JP6073140B2 - Fluororesin water-based paint composition for polycarbonate and method for producing polycarbonate coated article - Google Patents
Fluororesin water-based paint composition for polycarbonate and method for producing polycarbonate coated article Download PDFInfo
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- JP6073140B2 JP6073140B2 JP2013005441A JP2013005441A JP6073140B2 JP 6073140 B2 JP6073140 B2 JP 6073140B2 JP 2013005441 A JP2013005441 A JP 2013005441A JP 2013005441 A JP2013005441 A JP 2013005441A JP 6073140 B2 JP6073140 B2 JP 6073140B2
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- Prior art keywords
- polycarbonate
- coating composition
- aqueous coating
- isocyanate
- fluorine
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- 229920000515 polycarbonate Polymers 0.000 title claims description 66
- 239000004417 polycarbonate Substances 0.000 title claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 37
- 239000000203 mixture Substances 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003973 paint Substances 0.000 title description 9
- 239000008199 coating composition Substances 0.000 claims description 66
- 229920001577 copolymer Polymers 0.000 claims description 52
- -1 isocyanate compound Chemical class 0.000 claims description 50
- 239000012948 isocyanate Substances 0.000 claims description 46
- 229910052731 fluorine Inorganic materials 0.000 claims description 42
- 239000011737 fluorine Substances 0.000 claims description 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 37
- 150000002513 isocyanates Chemical class 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 description 52
- 238000000576 coating method Methods 0.000 description 48
- 239000000047 product Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 229920003002 synthetic resin Polymers 0.000 description 15
- 239000000057 synthetic resin Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 7
- 239000004611 light stabiliser Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OHJYHAOODFPJOD-UHFFFAOYSA-N 2-(2-ethylhexoxy)ethanol Chemical compound CCCCC(CC)COCCO OHJYHAOODFPJOD-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 2
- OADIZUFHUPTFAG-UHFFFAOYSA-N 2-[2-(2-ethylhexoxy)ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCO OADIZUFHUPTFAG-UHFFFAOYSA-N 0.000 description 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 2
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 2
- 241000156978 Erebia Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- SXJSETSRWNDWPP-UHFFFAOYSA-N (2-hydroxy-4-phenylmethoxyphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C(O)=CC=1OCC1=CC=CC=C1 SXJSETSRWNDWPP-UHFFFAOYSA-N 0.000 description 1
- OMWSZDODENFLSV-UHFFFAOYSA-N (5-chloro-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=C(Cl)C=C1C(=O)C1=CC=CC=C1 OMWSZDODENFLSV-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ADQQGJLCEXHTRW-UHFFFAOYSA-N 1-(dimethylamino)hexan-1-ol Chemical compound CCCCCC(O)N(C)C ADQQGJLCEXHTRW-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- HAVHPQLVZUALTL-UHFFFAOYSA-N 1-ethenoxypropan-2-ol Chemical compound CC(O)COC=C HAVHPQLVZUALTL-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 description 1
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- IMJYRYAZVATGLW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2,2-dimethylpropyl)phenol Chemical compound CC(C)(C)CC1=CC(CC(C)(C)C)=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IMJYRYAZVATGLW-UHFFFAOYSA-N 0.000 description 1
- PITPRNOGWXAZAW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-methoxyphenol Chemical compound COC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 PITPRNOGWXAZAW-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DOTYDHBOKPPXRB-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DOTYDHBOKPPXRB-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- IEMHIOUNBGZEAG-UHFFFAOYSA-N 4-tert-butyl-2-(5-chlorobenzotriazol-2-yl)phenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 IEMHIOUNBGZEAG-UHFFFAOYSA-N 0.000 description 1
- QVJGSQBLTKJRSE-UHFFFAOYSA-N 9-ethenoxynonan-1-ol Chemical compound OCCCCCCCCCOC=C QVJGSQBLTKJRSE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- JFHGLVIOIANSIN-UHFFFAOYSA-N dimethyl butanedioate;1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound COC(=O)CCC(=O)OC.CC1(C)CC(O)CC(C)(C)N1CCO JFHGLVIOIANSIN-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
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- 239000005357 flat glass Substances 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 125000001165 hydrophobic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000002609 medium Substances 0.000 description 1
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- 229960001047 methyl salicylate Drugs 0.000 description 1
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- GGTURNAQPMBJID-UHFFFAOYSA-L nickel(2+);4-octyl-2-(5-octyl-2-oxidophenyl)sulfanylphenolate Chemical compound [Ni+2].CCCCCCCCC1=CC=C([O-])C(SC=2C(=CC=C(CCCCCCCC)C=2)[O-])=C1 GGTURNAQPMBJID-UHFFFAOYSA-L 0.000 description 1
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- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical compound OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 description 1
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- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
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- INRGAWUQFOBNKL-UHFFFAOYSA-N {4-[(Vinyloxy)methyl]cyclohexyl}methanol Chemical compound OCC1CCC(COC=C)CC1 INRGAWUQFOBNKL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、ポリカーボネートへの塗布に使用されるポリカーボネート用含フッ素樹脂水性塗料組成物およびポリカーボネート塗装物品の製造方法に関する。 The present invention relates to a fluororesin aqueous coating composition for polycarbonate used for application to polycarbonate and a method for producing a polycarbonate coated article.
ポリカーボネートは、耐破壊性、透明性、軽量性、易加工性などの特性に優れるため、近年、窓材（自動車等の車両用の窓材、家屋、ビル等の建物に取り付けられる建材用の窓材等。）や、公共施設等の屋根、バルコニー、カーポート、アーケード、高速道路の透光性遮音壁等の建材としての使用が広く検討されている。 Polycarbonate is superior in properties such as fracture resistance, transparency, light weight, and easy processability. In recent years, window materials (windows for vehicles such as automobiles, windows for building materials attached to buildings such as houses and buildings) In addition, the use as building materials such as roofs of public facilities and the like, balconies, carports, arcades, and translucent sound insulation walls of expressways has been widely studied.
ところが、ポリカーボネートは耐候性が不充分であり、屋外で使用すると、紫外線の影響により白化、黄変等が発生しやすい。白化、黄変等を防止するためには、ポリカーボネートに、紫外線吸収剤、光安定剤などの添加剤を配合することが考えられる。しかし、充分な耐候性を得るためには、多量の添加剤を配合する必要があり、添加剤のコストが嵩む。 However, polycarbonate has insufficient weather resistance, and when used outdoors, whitening, yellowing, etc. are likely to occur due to the influence of ultraviolet rays. In order to prevent whitening, yellowing, etc., it is conceivable to add additives such as ultraviolet absorbers and light stabilizers to the polycarbonate. However, in order to obtain sufficient weather resistance, it is necessary to add a large amount of additives, which increases the cost of the additives.
そこで、ポリカーボネートからなる基材の表面に、紫外線吸収剤、光安定剤などの添加剤を含有するコーティング剤を塗布し、塗膜を形成する方法が検討されている。この方法では、塗膜を形成するコーティング剤のみに添加剤を配合すればよいため、添加剤の使用量を減らすことができる。
例えば特許文献１〜３には、基材の表面に塗膜を形成し、耐候性などの特性を付与する技術が開示されている。
Therefore, a method of forming a coating film by applying a coating agent containing additives such as an ultraviolet absorber and a light stabilizer on the surface of a substrate made of polycarbonate has been studied. In this method, since the additive only needs to be added to the coating agent that forms the coating film, the amount of the additive used can be reduced.
For example, Patent Documents 1 to 3 disclose techniques for forming a coating film on the surface of a substrate and imparting characteristics such as weather resistance.
しかしながら、従来のコーティング剤を用いてポリカーボネート基材の表面に形成された塗膜は、ポリカーボネート基材との密着性が不充分な場合があった。そのため、コーティング剤に、例えばコロイダルシリカを配合して密着性を向上させることが検討されているが、コロイダルシリカを配合したコーティング液は、貯蔵安定性が低下する懸念がある。また、該コーティング液により形成された塗膜は、クラックや剥がれが生じやすい傾向がある。
密着性を向上させるためには、ポリカーボネート基材上にあらかじめプライマー層（接着層）を設ける方法もあるが、この方法では材料コスト、工程数が増加する。
However, a coating film formed on the surface of a polycarbonate substrate using a conventional coating agent sometimes has insufficient adhesion to the polycarbonate substrate. For this reason, it has been studied to improve the adhesion by, for example, adding colloidal silica to the coating agent, but the coating liquid containing colloidal silica has a concern that the storage stability is lowered. Moreover, the coating film formed with this coating liquid tends to be easily cracked or peeled off.
In order to improve the adhesion, there is a method of providing a primer layer (adhesive layer) in advance on a polycarbonate substrate, but this method increases the material cost and the number of steps.
本発明は、ポリカーカーボネート基材への密着性に優れ、優れた密着性が高温高湿条件下で保持された後も持続する塗膜を形成できる、ポリカーボネート用含フッ素樹脂水性塗料組成物と、該組成物を用いたポリカーボネート塗装物品の製造方法を提供することを目的とする。 The present invention is excellent in adhesiveness to a polycarbonate base material, and can form a coating film that lasts even after excellent adhesiveness is maintained under high-temperature and high-humidity conditions. An object of the present invention is to provide a method for producing a polycarbonate coated article using the composition.
本発明者は、鋭意検討を行った結果、耐候性に優れる含フッ素樹脂をベース樹脂とし、イソシアネート系硬化剤とオキサゾリン基含有ポリマーとを組み合わせて配合することにより、プライマー層を設けなくても、ポリカーボネート基材に良好に密着する水性塗料組成物が得られることを見出して、本発明を完成するに至った。
本発明は、以下の構成を有する。
［１］水酸基を有する含フッ素共重合体（Ａ）と、イソシアネート系硬化剤（Ｂ）と、オキサゾリン基含有ポリマー（Ｃ）と、水とを含有することを特徴とするポリカーボネート用含フッ素樹脂水性塗料組成物。
［２］前記含フッ素共重合体（Ａ）と前記イソシアネート系硬化剤（Ｂ）の合計１００質量部に対して、前記オキサゾリン基含有ポリマー（Ｃ）が１２〜４０質量部配合された、［１］に記載のポリカーボネート用含フッ素樹脂水性塗料組成物。
［３］前記イソシアネート系硬化剤（Ｂ）が、該イソシアネート系硬化剤（Ｂ）中のイソシアネート基が保護されたブロックイソシアネート化合物である、［１］または［２］に記載のポリカーボネート用含フッ素樹脂水性塗料組成物。
［４］前記含フッ素共重合体（Ａ）中の水酸基の全モル数に対する、前記イソシアネート系硬化剤（Ｂ）中のイソシアネート基の全モル数の比率（ＮＣＯ／ＯＨ）が、０．２〜２．０である、［１］〜［３］のいずれかに記載のポリカーボネート用含フッ素樹脂水性塗料組成物。
［５］前記含フッ素共重合体（Ａ）は、フルオロオレフィン系化合物に基く構成単位（ｕ１）と、水酸基を有する単量体に基づく構成単位（ｕ２）と、水酸基を有しない単量体に基づく構成単位（ｕ３）とを有する、［１］〜［４］のいずれかに記載のポリカーボネート用含フッ素樹脂水性塗料組成物。
［６］硬化触媒を含有する、［１］〜［５］のいずれかに記載のポリカーボネート用含フッ素樹脂水性塗料組成物。
［７］前記硬化触媒が、ジアザビシクロウンデセン系触媒、有機チタン系触媒、有機酸アミン塩系触媒およびアミン系触媒からなる群から選ばれる１種以上を含む、［６］に記載のポリカーボネート用含フッ素樹脂水性塗料組成物。
［８］紫外線吸収剤を含有する、［１］〜［７］のいずれかに記載のポリカーボネート用含フッ素樹脂水性塗料組成物。
［９］［１］〜［８］のいずれかに記載のポリカーボネート用含フッ素樹脂水性塗料組成物を、ポリカーボネートからなる基材の表面に塗布し、硬化させることを特徴とするポリカーボネート塗装物品の製造方法。
As a result of intensive studies, the inventor uses a fluorine-containing resin having excellent weather resistance as a base resin, and by blending a combination of an isocyanate curing agent and an oxazoline group-containing polymer, even without providing a primer layer, The inventors have found that an aqueous coating composition that adheres well to a polycarbonate substrate can be obtained, and have completed the present invention.
The present invention has the following configuration.
[1] A fluorine-containing resin aqueous solution for polycarbonate, which contains a fluorine-containing copolymer (A) having a hydroxyl group, an isocyanate curing agent (B), an oxazoline group-containing polymer (C), and water. Paint composition.
[2] 12 to 40 parts by mass of the oxazoline group-containing polymer (C) is blended with respect to 100 parts by mass in total of the fluorine-containing copolymer (A) and the isocyanate curing agent (B). ] The fluororesin water-based coating composition for polycarbonates as described in any one of Claims 1-3.
[3] The fluororesin for polycarbonate according to [1] or [2], wherein the isocyanate curing agent (B) is a blocked isocyanate compound in which an isocyanate group in the isocyanate curing agent (B) is protected. Water-based paint composition.
[4] The ratio (NCO / OH) of the total number of moles of isocyanate groups in the isocyanate curing agent (B) to the total number of moles of hydroxyl groups in the fluorine-containing copolymer (A) is 0.2 to The fluororesin aqueous coating composition for polycarbonate according to any one of [1] to [3], which is 2.0.
[5] The fluorine-containing copolymer (A) comprises a structural unit (u1) based on a fluoroolefin compound, a structural unit (u2) based on a monomer having a hydroxyl group, and a monomer having no hydroxyl group. The fluororesin aqueous coating composition for polycarbonate according to any one of [1] to [4], comprising a structural unit (u3) based thereon.
[6] The fluororesin aqueous coating composition for polycarbonate according to any one of [1] to [5], which contains a curing catalyst.
[7] The polycarbonate according to [6], wherein the curing catalyst includes one or more selected from the group consisting of a diazabicycloundecene catalyst, an organic titanium catalyst, an organic acid amine salt catalyst, and an amine catalyst. Fluorine-containing resin water-based coating composition.
[8] The fluororesin aqueous coating composition for polycarbonate according to any one of [1] to [7], which contains an ultraviolet absorber.
[9] Manufacture of a polycarbonate coated article, wherein the fluororesin aqueous coating composition for polycarbonate according to any one of [1] to [8] is applied to the surface of a substrate made of polycarbonate and cured. Method.
本発明によれば、ポリカーカーボネート基材への密着性に優れ、優れた密着性が高温高湿条件下で保持された後も持続する塗膜を形成できる、ポリカーボネート用含フッ素樹脂水性塗料組成物をできる。また、本発明によれば、ポリカーボネート基材と塗膜とが高温高湿条件下でも良好に密着したポリカーボネート塗装物品を製造できる。 ADVANTAGE OF THE INVENTION According to this invention, the fluorine-containing resin aqueous coating composition for polycarbonates which can form the coating film which is excellent in the adhesiveness to a polycarbonate base material, and can maintain after the outstanding adhesiveness was hold | maintained on high temperature, high humidity conditions Can do. Moreover, according to the present invention, a polycarbonate coated article in which the polycarbonate base material and the coating film are in good contact even under high temperature and high humidity conditions can be produced.
本発明のポリカーボネート用含フッ素樹脂水性塗料組成物（以下、「水性塗料組成物」ともいう。）は、水酸基を有する含フッ素共重合体（Ａ）と、イソシアネート系硬化剤（Ｂ）と、オキサゾリン基含有ポリマー（Ｃ）と、水とを含有し、ポリカーボネートからなる基材（以下、「ポリカーボネート基材」ともいう。）への塗膜形成に使用される。 The fluororesin aqueous coating composition for polycarbonate of the present invention (hereinafter also referred to as “aqueous coating composition”) includes a fluorocopolymer having a hydroxyl group (A), an isocyanate curing agent (B), and an oxazoline. It contains a group-containing polymer (C) and water, and is used for forming a coating film on a substrate made of polycarbonate (hereinafter also referred to as “polycarbonate substrate”).
〔水酸基を有する含フッ素共重合体（Ａ）〕
本発明の水性塗料組成物は、水に合成樹脂が乳化または分散または溶解している組成物であって、前記合成樹脂は、水酸基を有する含フッ素共重合体（Ａ）（以下、「含フッ素共重合体（Ａ）」ともいう。）を含んでいる。
[Fluorine-containing copolymer having a hydroxyl group (A)]
The aqueous coating composition of the present invention is a composition in which a synthetic resin is emulsified, dispersed or dissolved in water, and the synthetic resin is a fluorine-containing copolymer (A) having a hydroxyl group (hereinafter referred to as “fluorine-containing”). Copolymer (A) ").
含フッ素共重合体（Ａ）は、フッ素を含有するとともに、水酸基を含有する共重合体であれば特に制限はないが、フルオロオレフィン系化合物に基づく構成単位（ｕ１）と、水酸基を有する単量体に基づく構成単位（ｕ２）と、水酸基を有しない単量体に基づく構成単位（ｕ３）とを有する共重合体が好ましい。 The fluorine-containing copolymer (A) is not particularly limited as long as it contains fluorine and also contains a hydroxyl group, but the structural unit (u1) based on the fluoroolefin compound and a single monomer having a hydroxyl group A copolymer having a structural unit (u2) based on a body and a structural unit (u3) based on a monomer having no hydroxyl group is preferable.
（構成単位（ｕ１））
重合により構成単位（ｕ１）を形成するフルオロオレフィン系化合物としては、例えば、下記の化合物が挙げられる。
ＣＦ２＝ＣＦ２、ＣＣｌＦ＝ＣＦ２、ＣＨＣｌ＝ＣＦ２、ＣＣｌ２＝ＣＦ２、ＣＣｌＦ＝ＣＣｌＦ、ＣＨＦ＝ＣＣｌ２、ＣＨ２＝ＣＣｌＦ、ＣＣｌ２＝ＣＣｌＦ等のフルオロエチレン。
ＣＦ２ＣｌＣＦ＝ＣＦ２、ＣＦ３ＣＣｌ＝ＣＦ２、ＣＦ３ＣＦ＝ＣＦＣｌ、ＣＦ２ＣｌＣＣｌ＝ＣＦ２、ＣＦ２ＣｌＣＦ＝ＣＦＣｌ、ＣＦＣｌ２ＣＦ＝ＣＦ２、ＣＦ３ＣＣｌ＝ＣＣｌＦ、ＣＦ３ＣＣｌ＝ＣＣｌ２、ＣＣｌＦ２ＣＦ＝ＣＣｌ２、ＣＣｌ３ＣＦ＝ＣＦ２、ＣＦ２ＣｌＣＣｌ＝ＣＣｌ２、ＣＦＣｌ２ＣＣｌ＝ＣＣｌ２、ＣＦ３ＣＦ＝ＣＨＣｌ、ＣＣｌＦ２ＣＦ＝ＣＨＣｌ、ＣＨ３ＣＣｌ＝ＣＨＣｌ、ＣＨＦ２ＣＣｌ＝ＣＣｌ２、ＣＦ２ＣｌＣＨ＝ＣＣｌ２、ＣＦ２ＣｌＣＣｌ＝ＣＨＣｌ、ＣＣｌ３ＣＦ＝ＣＨＣｌ、ＣＨ２ＢｒＣＦ＝ＣＣｌ２等のフルオロプロペン類。
ＣＦ３ＣＣｌ＝ＣＦＣＦ３、ＣＦ２＝ＣＦＣＦ２ＣＣｌＦ２、ＣＦ３ＣＦ２ＣＦ＝ＣＣｌ２等の炭素数４以上のフルオロオレフィン系化合物。
これらの中で、ＣＦ２＝ＣＦ２、ＣＣｌＦ＝ＣＦ２が、塗膜の耐候性に優れる点で好ましい。
(Structural unit (u1))
As a fluoroolefin type compound which forms a structural unit (u1) by superposition | polymerization, the following compound is mentioned, for example.
Fluoroethylene such as CF 2 = CF 2 , CClF = CF 2 , CHCl = CF 2 , CCl 2 = CF 2 , CClF = CClF, CHF = CCl 2 , CH 2 = CClF, CCl 2 = CClF.
CF 2 ClCF = CF 2 , CF 3 CCl = CF 2 , CF 3 CF = CFCl, CF 2 ClCCl = CF 2 , CF 2 ClCF = CFCl, CFCl 2 CF = CF 2 , CF 3 CCl = CClF, CF 3 CCl = CCl 2, CClF 2 CF = CCl 2, CCl 3 CF = CF 2, CF 2 ClCCl = CCl 2, CFCl 2 CCl = CCl 2, CF 3 CF = CHCl, CClF 2 CF = CHCl, CH 3 CCl = CHCl, CHF 2 CCl = CCl 2, CF 2 ClCH = CCl 2, CF 2 ClCCl = CHCl, CCl 3 CF = CHCl, fluoropropenes such as CH 2 BrCF = CCl 2.
CF 3 CCl = CFCF 3, CF 2 = CFCF 2 CClF 2, CF 3 CF 2 CF = C 4+ fluoroolefin compounds carbons such as CCl 2.
Among these, CF 2 = CF 2 and CClF = CF 2 are preferable from the viewpoint of excellent weather resistance of the coating film.
含フッ素共重合体（Ａ）の構成単位全体のうち、構成単位（ｕ１）の含有割合は、３０〜７０モル％が好ましく、４０〜６０モル％がより好ましく、４５〜５５モル％がさらに好ましい。
構成単位（ｕ１）の含有割合が上記範囲であると、充分な耐候性の塗膜が得られやすく、また、含フッ素共重合体（Ａ）のガラス転移温度が高くなりすぎず、非晶質で良好な塗膜が得られやすい。
含フッ素共重合体（Ａ）の分子中に存在する構成単位（ａ１）は１種でもよく、２種以上でもよい。
30-70 mol% is preferable, as for the content rate of a structural unit (u1) among the whole structural units of a fluorine-containing copolymer (A), 40-60 mol% is more preferable, and 45-55 mol% is further more preferable. .
When the content ratio of the structural unit (u1) is in the above range, it is easy to obtain a sufficiently weather-resistant coating film, and the glass transition temperature of the fluorinated copolymer (A) does not become too high. It is easy to obtain a good coating film.
The structural unit (a1) present in the molecule of the fluorinated copolymer (A) may be one type or two or more types.
（構成単位（ｕ２））
構成単位（ｕ２）を構成する水酸基を有する単量体としては、例えば、水酸基含有ビニルエーテル、水酸基含有ビニルエステル、水酸基含有アリルエーテル、水酸基含アリルエステル等の水酸基を有するエチレン性単量体である。
(Structural unit (u2))
Examples of the monomer having a hydroxyl group constituting the structural unit (u2) include ethylenic monomers having a hydroxyl group such as a hydroxyl group-containing vinyl ether, a hydroxyl group-containing vinyl ester, a hydroxyl group-containing allyl ether, and a hydroxyl group-containing allyl ester.
水酸基含有ビニルエーテルとしては、２−ヒドロキシエチルビニルエーテル、ヒドロキシメチルビニルエーテル、３−ヒドロキシプロピルビニルエーテル、４−ヒドロキシブチルビニルエーテル、９−ヒドロキシノニルビニルエーテル、１−ヒドロキシメチル−４−ビニロキシメチルシクロヘキサン、３−クロロ−２−ヒドロキシプロピルビニルエーテル等のヒドロキシアルキルビニルエーテル類が挙げられる。これらの中でも２−ヒドロキシエチルビニルエーテル、４−ヒドロキシブチルビニルエーテルが好ましい。 Examples of the hydroxyl group-containing vinyl ether include 2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether, 1-hydroxymethyl-4-vinyloxymethylcyclohexane, 3-chloro- And hydroxyalkyl vinyl ethers such as 2-hydroxypropyl vinyl ether. Among these, 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether are preferable.
水酸基含有ビニルエステルとしては、ヒドロキシエチル（メタ）アクリレート等のカルボン酸ヒドロキシアルキルエステル類が挙げられる。 Examples of the hydroxyl group-containing vinyl ester include carboxylic acid hydroxyalkyl esters such as hydroxyethyl (meth) acrylate.
これらのなかでは、水酸基含有ビニルエーテルまたは水酸基含有ビニルエステルが好ましく、水酸基含有ビニルエーテルがより好ましい。なかでも、重合性、架橋性の点から、ヒドロキシアルキルビニルエーテル類が好ましい。 Among these, a hydroxyl group-containing vinyl ether or a hydroxyl group-containing vinyl ester is preferable, and a hydroxyl group-containing vinyl ether is more preferable. Of these, hydroxyalkyl vinyl ethers are preferred from the viewpoints of polymerizability and crosslinkability.
含フッ素共重合体（Ａ）の構成単位全体のうち、構成単位（ｕ２）の含有割合は、５〜４０モル％が好ましく、８〜３５モル％がより好ましい。
構成単位（ｕ２）の含有割合が上記範囲の下限値以上であると、成膜時に架橋をした際、充分な架橋密度が得られやすい。また、上記範囲の上限値以下であると、塗膜にしたときに充分な耐水性が得られやすい。
含フッ素共重合体（Ａ）の分子中に存在する構成単位（ｕ２）は１種でもよく、２種以上でもよい。
5-40 mol% is preferable and, as for the content rate of a structural unit (u2) among the whole structural units of a fluorine-containing copolymer (A), 8-35 mol% is more preferable.
When the content ratio of the structural unit (u2) is not less than the lower limit of the above range, a sufficient crosslinking density is easily obtained when crosslinking is performed during film formation. Moreover, when it is below the upper limit of the said range, sufficient water resistance is easy to be obtained when it is set as a coating film.
The structural unit (u2) present in the molecule of the fluorinated copolymer (A) may be one type or two or more types.
（構成単位（ｕ３））
構成単位（ｕ３）を構成する水酸基を有しない単量体としては、水酸基を有しないエチレン性単量体であり、例えば、アルキルビニルエーテル、アルキルカルボン酸ビニルエステル、アルキルアリルエーテル、アルキルカルボン酸アリルエステル等が挙げられ、フッ素原子を有しない単量体であることが好ましい。構成単位（ｕ３）を構成する水酸基を有しない単量体は、これらのなかから、所望の塗膜物性（硬度、光沢、顔料分散性など）に応じて、適宜選択される。
(Structural unit (u3))
The monomer having no hydroxyl group constituting the structural unit (u3) is an ethylenic monomer having no hydroxyl group, such as alkyl vinyl ether, alkyl carboxylic acid vinyl ester, alkyl allyl ether, alkyl carboxylic acid allyl ester. It is preferable that it is a monomer which does not have a fluorine atom. The monomer having no hydroxyl group constituting the structural unit (u3) is appropriately selected from these in accordance with desired film properties (hardness, gloss, pigment dispersibility, etc.).
構成単位（ｕ３）を構成する水酸基を有しない単量体としては、具体的には、エチルビニルエーテル、ｎ−ブチルビニルエーテル、シクロヘキシルビニルエーテル等のビニルエーテル、酢酸ビニル、吉草酸ビニル、またはピバリン酸ビニル等のカルボン酸ビニルが好ましく、特に、エチルビニルエーテルまたはシクロヘキシルビニルエーテルに基づく構成単位は、構成単位（ｕ１）との交互共重合性がよく、含フッ素共重合体（Ａ）のガラス転位温度を調整しやすい点で、好ましい。 Specific examples of the monomer having no hydroxyl group constituting the structural unit (u3) include vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl valerate, and vinyl pivalate. Vinyl carboxylates are preferred, and in particular, a structural unit based on ethyl vinyl ether or cyclohexyl vinyl ether has good alternating copolymerization with the structural unit (u1) and can easily adjust the glass transition temperature of the fluorinated copolymer (A). It is preferable.
含フッ素共重合体（Ａ）の構成単位全体のうち、構成単位（ｕ３）の含有割合は、０〜４５モル％が好ましく、３〜３５モル％がより好ましく、５〜３０モル％がさらに好ましい。
構成単位（ｕ３）の含有割合が上記範囲であると、得られる塗膜の柔軟性が良好となる。
含フッ素共重合体（Ａ）の分子中に存在する構成単位（ｕ３）は１種でもよく、２種以上でもよい。
The content of the structural unit (u3) in the entire structural unit of the fluorinated copolymer (A) is preferably 0 to 45 mol%, more preferably 3 to 35 mol%, and further preferably 5 to 30 mol%. .
When the content ratio of the structural unit (u3) is within the above range, the resulting coating film has good flexibility.
The structural unit (u3) present in the molecule of the fluorine-containing copolymer (A) may be one type or two or more types.
含フッ素共重合体（Ａ）の質量平均分子量（Ｍｗ）は、３，０００〜２００，０００が好ましい。含フッ素共重合体（Ａ）のＭｗが上記範囲の下限値以上であると、形成される塗膜の耐候性が良好になりやすい。また、含フッ素共重合体（Ａ）のＭｗが上記範囲の上限値以下であると、水性塗料組成物の粘度が適度となり、取扱い性が良好になりやすい。含フッ素共重合体（Ａ）のＭｗは、ポリスチレンを標準物質として、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定される値である。 The mass average molecular weight (Mw) of the fluorinated copolymer (A) is preferably from 3,000 to 200,000. When the Mw of the fluorinated copolymer (A) is at least the lower limit of the above range, the weather resistance of the formed coating film tends to be good. Further, when the Mw of the fluorinated copolymer (A) is not more than the upper limit of the above range, the viscosity of the aqueous coating composition becomes appropriate, and the handleability tends to be good. Mw of the fluorinated copolymer (A) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
含フッ素共重合体（Ａ）の水酸基価は、５〜３００［ｍｇＫＯＨ／ｇ］が好ましく、５〜１５０［ｍｇＫＯＨ／ｇ］がより好ましい。含フッ素共重合体（Ａ）の水酸基価が上記範囲内であると、成膜時に充分な架橋密度が得られやすく、塗膜の耐水性も優れる。 5-300 [mgKOH / g] is preferable and, as for the hydroxyl value of a fluorine-containing copolymer (A), 5-150 [mgKOH / g] is more preferable. When the hydroxyl value of the fluorinated copolymer (A) is within the above range, a sufficient crosslinking density can be easily obtained during film formation, and the water resistance of the coating film is excellent.
〔その他の合成樹脂〕
本発明の水性塗料組成物には、含フッ素共重合体（Ａ）以外の他の合成樹脂が、含フッ素共重合体（Ａ）と共に水に乳化または分散または溶解していてもよい。
他の合成樹脂としては、含フッ素共重合体（Ａ）以外のフッ素系樹脂、フェノール系樹脂、アルキド系樹脂、メラミン系樹脂、ユリア系樹脂、ビニル系樹脂、エポキシ系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、アクリル系樹脂などの合成樹脂が挙げられる。
含フッ素共重合体（Ａ）以外のフッ素系樹脂としては、特許第２９５５３３６号に記載のフルオロオレフィンに基づく構成単位および親水性部位を有するマクロモノマーに基づく構成単位を必須構成成分とする含フッ素共重合体が挙げられる。ここで、親水性部位とは、親水性基を有する部位、または親水性の結合を有する部位、およびこれらの組合せからなる部位を意味する。また、マクロモノマーとは片末端にラジカル重合性不飽和基を有する低分子量のポリマーまたはオリゴマーのことである。この含フッ素共重合体を含有させた場合は、水性塗料組成物の機械的安定性および化学的安定性が改良される点で好ましい。
[Other synthetic resins]
In the aqueous coating composition of the present invention, a synthetic resin other than the fluorinated copolymer (A) may be emulsified, dispersed or dissolved in water together with the fluorinated copolymer (A).
Other synthetic resins include fluorine resins other than the fluorine-containing copolymer (A), phenol resins, alkyd resins, melamine resins, urea resins, vinyl resins, epoxy resins, polyester resins, polyurethanes. And synthetic resins such as acrylic resins and acrylic resins.
Examples of the fluorine-based resin other than the fluorine-containing copolymer (A) include a fluorine-containing copolymer having a structural unit based on a fluoroolefin and a structural unit based on a macromonomer having a hydrophilic portion described in Japanese Patent No. 2955336 as essential components. A polymer is mentioned. Here, the hydrophilic part means a part having a hydrophilic group, a part having a hydrophilic bond, or a part composed of a combination thereof. The macromonomer is a low molecular weight polymer or oligomer having a radical polymerizable unsaturated group at one end. When this fluorine-containing copolymer is contained, it is preferable in terms of improving the mechanical stability and chemical stability of the aqueous coating composition.
本発明の水性塗料組成物において、水に乳化または分散または溶解している合成樹脂中に占める含フッ素共重合体（Ａ）の比率は、１０〜１００質量％が好ましく、５０〜１００質量％がより好ましく、優れた耐候性を付与する観点からは５５〜１００質量％がさらに好ましい。 In the aqueous coating composition of the present invention, the proportion of the fluorinated copolymer (A) in the synthetic resin emulsified, dispersed or dissolved in water is preferably 10 to 100% by mass, and 50 to 100% by mass. More preferably, 55-100 mass% is further more preferable from the viewpoint of imparting excellent weather resistance.
〔イソシアネート系硬化剤（Ｂ）〕
本発明の水性塗料組成物は、イソシアネート系硬化剤（Ｂ）を含む。含フッ素共重合体（Ａ）の水酸基（ＯＨ）と、イソシアネート系硬化剤（Ｂ）のイソシアネート基（ＮＣＯ）が反応することにより、含フッ素共重合体（Ａ）が架橋して硬化する。
イソシアネート系硬化剤（Ｂ）としては、ポリイソシアネート化合物または該ポリイソシアネート化合物のイソシアネート基がブロック化剤により保護されたブロックイソシアネート化合物が使用でき、ブロックイソシアネート化合物が水性塗料組成物の貯蔵安定性の点で好ましい。
イソシアネート系硬化剤（Ｂ）は、１種を用いてもよく、２種以上を併用してもよい。
[Isocyanate curing agent (B)]
The aqueous coating composition of the present invention contains an isocyanate curing agent (B). By reacting the hydroxyl group (OH) of the fluorinated copolymer (A) with the isocyanate group (NCO) of the isocyanate curing agent (B), the fluorinated copolymer (A) is crosslinked and cured.
As the isocyanate-based curing agent (B), a polyisocyanate compound or a blocked isocyanate compound in which an isocyanate group of the polyisocyanate compound is protected by a blocking agent can be used, and the blocked isocyanate compound is a storage stability point of an aqueous coating composition. Is preferable.
As the isocyanate curing agent (B), one type may be used, or two or more types may be used in combination.
ポリイソシアネート化合物としては、ヘキサメチレンジイソシアネートなどの脂肪族ポリイソシアネート類；ｍ−またはｐ−フェニレンジイソシアネート、２，４−または２，６−トリレンジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、ナフタレン−１，５−ジイソシアネート、４，４’−ジイソシアネート−３，３’−ジメチルジフェニルなどの芳香族ポリイソシアネート類；ビス−（イソシアネートシクロヘキシル）メタン、イソホロンジイソシアネートなどの脂環式ポリイソシアネート類；クルードトリレンジイソシアネート、クルードジフェニルメタンジイソシアネートなどのクルードポリイソシアネート類；カルボジイミド変性ジフェニルメタンジイソシアネート、ポリオール変性ジフェニルメタンジイソシアネート、ポリオール変性ヘキサメチレンジイソシアネートなどの変性ポリイソシアネート類等が挙げられる。 Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate; m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, naphthalene-1 , 5-diisocyanate, aromatic polyisocyanates such as 4,4′-diisocyanate-3,3′-dimethyldiphenyl; alicyclic polyisocyanates such as bis- (isocyanatocyclohexyl) methane, isophorone diisocyanate; Crude polyisocyanates such as crude diphenylmethane diisocyanate; carbodiimide-modified diphenylmethane diisocyanate, polyol-modified diphenylmethane diisocyanate Aneto, modified polyisocyanates such as such as a polyol-modified hexamethylene diisocyanate.
これらのポリイソシアネート類はビューレット型、イソシアヌレート環型、ウレトジオン型等により、２量体または３量体になっているものであってもよい。 These polyisocyanates may be dimers or trimers by burette type, isocyanurate ring type, uretdione type and the like.
ブロック化剤としては、アルコール類、フェノール類、カプロラクタム類、オキシム類、活性メチレン化合物類などが例示される。これらのうち低温で解離するものが、未硬化膜を硬化させる際の加熱温度を低くできる点で好ましい。
通常、ブロック化剤は１４０℃以上で解離するものが多いが、低温解離型としては１２０℃以下で解離するものが良く、この様な性質のブロック化剤としては、炭素数１〜３のアルキル基を１個または２個有するピラゾール誘導体が挙げられる。なかでもジメチルピラゾールが好ましく、３，５−ジメチルピラゾールがより好ましい。
Examples of the blocking agent include alcohols, phenols, caprolactams, oximes, and active methylene compounds. Among these, those that dissociate at a low temperature are preferable in that the heating temperature for curing the uncured film can be lowered.
Usually, a blocking agent often dissociates at 140 ° C. or higher, but a low-temperature dissociation type is preferably dissociated at 120 ° C. or lower. As a blocking agent having such properties, an alkyl having 1 to 3 carbon atoms is preferable. Examples include pyrazole derivatives having one or two groups. Of these, dimethylpyrazole is preferable, and 3,5-dimethylpyrazole is more preferable.
ブロックイソシアネート化合物の好ましい具体例としては、ヘキサメチレンジイソシアネートを、３，５−ジメチルピラゾールでブロックしたＢａｘｅｎｄｅｎ社製のＴｒｉｘｅｎｅ７９８６（製品名）、Ｔｒｉｘｅｎｅ Ａｑｕａ ＢＩ２２０（製品名）などが挙げられる。 Preferable specific examples of the blocked isocyanate compound include Trixene 7986 (product name) and Trixene Aqua BI220 (product name) manufactured by Baxenden, in which hexamethylene diisocyanate is blocked with 3,5-dimethylpyrazole.
本発明の水性塗料組成物において、含フッ素共重合体（Ａ）中の水酸基の全モル数に対する、イソシアネート系硬化剤（Ｂ）中のイソシアネート基の全モル数の比率（ＮＣＯ／ＯＨ）は、０．２〜２．０が好ましく、０．４〜１．０がより好ましく、０．４〜０．６がさらに好ましい。
該比率（ＮＣＯ／ＯＨ）が上記範囲内であると、ポリカーボネート基材上に形成されて高温高湿条件下で保持された後でも、より優れた密着性を保持する塗膜を形成できる。また、上記範囲の上限値以下であると、塗膜の透明性が優れ、上記範囲の上限値以下であると、塗膜の耐水性、耐候性も優れやすい。上記範囲の下限値以上であると、耐溶剤性、塗膜硬度の良好な塗膜が得られやすい。
In the aqueous coating composition of the present invention, the ratio of the total number of moles of isocyanate groups in the isocyanate-based curing agent (B) to the total number of moles of hydroxyl groups in the fluorine-containing copolymer (A) (NCO / OH) is: 0.2-2.0 are preferable, 0.4-1.0 are more preferable, and 0.4-0.6 are still more preferable.
When the ratio (NCO / OH) is within the above range, it is possible to form a coating film that maintains better adhesion even after being formed on a polycarbonate substrate and held under high temperature and high humidity conditions. Moreover, the transparency of a coating film is excellent in it being below the upper limit of the said range, and the water resistance of a coating film and a weather resistance are easy to be excellent in it being below the upper limit of the said range. When it is at least the lower limit of the above range, it is easy to obtain a coating film having good solvent resistance and coating film hardness.
〔オキサゾリン基含有ポリマー（Ｃ）〕
本発明の水性塗料組成物は、下記式（１）で表されるオキサゾリン基を有するオキサゾリン基含有ポリマー（Ｃ）を含む。オキサゾリン基含有ポリマー（Ｃ）を上述のイソシアネート系硬化剤（Ｂ）と共に含有することにより、水性塗料組成物から形成された塗膜のポリカーボネート基材への密着性は、高温高湿条件下で保持された後でも、良好に持続する。
[Oxazoline group-containing polymer (C)]
The aqueous coating composition of the present invention contains an oxazoline group-containing polymer (C) having an oxazoline group represented by the following formula (1). By containing the oxazoline group-containing polymer (C) together with the above-mentioned isocyanate curing agent (B), the adhesion of the coating film formed from the aqueous coating composition to the polycarbonate substrate is maintained under high temperature and high humidity conditions. Even after being done, it will persist well.
オキサゾリン基含有ポリマー（Ｃ）は、例えば、オキサゾリン基を有する単量体（ｃ１）と、必要に応じて使用される他の単量体（ｃ２）とを重合することにより得られる。
オキサゾリン基を有する単量体（ｃ１）としては、オキサゾリン基と重合性の不飽和結合とを有する単量体が使用でき、例えば、２−ビニル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン等が挙げられる。
The oxazoline group-containing polymer (C) can be obtained, for example, by polymerizing a monomer (c1) having an oxazoline group and another monomer (c2) used as necessary.
As the monomer (c1) having an oxazoline group, a monomer having an oxazoline group and a polymerizable unsaturated bond can be used, for example, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline. Etc.
必要に応じて使用される他の単量体（ｃ２）としては、オキサゾリン基とは反応せず、オキサゾリン基を有する単量体（ｃ１）の不飽和結合と反応して重合する単量体であればよく、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸メトキシポリエチレングリコール、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−アミノエチルおよびその塩等の（メタ）アクリル酸エステル類；（メタ）アクリルニトリル等の不飽和ニトリル類；（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−（２−ヒドロキシエチル）（メタ）アクリルアミド等の不飽和アミド類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル等のビニルエーテル類；エチレン、プロピレン等のα−オレフィン類；塩化ビニル、塩化ビニリデン、フッ化ビニル等の含ハロゲンα，β−不飽和単量体類；スチレン、α−メチルスチレン、スチレンスルホン酸ナトリウム等のα，β−不飽和芳香族単量体類が挙げられ、これらの１種または２種以上の混合物を使用できる。 The other monomer (c2) used as necessary is a monomer that does not react with the oxazoline group but reacts with the unsaturated bond of the monomer (c1) having an oxazoline group to polymerize. For example, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth ) (Meth) acrylic acid esters such as 2-aminoethyl acrylate and salts thereof; unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) acrylamide, N- (2- Hydroxyethyl) unsaturated amides such as (meth) acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; styrene, α-methylstyrene, Examples include α, β-unsaturated aromatic monomers such as sodium styrenesulfonate, and one or a mixture of two or more thereof can be used.
オキサゾリン基含有ポリマー（Ｃ）は、例えば、オキサゾリン基を有する単量体（ｃ１）と、必要に応じて使用される他の単量体（ｃ２）とを公知の重合法により、水性媒体中で重合する方法で製造できる。
水性媒体としては、水；または、水とメタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ターシャリーブタノール、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコール、アセトン、メチルエチルケトン等の混合溶液；が挙げられる。
The oxazoline group-containing polymer (C) is prepared by, for example, using a monomer (c1) having an oxazoline group and another monomer (c2) used as necessary in an aqueous medium by a known polymerization method. It can be produced by a polymerization method.
Examples of the aqueous medium include water; or a mixed solution of water and methanol, ethanol, propanol, isopropanol, butanol, tertiary butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, acetone, methyl ethyl ketone, and the like. It is done.
オキサゾリン基を有する単量体（ｃ１）と、必要に応じて使用される他の単量体（ｃ２）との単量体混合物中、オキサゾリン基を有する単量体（ｃ１）の割合は、５質量％以上であることが好ましい。この範囲であると、適切なオキサゾリン価のオキサゾリン基含有ポリマー（Ｃ）が得られ、これをイソシアネート系硬化剤（Ｂ）と併用することによる効果、すなわち、高温高湿条件下で保持された後でも、ポリカーボネート基材への密着性に優れる塗膜を形成できる効果が充分に得られる。オキサゾリン基含有ポリマー（Ｃ）のオキサゾリン価は、１２０００［ｇ−ｓｏｌｉｄ／ｅｑ．］以下が好ましく、５０〜１００００［ｇ−ｓｏｌｉｄ／ｅｑ．］がより好ましく、１２０〜５５０［ｇ−ｓｏｌｉｄ／ｅｑ．］が特に好ましい。
なお、ここで「オキサゾリン価」とは、オキサゾリン基１ｍｏｌ当たりの重合体の質量である。
The ratio of the monomer (c1) having an oxazoline group in the monomer mixture of the monomer (c1) having an oxazoline group and another monomer (c2) used as necessary is 5 It is preferable that it is mass% or more. Within this range, an oxazoline group-containing polymer (C) having an appropriate oxazoline value is obtained, and the effect obtained by using this in combination with the isocyanate curing agent (B), that is, after being held under high temperature and high humidity conditions However, the effect which can form the coating film which is excellent in the adhesiveness to a polycarbonate base material is fully acquired. The oxazoline value of the oxazoline group-containing polymer (C) is 12000 [g-solid / eq. ] The following is preferable, 50-10000 [g-solid / eq. ] Is more preferable, 120-550 [g-solid / eq. ] Is particularly preferable.
Here, the “oxazoline value” is the mass of the polymer per 1 mol of the oxazoline group.
オキサゾリン基含有ポリマー（Ｃ）は、含フッ素共重合体（Ａ）とイソシアネート系硬化剤（Ｂ）の合計１００質量部に対して、固形分基準で、１２〜４０質量部配合されることが好ましく、１４〜４０質量部がより好ましく、１４〜２０質量部がさらに好ましい。オキサゾリン基含有ポリマー（Ｃ）の配合量が上記範囲の下限値以上であると、高温高湿条件下で保持された後でも、ポリカーボネート基材への密着性に優れる塗膜を形成でき、上記範囲の上限値以下であると、塗膜の透明性も優れる。 The oxazoline group-containing polymer (C) is preferably blended in an amount of 12 to 40 parts by mass based on the solid content with respect to 100 parts by mass in total of the fluorine-containing copolymer (A) and the isocyanate curing agent (B). 14-40 mass parts is more preferable, and 14-20 mass parts is further more preferable. When the blending amount of the oxazoline group-containing polymer (C) is not less than the lower limit of the above range, a coating film having excellent adhesion to a polycarbonate substrate can be formed even after being held under high temperature and high humidity conditions. When the amount is not more than the upper limit, the transparency of the coating film is also excellent.
〔硬化触媒〕
本発明の水性塗料組成物は、硬化触媒を含有することが好ましい。硬化触媒としては、水分散性または水溶性等を有し、水性塗料組成物への配合時に、水性塗料組成物の液の均一性を損なわず、沈殿物を生じ難いものが好ましい。
硬化触媒は、樹脂の硬化触媒として公知の化合物から適宜選択して用いることができるが、本発明の水性塗料において、含フッ素共重合体（Ａ）の乳化または溶解または分散の安定性を保ちつつ、良好な硬化促進効果が得られやすい硬化触媒として、以下の化合物が挙げられる。
１，８−ジアザビシクロ（５，４，０）ウンデセン−７のギ酸塩、フェノール塩、オクチル酸塩、オレイン酸塩、ｐ−トルエンスルホン酸塩等のジアザビシクロウンデセン系触媒；
チタンジイソプロポキシビス（トリエタノールアミネート）、チタンジ−ｎ−ブトキシビス（トリエタノールアミネート）、チタンラクテート、チタンラクテートアンモニウム塩等の有機チタン系触媒；
ｐ−トルエンスルホン酸アミン塩、ドデシルベンゼンスルホン酸アミン塩、ジノニルナフタレンスルホン酸アミン塩、ジノニルナフタレンジスルホン酸アミン塩、アルキルリン酸アミン塩等の、有機酸アミン塩系触媒；
トリエチレンジアミン、Ｎ，Ｎ−ジメチルベンジルアミン、Ｎ，Ｎ−ジメチルアミノヘキサノール等のアミン系触媒。
[Curing catalyst]
The aqueous coating composition of the present invention preferably contains a curing catalyst. As the curing catalyst, a catalyst having water dispersibility or water solubility and the like, which does not impair the uniformity of the liquid of the aqueous coating composition and does not easily generate a precipitate when blended into the aqueous coating composition is preferable.
The curing catalyst can be appropriately selected and used from known compounds as a curing catalyst for the resin. In the aqueous coating material of the present invention, while maintaining the stability of emulsification, dissolution or dispersion of the fluorinated copolymer (A). Examples of the curing catalyst that can easily obtain a good curing accelerating effect include the following compounds.
Diazabicycloundecene catalyst such as formate, phenol salt, octylate, oleate, p-toluenesulfonate of 1,8-diazabicyclo (5,4,0) undecene-7;
Organotitanium catalysts such as titanium diisopropoxybis (triethanolaminate), titanium di-n-butoxybis (triethanolaminate), titanium lactate, titanium lactate ammonium salt;
organic acid amine salt catalysts such as p-toluenesulfonic acid amine salt, dodecylbenzenesulfonic acid amine salt, dinonylnaphthalenesulfonic acid amine salt, dinonylnaphthalenedisulfonic acid amine salt, alkylphosphoric acid amine salt;
Amine-based catalysts such as triethylenediamine, N, N-dimethylbenzylamine, N, N-dimethylaminohexanol;
これらの硬化触媒は１種を単独で用いても、２種以上を併用してもよい。より強度が高い塗膜（硬化膜）が得られやすい点で、２種以上を併用することが好ましい。
例えば、ジアザビシクロウンデセン系触媒から選ばれる１種以上と、有機チタン系触媒から選ばれる１種以上を併用することが好ましい。
または、ジアザビシクロウンデセン系触媒から選ばれる１種以上と、有機酸アミン塩系触媒から選ばれる１種以上を併用することが好ましい。
特に、ジアザビシクロウンデセン系触媒として、１，８−ジアザビシクロ（５，４，０）ウンデセン−７のギ酸塩を用い、これと有機チタン系触媒から選ばれる１種以上、または有機酸アミン塩系触媒から選ばれる１種以上とを併用することがより好ましい。
有機チタン系触媒としては、チタンジイソプロポキシビス（トリエタノールアミネート）が特に好ましい。
有機酸アミン塩としては、ドデシルベンゼンスルホン酸アミン塩、Ｕ−ＣＡＴ １８Ｘ（製品名、サンアプロ社製、特殊アミン塩）が特に好ましい。
These curing catalysts may be used alone or in combination of two or more. It is preferable to use two or more kinds in combination in that a coating film (cured film) having higher strength is easily obtained.
For example, it is preferable to use in combination one or more selected from diazabicycloundecene catalysts and one or more selected from organic titanium catalysts.
Alternatively, it is preferable to use one or more selected from diazabicycloundecene catalysts and one or more selected from organic acid amine salt catalysts in combination.
In particular, 1,8-diazabicyclo (5,4,0) undecene-7 formate is used as the diazabicycloundecene catalyst, and one or more selected from these and organic titanium catalysts, or organic acid amine salts It is more preferable to use in combination with one or more selected from the system catalysts.
As the organic titanium catalyst, titanium diisopropoxybis (triethanolaminate) is particularly preferable.
As the organic acid amine salt, dodecylbenzenesulfonic acid amine salt, U-CAT 18X (product name, manufactured by San Apro, special amine salt) is particularly preferable.
本発明の水性塗料組成物における硬化触媒の含有量は、水性塗料組成物１００質量％中、０．００１〜３．０質量％が好ましく、０．００１〜１．０質量％がより好ましい。上記範囲の下限値以上であると、良好な硬化促進効果が得られやすく、上記範囲の上限値以下であると良好な貯蔵安定性が得られやすい。 0.001-3.0 mass% is preferable in 100 mass% of aqueous coating compositions, and, as for content of the curing catalyst in the aqueous coating composition of this invention, 0.001-1.0 mass% is more preferable. When it is at least the lower limit of the above range, a good curing accelerating effect is easily obtained, and when it is at most the upper limit of the above range, good storage stability is easily obtained.
〔その他の成分〕
本発明の水性塗料は、造膜助剤、表面調整剤（レベリング剤）、増粘剤、紫外線吸収剤、光安定剤、消泡剤、シランカップリング剤等の添加剤を適宜含有することが好ましい。
[Other ingredients]
The water-based paint of the present invention may appropriately contain additives such as a film-forming aid, a surface conditioner (leveling agent), a thickener, an ultraviolet absorber, a light stabilizer, an antifoaming agent, and a silane coupling agent. preferable.
造膜助剤としては、ジエチレングリコールモノ−２−エチルヘキシルエーテル（以下、「ＥＨＤＧ」ともいう。）、エチレングリコールモノ−２−エチルヘキシルエーテル（以下、「ＥＨＧ」ともいう。）、ジエチレングリコールモノエチルエーテルアセテート、２，２，４−トリメチル−１，３−ペンタンジオールモノ（２−メチルプロピオネート）、ジエチレングリコールジエチルエーテル等が挙げられる。造膜助剤を含有させる場合、その含有量は、含フッ素共重合体（Ａ）とその他の合成樹脂の合計（固形分）の１００質量部に対し、３０質量部以下が好ましく、２０質量部以下がより好ましい。 Examples of film-forming aids include diethylene glycol mono-2-ethylhexyl ether (hereinafter also referred to as “EHDG”), ethylene glycol mono-2-ethylhexyl ether (hereinafter also referred to as “EHG”), diethylene glycol monoethyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol mono (2-methylpropionate), diethylene glycol diethyl ether and the like can be mentioned. When the film-forming auxiliary is included, the content is preferably 30 parts by mass or less, and 20 parts by mass with respect to 100 parts by mass of the total (solid content) of the fluorinated copolymer (A) and other synthetic resins. The following is more preferable.
表面調整剤としては、ポリエーテル変性ポリジメチルシロキサン、ポリエーテル変性シロキサン等が好ましく挙げられる。
増粘剤としては、ポリウレタン系会合性増粘剤等が好ましく挙げられる。
Preferred examples of the surface conditioner include polyether-modified polydimethylsiloxane and polyether-modified siloxane.
Preferred examples of the thickener include polyurethane-based associative thickeners.
本発明の水性塗料組成物は、紫外線吸収剤を含有することが好ましい。該水性塗料組成物は、含フッ素共重合体（Ａ）を含有し、該含フッ素共重合体（Ａ）は耐候性に優れるため、紫外線吸収剤をさらに含むことにより、耐候性が非常に優れる塗膜を形成できる。 The aqueous coating composition of the present invention preferably contains an ultraviolet absorber. The water-based coating composition contains a fluorine-containing copolymer (A), and the fluorine-containing copolymer (A) is excellent in weather resistance. Therefore, the weather resistance is extremely excellent by further including an ultraviolet absorber. A coating film can be formed.
紫外線吸収剤としては、公知の種々のものが使用できる。特に透明塗料として上塗り塗装で用いる場合に適した紫外線吸収剤としては、
サリチル酸メチル、サリチル酸フェニル、サリチル酸クレジル、サリチル酸ベンジル等のサリチル酸エステル類；
２−ヒドロキシベンゾフェノン、２−ヒドロキシ−４−ベンジロキシベンゾフェノン、２−ヒドロキシ−４−オクトキシベンゾフェノン、２−ヒドロキシ−５−クロロベンゾフェノン、２−アミノベンゾフェノン、アデカ・アーガス社製のＴ−５７として販売されているような高分子量変性品等のベンゾフェノン類；
２−（２’−ヒドロキシ−５’−ｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−５’−メトキシフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ネオペンチルフェニル）ベンゾトリアゾール、チバ・ガイギー社製のチヌビン９００、１１３０として販売されているような高分子量変性品等のベンゾトリアゾール類；
２−シアノ−３，３−ジフェニルアクリル酸エチル、２−シアノ−３，３−ジフェニルアクリル酸２−エチルヘキシル、α−シアノ−β−メチル−４−メトキシ桂皮酸メチル等の置換アクリロニトリル類；
２，２’−チオビス（４−オクチルフェノレート）ニッケル錯塩、｛２，２’−チオビス（４−ｔ−オクチルフェノラート）｝−ｎ−ブチルアミン・ニッケル錯塩等のニッケル錯塩；
センカ社製のシャインガードＴＡ−２２として販売されているような水系のヒドロキシフェニルトリアジン類；
ｐ−メトキシベンジリデンマロン酸ジメチル、レゾルシノールモノ安息香酸エステル、ヘキサメチルリン酸トリアミド、２，５−ジフェニル−ｐ−ベンゾキノン等の紫外線吸収剤；およびビス（２，２，６，６−テトラメチル−４−ピペリジン）セバケート、コハク酸ジメチル−１−（２−ヒドロキシエチル）−４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン重縮合物、２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロン酸ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）等があり、これらは１種または２種以上の混合物として組み合わせて用いることもできる。
Various known ultraviolet absorbers can be used. Especially as a UV absorber suitable for use in top coating as a transparent paint,
Salicylic acid esters such as methyl salicylate, phenyl salicylate, cresyl salicylate, benzyl salicylate;
2-hydroxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, 2-aminobenzophenone, sold as T-57 manufactured by Adeka Argus Benzophenones such as modified high molecular weight products;
2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 5′-methoxyphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-neopentylphenyl) benzotriazole, high as sold as Tinuvin 900, 1130 from Ciba Geigy Benzotriazoles such as molecular weight modified products;
Substituted acrylonitriles such as ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, methyl α-cyano-β-methyl-4-methoxycinnamate;
Nickel complex salts such as 2,2′-thiobis (4-octylphenolate) nickel complex salt, {2,2′-thiobis (4-t-octylphenolate)}-n-butylamine / nickel complex salt;
Water-based hydroxyphenyltriazines such as those sold as Singuard's Shine Guard TA-22;
UV absorbers such as dimethyl p-methoxybenzylidenemalonate, resorcinol monobenzoate, hexamethylphosphoric triamide, 2,5-diphenyl-p-benzoquinone; and bis (2,2,6,6-tetramethyl-4 -Piperidine) sebacate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 2- (3,5-di-t-butyl- 4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) and the like, and these should be used in combination as one kind or a mixture of two or more kinds You can also.
紫外線吸収剤は、含フッ素共重合体（Ａ）とその他の合成樹脂の合計（固形分）の１００質量部あたり０．１〜２０質量部、特には０．１〜１０質量部の範囲で使用することが好ましい。紫外線吸収剤の量が少なすぎる場合においては、耐光性の改良効果が充分に得られず、また、多すぎる場合には、その効果が飽和してしまい、適当とはいえない。 The ultraviolet absorber is used in the range of 0.1 to 20 parts by mass, particularly 0.1 to 10 parts by mass per 100 parts by mass of the total (solid content) of the fluorinated copolymer (A) and other synthetic resins. It is preferable to do. When the amount of the ultraviolet absorber is too small, the effect of improving the light resistance cannot be sufficiently obtained. When the amount is too large, the effect is saturated, which is not appropriate.
光安定剤としてはアデカ・アーガス社製のＭＡＲＫ ＬＡ ５７，６２，６３，６７，６８（いずれも製品名）、チバ・ガイギー社製のチヌビン６２２ＬＤ（製品名）、チヌビン１２３ＤＷ（製品名）などのようなヒンダードアミン系の光安定剤が挙げられる。これらは、１種または２種以上の混合物として紫外線吸収剤と組み合わせて用いることもできる。 Examples of light stabilizers include MARK LA 57, 62, 63, 67, 68 (all product names) manufactured by Adeka Argus, Tinuvin 622LD (product name), and Tinuvin 123DW (product name) manufactured by Ciba-Geigy. Such hindered amine light stabilizers can be mentioned. These can also be used in combination with an ultraviolet absorber as one kind or a mixture of two or more kinds.
消泡剤としては、脂肪酸塩類、高級アルコール硫酸塩類、液体脂肪油硫酸エステル類、脂肪族アミンおよび脂肪族アミドの硫酸塩類、脂肪族アルコールリン酸エステル類、二塩基性脂肪酸エステルのスルホン酸塩類、脂肪酸アミドスルホン酸塩類、アルキルアリルスルホン酸塩類、ホルマリン縮合のナフタリンスルホン酸塩類、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェノールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、ポリオキシエチレンソルビタンアルキルエステル類、アクリル系ポリマー、シルコーン混合アクリル系ポリマー、ビニル系ポリマー、ポリシロキサン化合物などが挙げられる。
消泡剤の消泡効果は親水基と疎水基のバランス（ＨＬＢ価）で左右され、ＨＬＢが６以下、特に４以下のものが好ましく採用される。
Antifoaming agents include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, sulfates of aliphatic amines and aliphatic amides, aliphatic alcohol phosphates, sulfonates of dibasic fatty acid esters, Fatty acid amide sulfonates, alkyl allyl sulfonates, formalin condensed naphthalene sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan Examples include alkyl esters, acrylic polymers, silcorn mixed acrylic polymers, vinyl polymers, polysiloxane compounds, and the like.
The antifoaming effect of the antifoaming agent depends on the balance (HLB value) between the hydrophilic group and the hydrophobic group, and those having an HLB of 6 or less, particularly 4 or less are preferably employed.
カップリング剤としては、 アミノ基、エポキシ基、ビニル基、（メタ）アクリル基、メルカプト基などを有するシランカップリング剤が挙げられ、例えば、東レ・ダウコーニング社製の「Ｚ−６０４０（製品名）」として販売されているグリシドキシプロピルトリメトキシシラン等が挙げられる。 Examples of the coupling agent include silane coupling agents having an amino group, an epoxy group, a vinyl group, a (meth) acryl group, a mercapto group, and the like. For example, “Z-6040 (product name) manufactured by Toray Dow Corning Co., Ltd. ) "Is sold as glycidoxypropyltrimethoxysilane.
なお、塗膜の光沢を調整する必要がある場合は、常用の無機または有機のツヤ消剤を添加すればよい。
また、着色が必要な場合には、市販の有機顔料、無機顔料、有機染料、これらを複合化した顔料もしくは染料等の着色材を分散若しくは混合添加すればよい。
In addition, when it is necessary to adjust the gloss of the coating film, a conventional inorganic or organic delustering agent may be added.
Further, when coloring is necessary, a commercially available organic pigment, inorganic pigment, organic dye, or a coloring material such as a pigment or dye obtained by combining these may be dispersed or mixed.
〔水性塗料組成物〕
本発明の水性塗料組成物は、有機溶媒を含まないもの、または有機溶媒を含み、水性塗料用組成物の全質量中における有機溶媒の含有量が１０質量％以下であるもの、好ましくは３質量％以下であるもののいずれかであることが好ましい。
含有し得る有機溶媒としては、例えば、含フッ素共重合体（Ａ）、イソシアネート系硬化剤（Ｂ）、オキサゾリン基含有ポリマー（Ｃ）の各製造工程に由来する残留物、これらを乳化、分散、溶解させるために使用される媒体としての有機溶媒、上述の各添加剤に含まれる有機溶媒等が挙げられる。
[Water-based paint composition]
The aqueous coating composition of the present invention does not contain an organic solvent, or contains an organic solvent, and the content of the organic solvent in the total mass of the aqueous coating composition is 10% by mass or less, preferably 3%. % Or less is preferable.
Examples of the organic solvent that can be contained include, for example, a residue derived from each production step of the fluorine-containing copolymer (A), the isocyanate curing agent (B), and the oxazoline group-containing polymer (C), and emulsifying, dispersing, and the like. Examples thereof include an organic solvent as a medium used for dissolution, an organic solvent contained in each of the above-described additives, and the like.
本発明の水性塗料組成物は、含フッ素共重合体（Ａ）を含む合成樹脂が水に乳化または溶解または分散している組成物であればよく、例えば含フッ素共重合体（Ａ）を含む合成樹脂が水に乳化しているエマルション塗料組成物が好適である。 The water-based coating composition of the present invention may be a composition in which the synthetic resin containing the fluorine-containing copolymer (A) is emulsified, dissolved or dispersed in water, and includes, for example, the fluorine-containing copolymer (A). An emulsion coating composition in which a synthetic resin is emulsified in water is preferred.
エマルション塗料組成物は、乳化重合で製造された合成樹脂のエマルションと、他の成分、すなわち、イソシアネート系硬化剤（Ｂ）およびオキサゾリン基含有ポリマー（Ｃ）と、必要に応じて使用される添加剤とを混合する方法で調製できる。合成樹脂のエマルションは、例えば、比較的多量に界面活性剤を用いた乳化重合により製造する方法、親水性マクロマーをフルオロオレフィン、ビニルエーテルなどと共重合させて、界面活性剤を用いないで製造する方法、合成樹脂を溶液重合などの別の方法で製造し、その後、該合成樹脂からエマルションを調製する方法等で製造できる。 The emulsion paint composition comprises an emulsion of a synthetic resin produced by emulsion polymerization, other components, that is, an isocyanate-based curing agent (B) and an oxazoline group-containing polymer (C), and additives used as necessary And can be prepared by mixing them. Synthetic resin emulsions, for example, are produced by emulsion polymerization using a relatively large amount of a surfactant, and are produced by copolymerizing a hydrophilic macromer with a fluoroolefin, vinyl ether, etc. without using a surfactant. The synthetic resin can be produced by another method such as solution polymerization, and then an emulsion is prepared from the synthetic resin.
本発明の水性塗料組成物において、含フッ素共重合体（Ａ）とイソシアネート系硬化剤（Ｂ）とオキサゾリン基含有ポリマー（Ｃ）との合計の固形分濃度は、ポリカーボネート基材を保護するための充分な膜厚を得る点から、１０〜６０質量％であることが好ましく、１０〜５０質量％であることがより好ましい。 In the aqueous coating composition of the present invention, the total solid concentration of the fluorine-containing copolymer (A), the isocyanate curing agent (B), and the oxazoline group-containing polymer (C) is for protecting the polycarbonate substrate. From the viewpoint of obtaining a sufficient film thickness, it is preferably 10 to 60% by mass, and more preferably 10 to 50% by mass.
〔ポリカーボネート塗装物品の製造方法〕
本発明のポリカーボネート塗装物品の製造方法は、本発明の水性塗料組成物をポリカーボネート基材の表面に塗布して未硬化膜を形成し、該未硬化膜を例えば加熱により硬化させる方法である。
水性塗料組成物のポリカーボネート基材上への塗布は、ロールコーター、バーコーター等を用いた公知の方法を採用できる。
[Production method of polycarbonate coated article]
The method for producing a polycarbonate coated article of the present invention is a method in which the aqueous coating composition of the present invention is applied to the surface of a polycarbonate substrate to form an uncured film, and the uncured film is cured, for example, by heating.
A known method using a roll coater, a bar coater or the like can be adopted for applying the aqueous coating composition onto the polycarbonate substrate.
未硬化膜を硬化させるために加熱する際の加熱温度は、水の沸点以上が好ましく、イソシアネート系硬化剤（Ｂ）として、ブロックイソシアネート化合物を用いる場合には、ブロックイソシアネート化合物のブロック化剤が解離する温度（解離温度）以上とする。上限は、水性塗料組成物中の成分の熱分解が生じない温度範囲とする。
例えば、イソシアネート系（Ｂ）硬化剤が、解離温度が１２０℃以下である低温解離型のブロックイソシアネート化合物である場合、加熱温度は１１０〜２５０℃が好ましい。加熱温度が高いほど、未硬化膜の乾燥および硬化は速く進む。加熱時間は、加熱温度に応じて、好ましい硬化状態が得られる時間に設定することができる。
本発明の水性塗料組成物は短時間の加熱で硬化させることができ、数分間（例えば２〜５分間）の加熱でも硬化させることが可能である。
The heating temperature for heating to cure the uncured film is preferably equal to or higher than the boiling point of water. When a blocked isocyanate compound is used as the isocyanate curing agent (B), the blocking agent of the blocked isocyanate compound is dissociated. Temperature (dissociation temperature) or higher. The upper limit is a temperature range in which thermal decomposition of components in the aqueous coating composition does not occur.
For example, when the isocyanate-based (B) curing agent is a low-temperature dissociation type blocked isocyanate compound having a dissociation temperature of 120 ° C. or lower, the heating temperature is preferably 110 to 250 ° C. The higher the heating temperature, the faster the drying and curing of the uncured film. The heating time can be set to a time during which a preferable cured state is obtained according to the heating temperature.
The aqueous coating composition of the present invention can be cured by heating for a short time, and can also be cured by heating for several minutes (for example, 2 to 5 minutes).
以上説明したように、本発明の水性塗料組成物は、含フッ素共重合体（Ａ）をベースとし、イソシアネート系硬化剤（Ｂ）とオキサゾリン基含有ポリマー（Ｃ）とを共に配合したものである。そのため、イソシアネート系硬化剤（Ｂ）とオキサゾリン基含有ポリマー（Ｃ）の相乗効果により、該水性塗料組成物で形成された塗膜は、ポリカーボネート基材に対して優れた密着性を発揮し、高温高湿条件下に保持された場合でも密着性が良好に持続する。そのため、本発明の水性塗料組成物を塗布するにあたって、あらかじめポリカーボネート基材に対してプライマー層を設ける必要がない。また、密着性向上のために、コロイダルシリカを配合する必要がないため、コロイダルシリカを配合することに起因する水性塗料組成物の貯蔵安定性低下、塗膜におけるクラック発生等の懸念が生じない。
本発明の水性塗料組成物の奏する優れた密着性は、ポリカーボネート基材に対して選択的に発揮される。この詳細な理由は明らかではないが、後述するように、本発明の水性塗料組成物から形成された塗膜を例えばポリエチレンテレフタレート基材やガラス基材に対して設けても、ポリカーボネート基材に対して発揮されるような、高温高湿条件下での優れた密着性は得られない。
As described above, the water-based coating composition of the present invention is based on the fluorine-containing copolymer (A), and contains both the isocyanate curing agent (B) and the oxazoline group-containing polymer (C). . Therefore, due to the synergistic effect of the isocyanate-based curing agent (B) and the oxazoline group-containing polymer (C), the coating film formed from the aqueous coating composition exhibits excellent adhesion to the polycarbonate substrate, and has a high temperature. Even when kept under high-humidity conditions, the adhesiveness is maintained well. Therefore, when applying the water-based coating composition of the present invention, it is not necessary to previously provide a primer layer on the polycarbonate substrate. Moreover, since it is not necessary to mix | blend colloidal silica in order to improve adhesiveness, concerns, such as the storage stability fall of the water-based coating composition resulting from mix | blending colloidal silica, and the crack generation in a coating film, do not arise.
The excellent adhesion exhibited by the aqueous coating composition of the present invention is selectively exhibited with respect to the polycarbonate substrate. Although the detailed reason is not clear, as will be described later, even if a coating film formed from the aqueous coating composition of the present invention is provided on, for example, a polyethylene terephthalate base material or a glass base material, As a result, excellent adhesion under high temperature and high humidity conditions cannot be obtained.
本発明の水性塗料組成物は、例えば屋外において、窓材（自動車等の車両用の窓材、家屋、ビル等の建物に取り付けられる建材用の窓材等）、公共施設等の屋根、バルコニー、カーポート、アーケード、高速道路の透光性遮音壁等の建材などとして使用されるポリカーボネート基材の表面のコーティングに好適に使用される。本発明の水性塗料組成物を、ポリカーボネート基材の表面に塗布し、硬化させることにより、ポリカーボネート塗装物品を製造できる。 The water-based paint composition of the present invention, for example, outdoors, window materials (window materials for vehicles such as automobiles, window materials for building materials attached to buildings such as houses and buildings), roofs of public facilities, balconies, It is suitably used for coating the surface of a polycarbonate substrate used as a building material such as a carport, an arcade, and a light-transmitting sound insulation wall of an expressway. A polycarbonate coated article can be produced by applying the aqueous coating composition of the present invention to the surface of a polycarbonate substrate and curing it.
以下、本発明について、実施例および比較例を用いて具体的に説明する。
なお、下記の表１に示す各成分は、以下のとおりである。
〔含フッ素共重合体（Ａ１）〕
旭硝子社製、フルオロオレフィン系化合物に基く構成単位（ｕ１）と、水酸基を有する単量体に基づく構成単位（ｕ２）と、水酸基を有しない単量体に基づく構成単位（ｕ３）とを有する、フッ素樹脂エマルション「ルミフロンＦＥ−４４００（商品名）」（水酸基価＝５５ｍｇＫＯＨ／ｇ；固形分４８質量％。）。
〔イソシアネート系硬化剤（Ｂ１）〕
Ｂａｘｅｎｄｅｎ社製のブロックイソシアネート化合物「Ｔｒｉｘｅｎｅ Ａｑｕａ ＢＩ２２０（製品名）」：ヘキサメチレンジイソシアネートと３，５−ジメチルピラゾール（ブロック化剤）との反応物、解離温度１１０〜１２０℃、固形分４０質量％、溶媒は水およびＣｏａｓｏｌ混合液。なお、Ｃｏａｓｏｌとはジカルボン酸とジイソブチルエーテルの混合物である。
〔オキサゾリン基含有ポリマー（Ｃ）〕
日本触媒社製「エポクロスＷＳ−７００（製品名）」：アクリル系の主鎖を有するオキサゾリン基含有ポリマー、溶媒は水、ｐＨ７〜１０、オキサゾリン価（［ｇ−ｓｏｌｉｄ／ｅｑ．］、計算値）＝２２０、固形分２５質量％。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
In addition, each component shown in the following Table 1 is as follows.
[Fluoropolymer (A1)]
Asahi Glass Co., Ltd., having a structural unit (u1) based on a fluoroolefin compound, a structural unit (u2) based on a monomer having a hydroxyl group, and a structural unit (u3) based on a monomer having no hydroxyl group, Fluororesin emulsion “Lumiflon FE-4400 (trade name)” (hydroxyl value = 55 mg KOH / g; solid content 48 mass%).
[Isocyanate curing agent (B1)]
Block isocyanate compound “Trixene Aqua BI220 (product name)” manufactured by Baxenden: reaction product of hexamethylene diisocyanate and 3,5-dimethylpyrazole (blocking agent), dissociation temperature of 110 to 120 ° C., solid content of 40% by mass, Solvent is water and Coasol mixture. Coasol is a mixture of dicarboxylic acid and diisobutyl ether.
[Oxazoline group-containing polymer (C)]
“Epocross WS-700 (product name)” manufactured by Nippon Shokubai Co., Ltd .: Oxazoline group-containing polymer having an acrylic main chain, solvent is water, pH 7 to 10, oxazoline value ([g-solid / eq.], Calculated value) = 220, solid content 25% by weight.
〔カップリング剤〕
東レ・ダウコーニング社製シランカップリング剤「Ｚ６０４０（製品名）」：グリシドキシプロピルトリメトキシシラン。
〔表面調整剤（レベリング剤）〕
サンノプコ社製「ＳＮウェット１２６（製品名）」：変性シリコーン系湿潤剤（有効成分９３質量％）。
[Coupling agent]
Silane coupling agent "Z6040 (product name)" manufactured by Toray Dow Corning: Glycidoxypropyltrimethoxysilane.
[Surface conditioner (leveling agent)]
“SN Wet 126 (product name)” manufactured by San Nopco: modified silicone wetting agent (active ingredient 93% by mass).
〔紫外線吸収剤〕
センカ社製「シャインガードＴＡ−２２（製品名）」：ヒドロキシフェニルトリアジン誘導体、有効成分３０質量％。
〔光安定剤〕
ＢＡＳＦ社製「チヌビン１２３ＤＷ（製品名）」：ヒンダードアミン系光安定剤、有効成分３０質量％。
[Ultraviolet absorber]
“Shinguard TA-22 (product name)” manufactured by Senka Co., Ltd .: hydroxyphenyltriazine derivative, 30% by mass of active ingredient.
(Light stabilizer)
“TINUVIN 123DW (product name)” manufactured by BASF: hindered amine light stabilizer, 30% by mass of active ingredient.
〔硬化触媒１〕
サンアプロ社製「Ｕ−ＣＡＴ ＳＡ ６０３（製品名）」：ジアザビシクロウンデセンギ酸塩。
〔硬化触媒２〕
マツモトファインケミカル社製「オルガチックスＴＣ−４００（製品名）」：チタンジイソプロポキシビス（トリエタノールアミネート)の２−プロパノール溶液、有効成分８０質量％。
[Curing catalyst 1]
“U-CAT SA 603 (product name)” manufactured by San Apro, Inc .: diazabicycloundescenate.
[Curing catalyst 2]
“Orgachix TC-400 (product name)” manufactured by Matsumoto Fine Chemical Co., Ltd .: 2-propanol solution of titanium diisopropoxybis (triethanolaminate), 80% by mass of active ingredient.
〔造膜助剤１〕
ジエチレングリコールモノ−２−エチルヘキシルエーテル。
〔造膜助剤２〕
エチレングリコールモノ−２−エチルヘキシルエーテル。
[Film-forming aid 1]
Diethylene glycol mono-2-ethylhexyl ether.
[Film-forming aid 2]
Ethylene glycol mono-2-ethylhexyl ether.
〔例１〕
表１に示す配合量で、含フッ素共重合体（Ａ１）、イソシアネート系硬化剤（Ｂ１）、オキサゾリン基含有ポリマー（Ｃ１）、その他の各種成分を混合し、水を加えて全量を１００質量部とし、エマルション形態の水性塗料組成物を得た。
なお、表１中の配合量の単位は質量部である。
また、表１中に記載の各成分について、固形分量（有効成分量）が１００質量％ではないものについては、各成分それぞれの固形分量（有効成分量）を記載した。固形分量（有効成分量）の単位は質量％である。例えば、表１中、含フッ素共重合体（Ａ１）は、配合量が「５０．２（質量部）」、固形分量（有効成分量）が「４８（質量％）」であるため、水性塗料組成物１００質量部中に含まれる含フッ素共重合体（Ａ１）の固形分量（有効成分量）は、「５０．２×０．４８＝２４．１（質量部）」である。水性塗料組成物１００質量部中に含まれる各成分の固形分量（有効成分量）についても、表１に記載した。
また、表２に示すように、例１の水性塗料組成物において、含フッ素共重合体（Ａ１）とイソシアネート系硬化剤（Ｂ１）の合計１００質量部に対する、オキサゾリン基含有ポリマー（Ｃ１）の配合量（固形分基準）は１８質量部で、含フッ素共重合体（Ａ１）中の水酸基の全モル数に対する、イソシアネート系硬化剤（Ｂ１）中のイソシアネート基の全モル数の比率（ＮＣＯ／ＯＨ）は０．４である。
[Example 1]
Fluoropolymer (A1), isocyanate-based curing agent (B1), oxazoline group-containing polymer (C1), and other various components are mixed in the amounts shown in Table 1, and water is added to make the total amount 100 parts by mass. An aqueous coating composition in the form of an emulsion was obtained.
In addition, the unit of the compounding quantity in Table 1 is a mass part.
Moreover, about each component as described in Table 1, about the thing whose solid content (effective component amount) is not 100 mass%, each component's solid content (effective component amount) was described. The unit of the solid content (active ingredient amount) is mass%. For example, in Table 1, the fluorine-containing copolymer (A1) has a compounding amount of “50.2 (parts by mass)” and a solid content (active ingredient amount) of “48 (mass%)”. The solid content (active ingredient amount) of the fluorine-containing copolymer (A1) contained in 100 parts by mass of the composition is “50.2 × 0.48 = 24.1 (parts by mass)”. The solid content (effective component amount) of each component contained in 100 parts by mass of the aqueous coating composition is also shown in Table 1.
Moreover, as shown in Table 2, in the aqueous coating composition of Example 1, the blending of the oxazoline group-containing polymer (C1) with respect to a total of 100 parts by mass of the fluorine-containing copolymer (A1) and the isocyanate-based curing agent (B1). The amount (based on solid content) is 18 parts by mass, and the ratio of the total number of moles of isocyanate groups in the isocyanate curing agent (B1) to the total number of moles of hydroxyl groups in the fluorine-containing copolymer (A1) (NCO / OH ) Is 0.4.
〔例２〜１４〕
表１に示す水以外の成分のうち、イソシアネート系硬化剤（Ｂ１）とオキサゾリン基含有ポリマー（Ｃ１）の配合量のみを例１から変更し、さらに水の量を調整することにより全量を１００質量部とし、表２に示す例２〜１４のエマルション形態の水性塗料組成物を調製した。
[Examples 2 to 14]
Of the components other than water shown in Table 1, only the blending amount of the isocyanate curing agent (B1) and the oxazoline group-containing polymer (C1) is changed from Example 1, and the total amount is adjusted to 100 mass by adjusting the amount of water. The aqueous coating composition in the emulsion form of Examples 2 to 14 shown in Table 2 was prepared.
〔塗膜の密着性〕
以下のようにして、各例で得られた水性塗料組成物から塗膜を形成し、その密着性を評価した。
ポリカーボネート基材（ポリカーボネート板、タキロン社製、「ＰＣ１６００ポリカーボネートプレート（製品名）」）に、バーコーターを用いて水性塗料組成物を塗布し、未硬化膜を形成した後、１２０℃の恒温乾燥器中で２０分乾燥させて、乾燥膜厚が約５μｍの塗膜を形成した。
形成された塗膜付きのポリカーボネート基材を、温度１２１℃、湿度１００％ＲＨ、圧力０．１０５ＭＰａの高温高湿条件下で４８時間保持するプレッシャークッカー試験（以下、「ＰＣＴ試験」ともいう。）に供し、該ＰＣＴ試験前後における塗膜の密着性を評価した。
密着性は、ＪＩＳ Ｋ ５６００−５−６に記載の１ｍｍ角×１００マス・クロスカット法に従って行い、下記の基準にて３段階で評価した。
○：クロスカット部の剥離面積が５％以下（ＪＩＳ Ｋ ５６００−５−６分類の「０〜１」に対応。）。
△：クロスカット部の剥離面積が５％を超えて、６５％未満（ＪＩＳ Ｋ ５６００−５−６分類の「２〜４」に対応。）。
×：クロスカット部の剥離面積が６５％以上（ＪＩＳ Ｋ ５６００−５−６分類の「５」に対応。）。
[Adhesion of coating film]
A coating film was formed from the aqueous coating composition obtained in each example as described below, and the adhesion was evaluated.
After applying an aqueous coating composition to a polycarbonate substrate (polycarbonate plate, manufactured by Takiron, “PC1600 polycarbonate plate (product name)”) using a bar coater to form an uncured film, a constant temperature dryer at 120 ° C. The film was dried for 20 minutes to form a coating film having a dry film thickness of about 5 μm.
A pressure cooker test (hereinafter, also referred to as “PCT test”) in which the formed polycarbonate substrate with a coating film is held for 48 hours under a high temperature and high humidity condition of a temperature of 121 ° C., a humidity of 100% RH, and a pressure of 0.105 MPa. The coating film adhesion before and after the PCT test was evaluated.
Adhesion was performed according to the 1 mm square × 100 mass crosscut method described in JIS K 5600-5-6, and evaluated in three stages according to the following criteria.
○: The peeled area of the crosscut portion is 5% or less (corresponding to “0 to 1” of JIS K 5600-5-6 classification).
(Triangle | delta): The peeling area of a crosscut part exceeds 5%, and is less than 65% (corresponding to "2-4" of JISK5600-5-6 classification).
X: The peeled area of the crosscut portion is 65% or more (corresponding to “5” in JIS K 5600-5-6 classification).
表２の結果に示されるように、イソシアネート系硬化剤（Ｂ１）とオキサゾリン基含有ポリマー（Ｃ１）とを併用した例１〜８の水性塗料組成物から形成された塗膜は、ＰＣＴ試験前はもちろん、高温高湿条件下におけるＰＣＴ試験後にも、ポリカーボネート基材に対して優れた密着性を有していた。
これに対して、イソシアネート系硬化剤（Ｂ１）を配合していない例１４の水性塗料組成物は、ＰＣＴ試験前の密着性は優れたが、ＰＣＴ試験後にはクロスカット部の剥離面積が６５％以上となり密着性が低下した。また、オキサゾリン基含有ポリマー（Ｃ１）を配合していない例１０〜１２の水性塗料組成物も、ＰＣＴ試験前の密着性は優れたが、ＰＣＴ試験後には低下した。オキサゾリン基含有ポリマー（Ｃ１）を配合しておらず、イソシアネート系硬化剤（Ｂ１）の配合量が比較的多い例１３の水性塗料組成物や、イソシアネート系硬化剤（Ｂ１）とオキサゾリン基含有ポリマー（Ｃ１）のいずれをも配合していない例９の水性塗料組成物から形成された塗膜は、ＰＣＴ試験前の密着性も不充分であった。
As shown in the results of Table 2, before the PCT test, the coating film formed from the aqueous coating composition of Examples 1 to 8 in which the isocyanate curing agent (B1) and the oxazoline group-containing polymer (C1) were used in combination. Of course, even after the PCT test under high temperature and high humidity conditions, it had excellent adhesion to the polycarbonate substrate.
On the other hand, the aqueous coating composition of Example 14 in which the isocyanate-based curing agent (B1) was not blended was excellent in adhesion before the PCT test, but after the PCT test, the peeled area of the crosscut portion was 65%. As a result, the adhesion decreased. In addition, the water-based paint compositions of Examples 10 to 12 in which the oxazoline group-containing polymer (C1) was not blended were excellent in adhesion before the PCT test, but decreased after the PCT test. The aqueous coating composition of Example 13, which contains no oxazoline group-containing polymer (C1) and has a relatively large amount of isocyanate-based curing agent (B1), or an isocyanate-based curing agent (B1) and an oxazoline group-containing polymer ( The coating film formed from the aqueous coating composition of Example 9 in which none of C1) was blended also had insufficient adhesion before the PCT test.
なお、例１の水性塗料組成物を用いて、ポリエチレンテレフタレート基材におけるコロナ表面処理された表面に、塗膜を形成したが、該塗膜の密着性は、ＰＣＴ試験前で「○」、ＰＣＴ試験後で「×」という結果であった。また、例１の水性塗料組成物を用いて、フロート板ガラス（ＪＩＳ Ｒ３２０２）の表面に、塗膜を形成したが、該塗膜の密着性は、ＰＣＴ試験前で「×」、ＰＣＴ試験後で「×」という結果であった。塗膜の形成方法、乾燥条件等はポリカーボネート基材を用いた場合と同様にした。
この結果から、本発明の水性塗料組成物の優れた密着性は、ポリカーボネート基材に対して選択的に発揮されることがわかった。
In addition, although the coating film was formed in the surface by which the corona surface treatment in the polyethylene terephthalate base material was carried out using the water-based coating composition of Example 1, the adhesiveness of the coating film was “O” before the PCT test. The result was “x” after the test. In addition, a coating film was formed on the surface of a float plate glass (JIS R3202) using the aqueous coating composition of Example 1. The adhesion of the coating film was “x” before the PCT test, and after the PCT test. The result was “x”. The method for forming the coating film, the drying conditions, and the like were the same as when the polycarbonate substrate was used.
From this result, it was found that the excellent adhesion of the water-based coating composition of the present invention is exhibited selectively with respect to the polycarbonate substrate.
Claims (8)
前記含フッ素共重合体（Ａ）は、フルオロオレフィン系化合物に基く構成単位（ｕ１）と、水酸基を有する単量体に基づく構成単位（ｕ２）と、水酸基を有しない単量体に基づく構成単位（ｕ３）とを有することを特徴とするポリカーボネート用含フッ素樹脂水性塗料組成物。 A fluorine-containing copolymer having a hydroxyl group (A), an isocyanate-based curing agent (B), an oxazoline group-containing polymer (C), and water ;
The fluorine-containing copolymer (A) includes a structural unit (u1) based on a fluoroolefin compound, a structural unit (u2) based on a monomer having a hydroxyl group, and a structural unit based on a monomer having no hydroxyl group. (u3) and polycarbonate for fluororesin aqueous coating composition characterized in that it have a.
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