JP3660077B2 - Curable resin composition and paint containing the same - Google Patents
Curable resin composition and paint containing the same Download PDFInfo
- Publication number
- JP3660077B2 JP3660077B2 JP27877196A JP27877196A JP3660077B2 JP 3660077 B2 JP3660077 B2 JP 3660077B2 JP 27877196 A JP27877196 A JP 27877196A JP 27877196 A JP27877196 A JP 27877196A JP 3660077 B2 JP3660077 B2 JP 3660077B2
- Authority
- JP
- Japan
- Prior art keywords
- curable resin
- resin composition
- silicone
- group
- vinyl polymer
- 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.)
- Expired - Fee Related
Links
- 239000011342 resin composition Substances 0.000 title claims description 41
- 239000003973 paint Substances 0.000 title claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 71
- 229920002554 vinyl polymer Polymers 0.000 claims description 67
- -1 polysiloxane group Polymers 0.000 claims description 59
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 23
- 239000012948 isocyanate Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000005056 polyisocyanate Substances 0.000 claims description 10
- 229920001228 polyisocyanate Polymers 0.000 claims description 10
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 10
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 37
- 239000000178 monomer Substances 0.000 description 19
- 238000001723 curing Methods 0.000 description 18
- 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 14
- 229920000642 polymer Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 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 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000007983 Tris buffer Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 1
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- DZKUKLGGGNLHNY-UHFFFAOYSA-N 1,1-dimethoxybutane Chemical compound CCCC(OC)OC DZKUKLGGGNLHNY-UHFFFAOYSA-N 0.000 description 1
- XPIJMQVLTXAGME-UHFFFAOYSA-N 1,1-dimethoxycyclohexane Chemical compound COC1(OC)CCCCC1 XPIJMQVLTXAGME-UHFFFAOYSA-N 0.000 description 1
- UIOXNNAWANDJCZ-UHFFFAOYSA-N 1,1-dimethoxypropane Chemical compound CCC(OC)OC UIOXNNAWANDJCZ-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
- ZVDJGAZWLUJOJW-UHFFFAOYSA-N 1-(4-ethenylphenyl)ethyl-trimethoxysilane Chemical compound CO[Si](OC)(OC)C(C)C1=CC=C(C=C)C=C1 ZVDJGAZWLUJOJW-UHFFFAOYSA-N 0.000 description 1
- PVDLDPULAQGSCP-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;1,1,2-trifluoroethene Chemical group FC=C(F)F.FC(F)=C(F)Cl PVDLDPULAQGSCP-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- DRYJUBPIARAFOC-UHFFFAOYSA-N 2,5-dimethyl-4-oxohexa-2,5-dienoic acid Chemical class CC(=C)C(=O)C=C(C)C(O)=O DRYJUBPIARAFOC-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- MLOKHANBEXWBKS-UHFFFAOYSA-N 3-triacetyloxysilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](OC(C)=O)(OC(C)=O)OC(C)=O MLOKHANBEXWBKS-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、硬化性樹脂組成物に関する。さらに詳しくは、シリコーン変性ビニル系重合体と、イソシアネート化合物と、水酸基含有溶剤とを主成分とする、耐汚染性および耐溶剤性に優れた硬化性樹脂組成物に関するものであり、この硬化性樹脂組成物は塗料、コーティング剤、非粘着剤、表面処理剤、シーリング材などに有用である。
【０００２】
【従来の技術】
従来より、主鎖がビニル系重合体で側鎖にポリシロキサン基、加水分解性シリル基、水酸基、およびカルボン酸基を有する重合体が知られている（特開昭６１−７８８０６）。また、加水分解性シリル基含有ビニル系単量体と水酸基、カルボン酸基、アミノ基等の活性水素を有するビニル系単量体を共重合する場合、重合度のコントロールが出来ず、高重合物が生成する問題があること、およびその重合物は保存安定性に劣るという問題点があることが知られている（特開昭５７−５５９５３）。
【０００３】
更に、加水分解性シリル基を有する重合物を水分により硬化させる際に、有機金属化合物を硬化触媒として使用することは公知である（特開昭５７−５５９５４）が、有機金属化合物を用いてシリコーン変性ビニル系重合体を硬化させる場合、得られる硬化物の耐汚染性能および耐溶剤性能が不充分であるという問題点がある。
【０００４】
【発明が解決しようとする課題】
本発明者らは上記問題を解決するために鋭意検討を重ねた結果、シリコーン変性ビニル系重合体を重合により製造する際に炭素数が１〜６の溶剤であって、且つ水酸基を有する溶剤を使用すると、重合時の重合コントロールを容易にし、更に製造したシリコーン変性ビニル系重合体の保存安定性が高まることを知得した。従来、水酸基含有溶剤はイソシアネート化合物の硬化不良物質として知られており、水酸基を側鎖に持つシリコーン変性ビニル系重合体も同様の性質を示すものと考えられる。ところが、驚くことに本シリコーン変性ビニル系重合体とイソシアネート化合物と炭素数１〜６の水酸基含有溶剤とからなる硬化性樹脂組成物は硬化不良を起こさず、しかも従来より知られている有機金属化合物を用いた加水分解性シリル基架橋によるものよりも硬化が進むために、耐汚染性および耐溶剤性が格段に向上することを見い出し、本発明を完成するに至った。
【０００５】
従って、本発明の目的とするところは、シリコーン変性ビニル系重合体を用いてなる、耐汚染性、耐溶剤性に優れ、取扱容易な硬化性樹脂組成物、及び同硬化性樹脂組成物を含む塗料等を提供することにある。
【０００６】
【課題を解決するための手段】
上記目的を達成するために本発明は、
主鎖がビニル系重合体であると共に側鎖にポリシロキサン基と加水分解性シリル基と水酸基とカルボン酸基とを有するシリコーン変性ビニル系重合体と、炭素数１〜６の水酸基含有溶剤の少なくとも１種と、およびイソシアネート化合物とからなることを特徴とする硬化性樹脂組成物を提案するもので、
シリコーン変性ビニル系重合体の重量平均分子量が５０００〜１５００００であること、
シリコーン変性ビニル系重合体が炭素数１〜６の水酸基含有溶剤の少なくとも１種を含む溶剤中で重合して製造されたものであること、
水酸基含有溶剤がイソプロピルアルコールであること、
シリコーン変性ビニル系重合体の水酸基とポリイソシアネート化合物のＮＣＯ基の比率が１／０．２〜１／１．５であることを含む。
【０００７】
また、本発明は上記硬化性樹脂組成物の塗料用硬化性樹脂組成物としての使用である。
【０００８】
更に、本発明は上記硬化性樹脂組成物を含む塗料である。
【０００９】
また更に、本発明は上記硬化性樹脂組成物を含む金属被覆用硬化性樹脂組成物である。
【００１０】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【００１１】
本発明硬化性樹脂組成物の特徴は、主鎖がビニル系重合体で側鎖にポリシロキサン基、加水分解性シリル基、水酸基およびカルボン酸基を有するシリコーン変性ビニル系重合体を、イソシアネート化合物の硬化不良の原因物質である水酸基含有溶剤の存在下に、イソシアネート化合物を用いて硬化させることにある。
【００１２】
主鎖がビニル系重合体で側鎖にポリシロキサン基、加水分解性シリル基、水酸基およびカルボン酸基を有するシリコーン変性ビニル系重合体は、
（１）ビニル基含有ポリシロキサン、
（２）ビニル基含有シラン化合物、
（３）水酸基を含有するビニル化合物、
（４）カルボン酸を含有するビニル化合物、及び
（５）その他の重合性ビニル化合物
の５種類の単量体を重合させること等により得られる。
【００１３】
（１）のビニル基含有ポリシロキサンとしては、下記一般式（ａ）
【００１４】
【化１】
側鎖のメチル基がフェニル基に一部置換された片末端ビニル基含有ポリシロキサン、または
下記一般式、
【００１５】
【化２】
メチル基がフェニル基に一部置換された両末端ビニル基含有ポリシロキサンが挙げられる。
【００１６】
ここで、Ｒ1の具体的な基としては
【００１７】
【化３】
【００１８】
ビニル基含有ポリシロキサンの具体例としては片末端もしくは両末端ビニルジメチルポリシロキサン、片末端もしくは両末端メタクリロキシプロピルジメチルポリシロキサン、メタクリル酸トリス（トリメチルシロキシ）シリルプロピル等が挙げられる。
【００１９】
これらのビニル含有ポリシロキサンの粘度範囲は３〜１０００（１０-3Ｐａ・ｓ）程度が好ましい。重量平均分子量は２００〜１０００００の範囲にあることが好ましい。
【００２０】
ビニル基含有ポリシロキサンの使用割合は重合に使用する全単量体の０．１〜２０重量％が好ましく、またビニル基含有ポリシロキサンを２種以上併用して使用しても良い。ビニル系重合体の側鎖にポリシロキサン鎖を組み込むことにより、すべり性、はっ水性、離型性、柔軟性等を付与することができる。
【００２１】
（２）のビニル基含有シラン化合物としては、ケイ素原子に直結したビニル基と、更にケイ素原子に直結した加水分解性の官能基を１乃至３個有する化合物である。官能基としては、特に限定されないが、炭素数１から４のアルコキシ基、またはアセトキシ基が使用し易く、且つ好ましい結果が得られる。
【００２２】
このような加水分解性シリル基を含むビニル基含有シラン化合物の具体例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、メチルビニルジメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルメチルジメトキシシラン、γ−アクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルジメチルメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、ビニルトリアセトキシシラン、γ−メタクリロキシプロピルトリアセトキシシラン、スチリルトリメトキシシラン、スチリルメチルジメトキシラン、スチリルエチルトリメトキシシラン等が挙げられる。
【００２３】
シリコーン変性ビニル系重合体の側鎖に導入された加水分解性のシリル基は、空気中の水分により加水分解を受け、活性なシラノール基となり、そのシラノール基がシラノール基同士および／またはアルコキシシリル基と縮合反応をするために樹脂の架橋成分として利用できる。また、この架橋反応で生成するシロキサン結合は結合エネルギーが高いため、耐候性に優れている。一方、アルコキシシリル基は無機物表面の水酸化物あるいは吸着水とカップリング反応をするので、更に密着性が向上する等の利点もある。
【００２４】
上記のシラン化合物は、少なくとも１種以上を使用することができ、使用割合は、全単量体の１〜２５重量％が好ましい。１重量％未満では、得られる硬化性樹脂の無機物に対する密着性および耐候性に劣る傾向にある。使用割合が、３０重量％を越えると、得られるシリコーン変性ビニル系重合体の保存安定性が低下する傾向にある。
【００２５】
（３）の水酸基を含有するビニル化合物としては、メタクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシブチル、メタクリル酸ポリエチレングリコール、メタクリル酸グリセロール等の水酸基含有のメタクリル酸エステル類、アクリル酸２−ヒドロキシエチル、アクリル酸２−ヒドロキシブチル、アクリル酸ポリプロピレングリコール、アクリル酸２−ヒドロキシ−３−フェニルオキシプロピル等のアクリル酸エステル類、ヒドロキシエチルビニルエーテル、ヒドロキシプロピルビニルエーテル等のビニルエーテル類などが挙げられる。
【００２６】
これらの水酸基含有ビニル化合物は、少なくとも１種以上が使用され、使用割合は全単量体の５〜３０重量％が好ましい。ビニル系重合体の側鎖に組み込まれた水酸基により、イソシアネート化合物等の硬化剤によって架橋硬化が可能となる。
【００２７】
（４）のカルボン酸を含有するビニル化合物としては、アクリル酸、メタクリル酸、マレイン酸、イタコン酸及び酸無水物である無水マレイン酸などを挙げることができる。カルボン酸基含有ビニル化合物系の単量体を添加、重合することにより、得られる硬化性樹脂の付着性及び他樹脂をブレンドする際の相溶性、顔料などの無機フィラーの分散性の向上を図ることができる。また、ビニル系単量体の中でも、エポキシ基を含有するビニル単量体を使用した場合に、この官能基と加熱することにより熱架橋させることもできる。このカルボン酸基含有ビニル系単量体の使用割合は、全単量体の０．１〜５重量％が好ましい。
【００２８】
（５）の、その他の重合性ビニル化合物としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシルのようなアクリル酸エステル類、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−ブチル、メタクリル酸シクロヘキシル、メタクリル酸グリシジル、メタクリル酸ジメチルアミノエチル、メタクリル酸ラウリル、メタクリル酸ステアリルのようなメタクリル酸エステル類及びスチレン、α−メチルスチレン、クロロメチルスチレンのようなスチレン類、メチルビニルエーテル、ｎ−ブチルビニルエーテル、シクロヘキシルビニルエーテルのようなビニルエーテル類、酢酸ビニル、安息香酸ビニルのようなビニルエステル類、フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、クロロトリフルオロエチレン、フルオロアルキルトリフルオロエチレンのようなフルオロオレフィン類、エチレン、プロピレン、塩化ビニルのようなオレフィン類などが挙げられる。これらの単量体は、単独で使用することもできるが、２種以上を組み合わせて使用することが好ましい。
【００２９】
使用割合は、全単量体の２０〜９０重量％が好ましいが、特に５０〜８０重量％が好ましい。
【００３０】
上記（１）〜（５）の単量体を重合してシリコーン変性ビニル系重合体を製造する際の重合反応においては、重合時に高重合物の発生を抑制するため、及び得られた重合体の保存安定性を向上させるために、炭素数１〜６の水酸基含有溶剤の少なくとも一種を必須成分として共存させるものである。
【００３１】
重合の際の上記水酸基含有溶剤の使用量は、全単量体重量に対して０．２〜２倍量とすることが望ましい。
【００３２】
水酸基含有溶剤としては、メタノール、エタノール、１−プロパノール、イソプロパノール、１−ブタノール、イソブタノール、２−ブタノール、２−メチル−２−プロパノール、１−ペンタノール、３−ペンタノール、４−メチル−２−ペンタノール、１−ヘキサノール、シクロヘキサノールのような炭素数１〜 のアルキルアルコール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、３−メトキシブタノール、３−メチル−３−メトキシブタノール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルのようなエーテルアルコールなどが挙げられる。
【００３３】
これらの水酸基含有溶剤の１種または２種以上を組み合わせた水酸基含有溶剤だけで重合をすることもできるが、さらに反応溶剤として、トルエン、キシレン、ｎ−ヘキサン、シクロヘキサンのような炭化水素類、酢酸エチル、酢酸ブチルのような酢酸エステル類、セロソルブアセテート、プロピレングリコールメチルエーテルアセテートのようなエーテル類、アセトン、メチルエチルケトン、アセト酢酸エチル、アセチルアセトン、メチルイソブチルケトン、ジアセトンアルコールのようなケトン類を水酸基含有溶剤と併用して重合することもできる。
【００３４】
上記単量体を用いてシリコーン変性ビニル系重合体を製造する重合方法としては、溶液重合が好ましい。即ち、攪拌装置、還流冷却器、温度計等を備えた反応容器に、上記溶剤を仕込んでおき、好ましくは５０〜１５０℃の温度で上記単量体各種を混合したものと、重合開始剤とをそれぞれの滴下槽から反応容器に徐々に滴下し反応させる。滴下時間は２〜６時間程度が実用上好ましい。滴下終了後、未反応の単量体を重合させるために、滴下時と同温度もしくは反応温度を上げて数時間加熱を続けても良く、さらに重合開始剤を追加補充してもよい。
【００３５】
重合開始剤としては、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシオクトエート、ｔ−ブチルパーオキシベンゾエートのような有機過酸化物やアゾビスイソブチロニトリル、アゾビスジメチルバレロニトリルのようなアゾ化合物が好適に使用できる。添加量等は公知の方法が適宜参照できる。
【００３６】
得られるシリコ−ン変性ビニル系重合体の重合度は、重量平均分子量で５０００ないし１５００００とする事が好ましい。重合度は、ラジカル発生剤の種類及び使用量、重合温度、及び連鎖移動剤の使用によって調節することができる。連鎖移動剤としては、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、及びγ−メルカプトプロピルトリメトキシシラン等が好適に使用できる。重量平均分子量が５０００未満の場合は、未重合の単量体が残存し易く、好ましくない。一方、重量平均分子量が１５００００を越える場合には、得られる硬化性樹脂組成物は、その塗布時に糸引き等の欠陥を生じることが多い。
【００３７】
以上のようにして本硬化性樹脂組成物に使用するシリコ−ン変性ビニル系重合体を得ることができる。
【００３８】
次に、本発明の硬化性樹脂組成物に使用される硬化剤成分であるイソシアネート化合物について説明する。
【００３９】
イソシアネート化合物の具体例としては、脂肪族系のキシレンジイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネートもしくはこれらの多価アルコール付加タイプ、ビュレットタイプ、トリマータイプ、芳香族系のトリレンジイソシアネート、ジフェニルメタンジイソシアネートのようなポリイソシアネート化合物、およびブロックイソシアネート化合物等が挙げられる。 ポリイソシアネート化合物の代表的な市販品としては、武田薬品工業（株）製の「タケネートＤ−１１０Ｎ、Ｄ−１４０Ｎ、Ｄ−１６０Ｎ、Ｄ−１６５Ｎ９０ＣＸ、Ｄ−１７０Ｎ、Ｄ−１８０Ｎ、Ｄ−１０２、Ｄ−２０２」、日本ポリウレタン工業（株）製の「コロネートＥＨ、ＨＬ、Ｌ」等が挙げられる。ブロックイソシアネート化合物の市販品としては、武田薬品工業（株）製の「タケネートＢ−８１５Ｎ、Ｂ−８２０ＮＳＵ、Ｂ−８４２Ｎ、Ｂ−８４６Ｎ、Ｂ−８７０Ｎ」、日本ポリウレタン工業（株）製の「コロネート２５０７、２５１５」等が挙げられる。
【００４０】
これらはそれぞれ単独で使用することができるが、２種以上併用して使用することもできる。また、水酸基含有溶剤を除く有機溶剤を用いて、適正な粘度になるように希釈して使用することもできる。これらのイソシアネート化合物をシリコーン変性ビニル系重合体の側鎖の水酸基と反応させ、架橋硬化させる。
【００４１】
シリコーン変性ビニル系重合体とイソシアネート化合物の使用割合は、ＯＨ基／ＮＣＯ基の比率で表すことができ、それぞれの使用量はシリコーン変性ビニル系重合体の水酸基価とイソシアネート化合物のＮＣＯ含量とから公知慣用の方法で計算により算出できる。たとえば、ＯＨ／ＮＣＯ＝１の時のシリコーン変性ビニル系重合体１００ｇに対するイソシアネート化合物の必要量は、ＯＨ価／ＮＣＯ含量×７．４９で表される。本発明の硬化性樹脂組成物においては、シリコーン変性ビニル系重合体とイソシアネート化合物との配合量はＯＨ／ＮＣＯ＝１／０．１〜１／２．０とすることが好ましい。
【００４２】
イソシアネート化合物の一種であるポリイソシアネート化合物を使用する場合は、ＯＨ／ＮＣＯ比は０．２〜１．５の範囲で配合した方が好ましい結果となる。ＯＨ／ＮＣＯ比が０．２未満では得られる硬化物の耐汚染性、耐溶剤性が劣っており、１．５を超える場合は耐衝撃性等の加工性が劣ることになる。
【００４３】
なお、シリコーン変性ビニル系重合体の硬化剤としてイソシアネート化合物のかわりにメチルエーテル化メラミン、ブチルエーテル化メラミン等のアルコール類でエーテル化したメラミン化合物も使用できるが、耐酸性、耐候性がイソシアネート硬化品より劣ることが多く、この面から好ましくない。
【００４４】
本発明の硬化性樹脂組成物に配合する炭素数１〜６の水酸基含有溶剤は、前記シリコーン変性ビニル系重合体を重合反応により製造するときに用いたものと同様のアルコールが用いられる。ビニル系重合体を重合反応により製造する際に用いる水酸基含有溶媒の使用量が充分の量の場合はあらためて配合する必要がないが、不充分の場合には必要量を硬化性樹脂の製造時に配合すれば良い。
【００４５】
硬化性樹脂組成物中の炭素数１〜６の水酸基含有溶剤の合計配合量はシリコーン変性ビニル系重合体１００重量部に対し２０〜５００重量部とすることが反応性、及び保存性の点で好ましいものである。
【００４６】
本発明の硬化性樹脂組成物は上記のシリコーン変性ビニル系重合体と、イソシアネート化合物と、水酸基含有溶剤とを上記の比率で混合することにより製造するものである。混合方法は公知の方法により、特に制限はない。
【００４７】
上記硬化性樹脂組成物は、必要に応じて、または目的に応じてさらに他の溶剤を添加してもよい。重合時に使用する溶剤でさらに希釈してもよい。特に高温で焼き付け硬化させる場合においては、高沸点の溶剤を添加してもよい。高沸点の溶剤を添加することにより、硬化後の塗膜のレベリング性を向上できることが多い。このような高沸点溶剤としては、ブチルカルビトール、カルビトールアセテート、アミルアセテート、ソルベッソ１００、ソルベッソ１５０、スワゾール１０００、スワゾール１５００、スワゾール１８００、イソホロン、ミネラルスピリットが挙げられる。その他添加可能な添加剤としては、分散剤、消泡剤、増粘剤、沈降防止剤、たれ防止剤、レベリング剤、艶消し剤、擦り傷防止剤、紫外線吸収剤、光安定剤、酸化防止剤、抗菌剤等が挙げられる。それぞれの用途により、使い分けすることが好ましい。
【００４８】
本発明の硬化性樹脂組成物には必要に応じてさらに顔料を添加しても良い。顔料としては、炭酸カルシウム、硫酸バリウム、シリカ、アルミナ、クレイ、タルク、カオリン、アエロジルのような体質顔料、酸化チタン、酸化鉄、カーボンブラック、酸化カドミウム、黄鉛、オーカー、アルミ燐片、透明酸化鉄のような無機顔料、及びアゾ系、アゾレーキ系、フタロシアニン系、イソインドリノン系、キナクリドン系、ジオキサジンバイオレット、ペリノン・ペリレン系のような有機顔料が挙げられる。このような有機顔料は、シリコーン変性ビニル系重合体に直接分散してもよいが、あらかじめ他の有機系樹脂、たとえばアクリル樹脂、ポリエステル樹脂またはセルロースアセテートブチレートなどを使用してそのマスターバッチにより顔料分散したものとブレンドしてもよい。顔料の使用量は、シリコーン変性ビニル系重合体に使用する固形分１００重量部に対して０．０１〜１００重量部が望ましい。これらの顔料は、塗布される基材の装飾性を向上すること以外に、塗膜の機械的強度を向上させることもできる。
【００４９】
本発明の硬化性樹脂組成物に硬化を促進するために硬化触媒を添加してもよい。硬化触媒としては有機金属化合物、アミン化合物および酸性化合物などが挙げられる。
【００５０】
有機金属化合物の具体例としては、オクチル酸錫、ジ−ｎ−ブチル錫ジオクテート、ジ−ｎ−ブチル錫ジラウレート、ジ−ｎ−オクチル錫ビス（イソオクチルチオグリコレート）、ジ−ｎ−ブチル錫サルファイド、ジ−ｎ−オクチル錫オキサイドのような有機錫化合物、オクテン酸亜鉛、ナフテン酸マグネシウム、もしくはテトライソプロポキシチタン、テトラ−ｎ−ブトキシチタン、イソプロピルトリイソステアロイルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネートのような有機チタニウム化合物、アルミニウムイソプロピレート、アルミニウムトリス（アセチルアセトネート）のような有機アルミニウム化合物等が挙げられる。
【００５１】
アミン化合物としてはトリエチルアミン、エチレンジアミン、ジエチレントリアミン、ジメチルアミノエタノール、イソホロンジアミン等が挙げられる。酸性化合物としてはパラトルエンスルホン酸、ドデシルベンゼンスルホン酸、フタル酸、無水フタル酸、燐酸、モノアルキル燐酸、ジアルキル燐酸またはそれらの有機アミンブロック化合物が挙げられる。
【００５２】
これらの硬化触媒は必要に応じて１種または２種以上併用して使用することができる。使用量は、シリコーン変性ビニル系重合体の固形分１００重量部に対して０．００１〜５重量部が好ましい。添加量が、０．００１重量部未満では硬化促進の効果が少なく、５重量部を越えると硬化時に発生する硬化歪が大きくなって付着性、加工性が低下する傾向にある。
【００５３】
本発明の硬化性樹脂組成物、またはその構成成分であるシリコーン変性ビニル系重合体およびイソシアネート化合物それぞれに脱水剤として加水分解性のエステルを添加することができる。加水分解性のエステルを添加することで、系中の水分を除去でき、保存安定性を一層向上させることができる。この場合の加水分解性のエステルとしては、ジメトキシメタン、１，１−ジメトキシエタン、１，１−ジメトキシプロパン、１，１−ジメトキシブタン、１，１−ジメトキシシクロヘキサン、オルトギ酸メチル、オルトギ酸エチル、オルト酢酸メチル、オルト酢酸エチル、ジメチルジメトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、メチルシリケート、エチルシリケートが挙げられる。
【００５４】
加水分解性エステルの使用量は、シリコーン変性ビニル系重合体およびポリイソシアネートそれぞれ１００重量部に対して、０．１〜５０重量部が好ましい。
【００５５】
以上のようにして、本発明に係わる硬化性樹脂組成物が得られる。本発明の硬化性樹脂組成物を塗布にする際には、ロールコーター法、ブレードコーター法、グラビアコーター法、ビートコーター法、カーテンフローコーター法、浸漬塗布法、及びスプレー塗布法のいづれも可能である。また、硬化性樹脂組成物の硬化に際しては、常温〜３００℃の任意の温度で硬化できるが、６０〜２５０℃の温度で５秒〜６０分加熱硬化することが好ましい。加熱硬化の場合は、加熱温度が高い程加熱時間は短くでき、硬化触媒を併用することでさらに短縮でき得る。
【００５６】
本発明の硬化性樹脂組成物の塗膜の厚みとしては、０．５〜５０μｍが好ましい。たとえば、本発明の硬化性組成物を金属に塗布した場合、０．５μｍ以下では、塗板に干渉縞が発生することが多く、外観上好ましくない。逆に５０μｍを越えると、塗材を加工する際に、塗膜に割れ及び剥がれが、発生し易くなり、好ましくない。
【００５７】
本発明に係わる硬化性樹脂組成物の被塗物としては、金属、無機物、有機物、および複合材料が挙げられる。金属としては、ステンレス、アルミニウム、ブリキ、トタン、軟鋼板、銅、真鍮、各種メッキ鋼鈑およびチタン等が挙げられる。化成処理、アルマイト処理などの表面処理を施した基材でも好適に使用できる。無機物としては、ガラス、モルタル、スレート、コンクリート及び瓦等が挙げられる。有機物としては、表面処理したポリプロピレン、ポリエチレン、アクリル、ポリカーボネート、ポリスチレン、ＰＥＴ、ナイロン、ポリエステル、ゴム、及びエラストマーのようなプラスチック成形品およびこれらをフィルム状に加工した製品などが挙げられる。複合材としてはＦＲＰ、ＦＲＴＰ、積層板および金属と有機物を圧着したサンドイッチ材などが挙げられる。
【００５８】
【実施例】
以下、実施例により本発明を具体的且つ詳細に説明するが、本発明は実施例により限定されるものではない。尚、実施例中の部はいずれも重量部を表すものである。
【００５９】
シリコ−ン変性ビニル系重合体の合成
（合成例１）
攪拌装置、還流冷却器、温度計、窒素ガス導入管を取り付けたフラスコに、イソプロピルアルコール１００部を仕込み、７０℃に加熱した。攪拌、窒素雰囲気下でメタクリル酸メチル４０部、メタクリル酸ｎ−ブチル２０部、メタクリル酸２−ヒドロキシエチル１８部、アクリル酸ｎ−ブチル８部、γ−メタクリロキシプロピルトリメトキシシラン１２部、片末端メタクリロキシプロピルジメチルポリシロキサン（重量平均分子量５５００）１部、メタクリル酸１部及びアゾビスイソブチロニトリル１部の混合液を４時間かけて滴下した。さらにアゾビスイソブチロニトリル１部を酢酸エチル２０部に溶かして添加して同温度で４時間反応を続け、高重合物のない重量平均分子量５３０００のシリコーン変性ビニル系重合体を得た。
【００６０】
この重合体溶液にプロピレングリコールモノメチルエーテル２００部と酢酸エチル８０部を加えて固形分濃度２０％になるように調製した（水酸基価１６ｍｇ／ｇ）。
【００６１】
（合成例２）
攪拌装置、還流冷却器、温度計、窒素ガス導入管を取り付けたフラスコに、イソプロピルアルコール１００部を仕込み、７０℃に加熱した。攪拌、窒素雰囲気下でメタクリル酸メチル４０部、メタクリル酸ｎ−ブチル２４部、メタクリル酸２−ヒドロキシエチル１８部、アクリル酸ｎ−ブチル１０部、γ−メタクリロキシプロピルトリメトキシシラン６部、片末端メタクリロキシプロピルジメチルポリシロキサン（重量平均分子量５５００）１部、メタクリル酸１部、及びアゾビスイソブチロニトリル１部の混合液を４時間かけて滴下した。さらにアゾビスイソブチロニトリル１部を酢酸エチル２０部に溶かして添加し、同温度で４時間反応を続け、高重合物のない重量平均分子量５７０００のシリコーン変性ビニル系重合体を得た。この樹脂溶液にイソプロピルアルコール２００部と酢酸エチル８０部を加えて固形分濃度２０％になるように調製した（水酸基価１６ｍｇ／ｇ）。
【００６２】
（合成例３）
攪拌装置、還流冷却器、温度計、窒素ガス導入管を取り付けたフラスコに、イソプロピルアルコール１００部を仕込み７０℃に加熱した。攪拌、窒素雰囲気下でメタクリル酸メチル４０部、メタクリル酸ｎ−ブチル２０部、メタクリル酸２−ヒドロキシエチル１８部、アクリル酸ｎ−ブチル１０部、γ−メタクリロキシプロピルトリメトキシシラン６部、メタクリル酸トリス（トリメチルシロキシ）シリルプロピル３部、片末端メタクリロキシプロピルジメチルポリシロキサン（重量平均分子量５５００）２部、メタクリル酸１部及びアゾビスイソブチロニトリル１部の混合液を４時間かけて滴下した。さらにアゾビスイソブチロニトリル１部を酢酸エチル２０部に溶かして添加して同温度で４時間反応を続け、高重合物のない重量平均分子量５５０００のシリコーン変性ビニル系重合体を得た。この樹脂溶液にイソプロピルアルコール２００部と酢酸エチル８０部を加えて固形分濃度２０％になるように調製した（水酸基価１６ｍｇ／ｇ）。
【００６３】
（実施例１）
合成例１で得られたシリコーン変性ビニル系重合体１００部に武田薬品工業(株)製のポリイソシアネート化合物（タケネートＤ−１４０Ｎ）を酢酸エチルでＮＶ６０％に調製したもの（ＮＣＯ含量８．６％）を１０部混合し、充分攪拌した。この時のＯＨ／ＮＣＯ比は１／０．７２であった。
【００６４】
（実施例２）
合成例２で得られたシリコーン変性ビニル系重合体１００部に武田薬品工業(株)製のポリイソシアネート化合物（タケネートＤ−１４０Ｎ）を酢酸エチルでＮＶ６０％に調製したもの（ＮＣＯ含量８．６％）を１０部混合し、充分攪拌した。この時のＯＨ／ＮＣＯ比は１／０．７２であった。
【００６５】
（実施例３）
合成例３で得られたシリコーン変性ビニル系重合体１００部に武田薬品工業(株)製のポリイソシアネート化合物（タケネートＤ−１４０Ｎ）を酢酸エチルでＮＶ６０％に調製したもの（ＮＣＯ含量８．６％）を１０部混合し、充分攪拌した。この時のＯＨ／ＮＣＯ比は１／０．７２であった。
【００６６】
（比較例１）
合成例２で得られたシリコーン変性ビニル系重合体１００部に武田薬品工業(株)製のポリイソシアネート化合物（タケネートＤ−１４０Ｎ）を酢酸エチルでＮＶ６０％に調製したもの（ＮＣＯ含量８．６％）を２部混合し、充分攪拌した。この時のＯＨ／ＮＣＯ比は１／０．１４であった。
【００６７】
（比較例２）
合成例２で得られたシリコーン変性ビニル系重合体１００部に武田薬品工業(株)製のポリイソシアネート化合物（タケネートＤ−１４０Ｎ）を酢酸エチルでＮＶ６０％に調製したもの（ＮＣＯ含量８．６％）を２２．５部混合し、充分攪拌した。この時のＯＨ／ＮＣＯ比は１／１．６２であった。
【００６８】
（比較例３）
合成例２で得られたシリコーン変性ビニル系重合体１００部にジブチル錫ジラウレートの４％酢酸エチル溶液を１．５部（０．３ｐｈｒ）混合し、充分攪拌した。
【００６９】
実施例１〜３および比較例１〜３の硬化性樹脂組成物をアルミ板（ＪＩＳＨ４０００ Ａ１０５０Ｐ）にバーコータを用いて乾燥膜厚が７μｍになるように塗り付け、１５０℃で３０分乾燥した後、下記の評価を実施した。結果をまとめて表１に示す。
【００７０】
（耐汚染性）
油性マジックを用いて塗膜面に印字し、３０分経過後にティッシュペーパーで拭き取る。
○：印字跡消失 △：印字跡が僅かに残る ×：印字跡がはっきり残る。
【００７１】
（耐溶剤性１）
キシレンを浸けたフェルトを太平理化工業(株)製のラビングテスターに取り付け荷重１．２ｋｇで１００回塗膜面を往復させ、減少した塗膜の厚みを測定した。膜減りが少ない程耐溶剤性が優れている。
【００７２】
（耐溶剤性２）
メチルエチルケトンを浸けたフェルトを太平理化工業(株)製のラビングテスターに取り付け荷重１．２ｋｇで２０回塗膜面を往復させ、減少した塗膜の厚みを測定した。
【００７３】
（耐衝撃性）
テスター産業(株)製のデュポン式試験器を用いて１／４Ｒの撃ち型と受け台を取り付け、高さ３０ｃｍより３００ｇのおもりを塗膜面に落として変形させた。変形部にセロハンテープを貼り付け素早く剥がし、塗膜剥離の有無を観察した。
○：剥離なし ×：剥離あり
【００７４】
【表１】
【発明の効果】
本発明の硬化性樹脂組成物は上記の構成としたので、保存安定性に優れたものである。更に、得られる硬化物は従来の有機金属による硬化性組成物に比べて耐汚染性、耐溶剤性がより優れている。従って、落書き防止または張り紙防止などを初めとして非粘着な硬化物を得るのに有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a curable resin composition. More particularly, the present invention relates to a curable resin composition having a main component of a silicone-modified vinyl polymer, an isocyanate compound, and a hydroxyl group-containing solvent, and having excellent stain resistance and solvent resistance. The composition is useful for paints, coating agents, non-adhesives, surface treatment agents, sealing materials and the like.
[0002]
[Prior art]
Conventionally, a polymer having a main chain of a vinyl polymer and a side chain containing a polysiloxane group, a hydrolyzable silyl group, a hydroxyl group, and a carboxylic acid group is known (Japanese Patent Laid-Open No. 61-78806). In addition, when copolymerizing a hydrolyzable silyl group-containing vinyl monomer and a vinyl monomer having an active hydrogen such as a hydroxyl group, a carboxylic acid group, or an amino group, the degree of polymerization cannot be controlled, and a high polymer It is known that there is a problem that the polymer is produced, and that the polymer is inferior in storage stability (Japanese Patent Laid-Open No. 57-55953).
[0003]
Furthermore, it is known that an organic metal compound is used as a curing catalyst when a polymer having a hydrolyzable silyl group is cured with moisture (Japanese Patent Laid-Open No. 57-55954). When the modified vinyl polymer is cured, there is a problem that the resulting cured product has insufficient stain resistance and solvent resistance.
[0004]
[Problems to be solved by the invention]
As a result of intensive studies to solve the above problems, the present inventors have found that a solvent having 1 to 6 carbon atoms and a solvent having a hydroxyl group when producing a silicone-modified vinyl polymer by polymerization. It has been found that when used, the polymerization control during polymerization is facilitated, and the storage stability of the produced silicone-modified vinyl polymer is further increased. Conventionally, a hydroxyl group-containing solvent is known as a poorly cured substance of an isocyanate compound, and a silicone-modified vinyl polymer having a hydroxyl group in a side chain is considered to exhibit similar properties. Surprisingly, however, the curable resin composition comprising the silicone-modified vinyl polymer, the isocyanate compound, and the hydroxyl group-containing solvent having 1 to 6 carbon atoms does not cause poor curing, and is a conventionally known organometallic compound. It was found that the stain resistance and the solvent resistance were remarkably improved because the curing proceeded more than by the hydrolyzable silyl group cross-linking using, so that the present invention was completed.
[0005]
Therefore, the object of the present invention includes a curable resin composition that is excellent in stain resistance and solvent resistance and is easy to handle, and the curable resin composition, which uses a silicone-modified vinyl polymer. It is to provide paints and the like.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the present invention
A silicone-modified vinyl polymer having a main chain of a vinyl polymer and having a polysiloxane group, a hydrolyzable silyl group, a hydroxyl group and a carboxylic acid group in the side chain, and at least a hydroxyl group-containing solvent having 1 to 6 carbon atoms Proposing a curable resin composition characterized by comprising one kind and an isocyanate compound,
The weight average molecular weight of the silicone-modified vinyl polymer is 5000 to 150,000,
The silicone-modified vinyl polymer is produced by polymerizing in a solvent containing at least one kind of a hydroxyl group-containing solvent having 1 to 6 carbon atoms,
The hydroxyl group-containing solvent is isopropyl alcohol,
The ratio of the hydroxyl group of the silicone-modified vinyl polymer and the NCO group of the polyisocyanate compound is 1 / 0.2 to 1 / 1.5.
[0007]
Moreover, this invention is use as a curable resin composition for coating materials of the said curable resin composition.
[0008]
Furthermore, this invention is a coating material containing the said curable resin composition.
[0009]
Furthermore, this invention is a curable resin composition for metal coating containing the said curable resin composition.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0011]
The curable resin composition of the present invention is characterized in that a silicone-modified vinyl polymer having a main chain of a vinyl polymer and a side chain having a polysiloxane group, a hydrolyzable silyl group, a hydroxyl group and a carboxylic acid group It is to be cured using an isocyanate compound in the presence of a hydroxyl group-containing solvent which is a causative substance of curing failure.
[0012]
A silicone-modified vinyl polymer having a main chain having a vinyl polymer and a side chain having a polysiloxane group, a hydrolyzable silyl group, a hydroxyl group and a carboxylic acid group,
(1) vinyl group-containing polysiloxane,
(2) vinyl group-containing silane compound,
(3) a vinyl compound containing a hydroxyl group,
(4) a vinyl compound containing a carboxylic acid, and
(5) Other polymerizable vinyl compounds
It is obtained by polymerizing these five types of monomers.
[0013]
As the vinyl group-containing polysiloxane (1), the following general formula (a)
[0014]
[Chemical 1]
One-terminal vinyl group-containing polysiloxane in which the methyl group in the side chain is partially substituted with a phenyl group, or
The following general formula,
[0015]
[Chemical formula 2]
Examples thereof include both-terminal vinyl group-containing polysiloxanes in which methyl groups are partially substituted with phenyl groups.
[0016]
Where R 1 As a specific group of
[0017]
[Chemical 3]
[0018]
Specific examples of the vinyl group-containing polysiloxane include one-end or both-end vinyldimethylpolysiloxane, one-end or both-end methacryloxypropyldimethylpolysiloxane, and tris (trimethylsiloxy) silylpropyl methacrylate.
[0019]
These vinyl-containing polysiloxanes have a viscosity range of 3 to 1000 (10 -3 Pa · s) is preferred. The weight average molecular weight is preferably in the range of 200 to 100,000.
[0020]
The proportion of the vinyl group-containing polysiloxane used is preferably 0.1 to 20% by weight of the total monomers used in the polymerization, and two or more vinyl group-containing polysiloxanes may be used in combination. By incorporating a polysiloxane chain into the side chain of the vinyl polymer, slipperiness, water repellency, releasability, flexibility and the like can be imparted.
[0021]
The vinyl group-containing silane compound (2) is a compound having 1 to 3 vinyl groups directly bonded to silicon atoms and one or more hydrolyzable functional groups directly bonded to silicon atoms. Although it does not specifically limit as a functional group, A C1-C4 alkoxy group or an acetoxy group is easy to use, and a preferable result is obtained.
[0022]
Specific examples of such a vinyl group-containing silane compound containing a hydrolyzable silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, methylvinyldimethoxysilane, and γ-acryloxypropyl. Trimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ -Methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltriacetoxysilane, styryltrimeth Shishiran, styryl methyldimethoxysilane run, styrylethyltrimethoxysilane and the like.
[0023]
The hydrolyzable silyl group introduced into the side chain of the silicone-modified vinyl polymer is hydrolyzed by moisture in the air and becomes an active silanol group, and the silanol group is a silanol group and / or an alkoxysilyl group. It can be used as a crosslinking component of the resin for the condensation reaction. Moreover, since the siloxane bond produced | generated by this crosslinking reaction has high bond energy, it is excellent in weather resistance. On the other hand, since the alkoxysilyl group undergoes a coupling reaction with the hydroxide or adsorbed water on the surface of the inorganic substance, there is an advantage that adhesion is further improved.
[0024]
One or more of the above silane compounds can be used, and the use ratio is preferably 1 to 25% by weight of the total monomers. If it is less than 1% by weight, the resulting curable resin tends to be inferior in adhesion to an inorganic substance and weather resistance. When the use ratio exceeds 30% by weight, the storage stability of the resulting silicone-modified vinyl polymer tends to be lowered.
[0025]
Examples of the vinyl compound containing a hydroxyl group (3) include 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, polyethylene glycol methacrylate, glycerol methacrylate, and other hydroxyl group-containing methacrylates, 2-hydroxy acrylate. Examples thereof include acrylic esters such as ethyl, 2-hydroxybutyl acrylate, polypropylene glycol acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, and vinyl ethers such as hydroxyethyl vinyl ether and hydroxypropyl vinyl ether.
[0026]
At least one of these hydroxyl group-containing vinyl compounds is used, and the use ratio is preferably 5 to 30% by weight of the total monomers. The hydroxyl group incorporated in the side chain of the vinyl polymer enables crosslinking and curing by a curing agent such as an isocyanate compound.
[0027]
Examples of the vinyl compound containing a carboxylic acid (4) include acrylic acid, methacrylic acid, maleic acid, itaconic acid and maleic anhydride which is an acid anhydride. Addition and polymerization of carboxylic acid group-containing vinyl compound-based monomers improve adhesion of the resulting curable resin, compatibility when blending with other resins, and dispersibility of inorganic fillers such as pigments be able to. Further, among vinyl monomers, when a vinyl monomer containing an epoxy group is used, it can be thermally crosslinked by heating with this functional group. The use ratio of the carboxylic acid group-containing vinyl monomer is preferably 0.1 to 5% by weight of the total monomers.
[0028]
As other polymerizable vinyl compounds of (5), acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacryl Methacrylic acid esters such as n-butyl acid, cyclohexyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, lauryl methacrylate, stearyl methacrylate, and styrenes such as styrene, α-methylstyrene, chloromethylstyrene, Vinyl ethers such as methyl vinyl ether, n-butyl vinyl ether and cyclohexyl vinyl ether, vinyl esters such as vinyl acetate and vinyl benzoate, vinyl fluoride, vinylidene fluoride, trifluoroethylene Chlorotrifluoroethylene, fluoroolefins such as fluoroalkyl trifluoroethylene, ethylene, propylene, and the like olefins such as vinyl chloride. These monomers can be used alone, but are preferably used in combination of two or more.
[0029]
The use ratio is preferably 20 to 90% by weight of the total monomer, and particularly preferably 50 to 80% by weight.
[0030]
In the polymerization reaction for producing the silicone-modified vinyl polymer by polymerizing the monomers (1) to (5) above, in order to suppress generation of a high polymer during polymerization, and the obtained polymer In order to improve the storage stability, at least one kind of a hydroxyl group-containing solvent having 1 to 6 carbon atoms coexists as an essential component.
[0031]
The amount of the hydroxyl group-containing solvent used in the polymerization is desirably 0.2 to 2 times the total monomer weight.
[0032]
Examples of the hydroxyl group-containing solvent include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 3-pentanol, and 4-methyl-2. -C1-C1 alkyl alcohols such as pentanol, 1-hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, propylene glycol monomethyl Examples include ether and ether alcohol such as propylene glycol monoethyl ether.
[0033]
Polymerization can be carried out only with a hydroxyl group-containing solvent in which one or more of these hydroxyl group-containing solvents are combined, but as a reaction solvent, hydrocarbons such as toluene, xylene, n-hexane and cyclohexane, acetic acid Acetic acid esters such as ethyl and butyl acetate, ethers such as cellosolve acetate and propylene glycol methyl ether acetate, ketones such as acetone, methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methylisobutylketone and diacetone alcohol Polymerization can also be performed in combination with a solvent.
[0034]
As a polymerization method for producing a silicone-modified vinyl polymer using the monomer, solution polymerization is preferable. That is, the above-mentioned solvent is charged into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, etc., and preferably a mixture of various monomers described above at a temperature of 50 to 150 ° C., a polymerization initiator, Are gradually dropped from each dropping tank into the reaction vessel to cause a reaction. The dropping time is preferably about 2 to 6 hours in practice. After completion of the dropwise addition, in order to polymerize the unreacted monomer, heating may be continued for several hours at the same temperature as the dropwise addition or the reaction temperature, and a polymerization initiator may be additionally replenished.
[0035]
Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, t-butyl peroxyoctate, and t-butyl peroxybenzoate, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile. It can be used suitably. A known method can be appropriately referred to for the addition amount and the like.
[0036]
The degree of polymerization of the resulting silicone-modified vinyl polymer is preferably 5000 to 150,000 in terms of weight average molecular weight. The degree of polymerization can be adjusted by the type and amount of the radical generator, the polymerization temperature, and the use of a chain transfer agent. As the chain transfer agent, n-dodecyl mercaptan, t-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane and the like can be preferably used. When the weight average molecular weight is less than 5,000, an unpolymerized monomer tends to remain, which is not preferable. On the other hand, when the weight average molecular weight exceeds 150,000, the resulting curable resin composition often has defects such as stringing when applied.
[0037]
As described above, the silicone-modified vinyl polymer used in the present curable resin composition can be obtained.
[0038]
Next, the isocyanate compound which is a hardening | curing agent component used for the curable resin composition of this invention is demonstrated.
[0039]
Specific examples of the isocyanate compound include aliphatic xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or polyhydric alcohol addition type, burette type, trimer type, aromatic tolylene diisocyanate, and polyphenyls such as diphenylmethane diisocyanate. An isocyanate compound, a block isocyanate compound, etc. are mentioned. As a typical commercial item of a polyisocyanate compound, “Takenate D-110N, D-140N, D-160N, D-165N90CX, D-170N, D-180N, D-102, manufactured by Takeda Pharmaceutical Co., Ltd.,” D-202 "," Coronate EH, HL, L "manufactured by Nippon Polyurethane Industry Co., Ltd. Commercially available block isocyanate compounds include “Takenate B-815N, B-820NSU, B-842N, B-846N, B-870N” manufactured by Takeda Pharmaceutical Co., Ltd., “Coronate” manufactured by Nippon Polyurethane Industry Co., Ltd. 2507, 2515 "and the like.
[0040]
These can be used alone, but can be used in combination of two or more. Moreover, it can also be used by diluting so that it may become an appropriate viscosity using the organic solvent except a hydroxyl-containing solvent. These isocyanate compounds are reacted with the hydroxyl group of the side chain of the silicone-modified vinyl polymer to be crosslinked and cured.
[0041]
The use ratio of the silicone-modified vinyl polymer and the isocyanate compound can be expressed by the ratio of OH group / NCO group, and the amount used is known from the hydroxyl value of the silicone-modified vinyl polymer and the NCO content of the isocyanate compound. It can be calculated by a conventional method. For example, the required amount of the isocyanate compound with respect to 100 g of the silicone-modified vinyl polymer when OH / NCO = 1 is represented by OH number / NCO content × 7.49. In the curable resin composition of the present invention, the blend amount of the silicone-modified vinyl polymer and the isocyanate compound is preferably OH / NCO = 1 / 0.1 to 1 / 2.0.
[0042]
When a polyisocyanate compound which is a kind of isocyanate compound is used, it is preferable that the OH / NCO ratio is blended in the range of 0.2 to 1.5. If the OH / NCO ratio is less than 0.2, the resulting cured product has poor stain resistance and solvent resistance. If it exceeds 1.5, workability such as impact resistance is poor.
[0043]
In addition, melamine compounds etherified with alcohols such as methyl etherified melamine and butyl etherified melamine can be used as a curing agent for silicone-modified vinyl polymers in place of isocyanate compounds, but the acid resistance and weather resistance are higher than those of isocyanate cured products. It is often inferior and is not preferable from this aspect.
[0044]
As the hydroxyl group-containing solvent having 1 to 6 carbon atoms to be blended in the curable resin composition of the present invention, the same alcohol as that used when the silicone-modified vinyl polymer is produced by a polymerization reaction is used. If the amount of the hydroxyl group-containing solvent used when producing the vinyl polymer by the polymerization reaction is sufficient, there is no need to add it again, but if it is insufficient, the required amount is added when producing the curable resin. Just do it.
[0045]
In terms of reactivity and storage stability, the total amount of the hydroxyl group-containing solvent having 1 to 6 carbon atoms in the curable resin composition is 20 to 500 parts by weight with respect to 100 parts by weight of the silicone-modified vinyl polymer. It is preferable.
[0046]
The curable resin composition of the present invention is produced by mixing the above silicone-modified vinyl polymer, an isocyanate compound, and a hydroxyl group-containing solvent in the above ratio. The mixing method is a known method and is not particularly limited.
[0047]
The curable resin composition may further contain another solvent as necessary or according to the purpose. You may further dilute with the solvent used at the time of superposition | polymerization. Particularly in the case of baking and curing at a high temperature, a solvent having a high boiling point may be added. By adding a high boiling point solvent, the leveling property of the cured coating film can often be improved. Examples of such a high boiling point solvent include butyl carbitol, carbitol acetate, amyl acetate, Solvesso 100, Solvesso 150, Swazol 1000, Swazole 1500, Swazole 1800, isophorone, and mineral spirit. Other additives that can be added include dispersants, defoamers, thickeners, anti-settling agents, anti-sagging agents, leveling agents, matting agents, anti-scratch agents, UV absorbers, light stabilizers, and antioxidants. And antibacterial agents. It is preferable to use properly according to each use.
[0048]
You may add a pigment further to the curable resin composition of this invention as needed. Pigments include calcium carbonate, barium sulfate, silica, alumina, clay, talc, kaolin, Aerosil, and other pigments, titanium oxide, iron oxide, carbon black, cadmium oxide, yellow lead, ocher, aluminum phosphor, transparent oxide Inorganic pigments such as iron, and organic pigments such as azo, azo lake, phthalocyanine, isoindolinone, quinacridone, dioxazine violet, and perinone / perylene. Such an organic pigment may be directly dispersed in the silicone-modified vinyl polymer. However, the pigment may be mixed in advance with a master batch using another organic resin such as an acrylic resin, a polyester resin, or cellulose acetate butyrate. It may be blended with the dispersion. The amount of the pigment used is desirably 0.01 to 100 parts by weight with respect to 100 parts by weight of the solid content used in the silicone-modified vinyl polymer. These pigments can also improve the mechanical strength of the coating film in addition to improving the decorativeness of the substrate to be applied.
[0049]
A curing catalyst may be added to the curable resin composition of the present invention in order to accelerate curing. Examples of the curing catalyst include organometallic compounds, amine compounds and acidic compounds.
[0050]
Specific examples of the organometallic compound include tin octylate, di-n-butyltin dioctate, di-n-butyltin dilaurate, di-n-octyltin bis (isooctylthioglycolate), and di-n-butyltin. Sulfide, organotin compounds such as di-n-octyltin oxide, zinc octenoate, magnesium naphthenate, or tetraisopropoxy titanium, tetra-n-butoxy titanium, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) Examples thereof include an organic titanium compound such as titanate, an aluminum isopropylate, an organic aluminum compound such as aluminum tris (acetylacetonate), and the like.
[0051]
Examples of the amine compound include triethylamine, ethylenediamine, diethylenetriamine, dimethylaminoethanol, and isophoronediamine. Examples of the acidic compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, phthalic acid, phthalic anhydride, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, or organic amine block compounds thereof.
[0052]
These curing catalysts can be used alone or in combination of two or more as required. The amount used is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the solid content of the silicone-modified vinyl polymer. If the addition amount is less than 0.001 part by weight, the effect of promoting the curing is small, and if it exceeds 5 parts by weight, the curing strain generated at the time of curing tends to increase and the adhesion and workability tend to be lowered.
[0053]
A hydrolyzable ester can be added as a dehydrating agent to each of the curable resin composition of the present invention or the silicone-modified vinyl polymer and isocyanate compound which are constituents thereof. By adding a hydrolyzable ester, water in the system can be removed, and the storage stability can be further improved. Examples of hydrolyzable esters in this case include dimethoxymethane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-dimethoxybutane, 1,1-dimethoxycyclohexane, methyl orthoformate, ethyl orthoformate, Methyl orthoacetate, ethyl orthoacetate, dimethyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Examples include trimethoxysilane, γ-aminopropyltriethoxysilane, methyl silicate, and ethyl silicate.
[0054]
The use amount of the hydrolyzable ester is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of each of the silicone-modified vinyl polymer and the polyisocyanate.
[0055]
As described above, the curable resin composition according to the present invention is obtained. When applying the curable resin composition of the present invention, any of roll coater method, blade coater method, gravure coater method, beat coater method, curtain flow coater method, dip coating method, and spray coating method can be used. is there. Moreover, when hardening | curing curable resin composition, although it can harden | cure at normal temperature-300 degreeC arbitrary temperature, it is preferable to heat-harden at the temperature of 60-250 degreeC for 5 second-60 minutes. In the case of heat curing, the higher the heating temperature, the shorter the heating time, and it can be further shortened by using a curing catalyst in combination.
[0056]
As thickness of the coating film of the curable resin composition of this invention, 0.5-50 micrometers is preferable. For example, when the curable composition of the present invention is applied to a metal, if it is 0.5 μm or less, interference fringes often occur on the coated plate, which is not preferable in appearance. On the other hand, if the thickness exceeds 50 μm, cracking and peeling off of the coating film tend to occur when the coating material is processed, which is not preferable.
[0057]
Examples of the object to be coated with the curable resin composition according to the present invention include metals, inorganic substances, organic substances, and composite materials. Examples of the metal include stainless steel, aluminum, tin plate, tin, mild steel plate, copper, brass, various plated steel plates, and titanium. A substrate subjected to a surface treatment such as a chemical conversion treatment or an alumite treatment can also be suitably used. Examples of the inorganic material include glass, mortar, slate, concrete and roof tile. Examples of the organic substance include plastic molded products such as surface-treated polypropylene, polyethylene, acrylic, polycarbonate, polystyrene, PET, nylon, polyester, rubber, and elastomer, and products obtained by processing these into a film. Examples of the composite material include FRP, FRTP, a laminate, and a sandwich material in which a metal and an organic material are pressure-bonded.
[0058]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely and in detail, this invention is not limited by an Example. In addition, all the parts in an Example represent a weight part.
[0059]
Synthesis of silicone-modified vinyl polymer
(Synthesis Example 1)
A flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet tube was charged with 100 parts of isopropyl alcohol and heated to 70 ° C. Stirring under nitrogen atmosphere 40 parts methyl methacrylate, 20 parts n-butyl methacrylate, 18 parts 2-hydroxyethyl methacrylate, 8 parts n-butyl acrylate, 12 parts γ-methacryloxypropyltrimethoxysilane, one end A mixed solution of 1 part of methacryloxypropyldimethylpolysiloxane (weight average molecular weight 5500), 1 part of methacrylic acid and 1 part of azobisisobutyronitrile was added dropwise over 4 hours. Further, 1 part of azobisisobutyronitrile was dissolved in 20 parts of ethyl acetate and added, and the reaction was continued at the same temperature for 4 hours to obtain a silicone-modified vinyl polymer having a weight average molecular weight of 53,000 and no high polymer.
[0060]
To this polymer solution, 200 parts of propylene glycol monomethyl ether and 80 parts of ethyl acetate were added to prepare a solid content concentration of 20% (hydroxyl value 16 mg / g).
[0061]
(Synthesis Example 2)
A flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet tube was charged with 100 parts of isopropyl alcohol and heated to 70 ° C. Stirring under nitrogen atmosphere 40 parts methyl methacrylate, 24 parts n-butyl methacrylate, 18 parts 2-hydroxyethyl methacrylate, 10 parts n-butyl acrylate, 6 parts γ-methacryloxypropyltrimethoxysilane, one end A mixed solution of 1 part of methacryloxypropyldimethylpolysiloxane (weight average molecular weight 5500), 1 part of methacrylic acid and 1 part of azobisisobutyronitrile was added dropwise over 4 hours. Furthermore, 1 part of azobisisobutyronitrile was dissolved in 20 parts of ethyl acetate and added, and the reaction was continued for 4 hours at the same temperature to obtain a silicone-modified vinyl polymer having a weight average molecular weight of 57,000 and no high polymer. To this resin solution, 200 parts of isopropyl alcohol and 80 parts of ethyl acetate were added to prepare a solid concentration of 20% (hydroxyl value 16 mg / g).
[0062]
(Synthesis Example 3)
A flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet tube was charged with 100 parts of isopropyl alcohol and heated to 70 ° C. Stirring under a nitrogen atmosphere 40 parts methyl methacrylate, 20 parts n-butyl methacrylate, 18 parts 2-hydroxyethyl methacrylate, 10 parts n-butyl acrylate, 6 parts γ-methacryloxypropyltrimethoxysilane, methacrylic acid A mixed solution of 3 parts of tris (trimethylsiloxy) silylpropyl, 2 parts of one-end methacryloxypropyldimethylpolysiloxane (weight average molecular weight 5500), 1 part of methacrylic acid and 1 part of azobisisobutyronitrile was added dropwise over 4 hours. . Further, 1 part of azobisisobutyronitrile was dissolved in 20 parts of ethyl acetate and added, and the reaction was continued for 4 hours at the same temperature to obtain a silicone-modified vinyl polymer having a weight average molecular weight of 55000 and no high polymer. To this resin solution, 200 parts of isopropyl alcohol and 80 parts of ethyl acetate were added to prepare a solid concentration of 20% (hydroxyl value 16 mg / g).
[0063]
(Example 1)
A polyisocyanate compound (Takenate D-140N) manufactured by Takeda Pharmaceutical Co., Ltd. was prepared to NV 60% with ethyl acetate (NCO content 8.6%) to 100 parts of the silicone-modified vinyl polymer obtained in Synthesis Example 1. ) Was mixed and thoroughly stirred. The OH / NCO ratio at this time was 1 / 0.72.
[0064]
(Example 2)
To 100 parts of the silicone-modified vinyl polymer obtained in Synthesis Example 2, a polyisocyanate compound (Takenate D-140N) manufactured by Takeda Pharmaceutical Co., Ltd. was prepared with ethyl acetate to NV 60% (NCO content 8.6%) ) Was mixed and thoroughly stirred. The OH / NCO ratio at this time was 1 / 0.72.
[0065]
(Example 3)
To 100 parts of the silicone-modified vinyl polymer obtained in Synthesis Example 3, a polyisocyanate compound (Takenate D-140N) manufactured by Takeda Pharmaceutical Co., Ltd. prepared with ethyl acetate to NV 60% (NCO content 8.6%) ) Was mixed and thoroughly stirred. The OH / NCO ratio at this time was 1 / 0.72.
[0066]
(Comparative Example 1)
To 100 parts of the silicone-modified vinyl polymer obtained in Synthesis Example 2, a polyisocyanate compound (Takenate D-140N) manufactured by Takeda Pharmaceutical Co., Ltd. was prepared with ethyl acetate to NV 60% (NCO content 8.6%) ) Was mixed and sufficiently stirred. The OH / NCO ratio at this time was 1 / 0.14.
[0067]
(Comparative Example 2)
To 100 parts of the silicone-modified vinyl polymer obtained in Synthesis Example 2, a polyisocyanate compound (Takenate D-140N) manufactured by Takeda Pharmaceutical Co., Ltd. was prepared with ethyl acetate to NV 60% (NCO content 8.6%) 22.5 parts) and mixed well. The OH / NCO ratio at this time was 1 / 1.62.
[0068]
(Comparative Example 3)
To 100 parts of the silicone-modified vinyl polymer obtained in Synthesis Example 2, 1.5 parts (0.3 phr) of a 4% ethyl acetate solution of dibutyltin dilaurate was mixed and sufficiently stirred.
[0069]
The curable resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were applied to an aluminum plate (JISH4000 A1050P) using a bar coater so that the dry film thickness was 7 μm, and dried at 150 ° C. for 30 minutes. The following evaluation was performed. The results are summarized in Table 1.
[0070]
(Contamination resistance)
Print on the surface of the coating film using an oil-based magic, and wipe with tissue paper after 30 minutes.
○: Disappearance of print marks Δ: Print marks remain slightly ×: Print marks remain clearly.
[0071]
(Solvent resistance 1)
The felt soaked in xylene was attached to a rubbing tester manufactured by Taihei Rika Kogyo Co., Ltd., and the coating film surface was reciprocated 100 times with a load of 1.2 kg, and the thickness of the reduced coating film was measured. The smaller the film loss, the better the solvent resistance.
[0072]
(Solvent resistance 2)
A felt soaked with methyl ethyl ketone was attached to a rubbing tester manufactured by Taihei Rika Kogyo Co., Ltd., and the coating film surface was reciprocated 20 times with a load of 1.2 kg, and the thickness of the reduced coating film was measured.
[0073]
(Impact resistance)
Using a DuPont tester manufactured by Tester Sangyo Co., Ltd., a 1 / 4R shooting mold and a cradle were attached, and a weight of 300 g from a height of 30 cm was dropped on the coating surface to deform it. A cellophane tape was applied to the deformed part and peeled off quickly, and the presence or absence of peeling of the coating film was observed.
○: No peeling ×: With peeling
[0074]
[Table 1]
【The invention's effect】
Since the curable resin composition of the present invention has the above configuration, it has excellent storage stability. Furthermore, the obtained cured product is more excellent in stain resistance and solvent resistance than conventional curable compositions made of organic metals. Therefore, it is useful for obtaining a non-sticky cured product such as prevention of graffiti or sticker.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27877196A JP3660077B2 (en) | 1996-09-30 | 1996-09-30 | Curable resin composition and paint containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27877196A JP3660077B2 (en) | 1996-09-30 | 1996-09-30 | Curable resin composition and paint containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10101765A JPH10101765A (en) | 1998-04-21 |
| JP3660077B2 true JP3660077B2 (en) | 2005-06-15 |
Family
ID=17601964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27877196A Expired - Fee Related JP3660077B2 (en) | 1996-09-30 | 1996-09-30 | Curable resin composition and paint containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3660077B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0989162A4 (en) * | 1998-03-31 | 2002-11-06 | Daicel Chem | THERMOPLASTIC RESIN COMPOSITION, WATER-BASED COMPOSITION, SELF-ADHESIVE, THERMOSENSITIVE ADHESIVE AND THERMOSENSITIVE SHEET |
| DE602004020770D1 (en) * | 2003-06-27 | 2009-06-04 | Dow Corning Toray Co Ltd | COATING COMPOSITION |
| FR2880021B1 (en) * | 2004-12-23 | 2007-02-09 | Rhodia Chimie Sa | ISOCYANATE COMPOSITIONS HAVING GOOD MIXING PROPERTIES AND THE USE OF SILYLATED DERIVATIVES AS ADJUVANTS OF ISOCYANATE COMPOSITIONS, IN PARTICULAR MIXING |
| JP2009298882A (en) * | 2008-06-11 | 2009-12-24 | Dow Corning Toray Co Ltd | Coating agent composition |
| CN112680179B (en) * | 2020-12-25 | 2022-10-28 | 苏州禾川化学技术服务有限公司 | Nano interface treating agent for silicon sulfide rubber and preparation method thereof |
| JP7786123B2 (en) * | 2021-10-18 | 2025-12-16 | 株式会社レゾナック | Resin composition, photosensitive resin composition, cured resin film, color filter, and image display element |
-
1996
- 1996-09-30 JP JP27877196A patent/JP3660077B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10101765A (en) | 1998-04-21 |
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