JP2019189699A - Coating modifier, and coating composition - Google Patents
Coating modifier, and coating composition Download PDFInfo
- Publication number
- JP2019189699A JP2019189699A JP2018081349A JP2018081349A JP2019189699A JP 2019189699 A JP2019189699 A JP 2019189699A JP 2018081349 A JP2018081349 A JP 2018081349A JP 2018081349 A JP2018081349 A JP 2018081349A JP 2019189699 A JP2019189699 A JP 2019189699A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- group
- monomer
- coating
- paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 87
- 238000000576 coating method Methods 0.000 title claims abstract description 87
- 239000008199 coating composition Substances 0.000 title claims abstract description 84
- 239000003607 modifier Substances 0.000 title claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 106
- 239000011737 fluorine Substances 0.000 claims abstract description 94
- 239000000178 monomer Substances 0.000 claims abstract description 94
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 93
- -1 acrylate ester Chemical class 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 21
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 11
- 125000000962 organic group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 5
- 229920001577 copolymer Polymers 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 54
- 239000003973 paint Substances 0.000 claims description 43
- 239000003822 epoxy resin Substances 0.000 claims description 29
- 229920000647 polyepoxide Polymers 0.000 claims description 29
- 229920002313 fluoropolymer Polymers 0.000 claims description 27
- 239000004811 fluoropolymer Substances 0.000 claims description 23
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 125000002015 acyclic group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004640 Melamine resin Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 50
- 238000012360 testing method Methods 0.000 description 49
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 229920005862 polyol Polymers 0.000 description 20
- 238000001723 curing Methods 0.000 description 18
- 150000002430 hydrocarbons Chemical group 0.000 description 16
- 150000003077 polyols Chemical class 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 14
- 239000010959 steel Substances 0.000 description 14
- 239000002981 blocking agent Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000012948 isocyanate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 8
- 241000195493 Cryptophyta Species 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- 150000002596 lactones Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- NXZGIDGNDLSFDH-UHFFFAOYSA-N prop-2-enoic acid;1h-pyrazole Chemical compound C=1C=NNC=1.OC(=O)C=C NXZGIDGNDLSFDH-UHFFFAOYSA-N 0.000 description 2
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
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- 125000002733 (C1-C6) fluoroalkyl group Chemical group 0.000 description 1
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VFRMAHVDXYSEON-UHFFFAOYSA-N 1,1-diiodoethene Chemical compound IC(I)=C VFRMAHVDXYSEON-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本開示は、フルオロアルキル基を有する含フッ素単量体を含む含フッ素重合体を含んでなる塗料改質剤（塗料用添加剤）に関する。本開示は、塗料改質剤および塗料を含んでなる塗料組成物にも関する。 The present disclosure relates to a paint modifier (paint additive) comprising a fluoropolymer containing a fluoromonomer having a fluoroalkyl group. The present disclosure also relates to a coating composition comprising a coating modifier and a coating.
従来、橋梁などの建築物を環境から保護するために、種々の塗料組成物または塗料添加剤が提案されている。 Conventionally, various coating compositions or coating additives have been proposed in order to protect buildings such as bridges from the environment.
特許文献１（特表２００１−５２４５７３号公報）および特許文献２（特表２００１−５２４５５９号公報）は、アクリルポリマーおよびフルオロアルキル基含有重合体を含んでなる塗料組成物を開示している。
特許文献３（特表２０１３−５３１７０８号公報）は、塩化ビニリデン繰り返し単位およびＥＯ鎖を含有した含フッ素重合体を含むコーティング組成物を開示している。
特許文献４（特開平１０−１６８１４０号公報）は、フルオロアルキル基含有（メタ）アクリル酸エステルに由来する構成単位およびポリアルキレングリコール（メタ）アクリレートに由来する構成単位を含む共重合体を含有してなる塗料添加剤を開示している。
Patent Literature 1 (Japanese Patent Publication No. 2001-524573) and Patent Literature 2 (Japanese Patent Publication No. 2001-524559) disclose a coating composition comprising an acrylic polymer and a fluoroalkyl group-containing polymer.
Patent Document 3 (Japanese Patent Publication No. 2013-531708) discloses a coating composition containing a fluoropolymer containing a vinylidene chloride repeating unit and an EO chain.
Patent Document 4 (Japanese Patent Laid-Open No. 10-168140) contains a copolymer containing a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester and a structural unit derived from a polyalkylene glycol (meth) acrylate. A paint additive is disclosed.
特許文献５（特開平６−２４０２０１号公報）は、炭素数８のフルオロアルキル基を持つ含フッ素重合体を粉体塗料に添加してインク汚染性、レベリング性、撥水撥油性を付与する技術を開示している。 Patent Document 5 (Japanese Patent Laid-Open No. 6-240201) discloses a technique for imparting ink contamination, leveling and water / oil repellency by adding a fluoropolymer having a C8 fluoroalkyl group to a powder coating. Is disclosed.
本開示の目的は、優れた防汚性を基材（例えば、橋梁などの建築物）に与える塗料組成物を提供することにある。 An object of the present disclosure is to provide a coating composition that imparts excellent antifouling properties to a substrate (for example, a building such as a bridge).
本開示は、
ａ）式：
CH2=C(-X)-C(=O)-Y-Z-Rf
［式中、Xは、水素原子、一価の有機基またはハロゲン原子であり、
Yは、-O-または-NH-であり、
Zは、直接結合または二価の有機基であり、
Rfは、炭素数１〜６のパーフルオロアルキル基である。］
で示される含フッ素単量体から誘導された繰り返し単位、および
（ｂ）炭化水素基を有する非フッ素単量体から誘導された繰り返し単位
を有する含フッ素重合体を含んでなる塗料改質剤を提供する。
This disclosure
a) Formula:
CH 2 = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a C1-C6 perfluoroalkyl group. ]
A coating modifier comprising: a repeating unit derived from a fluorine-containing monomer represented by formula (b); and (b) a fluorine-containing polymer having a repeating unit derived from a non-fluorine monomer having a hydrocarbon group. provide.
非フッ素単量体（ｂ）は、式：
CH2=CA11-C(=O)-O-A12
［式中、A11は、水素原子、炭素数１〜３０直鎖状または分岐状のアルキル基、シアノ基、置換または非置換のベンジル基、置換または非置換のフェニル基、またはフッ素原子以外のハロゲン原子であり、
A12は、炭素数１〜４０の炭化水素基である。]
で示される（メタ）アクリレートエステル単量体であることが好ましい。
The non-fluorine monomer (b) has the formula:
CH 2 = CA 11 -C (= O) -OA 12
[Wherein A 11 is other than a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a fluorine atom. A halogen atom,
A 12 is a hydrocarbon group having 1 to 40 carbon atoms. ]
It is preferable that it is a (meth) acrylate ester monomer shown by these.
加えて、本開示は、
（１）含フッ素重合体を含んでなる塗料改質剤、および
（２）樹脂を含んでなる塗料
を含んでなる塗料組成物を提供する。
追加的に、本開示は、単量体（ａ）および単量体（ｂ）を重合して含フッ素重合体を得た後に、含フッ素重合体を塗料と混合することを含んでなる、塗料組成物の製造方法を提供する。
In addition, this disclosure
(1) A coating composition comprising a fluoropolymer, and (2) a coating composition comprising a coating comprising a resin.
Additionally, the present disclosure provides a paint comprising polymerizing the monomer (a) and the monomer (b) to obtain a fluoropolymer, and then mixing the fluoropolymer with the paint. A method for producing the composition is provided.
さらに、本開示は、塗料組成物を基材の表面に塗布して塗膜を形成し、基材に防汚性を付与することを含む、基材の塗装方法を提供する。
さらに加えて、本開示は、塗料組成物を基材の表面に塗布することによって形成されている塗料組成物の膜を提供する。
Furthermore, this indication provides the coating method of a base material including apply | coating a coating composition on the surface of a base material, forming a coating film, and providing antifouling property to a base material.
In addition, the present disclosure provides a coating composition film formed by applying the coating composition to a surface of a substrate.
本開示によれば、優れた防汚性を有する塗膜が形成される。防汚性とは、汚れが付着しにくいこと（優れた汚れ難付着性）、および汚れが付着しても除去しやすいこと（優れた汚れ離脱性）を意味する。すなわち、汚れ（例えば、塩、藻、土およびカーボン）が塗膜表面に付着しにくく、かつ汚れが塗膜表面に付着しても容易に剥がれる。特に、塩化ナトリウムなどの塩に対する防汚性が高い。例えば、海水に浸っている基材（例えば、金属、コンクリートおよび木材）が塗膜によって海水から良好に保護され、塩害が防止される。また、本開示により、優れた耐傷つき性をもつ塗料組成物を提供することもできる。
本開示によれば、基材が良好に保護される。特に、鋼板などの金属の錆が良好に防止される。
According to the present disclosure, a coating film having excellent antifouling properties is formed. The antifouling property means that dirt is difficult to adhere (excellent dirt adhesion) and easy to remove even if dirt is attached (excellent dirt release property). That is, dirt (for example, salt, algae, soil, and carbon) hardly adheres to the surface of the coating film, and even if dirt adheres to the coating film surface, it easily peels off. In particular, the antifouling property against salts such as sodium chloride is high. For example, a base material (for example, metal, concrete and wood) immersed in seawater is well protected from seawater by the coating film, and salt damage is prevented. The present disclosure can also provide a coating composition having excellent scratch resistance.
According to the present disclosure, the substrate is well protected. In particular, rusting of a metal such as a steel plate is prevented well.
塗料組成物は、（１）塗料改質剤、および（２）塗料を含んでなる。 The coating composition comprises (1) a coating modifier and (2) a coating.
（１）塗料改質剤
塗料改質剤は、含フッ素重合体を含んでなる。一般に、塗料改質剤は、含フッ素重合体および有機溶剤を含んでなるかまたはこれらからなる溶液である。
含フッ素重合体は、含フッ素単量体（ａ）から誘導された繰り返し単位および非フッ素単量体（ｂ）から誘導された繰り返し単位を有する共重合体である。含フッ素単量体（ａ）は、炭素数１〜６のフルオロアルキル基を有する単量体であり、非フッ素単量体（ｂ）は非環状の炭化水素基、および／または窒素、酸素もしくは硫黄原子を含んでいてもよい環状の炭化水素基を有する単量体である。非フッ素単量体（ｂ）は、好ましくは炭素数１４以上の非環状炭化水素基、および／または環状炭化水素基を有する非フッ素非架橋性単量体である。非フッ素単量体（ｂ）の炭化水素基は、飽和または不飽和であるが、飽和であることが好ましい。含フッ素重合体は、必要に応じて、含フッ素単量体（ａ）および非フッ素単量体（ｂ）以外の他の単量体（ｃ）から誘導された繰り返し単位を有してよい。
(1) Paint modifier The paint modifier comprises a fluoropolymer. In general, the paint modifier is a solution comprising or consisting of a fluoropolymer and an organic solvent.
The fluorine-containing polymer is a copolymer having a repeating unit derived from the fluorine-containing monomer (a) and a repeating unit derived from the non-fluorine monomer (b). The fluorine-containing monomer (a) is a monomer having a C1-C6 fluoroalkyl group, and the non-fluorine monomer (b) is an acyclic hydrocarbon group and / or nitrogen, oxygen or A monomer having a cyclic hydrocarbon group which may contain a sulfur atom. The non-fluorine monomer (b) is preferably a non-fluorine non-crosslinkable monomer having an acyclic hydrocarbon group having 14 or more carbon atoms and / or a cyclic hydrocarbon group. The hydrocarbon group of the non-fluorine monomer (b) is saturated or unsaturated, but is preferably saturated. The fluorine-containing polymer may have a repeating unit derived from a monomer (c) other than the fluorine-containing monomer (a) and the non-fluorine monomer (b) as necessary.
含フッ素単量体（ａ）は、式：
CH2=C(-X)-C(=O)-Y-Z-Rf
［式中、Xは、水素原子、一価の有機基またはハロゲン原子であり、
Yは、-O-または-NH-であり、
Zは、直接結合または二価の有機基であり、
Rfは、炭素数1〜6のパーフルオロアルキル基である。］
で示される化合物である。
The fluorine-containing monomer (a) has the formula:
CH 2 = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a C 1-6 perfluoroalkyl group. ]
It is a compound shown by these.
Xは、例えば、水素原子、メチル基、ハロゲン、炭素数2〜21の直鎖状または分岐状のアルキル基、CFX1X2基（但し、X1およびX2は、水素原子、フッ素原子、塩素原子、臭素原子、またはヨウ素原子である。）、シアノ基、炭素数1〜21の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基である。
含フッ素重合体においては、Xは、水素原子、メチル基、フッ素原子、または塩素原子であることが好ましい。Xは、水素原子またはメチル基、特にメチル基であることがさらに好ましい。
X is, for example, a hydrogen atom, a methyl group, a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, or a CFX 1 X 2 group (where X 1 and X 2 are a hydrogen atom, a fluorine atom, A chlorine atom, a bromine atom, or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. is there.
In the fluorinated polymer, X is preferably a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom. X is more preferably a hydrogen atom or a methyl group, particularly a methyl group.
Yは、-O-であることが好ましい。 Y is preferably -O-.
Zは、例えば、直接結合、炭素数1〜20の直鎖状のアルキレン基または分岐状のアルキレン基[例えば、式−(CH2)x−（式中、xは1〜10である。）で示される基]、あるいは式−SO2N(R1)R2−または式−CON(R1)R2−で示される基（式中、R1は、炭素数1〜10のアルキル基であり、R2は、炭素数1〜10の直鎖状のアルキレン基または分岐状のアルキレン基である。）、あるいは式−CH2CH(OR3)CH2−（式中、R3は、水素原子、または炭素数1〜10のアシル基（例えば、ホルミルまたはアセチルなど）を表す。）で示される基、あるいは、式−Ar−(CH2)r−（式中、Arは、置換基を必要により有するアリーレン基であり、rは0〜10である。）で示される基、あるいは−（CH2）m−SO2−（CH2）n−基または-（CH2）m−S−（CH2）n−基（但し、mは1〜10、nは0〜10である。）である。
含フッ素重合体において、Zは、直接結合、炭素数1〜20のアルキレン基、−SO2N(R1)R2−であることが好ましい。
Z is, for example, a direct bond, a linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group [for example, the formula — (CH 2 ) x — (wherein x is 1 to 10). Or a group represented by the formula —SO 2 N (R 1 ) R 2 — or a formula —CON (R 1 ) R 2 — (wherein R 1 is an alkyl group having 1 to 10 carbon atoms) And R 2 is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group.) Or a formula —CH 2 CH (OR 3 ) CH 2 — (wherein R 3 is , A hydrogen atom, or a group represented by an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl), or a group represented by the formula —Ar— (CH 2 ) r — (wherein Ar is a substituent) An arylene group optionally having a group, and r is 0 to 10.), a — (CH 2 ) m —SO 2 — (CH 2 ) n — group or a — (CH 2 ) m — S- (CH 2) n - group (where, m is 1 to 10, n is 0 A 10 is.).
In the fluorinated polymer, Z is preferably a direct bond, an alkylene group having 1 to 20 carbon atoms, or —SO 2 N (R 1 ) R 2 —.
Rfは、パーフルオロアルキル基であることが好ましいが、水素原子を有するフルオロアルキル基であってもよい。Rfの炭素数は４〜６、例えば４または６であることが好ましい。Rfの炭素数は６であることが特に好ましい。Rfの例は、−CF2CF2CF2CF3、−CF2CF(CF3)2、−C(CF3)3、−(CF2)5CF3、−(CF2)3CF(CF3)2である。 Rf is preferably a perfluoroalkyl group, but may be a fluoroalkyl group having a hydrogen atom. Rf has preferably 4 to 6, for example, 4 or 6, carbon atoms. Rf has particularly preferably 6 carbon atoms. Examples of Rf are -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) 2 , -C (CF 3 ) 3 ,-(CF 2 ) 5 CF 3 ,-(CF 2 ) 3 CF ( CF 3) 2.
含フッ素単量体（ａ）の具体例としては、例えば以下のものを例示できるが、これらに限定されるものではない。
CH2=C(−H)−C(=O)−O−(CH2)2−Rf
CH2=C(−H)−C(=O)−O−C6H4−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−Rf
CH2=C(−H)−C(=O)−O−(CH2)2N(−CH3)SO2−Rf
CH2=C(−H)−C(=O)−O−(CH2)2N(−C2H5)SO2−Rf
CH2=C(−H)−C(=O)−O−CH2CH(−OH)CH2−Rf
CH2=C(−H)−C(=O)−O−CH2CH(−OCOCH3)CH2−Rf
CH2=C(−H)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−H)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−H)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−H)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−H)−C(=O)−NH−(CH2)2−Rf
CH2=C(−CH3)−C(=O)−O−(CH2)2−Rf
CH2=C(−CH3)−C(=O)−O−C6H4−Rf
CH2=C(−CH3)−C(=O)−O−(CH2)2N(−CH3)SO2−Rf
CH2=C(−CH3)−C(=O)−O−(CH2)2N(−C2H5)SO2−Rf
CH2=C(−CH3)−C(=O)−O−CH2CH(−OH)CH2−Rf
CH2=C(−CH3)−C(=O)−O−CH2CH(−OCOCH3)CH2−Rf
Specific examples of the fluorine-containing monomer (a) include, but are not limited to, for example, the following.
CH 2 = C (−H) −C (= O) −O− (CH 2 ) 2 −Rf
CH 2 = C (−H) −C (= O) −O−C 6 H 4 −Rf
CH 2 = C (−Cl) −C (= O) −O− (CH 2 ) 2 −Rf
CH 2 = C (−H) −C (= O) −O− (CH 2 ) 2 N (−CH 3 ) SO 2 −Rf
CH 2 = C (−H) −C (= O) −O− (CH 2 ) 2 N (−C 2 H 5 ) SO 2 −Rf
CH 2 = C (-H) -C (= O) -O-CH 2 CH (-OH) CH 2 -Rf
CH 2 = C (-H) -C (= O) -O-CH 2 CH (-OCOCH 3 ) CH 2 -Rf
CH 2 = C (−H) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−H) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−H) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−H) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-H) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−CH 3 ) −C (= O) −O− (CH 2 ) 2 −Rf
CH 2 = C (−CH 3 ) −C (= O) −O−C 6 H 4 −Rf
CH 2 = C (-CH 3 ) -C (= O) -O- (CH 2 ) 2 N (-CH 3 ) SO 2 -Rf
CH 2 = C (−CH 3 ) −C (= O) −O− (CH 2 ) 2 N (−C 2 H 5 ) SO 2 −Rf
CH 2 = C (-CH 3 ) -C (= O) -O-CH 2 CH (-OH) CH 2 -Rf
CH 2 = C (-CH 3 ) -C (= O) -O-CH 2 CH (-OCOCH 3 ) CH 2 -Rf
CH2=C(−CH3)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CH3)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CH3)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CH3)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CH3)−C(=O)−NH−(CH2)2−Rf
CH2=C(−F)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−F)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−F)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−F)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−F)−C(=O)−NH−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−NH−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−NH−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−NH−(CH2)2−Rf
CH 2 = C (−CH 3 ) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CH 3 ) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CH 3 ) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CH 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CH 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-F) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -S-Rf
CH 2 = C (−Cl) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -SO 2 -Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 2 -SO 2- (CH 2 ) 2 -Rf
CH 2 = C (-Cl) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CF 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CF 2 H) -C (= O) -NH- (CH 2 ) 2 -Rf
CH2=C(−CN)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CN)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CN)−C(=O)−NH−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−S−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−S−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−SO2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−NH−(CH2)2−Rf
CH2=C(−F)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−F)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−F)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−F)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−F)−C(=O)−NH−(CH2)3−Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CN) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −S−Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-CF 2 CF 3 ) -C (= O) -NH- (CH 2 ) 2 -Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−F) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (-F) -C (= O) -NH- (CH 2 ) 3 -Rf
CH2=C(−Cl)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−Cl)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CF3)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CF2H)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−CN)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CN)−C(=O)−O−(CH2)3−SO2−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)3−S−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)3−S−(CH2)2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)3−SO2−Rf
CH2=C(−CF2CF3)−C(=O)−O−(CH2)2−SO2−(CH2)2−Rf
これらのうち、CH2=CH−C(=O)−O−(CH2)2−Rf、CH2=C(−CH3)−C(=O)−O−(CH2)2−Rfが好ましい。
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -S-Rf
CH 2 = C (−Cl) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (-Cl) -C (= O) -O- (CH 2 ) 3 -SO 2 -Rf
CH 2 = C (−Cl) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CF 3 ) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CF 2 H) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CN) −C (= O) −O− (CH 2 ) 3 −SO 2 − (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 3 −S−Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 3 −S− (CH 2 ) 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 3 −SO 2 −Rf
CH 2 = C (−CF 2 CF 3 ) −C (= O) −O− (CH 2 ) 2 −SO 2 − (CH 2 ) 2 −Rf
Of these, CH 2 = CH-C ( = O) -O- (CH 2) 2 -Rf, CH 2 = C (-CH 3) -C (= O) -O- (CH 2) 2 -Rf Is preferred.
非フッ素単量体（ｂ）は、炭化水素基を有する非フッ素単量体である。
非フッ素単量体は、式：
CH2=CA11-C(=O)-O-A12
［式中、A11は、水素原子、炭素数１〜３０直鎖状または分岐状のアルキル基、シアノ基、置換または非置換のベンジル基、置換または非置換のフェニル基、またはフッ素原子以外のハロゲン原子であり、
A12は、炭素数１〜４０の炭化水素基である。]
で示される（メタ）アクリレートエステル単量体であることが好ましい。
The non-fluorine monomer (b) is a non-fluorine monomer having a hydrocarbon group.
Non-fluorine monomers have the formula:
CH 2 = CA 11 -C (= O) -OA 12
[Wherein A 11 is other than a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a fluorine atom. A halogen atom,
A 12 is a hydrocarbon group having 1 to 40 carbon atoms. ]
It is preferable that it is a (meth) acrylate ester monomer shown by these.
炭化水素基の炭素数は、１〜４０、好ましくは４〜４０、特に１４〜４０であってよい。
炭化水素基の例は、炭素数１〜４０、好ましくは１４〜４０の直鎖状または分岐状の飽和または不飽和（例えば、エチレン性不飽和）の脂肪族炭化水素基、炭素数４〜４０、好ましくは６〜４０、例えば１４〜４０の飽和または不飽和（例えば、エチレン性不飽和）の環状脂肪族基、炭素数６〜４０、好ましくは１４〜４０の芳香族炭化水素基、炭素数７〜４０、好ましくは１４〜４０の芳香脂肪族炭化水素基である。
炭化水素基は、炭素数１４〜４０の非環状炭化水素基または炭素数４〜４０の環状炭化水素基であることが好ましい。
The carbon number of the hydrocarbon group may be 1-40, preferably 4-40, in particular 14-40.
Examples of the hydrocarbon group include a linear or branched saturated or unsaturated (for example, ethylenically unsaturated) aliphatic hydrocarbon group having 1 to 40 carbon atoms, preferably 14 to 40 carbon atoms, and 4 to 40 carbon atoms. , Preferably 6 to 40, for example 14 to 40 saturated or unsaturated (for example, ethylenically unsaturated) cyclic aliphatic group, 6 to 40 carbon atoms, preferably 14 to 40 aromatic hydrocarbon groups, carbon number 7 to 40, preferably 14 to 40 araliphatic hydrocarbon groups.
The hydrocarbon group is preferably an acyclic hydrocarbon group having 14 to 40 carbon atoms or a cyclic hydrocarbon group having 4 to 40 carbon atoms.
（メタ）アクリレートエステル単量体の具体例は、
非環状炭化水素基を有する（メタ）アクリレートエステル単量体として、
セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート；
環状炭化水素含有基を有する（メタ）アクリレートエステル単量体として、
シクロヘキシル（メタ）アクリレート、t−ブチルシクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、トリシクロペンタニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、2−メチル−2−アダマンチル（メタ）アクリレート、2−エチル−2−アダマンチル（メタ）アクリレートである。
ステアリル（メタ）アクリレートおよびベヘニル（メタ）アクリレートが好ましい。
Specific examples of (meth) acrylate ester monomers are:
As a (meth) acrylate ester monomer having an acyclic hydrocarbon group,
Cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate;
As a (meth) acrylate ester monomer having a cyclic hydrocarbon-containing group,
Cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate.
Stearyl (meth) acrylate and behenyl (meth) acrylate are preferred.
含フッ素重合体は、A12が炭素数１〜１３の非環状炭化水素基である上記式：CH2=CA11-C(=O)-O-A12で示される（メタ）アクリレートエステル単量体から誘導された繰り返し単位を有しないことが好ましい。 The fluorinated polymer is a (meth) acrylate ester monomer represented by the above formula: CH 2 = CA 11 -C (= O) -OA 12 wherein A 12 is an acyclic hydrocarbon group having 1 to 13 carbon atoms It preferably has no repeating unit derived from.
含フッ素重合体は、必要に応じて、単量体（ａ）および単量体（ｂ）以外である他の単量体（ｃ）から誘導された繰り返し単位を有する。
１つの態様において、他の単量体（ｃ）は、式：
CH2=CA-T
［式中、Aは、水素原子、メチル基、またはフッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）であり、
Tは、水素原子、フッ素原子以外のハロゲン原子（例えば、塩素原子、臭素原子およびヨウ素原子）、または炭素数１〜４０（例えば５〜２０）の炭化水素基である。］
で示される化合物であってよい。
The fluorine-containing polymer has a repeating unit derived from the monomer (c) other than the monomer (a) and the monomer (b) as necessary.
In one embodiment, the other monomer (c) has the formula:
CH 2 = CA-T
[Wherein, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
T is a hydrogen atom, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom), or a hydrocarbon group having 1 to 40 (for example, 5 to 20) carbon atoms. ]
It may be a compound shown by these.
他の単量体（ｃ）は、例えば、ハロゲン化オレフィン単量体であってよい。
ハロゲン化オレフィン単量体は、フッ素原子を有しない。
ハロゲン化オレフィン単量体は、１〜１０の塩素原子、臭素原子またはヨウ素原子で置換されている炭素数２〜２０のオレフィンであってよい。ハロゲン化オレフィン単量体は、炭素数２〜２０、特に１〜５の塩素原子を有する炭素数２〜５のオレフィンであることが好ましい。ハロゲン化オレフィン単量体の好ましい具体例は、ハロゲン化ビニル、例えば塩化ビニル、臭化ビニル、ヨウ化ビニル、ハロゲン化ビニリデン、例えば塩化ビニリデン、臭化ビニリデン、ヨウ化ビニリデンである。撥水撥油性（特に撥水撥油性の耐久性）が高くなるので、塩化ビニルが好ましい。含フッ素重合体は塩化ビニリデンから誘導される繰り返し単位を有しないことが好ましい。
The other monomer (c) may be, for example, a halogenated olefin monomer.
The halogenated olefin monomer does not have a fluorine atom.
The halogenated olefin monomer may be an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atom, bromine atom or iodine atom. The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms, particularly 1 to 5 carbon atoms having a chlorine atom. Preferred specific examples of the halogenated olefin monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride is preferred because of high water and oil repellency (especially durability of water and oil repellency). The fluoropolymer preferably does not have a repeating unit derived from vinylidene chloride.
他の態様において、他の単量体（ｃ）は、好ましくは、フッ素原子を含まない非フッ素架橋性単量体である。非フッ素架橋性単量体は、少なくとも１つの反応性基および／またはオレフィン性炭素−炭素二重結合（好ましくは、（メタ）アクリレート基）を有し、フッ素を含有しない化合物であってよい。非フッ素架橋性単量体は、少なくとも２つのオレフィン性炭素−炭素二重結合（好ましくは、（メタ）アクリレート基）を有する化合物、あるいは少なくとも１つのオレフィン性炭素−炭素二重結合および少なくとも１つの反応性基を有する化合物であってよい。反応性基の例は、ヒドロキシル基、エポキシ基、クロロメチル基、ブロックイソシアネート基、アミノ基、カルボキシル基、グリシジル基などである。
反応性基、例えば、ヒドロキシル基を有することによって、防汚性および撥水撥油性の耐久性を付与できる。
In another embodiment, the other monomer (c) is preferably a non-fluorine crosslinkable monomer containing no fluorine atom. The non-fluorine crosslinkable monomer may be a compound having at least one reactive group and / or an olefinic carbon-carbon double bond (preferably a (meth) acrylate group) and not containing fluorine. The non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably a (meth) acrylate group), or at least one olefinic carbon-carbon double bond and at least one It may be a compound having a reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, glycidyl groups, and the like.
By having a reactive group such as a hydroxyl group, antifouling and water / oil repellency durability can be imparted.
非フッ素架橋性単量体は、反応性基を有するモノ（メタ）アクリレート、ジ（メタ）アクリレートまたはモノ（メタ）アクリルアミドであってよい。あるいは、非フッ素架橋性単量体は、ジ（メタ）アクリレートであってよい。 The non-fluorine crosslinkable monomer may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer may be di (meth) acrylate.
非フッ素架橋性単量体の例は、ヒドロキシル基を有するビニル単量体（特に、（メタ）アクリレート単量体）である。
非フッ素架橋性単量体の具体例は、ジアセトン（メタ）アクリルアミド、N−メチロール（メタ）アクリルアミド、ヒドロキシメチル(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレート、2,3−ジヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル（メタ）アクリレート、3−クロロ−2−ヒドロキシプロピル(メタ)アクリレート、2-アセトアセトキシエチル（メタ）アクリレート、ブタジエン、イソプレン、クロロプレン、モノクロロ酢酸ビニル、メタクリル酸ビニル、グリシジル(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレートである。
Examples of non-fluorine crosslinkable monomers are vinyl monomers having hydroxyl groups (particularly (meth) acrylate monomers).
Specific examples of non-fluorine crosslinkable monomers include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate is there.
非フッ素架橋性単量体は、イソシアナトアクリレート単量体などであってよい。
イソシアナトアクリレート単量体の具体例は、2−イソシアナトエチル（メタ）アクリレート、3−イソシアナトプロピル（メタ）アクリレート、4−イソシアナトブチル（メタ）アクリレート、2−イソシアナトエチル（メタ）アクリレートの2−ブタノンオキシム付加体、2−イソシアナトエチル（メタ）アクリレートのピラゾール付加体、2−イソシアナトエチル（メタ）アクリレートの3,5−ジメチルピラゾール付加体、2−イソシアナトエチル（メタ）アクリレートの3−メチルピラゾール付加体、2−イソシアナトエチル（メタ）アクリレートのε−カプロラクタム付加体、3−イソシアナトプロピル（メタ）アクリレートの2−ブタノンオキシム付加体、3−イソシアナトプロピル（メタ）アクリレートのピラゾール付加体、3−イソシアナトプロピル（メタ）アクリレートの3,5−ジメチルピラゾール付加体、3−イソシアナトプロピル（メタ）アクリレートの3−メチルピラゾール付加体、3−イソシアナトプロピル（メタ）アクリレートのε−カプロラクタム付加体、4−イソシアナトブチル（メタ）アクリレートの2−ブタノンオキシム付加体、4−イソシアナトブチル（メタ）アクリレートのピラゾール付加体、4−イソシアナトブチル（メタ）アクリレートの3,5−ジメチルピラゾール付加体、4−イソシアナトブチル（メタ）アクリレートの3−メチルピラゾール付加体、4−イソシアナトブチル（メタ）アクリレートのε−カプロラクタム付加体などである。
The non-fluorine crosslinkable monomer may be an isocyanato acrylate monomer.
Specific examples of the isocyanato acrylate monomer include 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, and 2-isocyanatoethyl (meth) acrylate. 2-butanone oxime adduct, 2-isocyanatoethyl (meth) acrylate pyrazole adduct, 2-isocyanatoethyl (meth) acrylate 3,5-dimethylpyrazole adduct, 2-isocyanatoethyl (meth) acrylate 3-methylpyrazole adduct, ε-caprolactam adduct of 2-isocyanatoethyl (meth) acrylate, 2-butanone oxime adduct of 3-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate Pyrazole adduct of 3-isocyanatopropi 3,5-dimethylpyrazole adduct of ru (meth) acrylate, 3-methylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, ε-caprolactam adduct of 3-isocyanatopropyl (meth) acrylate, 4- 2-butanone oxime adduct of isocyanatobutyl (meth) acrylate, pyrazole adduct of 4-isocyanatobutyl (meth) acrylate, 3,5-dimethylpyrazole adduct of 4-isocyanatobutyl (meth) acrylate, 4- Examples include 3-methylpyrazole adduct of isocyanatobutyl (meth) acrylate and ε-caprolactam adduct of 4-isocyanatobutyl (meth) acrylate.
含フッ素重合体はポリオキシアルキレン基（ポリオキシアルキレン基においてオキシアルキレン基の数が２以上である。）を有しないことが好ましい。例えば、非フッ素単量体（ｂ）および他の単量体（ｃ）はポリオキシアルキレン基を有しないことが好ましい。これにより、含フッ素重合体は、良好な防汚性を付与できる。 The fluoropolymer preferably does not have a polyoxyalkylene group (the number of oxyalkylene groups in the polyoxyalkylene group is 2 or more). For example, the non-fluorine monomer (b) and the other monomer (c) preferably do not have a polyoxyalkylene group. Thereby, a fluoropolymer can provide favorable antifouling property.
本明細書において、「（メタ）アクリレート」とは、アクリレートまたはメタクリレートを意味し、「（メタ）アクリルアミド」とは、アクリルアミドまたはメタクリルアミドを意味する。 In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.
単量体（ａ）〜（ｃ）のそれぞれは、単独であってよく、あるいは２種以上の組み合わせであってもよい。
含フッ素重合体は、単独であってよく、あるいは２種以上の組み合わせであってもよい。
Each of the monomers (a) to (c) may be a single monomer or a combination of two or more.
The fluorine-containing polymer may be used alone or in combination of two or more.
含フッ素単量体（ａ）の量は、含フッ素重合体に対して、２０〜９８重量％、例えば３０〜９０重量％、特に４０〜８０重量％であってよい。
単量体（ａ）と単量体（ｂ）の重量比は、２０：８０〜８０：２０、３０：７０〜７０：３０、例えば３５：６０〜６５：３５であってよい。
The amount of the fluorine-containing monomer (a) may be 20 to 98% by weight, for example 30 to 90% by weight, particularly 40 to 80% by weight, based on the fluorine-containing polymer.
The weight ratio of the monomer (a) to the monomer (b) may be 20:80 to 80:20, 30:70 to 70:30, for example 35:60 to 65:35.
単量体（ｃ）を含む含フッ素重合体において、単量体（ａ）と単量体（ｂ）と単量体（ｃ）の重量比は、２０：７５：５〜８０：５：１５、好ましくは３０：６５：５〜７０：１５：１５、例えば４０：５３：７〜６５：２５：１０であってよい。あるいは、単量体（ｃ）の量は、単量体（ａ）と単量体（ｂ）の合計１００重量部に対して、１〜３０重量部、好ましくは３〜２０重量部、より好ましくは５〜１５、例えば７〜１２重量部であってよい。 In the fluoropolymer containing the monomer (c), the weight ratio of the monomer (a), the monomer (b) and the monomer (c) is 20: 75: 5 to 80: 5: 15. , Preferably 30: 65: 5 to 70:15:15, for example 40: 53: 7 to 65:25:10. Alternatively, the amount of monomer (c) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 100 parts by weight in total of monomer (a) and monomer (b). May be 5-15, such as 7-12 parts by weight.
含フッ素重合体の分子量は、例えば、ＧＰＣ（ゲルパーミエーションクロマトグラフ）測定でポリスチレン換算した場合、一般に１，０００〜１，０００，０００、特に２，０００〜５０，０００であってよい。 The molecular weight of the fluorinated polymer may be generally 1,000 to 1,000,000, particularly 2,000 to 50,000, for example, when converted to polystyrene by GPC (gel permeation chromatography) measurement.
含フッ素重合体は、重合開始剤、溶媒、必要に応じて連鎖移動剤を用いて、既知の方法にて重合することによって製造できる。含フッ素重合体は、有機溶媒中の溶液重合、または水中の乳化重合などによって製造できる。
塗料改質剤は、含フッ素重合体の有機溶媒溶液であることが好ましい。
The fluorine-containing polymer can be produced by polymerizing by a known method using a polymerization initiator, a solvent, and optionally a chain transfer agent. The fluorine-containing polymer can be produced by solution polymerization in an organic solvent or emulsion polymerization in water.
The paint modifier is preferably an organic solvent solution of a fluoropolymer.
（２）塗料
塗料は、樹脂（すなわち、塗料樹脂）を含んでなる。樹脂は、熱硬化性または熱可塑性であり、一般に、熱硬化性である。樹脂の例は、ウレタン樹脂、エポキシ樹脂、フッ素樹脂、メラミン樹脂である。
(2) Paint The paint comprises a resin (that is, a paint resin). The resin is thermosetting or thermoplastic and is generally thermosetting. Examples of the resin are urethane resin, epoxy resin, fluororesin, and melamine resin.
エポキシ樹脂は、分子内に２個以上のオキシラン環（エポキシ基）を有する化合物である。通常、硬化剤（アミン系硬化剤、酸または酸無水物系硬化剤、塩基性活性水素化合物、イミダゾール類などの活性水素化合物）と併用して、二液硬化型塗料として用いられる。また、硬化反応速度制御のため、触媒を添加することも可能である。 The epoxy resin is a compound having two or more oxirane rings (epoxy groups) in the molecule. Usually, it is used in combination with a curing agent (an active curing compound such as an amine curing agent, an acid or acid anhydride curing agent, a basic active hydrogen compound, or an imidazole) as a two-component curable coating. In addition, a catalyst may be added for controlling the curing reaction rate.
エポキシ樹脂の例は、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、臭素化エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、ビスフェノールＡ型ノボラック系エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンフェノール型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、３官能型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、４官能型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡ含核ポリオール型エポキシ樹脂、ポリプロピレングリコール型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリオキザール型エポキシ樹脂、脂環型エポキシ樹脂、脂環式多官能エポキシ化合物、トリグリシジルイソシアネート（ＴＧＩＣ）などの複素環型エポキシ樹脂である。 Examples of epoxy resins are bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene Type epoxy resin, bisphenol A type novolak epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene phenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylol Ethane type epoxy resin, tetrafunctional type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypro Heterocyclic epoxy resins such as lenglycol type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, glioxal type epoxy resins, alicyclic epoxy resins, alicyclic polyfunctional epoxy compounds, and triglycidyl isocyanate (TGIC) It is.
アミン系硬化剤の例は、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン等の脂肪族ポリアミン；イソホロンジアミン、１，３−ビスアミノメチルシクロヘキサン等の脂環族ポリアミン；ジアミノジフェニルメタン、ジアミノジフェニルスルフォン等の芳香族ポリアミン；直鎖状ジアミン、テトラメチルグアニジン、トリエタノールアミン、ピペリジン、ピリジン、ベンジルジメチルアミン等の２級アミン類または３級アミン類；ダイマー酸とジエチレントリアミン、トリエチレンテトラミン等のポリアミンとを反応させて得たポリアミドアミンである。 Examples of amine curing agents include: aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; alicyclic polyamines such as isophoronediamine and 1,3-bisaminomethylcyclohexane; aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone ; Secondary amines or tertiary amines such as linear diamine, tetramethylguanidine, triethanolamine, piperidine, pyridine, benzyldimethylamine; obtained by reacting dimer acid with polyamines such as diethylenetriamine and triethylenetetramine Polyamidoamine.
酸または酸無水物系硬化剤の例は、アジピン酸、アゼライン酸、トリメリット酸、ピロメリット酸、デカンジカルボン酸等のポリカルボン酸；無水フタル酸、無水トリメリット酸、無水ピロメリット酸、３，３’，４，４’−ベンゾフェノンテトラカルボン酸無水物等の芳香族無水物；無水マレイン酸、無水コハク酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸等の環状脂肪族酸無水物；ポリアジピン酸無水物、ポリアゼライン酸無水物、ポリセバシン酸無水物、ドデセニル無水コハク酸、ポリ（エチル）オクタデカン二酸無水物等の脂肪族酸無水物である。 Examples of acid or acid anhydride curing agents include polycarboxylic acids such as adipic acid, azelaic acid, trimellitic acid, pyromellitic acid, decanedicarboxylic acid; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3 , 3 ′, 4,4′-benzophenone tetracarboxylic anhydride, etc .; cyclic aliphatic acid anhydrides such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride; polyadipine Aliphatic acid anhydrides such as acid anhydrides, polyazeline acid anhydrides, polysebacic acid anhydrides, dodecenyl succinic anhydrides, poly (ethyl) octadecanedioic acid anhydrides.
塩基性活性水素化合物の例は、有機酸ジヒドラジドである。 An example of a basic active hydrogen compound is an organic acid dihydrazide.
イミダゾール類の例は、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−ヘプタンデシルイミダゾールである。 Examples of imidazoles are 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptanedecylimidazole.
触媒の例は、３級アミン、イミダゾール、三フッ化ホウ素−アミン錯体、有機酸化合物、フェノール類、有機金属化合物である。 Examples of the catalyst are tertiary amines, imidazoles, boron trifluoride-amine complexes, organic acid compounds, phenols, and organometallic compounds.
ウレタン樹脂は、水酸基を２個以上有する化合物（ポリオール）、および２個以上のイソシアネート基を有する化合物（イソシアネート化合物）である硬化剤から形成される。ウレタン樹脂は、二液硬化型塗料として用いることができる。 The urethane resin is formed from a curing agent that is a compound having two or more hydroxyl groups (polyol) and a compound having two or more isocyanate groups (isocyanate compound). The urethane resin can be used as a two-component curable paint.
イソシアネート化合物は、水酸基以外にも、アミノ基、メルカプト基、カルボキシル基などの官能基をもつ活性水素化合物とも硬化反応する。そのため、ポリオールとこれら活性水素化合物との併用、あるいはポリオール分子中にこれら活性水素官能基の導入する等により、硬化塗膜強度や塗料安定性の調整も可能である。 In addition to hydroxyl groups, isocyanate compounds also undergo a curing reaction with active hydrogen compounds having functional groups such as amino groups, mercapto groups, and carboxyl groups. Therefore, it is possible to adjust the strength of the cured coating film and the coating stability by using a combination of polyol and these active hydrogen compounds, or introducing these active hydrogen functional groups into the polyol molecule.
硬化反応速度制御のため、触媒を添加することも可能である。イソシアネート化合物は、あらかじめイソシアネート基をブロック剤によりマスキングしておくことで、塗料中でポリオールと共存させておき、塗膜形成時に加熱硬化が可能な、一液硬化型塗料とすることもできる。 In order to control the curing reaction rate, it is also possible to add a catalyst. The isocyanate compound can be made into a one-component curable coating material in which an isocyanate group is masked with a blocking agent in advance so that it can coexist with a polyol in the coating material and can be cured by heating at the time of coating film formation.
さらに、イソシアネート化合物の分子量を高くすることで、硬化反応を遅くさせ、大気中の水分と反応硬化させる、いわゆる湿気硬化型塗料とすることもできる。 Furthermore, by increasing the molecular weight of the isocyanate compound, a so-called moisture-curing coating material that slows the curing reaction and reacts with moisture in the atmosphere can be obtained.
ポリオールの例は、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパンなどの多価アルコールや、ポリプロピレングリコール、ポリテトラメチレングリコール、縮合系ポリエステルポリオール、ラクトン系ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、水添ポリブタジエンポリオール、アクリルポリオール、含リンポリオール、ひまし油ポリオール、水添ひまし油ポリオール、フェノール系ポリオールである。好ましいポリオールは、プロピレングリコールとの付加重合体、縮合系ポリエステルポリオール、ラクトン系ポリエステルポリオール、アクリルポリオール、ポリカーボネートポリオール、フェノール系ポリオールである。ポリオールは、必要により、２種以上を混合して使用しても良い。 Examples of polyols include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, polypropylene glycol, polytetramethylene Glycols, condensed polyester polyols, lactone polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, acrylic polyols, phosphorus-containing polyols, castor oil polyols, hydrogenated castor oil polyols, and phenolic polyols. Preferred polyols are addition polymers with propylene glycol, condensation polyester polyols, lactone polyester polyols, acrylic polyols, polycarbonate polyols, and phenol polyols. If necessary, two or more kinds of polyols may be mixed and used.
イソシアネート化合物は、１分子中に２個のイソシアネート基を有する化合物である。イソシアネート化合物の例は、ヘキサメチレンジイソシアネート（ＨＭＤＩ）、トリメチルヘキサメチレンジイソシアネート（ＴＭＤＩ）等の脂肪族ジイソシアネート類；イソホロンジイソシアネート（ＩＰＤＩ）等の脂環族ジイソシアネート類；キシリレンジイソシアネート（ＸＤＩ）等の芳香族−脂肪族ジイソシアネート類；トリレンジイソシアネート（ＴＤＩ）、４，４−ジフェニルメタンジイソシアネート（ＭＤＩ）等の芳香族ジイソシアネート類；ダイマー酸ジイソシアネート（ＤＤＩ）、水添ＴＤＩ（ＨＴＤＩ）、水添ＸＤＩ（Ｈ６ＸＤＩ）、水添ＭＤＩ（Ｈ１２ＭＤＩ）等の水添ジイソシアネート類；これらの２量体、３量体、４量体以上の多量体のポリイソシアネート類；これらとトリメチロールプロパン等の多価アルコール、水または低分子量ポリエステル樹脂との付加物である。 The isocyanate compound is a compound having two isocyanate groups in one molecule. Examples of isocyanate compounds include aliphatic diisocyanates such as hexamethylene diisocyanate (HMDI) and trimethylhexamethylene diisocyanate (TMDI); alicyclic diisocyanates such as isophorone diisocyanate (IPDI); and aromatics such as xylylene diisocyanate (XDI). -Aliphatic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI); dimer acid diisocyanate (DDI), hydrogenated TDI (HTDI), hydrogenated XDI (H6XDI), Hydrogenated diisocyanates such as hydrogenated MDI (H12MDI); these dimers, trimers, tetramers and higher polyisocyanates; and these and polyvalent alcohols such as trimethylolpropane , Adducts with water or a low molecular weight polyester resin.
ポリオールとイソシアネート化合物は、混合した時点からウレタン硬化反応が開始するので、ポットライフが短い。このポットライフを延長させるため、イソシアネート化合物の反応基（イソシアネート基）を適当なブロック剤でブロックしたブロックイソシアネート化合物として使用することもできる。 Since the urethane curing reaction starts when the polyol and the isocyanate compound are mixed, the pot life is short. In order to extend this pot life, it can also be used as a blocked isocyanate compound in which the reactive group (isocyanate group) of the isocyanate compound is blocked with an appropriate blocking agent.
ブロック剤の例は、メチルエチルケトオキシム、アセトキシム、シクロヘキサノンオキシム、アセトフェノンオキシム、ベンゾフェノンオキシム等のオキシム系ブロック剤；ｍ−クレゾール、キシレノール等のフェノール系ブロック剤；メタノール、エタノール、ブタノール、２−エチルヘキサノール、シクロヘキサノール、エチレングリコールモノエチルエーテル等のアルコール系ブロック剤；ε−カプロラクタム等のラクタム系ブロック剤；マロン酸ジエチル、アセト酢酸エステル等のジケトン系ブロック剤；チオフェノール等のメルカプタン系ブロック剤；チオ尿素等の尿素系ブロック剤；イミダゾール系ブロック剤；カルバミン酸系ブロック剤である。 Examples of blocking agents include oxime blocking agents such as methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; phenol blocking agents such as m-cresol and xylenol; methanol, ethanol, butanol, 2-ethylhexanol, cyclo Alcohol-based blocking agents such as hexanol and ethylene glycol monoethyl ether; Lactam-based blocking agents such as ε-caprolactam; Diketone-based blocking agents such as diethyl malonate and acetoacetate; Mercaptan-based blocking agents such as thiophenol; A urea-based blocking agent; an imidazole-based blocking agent; and a carbamic acid-based blocking agent.
触媒の例は、三級アミン類、有機金属化合物や三級アミン類のカルボン酸塩である。三級アミン類の例は、トリエチレンジアミン、テトラメチルグアニジン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサン−１，６−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジエチレントリアミン、ビス（２−ジメチルアミノエチル）エーテル、１，２−ジメチルイミダゾール、Ｎ−メチル−Ｎ’−（２−ジメチルアミノ）エチルピペラジン、ジアザビシクロウンデセンである。有機金属化合物の例は、スタナスオクトエート、ジブチルチンジアセテート、ジブチルチンジラウレート、ジブチルチンマーカプチド、ジブチルチンチオカルボキシレート、ジブチルチンジマレエート、ジオクチルチンマーカプチド、ジオクチルチンチオカルボキシレート、フェニル水銀プロピオン酸塩、オクテン酸鉛である。三級アミン類のカルボン酸塩の例は、上記三級アミン類のカルボン酸塩である。 Examples of the catalyst are tertiary amines, organometallic compounds, and carboxylates of tertiary amines. Examples of tertiary amines are triethylenediamine, tetramethylguanidine, N, N, N ′, N′-tetramethylhexane-1,6-diamine, N, N, N ′, N ″, N ″ -pentamethyl Diethylenetriamine, bis (2-dimethylaminoethyl) ether, 1,2-dimethylimidazole, N-methyl-N ′-(2-dimethylamino) ethylpiperazine, diazabicycloundecene. Examples of organometallic compounds are stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marker peptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin marker peptide, dioctyltin thiocarboxylate, phenylmercury propion Acid salt, lead octenoate. Examples of tertiary amine carboxylates are the tertiary amine carboxylates.
フッ素樹脂の例は、テトラフルオロエチレン、トルフルオロモノクロルエチレンまたはビニリデンジフルオライドの単独重合体または共重合体である。 Examples of the fluororesin are a homopolymer or a copolymer of tetrafluoroethylene, trifluoromonochloroethylene or vinylidene difluoride.
メラミン樹脂の例は、メラミンとアルデヒドとの反応によって得られる部分もしくは完全メチロール化メラミン樹脂である。アルデヒドの例は、ホルムアルデヒド、パラホルムアルデヒドである。また、メチロール化メラミン樹脂のメチロール基をアルコールによって部分的にもしくは完全にエーテル化したものも使用することができる。エーテル化に用いられるアルコールの例は、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、２−エチルブタノール、２−エチルヘキサノールである。 Examples of melamine resins are partial or fully methylolated melamine resins obtained by reaction of melamine with aldehydes. Examples of aldehydes are formaldehyde and paraformaldehyde. Moreover, what methylated the methylol group of the methylol-ized melamine resin partially or completely etherified with alcohol can also be used. Examples of alcohols used for etherification are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylbutanol, 2-ethylhexanol.
一般に、塗料は、樹脂に加えて、有機溶剤を含んでなる。さらに、塗料は、顔料および助剤の少なくとも１種を含んでなることが好ましい。
顔料の例は、着色顔料（酸化チタン、カーボンブラック、インジゴ、キナクリドン、パールマイカ）、防錆顔料、金属顔料（例えば、酸化チタン、カーボンブラック、インジゴ、キナクリドン、パールマイカ）である。
助剤の例は、分散剤、乾燥剤、可塑剤、消泡剤、酸化防止剤（例えば、ヒンダードフェノール）、紫外線吸収剤（例えばベンゾトリアゾール、ベンゾフェノン）、レオロジーコントロール剤（例えば、ヒドロキシエチルセルロース、尿素化合物、マイクロゲル）、硬化促進剤（例えば、錫化合物、亜鉛化合物、アミン化合物）である。
有機溶剤の例は、炭化水素、アルコール、エステル、ケトン、セロソルブである。
Generally, the coating material contains an organic solvent in addition to the resin. Furthermore, the paint preferably contains at least one of a pigment and an auxiliary agent.
Examples of pigments are colored pigments (titanium oxide, carbon black, indigo, quinacridone, pearl mica), rust preventive pigments, and metal pigments (for example, titanium oxide, carbon black, indigo, quinacridone, pearl mica).
Examples of auxiliaries include dispersants, desiccants, plasticizers, antifoaming agents, antioxidants (eg hindered phenols), UV absorbers (eg benzotriazole, benzophenone), rheology control agents (eg hydroxyethylcellulose, Urea compounds, microgels) and curing accelerators (for example, tin compounds, zinc compounds, amine compounds).
Examples of organic solvents are hydrocarbons, alcohols, esters, ketones, cellosolves.
塗料は、単独であってよく、あるいは２種以上の組み合わせであってもよい。 The paint may be used alone or in combination of two or more.
塗料は、例えば一般的に市販されている塗料を用いることもできる。たとえばウレタン塗料としては、セラＭレタン、セラＭレタン弾性、セラテクトＵマイルド上塗、アレスレタン（関西ペイント社製）、ハイポン５０ファイン、ハイポン５０上塗（日本ペイント社製）、ＶトップＨ上塗、ＶトップＨB上塗（大日本塗料社製）、NYポリン（神東塗料社製）などが挙げられる。エポキシ塗料としては、エスコ、エスコNB、エポマリンGX（関西ペイント社製）、ハイポン９０ファイン、ハイポン９０モイスタック（日本ペイント社製）、エポニックス＃２０上塗、エポニックス＃３１００ＡＰ（大日本塗料社製）、ネオゴ−セ−＃２３００（神東塗料社製）などが挙げられる。塗料は、ここに挙げた市販品に限定されるものではなく、新たに合成して使用してもよく、塗料であれば用いることができる。 For example, a commercially available paint can be used as the paint. For example, urethane paints include Sera M Retan, Sera M Retan Elastic, Seratect U Mild Topcoat, Aresletan (manufactured by Kansai Paint), Hypon 50 Fine, Hypon 50 Topcoat (manufactured by Nippon Paint), V Top H Topcoat, V Top HB Examples include top coat (Dainippon Paint Co., Ltd.), NY porin (Shinto Paint Co., Ltd.), etc. Epoxy paints include Esco, Esco NB, Epomarine GX (manufactured by Kansai Paint Co., Ltd.), Hypon 90 Fine, Hypon 90 Moi Stack (manufactured by Nippon Paint Co., Ltd.), Eponics # 20 topcoat, Eponics # 3100AP (manufactured by Dainippon Paint Co., Ltd.), Neogo -Se- # 2300 (manufactured by Shinto Paint Co., Ltd.) The paint is not limited to the commercial products listed here, and may be newly synthesized and used, and any paint can be used.
（３）塗料組成物
塗料組成物は、含フッ素重合体を含む塗料改質剤（１）、および樹脂を含む塗料（２）を含んでなる。
含フッ素重合体の量が、樹脂１００重量部に対して、０．１〜２０重量部、例えば０．２〜１０重量部、特に０．５〜５重量部であってよい。含フッ素重合体の量は、塗料組成物に対して、０．０１〜１０重量％であってよい。
塗料組成物は、樹脂を含む塗料と塗料改質剤を混合することによって製造できる。例えば、樹脂および有機溶剤を含む塗料に、含フッ素重合体および有機溶剤を含む塗料改質剤を添加することによって、塗料組成物を製造できる。塗料における有機溶剤は、塗料改質剤における有機溶剤と同じであっても異なっていてもよい。
塗料組成物を、金属（例えば、鋼板）などの基材に塗布して、（例えば、常温または屋外気温で）有機溶剤を揮発させて、樹脂の被膜を形成する。
(3) Coating composition The coating composition comprises a coating modifier (1) containing a fluoropolymer, and a coating (2) containing a resin.
The amount of the fluoropolymer may be 0.1 to 20 parts by weight, for example 0.2 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the resin. The amount of the fluoropolymer may be 0.01 to 10% by weight with respect to the coating composition.
The paint composition can be produced by mixing a paint containing a resin and a paint modifier. For example, a coating composition can be produced by adding a coating modifier containing a fluoropolymer and an organic solvent to a coating containing a resin and an organic solvent. The organic solvent in the paint may be the same as or different from the organic solvent in the paint modifier.
The coating composition is applied to a base material such as a metal (for example, a steel plate), and the organic solvent is volatilized (for example, at room temperature or outdoor temperature) to form a resin film.
以下に実施例を挙げて詳細を説明するが、本開示はこれら実施例にのみ限定されるものではない。
実施例において、特記しない限り、部、％および比は、重量部、重量％および重量比を意味する。
物性は次のようにして測定した。
Examples will be described in detail below, but the present disclosure is not limited to these examples.
In the examples, unless otherwise indicated, parts, percentages and ratios mean parts by weight, percentages by weight and ratios by weight.
The physical properties were measured as follows.
静的接触角
水、ｎ−ヘキサデカンおよびエタノールにて接触角測定（室温（２５℃）および液滴２μｌ）を行った。
Contact angle measurement (room temperature (25 ° C.) and droplet 2 μl) was performed with static contact angle water, n-hexadecane and ethanol.
防汚性
以下のようにして、土、塩、藻について、防汚性を評価した。
Antifouling property Antifouling property was evaluated for soil, salt, and algae as follows.
土と塩は、それぞれ50%、3.5%水溶液（すなわち、土の５０％縣濁水および塩の３．５％水溶液）を塗装した鋼板に１滴のせて１晩乾燥後、付着性・剥離性を求めた。
評価基準
○：塗板を１０度傾けた際、汚れがすぐに落ちる。
○△：塗板を１０度傾けても汚れが落ちないが、４５度傾けると汚れが落ちる。
△：塗板を４５度傾けても汚れが落ちないが、鋼板背面から叩くと落ちる。
×：塗板を４５度傾けても、さらに鋼板背面から叩いても汚れが落ちない。
Soil and salt are 50% and 3.5% aqueous solution (that is, 50% suspended water of soil and 3.5% aqueous solution of salt, respectively). Asked.
Evaluation criteria ○: When the coated plate is tilted by 10 degrees, the dirt immediately falls.
○ △: Dirt is not removed even when the coated plate is tilted 10 degrees, but dirt is removed when tilted 45 degrees.
Δ: Dirt is not removed even if the coated plate is tilted 45 degrees, but it falls when it is struck from the back of the steel plate.
X: Dirt is not removed even if the coated plate is tilted 45 degrees and is further struck from the back surface of the steel plate.
藻は、金魚飼育中の水槽に塗装した鋼板を3ヶ月入れ、藻の付着度合いを求めた。
評価基準
○：藻が塗膜表面に付着しない。
△：藻は塗膜表面に付着するが、水面から鋼板を上げると剥がれる。
×：藻は塗膜表面に付着し、水面から鋼板を上げても剥がれない。
For the algae, a painted steel plate was placed in a water tank during goldfish breeding for 3 months, and the degree of algae adhesion was determined.
Evaluation criteria ○: Algae does not adhere to the coating film surface.
(Triangle | delta): Algae adheres to the coating-film surface, but peels when a steel plate is raised from the water surface.
X: Algae adheres to the coating surface and does not peel off even when the steel plate is lifted from the water surface.
摩擦係数
表面性測定機を用いて、摩擦子として鋼球を用いて、ＡＳＴＭ Ｄ１８９４に準拠し、静摩擦係数および動摩擦係数を測定した。
Using a friction coefficient surface property measuring machine, a static ball coefficient and a dynamic friction coefficient were measured in accordance with ASTM D1894 using a steel ball as a friction element.
耐傷つき性
塗膜表面を、スコッチブライト（３M社製）を用いて荷重１００ｇｆ、１００ｍｍ／ｍｉｎの速度で１０往復擦りつける。その後、塗膜表面を表面粗度計にて、測定距離４０mmにおける、Ｒａ（算術平均粗さ）およびＲzjis(十点平均粗さ)を測定した。これらの数値の低いものを傷が付き難いと判定した。
The scratch-resistant coating film surface is rubbed back and forth 10 times at a load of 100 gf and a speed of 100 mm / min using Scotch Bright (manufactured by 3M). Thereafter, Ra (arithmetic average roughness) and Rzjis (ten-point average roughness) at a measurement distance of 40 mm were measured on the surface of the coating film with a surface roughness meter. Those with low numerical values were judged to be difficult to be scratched.
重合体例１〜１６
表１に示す単量体（含フッ素単量体および非フッ素単量体）を、イソプロピルアルコール（ＩＰＡ）１００重量部と混合し重合することによって、含フッ素共重合体の溶液を製造した。次いで、蒸留により有機溶媒（ＩＰＡ）を除去し、塊状の含フッ素共重合体を得た。含フッ素共重合体における単量体組成は、仕込んだ単量体の組成とほぼ同様であった。
表１は、重合体例１〜１６で使用した単量体を示す。
Polymer Examples 1-16
Monomers (fluorinated monomers and non-fluorinated monomers) shown in Table 1 were mixed with 100 parts by weight of isopropyl alcohol (IPA) and polymerized to prepare a solution of a fluorinated copolymer. Subsequently, the organic solvent (IPA) was removed by distillation to obtain a massive fluorine-containing copolymer. The monomer composition in the fluorinated copolymer was almost the same as the charged monomer composition.
Table 1 shows the monomers used in Polymer Examples 1-16.
表１における略号の意味は、次のとおりである。
Ｃ６ＦＡ：ＣＨ２＝Ｃ(−Ｈ)−Ｃ（＝Ｏ)−Ｏ−(ＣＨ２)２−Ｃ６Ｆ１３
Ｃ６ＦＭＡ：ＣＨ２＝Ｃ(−ＣＨ３)−Ｃ（＝Ｏ)−Ｏ−(ＣＨ２)２−Ｃ６Ｆ１３
Ｃ６ＦＣＬＡ：ＣＨ２＝Ｃ(−Ｃｌ)−Ｃ（＝Ｏ)−Ｏ−(ＣＨ２)２−Ｃ６Ｆ１３
ＬＡ：アクリル酸ラウリル
ＳｔＡ：アクリル酸ステアリル
ＶＡ：アクリル酸ベヘニル
ＣＨＭＡ：メタクリル酸シクロヘキシル
ＥＯＡ−１：ＣＨ２＝Ｃ(−Ｈ)−Ｃ（＝Ｏ)−Ｏ−(ＣＨ２ＣＨ２Ｏ)ｎ−Ｈ
ｎ数の平均 4.5
ＥＯＡ−２：ＣＨ２＝Ｃ(−Ｈ)−Ｃ（＝Ｏ)−Ｏ−(ＣＨ２ＣＨ２Ｏ)ｎ−Ｈ
ｎ数の平均 8
２−ＨＥＡ：アクリル酸２−ヒドロキシエチル
２−ＨＥMＡ：メタクリル酸２−ヒドロキシエチル
ＶＤＣ：塩化ビニリデン
The meanings of the abbreviations in Table 1 are as follows.
C6FA: CH 2 = C (-H ) -C (= O) -O- (CH 2) 2 -C 6 F 13
C6FMA: CH 2 = C (-CH 3) -C (= O) -O- (CH 2) 2 -C 6 F 13
C6FCLA: CH 2 = C (-Cl ) -C (= O) -O- (CH 2) 2 -C 6 F 13
LA: lauryl acrylate StA: stearyl acrylate VA: behenyl acrylate CHMA: cyclohexyl methacrylate EOA-1: CH 2 ═C (—H) —C (═O) —O— (CH 2 CH 2 O) n— H
n number average 4.5
EOA-2: CH 2 = C (-H) -C (= O) -O- (CH 2 CH 2 O) n-H
n number average 8
2-HEA: 2-hydroxyethyl acrylate 2-HEMA: 2-hydroxyethyl methacrylate VDC: vinylidene chloride
実施例１
重合体例１で得られた含フッ素共重合体０．６重量部と、メチルエチルケトン（MEK）２．４重量部を混合した溶液を、エポニックス＃１０上塗硬化剤（大日本塗料社製）２０重量部と混合してかきまぜた。その後、エポニックス＃１０上塗主剤（大日本塗料社製）８０重量部と混合して、エポキシ塗料を含む塗料組成物を得た。この塗料組成物を、鋼板に塗布して一晩乾燥することで、塗膜を得た。
塗料組成物の組成および試験結果を表２および表５に示す。
Example 1
A solution prepared by mixing 0.6 parts by weight of the fluorinated copolymer obtained in Polymer Example 1 and 2.4 parts by weight of methyl ethyl ketone (MEK) was added to 20 parts by weight of Eponics # 10 topcoat curing agent (Dainippon Paint Co., Ltd.). And mixed. Thereafter, it was mixed with 80 parts by weight of Eponics # 10 top coating agent (manufactured by Dainippon Paint Co., Ltd.) to obtain a coating composition containing an epoxy coating. This coating composition was applied to a steel plate and dried overnight to obtain a coating film.
The composition of the coating composition and the test results are shown in Tables 2 and 5.
実施例２
重合体例２で得られた含フッ素共重合体０．３重量部と、MEK１．２重量部を混合した溶液を、エポニックス＃１０上塗硬化剤（大日本塗料社製）２０重量部と混合してかきまぜた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 2
A solution obtained by mixing 0.3 part by weight of the fluorinated copolymer obtained in Polymer Example 2 and 1.2 parts by weight of MEK was mixed with 20 parts by weight of Eponics # 10 topcoat curing agent (Dainippon Paint Co., Ltd.). A coating film was obtained in the same manner as in Example 1 except for stirring.
The composition of the coating composition and the test results are shown in Table 2.
実施例３
重合体例２で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 3
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 2 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例４
含フッ素共重合体１．８重量部、ＭＥＫ７．２重量部とした以外は、実施例２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 4
A coating film was obtained in the same manner as in Example 2 except that 1.8 parts by weight of the fluorinated copolymer and 7.2 parts by weight of MEK were used.
The composition of the coating composition and the test results are shown in Table 2.
実施例５
重合体例３で得られた含フッ素共重合体を用いた以外は、実施例２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 5
A coating film was obtained in the same manner as in Example 2 except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例６
重合体例３で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 6
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例７
重合体例３で得られた含フッ素共重合体を用いた以外は、実施例４と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 7
A coating film was obtained in the same manner as in Example 4 except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例８
重合体例４で得られた含フッ素共重合体を用いた以外は、実施例２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 8
A coating film was obtained in the same manner as in Example 2 except that the fluorine-containing copolymer obtained in Polymer Example 4 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例９
重合体例４で得られた含フッ素共重合体を用いた以外は、実施例４と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 9
A coating film was obtained in the same manner as in Example 4 except that the fluorine-containing copolymer obtained in Polymer Example 4 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１０
重合体例５で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 10
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 5 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１１
重合体例６で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 11
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 6 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１２
重合体例７で得られた含フッ素共重合体を用いた以外は、実施例２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 12
A coating film was obtained in the same manner as in Example 2 except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１３
重合体例７で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 13
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１４
重合体例７で得られた含フッ素共重合体を用いた以外は、実施例４と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 14
A coating film was obtained in the same manner as in Example 4 except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１５
重合体例８で得られた含フッ素共重合体を用いた以外は、実施例２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 15
A coating film was obtained in the same manner as in Example 2 except that the fluorine-containing copolymer obtained in Polymer Example 8 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１６
重合体例８で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 16
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 8 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１７
重合体例９で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 17
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 9 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１８
重合体例１０で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 18
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 10 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例１９
重合体例１１で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 19
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 11 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例２０
重合体例１２で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 20
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 12 was used.
The composition of the coating composition and the test results are shown in Table 2.
実施例２１
重合体例１３で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Example 21
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 13 was used.
The composition of the coating composition and the test results are shown in Table 2.
比較例１
重合体例１４で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Comparative Example 1
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 14 was used.
The composition of the coating composition and the test results are shown in Table 2.
比較例２
重合体例１５で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Comparative Example 2
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 15 was used.
The composition of the coating composition and the test results are shown in Table 2.
比較例３
重合体例１６で得られた含フッ素共重合体を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表２に示す。
Comparative Example 3
A coating film was obtained in the same manner as in Example 1 except that the fluorine-containing copolymer obtained in Polymer Example 16 was used.
The composition of the coating composition and the test results are shown in Table 2.
比較例４
エポニックス＃１０上塗硬化剤（大日本塗料社製）２０重量部と、エポニックス＃１０上塗主剤（大日本塗料社製）８０重量部と混合して塗料組成物を得た。この塗料組成物を、鋼板に塗布して一晩乾燥することで、塗膜を得た。なお、この塗料の乾燥後固形分は６１％であった。
塗料組成物の組成および試験結果を表２および表５に示す。
Comparative Example 4
A coating composition was obtained by mixing 20 parts by weight of Eponics # 10 top coat curing agent (Dainippon Paint Co., Ltd.) and 80 parts by weight of Eponics # 10 top coating agent (Dainippon Paint Co., Ltd.). This coating composition was applied to a steel plate and dried overnight to obtain a coating film. The solid content after drying of this paint was 61%.
The composition of the coating composition and the test results are shown in Tables 2 and 5.
実施例３１
重合体例１で得られた含フッ素共重合体０．５７重量部と、MEK２．４重量部を混合した溶液を、アレスレタン硬化剤（関西ペイント社製）２０重量部と混合してかきまぜた。その後、アレスレタン（白）ベース（関西ペイント社製）８０重量部と混合して、ウレタン樹脂を含む塗料組成物を得た。この塗料組成物を、鋼板に塗布して一晩乾燥することで、塗膜を得た。
塗料組成物の組成および試験結果を表３および表４に示す。
Example 31
A solution prepared by mixing 0.57 parts by weight of the fluorinated copolymer obtained in Polymer Example 1 and 2.4 parts by weight of MEK was mixed with 20 parts by weight of Arestane curing agent (manufactured by Kansai Paint Co., Ltd.) and stirred. Thereafter, it was mixed with 80 parts by weight of Arestane (white) base (manufactured by Kansai Paint Co., Ltd.) to obtain a coating composition containing a urethane resin. This coating composition was applied to a steel plate and dried overnight to obtain a coating film.
The composition of the coating composition and the test results are shown in Tables 3 and 4.
実施例３２
重合体例２で得られた含フッ素共重合体０．２９重量部と、MEK１．２重量部を混合した溶液を用いた以外は、実施例１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３および表４に示す。
Example 32
A coating film was obtained in the same manner as in Example 1 except that a solution obtained by mixing 0.29 parts by weight of the fluorinated copolymer obtained in Polymer Example 2 and 1.2 parts by weight of MEK was used.
The composition of the coating composition and the test results are shown in Tables 3 and 4.
実施例３３
重合体例２で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３および表４に示す。
Example 33
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 2 was used.
The composition of the coating composition and the test results are shown in Tables 3 and 4.
実施例３４
含フッ素共重合体１．７１重量部、ＭＥＫ７．２重量部とした以外は、実施例３２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３および表４に示す。
Example 34
A coating film was obtained in the same manner as in Example 32 except that 1.71 parts by weight of the fluorinated copolymer and 7.2 parts by weight of MEK were used.
The composition of the coating composition and the test results are shown in Tables 3 and 4.
実施例３５
重合体例３で得られた含フッ素共重合体を用いた以外は、実施例３２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 35
A coating film was obtained in the same manner as in Example 32 except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例３６
重合体例３で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 36
A coating film was obtained in the same manner as in Example 31 except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例３７
重合体例３で得られた含フッ素共重合体を用いた以外は、実施例３４と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 37
A coating film was obtained in the same manner as in Example 34 except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例３８
重合体例４で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 38
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 4 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例３９
重合体例５で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 39
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 5 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４０
重合体例６で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 40
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 6 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４１
重合体例７で得られた含フッ素共重合体を用いた以外は、実施例３２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 41
A coating film was obtained in the same manner as in Example 32 except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４２
重合体例７で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 42
A coating film was obtained in the same manner as in Example 31 except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４３
重合体例７で得られた含フッ素共重合体を用いた以外は、実施例３４と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 43
A coating film was obtained in the same manner as in Example 34 except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４４
重合体例８で得られた含フッ素共重合体を用いた以外は、実施例３２と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 44
A coating film was obtained in the same manner as in Example 32 except that the fluorine-containing copolymer obtained in Polymer Example 8 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４５
重合体例８で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 45
A coating film was obtained in the same manner as in Example 31 except that the fluorine-containing copolymer obtained in Polymer Example 8 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４６
重合体例９で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 46
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 9 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４７
重合体例１０で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 47
A coating film was obtained in the same manner as in Example 31 except that the fluorine-containing copolymer obtained in Polymer Example 10 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４８
重合体例１１で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 48
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 11 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例４９
重合体例１２で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 49
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 12 was used.
The composition of the coating composition and the test results are shown in Table 3.
実施例５０
重合体例１３で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Example 50
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 13 was used.
The composition of the coating composition and the test results are shown in Table 3.
比較例１１
重合体例１４で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Comparative Example 11
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 14 was used.
The composition of the coating composition and the test results are shown in Table 3.
比較例１２
重合体例１５で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Comparative Example 12
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 15 was used.
The composition of the coating composition and the test results are shown in Table 3.
比較例３
重合体例１６で得られた含フッ素共重合体を用いた以外は、実施例３１と同様の方法で塗膜を得た。
塗料組成物の組成および試験結果を表３に示す。
Comparative Example 3
A coating film was obtained in the same manner as in Example 31 except that the fluorine-containing copolymer obtained in Polymer Example 16 was used.
The composition of the coating composition and the test results are shown in Table 3.
比較例１４
アレスレタン硬化剤（関西ペイント社製）２０重量部と、アレスレタン（白）ベース（関西ペイント社製）８０重量部と混合して塗料組成物を得た。この塗料組成物を、鋼板に塗布して一晩乾燥することで、塗膜を得た。なお、この塗料の乾燥後固形分は５７％であった。
塗料組成物の組成および試験結果を表３および表４に示す。
Comparative Example 14
A coating composition was obtained by mixing 20 parts by weight of Arestane curing agent (manufactured by Kansai Paint) and 80 parts by weight of Arestane (white) base (manufactured by Kansai Paint). The coating composition was applied to a steel plate and dried overnight to obtain a coating film. The solid content after drying of this paint was 57%.
The composition of the coating composition and the test results are shown in Tables 3 and 4.
塗料組成物は、橋梁および家屋などの建築物（例えば、港湾構造物、家屋の外壁、建材）、機械（例えば、機械設備の外装、工作機械）、車輌、船舶に使用できる。塗料組成物の塗布する基材の例は、金属（特に、鋼板などの鋼）、コンクリート、木材である。 The coating composition can be used for buildings such as bridges and houses (for example, harbor structures, outer walls of houses, building materials), machines (for example, exteriors of machine equipment, machine tools), vehicles, and ships. Examples of the substrate to which the coating composition is applied are metal (particularly steel such as a steel plate), concrete, and wood.
Claims (14)
CH2=C(-X)-C(=O)-Y-Z-Rf
［式中、Xは、水素原子、一価の有機基またはハロゲン原子であり、
Yは、-O-または-NH-であり、
Zは、直接結合または二価の有機基であり、
Rfは、炭素数１〜６のパーフルオロアルキル基である。］
で示される含フッ素単量体から誘導された繰り返し単位、および
（ｂ）式：
CH2=CA11-C(=O)-O-A12
［式中、A11は、水素原子、炭素数１〜３０直鎖状または分岐状のアルキル基、シアノ基、置換または非置換のベンジル基、置換または非置換のフェニル基、またはフッ素原子以外のハロゲン原子であり、
A12は、炭素数１〜４０の炭化水素基である。]
で示される（メタ）アクリレートエステル単量体である非フッ素単量体から誘導された繰り返し単位
を有する含フッ素重合体を含んでなる塗料改質剤。 (A) Formula:
CH 2 = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a C1-C6 perfluoroalkyl group. ]
A repeating unit derived from a fluorine-containing monomer represented by formula (b):
CH 2 = CA 11 -C (= O) -OA 12
[Wherein A 11 is other than a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a fluorine atom. A halogen atom,
A 12 is a hydrocarbon group having 1 to 40 carbon atoms. ]
A coating modifier comprising a fluorine-containing polymer having a repeating unit derived from a non-fluorine monomer which is a (meth) acrylate ester monomer represented by:
Xは、水素原子、メチル基または塩素原子であり、
Zは、直接結合、炭素数１〜２０の直鎖状または分岐状のアルキレン基であり、
Rfは、炭素数４〜６のパーフルオロアルキル基である請求項１に記載の塗料改質剤。 In the fluorine-containing monomer (a),
X is a hydrogen atom, a methyl group or a chlorine atom,
Z is a direct bond, a linear or branched alkylene group having 1 to 20 carbon atoms,
The paint modifier according to claim 1, wherein Rf is a perfluoroalkyl group having 4 to 6 carbon atoms.
非フッ素架橋性単量体が、式：
CH2=CA-T
［式中、Aは、水素原子、メチル基、またはフッ素原子以外のハロゲン原子であり、
Tは、水素原子、フッ素原子以外のハロゲン原子、または炭素数１〜４０の炭化水素基である。］
で示される化合物であり、
非フッ素架橋性単量体が、少なくとも２つのオレフィン性炭素−炭素二重結合を有する化合物、あるいは少なくとも１つのオレフィン性炭素−炭素二重結合および少なくとも１つの反応性基を有する化合物であり、
単量体（ｃ）の量が、単量体（ａ）と単量体（ｂ）の合計１００重量部に対して、１〜３０重量部である請求項１〜５のいずれかに記載の塗料改質剤。 The fluorine-containing copolymer further includes a repeating unit formed from a non-fluorine crosslinkable monomer or another monomer (c) that is a non-fluorine crosslinkable monomer,
The non-fluorine crosslinkable monomer has the formula:
CH 2 = CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom,
T is a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 40 carbon atoms. ]
A compound represented by
The non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds, or a compound having at least one olefinic carbon-carbon double bond and at least one reactive group;
The amount of the monomer (c) is 1 to 30 parts by weight with respect to 100 parts by weight of the total of the monomer (a) and the monomer (b). Paint modifier.
（２）樹脂を含んでなる塗料
を含んでなる塗料組成物。 (1) A paint modifier comprising a fluoropolymer according to any one of claims 1 to 8, and (2) a paint composition comprising a paint comprising a resin.
単量体（ａ）および単量体（ｂ）を重合して含フッ素重合体を得た後に、含フッ素重合体を塗料と混合することを含んでなる製造方法。 It is a manufacturing method of the coating composition in any one of Claims 9-11, Comprising:
A production method comprising polymerizing the monomer (a) and the monomer (b) to obtain a fluoropolymer, and then mixing the fluoropolymer with a paint.
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|---|---|---|---|---|
| DE112020005048T5 (en) | 2019-10-16 | 2022-11-03 | Denso Corporation | charger |
| WO2024085570A1 (en) * | 2022-10-17 | 2024-04-25 | 한국화학연구원 | Fluorine-based polymer and method for preparing same |
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