JP6635025B2 - Compositions and articles for fluorine-containing coatings - Google Patents
Compositions and articles for fluorine-containing coatings Download PDFInfo
- Publication number
- JP6635025B2 JP6635025B2 JP2016507737A JP2016507737A JP6635025B2 JP 6635025 B2 JP6635025 B2 JP 6635025B2 JP 2016507737 A JP2016507737 A JP 2016507737A JP 2016507737 A JP2016507737 A JP 2016507737A JP 6635025 B2 JP6635025 B2 JP 6635025B2
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- Prior art keywords
- fluorine
- composition
- monomer
- group
- structural unit
- Prior art date
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- 229910052731 fluorine Inorganic materials 0.000 title claims description 106
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 95
- 239000011737 fluorine Substances 0.000 title claims description 95
- 239000000203 mixture Substances 0.000 title claims description 93
- 238000000576 coating method Methods 0.000 title claims description 85
- 239000000178 monomer Substances 0.000 claims description 126
- 239000003973 paint Substances 0.000 claims description 90
- -1 hydroxyalkyl vinyl ethers Chemical class 0.000 claims description 85
- 239000011248 coating agent Substances 0.000 claims description 82
- 229920002313 fluoropolymer Polymers 0.000 claims description 72
- 239000004811 fluoropolymer Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 20
- 239000008199 coating composition Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 19
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 5
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- 150000001721 carbon Chemical group 0.000 description 5
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
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- 239000007787 solid Substances 0.000 description 5
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- 238000004383 yellowing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000006224 matting agent Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 125000005370 alkoxysilyl group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 230000007613 environmental effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 235000015096 spirit Nutrition 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
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- 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 2
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
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- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- JMFYZMAVUHNCPW-UHFFFAOYSA-N dimethyl 2-[(4-methoxyphenyl)methylidene]propanedioate Chemical compound COC(=O)C(C(=O)OC)=CC1=CC=C(OC)C=C1 JMFYZMAVUHNCPW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- SKDCBUQQYLPHDI-UHFFFAOYSA-N hydroxy 2-methylpentan-2-yl carbonate Chemical class CCCC(C)(C)OC(=O)OO SKDCBUQQYLPHDI-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- ZKALVNREMFLWAN-UHFFFAOYSA-N n-(4-methylpentan-2-ylidene)hydroxylamine Chemical compound CC(C)CC(C)=NO ZKALVNREMFLWAN-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- CPHCIYGRSFZNRD-UHFFFAOYSA-N n-methyl-1-(4,5,6,7-tetrahydro-1h-indazol-3-yl)methanamine Chemical compound C1CCCC2=C1NN=C2CNC CPHCIYGRSFZNRD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- DDBNQTLBNWVNAS-UHFFFAOYSA-N o-ethenylhydroxylamine Chemical class NOC=C DDBNQTLBNWVNAS-UHFFFAOYSA-N 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZQMAPKVSTSACQB-UHFFFAOYSA-N prop-2-enyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC=C ZQMAPKVSTSACQB-UHFFFAOYSA-N 0.000 description 1
- HPCIWDZYMSZAEZ-UHFFFAOYSA-N prop-2-enyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC=C HPCIWDZYMSZAEZ-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 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
- 229960001860 salicylate Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IWPOSDLLFZKGOW-AATRIKPKSA-N trans-beta-octenoic acid Chemical compound CCCC\C=C\CC(O)=O IWPOSDLLFZKGOW-AATRIKPKSA-N 0.000 description 1
- XXHDAWYDNSXJQM-ONEGZZNKSA-N trans-hex-3-enoic acid Chemical compound CC\C=C\CC(O)=O XXHDAWYDNSXJQM-ONEGZZNKSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/24—Trifluorochloroethene
- C08F214/242—Trifluorochloroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Description
本発明は、含フッ素塗料用組成物および物品に関する。 The present invention relates to a composition for a fluorine-containing paint and an article.
輸送用機器、土木部材、建築部材、電子部品等の様々な被塗装物に対する塗装に用いる塗料用組成物としては、耐久性に優れた塗膜を形成できることから、含フッ素重合体を含む含フッ素塗料用組成物が広く用いられている。 As a coating composition used for coating various objects to be coated such as transportation equipment, civil engineering members, building members, and electronic components, it is possible to form a coating film having excellent durability. Paint compositions are widely used.
含フッ素塗料用組成物としては、例えば、以下のものが知られている。
(i)フルオロオレフィンに基づく構成単位と、架橋性基(水酸基、カルボキシ基等)を有する構成単位と、アルキル基と重合性不飽和基がエーテル結合またはエステル結合で連結された単量体(アルキルビニルエーテル類、アルキルビニルエステル類等)に基づく構成単位と、を有する含フッ素重合体を含む含フッ素塗料用組成物(例えば、特許文献1、2)。
(ii)フルオロオレフィンに基づく構成単位と、親水性部位(ポリオキシエチレン鎖等)を有するマクロモノマーに基づく構成単位と、水酸基を有する単量体に基づく構成単位と、を有する含フッ素重合体を含む含フッ素塗料用組成物(特許文献3)。As the composition for a fluorine-containing coating, for example, the following are known.
(I) a monomer (alkyl) in which a structural unit based on a fluoroolefin, a structural unit having a crosslinkable group (hydroxyl group, carboxy group, etc.), and an alkyl group and a polymerizable unsaturated group are connected by an ether bond or an ester bond. And a structural unit based on vinyl ethers, alkyl vinyl esters, and the like), and a composition for a fluorine-containing paint containing a fluorine-containing polymer (for example, Patent Documents 1 and 2).
(Ii) a fluoropolymer having a structural unit based on a fluoroolefin, a structural unit based on a macromonomer having a hydrophilic site (polyoxyethylene chain or the like), and a structural unit based on a monomer having a hydroxyl group. A composition for fluorine-containing paint containing (Patent Document 3).
含フッ素塗料用組成物を塗装して塗膜を形成する際には、塗膜表面に優れた撥水性が要求されることが多い。そのため、含フッ素塗料用組成物(i)、(ii)よりも撥水性に優れた塗膜を形成できる含フッ素塗料用組成物を得ることは重要である。 When applying a composition for a fluorine-containing paint to form a coating film, the surface of the coating film is often required to have excellent water repellency. Therefore, it is important to obtain a composition for a fluorine-containing paint capable of forming a coating film having better water repellency than the compositions (i) and (ii) for the fluorine-containing paint.
本発明は、優れた撥水性を有する塗膜を形成できる含フッ素塗料用組成物、および該含フッ素塗料用組成物により形成した塗膜を有する物品の提供を目的とする。 An object of the present invention is to provide a composition for a fluorine-containing paint capable of forming a coating film having excellent water repellency, and an article having a coating film formed from the composition for a fluorine-containing paint.
前記の課題を達成するために、本発明は以下の構成を採用した。
[1]フルオロオレフィン(a1)(ただし、下記の単量体(a3)を除く。)に基づく構成単位(α1)、架橋性基を有し、フッ素原子を有しない構成単位(α2)、CX1X2=CX3−CF3(ただし、X1〜X3はそれぞれ独立に水素原子、塩素原子またはフッ素原子であり、X1〜X3の少なくとも1つが水素原子である。)で表される単量体(a3)に基づく構成単位(α3)、およびアルキル基と重合性不飽和基とがエーテル結合を介して、またはエステル結合を介して連結された単量体(a4)に基づく構成単位(α4)を有する含フッ素重合体(A)を含む含フッ素塗料用組成物。
[2]前記含フッ素重合体(A)が、全構成単位に対して、前記構成単位(α1)の40〜60モル%、前記構成単位(α2)の2〜30モル%、前記構成単位(α3)の0.01〜5モル%、および前記構成単位(α4)の5〜50モル%を有する、前記[1]の含フッ素塗料用組成物。
[3]前記構成単位(α2)が、水酸基を有する単量体(a2−1)に基づく構成単位を含む、前記[1]または[2]の含フッ素塗料用組成物。
[4]前記水酸基を有する単量体(a2−1)が、ヒドロキシアルキルビニルエーテル類、ポリエチレングリコールモノビニルエーテル類、及びヒドロキシアルキルアリルエーテル類から選ばれる少なくとも1種である前記[3]の含フッ素塗料用組成物。
[5]前記含フッ素重合体(A)の水酸基価が、30〜200mgKOH/gである前記[3]または[4]の含フッ素塗料用組成物。
[6]前記フルオロオレフィン(a1)が、テトラフルオロエチレン及びクロロトリフルオロエチレンから選ばれる少なくとも1種である前記[1]〜[5]のいずれかの含フッ素塗料用組成物。
[7]前記単量体(a3)が、CF2=CF−CF3、CF2=CH−CF3、及びCHF=CF−CF3から選ばれる少なくとも1種である前記[1]〜[6]のいずれかの含フッ素塗料用組成物。
[8]前記単量体(a4)が、下記の単量体(a4−1)〜(a4−3)から選ばれる少なくとも1種である前記[1]〜[7]のいずれかの含フッ素塗料用組成物。
R4−O−Y1 ・・・(a4−1)
R5−C(O)O−Y2 ・・・(a4−2)
R6−OC(O)−Y3 ・・・(a4−3)
(ただし、R4〜R6はそれぞれ独立に4級炭素原子を含まない直鎖状または分岐鎖状の炭素数2〜20のアルキル基であり、Y1〜Y3はそれぞれ独立に重合性不飽和基である。)
[9]前記単量体(a4)における重合性不飽和基が、エチレン性不飽和二重結合を有する基である前記[1]〜[8]のいずれかの含フッ素塗料用組成物。
[10]被塗装物と、前記[1]〜[9]のいずれかの含フッ素塗料用組成物により該被塗装物上に形成された塗膜と、を有する物品。In order to achieve the above object, the present invention employs the following configurations.
[1] Structural unit (α1) based on fluoroolefin (a1) (excluding the following monomer (a3)), structural unit (α2) having a crosslinkable group and having no fluorine atom, CX 1 X 2 = CX 3 -CF 3 (wherein, X 1 to X 3 are each independently a hydrogen atom, a chlorine atom or a fluorine atom, and at least one of X 1 to X 3 is a hydrogen atom). (Α3) based on the monomer (a3), and a monomer (a4) in which an alkyl group and a polymerizable unsaturated group are linked via an ether bond or an ester bond. A composition for a fluorinated paint containing a fluorinated polymer (A) having a unit (α4).
[2] The fluorinated polymer (A) is 40 to 60 mol% of the structural unit (α1), 2 to 30 mol% of the structural unit (α2), and the structural unit ( The composition for a fluorine-containing paint according to the above [1], comprising 0.01 to 5 mol% of α3) and 5 to 50 mol% of the structural unit (α4).
[3] The composition for a fluorine-containing paint according to the above [1] or [2], wherein the structural unit (α2) includes a structural unit based on a monomer (a2-1) having a hydroxyl group.
[4] The fluorine-containing paint according to [3], wherein the hydroxyl group-containing monomer (a2-1) is at least one selected from hydroxyalkyl vinyl ethers, polyethylene glycol monovinyl ethers, and hydroxyalkyl allyl ethers. Composition.
[5] The composition for a fluorine-containing paint according to the above [3] or [4], wherein the hydroxyl value of the fluoropolymer (A) is from 30 to 200 mgKOH / g.
[6] The composition for a fluorine-containing coating according to any one of the above [1] to [5], wherein the fluoroolefin (a1) is at least one selected from tetrafluoroethylene and chlorotrifluoroethylene.
[7] The monomer (a3) is, CF 2 = CF-CF 3 , CF 2 = CH-CF 3, and CHF = the at least one selected from CF-CF 3 [1] ~ [6 ] The composition for any fluorine-containing paint according to any one of [1] to [10].
[8] The fluorine-containing monomer according to any one of [1] to [7], wherein the monomer (a4) is at least one selected from the following monomers (a4-1) to (a4-3). Compositions for paints.
R 4 -O-Y 1 (a4-1)
R 5 -C (O) O- Y 2 ··· (a4-2)
R 6 -OC (O) -Y 3 (a4-3)
(However, R 4 to R 6 are each independently a linear or branched alkyl group having 2 to 20 carbon atoms not containing a quaternary carbon atom, and Y 1 to Y 3 are each independently a polymerizable non-polymerizable group. It is a saturated group.)
[9] The composition for a fluorine-containing paint according to any one of the above [1] to [8], wherein the polymerizable unsaturated group in the monomer (a4) is a group having an ethylenically unsaturated double bond.
[10] An article having an object to be coated and a coating film formed on the object to be coated with the composition for a fluorinated paint according to any one of the above [1] to [9].
本発明の含フッ素塗料用組成物は、撥水性に優れた塗膜を形成できる。
また、本発明の物品は、撥水性に優れた塗膜を有している。The composition for a fluorine-containing paint of the present invention can form a coating film having excellent water repellency.
Further, the article of the present invention has a coating film having excellent water repellency.
本明細書においては、単量体が重合することで直接形成される繰り返し単位と、単量体の重合によって形成される繰り返し単位の一部を化学変換することで得られる繰り返し単位とを総称して「構成単位」という。
本明細書において、単量体は、重合性の二重結合を有する化合物を表す。
本明細書において、架橋性基とは、架橋性基同士、または硬化剤と反応して架橋構造を形成する基を意味する。架橋性基としては、例えば、水酸基、カルボキシ基、アミノ基、エポキシ基、加水分解性シリル基、イソシアネート基等が挙げられる。
本明細書において、(メタ)アクリル酸の記載は、アクリル酸およびメタクリル酸の少なくとも一方を表す。In the present specification, a repeating unit directly formed by polymerization of a monomer and a repeating unit obtained by chemically converting a part of a repeating unit formed by polymerization of a monomer are collectively referred to. Are referred to as “structural units”.
In the present specification, the monomer represents a compound having a polymerizable double bond.
In the present specification, a crosslinkable group means a group that forms a crosslinked structure by reacting with each other or with a curing agent. Examples of the crosslinkable group include a hydroxyl group, a carboxy group, an amino group, an epoxy group, a hydrolyzable silyl group, and an isocyanate group.
In this specification, description of (meth) acrylic acid indicates at least one of acrylic acid and methacrylic acid.
≪含フッ素塗料用組成物≫
本発明の含フッ素塗料用組成物は、含フッ素重合体(A)を含有する。本発明の含フッ素塗料用組成物が含フッ素重合体(A)を含有することで、撥水性に優れた塗膜を形成できる。
また、本発明の含フッ素塗料用組成物は、硬化剤(B)を含有することが好ましい。また、本発明の含フッ素塗料用組成物は、溶媒(C)、含フッ素重合体(A)以外の樹脂(D)、その他の成分(E)を含有してもよい。
本発明の含フッ素塗料用組成物は、溶剤型塗料としてもよく、水性分散型塗料としてもよく、粉体塗料としてもよい。組成 Composition for fluorine-containing paint≫
The composition for a fluorine-containing paint of the present invention contains a fluorine-containing polymer (A). When the composition for a fluorinated paint of the present invention contains the fluorinated polymer (A), a coating film having excellent water repellency can be formed.
Further, the composition for a fluorine-containing paint of the present invention preferably contains a curing agent (B). Further, the composition for a fluorine-containing paint of the present invention may contain a solvent (C), a resin (D) other than the fluoropolymer (A), and other components (E).
The composition for a fluorine-containing paint of the present invention may be a solvent-type paint, an aqueous dispersion-type paint, or a powder paint.
<含フッ素重合体(A)>
含フッ素重合体(A)は、下記の構成単位(α1)〜(α4)を有する含フッ素重合体である。含フッ素重合体(A)は、構成単位(α1)〜(α4)に加えて、構成単位(α1)〜(α4)以外の構成単位(α5)を有していてもよい。
構成単位(α1):フルオロオレフィン(a1)(ただし、下記の単量体(a3)を除く。)に基づく構成単位、
構成単位(α2):架橋性基を有し、フッ素原子を有しない構成単位、
構成単位(α3):CX1X2=CX3−CF3(ただし、X1〜X3はそれぞれ独立に水素原子、塩素原子またはフッ素原子であり、X1〜X3の少なくとも1つが水素原子である。)で表される単量体(a3)に基づく構成単位、
構成単位(α4):アルキル基と重合性不飽和基とがエーテル結合を介して、またはエステル結合を介して連結された単量体(a4)に基づく構成単位。<Fluorine-containing polymer (A)>
The fluoropolymer (A) is a fluoropolymer having the following structural units (α1) to (α4). The fluoropolymer (A) may have a structural unit (α5) other than the structural units (α1) to (α4) in addition to the structural units (α1) to (α4).
Structural unit (α1): Structural unit based on fluoroolefin (a1) (however, excluding the following monomer (a3))
Structural unit (α2): a structural unit having a crosslinkable group and no fluorine atom,
Structural unit (α3): CX 1 X 2 CCX 3 —CF 3 (where X 1 to X 3 are each independently a hydrogen atom, a chlorine atom or a fluorine atom, and at least one of X 1 to X 3 is a hydrogen atom A) a structural unit based on the monomer (a3) represented by
Structural unit (α4): A structural unit based on a monomer (a4) in which an alkyl group and a polymerizable unsaturated group are linked via an ether bond or via an ester bond.
[構成単位(α1)]
構成単位(α1)はフルオロオレフィン(a1)(ただし単量体(a3)を除く。)に基づく構成単位である。フルオロオレフィン(a1)は、オレフィン炭化水素(一般式CnH2n)の水素原子の1個以上がフッ素原子で置換された化合物である。フルオロオレフィンにおいては、フッ素原子で置換されていない水素原子の1個以上が塩素原子で置換されていてもよい。
フルオロオレフィン(a1)におけるフッ素原子の数は、2以上が好ましく、3〜6がより好ましく、3または4がさらに好ましい。フルオロオレフィン(a1)におけるフッ素原子の数が2以上であれば、耐候性に優れた塗膜を形成しやすい。[Structural unit (α1)]
The structural unit (α1) is a structural unit based on the fluoroolefin (a1) (excluding the monomer (a3)). The fluoroolefin (a1) is a compound in which one or more hydrogen atoms of an olefin hydrocarbon (general formula C n H 2n ) are substituted with a fluorine atom. In the fluoroolefin, one or more hydrogen atoms not substituted with a fluorine atom may be substituted with a chlorine atom.
The number of fluorine atoms in the fluoroolefin (a1) is preferably 2 or more, more preferably 3 to 6, and still more preferably 3 or 4. When the number of fluorine atoms in the fluoroolefin (a1) is 2 or more, it is easy to form a coating film having excellent weather resistance.
フルオロオレフィン(a1)としては、テトラフルオロエチレン(以下、TFEという。)、クロロトリフルオロエチレン(以下、CTFEという。)、ヘキサフルオロプロピレン、フッ化ビニリデン、フッ化ビニル等の炭素数2〜3のフルオロオレフィンが好ましく、耐候性、耐溶剤性に優れた塗膜を形成しやすい点から、TFE、CTFEがより好ましく、硬化剤分散性、顔料分散性、および密着性の観点からCTFEが最も好ましい。
構成単位(α1)は、1種でもよく、2種以上でもよい。Examples of the fluoroolefin (a1) include those having 2 to 3 carbon atoms such as tetrafluoroethylene (hereinafter, referred to as TFE), chlorotrifluoroethylene (hereinafter, referred to as CTFE), hexafluoropropylene, vinylidene fluoride, and vinyl fluoride. Fluoroolefin is preferred, and TFE and CTFE are more preferred from the viewpoint of easily forming a coating film having excellent weather resistance and solvent resistance, and CTFE is most preferred from the viewpoint of curing agent dispersibility, pigment dispersibility, and adhesion.
The structural unit (α1) may be one type or two or more types.
[構成単位(α2)]
構成単位(α2)は、架橋性基を有し、フッ素原子を有しない構成単位である。含フッ素重合体(A)が構成単位(α2)を有することにより、含フッ素重合体(A)中に架橋性基が導入される。本発明の含フッ素塗料組成物が硬化剤を含有する場合は、該架橋性基と硬化剤との架橋反応により本発明の含フッ素塗料組成物から形成された塗膜が硬化する。また、架橋性基の種類によっては乾燥するだけで硬化する場合もあり、この場合は含フッ素塗料用組成物への硬化剤の添加は不要である。塗膜を硬化させることにより、塗膜に硬度、機械的強度、防水、防湿性、耐溶剤性等が付与される。[Structural unit (α2)]
The structural unit (α2) is a structural unit having a crosslinkable group and no fluorine atom. When the fluoropolymer (A) has the structural unit (α2), a crosslinkable group is introduced into the fluoropolymer (A). When the fluorine-containing coating composition of the present invention contains a curing agent, a coating film formed from the fluorine-containing coating composition of the present invention is cured by a crosslinking reaction between the crosslinking group and the curing agent. In addition, depending on the type of the crosslinkable group, it may be cured only by drying, and in this case, it is unnecessary to add a curing agent to the composition for a fluorine-containing coating. By curing the coating film, hardness, mechanical strength, waterproofness, moisture resistance, solvent resistance, and the like are imparted to the coating film.
構成単位(α2)は、架橋性基を有し、フッ素原子を有しない単量体(a2)に基づく構成単位であることが好ましい。また、単量体(a2)は、4級炭素原子や環構造を含まないことが好ましい。単量体(a2)としては、例えば、下記単量体(a2−1)〜(a2−6)が挙げられる。
(a2−1)水酸基を有する単量体。
(a2−2)カルボキシ基を有する単量体。
(a2−3)加水分解性シリル基を有する単量体。
(a2−4)アミノ基を有する単量体。
(a2−5)エポキシ基を有する単量体。
(a2−6)イソシアネート基を有する単量体。The structural unit (α2) is preferably a structural unit based on a monomer (a2) having a crosslinkable group and no fluorine atom. Further, the monomer (a2) preferably does not contain a quaternary carbon atom or a ring structure. Examples of the monomer (a2) include the following monomers (a2-1) to (a2-6).
(A2-1) A monomer having a hydroxyl group.
(A2-2) A monomer having a carboxy group.
(A2-3) A monomer having a hydrolyzable silyl group.
(A2-4) A monomer having an amino group.
(A2-5) a monomer having an epoxy group;
(A2-6) A monomer having an isocyanate group.
単量体(a2)としては、架橋反応性、入手容易性や重合体への導入容易性の点から、単量体(a2−1)または単量体(a2−2)を含むことが好ましく、単量体(a2−1)を含むことが特に好ましい。
単量体(a2)が単量体(a2−1)または単量体(a2−2)を含む場合、単量体(a2)における単量体(a2−1)または単量体(a2−2)の割合は、2モル%以上が好ましく、8モル%以上がより好ましい。The monomer (a2) preferably contains the monomer (a2-1) or the monomer (a2-2) from the viewpoints of crosslinking reactivity, availability, and ease of introduction into a polymer. And the monomer (a2-1).
When the monomer (a2) includes the monomer (a2-1) or the monomer (a2-2), the monomer (a2-1) or the monomer (a2-) in the monomer (a2) is used. The ratio of 2) is preferably at least 2 mol%, more preferably at least 8 mol%.
単量体(a2−1)としては、水酸基を有する炭素数2〜20の直鎖状または分岐状のアルキル基が、重合性不飽和基(ビニル基、アリル基、1−プロペニル基等)とエーテル結合またはエステル結合で連結してなる単量体が好ましい。また、エマルジョンタイプの含フッ素塗料用組成物とする場合、単量体(a2−1)としては、水酸基を有し、かつポリオキシエチレン鎖等の親水性ブロックを有する単量体を使用することもできる。 As the monomer (a2-1), a linear or branched alkyl group having 2 to 20 carbon atoms having a hydroxyl group may be a polymerizable unsaturated group (such as a vinyl group, an allyl group, or a 1-propenyl group). Monomers linked by an ether bond or an ester bond are preferred. In the case of an emulsion type composition for fluorine-containing paint, a monomer having a hydroxyl group and having a hydrophilic block such as a polyoxyethylene chain is used as the monomer (a2-1). Can also.
単量体(a2−1)の具体例としては、例えば、以下の化合物が挙げられる。
2−ヒドロキシエ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、2−ヒドロキシプロピルビニルエーテル、2−ヒドロキシ−2−メチル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、4−ヒドロキシ−2−メチルブチルビニルエーテル、5−ヒドロキシペンチルビニルエーテル、6−ヒドロキシヘキシ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;
シクロヘキサンジメタノールモノビニルエーテル等の脂環族ジオールのモノビニルエーテル類;
ジエチレングリコールモノビニルエーテル、トリエチレングリコールモノビニルエーテル、テトラエチレングリコールモノビニルエーテル等のポリエチレングリコールモノビニルエーテル類;
ヒドロキシエチルアリルエーテル、ヒドロキシブチルアリルエーテル、2−ヒドロキシエチルアリルエーテル、4−ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテル等のヒドロキシアルキルアリルエーテル類;
ヒドロキシエチルビニルエステル、ヒドロキシブチルビニルエステル等のヒドロキシアルキルビニルエステル類;
ヒドロキシエチルアリルエステル、ヒドロキシブチルアリルエステル等のヒドロキシアルキルアリルエステル類;
ヒドロキシエチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキルエステル類等。Specific examples of the monomer (a2-1) include, for example, the following compounds.
2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, Hydroxyalkyl vinyl ethers such as 6-hydroxyhexyl vinyl ether;
Monovinyl ethers of alicyclic diols such as cyclohexane dimethanol monovinyl ether;
Polyethylene glycol monovinyl ethers such as diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, and tetraethylene glycol monovinyl ether;
Hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether, hydroxybutyl allyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether;
Hydroxyalkyl vinyl esters such as hydroxyethyl vinyl ester and hydroxybutyl vinyl ester;
Hydroxyalkyl allyl esters such as hydroxyethyl allyl ester and hydroxybutyl allyl ester;
Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate;
ポリエチレングリコールモノビニルエーテル類以外のポリオキシエチレン鎖を有する単量体(a2−1)としては、前記した化合物の水酸基にエチレンオキシドを開環付加重合して得られる化合物が挙げられる。例えば、4−ヒドロキシブチルビニルエーテルやシクロヘキサンジメタノールモノビニルエーテルにエチレンオキシドを開環付加重合して得られる、末端に水酸基を有し、かつポリオキシエチレン鎖を有する化合物が得られる。
ポリオキシエチレン鎖を有する単量体(a2−1)を使用する場合には、ポリオキシエチレン鎖を有する単量体(a2−1)と、ポリオキシエチレン鎖を有さない単量体(a2−1)とを組み合わせて使用することが好ましい。なお、単量体(a2−1)としてポリオキシエチレン鎖を有する単量体(a2−1)をのみを使用してもよい。Examples of the monomer (a2-1) having a polyoxyethylene chain other than polyethylene glycol monovinyl ethers include a compound obtained by ring-opening addition polymerization of ethylene oxide to a hydroxyl group of the above compound. For example, a compound having a hydroxyl group at a terminal and a polyoxyethylene chain obtained by ring-opening addition polymerization of ethylene oxide with 4-hydroxybutyl vinyl ether or cyclohexanedimethanol monovinyl ether is obtained.
When a monomer (a2-1) having a polyoxyethylene chain is used, a monomer (a2-1) having a polyoxyethylene chain and a monomer (a2) having no polyoxyethylene chain are used. -1) is preferably used in combination. In addition, you may use only the monomer (a2-1) which has a polyoxyethylene chain as a monomer (a2-1).
単量体(a2−1)としては、交互共重合性に優れ、耐候性に優れた塗膜を形成しやすい点から、ヒドロキシアルキルビニルエーテル類、ポリエチレングリコールモノビニルエーテル類、またはヒドロキシアルキルアリルエーテル類が好ましく、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、ジエチレングリコールモノビニルエーテル、ヒドロキシブチルアリルエーテル、または2−ヒドロキシエチルアリルエーテルがより好ましい。 As the monomer (a2-1), hydroxyalkyl vinyl ethers, polyethylene glycol monovinyl ethers, or hydroxyalkyl allyl ethers are preferable because they are excellent in alternate copolymerizability and easily form a coating film having excellent weather resistance. Preferably, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, hydroxybutyl allyl ether, or 2-hydroxyethyl allyl ether is more preferable.
単量体(a2−2)としては、重合性不飽和基に1〜2個のカルボキシ基が直接または直鎖状のアルキレン基を介して結合した単量体、または、重合性不飽和基に2個のカルボキシ基が直接または直鎖状のアルキレン基を介して結合した単量体のモノアルキルエステルが好ましい。前記モノアルキルエステルのアルキル基は、4級炭素原子を含まない、炭素数2〜20の直鎖状または分岐鎖状のアルキル基であることが好ましい。 As the monomer (a2-2), a monomer in which one or two carboxy groups are bonded to a polymerizable unsaturated group directly or via a linear alkylene group, or a polymerizable unsaturated group Monoalkyl esters of monomers in which two carboxy groups are linked directly or via a linear alkylene group are preferred. The alkyl group of the monoalkyl ester is preferably a linear or branched alkyl group having 2 to 20 carbon atoms and not containing a quaternary carbon atom.
単量体(a2−2)の具体例としては、例えば、以下の化合物が挙げられる。
3−ブテン酸、4−ペンテン酸、2−ヘキセン酸、3−ヘキセン酸、5−ヘキセン酸、2−ヘプテン酸、3−ヘプテン酸、6−ヘプテン酸、3−オクテン酸、7−オクテン酸、2−ノネン酸、3−ノネン酸、8−ノネン酸、9−デセン酸、10−ウンデセン酸、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、桂皮酸等の不飽和カルボン酸類;
ビニルオキシ吉草酸、3−ビニルオキシプロピオン酸、3−(2−ビニルオキシブトキシカルボニル)プロピオン酸、3−(2−ビニルオキシエトキシカルボニル)プロピオン酸等の飽和カルボン酸ビニルエーテル類;
アリルオキシ吉草酸、3−アリルオキシプロピオン酸、3−(2−アリロキシブトキシカルボニル)プロピオン酸、3−(2−アリロキシエトキシカルボニル)プロピオン酸等の飽和カルボン酸アリルエーテル類;
3−(2−ビニロキシエトキシカルボニル)プロピオン酸、3−(2−ビニロキシブトキシカルボニル)プロピオン酸等のカルボン酸ビニルエーテル類;
アジピン酸モノビニル、コハク酸モノビニル、フタル酸ビニル、ピロメリット酸ビニル等の飽和多価カルボン酸モノビニルエステル類;
イタコン酸、マレイン酸、フマル酸、マレイン酸無水物、イタコン酸無水物等の不飽和ジカルボン酸類またはその分子内酸無水物;
イタコン酸モノエステル、マレイン酸モノエステル、フマル酸モノエステル等の不飽和カルボン酸モノエステル類等。Specific examples of the monomer (a2-2) include, for example, the following compounds.
3-butenoic acid, 4-pentenoic acid, 2-hexenoic acid, 3-hexenoic acid, 5-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 6-heptenoic acid, 3-octenoic acid, 7-octenoic acid, Unsaturated carboxylic acids such as 2-nonenoic acid, 3-nonenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, and cinnamic acid;
Saturated carboxylic acid vinyl ethers such as vinyloxyvaleric acid, 3-vinyloxypropionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid, and 3- (2-vinyloxyethoxycarbonyl) propionic acid;
Saturated carboxylic acid allyl ethers such as allyloxyvaleric acid, 3-allyloxypropionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, and 3- (2-allyloxyethoxycarbonyl) propionic acid;
Carboxylic acid vinyl ethers such as 3- (2-vinyloxyethoxycarbonyl) propionic acid and 3- (2-vinyloxybutoxycarbonyl) propionic acid;
Monovinyl esters of saturated polycarboxylic acids such as monovinyl adipate, monovinyl succinate, vinyl phthalate and vinyl pyromellitic acid;
Unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride, or intramolecular acid anhydrides thereof;
Unsaturated carboxylic acid monoesters such as itaconic acid monoester, maleic acid monoester and fumaric acid monoester;
単量体(a2−2)としては、入手容易性や重合性の点から、クロトン酸、イタコン酸、マレイン酸、マレイン酸モノエステル、フマル酸、フマル酸モノエステル、3−アリルオキシプロピオン酸、または10−ウンデセン酸が好ましい。 As the monomer (a2-2), from the viewpoint of availability and polymerizability, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, 3-allyloxypropionic acid, Or 10-undecenoic acid is preferred.
単量体(a2−3)としては、加水分解性シリル基と重合性不飽和基とが、直接、エーテル結合を介して、またはエステル結合を介して結合した単量体が好ましい。
加水分解性シリル基としては、下式(1)で表されるアルコキシシリル基が好ましい。
−Q−SiR1 p(OR2)3−p ・・・(1)
(Qは、直鎖アルキレン基、直鎖オキシアルキレン基、直鎖オキシアルキレンカルボニル基またはカルボニルオキシアルキレン基である。R1およびR2は、それぞれ独立にアルキル基であり、R1およびR2は同一であってもよく、異なっていてもよい。pは、0〜2の整数である。)
R1およびR2としては、それぞれ独立にメチル基、エチル基、またはプロピル基が好ましい。
pは0または1が好ましく、0より好ましい。As the monomer (a2-3), a monomer in which a hydrolyzable silyl group and a polymerizable unsaturated group are directly bonded via an ether bond or via an ester bond is preferable.
As the hydrolyzable silyl group, an alkoxysilyl group represented by the following formula (1) is preferable.
-Q-SiR 1 p (OR 2 ) 3-p (1)
(Q is a linear alkylene group, a linear oxyalkylene group, a linear oxyalkylenecarbonyl group or a carbonyloxyalkylene group. R 1 and R 2 are each independently an alkyl group, and R 1 and R 2 are May be the same or different; p is an integer of 0 to 2)
Each of R 1 and R 2 is preferably independently a methyl group, an ethyl group, or a propyl group.
p is preferably 0 or 1, more preferably 0.
また、単量体(a2−3)としては、水酸基と反応する官能基と、アルコキシシリル基を有する化合物を、単量体(a2−1)と反応させることで得られる単量体を用いてもよい。例えば、単量体(a2−1)と下記化合物(2)とを反応させて得られる単量体(a2−3A)が挙げられる。単量体(a2−3A)は、下記基(3)を有する。
OCN(CH2)bSiXaR3 3−a ・・・(2)
−C(=O)NH(CH2)bSiXaR3 3−a ・・・(3)
(ただし、前記式中、R3は水素原子または炭素数1〜10の1価の炭化水素基であり、Xは炭素数1〜5のアルコキシ基であり、aは1〜3の整数であり、bは1〜5の整数である。)Further, as the monomer (a2-3), a monomer obtained by reacting a compound having a functional group that reacts with a hydroxyl group and an alkoxysilyl group with the monomer (a2-1) is used. Is also good. For example, a monomer (a2-3A) obtained by reacting the monomer (a2-1) with the following compound (2) may be mentioned. The monomer (a2-3A) has the following group (3).
OCN (CH 2) b SiX a R 3 3-a ··· (2)
-C (= O) NH (CH 2) b SiX a R 3 3-a ··· (3)
(Wherein, R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an alkoxy group having 1 to 5 carbon atoms, and a is an integer of 1 to 3) , B is an integer of 1 to 5.)
R3における1価の炭化水素基の炭素数が10以下であれば、基(3)が嵩高くなりすぎることが抑制されるので、硬化塗膜を形成させる場合にアルコキシ基(X)の縮合反応が立体障害によって進行しにくくなることを抑制できる。そのため、塗膜の硬化性が良好になり、優れた耐久性、耐候性、耐擦傷性および耐衝撃性を有する塗膜が形成されやすくなる。
R3は、炭素数1〜10の1価の炭化水素基が好ましく、炭素数1〜5の1価の炭化水素基がより好ましく、メチル基またはエチル基がさらに好ましい。
Xは、エトキシ基またはメトキシ基が好ましい。
bは、2〜4の整数が好ましい。When the number of carbon atoms of the monovalent hydrocarbon group in R 3 is 10 or less, the group (3) is prevented from becoming too bulky, and condensing the alkoxy group (X) when forming a cured coating film. It is possible to suppress that the reaction does not easily progress due to steric hindrance. Therefore, the curability of the coating film is improved, and a coating film having excellent durability, weather resistance, scratch resistance, and impact resistance is easily formed.
R 3 is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 5 carbon atoms, and still more preferably a methyl group or an ethyl group.
X is preferably an ethoxy group or a methoxy group.
b is preferably an integer of 2 to 4.
単量体(a2−3)としては、入手容易であることから、CH2=CHCO2(CH2)3Si(OCH3)3、CH2=CHCO2(CH2)3Si(OC2H5)3、CH2=CHSi(OCH3)3、CH2=CHSi(OC2H5)3、CH2=CHO(CH2)4OCONH(CH2)3Si(OCH3)3、CH2=CHO(CH2)4OCONH(CH2)3Si(OC2H5)3が好ましい。Since the monomer (a2-3) is easily available, CH 2 、 CHCO 2 (CH 2 ) 3 Si (OCH 3 ) 3 and CH 2 CHCHCO 2 (CH 2 ) 3 Si (OC 2 H) 5) 3, CH 2 = CHSi (OCH 3) 3, CH 2 = CHSi (OC 2 H 5) 3, CH 2 = CHO (CH 2) 4 OCONH (CH 2) 3 Si (OCH 3) 3, CH 2 = CHO (CH 2 ) 4 OCONH (CH 2 ) 3 Si (OC 2 H 5 ) 3 is preferred.
単量体(a2−4)としては、例えば、以下の化合物が挙げられる。
CH2=C−O−(CH2)c−NH2(ただし、cは0または1〜10の整数である。)等のアミノビニルエーテル類;
CH2=CH−O−CO(CH2)d−NH2(ただし、dは1〜10の整数である。)等のアリルアミン類;
アミノメチルスチレン、ビニルアミン、アクリルアミド、ビニルアセトアミド、ビニルホルムアミド等。Examples of the monomer (a2-4) include the following compounds.
Amino vinyl ethers such as CH 2 CC—O— (CH 2 ) c —NH 2 (where c is 0 or an integer of 1 to 10);
Allylamines such as CH 2 CHCH—O—CO (CH 2 ) d —NH 2 (where d is an integer of 1 to 10);
Aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinylformamide and the like.
単量体(a2−5)としては、例えば、グリシジルビニルエーテル、グリシジルメタクリレート、3,4−エポキシシクロへキシルメチルメタクリレート、3,4−エポキシシクロへキシルメチルビニルエーテル、4−ビニロキシメチルシクロへキシルグリシジルエーテル等が挙げられる。 Examples of the monomer (a2-5) include glycidyl vinyl ether, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl vinyl ether, and 4-vinyloxymethylcyclohexylglycidyl. Ether and the like.
単量体(a2−6)としては、例えば、アリルイソシアネート、ジメチルビニルフェニルメチルイソシアネート等が挙げられる。 Examples of the monomer (a2-6) include allyl isocyanate, dimethylvinylphenylmethyl isocyanate, and the like.
構成単位(α2)は、単量体(a2)を重合することで直接形成される構成単位には限定されない。例えば、構成単位(α2)は、以下に示す方法で得られる構成単位であってもよい。
ビニルエステル単量体を重合して得られる重合体をケン化することにより、該重合体中のエステル基を有する構成単位を、水酸基を有する構成単位に変換する方法、
単量体(a2−1)を重合した重合体に多価カルボン酸またはその無水物を反応させてカルボキシ基を導入する方法、
単量体(a2−1)を重合した重合体に化合物(2)を反応させてアルコキシシリル基を導入する方法、
単量体(a2−1)を重合した重合体に多価イソシアネート化合物を反応させてイソシアネート基を導入する方法等。The structural unit (α2) is not limited to a structural unit directly formed by polymerizing the monomer (a2). For example, the structural unit (α2) may be a structural unit obtained by the following method.
A method of converting a structural unit having an ester group in the polymer to a structural unit having a hydroxyl group by saponifying a polymer obtained by polymerizing a vinyl ester monomer,
A method of reacting a polymer obtained by polymerizing the monomer (a2-1) with a polyvalent carboxylic acid or an anhydride thereof to introduce a carboxy group,
A method of reacting the compound (2) with a polymer obtained by polymerizing the monomer (a2-1) to introduce an alkoxysilyl group,
A method of reacting a polymer obtained by polymerizing the monomer (a2-1) with a polyvalent isocyanate compound to introduce an isocyanate group.
含フッ素重合体(A)が、構成単位(α2)として単量体(a2−2)に基づく構成単位を有する場合は、塩基性化合物によって構成単位(α2)のカルボキシ基の一部または全部を中和してもよい。これにより、含フッ素重合体(A)を水に分散させることが容易になり、有機溶剤の含有量が少ない、もしくは有機溶剤含まない水性分散型塗料とすることができる。 When the fluoropolymer (A) has a structural unit based on the monomer (a2-2) as the structural unit (α2), a part or all of the carboxy group of the structural unit (α2) is changed by a basic compound. It may be neutralized. As a result, the fluoropolymer (A) can be easily dispersed in water, and an aqueous dispersion-type paint having a small content of an organic solvent or containing no organic solvent can be obtained.
カルボキシ基を中和する塩基性化合物としては、塗膜中に塩基性化合物が残留しにくくなることから、沸点が200℃以下の化合物が好ましい。
具体的には、例えば、アンモニア;モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、モノブチルアミン、ジブチルアミン等の1級、2級または3級のアルキルアミン類;モノエタノールアミン、モノイソプロパノールアミン、ジメチルアミノエタノール、ジエチルアミノエタノール等のアルカノールアミン類;エチレンジアミン、プロピレンジアミン、テトラメチレンジアミン、へキサメチレンジアミン等のジアミン類;エチレンイミン、プロピレンイミン等のアルキレンイミン類;ピペラジン、モルホリン、ピラジン、ピリジン等が挙げられる。As the basic compound that neutralizes the carboxy group, a compound having a boiling point of 200 ° C. or less is preferable because the basic compound hardly remains in the coating film.
Specifically, for example, ammonia; primary, secondary or tertiary such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine and dibutylamine Alkanolamines such as monoethanolamine, monoisopropanolamine, dimethylaminoethanol and diethylaminoethanol; diamines such as ethylenediamine, propylenediamine, tetramethylenediamine and hexamethylenediamine; ethyleneimine and propyleneimine Alkylene imines; piperazine, morpholine, pyrazine, pyridine and the like.
構成単位(α2)のカルボキシ基を中和する場合、構成単位(α2)におけるカルボキシル基を有する全構成単位に対して、該カルボキシル基が塩基性化合物で中和された構成単位の割合は、30〜100モル%が好ましく、70〜100モル%がより好ましい。
構成単位(α2)は、1種でもよく、2種以上でもよい。When the carboxy group of the structural unit (α2) is neutralized, the ratio of the structural unit in which the carboxyl group is neutralized with a basic compound to all the structural units having a carboxyl group in the structural unit (α2) is 30. -100 mol% is preferable, and 70-100 mol% is more preferable.
The structural unit (α2) may be one type or two or more types.
[構成単位(α3)]
構成単位(α3)は、CX1X2=CX3−CF3(ただし、X1〜X3はそれぞれ独立に水素原子、塩素原子またはフッ素原子であり、X1〜X3の少なくとも1つが水素原子である。)で表される単量体(a3)に基づく構成単位である。含フッ素重合体(A)が構成単位(α3)を有することで、優れた撥水性を有する塗膜を形成できる含フッ素塗料用組成物となる。この効果は、構成単位(α3)の側鎖の末端の−CF3基によって得られると考えられる。[Structural unit (α3)]
The structural unit (α3) is CX 1 X 2 = CX 3 -CF 3 (where X 1 to X 3 are each independently a hydrogen atom, a chlorine atom or a fluorine atom, and at least one of X 1 to X 3 is hydrogen) Is a structural unit based on the monomer (a3) represented by the formula: When the fluorinated polymer (A) has the structural unit (α3), the composition for a fluorinated paint can form a coating film having excellent water repellency. It is considered that this effect is obtained by the —CF 3 group at the terminal of the side chain of the structural unit (α3).
単量体(a3)としては、例えば、以下の化合物が挙げられる。
CH2=CH−CF3、CH2=CF−CF3、CF2=CH−CF3、CF2=CF−CF3、CFCl=CH−CF3、CFCl=CF−CF3、CHF=CF−CF3、CHF=CH−CF3、CCl2=CH−CF3、CCl2=CF−CF3、CHCl=CH−CF3、CHCl=CF−CF3等。Examples of the monomer (a3) include the following compounds.
CH 2 = CH-CF 3, CH 2 = CF-CF 3, CF 2 = CH-CF 3, CF 2 = CF-CF 3, CFCl = CH-CF 3, CFCl = CF-CF 3, CHF = CF- CF 3, CHF = CH-CF 3, CCl 2 = CH-CF 3, CCl 2 = CF-CF 3, CHCl = CH-CF 3, CHCl = CF-CF 3 and the like.
なかでも、単量体(a3)としては、入手の容易さから、CF2=CF−CF3、CF2=CH−CF3、CHF=CF−CF3が好ましい。
構成単位(α3)は、1種でもよく、2種以上でもよい。Above all, as the monomer (a3), CF 2 −CF—CF 3 , CF 2 CHCH—CF 3 , and CHF = CF—CF 3 are preferable in terms of availability.
The structural unit (α3) may be one type or two or more types.
[構成単位(α4)]
含フッ素重合体(A)は、アルキル基と重合性不飽和基とがエーテル結合またはエステル結合で連結された単量体(a4)に基づく構成単位(α4)を有する。
単量体(a4)におけるアルキル基は、直鎖状であってもよく、分岐鎖状であってもよい。また、該アルキル基は、4級炭素原子を有さないことが好ましい。
単量体(a4)におけるアルキル基の炭素数は、2〜20が好ましい。[Structural unit (α4)]
The fluoropolymer (A) has a structural unit (α4) based on a monomer (a4) in which an alkyl group and a polymerizable unsaturated group are linked by an ether bond or an ester bond.
The alkyl group in the monomer (a4) may be linear or branched. Preferably, the alkyl group does not have a quaternary carbon atom.
The alkyl group in the monomer (a4) preferably has 2 to 20 carbon atoms.
単量体(a4)としては、例えば、下記の単量体(a4−1)〜(a4−3)が挙げられる。
R4−O−Y1 ・・・(a4−1)
R5−C(O)O−Y2 ・・・(a4−2)
R6−OC(O)−Y3 ・・・(a4−3)
(ただし、R4〜R6はそれぞれ独立に4級炭素原子を含まない直鎖状または分岐鎖状の炭素数2〜20のアルキル基であり、Y1〜Y3はそれぞれ独立に重合性不飽和基である。)Examples of the monomer (a4) include the following monomers (a4-1) to (a4-3).
R 4 -O-Y 1 (a4-1)
R 5 -C (O) O- Y 2 ··· (a4-2)
R 6 -OC (O) -Y 3 (a4-3)
(However, R 4 to R 6 are each independently a linear or branched alkyl group having 2 to 20 carbon atoms not containing a quaternary carbon atom, and Y 1 to Y 3 are each independently a polymerizable non-polymerizable group. It is a saturated group.)
単量体(a4−1)〜(a4−3)に基づく構成単位は、塗膜に優れた柔軟性や被塗装物との密着性を付与できる。
塗膜の柔軟性や被塗装物との密着性の度合いは、アルキル基の構造と連結結合の種類との組み合わせによって異なる。また、連結結合(エーテル結合、エステル結合)の種類と重合性不飽和基の構造の組み合わせは、単量体(a4−1)〜(a4−3)の共重合性に影響する。そのため、R4〜R6のアルキル基の構造、連結結合の種類、およびY1〜Y3の重合性不飽和基の構造の組み合わせは、要求性能や共重合性に応じて適宜選択すればよい。
単量体(a4−2)と単量体(a4−3)では、光による分解や加水分解を受けにくい点では、単量体(a4−2)の方が好ましい。Structural units based on the monomers (a4-1) to (a4-3) can impart excellent flexibility to a coating film and adhesion to an object to be coated.
The flexibility of the coating film and the degree of adhesion to the object to be coated differ depending on the combination of the structure of the alkyl group and the type of the connecting bond. Further, the combination of the type of the linking bond (ether bond, ester bond) and the structure of the polymerizable unsaturated group affects the copolymerizability of the monomers (a4-1) to (a4-3). Therefore, the combination of the structure of the alkyl group of R 4 to R 6 , the type of the connecting bond, and the structure of the polymerizable unsaturated group of Y 1 to Y 3 may be appropriately selected according to the required performance and copolymerizability. .
The monomer (a4-2) and the monomer (a4-3) are more preferably the monomer (a4-2) in that they are less susceptible to decomposition or hydrolysis by light.
R4〜R6のアルキル基は、直鎖状であってもよく、分岐鎖状であってもよい。
R4〜R6のアルキル基の炭素数は、入手が容易な点では、2〜9が好ましく、2〜6がより好ましい。また、該アルキル基の炭素数は、塗膜の柔軟性の点では、8〜18が好ましい。
Y1〜Y3の重合性不飽和基としては、エチレン性不飽和二重結合を有する基が好ましく、ビニル基、アリル基、1−プロペニル基がより好ましい。The alkyl group of R 4 to R 6 may be linear or branched.
The carbon number of the alkyl group of R 4 to R 6 is preferably 2 to 9, and more preferably 2 to 6, in terms of easy availability. Further, the number of carbon atoms of the alkyl group is preferably from 8 to 18 from the viewpoint of the flexibility of the coating film.
As the polymerizable unsaturated group of Y 1 to Y 3 , a group having an ethylenically unsaturated double bond is preferable, and a vinyl group, an allyl group, and a 1-propenyl group are more preferable.
単量体(a4−1)としては、アルキルビニルエーテル類、アルキルアリルエーテル類が好ましく、エチルビニルエーテル、n−プロピルビニルエーテル、n−ブチルビニルエーテル、オクタデシルビニルエーテル、2−エチルヘキシルビニルエーテル、イソプロピルビニルエーテル、イソブチルビニルエーテル、シクロヘキシルビニルエーテル、エチルアリルエーテル、n−プロピルアリルエーテル、n−ブチルアリルエーテル、オクタデシルアリルエーテル、2−エチルヘキシルアリルエーテル、イソプロピルアリルエーテル、イソブチルアリルエーテルがより好ましく、エチルビニルエーテル、2−エチルヘキシルビニルエーテル、エチルアリルエーテル、2−エチルヘキシルアリルエーテルがさらに好ましい。 As the monomer (a4-1), alkyl vinyl ethers and alkyl allyl ethers are preferable, and ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, octadecyl vinyl ether, 2-ethylhexyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, and cyclohexyl Vinyl ether, ethyl allyl ether, n-propyl allyl ether, n-butyl allyl ether, octadecyl allyl ether, 2-ethylhexyl allyl ether, isopropyl allyl ether, and isobutyl allyl ether are more preferable, and ethyl vinyl ether, 2-ethylhexyl vinyl ether, and ethyl allyl ether are more preferable. And 2-ethylhexyl allyl ether are more preferred.
単量体(a4−2)としては、カルボン酸ビニルエステル類、カルボン酸アリルエステル類が好ましく、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、ビニルイソ酪酸ビニル、バーサチック酸ビニル、プロピオン酸アリル、酪酸アリル、カプロン酸アリル、ラウリン酸アリル、ステアリン酸アリル、ビニルイソ酪酸アリル、バーサチック酸アリルがより好ましい。 As the monomer (a4-2), vinyl carboxylate and allyl carboxylate are preferable, and vinyl propionate, vinyl butyrate, vinyl caproate, vinyl laurate, vinyl stearate, vinyl isobutyrate, versatic acid Vinyl, allyl propionate, allyl butyrate, allyl caproate, allyl laurate, allyl stearate, allyl vinyl isobutyrate, and allyl versatate are more preferred.
単量体(a4−3)としては、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ブチルメタクリレート、イソブチルメタクリレート、シクロヘキシルメタクリレート等の(メタ)アクリル酸エステル類が好ましい。 As the monomer (a4-3), (meth) acrylates such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, and cyclohexyl methacrylate are preferable.
単量体(a4)としては、単量体(a4−1)、単量体(a4−2)が好ましく、アルキルビニルエーテル類、カルボン酸ビニルエステル類がより好ましい。
単量体(a4)を使用する場合は、2種以上を併用することが好ましく、その場合はエチルビニルエーテルおよび2−エチルヘキシルビニルエーテルの少なくとも一方を必須とすることがより好ましい。As the monomer (a4), a monomer (a4-1) and a monomer (a4-2) are preferable, and alkyl vinyl ethers and vinyl carboxylate are more preferable.
When using the monomer (a4), it is preferable to use two or more kinds in combination, and in that case, it is more preferable to use at least one of ethyl vinyl ether and 2-ethylhexyl vinyl ether.
[構成単位(α5)]
含フッ素重合体(A)は、単量体(a1)、単量体(a2)、単量体(a3)および単量体(a4)以外のその他の単量体(a5)に基づく構成単位(α5)を有していてもよい。
その他の単量体(a5)としては、例えば、エチレン性単量体(エチレン、プロピレン等)、単量体(a4)におけるアルキル基の代わりに炭素数4〜10の脂環式基を有する単量体(シクロヘキシルビニルエーテル等のシクロアルキルビニルエーテル等)等が挙げられる。[Structural unit (α5)]
The fluoropolymer (A) is a structural unit based on a monomer (a5) other than the monomer (a1), the monomer (a2), the monomer (a3) and the monomer (a4). (Α5).
Examples of the other monomer (a5) include an ethylenic monomer (ethylene, propylene, etc.) and a monomer having an alicyclic group having 4 to 10 carbon atoms in place of the alkyl group in the monomer (a4). And cycloalkyl vinyl ethers such as cyclohexyl vinyl ether.
[単量体の組み合わせ]
本発明における含フッ素重合体(A)を製造するために使用する好ましい単量体の組み合わせとしては、テトラフルオロエチレン/ヒドロキシアルキルビニルエーテル/CHF=CFCF3/アルキルビニルエーテルの組み合わせ、テトラフルオロエチレン/ヒドロキシアルキルビニルエーテル/CF2=CHCF3/アルキルビニルエーテルの組み合わせ、テトラフルオロエチレン/ヒドロキシアルキルビニルエーテル/CF2=CFCF3/アルキルビニルエーテルの組み合わせ、テトラフルオロエチレン/ヒドロキシアルキルビニルエーテル/CF2=CHCF3/アルキルビニルエステルの組み合わせ、クロロトリフルオロエチレン/ヒドロキシアルキルビニルエーテル/CHF=CFCF3/アルキルビニルエーテルの組み合わせ、クロロトリフルオロエチレン/ヒドロキシアルキルビニルエーテル/CF2=CHCF3/アルキルビニルエーテルの組み合わせ、クロロトリフルオロエチレン/ヒドロキシアルキルビニルエーテル/CF2=CFCF3/アルキルビニルエーテルの組み合わせ、クロロトリフルオロエチレン/ヒドロキシアルキルビニルエーテル/CF2=CHCF3/アルキルビニルエステルの組み合わせ等が挙げられる。[Combination of monomers]
Preferred combinations of monomers used for producing the fluoropolymer (A) in the present invention include a combination of tetrafluoroethylene / hydroxyalkyl vinyl ether / CHF = CFCF 3 / alkyl vinyl ether, and a combination of tetrafluoroethylene / hydroxyalkyl combinations of vinyl ether / CF 2 = CHCF 3 / alkyl vinyl ether, tetrafluoroethylene / hydroxyalkyl vinyl ether / CF 2 = CFCF 3 / alkyl vinyl ether combination of tetrafluoroethylene / hydroxyalkyl vinyl ether / CF 2 = CHCF 3 / alkyl vinyl ester Combination of chlorotrifluoroethylene / hydroxyalkyl vinyl ether / CHF = CFCF 3 / alkyl vinyl ether Combination, chlorotrifluoroethylene / combinations of hydroxyalkyl vinyl ether / CF 2 = CHCF 3 / alkyl vinyl ether, a combination of chlorotrifluoroethylene / hydroxyalkyl vinyl ether / CF 2 = CFCF 3 / alkyl vinyl ether, chlorotrifluoroethylene / hydroxyalkyl vinyl ether / CF 2 CHCHCF 3 / alkyl vinyl ester and the like.
(各構成単位の割合)
含フッ素重合体(A)中の全構成単位に対する構成単位(α1)の割合は、40〜60モル%が好ましく、45〜55モル%がより好ましい。構成単位(α1)の割合が下限値以上であれば、優れた耐候性を有する塗膜を形成しやすい。構成単位(α1)の割合が上限値以下であれば、塗膜の透明性が得られる。(Ratio of each structural unit)
The ratio of the structural unit (α1) to all the structural units in the fluoropolymer (A) is preferably from 40 to 60 mol%, more preferably from 45 to 55 mol%. When the proportion of the structural unit (α1) is at least the lower limit, a coating film having excellent weather resistance will be easily formed. When the proportion of the structural unit (α1) is equal to or less than the upper limit, transparency of the coating film can be obtained.
含フッ素重合体(A)中の全構成単位に対する構成単位(α2)の割合は、2〜30モル%が好ましく、8〜25モル%がより好ましい。構成単位(α2)の割合が下限値以上であれば、充分な架橋密度の塗膜を形成しやすい。構成単位(α2)の割合が上限値以下であれば、良好な耐水性を有する塗膜を形成しやすい。 The proportion of the structural unit (α2) to all the structural units in the fluoropolymer (A) is preferably from 2 to 30 mol%, more preferably from 8 to 25 mol%. When the proportion of the structural unit (α2) is equal to or more than the lower limit, a coating film having a sufficient crosslinking density is easily formed. When the proportion of the structural unit (α2) is equal to or less than the upper limit, a coating film having good water resistance is easily formed.
含フッ素重合体(A)中の全構成単位に対する構成単位(α3)の割合は、0.01〜5モル%が好ましく、0.1〜5モル%がより好ましい。構成単位(α3)の割合が下限値以上であれば、優れた撥水性を有する塗膜を形成しやすい。構成単位(α3)の割合が上限値以下であれば、得られる含フッ素重合体(A)の分子量が安定する。 The proportion of the structural unit (α3) to all the structural units in the fluoropolymer (A) is preferably from 0.01 to 5 mol%, more preferably from 0.1 to 5 mol%. When the proportion of the structural unit (α3) is at least the lower limit, a coating film having excellent water repellency can be easily formed. When the proportion of the structural unit (α3) is at most the upper limit, the molecular weight of the obtained fluoropolymer (A) will be stable.
含フッ素重合体(A)中の全構成単位に対する構成単位(α4)の割合は、5〜50モル%が好ましく、15〜40モル%がより好ましい。 The ratio of the structural unit (α4) to all the structural units in the fluoropolymer (A) is preferably from 5 to 50 mol%, more preferably from 15 to 40 mol%.
含フッ素重合体(A)の好ましい組成は、構成単位(α1)が40〜60モル%、構成単位(α2)が2〜30モル%、構成単位(α3)が0.01〜5モル%、構成単位(α4)が5〜50モル%(構成単位(α1)〜(α4)の合計が100モル%)である。 The preferred composition of the fluoropolymer (A) is such that the structural unit (α1) is 40 to 60 mol%, the structural unit (α2) is 2 to 30 mol%, and the structural unit (α3) is 0.01 to 5 mol%. The structural unit (α4) is 5 to 50 mol% (the total of the structural units (α1) to (α4) is 100 mol%).
含フッ素重合体(A)に含まれる架橋性基の量は、塗膜の機械物性に影響し、架橋性基の含有量が多いほど硬化が充分となりやすく、塗膜の機械物性が良好になる。一方、架橋性基の含有量が少ないほど、塗膜が硬くなりすぎることを抑制しやすく、柔軟性が良好になる。 The amount of the crosslinkable group contained in the fluoropolymer (A) affects the mechanical properties of the coating film, and the greater the content of the crosslinkable group, the more easily the curing becomes satisfactory, and the better the mechanical properties of the coating film. . On the other hand, as the content of the crosslinkable group is smaller, it is easier to suppress the coating film from becoming too hard, and the flexibility becomes better.
含フッ素重合体(A)が、単量体(a2−1)に基づく構成単位(α2)を有する場合、含フッ素重合体(A)の水酸基価は、30〜200mgKOH/gが好ましく、40〜150mgKOH/gがより好ましい。
含フッ素重合体(A)は、1種でもよく、2種以上でもよい。When the fluoropolymer (A) has a structural unit (α2) based on the monomer (a2-1), the hydroxyl value of the fluoropolymer (A) is preferably 30 to 200 mgKOH / g, and 40 to 200 mgKOH / g. 150 mgKOH / g is more preferred.
The fluorinated polymer (A) may be one type or two or more types.
含フッ素重合体(A)の製造方法としては、特に限定されず、フルオロオレフィン(a1)、単量体(a2)、単量体(a3)および単量体(a4)を含み、必要に応じて単量体(a5)を含む単量体混合物を公知の方法で重合させる方法が好ましい。 The method for producing the fluoropolymer (A) is not particularly limited, and includes the fluoroolefin (a1), the monomer (a2), the monomer (a3), and the monomer (a4). The method of polymerizing the monomer mixture containing the monomer (a5) by a known method is preferred.
重合方法は、公知のラジカル重合法が採用できる。重合形態としては、特に限定されず、溶液重合、懸濁重合、乳化重合等を採用できる。
具体的には、本発明の含フッ素塗料用組成物を溶剤型塗料とする場合は、例えば、溶液重合を採用できる。また、本発明の含フッ素塗料用組成物を水性分散型塗料とする場合は、例えば、含フッ素重合体(A)の重合方法として乳化重合を採用することでエマルジョンタイプの重合体溶液を得て、該重合体溶液を塗料の製造に用いることができる。また、溶液重合により含フッ素重合体(A)を製造した後に、反応液に水を加え、有機溶剤を除去してディスパージョンタイプの重合体溶液として、該重合体溶液を塗料の製造に用いることもできる。なかでも、塗膜の耐水性の点では、ディスパージョンタイプの重合体溶液を製造して、該重合体溶液を用いてディスパージョンタイプの水性分散型塗料とすることが好ましい。As the polymerization method, a known radical polymerization method can be adopted. The polymerization form is not particularly limited, and solution polymerization, suspension polymerization, emulsion polymerization, and the like can be employed.
Specifically, when the composition for a fluorine-containing paint of the present invention is used as a solvent type paint, for example, solution polymerization can be adopted. When the composition for a fluorine-containing coating composition of the present invention is used as an aqueous dispersion type coating composition, for example, an emulsion-type polymer solution is obtained by employing emulsion polymerization as a polymerization method for the fluorine-containing polymer (A). The polymer solution can be used for producing a paint. Further, after producing the fluorinated polymer (A) by solution polymerization, water is added to the reaction solution, the organic solvent is removed, and the dispersion is used as a dispersion-type polymer solution. Can also. Among them, from the viewpoint of water resistance of the coating film, it is preferable to prepare a dispersion type polymer solution and use the polymer solution to obtain a dispersion type aqueous dispersion type paint.
重合溶媒としては、例えば、イオン交換水;メタノール、エタノール、ブタノール、プロパノール等のアルコール系溶剤;n−へキサン、n−ヘプタン等の飽和炭化水素系溶剤;トルエン、キシレン等の芳香族炭化水素系溶剤;メチルエチルケトン、シクロヘキサノン、アセトン等のケトン系溶剤;酢酸エチル、酢酸ブチル等のエステル系溶剤等が挙げられる。 Examples of the polymerization solvent include ion-exchanged water; alcohol solvents such as methanol, ethanol, butanol, and propanol; saturated hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene. Solvents: ketone solvents such as methyl ethyl ketone, cyclohexanone and acetone; ester solvents such as ethyl acetate and butyl acetate;
ラジカル重合開始剤としては、例えば、以下の化合物が挙げられる。
ジイソプロピルパーオキシジカーボネート、ジ−n−プロピルパーオキシジカーボネート等のパーオキシジカーボネート類;t−ヘキシルパーオキシピバレート、t−ブチルパーオキシピバレート等のパーオキシエステル類;シクロヘキサノンパーオキサイド、メチルエチルケトンパーオキサイド等のケトンパーオキサイド類;1,1−ビス(t−ヘキシルパーオキシ)シクロへキサン、1,1−ビス(t−ブチルパーオキシ)シクロへキサン等のパーオキシケタール類;t−ヘキシルパーオキシ−n−ブチルカーボネート、t−ブチルパーオキシ−n−プロピルカーボネート等のパーオキシカーボネートエステル類;イソブチリルパーオキサイド、ラウロイルパーオキサイド等のジアシルパーオキサイド類;ジクミルパーオキサイド、ジ−t−ブチルパーオキサイド等のジアルキルパーオキサイド類等。Examples of the radical polymerization initiator include the following compounds.
Peroxydicarbonates such as diisopropylperoxydicarbonate and di-n-propylperoxydicarbonate; Peroxyesters such as t-hexylperoxypivalate and t-butylperoxypivalate; cyclohexanone peroxide, methyl ethyl ketone Ketone peroxides such as peroxides; peroxyketals such as 1,1-bis (t-hexylperoxy) cyclohexane and 1,1-bis (t-butylperoxy) cyclohexane; t-hexyl Peroxycarbonate esters such as peroxy-n-butyl carbonate and t-butylperoxy-n-propyl carbonate; diacyl peroxides such as isobutyryl peroxide and lauroyl peroxide; dicumyl peroxide; - dialkyl peroxides such as butyl peroxide and the like.
重合時の反応温度は、使用するラジカル重合開始剤によっても異なるが、0〜130℃が好ましい。反応時間は1〜50時間が好ましい。
また、重合反応中には微量の塩酸またはフッ酸が生成する場合があるため、重合時に緩衝液をあらかじめ添加しておくことが好ましい。The reaction temperature during the polymerization varies depending on the radical polymerization initiator used, but is preferably from 0 to 130 ° C. The reaction time is preferably 1 to 50 hours.
Since a small amount of hydrochloric acid or hydrofluoric acid may be generated during the polymerization reaction, it is preferable to add a buffer solution in advance during the polymerization.
本発明の含フッ素塗料用組成物をディスパージョンタイプの水性分散型塗料とする場合は、含フッ素重合体(A)中に構成単位(α2)としてカルボキシ基を有する構成単位を導入し、該カルボキシ基を塩基性化合物で中和しながら水で希釈して、その後に有機溶剤を減圧下で除去する方法が好ましい。 When the composition for a fluorine-containing coating composition of the present invention is used as a dispersion type aqueous dispersion type coating composition, a structural unit having a carboxy group as a structural unit (α2) is introduced into the fluoropolymer (A), and the carboxy group is introduced. A method is preferred in which the group is diluted with water while neutralizing the group with a basic compound, and then the organic solvent is removed under reduced pressure.
本発明の含フッ素塗料用組成物をエマルジョンタイプの水性分散型塗料とする場合は、例えば、ポリオキシエチレン鎖を有する単量体(a2−1)を使用して乳化重合法で側鎖にポリオキシエチレン鎖を有する含フッ素重合体(A)の水乳化物を得て、該水乳化物を溶媒で希釈する等して水性分散型塗料の製造に使用することができる。
乳化重合を採用する場合には、水中、かつアニオン系、ノニオン系の乳化剤の存在下、水溶性過酸化物、過硫酸塩、水溶性アゾ化合物等の開始剤を用いることで重合を実施できる。
また、ポリオキシエチレン鎖を有する単量体(a2−1)を共重合して側鎖にポリオキシエチレン鎖を有する含フッ素重合体(A)を得て、該含フッ素重合体(A)を水に分散した水分散液を水性分散型塗料の製造に使用することもできる。When the composition for a fluorine-containing coating composition of the present invention is used as an emulsion-type aqueous dispersion type coating composition, for example, a monomer having a polyoxyethylene chain (a2-1) is used to form a polymer into a side chain by an emulsion polymerization method. An aqueous emulsion of the fluorinated polymer (A) having an oxyethylene chain is obtained, and the aqueous emulsion can be diluted with a solvent or the like, and used for the production of an aqueous dispersion type coating.
In the case of employing emulsion polymerization, polymerization can be carried out by using an initiator such as a water-soluble peroxide, a persulfate, or a water-soluble azo compound in water and in the presence of an anionic or nonionic emulsifier.
Further, a monomer (a2-1) having a polyoxyethylene chain is copolymerized to obtain a fluorinated polymer (A) having a polyoxyethylene chain in a side chain, and the fluorinated polymer (A) is An aqueous dispersion dispersed in water can also be used for producing an aqueous dispersion type paint.
<硬化剤(B)>
本発明の含フッ素塗料用組成物には、硬化剤(B)を配合することが好ましい。なお、架橋性基の種類によっては乾燥するだけで硬化が可能となるため、その場合には硬化剤(B)を配合しなくてもよい。<Curing agent (B)>
The composition for a fluorine-containing paint of the present invention preferably contains a curing agent (B). Note that, depending on the type of the crosslinkable group, curing can be performed only by drying, and in that case, the curing agent (B) may not be blended.
硬化剤(B)は、含フッ素重合体(A)が有する架橋性基によって適宜選択すればよい。
例えば、架橋性基が水酸基の場合には、硬化剤(B)としては、イソシアネート系硬化剤、メラミン樹脂、シリケート化合物、イソシアネート含有シラン化合物等が挙げられる。
架橋性基がカルボキシ基の場合には、硬化剤(B)としては、アミノ系硬化剤、エポキシ系硬化剤等が挙げられる。
架橋性基が加水分解性シリル基の場合には、硬化剤(B)としては、金属アルコキシド等が挙げられる。架橋性基が加水分解性シリル基の場合には、硬化剤(B)を用いずに硬化することもできる。
架橋性基がアミノ基の場合には、硬化剤(B)としては、カルボニル基含有硬化剤、エポキシ系硬化剤、酸無水物系硬化剤等が挙げられる。
架橋性基がエポキシ基の場合には、硬化剤(B)としては、カルボキシル基含有硬化剤等が挙げられる。
架橋性基がイソシアネート基の場合には、硬化剤(B)としては、水酸基含有硬化剤等が挙げられる。The curing agent (B) may be appropriately selected depending on the crosslinkable group of the fluoropolymer (A).
For example, when the crosslinking group is a hydroxyl group, examples of the curing agent (B) include an isocyanate-based curing agent, a melamine resin, a silicate compound, and an isocyanate-containing silane compound.
When the crosslinkable group is a carboxy group, examples of the curing agent (B) include an amino-based curing agent and an epoxy-based curing agent.
When the crosslinkable group is a hydrolyzable silyl group, examples of the curing agent (B) include metal alkoxides. When the crosslinkable group is a hydrolyzable silyl group, it can be cured without using the curing agent (B).
When the crosslinkable group is an amino group, examples of the curing agent (B) include a carbonyl group-containing curing agent, an epoxy curing agent, and an acid anhydride curing agent.
When the crosslinkable group is an epoxy group, examples of the curing agent (B) include a carboxyl group-containing curing agent.
When the crosslinking group is an isocyanate group, examples of the curing agent (B) include a hydroxyl group-containing curing agent.
架橋性基が水酸基の場合の硬化剤(B)としては、ポリイソシアネートが好ましく、無黄変ポリイソシアネートまたは無黄変ポリイソシアネートの変性体がより好ましい。
無黄変ポリイソシアネートとしては、イソホロンジイソシアネート(IPDI)、ヘキサメチレンジイソシアネート(HMDI)、ヘキサンジイソシアネート(HDI)が好ましい。When the crosslinking group is a hydroxyl group, the curing agent (B) is preferably a polyisocyanate, and more preferably a non-yellowing polyisocyanate or a modified non-yellowing polyisocyanate.
As the non-yellowing polyisocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), and hexane diisocyanate (HDI) are preferable.
無黄変ポリイソシアネートの変性体としては、前記無黄変ポリイソシアネートの変性体が好ましい。
変性体としては、イプシロンカプロラクタム(E−CAP)、メチルエチルケトンオキシム(MEK−OX)、メチルイソブチルケトンオキシム(MIBK−OX)、ピラリジンまたはトリアジン(TA)によってイソシアネート基をブロックしたもの、ポリイソシアネート同士をカップリングしてウレトジオン結合を形成したものが好ましい。また、常温で固形を呈すようにアダクト体としたもの、水分散しやすいように乳化剤を用いて乳化状態としたものも好ましい。本発明の含フッ素塗料用組成物を水性分散型塗料とする場合は、親水性部位(ポリオキシアルキレン鎖等)を有するポリイソシアネート、または水中に乳化させたポリイソシアネートを硬化剤(B)として使用することが好ましい。As the modified non-yellowing polyisocyanate, a modified non-yellowing polyisocyanate is preferable.
Examples of the modified product include epsilon caprolactam (E-CAP), methyl ethyl ketone oxime (MEK-OX), methyl isobutyl ketone oxime (MIBK-OX), a product in which an isocyanate group is blocked by pyrazine or triazine (TA), and a polyisocyanate compound. What formed a uretdione bond by ringing is preferable. Also, an adduct so as to exhibit a solid at room temperature or an emulsified state using an emulsifier so as to be easily dispersed in water is preferable. When the composition for a fluorine-containing paint of the present invention is used as an aqueous dispersion type paint, a polyisocyanate having a hydrophilic site (polyoxyalkylene chain or the like) or a polyisocyanate emulsified in water is used as a curing agent (B). Is preferred.
<溶媒(C)>
本発明の含フッ素塗料用組成物は、溶媒(C)を配合して粘度を低下させることにより、塗工性能や作業性を向上させることができる。なお、本発明の含フッ素塗料用組成物は、溶媒(C)を用いずに粉体塗料としてもよい。
溶媒(C)としては、水を用いてもよく、有機溶剤を用いてもよい。環境負荷を低減する点では、溶媒(C)は水を含むことが好ましい。<Solvent (C)>
The composition for a fluorine-containing paint of the present invention can improve coating performance and workability by blending the solvent (C) to lower the viscosity. The composition for a fluorine-containing paint of the present invention may be a powder paint without using the solvent (C).
As the solvent (C), water may be used, or an organic solvent may be used. From the viewpoint of reducing the environmental load, the solvent (C) preferably contains water.
有機溶剤としては、特に限定されず、例えば、アセトン、メチルエチルケトン、メチルプロピルケトン、エチルブチルケトン、ジイソブチルケトン、シクロヘキサノン、イソホロン等のケトン類;酢酸メチル、酢酸エチル、酢酸n−プロピル、酢酸イソプロピル、酢酸n−ブチル、酢酸イソブチル、酢酸t−ブチル等のエステル類;トルエン、キシレン、エチルベンゼン、芳香族石油ナフサ、テトラリン、テレピン油、ソルベッソ♯100(エクソン化学(株)登録商標)、ソルベッソ♯150(エクソン化学(株)登録商標)等の芳香族炭化水素類;ジオキキサン、テトラヒドロフラン、シクロペンチルメチルエーテル等エーテル類;プロピレングリコールモノメチルエーテルアセテート、酢酸メトキシブチル等のエーテルエステル類;ジメチルスルホキシド、N,N−ジメチルホルムアミド等の非プロトン性極性溶媒等が挙げられる。 The organic solvent is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, ethyl butyl ketone, diisobutyl ketone, cyclohexanone, and isophorone; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and acetic acid. Esters such as n-butyl, isobutyl acetate and t-butyl acetate; toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine, Solvesso # 100 (registered trademark of Exxon Chemical Co., Ltd.), Solvesso # 150 (Exxon Aromatic hydrocarbons such as Chemical Co., Ltd.); ethers such as dioxane, tetrahydrofuran and cyclopentyl methyl ether; ether esters such as propylene glycol monomethyl ether acetate and methoxybutyl acetate; Sulfoxide, N, aprotic polar solvents such as N- dimethylformamide.
有機溶剤としては、環境負荷を低減する点では、PRTR法、HAPs規制に対応した溶剤、すなわち、芳香族化合物を含有しない有機溶剤が好ましい。また、労働安全衛生法による有機溶剤の分類において、第三種有機溶剤に分類されている有機溶剤も好ましい。具体的には、PRTR法、HAPs規制に該当しない、エステル系溶剤、ケトン系溶剤;第三種有機溶剤に分類されている、パラフィン系溶剤、ナフテン系溶剤が好ましい。 As the organic solvent, a solvent that complies with the PRTR method and the HAPs regulations, that is, an organic solvent that does not contain an aromatic compound is preferable from the viewpoint of reducing the environmental burden. Further, in the classification of organic solvents according to the Occupational Safety and Health Law, organic solvents classified as a third type organic solvent are also preferable. Specifically, preferred are paraffin-based solvents and naphthene-based solvents, which are not classified under the PRTR method and HAPs regulations, and are classified as ester solvents and ketone solvents;
パラフィン系溶剤またはナフテン系溶剤を用いる場合には、市販の弱溶剤を用いることが好ましい。
弱溶剤とは、労働安全衛生法による有機溶剤の分類において、第三種有機溶剤とされているものである。具体的には、ガソリン、コールタールナフサ(ソルベントナフサを含む)、石油エーテル、石油ナフサ、石油ベンジン、テレピン油、ミネラルスピリット(ミネラルシンナー、ペトロリウムスピリット、ホワイトスピリットおよびミネラルターペンを含む)からなる群から選ばれる1種、または2種以上の混合物である。When a paraffin solvent or a naphthene solvent is used, it is preferable to use a commercially available weak solvent.
Weak solvents are classified as a third-class organic solvent in the classification of organic solvents according to the Industrial Safety and Health Law. Specifically, the group consisting of gasoline, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine, mineral spirits (including mineral thinners, petroleum spirits, white spirits and mineral terpenes) Or a mixture of two or more selected from the group consisting of:
また、弱溶剤のアニリン点は、30℃〜70℃が好ましく、40〜60℃がより好ましい。なお、アニリン点はJIS K 2256に記載のアニリン点試験方法に準じて測定される。
弱溶剤としては、引火点が室温以上であることから、ミネラルスピリットが好ましい。Further, the aniline point of the weak solvent is preferably 30C to 70C, more preferably 40C to 60C. The aniline point is measured according to the aniline point test method described in JIS K2256.
Mineral spirit is preferred as the weak solvent because its flash point is above room temperature.
溶媒(C)として弱溶剤を用いる際には、含フッ素重合体(A)の重合溶媒として該弱溶剤を使用する、または弱溶剤以外の重合溶媒中で重合した後に該重合溶媒の一部または全部を弱溶剤に置換することが好ましい。
また、含フッ素重合体(A)の重合溶媒と、使用しようとする溶媒(C)とが異なる際には、含フッ素重合体(A)の重合後に重合溶媒の一部または全部を溶媒(C)に置換することが好ましい。When a weak solvent is used as the solvent (C), the weak solvent is used as a polymerization solvent for the fluoropolymer (A), or a part of the polymerization solvent is used after polymerization in a polymerization solvent other than the weak solvent. It is preferable to replace all with a weak solvent.
When the polymerization solvent of the fluoropolymer (A) is different from the solvent (C) to be used, a part or all of the polymerization solvent is replaced with the solvent (C) after the polymerization of the fluoropolymer (A). ) Is preferable.
本発明の含フッ素塗料用組成物を水性分散型塗料とする場合には、環境保護の点から、有機溶剤の量ができるだけ少ないことが好ましい。この場合、本発明の含フッ素塗料用組成物(100質量%)中の有機溶剤の割合は、10質量%以下が好ましく、5質量%以下がより好ましく、0.5%以下がさらに好ましい。
本発明の含フッ素塗料用組成物を水性分散型塗料とする場合に含まれる有機溶剤としては、アセトン、メチルエチルケトン、イソプロピルアルコールが好ましい。When the composition for a fluorine-containing paint of the present invention is used as an aqueous dispersion type paint, the amount of the organic solvent is preferably as small as possible from the viewpoint of environmental protection. In this case, the proportion of the organic solvent in the composition for a fluorine-containing paint (100% by mass) of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 0.5% or less.
As the organic solvent contained when the composition for a fluorine-containing paint of the present invention is used as an aqueous dispersion type paint, acetone, methyl ethyl ketone, and isopropyl alcohol are preferable.
<樹脂(D)>
本発明の含フッ素塗料用組成物は、含フッ素重合体(A)以外の樹脂(D)を含有してもよい。
樹脂(D)としては、フッ素系合成樹脂(ただし、含フッ素重合体(A)を除く。)、フェノール系合成樹脂、アルキド系合成樹脂、メラミン系合成樹脂、ユリア系合成樹脂、ビニル系合成樹脂、エポキシ系合成樹脂、ポリエステル系合成樹脂、ポリウレタン系合成樹脂、アクリル系合成樹脂等が挙げられる。<Resin (D)>
The composition for a fluorinated paint of the present invention may contain a resin (D) other than the fluorinated polymer (A).
As the resin (D), a fluorine-based synthetic resin (excluding the fluoropolymer (A)), a phenol-based synthetic resin, an alkyd-based synthetic resin, a melamine-based synthetic resin, a urea-based synthetic resin, and a vinyl-based synthetic resin , An epoxy synthetic resin, a polyester synthetic resin, a polyurethane synthetic resin, an acrylic synthetic resin, and the like.
樹脂(D)としては、フッ素系合成樹脂(ただし、含フッ素重合体(A)を除く。)が好ましい。フッ素系合成樹脂としては、特許第2955336号公報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重合体が挙げられる。
なお、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、およびこれらの組み合せからなる部位を意味する。また、マクロモノマーとは一方の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を意味する。
また、樹脂(D)としては、耐候性の点では、アクリル系合成樹脂を含むことも好ましい。As the resin (D), a fluorine-based synthetic resin (however, excluding the fluoropolymer (A)) is preferable. Examples of the fluorine-based synthetic resin include a fluoropolymer having a structural unit based on a fluoroolefin described in Japanese Patent No. 2955336 and a structural unit based on a macromonomer having a hydrophilic portion as essential components.
In addition, the hydrophilic site means a site having a hydrophilic group, a site having a hydrophilic bond, and a site composed of a combination thereof. The macromonomer means a low molecular weight polymer or oligomer having a radically polymerizable unsaturated group at one terminal.
It is also preferable that the resin (D) contains an acrylic synthetic resin from the viewpoint of weather resistance.
<他の成分(E)>
本発明の含フッ素塗料用組成物は、他の成分(E)を含有してもよい。
他の成分(E)としては、硬化促進剤、密着性改良剤、顔料、レベリング剤、紫外線吸収剤、光安定剤、増粘剤、造膜助剤、表面調整剤、つや消し剤、消泡剤等が挙げられる。<Other components (E)>
The composition for a fluorine-containing paint of the present invention may contain another component (E).
Other components (E) include a curing accelerator, an adhesion improver, a pigment, a leveling agent, an ultraviolet absorber, a light stabilizer, a thickener, a film forming aid, a surface conditioner, a matting agent, and a defoaming agent. And the like.
硬化促進剤としては、例えば、スズ系、その他金属系、有機酸系、アミノ系硬化促進剤等が挙げられる。硬化促進剤は、1種でもよく、2種以上でもよい。 Examples of the curing accelerator include tin-based, other metal-based, organic acid-based, and amino-based curing accelerators. The curing accelerator may be one type or two or more types.
密着性改良剤としては、特に限定されず、シランカップリング剤が好ましい。
シランカップリング剤としては、例えば、3−アミノプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシラン、N−2−(アミノエチル)−3−アミノプロピルトリメトキシシラン、ウレイドプロピルトリエトキシシラン等のアミノアルキルシラン類;ビニルトリエトキシシラン、ビニルトリメトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン等の不飽和アルキルシラン類;2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−グリシドキシプロピルトリメトキシシラン等のエポキシシラン類;3−メルカプトプロピルトリメトキシシラン、3−イソシアネートプロピルトリエトキシシラン、メチルトリエトキシシラン、メチルトリメトキシシラン等が挙げられる。
密着性改良剤は、1種でもよく、2種以上でもよい。The adhesion improver is not particularly limited, and a silane coupling agent is preferable.
Examples of the silane coupling agent include, for example, amino such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and ureidopropyltriethoxysilane. Alkylsilanes; unsaturated alkylsilanes such as vinyltriethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyl Epoxysilanes such as trimethoxysilane, 3-glycidoxypropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methyltriethoxysilane, methyltrimethy Shishiran, and the like.
The adhesion improver may be one type or two or more types.
顔料としては、白色顔料である酸化チタン、炭酸カルシウム、黒色顔料であるカーボンブラック、その他複合金属類等が挙げられる。顔料は、1種でもよく、2種以上でもよい。
レベリング剤としては、例えば、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挙げられる。レベリング剤は、1種でもよく、2種以上でもよい。Examples of the pigment include titanium oxide and calcium carbonate which are white pigments, carbon black which is a black pigment, and other composite metals. The pigment may be one kind or two or more kinds.
Examples of the leveling agent include polyether-modified polydimethylsiloxane and polyether-modified siloxane. One or two or more leveling agents may be used.
紫外線吸収剤としては、公知の種々のものが使用でき、例えば、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等が挙げられる。具体的には、以下の化合物が挙げられる。
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・アーガス社製の製品名「T−57」等の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・ガイギー社製の製品名「チヌビン900」、「チヌビン1130」等の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;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。
紫外線吸収剤は、1種でもよく、2種以上でもよい。Various known ultraviolet absorbers can be used, and examples thereof include an ultraviolet absorber suitable for use in a top coat as a transparent paint. Specifically, the following compounds are mentioned.
Salicylic 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, benzophenones such as high-molecular-weight modified products such as product name “T-57” manufactured by Adeka Argus Co .; 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, -(2'-hydroxy-5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5′-di-neopentylphenyl) benzotriazole, -Benzotriazoles such as high molecular weight modified products such as product names "Tinuvin 900" and "Tinuvin 1130" manufactured by Geigy; ethyl 2-cyano-3,3-diphenylacrylate, 2-cyano-3,3-diphenyl Substituted acrylonitriles such as 2-ethylhexyl acrylate and methyl α-cyano-β-methyl-4-methoxycinnamate; 2,2′-thiobis (4-octylphenolate) nickel complex salt, {2,2′-thiobis ( 4-t-octylphenolate)}-n-butylamine / nickel complex such as nickel complex; dimethyl p-methoxybenzylidenemalonate, resorcinol monobenzoate, hexamethylphosphoric triamide, 2,5-diphenyl-p-benzoquinone UV absorbers such as bis (2,2,6,6-tetramethyl-4-piperi B) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate polycondensate, 2- (3,5-di-t-butyl-4) -Hydroxybenzyl) -2-n-butylmalonic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl) and the like.
The UV absorber may be one type, or two or more types.
光安定剤としては、例えば、ヒンダードアミン系の光安定剤等が挙げられる。具体的には、アデカスタブLA62、アデカスタブLA67(以上、アデカアーガス化学社製、商品名)、チヌビン292、チヌビン144、チヌビン123、チヌビン440(以上、チバ・スペシャルティ・ケミカルズ社製、商品名)等が挙げられる。
光安定剤は、1種でもよく、2種以上でもよく、紫外線吸収剤と組み合わせて用いてもよい。Examples of the light stabilizer include a hindered amine light stabilizer. Specifically, Adekastab LA62, Adekastab LA67 (all trade names, manufactured by Adeka Argus Chemical Co., Ltd.), Tinuvin 292, Tinuvin 144, Tinuvin 123, Tinuvin 440 (all trade names, manufactured by Ciba Specialty Chemicals Co., Ltd.), etc. No.
The light stabilizer may be one type, or two or more types, and may be used in combination with an ultraviolet absorber.
増粘剤としては、例えば、ポリウレタン系会合性増粘剤等が挙げられる。増粘剤は、1種でもよく、2種以上でもよい。
造膜助剤としては、例えば、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−トリメチルー1,3−ペンタジオールモノ(2−メチルプロパネート)、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。造膜助剤は、1種でもよく、2種以上でもよい。Examples of the thickener include a polyurethane-based associative thickener and the like. The thickener may be one type or two or more types.
Examples of the film-forming aid include diethylene glycol monoethyl ether acetate, 2,2,4-trimethyl-1,3-pentadiol mono (2-methylpropanoate), diethylene glycol diethyl ether, and the like. The film-forming auxiliary may be one kind or two or more kinds.
表面調整剤としては、例えば、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挙げられる。表面調整剤は、1種でもよく、2種以上でもよい。
つや消し剤としては、例えば、超微粉合成シリカ等など常用の無機または有機のつや消し剤が挙げられる。つや消し剤は、1種でもよく、2種以上でもよい。Examples of the surface conditioner include polyether-modified polydimethylsiloxane and polyether-modified siloxane. The surface conditioner may be one type or two or more types.
Examples of the matting agent include common inorganic or organic matting agents such as ultrafine synthetic silica. The matting agent may be one type or two or more types.
消泡剤としては、例えば、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イドの硫酸塩類、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等が挙げられる。
消泡剤は、1種でもよく、2種以上でもよい。Examples of the antifoaming agent include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, sulfates of aliphatic amines and aliphatic amids, fatty alcohol phosphates, and sulfonic acid of dibasic fatty acid esters. Salts, fatty acid amide sulfonates, alkyl allyl sulfonates, formalin condensed naphthalene sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxy Examples include ethylene sorbitan alkyl esters, acrylic polymers, silcon-mixed acrylic polymers, vinyl polymers, and polysiloxane compounds.
The antifoaming agent may be one type or two or more types.
<含フッ素塗料用組成物>
含フッ素塗料用組成物は、含フッ素重合体(A)を含有し、必要に応じて前記の硬化剤(B)、溶媒(C)、樹脂(D)、その他の成分(E)を含有する。
含フッ素塗料用組成物の形態としては、有機溶媒に含フッ素重合体(A)が分散または溶解した有機溶剤系塗料;水を主成分とした媒体に乳化剤により含フッ素重合体(A)が分散した乳化系塗料;水を主成分とし、乳化剤を含まない媒体に含フッ素重合体(A)が分散した水分散系塗料;媒体を含まない粉体塗料の形態が挙げられる。<Composition for fluorine-containing paint>
The composition for a fluorinated paint contains a fluorinated polymer (A) and, if necessary, the above-mentioned curing agent (B), solvent (C), resin (D), and other components (E). .
As the form of the composition for a fluorine-containing paint, an organic solvent-based paint in which the fluorine-containing polymer (A) is dispersed or dissolved in an organic solvent; the fluorine-containing polymer (A) is dispersed in a medium containing water as a main component by an emulsifier. Emulsified paint; water-based paint in which the fluoropolymer (A) is dispersed in a medium containing water as a main component and not containing an emulsifier; and powder paint containing no medium.
本発明の含フッ素塗料用組成物(100質量%)中の含フッ素重合体(A)の含有量は、5〜85質量%が好ましく、20〜75質量%がより好ましい。含フッ素重合体(A)の含有量が下限値以上であれば、優れた撥水性を有する塗膜を形成しやすい。含フッ素重合体(A)の含有量が上限値以下であれば、表面が平滑な塗膜を形成しやすい。 The content of the fluorinated polymer (A) in the composition for a fluorinated coating material (100% by mass) of the present invention is preferably from 5 to 85% by mass, more preferably from 20 to 75% by mass. When the content of the fluoropolymer (A) is at least the lower limit, a coating having excellent water repellency can be easily formed. When the content of the fluoropolymer (A) is equal to or less than the upper limit, a coating film having a smooth surface is easily formed.
本発明の含フッ素塗料用組成物における合成樹脂の全量、すなわち含フッ素重合体(A)と樹脂(D)の合計に対する含フッ素重合体(A)の割合は、10〜100質量%が好ましく、70〜100質量%がより好ましい。前記含フッ素重合体(A)の割合が100質量%であるとは、本が発明の含フッ素塗料用組成物が樹脂(D)を含まないことを意味する。前記含フッ素重合体(A)の割合が下限値以上であれば、優れた撥水性を有する塗膜を形成しやすい。 The total amount of the synthetic resin in the composition for a fluorinated paint of the present invention, that is, the proportion of the fluorinated polymer (A) to the total of the fluorinated polymer (A) and the resin (D) is preferably from 10 to 100% by mass, 70-100 mass% is more preferable. When the proportion of the fluoropolymer (A) is 100% by mass, it means that the composition for a fluorine-containing paint of the present invention does not contain the resin (D). When the proportion of the fluoropolymer (A) is at least the lower limit, a coating film having excellent water repellency can be easily formed.
本発明の含フッ素塗料用組成物が溶媒(C)を含む場合、含フッ素塗料用組成物における合成樹脂の固形分濃度、すなわち含フッ素重合体(A)と樹脂(D)の合計の固形分濃度は、20〜80質量%が好ましく、30〜70質量%がより好ましい。 When the composition for a fluorine-containing coating composition of the present invention contains a solvent (C), the solid content concentration of the synthetic resin in the composition for a fluorine-containing coating composition, that is, the total solid content of the fluoropolymer (A) and the resin (D) The concentration is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass.
本発明の含フッ素塗料用組成物に硬化剤(B)を用いる場合、含フッ素重合体(A)と硬化剤(B)の合計質量に対する含フッ素重合体(A)の割合は、30〜90質量%が好ましく、40〜85質量%がより好ましく、30〜80質量%がさらに好ましい。前記含フッ素重合体(A)の割合が下限値以上あれば、耐候性に優れた塗膜を形成しやすい。前記含フッ素重合体(A)の割合が上限値以下であれば、塗膜にクラックが発生することを抑制しやすく、また被塗装物との密着性、耐久性、耐擦傷性および耐衝撃性が良好な塗膜を形成しやすい。 When the curing agent (B) is used in the composition for a fluorinated coating material of the present invention, the ratio of the fluorinated polymer (A) to the total mass of the fluorinated polymer (A) and the curing agent (B) is 30 to 90. % By mass is preferable, 40 to 85% by mass is more preferable, and 30 to 80% by mass is further preferable. When the proportion of the fluoropolymer (A) is at least the lower limit, it is easy to form a coating film having excellent weather resistance. When the proportion of the fluoropolymer (A) is at most the upper limit, it is easy to suppress the occurrence of cracks in the coating film, and the adhesion, durability, abrasion resistance and impact resistance to the object to be coated. Is easy to form a good coating film.
<含フッ素塗料用組成物の製造方法>
本発明の含フッ素塗料用組成物の製造方法は、特に限定されず、例えば、前記した重合方法で得られた含フッ素重合体(A)を含む溶剤型の重合体溶液と、必要に応じて使用する硬化剤(B)、溶媒(C)、樹脂(D)、他の成分(E)とを混合することで溶剤型塗料が得られる。また、含フッ素重合体(A)を含むエマルションタイプもしくはディスパージョンタイプの水性分散型の重合体溶液と、必要に応じて使用する硬化剤(B)、溶媒(C)、樹脂(D)、他の成分(E)とを混合することで、エマルションタイプまたはディスパージョンタイプの水性分散型塗料が得られる。
各成分の混合方法としては、塗料用組成物の製造に通常用いられる方法が使用できる。例えば、ボールミル、ペイントシェーカー、サンドミル、ジェットミル、ロッキングミル、アトライター、三本ロール、ニーダー等を用いる方法が挙げられる。<Method for producing composition for fluorine-containing paint>
The method for producing the composition for a fluorine-containing paint of the present invention is not particularly limited. For example, a solvent-type polymer solution containing the fluorine-containing polymer (A) obtained by the above-described polymerization method may be used, if necessary. By mixing the used curing agent (B), solvent (C), resin (D), and other components (E), a solvent-type paint can be obtained. Further, an emulsion-type or dispersion-type aqueous dispersion type polymer solution containing the fluoropolymer (A) and a curing agent (B), a solvent (C), a resin (D), and the like, which are used as necessary. By mixing with the component (E), an emulsion-type or dispersion-type aqueous dispersion-type coating material can be obtained.
As a method for mixing the components, a method usually used for producing a coating composition can be used. For example, a method using a ball mill, a paint shaker, a sand mill, a jet mill, a rocking mill, an attritor, a three roll, a kneader and the like can be mentioned.
また、本発明の含フッ素塗料用組成物を粉体塗料とする場合は、例えば、重合で得られた含フッ素重合体(A)と、必要に応じて使用する硬化剤(B)、樹脂(D)、他の成分(E)とを混合した後に溶融混練し、得られた混練物を粉砕して粉末状にする方法が挙げられる。混練物は、冷却後、ペレットとすることが好ましい。
混合に用いる装置としては、例えば、高速ミキサ、V型ミキサ、反転ミキサ等が挙げられる。
溶融混練に用いる装置としては、例えば、1軸押出機、2軸押出機、遊星ギア等が挙げられる。
粉砕に用いる装置としては、例えば、ピンミル、ハンマーミル、ジェットミル等の粉砕機が挙げられる。When the composition for a fluorine-containing paint of the present invention is used as a powder paint, for example, a fluorine-containing polymer (A) obtained by polymerization, a curing agent (B), and a resin ( D) and a method of mixing with another component (E), followed by melt-kneading, and pulverizing the obtained kneaded material into a powder. The kneaded material is preferably formed into pellets after cooling.
As an apparatus used for mixing, for example, a high-speed mixer, a V-type mixer, an inverting mixer, and the like are given.
Examples of the apparatus used for melt kneading include a single-screw extruder, a twin-screw extruder, and a planetary gear.
Examples of an apparatus used for pulverization include pulverizers such as a pin mill, a hammer mill, and a jet mill.
<作用効果>
本発明の含フッ素塗料用組成物は、単量体(a3)に基づく構成単位(α3)を有する特定の含フッ素重合体(A)を含むため、優れた撥水性を有する塗膜を形成できる。<Effects>
Since the composition for a fluorinated paint of the present invention contains the specific fluorinated polymer (A) having the structural unit (α3) based on the monomer (a3), a coating film having excellent water repellency can be formed. .
≪物品≫
本発明の物品は、被塗装物と、本発明の含フッ素塗料用組成物により該被塗装物上に形成された塗膜と、を有する。≪Goods≫
The article of the present invention has an object to be coated and a coating film formed on the object to be coated with the composition for a fluorine-containing coating of the present invention.
<被塗装物>
被塗装物としては、特に限定されず、自動車、船舶、鉄道車両、飛行機等の輸送用機器、工場、発電所等の設備、建築物等が挙げられる。<Object to be coated>
The object to be coated is not particularly limited, and examples thereof include transportation equipment such as automobiles, ships, railway vehicles, and airplanes, facilities such as factories and power plants, and buildings.
<物品の製造方法>
本発明の物品の製造方法としては、本発明の含フッ素塗料用組成物を用いる以外は、公知の方法を採用できる。例えば、本発明の含フッ素塗料用組成物を被塗装物の表面に塗布し、乾燥または加熱する方法が挙げられる。
塗装には、本発明の含フッ素塗料用組成物を二液硬化型のキットとして用いてもよく、硬化剤としてイソシアネート基をブロックしたイソシアネート系硬化剤を用いる場合等は本発明の含フッ素塗料用組成物に該イソシアネート系硬化剤が予め配合された一液型の塗料を用いてもよい。<Production method>
As a method for producing the article of the present invention, a known method can be adopted except that the composition for a fluorine-containing coating of the present invention is used. For example, there is a method in which the composition for a fluorine-containing paint of the present invention is applied to the surface of an object to be coated and dried or heated.
For the coating, the composition for a fluorine-containing paint of the present invention may be used as a two-part curing type kit for the fluorine-containing paint of the present invention. A one-pack type coating material in which the isocyanate-based curing agent is previously added to the composition may be used.
塗装方法としては、スプレー塗装、エアスプレー塗装、はけ塗り、浸漬法、ロールコート、フローコート等の方法が挙げられる。
乾燥方法は、特に限定されず、公知の方法を採用できる。
乾燥温度は、5〜100℃が好ましく、室温〜80℃が好ましい。Examples of the coating method include spray coating, air spray coating, brush coating, dipping, roll coating, and flow coating.
The drying method is not particularly limited, and a known method can be employed.
The drying temperature is preferably 5 to 100C, and more preferably room temperature to 80C.
また、本発明の含フッ素塗料用組成物が溶媒(C)を含み、硬化塗膜を形成する場合は、例えば、塗布後に加熱して硬化させることで塗膜を形成できる。
硬化温度は、50〜200℃が好ましく、60〜150℃が好ましい。
塗布層を加熱する場合の加熱方法としては、特に制限はなく、例えば、密封式硬化炉、連続硬化が可能なトンネル炉等が挙げられる。加熱源は、特に限定されず、熱風循環、赤外線加熱、高周波加熱等を採用できる。なかでも、連続生産性の点から、トンネル炉、熱の伝わり方が均一で、均一な硬化塗膜が得られやすい点から、熱風循環、赤外線加熱が好ましい。When the composition for a fluorine-containing coating composition of the present invention contains a solvent (C) and forms a cured coating film, for example, the coating film can be formed by heating and curing after application.
The curing temperature is preferably from 50 to 200C, more preferably from 60 to 150C.
The heating method for heating the coating layer is not particularly limited, and examples thereof include a sealed curing furnace and a tunnel furnace capable of continuous curing. The heating source is not particularly limited, and hot air circulation, infrared heating, high-frequency heating, or the like can be employed. Of these, hot air circulation and infrared heating are preferred from the viewpoint of continuous productivity, from the viewpoint of uniformity of heat transfer in a tunnel furnace and easy formation of a uniform cured coating film.
また、本発明の含フッ素塗料用組成物を粉体塗料とする場合は、例えば、静電塗装機、摩擦帯電塗装機、流動浸漬、クラウド塗装機、エレクトリックマグネティックブラシ(乾式コピー類似の塗装方法)により粉末状態(予熱流動浸漬塗装の場合は溶融状態)で塗装し、120〜300℃で一定時間焼付けを行う方法等が挙げられる。 When the composition for a fluorine-containing coating of the present invention is used as a powder coating, for example, an electrostatic coating machine, a triboelectric coating machine, a fluid immersion, a cloud coating machine, an electric magnetic brush (a coating method similar to dry copy) In a powder state (in a molten state in the case of preheating fluid immersion coating), and baking at 120 to 300 ° C. for a certain time.
<作用効果>
以上説明した本発明の物品は、本発明の含フッ素塗料用組成物を用いているため、優れた撥水性を有する塗膜を有している。一般にフッ素樹脂は、フッ素含有量が上がると表面の撥水性が向上することが知られているが、含フッ素重合体(A)においても、構成単位(α3)を有するとフッ素含有量が上がる。しかし、本発明においては含フッ素重合体(A)中の構成単位(α3)の含有量が少量であっても、フッ素含有量の上昇だけからは予想できない顕著は撥水性の向上が見られる。これは、本発明の塗料組成物が塗膜となった際に、構成単位(α3)中の−CF3基が塗膜の外側を向いていることによるものと推測される。<Effects>
Since the article of the present invention described above uses the composition for a fluorine-containing coating of the present invention, it has a coating film having excellent water repellency. It is generally known that the fluorine resin has an improved water repellency on the surface when the fluorine content increases. However, the fluorine content of the fluorine-containing polymer (A) also increases when it has the structural unit (α3). However, in the present invention, even when the content of the structural unit (α3) in the fluoropolymer (A) is small, a remarkable improvement in water repellency is observed which cannot be expected only from an increase in the fluorine content. This is presumed to be due to the fact that the —CF 3 group in the structural unit (α3) faces the outside of the coating film when the coating composition of the present invention forms a coating film.
以下、実施例によって本発明を詳細に説明するが、本発明は以下の記載によっては限定されない。
[水酸基価の測定]
水酸基価は、JIS K 1557−1(2007年度版)に準じて測定した。Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the following description.
[Measurement of hydroxyl value]
The hydroxyl value was measured according to JIS K1557-1 (2007 version).
[重合体の組成]
重合体の組成は、13C−NMRにより分析した。[Polymer composition]
The composition of the polymer was analyzed by 13 C-NMR.
[水の接触角]
得られた含フッ素塗料用組成物を、スレート板にアクリル系エマルション下塗り材を塗装した試験体にスプレー塗装し、室温(23℃)で2週間乾燥させて塗膜を形成した。
塗膜の表面における接触角の測定は、接触角計(協和界面科学社製,製品名:CA−A)を用い、25℃の条件下、液滴法で行った。塗膜の上に、約1μLの水を滴下して接触角を測定した。[Water contact angle]
The obtained composition for a fluorine-containing paint was spray-coated on a test body in which an acrylic emulsion undercoat material was applied to a slate plate, and dried at room temperature (23 ° C.) for 2 weeks to form a coating film.
The contact angle on the surface of the coating film was measured by a droplet method using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name: CA-A) at 25 ° C. About 1 μL of water was dropped on the coating film, and the contact angle was measured.
[実施例1]
内容積2500mLのステンレス製撹拌機付き耐圧反応器にキシレンの590g、エタノールの170g、単量体(a2)である4−ヒドロキシブチルビニルエーテル(HBVE)の132g、単量体(a4)であるエチルビニルエーテル(EVE)の212g、シクロヘキシルビニルエーテル(CHVE)の214g、炭酸カリウムの11gおよびパーブチルピバレード(PBPV)の7gを仕込み、窒素による脱気により液中の溶存酸素を除去した。次に、フルオロオレフィン(a1)であるクロロトリフルオロエチレン(CClF=CF2、CTFE)の659g、および単量体(a3)であるCHF=CF−CF3の20gを導入して徐々に昇温し、温度65℃に維持しながら反応を続けた。10時間後、反応器を冷却して反応を停止した。得られた反応液を室温まで冷却した後、未反応の単量体をパージし、珪藻土で濾過して固形物を除去した。次にキシレンの一部とエタノールを減圧留去により除去し、含フッ素重合体(A−1)を含む重合体溶液(1)を得た。
含フッ素重合体(A−1)の組成は、CTFEに基づく構成単位/CHF=CF−CF3に基づく構成単位/EVEに基づく構成単位/CHVEに基づく構成単位/HBVEに基づく構成単位=49.2/1.5/24.5/14.7/10.1(モル%)であり、水酸基価は55mgKOH/gであった。また、重合体溶液(1)の固形分濃度は60質量%であった。
重合体溶液(1)の100g、ジブチルチンジラウレート(キシレンで10−4倍に希釈して3gとしたもの)、ヘキサメチレンジイソシアネート(HDI)のヌレートタイプのポリイソシアネート樹脂(日本ポリウレタン社製、商品名:コロネートHX)を加えて混合し、含フッ素塗料用組成物(I−1)を得た。[Example 1]
590 g of xylene, 170 g of ethanol, 132 g of 4-hydroxybutyl vinyl ether (HBVE) as the monomer (a2), and ethyl vinyl ether as the monomer (a4) in a pressure-resistant reactor equipped with a stirrer made of stainless steel and having a capacity of 2500 mL. 212 g of (EVE), 214 g of cyclohexyl vinyl ether (CHVE), 11 g of potassium carbonate and 7 g of perbutyl pivalide (PBPV) were charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen. Next, 659 g of chlorotrifluoroethylene (CCIF = CF 2 , CTFE) as the fluoroolefin (a1) and 20 g of CHF = CF—CF 3 as the monomer (a3) were introduced, and the temperature was gradually raised. Then, the reaction was continued while maintaining the temperature at 65 ° C. After 10 hours, the reaction was stopped by cooling the reactor. After the obtained reaction solution was cooled to room temperature, unreacted monomers were purged, and the solid was removed by filtration through diatomaceous earth. Next, a part of xylene and ethanol were removed by distillation under reduced pressure to obtain a polymer solution (1) containing the fluoropolymer (A-1).
Fluoropolymer (A-1) The composition of the structural unit = 49 based on the configuration unit / HBVE based on structural units / CHVE-based constituent unit / EVE-based constituent unit / CHF = CF-CF 3 based on CTFE. It was 2 / 1.5 / 24.5 / 14.7 / 10.1 (mol%), and the hydroxyl value was 55 mgKOH / g. Further, the solid content concentration of the polymer solution (1) was 60% by mass.
100 g of the polymer solution (1), dibutyltin dilaurate ( 10-4 times diluted to 3 g with xylene to 3 g), and a nurate type polyisocyanate resin of hexamethylene diisocyanate (HDI) (trade name, manufactured by Nippon Polyurethane Co., Ltd.) : Coronate HX) was added and mixed to obtain a composition (I-1) for a fluorine-containing coating.
[実施例2〜5]
反応条件を表1に示すとおりに変更した以外は、実施例1と同様にして含フッ素重合体(A−2)〜(A−5)を含む重合体溶液(2)〜(5)を得た。また、重合体溶液(2)〜(5)を用いる以外は実施例1と同様にして含フッ素塗料用組成物(I−2)〜(I−5)を得た。[Examples 2 to 5]
Except that the reaction conditions were changed as shown in Table 1, polymer solutions (2) to (5) containing fluoropolymers (A-2) to (A-5) were obtained in the same manner as in Example 1. Was. Also, compositions for fluorine-containing paints (I-2) to (I-5) were obtained in the same manner as in Example 1 except that the polymer solutions (2) to (5) were used.
[比較例1〜2]
反応条件を表1に示すとおりに変更した以外は、実施例1と同様にして含フッ素重合体(A’−1)〜(A’−2)を含む重合体溶液(1’)〜(2’)を得た。また、重合体溶液(1’)〜(2’)を用いる以外は実施例1と同様にして含フッ素塗料用組成物(I’−1)〜(I’−2)を得た。[Comparative Examples 1-2]
Polymer solutions (1 ′) to (2 ′) containing fluoropolymers (A′-1) to (A′-2) in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 1. ') Got. Further, the compositions for fluorine-containing paints (I'-1) to (I'-2) were obtained in the same manner as in Example 1 except that the polymer solutions (1 ') to (2') were used.
各例の反応条件、含フッ素重合体の組成および評価結果を表1に示す。 Table 1 shows the reaction conditions, the composition of the fluoropolymer, and the evaluation results of each example.
表1に示すように、構成単位(α1)〜(α4)を有する含フッ素重合体(A−1)〜(A−5)を含む含フッ素塗料用組成物(I−1)〜(I−5)を用いた実施例1〜5では、塗膜の水接触角が大きく、優れた撥水性が得られた。
一方、構成単位(α3)を有さない含フッ素重合体(A’−1)、(A’−2)を含む含フッ素塗料用組成物(I’−1)、(I’−2)を用いた比較例1、2では、実施例1〜5に比べて塗膜の水接触角が小さく、撥水性が劣っていた。As shown in Table 1, the compositions for fluorine-containing paints (I-1) to (I-) containing the fluoropolymers (A-1) to (A-5) having the structural units (α1) to (α4). In Examples 1 to 5 using 5), the water contact angle of the coating film was large, and excellent water repellency was obtained.
On the other hand, the fluorine-containing coating compositions (I'-1) and (I'-2) containing the fluoropolymers (A'-1) and (A'-2) having no structural unit (α3) were used. In Comparative Examples 1 and 2 used, the water contact angle of the coating film was smaller than in Examples 1 to 5, and the water repellency was inferior.
本発明により提供される、優れた撥水性を有する塗膜を形成できる含フッ素塗料用組成物、および該含フッ素塗料用組成物により形成した塗膜を有する物品は、塗膜表面に優れた撥水性が要求される様々な分野で広く使用できる。
なお、2014年3月13日に出願された日本特許出願2014−050799号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。The composition for a fluorine-containing paint capable of forming a coating having excellent water repellency provided by the present invention, and an article having a coating formed by the composition for a fluorine-containing coating have excellent repellency on the surface of the coating. It can be widely used in various fields where water is required.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2014-050799 filed on Mar. 13, 2014 are cited here and incorporated as the disclosure of the specification of the present invention. Things.
Claims (13)
前記含フッ素重合体(A)が、全構成単位に対して、前記構成単位(α3)を0.01〜5モル%有する、含フッ素塗料用組成物。 Structural unit (α1) based on fluoroolefin (a1) (excluding the following monomer (a3)), structural unit (α2) having a crosslinkable group and having no fluorine atom, CX 1 X 2単 CX 3 —CF 3 (where X 1 to X 3 are each independently a hydrogen atom, a chlorine atom or a fluorine atom, and at least one of X 1 to X 3 is a hydrogen atom). A structural unit (α3) based on the compound (a3), and a structural unit (α4) based on a monomer (a4) in which an alkyl group and a polymerizable unsaturated group are linked via an ether bond or an ester bond. ) a fluorine-containing coating composition comprising the fluoropolymer (a) having,
A composition for a fluorinated paint, wherein the fluorinated polymer (A) has 0.01 to 5 mol% of the structural unit (α3) based on all structural units.
R4−O−Y1 ・・・(a4−1)
R5−C(O)O−Y2 ・・・(a4−2)
R6−OC(O)−Y3 ・・・(a4−3)
(ただし、R4〜R6はそれぞれ独立に4級炭素原子を含まない直鎖状または分岐鎖状の炭素数2〜20のアルキル基であり、Y1〜Y3はそれぞれ独立に重合性不飽和基である。) The fluorine-containing paint according to any one of claims 1 to 7 , wherein the monomer (a4) is at least one selected from the following monomers (a4-1) to (a4-3). Composition.
R 4 -O-Y 1 (a4-1)
R 5 -C (O) O- Y 2 ··· (a4-2)
R 6 -OC (O) -Y 3 (a4-3)
(However, R 4 to R 6 are each independently a linear or branched alkyl group having 2 to 20 carbon atoms not containing a quaternary carbon atom, and Y 1 to Y 3 are each independently a polymerizable non-polymerizable group. It is a saturated group.)
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CN108377646B (en) * | 2015-12-18 | 2020-01-21 | Agc株式会社 | Coated body and building exterior member |
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