JP2006199906A - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
- Publication number
- JP2006199906A JP2006199906A JP2005036719A JP2005036719A JP2006199906A JP 2006199906 A JP2006199906 A JP 2006199906A JP 2005036719 A JP2005036719 A JP 2005036719A JP 2005036719 A JP2005036719 A JP 2005036719A JP 2006199906 A JP2006199906 A JP 2006199906A
- Authority
- JP
- Japan
- Prior art keywords
- curable resin
- resin composition
- compounds
- derivatives
- lewis acid
- 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 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000002841 Lewis acid Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 26
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 6
- -1 boron halides Chemical class 0.000 claims description 42
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 26
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 229910015900 BF3 Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 150000002736 metal compounds Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000945 filler Substances 0.000 description 17
- 229920002050 silicone resin Polymers 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000003606 tin compounds Chemical class 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- DBIWHDFLQHGOCS-UHFFFAOYSA-N piperidine;trifluoroborane Chemical compound FB(F)F.C1CCNCC1 DBIWHDFLQHGOCS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- GHKSKVKCKMGRDU-UHFFFAOYSA-N 2-(3-aminopropylamino)ethanol Chemical group NCCCNCCO GHKSKVKCKMGRDU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- XMMDVXFQGOEOKH-UHFFFAOYSA-N n'-dodecylpropane-1,3-diamine Chemical group CCCCCCCCCCCCNCCCN XMMDVXFQGOEOKH-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- RHPBLLCTOLJFPH-UHFFFAOYSA-N piperidin-2-ylmethanamine Chemical compound NCC1CCCCN1 RHPBLLCTOLJFPH-UHFFFAOYSA-N 0.000 description 2
- LTEKQAPRXFBRNN-UHFFFAOYSA-N piperidin-4-ylmethanamine Chemical compound NCC1CCNCC1 LTEKQAPRXFBRNN-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NSMWYRLQHIXVAP-WDSKDSINSA-N (2s,5s)-2,5-dimethylpiperazine Chemical compound C[C@H]1CN[C@@H](C)CN1 NSMWYRLQHIXVAP-WDSKDSINSA-N 0.000 description 1
- IFNWESYYDINUHV-OLQVQODUSA-N (2s,6r)-2,6-dimethylpiperazine Chemical compound C[C@H]1CNC[C@@H](C)N1 IFNWESYYDINUHV-OLQVQODUSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- XULIXFLCVXWHRF-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidine Chemical compound CN1C(C)(C)CCCC1(C)C XULIXFLCVXWHRF-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical group CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HDYFAPRLDWYIBU-UHFFFAOYSA-N 1-silylprop-2-en-1-one Chemical class [SiH3]C(=O)C=C HDYFAPRLDWYIBU-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- KRPRVQWGKLEFKN-UHFFFAOYSA-N 3-(3-aminopropoxy)propan-1-amine Chemical compound NCCCOCCCN KRPRVQWGKLEFKN-UHFFFAOYSA-N 0.000 description 1
- ANOPCGQVRXJHHD-UHFFFAOYSA-N 3-[3-(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]propan-1-amine Chemical compound C1OC(CCCN)OCC21COC(CCCN)OC2 ANOPCGQVRXJHHD-UHFFFAOYSA-N 0.000 description 1
- ULRCHFVDUCOKTE-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCN ULRCHFVDUCOKTE-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- UVLSCMIEPPWCHZ-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-amine Chemical group NCCCN1CCNCC1 UVLSCMIEPPWCHZ-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- OMNVECQLILUEFL-UHFFFAOYSA-N 4-(3-aminopropyl)aniline Chemical compound NCCCC1=CC=C(N)C=C1 OMNVECQLILUEFL-UHFFFAOYSA-N 0.000 description 1
- OXEZLYIDQPBCBB-UHFFFAOYSA-N 4-(3-piperidin-4-ylpropyl)piperidine Chemical compound C1CNCCC1CCCC1CCNCC1 OXEZLYIDQPBCBB-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 1
- RIUXWEGBWYUUEF-UHFFFAOYSA-N 4-bromo-2-cyclopropyl-1h-pyrrolo[2,3-b]pyridine Chemical group C=1C=2C(Br)=CC=NC=2NC=1C1CC1 RIUXWEGBWYUUEF-UHFFFAOYSA-N 0.000 description 1
- DUZLHGMYNVZMCO-UHFFFAOYSA-N 6-[2-[3-[2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]ethyl]-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(CCC2OCC3(CO2)COC(CCC=2N=C(N)N=C(N)N=2)OC3)=N1 DUZLHGMYNVZMCO-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- AMRPLQKEXNYDGZ-UHFFFAOYSA-N N'-[2-[diethoxy(2-phenylethyl)silyl]oxypropyl]ethane-1,2-diamine Chemical compound NCCNCC(C)O[Si](OCC)(OCC)CCC1=CC=CC=C1 AMRPLQKEXNYDGZ-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UGJVZXBXVRMUSG-UHFFFAOYSA-K [B+3].[F-].[F-].[F-] Chemical compound [B+3].[F-].[F-].[F-] UGJVZXBXVRMUSG-UHFFFAOYSA-K 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical class [SiH4].N=C=O NOKSMMGULAYSTD-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
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical group NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- VLVOIQGDDTVQOB-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)hexane-1,6-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCCCCCN VLVOIQGDDTVQOB-UHFFFAOYSA-N 0.000 description 1
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical group CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
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- KGHYGBGIWLNFAV-UHFFFAOYSA-N n,n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)NCCNC(C)(C)C KGHYGBGIWLNFAV-UHFFFAOYSA-N 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- HIDKSOTTZRMUML-UHFFFAOYSA-M potassium;dodecanoate Chemical group [K+].CCCCCCCCCCCC([O-])=O HIDKSOTTZRMUML-UHFFFAOYSA-M 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical group CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- NGXSWUFDCSEIOO-UHFFFAOYSA-N pyrrolidin-3-amine Chemical group NC1CCNC1 NGXSWUFDCSEIOO-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、変成シリコーン樹脂並びにルイス酸及びその誘導体から選ばれる一種以上の化合物を含有する湿気硬化型接着剤組成物並びにその製造方法に関する。より詳しくは、湿気と加水分解性シリル基との反応を極めて高く触媒するルイス酸及びその誘導体から選ばれる一種以上の化合物を含有する硬化速度が極めて速い湿気硬化性樹脂組成物並びにその製造方法に関する。 The present invention relates to a moisture-curable adhesive composition containing a modified silicone resin, one or more compounds selected from Lewis acids and derivatives thereof, and a method for producing the same. More specifically, the present invention relates to a moisture curable resin composition having a very fast curing rate and containing one or more compounds selected from Lewis acids and derivatives thereof that catalyze the reaction between moisture and hydrolyzable silyl groups, and a method for producing the same. .
従来、分子内に加水分解性シリル基を有する硬化性樹脂の硬化触媒として、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジオクチル錫ジラウレート等の有機錫化合物が汎用されている。特に、硬化性樹脂として特許文献１などに記載のシリル化ウレタン系樹脂を用いた場合には、有機錫化合物を配合することにより硬化速度の比較的速い硬化性樹脂組成物を得ることができる。また、特許文献２及び３などに記載の特定の有機錫化合物系硬化触媒を用いると、さらに硬化速度の速い硬化性樹脂組成物を得ることができる。 Conventionally, organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin dilaurate have been widely used as curing catalysts for curable resins having hydrolyzable silyl groups in the molecule. In particular, when the silylated urethane resin described in Patent Document 1 is used as the curable resin, a curable resin composition having a relatively high curing rate can be obtained by blending the organic tin compound. Moreover, when the specific organotin compound-based curing catalyst described in Patent Documents 2 and 3 is used, a curable resin composition having a higher curing rate can be obtained.
しかしながら、従来から公知である、いわゆる変成シリコーン樹脂は、反応性基がメチルジメトキシシリル基であるため、このような有機錫化合物を多量に配合しても、高まる硬化速度には限界がある。さらに、硬化触媒として有機錫化合物を多量に配合しても、思うような硬化速度は得られず、多量に配合しすぎると希釈効果あるいは可塑効果などにより硬化速度がむしろ遅くなる現象が起こってしまう。また、重金属である錫化合物の含有量が増えると、危険性・有害性が高くなったりするという別の問題が起こる。 However, conventionally known so-called modified silicone resins have methyldimethoxysilyl groups as the reactive groups, and therefore there is a limit to the curing rate that can be increased even if a large amount of such an organic tin compound is blended. Furthermore, even if a large amount of an organotin compound is blended as a curing catalyst, the desired curing rate cannot be obtained. If a large amount is blended, a phenomenon that the curing rate is rather slow due to a dilution effect or a plastic effect may occur. . In addition, when the content of the tin compound, which is a heavy metal, increases, another problem arises in that the danger / harmfulness increases.
さらに、有機錫化合物等を多量に配合した硬化性樹脂組成物を、例えばポリウレタン系あるいはポリエステル系等の分子内に加水分解性基を含有するプラスチックに対する接着剤あるいはシーリング材等に用いる場合、硬化性組成物中の有機錫化合物がそれらプラスチックを劣化させてしまうことがあった。 Furthermore, when a curable resin composition containing a large amount of an organic tin compound or the like is used as an adhesive or a sealing material for a plastic containing a hydrolyzable group in a molecule such as polyurethane or polyester, the curability The organotin compound in the composition may deteriorate these plastics.
また、変成シリコーン樹脂の硬化触媒としては、有機錫化合物の外にも、重金属を含有しないものとして、有機酸及びアミン化合物も知られている。しかしながら、これらを用いても、速い硬化速度は得られない。このため、これらの化合物は有機錫化合物と併用する助触媒として使用されているのが実情である。 In addition to organic tin compounds, organic acid and amine compounds are also known as modified silicone resin curing catalysts that do not contain heavy metals. However, even if these are used, a high curing rate cannot be obtained. For this reason, these compounds are actually used as cocatalysts in combination with organotin compounds.
また、塩化アルミニウム等の金属ハロゲン化物、あるいは、三塩化ホウ素等のハロゲン化ホウ素化合物などのルイス酸化合物は、加熱硬化性のエポキシ樹脂の硬化触媒として著名であるが（例えば特許文献４及び５など）、これを変成シリコーンあるいはシリル化ウレタン樹脂等の分子内に加水分解性シリル基を有する硬化性樹脂の硬化触媒として使用した例は未だ報告されていなかった。 Further, Lewis acid compounds such as metal halides such as aluminum chloride or boron halide compounds such as boron trichloride are well-known as curing catalysts for heat-curable epoxy resins (for example, Patent Documents 4 and 5). No example has been reported yet in which this is used as a curing catalyst for a curable resin having a hydrolyzable silyl group in the molecule, such as a modified silicone or silylated urethane resin.
そこで、本発明者らが鋭意研究した結果、ルイス酸及び／又はその誘導体が、分子内に加水分解性シリル基等を有する硬化性樹脂に対する極めて有用な硬化触媒として働くことを見出し、速硬化かつ貯蔵安定性に優れる硬化性樹脂組成物を発明するに至った（特許文献６）。しかしながら、該発明においては、硬化性樹脂の分子内に特定の結合あるいは特定の加水分解性シリル基が含有されている場合にしか速硬化性が付与されず、その効果は十分ではなかった。すなわち、現在最も広範的に使用されている分子内にメチルジメトキシシリル基を有する変成シリコーン樹脂にルイス酸及び／又はその誘導体を使用しても、速硬化性が付与できないのみならず、実用的な硬化速度すらも得られなかった（特許文献６−比較例１）。
本発明者らは、上記課題を解決するべくさらに研究を続け、変成シリコーン樹脂においても、ルイス酸及び／又はその誘導体を使用して、実用的な硬化速度のみならず、速硬化性をも付与することができることを見出し、本発明に至ったものである。さらには、本発明により、変成シリコーン樹脂からなる硬化性樹脂組成物において、重金属化合物を含まない触媒を用い、なおかつ、硬化速度が極めて速い硬化性樹脂組成物を提供することが可能となる。 The present inventors have continued research to solve the above problems, and in the modified silicone resin, not only a practical curing rate but also a fast curing property is imparted using a Lewis acid and / or a derivative thereof. The present inventors have found that it is possible to achieve this, and have reached the present invention. Furthermore, according to the present invention, it is possible to provide a curable resin composition that uses a catalyst that does not contain a heavy metal compound in a curable resin composition made of a modified silicone resin and that has an extremely high curing rate.
上記の目的を達成するために、本発明は次の第１〜６の発明から構成される。 In order to achieve the above object, the present invention comprises the following first to sixth inventions.
すなわち、第１の発明は、分子内に下記一般式（１）で表される加水分解性シリル基を有する常温で液状の硬化性樹脂（Ａ）、ルイス酸及びその誘導体から選ばれる一種以上の化合物（Ｂ）を含有してなる硬化性樹脂組成物である。なお、以下、「ルイス酸及びその誘導体から選ばれる一種以上の化合物（Ｂ）」を単に「ルイス酸系化合物（Ｂ）」と記載することがある。
但し、Ｘはメトキシ基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは１を、それぞれ示す。X represents a methoxy group, R 1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 1.
第２の発明は、ルイス酸系化合物（Ｂ）が、ハロゲン化ホウ素及びその誘導体から選ばれる一種以上の化合物（Ｂ１）である発明１の硬化性樹脂組成物である。なお、以下、「ハロゲン化ホウ素及びその誘導体から選ばれる一種以上の化合物（Ｂ１）」を単に「ハロゲン化ホウ素系化合物（Ｂ１）」と記載することがある。 The second invention is the curable resin composition of Invention 1, wherein the Lewis acid compound (B) is one or more compounds (B1) selected from boron halides and derivatives thereof. Hereinafter, “one or more compounds selected from boron halides and derivatives thereof (B1)” may be simply referred to as “boron halide compounds (B1)”.
第３の発明は、ルイス酸系化合物（Ｂ）が、三フッ化ホウ素及びその誘導体から選ばれる一種以上の化合物（Ｂ２）である発明１の硬化性樹脂組成物である。なお、以下、「三フッ化ホウ素及びその誘導体から選ばれる一種以上の化合物（Ｂ２）」を単に「三フッ化ホウ素系化合物（Ｂ２）」と記載することがある。 3rd invention is a curable resin composition of invention 1 whose Lewis' acid type compound (B) is 1 or more types of compounds (B2) chosen from boron trifluoride and its derivative (s). Hereinafter, “one or more compounds selected from boron trifluoride and derivatives thereof (B2)” may be simply referred to as “boron trifluoride compound (B2)”.
第４の発明は、硬化性樹脂（Ａ）と、ルイス酸系化合物（Ｂ）との混合時及び／又は混合後において、４０℃以上の加熱工程を設けることを特徴とする硬化性樹脂組成物の製造方法である。 4th invention provides the heating process of 40 degreeC or more at the time of mixing and / or after mixing with curable resin (A) and a Lewis' acid type compound (B), The curable resin composition characterized by the above-mentioned. It is a manufacturing method.
第５の発明は、ルイス酸系化合物（Ｂ）が、ハロゲン化ホウ素系化合物（Ｂ１）である発明４の硬化性樹脂組成物の製造方法である。 5th invention is a manufacturing method of curable resin composition of invention 4 whose Lewis' acid type compound (B) is a boron halide type compound (B1).
第６の発明は、ルイス酸系化合物（Ｂ）が、三フッ化ホウ素系化合物（Ｂ２）である発明４の硬化性樹脂組成物の製造方法である。 6th invention is a manufacturing method of curable resin composition of invention 4 whose Lewis' acid type compound (B) is a boron trifluoride type compound (B2).
第１の発明に係る硬化性樹脂組成物は、硬化性樹脂（Ａ）及びルイス酸系化合物（Ｂ）を含有する。ルイス酸系化合物（Ｂ）は、触媒中に重金属を含まないため、環境問題を生じる可能性が少ない。 The curable resin composition according to the first invention contains a curable resin (A) and a Lewis acid compound (B). Since the Lewis acid compound (B) does not contain a heavy metal in the catalyst, it is less likely to cause environmental problems.
第４の発明に係る硬化性樹脂組成物の製造方法は、硬化性樹脂（Ａ）とルイス酸系化合物（Ｂ）との混合時及び／又は混合後において、４０℃以上の加熱工程を設けることによって、さらに硬化速度を極めて速くすることができる。硬化速度が極めて速くなる理由としては、ルイス酸系化合物（Ｂ）が、硬化性樹脂（Ａ）とともに４０℃以上の環境にさらされることによって、硬化性樹脂（Ａ）中の加水分解性シリル基との相互作用がより強化されて、加水分解性メトキシ基の脱離能が高まり、その結果として、シリル基同士のカップリング反応が促進されるということが推察される。 In the method for producing a curable resin composition according to the fourth invention, a heating step of 40 ° C. or higher is provided during and / or after mixing of the curable resin (A) and the Lewis acid compound (B). Can further increase the curing rate. The reason why the curing speed is extremely high is that the Lewis acid compound (B) is exposed to an environment of 40 ° C. or more together with the curable resin (A), so that the hydrolyzable silyl group in the curable resin (A). It is inferred that the interaction with the silyl group is further strengthened and the ability to remove the hydrolyzable methoxy group is enhanced, and as a result, the coupling reaction between silyl groups is promoted.
一般的に、加水分解性シリル基のアルコキシ基としては、炭素数１〜６のアルコキシ基が用いられるが、本発明における方法で製造した場合、それらの全てにおいて相対的に硬化を速めることができる。これらの中では、炭素数１のメトキシ基の反応性が高く、本発明における製造方法の効果が最も顕著である。 Generally, as the alkoxy group of the hydrolyzable silyl group, an alkoxy group having 1 to 6 carbon atoms is used, but when produced by the method of the present invention, curing can be relatively accelerated in all of them. . Among these, the reactivity of the methoxy group having 1 carbon atom is high, and the effect of the production method in the present invention is most remarkable.
第２、第５の発明に係る硬化性樹脂組成物及びその製造方法は、ルイス酸系化合物（Ｂ）が、ハロゲン化ホウ素及びその誘導体から選ばれる一種以上の化合物（Ｂ１）であることを特徴とする。ハロゲン化ホウ素系化合物（Ｂ１）は、ルイス酸系化合物（Ｂ）のなかでも硬化速度が極めて速い。 In the curable resin composition and the method for producing the same according to the second and fifth inventions, the Lewis acid compound (B) is one or more compounds (B1) selected from boron halides and derivatives thereof. And The boron halide compound (B1) has a very fast curing rate among the Lewis acid compounds (B).
第３、第６の発明に係る硬化性樹脂及びその製造方法は、ルイス酸系化合物（Ｂ）が、三フッ化ホウ素及びその誘導体から選ばれる一種以上の化合物（Ｂ２）であることを特徴とする。三フッ化ホウ素系化合物（Ｂ２）は、ハロゲン化ホウ素系化合物（Ｂ１）のなかでも特に入手しやすく、その触媒能も優れている。 The curable resin and the production method thereof according to the third and sixth inventions are characterized in that the Lewis acid compound (B) is one or more compounds (B2) selected from boron trifluoride and derivatives thereof. To do. The boron trifluoride compound (B2) is particularly easily available among the boron halide compounds (B1), and its catalytic ability is also excellent.
１．硬化性樹脂（Ａ）について
本発明に好適に用いられる硬化性樹脂（Ａ）は、分子内に下記一般式（１）で表される加水分解性シリル基を含む硬化性樹脂である。
上記一般式（１）において、Ｘはメトキシ基を、Ｒ１は炭素数１〜２０個のアルキル基を、ｎは１を、それぞれ示す。In the general formula (1), X represents a methoxy group, R 1 represents an alkyl group having 1 to 20 carbon atoms, and n represents 1.
本発明に好適に用いられる硬化性樹脂（Ａ）としては、特公昭４５−３６３１９号、同４６−１２１５４号、同４９−３２６７３号、特開昭５０−１５６５９９号、同５１−７３５６１号、同５４−６０９６号、同５５−８２１２３号、同５５−１２３６２０号、同５５−１２５１２１号、同５５−１３１０２２号、同５５−１３５１３５号、同５５−１３７１２９号の各公報等に提案されている一般に変成シリコーン樹脂と呼ばれる硬化性樹脂が含まれるが、特に限定されるものではなく、従来公知のポリマーが使用できる。 Examples of the curable resin (A) preferably used in the present invention include Japanese Patent Publication Nos. 45-36319, 46-12154, 49-32673, JP-A-50-156599, 51-73561, 54-6096, 55-82123, 55-123620, 55-125121, 55-133102, 55-135135, 55-137129, etc. A curable resin called a modified silicone resin is included, but is not particularly limited, and a conventionally known polymer can be used.
また、硬化性樹脂（Ａ）の主鎖骨格は特に限定されず、要求される性能・用途等に応じて適宜選択し得る。主鎖骨格について、一例を挙げれば、ポリオキシアルキレン、飽和炭化水素系重合体、ビニル重合体（例えば、（メタ）アクリル酸エステルモノマー共重合体）、ポリチオール、ポリエステル、オルガノポリシロキサン及びポリカーボネート等がある。これらのうち、好ましくは、ポリオキシアルキレン、飽和炭化水素系重合体及びビニル重合体であり、さらに好ましくは、ポリオキシアルキレン及びビニル重合体である。 Further, the main chain skeleton of the curable resin (A) is not particularly limited, and can be appropriately selected according to required performance and use. Examples of the main chain skeleton include polyoxyalkylene, saturated hydrocarbon polymer, vinyl polymer (for example, (meth) acrylic acid ester monomer copolymer), polythiol, polyester, organopolysiloxane, and polycarbonate. is there. Of these, polyoxyalkylene, saturated hydrocarbon polymer and vinyl polymer are preferable, and polyoxyalkylene and vinyl polymer are more preferable.
また、これら主鎖骨格への加水分解性シリル基の導入方法としては、ヒドロシラン化合物を用いたヒドロシリル化反応や、メルカプトシラン化合物を用いたラジカル付加反応によるものが知られている。さらに、これら硬化性樹脂（Ａ）及び／又は他の硬化性化合物の存在下で、（メタ）アクリル酸モノマー、（メタ）アクリル酸エステルモノマー等を共重合せしめてもよい。 As a method for introducing a hydrolyzable silyl group into these main chain skeletons, a hydrosilylation reaction using a hydrosilane compound or a radical addition reaction using a mercaptosilane compound is known. Furthermore, in the presence of these curable resins (A) and / or other curable compounds, a (meth) acrylic acid monomer, a (meth) acrylic acid ester monomer, or the like may be copolymerized.
硬化性樹脂（Ａ）の分子量は特に限定されないが、数平均分子量が５００〜５００，０００が好ましく、１，０００〜１００，０００がより好ましく、２，０００〜２０，０００が特に好ましい。 The molecular weight of the curable resin (A) is not particularly limited, but the number average molecular weight is preferably 500 to 500,000, more preferably 1,000 to 100,000, and particularly preferably 2,000 to 20,000.
硬化性樹脂（Ａ）は市販されており、本発明ではそれらを用いることができる。市販品としては例えば、カネカ社製商品名；Ｓ２０３、Ｓ３０３、ＳＡＴ２００、ＳＡＴ０７０、ＭＡ４４０、ＭＡ４４７、エピオンシリーズ、ＳＡシリーズ，ＯＲシリーズ等、旭硝子社製商品名；ＥＳ−Ｓ２４１０、ＥＳ−Ｓ２４２０、ＥＳ−Ｓ３４３０、ＥＳ−Ｓ３４６０等が挙げられる。 The curable resin (A) is commercially available and can be used in the present invention. Commercially available products include, for example, trade names manufactured by Kaneka Corporation; S203, S303, SAT200, SAT070, MA440, MA447, Epion series, SA series, OR series, etc., trade names manufactured by Asahi Glass Co., Ltd .; S3430, ES-S3460, etc. are mentioned.
２．ルイス酸及びその誘導体から選ばれる一種以上の化合物（Ｂ）について
本発明の組成物の一成分であるルイス酸及びその誘導体から選ばれる一種以上の化合物（Ｂ）は、硬化性樹脂（Ａ）の硬化触媒として有用であり、極めて短時間裡に硬化性樹脂（Ａ）を硬化させる。 2. One or more compounds (B) selected from Lewis acids and derivatives thereof One or more compounds (B) selected from Lewis acids and derivatives thereof, which are one component of the composition of the present invention, are curable resins (A). It is useful as a curing catalyst and cures the curable resin (A) in a very short time.
ルイス酸及びその誘導体から選ばれる一種以上の化合物（Ｂ）のうち、ルイス酸としては、塩化チタン、塩化すず、塩化ジルコニウム、塩化アルミニウム、塩化鉄、塩化亜鉛、臭化亜鉛、塩化銅、塩化アンチモン等の金属ハロゲン化物、及び、三フッ化ホウ素、三塩化ホウ素、三臭化ホウ素等のハロゲン化ホウ素化合物、トリフルオロメタンスルホン酸トリメチルシリル、スカンジウムトリフラート、イットリウムトリフラート、ジンクトリフラート等の金属トリフラート化合物等が挙げられる。上記硬化性樹脂（Ａ）に及ぼす効果は、上記ルイス酸の酸性の強さによって影響されるものと考えられる。 Among one or more compounds (B) selected from Lewis acids and derivatives thereof, Lewis acids include titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, zinc chloride, zinc bromide, copper chloride, and antimony chloride. And metal halides such as boron trifluoride, boron trichloride, boron tribromide, metal triflate compounds such as trimethylsilyl trifluoromethanesulfonate, scandium triflate, yttrium triflate, zinc triflate, etc. It is done. The effect on the curable resin (A) is considered to be influenced by the acid strength of the Lewis acid.
ルイス酸の誘導体としては、上記ルイス酸とルイス塩基との錯体、例えば、上記ルイス酸のアミン錯体、アルコール錯体、エーテル錯体等、チオール錯体、スルフィド錯体、カルボン酸錯体、水錯体等が例示される。 Examples of Lewis acid derivatives include complexes of the above Lewis acids and Lewis bases, such as amine complexes, alcohol complexes, ether complexes of the above Lewis acids, thiol complexes, sulfide complexes, carboxylic acid complexes, water complexes, and the like. .
アミン錯体に用いるアミン化合物としては、アンモニア、モノエチルアミン、トリエチルアミン、ピペリジン、アニリン、モルホリン、シクロヘキシルアミン、ｎ−ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、グアニジン、２，２，６，６−テトラメチルピペリジン、１，２，２，６，６−ペンタメチルピペリジン、Ｎ−メチル−３，３′−イミノビス（プロピルアミン）、エチレンジアミン、ジエチレントリアミン、トリエチレンジアミン、ペンタエチレンジアミン、１，２−ジアミノプロパン、１，３−ジアミノプロパン、１，２−ジアミノブタン、１，４−ジアミノブタン、１，９−ジアミノノナン、ＡＴＵ（３，９−ビス（３−アミノプロピル）−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカン）、ＣＴＵグアナミン、ドデカン酸ジヒドラジド、ヘキサメチレンジアミン、ｍ−キシリレンジアミン、ジアニシジン、４，４′−ジアミノ−３，３′−ジエチルジフェニルメタン、ジアミノジフェニルエーテル、３，３′−ジメチル−４，４′−ジアミノジフェニルメタン、トリジンベース、ｍ−トルイレンジアミン、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、メラミン、１，３−ジフェニルグアニジン、ジ−ｏ−トリルグアニジン、１，１，３，３−テトラメチルグアニジン、ビス（アミノプロピル）ピペラジン、Ｎ−（３−アミノプロピル）−１，３−プロパンジアミン、ビス（３−アミノプロピル）エーテル、サンテクノケミカル社製ジェファーミン等の複数の第一級アミノ基を有する化合物、ピペラジン、シス−２，６−ジメチルピペラジン、シス−２，５−ジメチルピペラジン、２−メチルピペラジン、Ｎ，Ｎ′−ジ−ｔ−ブチルエチレンジアミン、２−アミノメチルピペリジン、４−アミノメチルピペリジン、１，３−ジ−（４−ピペリジル）−プロパン、４−アミノプロピルアニリン、ホモピペラジン、Ｎ，Ｎ′−ジフェニルチオ尿素、Ｎ，Ｎ′−ジエチルチオ尿素、Ｎ−メチル−１，３−プロパンジアミン等の複数の第二級アミノ基を有する化合物、更に、メチルアミノプロピルアミン、エチルアミノプロピルアミン、エチルアミノエチルアミン、ラウリルアミノプロピルアミン、２−ヒドロキシエチルアミノプロピルアミン、１−（２−アミノエチル）ピペラジン、Ｎ−アミノプロピルピペラジン、３−アミノピロリジン、１−ｏ−トリルビグアニド、２−アミノメチルピペラジン、Ｎ−アミノプロピルアニリン、エチルアミンエチルアミン、２−ヒドロキシエチルアミノプロピルアミン、ラウリルアミノプロピルアミン、２−アミノメチルピペリジン、４−アミノメチルピペリジン、式 Ｈ２Ｎ（Ｃ２Ｈ４ＮＨ）ｎＨ（ｎ≒５）で表わされる化合物（商品名：ポリエイト、東ソー社製）、Ｎ−アルキルモルホリン、１，８−ジアザビシクロ［５．４．０］ウンデセン−７、６−ジブチルアミノ−１，８−ジアザビシクロ［５．４．０］ウンデセン−７、１，５−ジアザビシクロ［４．３．０］ノネン−５、１，４−ジアザビシクロ［２．２．２］オクタン、ピリジン、Ｎ−アルキルピペリジン、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン、７−メチル−１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン等の複環状第三級アミン化合物等の他、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジエトキシシラン、４−アミノ−３−ジメチルブチルトリエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルメチルジエトキシシラン、Ｎ−３−［アミノ（ジプロピレンオキシ）］アミノプロピルトリエトキシシラン、（アミノエチルアミノメチル）フェネチルトリエトキシシラン、Ｎ−（６−アミノヘキシル）アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）−１１−アミノウンデシルトリエトキシシラン等のアミノシラン化合物が挙げられる。Amine compounds used for the amine complex include ammonia, monoethylamine, triethylamine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, guanidine, 2,2,6,6-tetra Methylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N-methyl-3,3'-iminobis (propylamine), ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1,2-diaminopropane, 1 , 3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, 1,9-diaminononane, ATU (3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxa Spyro[ .5] undecane), CTU guanamine, dodecanoic acid dihydrazide, hexamethylenediamine, m-xylylenediamine, dianisidine, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenyl ether, 3,3'-dimethyl- 4,4'-diaminodiphenylmethane, tolidine base, m-toluylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, melamine, 1,3-diphenylguanidine, di-o-tolylguanidine, 1, 1,3,3-tetramethylguanidine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether, Jeffamine manufactured by Sun Techno Chemical Co., Ltd. Multiple primary amino A compound having: piperazine, cis-2,6-dimethylpiperazine, cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N'-di-t-butylethylenediamine, 2-aminomethylpiperidine, 4-amino Methylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-aminopropylaniline, homopiperazine, N, N'-diphenylthiourea, N, N'-diethylthiourea, N-methyl-1,3 A compound having a plurality of secondary amino groups such as propanediamine, methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxyethylaminopropylamine, 1- (2- Aminoethyl) piperazine, N-aminopropylpiperazine, 3- Aminopyrrolidine, 1-o-tolylbiguanide, 2-aminomethylpiperazine, N-aminopropylaniline, ethylamineethylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, compounds of the formula H 2 n (C 2 H 4 NH) n H (n ≒ 5) ( trade name: Porieito, manufactured by Tosoh Corporation), N- alkyl morpholine, 1,8-diazabicyclo [5.4.0] Undecene-7,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5, 1,4-diazabicyclo [2.2 .2] Octane, pyridine, N-alkylpiperidine, 1,5,7-triazabicyclo [4.4. In addition to bicyclic tertiary amine compounds such as deca-5-ene and 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, γ-aminopropyltri Ethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ- Aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, N- (6-aminohexyl) aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -11-aminoundec Examples thereof include aminosilane compounds such as rutriethoxysilane.
アルコール錯体に用いるアルコール類としては、メタノール、エタノール、ｎ−プロパノール、ｎ−ブタノール等の一級アルコール、イソプロパノール、２−ブタノール等のニ級アルコール等が例示される。エーテル錯体に用いるエーテル類としては、ジメチルエーテル、ジエチルエーテル、ジｎ−ブチルエーテル等が例示される。 Examples of alcohols used in the alcohol complex include primary alcohols such as methanol, ethanol, n-propanol and n-butanol, and secondary alcohols such as isopropanol and 2-butanol. Examples of ethers used in the ether complex include dimethyl ether, diethyl ether, and di-n-butyl ether.
上記ルイス酸の中では、塩化チタン（ＩＶ）、塩化すず（ＩＶ）、塩化ジルコニウム（ＩＶ）、塩化アルミニウム（ＩＩＩ）、スカンジウムトリフラート、イットリウムトリフラート、トリフルオロメタンスルホン酸トリメチルシリル、三塩化ホウ素、三フッ化ホウ素が好ましい。これらのうちでも、塩化ジルコニウム（ＩＶ）、トリフルオロメタンスルホン酸トリメチルシリル、ハロゲン化ホウ素（Ｂ１）が好ましく、特にハロゲン化ホウ素のうちでも、触媒活性や入手のしやすさの点から三フッ化ホウ素（Ｂ２）が特に好ましい。また、上記ルイス酸の錯体としては、ハロゲン化ホウ素の錯体（Ｂ１）が好ましく、それらのなかでも特に三フッ化ホウ素の錯体（Ｂ２）が、取り扱いが容易であるなどの点で、好ましい。 Among the above Lewis acids, titanium chloride (IV), tin chloride (IV), zirconium chloride (IV), aluminum chloride (III), scandium triflate, yttrium triflate, trimethylsilyl trifluoromethanesulfonate, boron trichloride, trifluoride Boron is preferred. Among these, zirconium chloride (IV), trimethylsilyl trifluoromethanesulfonate, and boron halide (B1) are preferable, and boron trifluoride (B1) is particularly preferable from the viewpoint of catalytic activity and availability. B2) is particularly preferred. Further, as the Lewis acid complex, a boron halide complex (B1) is preferable, and among them, a boron trifluoride complex (B2) is particularly preferable in terms of easy handling.
また、三フッ化ホウ素の錯体の中でも、安定性と触媒活性を兼ね備えたアミン錯体が特に好ましい。ルイス酸やその誘導体は、上記の化合物を成分とする市販品を用いることができ、市販品としては、エアプロダクツ・ジャパン社製、商品名：アンカー１０４０，１１１５，１１７０，１２２２、ＢＡＫ１１７１等が挙げられる。 Among the boron trifluoride complexes, amine complexes having both stability and catalytic activity are particularly preferred. As the Lewis acid and derivatives thereof, commercially available products containing the above compounds as components can be used. Examples of commercially available products include Air Products Japan, trade names: Anchors 1040, 1115, 1170, 1222, BAK1171, and the like. It is done.
ルイス酸系化合物（Ｂ）は、単独で用いてもよいし、二種以上併用してもよい。また、ルイス酸系化合物（Ｂ）の配合割合は、好ましくは硬化性樹脂（Ａ）１００重量部あたり０．００１〜１０重量部であり、特に好ましくは０．０１〜５重量部である。 A Lewis acid type compound (B) may be used independently and may be used together 2 or more types. The blending ratio of the Lewis acid compound (B) is preferably 0.001 to 10 parts by weight, particularly preferably 0.01 to 5 parts by weight, per 100 parts by weight of the curable resin (A).
本発明に係る硬化性樹脂組成物の製造方法は、硬化性樹脂（Ａ）とルイス酸系化合物（Ｂ）と混合時及び／又は混合後において、４０℃以上の加熱工程を設けることが好ましい。４０℃以上の熱をかけることにより、本発明にかかる硬化性樹脂組成物の硬化速度がさらに向上する。 In the method for producing a curable resin composition according to the present invention, it is preferable to provide a heating step of 40 ° C. or higher during and / or after mixing the curable resin (A) and the Lewis acid compound (B). By applying heat of 40 ° C. or higher, the curing rate of the curable resin composition according to the present invention is further improved.
本発明の効果を得るために必要な加熱工程の温度と時間は、温度が低いと長時間の加熱時間が必要であるが、温度が高いと加熱時間は短くてよい。例えば、温度を８０℃に設定した場合、加熱時間は１時間〜数時間が必要であるが、温度を１００℃に設定した場合、加熱時間は３０分〜１時間程度で十分となる。逆に、温度を４０℃に設定した場合も硬化は速くなるが、１日〜数日の加熱時間が必要となる。さらに温度を下げて、３０℃に設定した場合も硬化は速くなるが、数日から数週間が必要となり、あまり現実的ではない。 The temperature and time of the heating step necessary for obtaining the effects of the present invention require a long heating time when the temperature is low, but the heating time may be short when the temperature is high. For example, when the temperature is set to 80 ° C., the heating time is 1 hour to several hours, but when the temperature is set to 100 ° C., the heating time is approximately 30 minutes to 1 hour. On the contrary, when the temperature is set to 40 ° C., the curing speeds up, but a heating time of one day to several days is required. When the temperature is further lowered and the temperature is set to 30 ° C., the curing becomes faster, but it takes several days to several weeks and is not very realistic.
本発明の硬化性樹脂組成物は、硬化性樹脂（Ａ）及びルイス酸系化合物（Ｂ）を必須成分として含有するものであるが、それらの成分以外に、さらに、他の硬化触媒、シランカップリング剤、充填材、各種添加剤などを要求される性能に応じて配合することができる。 The curable resin composition of the present invention contains the curable resin (A) and the Lewis acid compound (B) as essential components. In addition to these components, the curable resin composition further includes other curing catalysts, silane cups. A ring agent, a filler, various additives, etc. can be mix | blended according to the performance requested | required.
本発明に係る硬化性樹脂組成物に配合できる上記硬化触媒としては、公知の触媒化合物を、本発明の効果を損なわない範囲内で使用できる。具体例としては、有機錫化合物、有機ビスマス化合物、有機チタン化合物等の有機金属化合物、アミン化合物等の塩基性化合物、リン酸系化合物等の酸性化合物等が挙げられる。 As the curing catalyst that can be blended in the curable resin composition according to the present invention, a known catalyst compound can be used within a range that does not impair the effects of the present invention. Specific examples include organic tin compounds, organic bismuth compounds, organic metal compounds such as organic titanium compounds, basic compounds such as amine compounds, and acidic compounds such as phosphoric acid compounds.
本発明に係る硬化性樹脂組成物に配合できる上記シランカップリング剤としては、公知のシランカップリング剤が使用できる。具体的には、アミノシラン化合物、エポキシシラン化合物、メルカプトシラン化合物、（メタ）アクリルシラン化合物、イソシアネートシラン化合物、ビニルシラン化合物等が挙げられる。 A known silane coupling agent can be used as the silane coupling agent that can be blended in the curable resin composition according to the present invention. Specific examples include aminosilane compounds, epoxysilane compounds, mercaptosilane compounds, (meth) acrylsilane compounds, isocyanate silane compounds, and vinylsilane compounds.
上記シランカップリング剤は、単独で用いてもよいし、二種以上併用してもよいが、少なくともアミノシラン化合物を用いることが好ましい。上記シランカップリング剤の配合割合は、好ましくは硬化性樹脂（Ａ）１００重量部あたり０．１〜２０重量部であり、特に好ましくは１〜１０重量部である。 Although the said silane coupling agent may be used independently and may be used together 2 or more types, it is preferable to use an aminosilane compound at least. The blending ratio of the silane coupling agent is preferably 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight per 100 parts by weight of the curable resin (A).
本発明に係る硬化性樹脂組成物に配合できる上記充填剤としては、公知の充填材が使用できる。具体的には、炭酸カルシウム系充填剤、各種処理炭酸カルシウム系充填剤、炭酸マグネシウム系充填剤、有機高分子系充填剤、クレー系充填剤、タルク系充填剤、シリカ系充填剤、フュームドシリカ系充填剤、ガラスバルーン、プラスチックバルーン等の各種バルーン系充填剤、水酸化アルミニウム、水酸化マグネシウム等の金属水酸化物系充填剤、フィブリル化繊維系充填剤等が挙げられる。 As the filler that can be blended in the curable resin composition according to the present invention, known fillers can be used. Specifically, calcium carbonate filler, various treated calcium carbonate filler, magnesium carbonate filler, organic polymer filler, clay filler, talc filler, silica filler, fumed silica Examples thereof include various balloon fillers such as glass balloons, glass balloons and plastic balloons, metal hydroxide fillers such as aluminum hydroxide and magnesium hydroxide, and fibrillated fiber fillers.
上記シリカ系充填材としては、親水性シリカ系粉体、疎水性シリカ系粉体、溶融石英ガラス系粉体等が挙げられるが、これらの中では、特に、疎水性シリカ系粉体が好ましい。上記充填材は、単独で用いてもよいし、二種以上併用してもよい。また、上記充填材は、粒径が１０ｎｍ〜５００μｍのものが好適であるが、好ましくは１００ｎｍ〜２００μｍ、特に好ましくは１．０〜１００μｍのものである。さらに、上記充填材の配合割合は、硬化性樹脂（Ａ）１００重量部あたり、１〜５００重量部を含有するのが好適であるが、好ましくは１〜３００重量部、特に好ましくは１〜２００重量部である。 Examples of the silica-based filler include hydrophilic silica-based powders, hydrophobic silica-based powders, and fused silica glass-based powders. Among these, hydrophobic silica-based powders are particularly preferable. The said filler may be used independently and may be used together 2 or more types. The filler preferably has a particle size of 10 nm to 500 μm, preferably 100 nm to 200 μm, particularly preferably 1.0 to 100 μm. Furthermore, the blending ratio of the filler is preferably 1 to 500 parts by weight per 100 parts by weight of the curable resin (A), preferably 1 to 300 parts by weight, particularly preferably 1 to 200 parts by weight. Parts by weight.
本発明に係る硬化性樹脂組成物に配合できる上記各種添加剤としては、本発明の効果を損なわない範囲内で、粘着性付与剤（タッキファイアー）、揺変剤、脱水剤、希釈剤、可塑剤、難燃剤、オリゴマー、老化防止剤、紫外線吸収剤、顔料、チタネートカップリング剤、アルミニウムカップリング剤、桐油等の乾性油等の公知の原料が挙げられるが、これらに限定されるものではない。 The various additives that can be blended in the curable resin composition according to the present invention include a tackifier, a thixotropic agent, a dehydrating agent, a diluent, a plasticizer within a range not impairing the effects of the present invention. Well-known raw materials such as agents, flame retardants, oligomers, anti-aging agents, ultraviolet absorbers, pigments, titanate coupling agents, aluminum coupling agents, and tung oil, but are not limited thereto. .
本発明の硬化性樹脂組成物は、例えば、電気電子用、建材用、家庭用、各種工事用等で用いられる接着剤、シーラント、塗料、コーティング剤、目止め剤（例えば、コンクリートのひび割れ補修において注入剤が漏れないようにひび割れを覆う目止め剤）、注型剤、被覆剤等に有効に用いることができる。 The curable resin composition of the present invention can be used, for example, in adhesives, sealants, paints, coating agents, sealants (for example, repairing cracks in concrete) used for electrical and electronic products, building materials, households, and various constructions. It can be effectively used as a sealing agent for covering cracks so as to prevent the injection agent from leaking, a casting agent, a coating agent, and the like.
実施例により本発明を更に詳細に説明する。本発明は下記の実施例に限定されるものではない。 The invention is explained in more detail by means of examples. The present invention is not limited to the following examples.
（実施例１）
Ｓ３０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ及び三フッ化ホウ素モノエチルアミン錯体を５ｇ反応容器に入れた後、反応容器内に窒素を充填した。その後、１００℃で３０分間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。Example 1
500 g of S303 (trade name manufactured by Kaneka Corporation; modified silicone resin) and 5 g of boron trifluoride monoethylamine complex were placed in a reaction vessel, and then the reaction vessel was filled with nitrogen. Then, the curable resin composition was obtained by knead | mixing for 30 minutes at 100 degreeC. The obtained curable resin composition was filled in an airtight container.
（実施例２）
Ｓ３０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ及び三フッ化ホウ素ピペリジン錯体を５ｇ反応容器に入れた後、反応容器内に窒素を充填した。その後、１００℃で３０分間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。(Example 2)
500 g of S303 (trade name manufactured by Kaneka Corporation; modified silicone resin) and 5 g of boron trifluoride piperidine complex were placed in a reaction vessel, and then the reaction vessel was filled with nitrogen. Then, the curable resin composition was obtained by knead | mixing for 30 minutes at 100 degreeC. The obtained curable resin composition was filled in an airtight container.
（実施例３）
Ｓ３０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ及び三フッ化ホウ素ピペリジン錯体を５ｇ反応容器に入れた後、真空ポンプで１００ｍｍＨｇ以下まで減圧しながら１００℃で３０分間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。(Example 3)
500 g of S303 (trade name manufactured by Kaneka Corporation; modified silicone resin) and 5 g of boron trifluoride piperidine complex were placed in a reaction vessel, and then kneaded at 100 ° C. for 30 minutes while reducing the pressure to 100 mmHg or less with a vacuum pump. A curable resin composition was obtained. The obtained curable resin composition was filled in an airtight container.
（参考例１）
Ｓ３０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ反応容器に入れた後、真空ポンプで減圧しながら１００℃で３０分間撹拌した。室温まで冷却した後、反応容器内に窒素を充填した。ここに、三フッ化ホウ素ピペリジン錯体を５ｇ添加し、さらに室温で３０分混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。(Reference Example 1)
500 g of S303 (trade name manufactured by Kaneka Corporation; modified silicone resin) was placed in a reaction vessel, and then stirred at 100 ° C. for 30 minutes while reducing the pressure with a vacuum pump. After cooling to room temperature, the reaction vessel was filled with nitrogen. Here, 5 g of boron trifluoride piperidine complex was added, and further kneaded at room temperature for 30 minutes to obtain a curable resin composition. The obtained curable resin composition was filled in an airtight container.
（皮張り時間の測定）
実施例１〜３及び参考例１で得られた硬化性樹脂組成物をそれぞれ２３℃で１日間静置した後、皮張り時間を測定した。それぞれの皮張り時間を表１に示した。皮張り時間は、硬化性樹脂組成物を、２３℃及び相対湿度５０％の雰囲気下に放置し、指触により表面に張った硬化皮膜が指に転着しなくなるまでの時間として求めた。(Measure skinning time)
The curable resin compositions obtained in Examples 1 to 3 and Reference Example 1 were each allowed to stand at 23 ° C. for 1 day, and then the skinning time was measured. The respective skinning times are shown in Table 1. The skinning time was determined as the time until the cured film stretched on the surface by finger touch was not transferred to the finger after leaving the curable resin composition in an atmosphere of 23 ° C. and 50% relative humidity.
表１の結果から、本発明に係る硬化性樹脂組成物は１００℃の加熱工程を設けることによって、硬化速度が促進されていることが分かる。 From the results of Table 1, it can be seen that the curing rate of the curable resin composition according to the present invention is accelerated by providing a heating step at 100 ° C.
（実施例４）
Ｓ２０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ及び三フッ化ホウ素モノエチルアミン錯体を５ｇ反応容器に入れた後、反応容器内に窒素を充填した。その後、８０℃で５時間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。Example 4
500 g of S203 (trade name manufactured by Kaneka Corporation; modified silicone resin) and 5 g of boron trifluoride monoethylamine complex were placed in a reaction vessel, and then the reaction vessel was filled with nitrogen. Then, the curable resin composition was obtained by knead | mixing for 5 hours at 80 degreeC. The obtained curable resin composition was filled in an airtight container.
（実施例５）
Ｓ２０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ及び三フッ化ホウ素モノエチルアミン錯体を５ｇ反応容器に入れた後、真空ポンプで１００ｍｍＨｇ以下まで減圧しながら８０℃で１０分間混練りした。真空ポンプからの弁を閉じ、１００ｍｍＨｇ以下に保ったまま８０℃で５時間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。(Example 5)
500 g of S203 (trade name manufactured by Kaneka Corporation; modified silicone resin) and 5 g of boron trifluoride monoethylamine complex were placed in a reaction vessel, and then kneaded at 80 ° C. for 10 minutes while reducing the pressure to 100 mmHg or less with a vacuum pump. The valve from the vacuum pump was closed and kneaded at 80 ° C. for 5 hours while being kept at 100 mmHg or less to obtain a curable resin composition. The obtained curable resin composition was filled in an airtight container.
（参考例２）
Ｓ２０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ及び三フッ化ホウ素モノエチルアミン錯体を５ｇ反応容器に入れた後、反応容器内に窒素を充填した。その後、室温で５時間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。(Reference Example 2)
500 g of S203 (trade name manufactured by Kaneka Corporation; modified silicone resin) and 5 g of boron trifluoride monoethylamine complex were placed in a reaction vessel, and then the reaction vessel was filled with nitrogen. Then, the curable resin composition was obtained by kneading for 5 hours at room temperature. The obtained curable resin composition was filled in an airtight container.
（皮張り時間の測定）
実施例４、５及び参考例２で得られた硬化性樹脂組成物をそれぞれ２３℃で１日間静置した後、実施例１と同様の方法で皮張り時間を測定した。それぞれの皮張り時間を表２に示した。(Measure skinning time)
The curable resin compositions obtained in Examples 4 and 5 and Reference Example 2 were each allowed to stand at 23 ° C. for 1 day, and then the skinning time was measured in the same manner as in Example 1. Each skinning time is shown in Table 2.
表２の結果から、本発明に係る硬化性樹脂組成物は８０℃の加熱工程を設けることによって、硬化速度が促進されていることが分かる。 From the results of Table 2, it can be seen that the curing rate of the curable resin composition according to the present invention is accelerated by providing a heating step at 80 ° C.
（実施例６）
Ｓ３０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ、三フッ化ホウ素ピペリジン錯体を５ｇ及びトルエンを２５ｇ反応容器に入れた後、反応容器内に窒素を充填した。その後、室温で３０分間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。(Example 6)
500 g of S303 (trade name manufactured by Kaneka Corporation; modified silicone resin), 5 g of boron trifluoride piperidine complex, and 25 g of toluene were placed in a reaction vessel, and then the reaction vessel was filled with nitrogen. Then, the curable resin composition was obtained by kneading for 30 minutes at room temperature. The obtained curable resin composition was filled in an airtight container.
（実施例７）
Ｓ３０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ、三フッ化ホウ素ピペリジン錯体を５ｇ及びトルエンを２５ｇ反応容器に入れた後、真空ポンプで１００ｍｍＨｇ以下まで減圧しながら室温で１０分間混練りした。真空ポンプからの弁を閉じ、１００ｍｍＨｇ以下に保ったまま室温で３０分間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。(Example 7)
500 g of S303 (trade name manufactured by Kaneka Corporation; modified silicone resin), 5 g of boron trifluoride piperidine complex, and 25 g of toluene were placed in a reaction vessel, and then kneaded at room temperature for 10 minutes while reducing the pressure to 100 mmHg or less with a vacuum pump. . The valve | bulb from a vacuum pump was closed and the curable resin composition was obtained by kneading for 30 minutes at room temperature, keeping at 100 mmHg or less. The obtained curable resin composition was filled in an airtight container.
（参考例３）
Ｓ３０３（カネカ社製商品名；変成シリコーン樹脂）を５００ｇ反応容器に入れた後、反応容器内に窒素を充填した。ここに、三フッ化ホウ素ピペリジン錯体を５ｇ及びトルエンを２５ｇ混合した触媒溶液を添加し、さらに室温で３０分間混練りすることで、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を密閉容器に充填した。(Reference Example 3)
500 g of S303 (trade name manufactured by Kaneka Corporation; modified silicone resin) was placed in a reaction vessel, and then the reaction vessel was filled with nitrogen. A curable resin composition was obtained by adding a catalyst solution in which 5 g of boron trifluoride piperidine complex and 25 g of toluene were mixed, and kneading for 30 minutes at room temperature. The obtained curable resin composition was filled in an airtight container.
（皮張り時間の測定）
実施例６、７で得られた硬化性樹脂組成物をそれぞれ５０℃で３日間静置した後、実施例１と同様の方法で皮張り時間を測定した。また、参考例３で得られた硬化性樹脂組成物の皮張り時間を実施例１と同様の方法で測定した。それぞれの皮張り時間を表３に示した。(Measure skinning time)
The curable resin compositions obtained in Examples 6 and 7 were each allowed to stand at 50 ° C. for 3 days, and then the skinning time was measured in the same manner as in Example 1. Further, the skinning time of the curable resin composition obtained in Reference Example 3 was measured by the same method as in Example 1. Each skinning time is shown in Table 3.
表３の結果から、本発明に係る硬化性樹脂組成物は５０℃の加熱工程を設けることによって、硬化速度が促進されていることが分かる。 From the results in Table 3, it can be seen that the curing rate of the curable resin composition according to the present invention is accelerated by providing a heating step at 50 ° C.
本発明に係る硬化性樹脂組成物は、例えば、接着剤、シーラント、塗料、コーティング剤、目止め剤、注型材、被覆材などの用途に好適に利用でき、さらには硬化触媒として重金属を含まないことから、産業上非常に有用である。 The curable resin composition according to the present invention can be suitably used for applications such as adhesives, sealants, paints, coating agents, sealants, casting materials, coating materials, and further does not contain heavy metals as a curing catalyst. Therefore, it is very useful industrially.
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| JP2005054174A (en) * | 2003-07-18 | 2005-03-03 | Konishi Co Ltd | Curable resin composition and moisture-curing adhesive composition |
| JP2006052296A (en) * | 2004-08-11 | 2006-02-23 | Konishi Co Ltd | Curable resin composition and moisture-curable type adhesive composition |
| JP2006199721A (en) * | 2005-01-18 | 2006-08-03 | Konishi Co Ltd | Curing catalyst for curable silicone-based resin and curable silicone-based resin composition |
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| JP2006199730A (en) * | 2005-01-18 | 2006-08-03 | Konishi Co Ltd | Curable resin composition and moisture-curable adhesive |
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| JP2006199730A (en) * | 2005-01-18 | 2006-08-03 | Konishi Co Ltd | Curable resin composition and moisture-curable adhesive |
| JP2006199905A (en) * | 2005-01-18 | 2006-08-03 | Konishi Co Ltd | Curable resin composition |
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| US8962716B2 (en) | 2007-02-13 | 2015-02-24 | Kaneka Corporation | Curable composition |
| JP2008260932A (en) * | 2007-03-20 | 2008-10-30 | Konishi Co Ltd | Curable resin composition |
| JP2011506740A (en) * | 2007-12-20 | 2011-03-03 | ブルースター・シリコーン・フランス・エスアエス | Organopolysiloxane compositions that can be vulcanized to elastomers at room temperature and novel organopolysiloxane polycondensation catalysts |
| JP2010077226A (en) * | 2008-09-24 | 2010-04-08 | Konishi Co Ltd | Curable resin composition |
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