JPH04178408A - Fluorine-containing copolymer and fluorine-based coating consisting essentially of the same copolymer - Google Patents
Fluorine-containing copolymer and fluorine-based coating consisting essentially of the same copolymerInfo
- Publication number
- JPH04178408A JPH04178408A JP30377590A JP30377590A JPH04178408A JP H04178408 A JPH04178408 A JP H04178408A JP 30377590 A JP30377590 A JP 30377590A JP 30377590 A JP30377590 A JP 30377590A JP H04178408 A JPH04178408 A JP H04178408A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- copolymer
- vinyl ether
- formula
- vinyl
- 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.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 65
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 51
- 239000011737 fluorine Substances 0.000 title claims description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 41
- 238000000576 coating method Methods 0.000 title description 19
- 239000011248 coating agent Substances 0.000 title description 17
- GJNDXPONYMDBFD-UHFFFAOYSA-N 1-ethenoxy-2,2-dimethylpropane Chemical compound CC(C)(C)COC=C GJNDXPONYMDBFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 21
- 239000003795 chemical substances by application Substances 0.000 abstract description 17
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 239000003505 polymerization initiator Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- -1 l=cHF Chemical class 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 150000002170 ethers Chemical class 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 2
- XMJQCVMNFPEJLN-UHFFFAOYSA-N 1-ethenoxy-4-methylpentane Chemical compound CC(C)CCCOC=C XMJQCVMNFPEJLN-UHFFFAOYSA-N 0.000 description 2
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical compound CCCCCOC=C IOSXLUZXMXORMX-UHFFFAOYSA-N 0.000 description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical class CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- YYMCVDNIIFNDJK-XFQWXJFMSA-N (z)-1-(3-fluorophenyl)-n-[(z)-(3-fluorophenyl)methylideneamino]methanimine Chemical compound FC1=CC=CC(\C=N/N=C\C=2C=C(F)C=CC=2)=C1 YYMCVDNIIFNDJK-XFQWXJFMSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- CHHASAIQKXOAOX-UHFFFAOYSA-N 1-(2,2-dimethylpropoxy)-2,2-dimethylpropane Chemical group CC(C)(C)COCC(C)(C)C CHHASAIQKXOAOX-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- HAVHPQLVZUALTL-UHFFFAOYSA-N 1-ethenoxypropan-2-ol Chemical compound CC(O)COC=C HAVHPQLVZUALTL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- RCSBILYQLVXLJG-UHFFFAOYSA-N 2-Propenyl hexanoate Chemical compound CCCCCC(=O)OCC=C RCSBILYQLVXLJG-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- OUELSYYMNDBLHV-UHFFFAOYSA-N 2-ethenoxyethylbenzene Chemical compound C=COCCC1=CC=CC=C1 OUELSYYMNDBLHV-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- PZDULXHVYJWWRI-UHFFFAOYSA-N 3-ethenoxypropylsilyloxy(trimethyl)silane Chemical compound C(=C)OCCC[SiH2]O[Si](C)(C)C PZDULXHVYJWWRI-UHFFFAOYSA-N 0.000 description 1
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- YQMANMTVEHKOHX-UHFFFAOYSA-N 4-ethenoxybutan-2-ol Chemical compound CC(O)CCOC=C YQMANMTVEHKOHX-UHFFFAOYSA-N 0.000 description 1
- BCTDCDYHRUIHSF-UHFFFAOYSA-N 5-ethenoxypentan-1-ol Chemical compound OCCCCCOC=C BCTDCDYHRUIHSF-UHFFFAOYSA-N 0.000 description 1
- ASPUDHDPXIBNAP-UHFFFAOYSA-N 6-ethenoxyhexan-1-ol Chemical compound OCCCCCCOC=C ASPUDHDPXIBNAP-UHFFFAOYSA-N 0.000 description 1
- ZMFWTUBNIJBJDB-UHFFFAOYSA-N 6-hydroxy-2-methylquinoline-4-carboxylic acid Chemical compound C1=C(O)C=CC2=NC(C)=CC(C(O)=O)=C21 ZMFWTUBNIJBJDB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003609 aryl vinyl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- WQTNGCZMPUCIEX-UHFFFAOYSA-N dimethoxy-methyl-prop-2-enylsilane Chemical compound CO[Si](C)(OC)CC=C WQTNGCZMPUCIEX-UHFFFAOYSA-N 0.000 description 1
- ORHSGYTWJUDWKU-UHFFFAOYSA-N dimethoxymethyl(ethenyl)silane Chemical compound COC(OC)[SiH2]C=C ORHSGYTWJUDWKU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- HJVKTYVDOZVQPA-UHFFFAOYSA-N ethenoxycyclopentane Chemical compound C=COC1CCCC1 HJVKTYVDOZVQPA-UHFFFAOYSA-N 0.000 description 1
- KDBPJFGPBDDBGC-UHFFFAOYSA-N ethenoxymethanol Chemical compound OCOC=C KDBPJFGPBDDBGC-UHFFFAOYSA-N 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NLDFTWSUPLJCQD-UHFFFAOYSA-N prop-1-en-2-yl propanoate Chemical class CCC(=O)OC(C)=C NLDFTWSUPLJCQD-UHFFFAOYSA-N 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- AIPJCMMALQPRMK-UHFFFAOYSA-N prop-2-enyl cyclohexanecarboxylate Chemical compound C=CCOC(=O)C1CCCCC1 AIPJCMMALQPRMK-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
(産業上の利用分野)
本発明は、新規な含フッ素共重合体及び該共重合体を主
成分とするフッ素系塗料に関するものである。 さらに
詳しく言えば、本発明は、有ll溶剤に溶解し、かつ硬
化剤との相溶性が良好である上、常温で硬化可能な含フ
ッ素共重合体、及びこのものを主成分とする、光沢があ
り、かつ硬質で耐候性に優れた塗膜を与えうるフッ素系
塗料に関するものである。(Industrial Application Field) The present invention relates to a novel fluorine-containing copolymer and a fluorine-based paint containing the copolymer as a main component. More specifically, the present invention provides a fluorine-containing copolymer that is soluble in a solvent, has good compatibility with a curing agent, and is curable at room temperature, The present invention relates to a fluorine-based paint that can provide a coating film that is hard and has excellent weather resistance.
従来、含フッ素共重合体は耐熱性、機械的特性、耐薬品
性、耐候性などに極めて優れていることから多くの分野
において幅広(用いられている。その用途の1つとして
塗料の塗膜形成成分としての利用がある0例えばテトラ
フルオロエチレン重合体やフン化ビニリデン重合体など
を用いたフッ素樹脂塗料が知られており、このものは優
れた潤滑性、非粘着性、耐候性及び耐薬品性などを有す
ることから、コーテイング材として化学工業、食品、建
築、機械などの分野に使用されている。
しかしながら、前記フッ素樹脂塗料は高温での焼付けが
必要であり、利用範囲が1lJtlldされるのを免れ
ないという欠点を有し、このため、近年、有機溶剤に可
溶で、かつ室温で硬化可能な反応基をもつ含フッ素共重
合体を用いた溶剤型塗料の開発が試みられている。
含フン素重合体を有機溶剤に対して可溶化するためには
、適当な共重合成分を導入することにより、フン素樹脂
の結晶性を乱し、内部可塑化することが必要であり、こ
のような例としてこれまで種々の共重合体が開示されて
いる(特開昭57−34107号公報、特開昭61−2
75311号公報、同61−57609号公報、同62
−174213号公報、同63−182312号公報)
。
しかしながら、これらの共重合体を塗料として用いた場
合、形成した塗膜の硬度、光沢が低い上に、硬化剤との
相溶性の点でも不充分という欠点がある。Conventionally, fluorine-containing copolymers have been widely used in many fields due to their extremely excellent heat resistance, mechanical properties, chemical resistance, weather resistance, etc.One of their uses is in the coating of paints. For example, fluororesin paints using tetrafluoroethylene polymers and vinylidene fluoride polymers are known, and these paints have excellent lubricity, non-stick properties, weather resistance, and chemical resistance. Because of its properties, it is used as a coating material in fields such as the chemical industry, food, architecture, and machinery. However, the fluororesin paint requires baking at a high temperature, and its range of use is limited to 1 lJtlld. Therefore, in recent years, attempts have been made to develop solvent-based coatings using fluorine-containing copolymers that are soluble in organic solvents and have reactive groups that can be cured at room temperature. In order to solubilize a fluorine-containing polymer in an organic solvent, it is necessary to disrupt the crystallinity of the fluorine-containing resin and internally plasticize it by introducing an appropriate copolymerization component. As examples of such copolymers, various copolymers have been disclosed so far (Japanese Patent Laid-Open Nos. 57-34107 and 61-2).
Publication No. 75311, Publication No. 61-57609, Publication No. 62
-174213 publication, 63-182312 publication)
. However, when these copolymers are used as coatings, they have the disadvantage that the formed coating film has low hardness and gloss, and is also insufficient in compatibility with curing agents.
本発明は、このような従来の有機溶剤に可溶な含フッ素
共重合体が有する欠点を克服し、有機溶剤に対する溶解
性や硬化剤との相溶性が良好な、新規常温硬化性含フッ
素共重合体、及びこのものを主成分とする、光沢があり
、かつ硬質で耐候性に優れた塗膜を与えうるフッ素系塗
料を提供することを目的としてなされたものである。
に課題を解決するための手段】
本発明者らは、上記の点に鑑み、鋭意研究を重ねた結果
、含フッ素共重合体の重合単量体として特定の単量体を
用いることにより上記課題を解決し得ることを見出し、
本発明を完成するに至った。
すなわち、本発明は;
■下記(A)及び(B)を必須の構成成分とし、さらに
(C)及び/又は(D)をも構成成分として含んでなる
、含フッ素共重合体。
(A)式;
%式%(1)
(式中、v、x、y及びZは同一でも異なっていてもよ
く、それぞれH,F、CI、炭素数1〜6のアルキル基
、及び炭素数1〜6のハロ置換アルキル基から選ばれる
1種を示し、かつ、そのうちの少なくとも1つはFであ
る。)
で表されるフルオロオレフィンの共重合した単位:20
〜97モル%
(B)ネオペンチルビニルエーテルの共重合した単位:
3〜80モル%。
(C)官能基含有単量体の共重合した単位:0〜40モ
ル%
(D)その他の単量体の共重合した単位:0〜40モル
%
及び
■ 上記含フッ素共重合体を主成分とするフッ素系塗料
を提供するものである。
以下、本発明の詳細な説明する。
本発明の共重合体において、(A)単位を形成するフル
オロオレフィンは分子中に少なくとも1個のフッ素原子
を有するオレフィンであって、好ましいものとしては、
オレフィンの水素原子がすべてフッ素原子及び他のハロ
ゲン原子に置換されているバーハロオレフィンが挙げら
れる。
このようなフルオロオレフィンの具体例としては、CH
z□Ch 、CHF=CFz 、CHt=CFz 、
CHz=CHF、CCf F=CFア、CHCIl、C
F、、CCl z=cFz 、CCI F=CCIP
、 CHF=CCj!z 、CHz=CCj!F 、
CC12=CCj2Fなどのフルオロエチレン系;
ChCF=Ch 、CFICF=CHF 、 CFiC
H=CFz 、CF3CF=CHz 、 CF3CF=
CHF 、 CHhCF=CHF、 CFiCH=CH
z 、CHsCF =CFx 、CH1CI’l =C
h 、CHsCF=CHz 、CFtCICF=CF2
、ChCCl =CFt、 CFsCF = CFC1
2、CFzCI CCl =CF2、ChCfCF=C
FCI CFCLCF=Ch 、Ch ccz=CC
IF 、、CFsCC1!、=CCff1z 、CCi
!、FzCF=CG 12、CCfICF=CF! 、
cFzczccz=cczz、CFCf tcC#、=
CC1! 、CF、CF=CHC/! 、、CCj!
hcF=cH(/! 。
cpscc z =CHC/!、CHFtCC1=CC
1,z 、ChC1CH=CC2□ 、CFtCICC
I!=CHCl5 CCj2iCF=CHCj!、
CFtiICF=CFt、 CFJrCH=Ch 、
CF3CBr=CHBr 、 CFtCI CBr=
C1b 、CHzBrCF=CCf z 、CFs
CBr=CHt、CF、CH=CI(Br、 CFJr
C)l=cHF 、 CFJrCF=Chなどのフルオ
ロプロペン系;
CFsCF、CF=Ch、CFsCF;CFCFs 、
CFsC)I=CFCh、CFt=CFCFgCHh
、CFsCFzCF=C!lx、 CFsCH=CHC
Fs、Ch=CFCFtCHs、CFt=CFCHzC
Hs、CFsCHzCH=CHz、CFコCH=CHC
H3、Ch=CHCHtCHs、CHsChC)l=c
tlz、CFHzCH=CHCFlh 、 CI(sc
FzcH=cHs、CHt=CFCHzCH3、CF。
(Ch)冨CF−CFt 、Ch(CFt)icF=c
Fzなどの炭素数4以上のフルオロオレフィン化合物を
挙げることができるが、これらの中で、式;
(式中、P及びQは同一でも異なっていてもよく、それ
ぞれH,F、CIまたはCF、を示す)で示されるフル
オロエチレン化合物及びフルオロプロペン化合物が好ま
しく、特にテトラフルオロエチレン(CF、=CF、)
、クロロトリフルオロエチレン(CF、=CF(1)及
びヘキサフルオロプロペンCCFt =CFCFi )
が好適である。これらのフルオロオレフィンはそれぞれ
単独で用いてもよいし、2種以上を組み合わせて用いて
もよい。
本発明の共重合体においては、前記フルオロオレフィン
から形成される単位の含有量は20〜97モル%、好ま
しくは40〜60モル%の範囲にあることが必要である
。
本発明の共重合体においては、ネオペンチルビニルエー
テルから形成される(B)単位の含有量は3〜80モル
%、好ましくは5〜50モル%の範囲にあることが必要
である。この含有量が3モル%未満では剛性に劣り、か
つ硬化剤との相溶性が低いし、80モル%を超えると耐
候性が低下する。
本発明の共重合体においては、前記の(A)、及び(B
)単位以外に、さらに各々40モル%を超えない範囲で
(C)官能基含有単量体の共重合した単位及び/又は(
D)その他の単量体の共重合した単位を含むことができ
る。
(C)単位を形成する官能性基含有単量体としでは、例
えば−数式(i)で表されるヒドロキシ基含有不飽和エ
ーテル類、−数式(ii)で表されるエポキシ基含有不
飽和エーテル類、−数式(ii)で表される加水分解性
シリル基含有ビニル単量体等が挙げられる。
(i ) CHt=CH−(CHx)t −0−R’−
0H(式中、R4は炭素数1〜6のアルキレン基であり
、iは0または1を示す、)
(ii)
(式中、jは0またはlであり、kは0〜5の整数を示
し、lは1〜5の整数を示す)(式中、m、nは0また
は1であり、R’、R−1R1は1価のを機基を示すが
、少なくとも1つは炭素数1〜6のアルコキシ基である
)。
ヒドロキシ基含有不飽和エーテル!![式(i)1の具
体例としては、例えば、ヒドロキシメチルビニルエーテ
ル、ヒドロキシエチルビニルエーテル、3−ヒドロキシ
プロピルビニルエーテル、2−ヒドロキシプロビルビニ
ルエーテル、4−ヒドロキシブチルビニルエーテル、3
−ヒドロキシブチルビニルエーテル、2−ヒドロキシ−
2−メチルプロピルビニルエーテル、5−ヒドロキシペ
ンチルビニルエーテル、6−ヒドロキシへキシルビニル
エーテル、エチレングリコールモノアリルエーテルなど
が挙げられる。
エポキシ基含有不飽和エーテル!![式(ii ) ]
の具体例としては、例えば、
\1
CHz=CH−0−CHz−CHz−0−CHz−CH
−CHz\1
CHz=CH−CHz−0−CHi−CHz−GO−C
Hz\1
等が挙げられる。
加水分解性シリル基含有ビニル単量体[式(ii)]
の具体例としては、例えば、ビニルトリメトキシシラン
、ビニルトリエトキシシラン、ビニルジメトキシメチル
シラン、アリルトリメトキシシラン、アリルトリエトキ
シシラン、アリルジメトキシメチルシラン、ビニロキシ
プロピルトリメチルシロキシシラン、ビニロキシエトキ
シプロピルトリメチルシロキシシラン等が挙げられる。
上記(C)単位を形成する官能性基含有単量体は、それ
ぞれ単独で用いても良いし、2種以上組み合わせて用い
ても良い。
また、前記(D)単位を形成する共重合可能な単量体と
しては、例えばエチレン、プロピレン、イソブチレンな
どのオレフィン類;塩化ビニル、塩化ビニリデンなどの
ハロオレフィン類;酢酸ビニル、n−酪酸ビニル、安息
香酸ビニル、p−を−ブチル安息香酸ビニル、ピバリン
酸ビニル、2−エチルヘキサン酸ビニル、バーサチック
酸ビニルなどのカルボン酸ビニルエステル類;酢酸イソ
プロペニル、プロピオン類イソプロペニルなどのカルボ
ン酸イソプロペニルエステル類;エチルビニルエーテル
、プロピルビニルエーテル、イソプロピルビニルエーテ
ル、ブチルビニルエーテル、tert−7”チルビニル
エーテル、ペンチルビニルエーテル、ヘキシルビニルエ
ーテル、イソヘキシルビニルエーテル、オクチルビニル
エーテル、4−メチル−1−ペンチルビニルエーテルな
どの鎖状アルキルビニルエーテル類;ペンタフルオロビ
ニルエーテル等のフルオロビニルエーテル類;シクロペ
ンチルビニルエーテル、シクロヘキシルビニルエーテル
などのシクロアルキルビニルエーテル類;フェニルビニ
ルエーテル、o−1m−1P−トリルビニルエーテルな
どのアリールビニルエーテル類;ベンジルビニルエーテ
ル、フェネチルビニルエーテルなどのアラルキルビニル
エーテル類纂スチレン、ビニルトルエンなどの芳香族ビ
ニル化合物;ギ酸アリル、酢酸アリル、プロピオン酸ア
リル、m#アリル、カプロン酸アリル、安息香酸アリル
、シクロヘキサンカルボン酸アリル、シクロへキシルプ
ロピオン酸アリル等のカルボン酸アリル頻;アリルエチ
ルエーテル、アリルフェニルエーテル等のアリルエーテ
ル類;フマル酸、マレイン酸などの不飽和結合含有多塩
基酸のジ又はモノエステル類や酸無水物類;ヒドロキシ
エチルアクリレート、ヒドロキシエチルメタクリレート
、メチルメタクリレート、グリシジルメタクリレートな
どのアクリル酸やメタクリル酸のエステル類;アクリル
アミド、N−メチロールアクリルアミドなどのアクリル
アミド類等が挙げられる。
これらの単量体は1種用いても良いし、2種以上組み合
わせて用いてもよい。
本発明のフッ素共重合体は、溶媒の存在下又は不存在下
に、所定割合の単量体混合物を、重合開始源として重合
開始剤や電離性放射線などを用い共重合させることによ
り製造することができる。
該重合開始剤としては、重合形式や所望に応じて用いら
れる溶媒の種類に応じて、水溶性のものあるいは油溶性
のものが適宜用いられる。
油溶性開始剤としては、例えばアゾビスイソブチロニト
リル、2,2°−アゾビス−(2,4−ジメチルバレロ
ニトリル)等のアゾ化合物;を−ブチルパーオキシイソ
ブチレート、t−ブチルパーオキシアセテートなどのパ
ーオキシエステル型過酸化物;ジイソプロピルパーオキ
シジカーボネートなどのジアルキルパーオキシジカーボ
ネート;ベンゾイルパーオキシドなどが挙げられる。
水溶性重合開始剤としては、例えば過硫酸カリウムなど
の過硫酸塩、過酸化水素、あるいはこれらと亜硫酸水素
ナトリウム、チオ硫酸ナトリウムなどの還元剤との組合
せから成るレドックス開始剤;さらには、これらに少量
の鉄、第一鉄塩、硝酸銀などを共存させた系などの無機
系開始剤;ジコハク酸パーオキシド、ジグルタール酸パ
ーオキシド、モノコハク酸パーオキシドなどの二塩基酸
過酸化物、アゾビスイソブチルアミジンニ塩基酸塩など
の有機系開始剤が挙げられる。
これらの重合開始剤の使用量は、その種類、共重合反応
条件などに応じて適宜選ばれるが、通常使用する単量体
全量に対して、0.005〜5重量%、好ましくは0.
05〜0.5重量%の範囲で選ばれる。
また、重合方法については特に制限はなく、例えば塊状
重合法、懸濁重合法、乳化重合法、溶液重合法などを用
いることができるが、重合反応操作の安定性等の点から
、キシレン、トルエン等の低級アルキル置換ベンゼン;
メチルイソブチルケトン等のケトン1ift−ブタノー
ル等のアルコールW4:酢酸ブチル等のエステル類;フ
ッ素原子1個以上を有する飽和ハロゲン化炭化水素類な
どを溶媒とする溶液重合法、水性媒体中での乳化重合法
、溶媒との分離を不用とする塊状重合法などが好ましく
用いられる。
(C)単位を形成する官能性基含有単量体としてヒドロ
キシ基含有不飽和エーテル類を使用する場合は、フッ素
系共重合体を再現性良く製造する目的において、炭酸カ
リウムやアミン化合物等の塩基性物質の添加は有効であ
る。
さらに、重合形式については特に制限はなく、回分式、
半連続式、連続式のいずれも用いることができる。
該共重合反応における反応温度は、通常−30〜+15
0°Cの範囲内で、重合開始源や重合媒体の種類に応じ
て適宜選ばれ、通常0〜100°C1好ましくは10〜
90℃の範囲で選ばれる。また、反応圧力については特
に制限はないが、通常1〜100 kg/cj、好まし
くは2〜50kg/dの範囲で選ばれる。さらに、該共
重合反応は、適当な連鎖移動剤を添加して行うことがで
きる。
かくして得られた生成物は、主鎖中に、式;
%式%()
(式中、■、X、Y及びZは同一でも異なりていてもよ
く、それぞれH,F、CI、炭素数1〜6のアルキル基
、及び炭素数1〜6の)\ロ置換アルキル基から選ばれ
る1種を示し、かつ、そのうちの少なくとも1つはFで
ある。)
なる構造で、更に好ましくは、
式:
(式中、P及びQは同一でも異なっていてもよく、それ
ぞれH,F、CIまたはCF xを示す。
なる構造でフッ素を含有しており、かつ式;
H
−C−C−CH3
HOCHt −CCHs
CH。
なるネオペンチルエーテル単位を必須成分として有して
おり、かつ好ましくは、下記、式(i)〜(iii)で
示す構造の少なくとも1種の官能基をも有する含フッ素
共重合体である。
(i)
−CH,−CH−
\
(CHま) !−0−R’−OH。
(式中、R4は炭素数1〜6のアルキレン基であり、i
はO又は1を示す、)
(ii)
(式中、jは0又は1、kは0〜5.1は1〜5の整数
を示す、)
(ij)
−C)It−CB
(0)s −(CHz) n −5i−R’\R7
(式中、m、nは0又は1、R5、R6、R7は1価の
有機基を示すが、うち少なくとも一つは炭素数1〜6の
アルコキシ基を示す。)本発明の含フッ素共重合体の分
子量は、テトラヒドロフランを溶媒にし、分子量既知の
単分散ポリスチレンを標準物質として用い、ゲルパーミ
ェーションクロマトグラフ(cpc)法により測定して
求めた数平均分子量(’M n )が、1.000〜2
00,000、好ましくは2,000〜1oo、ooo
の範囲であり、ガラス転移温度(Tg)は通常−50〜
120 ”C1好ましくは一10〜100°Cである。
このような組成及び分子量、ガラス転移温度を有する本
発明の含フッ素共重合体は、有機溶剤に可溶で、かつ硬
化剤との相溶性に優れる上、該共重合体を主成分とする
塗料の硬化塗膜は光沢があり、かつ硬度で耐候性に優れ
たものとなる。
本発明の含フッ素共重合体において、(C)単位を形成
する官能性基含有単量体として、ヒドロキシ基含有不飽
和エーテル類を使用する場合は、得られた含フッ素共重
合体は、硬化部位としてヒドロキシル基を含有するもの
となり、通常の熱硬化アクリル塗料に用いられている硬
化剤、例えば多価イソシアネート類、ブロック化多価イ
ソシアネート類、メラミン硬化剤、尿素樹脂硬化剤、多
塩基酸硬化剤などを用いて加熱硬化させることができる
。
さらに、上記ヒドロキシ基含有含フッ素共重合体は、多
価イソシアネート類を用いることによって常温で硬化さ
せることもできる。
該多価イソシアネート類としては、例えばヘキサメチレ
ンジイソシアネート、イソホロンジイソシアネートなど
の無黄変性ジイソシアネートやその付加物、イソシアヌ
レート環を有する多価イソシアネートなどが好ましく挙
げられるが、これらの中で特に含フッ素共重合体と相溶
性の良好なイソシアヌレート環を有する多価インシアネ
ートが好適である。これらの多価インシアネート類を用
いて常温硬化させる場合、ジブチルチンジラウレート等
の公知の触媒を添加して、硬化を促進させることもでき
る。
本発明の含フッ素共重合体において、(C)単位を形成
する官能性基含有単量体としてエポキシ基含有不飽和エ
ーテル類を使用する場合は、得られた含フッ素共重合体
は、硬化部位としてエポキシ基を含有するものであり、
硬化剤としてポリアミン類、酸無水物類、ポリフェノー
ル類、ポリメルカプタン類等の重付加型硬化剤;イミダ
ゾール類、BF、等の触媒型硬化剤を用いることにより
、加熱硬化、あるいは常温硬化をさせることができる。
また、本発明の含フッ素共重合体において、(C)単位
を形成する官能性基含有単量体として、加水分解性シリ
ル基含有ビニル単量体を使用する場合は、得られた含フ
ッ素共重合体は、硬化部位として加水分解性シリル基を
含有するものであり、ブチルアミン等のアミン化合物や
ジブチルチンジラウレート等の硬化触媒を用いて、湿気
硬化させることができる。
また、本発明の含フッ素共重合体は、前記(C)単位を
含まない場合も、ラッカー型コーティング材料として使
用することができる。
本発明は、前記の新規な含フッ素共重合体と共に、この
ものを主成分とするフッ素系塗料を提供するものであり
、該含フッ素共重合体を溶液型塗料とするにあたっては
、種々の溶剤を用いることができる。
該溶剤としては、例えばトルエンやキシレンなどの芳香
族炭化水素1!:n−ブタノールなどのアルコール類;
メチルイソブチルケトンなどのケトン類;エチルセロソ
ルブなどのグリコールエーテル類;さらには市販の各種
シンナーなどが挙げられる。これらの溶剤に該含フッ素
共重合体を溶解させて得られる溶液は、いずれも無色透
明である。
この溶液型塗料の調製は、該含フッ素共重合体と溶剤と
を、例えばボールミル、ペイトンシェーカー、サンドミ
ル、ジェットミル、三本ロール、ニーダ−など、通常塗
料の調製に用いられている混合機を用いて均質に混合す
ることにより行うことができる。この際、所望に応じ、
顔料、分散安定剤、粘度調節剤、レベリング剤、ゲル化
防止剤、紫外線吸収剤などを添加することもできる。
(実施例)
以下、実施例により更に詳細に説明するが、本発明はか
かる実施例により何ら限定されるものではない。
なお、実施例中の%はすべて重量%を示すものとし、ま
た使用する略号は以下の通りとする。
〔単量体〕
CTFE:クロロトリフルオロエチレンHBVE :ヒ
ドロキシプチルビニルエーテルIBVE:イソブチルビ
ニルエーテル
NPVE :不才ペンチルビニルエーテル■ 各種樹脂
の分子量;
ゲルパーミエイシゴンクロマトグラフィを用いて、ポリ
スチレン標品検量線より求めた。
(使用機器)・装置:島津製作所 LC−3A・カラム
:東ソー■
TSKgel G−5000HXL
〃G−4000HXL
N G−2000HXL
・検出器:島津製作所 RID−6A
・データ処理:島津製作所C−R4A
・キャリヤー:テトラヒドロフラ
ン
■ 各種樹脂のガラス転移温度(Tg):下記の機器及
び測定条件で行った。
(使用機器)
示差熱熱重量同時測定袋W(セイコー電子工業■製)
5SC5000DSC200(測定条件)−80→9
0℃昇温(5℃/分)■ 水酸基価:
JIS K−0070ニ準して行った。
■ 光沢・屈曲性:
JIS K−5400に準じて測定した。
■ 塗膜硬度:
l5O−1522に準じて測定した。
■ 耐候性:
ASTM G−53に準拠して求めた。
実施例1
内容積11のステンレス鋼製かきまぜ機付オートクレー
ブに炭酸カリウム7.7gを仕込み、オートクレーブ内
を窒素ガスで3回置換した。
次いで、NPVE 58g、HBVE 23g。
CTFE 117g、t−ブチルパーオキシピバレー
ト 1.7g、及びキシレン231gを仕込み、内温を
65°Cまで徐々に昇温した。8時間重合を行った後、
未反応のCTFEを除、去し、オートクレーブを開放し
て生成した共重合体溶液を取り出した。この共重合体溶
液から炭酸カリウムをろ過除去した後、n−ヘキサンで
再沈し、乾燥を行った。共重合体の収量は220gであ
った。
得られた共重合体の数平均分子量は13.00Oであり
、ガラス転移温度は92℃、水#基価は50■KOH/
gであった。また、元素分析の結果により求めたこの共
重合体の組成比は、CTFE単位/NPVE単位/HB
VE単位モル比が50/40/10であった。
実施例2
内容積llのステンレス鋼製かきまぜ機付オートクレー
ブに炭酸カリウム7.7gを仕込み、オートクレーブ内
を窒素ガスで3回置換した。
ついで、NPVE 68g、IBVE 20g。
HBVE 23g、CTFE 117g、t−ブチ
ルパーオキシピバレート 1.7g、及びキシレン22
8gを仕込み、内温を65°Cまで徐々に昇温した。8
時間重合を行った後、未反応のCTFEを除去し、オー
トクレーブを開放して生成した共重合体溶液を取り出し
た。
この共重合体溶液から炭酸カリウムをろ過除去した後、
n−へキサンで再沈し、乾燥を行った。
共重合体の収量は210gであった。
得られた共重合体の数平均分子量は12.000であり
、ガラス転移温度は75°C5水酸基価は501mgK
OH/gであった6
実施例3
内容積11のステンレス鋼製かきまぜ機付オートクレー
ブに炭酸カリウム7.7gを仕込み、オートクレーブ内
を窒素ガスで3回置換した。
次いで、NPVE 34g、IBVE 50g、H
BVE 23g、CTFE 117g、t−ブチル
パーオキシビバレート 1.7g、及びキシレン224
gを仕込み、内温を65゛Cまで徐々に昇温した。8時
間重合を行った後、未反応のCTFEを除去し、オート
クレーブを開放して生成した共重合体溶液を取り出した
。
この共重合体溶液から炭酸カリウムをろ過除去した後、
n−へキサンで再沈し、乾燥を行った。
共重合体の収量は205gであった。
得られた共重合体の数平均分子量は12,500であり
、ガラス転移温度は49°C1水酸基価は50gKOH
/gであった。
実施例4〜6
実施例1〜3で得られた各々の含フッ素共重合体10g
をキシレンLogに溶解させ、硬化剤として「デュラネ
ー)TPAJ (旭化成工業■製)をNC010H=
1/1となるように、各々に配合した後、キシレンをシ
ンナーとしてフォードカップ#4で15秒に調整後、塗
装した。
得られた塗膜を120℃にて1時間焼付後、塗膜物性の
測定を行った。(実施例4〜6)その結果を第1表に示
す。
比較例1
内容積11のステンレス鋼製かきまぜ機付オートクレー
ブに炭酸カリウム7.7gを仕込み、オートクレーブ内
を窒素ガスで3回置換した。つイテ、IBVE 80
g、HBVE 23g、CTFE 117g、及び
キシレン220gを仕込み、内温を65℃まで徐々に昇
温した。8時間重合を行った後、未反応のCTFEを除
去し、オートクレーブを開放して生成した共重合体溶液
を取り出した。
この共重合体溶液から炭酸カリウムをろ過除去した後、
n−へキサンで再沈し、乾燥を行った。
共重合体の収量は192gであった。
得られた共重合体の数平均分子量は12,000であり
、ガラス転移温度は20°C1水酸基価は52xKOH
/gであった。
比較例2
比較例1で得られた含フッ素共重合体を実施例4〜6と
同様の方法で焼付成膜し、塗膜物性の測定を行った。
その結果を第1表に示す。
第1表に見られる如く、本発明によりなる含フッ素共重
合体は高い硝子転移温度を有し、かつ塗料樹脂として用
いた場合に、優れた塗膜透明性と光沢を発揮し、更に高
い塗膜硬度を有している。
(発明の効果)
本発明によると、使用するフルオロオレフィンの種類の
制限を受けることなく、有機溶剤に対する溶解性が良好
な上、硬化剤との相溶性が良好で、かつ常温で硬化が可
能な含フッ素共重合体を容易に与えることができる。
また、該含フッ素共重合体を主成分とする本発明のフッ
素系塗料は、光沢があり、かつ硬質で耐候性に優れた塗
膜を温和な条件で与えることができ、例えばカラー剛板
、カラーアルミニウム板、アルミニウムサツシ用の焼付
は塗料として、あるいは現場施工可能な常乾型塗料とし
て有用である。
さらに、基材の材質についても、金属材料をはじめ、ガ
ラス、コンクリートなどの無機材料、FRP、ポリエチ
レン、ポリプロピレン、エチレン−酢酸ビニル共重合体
、ナイロン、アクリル樹脂、ポリエステル、エチレン−
ポリビニルアルコール共重合体、ポリ塩化ビニル、ポリ
塩化ビニリデンなどのプラスチックや木材などの有機材
料の塗装に好適に用いられる。
また、該フッ素系塗料はアルミプール、外装用色ガラス
、セメントガワラなどの特定の用途においても有用であ
る。
(ほか1名)The present invention overcomes the drawbacks of conventional fluorine-containing copolymers that are soluble in organic solvents, and provides a novel room-temperature-curable fluorine-containing copolymer that has good solubility in organic solvents and compatibility with curing agents. The purpose of this invention is to provide a polymer and a fluorine-based paint containing the polymer as a main component that can provide a glossy, hard coating film with excellent weather resistance. [Means for Solving the Problem] In view of the above-mentioned points, the present inventors have conducted extensive research and have found that the above-mentioned problem can be solved by using a specific monomer as a polymerization monomer of a fluorine-containing copolymer. found that it can be solved,
The present invention has now been completed. That is, the present invention provides: (1) A fluorine-containing copolymer comprising the following (A) and (B) as essential constituents, and further containing (C) and/or (D) as constituents. (A) Formula; %Formula%(1) (In the formula, v, x, y and Z may be the same or different, and each represents H, F, CI, an alkyl group having 1 to 6 carbon atoms, and a carbon number 1 to 6 halo-substituted alkyl groups, and at least one of them is F.) Copolymerized unit of fluoroolefin: 20
~97 mol% (B) Copolymerized unit of neopentyl vinyl ether:
3-80 mol%. (C) Copolymerized units of functional group-containing monomer: 0 to 40 mol% (D) Copolymerized units of other monomers: 0 to 40 mol% and ■ The above fluorine-containing copolymer as the main component The present invention provides a fluorine-based paint that has the following properties. The present invention will be explained in detail below. In the copolymer of the present invention, the fluoroolefins forming the unit (A) are olefins having at least one fluorine atom in the molecule, and are preferably:
Examples include barhaloolefins in which all hydrogen atoms of the olefin are replaced with fluorine atoms and other halogen atoms. Specific examples of such fluoroolefins include CH
z□Ch, CHF=CFz, CHt=CFz,
CHz=CHF, CCf F=CFa, CHCIl, C
F,, CCl z=cFz, CCI F=CCIP
, CHF=CCj! z, CHz=CCj! F,
Fluoroethylene type such as CC12=CCj2F; ChCF=Ch, CFICF=CHF, CFiC
H=CFz, CF3CF=CHz, CF3CF=
CHF, CHhCF=CHF, CFiCH=CH
z, CHsCF = CFx, CH1CI'l = C
h, CHsCF=CHz, CFtCICF=CF2
, ChCCl = CFt, CFsCF = CFC1
2, CFzCI CCl = CF2, ChCfCF=C
FCI CFCLCF=Ch, Ch ccz=CC
IF,,CFsCC1! , = CCff1z , CCi
! , FzCF=CG 12, CCfICF=CF! ,
cFzczccz=cczz, CFCf tcC#,=
CC1! , CF, CF=CHC/! ,,CCj!
hcF=cH(/!. cpscc z =CHC/!, CHFtCC1=CC
1,z, ChC1CH=CC2□, CFtCICC
I! =CHCl5 CCj2iCF=CHCj! ,
CFtiICF=CFt, CFJrCH=Ch,
CF3CBr=CHBr, CFtCICBr=
C1b, CHzBrCF=CCfz, CFs
CBr=CHt, CF, CH=CI(Br, CFJr
C) Fluoropropene series such as l=cHF, CFJrCF=Ch; CFsCF, CF=Ch, CFsCF; CFCFs,
CFsC)I=CFCh, CFt=CFCFgCHh
, CFsCFzCF=C! lx, CFsCH=CHC
Fs, Ch=CFCFtCHs, CFt=CFCHzC
Hs, CFsCHzCH=CHz, CFkoCH=CHC
H3, Ch=CHCHtCHs, CHsChC)l=c
tlz, CFHzCH=CHCFlh, CI(sc
FzcH=cHs, CHt=CFCHzCH3, CF. (Ch) TomiCF−CFt, Ch(CFt)icF=c
Examples include fluoroolefin compounds having 4 or more carbon atoms such as Fz, among which the formula; fluoroethylene compounds and fluoropropene compounds are preferred, especially tetrafluoroethylene (CF,=CF,)
, chlorotrifluoroethylene (CF, =CF(1) and hexafluoropropene CCFt =CFCFi)
is suitable. These fluoroolefins may be used alone or in combination of two or more. In the copolymer of the present invention, the content of units formed from the fluoroolefins needs to be in the range of 20 to 97 mol%, preferably 40 to 60 mol%. In the copolymer of the present invention, the content of (B) units formed from neopentyl vinyl ether needs to be in the range of 3 to 80 mol%, preferably 5 to 50 mol%. If the content is less than 3 mol%, the rigidity will be poor and the compatibility with the curing agent will be low, and if it exceeds 80 mol%, the weather resistance will decrease. In the copolymer of the present invention, the above (A) and (B
) In addition to the units, copolymerized units of the functional group-containing monomer (C) and/or (
D) It may contain copolymerized units of other monomers. Examples of the functional group-containing monomer forming the unit (C) include - hydroxy group-containing unsaturated ethers represented by formula (i), - epoxy group-containing unsaturated ethers represented by formula (ii) Examples include hydrolyzable silyl group-containing vinyl monomers represented by formula (ii). (i) CHt=CH-(CHx)t-0-R'-
0H (In the formula, R4 is an alkylene group having 1 to 6 carbon atoms, and i represents 0 or 1.) (ii) (In the formula, j is 0 or l, and k is an integer of 0 to 5. (wherein, m and n are 0 or 1, R' and R-1R1 represent a monovalent group, and at least one has 1 carbon number) to 6 alkoxy groups). Unsaturated ether containing hydroxyl group! ! [Specific examples of formula (i) 1 include hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3
-Hydroxybutyl vinyl ether, 2-hydroxy-
Examples include 2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, and ethylene glycol monoallyl ether. Unsaturated ether containing epoxy group! ! [Formula (ii)]
As a specific example, for example, \1 CHz=CH-0-CHz-CHz-0-CHz-CH
-CHz\1 CHz=CH-CHz-0-CHi-CHz-GO-C
Examples include Hz\1. Hydrolyzable silyl group-containing vinyl monomer [formula (ii)]
Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, allyltrimethoxysilane, allyltriethoxysilane, allyldimethoxymethylsilane, vinyloxypropyltrimethylsiloxysilane, vinyloxyethoxypropyltrimethyl Examples include siloxysilane. The functional group-containing monomers forming the unit (C) may be used alone or in combination of two or more. In addition, examples of the copolymerizable monomer forming the unit (D) include olefins such as ethylene, propylene, and isobutylene; haloolefins such as vinyl chloride and vinylidene chloride; vinyl acetate, vinyl n-butyrate, Carboxylic acid vinyl esters such as vinyl benzoate, p-butyl vinyl benzoate, vinyl pivalate, vinyl 2-ethylhexanoate, and vinyl versatate; carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionates. Chain alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-7'' thyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1-pentyl vinyl ether; Fluorovinyl ethers such as pentafluorovinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and o-1m-1P-tolyl vinyl ether; aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; styrene; Aromatic vinyl compounds such as vinyl toluene; Allyl carboxylates such as allyl formate, allyl acetate, allyl propionate, m# allyl, allyl caproate, allyl benzoate, allyl cyclohexanecarboxylate, allyl cyclohexylpropionate; Allyl ethers such as ethyl ether and allyl phenyl ether; di- or monoesters and acid anhydrides of unsaturated bond-containing polybasic acids such as fumaric acid and maleic acid; hydroxyethyl acrylate, hydroxyethyl methacrylate, methyl methacrylate, glycidyl Examples include esters of acrylic acid and methacrylic acid such as methacrylate; acrylamides such as acrylamide and N-methylol acrylamide; these monomers may be used alone or in combination of two or more. The fluorine copolymer of the present invention is produced by copolymerizing a monomer mixture of a predetermined ratio in the presence or absence of a solvent using a polymerization initiator, ionizing radiation, etc. as a polymerization initiation source. As the polymerization initiator, a water-soluble one or an oil-soluble one can be used as appropriate depending on the type of polymerization and the type of solvent used as desired. Examples of oil-soluble initiators include azo compounds such as azobisisobutyronitrile and 2,2°-azobis-(2,4-dimethylvaleronitrile); Examples include peroxyester type peroxides such as acetate; dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate; benzoyl peroxide, and the like. Examples of water-soluble polymerization initiators include redox initiators consisting of persulfates such as potassium persulfate, hydrogen peroxide, or combinations of these with reducing agents such as sodium bisulfite and sodium thiosulfate; Inorganic initiators such as systems in which small amounts of iron, ferrous salts, silver nitrate, etc. coexist; dibasic acid peroxides such as disuccinic acid peroxide, diglutaric acid peroxide, monosuccinic acid peroxide, azobisisobutyramidine dibasic acid Examples include organic initiators such as salts. The amount of these polymerization initiators to be used is appropriately selected depending on the type thereof, copolymerization reaction conditions, etc., but is 0.005 to 5% by weight, preferably 0.005 to 5% by weight, based on the total amount of monomers normally used.
The amount is selected within the range of 0.05 to 0.5% by weight. There are no particular restrictions on the polymerization method, and for example, bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, etc. can be used, but from the standpoint of stability of the polymerization reaction, xylene, toluene, Lower alkyl substituted benzenes such as;
Ketones such as methyl isobutyl ketone 1ift-Alcohols such as butanol W4: Esters such as butyl acetate; Solution polymerization using a saturated halogenated hydrocarbon having one or more fluorine atoms as a solvent, emulsion polymerization in an aqueous medium A bulk polymerization method that does not require separation from a solvent is preferably used. (C) When using hydroxyl group-containing unsaturated ethers as the functional group-containing monomer forming the unit, bases such as potassium carbonate or amine compounds should be used for the purpose of producing fluorine-based copolymers with good reproducibility. Addition of sexual substances is effective. Furthermore, there are no particular restrictions on the polymerization format; batchwise,
Either a semi-continuous type or a continuous type can be used. The reaction temperature in the copolymerization reaction is usually -30 to +15
Within the range of 0°C, it is appropriately selected depending on the polymerization initiation source and the type of polymerization medium, usually 0 to 100°C, preferably 10 to
Selected within the range of 90°C. Further, the reaction pressure is not particularly limited, but is usually selected within the range of 1 to 100 kg/cj, preferably 2 to 50 kg/d. Furthermore, the copolymerization reaction can be carried out by adding a suitable chain transfer agent. The product thus obtained has, in the main chain, the formula; -6 alkyl groups, and )\ro-substituted alkyl groups having 1 to 6 carbon atoms, and at least one of them is F. ), more preferably, it has the structure: (wherein P and Q may be the same or different and each represents H, F, CI or CF Formula; H -C-C-CH3 HOCHt -CCHs CH. It has a neopentyl ether unit as an essential component, and preferably has at least one type of structure shown in the following formulas (i) to (iii). It is a fluorine-containing copolymer that also has a functional group. (i) -CH, -CH- \ (CHma) !-0-R'-OH. (In the formula, R4 is an alkylene group having 1 to 6 carbon atoms. and i
represents O or 1, ) (ii) (In the formula, j is 0 or 1, and k represents an integer from 1 to 5.) (ij) -C)It-CB (0) s - (CHz) n -5i-R'\R7 (wherein m and n are 0 or 1, R5, R6 and R7 represent monovalent organic groups, at least one of which has 1 to 6 carbon atoms) ) The molecular weight of the fluorine-containing copolymer of the present invention was measured by gel permeation chromatography (CPC) using tetrahydrofuran as a solvent and monodisperse polystyrene of known molecular weight as a standard substance. The number average molecular weight ('M n ) determined by
00,000, preferably 2,000-1oo, ooo
The glass transition temperature (Tg) is usually -50 to
120"C1 is preferably -10 to 100°C. The fluorine-containing copolymer of the present invention having such a composition, molecular weight, and glass transition temperature is soluble in an organic solvent and compatible with a curing agent. In addition, the cured coating film of a paint containing the copolymer as a main component is glossy, hard, and has excellent weather resistance.In the fluorine-containing copolymer of the present invention, the (C) unit When a hydroxy group-containing unsaturated ether is used as the functional group-containing monomer to be formed, the resulting fluorine-containing copolymer will contain hydroxyl groups as a curing site, and will not be able to be used as a normal thermosetting acrylic. It can be cured by heating using a curing agent used in paints, such as polyvalent isocyanates, blocked polyvalent isocyanates, melamine curing agents, urea resin curing agents, polybasic acid curing agents, etc. The hydroxy group-containing fluorine-containing copolymer can also be cured at room temperature by using polyvalent isocyanates. Examples of the polyvalent isocyanates include non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and addition thereof. Among them, polyvalent incyanates having an isocyanurate ring and having good compatibility with the fluorine-containing copolymer are particularly preferred. When curing at room temperature using a valent incyanate, a known catalyst such as dibutyltin dilaurate can be added to accelerate curing. In the fluorine-containing copolymer of the present invention, (C) units are formed. When using an epoxy group-containing unsaturated ether as a functional group-containing monomer, the obtained fluorine-containing copolymer contains an epoxy group as a curing site,
Polyaddition type curing agents such as polyamines, acid anhydrides, polyphenols, polymercaptans, etc.; catalytic curing agents such as imidazoles, BF, etc. are used as curing agents to perform heat curing or room temperature curing. I can do it. In addition, in the fluorine-containing copolymer of the present invention, when a hydrolyzable silyl group-containing vinyl monomer is used as the functional group-containing monomer forming the unit (C), the obtained fluorine-containing copolymer The polymer contains a hydrolyzable silyl group as a curing site, and can be moisture-cured using an amine compound such as butylamine or a curing catalyst such as dibutyltin dilaurate. Furthermore, the fluorine-containing copolymer of the present invention can be used as a lacquer-type coating material even when it does not contain the (C) unit. The present invention provides the above-mentioned novel fluorine-containing copolymer as well as a fluorine-based paint containing this fluorine-containing copolymer as a main component. can be used. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene. : Alcohols such as n-butanol;
Examples include ketones such as methyl isobutyl ketone; glycol ethers such as ethyl cellosolve; and various commercially available thinners. Solutions obtained by dissolving the fluorine-containing copolymer in these solvents are colorless and transparent. The solution-type paint is prepared by mixing the fluorine-containing copolymer and a solvent using a mixer commonly used for preparing paints, such as a ball mill, Peyton shaker, sand mill, jet mill, three-roll mill, kneader, etc. This can be done by mixing homogeneously using At this time, if desired,
Pigments, dispersion stabilizers, viscosity modifiers, leveling agents, antigelation agents, ultraviolet absorbers, etc. can also be added. (Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. It should be noted that all percentages in the examples indicate weight percentages, and the abbreviations used are as follows. [Monomers] CTFE: Chlorotrifluoroethylene HBVE: Hydroxybutyl vinyl ether IBVE: Isobutyl vinyl ether NPVE: Pentyl vinyl ether ■ Molecular weights of various resins: Determined from polystyrene standard calibration curves using gel permeability chromatography. (Equipment used)・Apparatus: Shimadzu LC-3A・Column: Tosoh TSKgel G-5000HXL 〃G-4000HXL NG-2000HXL ・Detector: Shimadzu RID-6A ・Data processing: Shimadzu C-R4A ・Carrier: Tetrahydrofuran ■ Glass transition temperature (Tg) of various resins: Measurement was carried out using the following equipment and measurement conditions. (Equipment used) Differential thermal thermogravimetric simultaneous measurement bag W (manufactured by Seiko Electronic Industries ■)
5SC5000DSC200 (measurement conditions) -80→9
0° C. temperature increase (5° C./min) ■ Hydroxyl value: Conducted according to JIS K-0070. ■ Gloss/Flexibility: Measured according to JIS K-5400. (2) Coating film hardness: Measured according to 15O-1522. ■ Weather resistance: Determined in accordance with ASTM G-53. Example 1 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 11 and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Next, NPVE 58g, HBVE 23g. 117 g of CTFE, 1.7 g of t-butyl peroxypivalate, and 231 g of xylene were charged, and the internal temperature was gradually raised to 65°C. After polymerization for 8 hours,
Unreacted CTFE was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After removing potassium carbonate from this copolymer solution by filtration, it was reprecipitated with n-hexane and dried. The yield of copolymer was 220 g. The number average molecular weight of the obtained copolymer was 13.00O, the glass transition temperature was 92°C, and the water #base value was 50■KOH/
It was g. In addition, the composition ratio of this copolymer determined from the results of elemental analysis is CTFE units/NPVE units/HB
The molar ratio of VE units was 50/40/10. Example 2 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Next, 68g of NPVE and 20g of IBVE. HBVE 23g, CTFE 117g, t-butylperoxypivalate 1.7g, and xylene 22g
8 g was charged, and the internal temperature was gradually raised to 65°C. 8
After polymerization for a certain period of time, unreacted CTFE was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After filtering and removing potassium carbonate from this copolymer solution,
It was reprecipitated with n-hexane and dried. The yield of copolymer was 210 g. The number average molecular weight of the obtained copolymer was 12.000, the glass transition temperature was 75°C, and the hydroxyl value was 501mgK.
OH/g.6 Example 3 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 11 and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Next, NPVE 34g, IBVE 50g, H
23 g of BVE, 117 g of CTFE, 1.7 g of t-butyl peroxyvivalate, and 224 g of xylene.
g was charged, and the internal temperature was gradually raised to 65°C. After 8 hours of polymerization, unreacted CTFE was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After filtering and removing potassium carbonate from this copolymer solution,
It was reprecipitated with n-hexane and dried. The yield of copolymer was 205 g. The number average molecular weight of the obtained copolymer was 12,500, the glass transition temperature was 49°C, the hydroxyl value was 50gKOH
/g. Examples 4 to 6 10 g of each fluorine-containing copolymer obtained in Examples 1 to 3
was dissolved in xylene Log, and as a curing agent "Duraney" TPAJ (manufactured by Asahi Kasei Corporation) was added as NC010H=
After blending each with a ratio of 1/1, xylene was used as a thinner and after adjusting for 15 seconds with Ford Cup #4, the coating was applied. After baking the obtained coating film at 120° C. for 1 hour, the physical properties of the coating film were measured. (Examples 4 to 6) The results are shown in Table 1. Comparative Example 1 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 11 and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Tsuite, IBVE 80
g, 23 g of HBVE, 117 g of CTFE, and 220 g of xylene were charged, and the internal temperature was gradually raised to 65°C. After 8 hours of polymerization, unreacted CTFE was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After filtering and removing potassium carbonate from this copolymer solution,
It was reprecipitated with n-hexane and dried. The yield of copolymer was 192 g. The number average molecular weight of the obtained copolymer was 12,000, the glass transition temperature was 20°C, the hydroxyl value was 52xKOH
/g. Comparative Example 2 The fluorine-containing copolymer obtained in Comparative Example 1 was baked into a film in the same manner as in Examples 4 to 6, and the physical properties of the film were measured. The results are shown in Table 1. As shown in Table 1, the fluorine-containing copolymer of the present invention has a high glass transition temperature, and when used as a coating resin, exhibits excellent coating film transparency and gloss, and also exhibits high coating film transparency and gloss. It has film hardness. (Effects of the Invention) According to the present invention, the fluoroolefin has good solubility in organic solvents, good compatibility with a curing agent, and can be cured at room temperature without being subject to restrictions on the type of fluoroolefin used. A fluorine-containing copolymer can be easily provided. Furthermore, the fluorine-based paint of the present invention containing the fluorine-containing copolymer as a main component can provide a glossy, hard, and weather-resistant coating film under mild conditions. Baking for colored aluminum plates and aluminum sashes is useful as a paint or as an air-drying paint that can be applied on-site. Furthermore, regarding the material of the base material, including metal materials, inorganic materials such as glass and concrete, FRP, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, nylon, acrylic resin, polyester, ethylene-vinyl acetate copolymer,
It is suitably used for coating plastics such as polyvinyl alcohol copolymers, polyvinyl chloride, and polyvinylidene chloride, and organic materials such as wood. The fluorine-based paint is also useful in specific applications such as aluminum swimming pools, exterior colored glass, and cement roofs. (1 other person)
Claims (2)
んでなることを特徴とする含フッ素共重合体。 (A)式: ▲数式、化学式、表等があります▼・・・( I ) (式中、V、X、Y及びZは同一でも異なっていてもよ
く、それぞれH、F、Cl、炭素数1〜6のアルキル基
、及び炭素数1〜6のハロ置換アルキル基から選ばれる
1種を示し、かつ、そのうちの少なくとも1つはFであ
る。) で表されるフルオロオレフィンの共重合した単位:20
〜97モル% (B)ネオペンチルビニルエーテルの共重合した単位:
3〜80モル%。(1) A fluorine-containing copolymer comprising the following (A) and (B) as essential components. (A) Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, V, X, Y, and Z may be the same or different, and each represents H, F, Cl, and the number of carbon atoms. A copolymerized unit of a fluoroolefin, which represents one selected from an alkyl group having 1 to 6 carbon atoms and a halo-substituted alkyl group having 1 to 6 carbon atoms, and at least one of them is F.) :20
~97 mol% (B) Copolymerized unit of neopentyl vinyl ether:
3-80 mol%.
んでなることを特徴とする含フッ素共重合体を主成分と
する塗料。 (A)式; ▲数式、化学式、表等があります▼・・・( I ) (式中、V、X、Y及びZは同一でも異なっていてもよ
く、それぞれH、F、Cl、炭素数1〜6のアルキル基
、及び炭素数1〜6のハロ置換アルキル基から選ばれる
1種を示し、かつ、そのうちの少なくとも1つはFであ
る。) で表されるフルオロオレフィンの共重合した単位:20
〜97モル% (B)ネオペンチルビニルエーテルの共重合した単位:
3〜80モル%。(2) A paint whose main component is a fluorine-containing copolymer, which is characterized by containing the following (A) and (B) as essential components. (A) Formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, V, X, Y, and Z may be the same or different, and each represents H, F, Cl, and the number of carbon atoms. A copolymerized unit of a fluoroolefin, which represents one selected from an alkyl group having 1 to 6 carbon atoms and a halo-substituted alkyl group having 1 to 6 carbon atoms, and at least one of them is F.) :20
~97 mol% (B) Copolymerized unit of neopentyl vinyl ether:
3-80 mol%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30377590A JPH04178408A (en) | 1990-11-13 | 1990-11-13 | Fluorine-containing copolymer and fluorine-based coating consisting essentially of the same copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30377590A JPH04178408A (en) | 1990-11-13 | 1990-11-13 | Fluorine-containing copolymer and fluorine-based coating consisting essentially of the same copolymer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04178408A true JPH04178408A (en) | 1992-06-25 |
Family
ID=17925139
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30377590A Pending JPH04178408A (en) | 1990-11-13 | 1990-11-13 | Fluorine-containing copolymer and fluorine-based coating consisting essentially of the same copolymer |
Country Status (1)
Country | Link |
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JP (1) | JPH04178408A (en) |
-
1990
- 1990-11-13 JP JP30377590A patent/JPH04178408A/en active Pending
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