JPH02153963A - Cold-setting resin composition - Google Patents
Cold-setting resin compositionInfo
- Publication number
- JPH02153963A JPH02153963A JP30842388A JP30842388A JPH02153963A JP H02153963 A JPH02153963 A JP H02153963A JP 30842388 A JP30842388 A JP 30842388A JP 30842388 A JP30842388 A JP 30842388A JP H02153963 A JPH02153963 A JP H02153963A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silane compound
- formula
- hydrolyzable
- resin composition
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- -1 silane compound Chemical class 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 229910000077 silane Inorganic materials 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 2
- 125000005059 halophenyl group Chemical group 0.000 claims description 2
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 9
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 abstract description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 238000001723 curing Methods 0.000 description 24
- 239000003973 paint Substances 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 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 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- YBGHFLPNIGPGHX-UHFFFAOYSA-N calcium;octan-1-olate Chemical compound [Ca+2].CCCCCCCC[O-].CCCCCCCC[O-] YBGHFLPNIGPGHX-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000000470 constituent Substances 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
- 230000006866 deterioration Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 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
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野〕
本発明は常温硬化性樹脂組成物に関し、さらに詳しくは
高硬度の硬化物を与える塗料として特に有用な常温硬化
性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a room temperature curable resin composition, and more particularly to a room temperature curable resin composition that is particularly useful as a coating material that provides a cured product with high hardness.
(従来の技術〕
従来、常温硬化型の塗料はおもに木工用、プラスチック
用などに用いられていて、例えば木工用ではアクリルポ
リオールを主剤とし、ポリイソシアネートプレポリマー
を硬化剤とする2液反応型のアクリルウレタン塗料があ
る。(Prior art) Conventionally, room-temperature-curing paints have been mainly used for woodworking, plastics, etc. For example, for woodworking, two-component reaction-type paints containing acrylic polyol as the main ingredient and polyisocyanate prepolymer as the curing agent have been used. There is acrylic urethane paint.
また、常温硬化型で珪素化合物を含む組成物として末端
又は側鎖に加水分解シリル基を含有するビニル系樹脂と
硬化触媒とからなる組成物(■特開昭57−17295
0号公報、■特開昭58−157810号公報)が知ら
れている。In addition, as a room-temperature curing composition containing a silicon compound, a composition consisting of a vinyl resin containing a hydrolyzed silyl group at the terminal or side chain and a curing catalyst (Japanese Patent Application Laid-Open No. 57-17295
(Japanese Patent Laid-Open No. 157810/1982) are known.
更に塩基性窒素原子を有するビニル系重合体に、硬化剤
として1分子中にエポキシ基と加水分解性シリル基とを
有する化合物とエポキシ基を含有せずに加水分解性シリ
ル基全必須の基として含有する化合物及び/又はシラノ
ール基を含有する化合物とを配合してなる組成物(■特
開昭61−225244号公報)も知られている。Furthermore, in a vinyl polymer having a basic nitrogen atom, a compound having an epoxy group and a hydrolyzable silyl group in one molecule as a curing agent and a hydrolyzable silyl group without containing an epoxy group as all essential groups. A composition comprising a compound containing a silanol group and/or a compound containing a silanol group (2) is also known.
(発明が解決しようとする課題〕
ところで、近年、高級家具の表面の傷付きを防止するた
め、高硬度の木工用塗料の開発が望まれている。又、プ
ラスチック用の分野においてもより高い硬度の得られる
常温硬化型塗料が必要とされている。(Problems to be Solved by the Invention) In recent years, there has been a desire to develop high-hardness wood paints in order to prevent scratches on the surfaces of high-end furniture.Also, in the field of plastics, higher hardness paints have been desired. There is a need for a room-temperature curing coating that provides the following properties.
しかし、前記の従来型組成物を用いて得られる硬化物に
あっては硬度が不十分1に低温硬化が不十分)であり、
又硬度が湿度の影響をうけやすく特に高湿下で著しく硬
度が低下するという問題があった。However, the cured product obtained using the conventional composition has insufficient hardness (1) and insufficient low temperature curing.
Another problem is that the hardness is easily affected by humidity, and the hardness decreases significantly especially under high humidity.
本発明の目的は、従来の組成物を用いて得られる硬化物
に較べ硬度が著しく向上し、高湿下にあっても高硬度の
硬化物が得られる常温硬化性樹脂組成物を提供すること
である。An object of the present invention is to provide a room-temperature curable resin composition that has significantly improved hardness compared to cured products obtained using conventional compositions, and that allows a cured product with high hardness to be obtained even under high humidity. It is.
(課題を解決するための手段〕
本発明は、側鎖又は鎖状分子末端に加水分解性基と結合
した珪素原子を有する線状重合体と、エポキシ基を含有
する加水分解性シラン化合物とを主成分とする重合体組
成物囚及び、一般式%式%
1式中R1、R1はそれぞれ水素原子又はアルキル基、
アルケニル基、アルキニル基、アリール基、シアノアル
キル基、トリフルオロプロピル基及びハロフェニル基よ
りなる群から選ばれ、R3は炭素原子3ないし6個を有
するアルキレン基又は次式
%式%
るアルキレン基、Qは次式
炭素原子3ないし6個を有する1価の炭化水素基%Yは
炭素原子6個以下のアルキル基又はアルコキシアルキル
基、及びaは0又は1の値を表わす。)
で表わされる加水分解性シラン化合物(B−1)を主成
分とする硬化剤(ト)、からなる常温硬化性樹脂組成物
である。(Means for Solving the Problems) The present invention comprises a linear polymer having a silicon atom bonded to a hydrolyzable group at the end of a side chain or a chain molecule, and a hydrolyzable silane compound containing an epoxy group. The polymer composition as the main component and the general formula % formula % where R1 and R1 are each a hydrogen atom or an alkyl group,
selected from the group consisting of an alkenyl group, an alkynyl group, an aryl group, a cyanoalkyl group, a trifluoropropyl group, and a halophenyl group, and R3 is an alkylene group having 3 to 6 carbon atoms or an alkylene group having the following formula %, Q is a monovalent hydrocarbon group having 3 to 6 carbon atoms, %Y is an alkyl group or an alkoxyalkyl group having 6 or less carbon atoms, and a is a value of 0 or 1. ) A curing agent (g) whose main component is a hydrolyzable silane compound (B-1) represented by:
本発明の組成物を構成する主要な要素である側鎖又は鎖
状分子末端に加水分解性基と結合した珪素原子を有する
重合体は、遊離の炭素−炭素二重結合を有する重合体を
合成し、これと珪素に結合した水素原子と加水分解性基
とを有するシラン化合物とのヒドロシリル化反応によっ
て加水分解性基を有する珪素原子を該1合体に導入する
ことによっても調製することができるが、重合性の二重
結合を有し珪素原子を有しない化合物と重合性の二重結
合及び加水分解性基を有するシラン化合物との共重合に
よシ調製するのが簡便であり好ましい。The polymer having a silicon atom bonded to a hydrolyzable group at the end of a side chain or chain molecule, which is a main element constituting the composition of the present invention, is a polymer having a free carbon-carbon double bond. However, it can also be prepared by introducing a silicon atom having a hydrolyzable group into the monomer through a hydrosilylation reaction between this and a silane compound having a hydrogen atom bonded to silicon and a hydrolyzable group. It is convenient and preferable to prepare by copolymerization of a compound having a polymerizable double bond and no silicon atom and a silane compound having a polymerizable double bond and a hydrolyzable group.
次に硬化剤(B)の主成分である加水分解性シラン化合
物(B−1)は、アリルアミンとカルボニル化合物とか
ら一般式
%式%
(式中R1,R2け各乎臀と同じ意味を表わす。)で表
わされるケチミンを合成し、これと珪素に結合した水素
原子と加水分解性基とを有するシラン化合物とのヒドロ
シリル化反応によって加水分解性基金有する珪素原子を
該ケチミン化合物に導入することによっても調製するこ
とかできるが、アミノ基を含有する加水分解性クラン化
合物とカルボニル化合物との反応により調製するのが簡
便であり好ましい。但し、生°成した水によって加水分
解性基の縮合が起こらぬよう反応系中に適当な脱水剤を
存在させるか、又は共沸脱水法などにより生成する水を
速やかに取り除くことが必要である。Next, the hydrolyzable silane compound (B-1), which is the main component of the curing agent (B), is made from allylamine and a carbonyl compound with the general formula % (in the formula, R1 and R2 each have the same meaning as ), and by introducing a silicon atom having a hydrolyzable group into the ketimine compound through a hydrosilylation reaction between this and a silane compound having a silicon-bonded hydrogen atom and a hydrolyzable group. Although it is also possible to prepare the compound by reacting a hydrolyzable clan compound containing an amino group with a carbonyl compound, it is convenient and preferred. However, it is necessary to have an appropriate dehydrating agent in the reaction system to prevent condensation of hydrolyzable groups due to the generated water, or to quickly remove the generated water by an azeotropic dehydration method, etc. .
本発明に於て使用する原料のうち重合性の二重結合を有
し珪素原子を有しない化合物の代表的なものとしてはグ
リシジルメタクリレート、グリシジルアクリレート、メ
チルメタクリレート、メチルアクリレート、エチルメタ
クリレート、エチルアクリレート、n−ブチルメタクリ
レート、n−ブチルアクリレート、2−エチルへキシル
メタクリレート、2−エチルへキシルアクリレート、ラ
ウリルメタクリレート、ラウリルアクリレート、シクロ
ヘキシルメタクリレート、シクロヘキシルアクリレート
、2−ヒドロキシエチルメタクリレート、2−ヒドロキ
シエチルアクリレート、等のごときメタクリル酸エステ
ル類やアクリル酸エステル類の他、メタクリル酸、アク
リル酸、アクリロニトリル、無水フマル酸やスチレン、
ビニルトルエンのコトキ芳香族とニルモノマーなどを挙
げることができる。Among the raw materials used in the present invention, typical compounds having a polymerizable double bond and no silicon atom include glycidyl methacrylate, glycidyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, lauryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, etc. In addition to methacrylic acid esters and acrylic esters, methacrylic acid, acrylic acid, acrylonitrile, fumaric anhydride, styrene,
Examples include vinyl toluene aromatics and vinyl monomers.
前記重合性の二重結合及び加水分解性基を有するシラン
化合物の代表例としてはビニルトリメトキシシラン、ビ
ニルトリエトキシシラン、ビニルトリス(2−メトキシ
エトキシ)シラン、3−メタクリロキシプロピルトリメ
トキシシラン等を挙げることができる。Typical examples of the silane compounds having a polymerizable double bond and a hydrolyzable group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, etc. can be mentioned.
又、エポキシ基を含有する加水分解性シラン化合物とし
ては、3−グリシドキシプロビルトリメトキシシラン、
3−グリシドキシプロビルメチルジメトキシシラン、2
−(3,4−エポキシシクロヘキシル)エチルトリメト
キシシラン等が代表的なものとして挙げられるが、硬化
性などの点からすれば3−グリシドキシプロビルトリメ
トキシシランが特に望ましい。In addition, examples of hydrolyzable silane compounds containing epoxy groups include 3-glycidoxyprobyltrimethoxysilane,
3-glycidoxypropylmethyldimethoxysilane, 2
Typical examples include -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, but 3-glycidoxypropyltrimethoxysilane is particularly desirable from the viewpoint of curability.
次に前記アミノ基を含有する加水分解性シラン化合物と
しては、N−(2−7ミノエチル)−3−アミノプロピ
ルメチルジメトキシシラン、N−(2−アミノエチル)
−3−アミノプロピルトリメトキシシラン、3−アミノ
プロピルトリエトキシシラン等が挙げられる。Next, as the hydrolyzable silane compound containing an amino group, N-(2-7minoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)
-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like.
そして、前記カルボニル化合物は一般式%式%
(式中R9、R10は各々R1と同じ意味を表わす。)
で表わされる。The carbonyl compound has the general formula % (in the formula, R9 and R10 each represent the same meaning as R1).
It is expressed as
本発明の常温硬化性樹脂組成物には、又、アルコキシシ
ラン架橋剤としての加水分解性シラン化合物を適量配合
できる。The room temperature curable resin composition of the present invention may also contain an appropriate amount of a hydrolyzable silane compound as an alkoxysilane crosslinking agent.
該シラン化合物は、前記重合体組成物(2)、前記の硬
化剤(B)のいずれかもしくは双方又はこれらの混合物
に混合できる。The silane compound can be mixed with either or both of the polymer composition (2), the curing agent (B), or a mixture thereof.
前記アルコキシシラン架橋剤としての加水分解性シラン
化合物の例としては、珪酸エチル、珪酸メチル等のアル
キルシリケート類、及び咳アルキルシリケート類の部分
加水分解縮合物並びにメチルトリメトキシシランを代表
例とするアルキルトリアルコキシシラン、ビニルトリメ
トキシシランを代表例とするアルケニルトリアルコキシ
シラン、フェニルトリメトキシシラン全代表例とするフ
ェニルトリアルコキシシラン等及び、該トリプルコキシ
シラン類の部分加水分解縮合物等が挙げられる。Examples of the hydrolyzable silane compound as the alkoxysilane crosslinking agent include alkyl silicates such as ethyl silicate and methyl silicate, partially hydrolyzed condensates of alkyl silicates, and alkyl silanes of which methyltrimethoxysilane is a representative example. Examples include trialkoxysilane, alkenyltrialkoxysilane of which vinyltrimethoxysilane is a typical example, phenyltrialkoxysilane of which phenyltrimethoxysilane is a representative example, and partially hydrolyzed condensates of the triplekoxysilanes. .
次に本発明の常温硬化性樹脂組成物’IJ造する方法に
ついて説明する。Next, a method for producing the room temperature curable resin composition 'IJ' of the present invention will be explained.
まず、重合体組成物(4)は好ましくは1合性の二重結
合を有し珪素原子を有さない化合物(以下「ビニル系X
L量体」という。)と重合性の二重結合及び加水分解性
基金有するシラン化合物(以下「重合性シラン化合物」
という。)と全共重合させることによって卯鎖又は鎖状
分子末端に加水分解性基と結合した珪素原子を有する線
状の共重合体を調製し、該重合体にエポキシ基金含有す
る加水分解性シラン化合物を混合することによって得ら
れる。前記共重合に尚たっては重合性シラン化合物の全
単量体(即ちビニル系単量体と重合性シラン化合物との
合計量)中に占める割合を1〜30x量%、好ましくは
5〜2011量%となるように共重合させるのがよく、
又エポキシ基金含有する加水分解性シラン化合物の該共
重合体に対する混合割合は重量比で0.1〜1.0、好
ましくは0.3〜0.7とするのがよい。これらの範囲
をはずれた条件では、下限未満の範囲もしくは上限を越
えた範囲のいずれであっても、本発明の樹脂組成物の安
定性の低下もしくは該組成物の硬化物の硬度の低下、又
は白化等の塗膜外観の悪化が認められる傾向にあるため
好ましくない。First, the polymer composition (4) is preferably a compound having a monopolytic double bond and no silicon atom (hereinafter referred to as "vinyl X
It is called "L-mer". ) and a silane compound having a polymerizable double bond and a hydrolyzable group (hereinafter "polymerizable silane compound")
That's what it means. ) to prepare a linear copolymer having a silicon atom bonded to a hydrolyzable group at the end of a chain or chain molecule, and a hydrolyzable silane compound containing an epoxy group in the polymer. obtained by mixing. In the copolymerization, the proportion of the polymerizable silane compound in the total monomers (i.e., the total amount of the vinyl monomer and the polymerizable silane compound) is 1 to 30% by weight, preferably 5 to 2011% by weight. It is best to copolymerize so that the
The mixing ratio of the hydrolyzable silane compound containing the epoxy base to the copolymer is preferably 0.1 to 1.0, preferably 0.3 to 0.7 in terms of weight ratio. Conditions outside these ranges, whether below the lower limit or exceeding the upper limit, may cause a decrease in the stability of the resin composition of the present invention or a decrease in the hardness of the cured product of the composition, or This is not preferred because it tends to cause deterioration in the appearance of the paint film such as whitening.
前記のビニル系単量体と重合性シラン化合物との共重合
に当たっては従来公知のいずれの重合方法も適用できる
が、有機溶媒中でのラジカル重合によるものが最も簡便
かつ容易である。Any conventionally known polymerization method can be applied to the copolymerization of the vinyl monomer and the polymerizable silane compound, but radical polymerization in an organic solvent is the simplest and easiest method.
この除用いる有機溶媒としては本発明に於て用いる各化
合物の安定性もしくは本発明の組成物を製造する際の各
反応に影響金与えない限りに於て不活性の有機溶媒が、
共重合反応をコントロールし容易かつ円滑ならしめる点
で有利である。このような溶媒としては例えば、トルエ
ン、キシレン、シクロヘキサン、n−へキサン、モしく
は高沸点の芳香族炭化水素系浴剤等の各種炭化水素類例
えば丸善石油■製″スワゾール”(商標)、メタノール
、エタノール、イソブタノール、n−プロパツール、n
−ブタノール、イソブタノール、3−ブタノール、エチ
レングリコール七ツメチルエーテル等のアルコール類、
酢酸メチル、酢酸エチル、酢酸n−ブチル、エチルセロ
ンルプアセテート等のエステル類が挙げられ、これらは
単独であるいは混合して用いることができる。The organic solvent to be removed may be an inert organic solvent as long as it does not affect the stability of each compound used in the present invention or each reaction in producing the composition of the present invention.
This is advantageous in that the copolymerization reaction can be controlled easily and smoothly. Examples of such solvents include toluene, xylene, cyclohexane, n-hexane, and various hydrocarbons such as high-boiling aromatic hydrocarbon bath agents, such as "Swazol" (trademark) manufactured by Maruzen Sekiyu, Methanol, ethanol, isobutanol, n-propertool, n
-Alcohols such as butanol, isobutanol, 3-butanol, ethylene glycol 7-methyl ether,
Examples include esters such as methyl acetate, ethyl acetate, n-butyl acetate, and ethylselonupacetate, and these can be used alone or in combination.
次に硬化剤(B) ’に作るには、まずアミノ基金含有
する加水分解性シラン化合物とカルボニル化合物を反応
させ、その際に生成する水を脱水剤で又は共沸脱水によ
り取り除くことにより加水分解性シラン化合物(B−1
)t−製造する。このとき用いる脱水剤としては、モレ
キュラーシープスなどの各種ゼオライト類等があげられ
る。Next, to make the curing agent (B)', first, a hydrolyzable silane compound containing an amino base is reacted with a carbonyl compound, and the water produced at that time is removed with a dehydrating agent or by azeotropic dehydration. Silane compound (B-1
)t-manufacture. Examples of the dehydrating agent used at this time include various zeolites such as Molecular Sheeps.
こうして製造した加水分解性シラン化合物(B−1)を
必須の成分として、場合によってこれに前記の有機溶剤
類を添加混合して硬化剤の)をFARする。この時珪酸
メチル、珪酸エチル等のアルキルシリケート類、もしく
は該アルキルシリケート類の部分加水分解縮合物、又は
メチルトリメトキシシランを代表例とするアルキルトリ
アルコキシシラン、ビニルトリメトキシシランを代表例
とするアルケニルトリアルコキシシラン、フェニルトリ
メトキシシラン全代表例とするフェニルトリアルコキシ
シラン等、もしくti該トリアルコキシシラン類の部分
加水分解縮合物等の加水分解性アルコキシシラン類をア
ルコキシシラン架橋剤として添加することもできる。そ
のときの使用量は限定されないが好ましくは、主成分の
加水分解性シラン化合物(B−1)に対して′N量比で
1/10から172とするのが実施しやすい。The hydrolyzable silane compound (B-1) produced in this way is used as an essential component, and if necessary, the above-mentioned organic solvents are added thereto and mixed to FAR the curing agent. At this time, alkyl silicates such as methyl silicate and ethyl silicate, or partially hydrolyzed condensates of the alkyl silicates, or alkyltrialkoxysilanes such as methyltrimethoxysilane, and alkenyls such as vinyltrimethoxysilane are used. Addition of hydrolyzable alkoxysilanes such as phenyltrialkoxysilanes, all representative examples of trialkoxysilanes and phenyltrimethoxysilanes, or partially hydrolyzed condensates of the trialkoxysilanes, as an alkoxysilane crosslinking agent. You can also do it. The amount to be used at this time is not limited, but it is preferable that the ratio of N to the hydrolyzable silane compound (B-1) as the main component is from 1/10 to 172.
そしてこのアルコキシシラン架橋剤としての加水分解性
アルコキシシラン類は硬化剤CB)ではなく、重合体組
成物(4)に添加して使用することもできるし、或は又
重合体組成初回と硬化剤の)の両者に添加して使用して
もよい。Hydrolyzable alkoxysilanes as alkoxysilane crosslinking agents can be used by adding them to the polymer composition (4) instead of the curing agent CB), or alternatively, they can be used by adding them to the polymer composition (4) as well as the curing agent. ) may be added to both.
なお、本発明の常温硬化性樹脂組成物は便化触媒を混合
しなくとも良好な硬化性を有するのであるが、前記の各
加水分解性シラン化合物を加水分解縮合させるための触
媒を用いることKより、硬化反応を促進させ、低温硬化
性を更に向上させることが可鉋である。そしてこのよう
な加水分解縮合触媒(0として代表的なものには、水酸
化ナトリウム、水酸化カリウム、ナトリウムメチラート
もしくはテトラメチルアンモニウムハイドライドのごと
き塩基性化合物類、テトライソプロピルチタネート、ア
ルミニウムアセチルアセトン、オクチル酸鉛、オクチル
酸亜鉛、オクチル酸カルシウム、ナフテン酸鉛、ジプチ
ル錫ジアセテート、ジブチル錫ジラウレート、もしくは
ジブチル錫シマレートのごとき有機酸の金属塩類、戒は
p−)ルエンスルホン酸、トリクロル酢酸、燐酸のごと
き酸性化合物等がある。Although the room-temperature curable resin composition of the present invention has good curability even without the addition of a facilitation catalyst, it is possible to use a catalyst for hydrolyzing and condensing each of the hydrolyzable silane compounds described above. Therefore, it is possible to accelerate the curing reaction and further improve low-temperature curability. Such hydrolytic condensation catalysts (typical examples include basic compounds such as sodium hydroxide, potassium hydroxide, sodium methylate or tetramethylammonium hydride, tetraisopropyltitanate, aluminum acetylacetone, octylic acid) Metal salts of organic acids such as lead, zinc octylate, calcium octylate, lead naphthenate, diptyltin diacetate, dibutyltin dilaurate, or dibutyltin simalate; There are acidic compounds, etc.
この加水分解縮合触媒Qは、前記硬化剤の)又はアルコ
キシシラン架橋剤に加えて使用してもよく、重合体組成
初回及び硬化剤(B)の王者の混合物又は重合体組成初
回、硬化剤(刊及びアルコキシシラン架橋剤の王者の混
合物に加えてもよい。This hydrolytic condensation catalyst Q may be used in addition to the curing agent (B) or the alkoxysilane crosslinking agent, or may be a mixture of the polymer composition initial and curing agent (B) or the polymer composition initial, curing agent (B). It may be added to a mixture of alkoxysilane and alkoxysilane crosslinkers.
本発明の常温硬化性樹脂組成物は、上に説明のごとく調
製した重合体組成初回と硬化剤(B)とを各々の成分に
含まれるエポキシ基と>C−N−基との割合がエポキシ
基に対するンC−N−基のモル比で0.8〜3.0とな
るように混合し、さらに必要に応じてC成分としての加
水分解縮合触媒を、前記重合体組成物(4)と硬化剤混
合物の)との溶媒を含む総量に対して0.001〜1重
量%程度添加することによって製造するのが好ましい。The room-temperature curable resin composition of the present invention is prepared by combining the polymer composition prepared as described above and the curing agent (B) such that the ratio of epoxy groups to >C-N- groups contained in each component is epoxy. The polymer composition (4) is mixed with a hydrolytic condensation catalyst as a component C, if necessary, so that the molar ratio of the C-N-group to the C-N group is 0.8 to 3.0. It is preferable to manufacture by adding about 0.001 to 1% by weight based on the total amount of the curing agent mixture including the solvent and the curing agent mixture.
本発明の常温硬化性樹脂組成物には又、さらに有機系又
は無機系の染料や顔料をはじめ、つや消し剤、紫外線吸
収剤、充填剤、流動FA爬剤などの各種の添加剤を配合
することも可能であり、これらの添加剤が本発明の常温
硬化性樹脂組成物の硬化反応’kffi害するようなも
のでない限りなんら問題は危い。The room temperature curable resin composition of the present invention may further contain various additives such as organic or inorganic dyes and pigments, matting agents, ultraviolet absorbers, fillers, and fluid FA agents. However, there is no problem unless these additives impair the curing reaction of the room-temperature curable resin composition of the present invention.
なお、本発明の常温硬化性樹脂組成物は各種の基材に塗
布され、ついで常温で乾燥されることにより高硬度の硬
化物を与えるものであるが、硬化速度をさらに速める必
要がある場合に加温することを妨げるものではなく、そ
うしたからといって得られる効果が減少するものではな
い。The room temperature curable resin composition of the present invention is applied to various substrates and then dried at room temperature to give a cured product with high hardness. This does not preclude heating, nor does it diminish the benefits obtained.
以上のようにして得られる本発明の常温硬化性樹脂組成
物は、木工製品、各種プラスチック製品等の塗料や表面
改質剤、充填剤などとして広範囲に利用することができ
る。The room temperature curable resin composition of the present invention obtained as described above can be widely used as a paint, a surface modifier, a filler, etc. for wood products, various plastic products, etc.
【実施例)
以下、実施例及び比較例により本発明をより具体的に説
明するが、本発明はこれらの実施例のみに限定されるも
のではない。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
なお、以下の実施例においては部及び%は、特に断わり
のないかぎり、すべて産量基準である。In addition, in the following examples, all parts and percentages are based on production volume unless otherwise specified.
(重合体組成物(2)の調製)
v41A41
部拌装置・、温度計、還流冷却器及び窒素導入管を備え
た反応器にキシレン100部、n−ブタノール50部を
仕込み、窪素雰囲気下で90℃に昇温してからメチルメ
タクリレート55部、グリシジルメタクリレート20部
、n−ブチルメタクリレート15部、3−メタクリロキ
シプaピルトリメトキシシラン(以下rMOPS−M」
と略称する。)10部及び過酸化物触媒(日本油脂e+
製品、[ナイパーBMT J (登録商標)(パーオキ
サイド20%))2.5部からなる混合液を3時間かけ
て滴下した。滴下終了後も3時間同温度に保持して樹脂
分が40%である重合体組成物(A−1)の溶液金得た
。この重合物(A−1)の溶液100部に3−グリシド
キシプロビルトリメトキシシラン(以下1”GP8−M
Jと略称する。)12部を混合して重合体組成初回の溶
液を得た。この溶液’kl[合体組成物(IA)とする
。(Preparation of Polymer Composition (2)) 100 parts of xylene and 50 parts of n-butanol were charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the mixture was heated under a silicon atmosphere. After raising the temperature to 90°C, 55 parts of methyl methacrylate, 20 parts of glycidyl methacrylate, 15 parts of n-butyl methacrylate, and 3-methacryloxypyltrimethoxysilane (hereinafter referred to as rMOPS-M) were added.
It is abbreviated as. ) 10 parts and peroxide catalyst (NOF e+
A liquid mixture consisting of 2.5 parts of the product, [Niper BMT J (registered trademark) (peroxide 20%)] was added dropwise over 3 hours. After the dropwise addition was completed, the same temperature was maintained for 3 hours to obtain a solution of polymer composition (A-1) having a resin content of 40%. Add 100 parts of this polymer (A-1) solution to 3-glycidoxyprobyltrimethoxysilane (hereinafter referred to as 1"GP8-M).
It is abbreviated as J. ) were mixed to obtain an initial solution of the polymer composition. This solution 'kl [is referred to as the combined composition (IA).
v4#!例2〜4
ビニル系単量体及び重合性シラン化合物の使用i(部)
を第1表に示すごとく変更した以外は調製例1と同様に
して重合物(A−2)〜(A−4)を得た。この重合物
(A−2)〜(A−4)の溶液それぞれ100部にGP
S−Mt−第2表に示すごとく混合して重合体組成物(
2A)〜(5A)を得た。v4#! Examples 2-4 Use of vinyl monomer and polymerizable silane compound i (part)
Polymers (A-2) to (A-4) were obtained in the same manner as in Preparation Example 1, except for changing as shown in Table 1. Add GP to 100 parts of each of the solutions of polymers (A-2) to (A-4).
S-Mt-Polymer composition (
2A) to (5A) were obtained.
第1表
但し、 MMA:メチルメタクリレートGMAニゲリシ
ジルメタクリレート
c)(MA−ニジクロヘキシルメタクリレートBMAニ
ブチルメタクリレート
LMA:ラウリルメタクリンート
第2表 重合体組成物Aの組成
(硬化剤混合物の)の調製)
攪拌装置、温度計、還流冷却器及び窒素導入管を備えた
反応器に4−メチル−2−ペンタノ7100部とモレキ
ュラーシープス3A(商標)100部を仕込み、窒素雰
囲気下で80°CK昇温してから3−アミノプロピルト
リエトキシシラン(以下rAPS−EJという。)12
0部を2時間かけて滴下した。滴下終了後も5時間同温
度に保持した俵、この反応混合物を蒸留して4−メチル
−2−ペンタノンとAPS−Eft除去した。別のフラ
クションを112〜116°Cの温度で3〜4 tlH
gの圧力下に収集し、化合物(IB)’に得た。ガスク
ロマトグラフィーによる分析が示すところによればこの
液体は98%純度であり、痕跡量の原料4−メチル−マ
ススペクトルは次に示す構造:
caac鉱N−CHtCHtCHt−8i(OCLCH
s)!?
Ht
CH=CHs
」
Hs
に一致する。Table 1 However, MMA: Methyl methacrylate GMA Nigericidyl methacrylate c) (MA- Nidichlohexyl methacrylate BMA Nibutyl methacrylate LMA: Lauryl methacrylate Table 2 Preparation of the composition of polymer composition A (of the curing agent mixture) ) 7100 parts of 4-methyl-2-pentano and 100 parts of Molecular Sheeps 3A (trademark) were charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, and the mixture was heated to 80°C under a nitrogen atmosphere. After heating, add 3-aminopropyltriethoxysilane (hereinafter referred to as rAPS-EJ) 12
0 part was added dropwise over 2 hours. After the completion of the dropwise addition, the bales were kept at the same temperature for 5 hours, and the reaction mixture was distilled to remove 4-methyl-2-pentanone and APS-Eft. Another fraction was incubated at a temperature of 112-116 °C for 3-4 tlH.
Compound (IB)' was obtained by collecting under a pressure of 100 g. Analysis by gas chromatography shows that the liquid is 98% pure, and the trace material 4-methyl mass spectrum shows the structure: caacite N-CHtCHtCHt-8i (OCLCH
s)! ? Ht CH=CHs ” Hs.
この化合物(IB)90部にエチルシリケー物
ト部分加水分解1日本コルコート社#!ES−40(登
録商標))10部を混合して硬化剤混合物(2B )t
−得、更に触媒C)としてジブチル錫ジアセテート0.
1部を添加混合して硬化剤混合物(3B)を調製した。90 parts of this compound (IB) was partially hydrolyzed with ethyl silicate 1 Nippon Colcoat #! ES-40 (registered trademark)) to form a curing agent mixture (2B)t.
- dibutyltin diacetate as catalyst C).
1 part was added and mixed to prepare a curing agent mixture (3B).
実施例1〜4、比較例1.2
調製例1〜5で得られた重合体組成物(IA)〜(5A
)の溶液をトルエンと酢酸ブチルとの1:1混合溶剤を
加えて有効成分濃度35%に希釈した後、この希釈溶液
100部に対して硬化剤(IB)〜(3B)を第3表及
び第4表に示す量添加混合して硬化性樹脂組成物を調製
した。Examples 1 to 4, Comparative Example 1.2 Polymer compositions (IA) to (5A) obtained in Preparation Examples 1 to 5
) was diluted to an active ingredient concentration of 35% by adding a 1:1 mixed solvent of toluene and butyl acetate, and then hardening agents (IB) to (3B) were added to 100 parts of this diluted solution as shown in Table 3. A curable resin composition was prepared by adding and mixing the amounts shown in Table 4.
次いでこの硬化性樹脂組成物を乾燥膜厚が約10μmと
なるようにバーコーターでガラス板に塗布して、常温常
温下及び高温下条件としてNH4C1の飽和溶液で相対
湿度79%に調湿した25℃のデシケータ−内において
硬化させ、それぞれの硬化塗膜を得た。このようにして
得られた各塗膜の表面傷つき性を評価するため鉛筆硬度
を測定した。結果を第3表及び第4弐に示す。Next, this curable resin composition was applied to a glass plate with a bar coater so that the dry film thickness was about 10 μm, and the relative humidity was adjusted to 79% with a saturated solution of NH4C1 under normal temperature and high temperature conditions. It was cured in a desiccator at ℃ to obtain each cured coating film. In order to evaluate the surface scratch resistance of each coating film thus obtained, pencil hardness was measured. The results are shown in Tables 3 and 4.
第
表
第
表
(注)鉛筆硬度:JIS G−3312(着色亜鉛板
)の8.4鉛筆硬度試験により測定し、表面に傷のつか
ない最大硬度を表示。Table 1 (Note) Pencil hardness: Measured according to the 8.4 pencil hardness test of JIS G-3312 (colored zinc plate), and the maximum hardness without scratching the surface is indicated.
ζこで、比較例1は重合体組成初回においてエポキシ基
を含有する加水分解製シラン化合物を欠く例であシ、比
較例2は重合体組成初回の構成要素のうち共重合体が加
水分解性基と結合した珪素原子を欠く例であって、それ
ぞれ塗膜の硬度が低いか塗膜外観が不良であるかの欠点
を有している。ζHere, Comparative Example 1 is an example in which the hydrolyzable silane compound containing an epoxy group is absent in the initial polymer composition, and Comparative Example 2 is an example in which the copolymer is hydrolyzable among the constituent elements in the initial polymer composition. These examples lack a silicon atom bonded to a group, and each has drawbacks such as low coating film hardness or poor coating film appearance.
(発明の効果)
上記実施例によって明らかなごとく、本発明によって常
温で、しかも高湿度下であっても高硬度の硬化物を得る
ことが可能となった。これは木工用あるいはプラスチッ
ク用の高硬度塗料を提供するものであり、産業上の利益
は計り知れないものがある。(Effects of the Invention) As is clear from the above examples, the present invention made it possible to obtain a cured product with high hardness at room temperature and even under high humidity. This provides a highly hard paint for wood or plastics, and the industrial benefits are immeasurable.
以上that's all
Claims (5)
た珪素原子を有する線状重合体と、エポキシ基を含有す
る加水分解性シラン化合物とを主成分とする重合体組成
物(A)及び次の一般式▲数式、化学式、表等がありま
す▼ {式中R^1、R^2は各々水素原子又はアルキル基、
アルケニル基、アルキニル基、アリール基、シアノアル
キル基、トリフルオロプロピル基及びハロフエニル基よ
りなる群から選ばれ、R^3は炭素原子3ないし6個を
有するアルキレン基又は次式 ▲数式、化学式、表等があります▼ (式中R^4、R^5は各々炭素原子1ないし6個を有
するアルキレン基、Qは次式 ▲数式、化学式、表等があります▼ (式中R^6、R^7、R^8は各々R^1と同じ意味
を表わす。)で表わされる基である。)で表わされる基
、Xは炭素原子3ないし6個を有する1価の炭化水素基
、Yは炭素原子6個以下のアルキル基又はアルコキシア
ルキル基、及びaは0又は1の値を表わす。} で表わされる加水分解性シラン化合物(B−1)を主成
分とする硬化剤(B)からなる常温硬化性樹脂組成物。(1) A polymer composition (A ) and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ {In the formula, R^1 and R^2 are each a hydrogen atom or an alkyl group,
selected from the group consisting of an alkenyl group, an alkynyl group, an aryl group, a cyanoalkyl group, a trifluoropropyl group, and a halophenyl group, and R^3 is an alkylene group having 3 to 6 carbon atoms or the following formula ▲ Numerical formula, chemical formula, table etc. ▼ (In the formula, R^4 and R^5 are alkylene groups each having 1 to 6 carbon atoms, and Q is the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^6 and R^ 7, R^8 each has the same meaning as R^1. ) is a group represented by ), X is a monovalent hydrocarbon group having 3 to 6 carbon atoms, Y is a carbon an alkyl group or an alkoxyalkyl group having up to 6 atoms, and a represents a value of 0 or 1; } A room temperature curable resin composition comprising a curing agent (B) containing a hydrolyzable silane compound (B-1) represented by the formula (B-1) as a main component.
剤(B)及びアルコキシシラン架橋剤としての加水分解
性シラン化合物を混合してなる常温硬化性樹脂組成物。(2) A cold-curable resin composition obtained by mixing the polymer composition (A) according to claim (1), a curing agent (B), and a hydrolyzable silane compound as an alkoxysilane crosslinking agent.
記載の3成分の他に加水分解性シラン化合物の加水分解
・縮合を促進させるための触媒を混合してなる常温硬化
性樹脂組成物。(3) Room-temperature curing obtained by mixing a catalyst for promoting hydrolysis and condensation of a hydrolyzable silane compound in addition to the two components described in claim (1) or the three components described in claim (2). resin composition.
珪素原子を有する線状重合体が、重合性の二重結合を有
し珪素原子を有しない化合物と重合性の二重結合及び加
水分解性基を有するシラン化合物との共重合により得ら
れるものである請求項(1)ないし(3)のいずれかに
記載の常温硬化性樹脂組成物。(4) A linear polymer having a silicon atom bonded to a hydrolyzable group at the end of a side chain or a chain molecule has a polymerizable double bond and a compound having no silicon atom has a polymerizable double bond and a silane compound having a hydrolyzable group.
ン化合物が珪酸エチル又はその部分加水分解縮合物であ
る、請求項(2)ないし(4)項のいずれかに記載の常
温硬化性樹脂組成物。(5) The room temperature curable resin composition according to any one of claims (2) to (4), wherein the hydrolyzable silane compound as the alkoxysilane crosslinking agent is ethyl silicate or a partially hydrolyzed condensate thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30842388A JP2750881B2 (en) | 1988-12-06 | 1988-12-06 | Room temperature curable resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30842388A JP2750881B2 (en) | 1988-12-06 | 1988-12-06 | Room temperature curable resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02153963A true JPH02153963A (en) | 1990-06-13 |
JP2750881B2 JP2750881B2 (en) | 1998-05-13 |
Family
ID=17980876
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30842388A Expired - Lifetime JP2750881B2 (en) | 1988-12-06 | 1988-12-06 | Room temperature curable resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2750881B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05247065A (en) * | 1992-03-05 | 1993-09-24 | Shin Etsu Chem Co Ltd | Organic silicon compound and its production |
US5362772A (en) * | 1993-07-09 | 1994-11-08 | E. I. Du Pont De Nemours And Company | Crosslinked microgel for cathodic electrocoating compositions |
JP2002146284A (en) * | 2000-11-07 | 2002-05-22 | Dainippon Toryo Co Ltd | Solventless coating material composition |
US8022159B2 (en) | 2008-11-24 | 2011-09-20 | The Goodyear Tire & Rubber Company | Terminating compounds, polymers, and their uses in rubber compositions and tires |
-
1988
- 1988-12-06 JP JP30842388A patent/JP2750881B2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05247065A (en) * | 1992-03-05 | 1993-09-24 | Shin Etsu Chem Co Ltd | Organic silicon compound and its production |
US5362772A (en) * | 1993-07-09 | 1994-11-08 | E. I. Du Pont De Nemours And Company | Crosslinked microgel for cathodic electrocoating compositions |
JP2002146284A (en) * | 2000-11-07 | 2002-05-22 | Dainippon Toryo Co Ltd | Solventless coating material composition |
US8022159B2 (en) | 2008-11-24 | 2011-09-20 | The Goodyear Tire & Rubber Company | Terminating compounds, polymers, and their uses in rubber compositions and tires |
Also Published As
Publication number | Publication date |
---|---|
JP2750881B2 (en) | 1998-05-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6140445A (en) | Silane functional oligomer | |
JP4868783B2 (en) | Polysiloxanes modified with polyesters and their use as additives for thermoplastics, molding compounds and coating materials | |
JP2001522925A5 (en) | ||
WO1996035755A1 (en) | Curable resin composition | |
EP3119847B1 (en) | Alkoxy group-containing silicones with reactive functional groups of defined reactivity | |
JPH0443113B2 (en) | ||
TWI276630B (en) | Novel silane coupling agent and method for manufacturing the same | |
CN1675277A (en) | Silane-crosslinkable coating formulations | |
US5464901A (en) | Curable resin composition comprising a silicone resin having epoxy and phenyl groups in the molecule and a vinyl polymer having a group reactive with the epoxy group | |
JPH0558009B2 (en) | ||
JP7467891B2 (en) | ORGANOPOLYSILOXANE AND COATING COMPOSITION CONTAINING SAME | |
JPS6178806A (en) | Thermosetting acrylic resin composition for coating | |
KR20020003289A (en) | Water-based curable resin composition | |
JPH02153963A (en) | Cold-setting resin composition | |
JPH0369950B2 (en) | ||
US4721750A (en) | Primer composition | |
JPS58173158A (en) | Cold cure resin composition | |
JP3115928B2 (en) | Silicone compound, vinyl copolymer thereof, and coating composition using the same | |
JP2574157B2 (en) | Room temperature curable resin composition | |
JP3161595B2 (en) | Non-staining paint composition | |
JP5924536B2 (en) | Metal surface treatment agent and metal material treated with the surface treatment agent | |
JPH03252414A (en) | Silicone-based composition for coating | |
JPH01304111A (en) | Cold-setting resin composition | |
JP2006193469A (en) | Silicate composition and water-based coating containing the same | |
JPH07126332A (en) | Vinyl copolymer, its production, and room-temperature-curable resin composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080227 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090227 Year of fee payment: 11 |
|
EXPY | Cancellation because of completion of term | ||
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090227 Year of fee payment: 11 |