸性を示したり、物理的性能を充分発揮するこ
とができないので好ましくない。また、４０重量％を超
える場合には非水系ディスパージョンの製造途中でゲル
化したり、架橋高分子微粒子の架橋密度が高くなりすぎ
るため、所望のα−シアノアクリレートによる膨潤度が
得られず、その結果、接着性能等が低下するので好まし
くない。The blending ratio of component A, component B, and component C, which are the raw material components constituting the crosslinked polymer fine particles, is 0.1 to 49% of component A.
．． 9% by weight, B component 50-99.8% by weight, C component 0.
It is preferably 1 to 40% by weight, and particularly when using two or more ethylenically unsaturated monomers having functional groups that can react with each other to form a crosslinked structure as the C component, it is within the above range. It is desirable to equalize the number of moles of functional groups that react. At this time, if the C component is less than 0.1% by weight, the α-cyanoacrylate adhesive composition of the present invention
It is not preferable because it exhibits remarkable stringiness and cannot exhibit sufficient physical performance. In addition, if it exceeds 40% by weight, gelation may occur during the production of the non-aqueous dispersion, or the crosslinking density of the crosslinked polymer fine particles will become too high, making it impossible to obtain the desired degree of swelling due to α-cyanoacrylate. As a result, adhesive performance etc. deteriorate, which is not preferable.
前記Ａ成分、Ｂ成分及びＣ成分を原料成分として含む架
橋高分子微粒子は、後述の製造方法により容易に得るこ
とができる。Crosslinked polymer fine particles containing component A, component B, and component C as raw material components can be easily obtained by the production method described below.
本発明の接着剤組成物に用いるα−シアノアクリレート
としては、α−シアノアクリル酸のメチル、エチル、ク
ロロエチル、ｎ−プロピル、ｊ−プロピル、アリル、プ
ロパギル、ｎ−ブチル、ｉ−ブチル、ｔ−ブチル、ｎ−
ペンチル、ｎ−ヘキシル、シクロヘキシル、フェニル、
テトラヒドロフルフリル、ペンチル、２−エチルヘキシ
ル、ｎ−オクチル、ｎ−ノニル、ｎ−デシル、ｎ−ドデ
シル、２−エトキシエチル、３−メトキシブチル、２−
エトキシ−２−エトキシエチル、２，２．２−トリフル
オロエチル、ヘキサフルオロイソプロピル等のエステル
類等を好ましく挙げることができる。The α-cyanoacrylate used in the adhesive composition of the present invention includes methyl, ethyl, chloroethyl, n-propyl, j-propyl, allyl, propargyl, n-butyl, i-butyl, and t-cyanoacrylate. Butyl, n-
pentyl, n-hexyl, cyclohexyl, phenyl,
Tetrahydrofurfuryl, pentyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, 2-ethoxyethyl, 3-methoxybutyl, 2-
Preferable examples include esters such as ethoxy-2-ethoxyethyl, 2,2.2-trifluoroethyl, and hexafluoroisopropyl.
本発明の接着剤組成物において、必須の構成成分として
含有される前記架橋高分子微粒子と、α−シアノアクリ
レートとの配合割合は、架橋高分子微粒子０．１〜５０
重量％、α−シアノアクリレート５０〜９９．９重量％
の範囲である。この際架橋高分子微粒子の配合割合が０
．１重量％未満の場合には、高チクソトロピー化および
物性面での改良効果が小さく、また５０重量％を超える
場合には、最終接着剤組成物の粘度が高くなりすぎ実用
的でないので前記配合割合範囲とする必要がある。In the adhesive composition of the present invention, the blending ratio of the crosslinked polymer fine particles contained as an essential component and α-cyanoacrylate is 0.1 to 50% of the crosslinked polymer fine particles.
Weight%, α-cyanoacrylate 50-99.9% by weight
is within the range of At this time, the blending ratio of crosslinked polymer fine particles is 0.
．． If it is less than 1% by weight, the effects of increasing thixotropy and improving physical properties will be small, and if it exceeds 50% by weight, the viscosity of the final adhesive composition will become too high to be practical, so the above-mentioned blending ratio It needs to be within the range.
本発明において、前記各成分を含む接着剤組成物中の架
橋高分子微粒子は、接着剤組成物の剥離強度および耐衝
撃性などの物理的性能の向上、および耐水性、耐薬品性
の向上に大きく寄与する成分であって、α−シアノアク
リレートにより膨潤するため、接着硬化後の該組成物の
内部構造は、ポリ−α−シアノアクリレートが該微粒子
内部を貫通したり、該微粒子の三次元高分子網目と絡み
合った状態となる。このため、硬化物とした際にガラス
転移温度を低下させることが可能であり。In the present invention, the crosslinked polymer fine particles in the adhesive composition containing each of the above components improve physical properties such as peel strength and impact resistance of the adhesive composition, and improve water resistance and chemical resistance. Since poly-α-cyanoacrylate is a major contributing component and swells due to α-cyanoacrylate, the internal structure of the composition after adhesive curing is such that poly-α-cyanoacrylate penetrates inside the fine particles, and the three-dimensional height of the fine particles increases. It becomes entangled with the molecular network. For this reason, it is possible to lower the glass transition temperature when it is made into a cured product.
しかも三次元高分子網目構造を導入することにより水や
薬品等の浸透速度を著しく低下させることができる。Moreover, by introducing a three-dimensional polymer network structure, the permeation rate of water, chemicals, etc. can be significantly reduced.
また架橋高分子微粒子は、α−シアノ７クリレート中に
おいても１粒子の形体を保ち、流動性調整機能を備える
成分である。Further, the crosslinked polymer fine particles maintain the shape of one particle even in α-cyano 7 acrylate, and are a component having a fluidity adjusting function.
本発明の接着剤組成物を製造するには、まず（Ａ）工程
として、非水系ディスパージョン法により架橋高分子微
粒子を製造し、非水系ディスパージョン中の微量水分を
除去する。架橋高分子微粒子を製造するには、前記Ａ成
分、Ｂ成分、Ｃ成分を含む原料成分と、前記溶媒とを用
いて、前述の非水系ディスパージョン法により得ること
ができる。得られる架橋高分子微粒子を含む非水系ディ
スパージョンには、通常微量の水分が含まれているので
、該水分を除去する必要がある。該微量水分を除去する
には１例えばオルトカルボン酸エステル類を用いて分解
除去する方法、具体的には。To produce the adhesive composition of the present invention, first, in step (A), crosslinked polymer fine particles are produced by a non-aqueous dispersion method, and trace amounts of water in the non-aqueous dispersion are removed. The crosslinked polymer fine particles can be produced by the above-mentioned non-aqueous dispersion method using the raw material components including the A component, B component, and C component and the solvent. The resulting non-aqueous dispersion containing crosslinked polymer fine particles usually contains a trace amount of water, so it is necessary to remove this water. In order to remove the trace amount of moisture, for example, a method of decomposing and removing using orthocarboxylic acid esters is used.
オルト蟻酸メチル、オルト蟻酸エチル、オルト酢酸メチ
ル、オルト酢酸エチル等のオルトカルボン酸エステル類
を添加し、３０〜９０℃の温度範囲で反応させる方法に
より残存水分を分解除去することができる。ここで分解
温度が３０℃未満の場合、水分解に長時間を要し、また
９０’Ｃを超える場合、反応装置中の空隙部に水滴が不
着し、水分の除去が不十分となるため好ましくない。こ
の水分除去法においては、分解生成物としてメチルアル
コール、エチルアルコール、蟻酸メチル、蟻酸エチル、
酢酸メチル、酢酸エチル等が副生ずるが、これらは低沸
点の有機溶剤であるためα−シアノアクリレートと混合
する前の段階で容易に除去することができる。また共沸
蒸留法、具体的には、水と有機溶剤とを共沸蒸留させ、
好ましくは５０〜１００℃で水分を留去することもでき
る。更には乾燥剤により除去する方法、具体的には高分
子吸収材、例えば「スミカゲルＳ−５０４，ｒ同５Ｐ−
５２０Ｊ、ｒ同Ｎ−１００Ｊ 、 「同ＮＰ −１０
２０Ｊ、ｒ同Ｆ−０３Ｊ、ｒ同Ｆ−５１ノ。Residual moisture can be decomposed and removed by adding orthocarboxylic acid esters such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate and reacting at a temperature range of 30 to 90°C. If the decomposition temperature is less than 30°C, it will take a long time to decompose water, and if it exceeds 90'C, water droplets will stick to the voids in the reactor, making removal of water insufficient. do not have. In this water removal method, the decomposition products include methyl alcohol, ethyl alcohol, methyl formate, ethyl formate,
Methyl acetate, ethyl acetate, etc. are produced as by-products, but since these are organic solvents with low boiling points, they can be easily removed before mixing with α-cyanoacrylate. Also, azeotropic distillation method, specifically, azeotropic distillation of water and organic solvent,
Water can also be distilled off preferably at 50 to 100°C. Furthermore, a method of removing with a desiccant, specifically a polymer absorbent material, such as "Sumikagel S-504, r 5P-
520J, rDoN-100J, “DoDo NP-10
20J, rDoF-03J, rDoF-51no.
「同Ｆ−７５Ｊ（いずれも商品名、住人化学工業（株）
製）、アクアキープ４Ｓ、同１０ＳＨ（いずれも商品名
、製鉄化学工業（株）製）、もしくはモレキュラーシー
ブを充填したカラム中に非水系ディスパージョンを通す
か、または前記高分子吸収材、モレキュラーシーブ、あ
るいは硫酸ナトリウム、塩化カルシウム及びこれらの混
合物等から選択される無機物塩の脱水物を非水系ディス
パージョン中に混合し撹拌した後、濾別する方法により
除去することもできる。"F-75J (all product names, Sumima Kagaku Kogyo Co., Ltd.)
), Aqua Keep 4S, Aqua Keep 10SH (all trade names, manufactured by Seitetsu Kagaku Kogyo Co., Ltd.), or pass a non-aqueous dispersion through a column packed with molecular sieve, or pass the non-aqueous dispersion through a column packed with the polymer absorbent or molecular sieve. Alternatively, it can also be removed by mixing a dehydrated inorganic salt selected from sodium sulfate, calcium chloride, a mixture thereof, etc. in a non-aqueous dispersion, stirring the mixture, and then filtering the mixture.
次いで本発明の製造方法では、（Ｂ）工程で得られる非
水系ディスパージョンとα−シアノアクリレートとを混
合し、架橋高分子微粒子を膨潤させる。前記非水系ディ
スパージョンとα−シアノアクリレートとを混合させる
には、両者を一度に混合した場合、非水系ディスパージ
ョンの分散媒相の極性が低い状態から高い状態へと瞬時
に変化して、分散安定剤の分散安定化効果が損なわれ、
架橋高分子微粒子が凝集してしまい、再分散が困難とな
る場合があるため、非水系ディスパージョンかα−シア
ノアクリレートのいずれか一方を撹拌しながら残りの成
分を少量ずつ徐々に添加し、所定量まで加えることが望
ましい。Next, in the production method of the present invention, the nonaqueous dispersion obtained in step (B) and α-cyanoacrylate are mixed to swell the crosslinked polymer fine particles. In order to mix the non-aqueous dispersion and α-cyanoacrylate, when both are mixed at once, the polarity of the dispersion medium phase of the non-aqueous dispersion changes instantaneously from a low state to a high state, resulting in dispersion. The dispersion stabilizing effect of the stabilizer is impaired,
Since the crosslinked polymer fine particles may aggregate and become difficult to redisperse, gradually add the remaining ingredients little by little to either the nonaqueous dispersion or α-cyanoacrylate while stirring. It is desirable to add up to a fixed amount.
次に、α−シアノアクリレートにより架橋高分子微粒子
が完全に膨潤するまで静置もしくは撹拌した状態で熟成
させる。本発明のα−シアノアクリレート系接着剤組成
物では、架橋高分子微粒子の三次元高分子網目に対して
ポリ−α−シアノアクリレートが貫通もしくは絡み合う
ようにする必要があるので、前記熟成に要する時間は粒
子を形成するポリマ一種および架橋構造の密度によって
異なるが、国中の報文（日本物理学会誌第４１巻。Next, the crosslinked polymer fine particles are allowed to stand still or are aged with stirring until they are completely swollen with α-cyanoacrylate. In the α-cyanoacrylate adhesive composition of the present invention, since it is necessary for the poly-α-cyanoacrylate to penetrate or become entangled with the three-dimensional polymer network of the crosslinked polymer fine particles, the time required for the aging is Although it differs depending on the type of polymer forming the particles and the density of the crosslinked structure, it is determined by a national report (Journal of the Physical Society of Japan, Vol. 41).
第７号、５４２頁（１９８６））に記載されるように、
１溶媒の粒子内部への浸透に要する時間は粒子径の二乗
に比例し、本発明で用いる微粒子ではごく短時間のうち
に膨潤を完了させることができる。具体的には、前記の
ような粒子構造を考慮して、１日程度の熟成を行なえば
充分である。また前記架橋高分子微粒子の膨潤度は、α
−シアノアクリレートを該微粒子の重量に対して、１０
重量％以上吸収させるのが好ましい。この際α−シアノ
アクリレートによる膨潤度が１０重量％未満の場合には
、硬化時に該架橋高分子微粒子内部を貫通あるいは絡み
合うポリ−α−シアノアクリレートの割合が小さくなり
、前記構造による効果が充分発揮されないので好ましく
ない。No. 7, p. 542 (1986)),
The time required for one solvent to penetrate into the inside of a particle is proportional to the square of the particle diameter, and the swelling of the fine particles used in the present invention can be completed in a very short time. Specifically, in consideration of the particle structure as described above, aging for about one day is sufficient. Further, the degree of swelling of the crosslinked polymer fine particles is α
- 10% of cyanoacrylate based on the weight of the fine particles
It is preferable to absorb more than % by weight. At this time, if the degree of swelling by α-cyanoacrylate is less than 10% by weight, the proportion of poly-α-cyanoacrylate penetrating or intertwining with the inside of the crosslinked polymer fine particles during curing will be small, and the effect of the above structure will be fully exerted. This is not desirable because it is not possible.
次に本発明の製造方法では、（Ｃ）工程として前記（Ｂ
）工程により得られる非水系ディスパージョンとα−シ
アノアクリレートとの混合物から、非水系ディスパージ
ョンの分散溶媒を除去することにより接着剤組成物を得
ることができる。前記分散溶媒を除去するには、好まし
くは０〜６０’Ｃの温度範囲で、更に好ましくは減圧上
脱溶剤処理すれば良い。脱溶剤操作をＯ”Ｃ未満で行な
う場合には長時間を必要とするほか、完全に溶剤を除去
できない場合があり、また、６０”Ｃを超える場合には
、α−シアノアクリレートが熱重合する場合があるため
好ましくない。この脱溶剤操作も本発明において重要で
あり、溶剤の除去が完全に行なわれなかった場合には、
セットタイムや最高接着強度の到達時間の遅延あるいは
素材の軟化などの問題を生じる。Next, in the manufacturing method of the present invention, as the step (C), the above (B
An adhesive composition can be obtained by removing the dispersion solvent of the non-aqueous dispersion from the mixture of the non-aqueous dispersion and α-cyanoacrylate obtained in step ). In order to remove the dispersion solvent, the solvent may be removed preferably at a temperature of 0 to 60'C, more preferably under reduced pressure. If the solvent removal operation is carried out at a temperature below 0"C, it will take a long time and the solvent may not be completely removed. If the temperature exceeds 60"C, α-cyanoacrylate will thermally polymerize. This is not preferable because there are cases where this is the case. This solvent removal operation is also important in the present invention, and if the solvent is not completely removed,
This causes problems such as a delay in set time, time to reach the maximum adhesive strength, and softening of the material.
また最終的に得られる本発明のα−シアノアクリレート
系の接着剤組成物には、アニオン重合防止剤、ラジカル
重合防止剤、可塑剤、潜在性硬化促進剤等を適量添加す
ることもできる。Further, an appropriate amount of an anionic polymerization inhibitor, a radical polymerization inhibitor, a plasticizer, a latent curing accelerator, etc. can be added to the α-cyanoacrylate adhesive composition of the present invention finally obtained.
〈発明の効果〉
本発明の接着剤組成物は、三次元高分子網目構造を有す
る架橋高分子微粒子に、ポリ−α−シアノアクリレート
が貫通及び絡み合っているので、適度な粘度と高いチキ
ソトロピー性を有し、優れた接着性能、特に高い接着強
度と優れた耐水性および耐衝撃性を有し、木材、皮革１
紙等の多孔質材にも作業性良く接着することができ、し
かも流動性も容易に調整することができる。従って家庭
用、工業用等の広い範囲の接着剤組成物として極めて有
用である。<Effects of the Invention> The adhesive composition of the present invention has moderate viscosity and high thixotropy because poly-α-cyanoacrylate penetrates and intertwines with crosslinked polymer fine particles having a three-dimensional polymer network structure. It has excellent adhesive performance, especially high adhesive strength and excellent water resistance and impact resistance, and is suitable for wood, leather, etc.
It can be bonded to porous materials such as paper with good workability, and fluidity can also be easily adjusted. Therefore, it is extremely useful as an adhesive composition for a wide range of household and industrial uses.
また本発明の製造方法では、前記接着剤組成物を効率良
く、シかも安定に得ることができる。Further, in the production method of the present invention, the adhesive composition can be obtained efficiently and stably.
〈実施例〉
次に、製造例、実施例、比較例によって本発明を更に詳
細に説明する。尚、例中、部は重量部、％は重量％であ
る。<Example> Next, the present invention will be explained in more detail with reference to production examples, examples, and comparative examples. In addition, in the examples, parts are parts by weight, and % is weight %.
ス１ｊリニ二上
撹拌機、温度計、還流冷却器を取り付けたディーンスタ
ークトラップおよび窒素ガス導入管を備えた４つロフラ
スコに、１２−ヒドロキシステアリン酸１５００部を入
れ、窒素気流下昇温し、２００℃の温度で撹拌して、酸
価が３９になったところで反応を終了し、放冷後１５９
部のトルエンを加え加熱残分９０重量％の１２−ヒドロ
キシステアリン酸５モル縮合体溶液を得た。次いで、得
られた１２−ヒドロキシステアリン酸５モル縮合体溶液
を用いて、以下に示す組成の混合物を。1500 parts of 12-hydroxystearic acid was placed in a four-bottle flask equipped with a Dean-Stark trap equipped with an upper stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, and the temperature was raised under a nitrogen stream. Stirring was carried out at a temperature of 200°C, and the reaction was terminated when the acid value reached 39. After cooling, the reaction reached 159°C.
of toluene was added to obtain a 5 mol 12-hydroxystearic acid condensate solution with a heating residue of 90% by weight. Next, the obtained 12-hydroxystearic acid 5 molar condensate solution was used to prepare a mixture having the composition shown below.
撹拌機、温度計、還流冷却器、窒素ガス導入管をつけた
４つロフラスコ中で還流温度において撹拌し、加熱残分
酸価が０．３以下になるまでエステル化反応を続けるこ
とにより、加熱残分８０重量％の１２−ヒドロキシステ
アリン酸縮合体とグリシジルメタクリレートのエステル
化物溶液（以下Ｓ−１と略す）を得た。Stir at reflux temperature in a four-bottle flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, and heat by continuing the esterification reaction until the acid value of the heated residue becomes 0.3 or less. An esterified solution of a 12-hydroxystearic acid condensate and glycidyl methacrylate (hereinafter abbreviated as S-1) with a residue of 80% by weight was obtained.
１２−ヒドロキシステアリン酸５モル縮合体溶液１５８
６．６７部
グリシジルメタクリレート １４２．００部ジメチルベ
ンジルアミン ３．９３部ヒドロキノン
１．９６部トルエン ２２
７．９４部ｌＬ五↓二Ｉ
ｍ造例１−１で用いた４つロフラスコに３０．００部の
トルエンを入れ、窒素気流下撹拌しながら昇温し１００
℃に加熱した。次いで１００℃で、以下に示す組成の混
合物を一定の速度で２時間かけて滴下し、更に２時間１
００℃に保つことによって加熱残分が６０重量％である
分散安定剤溶液（以下Ｓ−２と略す）を得た。12-hydroxystearic acid 5 molar condensate solution 158
6.67 parts glycidyl methacrylate 142.00 parts dimethylbenzylamine 3.93 parts hydroquinone
1.96 parts toluene 22
7.94 parts lL 5↓2I mPour 30.00 parts of toluene into the four-bottle flask used in Preparation Example 1-1, and raise the temperature while stirring under a nitrogen stream to 100 parts.
heated to ℃. Next, at 100°C, a mixture having the composition shown below was added dropwise at a constant rate over a period of 2 hours, and then for an additional 2 hours.
By maintaining the temperature at 00°C, a dispersion stabilizer solution (hereinafter abbreviated as S-2) having a heating residue of 60% by weight was obtained.
Ｓ−１３７，５０部
２−ヒドロキシエチルメタクリレートにラフ１−ン化合
物が４モル付加したビニル型単量体（商品名、「プラク
セルＦＭ−４Ｊ 、ダイセル化学工業（株）製）
１３．３２部２−エチルへキシルアクリレー
ト
１６．６８部
ｔ−ブチルペルオキシ−２−エチルへキソエート
１ 、 ８０ 部１１１引Ｙ二」−
４つロフラスコに撹拌機、冷却器、温度計及び滴下ロー
トを取り付け、前記Ｓ−２１２，９０部、ｎ−へブタン
５４．３３部及び酢酸エチル１５．７５部を加え、撹拌
しながら昇温し還流温度まで加熱した。次いで以下に示
す組成の混合物を一定の速度で２時間かけて滴下し、更
に２時間還流を継続して加熱残分３５７重量％、２５℃
における粘度が０．２ポイズである乳白色の非水系ディ
スパージョン（Ａ１）を得た。S-137, 50 parts Vinyl type monomer with 4 moles of rough 1-compound added to 2-hydroxyethyl methacrylate (trade name: "Plaxel FM-4J", manufactured by Daicel Chemical Industries, Ltd.)
13.32 parts 2-ethylhexyl acrylate 16.68 parts t-butylperoxy-2-ethylhexoate
1, 80 parts 111 parts Y2'' - A four-piece Lof flask was equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, and 90 parts of the above S-212, 54.33 parts of n-hebutane, and 15.75 parts of ethyl acetate were added. The mixture was heated to reflux temperature while stirring. Next, a mixture having the composition shown below was added dropwise at a constant rate over 2 hours, and reflux was continued for another 2 hours until the heating residue was 357% by weight and 25°C.
A milky white non-aqueous dispersion (A1) having a viscosity of 0.2 poise was obtained.
メチルアクリレート ３１．３６部エチレング
リコールジメタクリレート
０．６４部
ｔ−ブチルペルオキシ−２−エチルへキソエート
０ 、 ６４ 部得られたＡ１は５
０℃で１ケ月放置後も安定であり、粒子の沈降、相分離
、粘度の変化は全く見られなかった。Methyl acrylate 31.36 parts Ethylene glycol dimethacrylate 0.64 parts t-Butyl peroxy-2-ethyl hexoate
0.64 copies of A1 were obtained.
It remained stable even after being left at 0°C for one month, with no particle sedimentation, phase separation, or viscosity change observed.
次に、モレキュラーシーブ３Ａ１／８を、内径３０ｎ＋
ｎ＋のクロマトグラフィー用ガラス管に５０部充填し、
得られたＡｌ １０００部を毎分５０部の速度で通過
させ乾燥した。乾燥処理したＡ１の水分は、カールフィ
ッシャー水分計で計測限界以下であった。得られたＡ１
の成分量及び性質を表１に示す。Next, attach the molecular sieve 3A1/8 with an inner diameter of 30n+
Fill 50 parts into an n+ chromatography glass tube,
1000 parts of the obtained Al was passed through it at a rate of 50 parts per minute to dry it. The moisture content of the dried A1 was below the measurement limit using a Karl Fischer moisture meter. Obtained A1
The component amounts and properties of are shown in Table 1.
１１υ１λ１」−
製造例１−３の４つロフラスコを用い、以下に示す組成
にて１部造例１−３と全く同様の方法で非水系ディスパ
ージョン（Ａ２）および（Ａ３）を製造した。11υ1λ1'' - Non-aqueous dispersions (A2) and (A3) were produced in exactly the same manner as in One-Part Production Example 1-3 with the compositions shown below using the four-loaf flask of Production Example 1-3.
一ト ′ディスパージョンＡ２の ゝ
Ｓ−２１８，２５部
ｎ−へブタン ５４．３３部酢酸エチル
１５．７５部メチルアクリレート
２５．０４部エチレングリコールジメタクリレート
０．５１部
ｔ−ブチルペルオキシ−２−エチルへキシルヘキソエー
ト ０．６４部６水、ディスパージ
ョンＡ３の
Ｓ−２４，５９部
ｎ−へブタン ５１．３４部酢酸エチル
１４．９０部メチルアクリレート
２５．５３部エチレングリコールジメタクリレート
０．５２部
ｔ−ブチルペルオキシ−２−エチルへキシルヘキソエー
ト ０．５２部得られたＡ２及びＡ３
の成分量及び性質を表１去】１１上
乾燥窒素導入用キャピラリー管、真空撹拌機、温度計、
滴下ロート、液体窒素トラップを間に入れた減圧装置を
備えた４つロフラスコに、α−シアノアクリル酸エチル
を２００部入れ、撹拌しながら室温にて滴下ロートより
製造例１−３で得られたＡｌ ２８，６部を一定の速
度で２０分間かけて滴下した。滴下終了後、室温にて更
に３０分間撹拌を継続した０次にキャピラリー管より乾
燥窒素を流しながらフラスコ内をＩＱｍｍＨＨの減圧状
態にし、撹拌しながら４０℃に昇温しで、Ａ１に含まれ
るトルエン、ｎ−へブタンおよび酢酸エチルを除去した
。得られた内部架橋高分子微粒子含有α−シアノアクリ
ル酸エチル（Ｂ１）は、チキソトロピー性を示す無色透
明な液体であった。Dispersion A2 ゝS-218, 25 parts n-hebutane 54.33 parts ethyl acetate
15.75 parts methyl acrylate
25.04 parts Ethylene glycol dimethacrylate 0.51 parts t-Butylperoxy-2-ethylhexylhexoate 0.64 parts 6 Water, S-24 of Dispersion A3, 59 parts n-Hebutane 51.34 parts Ethyl acetate
14.90 parts methyl acrylate
25.53 parts Ethylene glycol dimethacrylate 0.52 parts t-Butylperoxy-2-ethylhexylhexoate 0.52 parts Obtained A2 and A3
Table 1 shows the amount and properties of the components.11 Capillary tube for introducing dry nitrogen, vacuum stirrer, thermometer,
200 parts of ethyl α-cyanoacrylate was placed in a four-bottle flask equipped with a dropping funnel and a vacuum device with a liquid nitrogen trap in between, and the mixture obtained in Production Example 1-3 was added through the dropping funnel at room temperature while stirring. 28.6 parts of Al was added dropwise at a constant rate over 20 minutes. After the dropwise addition was completed, stirring was continued for another 30 minutes at room temperature. Next, dry nitrogen was flowed through the capillary tube to reduce the pressure inside the flask to IQmmHH, and the temperature was raised to 40°C while stirring to remove the toluene contained in A1. , n-hebutane and ethyl acetate were removed. The obtained ethyl cyanoacrylate (B1) containing internally crosslinked polymer fine particles was a colorless and transparent liquid exhibiting thixotropic properties.
得られた接着剤組成物について、以下に示す測定を行っ
た。チキソトロピー指数、性状、顕微鏡観察結果を表１
に示し、引張り剪断剥離強度、耐水性試験の結果を表３
に示す。The following measurements were performed on the obtained adhesive composition. Table 1 shows the thixotropic index, properties, and microscopic observation results.
The results of the tensile shear peel strength and water resistance tests are shown in Table 3.
Shown below.
（各測定方法）
チキソトロピー性の測
ブルックフィールド型粘度計により、２０℃において６
ｒｐｍ、 ６０ｒｐｍの粘度を測定し、チキソトロピー
指数を次式より算出した。(Measurement methods) Using a thixotropic Brookfield viscometer, at 20°C
The viscosity at 60 rpm was measured, and the thixotropic index was calculated from the following formula.
目視により行った。This was done by visual inspection.
機紐 Ｘ１００Ｏ 位相差顕微鏡により行った。Machine string X100O This was done using a phase contrast microscope.
張り 断珈離強
ＪＩＳ Ｋ ６８６１に準拠し、２０℃、６０％Ｒ
Ｈの条件下で鋼板を接着し、２４時間後に試験を行なっ
た。Tension Breaking strength JIS K 6861 20℃, 60%R
The steel plates were bonded under the conditions of H, and the test was conducted 24 hours later.
圃水作区履
ＪＩＳ Ｋ ６８６１に準拠して作製した鋼板試験
片を２４時間静置後、２０℃の水中に７時間浸漬し、水
を拭き取った後、２０℃、６０％ＲＨの条件下に２４時
間静置してから上記の引張り剪断剥離試験を行なった。A steel plate test piece prepared in accordance with JIS K 6861 was left standing for 24 hours, then immersed in water at 20°C for 7 hours, wiped off the water, and then placed under the conditions of 20°C and 60% RH. After standing for 24 hours, the above-mentioned tensile shear peeling test was conducted.
実施例１の装置を用い、表２に示す配合にて実施例１と
全く同様の方法で、架橋高分子微粒子含有α−シアノア
クリル酸エチル（Ｂ２）〜（８５）を得た。Ethyl cyanoacrylates (B2) to (85) containing crosslinked polymer fine particles were obtained using the apparatus of Example 1 and using the formulations shown in Table 2 in exactly the same manner as in Example 1.
得られたα−シアノアクリレート系接着剤組成物（Ｂ２
）〜（Ｂ５）の組成、チキソトロピー性および性状を表
２に示す。また引張剪断剥離強度及び耐水性の測定結果
を表３に示す。The obtained α-cyanoacrylate adhesive composition (B2
) to (B5), the compositions, thixotropic properties and properties are shown in Table 2. Table 3 also shows the measurement results of tensile shear peel strength and water resistance.
ル艶剪
比較例として、市販品のα−シアノアクリル酸エチル（
「シアノボンドＲＰＪ 、商品名、田岡化学工業（株）
製）の性質を実施例１と同様に調べた。その結果を表２
に示す。また実施例と同様な試験を行った結果を表３に
示す。As a comparison example, commercially available α-cyanoacrylate ethyl (
“Cyanobond RPJ, product name, Taoka Chemical Industry Co., Ltd.
The properties of the product were investigated in the same manner as in Example 1. Table 2 shows the results.
Shown below. In addition, Table 3 shows the results of tests similar to those in Examples.
Claims (1)
分子微粒子０．１〜５０．０重量％とα−シアノアクリ
レート５０．０〜９９．９重量％とを含むことを特徴と
する接着剤組成物。 ２）前記架橋高分子微粒子が、平均粒径０．０１〜１０
０μｍであり、α−シアノアクリレートによる膨潤度が
１０重量％以上であることを特徴とする請求項１記載の
接着剤組成物。 ３）前記架橋高分子微粒子を構成する成分が、Ａ；両親
媒性である分散安定剤０．１〜４９．９重量％、Ｂ；エ
チレン性不飽和単量体５０．０〜９９．８重量％及びＣ
；前記Ｂ成分と反応して架橋構造を形成する多官能反応
性化合物０．１〜４０．０重量％を含むことを特徴とす
る請求項１又は２に記載の接着剤組成物。 ４）α−シアノアクリレート系接着剤組成物を製造する
にあたり、 （Ａ）非水系ディスパージョン法により架橋高分子微粒
子を製造し、非水系ディスパージョン中の微量水分を除
去する工程と、 （Ｂ）該架橋高分子微粒子を含む非水系ディスパージョ
ンとα−シアノアクリレートとを混合し架橋高分子微粒
子を膨潤させる工程と、 （Ｃ）前記（Ｂ）工程により得られる非水系ディスパー
ジョンとα−シアノアクリレートとの混合物から非水系
ディスパージョンの分散溶媒を除去する工程とを含むこ
とを特徴とする接着剤組成物の製造方法。[Scope of Claims] 1) Contains 0.1 to 50.0% by weight of crosslinked polymer fine particles synthesized by a non-aqueous dispersion method and 50.0 to 99.9% by weight of α-cyanoacrylate. Adhesive composition. 2) The crosslinked polymer fine particles have an average particle size of 0.01 to 10
The adhesive composition according to claim 1, wherein the adhesive composition has a diameter of 0 μm and a degree of swelling by α-cyanoacrylate of 10% by weight or more. 3) The components constituting the crosslinked polymer fine particles are A: 0.1 to 49.9% by weight of an amphiphilic dispersion stabilizer, and B: 50.0 to 99.8% by weight of an ethylenically unsaturated monomer. % and C
The adhesive composition according to claim 1 or 2, comprising 0.1 to 40.0% by weight of a polyfunctional reactive compound that reacts with component B to form a crosslinked structure. 4) In producing the α-cyanoacrylate adhesive composition, (A) producing crosslinked polymer fine particles by a non-aqueous dispersion method and removing trace amounts of water in the non-aqueous dispersion; (B) a step of mixing the non-aqueous dispersion containing the cross-linked polymer fine particles and α-cyanoacrylate to swell the cross-linked polymer fine particles; (C) the non-aqueous dispersion obtained in step (B) and α-cyanoacrylate; and removing a dispersion solvent of a non-aqueous dispersion from a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1131267A JP2715548B2 (en) | 1989-05-26 | 1989-05-26 | Adhesive composition and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1131267A JP2715548B2 (en) | 1989-05-26 | 1989-05-26 | Adhesive composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02311583A true JPH02311583A (en) | 1990-12-27 |
| JP2715548B2 JP2715548B2 (en) | 1998-02-18 |
Family
ID=15053935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1131267A Expired - Fee Related JP2715548B2 (en) | 1989-05-26 | 1989-05-26 | Adhesive composition and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2715548B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06280189A (en) * | 1993-05-12 | 1994-10-04 | Okumura Ayako | Method for hardening paper strip |
| JP2008276264A (en) * | 1997-10-30 | 2008-11-13 | Rohm & Haas Electronic Materials Llc | Method for preparing a photoresist composition |
| JP2012503713A (en) * | 2008-09-26 | 2012-02-09 | ヘンケル コーポレイション | Non-flowable cyanoacrylate composition |
| US11613677B2 (en) | 2017-12-15 | 2023-03-28 | Lg Chem, Ltd. | Water-based acrylic pressure-sensitive adhesive for clothing, and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5330642A (en) * | 1976-07-14 | 1978-03-23 | Loctite Ireland Ltd | Composition of thixotropy *pseudoliquidity* hardening adhesive |
| JPS633072A (en) * | 1986-06-24 | 1988-01-08 | Toagosei Chem Ind Co Ltd | Adhesive composition |
-
1989
- 1989-05-26 JP JP1131267A patent/JP2715548B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5330642A (en) * | 1976-07-14 | 1978-03-23 | Loctite Ireland Ltd | Composition of thixotropy *pseudoliquidity* hardening adhesive |
| JPS633072A (en) * | 1986-06-24 | 1988-01-08 | Toagosei Chem Ind Co Ltd | Adhesive composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06280189A (en) * | 1993-05-12 | 1994-10-04 | Okumura Ayako | Method for hardening paper strip |
| JP2008276264A (en) * | 1997-10-30 | 2008-11-13 | Rohm & Haas Electronic Materials Llc | Method for preparing a photoresist composition |
| JP2012503713A (en) * | 2008-09-26 | 2012-02-09 | ヘンケル コーポレイション | Non-flowable cyanoacrylate composition |
| US11613677B2 (en) | 2017-12-15 | 2023-03-28 | Lg Chem, Ltd. | Water-based acrylic pressure-sensitive adhesive for clothing, and preparation method thereof |
| EP3650513B1 (en) * | 2017-12-15 | 2024-01-31 | Lg Chem, Ltd. | Water-based acrylic pressure-sensitive adhesive for clothing, and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2715548B2 (en) | 1998-02-18 |
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