WO2012070637A1 - チオエーテル含有アルコキシシラン誘導体およびその用途 - Google Patents
チオエーテル含有アルコキシシラン誘導体およびその用途 Download PDFInfo
- Publication number
- WO2012070637A1 WO2012070637A1 PCT/JP2011/077129 JP2011077129W WO2012070637A1 WO 2012070637 A1 WO2012070637 A1 WO 2012070637A1 JP 2011077129 W JP2011077129 W JP 2011077129W WO 2012070637 A1 WO2012070637 A1 WO 2012070637A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- thioether
- ppm
- formula
- containing alkoxysilane
- Prior art date
Links
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 40
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 24
- -1 thiol compound Chemical class 0.000 claims description 20
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 15
- 125000000466 oxiranyl group Chemical group 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 150000007529 inorganic bases Chemical class 0.000 abstract description 3
- 229940125904 compound 1 Drugs 0.000 abstract 1
- 229940125782 compound 2 Drugs 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 13
- 125000003396 thiol group Chemical group [H]S* 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 0 CC(C)[*+](CCC*(CCC12)C1C2C(C(C)(C)C)=C)C1C*C1 Chemical compound CC(C)[*+](CCC*(CCC12)C1C2C(C(C)(C)C)=C)C1C*C1 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 3
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- BAXXIBXLWXEPGF-UHFFFAOYSA-N 2-benzyl-1-methylbenzimidazole Chemical compound N=1C2=CC=CC=C2N(C)C=1CC1=CC=CC=C1 BAXXIBXLWXEPGF-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- GVQDVIAKPKRTFJ-UHFFFAOYSA-N 2-ethyl-1,4-dimethylimidazole Chemical compound CCC1=NC(C)=CN1C GVQDVIAKPKRTFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- IFTRQJLVEBNKJK-UHFFFAOYSA-N CCC1CCCC1 Chemical compound CCC1CCCC1 IFTRQJLVEBNKJK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LDTLDBDUBGAEDT-UHFFFAOYSA-N methyl 3-sulfanylpropanoate Chemical compound COC(=O)CCS LDTLDBDUBGAEDT-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
Definitions
- the present invention relates to a novel thioether-containing alkoxysilane derivative suitably used for an adhesion improver and the like and its use.
- silane coupling agents have a structure having an alkyl group having 1 to 5 carbon atoms as the main skeleton, so the boiling point is low, and a large amount (for example, 10 to 20 weight) is required for coatings that require high temperature coating. %) Had to be added.
- a salt such as titanium or zirconium, an amine such as imidazole, a phosphate ester, a urethane resin, a thiol
- adhesion can be achieved for the first time by adding adhesion aids such as compounds at the same time.
- adhesion assistants not only increases the number of steps, but also requires an optimization operation of the adhesion assistant species and addition amount that do not impair the coating properties.
- the main skeleton connecting the trialkoxysilyl group and the reactive group is constituted by a carbon-carbon bond. Therefore, the molecule is rigid and the reaction efficiency of the alkoxysilyl group or reactive group is low.
- an object of the present invention is to provide a novel thioether-containing alkoxysilane derivative excellent in the effect of improving adhesion to an inorganic substrate and its use.
- the present inventors have found that a thioether-containing alkoxysilane derivative having a specific structure has an excellent adhesion improving effect, and have completed the invention. That is, the present invention includes the following [1] to [4].
- [1] A thioether-containing alkoxysilane derivative represented by the following formula 1. (In the formula, a and b are integers of 0 to 2, c is an integer of 1 to 3, and a + b + c 3.
- R 1 is a trivalent group represented by the following formula 2.
- R 2 is a divalent group represented by —CH 2 —CHR 5 — or —CR 5 (CH 3 ) —
- R 3 is represented by —CH 2 —CHR 6 — or —CR 6 (CH 3 ) —.
- R 5 and R 6 are each independently a hydrogen atom or a methyl group
- R 4 is a methyl group or an ethyl group.
- m is 1 or 2.
- R 4 is a methyl group or an ethyl group, and R 5 is a hydrogen atom or a methyl group.
- m is 1 or 2.
- [3] The thioether-containing alkoxysilane derivative according to [2], wherein the oxirane ring-containing compound represented by the following formula 5 is further reacted simultaneously.
- R 6 is a hydrogen atom or a methyl group.
- An adhesion improver comprising the thioether-containing alkoxysilane derivative according to any one of [1] to [3] as an active ingredient.
- the thioether-containing alkoxysilane derivative of the present invention has an excellent adhesion improving effect, and it is necessary to add an adhesion aid by adding a relatively small amount of, for example, 0.1 to 10% by weight to the coating material. It is possible to impart high adhesion to the paint without having to do so.
- the bond angle of thiol is larger than the bond angle of carbon, a molecule having a thiol ether group in the molecule can have various structures than a molecule bonded only by carbon. Therefore, the orientation of the thioether-containing alkoxysilane derivative of the present invention to the base material is higher than that of the alkoxysilane derivative bonded only with carbon, and the adhesion can be improved.
- the present invention has a wider bond angle of thioether compared to conventional silane coupling agents, so the degree of freedom in the molecular structure can be increased and dense molecular orientation can be achieved, and the boiling point is higher than that of the same molecular weight. And low volatility. Therefore, for example, even if a relatively small amount of 0.1 to 10% by weight is added to the paint, it is possible to impart high adhesion to the silicon substrate without requiring the addition of an adhesion aid. .
- the thioether-containing alkoxysilane derivative of the present invention has an isocyanurate ring in the main skeleton, it has excellent localization to the base material, and an alkoxysilane group present at the molecular end forms a chemical bond with the base material. Alternatively, it exhibits excellent adhesion by physical adsorption.
- the thioether bond existing in the molecule can change the bond angle and bond length more flexibly than the bond of atoms such as C, O, and N, and can take various conformations. It is considered that the orientation is increased.
- the present invention is a reaction product of a low-volatility polyvalent thiol compound and an alkoxysilyl group-containing compound, it is less volatile than a general alkoxysilyl group-containing compound.
- the S atom derived from the thioether bond has a larger atomic radius because the outermost shell of atoms such as C, O, and N is the L shell while the outermost shell is the M shell. Therefore, by having S atoms, it is possible to interact with molecules that are located farther away, so that the intermolecular force is improved, leading to low volatility.
- the present invention can impart high adhesion to the coating material without requiring the addition of an adhesion aid even when added in a relatively small amount of 0.1 to 10% by weight, for example.
- the thioether-containing alkoxysilane derivative is excellent in adhesion imparting effect, it is useful as an adhesion improver that imparts adhesion to paints and the like.
- Example 1-1 It is a nuclear magnetic resonance spectrum of Example 1-1. It is a nuclear magnetic resonance spectrum of Example 1-2. It is a nuclear magnetic resonance spectrum of Example 1-3. It is a nuclear magnetic resonance spectrum of Example 1-4.
- the thioether-containing alkoxysilane derivative of the present invention is a compound represented by the following formula 1.
- a and b are integers of 0 to 2
- c is an integer of 1 to 3
- a + b + c 3.
- R 1 is a trivalent group represented by the following formula 2.
- 2 is a divalent group represented by —CH 2 —CHR 5 — or —CR 5 (CH 3 ) —
- R 3 is represented by —CH 2 —CHR 6 — or —CR 6 (CH 3 ) —.
- R 5 and R 6 are each independently a hydrogen atom or a methyl group
- R 4 is a methyl group or an ethyl group.
- m is 1 or 2.
- b is 1 or more from the viewpoint of improving the adhesion.
- the thioether-containing alkoxysilane derivative of the present invention represented by Formula 1 is compatible with many resins, it can be used for a wide range of applications, and has high adhesion with a small amount (for example, 0.1 to 10% by weight). Sex can be obtained.
- FRP fiber reinforced plastic
- FRTP fiber reinforced thermoplastic
- resin concrete artificial marble
- plastic It is useful as an adhesion improver for composite materials combining inorganic materials and resins, such as magnets, rubber magnets, and magnetic tapes.
- blending the thioether-containing alkoxysilane derivative of the present invention in the resin component is effective in improving the adhesion to the inorganic substrate.
- it is suitable as an adhesion improver when various paints are applied to an inorganic base material such as a glass substrate.
- the thioether-containing alkoxysilane derivative represented by the above formula 1 includes at least an alkoxysilyl group [—Si (OR 4 ) 3] and a compound having a double bond (hereinafter also referred to as “component A”), a thiol group (— It can be obtained by reacting with a polyvalent thiol compound having SH) (hereinafter sometimes referred to as B component). Specifically, it can be obtained by reacting at least an alkoxysilyl group-containing compound represented by the following formula 3 with a polyvalent thiol compound represented by the following formula 4.
- R 4 is a methyl group or an ethyl group
- R 5 is a hydrogen atom or a methyl group.
- m is an integer of 1 or 2.
- alkoxysilyl group-containing compound represented by Formula 3 examples include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxy. Silane or the like can be used.
- the thioether-containing alkoxysilane derivative of the present invention is added to a resin composition having a functional group that reacts with an oxirane ring, the alkoxysilyl group-containing compound represented by Formula 3 and the formula 4
- an oxirane ring-containing compound represented by the following formula 5 is preferably reacted at the same time. Thereby, higher adhesiveness can be provided.
- R 6 is a hydrogen atom or a methyl group.
- Examples of the oxirane ring-containing compound represented by Formula 5 include glycidyl (meth) acrylate.
- the A component and the B component are reacted in the presence of a catalyst or a radical generator. This is because if a catalyst or a radical generator is added, the reaction can be performed in a shorter time and with a higher yield.
- the catalyst is preferably an amine base catalyst, and primary, secondary or tertiary amines, or imidazole compounds can be used.
- imidazole compounds include 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, imidazole analogues such as 1-phenylimidazole, 1-methyl-2-oxymethylimidazole, Oxyalkyl derivatives such as 1-methyl-2-oxyethylimidazole, nitro and amino derivatives such as 1-methyl-4 (5) -nitroimidazole, 1,2-dimethyl-5 (4) -aminoimidazole, benzimidazole, Examples thereof include 1-methylbenzimidazole and 1-methyl-2-benzylbenzimidazole.
- a peroxide or an azo compound is preferable.
- the peroxide include dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, dilauroyl peroxide, tert-butyl hydroperoxide and the like.
- the azo compound include azobis (iso-butyronitrile) and 2,2'-azobis (2-methylbutanenitrile).
- both of the two carbons forming the double bond of the A component bind to S of the thiol.
- the ratio of the two products varies depending on the reaction conditions. For example, when a base catalyst such as an amine is added to the reaction system as a catalyst for this reaction, a large amount of product (1) is generated and When added to, a large amount of product (2) tends to be formed. In many cases, the thioether-containing alkoxysilane derivative after production is a mixture of the products (1) and (2).
- V represents a residue (isocyanurate ring-containing residue) bonded to the B component thiol group.
- Equation 7 The number of added A components in Equation 7 corresponds to c in Equation 1.
- the thioether-containing alkoxysilane derivative after production is a mixture of substances having different numbers of addition-reacted substituents.
- the reaction can be carried out at a temperature of 5 ° C. or higher.
- a base catalyst or a radical generator is added at 60 to 80 ° C. It is preferable to do.
- the reaction can be allowed to proceed even without a solvent.
- the reaction can be carried out at a low temperature, for example, when the viscosity is to be lowered, the reaction can be carried out by adding a solvent.
- a solvent that does not react with an alkoxysilyl group, a double bond, or a thiol group, for example, alcohols, ketones, esters, or aromatics is preferable.
- Alcohols that do not react with alkoxysilyl groups, double bonds, and thiol groups are preferably those having 3 or less carbon atoms and primary, and those having a boiling point higher than the reaction temperature (for example, a boiling point of 50 to 190 ° C.). Is preferred. The reason is that when the boiling point is lower than the above range, it is difficult to produce when industrialized. When the boiling point is higher than the above range, it is difficult to remove the solvent when the solvent needs to be removed. Because it becomes. Therefore, the boiling point should be as high as possible. More preferred as alcohols are methanol and ethanol.
- the alcohol as the reaction solvent and the alkoxysilyl group-containing compound represented by the above formula 3 may cause a transesterification reaction during the reaction, which may reduce the yield of the target product. Therefore, in the above formula 3, it is preferable to use methanol as a reaction solvent when a compound having R 4 is a methyl group, and to use ethanol as a reaction solvent when a compound having R 4 is an ethyl group.
- ketones that do not react with the alkoxysilyl group, double bond, or thiol group those having a boiling point higher than the reaction temperature are preferred, and those having 6 or less carbon atoms are preferred from the viewpoint of solubility.
- examples of those satisfying these include methyl ethyl ketone and methyl isobutyl ketone.
- esters that do not react with the alkoxysilyl group, double bond, or thiol group those having a boiling point higher than the reaction temperature are preferable, and those having a straight chain carbon number of 6 or less are preferable from the viewpoint of solubility.
- examples of those satisfying these include ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, methyl lactate, ethyl lactate, and butyl lactate.
- Adhesion improver The thioether-containing alkoxysilane derivative of the present invention can be used as an adhesion improver because it has a high adhesion improving performance especially for inorganic substrates such as glass and metal.
- Adhesion improver comprising thioether-containing alkoxysilane derivative as an active ingredient should exhibit high adhesion improvement effect by blending with epoxy resin, urethane resin, acrylic resin, polyimide resin, compound having double bond, etc. Can do.
- a thioether-containing alkoxysilane derivative which is a compound represented by Formula 1 and a is not 0 has a thiol group and reacts with an epoxy group, a double bond, and an isocyanate group. For this reason, a higher adhesion effect can be exhibited by adding a thioether-containing alkoxysilane derivative in which a is not 0 in Formula 1 to an epoxy resin, an acrylic resin, a urethane resin, or a compound having a double bond.
- the thioether-containing alkoxysilane derivative represented by the formula 1, wherein b is not 0, has an oxirane ring and reacts with an epoxy group, a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, an amino group, and an amide group. To do. For this reason, by adding a thioether-containing alkoxysilane derivative in which b is not 0 in Formula 1 to a resin composition having a functional group that reacts with an oxirane ring, a higher adhesion effect can be exhibited.
- An adhesion improver comprising a thioether-containing alkoxysilane derivative as an active ingredient exhibits high adhesion when added as an active ingredient in an amount of preferably 0.1 to 30% by mass, more preferably 0.1 to 15% by mass. be able to.
- IR Infrared absorption spectrum analysis
- NMR Nippon Bruker Co., Ltd., 400 MHz-Advanced 400, conditions: 16 times of accumulation, solvent: heavy chloroform
- A-2 3-acryloxypropyltrimethoxysilane.
- the structure is shown in the following formula 13.
- A-3 3-methacryloxypropyltriethoxysilane. The structure is shown in the following formula 14.
- ⁇ Multivalent thiol compound Component B> B-1: Tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate. The structure is shown in the following formula 15 (viscosity 5.4 Pa ⁇ s).
- ⁇ Oxirane ring-containing compound Component C> C-1: Glycidyl methacrylate. The structure is shown in the following formula 17.
- Example 1-1 to 1-4 Comparative Example 1
- a separable four-necked flask was equipped with a thermometer and a reflux tube, and the inside was made a nitrogen atmosphere.
- a component, B component and C component were charged according to the following Table 1, and reacted at 90 ° C. for 8 hours according to the conditions of Table 1.
- Table 1 shows the viscosity after the reaction.
- Example 1-2 3627cm -1: 91% T, 2947cm -1: 65% T, 2841cm -1: 76% T, 2571cm -1: 97% T, 2360cm -1: 98% T, 1736cm -1: 14% T, 1693cm - 1 : 9% T, 1462 cm ⁇ 1 : 15% T, 1352 cm ⁇ 1 : 57% T, 1284 cm ⁇ 1 : 62% T, 1244 cm ⁇ 1 : 42% T, 1159 cm ⁇ 1 : 32% T, 1084 cm ⁇ 1 : 33% T, 822 cm ⁇ 1 : 59% T, 764 cm ⁇ 1 : 46% T
- FIG. 1 shows the NMR spectrum of Example 1-1
- FIG. 2 shows the NMR spectrum of Example 1-2
- FIG. 3 shows the NMR spectrum of Example 1-3
- FIG. 4 shows the NMR spectrum of Example 1-4. Respectively.
- Examples 2-1 to 2-4 Comparative Examples 2-1 to 2-2
- an epoxy resin 95% by mass of YDPN638 (phenol novolac type epoxy resin: product name, manufactured by Toto Kasei Co., Ltd.) and 5% by mass of EH-4344S (imidazole type catalyst: product name, manufactured by Adeka Co., Ltd.)
- E-1 Into E-1, the above Examples 1-1 to 1-4, Comparative Example 1 and B-1 alone were blended as adhesion improvers according to the blending amounts shown in Table 2.
- the blended sample is applied to OA-10 [non-alkali glass: product name, manufactured by Nippon Denki Glass Co., Ltd.] with a bar coater and cured at 150 ° C. for 1 hour to form a cured film as a resin molded product. Obtained.
- the adhesion of the obtained cured film was evaluated, and the results are shown in Table 2. In addition, the numerical value in Table 2 is g.
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Abstract
Description
〔1〕下記式1で表されるチオエーテル含有アルコキシシラン誘導体。
(式中のaおよびbは0~2の整数であり、cは1~3の整数であり、a+b+c=3である。R1は下記式2で表される3価の基であり、R2は-CH2-CHR5-あるいは-CR5(CH3)-で表される2価の基あり、R3は-CH2-CHR6-あるいは-CR6(CH3)-で表される2価の基あり、R5とR6はそれぞれ独立に水素原子またはメチル基であり、R4はメチル基またはエチル基である。)
(式中のmは1または2である。)
〔2〕下記式3で表されるアルコキシシリル基含有化合物と、下記式4で表される多価チオール化合物とを反応させてなる、〔1〕に記載のチオエーテル含有アルコキシシラン誘導体。
(式中のR4はメチル基またはエチル基であり、R5は水素原子またはメチル基である。)
(式中のmは1または2である。)
〔3〕さらに、下記式5で表されるオキシラン環含有化合物を同時に反応させてなる、〔2〕に記載のチオエーテル含有アルコキシシラン誘導体。
(R6は水素原子またはメチル基である。)
〔4〕〔1〕~〔3〕のいずれかに記載のチオエーテル含有アルコキシシラン誘導体を有効成分とする密着性向上剤。
本発明のチオエーテル含有アルコキシシラン誘導体は、下記式1で表される化合物である。
(式中のaおよびbは0~2の整数であり、cは1~3の整数であり、a+b+c=3である。R1は下記式2で表される3価の基であり、R2は-CH2-CHR5-あるいは-CR5(CH3)-で表される2価の基あり、R3は-CH2-CHR6-あるいは-CR6(CH3)-で表される2価の基あり、R5とR6はそれぞれ独立に水素原子またはメチル基であり、R4はメチル基またはエチル基である。)
(式中のmは1または2である。)
前記式1で表されるチオエーテル含有アルコキシシラン誘導体は、少なくともアルコキシシリル基〔-Si(OR4)3〕と二重結合を有する化合物(以下、A成分ということがある)と、チオール基(-SH)を有する多価チオール化合物(以下、B成分ということがある)とを反応させることによって得ることができる。具体的には、少なくとも下記式3で表されるアルコキシシリル基含有化合物と、下記式4で表される多価チオール化合物とを反応させることにより得ることができる。
(式中のR4はメチル基またはエチル基であり、R5は水素原子またはメチル基である。)
(式中のmは1または2の整数である。)
(R6は水素原子またはメチル基である。)
本発明のチオエーテル含有アルコキシシラン誘導体は、特にガラスや金属等の無機基材に対して高い密着性向上性能を有していることから、密着性向上剤として用いることができる。チオエーテル含有アルコキシシラン誘導体を有効成分とする密着性向上剤は、エポキシ樹脂、ウレタン樹脂、アクリル樹脂、ポリイミド樹脂、二重結合を有する化合物等に配合することによって、高い密着性向上効果を発揮することができる。
機種;日本分光(株)製 FT/IR-600
セル;KBr上に展開、分解;4cm-1、積算回数;16回
<核磁気共鳴スペクトル分析(NMR)>
機種;日本ブルカー(株)製、400MHz-Advance400、条件;積算回数16回、溶媒;重クロロホルム
<粘度>
機種;東機産業(株)製(R型粘度計)、温度;25℃
<密着性評価>
硬化膜を形成したサンプルを温度121℃、相対湿度(RH)100%で30時間処理した後、JIS K5600-5-6に規定される塗膜の機械的性質-付着性(クロスカット法)試験法で評価を行った。この試験で、全く剥離の無いものを「○」とした。さらには、温度121℃、相対湿度(RH)100%で40時間処理した後のサンプルに対し同様な試験を行った結果、全く剥離の無いものを「◎」とした。剥離が観測されたものは「×」とした。
ジアザビシクロウンデセン(DBU)。
セパラブルの4つ口フラスコに温度計と還流管を備え、内部を窒素雰囲気にした。この4つ口フラスコに、下記表1に従いA成分、B成分およびC成分を仕込み、表1の条件に従い90℃で8時間反応させた。反応後の粘度を表1に示す。
<IRの結果>
(実施例1-1)
3629cm-1:92%T、2945cm-1:51%T、2841cm-1:59%T、1736cm-1:21%T、1697cm-1:18%T、1462cm-1:26%T、1371cm-1:70%T、1192cm-1:32%T、1086cm-1:21%T、820cm-1:45%T、764cm-1:52%T
3627cm-1:91%T、2947cm-1:65%T、2841cm-1:76%T、2571cm-1:97%T、2360cm-1:98%T、1736cm-1:14%T、1693cm-1:9%T、1462cm-1:15%T、1352cm-1:57%T、1284cm-1:62%T、1244cm-1:42%T、1159cm-1:32%T、1084cm-1:33%T、822cm-1:59%T、764cm-1:46%T
2925cm-1:63%T、1734cm-1:74%T、1697cm-1:73%T、1462cm-1:69%T、1373cm-1:84%T、1080cm-1:76%T、958cm-1:83%T、764cm-1:80%T
3527cm-1:77%T、2949cm-1:49%T、2841cm-1:66%T、2571cm-1:92%T、2360cm-1:93%T、1734cm-1:16%T、1695cm-1:13%T、1462cm-1:17%T、1371cm-1:44%T、1352cm-1:46%T、1161cm-1:23%T、1084cm-1:25%T、820cm-1:49%T、764cm-1:34%T、671cm-1:89%T
実施例1-1のNMRスペクトルを図1に、実施例1-2のNMRスペクトルを図2に、実施例1-3のNMRスペクトルを図3に、実施例1-4のNMRスペクトルを図4にそれぞれ示す。
a:3.5~3.6ppm、b:0.6~0.7ppm、c:1.7~1.8、d:4.3~4.4ppm、e:2.5~2.7ppm、f:1.1~1.3ppm、g:2.6~2.8ppm、h:2.6~2.8ppm、i:2.6~2.7ppm、j:4.2~4.4ppm、k:3.4~3.5ppm
a:3.5~3.6ppm、b:0.6~0.7ppm、c:1.7~1.8、d:4.3~4.4ppm、e:2.5~2.7ppm、g:2.6~2.8ppm、h:2.6~2.8ppm、i:2.6~2.7ppm、j:4.1~4.2ppm、k:3.5~3.6ppm、l:3.4~3.5ppm、m:4.0~4.2ppm、n:2.4~2.6ppm、o:2.7~2.9ppm、p:1.6~1.7ppm
a:1.2~1.3ppm、a’:3.7~3.9ppm、b:0.6~0.7ppm、c:1.7~1.8、d:4.3~4.4ppm、e:2.5~2.7ppm、f:1.1~1.3ppm、g:2.6~2.8ppm、h:2.6~2.8ppm、i:2.6~2.7ppm、j:4.1~4.2ppm、k:3.7~3.8ppm、l:3.7~3.8ppm、m:4.0~4.2ppm、n:2.5~2.6ppm、o:2.7~2.9ppm、p:1.7~1.8ppm
a:1.2~1.3ppm、b:0.6~0.7ppm、c:1.7~1.8、d:4.3~4.4ppm、e:2.5~2.7ppm、f:1.0~1.2ppm、g:2.6~2.8ppm、h:2.6~2.8ppm、i:2.5~2.7ppm、j:4.1~4.2ppm、k:3.7~3.8ppm、l:3.7~3.8ppm、m:4.0~4.2ppm、n:2.5~2.6ppm、o:2.7~2.9ppm、p:2.6~2.8ppm、q:2.6~2.8ppm、r:1.1~1.3ppm、s:4.0~4.2ppm、t:2.8~2.9ppm、u:2.5~2.7ppm
エポキシ樹脂として、95質量%のYDPN638〔フェノールノボラック型エポキシ樹脂:東都化成(株)製、商品名〕と、5質量%のEH-4344S〔イミダゾール型触媒:(株)アデカ製、商品名〕の混合物を選択した(E-1)。このE-1へ、密着性向上剤として上記実施例1-1~1-4、比較例1、及びB-1単独を、表2の配合量に従って配合した。当該配合したサンプルをOA-10〔無アルカリガラス:日本電気硝子(株)製、商品名〕にバーコーターで塗布し、150℃、1時間の条件で硬化させて樹脂成形物としての硬化膜を得た。得られた硬化膜の密着性を評価し、それらの結果を表2に示す。なお、表2中の数値はgである。
Claims (4)
- 請求項1ないし請求項3のいずれかに記載のチオエーテル含有アルコキシシラン誘導体を有効成分とする密着性向上剤。
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JP2012545799A JP5838972B2 (ja) | 2010-11-25 | 2011-11-25 | チオエーテル含有アルコキシシラン誘導体およびその用途 |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012164870A1 (ja) * | 2011-05-30 | 2012-12-06 | 日油株式会社 | 硬化性樹脂組成物 |
JP2015502919A (ja) * | 2011-11-01 | 2015-01-29 | コリア インスティチュート オブ インダストリアル テクノロジー | アルコキシシリル基を有するイソシアヌレートエポキシ化合物、その製造方法、それを含む組成物、該組成物の硬化物及び該組成物の用途 |
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- 2011-11-25 JP JP2012545799A patent/JP5838972B2/ja active Active
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US9150686B2 (en) | 2011-08-25 | 2015-10-06 | Korea Institute Of Industrial Technology | Epoxy compound having alkoxysilyl group, method of preparing the same, composition and cured product comprising the same, and uses thereof |
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JP2015502919A (ja) * | 2011-11-01 | 2015-01-29 | コリア インスティチュート オブ インダストリアル テクノロジー | アルコキシシリル基を有するイソシアヌレートエポキシ化合物、その製造方法、それを含む組成物、該組成物の硬化物及び該組成物の用途 |
US9902803B2 (en) | 2012-03-14 | 2018-02-27 | Korea Institute Of Industrial Technology | Epoxy compound having alkoxy silyl group, composition comprising same, cured product, use thereof and method for preparing epoxy compound having alkoxy silyl group |
US10689482B2 (en) | 2012-04-02 | 2020-06-23 | Korea Institute Of Industrial Technology | Epoxy compound having alkoxysilyl group, composition and hardened material comprising same, use for same, and production method for epoxy compound having alkoxysilyl group |
US9670309B2 (en) | 2012-07-06 | 2017-06-06 | Korea Institute Of Industrial Technology | Novolac-based epoxy compound, production method for same, composition and cured article comprising same, and use for same |
EP3424933A1 (en) * | 2013-06-12 | 2019-01-09 | Shin-Etsu Chemical Co., Ltd. | Thiocarbamatoalkyl-substituted 2,4,6-trioxo-1,3,5-triazines as adhesion improvers |
JP2015168679A (ja) * | 2014-03-11 | 2015-09-28 | 日油株式会社 | チオエーテル含有(メタ)アクリレート誘導体、およびこれを含有する密着性向上剤 |
WO2015137264A1 (ja) * | 2014-03-11 | 2015-09-17 | 日油株式会社 | チオエーテル含有(メタ)アクリレート誘導体、およびこれを含有する密着性向上剤 |
JP2019179141A (ja) * | 2018-03-30 | 2019-10-17 | 日油株式会社 | 液晶パネル用封止材 |
JP7056321B2 (ja) | 2018-03-30 | 2022-04-19 | 日油株式会社 | 液晶パネル用封止材 |
US11840601B2 (en) | 2019-11-15 | 2023-12-12 | Korea Institute Of Industrial Technology | Composition of alkoxysilyl-functionalized epoxy resin and composite thereof |
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CN102666556B (zh) | 2015-02-18 |
JP5838972B2 (ja) | 2016-01-06 |
TWI453212B (zh) | 2014-09-21 |
KR20130064821A (ko) | 2013-06-18 |
TW201226414A (en) | 2012-07-01 |
CN102666556A (zh) | 2012-09-12 |
JPWO2012070637A1 (ja) | 2014-05-19 |
KR101552026B1 (ko) | 2015-09-09 |
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