JP2008255259A - Curable resin composition and coated article applied with the curable resin composition - Google Patents
Curable resin composition and coated article applied with the curable resin composition Download PDFInfo
- Publication number
- JP2008255259A JP2008255259A JP2007100288A JP2007100288A JP2008255259A JP 2008255259 A JP2008255259 A JP 2008255259A JP 2007100288 A JP2007100288 A JP 2007100288A JP 2007100288 A JP2007100288 A JP 2007100288A JP 2008255259 A JP2008255259 A JP 2008255259A
- Authority
- JP
- Japan
- Prior art keywords
- component
- group
- curable resin
- resin composition
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims description 37
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000003086 colorant Substances 0.000 claims abstract description 22
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 3
- -1 acryl polyol Chemical class 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 30
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 229920003002 synthetic resin Polymers 0.000 claims description 8
- 239000000057 synthetic resin Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 26
- 239000000203 mixture Substances 0.000 abstract description 22
- 239000005056 polyisocyanate Substances 0.000 abstract description 19
- 229920001228 polyisocyanate Polymers 0.000 abstract description 19
- 239000003431 cross linking reagent Substances 0.000 abstract description 7
- 230000009257 reactivity Effects 0.000 abstract description 7
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- 238000010186 staining Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 238000001723 curing Methods 0.000 description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 19
- 229920002554 vinyl polymer Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000012948 isocyanate Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 238000011109 contamination Methods 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 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 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- BVNZLSHMOBSFKP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxysilane Chemical compound CC(C)(C)O[SiH3] BVNZLSHMOBSFKP-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- NQQRXZOPZBKCNF-NSCUHMNNSA-N (e)-but-2-enamide Chemical compound C\C=C\C(N)=O NQQRXZOPZBKCNF-NSCUHMNNSA-N 0.000 description 1
- BSSNZUFKXJJCBG-OWOJBTEDSA-N (e)-but-2-enediamide Chemical compound NC(=O)\C=C\C(N)=O BSSNZUFKXJJCBG-OWOJBTEDSA-N 0.000 description 1
- OZDOQMMXEACZAA-NRFIWDAESA-L (z)-4-butoxy-4-oxobut-2-enoate;dibutyltin(2+) Chemical compound CCCCOC(=O)\C=C/C(=O)O[Sn](CCCC)(CCCC)OC(=O)\C=C/C(=O)OCCCC OZDOQMMXEACZAA-NRFIWDAESA-L 0.000 description 1
- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 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
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-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
- UEVZIKFSVBYKAC-UHFFFAOYSA-N 1-(1,1-dibutoxyethoxy)butane Chemical compound CCCCOC(C)(OCCCC)OCCCC UEVZIKFSVBYKAC-UHFFFAOYSA-N 0.000 description 1
- SGJBIFUEFLWXJY-UHFFFAOYSA-N 1-(dibutoxymethoxy)butane Chemical compound CCCCOC(OCCCC)OCCCC SGJBIFUEFLWXJY-UHFFFAOYSA-N 0.000 description 1
- KCHZPZSUZAOTIQ-UHFFFAOYSA-N 1-(ethoxy-methyl-propylsilyl)oxyethyl prop-2-enoate Chemical compound C(C=C)(=O)OC(C)O[Si](OCC)(C)CCC KCHZPZSUZAOTIQ-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-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
- 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- CEYHHQSTMVVZQP-UHFFFAOYSA-N 2-ethenoxyethanamine Chemical compound NCCOC=C CEYHHQSTMVVZQP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- JGBOVFKUKBGAJQ-UHFFFAOYSA-N 2-methylidenebutanediamide Chemical compound NC(=O)CC(=C)C(N)=O JGBOVFKUKBGAJQ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- JMGZKPMMFXFSGK-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl prop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C=C JMGZKPMMFXFSGK-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- HGEKXQRHZRDGKO-UHFFFAOYSA-N 3-tripropoxysilylpropyl prop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C=C HGEKXQRHZRDGKO-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
- OJCJXAFEYLJNRF-UHFFFAOYSA-N 4-ethenylcyclohexa-2,4-dien-1-ol Chemical compound OC1CC=C(C=C)C=C1 OJCJXAFEYLJNRF-UHFFFAOYSA-N 0.000 description 1
- KYQMQSJMTYTXLD-UHFFFAOYSA-N 4-ethenylphenol;prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1.OC1=CC=C(C=C)C=C1 KYQMQSJMTYTXLD-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- LUHRVCWDUSUHMP-FTHVFMQUSA-L 4-o-[[(e)-4-(2-ethylhexoxy)-4-oxobut-2-enoyl]oxy-dioctylstannyl] 1-o-(2-ethylhexyl) (e)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)/C=C/C(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)\C=C\C(=O)OCC(CC)CCCC LUHRVCWDUSUHMP-FTHVFMQUSA-L 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GKEKEUVQLNJSGA-XGVHMZQUSA-L C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C.C(CCC)[Sn+2]CCCC.C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C Chemical compound C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C.C(CCC)[Sn+2]CCCC.C(CCCCC(C)C)C([C@H]([C@H]([C@@H]([C@H](C(=O)[S-])O)O)O)O)(O)CCCCCC(C)C GKEKEUVQLNJSGA-XGVHMZQUSA-L 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
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- UHGHZQYYPSGQDA-UHFFFAOYSA-L dibutyltin(2+);9-methyl-2-(7-methyloctyl)-2-(sulfanylmethyl)decanoate Chemical compound CCCC[Sn+2]CCCC.CC(C)CCCCCCC(CS)(C([O-])=O)CCCCCCC(C)C.CC(C)CCCCCCC(CS)(C([O-])=O)CCCCCCC(C)C UHGHZQYYPSGQDA-UHFFFAOYSA-L 0.000 description 1
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- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 125000003438 dodecyl 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])C([H])([H])* 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- 229960004592 isopropanol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000005722 itchiness Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical class CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 0.000 description 1
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 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 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical group CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、塗料用硬化性樹脂組成物に関するものである。 The present invention relates to a curable resin composition for paints.
従来、建築物を保護したり、意匠性を付与する目的で塗料は使用され、中でもアクリルウレタン樹脂塗料、アクリルシリコン樹脂塗料、フッ素樹脂塗料は耐候性に優れる塗料として定着している。また一方で、排気ガス等の都市型汚染から外観を保護する為に、低汚染型塗料が開発・上市されている。外装用の低汚染型塗料としては、特定のシリコン化合物を用いて塗膜表面を親水性にする手法が一般的であり、その性能を充分に発揮する為に、有機金属化合物をはじめとする触媒が添加される（例えば特許文献１参照）。 Conventionally, paints have been used for the purpose of protecting buildings or imparting design properties. Among them, acrylic urethane resin paints, acrylic silicon resin paints, and fluororesin paints have been established as paints having excellent weather resistance. On the other hand, low-contamination paints have been developed and marketed to protect the appearance from urban pollution such as exhaust gas. As a low-contamination paint for exteriors, a technique to make the coating surface hydrophilic by using a specific silicon compound is common, and in order to fully demonstrate its performance, catalysts such as organometallic compounds are used. Is added (see, for example, Patent Document 1).
水酸基含有樹脂を使用した塗料では、ポリイソシアナート化合物を架橋剤に用いることが一般的であるが、低温時の反応速度が問題となる場合があった。そのために、触媒である有機金属化合物が使用されることがあるが、有機金属化合物とポリイソシアナート化合物を１パックとすると、ポリイソシアナート化合物の高分子量化が起こり、充分な性能が得られなくなったり、ゲル化するなどの問題があった。 In a paint using a hydroxyl group-containing resin, it is common to use a polyisocyanate compound as a cross-linking agent, but the reaction rate at low temperatures may be a problem. For this reason, an organometallic compound as a catalyst may be used. However, when the organometallic compound and the polyisocyanate compound are used in one pack, the polyisocyanate compound has a high molecular weight, and sufficient performance cannot be obtained. Or gelled.
一方、付着性を向上させることを目的にウレタン架橋を併用したアクリルシリコン樹脂塗料が開発されているが、有機金属化合物とポリイソシアナートを共存させるために単官能イソシアナートを配合することで、１パックでも安定な硬化剤組成物が提案されている（例えば特許文献２参照）。
しかしながら、単官能イソシアナートは湿分との反応性が極めて高い為に、安全上問題があったり、該硬化剤組成物を用いた塗料では、塗料用着色剤である種ペンを使用した場合に、調色安定性が低下するなどの問題があった。 However, the monofunctional isocyanate has a very high reactivity with moisture, so there is a safety problem. In the paint using the curing agent composition, when a seed pen which is a colorant for paint is used. There was a problem that the toning stability was lowered.
本発明は、前記のごとき実情に鑑みてなされたものであり、その目的とするところは、架橋剤であるポリイソシアナートと、その触媒である有機金属化合物が安定な１パックの状態となった硬化剤を提供するとともに、安定した調色性を有する塗料組成物および塗装物を提供することである。さらには、水酸基含有樹脂と該硬化剤を使用した塗料において、特定のシリコン化合物を用いることにより、充分な低汚染性を有した低汚染型塗料を提供することが可能となる。 The present invention has been made in view of the circumstances as described above, and the object of the present invention is that a polyisocyanate as a crosslinking agent and an organometallic compound as a catalyst thereof are in a stable one-pack state. A curing agent is provided, and a coating composition and a coated product having stable toning properties are provided. Furthermore, by using a specific silicon compound in a paint using a hydroxyl group-containing resin and the curing agent, it is possible to provide a low-contamination paint having sufficiently low contamination.
水酸基含有塗料用樹脂の架橋剤であるポリイソシアナートと、その触媒である有機金属化合物に対して、メルカプト基含有化合物を配合することで、１パックとして安定な状態の硬化剤が得られることを見出した。また、該硬化剤を使用した塗料組成物は、安定した調色性が得られることを見出した。 By adding a mercapto group-containing compound to a polyisocyanate that is a crosslinking agent for a hydroxyl group-containing coating resin and an organometallic compound that is a catalyst thereof, a stable curing agent can be obtained as one pack. I found it. Moreover, it discovered that the coating composition using this hardening | curing agent was able to obtain the stable toning property.
すなわち本願は、
主鎖末端および／または側鎖に水酸基を含有する樹脂（Ａ）成分１００重量部に対して、一般式（Ｉ）：
（Ｒ１Ｏ）４−ａ−Ｓｉ−Ｒ２ ａ（Ｉ）
（式中、Ｒ１は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基および炭素数７〜１０のアラルキル基から選ばれた１価の炭化水素基、Ｒ２は炭素数１〜１０のアルキル基、炭素数が６〜１０のアリール基および炭素数が７〜１０のアラルキル基から選ばれた１価の炭化水素基、ａは０または１を示す）で表されるシリコン化合物及び／またはその部分加水分解縮合物（Ｂ）成分０〜２００重量部と、塗料用着色剤（Ｃ）成分０．０１〜１５０重量部、イソシアナート基を２個以上含有する化合物（Ｄ）０．１〜５０重量部、有機金属化合物（Ｅ）成分０．０１〜３０重量部およびメルカプト基含有化合物（Ｆ）成分０．０１〜１００重量部を含有してなる硬化性樹脂組成物（請求項１）。
That is, this application
With respect to 100 parts by weight of the resin (A) component containing a hydroxyl group at the main chain terminal and / or side chain, the general formula (I):
(R 1 O) 4-a -Si-R 2 a (I)
(In the formula, R 1 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and R 2 has 1 carbon atom. A monovalent hydrocarbon group selected from an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, a represents 0 or 1) And / or its partially hydrolyzed condensate (B) component 0 to 200 parts by weight, coating colorant (C) component 0.01 to 150 parts by weight, compound (D) 0 containing two or more isocyanate groups A curable resin composition comprising 1 to 50 parts by weight, 0.01 to 30 parts by weight of an organometallic compound (E) component and 0.01 to 100 parts by weight of a mercapto group-containing compound (F) component (claim) 1).
前記（Ａ）成分と（Ｂ）成分、（Ｃ）成分が１パック、（Ｄ）成分と（Ｅ）成分、（Ｆ）成分が１パックにされてなる２液型であることを特徴とする請求項１記載の硬化性樹脂組成物（請求項２）。 The (A) component, the (B) component, the (C) component are in one pack, the (D) component, the (E) component, and the (F) component are in one pack. A curable resin composition according to claim 1 (claim 2).
前記（Ａ）成分と（Ｃ）成分が１パック、（Ｂ）成分と（Ｄ）成分、（Ｅ）成分、（Ｆ）成分が１パックにされてなる２液型であることを特徴とする請求項１記載の硬化性樹脂組成物（請求項３）。 The (A) component and the (C) component are one pack, the (B) component and the (D) component, the (E) component, and the (F) component are one pack. A curable resin composition according to claim 1 (claim 3).
塗料用着色剤（Ｃ）が合成樹脂系濃縮型着色剤である請求項１〜３のいずれか一項に記載の硬化性樹脂組成物（請求項４）。 The curable resin composition according to any one of claims 1 to 3, wherein the coating colorant (C) is a synthetic resin-based concentrated colorant.
前記（Ａ）成分が分子内に一般式（ＩＩ）で表される加水分解性基と結合したシリル基および水酸基を含有する樹脂であり、該シリル基を含有する単量体単位を１〜８０重量％含有する共重合体である請求項1〜４のいずれか一項に記載の硬化性樹脂組成物（請求項５）。 The component (A) is a resin containing a silyl group and a hydroxyl group bonded to a hydrolyzable group represented by the general formula (II) in the molecule, and the monomer unit containing the silyl group is represented by 1 to 80 The curable resin composition according to any one of claims 1 to 4, which is a copolymer containing by weight (Claim 5).
Ｒ４ ｂ
｜
−Ｓｉ−（ＯＲ３）３−ｂ （ＩＩ）
（式中、Ｒ３は水素原子または炭素数１〜１０のアルキル基、Ｒ４は水素原子または炭素数１〜１０のアルキル基、炭素数６〜２５のアリール基および炭素数７〜１２のアラルキル基から選ばれた１価の炭化水素基、ｂは０〜２の整数を示す。）
前記（Ａ）成分が、水酸基含有フッ素樹脂および／またはアクリルポリオールである請求項１〜４のいずれか一項に記載の硬化性樹脂組成物（請求項６）。
R 4 b
｜
-Si- (OR 3) 3-b (II)
Wherein R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from the group, b represents an integer of 0 to 2)
The said (A) component is a hydroxyl-containing fluororesin and / or acryl polyol, The curable resin composition as described in any one of Claims 1-4 (Claim 6).
前記（Ａ）成分が前記一般式（ＩＩ）で表される加水分解性基と結合したシリル基および水酸基を含有する樹脂、水酸基含有フッ素樹脂、アクリルポリオールからなる群より選ばれる２種以上の樹脂を組み合わせるものである請求項１〜６のいずれか一項に記載の硬化性樹脂組成物（請求項７）。 Two or more resins selected from the group consisting of a resin containing a silyl group and a hydroxyl group, wherein the component (A) is bonded to the hydrolyzable group represented by the general formula (II), a hydroxyl group-containing fluororesin, and an acrylic polyol A curable resin composition according to any one of claims 1 to 6 (claim 7).
前記（Ｄ）成分中のイソシアナート基が前記（Ａ）成分中の水酸基に対して０．３〜２等量である請求項１〜７のいずれか一項に記載の硬化性樹脂組成物（請求項８）。 The isocyanate group in said (D) component is 0.3-2 equivalent with respect to the hydroxyl group in said (A) component, Curable resin composition as described in any one of Claims 1-7 ( Claim 8).
前記（Ｅ）成分が有機錫化合物である請求項１〜８のいずれか一項に記載の硬化性樹脂組成物（請求項９）。 The said (E) component is an organotin compound, The curable resin composition as described in any one of Claims 1-8 (Claim 9).
前記（Ｅ）成分が分子内にＳ原子を含有する有機錫化合物である請求項１〜９のいずれか一項に記載の硬化性樹脂組成物（請求項１０）。 The curable resin composition according to any one of claims 1 to 9, wherein the component (E) is an organotin compound containing an S atom in the molecule.
請求項１〜１０のいずれか一項に記載の硬化性樹脂組成物を塗布してなる塗装物（請求項１１）。
以上の構成によるものである。
A coated product obtained by applying the curable resin composition according to any one of claims 1 to 10 (claim 11).
This is due to the above configuration.
本発明の硬化性樹脂組成物は、低コスト・簡易な操作で製造できる。特には、水酸基含有塗料用樹脂の一般的な架橋剤であるポリイソシアナート化合物の反応性を向上させる硬化剤を提供することが可能となる。また、該硬化剤を使用した塗料組成物は、安定した調色性が得られる。さらに特定のシリコン化合物を使用した低汚染型塗料の性能を充分に発揮する硬化剤を提供することが可能となる。 The curable resin composition of the present invention can be produced with low cost and simple operation. In particular, it is possible to provide a curing agent that improves the reactivity of a polyisocyanate compound that is a general crosslinking agent for a hydroxyl group-containing coating resin. Moreover, the coating composition using this hardening | curing agent can obtain the stable toning property. Furthermore, it is possible to provide a curing agent that sufficiently exhibits the performance of a low-contamination paint using a specific silicon compound.
以下に本発明をその実施の形態に基づき詳細に説明する。 Hereinafter, the present invention will be described in detail based on an embodiment thereof.
（塗料用樹脂成分）
本発明で使用可能な樹脂（Ａ）成分は、イソシアナート基と反応する官能基である水酸基を含有していればよく、水酸基は主鎖の末端に結合していてもよく、側鎖に結合していてもよく、主鎖の末端および側鎖に結合していてもよい。このような樹脂（Ａ）成分は公知の方法で製造でき、市販品を使用することもできる。また、耐候性、耐薬品性に優れるという観点からアクリル系樹脂を樹脂成分として含有するものであることが好ましい。
(Resin component for paint)
The resin (A) component that can be used in the present invention only needs to contain a hydroxyl group that is a functional group that reacts with an isocyanate group, and the hydroxyl group may be bonded to the end of the main chain and bonded to the side chain. It may be bonded to the end of the main chain and to the side chain. Such a resin (A) component can be manufactured by a well-known method, and a commercial item can also be used for it. Moreover, it is preferable that it is what contains acrylic resin as a resin component from a viewpoint that it is excellent in a weather resistance and chemical resistance.
尚、前記樹脂（Ａ）成分の主鎖が実質的にアクリル共重合鎖からなるとは、樹脂（Ａ）成分の主鎖を構成する単位のうちの５０％以上、さらには７０％以上がアクリル系単量体単位から形成されていることを意味する。 Note that the main chain of the resin (A) component substantially consists of an acrylic copolymer chain means that 50% or more, more than 70% of the units constituting the main chain of the resin (A) component are acrylic. It means that it is formed from monomer units.
前記樹脂（Ａ）成分としては、例えば、加水分解性基と結合したシリル基および水酸基を含有する樹脂（Ａ−イ）や水酸基含有フッ素樹脂（Ａ−ロ）、アクリルポリオール（Ａ−ハ）樹脂などが挙げられる。 Examples of the resin (A) component include a silyl group bonded to a hydrolyzable group and a hydroxyl group-containing resin (AI), a hydroxyl group-containing fluororesin (A-ro), and an acrylic polyol (A-ha) resin. Etc.
（加水分解性基と結合したシリル基および水酸基を含有する樹脂）
前記樹脂（Ａ−イ）成分は、加水分解性シリル基が炭素原子に結合した形式で含有されているため、塗膜の耐水性、耐アルカリ性、耐酸性などが優れたものとなる。
(Resin containing a silyl group and a hydroxyl group bonded to a hydrolyzable group)
Since the resin (A-i) component is contained in a form in which a hydrolyzable silyl group is bonded to a carbon atom, the coating film has excellent water resistance, alkali resistance, acid resistance, and the like.
前記加水分解性基と結合したシリル基は、樹脂（Ａ−イ）成分の主鎖の末端に結合していてもよく、側鎖に結合していてもよく、主鎖の末端および側鎖に結合していてもよい。加水分解性基と結合したシリル基の導入方法としては、加水分解性基と結合したシリル基を含有する単量体をその他単量体と共重合する方法、シリケート化合物を反応させる方法、または水酸基含有共重合体にシリケート化合物を反応させる方法等がある。なかでも簡便な方法は、加水分解性基と結合したシリル基を含有する単量体とその他単量体を共重合する方法である。 The silyl group bonded to the hydrolyzable group may be bonded to the end of the main chain of the resin (A-i) component, may be bonded to the side chain, and may be bonded to the end of the main chain and the side chain. It may be bonded. As a method for introducing a silyl group bonded to a hydrolyzable group, a method of copolymerizing a monomer containing a silyl group bonded to a hydrolyzable group with another monomer, a method of reacting a silicate compound, or a hydroxyl group There is a method of reacting a silicate compound with the containing copolymer. Among these, a simple method is a method of copolymerizing a monomer containing a silyl group bonded to a hydrolyzable group and another monomer.
前記加水分解性基と結合したシリル基における加水分解性基とは、ハロゲン基やアルコキシ基等がある。その中で、反応制御の簡便さから下記一般式（ＩＩ）で表されるアルコキシ基が有用である。 Examples of the hydrolyzable group in the silyl group bonded to the hydrolyzable group include a halogen group and an alkoxy group. Among them, an alkoxy group represented by the following general formula (II) is useful because of easy reaction control.
Ｒ４ ｂ
｜
−Ｓｉ−（ＯＲ３）３−ｂ （ＩＩ）
一般式（ＩＩ）中のＲ３としては、水素原子または炭素数１〜１０のアルキル基、好ましくはたとえばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基などの炭素数１〜４のアルキル基である。前記アルキル基の炭素数が１０を超える場合には、加水分解性シリル基の反応性が低下するようになる。また、一般式（ＩＩ）中のＲ４としては、水素原子または炭素数１〜１０のアルキル基、好ましくは例えば前記 Ｒ３において例示された炭素数１〜４のアルキル基、フェニル基などのアリール基、ベンジル基などのアラルキル基から選ばれた１価の炭化水素基である。これらの中では、本発明の組成物の硬化性が優れるという点から炭素数１〜４のアルキル基が好ましい。
R 4 b
｜
-Si- (OR 3) 3-b (II)
R 3 in the general formula (II) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- An alkyl group having 1 to 4 carbon atoms such as a butyl group. When the carbon number of the alkyl group exceeds 10, the reactivity of the hydrolyzable silyl group is lowered. As the R 4 in formula (II), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably, for example, the exemplified alkyl group having 1 to 4 carbon atoms in R 3, aryl, such as phenyl group And a monovalent hydrocarbon group selected from an aralkyl group such as a benzyl group. In these, the C1-C4 alkyl group is preferable from the point that the sclerosis | hardenability of the composition of this invention is excellent.
前記一般式（ＩＩ）において、（ ＯＲ３）３−ｂは３−ｂが１以上３以下になるように、即ちｂが０〜２になるように選ばれるが、本発明の組成物の硬化性が良好になるという点から、ｂが０または１であることが好ましい。従って、Ｒ４の結合数は０または１であることが好ましい。ＯＲ３またはＲ４の数が複数個の場合は、それらは同一であっても異なっていてもよい。前記一般式（ＩＩ）で表される炭素原子に結合した反応性シリル基の具体例としては、例えば後述の樹脂（Ａ−イ）成分に共重合される加水分解性シリル基含有ビニル系単量体に含有される基が挙げられる。 In the general formula (II), (OR 3 ) 3-b is selected such that 3-b is 1 or more and 3 or less, that is, b is 0 to 2, but the composition of the present invention is cured. B is preferably 0 or 1 from the viewpoint of improving the properties. Therefore, the number of bonds of R 4 is preferably 0 or 1. When the number of OR 3 or R 4 is plural, they may be the same or different. Specific examples of the reactive silyl group bonded to the carbon atom represented by the general formula (II) include, for example, a hydrolyzable silyl group-containing vinyl monomer copolymerized with a resin (A-i) component described later. Examples include groups contained in the body.
次に、樹脂（Ａ−イ）成分の製法の一例について説明する。 Next, an example of a method for producing the resin (A-I) component will be described.
樹脂（Ａ−イ）成分は例えば、加水分解性シリル基含有ビニル系単量体（ａ）成分、水酸基含有ビニル系単量体および／またはその誘導体（ｂ）成分、その他の共重合可能な単量体（ｃ）成分をアゾビスイソブチロニトリルなどのラジカル重合開始剤を用いて溶液重合法などにより共重合することによって製造することができる。 Examples of the resin (A-i) component include a hydrolyzable silyl group-containing vinyl monomer (a) component, a hydroxyl group-containing vinyl monomer and / or its derivative (b) component, and other copolymerizable monomers. It can be produced by copolymerizing the monomer (c) component by a solution polymerization method using a radical polymerization initiator such as azobisisobutyronitrile.
加水分解性シリル基含有ビニル系単量体（ａ）成分の具体例としては、ビニルトリメトキシシラン、ビニルメチルジメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、ビニルトリイソプロポキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルトリ−ｎ−プロポキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、ビニルトリアセトキシシラン、β−（メタ）アクリロキシエチルトリメトキシシラン等が挙げられる。これらの加水分解性シリル基含有ビニル系単量体（ａ）成分は、単独で用いてもよいし、また２種以上を併用しても良い。 Specific examples of the hydrolyzable silyl group-containing vinyl monomer (a) component include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyltris (2-methoxyethoxy) silane. , Vinyltriisopropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxy Propylmethyldiethoxysilane, γ- (meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth) acryloxyethyltrimethoxysilane Etc. It is. These hydrolyzable silyl group-containing vinyl monomers (a) may be used alone or in combination of two or more.
取扱いの容易さ、価格および重合安定性、得られる組成物の硬化性が優れるという点から、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン等が特に好ましい。 Γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- from the viewpoint of easy handling, cost and polymerization stability, and excellent curability of the resulting composition (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and the like are particularly preferable.
加水分解性シリル基含有単量体（ａ）成分は、全単量体１００重量部中に０．１〜５０重量部用いて共重合されることが望ましい。０．１重量部未満では共重合することで期待される耐候性や付着性が低下し、５０重量部を越えると貯蔵安定性が悪化する傾向にある。 The hydrolyzable silyl group-containing monomer (a) component is preferably copolymerized using 0.1 to 50 parts by weight in 100 parts by weight of all monomers. If it is less than 0.1 part by weight, the weather resistance and adhesion expected by copolymerization are lowered, and if it exceeds 50 parts by weight, the storage stability tends to deteriorate.
水酸基含有ビニル系単量体および／またはその誘導体（ｂ）成分の具体例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、２−ヒドロキシエチルビニルエーテル、Ｎ−メチロール（メタ）アクリルアミド、４−ヒドロキシスチレンビニルトルエン、東亞合成化学工業（株）製のアロニクス５７００、４−ヒドロキシスチレン、日本触媒化学工業（株）製のＨＥ−１０、ＨＥ−２０、ＨＰ−１およびＨＰ−２（以上、何れも末端に水酸基を有するアクリル酸エステルオリゴマー）、日本油脂（株）製のブレンマーＰＰシリーズ、ブレンマーＰＥシリーズ、ブレンマーＰＥＰシリーズ等のポリアルキレングリコール（メタ）アクリレート誘導体、水酸基含有化合物とε―カプロラクトンとの反応により得られるε―カプロラクトン変性ヒドロキシアルキルビニル系共重合体化合物ＰｌａｃｃｅｌＦＭ−１、ＦＭ−４（以上ダイセル化学工業（株）製）、ＴＯＮＥＭ−２０１（ＵＣＣ社製）、ＨＥＡＣ−１（ダイセル化学工業（株）製）等のポリカーボネート含有ビニル系化合物などが挙げられる。 Specific examples of the hydroxyl group-containing vinyl monomer and / or its derivative (b) component include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, 4-hydroxystyrene vinyltoluene, Allix 5700, 4- Hydrostyrene, HE-10, HE-20, HP-1 and HP-2 (all of which are acrylate ester oligomers having a hydroxyl group at the terminal) manufactured by Nippon Shokubai Chemical Co., Ltd., manufactured by Nippon Oil & Fats Co., Ltd. Blemmer PP series, Blemmer PE series , Ε-caprolactone-modified hydroxyalkylvinyl copolymer compounds PlaccelFM-1, FM-4 (above Daicel) obtained by reaction of polyalkylene glycol (meth) acrylate derivatives such as Blemmer PEP series, hydroxyl group-containing compounds and ε-caprolactone Examples include polycarbonate-containing vinyl compounds such as Chemical Industry Co., Ltd., Tonemu-201 (UCC), and HEAC-1 (Daicel Chemical Industries, Ltd.).
中でも、イソシアナートとの反応性に優れ、耐候性や耐薬品性、耐衝撃性が良好な塗膜が得られるという点から、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートが好ましい。 Among them, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are excellent in reactivity with isocyanate, and can provide a coating film having excellent weather resistance, chemical resistance, and impact resistance. 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred.
これらの水酸基含有ビニル系単量体および／またはその誘導体（ｂ）成分は、単独で用いてもよいし、また２種以上を併用しても良い。 These hydroxyl group-containing vinyl monomers and / or derivatives (b) thereof may be used alone or in combination of two or more.
また、使用量としては、水酸基当量で３００以上、特には５００以上が好ましい。 The amount used is preferably 300 or more, particularly 500 or more in terms of hydroxyl equivalent.
その他共重合可能な単量体（ｃ）成分の具体例としては、（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、ベンジル（メタ）アクリレート、３，３，５−トリメチルシクロヘキシル（メタ）アクリレート、（メタ）アクリロニトリル、グリシジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、（メタ）アクリルアミド、α−エチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド等のアクリルアミド、（メタ）アクリロイルモルホリン、２−ヒドロキシエチル（メタ）アクリレート、２ーヒドロキシプロピル（メタ）アクリレート、（メタ）アクリル酸のヒドロキシアルキルエステル類とリン酸またはリン酸エステル類との縮合生成物などのリン酸エステル基含有（メタ）アクリル系化合物、ウレタン結合やシロキサン結合を含む（メタ）アクリレートやスチレン、αーメチルスチレン、クロロスチレン、スチレンスルホン酸、４ーヒドロキシスチレン、ビニルトルエンなどの芳香族炭化水素系ビニル化合物；マレイン酸、フマル酸、イタコン酸、（メタ）アクリル酸などの不飽和カルボン酸、これらのアルカリ金属塩、アンモニウム塩、アミン塩などの塩；無水マレイン酸などの不飽和カルボン酸の酸無水物、これら酸無水物と炭素数１〜２０の直鎖状または分岐鎖を有するアルコールまたはアミンとのジエステルまたはハーフエステルなどの不飽和カルボン酸のエステル；酢酸ビニル、プロピオン酸ビニル、ジアリルフタレートなどのビニルエステルやアリル化合物；ビニルピリジン、アミノエチルビニルエーテルなどのアミノ基含有ビニル系化合物；イタコン酸ジアミド、クロトン酸アミド、マレイン酸ジアミド、フマル酸ジアミド、Ｎ−ビニルピロリドンなどのアミド基含有ビニル系化合物；２ーヒドロキシエチルビニルエーテル、メチルビニルエーテル、シクロヘキシルビニルエーテル、塩化ビニル、塩化ビニリデン、クロロプレン、プロピレン、ブタジエン、イソプレン、フルオロオレフィンマレイミド、Ｎ−ビニルイミダゾール、ビニルスルホン酸などのその他ビニル系化合物などが挙げられる。 Specific examples of the copolymerizable monomer (c) component include (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, (meth ) Acrylonitrile, glycidyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl Acrylamides such as (meth) acrylamide and N-methylol (meth) acrylamide, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyalkyl esters of (meth) acrylic acid and Phosphoric acid ester group-containing (meth) acrylic compounds such as condensation products with phosphoric acid or phosphoric acid esters, (meth) acrylates or styrenes containing urethane bonds or siloxane bonds, α-methylstyrene, chlorostyrene, styrenesulfonic acid, Aromatic hydrocarbon vinyl compounds such as 4-hydroxystyrene and vinyltoluene; unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid and (meth) acrylic acid, alkali metal salts, ammonium salts and amine salts thereof of Unsaturated carboxylic acid anhydrides such as maleic anhydride, unsaturated carboxylic acids such as diesters or half esters of these acid anhydrides and linear or branched alcohols or amines having 1 to 20 carbon atoms; Esters; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; amino group-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; itaconic acid diamide, crotonic acid amide, maleic acid diamide, fumaric acid diamide, Amide group-containing vinyl compounds such as N-vinylpyrrolidone; 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoro Les fins maleimide, N- vinylimidazole, like other vinyl compounds such as vinyl sulfonic acid.
これらのその他単量体（ｃ）成分は、単独で用いてもよいし、また２種以上を併用しても良い。 These other monomer (c) components may be used alone or in combination of two or more.
このようにして得られた樹脂（Ａ−イ）成分は、本発明の組成物を用いて形成される塗膜の耐久性などの物性が優れるという点から、数平均分子量が、１０００〜３００００なかんずく３０００〜２５０００であることが好ましい。この際、必要に応じて、例えば、ｎ−ドデシルメルカプタンやγ―メルカプトプロピルトリメトキシシラン、γ―メルカプトプロピルトリエトキシシラン等の連鎖移動剤を使って、分子量を調整してもよい。 The resin (A-i) component thus obtained has a number average molecular weight of 1000 to 30000, in view of excellent physical properties such as durability of a coating film formed using the composition of the present invention. It is preferable that it is 3000-25000. At this time, the molecular weight may be adjusted using a chain transfer agent such as n-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane, if necessary.
（水酸基含有フッ素樹脂）
前記樹脂（Ａ−ロ）成分は、側鎖または末端にフッ素を含有しているため、特に得られる塗膜の耐候性や耐水性などが優れたものとなる。
(Hydroxyl-containing fluororesin)
Since the resin (A-B) component contains fluorine at the side chain or at the terminal, the weather resistance and water resistance of the obtained coating film are particularly excellent.
次に、樹脂（Ａ−ロ）成分の製法の一例について説明する。 Next, an example of a method for producing the resin (A-B) component will be described.
樹脂（Ａ−ロ）成分は、前記水酸基含有ビニル系単量体および／またはその誘導体（ｂ）成分、その他の共重合可能な単量体（ｃ）成分とともに、フッ素含有ビニル系単量体（ｄ）成分を樹脂（Ａ−イ）製造時と同様の方法で共重合することによって製造することができる。また、その際、前記加水分解性シリル基含有ビニル系単量体（ａ）成分を含んでいても構わない。 The resin (A-ro) component is a fluorine-containing vinyl monomer (a) together with the hydroxyl group-containing vinyl monomer and / or its derivative (b) component and other copolymerizable monomer (c) component. d) It can manufacture by copolymerizing a component by the method similar to the time of resin (A-I) manufacture. At that time, the hydrolyzable silyl group-containing vinyl monomer (a) component may be included.
前記フッ素含有ビニル系単量体（ｄ）成分の具体例としては、トリフルオロ（メタ）アクリレート、ペンタフルオロ（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３−テトラフルオロプロピルメタクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレートなどが挙げられる。 Specific examples of the fluorine-containing vinyl monomer (d) component include trifluoro (meth) acrylate, pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoro. Examples thereof include propyl methacrylate and β- (perfluorooctyl) ethyl (meth) acrylate.
これらのフッ素含有ビニル系単量体（ｄ）成分は、単独で用いてもよいし、また２種以上を併用しても良い。 These fluorine-containing vinyl monomer (d) components may be used alone or in combination of two or more.
（アクリルポリオール）
次に、樹脂（Ａ−ハ）成分の製法の一例について説明する。
(Acrylic polyol)
Next, an example of a method for producing the resin (A-C) component will be described.
樹脂（Ａ−ハ）成分は、前記水酸基含有ビニル系単量体および／またはその誘導体（ｂ）成分、その他の共重合可能な単量体（ｃ）成分を樹脂（Ａ−イ）製造時と同様の方法で共重合することによって製造することができる。 Resin (A-ha) component is the above-mentioned hydroxyl group-containing vinyl monomer and / or its derivative (b) component, other copolymerizable monomer (c) component at the time of resin (A-i) production It can be produced by copolymerizing in the same manner.
これら（Ａ−イ）、（Ａ−ロ）、（Ａ−ハ）成分は、２種以上を組み合わせて使用してもよい。 These (A-I), (A-B), and (A-C) components may be used in combination of two or more.
さらに、樹脂（Ａ）成分は可溶型だけではなく、分散安定剤樹脂等を用いた非水系ディスパージョン重合で得られる非水系重合体粒子（ＮＡＤ）の状態で使用してもよい。 Further, the resin (A) component may be used not only in a soluble type but also in a state of non-aqueous polymer particles (NAD) obtained by non-aqueous dispersion polymerization using a dispersion stabilizer resin or the like.
（オルガノシリケート）
本発明においては、前述の樹脂（Ａ）成分とともに、組成物から形成される塗膜の耐汚染性を向上させる目的で一般式（Ｉ）：
（Ｒ１Ｏ）４−ａ−Ｓｉ−Ｒ２ ａ（Ｉ）
（式中、Ｒ１は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基および炭素数７〜１０のアラルキル基から選ばれた１価の炭化水素基、Ｒ２は炭素数１〜１０のアルキル基、炭素数が６〜１０のアリール基および炭素数が７〜１０のアラルキル基から選ばれた１価の炭化水素基、ａは０または１を示す）で表されるシリコン化合物及び／またはその部分加水分解縮合物（Ｂ）成分を（以下、オルガノシリケート化合物（Ｂ）成分という）０〜２００重量部を使用することができる。
(Organosilicate)
In the present invention, together with the above-mentioned resin (A) component, for the purpose of improving the stain resistance of the coating film formed from the composition, the general formula (I):
(R 1 O) 4-a -Si-R 2 a (I)
(In the formula, R 1 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and R 2 has 1 carbon atom. A monovalent hydrocarbon group selected from an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, a represents 0 or 1) And / or its partially hydrolyzed condensate (B) component (hereinafter referred to as the organosilicate compound (B) component) 0 to 200 parts by weight can be used.
オルガノシリケート化合物（Ｂ）成分の具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラ−ｎ−プロポキシシラン、テトラ−ｉ−プロポキシシラン、テトラ−ｎ−ブトキシシラン、テトラ−ｉ−ブトキシシラン、テトラ−ｔ−ブトキシシラン及びそれらの部分加水分解・縮合物が例示できる。中でも得られる塗膜の耐汚染性が優れるという点から、メチルシリケート５１、エチルシリケート４５、エチルシリケート４０、エチルシリケート４８（以上、コルコート（株）製）、シリケート４５、シリケート４０（以上、多摩化学工業（株）製）が望ましい。上記化合物は１種単独でもよく、２種以上を併用しても良い。 Specific examples of the organosilicate compound (B) component include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra Examples thereof include t-butoxysilane and partial hydrolysis / condensates thereof. Among them, methyl silicate 51, ethyl silicate 45, ethyl silicate 40, ethyl silicate 48 (above, manufactured by Colcoat Co., Ltd.), silicate 45, silicate 40 (above, Tama Chemical Co., Ltd.) from the viewpoint that the obtained coating film has excellent contamination resistance. Industrial Co., Ltd.) is desirable. The said compound may be single 1 type, and may use 2 or more types together.
また、同一分子中に異なったアルコキシシリル基を含有するオルガノシリケートも使用可能である。例えば、メチルエチルシリケート、メチルプロピルシリケート、メチルブチルシリケート、エチルプロピルシリケート、プロピルブチルシリケートなどである。これら置換基の比率が０〜１００％の間で任意に変更可能である。また、これらのシリケートの部分加水分解・縮合物も使用可能であると記述したが、縮合度は１〜２０程度が好ましい。更に好ましい縮合度の範囲は、３〜１５である。 Organosilicates containing different alkoxysilyl groups in the same molecule can also be used. For example, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate and the like. The ratio of these substituents can be arbitrarily changed between 0 to 100%. Moreover, although it described that the partial hydrolysis and condensate of these silicates can also be used, about 1-20 are preferable for a condensation degree. A more preferable range of the condensation degree is 3-15.
前記（Ｂ）成分の使用量は、（Ａ）成分１００重量部に対して０〜２００重量部、好ましくは、３〜１５０重量部、より好ましくは５〜１００重量部である。オルガノシリケート化合物（Ｂ）成分の量が２００部を超えると、塗膜が濁るなど外観性が低下したり、クラックが発生したりするので好ましくない。 The amount of component (B) used is 0 to 200 parts by weight, preferably 3 to 150 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of component (A). If the amount of the organosilicate compound (B) component exceeds 200 parts, the coating properties may become cloudy and the appearance may be deteriorated or cracks may be generated.
（塗料用着色剤）
本発明に用いる塗料用着色剤（Ｃ）成分としては、無機または有機の顔料を使用しても良く、所謂種ペンと称される合成樹脂系濃縮型着色剤を使用しても良い。
(Colorant for paint)
As the colorant (C) for paint used in the present invention, an inorganic or organic pigment may be used, or a synthetic resin-based concentrated colorant called a so-called seed pen may be used.
無機顔料の具体例としては酸化チタン、群青、紺青、亜鉛華、ベンガラ、黄鉛、鉛白、カーボンブラック、透明酸化鉄、アルミニウム粉などが挙げられる。有機顔料の具体例としてはアゾ系顔料、キノリン系顔料、アントラキノン系顔料、フタロシアニン系顔料などが挙げられる。 Specific examples of the inorganic pigment include titanium oxide, ultramarine blue, bitumen, zinc white, red rose, yellow lead, white lead, carbon black, transparent iron oxide, and aluminum powder. Specific examples of the organic pigment include azo pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments.
合成樹脂系濃縮型着色剤は、一般に市販されているものも使用することができる。合成樹脂着色剤の使用方法としては、酸化チタン（白）などを使用して作成した白塗料に、該着色剤を添加、混合して目的とする色を作成する方法が一般的である。合成樹脂系濃縮型着色剤の具体例としては、カラーマックスＦＡ（日本ペイント（株）製）、ユニラント（横浜化成（株）製）、ユニバーサル・カララント（ビックケミー・ジャパン（株）製）、ロックトーンカララント（ロックペイント（株）製）などが挙げられる。簡便に調色ができるという点からは、合成樹脂系濃縮型着色剤を使用することが好ましい。 As the synthetic resin-based concentrated colorant, a commercially available product can be used. As a method of using a synthetic resin colorant, a method of creating a desired color by adding and mixing the colorant to a white paint prepared using titanium oxide (white) or the like is general. Specific examples of synthetic resin-based colorants include Color Max FA (manufactured by Nippon Paint Co., Ltd.), Unirant (manufactured by Yokohama Kasei Co., Ltd.), Universal Colorant (manufactured by Big Chemie Japan Co., Ltd.), and Rock Tone. Examples include colorants (manufactured by Rock Paint Co., Ltd.). From the viewpoint of easy color matching, it is preferable to use a synthetic resin-based concentrated colorant.
前記塗料用着色剤（Ｃ）成分の使用量は、（Ａ）成分１００重量部に対して０．０１〜１５０重量部、好ましくは、０．１〜１２０重量部、より好ましくは０．５〜１００重量部である。また、合成樹脂系濃縮型着色剤を白塗料に使用する場合には、その使用量は、白塗料に対して１０重量部以下、さらには5重量部以下であることが好ましい。１０重量部以上使用した場合には、調色に時間がかかったり、耐候性が悪化したりする可能性がある。 The amount of the paint colorant (C) component used is 0.01 to 150 parts by weight, preferably 0.1 to 120 parts by weight, more preferably 0.5 to 100 parts by weight based on 100 parts by weight of the component (A). 100 parts by weight. Further, when the synthetic resin-based concentrated colorant is used for white paint, the amount used is preferably 10 parts by weight or less, more preferably 5 parts by weight or less based on the white paint. When it is used in an amount of 10 parts by weight or more, it may take time for toning or the weather resistance may deteriorate.
（ポリイソシアナート化合物）
本発明においては、架橋剤としてイソシアナート基を２個以上有する化合物（Ｄ）成分（以下、ポリイソシアナート化合物（Ｄ）という）を使用する。前記、ポリイソシアナート化合物（Ｄ）成分としては、脂肪族系もしくは芳香族系のものが挙げられる。
(Polyisocyanate compound)
In the present invention, a compound (D) component having two or more isocyanate groups (hereinafter referred to as polyisocyanate compound (D)) is used as a crosslinking agent. Examples of the polyisocyanate compound (D) component include aliphatic and aromatic compounds.
脂肪族系多官能性イソシアナートの具体例として、ヘキサメチレンジイソシアナート、ジシクロヘキシルメタン４，４‘−イソシアナート、２，２，４−トリメチル−１，６−ジイソシアナート、イソフォロンジイソシアナートがある。 Specific examples of the aliphatic polyfunctional isocyanate include hexamethylene diisocyanate, dicyclohexylmethane 4,4′-isocyanate, 2,2,4-trimethyl-1,6-diisocyanate, and isophorone diisocyanate. There is.
芳香族多官能性イソシアナートとしては、２，４―トリレンジイソシアナート、２，６―トリレンジイソシアナート、ジフェニルメタン−４，４‘−ジイソシアナート、キシレンジイソシアナート、ポリメチレン−ポリフェニレル−ポリイソシアナートなどがある。 Aromatic polyfunctional isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylene diisocyanate, polymethylene-polyphenylene-polyisocyanate. There are naruto.
構造としてはともに単量体、ビュレット型、アダクト型、イソシアヌレート型がある。 The structure includes monomer, burette type, adduct type, and isocyanurate type.
これらの化合物は常温硬化用に用いることができるが、さらにこれらのイソシアナート基をブロック剤でマスクしたものを加熱硬化用に用いることもできる。そのブロック剤としてはメチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソ−プロピルアルコール、ｎ−ブチルアルコール、ｓｅｃ−ブチルアルコール、メチルセルソルブ、エチルセルソルブ、ブチルセルソルブ、ベンジルアルコール、フルフリルアルコール、シクロヘキシルアルコール、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ―クレゾール、ｐ−ｔｅｒｔ−ブチルフェノール、チモール、ｐ−ニトロフェノール、β―ナフトールなどがある。また、これらの化合物は、２種以上混合して用いることもできる。 These compounds can be used for curing at room temperature, but those obtained by masking these isocyanate groups with a blocking agent can also be used for heat curing. As the blocking agent, methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, benzyl alcohol, furfuryl alcohol, Examples include cyclohexyl alcohol, phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, thymol, p-nitrophenol, and β-naphthol. Moreover, these compounds can also be used in mixture of 2 or more types.
前記、ポリイソシアナート化合物（Ｄ）の使用量は、（Ａ）成分１００重量部に対して０．１〜５０重量部である。５０重量部以上の場合には、硬化剤のハンドリング性が低下する。また、前記ポリイソシアナート化合物（Ｄ）成分の使用量は、樹脂（Ａ）成分中の水酸基に対してイソシアナート基が好ましくは０．３〜２等量、さらに好ましくは０．５〜１．５等量である。（Ｄ）成分が少なすぎる場合には、得られる組成物の初期硬化性や有機塗膜への付着性が低下するようになり、また多すぎる場合には、該組成物を用いて得られた塗膜に未反応のイソシアナート基が残存し、耐候性の低下や塗り重ね時にちぢみを生じる原因となる。 The amount of the polyisocyanate compound (D) used is 0.1 to 50 parts by weight with respect to 100 parts by weight of the component (A). In the case of 50 parts by weight or more, the handling property of the curing agent is lowered. The amount of the polyisocyanate compound (D) used is preferably 0.3 to 2 equivalents, more preferably 0.5 to 1 in terms of isocyanate groups relative to the hydroxyl groups in the resin (A) component. 5 equivalents. (D) When there are too few components, initial sclerosis | hardenability of the composition obtained and the adhesiveness to an organic coating film will fall, and when too large, it was obtained using this composition. Unreacted isocyanate groups remain in the coating film, causing a decrease in weather resistance and causing itchiness during repeated coating.
（有機金属化合物）
本発明においては、触媒として有機金属化合物（Ｅ）を使用する。前記、有機金属化合物（Ｅ）成分の中では、錫系化合物が塗膜の硬化性の点から好ましい。
(Organic metal compound)
In the present invention, an organometallic compound (E) is used as a catalyst. Among the organometallic compound (E) component, a tin-based compound is preferable from the viewpoint of the curability of the coating film.
前記錫化合物の具体例としては、ジオクチル錫ビス（２−エチルヘキシルマレ−ト）、ジオクチル錫オキサイドまたはジブチル錫オキサイドとシリケ−トとの縮合物、ジブチル錫ジオクトエ−ト、ジブチル錫ジラウレ−ト、ジブチル錫ジステアレ−ト、ジブチル錫ジアセチルアセトナ−ト、ジブチル錫ビス（エチルマレ−ト）、ジブチル錫ビス（ブチルマレ−ト）、ジブチル錫ビス（２−エチルヘキシルマレ−ト）、ジブチル錫ビス（オレイルマレ−ト）、スタナスオクトエ−ト、ステアリン酸錫、ジ−ｎ−ブチル錫ラウレ−トオキサイドがある。また、分子内にＳ原子有する錫化合物としては、ジブチル錫ビスイソノニル−３―メルカプトプロピオネ−ト、ジオクチル錫ビスイソノニル−３−メルカプトプロピオネ−ト、オクチルブチル錫ビスイソノニル−３−メルカプトプロピオネ−ト、ジブチル錫ビスイソオクチルチオグルコレ−ト、ジオクチル錫ビスイソオクチルチオグルコレ−ト、オクチルブチル錫ビスイソオクチルチオグルコレ−トなどが挙げられる。 Specific examples of the tin compound include dioctyl tin bis (2-ethylhexyl maleate), dioctyl tin oxide or a condensate of dibutyl tin oxide and silicate, dibutyl tin dioctate, dibutyl tin dilaurate, dibutyl. Tin distearate, dibutyltin diacetylacetonate, dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (2-ethylhexylmaleate), dibutyltin bis (oleylmaleate) ), Stannous octoate, tin stearate, di-n-butyltin laurate oxide. Examples of tin compounds having S atoms in the molecule include dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, Examples thereof include dibutyltin bisisooctylthiogluconate, dioctyltin bisisooctylthiogluconate, and octylbutyltin bisisooctylthiogluconate.
前記錫化合物のうちでは、分子内にＳ原子を有する化合物が、イソシアナ−トを配合した場合の貯蔵安定性および可使時間が良好であることから好ましく、特に、ジブチル錫ビスイソノニル−３−メルカプト、ジブチル錫ビスイソオクチルチオグルコレ−トが硬化性と貯蔵安定性、可使時間のバランスの点から好ましい。 Among the tin compounds, compounds having an S atom in the molecule are preferable because they have good storage stability and pot life when an isocyanate is blended, and in particular, dibutyltin bisisononyl-3-mercapto, Dibutyltin bisisooctyl thiogluconate is preferred from the viewpoint of balance between curability, storage stability and pot life.
また、エチルアセトアセテ−トアルミニウムジイソプロピレ−ト、アルミニウムトリス（アセチルアセテート）、アルミニウムトリス（エチルアセトアセテート）、アルミニウムモノアセチルアセトネ−トビス（エチルアセトアセテート）、アルキルアセチルアセテ−トアルミニウムジイソプロピレ−トなどの有機アルミ化合物；有機チタネート化合物；有機亜鉛化合物等の有機金属化合物も挙げられる。 Also, ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetylacetate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), alkyl acetylacetate aluminum diisopropylate Organic aluminum compounds such as a rate; organic titanate compounds; organometallic compounds such as an organic zinc compound are also included.
前記有機金属化合物（Ｅ）成分は単独でもよく、また、２種類以上併用してもよい。 The organometallic compound (E) component may be used alone or in combination of two or more.
前記（Ｅ）成分の使用量は、（Ａ）成分１００重量部に対して０．０１〜３０重量部、好ましくは、０．１〜１０重量部、より好ましくは０．３〜５重量部である。有機金属化合物（Ｅ）成分の量が３０部を超えると、該組成物を用いて形成した塗膜の表面光沢など外観性の低下傾向が認められるので好ましくない。 The amount of component (E) used is 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of component (A). is there. When the amount of the organometallic compound (E) component exceeds 30 parts, it is not preferable because a tendency of appearance deterioration such as surface gloss of a coating film formed using the composition is observed.
（メルカプト基含有化合物）
本発明においては、メルカプト基含有化合物（Ｆ）成分を添加することにより、（Ｄ）成分と（Ｅ）成分を混合した場合の貯蔵安定性が向上する。前記、メルカプト基含有化合物（Ｆ）成分の具体例としては、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ブチルメルカプタン等のアルキルメルカプタン化合物やγーメルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン等のメルカプトシラン化合物等が挙げられる。
(Mercapto group-containing compound)
In this invention, the storage stability at the time of mixing (D) component and (E) component improves by adding a mercapto group containing compound (F) component. Specific examples of the mercapto group-containing compound (F) component include alkyl mercaptan compounds such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxy. And mercaptosilane compounds such as silane.
前記メルカプト基含有化合物（Ｆ）成分は単独でもよく、また、２種類以上併用してもよい。 The mercapto group-containing compound (F) component may be used alone or in combination of two or more.
前記（Ｆ）成分の使用量は、（Ａ）成分１００重量部に対して０．０１〜１００重量部、好ましくは、０．１〜５０重量部、より好ましくは０．３〜１０重量部である。メルカプト基含有化合物（Ｆ）成分の量が１００部を超えると、該組成物の硬化速度が充分に得られなかったり、外観性の低下傾向が認められるので好ましくない。 The amount of component (F) used is 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of component (A). is there. When the amount of the mercapto group-containing compound (F) component exceeds 100 parts, the curing rate of the composition cannot be sufficiently obtained, or a tendency to deteriorate the appearance is observed, which is not preferable.
（配合形態）
本発明の硬化性樹脂組成物における配合形態としては、１液でも２液でも良い。（Ｄ）成分として常温硬化用のポリイソシアナート化合物を使用する場合には、（Ａ）成分と（Ｄ）成分が１パックとなることは好ましくないので、主剤として樹脂（Ａ）成分とオルガノシリケート化合物（Ｂ）成分、塗料用着色剤（Ｃ）成分を混合し、硬化剤としてポリイソシアナート化合物（Ｄ）成分と有機金属化合物（Ｅ）成分、メルカプト含有化合物（Ｆ）成分を配合した２液の配合形態で使用されることが好ましい。また、主剤として（Ａ）成分と（Ｃ）成分、硬化剤として（Ｂ）成分、（Ｄ）成分、（Ｅ）成分、（Ｆ）成分を配合した２液の配合形態で使用されることが好ましい。さらに、ポリイソシアナート化合物（Ｄ）としてブロックタイプを使用した場合には、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、（Ｅ）成分、（Ｆ）成分を１パックとした１液の配合形態も可能となる。
(Formulation)
As a compounding form in the curable resin composition of this invention, 1 liquid or 2 liquid may be sufficient. When a polyisocyanate compound for room temperature curing is used as the component (D), it is not preferable that the component (A) and the component (D) become one pack, so the resin (A) component and the organosilicate are used as the main components. Two liquids in which a compound (B) component, a coating colorant (C) component are mixed, and a polyisocyanate compound (D) component, an organometallic compound (E) component, and a mercapto-containing compound (F) component are blended as a curing agent. It is preferable to be used in the blending form. Moreover, it may be used in a two-part blended form in which the main components (A) and (C) are combined, and the curing agent (B), (D), (E), and (F) are combined. preferable. Further, when the block type is used as the polyisocyanate compound (D), 1 component (A), (B) component, (C) component, (D) component, (E) component, (F) component is 1 A one-pack blending form as a pack is also possible.
（脱水剤）
樹脂（Ａ）成分に加水分解性シリル基含有ビニル系単量体（ａ）成分を用いた場合や、オルガノシリケート化合物（Ｂ）成分を使用する場合には、湿分との反応性を有するため、さらに脱水剤を配合することによって、組成物の保存安定性を向上させることができる。
(Dehydrating agent)
When the hydrolyzable silyl group-containing vinyl monomer (a) component is used as the resin (A) component or when the organosilicate compound (B) component is used, it has reactivity with moisture. Further, by adding a dehydrating agent, the storage stability of the composition can be improved.
脱水剤としては、例えば、オルソ蟻酸トリメチル、オルソ蟻酸トリエチルもしくはオルソ蟻酸トリブチル等のオルソ蟻酸トリアルキル；オルソ酢酸トリメチル、オルソ酢酸トリエチルもしくはオルソ酢酸トリブチル等のオルソ酢酸トリアルキル；またはオルソほう酸トリメチル、オルソほう酸トリエチル、オルソほう酸トリブチル等のオルソほう酸トリアルキル等のオルソカルボン酸エステルや、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン等の高活性シラン化合物などが挙げられる。 Examples of the dehydrating agent include trialkyl orthoformate, trialkyl orthoformate or tributyl orthoformate; trialkyl orthoformate such as trimethyl orthoacetate, triethyl orthoacetate or tributyl orthoacetate; or trimethyl orthoborate, orthoboric acid Examples thereof include orthocarboxylic acid esters such as trialkyl orthoborate such as triethyl and tributyl orthoborate, and highly active silane compounds such as tetramethoxysilane, tetraethoxysilane and methyltrimethoxysilane.
本発明の硬化性樹脂組成物には、通常塗料に用いられる例えば、希釈剤、紫外線吸収剤、光安定剤、タレ防止剤、レベリング剤や分散剤、色別れ防止剤などの添加剤；アミノシランなどのシランカップリング剤；ニトロセルロース、セルロースアセテートブチレートなどの繊維素；エポキシ樹脂、メラミン樹脂、塩化ビニル樹脂、フッ素樹脂、塩素化ポリプロピレン、塩化ゴム、ポリビニルブチラール、ポリシロキサンなどの樹脂などを適宜加えてもよい。 In the curable resin composition of the present invention, for example, diluents, ultraviolet absorbers, light stabilizers, anti-sagging agents, leveling agents and dispersants, color-separation preventing agents and the like that are usually used in paints; aminosilanes, etc. Silane coupling agent; Fibrin such as nitrocellulose and cellulose acetate butyrate; Add appropriate resin such as epoxy resin, melamine resin, vinyl chloride resin, fluororesin, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, polysiloxane May be.
本発明の顔料分散用硬化性樹脂組成物は、たとえば浸漬、吹き付け、刷毛、スプレ−などを用いた塗布などの通常の方法によって被塗物に塗布され、通常、常温でそのまま、または３０℃以上で焼き付けて硬化せしめる。 The pigment-dispersing curable resin composition of the present invention is applied to an object to be coated by an ordinary method such as dipping, spraying, brushing, spraying, or the like, and is usually left at room temperature or 30 ° C. or higher. Bake in to cure.
本発明の硬化性樹脂組成物は、例えば金属、セラミックス、ガラス、セメント、窯業系基材、プラスチック、木材、紙、繊維などからなる建築物、家電用品、産業機器などの塗装に好適に使用できる。 The curable resin composition of the present invention can be suitably used for coating, for example, a building made of metal, ceramics, glass, cement, ceramic base material, plastic, wood, paper, fiber, etc., household appliances, and industrial equipment. .
次に、本発明の顔料分散用硬化性樹脂組成物を実施例に基づいてさらに詳細に説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, the curable resin composition for dispersing a pigment of the present invention will be described in more detail based on examples, but the present invention is not limited only to such examples.
（塗料用硬化性樹脂組成物成分の製造方法：製造例ＡＢ−１〜３）
攪拌機、温度計、還流冷却器、窒素ガス導入管および滴下ロ−トを備えた反応器に表１の（イ）成分を仕込み、窒素ガスを導入しつつ１１０℃に昇温した後、表１の（ア）成分の混合物を滴下ロ−トから５時間かけて等速滴下した。次に、（ウ）成分の混合溶液を１時間かけて等速滴下した。その後、引き続き、１１０℃で２時間攪拌した後に、室温まで冷却した。最後に表１の（エ）成分を加えて攪拌し、水酸基含有塗料用硬化性樹脂（Ａ）を合成した。
(Manufacturing method of curable resin composition component for paint: Production example AB-1 to 3)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel was charged with the component (a) in Table 1, and the temperature was raised to 110 ° C. while introducing nitrogen gas. The mixture of the component (a) was dropped at a constant rate from the dropping funnel over 5 hours. Next, the mixed solution of the component (c) was dropped at a constant rate over 1 hour. Then, after stirring at 110 degreeC for 2 hours continuously, it cooled to room temperature. Finally, the component (d) in Table 1 was added and stirred to synthesize a hydroxyl group-containing curable resin (A) for paint.
得られた水酸基含有塗料用硬化性樹脂（Ａ）成分に対して、表１の（Ｂ）成分を加えて攪拌し、塗料用硬化性樹脂組成物（ＡＢ−１〜３）を得た。 With respect to the obtained hydroxyl group-containing curable resin for paint (A), the component (B) in Table 1 was added and stirred to obtain curable resin compositions for paint (AB-1 to 3).
得られた塗料用硬化性樹脂組成物（ＡＢ−１〜３）の固形分濃度、ＧＰＣで測定した数平均分子量を表１に示した。 Table 1 shows the solid content concentration of the obtained curable resin composition for paint (AB-1 to 3) and the number average molecular weight measured by GPC.
ソルベッソ１００：有機溶剤（エクソン・モービル(株)製）
ペガソールＡＮ４５：有機溶剤（エクソン・モービル(株)製）
シリケート４５： エチルシリケート部分加水分解縮合物（多摩化学工業（株）製）
ＥＳｉ４８：エチルシリケート部分加水分解縮合物（コルコート（株）製）
（硬化剤組成物の製造方法：製造例Ｈ−１〜５）
表２に記載の溶剤に（Ｅ）成分および（Ｆ）成分を添加攪拌混合した。３０分間静置したのち（Ｄ）成分および（Ｂ）成分を攪拌混合して表２に示す硬化剤（Ｈ−１〜５）を作成した。得られた硬化剤の外観、流動性を目視により確認した。また、ＪＩＳ Ｋ ５４００に準拠してガードナー色数による色調を測定した。さらに密閉し、５０℃条件下で１ヶ月静置したのち、外観、流動性およびガードナー色数を測定した。結果を表２に示した。
外観、流動性：○・・・透明液体で充分な流動性がある
×・・・ゲル化している
Solvesso 100: Organic solvent (manufactured by ExxonMobil Corp.)
Pegasol AN45: Organic solvent (Exxon Mobil Corporation)
Silicate 45: Ethyl silicate partial hydrolysis condensate (manufactured by Tama Chemical Industry Co., Ltd.)
ESi48: ethyl silicate partial hydrolysis condensate (manufactured by Colcoat Co., Ltd.)
(Manufacturing method of a hardening | curing agent composition: Manufacturing example H-1-5)
The components (E) and (F) were added to the solvents listed in Table 2 and mixed with stirring. After leaving still for 30 minutes, (D) component and (B) component were stirred and mixed and the hardening | curing agent (H-1-5) shown in Table 2 was created. The appearance and fluidity of the obtained curing agent were confirmed visually. Further, the color tone according to the Gardner color number was measured according to JIS K 5400. After further sealing and allowing to stand at 50 ° C. for 1 month, the appearance, fluidity and Gardner color number were measured. The results are shown in Table 2.
Appearance, fluidity: ○ ・ ・ ・ Clear liquid with sufficient fluidity
× ... gelled
ＴＳＡ１００：ポリイソシアナート化合物（旭化成（株）製）
ネオスタンＵ−３６０：Ｓ基含有有機錫化合物（日東化成（株）製）
（塗料の作成）
合成した塗料用硬化性樹脂組成物（ＡＢ−１〜３）を各重合溶剤で固形分濃度が５０％になるように希釈した。次に、表３に示すミルベース成分を順次添加し、ガラスビ−ズを用いてサンドミルで１時間分散させた。さらに、カットバック成分を添加し、開放下、１５００回転で３０分間攪拌し、表３に示す白エナメル（ＡＷ−１〜５）を得た。
TSA100: polyisocyanate compound (manufactured by Asahi Kasei Corporation)
Neostan U-360: S group-containing organotin compound (manufactured by Nitto Kasei Co., Ltd.)
(Creation of paint)
The synthesized curable resin composition for paint (AB-1 to 3) was diluted with each polymerization solvent so that the solid concentration was 50%. Next, the mill base components shown in Table 3 were sequentially added and dispersed with a glass bead for 1 hour using a glass bead. Further, a cutback component was added, and the mixture was stirred at 1500 rpm for 30 minutes while being open to obtain white enamel (AW-1 to 5) shown in Table 3.
ＫＰ−３７８８Ａ：弱溶剤型分散用樹脂（日本カーバイド工業（株）製）
ＪＲ８０５：酸化チタン（白）（テイカ（株）製）
ターレン６８２０−１０Ｍ：タレ防止剤（楠本化成（株）製）
（物性評価）
調色安定性
表４〜６に示す配合にて、表３で作成した白エナメルに各色の塗料用着色剤（Ｃ）成分を添加し、ディスパーにて５００ｒｐｍで１分間攪拌混合し、各色エナメル塗料を作成した。さらに、表２の硬化剤組成物を攪拌混合し、６ミルのアプリケーターでコート紙上に塗布し、７日間室温で養生した。各色エナメルを密閉下、室温で1日および５０℃で7日静置したあと、同様にコート紙上に塗布し、７日間室温で養生した。
KP-3788A: Weak solvent type dispersion resin (manufactured by Nippon Carbide Industries Co., Ltd.)
JR805: Titanium oxide (white) (manufactured by Teika)
Talen 6820-10M: Sagging inhibitor (manufactured by Enomoto Kasei Co., Ltd.)
(Evaluation of the physical properties)
Toning stability In the formulations shown in Tables 4 to 6, the colorant (C) component for each color paint was added to the white enamel prepared in Table 3, and the mixture was stirred and mixed at 500 rpm for 1 minute with a disper. It was created. Further, the curing agent compositions shown in Table 2 were mixed with stirring, applied onto coated paper with a 6 mil applicator, and cured at room temperature for 7 days. Each color enamel was allowed to stand for 1 day at room temperature and 7 days at 50 ° C. in a sealed state, and then coated on coated paper in the same manner and cured at room temperature for 7 days.
作成直後、室温1日、５０℃７日の塗板の色目の差：ΔＥをＣＲ３００（ミノルタ（株）製）で測定した。尚、ΔＥ1)を作成直後と室温１日静置の差、ΔＥ2)を作成直後と５０℃７日の差として表記した。ΔＥが小さいほど、調色安定性が良好なことを示している。 Immediately after the preparation, the color difference of the coated plate at room temperature for 1 day and 50 ° C. for 7 days: ΔE was measured with CR300 (manufactured by Minolta Co., Ltd.) ΔE1) is expressed as the difference between immediately after preparation and standing at room temperature for 1 day, and ΔE2) is expressed as the difference between immediately after preparation and 7 days at 50 ° C. The smaller ΔE, the better the toning stability.
塗膜の水接触角の測定
耐汚染性の指標となる塗膜の水接触角を接触角測定機（協和界面科学（株）製：ＣＡ−Ｓ１５０型）を用い測定した。評価は、上記作成直後のエナメルを使用して塗布した塗板を養生後、屋外に１４日間放置したのちに実施した。接触角が低いほど耐汚染性が優れていると言える。
Measurement of water contact angle of coating film The water contact angle of the coating film, which is an index of stain resistance, was measured using a contact angle measuring machine (manufactured by Kyowa Interface Science Co., Ltd .: CA-S150 type). The evaluation was carried out after the coated plate coated with the enamel immediately after the preparation was left for 14 days after curing. It can be said that the lower the contact angle, the better the stain resistance.
表２に示したとおり、（Ｄ）成分、（Ｅ）成分、（Ｆ）成分を１パックとした硬化剤Ｈ−１〜３と、単官能イソシアナートを配合したＨ−４は５０℃１ヶ月保存後も良好な外観、流動性を保っていたが、（Ｅ）成分および単官能イソシアナートを使用しなかった硬化剤Ｈ−５はゲル化が起こった。表４〜６に示した通り、本発明の組成物を用いた実施例１〜１５は、いずれも良好な調色安定性と耐汚染性を示したが、単官能イソシアナートを使用した比較例１〜３は色目の変化が大きかった。
As shown in Table 2, the curing agent H-1 to 3 containing 1 pack of the component (D), the component (E), and the component (F), and H-4 blended with a monofunctional isocyanate are 50 ° C. for 1 month. Although the external appearance and fluidity were maintained after storage, gelling occurred in the curing agent H-5 which did not use the component (E) and the monofunctional isocyanate. As shown in Tables 4 to 6, Examples 1 to 15 using the composition of the present invention all showed good toning stability and stain resistance, but a comparative example using a monofunctional isocyanate. 1 to 3 had a large change in color.
本発明の硬化性樹脂組成物は、低コスト・簡易な操作で製造できる。特には、水酸基含有塗料用樹脂の一般的な架橋剤であるポリイソシアナート化合物の反応性を向上させる硬化剤を提供することが可能となる。また、安定した調色性を有する塗料組成物および塗装物を提供することが可能となる。さらに、特定のシリコン化合物を使用した低汚染型塗料の性能を充分に発揮する硬化剤を提供することも可能となる。 The curable resin composition of the present invention can be produced with low cost and simple operation. In particular, it is possible to provide a curing agent that improves the reactivity of a polyisocyanate compound that is a general crosslinking agent for a hydroxyl group-containing coating resin. In addition, it is possible to provide a coating composition and a coated product having stable toning properties. Furthermore, it is possible to provide a curing agent that sufficiently exhibits the performance of a low-contamination paint using a specific silicon compound.
Claims (11)
（Ｒ１Ｏ）４−ａ−Ｓｉ−Ｒ２ ａ（Ｉ）
（式中、Ｒ１は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基および炭素数７〜１０のアラルキル基から選ばれた１価の炭化水素基、Ｒ２は炭素数１〜１０のアルキル基、炭素数が６〜１０のアリール基および炭素数が７〜１０のアラルキル基から選ばれた１価の炭化水素基、ａは０または１を示す）で表されるシリコン化合物及び／またはその部分加水分解縮合物（Ｂ）成分０〜２００重量部と、塗料用着色剤（Ｃ）成分０．０１〜１５０重量部、イソシアナート基を２個以上含有する化合物（Ｄ）０．１〜５０重量部、有機金属化合物（Ｅ）成分０．０１〜３０重量部およびメルカプト基含有化合物（Ｆ）成分０．０１〜１００重量部を含有してなる硬化性樹脂組成物。 With respect to 100 parts by weight of the resin (A) component containing a hydroxyl group at the main chain terminal and / or side chain, the general formula (I):
(R 1 O) 4-a -Si-R 2 a (I)
(In the formula, R 1 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and R 2 has 1 carbon atom. A monovalent hydrocarbon group selected from an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, a represents 0 or 1) And / or its partially hydrolyzed condensate (B) component 0 to 200 parts by weight, coating colorant (C) component 0.01 to 150 parts by weight, compound (D) 0 containing two or more isocyanate groups A curable resin composition comprising 1 to 50 parts by weight, 0.01 to 30 parts by weight of an organometallic compound (E) component and 0.01 to 100 parts by weight of a mercapto group-containing compound (F) component.
Ｒ４ ｂ
｜
−Ｓｉ−（ＯＲ３）３−ｂ （ＩＩ）
（式中、Ｒ３は水素原子または炭素数１〜１０のアルキル基、Ｒ４は水素原子または炭素数１〜１０のアルキル基、炭素数６〜２５のアリール基および炭素数７〜１２のアラルキル基から選ばれた１価の炭化水素基、ｂは０〜２の整数を示す。） The component (A) is a resin containing a silyl group and a hydroxyl group bonded to a hydrolyzable group represented by the general formula (II) in the molecule, and the monomer unit containing the silyl group is represented by 1 to 80 The curable resin composition according to any one of claims 1 to 4, which is a copolymer containing by weight.
R 4 b
｜
-Si- (OR 3) 3-b (II)
Wherein R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from the group, b represents an integer of 0 to 2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011246582A (en) * | 2010-05-26 | 2011-12-08 | Dic Corp | Curable resin composition, protective sheet for solar cell, and solar cell module |
| JP5702503B1 (en) * | 2014-09-16 | 2015-04-15 | 日本ペイントマリン株式会社 | Method for forming dry coating film and paint used therefor |
| JP2016204662A (en) * | 2015-04-21 | 2016-12-08 | ダイキン工業株式会社 | Aqueous dispersion, paint film and painting article |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11286648A (en) * | 1997-04-11 | 1999-10-19 | Kanegafuchi Chem Ind Co Ltd | Curable top-coating composition and object coated therewith |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11286648A (en) * | 1997-04-11 | 1999-10-19 | Kanegafuchi Chem Ind Co Ltd | Curable top-coating composition and object coated therewith |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011246582A (en) * | 2010-05-26 | 2011-12-08 | Dic Corp | Curable resin composition, protective sheet for solar cell, and solar cell module |
| JP5702503B1 (en) * | 2014-09-16 | 2015-04-15 | 日本ペイントマリン株式会社 | Method for forming dry coating film and paint used therefor |
| WO2016042840A1 (en) * | 2014-09-16 | 2016-03-24 | 日本ペイントマリン株式会社 | Method for forming dry coating film and coating used therein |
| JP2016059842A (en) * | 2014-09-16 | 2016-04-25 | 日本ペイントマリン株式会社 | Dry film formation method and coating material used therefor |
| US10376918B2 (en) | 2014-09-16 | 2019-08-13 | Nippon Paint Marine Coatings Co., Ltd. | Method of forming dry coating film and paint used for the same |
| JP2016204662A (en) * | 2015-04-21 | 2016-12-08 | ダイキン工業株式会社 | Aqueous dispersion, paint film and painting article |
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