JPH03106936A - Polysiloxane oligomer, polysiloxane resin composition, and curable resin composition - Google Patents
Polysiloxane oligomer, polysiloxane resin composition, and curable resin compositionInfo
- Publication number
- JPH03106936A JPH03106936A JP24479389A JP24479389A JPH03106936A JP H03106936 A JPH03106936 A JP H03106936A JP 24479389 A JP24479389 A JP 24479389A JP 24479389 A JP24479389 A JP 24479389A JP H03106936 A JPH03106936 A JP H03106936A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polysiloxane
- groups
- resin
- oligomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Polysiloxane Polymers 0.000 title claims abstract description 77
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 44
- 239000011342 resin composition Substances 0.000 title claims description 13
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 67
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 42
- 229910000077 silane Inorganic materials 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 6
- 150000001875 compounds Chemical group 0.000 claims description 44
- 125000003700 epoxy group Chemical group 0.000 claims description 28
- 125000000524 functional group Chemical group 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 42
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000009833 condensation Methods 0.000 abstract description 12
- 230000005494 condensation Effects 0.000 abstract description 12
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- 230000001476 alcoholic effect Effects 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- 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 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- DASQIKOOFDJYKA-UHFFFAOYSA-N CCIF Chemical compound CCIF DASQIKOOFDJYKA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229940090012 bentyl Drugs 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 101150065749 Churc1 gene Proteins 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 102100038239 Protein Churchill Human genes 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 2
- VLFKGWCMFMCFRM-UHFFFAOYSA-N [diacetyloxy(phenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 VLFKGWCMFMCFRM-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- SXWUUUJQQVXKKY-UHFFFAOYSA-N disilanyl-hydroxy-phenylsilane Chemical compound [SiH3][SiH2][SiH](O)C1=CC=CC=C1 SXWUUUJQQVXKKY-UHFFFAOYSA-N 0.000 description 2
- 238000009503 electrostatic coating Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- ZBZICERRZIMWGX-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZBZICERRZIMWGX-UHFFFAOYSA-N 0.000 description 1
- KUGVQHLGVGPAIZ-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KUGVQHLGVGPAIZ-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- XMJQCVMNFPEJLN-UHFFFAOYSA-N 1-ethenoxy-4-methylpentane Chemical compound CC(C)CCCOC=C XMJQCVMNFPEJLN-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OUELSYYMNDBLHV-UHFFFAOYSA-N 2-ethenoxyethylbenzene Chemical compound C=COCCC1=CC=CC=C1 OUELSYYMNDBLHV-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- QHQNYHZHLAAHRW-UHFFFAOYSA-N 2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN QHQNYHZHLAAHRW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VXASQTMYWZHWMX-UHFFFAOYSA-N 4-ethoxybutyl 2-methylprop-2-enoate Chemical compound CCOCCCCOC(=O)C(C)=C VXASQTMYWZHWMX-UHFFFAOYSA-N 0.000 description 1
- OYFJWLSZXKXLAT-UHFFFAOYSA-N 4-ethoxybutyl prop-2-enoate Chemical compound CCOCCCCOC(=O)C=C OYFJWLSZXKXLAT-UHFFFAOYSA-N 0.000 description 1
- DIVUSAVKQOLTNR-UHFFFAOYSA-N 4-methoxybutyl 2-methylprop-2-enoate Chemical compound COCCCCOC(=O)C(C)=C DIVUSAVKQOLTNR-UHFFFAOYSA-N 0.000 description 1
- GAKWESOCALHOKH-UHFFFAOYSA-N 4-methoxybutyl prop-2-enoate Chemical compound COCCCCOC(=O)C=C GAKWESOCALHOKH-UHFFFAOYSA-N 0.000 description 1
- SWDDLRSGGCWDPH-UHFFFAOYSA-N 4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN SWDDLRSGGCWDPH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 125000006538 C11 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VONSLYSEUXFYLE-UHFFFAOYSA-N Erychrosid Natural products C1C2(C)OC2(C)C(O)OC1C(C)C1C2(C)C(=O)CC3C4(C)C(=O)C=CCC4(O)C4OC4C3C2CC1 VONSLYSEUXFYLE-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910010342 TiF4 Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007938 ZrBr4 Inorganic materials 0.000 description 1
- 229910007998 ZrF4 Inorganic materials 0.000 description 1
- AFQFADKUEPBKOU-UHFFFAOYSA-N [1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,10,10,10-icosafluoro-9-(trifluoromethyl)decan-2-yl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C(F)(F)F AFQFADKUEPBKOU-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- IFXSTMWNLKCGIO-UHFFFAOYSA-N [diacetyloxy(2-hydroxyethyl)silyl] acetate Chemical compound OCC[Si](OC(C)=O)(OC(C)=O)OC(C)=O IFXSTMWNLKCGIO-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- BTHCBXJLLCHNMS-UHFFFAOYSA-N acetyloxysilicon Chemical compound CC(=O)O[Si] BTHCBXJLLCHNMS-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003609 aryl vinyl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 239000013522 chelant Substances 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
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- 239000004210 ether based solvent Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
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- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
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- 239000011976 maleic acid Substances 0.000 description 1
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- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
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- 229940065472 octyl acrylate Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
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- 230000002087 whitening effect Effects 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
産業上の利用分野
本発明は、新規なボリシロキサン系オリゴマー、ボリシ
ロキサン系樹脂組成物及び硬化性樹脂組成物に関する．
従来の技術
従来、すでに公知のボリシロキサンにおいて、アルコー
ル性水酸基と末端相当部分（ＳＬ）の水酸基又は加水分
解性基とをそれぞれ１個ずつ有する化合物では反応性が
低いため架橋構造を形成しにくいという欠点があり、両
末端相当部分に１個ずつの水酸基又は加水分解性基のみ
を有し、アルコール性水酸基を含まない化合物では縮合
のみで高分子化するために耐水性、耐薬品性、耐候性な
どが充分ではないという欠点があり、又両末端相当部分
に１個ずつのアルコール性水酸基を有する化合物では付
加中にゲル化しやすいので取扱いが困難で、グラフト体
を形成できないという欠点がある．
発明が解決しようとする課題
本発明は、従来公知のボリシロキサンにおける上記諸欠
点の解消を目的とする．
問題点を解決するための手段
本発明者は、特定の原料を用いて、ボリシロキサンに１
分子あたり平均１個の水酸基と、末端相当部分に少なく
とも２個以上の珪素原子に直接結合した水酸基及び／又
は加水分解性基とを有せしめることによって得られる新
規なポリシロキサン系才リゴマーにおいては、該オリゴ
マー成分を樹脂中に導入する際にゲル化することがなく
、縮合により架橋させることができ、上記目的を充分に
達成できることを見い出し，これに基づき本発明を完成
した．
即ち、本発明は、
■ 珪素原子に直接結合した水酸基及び／又は加水分解
性基（以下、「シラン基」と略すことがある．）を有す
るシラン化合物（Ａ）（以下、「シラン化合物（Ａ）」
という．）と下記一般式（１）
Ｒ８
／
ＨＯ−Ｒ’−Ｓｉ−Ｒ”
（ １ ）＼
Ｒ４
（式中、Ｒｌは炭素数ｌ〜６の２価の炭化水素基、Ｒ１
、Ｒｌ及びＲ，は水酸基、加水分解性基もしくは炭素数
１〜８の１価の炭化水素基を示す．但し、Ｒ３、Ｒ３及
びＲ４のすべてが炭素数１〜８の１価の炭化水素基であ
ることはない．）で示されるシランモノマ−（Ｂ）（以
下、「シランモノマ−（Ｂ）」という．）とを反応させ
てなり、且つ、その１分子当り平均ｌ個のＩＯ−Ｒ’一
基と、末端相当部分にシラン基を平均２個以上有するこ
とを特徴とするポリシロキサン系オリゴマー
■ 樹脂がシラン基とエボキシ基とを必須官能基成分と
して含有し、且つ、該シラン基が前記したボリシロキサ
ン系才リゴマーによって導入されていることを特徴とす
るボリシロキサン系樹脂組成物、
■ 前記したボリシロキサン系樹脂組成物に，有機金属
化合物、ルイス酸、プロトン酸及びアルミニウム化合物
から選ばれる１種以上の硬化反応触媒を含有することを
特徴とする硬化性樹脂組成物に関する．
本明細書において、珪素原子に直接結合した加水分解性
基は水又は湿気により加水分解してヒドロキシシラン基
を生成する基である．該基とじては、例えば下記一般式
で表わされるものを挙げることができる．
−Ｏ−Ｒ” （
２ ）〇
一
−ｏ−ｃ−８６（ ３ ）
Ｒ７
／
−ｏ−Ｎ＝ｃ （
４ ）＼
Ｒａ
Ｒ７
／
式中Ｒ６はＣ，〜４のアルキル基、Ｒ６〜Ｒ１は同一も
しくは異なってＣＩ−ｓのアルキル基、アリール基、ア
ラルキル基を示す．
一般式において、「Ｃ１１のアルキル基」としては、例
えばメチル、エチル、ｎ−プロビル、ｉｓｏブロビル、
ｎ−ブチル、ｉａｏブチル、ｓｅｃプチル、ｔｅｒｔブ
チル、ｎ−ベンチル、ｉｓｏベンチル、ｎ一才クチル、
ｉｓｏオクチル等を挙げることができる．「アリール
基」としては、例えばフェニル、トルイル、キシリル等
を挙げることができる．また「アラルキル基」としては
、例えばベンジル、フエネチル等を挙げることができる
．また、上記した珪素原子に結合した加水分解性基以外
にも加水分解性基として−＞Ｓｉ−Ｈ基゛を挙げること
ができる．
本発明において、貯蔵安定性、硬化性等の観点から上記
一般式（２）．（３）で表わされる基及びヒドロキシシ
ラン基が好適である．
本明細書において、末端相当部分とはボリシロキサン系
オリゴマーの末端に位置する１個または２個以上の珪素
を意味する．
本発明のポリシロキサン系オリゴマーは、主骨格がシロ
キサン結合で構成され、この主骨格の珪素原子に炭化水
素基、水酸基、加水分解性基などが直接に結合している
ものであって、上記シラン化合物（Ａ）とシランモノマ
ー（Ｂ）とを反応させることによって得られる．
該シラン化合物（Ａ）は１分子中に平均３個のシラン基
を有するものであって、好ましくは一般式（８）
Ｈ＋ｔ
（式中、Ｒ１は炭化水素基を、ＲＩＯ、Ｒ”及びＲ１ｍ
は加水分解性基もしくは水酸基を示す．）
で表わされる化合物である．
上記した一般式（８）においてＲ９としては好ましくは
炭素数１〜８の脂肪族炭化水素基（直鎖状であっても分
枝状であってもさしつかえない．）、アラルキル基及び
アリール基、更に好ましくはメチル基及びフェニル基で
ある．炭素数１〜８の脂肪族炭化水素基としては、例え
ばメチル、エチル、プロビル、ブチル、ベンチル、ヘキ
シル、ヘプチル、オクチル等を挙げることができる＠Ｒ
ｌ０、Ｒ１及びＲ′″は、すべて同一でも一部又は全部
が異なっていてもさしつかえない．Ｒ”、Ｒ１及びＲｏ
ｘとしては特にメトキシ基、エトキシ基、ブロボキシ基
、ブトキシ基，水酸基、アセトキシ基等が好ましい．
シラン化合物（Ａ）の好ましい具体例としては、メチル
トリメトキシシラン、フェニルトリメトキシシラン、プ
チルトリメトキシシラン、メチルトリエトキシシラン、
メチルトリブトキシシラン、フェニルトリシラノール、
メチルトリシラノール、メチルトリアセトキシシランフ
ェニルトリアセトキシシラン等が挙げられる．これらの
うちメチルトリメトキシシラン，フェニルトリメトキシ
シラン、フエニルトリシラノール、メチルトリアセトキ
シシラン及びフエニルトリアセトキシシラン等が特に好
ましい．
次に．シランモノマ−（Ｂ）は、前記一般式（１）で表
わされる化合物であって、該一般式にもとづいて、Ｒ２
、Ｒ３及びＲ４はすべて同一でも一部又は全部が異なっ
ていてもよい．但し、すべてが炭素数１〜８の炭化水素
基であってはならない．
該炭素数１〜８の炭化水素基としては，炭素数７
１〜８の脂肪族炭化水素基及び●リール基，更に好まし
くはメチル基及びフェニル基である．炭素数１〜８の炭
化水素基及びアリール基としては前記したものと同様の
ものを挙げることができる．Ｒ２、Ｒ８及びＲ４として
は特にメトキシ基、エトキシ基、水酸基、アセトキシ基
が好ましい．Ｒ１の炭素数１〜６の炭化水素基としては
、直鎖状もしくは分枝状いずれのものでちさしつかえな
く、例えばーＣＨｒ、−ＣＨ．−ＣＨ．−、−ＣＨｔ−
ＣＨ２−ＣＨ＠−、等を挙げることができる．中でも好
ましくは炭素数２〜４の脂肪族炭化水素基である．シラ
ンモノマ−（Ｂ）の好ましい具体例としては３−アミノ
ブロビルトリメトキシシラン、３−アミノプロピルトリ
エトキシシラン、４−アミノブチルトリエトキシシラン
、３−アミノブロビルトリシラノール、３−アミノプロ
ビルトリアセトキシシラン、２−アミノエチルトリメト
キシシラン、Ｎ一エチル−３−アミノプロビルトリメト
キシシラン、３−アミノブロビルトリブロボキシシラン
、３ーアミノブロビルトリプトキシシラン、これらのう
ち、３−アミノブロビルトリメトキシシラン、３−アミ
ノブロビルトリエトキシシラン、３一アミノブロビルト
リシラノール、３−アミノブロビルトリアセトキシシラ
ン等が特に好ましい．
本発明のポリシロキサン系オリゴマーは、上記シラン化
合物（Ａ）とシランモノマ−（Ｂ）とを混合し，反応さ
せることによって得られる．両化合物の混合比率は、該
両成分の合計量にもとづいて、シラン化合物（Ａ）が７
０〜９９．９９９モル％、好ましくは９０〜９９．９モ
ル％，より好ましくは、９５〜９９モル％、シランモノ
マ−（Ｂ）が３０〜０．００１モル％、好ましくは１０
−０．１モル％、より好ましくは５〜１モル％の範囲内
である．シラン化合物（Ａ）が７０モル％より少なくな
るとゲル化しやすくなる傾向が生じ、一方９９．９９９
モル％よりも多くなるとこれを用いるときに縮合を主体
として高分子化するために耐水性、耐薬品性、耐候性等
が低下するので好ましくない．
シラン化合物（Ａ）とシランモノマ−（Ｂ）との反応は
、両成分が有する珪素原子に直接結合した水酸基、及び
加水分解性基が加水分解して生ずる水酸基が脱水縮合す
ることにより行なわれ，目的のオリゴマーが生成する．
この際、反応条件によっては脱水縮合のみではなく、一
部加水分解性基の脱離による縮合も起こる．
シラン化合物（Ａ）とシランモノマー（Ｂ）が、いずれ
も珪素原子に直接結合する水酸基を有するときは、無溶
媒でも反応し得るが、両化合物を溶解でき且つ両化合物
に不活性な有機溶媒中で加熱撹拌下に脱水縮合反応させ
るのが好ましい．有機溶媒としては炭化水素系、エステ
ル系、ケトン系，アルコール系の各種溶媒が使用できる
．
シラン化合物（Ａ）及び／又はシランモノマ−（Ｂ）が
、珪素原子に直接結合する加水分解性基を有するときに
は、縮合に先立って加水分解させるのが好ましく、通常
水及び触媒の存在下で加熱撹拌することにより加水分解
、縮合させることができる．この場合の水の使用量は、
特に限定されないが、加水分解性基１モル当たり０．１
モル以上とするのが好ましい．０．１モルより６少なく
なると両化合物の反応が低下するおそれがある．触媒と
しては、酸触媒又はアルカリ触媒が使用でき、具体的に
は、酸触媒として塩酸、硫酸、リン酸、ギ酸、酢酸、ブ
ロビオン酸、アクリル酸、メタクリル酸などが使用でき
、アルカリ触媒として水酸化ナトリウム、トリエチルア
ミン、アンモニア等が使用できる．触媒の添加量は、上
記シラン化合物（Ａ）とシランモノマー（Ｂ）との合計
量に対し、０．０００１〜５重量％程度好ましくは０．
０１〜Ｏ．ｌ重量％の範囲内が適している．
上記反応の反応温度は、通常２０〜１８０℃程度が適当
であり、好ましくは５０−１２０℃である．また、反応
時間は、通常１〜４０時間程度とするのが適当である．
この反応系において、水溶性有機溶剤を添加してもさし
つかえない．水溶性有機溶剤は、縮合により水に難溶の
アルコールが生成する場合の反応系の均一化に有効であ
り、例えばアルコール系、エステル系、エーテル系、ケ
トン系などのものを好ましく使用できる．
また，本発明のボリシロキサン系オリゴ！一の製造にお
いて、上記シラン化合物（Ａ）とシランモノマ−（Ｂ）
との反応系中に、さらにＳｉに４個の水酸基及び／又は
加水分解性基が結合した例えばテトラアルコキシシラン
やＳｉに２個の水酸基及び／又は加水分解性基が結合し
た例えばジアルキルジアルコキシシランなどを併用して
も差支えなく、該シラン両化合物の２０モル％以下で併
用することができる．
シラン化合物（Ａ）とシランモノマー（Ｔ３）との反応
によって得られる本発明のボリシロキサン系オリゴマー
の主骨格は、シロキサン結合によって構成され、その主
骨格の構造は、主として直鎖（ｌｉｎｅａｒ）状、はし
ご（ｌａｄｄｅｒ）状およびこれらの混合系等が挙げら
れる．これらのうちはしご状の構造からなるもの又は混
合系であって、はしご状の部分を多く有するものを使用
するのが耐水性、耐候性、耐熱性、耐光性等の点から好
ましい．これらの構造は、シラン化合物（Ａ）とシラン
モノマ−（Ｂ）との混合比率、水ならびに酸触媒などの
配合量によって任意に選択できる．特に、本発明ポリシ
ロキサン系オリゴマーに関し、その１分子あたり平均１
個のアルコール性水酸基を有し、かつ末端相当部分にヒ
ドロキシシラン基及びシラン基が少なくとも平均２個以
上結合している．上記官能基が該ポリシロキサン系オリ
ゴマーの末端相当部分以外にも結合することは当然にあ
りうる．
また、本発明のポリシロキサン系オリゴマーの数平均分
子量は通常４００〜１００．０００程度の範囲にある．
分子量４００未満のものを得ようとするとシラン化合物
（Ａ）とシランモノマ−（Ｂ）との反応中にゲル化する
傾向にあり好ましくない．また分子量がｔｏｏ．ｏｏｏ
より大きいものは、このものを用いて樹脂に導入する際
に該樹脂との相溶性が劣るため該樹脂と化学結合しない
ボリシロキサン系オリゴマー成分が多くなり被膜性能が
悪くなる恐れがある．
本発明のボリシロキサン系オリゴマーは、その１分子当
り平均１個のアルコール性水酸基と末端相当部分に少な
くとも２個以上のシラン基を有することにより、該アル
コール性水酸基を利用して、他の樹脂に該成分を導入す
ることができ，又シラン基等の縮合によっても高分子化
あるいは架橋構造を取らせることができる．
本発明のボリシロキサン系オリゴマーは、該オリゴマー
成分を樹脂中に導入する際ゲル化することがなく、グラ
フト体を形成することができ、又縮合により容易に架橋
できるという極めて好適な特性を有しており、このもの
の架橋物は耐水性、耐薬品性，耐候性、耐熱性、耐光性
、耐摩耗性、撥水性、耐汚染性等に優れる．
本発明のボリシロキサン系オリゴマーは、分子中の水酸
基を利用して他の樹脂に該ボリシロキサン系才リゴマー
成分を導入することができる．該ボリシロキサン系才リ
ゴマー成分を導入した樹脂は、該ポリシロキサン系オリ
ゴマー成分に由来するシラン基の官能基同志を反応させ
て硬化樹脂を得ることができるが、好ましくは、低温硬
化性の観点から該官能基とエボキシ基とを必須官能基成
分として含有する樹脂である．そしてエボキシ基として
は更に硬化性に優れた塗膜が形或できることから脂環式
エボキシ基が好ましい．
次に、シラン基とエボキシ基とを含有するボリシロキサ
ン系樹脂組成物について説明する．ボリシロキサン系樹
脂組成物としてはシラン基とエボキシ基とを同一樹脂中
に含有する樹脂（Ｉ）：シラン基を有する樹脂（ＩＩ）
とエボキシ基を有する樹脂（ＩＴＩ）との混合樹脂が使
用できる．
該樹脂（Ｉ）〜（ＩＩＩ）の種類としては、特に制限な
しに従来のものから適宜選択して使用でき、例えばビニ
ル系樹脂、フッ素系樹脂、ポリエステル系樹脂、アルキ
ド系樹脂、シリコーン系樹脂，ウレタン系樹脂、ポリエ
ーテル系樹脂、エボキシ系樹脂及びこれらの変性物等を
挙げることができる．
ボリシロキサン系オリゴマー成分を樹脂中に導入する方
法は、ボリシロキサン系才リゴマー成分中のアルコール
性水酸基と樹脂中の官能基とを付加反応もしくは縮合反
応させることによって行なうことができる．該樹脂中の
官能基としてはポリシロキサン系オリゴマー成分中のア
ルコール性水酸基と反応する基であれば、特に制限なし
に例えばインシアネート基、カルボキシル基、酸無水基
等のものが使用できる．
また、エポキシ基を樹脂中に導入する方法としては、例
えばエボキシ基含有重合性不飽和単量体を原料として用
いて樹脂中に導入する方法や、予め樹脂中に官能基を導
入しておき、次に該樹脂中の官能基と反応する相補的官
能基とエボキシ基とを有するエボキシ化合物を反応させ
ることによってエボキシ基を導入する方法等を挙げるこ
とができる．後者の方法において、樹脂中の官能基と、
エボキシ化合物中の相補的官能基との組合わせとしては
、樹脂中の官能基／エボキシ化合物中の相補的官能基の
組合わせで水酸基／イソシアネート基、イソシアネート
基／水酸基、カルポキシル基／エポキシ基を好ましい例
として挙げることができる．
樹脂（１）は、１分子中に平均１個以上、好ましくは平
均４個以上のシラン基を有し、且つ、１分子中に平均１
個以上、好ましくは平均２個以上のエボキシ基を有し、
数平均分子量が２，０００〜２００，０００、好ましく
はｓ．ｏｏｏ〜ｓｏ，ｏｏｏのものであることが望まし
い．上記した官能基の数が上記した範囲を下回ると硬化
性が劣る傾向にあるので好ましくない．数平均分子量が
２．０００未満では耐候性、耐薬品性、硬化性等が低下
する傾向にあり、他方、２００．０００より大きいと、
樹脂組成物の粘度が高くなり、取り扱いが難しくなるの
で好ましくない．
樹脂（Ｉ）としては下記した（１）及び（２）のものを
挙げることができる．
（１）エボキシ基含有重合性不飽和単量体（ａ）、イソ
シアネート基含有重合性不飽和単量体（ｂ）及び必要に
応じてその他の重合性不飽和単量体（Ｃ）を重合反応さ
せて得られるエボキシ基及びイソシアネート基含有共重
合体に、ポリシロキサン系才リゴマーを反応させて得ら
れる樹脂．
エボキシ基含有重合性不飽和単量体（ａ）としては、１
分子中にエポキシ基と重合性不飽和基とを有する化合物
である．重合性不飽和基としては、例えば
ＣＨｔ＝ＣｆＲ”ＩＣＯＯ−
ＣＨ＊＝Ｃ（Ｒ”）ＣＣ−
ｎ
０
ＣＨｆｉ＝Ｃ（Ｒ”）Ｃ−Ｎ−
０
ＣＨ＊＝ＣＨＣ１｛ｘ−０−
ＣＨ．＝ＣＨＯ−
ＣＨ！＝ＣＨ−
ＣＩ．−Ｃ ［Ｒ川く】
（式中、Ｒ１は水素原子又はメチル基を示す．）
等を挙げることができる．
重合性不飽和基がＣＨ！＝ＣＴＲ”）ＣＯＯ−のエポキ
シ基含有重合性不飽和単量体としては、例えば下記一般
式（９）〜（２１）で表わされる化合物を挙げることが
できろ．
しては、
例えば
各式中、Ｒ”は前記と同じ意味を有し、Ｒ １４はＣ１
１の２価の炭化水素基、ＲｌｌはＣ Ｉ−１。の２価の
炭化水素基、ＲＩ＃はＣ，〜４アルキル基又は水素原子
を示す．Ｗは０及び１〜１０の整数を示す．
上記した２価の炭化水素基としては、例えば−ＣＨｓ−
．−ＣＨｔＣＨｘ−、−ＣＨ雪−ＣＨ＊−ＣＨｔ−−
ＣｔｊＨｔ。一、
−Ｃ＋Ｊｘ４−、
一Ｇ＋畠ＨＳＳ−・
等を挙げることができる．Ｒ１、Ｒ ＩＩ、Ｒ１は同一
６しくは異なっていてちよい．
−ｆｉ式（９）〜（２１）で表わされる具体例と重合性
不飽和基がＣＨＩ＝Ｃ（Ｒ”１Ｃ−Ｎ−のエボキシ含関
Ｏ
有重合性不飽和単量体としては、例えば下記一般式（２
２）〜（２４）で表わされるものを挙げることができる
．
各式中、Ｈａｍ、Ｒ １４及びＲ′６は前記と同じ意味
を有する．
一Ｍ式（２２）〜（２４）で表わされる化合物の具体例
としては、例えば
有重合性不飽和単量体としては、例えば下記一般式（２
５）〜（２７）で表わされる化合物を挙げることができ
る．
等を挙げることができる．
各式中，Ｒ１及びＲ”は前記と同じ意味を有する．
一般式（２５）〜（２７）で表わされる化合物の具体例
としては例えば
重合性不飽和基がＣＨ！＝Ｃ（Ｒ”Ｉｃ−Ｎ−のエポキ
シ含呵
０
有重合性不飽和単量体としては、例えば下記一般式（２
８）〜（３３）で表わされる化合物を挙げることができ
る．
各式中、Ｒ”、Ｒ １４、Ｒ”Ｉ Ｒ”及びＷは前記と
同様の意味を有する．
一般式（２８）〜（３３）で表わされる化合物の具体例
としては、例えば
を挙げることができる．
重合性不飽和基がＣＨ２＝ＣＨＣＨ．Ｑ−のエボキシ基
含有重合性不飽和単量体としては、例えば下記一般式（
３４）〜（３７）で表わされる化合物を挙げることがで
きる．
各式中，
Ｒｌｍ及びＲ １４は前記と同様の意味を有すー殻式（
３４）〜（３７）で表わされる化合物の具体例としては
、例えば
を挙げることができる．
重合性不飽和基がＣＩ．・ＣＨＯ−のエボキシ基含有不
飽和単量体としては、例えば下記一般式（３８）〜（４
０）で表わされる化合物を挙げることができる．
各式中Ｒ１及び｝｛＋４は前記と同様の意味を有す一般
式（３８）〜（４０）で表わされる化合物の具体例とし
ては、例えば
を挙げることができる．
重合性不飽和基が（：Ｈ．＝ＣＩ｛−のエボキシ基含有
不飽和単量体としては、例えば下記一般式（４１）〜（
４３）で表わされる化合物を挙げることができる．
る。
一般式（４１）〜（４３）で表わされる化合物の具体例
としては、例えば
ＣＬ゛ＣＨ−ＣＨ＊Ｏｏ
を挙げることができる．
重合性不飽和基がＣＨ！＝Ｃ（Ｒ”ｌＱ のエボキ
シ基含有不飽和単量体としては、例えば下記一般式（４
４）〜（４８）で表わされる化合物を挙げることができ
る．
（４６〉
各式中、Ｒ”、７１｛＋４及びＲ”は前記と同様の意味
を有する．
一般式（４４）〜（４８）で表わされる化合物の具体例
としては、例えば
を挙げることができる．
インシアネート基含有重合性不飽和単量体（ｂ）として
は、例えば後記水酸基含有重合性不飽和単量体（ｄ）と
ポリイソシアネート化合物（例えばトリレンジイソシア
ネート、イン才ロンジイソシアネート、キシレンジイソ
シアネート等）とをイソシアネート基を含有するように
反応させて得られる単量体；イソシアネートエチルアク
リレート、α．α−ジメチルーｍ−イソブロベニルペン
ジルイソシアネート等の単量体を挙げることができる．
水酸基含有重合性不飽和単量体としては、例えばビニル
アルコール及びその誘導体［例えばＣＨ＊”ＣＨＯＣＪ
４０Ｈ， ＣＨ＊”ＣＨＯ→ＣＩＨ．０ ５１等］；ア
リルアルコール及びその誘導体［例えば
ＣＨ＊＝ＣＨＣＨ＊ＯＣＪ４０Ｈ． ＣＨｉＩＩＣＨＣ
Ｈ＊Ｏ｛ＣＪ４０ ｈＨ等］：ヒドロキシアルキル（メ
タ）アクリレート［例えばヒドロキシエチル（メタ）ア
クリレート、ヒドロキシプロピル（メタ）アクリレート
等］ ；ポリアルキレングリコール（メタ）アクリレー
ト［例えばボリエチレングリコールモノ（メタ）アクリ
レート、ボリブロビレングリコール（メタ）アクリレー
ト等］等及びこれらの単量体とε一カブロラクトン、γ
−バレロラクトン等のラクトン類との付加物等を挙げる
ことができる．単量体（ａ）及び（ｂ）を必要に応じて
共重合できるその他の重合性不飽和単量体（ｃ）として
は、例えば
（ｃ−１）アクリル酸又はメタクリル酸の工又テル：例
えば、アクリル酸メチル、アクリル酸エチル、アクリル
酸プロビル、アクリル酸イソブロビル、アクリル酸ブチ
ル、アクリル酸ヘキシル、アクリル酸オクチル、アクリ
ル酸ラウリル、メククリル酸メチル、メタクリル酸エチ
ル、メタクリル酸プロビル，メタクリル酸イソブロビル
、メククリル酸ブチル、メタクリル酸ヘキシル、メタク
リル酸オクチル、メタクリル酸ラウリル等のアクリル酸
又はメタクリル酸の炭素数１−１８のアルキルエステル
：アクリル酸メトキシプチル、メタクリル酸メトキシブ
チル、アクリル酸メトキシエチル、メタクリル酸メトキ
シエチル、アクリル酸エトキシブチル、メタクリル酸エ
トキシブチル等のアクリル酸一又はメククリル酸の炭素
数２〜１８のアルコキシアルキルエステル等．
（ｃ−２）ビニル芳香族化合物：例えば、スチレン、α
−メチルスチレン、ビニルトルエン、ｐ一クロルスチレ
ン等．
（ｃ−３）その他：アクリロニトリル、メタクリ口ニト
リル等．
（ｃ−４）才レフィン系化合物：例えばエチレン，ブロ
ビレン、ブチレン、イソブレン、クロロブレン等．
（ｃ−５）ビニルエーテル及びアリルエーテル：例えば
エチルビニルエーテル、プロビルビニルエーテル、イソ
プロビルビニルエーテル、プチルビニルエーテル、ｔｅ
ｒｔ−プチルビニルエーテル、ベンチルビニルエーテル
、ヘキシルビニルエーテル、イソヘキシルビニルエーテ
ル、才クチルビニルエーテル、４−メチル−１−ベンチ
ルビニルエーテル等の鎖状アルキルビニルエーテル類、
シクロペンチルビニルエーテル、シクロヘキシルビニル
エーテル等のシクロアルキルビニルエーテル類、フェニ
ルビニルエーテル、〇一ｍ＋，ｐ−トリビニルエーテル
等のアリールビニ？エーテル類、ベンジルビニルエーテ
ル、フエネチルビニルエーテル等のアラルキルビニルエ
ーテル類等．
（ｃ−６）ビニルエステル及びブロペニルエステル：例
えば酢酸ビニル、乳酸ビニル、酪酸ビニル、イソ酩酸ビ
ニル、カブロン酸ビニル、イソカプロン酸ビニル、ビバ
リツク酸ビニル、カブリン酸ビニル等のビニルエステル
及び酢酸イソブロペニルブロピオン酸イソプロベニル等
のブロベニルエステル等．
（ｃ−７）一般式ＣＸ＊＝ＣＸ＊ （式中、Ｘは同一も
しくは異なってＨ， ＣＪ． Ｂｒ， Ｆ、アルキル
基又はハロアルキル基を示す．ただし、式中に少なくと
も１個のＦを含有する．）で表わされるフルオロオレフ
ィン：例えばＣＦｉ”Ｃｈ ， ＣＨＦ÷ＣＦｉ、ＣＨ
．＝ＣＦ． ． ＣＩ■＝ＣＨＦ ． ＣＣＩＦ＝ＣＦ
ｌ、ＣＩＣＩ＝ＣＦ．、ＣＣｌｍ＝ＣＦｌ、ＣＣＩＦ＝
ＣＧＩＰ ． ＣＨＦ＝ＣＣｌ．、ＣＨＩ＝ＣＧＩＰ、
ＣＣｌ．＝ＣＣＩＦ
ＣＦＩＣＦ＝ＣＦ！ ． ＣＦ．ＣＦ＝ＣＨＦ ． Ｃ
ＦＩＣＨ＝ＣＦｔ、ＣＦｓＣＦ”ＣＨｘ ． ＣＨＦ＊
ＣＦ＝ＣＨＦ． ＣＨｉＣＦ’ＣＦｉ、ＣＩ．ＣＦ−Ｃ
ＨＩ ． ＣＦ．Ｃｌ（：Ｆ＝ＣＦ． ． ＣＦＩＣＣ
Ｉ−ＣＦＩ、ＣＦｓＣＦ”ＣＦＣＩ． ＣＦｉＣＩＣＣ
ｌｌｌＣＦｈＣＦ＊（：ＩｃＦ”ｃＦｃＩ１ｃｐｃｔｘ
ｃｐ＝ｃｐｘ ． ＣＦ．ＣＣ１−ＣＧＩＦ ． ＣＦ
ＩＣＣＩ＝ＣＣ１ｆｉ 、ＣＣｌｈＣＦ”ＣＣ１ａ．
Ｃ（：ｌｓＣＦ”Ｃｈ、ＣｈＣＩＣＣｌ”ＣＣｌｇ
，（：ＦＣｌ．ＣＣｌ＝ＣＣ１． ． ＣＦｓＣＦ＝
ＣＩＣＩ． ＣＣＩＦ．ＣＦ＝ＣＩＣＩ、ＣＦｓＣＣ
ＣＣＨ（：ｌ ． ＣＨＦａＣＣＣＣＣ１ｓ．ＣＦｍ
ＣＩＣＨ”ＣＣｌｇ，ＣＦ．ＣＩＣＧ！＝（１：ＨＣＩ
． ＣＣ１１ＣＦ＝ＣＨＣｌ ． ＣＦ．ｌＣＦ
＝ＣＦ．．（：ＦｔＢｒＣＨ”ＣＦ＊ ．ＣＦｍＣＢ
ｒ”ＣＨＢｒ ．ＣＦｔＣＩＣＢｒ”ＣＨ＊．ＣＩ．Ｂ
ｒＣＦ”ＣＧ１ｍ．ＣＦｓＣＢｒ”ＣＨｓ、ＣＦｘＣＨ
冨ＣＨＢｒ−ＣＦ．ＢｒＣＨ”ＣＨＦ ．ＣＦＪｒＣＦ
”ＣＦｉ ．ＣＦｓＣＦｉＣＦ”Ｃｒｔ．ＣＦ．ＣＦ
＝ＣＦＣＦｓ 、ＣＦＩＣＨ＝ＣＦＣＦＳ 、ＣＦ
．−ＣＦＣＦ．ＣＨＦ！ 、ＣＦｓＣｌｈＣＦ”ＣＨ
ａ．ＣＦｓＣＨ”ＣＨＣＦｓ 、ＣＦｍ”ＣＦＣｈＣ
Ｈｓ、Ｃｈ＝ＣＦＣＨ＊ＣＨｓ．ＣＦｓＣｌｂＣＨ−Ｃ
Ｈｓ．ＣＦｓＣＨ”ＣＩＣＨｓ −ＣＦ１＝ＣＨＣＨ
ｆｆｉＣＨｓ、Ｃ｝！．ＣＦ．ＣＨ＝ＣＨ．．ＣＦＨＩ
ＧＨ＝ＣＩＣＦＨ． 、ＣＨｓＣＦ＊ＣＨ”ＣＨｉ、
ＣＩ．＝ＣＦＣＨヨＣＨＩ、ＣＦｓ（Ｃｈ）ｍｃＦ’ｃ
ｈ ． ＣＦｓ（ＣＦ＊）ｓｃＦ＝ｃＦｇ等．（ｃ−８
）バーフルオロアルキル（メタ）アクリレート：例えば
バーフルオロブチルエチルメタクリレート、バーフルオ
ロイソノニルエチルメタクリレート，バーフルオロオク
チルエチルメタクリレート等
を挙げることができる．これらの単量体は１種もしくは
２種以上混合に使用できる．
（２）１分子中に平均２個以上のカルボキシル基又は１
分子中に平均１個の無水カルポン酸基を有する樹脂に、
該カルボキシル基又は無水カルボン酸基と反応する官能
基（例えば水酸基、エボキシ基等）を有するエボキシ化
合物及びボリシロキサン系オリゴマーとを反応させて得
られる樹脂．
カルボキシル基又は無水カルボン酸基を有する樹脂とし
ては、カルボキシル基含有重合性不飽和単量体［例えば
（メク）オクリル酸、マレイン酸、クロトン酸、イタコ
ン酸等］又は無水カルボン酸基含有重合性不飽和単量体
［例えば無水マレイン酸，無水イタコン酸等］の単独重
合体もしくはこれらの単量体とその他の重合性不飽和単
量体（ｃ）との共重合体；多塩基酸［例えば（無水）フ
タル酸，イソフクル酸、テレフタル酸、アゼライン酸等
］と、多価アルコール［例えばエチレングリコール，ネ
オベンチルグリコール１．６−ヘキサンジオール、ペン
タエリスリトル、グリセリン等】及び必要に応じて一塩
基酸、一価アルコール等をカルボキシル基を有するよう
に反応させて得られるポリエステル（又はアルキド）樹
脂等を代表例として挙げることができる．
水酸基含有エポキシ化合物としては下記一般式（４９）
〜（５９）で表わされる化合物を挙げることができる．
Ｒ目
１
ＣＨＩ−Ｃ−Ｒ”ＯＨ
＼／
Ｏ
（４９）
各式中、Ｒ１、Ｒ１４、Ｒ１６、
同じ意味を有する．
一般式（４９）〜（５９）
の具体例としては、例えば
Ｈ
Ｒｌ８及びＷは前記と
で表わされる化合物
ＣＨ．−Ｃ−ＣＨ．−ＯＨ
＼／
０
を挙げることができる．
ポリエボキシ化合物としては下記一般式（６０）〜（６
７）で表わされる化合物を挙げることができる．
０
０
式中、Ｒ９、Ｒ”、
じ意味を有する．
一般式（６０）〜（６７）
の具体例としては、例えば
Ｒ”及びＷは前記と同
Ｒ目、
で表わされる化合物
（６４）
等を挙げることができる．
また、上記以外にも、例えば下記のものが使用できる．
アネート化合物との付加物（使用し得るポリイソシアネ
ート化合物としては、例えばヘキサメチレンジイソシア
ネートもしくはトリメチルヘキサメチレンジイソシアネ
ートの如き脂肪族ジイソシ７ネート類：水素添加キシリ
レンジイソシアネートもしくはイソホロンジイソシアネ
ートの如き環状脂肪族ジイソシアネートＲ：トリレンジ
イソシアネートもしくは４．４′−ジフエニルメタンジ
イソシアネートの如き芳香族ジイソシアネート類の如き
有機ジイソシアネートそれ自体、またはこれらの各有機
ジイソシアネートと多価アルコール、低分子量ポリエス
テル樹脂もしくは水等との付加物、あるいは上記した如
き各有機ジイソシアネート同志の重合体、更にはイソシ
アネート・ビウレット体等が挙げられるが、それらの代
表的な市販品の例としては「パーノックＤ−７５０、−
８００．ＤＮ−９５０、−９７０もしくはｌ５−４５５
Ｊ ［以上、大日本インキ化学工業■製品］、「デス
モジュールＬ．ＮＨＬ、ＩＬもしくはＮ３３９０Ｊ
［西ドイツ国バイエル社製品］、「タケネートＤ−１０
２、−２０２、−１１０Ｎもしくは−１２３ＮＪ ［
武田薬品工業■製品］、「コロネートＬ％ＨＬ．ＥＨも
しくは２０３ＪINDUSTRIAL APPLICATION FIELD The present invention relates to novel polysiloxane oligomers, polysiloxane resin compositions, and curable resin compositions. Conventional technology It has been said that among the already known polysiloxanes, compounds having one alcoholic hydroxyl group and one terminal equivalent (SL) hydroxyl group or hydrolyzable group have low reactivity and are difficult to form a crosslinked structure. There is a drawback: Compounds that have only one hydroxyl group or hydrolyzable group at both ends and do not contain alcoholic hydroxyl groups are polymerized only by condensation, resulting in poor water resistance, chemical resistance, and weather resistance. Furthermore, compounds having one alcoholic hydroxyl group at each terminal end tend to gel during addition, making them difficult to handle and making it impossible to form grafts. Problems to be Solved by the Invention The present invention aims to eliminate the above-mentioned drawbacks of conventionally known polysiloxanes. Means for Solving the Problems The present inventor has developed polysiloxane using specific raw materials.
In a novel polysiloxane-based oligomer obtained by having an average of one hydroxyl group per molecule and at least two or more hydroxyl groups and/or hydrolyzable groups directly bonded to silicon atoms in the terminal portion, The inventors have discovered that the oligomer component does not gel when introduced into the resin, can be crosslinked by condensation, and that the above object can be fully achieved, and based on this, the present invention has been completed. That is, the present invention provides: (1) a silane compound (A) having a hydroxyl group and/or a hydrolyzable group (hereinafter sometimes abbreviated as a "silane group") directly bonded to a silicon atom (hereinafter referred to as a "silane compound (A)"); )”
That's what it means. ) and the following general formula (1) R8 / HO-R'-Si-R"
(1)\R4 (wherein, Rl is a divalent hydrocarbon group having 1 to 6 carbon atoms, R1
, Rl and R represent a hydroxyl group, a hydrolyzable group, or a monovalent hydrocarbon group having 1 to 8 carbon atoms. However, R3, R3 and R4 are not all monovalent hydrocarbon groups having 1 to 8 carbon atoms. ) (hereinafter referred to as "silane monomer (B)"), and an average of 1 IO-R' groups per molecule and a portion corresponding to the terminal. A polysiloxane-based oligomer characterized by having two or more silane groups on average; ■ The resin contains a silane group and an epoxy group as essential functional group components, and the silane group is A polysiloxane resin composition characterized in that: (1) one or more curing reaction catalysts selected from organometallic compounds, Lewis acids, protonic acids, and aluminum compounds are introduced into the polysiloxane resin composition described above; It relates to a curable resin composition characterized by containing. In this specification, a hydrolyzable group directly bonded to a silicon atom is a group that is hydrolyzed by water or moisture to produce a hydroxysilane group. Examples of such groups include those represented by the following general formula. -O-R” (
2)〇1-o-c-86(3) R7/-o-N=c (
4)\Ra R7 / In the formula, R6 is a C, ~4 alkyl group, and R6 to R1 are the same or different and represent an alkyl group, an aryl group, or an aralkyl group of CI-s. In the general formula, examples of the "C11 alkyl group" include methyl, ethyl, n-probyl, isobrobyl,
n-butyl, iao-butyl, sec-butyl, tert-butyl, n-bentyl, iso-bentyl, n-butyl,
Examples include isooctyl. Examples of the "aryl group" include phenyl, tolyl, xylyl, and the like. Examples of the "aralkyl group" include benzyl and phenethyl. In addition to the above-mentioned hydrolyzable groups bonded to silicon atoms, examples of hydrolyzable groups include -->Si-H groups. In the present invention, the above general formula (2) is used from the viewpoint of storage stability, curability, etc. Groups represented by (3) and hydroxysilane groups are preferred. In this specification, the term "terminus equivalent" refers to one or more silicon atoms located at the end of the polysiloxane oligomer. The polysiloxane oligomer of the present invention has a main skeleton composed of siloxane bonds, and a hydrocarbon group, a hydroxyl group, a hydrolyzable group, etc. are directly bonded to the silicon atom of this main skeleton, and the above-mentioned silane It is obtained by reacting compound (A) and silane monomer (B). The silane compound (A) has an average of three silane groups in one molecule, and preferably has the general formula (8) H+t (wherein, R1 is a hydrocarbon group, RIO, R'' and R1m
indicates a hydrolyzable group or a hydroxyl group. ) is a compound represented by In the above general formula (8), R9 is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms (which may be linear or branched), an aralkyl group, an aryl group, More preferred are methyl and phenyl groups. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, bentyl, hexyl, heptyl, octyl, etc.@R
l0, R1 and R''' may be all the same or partially or completely different.R'', R1 and Ro
In particular, x is preferably a methoxy group, an ethoxy group, a broboxy group, a butoxy group, a hydroxyl group, an acetoxy group, or the like. Preferred specific examples of the silane compound (A) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane,
Methyltributoxysilane, phenyltrisilanol,
Examples include methyltrisilanol, methyltriacetoxysilane, phenyltriacetoxysilane, and the like. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol, methyltriacetoxysilane and phenyltriacetoxysilane are particularly preferred. next. The silane monomer (B) is a compound represented by the above general formula (1), and based on the general formula, R2
, R3 and R4 may all be the same or partially or completely different. However, all of the groups must not be hydrocarbon groups having 1 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms include an aliphatic hydrocarbon group having 7 to 8 carbon atoms and a lyl group, more preferably a methyl group and a phenyl group. Examples of the hydrocarbon group having 1 to 8 carbon atoms and the aryl group include those mentioned above. As R2, R8 and R4, methoxy, ethoxy, hydroxyl and acetoxy groups are particularly preferred. The hydrocarbon group having 1 to 6 carbon atoms for R1 may be either linear or branched, such as -CHr, -CH. -CH. -, -CHt-
CH2-CH@-, etc. can be mentioned. Among these, aliphatic hydrocarbon groups having 2 to 4 carbon atoms are preferred. Preferred specific examples of the silane monomer (B) include 3-aminobrobyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, 3-aminobrobyltrisilanol, 3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane. Acetoxysilane, 2-aminoethyltrimethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, 3-aminobrobyltribroboxysilane, 3-aminobrobyltriptoxysilane, among these, 3-amino Particularly preferred are brobyltrimethoxysilane, 3-aminobrobyltriethoxysilane, 3-aminobrobyltrisilanol, 3-aminobrobyltriacetoxysilane, and the like. The polysiloxane oligomer of the present invention can be obtained by mixing the silane compound (A) and the silane monomer (B) and reacting them. The mixing ratio of both compounds is based on the total amount of both components, and the silane compound (A) is 7.
0 to 99.999 mol%, preferably 90 to 99.9 mol%, more preferably 95 to 99 mol%, silane monomer (B) 30 to 0.001 mol%, preferably 10
-0.1 mol%, more preferably within the range of 5 to 1 mol%. When the silane compound (A) is less than 70 mol%, gelation tends to occur easily;
If it exceeds mol%, it is not preferable because when it is used, the polymerization mainly occurs through condensation, resulting in a decrease in water resistance, chemical resistance, weather resistance, etc. The reaction between the silane compound (A) and the silane monomer (B) is carried out by dehydration condensation of the hydroxyl group directly bonded to the silicon atom of both components and the hydroxyl group generated by hydrolysis of the hydrolyzable group. oligomers are generated.
At this time, depending on the reaction conditions, not only dehydration condensation but also some condensation due to elimination of hydrolyzable groups may occur. When the silane compound (A) and the silane monomer (B) both have a hydroxyl group directly bonded to the silicon atom, the reaction can be performed without a solvent, but in an organic solvent that can dissolve both compounds and is inert to both compounds. It is preferable to carry out the dehydration condensation reaction under heating and stirring. As the organic solvent, various solvents such as hydrocarbon, ester, ketone, and alcohol can be used. When the silane compound (A) and/or the silane monomer (B) have a hydrolyzable group directly bonded to a silicon atom, it is preferable to hydrolyze it prior to condensation, usually by heating and stirring in the presence of water and a catalyst. Hydrolysis and condensation can be carried out by doing this. The amount of water used in this case is
Although not particularly limited, 0.1 per mole of hydrolyzable group
It is preferable that the amount is mol or more. If the amount is less than 0.1 mole by 6, the reaction of both compounds may decrease. As a catalyst, an acid catalyst or an alkali catalyst can be used. Specifically, as an acid catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, brobionic acid, acrylic acid, methacrylic acid, etc. can be used, and as an alkali catalyst, hydroxide catalyst can be used. Sodium, triethylamine, ammonia, etc. can be used. The amount of the catalyst added is about 0.0001 to 5% by weight, preferably 0.0001 to 5% by weight, based on the total amount of the silane compound (A) and silane monomer (B).
01~O. A range of 1% by weight is suitable. The reaction temperature for the above reaction is usually about 20 to 180°C, preferably 50 to 120°C. Further, it is appropriate that the reaction time is usually about 1 to 40 hours. In this reaction system, it is possible to add a water-soluble organic solvent. The water-soluble organic solvent is effective in homogenizing the reaction system when a poorly water-soluble alcohol is produced by condensation, and for example, alcohol-based, ester-based, ether-based, and ketone-based solvents are preferably used. Moreover, the polysiloxane oligo of the present invention! In one production, the silane compound (A) and the silane monomer (B)
In addition, in the reaction system with, for example, tetraalkoxysilane in which four hydroxyl groups and/or hydrolyzable groups are bonded to Si, and for example, dialkyldialkoxysilane in which two hydroxyl groups and/or hydrolyzable groups are bonded to Si. There is no problem in using these silane compounds in combination, and they can be used together in an amount of 20 mol% or less of both silane compounds. The main skeleton of the polysiloxane oligomer of the present invention obtained by the reaction of the silane compound (A) and the silane monomer (T3) is composed of siloxane bonds, and the structure of the main skeleton is mainly linear, Examples include ladder type and mixed type. Among these, it is preferable to use one with a ladder-like structure or a mixed system with many ladder-like parts in terms of water resistance, weather resistance, heat resistance, light resistance, etc. These structures can be arbitrarily selected depending on the mixing ratio of the silane compound (A) and the silane monomer (B) and the amounts of water and acid catalyst. In particular, regarding the polysiloxane oligomer of the present invention, an average of 1
It has 2 alcoholic hydroxyl groups, and an average of at least 2 or more hydroxysilane groups and silane groups are bonded to the terminal portion. Naturally, it is possible that the above-mentioned functional group is bonded to a portion other than the terminal portion of the polysiloxane oligomer. Further, the number average molecular weight of the polysiloxane oligomer of the present invention is usually in the range of about 400 to 100,000.
If an attempt is made to obtain one with a molecular weight of less than 400, it tends to gel during the reaction between the silane compound (A) and the silane monomer (B), which is undesirable. Also, the molecular weight is too. ooooo
If the size is larger, the compatibility with the resin is poor when it is introduced into the resin, so there is a risk that the amount of polysiloxane oligomer components that do not chemically bond with the resin will increase, resulting in poor coating performance. The polysiloxane oligomer of the present invention has an average of one alcoholic hydroxyl group per molecule and at least two or more silane groups in the portion corresponding to the end, so that the polysiloxane oligomer can be used to form other resins using the alcoholic hydroxyl group. These components can be introduced, and polymerization or crosslinked structures can also be created by condensation of silane groups, etc. The polysiloxane-based oligomer of the present invention has extremely favorable properties in that it does not gel when the oligomer component is introduced into the resin, can form a graft body, and can be easily crosslinked by condensation. The crosslinked product has excellent water resistance, chemical resistance, weather resistance, heat resistance, light resistance, abrasion resistance, water repellency, stain resistance, etc. The polysiloxane oligomer of the present invention can introduce the polysiloxane oligomer component into other resins by utilizing the hydroxyl groups in the molecule. In the resin into which the polysiloxane oligomer component is introduced, a cured resin can be obtained by reacting the functional groups of the silane groups derived from the polysiloxane oligomer component, but preferably from the viewpoint of low temperature curability. This is a resin containing the above functional group and an epoxy group as essential functional group components. As the epoxy group, an alicyclic epoxy group is preferable because it can form a coating film with excellent curability. Next, a polysiloxane resin composition containing a silane group and an epoxy group will be explained. As a polysiloxane resin composition, a resin containing a silane group and an epoxy group in the same resin (I): a resin having a silane group (II)
A mixed resin consisting of a resin having an epoxy group (ITI) and an epoxy group-containing resin (ITI) can be used. The types of resins (I) to (III) can be appropriately selected and used from conventional resins without particular limitations, such as vinyl resins, fluorine resins, polyester resins, alkyd resins, silicone resins, Examples include urethane resins, polyether resins, epoxy resins, and modified products thereof. The polysiloxane oligomer component can be introduced into the resin by carrying out an addition reaction or condensation reaction between the alcoholic hydroxyl group in the polysiloxane oligomer component and the functional group in the resin. The functional group in the resin is not particularly limited as long as it reacts with the alcoholic hydroxyl group in the polysiloxane oligomer component, such as incyanate groups, carboxyl groups, acid anhydride groups, etc. can be used. In addition, methods for introducing epoxy groups into the resin include, for example, methods in which an epoxy group-containing polymerizable unsaturated monomer is used as a raw material and introduced into the resin, and a method in which a functional group is introduced into the resin in advance. Next, examples include a method of introducing an epoxy group by reacting an epoxy compound having an epoxy group with a complementary functional group that reacts with the functional group in the resin. In the latter method, functional groups in the resin and
As for the combination of complementary functional groups in the epoxy compound, hydroxyl group/isocyanate group, isocyanate group/hydroxyl group, carpoxyl group/epoxy group are preferable combinations of functional group in resin/complementary functional group in epoxy compound. This can be cited as an example. The resin (1) has an average of 1 or more silane groups in one molecule, preferably an average of 4 or more silane groups, and has an average of 1 or more silane groups in one molecule.
, preferably has an average of 2 or more epoxy groups,
The number average molecular weight is 2,000 to 200,000, preferably s. It is desirable that it be from ooo to so, ooo. If the number of the above-mentioned functional groups is less than the above-mentioned range, curability tends to be poor, which is not preferable. When the number average molecular weight is less than 2.000, weather resistance, chemical resistance, curability, etc. tend to decrease, while on the other hand, when it is greater than 200.000,
This is not preferable because the viscosity of the resin composition becomes high and it becomes difficult to handle. Examples of the resin (I) include those listed in (1) and (2) below. (1) Polymerization reaction of epoxy group-containing polymerizable unsaturated monomer (a), isocyanate group-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomers (C) as necessary A resin obtained by reacting a copolymer containing epoxy groups and isocyanate groups with a polysiloxane oligomer. As the epoxy group-containing polymerizable unsaturated monomer (a), 1
It is a compound that has an epoxy group and a polymerizable unsaturated group in its molecule. Examples of the polymerizable unsaturated group include CHt=CfR"ICOO- CH*=C(R")CC- n 0 CHfi=C(R")C-N- 0 CH*=CHC1{x-0- CH. =CHO- CH!=CH- CI.-C [R river] (In the formula, R1 represents a hydrogen atom or a methyl group.) etc. The polymerizable unsaturated group is CH!=CTR" ) Examples of the epoxy group-containing polymerizable unsaturated monomer of COO- include compounds represented by the following general formulas (9) to (21). For example, in each formula, R'' has the same meaning as above, R 14 is C1
1 divalent hydrocarbon group, Rll is C I-1. The divalent hydrocarbon group, RI# represents a C,~4 alkyl group or a hydrogen atom. W represents 0 and an integer from 1 to 10. Examples of the above divalent hydrocarbon group include -CHs-
．． -CHtCHx-, -CH snow-CH*-CHt--
CtjHt. 1, -C+Jx4-, 1G+Hata HSS-, etc. R1, R II, and R1 may be the same or different. -fi Specific examples represented by formulas (9) to (21) and a polymerizable unsaturated group in which CHI=C(R"1C-N- epoxy-containing O) Examples of the polymerizable unsaturated monomer include the following: General formula (2
2) to (24) can be mentioned. In each formula, Ham, R14 and R'6 have the same meanings as above. As specific examples of compounds represented by the 1M formulas (22) to (24), examples of the polymerizable unsaturated monomers include, for example, the following general formula (2
Compounds represented by 5) to (27) can be mentioned. etc. can be mentioned. In each formula, R1 and R" have the same meanings as above. As specific examples of compounds represented by general formulas (25) to (27), for example, the polymerizable unsaturated group is CH!=C(R"Ic- As the N-epoxy-containing 0 polymerizable unsaturated monomer, for example, the following general formula (2
Compounds represented by 8) to (33) can be mentioned. In each formula, R'', R14, R''I R'' and W have the same meanings as above. Specific examples of compounds represented by general formulas (28) to (33) include, for example. The epoxy group-containing polymerizable unsaturated monomer in which the polymerizable unsaturated group is CH2=CHCH.Q- can be, for example, the following general formula (
Compounds represented by 34) to (37) can be mentioned. In each formula, Rlm and R14 have the same meanings as above - shell formula (
Specific examples of the compounds represented by 34) to (37) include the following. The polymerizable unsaturated group is CI. - As the epoxy group-containing unsaturated monomer of CHO-, for example, the following general formulas (38) to (4
0) can be mentioned. Specific examples of compounds represented by general formulas (38) to (40) in which R1 and {+4 have the same meanings as above include the following. Examples of the epoxy group-containing unsaturated monomer in which the polymerizable unsaturated group is (:H.=CI{-) include the following general formulas (41) to (
43) can be mentioned. Ru. Specific examples of compounds represented by general formulas (41) to (43) include CL゛CH-CH*Oo. The polymerizable unsaturated group is CH! As the epoxy group-containing unsaturated monomer of =C(R"lQ, for example, the following general formula (4
Compounds represented by 4) to (48) can be mentioned. (46> In each formula, R", 71{+4 and R" have the same meanings as above. Specific examples of the compounds represented by general formulas (44) to (48) include, for example. Examples of the incyanate group-containing polymerizable unsaturated monomer (b) include the hydroxyl group-containing polymerizable unsaturated monomer (d) described below and a polyisocyanate compound (for example, tolylene diisocyanate, insairon diisocyanate, xylene diisocyanate, etc.). ) to contain an isocyanate group; examples include monomers such as isocyanate ethyl acrylate and α.α-dimethyl-m-isobrobenylpenzyl isocyanate.Hydroxyl group-containing polymerizability Examples of unsaturated monomers include vinyl alcohol and derivatives thereof [e.g. CH*”CHOCJ
40H, CH*”CHO→CIH.0 51 etc.]; allyl alcohol and its derivatives [e.g. CH*=CHCH*OCJ40H. CHiIICHC
H*O {CJ40 hH etc.]: Hydroxyalkyl (meth)acrylate [e.g. hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate etc.]; Polyalkylene glycol (meth)acrylate [e.g. polyethylene glycol mono(meth)acrylate , polybrobylene glycol (meth)acrylate, etc.] and these monomers and ε-cabrolactone, γ
- Examples include adducts with lactones such as valerolactone. Other polymerizable unsaturated monomers (c) that can be copolymerized with monomers (a) and (b) as necessary include (c-1) acrylic acid or methacrylic acid polymers: e.g. , methyl acrylate, ethyl acrylate, probyl acrylate, isobrobyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl meccrylate, ethyl methacrylate, probyl methacrylate, isobrobyl methacrylate, meccryl C1-18 alkyl esters of acrylic acid or methacrylic acid such as butyl acid, hexyl methacrylate, octyl methacrylate, lauryl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate , C2-18 alkoxyalkyl esters of acrylic acid or meccrylic acid such as ethoxybutyl acrylate and ethoxybutyl methacrylate. (c-2) Vinyl aromatic compound: For example, styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene, etc. (c-3) Others: acrylonitrile, methacrylonitrile, etc. (c-4) Lefin compounds: for example, ethylene, brobylene, butylene, isobrene, chlorobrene, etc. (c-5) Vinyl ethers and allyl ethers: e.g. ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, te
Chain alkyl vinyl ethers such as rt-butyl vinyl ether, benzyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, rt-butyl vinyl ether, 4-methyl-1-bentyl vinyl ether,
Cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, 〇1m+, p-trivinyl ether, etc. Ethers, aralkyl vinyl ethers such as benzyl vinyl ether, phenethyl vinyl ether, etc. (c-6) Vinyl esters and propenyl esters: for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutate, vinyl cabroate, vinyl isocaproate, vinyl bivaricate, vinyl cabrate, and isobropenyl acetate. Brobenyl esters such as isoprobenyl rubropionate, etc. (c-7) General formula CX*=CX* (wherein X is the same or different and represents H, CJ. Br, F, an alkyl group or a haloalkyl group. However, the formula contains at least one F ): For example, CFi"Ch, CHF÷CFi, CH
．． =CF. ．． CI■=CHF. CCIF=CF
l, CICI=CF. , CClm=CFl, CCIF=
CGIP. CHF=CCl. ,CHI=CGIP,
CCl. =CCIF CFICF=CF! ．． C.F. CF=CHF. C
FICH=CFt, CFsCF”CHx.CHF*
CF=CHF. CHiCF'CFi, CI. CF-C
HI. C.F. Cl(:F=CF..CFICC
I-CFI, CFsCF”CFCI.CFiCICC
lllCFhCF*(:IcF”cFcI1cpctx
cp=cpx. C.F. CC1-CGIF. C.F.
ICCI=CC1fi, CClhCF”CC1a.
C(:lsCF”Ch, ChCICCl”CClg
, (:FCl.CCl=CC1..CFsCF=
CICI. CCIF. CF=CICI, CFsCC
CCH(:l.CHFaCCCCCC1s.CFm
CICH”CClg,CF.CICG!=(1:HCI
．． CC11CF=CHCl. C.F. lCF
=CF. ．． (:FtBrCH”CF* .CFmCB
r”CHBr.CFtCICBr”CH*. C.I. B
rCF”CG1m.CFsCBr”CHs, CFxCH
TomiCHBr-CF. BrCH”CHF .CFJrCF
"CFi.CFsCFiCF"Crt. C.F. C.F.
=CFCFs, CFICH=CFCFS, CF
．． -CFCF. CHF! , CFsClhCF”CH
a. CFsCH"CHCFs, CFm"CFChC
Hs, Ch=CFCH*CHs. CFsClbCH-C
Hs. CFsCH"CICHs -CF1=CHCH
ffiCHs, C}! ．． C.F. CH=CH. ．． CFHI
GH=CICFH. , CHsCF*CH”CHi,
C.I. =CFCHyoCHI, CFs(Ch)mcF'c
h. CFs (CF*) scF=cFg etc. (c-8
) Perfluoroalkyl (meth)acrylate: Examples include perfluorobutylethyl methacrylate, perfluoroisononylethyl methacrylate, and perfluorooctylethyl methacrylate. These monomers can be used singly or in a mixture of two or more. (2) An average of 2 or more carboxyl groups or 1 carboxyl group in one molecule
A resin having an average of one carboxyl anhydride group in the molecule,
A resin obtained by reacting an epoxy compound having a functional group (such as a hydroxyl group or an epoxy group) that reacts with the carboxyl group or carboxylic anhydride group with a polysiloxane oligomer. As the resin having a carboxyl group or a carboxylic anhydride group, a polymerizable unsaturated monomer containing a carboxyl group [e.g. (meth)ocrylic acid, maleic acid, crotonic acid, itaconic acid, etc.] or a polymerizable monomer containing a carboxylic anhydride group is used. Homopolymers of saturated monomers [e.g. maleic anhydride, itaconic anhydride, etc.] or copolymers of these monomers with other polymerizable unsaturated monomers (c); polybasic acids [e.g. anhydrous) phthalic acid, isofucric acid, terephthalic acid, azelaic acid, etc.], a polyhydric alcohol (e.g. ethylene glycol, neobentyl glycol 1,6-hexanediol, pentaerythritol, glycerin, etc.), and a monobase as necessary. Typical examples include polyester (or alkyd) resins obtained by reacting acids, monohydric alcohols, etc. so that they have carboxyl groups. As the hydroxyl group-containing epoxy compound, the following general formula (49) is used.
Compounds represented by (59) can be mentioned. R eye 1 CHI-C-R”OH\/O (49) In each formula, R1, R14, R16 have the same meaning. Specific examples of general formulas (49) to (59) include, for example, H Rl8 and Examples of W include the compounds CH.-C-CH.-OH \/ 0 represented by the above. Examples of the polyepoxy compounds include the following general formulas (60) to (6
Examples include compounds represented by 7). 0 0 In the formula, R9, R'' have the same meanings. Specific examples of general formulas (60) to (67) include, for example, R'' and W are the same R as above, and the compound (64) etc. can be mentioned. In addition to the above, for example, the following can be used. Adducts with anate compounds (Polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate or isophorone diisocyanate R: Organic diisocyanates themselves such as aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or adducts of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc.; Polymers of each organic diisocyanate as mentioned above, as well as isocyanate biuret bodies, etc., can be mentioned, and examples of typical commercial products thereof include "Parnock D-750, -
800. DN-950, -970 or l5-455
J [The above are products of Dainippon Ink and Chemicals], “Desmodule L.NHL, IL or N3390J
[West German Bayer product] “Takenate D-10
2, -202, -110N or -123NJ [
Takeda Pharmaceutical ■Product], “Coronate L%HL.EH or 203J
該化合物はアルミニウム、亜鉛等の金属にアルキル基、
好ましくはＣＩ１。のアルキル基が結合したものである
．具体的には、例えばトリエチルアルミニウム、ジエチ
ル亜鉛等を挙げることができる．
（２）ルイス酸
金属ハロゲン化物又は金属にハロゲンと他の置換基を共
有する化合物並びにこれらの化合物の錯塩を挙げること
ができる．具体的には、例えばＡｒｃム、ＡＩＣＦ＊
、ＡＩＦｓ． ＡＪ（ＣＪｓｌＣＪｇ、ＡＪ（ＣｔＨｓ
ｌｓＣ７ １ ｓｎ’７’．、ＴｉＣＩ＜ 、ＴｉＢｒ
４、ＴｉＦ４、ＺｒＣム． ＺｒＢｒ４、ＺｒＦ４、Ｓ
ｎＣム． ＦｅＣム． ｓｂｃム、ｓｂｃム， ｐｃム
、ｐｃム、ＧａＣム、ＧａＦａ、ＩｎＦｓ、ＢＣム、Ｂ
Ｂｒｓ． ＢＦｓ ． ＢＦｓ：（ＯＣＪｓｌｇ．ＢＦ
４：（ＯＣＪｓｌｓ、ＢＣＪｓ： ［ＯＣＪｓｌ雪．
ＢＦｓ：ＮＨｓＣＪｓ ． ＢＦｓ：ＮＨ＊ＣＪ４０Ｈ
．ＢＦｓ ：ＮＨＣＨ２ＣＨ＊ＣＨ＠ＣＨ．、ＰＦ ｓ
Ｓ ＋０１ ｍ．（ＣＪｓｌ ４Ｐ＠ＣＨｓＣＯＯｅ
０
（Ｃ４Ｈｌｌｌ ａＰ’ ＣＨｓＣＯＯｅ、（Ｃ４Ｈｓ
ｌ ｓＰ＠ｃＨｓ （ＣＨｓＯｌ ｓＰＯｅ、（ＣＪｓ
）４Ｐ” Ｃ１ｅ、ＴＣ４ Ｈ＊ ｌ ｓ Ｐ， （
Ｃ→丁ｐ、ＣＪｅＰＨｔ 、（ＣＪｓ）ｔＰＨ．
ＮｉＣ７＊［（ＣＪｓ）ｍＰ］ｔ、ＣｏＢｒｔ（（ Ｑ
→−１．． ＋ （：）−＋ｒｐ、ｆｃＪｓｌ４Ｐ’
Ｂ ｅ（ＣＪＪ４、 （Ｃ４ＨＩ） ４ＰｅＢｒｅ（
（トＴＰ ｅＣＨ ＊ Ｉ ｅ等を挙げることができる
．（３）プロトン酸
該プロトン酸としては、具体的には、例えばメタンスル
ホン酸、エタンスルホン酸、トリフロロメ
●タンスルホン酸、ベンゼンスルホン酸、Ｐ一トルエン
スルホン酸等の有機プロトン酸類：リン酸、亜リン酸ホ
スフィン酸、ホスホン酸、硫酸、過塩素酸等の無機プロ
トン酸類を挙げることができる．
（４）アルミニウム化合物
該化合物としては、Ｓ ｉ −０−Ａβ結合を有する化
合物、具体的には例えばアルミニウムアルコキシドとア
ルコキシシランとの反応物及びケイ酸アルミニウムを挙
げることができる．
また上記以外にも酸化アルミニウム等も挙げることがで
きる．
上記硬化反応触媒の中でも金属キレート化合物は硬化性
に優れた塗膜を形成できることからこのものを使用する
ことが好ましい．
（１）〜（３）架橋反応硬化剤の配合量は前記樹脂組成
物、有機液体及び水性液体の固形分１００重量部に対し
て０，０１〜３０１ｉ量部程度とするのが適当である．
この範囲より少ないと架橋反応硬化性が低下する傾向に
あり、又この範囲より多いと硬化物中に残存して耐水性
を低下させる傾向にあるので好ましくない．好ましい配
合量はｏ．ｉ−ｉｏ重量部で、より好ましい配合量は１
〜５重量部である．
また（４）架橋反応硬化剤の配合量は前記樹脂、有機液
体及び水性液体の固形分１００重量部に対して１−ｔｏ
ｏ重量部程度とするのが適当である．この範囲より少な
いと架橋硬化性が低下する傾向にあり、又この範囲より
多いと塗膜の物性が低下する傾向にあるので好ましくな
い．本発明の硬化性組成物は塗料，接着剤、インキ等に
好適に使用できる．塗料としては室温乾燥のものから６
０〜１００℃の低温焼き付け型、１００−１６０℃の高
温焼付型のものまで、巾広く適用できる．被塗物として
は鉄板、プラスチック素材、木材等、従来塗料が塗られ
ているあらゆるものに塗装することができる．自動車車
体の塗装ち本発明の硬化性組成物が好適に適用される例
である．
上塗り塗料としてソリッドカラー、メタリックカラー、
クリヤー塗料などの形で、ウェットオンウェットの塗り
重ね塗装方法（いわゆる２ＣＩＢ塗装）、モノコート塗
装方式などの塗装方式で塗装できる．
自動車車体の中塗り塗料としても、自動車部品としての
各種プラスチックス材や金属部品材用の上塗り用、下塗
り用としても適用できる．本発明の硬化性組成物を塗料
として用いる場合の塗装方法は特に限定がなく、従来の
方法をそのまま用いることができる．例えばエアスプレ
ー静電エアスプレー、エアレススプレー、ベル静電塗装
、ミニベル静電塗装、ロール塗装、八ヶ塗りなどの方法
が適用できる．
本発明の硬化性組成物は、１４０℃以下の低温で容易に
架橋硬化させることができ、例えば、何ら加熱せず常温
で硬化させる場合には、通常８時間〜７日間程度で充分
に硬化させることができ、また４０〜１００℃程度に加
熱する場合には、５分〜３時間程度で充分に硬化させる
ことができる．
本発明において、ポリシロキサン系オリゴマーは該オリ
ゴマー中のアルコール性水酸基と該水酸基と反応する官
能基を有する樹脂とを反応させることによってゲル化増
粘させろことなくさまざまな種類の樹脂に導入すること
ができる．また、該ボリシロキサン系オリゴマー成分を
導入したポリシロキサン含有樹脂は、シロキサン結合を
有する側鎖の存在によって、極めて優れた表面特性を有
するものである．また該ボリシロキサン含有樹脂では、
側鎖のＳｔに結合した官能基は、従来のボリシロキサン
側鎖を有する樹脂におけるＳｉに結合した官能基に比し
て反応性が高く、しかもこの様な官能基が２個以上存在
するので、架橋性が良好であり、他の成分との相溶性も
良好である。
衷思舅
以下，本発明の実施例を示す．
ボリシロキサン系オリゴマーの製造例
オリゴマ−（１）
脱イオン水
３５％塩酸水溶液
１． １３４ｇ
２ｇ
これらの混合物を８０℃、５時間反応させた．得られた
才リゴマーの数平均分子量は２，０００、平均的に１分
子当り１個のアルコール性水酸基と、末端相当部分に４
個の水酸基を有していた．
オリゴマ−（２）
トルエン ４．５００ｇこれらの
混合物を１１７℃で３時間反応させ、脱水した．得られ
たオリゴマーの数平均分子量は７．０００，平均的に１
分子当り１個のアルコール性水酸基と末端相当部分に５
〜１０個の水酸基を有していた．
オリゴマ−（３）
フエニルトリメトキシシラン９．５０４ｇ（４８モル）
と２−ヒドロキシエチルトリアセトキシシラン５００ｇ
（２モル）とをオリゴマ−（１）と同様にして反応さ
せた．得られたオリゴマーの数平均分子量は約５，００
０で、平均的に１分子あたり、１個のアルコール性水酸
基と末端相当部分に５〜１０個のメトキシ基を有してい
た．
樹脂（ａ）の製造例
無水イタコン酸 １１２ｇｎ−プチ
ルメククリレート ６９２ｇアゾビスイソブチ
ロニトリル ３０ｇの混合物を酢酸ブチル中に
滴下し反応を行なって樹脂固形分タ０重量％の樹脂溶液
を得た６反応は１１０℃で行なった．次に
上記樹脂溶液 ２．ＯＯＯｇ前記オリ
ゴマー（１） ２，ＯＯＯｇメチルイソブ
チルケトン ２．０００ｇ上記した混合物を１３
０℃で６時間反応させ樹脂（ａ）溶液Ｃ樹脂固形分５０
重量％）を得た６樹脂は、数平均分子量３９，０００、
及びｌ分子当たりエボキシ基数３９個であった．
樹脂（ｂ）の製造例
ｎ−プチルメククリレート ６９５ｇスチレン
１５０ｇアゾビスイソブチ
ロニトリル ５ｇの混合物を酢酸ブチル中に
滴下し、反応を行なって樹脂固形分５０重量％の樹脂溶
液を得た．反応は１１０℃で行なった．次に、
上記樹脂溶液 ２．Ｏ○Ｏｇ前記オリ
ゴマ−（２） １．４００ｇ璧
Ｏｏ−Ｑ｛．−０−４Ｇ−（Ｇｌｔ）ｓ−Ｏｑ８
２ ８ ５ ｇ
メチルイソブチルケトン １．６８５ｇ上記した
混合物を１００℃で４時間反応させ樹脂（ｂ）溶液（樹
脂固形分５″Ｏ重量％）を得た．樹脂は数平均分子量９
５．０００及び１分子当たりエポキシ基数７６個であっ
た．
樹脂（ｃ）の製造例
トリメチロールプロパン １３７ｇネオベン
チルグリコール ９４５ｇ無水フタル酸
４４４ｇアジビンＷ！
１，００７ｇの混合物を２２０℃で酸価が２
以下になるまで縮合反応させた後、このものに下記のも
のインホロンジイソシアネート ｌ２０ｇメチル
イソブチルケトン １，５００ｇを加え、８０゜
Ｃで３時間反応させ、樹脂固形分５０重量％の樹脂溶液
を得た．次に、
上記樹脂溶液 ２．ＯＯＯｇ２８１ｇ
オリゴマ−（３） １．４５０ｇメチ
ルイソプチルケトン １．７３１ｇ上記混合物を
１４０℃で６時間反応させ，樹脂（ｃ）溶液（樹脂固形
分５０重量％）を得た．Ｉｉｉ４脂は数平均分子量２０
．○Ｏｏ及び１分子当たりエポキシ基３８個であった．
実施例１〜９
前記した樹脂（ａ）〜（ｃ）溶液及び、該樹脂溶液に硬
化反応触媒（樹脂固形分１００重量部に対してそれぞれ
２重量部）を配合し実施例の組成物を得た．
［塗膜性能試験］
実施例１〜９の各組成物を乾燥膜厚約２０μになるよう
に塗装した後、乾燥を行なって、試験に供した．
ゲル分率：乾燥させた塗膜をガラス板から剥がしとりソ
ックスレー抽出器で還流温度でアセトンを用いて６時間
抽出した後、塗膜の残分を重量％で表わした．
塗膜外観：素材はミガキ軟鋼板を用いた。塗面状態の異
常（ツヤボケ、チヂミ、ワレ、ハガレ）の有無を調べた
．
耐酸性：素材はガラス板を用いた．試験片を４０％Ｈ．
ＳＯ．・水溶液（４０℃）中に５時間浸漬し、塗膜外観
（ツヤボケ、白化等）を観察した．
貯蔵安定性：温度４０℃、湿度７０％で開放容器中に入
れて放置したときに増粘しない時間を測定した．
試験結果を第１表に示す．The compound has an alkyl group, a metal such as aluminum or zinc,
Preferably CI1. It is a combination of alkyl groups. Specific examples include triethylaluminum and diethylzinc. (2) Examples include Lewis acid metal halides, compounds in which the metal shares a halogen and other substituents, and complex salts of these compounds. Specifically, for example, Arcum, AICF*
, AIFs. AJ(CJslCJg, AJ(CtHs
lsC7 1 sn'7'. , TiCI< , TiBr
4, TiF4, ZrC. ZrBr4, ZrF4, S
nCmu. FeCmu. sbcm, sbcm, pcm, pcm, GaC, GaFa, InFs, BC, B
Brs. BFs. BFs: (OCJslg.BF
4: (OCJsls, BCJs: [OCJsl snow.
BFs:NHsCJs. BFs:NH*CJ40H
．． BFs: NHCH2CH*CH@CH. , PF s
S +01 m. (CJsl 4P@CHsCOOe 0 (C4Hll aP' CHsCOOe, (C4Hs
l sP@cHs (CHsOl sPOe, (CJs
)4P” C1e, TC4 H* l s P, (
C → Dingp, CJePHt, (CJs)tPH.
NiC7*[(CJs)mP]t, CoBrt((Q
→-1. ．． + (:)-+rp, fcJsl4P'
Be(CJJ4, (C4HI) 4PeBre(
(TP eCH * Ie, etc.) (3) Protonic acids The protonic acids include, for example, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, P Organic protonic acids such as monotoluenesulfonic acid; examples include inorganic protonic acids such as phosphoric acid, phosphorous phosphinic acid, phosphonic acid, sulfuric acid, perchloric acid, etc. (4) Aluminum compounds The compounds include Si Compounds having -0-Aβ bonds, specifically, for example, reaction products of aluminum alkoxide and alkoxysilane, and aluminum silicate can be mentioned. In addition to the above, aluminum oxide and the like can also be mentioned. The above-mentioned curing reaction Among the catalysts, it is preferable to use metal chelate compounds because they can form a coating film with excellent curability. It is appropriate that the amount is about 0.01 to 301 parts by weight per 100 parts by weight of the solid content of the aqueous liquid.
If it is less than this range, the crosslinking reaction curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable. The preferred amount is o. In terms of i-io parts by weight, the more preferred amount is 1
~5 parts by weight. (4) The amount of the crosslinking reaction curing agent is 1 to 100 parts by weight of the solid content of the resin, organic liquid, and aqueous liquid.
It is appropriate to use approximately 0 parts by weight. If it is less than this range, the crosslinking curability tends to decrease, and if it exceeds this range, the physical properties of the coating film tend to decrease, which is not preferable. The curable composition of the present invention can be suitably used in paints, adhesives, inks, etc. As for paint, 6 types should be dried at room temperature.
It can be applied to a wide range of applications, including low-temperature baking types from 0 to 100℃ and high-temperature baking types from 100 to 160℃. It can be applied to all kinds of objects that are conventionally coated with paint, such as iron plates, plastic materials, and wood. This is an example in which the curable composition of the present invention is suitably applied to the painting of automobile bodies. Solid color, metallic color,
It can be painted in the form of clear paint, etc., using a wet-on-wet layering method (so-called 2CIB painting), a monocoat method, and other painting methods. It can be used as an intermediate coating for automobile bodies, and as a top coat or undercoat for various plastic materials and metal parts used as automobile parts. When the curable composition of the present invention is used as a coating material, there are no particular limitations on the coating method, and conventional methods can be used as is. For example, methods such as air spray electrostatic air spray, airless spray, Bell electrostatic coating, Mini Bell electrostatic coating, roll coating, and Yatsuka coating can be applied. The curable composition of the present invention can be easily crosslinked and cured at a low temperature of 140°C or lower. For example, when it is cured at room temperature without any heating, it is usually sufficiently cured in about 8 hours to 7 days. Furthermore, when heated to about 40 to 100°C, it can be sufficiently cured in about 5 minutes to 3 hours. In the present invention, the polysiloxane oligomer can be introduced into various types of resins without gelation and thickening by reacting the alcoholic hydroxyl group in the oligomer with a resin having a functional group that reacts with the hydroxyl group. can. Furthermore, the polysiloxane-containing resin into which the polysiloxane oligomer component is introduced has extremely excellent surface properties due to the presence of side chains having siloxane bonds. In addition, in the polysiloxane-containing resin,
The functional group bonded to St in the side chain has higher reactivity than the functional group bonded to Si in conventional polysiloxane side chain resins, and since there are two or more such functional groups, It has good crosslinking properties and good compatibility with other components. Examples of the present invention will be described below. Production example of polysiloxane oligomer Oligomer (1) 35% aqueous hydrochloric acid solution in deionized water 1. 134g 2g These mixtures were reacted at 80°C for 5 hours. The number average molecular weight of the oligomer obtained was 2,000, with an average of 1 alcoholic hydroxyl group per molecule and 4
It had hydroxyl groups. Oligomer (2) Toluene 4.500g The mixture was reacted at 117°C for 3 hours and dehydrated. The number average molecular weight of the obtained oligomer was 7.000, with an average molecular weight of 1
One alcoholic hydroxyl group per molecule and 5 at the terminal corresponding portion.
It had ~10 hydroxyl groups. Oligomer (3) Phenyltrimethoxysilane 9.504g (48mol)
and 500g of 2-hydroxyethyltriacetoxysilane
(2 mol) was reacted in the same manner as oligomer (1). The number average molecular weight of the obtained oligomer was approximately 5,00
On average, each molecule had one alcoholic hydroxyl group and 5 to 10 methoxy groups at the terminal portion. Production example of resin (a) A mixture of 112 g of itaconic anhydride and 692 g of butyl meccrylate and 30 g of azobisisobutyronitrile was added dropwise to butyl acetate for reaction to obtain a resin solution with a resin solid content of 0% by weight. 6 Reactions were conducted at 110°C. Next, the above resin solution 2. OOOg of the above oligomer (1) 2, OOOg of methyl isobutyl ketone 2.000g of the above mixture
React at 0°C for 6 hours Resin (a) Solution C Resin solid content 50
The six resins obtained (weight%) had a number average molecular weight of 39,000,
and the number of epoxy groups per molecule was 39. Production Example of Resin (b) A mixture of 695 g of n-butyl meccrylate, 150 g of styrene, and 5 g of azobisisobutyronitrile was dropped into butyl acetate, and the reaction was carried out to obtain a resin solution with a resin solid content of 50% by weight. The reaction was conducted at 110°C. Next, the above resin solution 2. O○OgOligomer (2) 1.400g Oo-Q{. -0-4G-(Glt)s-Oq8
2 8 5 g
Methyl isobutyl ketone 1.685g The above mixture was reacted at 100°C for 4 hours to obtain a resin (b) solution (resin solid content 5''O wt%).The resin had a number average molecular weight of 9.
5.000 and the number of epoxy groups per molecule was 76. Production example of resin (c) Trimethylolpropane 137g Neobentyl glycol 945g Phthalic anhydride
444g Azibin W!
The acid value of 1,007g of the mixture was 2 at 220℃.
After a condensation reaction until the following was achieved, 20g of inphorone diisocyanate and 1,500g of methyl isobutyl ketone were added to the mixture, and the mixture was reacted at 80°C for 3 hours to obtain a resin solution with a resin solid content of 50% by weight. ．． Next, the above resin solution 2. OOOg 281g Oligomer (3) 1.450g Methyl isoptyl ketone 1.731g The above mixture was reacted at 140°C for 6 hours to obtain a resin (c) solution (resin solid content 50% by weight). III4 fat has a number average molecular weight of 20
．． ○Oo and 38 epoxy groups per molecule. Examples 1 to 9 The above-mentioned resin (a) to (c) solutions and a curing reaction catalyst (2 parts by weight for each 100 parts by weight of resin solid content) were blended into the resin solution to obtain compositions of Examples. Ta. [Coating Film Performance Test] Each of the compositions of Examples 1 to 9 was coated to a dry film thickness of approximately 20 μm, dried, and subjected to a test. Gel fraction: The dried coating film was peeled off from the glass plate and extracted with acetone at reflux temperature using a Soxhlet extractor for 6 hours, and the remaining content of the coating film was expressed in weight %. Paint film appearance: The material used was polished mild steel plate. The presence or absence of any abnormalities in the painted surface condition (blurring, blurring, cracking, peeling) was investigated. Acid resistance: A glass plate was used as the material. The test piece was heated to 40%H.
S.O. - Immersed in an aqueous solution (40°C) for 5 hours and observed the appearance of the paint film (blurring, whitening, etc.). Storage stability: The time without thickening when left in an open container at a temperature of 40°C and a humidity of 70% was measured. The test results are shown in Table 1.
Claims (1)
解性基を有するシラン化合物（Ａ）と、下記一般式（１
） ▲数式、化学式、表等があります▼（１） （式中、Ｒ＾１は炭素数１〜６の２価の炭化水素基、Ｒ
＾２、Ｒ＾３及びＲ＿４は水酸基、加水分解性基もしく
は炭素数１〜８の１価の炭化水素基を示す、但し、Ｒ＾
２、Ｒ＾３及びＲ＾４のすべてが炭素数１〜８の１価の
炭化水素基であることはない。）で示されるシランモノ
マー（Ｂ）とを反応させてなり、且つ、その１分子当り
平均１個のＨＯ−Ｒ＾１−基と、末端相当部分に珪素原
子に直接結合した水酸基及び／又は加水分解性基を平均
２個以上有することを特徴とするポリシロキサン系オリ
ゴマー。 ［２］樹脂が珪素原子に直接結合した水酸基及び／又は
加水分解性基とエポキシ基とを必須官能基成分として含
有し、且つ、該珪素原子に直接結合した水酸基及び／又
は加水分解性基が請求項１項記載のポリシロキサン系オ
リゴマーによって導入されていることを特徴とするポリ
シロキサン系樹脂組成物。 ［３］請求項２項に記載のポリシロキサン系樹脂組成物
に、有機金属化合物、ルイス酸、プロトン酸及びアルミ
ニウム化合物から選ばれる１種以上の硬化反応触媒を含
有することを特徴とする硬化性樹脂組成物。[Scope of Claims] [1] A silane compound (A) having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom, and a compound of the following general formula (1)
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, R^1 is a divalent hydrocarbon group having 1 to 6 carbon atoms, R
^2, R^3 and R_4 represent a hydroxyl group, a hydrolyzable group, or a monovalent hydrocarbon group having 1 to 8 carbon atoms, provided that R^
2, R^3 and R^4 are not all monovalent hydrocarbon groups having 1 to 8 carbon atoms. ), and an average of one HO-R^1- group per molecule thereof, and a hydroxyl group and/or hydration bonded directly to the silicon atom at the terminal corresponding portion. A polysiloxane oligomer having an average of two or more decomposable groups. [2] The resin contains a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom and an epoxy group as essential functional group components, and the hydroxyl group and/or hydrolyzable group directly bonded to the silicon atom A polysiloxane resin composition, characterized in that it is introduced by the polysiloxane oligomer according to claim 1. [3] Curing properties characterized by containing the polysiloxane resin composition according to claim 2, one or more curing reaction catalysts selected from organometallic compounds, Lewis acids, protonic acids, and aluminum compounds. Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24479389A JPH03106936A (en) | 1989-09-20 | 1989-09-20 | Polysiloxane oligomer, polysiloxane resin composition, and curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24479389A JPH03106936A (en) | 1989-09-20 | 1989-09-20 | Polysiloxane oligomer, polysiloxane resin composition, and curable resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03106936A true JPH03106936A (en) | 1991-05-07 |
Family
ID=17124016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24479389A Pending JPH03106936A (en) | 1989-09-20 | 1989-09-20 | Polysiloxane oligomer, polysiloxane resin composition, and curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03106936A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310885A (en) * | 1992-05-07 | 1993-11-22 | Printing Bureau Ministry Of Finance Japan | Alicyclic epoxy resin, production thereof, and ultraviolet-or electron-beam-curable resin composition containing the same |
| JP2006052296A (en) * | 2004-08-11 | 2006-02-23 | Konishi Co Ltd | Curable resin composition and moisture-curable type adhesive composition |
| JP2008518050A (en) * | 2004-10-25 | 2008-05-29 | ダウ・コーニング・コーポレイション | Coating composition containing a carbinol functional silicone resin or an anhydride functional silicone resin |
-
1989
- 1989-09-20 JP JP24479389A patent/JPH03106936A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310885A (en) * | 1992-05-07 | 1993-11-22 | Printing Bureau Ministry Of Finance Japan | Alicyclic epoxy resin, production thereof, and ultraviolet-or electron-beam-curable resin composition containing the same |
| JP2006052296A (en) * | 2004-08-11 | 2006-02-23 | Konishi Co Ltd | Curable resin composition and moisture-curable type adhesive composition |
| JP4676726B2 (en) * | 2004-08-11 | 2011-04-27 | コニシ株式会社 | Curable resin composition and moisture curable adhesive composition |
| JP2008518050A (en) * | 2004-10-25 | 2008-05-29 | ダウ・コーニング・コーポレイション | Coating composition containing a carbinol functional silicone resin or an anhydride functional silicone resin |
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