JP5225538B2 - Resin composition for weak solvent paint and pigment dispersion method - Google Patents
Resin composition for weak solvent paint and pigment dispersion method Download PDFInfo
- Publication number
- JP5225538B2 JP5225538B2 JP2005021719A JP2005021719A JP5225538B2 JP 5225538 B2 JP5225538 B2 JP 5225538B2 JP 2005021719 A JP2005021719 A JP 2005021719A JP 2005021719 A JP2005021719 A JP 2005021719A JP 5225538 B2 JP5225538 B2 JP 5225538B2
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- Prior art keywords
- component
- group
- carbon atoms
- pigment
- weak solvent
- 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
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- 239000002904 solvent Substances 0.000 title claims description 49
- 239000003973 paint Substances 0.000 title claims description 48
- 239000000049 pigment Substances 0.000 title claims description 46
- 239000011342 resin composition Substances 0.000 title claims description 29
- 239000006185 dispersion Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 56
- -1 bengara Chemical compound 0.000 claims description 49
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 25
- 239000012948 isocyanate Substances 0.000 claims description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229920006243 acrylic copolymer Polymers 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 12
- 150000001721 carbon Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002902 organometallic compounds Chemical class 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000007665 sagging Methods 0.000 claims description 5
- 229920006163 vinyl copolymer Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000001023 inorganic pigment Substances 0.000 claims description 4
- 239000012860 organic pigment Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 235000013799 ultramarine blue Nutrition 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 235000014692 zinc oxide Nutrition 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 238000003860 storage Methods 0.000 description 17
- 238000001723 curing Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000003125 aqueous solvent Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 150000003606 tin compounds Chemical class 0.000 description 6
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 208000034189 Sclerosis Diseases 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001312 palmitoyl group Chemical group O=C([*])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 3
- 239000000123 paper Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 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 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 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 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- 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
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 101100284369 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) has-1 gene Proteins 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 239000004568 cement Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical class CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl 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])[H] 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 230000000007 visual effect Effects 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
- 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
- FQJMHCIJFGVJAA-UHFFFAOYSA-N 1,1,1-triethoxy-2-methylpropane Chemical compound CCOC(OCC)(OCC)C(C)C FQJMHCIJFGVJAA-UHFFFAOYSA-N 0.000 description 1
- KOPMZTKUZCNGFY-UHFFFAOYSA-N 1,1,1-triethoxybutane Chemical compound CCCC(OCC)(OCC)OCC KOPMZTKUZCNGFY-UHFFFAOYSA-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
- FGWYWKIOMUZSQF-UHFFFAOYSA-N 1,1,1-triethoxypropane Chemical compound CCOC(CC)(OCC)OCC FGWYWKIOMUZSQF-UHFFFAOYSA-N 0.000 description 1
- BGLARIMANCDMQX-UHFFFAOYSA-N 1,1,1-trimethoxy-2-methylpropane Chemical compound COC(OC)(OC)C(C)C BGLARIMANCDMQX-UHFFFAOYSA-N 0.000 description 1
- JAFMOTJMRSZOJE-UHFFFAOYSA-N 1,1,1-trimethoxybutane Chemical compound CCCC(OC)(OC)OC JAFMOTJMRSZOJE-UHFFFAOYSA-N 0.000 description 1
- ZGMNAIODRDOMEK-UHFFFAOYSA-N 1,1,1-trimethoxypropane Chemical compound CCC(OC)(OC)OC ZGMNAIODRDOMEK-UHFFFAOYSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-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
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- JRVZITODZAQRQM-UHFFFAOYSA-N 1-isocyanato-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1N=C=O JRVZITODZAQRQM-UHFFFAOYSA-N 0.000 description 1
- BDQNKCYCTYYMAA-UHFFFAOYSA-N 1-isocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1 BDQNKCYCTYYMAA-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
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- 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
- 238000012546 transfer Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、弱溶剤型塗料用樹脂組成物および、その顔料分散方法に関する。さらに詳しくは、例えば金属、タイル、ガラス、セメント、窯業系成形物、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しうる塗料用樹脂組成物および、当該塗料用樹脂組成物を用いた顔料分散方法に関する。 The present invention relates to a resin composition for a weak solvent paint and a method for dispersing the pigment. More specifically, for example, a resin composition for paints that can be suitably used for coating metal, tile, glass, cement, ceramic moldings, plastic, wood, paper, textiles, buildings, household appliances, industrial equipment, etc. The present invention also relates to a pigment dispersion method using the coating resin composition.
従来、窯業系組成物、コンクリートや鉄鋼などからなる建築物、建材などの産業製品などの表面を、例えば、フッ素樹脂塗料、アクリルウレタン樹脂塗料、アクリルシリコン樹脂塗料などの塗料で被覆することによって建築物などの外観をよくしたり、防食性や耐候性等を向上させたりしている。 Conventionally, building by covering the surface of ceramic products, buildings made of concrete or steel, industrial products such as building materials with paints such as fluororesin paint, acrylic urethane resin paint, acrylic silicon resin paint, etc. It improves the appearance of objects and improves corrosion resistance and weather resistance.
中でも、耐候性、耐汚染性、無機基材や有機塗膜への密着性に優れた塗料としてシロキサン結合とウレタン結合を併用したアクリルシリコン樹脂塗料が挙げられる。
更に、本発明者らは、アクリルウレタン樹脂塗料の特徴である塗装作業性、厚塗性、汎用性と、アクリルシリコン塗料の特徴である耐候性、耐汚染性を両立させる為に、水酸基含有樹脂と加水分解性シリル基含有ビニル系重合体をブレンドすることが知られている。（例えば特許文献１参照）
Furthermore, the present inventors have developed a hydroxyl group-containing resin in order to achieve both the paint workability, thick coatability, and versatility that are the characteristics of acrylic urethane resin paints, and the weather resistance and stain resistance that are characteristics of acrylic silicon paints. It is known to blend a hydrolyzable silyl group-containing vinyl polymer. (For example, see Patent Document 1)
本発明は、アクリルシリコン樹脂塗料やアクリルウレタン樹脂塗料の優れた特徴を維持しつつ、これら塗料の顔料分散性や貯蔵安定性を改善した弱溶剤型塗料用樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a resin composition for a weak solvent type paint which has improved the pigment dispersibility and storage stability of these paints while maintaining the excellent characteristics of acrylic silicon resin paints and acrylic urethane resin paints. To do.
本発明は、以下の構成からなる新規な塗料用硬化性樹脂組成物を提供するものであり、これにより上記目的が達成される。すなわち、本発明は、
（１）ビニル系重合体からなり、分子内に下記一般式（１）
Ｒ2 a
|
（Ｒ1Ｏ）3-a−Ｓｉ− （１）
(式中、Ｒ1は、水素原子又は炭素数１〜１０のアルキル基を表す。Ｒ2は、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０アリール基及び炭素数７〜１０のアラルキル基からなる群より選択された１価を表す。Ｒ1又はＲ2が複数存在する場合には、同一であっても異なっていてもよい。ａは、０〜２の整数を表す。)
で表される炭素原子に結合した加水分解性シリル基を少なくとも１個有する共重合体（Ａ）成分、
水酸基含有アクリル樹脂（Ｂ）成分、
下記一般式（２）
（Ｒ3Ｏ）4-b−Ｓｉ−Ｒ4 b （２）
（式中、Ｒ3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７〜１２のアラルキル基から選ばれた１価の炭化水素基、Ｒ4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７〜１２のアラルキル基から選ばれた１価の炭化水素基、ｂは０または１を示す）で表されるシリコン化合物及び又はその加水分解縮合物（Ｃ）成分、アクリル系共重合体またはウレタンオリゴマーからなる顔料分散剤（Ｄ）成分、
顔料（Ｅ）成分、
弱溶剤（Ｆ）成分からなる弱溶剤型塗料用樹脂組成物に関する。
The present invention provides a novel curable resin composition for paints having the following constitution, whereby the above object is achieved. That is, the present invention
(1) a vinyl-based polymer, the following formula in the molecule (1)
R 2 a
|
(R 1 O) 3-a -Si- (1)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. It represents a monovalent group selected from the group consisting of 10 aralkyl groups, and when there are a plurality of R 1 or R 2 s, they may be the same or different, and a represents an integer of 0 to 2. .)
A copolymer (A) component having at least one hydrolyzable silyl group bonded to a carbon atom represented by:
Hydroxyl group-containing acrylic resin (B) component,
The following general formula (2)
(R 3 O) 4-b -Si-R 4 b (2)
(In the formula, R 3 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 12 carbon atoms, and R 4 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 12 carbon atoms, and b represents 0 or 1, and / or The hydrolysis-condensation product (C) component, a pigment dispersant (D) component comprising an acrylic copolymer or a urethane oligomer,
Pigment (E) component,
The present invention relates to a resin composition for a weak solvent type paint comprising a weak solvent (F) component.
本発明の弱溶剤型塗料用樹脂組成物において、水酸基含有アクリル樹脂（Ｂ）成分が可溶型樹脂（Ｂ−１）成分および／またはＮＡＤ型ポリオール分散体（Ｂ−２）成分であることが好ましい。 In weak solvent type coating resin composition of the present invention, it is a hydroxyl-containing acrylic resin (B) component soluble resin (B-1) component and / or NAD-type polyol dispersion (B-2) is a component Is preferred .
本発明の弱溶剤型塗料用樹脂組成物において、（Ｄ）成分のアクリル系共重合体がアミン価を有する顔料分散剤であることが好ましい。 In the resin composition for a weak solvent paint of the present invention, the acrylic copolymer as the component (D) is preferably a pigment dispersant having an amine value.
本発明の弱溶剤型塗料用樹脂組成物において、その他添加剤（Ｇ）成分としてタレ止め剤、色分かれ防止剤、消泡剤から選ばれる少なくとも１種を配合することが好ましい。 In the resin composition for weak solvent paints of the present invention, it is preferable to blend at least one selected from a sagging inhibitor, a color separation inhibitor and an antifoaming agent as the other additive (G) component.
本発明の弱溶剤型塗料用樹脂組成物において、（Ａ）成分が、（ａ）加水分解性基と結合したシリル基を含有するビニル系単量体、（ｂ）水酸基を含有するビニル系単量体、（ｃ）その他の共重合可能な単量体を共重合してなるビニル系共重合体であることが好ましい。 In the resin composition for weak solvent paints of the present invention, the component (A) is (a) a vinyl monomer containing a silyl group bonded to a hydrolyzable group, and (b) a vinyl monomer containing a hydroxyl group. It is preferably a vinyl copolymer obtained by copolymerization of a monomer, (c) other copolymerizable monomer.
本発明の弱溶剤型塗料用樹脂組成物において、前記（ｃ）その他の共重合可能な単量体のうち（ｄ）炭素数が５以上の（メタ）アクリル酸アルキルを含有してなることが好ましい。 In weak solvent type coating resin composition of the present invention, the (c) that of the other copolymerizable monomer (d) carbon atoms comprising the 5 or more (meth) acrylic acid alkyl Is preferred .
本発明の弱溶剤型塗料用樹脂組成物において、弱溶剤（Ｆ）成分が脂肪族炭化水素を含有してなることが好ましい。 In the weak solvent-type coating resin composition of the present invention, the weak solvent ( F ) component preferably contains an aliphatic hydrocarbon.
本発明の弱溶剤型塗料用樹脂組成物において、さらに有機金属系化合物（Ｈ）成分を配合してなることが好ましい。 In the resin composition for weak solvent paints of the present invention, it is preferable to further blend an organometallic compound (H) component.
本発明の弱溶剤型塗料用樹脂組成物において、さらに多官能イソシアナート化合物（Ｉ）成分を配合してなることが好ましい。 In the resin composition for a weak solvent paint of the present invention, it is preferable to further blend a polyfunctional isocyanate compound (I) component.
本発明はまた、水酸基含有弱溶剤可溶型アクリル樹脂（Ｂ−１）成分と、更に、顔料分散剤（Ｄ）成分、顔料（Ｅ）成分を含んでなるミルベース樹脂に、ビニル系重合体からなり、分子内に下記一般式（１）
Ｒ2 a
|
（Ｒ1Ｏ）3-a−Ｓｉ− （１）
(式中、Ｒ1は、水素原子又は炭素数１〜１０のアルキル基を表す。Ｒ2は、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０アリール基及び炭素数７〜１０のアラルキル基からなる群より選択された１価を表す。Ｒ1又はＲ2が複数存在する場合には、同一であっても異なっていてもよい。ａは、０〜２の整数を表す。)
で表される炭素原子に結合した加水分解性ケイ素基を少なくとも１個有する共重合体（Ａ）成分、下記一般式（２）
（Ｒ3Ｏ）4-b−Ｓｉ−Ｒ4 b （２）
（式中、Ｒ3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７〜１２のアラルキル基から選ばれた１価の炭化水素基、Ｒ4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７〜１２のアラルキル基から選ばれた１価の炭化水素基、ｂは０または１を示す）で表されるシリコン化合物及び又はその加水分解縮合物（Ｃ）成分、さらに、水酸基含有ＮＡＤ型アクリル樹脂（Ｂ−２）成分を用い又は用いずにレットダウンすることを特徴とする弱溶剤型塗料の顔料分散方法に関する。
The invention also provides a hydroxyl-containing weak solvent-soluble acrylic resin (B-1) component, further, a pigment dispersing agent (D) component, the mill base resin comprising a pigment component (E), vinyl-based polymer The following general formula (1)
R 2 a
|
(R 1 O) 3-a -Si- (1)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. It represents a monovalent group selected from the group consisting of 10 aralkyl groups, and when there are a plurality of R 1 or R 2 s, they may be the same or different, and a represents an integer of 0 to 2. .)
A copolymer (A) component having at least one hydrolyzable silicon group bonded to a carbon atom represented by the following general formula (2)
(R 3 O) 4-b -Si-R 4 b (2)
(In the formula, R 3 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 12 carbon atoms, and R 4 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 12 carbon atoms, and b represents 0 or 1, and / or a hydrolysis condensate (C) component, further, relates to a pigment dispersion method of weak solvent type coating material, characterized in that the let down with or without water acid group-containing NAD acrylic resin component (B-2).
本願構成により得られる弱溶剤型塗料用樹脂組成物を用いることにより、顔料分散性の優れた弱溶剤型塗料用樹脂組成物を得ることができ、また、顔料分散性が良好な顔料分散方法を提供できる。 By using the resin composition for weak solvent paints obtained by the composition of the present application, a resin composition for weak solvent paints excellent in pigment dispersibility can be obtained, and a pigment dispersion method with good pigment dispersibility can be obtained. Can be provided.
本発明の炭素原子に結合した加水分解性シリル基を少なくとも１個有する共重合体（Ａ）成分は、その主鎖が実質的にアクリル系単量体が共重合した主鎖からなる（以下、主鎖が実質的にアクリル系共重合鎖からなるともいう）共重合体であることが好ましく、得られる本発明の弱溶剤型塗料用樹脂組成物から形成される塗膜の耐候性、耐薬品性などが優れたものとなる。 The copolymer (A) component having at least one hydrolyzable silyl group bonded to a carbon atom of the present invention comprises a main chain in which the main chain is substantially copolymerized with an acrylic monomer (hereinafter, The main chain is preferably a copolymer (also referred to as substantially consisting of an acrylic copolymer chain), and the weather resistance and chemical resistance of the coating film formed from the resulting resin composition for weak solvent paints of the present invention is obtained. The property is excellent.
なお、前記共重合体（Ａ）の主鎖が実質的にアクリル共重合鎖からなるとは、共重合体（Ａ）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 copolymer (A) substantially consists of an acrylic copolymer chain means that 50% or more of the units constituting the main chain of the copolymer (A), more preferably 70% or more. It means that it is formed from an acrylic monomer unit.
また、共重合体（Ａ）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、耐酸性などがすぐれたものとなる。 In addition, since the copolymer (A) 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.
アクリル系共重合体（Ａ）において、加水分解性シリル基は、共重合体（Ａ）１分子あたり１個以上必要であり、２個以上、好ましくは３個以上であることが、本発明の組成物から形成される塗膜の耐候性、耐溶剤性などの耐久性が優れるという点から好ましい。 In the acrylic copolymer (A), one or more hydrolyzable silyl groups are required per molecule of the copolymer (A), and two or more, preferably three or more are present in the present invention. The coating film formed from the composition is preferable from the viewpoint of excellent durability such as weather resistance and solvent resistance.
前記加水分解性シリル基は、共重合体（Ａ）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い。加水分解性シリル基の導入方法としては、加水分解性シリル基を含有する単量体をその他の単量体と共重合する方法、シリケ−ト化合物を反応させる方法等がある。簡便な方法としては加水分解性シリル基を含有する単量体を他の単量体を共重合する方法である。 The hydrolyzable silyl group may be bonded to the end of the main chain of the copolymer (A) or may be bonded to a side chain. Examples of the method for introducing a hydrolyzable silyl group include a method of copolymerizing a monomer containing a hydrolyzable silyl group with another monomer, a method of reacting a silicate compound, and the like. As a simple method, a monomer containing a hydrolyzable silyl group is copolymerized with another monomer.
前記加水分解性ケイ素の加水分解性基は、ハロゲン基、アルコキシ基等がある。その中で、反応の制御の簡便さからアルコキシ基が好ましく、下記一般式（１）で示される。 Examples of the hydrolyzable group of the hydrolyzable silicon include a halogen group and an alkoxy group. Among them, an alkoxy group is preferable from the viewpoint of easy control of the reaction, and is represented by the following general formula (1).
Ｒ2 a
|
（Ｒ1Ｏ）3-a−Ｓｉ− （１）
(式中、Ｒ1は、水素原子又は炭素数１〜１０のアルキル基を表す。Ｒ2は、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０アリ−ル基及び炭素数７〜１０のアラルキル基からなる群より選択された１価を表す。Ｒ1又はＲ2が複数存在する場合には、同一であっても異なっていてもよい。ａは、０〜２の整数を表す。)。
R 2 a
|
(R 1 O) 3-a -Si- (1)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number. 1 represents a monovalent group selected from the group consisting of 7 to 10 aralkyl groups, and when a plurality of R 1 or R 2 are present, they may be the same or different. Represents.)
上記一般式（１）中のＲ1としては、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のアルキル基が好ましい。前記アルキル基の炭素数が１０を超える場合には、加水分解性基と結合したシリル基の反応性が低下するようになる。また、前記アルコキシ基の酸素に結合した基がたとえばフェニル基、ベンジル基などのアルキル基以外の基である場合にも、加水分解性基と結合したシリル基の反応性が低下するようになる。 As R < 1 > in the said General formula (1), C1-C4 alkyl groups, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, are preferable. . When the alkyl group has more than 10 carbon atoms, the reactivity of the silyl group bonded to the hydrolyzable group is lowered. Also, when the group bonded to oxygen of the alkoxy group is a group other than an alkyl group such as a phenyl group or a benzyl group, the reactivity of the silyl group bonded to the hydrolyzable group is lowered.
また、前記一般式（１）中のＲ2としては本発明の組成物が硬化性に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。 Moreover, as R < 2 > in the said General formula (1), a C1-C4 alkyl group is preferable from the point that the composition of this invention is excellent in sclerosis | hardenability.
前記一般式（１）において、（Ｒ1Ｏ）3-aは３−ａが１以上３以下になるように、すなわちａが０〜２になるように選ばれるが、アクリル系共重合体（Ｂ）の硬化性が良好になるという点からは、ａが０または１であるのが好ましい。したがって、Ｒ4の結合数は０〜１であるのが好ましい。 In the general formula (1), (R 1 O) 3-a is selected so that 3-a is 1 or more and 3 or less, that is, a is 0 to 2, but an acrylic copolymer ( From the viewpoint that the curability of B) becomes good, a is preferably 0 or 1. Accordingly, the number of bonds of R 4 is preferably 0-1.
一般式（１）中に存在する（Ｒ1Ｏ）3-aまたはＲ2 aの数が２個以上の場合、２個以上含まれるＲ1またはＲ2は同じであってもよく、異なっていてもよい。一般式（１）では示していないが、一般式（１）のケイ素原子は炭素原子に結合している構造を有している。 When the number of (R 1 O) 3-a or R 2 a present in the general formula (1) is 2 or more, R 1 or R 2 contained in two or more may be the same or different. May be. Although not shown in the general formula (1), the silicon atom of the general formula (1) has a structure bonded to a carbon atom.
前記（Ａ）成分は例えば、（ａ）加水分解性シリル基を含有するビニル系単量体、（ｂ）水酸基を含有するビニル系単量体、（ｃ）その他の共重合可能なモノマ−重量部を共重合することにより得ることができる。 The component (A) includes, for example, (a) a vinyl monomer containing a hydrolyzable silyl group, (b) a vinyl monomer containing a hydroxyl group, (c) other copolymerizable monomer weight. It can be obtained by copolymerizing the parts.
なお、共重合体（Ａ）中の前記単量体（ａ）の単位の含有割合は、本発明の組成物を用いて形成される塗膜の耐久性が優れる、強度が大きくなるという点から、１〜９０重量％、さらには２〜７０重量％、とくには３〜５０重量％であるのが好ましい。 In addition, the content ratio of the unit of the monomer (a) in the copolymer (A) is from the viewpoint that the durability of the coating film formed using the composition of the present invention is excellent and the strength is increased. 1 to 90% by weight, more preferably 2 to 70% by weight, and particularly preferably 3 to 50% by weight.
加水分解性シリル基含有ビニル共重合体（ａ）成分の具体例としては、たとえば Specific examples of the hydrolyzable silyl group-containing vinyl copolymer (a) component include:
などの一般式（３） General formula (3)
などの一般式（４） General formula (4)
などの一般式（５） General formula (5)
などの一般式（６） General formula (6)
などの一般式（７） General formula (7)
（式中、Ｒ7は、水素原子又は炭素数１〜１０のアルキル基を、Ｒ6は、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０アリ−ル基及び炭素数７〜１０のアラルキル基からなる群より選択された１価の基を、Ｒ5は、水素またはメチル基をそれぞれ表す。ａは、０〜２の整数を、ｎは１〜１２の整数を、ｐは１〜１４の整数を、ｑは０〜２２の整数をそれぞれ表す。Ｒ6又はＲ7が複数存在する場合には、同一であっても異なっていてもよい。）。 (Wherein R 7 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 6 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 carbon atoms. A monovalent group selected from the group consisting of -10 aralkyl groups, R 5 represents hydrogen or a methyl group, a is an integer of 0-2, n is an integer of 1-12, p Represents an integer of 1 to 14, and q represents an integer of 0 to 22. When a plurality of R 6 or R 7 are present, they may be the same or different.
これらの中では、共重合性および重合安定性、ならびに得られる組成物の硬化性および保存安定性が優れるという点から、前記一般式（４）で表される化合物が好ましい。
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く、２種類以上併用してもよい。前記水酸基含有ビニル系単量体（ｂ）としてはその誘導体も含めて用いることができる。具体例としては次のような化合物が例示できる。
In these, the compound represented by the said General formula (4) is preferable from the point that copolymerization property and polymerization stability, and the sclerosis | hardenability and storage stability of the composition obtained are excellent.
These hydrolyzable silyl group-containing vinyl monomers (a) may be used alone or in combination of two or more. As the hydroxyl group-containing vinyl monomer (b), derivatives thereof can be used. Specific examples include the following compounds.
２−ヒドロキシエチル（メタ）アクリレ−ト、２―ヒドロキシプロピル（メタ）アクリレ−ト、２−ヒドロキシブチル（メタ）アクリレ−ト、４−ヒドロキシブチル（メタ）アクリレ−ト、２−ヒドロキシエチルビニルエ−テル、Ｎ―メチロ−ル（メタ）アクリルアミド、２ーヒドロキシエチルビニルエーテル、４−ヒドロキシスチレン、東亜合成化学工業（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―２０（以上、いず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−）、日本油脂（株）製のブレンマ−ＰＰシリ−ズ（ポリプロピレングリコ−ルメタクリレ−ト）、ブレンマ−ＰＥシリ−ズ（ポリエチレングリコ−ルモノメタクリレ−ト）、ブレンマ−ＰＥＰシリ−ズ（ポリエチレングリコ−ルポリプロピレングリコ−ルメタクリレ−ト）、ブレンマ−ＡＰ−４００（ポリプロピレングリコ−ルモノアクリレ−ト）、ブレンマ−ＡＥ−３５０（ポリエチレングリコ−ルモノアクリレ−ト）およびブレンマ−ＧＬＭ（グリセロ−ルモノメタクリレ−ト）、Ｎ−メチロ−ル（メタ）アクリルアミドなどの（メタ）アクリル酸のヒドロキシアルキルエステル類。 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ester -Tell, N-methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether, 4-hydroxystyrene, Aronics 5700 manufactured by Toa Synthetic Chemical Industry Co., Ltd., 4-hydroxystyrene, manufactured by Nippon Shokubai Chemical Industry Co., Ltd. HE-10, HE-20, HP-1 and HP-20 (all of which are acrylate oligomers having a hydroxyl group at the terminal), Bremer-PP series (polypropylene glycol methacrylate) manufactured by NOF Corporation. -Bremmer-PE series (polyethylene glycol monomethacrylate) BLEMMER-PEP series (polyethylene glycol polypropylene glycol methacrylate), BLEMMA-AP-400 (polypropylene glycol monoacrylate), BLEMMA-AE-350 (polyethylene glycol monoacrylate) and BLEMMA-GLM Hydroxyalkyl esters of (meth) acrylic acid such as (glycerol monomethacrylate) and N-methylol (meth) acrylamide.
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であるＰｌａｃｃｅｌ ＦＡ―１、 Ｐｌａｃｃｅｌ ＦＡ―４、 Ｐｌａｃｃｅｌ ＦＭ―１、 Ｐｌａｃｃｅｌ ＦＭ―４（以上、ダイセル化学工業（株）製）、ＴＯＮＥ Ｍ−２０１（ＵＣＣ社製）、ポリカ−ボネ−ト含有ビニル系化合物（具体例としては、ＨＥＡＣ―１（ダイセル化学工業（株）製）などの水酸基を有するモノエチレン性不飽和モノマーを共重合モノマーとした１分子中に２以上の水酸基を有するアクリルポリオールが使用できる。 Placcel FA-1, Placcel FA-4, Placcel FM-1, Placcel FM-4 (and above, Daicel) which are ε-caprolactone-modified hydroxyalkylvinyl copolymer compounds obtained by reaction of a hydroxyl group-containing compound with ε-caprolactone Chemical Industry Co., Ltd.), TONE M-201 (UCC Co., Ltd.), polycarbonate-containing vinyl compound (specific examples include HEAC-1 (Daicel Chemical Industries, Ltd.)) An acrylic polyol having two or more hydroxyl groups in one molecule using a monoethylenically unsaturated monomer as a copolymerization monomer can be used.
中でも２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、２−ヒドロキシブチル（メタ）アクリレ−ト、４−ヒドロキシブチル（メタ）アクリレ−トは、イソシアナ−トとの反応性に優れ、耐候性、耐薬品性、耐衝撃性が良好な塗膜が得られる点から好ましい。
特に好ましくは、２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−トである。これらのアルコ−ル性水酸基含有ビニル系単量体（ｂ）成分は単独で用いてもよく、２種類以上併用してもよい。また、使用量としては、２〜４０重量％が好ましく、硬化性、密着性、耐溶剤性が十分に発現する点から、３〜３０重量％がさらに３〜２０重量％が特に好ましい。
Among them, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate are isocyanates. It is preferable in that a coating film having excellent reactivity and excellent weather resistance, chemical resistance and impact resistance can be obtained.
Particularly preferred are 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. These alcoholic hydroxyl group-containing vinyl monomers (b) may be used alone or in combination of two or more. Moreover, as a usage-amount, 2 to 40 weight% is preferable, and 3-30 weight% is especially preferable 3 to 20 weight% from the point from which sclerosis | hardenability, adhesiveness, and solvent resistance are fully expressed.
前記共重合可能モノマ−（ｃ）成分の具体例としては、メチル（メタ）アクリレ−ト、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレ−ト、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレ−ト、ｂｅｎｚｉｒｕ（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、トリフルオロエチル（メタ）アクリレート、ペンタフルオロプロピル（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、（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−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）アクリレートなどの（メタ）アクリル酸エステル誘導体が挙げられる。 Specific examples of the copolymerizable monomer (c) component include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl ( (Meth) acrylate, benziru (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meta) ) Phosphate ester group-containing (meth) acrylic compounds such as acrylates, isobornyl (meth) acrylates, condensation products of hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphate esters, urethane bonds Or white (Meth) acrylic acid ester derivatives such as (meth) acrylates containing an acid bond.
それ以外の共重合性のモノマ−としては、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、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；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。 Other copolymerizable monomers include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, vinyltoluene; maleic acid, fumaric acid, itaconic acid, (meth) acrylic acid Unsaturated carboxylic acids such as these, salts such as alkali metal salts, ammonium salts and amine salts thereof; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride, linear chains of 1 to 20 carbon atoms with these acid anhydrides Or esters of unsaturated carboxylic acids such as diesters or half esters with branched chain alcohols or amines; vinyl esters or allyl compounds such as vinyl acetate, vinyl propionate or diallyl phthalate; amino groups such as vinyl pyridine or aminoethyl vinyl ether Containing vinyl compounds; itaconic acid diamide, Amido group-containing vinyl compounds such as rotonic acid amide, maleic acid diamide, fumaric acid diamide, N-vinylpyrrolidone; methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N -Other vinyl compounds such as vinyl imidazole and vinyl sulfonic acid.
これらの共重合可能モノマ−（ｃ）成分は単独で用いてもよく、２種以上併用してもよい。本発明の（Ａ）成分においては、（Ａ）成分を構成する前記その他の共重合可能なビニル系単量体（ｃ）成分のうち、炭素数が５以上の（メタ）アクリル酸および／またはその誘導体（ｄ）成分を共重合させることが好ましい。 These copolymerizable monomer (c) components may be used alone or in combination of two or more. In the component (A) of the present invention, among the other copolymerizable vinyl monomers (c) constituting the component (A), (meth) acrylic acid having 5 or more carbon atoms and / or It is preferable to copolymerize the derivative (d) component.
前記（ｄ）成分の具体例としては、たとえば３，３，５，−トリメチルシクロヘキシル（メタ）アクリレ−ト、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレ−ト、２ーエチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレ−ト、ノニル（メタ）アクリレ−ト、デカニル（メタ）アクリレ−ト、ウンデカニル（メタ）アクリレ−ト、ラウリルメチル（メタ）アクリレ−ト、パルミトイル（メタ）アクリレ−ト、ステアリル（メタ）アクリレ−ト、ブレンマ−ＳＬＭＡ（(メタ)アクリル酸のＣ12〜Ｃ18アルキルエステルの混合物；日本油脂（株）製）などが挙げられる。 Specific examples of the component (d) include 3,3,5, -trimethylcyclohexyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Octyl (meth) acrylate, nonyl (meth) acrylate, decanyl (meth) acrylate, undecanyl (meth) acrylate, lauryl methyl (meth) acrylate, palmitoyl (meth) acrylate, stearyl (Meth) acrylate, blemma-SLMA (mixture of C 12 -C 18 alkyl ester of (meth) acrylic acid; manufactured by NOF Corporation) and the like.
弱溶剤が脂肪族系化合物を含む溶剤である場合の溶解性を向上されるという点から、２−エチルヘキシル（メタ）アクリレ−ト、オクチル（メタ）アクリレ−ト、ノニル（メタ）アクリレ−ト、デカニル（メタ）アクリレ−ト、ウンデカニル（メタ）アクリレ−ト、ラウリルメチル（メタ）アクリレ−ト、パルミトイル（メタ）アクリレ−ト、ステアリル（メタ）アクリレ−ト、ブレンマ−ＳＬＭＡが好ましい。特に、ラウリルメチル（メタ）アクリレ−ト、パルミトイル（メタ）アクリレ−ト、ステアリル（メタ）アクリレ−ト、ブレンマ−ＳＬＭＡがさらに好ましい。 In view of improving the solubility when the weak solvent is a solvent containing an aliphatic compound, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, Preferred are decanyl (meth) acrylate, undecanyl (meth) acrylate, laurylmethyl (meth) acrylate, palmitoyl (meth) acrylate, stearyl (meth) acrylate and blemma-SLMA. Particularly preferred are laurylmethyl (meth) acrylate, palmitoyl (meth) acrylate, stearyl (meth) acrylate, and blemma-SLMA.
使用量としては、２〜７０重量％が好ましく、重合時および希釈時の溶剤に対する溶解性よおび重合安定性の点から、５〜６０重量％がさらに好ましく、特に、５〜５０重量％がさらに好ましい。 The amount used is preferably 2 to 70% by weight, more preferably 5 to 60% by weight, particularly 5 to 50% by weight from the viewpoint of solubility in a solvent during polymerization and dilution and polymerization stability. preferable.
前記（ｂ）成分、（ｃ）成分と（ｄ）成分の使用量の合計は、加水分解性シリル基含有ビニル系単量体（ａ）成分の種類および使用量に応じて適宜調整すればよいが、通常用いる重合成分全量の１０〜９９重量％、さらには３０〜９８重量％、とくには５０〜９７重量％であるのが好ましい。また、（ａ）成分の使用量としては重合成分の１〜９０重量％、さらに２〜７０重量％、特には、３〜５０重量％が好ましい。 What is necessary is just to adjust suitably the sum total of the usage-amount of said (b) component, (c) component, and (d) component according to the kind and usage-amount of a hydrolyzable silyl group containing vinyl monomer (a) component. However, it is preferably 10 to 99% by weight, more preferably 30 to 98% by weight, and particularly preferably 50 to 97% by weight of the total amount of the polymerization components used. The amount of the component (a) used is preferably 1 to 90% by weight, more preferably 2 to 70% by weight, and particularly preferably 3 to 50% by weight of the polymerization component.
加水分解性シリル基含有重合体（Ａ）は、たとえば特開昭５４−３６３９５号公報、特開昭５７−５５９５４号公報などに記載のヒドロシリル化法また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用いた溶液重合法によって製造することができるが、合成の容易さなどの点から加水分解性基と結合したシリル基を含有する単量体を用い、アゾビスイソブチロニトリル、Ｖ−５９（和光純薬(株)製）などのアゾ系ラジカル重合開始剤を用いた溶液重合法によって製造することがとくに好ましい。 The hydrolyzable silyl group-containing polymer (A) contains, for example, a hydrosilylation method described in JP-A-54-36395, JP-A-57-55954, or a silyl group bonded to a hydrolyzable group. Azobisisobutyronitrile using a monomer containing a silyl group bonded to a hydrolyzable group from the standpoint of ease of synthesis. , V-59 (manufactured by Wako Pure Chemical Industries, Ltd.), etc., is particularly preferably produced by a solution polymerization method using an azo radical polymerization initiator.
また、前記溶液重合の際には、必要に応じて、たとえば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、γーメルカプトプロピルトリメトキシシラン、γーメルカプトプロピルトリエトキシシラン、（ＣＨ3Ｏ）3Ｓｉ−Ｓ−Ｓ−Ｓｉ（ＯＣＨ3）3，（ＣＨ3Ｏ）3Ｓｉ−Ｓ8−Ｓｉ（ＯＣＨ3）3などの連鎖移動剤を単独または２種以上併用することにより、得られる樹脂（Ａ）成分の分子量を調整してもよい。特に、たとえばγ−メルカプトプロピルトリメトキシシランなどのアルコキシシリル基を分子中に有する連鎖移動剤を用いた場合には、樹脂（Ａ）成分の末端に加水分解性シリル基を導入することができるので好ましい。かかる連鎖移動剤の使用量は、用いる重合成分全量の０．０５〜１０％、特には０．１〜８％であることが好ましい。 In the solution polymerization, if necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, (CH 3 O) 3 Si—S—S—Si (OCH 3 ) 3 , (CH 3 O) 3 Si—S 8 —Si (OCH 3 ) 3 or other chain transfer agents are used alone or in combination of two or more. The molecular weight of the resin (A) component to be obtained may be adjusted. In particular, when a chain transfer agent having an alkoxysilyl group in the molecule such as γ-mercaptopropyltrimethoxysilane is used, a hydrolyzable silyl group can be introduced at the end of the resin (A) component. preferable. The amount of the chain transfer agent used is preferably 0.05 to 10%, particularly 0.1 to 8% of the total amount of the polymerization components used.
本発明の水酸基含有アクリル樹脂（Ｂ）は、ポリウレタン技術分野において一般的に使用されるアクリルポリオールが用いられる。その場合、硬化剤であるポリイソシアナートと反応させることにより、形成される塗膜において、塗膜形成主要素となるものである。前記（Ａ）成分に添加することにより、塗装作業性の向上、旧塗膜の選択幅の拡大、鮮映性や高光沢の付与、耐溶剤性に優れるなどの性能付与を行なうことができる。また、前記単量体（ｂ）、（ｃ）、場合によっては（ｄ）成分を用いて適宜合成して用いることが可能である。 As the hydroxyl group-containing acrylic resin (B) of the present invention, acrylic polyols generally used in the polyurethane technical field are used. In that case, by reacting with a polyisocyanate that is a curing agent, it becomes a coating film forming main element in the formed coating film. By adding to the component (A), it is possible to improve the workability of coating, expand the selection range of the old coating film, impart vividness and high gloss, and impart performance such as excellent solvent resistance. Moreover, it is possible to synthesize | combine suitably using the said monomer (b), (c) and the component (d) depending on the case.
本発明に使用する前記水酸基含有アクリル樹脂の分子量は、重量平均分子量にて５０００〜１０００００、さらには１００００〜６００００が好ましい。分子量が５０００より小さくなる場合には、塗膜の硬化性、耐久性が劣り、１０００００より大きくなる場合には、塗膜の仕上がり性が十分でない傾向がある。さらに、水酸基価が１０〜１００ｍｇＫＯＨ／ｇ（ワニス：以下同様）、酸価が０．１〜３０ｍｇＫＯＨ／ｇであることが好ましく、水酸基価が１０ｍｇＫＯＨ／ｇより小さい場合は、架橋密度が低いため、各種塗膜物性、耐汚染性が劣り、逆に、１００ｍｇＫＯＨ／ｇより大きい場合は、加水分解性シリル基含有共重合体と混合した場合に、相溶性の低下や架橋密度が高くなり部分加水分解縮合物の表面配向性が阻害される傾向がある。 The molecular weight of the hydroxyl group-containing acrylic resin used in the present invention is preferably 5000 to 100,000, more preferably 10,000 to 60000 in terms of weight average molecular weight. When the molecular weight is less than 5000, the curability and durability of the coating film are inferior. When the molecular weight is greater than 100,000, the finish of the coating film tends to be insufficient. Further, the hydroxyl value is 10 to 100 mgKOH / g (varnish: the same applies hereinafter), the acid value is preferably 0.1 to 30 mgKOH / g, and when the hydroxyl value is less than 10 mgKOH / g, the crosslinking density is low. Various coating film properties and stain resistance are inferior. Conversely, when it is greater than 100 mgKOH / g, when mixed with a hydrolyzable silyl group-containing copolymer, the compatibility decreases and the crosslink density increases, resulting in partial hydrolysis. There is a tendency that the surface orientation of the condensate is inhibited.
酸価が０．１ｍｇＫＯＨ／ｇより小さいと顔料との分散性の低下および硬化性の低下が起こり、逆に、３０ｍｇＫＯＨ／ｇより大きいと、塗料としての貯蔵安定性の低下を引き起こす傾向がある。本発明に使用する水酸基含有アクリル樹脂は炭素原子に結合した加水分解性シリル基を含有しないものである。
本発明の水酸基含有アクリル樹脂（Ｂ）は可溶型樹脂（Ｂ−１）でも非水分散型樹脂（以下、ＮＡＤ）でもよい。可溶型樹脂（Ｂ−１）は、特に、顔料分散用樹脂として使用することができる。
When the acid value is less than 0.1 mg KOH / g, the dispersibility and the curability are lowered with the pigment, and conversely, when it is more than 30 mg KOH / g, the storage stability as a paint tends to be lowered. The hydroxyl group-containing acrylic resin used in the present invention does not contain a hydrolyzable silyl group bonded to a carbon atom.
The hydroxyl group-containing acrylic resin (B) of the present invention may be a soluble resin (B-1) or a non-aqueous dispersion resin (hereinafter referred to as NAD). The soluble resin (B-1) can be used particularly as a pigment dispersion resin.
ＮＡＤ型ポリオール樹脂分散体（Ｂ−２）成分は、非水系溶剤中に樹脂が分散したものであり、樹脂の一部分に、非水系溶剤に溶解可能な成分を用い、その他の部分に非水溶剤に溶解しない成分を用いたものである。ポリオール非水系溶剤に溶解可能な樹脂部分とは、非水系溶剤への溶解度が９９．０重量％以上のものをさし、逆に非水系溶剤に溶解しない樹脂部分とは、非水系溶剤へ全く溶解しないか、又は極少量（溶解度が１．０重量％未満）のものである。このようなＮＡＤ型樹脂分散体は、ＮＡＤ型樹脂粒子をポリオール成分を用いて合成し、イソシアナートを硬化剤として使用する２液タイプのものが用いることができる。 The NAD type polyol resin dispersion (B-2) component is a resin dispersed in a non-aqueous solvent. A component that can be dissolved in a non-aqueous solvent is used in a part of the resin, and a non-aqueous solvent is used in the other part. Ingredients that do not dissolve in are used. The resin portion that can be dissolved in the polyol non-aqueous solvent means that the solubility in the non-aqueous solvent is 99.0% by weight or more, and conversely, the resin portion that does not dissolve in the non-aqueous solvent is completely non-aqueous solvent. It does not dissolve or is very small (solubility is less than 1.0% by weight). As such an NAD type resin dispersion, a two-component type in which NAD type resin particles are synthesized using a polyol component and an isocyanate is used as a curing agent can be used.
ＮＡＤ型樹脂分散体（Ｂ−２）成分は、単独あるいは、同種のものも含めて２種類以上混合して使用することができる。前記（Ｂ−２）成分は、弱溶剤とよばれる溶解力の弱い溶剤類にも分散が可能となることから、溶解性パラメーター（以下、ＳＰ値）が６．５〜９．５程度のものであることが好ましい。 The NAD type resin dispersion (B-2) component can be used alone or in admixture of two or more kinds including those of the same type. Since the component (B-2) can be dispersed in a solvent having a weak solubility called a weak solvent, the solubility parameter (hereinafter referred to as SP value) is about 6.5 to 9.5. It is preferable that
ＮＡＤ型樹脂分散体（Ｂ−２）成分の重量平均分子量は、５０００〜１０００００、水酸基価が１０〜１００ｍｇＫＯＨ／ｇ、酸価が０．１〜３０ｍｇＫＯＨ／ｇのものが使用できる。重量平均分子量が５０００より小さい場合は、塗料として適度な粘性が得られず、各塗膜物性に劣り、逆に、１０００００より大きい場合は、加水分解性シリル基および水酸基を有するビニル系共重合体（Ａ）成分と混合した場合に、相溶性の低下、塗膜の鮮映性や光沢の低下が見られる傾向がある。また、水酸基価が１０ｍｇＫＯＨ／ｇより小さい場合は、架橋密度が低いため、各種塗膜物性、耐汚染性が低下し、逆に、１００ｍｇＫＯＨ／ｇより大きい場合は、加水分解性基と結合したシリル基および水酸基を有するビニル系共重合体（Ａ）成分と混合した場合に、相溶性の低下、架橋密度が高くなり部分加水分解縮合物の表面配向性が阻害される傾向がある。 The NAD type resin dispersion (B-2) component may have a weight average molecular weight of 5000 to 100,000, a hydroxyl value of 10 to 100 mgKOH / g, and an acid value of 0.1 to 30 mgKOH / g. When the weight average molecular weight is less than 5,000, an appropriate viscosity cannot be obtained as a paint and the coating film properties are inferior. On the contrary, when the weight average molecular weight is greater than 100,000, a vinyl copolymer having a hydrolyzable silyl group and a hydroxyl group. When mixed with the component (A), there is a tendency that the compatibility is lowered, the sharpness of the coating film and the gloss are lowered. In addition, when the hydroxyl value is less than 10 mgKOH / g, the crosslink density is low, so various coating film properties and stain resistance are reduced. Conversely, when the hydroxyl value is more than 100 mgKOH / g, silyl bonded to a hydrolyzable group is present. When mixed with a vinyl copolymer (A) component having a group and a hydroxyl group, the compatibility is lowered, the crosslink density is increased, and the surface orientation of the partially hydrolyzed condensate tends to be inhibited.
酸価が０．１ｍｇＫＯＨ／ｇより小さいと顔料との分散性の低下および硬化性の低下が起こり、逆に、３０ｍｇＫＯＨ／ｇより大きいと、塗料としての貯蔵安定性の低下を引き起こす傾向がある。上記、ＮＡＤ型ポリオールの場合は、前記（ｂ）〜（ｄ）の単量体を使用することができる。ＮＡＤ型ポリオール分散体（Ｂ−２）成分を使用する場合、作業性の向上、旧塗膜への影響が小さいなどの性能が付与される点で好ましい。 When the acid value is less than 0.1 mg KOH / g, the dispersibility and the curability are lowered with the pigment, and conversely, when it is more than 30 mg KOH / g, the storage stability as a paint tends to be lowered. In the case of the NAD type polyol, the monomers (b) to (d) can be used. When using a NAD type polyol dispersion (B-2) component, it is preferable at the point which performance, such as the improvement of workability | operativity and a small influence on an old coating film, is provided.
Ａ成分とＢ成分の配合割合は特に限定されるものではないが、コストバランス、耐候性、耐汚染性等の点よりＡ成分：Ｂ成分が重量比で好ましくは２０：８０〜８０：２０、更には３０：７０〜７０：３０、特には４０：６０〜６０：４０が好ましい。
又、（Ｂ−１）：（Ｂ−２）成分の配合割合は特に限定されるものではないが、顔料分散性、チキソ性付与の点より２０：８０〜６０：４０が好ましい。
The blending ratio of the A component and the B component is not particularly limited, but from the viewpoint of cost balance, weather resistance, stain resistance, etc., the A component: B component is preferably in a weight ratio of 20:80 to 80:20, Furthermore, 30:70 to 70:30, particularly 40:60 to 60:40 are preferable.
Further, the blending ratio of the component (B-1) :( B-2) is not particularly limited, but 20:80 to 60:40 is preferable from the viewpoint of imparting pigment dispersibility and thixotropy.
本発明においては、一般式（２）
（Ｒ3Ｏ）4-b−Ｓｉ−Ｒ4 b （２）
で表されるシリコン化合物及び又はその加水分解縮合物（Ｃ）成分が使用される。（Ｃ）成分を配合することによりさらに耐汚染性を向上させることができる。
Ｒ3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のアルキル基が好ましい。
In the present invention, the general formula (2)
(R 3 O) 4-b -Si-R 4 b (2)
And / or its hydrolysis condensate (C) component is used. Contamination resistance can be further improved by blending the component (C).
R 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group.
Ｒ4はＲ1と同様の炭素数１〜４のアルキル基、あるいは炭素数６〜９のアリール基、炭素数７〜９のアラルキル基から選ばれた１価の炭化水素基が好ましい。
ｂは本発明の組成物から形成される塗膜の硬化性が向上するという点からは、ｂが０であるのが好ましい。
一般式（２）中に存在する（Ｒ3Ｏ）4-bの数が複数個の場合、それらは同一であっても、異なっていてもよい。
R 4 is preferably a monovalent hydrocarbon group selected from an alkyl group having 1 to 4 carbon atoms similar to R 1 , an aryl group having 6 to 9 carbon atoms, and an aralkyl group having 7 to 9 carbon atoms.
b is preferably 0 from the viewpoint of improving the curability of the coating film formed from the composition of the present invention.
When there are a plurality of (R 3 O) 4-b present in the general formula (2), they may be the same or different.
前記（Ｃ）成分のシリコン化合物の具体例としては、たとえばテトラメチルシリケート、テトラエチルシリケート、テトラｎ−プロピルシリケート、テトラｉ−プロピルシリケート、テトラｎ−ブチルシリケート、テトラｉ−ブチルシリケートなどのテトラアルキルシリケート；メチルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、オクタデシルトリエトキシシランなどのアルキルトリアルコキシシランなどが挙げられる。 Specific examples of the silicon compound as the component (C) include tetraalkyl silicates such as tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetra i-propyl silicate, tetra n-butyl silicate and tetra i-butyl silicate. Alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and octadecyltriethoxysilane;
また、前記シリコン化合物の部分加水分解縮合物（Ｃ）成分の具体例としては、たとえば通常の方法で前記テトラアルキルシリケートやトリアルコキシシランに水を添加し、縮合させて得られるものがあげられる。具体的には、たとえば、メチルシリケート５１、エチルシリケート４０、エチルシリケート４８、ＨＡＳ−１、ＨＡＳ−１０ （以上、コルコート（株）製）、ＭＳ５１、ＭＳ５６、ＭＳ５６Ｓ（以上、三菱化学（株）製）、ＦＲ−３（メトキシ−エトキシ複合タイプシリケ−ト）、シリケ−ト４０、シリケ−ト４５、シリケ−ト４８、（以上、多摩化学（株）製）などのテトラアルコキシシランの部分加水分解縮合物や、たとえばＡＦＰ−１（信越化学工業（株）製）などのトリアルコキシシランの部分加水分解縮合物などが挙げられる。 Specific examples of the partially hydrolyzed condensate (C) component of the silicon compound include those obtained by condensing water by adding water to the tetraalkylsilicate or trialkoxysilane by an ordinary method. Specifically, for example, methyl silicate 51, ethyl silicate 40, ethyl silicate 48, HAS-1, HAS-10 (above, manufactured by Colcoat Co., Ltd.), MS51, MS56, MS56S (above, manufactured by Mitsubishi Chemical Corporation) ), FR-3 (methoxy-ethoxy complex type silicate), silicate 40, silicate 45, silicate 48, (above, manufactured by Tama Chemical Co., Ltd.), etc. And partially hydrolyzed condensates of trialkoxysilanes such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.).
前記（Ｃ）成分のシリコン化合物の部分加水分解縮合物のうちでは、耐汚染性を発現するのに樹脂（Ａ）および（Ｂ）成分と適度な相溶性を示す点、得られる本発明の組成物の硬化性が良好で、該組成物を用いて形成される塗膜の硬度が上昇することにより汚染物質の付着を制御するという点から、テトラアルコキシシランの部分加水分解縮合物を用いるのが好ましい。具体的には、メチルシリケート５１、ＭＳ５１、ＭＳ５６、ＭＳ５６Ｓ（テトラメトキシシランの部分加水分解縮合物）やエチルシリケート４０、エチルシリケート４８、ＨＡＳ−１シリケート４５（テトラエトキシシランの部分加水分解縮合物）、ＦＲ−３（メトキシ−エトキシ複合タイプシリケ−ト）などがあげられる。 Among the partially hydrolyzed condensates of the silicon compound as the component (C), the composition of the present invention is obtained in that it exhibits moderate compatibility with the resins (A) and (B) to exhibit stain resistance. It is preferable to use a partially hydrolyzed condensate of tetraalkoxysilane because the curability of the product is good and the adhesion of contaminants is controlled by increasing the hardness of the coating film formed using the composition. preferable. Specifically, methyl silicate 51, MS 51, MS 56, MS 56S (tetramethoxysilane partial hydrolysis condensate), ethyl silicate 40, ethyl silicate 48, HAS-1 silicate 45 (tetraethoxysilane partial hydrolysis condensate) FR-3 (methoxy-ethoxy composite type silicate) and the like.
特には、重量平均分子量が１０００より大きいテトラアルコキシシランの部分加水分解縮合物を用いるのが配合量を低減できる点から更に好ましい。具体的にはＭＳ５６、ＭＳ５６Ｓ、ＦＲ−３、シリケート４５およびエチルシリケート４８のような化合物があげられる。前記シリコン化合物等（Ｃ）成分は単独で用いてもよく、２種類以上併用してもよい。 In particular, it is more preferable to use a partially hydrolyzed condensate of tetraalkoxysilane having a weight average molecular weight of more than 1000 from the viewpoint that the blending amount can be reduced. Specific examples include compounds such as MS56, MS56S, FR-3, silicate 45, and ethyl silicate 48. (C) components, such as said silicon compound, may be used independently and may be used together 2 or more types.
前記（Ｃ）成分の使用量は（Ａ）および（Ｂ）の混合成分１００重量部に対して１〜１００重量部、更には２〜５０重量部、特には２〜３０重量部が好ましい。（Ｃ）成分の使用量が１００重量部をこえると塗膜の表面光沢などの外観性が低下したり、クラックなどが発生したりするようになる傾向がある。 The amount of the component (C) used is preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, and particularly preferably 2 to 30 parts by weight with respect to 100 parts by weight of the mixed components (A) and (B). When the amount of the component (C) used exceeds 100 parts by weight, the appearance such as the surface gloss of the coating film tends to deteriorate or cracks and the like tend to occur.
前記（Ｃ）成分は、（Ａ）成分との相溶性を向上させるため、（Ａ）成分の重合時に（Ｃ）成分を加えること、さらに、（Ａ）成分に（Ｃ）成分をホットブレンドすることができる。さらに、本発明の組成物を塗料化するために必要な成分として顔料分散剤（Ｄ）成分、および、顔料（Ｅ）成分が含有される。 In order to improve the compatibility of the component (C) with the component (A), the component (C) is added during the polymerization of the component (A), and the component (C) is hot blended with the component (A). be able to. Furthermore, a pigment dispersant (D) component and a pigment (E) component are contained as components necessary for coating the composition of the present invention.
顔料分散剤（Ｄ）成分としてはアクリル系共重合体、ウレタンオリゴマーが用いることができる。アクリル系共重合体からなる顔料分散剤（Ｄ）成分としては具体的にはフローレンＤＯＰＡ−１５ＢＨＦ、フローレンＤＯＰＡ−１７ＨＦ（以上、共栄社化学製）などのＤＯＰＡシリーズが挙げられる。アクリル系共重合体はアミン価を有していることが好ましく、その値は５〜１００ｍｇＫＯＨ／ｇが好ましく、特には１０〜５０ｍｇＫＯＨ／ｇが好ましい。ウレタンオリゴマーとしては具体的にはＴＧ−７１０（共栄社化学製）が挙げられる。顔料分散剤の添加量は顔料の粒子系等に影響されやすく、適宜、調整が必要である。 As the pigment dispersant (D) component, an acrylic copolymer and a urethane oligomer can be used. Specific examples of the pigment dispersant (D) component made of an acrylic copolymer include DOPA series such as Floren DOPA-15BHF and Floren DOPA-17HF (manufactured by Kyoeisha Chemical Co., Ltd.). The acrylic copolymer preferably has an amine value, and the value is preferably 5 to 100 mgKOH / g, and particularly preferably 10 to 50 mgKOH / g. Specific examples of the urethane oligomer include TG-710 (manufactured by Kyoeisha Chemical). The addition amount of the pigment dispersant is easily influenced by the particle system of the pigment and needs to be appropriately adjusted.
顔料（Ｅ）成分としては、たとえば、酸化チタン、群青、紺青、亜鉛華、ベンガラ、カーボンブラック、酸化鉄、アルミニウム粉、雲母などの無機顔料、アゾ系顔料、トリフェニルメタン系顔料、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の有機顔料などのを使用することが出来る。
前記（Ｂ）成分からなる組成物を用いて顔料分散を行なう場合、顔料（Ｅ）成分と顔料分散剤（Ｄ）成分の組み合わせにより効果が異なる。
Examples of the pigment (E) component include inorganic pigments such as titanium oxide, ultramarine blue, bitumen, zinc white, bengara, carbon black, iron oxide, aluminum powder, mica, azo pigments, triphenylmethane pigments, and quinoline pigments. Organic pigments such as anthraquinone pigments and phthalocyanine pigments can be used.
When pigment dispersion is performed using a composition comprising the component (B), the effect varies depending on the combination of the pigment (E) component and the pigment dispersant (D) component.
酸化チタン、赤錆、黄土などの無機系顔料についてはアミン価を有したアクリル系共重合体を用いることが好ましく、例えばフローレンＤＯＰＡ−１５ＢＨＦ、フローレンＤＯＰＡ−１７ＨＦ（共栄社化学製）などのＤＯＰＡシリーズが例示できる。ウレタンオリゴマーはクリアー分離を起こし易い傾向がある。
一方、一次粒子の小さいカーボンおよび有機系顔料についてはウレタンオリゴマーが適しており、例えばフローレンＤＯＰＡ−１５ＢＨＦのようなアクリル系共重合体は貯蔵安定性を低下させ好ましくない。これらの組み合わせにより分散された塗料を混合しても、調色性への影響は小さく良好な色分れ性が得られる。
For inorganic pigments such as titanium oxide, red rust, and ocher, it is preferable to use an acrylic copolymer having an amine value, for example, DOPA series such as Floren DOPA-15BHF and Floren DOPA-17HF (manufactured by Kyoeisha Chemical). it can. Urethane oligomers tend to cause clear separation.
On the other hand, urethane oligomers are suitable for carbon and organic pigments having small primary particles. For example, an acrylic copolymer such as Florene DOPA-15BHF is not preferable because it decreases storage stability. Even when paints dispersed by these combinations are mixed, the influence on the toning property is small and good color separation is obtained.
一方、汎用的に使用されるポリカルボン酸系の顔料分散剤は凝集を起こしたり、貯蔵後に増粘するなど安定性を低下させる傾向がある。
本発明の組成物には、さらに、その他添加剤（Ｇ）成分としてタレ止め剤、色分れ防止剤、消泡剤から選ばれる少なくとも１種を配合することができる。
On the other hand, polycarboxylic acid-based pigment dispersants that are used for general purposes tend to agglomerate or to increase the viscosity after storage, thereby reducing stability.
The composition of the present invention may further contain at least one selected from an anti-sagging agent, a color separation inhibitor and an antifoaming agent as the other additive (G) component.
タレ止め剤としては具体的には例えばターレン６８２０−１０Ｍ、ターレン６８２０−２０Ｍ、フローノンＥＤＭ−１０（以上、共栄社化学製）などの脂肪酸アマイドワックス系、ターレン２０００（共栄社化学製）などの長鎖脂肪酸エステル重合体などが挙げられる。これらのうち、ターレン６８２０シリーズやフローノンＥＤＭ−１０が垂れ限界膜厚を高く維持でき、且つ、耐候性を損ねない点で好ましい。 Specific examples of the anti-sagging agent include fatty acid amide waxes such as Talen 6820-10M, Talen 6820-20M, Flowon EDM-10 (above, manufactured by Kyoeisha Chemical Co., Ltd.), and long chain fatty acids such as Talen 2000 (manufactured by Kyoeisha Chemical Co., Ltd.). An ester polymer etc. are mentioned. Of these, the Talen 6820 series and Flownon EDM-10 are preferred in that they can maintain a high sagging limit film thickness and do not impair the weather resistance.
色分れ防止剤としては具体的には例えばフローレンＡＦ２０５、フローレンＡＦ５０５、フローレンＡＦ１００５（以上、共栄社化学製）などの特殊シリコン系が挙げられる。これらのうち、フローレンＡＦ２０５、フローレンＡＦ５０５が接触角を低く維持し、汚染性への影響が小さく好ましい。 Specific examples of the color separation preventive agent include special silicon series such as Floren AF205, Floren AF505, and Floren AF1005 (manufactured by Kyoeisha Chemical Co., Ltd.). Of these, Floren AF 205 and Floren AF 505 are preferable because they maintain a low contact angle and have little influence on contamination.
消泡剤としては具体的には例えばフローレンＡＣ９００、フローレンＡＣ９０３、フローレンＡＣ９０５（以上、共栄社化学製），ＯＸ−７７（楠本化成製）などのアクリル・ビニルエーテル系が挙げられる。これらのうち、フローレンＡＣ９０３、ＯＸ−７７が接触角を低く維持し、汚染性への影響が小さく好ましい。 Specific examples of the antifoaming agent include acrylic / vinyl ethers such as Floren AC900, Floren AC903, Floren AC905 (manufactured by Kyoeisha Chemical Co., Ltd.) and OX-77 (manufactured by Enomoto Kasei). Of these, Floren AC903 and OX-77 are preferable because they maintain a low contact angle and have little influence on the contamination.
本発明の弱溶剤（Ｆ）成分は、労働安全衛生法の第３種有機溶剤および第３種有機溶剤に相当する溶剤である。例えば、第３種有機溶剤である芳香族炭化水素を１００％含有するソルベッソ１００(エクソンモービル製)が挙げられる。また、好ましくは脂肪族炭化水素を含有するものが好ましい。具体的には、非水系で芳香族含有量が、５０％以下の溶剤が挙げられ、アイソパ−Ｅ、アイソパ−Ｇ、Ａソルベント（以上、新日本石油製）、ＬＡＷＳ（シェル化学製）、ペガソールＡＮ４５、エクソンナフサＮｏ．６、エクソンナフサＮｏ．５、エクソンナフサＮｏ．３、エクソ−ルＤ４０、エクソ−ルＤ８０（以上、エクソンモービル製）、ＩＰソルベント１６２０、ＩＰソルベント２０２８（以上、出光石油化学製）などが挙げられる。 The weak solvent (F) component of the present invention is a solvent corresponding to the type 3 organic solvent and the type 3 organic solvent of the Industrial Safety and Health Act. For example, Solvesso 100 (manufactured by ExxonMobil) containing 100% aromatic hydrocarbon, which is a third type organic solvent, may be mentioned. Further, those containing aliphatic hydrocarbons are preferred. Specific examples include solvents that are non-aqueous and have an aromatic content of 50% or less, such as Isopar E, Isopar G, A Solvent (above, Shin Nippon Oil), LAWS (manufactured by Shell Chemical), Pegasol AN45, Exxon naphtha no. 6. Exxon naphtha no. 5. Exxon naphtha no. 3, Exol D40, Exol D80 (Exxon Mobil), IP Solvent 1620, IP Solvent 2028 (Idemitsu Petrochemical).
本発明の弱溶剤成分は上記に示したように、（Ａ）および（Ｂ）成分の重合時も使用でき、また、本組成物の希釈溶剤、塗料化時の希釈溶剤、塗装時の希釈溶剤として用いることができる。使用量としては、特に制限はなく、適宜調整することができる。 As described above, the weak solvent component of the present invention can be used during the polymerization of the components (A) and (B), and can be used as a dilution solvent for the composition, a dilution solvent for coating, and a dilution solvent for coating. Can be used as There is no restriction | limiting in particular as usage-amount, It can adjust suitably.
本発明の組成物を用いて作製した塗料を硬化させる場合、有機金属化合物（Ｈ）および、架橋剤としてイソシアナ−ト基を２個以上有する多官能性イソシアナート化合物（Ｉ）成分を含有することができる。そして、それらを予め混合しておいて硬化剤として塗料に配合して用いることができる。硬化剤中には有機金属化合物、多官能性イソシアナート化合物の他に弱溶剤や後述する単官能性イソシアナート化合物を配合することができる。 When curing a paint produced using the composition of the present invention, it contains an organometallic compound (H) and a polyfunctional isocyanate compound (I) component having two or more isocyanate groups as a crosslinking agent. Can do. Then, they can be mixed in advance and used as a curing agent in a paint. In addition to the organometallic compound and the polyfunctional isocyanate compound, a weak solvent or a monofunctional isocyanate compound described later can be blended in the curing agent.
前記有機金属化合物（Ｈ）は硬化性点より錫系化合物、アルミキレート化合物が好ましく、貯蔵安定性、常温硬化性、ポットライフの点より分子内にＳ原子を有する錫化合物が更に好ましい。 The organometallic compound (H) is preferably a tin compound or an aluminum chelate compound from the viewpoint of curability, and more preferably a tin compound having an S atom in the molecule from the viewpoint of storage stability, room temperature curability, and pot life.
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−ブチル錫ラルレ−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, and 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ポットライフ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−トが硬化性、貯蔵安定性、ポットライフの点から好ましい。 Among the tin compounds, a compound having an S atom in the molecule is preferable because of good storage stability and pot life when an isocyanate is blended, and in particular, dibutyltin bisisononyl-3-mercaptopropione. From the viewpoint of curability, storage stability and pot life, dibutyltin bisisooctyl thiogluconate is preferable.
また、前記アルミキレート化合物も好ましく、エチルアセトアセートアルミニウムジイソプロピレート、アルミニウムトリス（アセチルアセトネート）、アルキルアセチルアセテートアルミニウムジイソプロピレート、アルミニウムトリス（エチルアセトアセテート）などがあげられる。 The aluminum chelate compound is also preferable, and examples thereof include ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetylacetonate), alkylacetylacetate aluminum diisopropylate, and aluminum tris (ethylacetoacetate).
前記アルミキレート化合物としては、アルミニウムトリス（エチルアセトアセテート）とアルミニウムトリス（アセチルアセトネート）がイソシアナートと配合した場合の貯蔵安定性およびポットライフのバランスが良好で、塗膜の接触角が小さくなるという点から好ましい。 As the aluminum chelate compound, the balance between storage stability and pot life when aluminum tris (ethyl acetoacetate) and aluminum tris (acetylacetonate) are blended with isocyanate is good, and the contact angle of the coating film becomes small. This is preferable.
前記有機金属化合物（Ｈ）成分は単独でもよく、また、２種類以上併用してもよく、その使用量は、（Ａ）および（Ｃ）の混合成分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、さらに好ましくは０．２〜５重量部である。さらに、有機金属化合物（Ｈ）成分の量が０．００１重量部より少ない場合、硬化性が不十分となり、また、３０重量部を超えると、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するために好ましくない。 The organometallic compound (H) component may be used alone or in combination of two or more, and the amount used is 0.01-30 with respect to 100 parts by weight of the mixed components (A) and (C). Parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight. Furthermore, if the amount of the organometallic compound (H) component is less than 0.001 part by weight, the curability becomes insufficient, and if it exceeds 30 parts by weight, the surface gloss of the coating film formed using the composition It is not preferable because the appearance tends to decrease.
前記、多官能性イソシアナ−ト化合物（Ｉ）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。 Examples of the polyfunctional isocyanate compound (I) include aliphatic and aromatic compounds.
脂肪族系多官能性イソシアナ−ト化合物の具体例として、常温硬化用でヘキサメチレンジイソシアナ−ト、ジシクロヘキシルメタン４，４‘−ジイソシアナ−ト、２，２，４−トリメチル−１，６−ヘキサメチレンジイソシアナ−ト、イソフォロンジイソシアナ−トがあり、構造としては単量体、ビュレット型、ウレジオ型、イソシアヌレ−ト型がある。 Specific examples of the aliphatic polyfunctional isocyanate compound include those for room temperature curing such as hexamethylene diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, 2,2,4-trimethyl-1,6- There are hexamethylene diisocyanate and isophorone diisocyanate, and the structure includes monomer, burette type, uregio type and isocyanurate type.
また、芳香族多官能性イソシアナ−トとしては、２，４―トリレンジイソシアナ−ト、２，６―トリレンジイソシアナ−ト、ジフェニルメタン−４，４‘−ジイソシアナ−ト、キシレンジイソシアナ−ト、ポリメチレン−ポリフェニレル−ポリイソシアナ−ト、などがある。これにも、ビュレット型、ウレジオ型、イソシアヌレ−ト型がある。 Examples of the aromatic polyfunctional isocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, and xylene diisocyanate. -Methylene, polymethylene-polyphenylel-polyisocyanate, and the like. There are also burette type, uregio type and isocyanurate type.
加熱硬化用としてはブロックタイプのものがある。そのブロック剤としてはメチルアルコ−ル、エチルアルコ−ル、ｎ−プロピルアルコ−ル、イソ−プロピルアルコ−ル、ｎ−ブチルアルコ−ル、ｓｅｃ−ブチルアルコ−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−ル、フルフリルアルコ−ル、シクロヘキシルアルコ−ル、フェノ−ル、ｏ−クレゾ−ル、ｍ−クレゾ−ル、ｐ―クレゾ−ル、ｐ−ｔｅｒｔ−ブチルフェノ−ル、チモ−ル、ｐ−ニトロフェノ−ル、β―ナフト−ルなどがある。 There is a block type 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 cell Solve, benzyl alcohol, furfuryl alcohol, cyclohexyl alcohol, phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, timole , P-nitrophenol, β-naphthol and the like.
前記多官能性イソシアナ−ト化合物（Ｉ）成分の使用量は、ＮＣＯ／ＯＨ比率で０．５〜２．０、好ましくは０．７〜１．５となるような比率で行なうことが好ましい。（Ｉ）成分が０．５より小さいと、得られる組成物の硬化性が低下するようになり、また、２．０を超えると、該組成物を用いて得られた塗膜に未反応のイソシアナ−ト化合物あるいはイソシアナ−ト基が残存し、塗り重ね時にちぢみを生じる原因となる他、塗膜表面の水との接触角が低下し難くなり、耐汚染性の改良に悪影響を与える。 The amount of the polyfunctional isocyanate compound (I) used is preferably such that the NCO / OH ratio is 0.5 to 2.0, preferably 0.7 to 1.5. When the component (I) is less than 0.5, the curability of the resulting composition is lowered, and when it exceeds 2.0, the coating film obtained using the composition is unreacted. The isocyanate compound or isocyanate group remains and causes stagnation during coating, and the contact angle with water on the surface of the coating film is difficult to decrease, which adversely affects the stain resistance.
本発明の組成物には、単官能イソシアナ−ト化合物（Ｊ）成分を用いることができる。単官能イソシア−ト化合物（Ｊ）成分を用いることにより硬化剤中の水分を除去することができる。具体例として、イソシアン酸、メチルイソシアナ−ト、エチルイソシアナ−ト、イソプロピルイソシアナ−ト、ヘキシルイソシアナ−ト、ビニルイソシアナ−ト、イソプロペニルイソシアナ−ト、フェニルイソシアナ−ト、トリルイソシアナ−ト、ニトロフェニルイソシアナ−ト、ナフチルイソシアナ−ト、トシルイソシアナ−トなどが挙げられるが、脱水能力および化合物自体の安定性の点からヘキシルイソシアナ−ト、トリルイソシアナ−ト、トシルイソシアナ−トが好ましい。中でも脱水効果の持続性の点からトシルイソシアナ−トが特に好ましい。これらは、単独または２種類以上併用することができる。 A monofunctional isocyanate compound (J) component can be used in the composition of the present invention. By using the monofunctional isocyanate compound (J) component, moisture in the curing agent can be removed. Specific examples include isocyanic acid, methyl isocyanate, ethyl isocyanate, isopropyl isocyanate, hexyl isocyanate, vinyl isocyanate, isopropenyl isocyanate, phenyl isocyanate, Examples include tolyl isocyanate, nitrophenyl isocyanate, naphthyl isocyanate, tosyl isocyanate, and the like. From the viewpoint of dehydration ability and stability of the compound itself, hexyl isocyanate, tolyl isocyanate. -Tosyl isocyanate is preferred. Of these, tosyl isocyanate is particularly preferred from the viewpoint of the durability of the dehydration effect. These can be used alone or in combination of two or more.
単官能イソシア−ト化合物（Ｊ）成分を用いることにより、硬化剤が脱水され、多官能イソシアナ−ト、有機金属化合物を混合した場合の貯蔵安定性が飛躍的に向上する。
前記単官能イソシアナ−ト化合物（Ｊ）成分の配合量としては前記硬化剤中に０．１〜１０重量部である。脱水効果と硬化性維持の点から、０．1〜５重量部が好ましく、０．２〜２重量部がさらに好ましい。
By using the monofunctional isocyanate compound (J) component, the curing agent is dehydrated, and the storage stability when the polyfunctional isocyanate and the organometallic compound are mixed is drastically improved.
As a compounding quantity of the said monofunctional isocyanate compound (J) component, it is 0.1-10 weight part in the said hardening | curing agent. From the point of dehydration effect and curability maintenance, 0.1-5 weight part is preferable, and 0.2-2 weight part is further more preferable.
樹脂（Ａ）成分には、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長期間にわたって優れたものにすることができる。 By adding a dehydrating agent to the resin (A) component, the storage stability of the composition can be improved over a long period of time.
前記脱水剤の具体例としてはたとえばオルトギ酸メチル、オルトギ酸エチル、オルト酢酸メチル、オルト酢酸エチル、オルトプロピオン酸トリメチル、オルトプロピオン酸トリエチル、オルトイソプロピオン酸トリメチル、オルトイソプロピオン酸トリエチル、オルト酪酸トリメチル、オルト酪酸トリエチル、オルトイソ酪酸トリメチル、オルトイソ酪酸トリエチルなどの加水分解性エステル化合物などが挙げられる。この中では、脱水効果，貯蔵安定性の点より、オルト酢酸メチル、オルト蟻酸メイチルが好ましい。これらは単独で用いてもよく、２種以上併用してもよい。
前記脱水剤は、塗料化時に加え、貯蔵安定性を向上させることができる。（Ａ）１００重量部に対して２０重量部以下、好ましくは１０重量部以下、さらに好ましくは５重量部以下で使用される。
Specific examples of the dehydrating agent include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate, trimethyl orthobutyrate. And hydrolysable ester compounds such as triethyl orthobutyrate, trimethyl orthoisobutyrate, and triethyl orthoisobutyrate. Of these, methyl orthoacetate and mayyl formate are preferred from the viewpoints of dehydration effect and storage stability. These may be used alone or in combination of two or more.
The dehydrating agent can improve storage stability in addition to coating. (A) 20 parts by weight or less, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight.
また、本発明の弱溶剤型塗料用樹脂組成物には、反応性希釈剤、紫外線吸収剤、光安定剤などの添加剤を適宜加えてもよい。 Moreover, you may add suitably additives, such as a reactive diluent, a ultraviolet absorber, and a light stabilizer, to the resin composition for weak solvent type coating materials of this invention.
本発明の塗料用樹脂組成物は、たとえばローラー、吹き付け、刷毛、浸漬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ことができる。 The resin composition for coatings of the present invention is applied to an object to be coated by a usual method such as roller, spraying, brushing, dipping, etc., and can usually be cured at normal temperature as it is or by baking at 30 ° C. or higher.
本発明の塗料用樹脂組成物は、たとえば、金属、タイル、セラミックス、ガラス、セメント、モルタル、窯業系成形物、プラスチック、木材、紙、繊維、鉄部などからなる建築物、家電用品、産業機器などの塗料として好適に使用される。さらに、無機質基材に対しては、微弾性中塗り、弾性中塗り上の上塗り塗料として使用することができる。 The resin composition for coatings of the present invention is, for example, a building made of metal, tile, ceramics, glass, cement, mortar, ceramic molding, plastic, wood, paper, fiber, iron, etc., household appliances, industrial equipment It is suitably used as a paint. Furthermore, for an inorganic substrate, it can be used as a fine-coating intermediate coating or a top coating on an elastic intermediate coating.
次に、本発明の塗料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, although the curable resin composition for coating materials of this invention is demonstrated in detail based on an Example, this invention is not limited only to this Example.
樹脂成分
（Ａ）成分の合成
攪拌機、温度計、冷却還流器、チッ素ガス導入管および滴下ロ−トを備えた反応器にペガソールＡＮ４５を５０重量部仕込み、チッ素ガスを導入しつつ１１０℃に昇温した後に、イソブチルメタクリレート６０重量部、２−エチルヘキシルメタクリレート１０重量部、２−エチルヘキシルアクリレート１０、２−ヒドロキシメタクリレート１０重量部、γ−メタクリロキシプロピルトリメトキシシラン１０重量部、２，２‘−アゾビス（２−メチルブチロニトリル）０．９重量部、ペガソールＡＮ４５ ２５重量部からなる成分を滴下ロ−トから５時間かけて等速滴下した。次に、上記反応容器中へ２，２‘−アゾビス（２−メチルブチロニトリル）０．１重量部、ペガソールＡＮ４５ ８重量部を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（Ａ成分）。
Resin component
Synthesis of component (A)
A reactor equipped with a stirrer, thermometer, cooling reflux, nitrogen gas inlet tube and dropping funnel was charged with 50 parts by weight of Pegasol AN45, and after raising the temperature to 110 ° C. while introducing nitrogen gas, isobutyl methacrylate 60 parts by weight, 2-ethylhexyl methacrylate 10 parts by weight, 2-ethylhexyl acrylate 10, 2-hydroxy methacrylate 10 parts by weight, γ-methacryloxypropyltrimethoxysilane 10 parts by weight, 2,2′-azobis (2-methylbutyro A component consisting of 0.9 parts by weight of nitrile and 25 parts by weight of Pegasol AN45 was added dropwise from the dropping funnel over a period of 5 hours. Next, 0.1 part by weight of 2,2′-azobis (2-methylbutyronitrile) and 8 parts by weight of Pegasol AN45 were dropped into the reaction vessel at a constant rate over 1 hour. Then, after stirring at 110 degreeC for 2 hours continuously, it cooled to room temperature (A component).
最後にオルト酢酸メチル０．５重量部、γ−メルカプトプロピルトリメトキシシラン１．５重量部、エチルシリケート４８ ２０重量部を加えて、ペガソールＡＮ４５で固形分濃度を５０％に調整した（Ａ＋Ｃ成分）。得られた樹脂の数平均分子量（ＧＰＣ）は１５，０００であった（ＡＣ−１）。 Finally, 0.5 parts by weight of methyl orthoacetate, 1.5 parts by weight of γ-mercaptopropyltrimethoxysilane and 20 parts by weight of ethyl silicate 48 were added, and the solid content concentration was adjusted to 50% with PEGASOL AN45 (A + C component). . The number average molecular weight (GPC) of the obtained resin was 15,000 (AC-1).
顔料分散処方
サンドグラインダー（アイメックス製）を用いて、表４及び５に示した配合でミルベース（１時間混練）を作製し、更に、レットダウン（３０分混合）を行ない塗料化を行なった。表１に使用した顔料種、表２に添加剤種、表３に硬化剤組成を示した。
Using a pigment dispersion prescription sand grinder (manufactured by IMEX), a mill base (kneaded for 1 hour) was prepared with the formulation shown in Tables 4 and 5, and further let down (mixed for 30 minutes) to make a paint. Table 1 shows the pigment types used, Table 2 shows the additive types, and Table 3 shows the curing agent composition.
硬化剤作製方法
ソルベッソ１００、Ｕ３５０を計量（重量部）、混合後、アディティブＴＩを加え室温で１０分以上脱水する。次いで、ＴＳＡ１００を加え混合した。
Curing agent preparation method Solvesso 100 and U350 are weighed (parts by weight), mixed, then added with additive TI and dehydrated at room temperature for 10 minutes or more. Next, TSA100 was added and mixed.
Ｕ３５０：分子内にＳ原子を有する錫化合物（メルカプト錫）（日東化成（株）製）
ＴＳＡ１００：多官能性イソシアナート化合物（旭化成ケミカルズ（株）製）
ソルベッソ１００：芳香族系弱溶剤（エクソンモービル（株）製）
アディティブＴＩ：単官能イソシアナート（住化バイエルウレタン（株））
得られた塗料の混色性については以下の方法に従って評価した。
U350: Tin compound having S atom in the molecule (mercaptotin) (manufactured by Nitto Kasei Co., Ltd.)
TSA100: polyfunctional isocyanate compound (manufactured by Asahi Kasei Chemicals Corporation)
Solvesso 100: Aromatic weak solvent (ExxonMobil Co., Ltd.)
Additive TI: Monofunctional isocyanate (Suika Bayer Urethane Co., Ltd.)
The color mixing property of the obtained paint was evaluated according to the following method.
混色性および光沢
表４〜５に示した配合（重量部）で調色塗料を得、得られた塗料の貯蔵安定性を表６、７に示した。
ＫＰ１７８８Ａ：日本カーバイド工業（株）製の可溶型のポリオール（（Ｂ−１）成分）
Ｕ−３５０１Ａ：日本カーバイド工業（株）製 ＮＡＤ型ポリオール樹脂（（Ｂ−２）成分）
塗料用シンナー：日亜ペイント（株）製。
Color mixing properties and glossiness Toning paints were obtained with the formulations (parts by weight) shown in Tables 4 to 5. Tables 6 and 7 show the storage stability of the obtained paints.
KP1788A: Soluble polyol (component (B-1)) manufactured by Nippon Carbide Industries Co., Ltd.
U-3501A: NAD type polyol resin (component (B-2)) manufactured by Nippon Carbide Industries Co., Ltd.
Paint thinner: manufactured by Nichia Paint Co., Ltd.
貯蔵安定性試験方法
マヨネーズ瓶に約１５０ｇ各塗料を採取し、４０℃乾燥機で２週間、４週間保存する。取り出し後、２３℃５５％ＲＨの雰囲気下でストーマー型粘度計により測定した（単位：ＫＵ）。
又、得られた調色塗料組成物を２３℃、相対湿度５５％の条件下でアート試験紙上に、１５０μのアプリケーターを用いて塗布し乾燥した。得られた塗装物に対して２時間後に基材の下半分を流し塗りし、垂直に立てかけた。２３℃、相対湿度５５％の条件下で２４時間養生後、１層目（アプリケーター部）と２層目（流し塗り部）との色相変化ΔＥをＣＲ３００（ミノルタ（株）製）にて、および６０°光沢をＧＭ２６８（ミノルタ（株）製）にて評価にて測定した。
Storage stability test method Approximately 150 g of each paint is collected in a mayonnaise bottle and stored in a dryer at 40C for 2 weeks and 4 weeks. After taking out, it was measured with a Stormer viscometer in an atmosphere of 23 ° C. and 55% RH (unit: KU).
Further, the obtained toning coating composition was applied onto an art test paper under conditions of 23 ° C. and relative humidity 55% using a 150 μ applicator and dried. After 2 hours, the lower half of the base material was cast on the obtained coated product and stood vertically. After curing for 24 hours under the conditions of 23 ° C. and 55% relative humidity, the hue change ΔE between the first layer (applicator part) and the second layer (flow coating part) is CR300 (manufactured by Minolta Co., Ltd.), and The 60 ° gloss was measured by evaluation with GM268 (manufactured by Minolta Co., Ltd.).
目視評価基準
○：色の違いが殆どわからない
○△：色の違いがわずかにわかる
×：色の違いが明確にわかる
表４、５で作成した調色塗料に表３の硬化剤と塗料用シンナー（日亜ペイント（株）製）を表８〜１０に示す配合部数（重量）で配合し、その結果を表８〜１０に示す。
Visual evaluation criteria ○: Almost no difference in color ○ △: A slight difference in color ×: A clear difference in color x: The toning paint prepared in Tables 4 and 5 and the curing agent and paint thinner in Table 3 (Nichia Paint Co., Ltd.) was blended in the number of parts (weight) shown in Tables 8-10, and the results are shown in Tables 8-10.
本発明により、貯蔵安定性と混色性（△Ｅの値が小さい、目視評価が良好、光沢値の差が少ない）が良好であることがわかる。 According to the present invention, it can be seen that storage stability and color mixing properties (ΔE value is small, visual evaluation is good, gloss value difference is small) are good.
Claims (9)
Ｒ2 a
|
（Ｒ1Ｏ）3-a−Ｓｉ− （１）
(式中、Ｒ1は、水素原子又は炭素数１〜１０のアルキル基を表す。Ｒ2は、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０アリール基及び炭素数７〜１０のアラルキル基からなる群より選択された１価を表す。Ｒ1又はＲ2が複数存在する場合には、同一であっても異なっていてもよい。ａは、０〜２の整数を表す。)
で表される炭素原子に結合した加水分解性シリル基を少なくとも１個有する共重合体（Ａ）成分、
水酸基含有アクリル樹脂（Ｂ）成分、
下記一般式（２）
（Ｒ3Ｏ）4-b−Ｓｉ−Ｒ4 b （２）
（式中、Ｒ3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７〜１２のアラルキル基から選ばれた１価の炭化水素基、Ｒ4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７〜１２のアラルキル基から選ばれた１価の炭化水素基、ｂは０または１を示す）で表されるシリコン化合物及び又はその加水分解縮合物（Ｃ）成分、アクリル系共重合体またはウレタンオリゴマーからなる顔料分散剤（Ｄ）成分、
顔料（Ｅ）成分、
弱溶剤（Ｆ）成分からなり、
顔料（Ｅ）成分として酸化チタン、群青、紺青、亜鉛華、ベンガラ、酸化鉄、アルミニウム粉および雲母から選択される無機系顔料を用いる場合には、顔料分散剤（Ｄ）成分として１０〜５０ｍｇＫＯＨ／ｇのアミン価を有するアクリル系共重合体を用い、
顔料（Ｅ）成分としてカーボンまたは有機系顔料を用いる場合には、顔料分散剤（Ｄ）成分としてウレタンオリゴマーを用い、
（Ａ）、（Ｂ）および（Ｄ）成分はそれぞれ異なる弱溶剤型塗料用樹脂組成物。 Consists vinyl-based polymer, the following formula in the molecule (1)
R 2 a
|
(R 1 O) 3-a -Si- (1)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. It represents a monovalent group selected from the group consisting of 10 aralkyl groups, and when there are a plurality of R 1 or R 2 s, they may be the same or different, and a represents an integer of 0 to 2. .)
A copolymer (A) component having at least one hydrolyzable silyl group bonded to a carbon atom represented by:
Hydroxyl group-containing acrylic resin (B) component,
The following general formula (2)
(R 3 O) 4-b -Si-R 4 b (2)
(In the formula, R 3 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 12 carbon atoms, and R 4 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 12 carbon atoms, and b represents 0 or 1, and / or The hydrolysis-condensation product (C) component, a pigment dispersant (D) component comprising an acrylic copolymer or a urethane oligomer,
Pigment (E) component,
It consists of a weak solvent (F) component,
When an inorganic pigment selected from titanium oxide, ultramarine blue, bitumen, zinc white, bengara, iron oxide, aluminum powder and mica is used as the pigment (E) component, 10 to 50 mgKOH / Using an acrylic copolymer having an amine value of g,
When carbon or an organic pigment is used as the pigment (E) component, a urethane oligomer is used as the pigment dispersant (D) component,
The components (A), (B) and (D) are different weak solvent paint resins.
Ｒ2 a
|
（Ｒ1Ｏ）3-a−Ｓｉ− （１）
(式中、Ｒ1は、水素原子又は炭素数１〜１０のアルキル基を表す。Ｒ2は、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０アリール基及び炭素数７〜１０のアラルキル基からなる群より選択された１価を表す。Ｒ1又はＲ2が複数存在する場合には、同一であっても異なっていてもよい。ａは、０〜２の整数を表す。)
で表される炭素原子に結合した加水分解性ケイ素基を少なくとも１個有する共重合体（Ａ）成分、下記一般式（２）
（Ｒ3Ｏ）4-b−Ｓｉ−Ｒ4 b （２）
（式中、Ｒ3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７〜１２のアラルキル基から選ばれた１価の炭化水素基、Ｒ4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７〜１２のアラルキル基から選ばれた１価の炭化水素基、ｂは０または１を示す）で表されるシリコン化合物及び又はその加水分解縮合物（Ｃ）成分、さらに、水酸基含有ＮＡＤ型アクリル樹脂（Ｂ−２）成分を用い又は用いずにレットダウンすることを特徴とし、
顔料（Ｅ）成分として酸化チタン、群青、紺青、亜鉛華、ベンガラ、酸化鉄、アルミニウム粉および雲母から選択される無機系顔料を用いる場合には、顔料分散剤（Ｄ）成分として１０〜５０ｍｇＫＯＨ／ｇのアミン価を有するアクリル系共重合体を用い、
顔料（Ｅ）成分としてカーボンまたは有機系顔料を用いる場合には、顔料分散剤（Ｄ）成分としてウレタンオリゴマーを用いる弱溶剤型塗料の顔料分散方法。 And a hydroxyl group-containing weakly solvent-soluble acrylic resin (B-1) component, further, a pigment dispersing agent (D) component, the mill base resin comprising a pigment component (E) consists vinyl-based polymer, the molecule The following general formula (1)
R 2 a
|
(R 1 O) 3-a -Si- (1)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. It represents a monovalent group selected from the group consisting of 10 aralkyl groups, and when there are a plurality of R 1 or R 2 s, they may be the same or different, and a represents an integer of 0 to 2. .)
A copolymer (A) component having at least one hydrolyzable silicon group bonded to a carbon atom represented by the following general formula (2)
(R 3 O) 4-b -Si-R 4 b (2)
(In the formula, R 3 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 12 carbon atoms, and R 4 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 12 carbon atoms, and b represents 0 or 1, and / or The hydrolysis condensate (C) component, and further, letting down with or without using the hydroxyl group-containing NAD type acrylic resin (B-2) component,
When an inorganic pigment selected from titanium oxide, ultramarine blue, bitumen, zinc white, bengara, iron oxide, aluminum powder and mica is used as the pigment (E) component, 10 to 50 mgKOH / Using an acrylic copolymer having an amine value of g,
In the case of using carbon or an organic pigment as the pigment (E) component, a pigment dispersion method for a weak solvent type paint using a urethane oligomer as the pigment dispersant (D) component.
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