JPH03166231A - Fluorine-contact vinyl-based nonaqueous polymer dispersion and production thereof - Google Patents
Fluorine-contact vinyl-based nonaqueous polymer dispersion and production thereofInfo
- Publication number
- JPH03166231A JPH03166231A JP30524889A JP30524889A JPH03166231A JP H03166231 A JPH03166231 A JP H03166231A JP 30524889 A JP30524889 A JP 30524889A JP 30524889 A JP30524889 A JP 30524889A JP H03166231 A JPH03166231 A JP H03166231A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- vinyl
- copolymer
- polymer dispersion
- containing copolymer
- 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
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 74
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 63
- 239000004815 dispersion polymer Substances 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 104
- 239000011737 fluorine Substances 0.000 claims abstract description 96
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229920001577 copolymer Polymers 0.000 claims abstract description 72
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 65
- -1 chlorotrifluoroethylene, tetrafluoroethylene Chemical group 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 8
- 150000002221 fluorine Chemical class 0.000 claims description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 239000003973 paint Substances 0.000 description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000010422 painting Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 3
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical group FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-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
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-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
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical compound CCCCCOC=C IOSXLUZXMXORMX-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
- KTJFJTQEJVXTHT-UHFFFAOYSA-N 1-ethenoxypropan-2-yl(dimethoxy)silane Chemical compound C(=C)OCC([SiH](OC)OC)C KTJFJTQEJVXTHT-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- ADCMLYKEZQPOKL-UHFFFAOYSA-N 2,3,6-trimethylheptan-4-one Chemical compound CC(C)CC(=O)C(C)C(C)C ADCMLYKEZQPOKL-UHFFFAOYSA-N 0.000 description 1
- KTIBRDNFZLYLNA-UHFFFAOYSA-N 2-(2-hydroxyethenoxy)ethenol Chemical class OC=COC=CO KTIBRDNFZLYLNA-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- ARMWSTGKHHACOF-UHFFFAOYSA-N 2-ethenoxyethyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCOC=C ARMWSTGKHHACOF-UHFFFAOYSA-N 0.000 description 1
- TYZRVQDBDAPABU-UHFFFAOYSA-N 2-ethenoxyethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCOC=C TYZRVQDBDAPABU-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 1
- XSJHWCBTRSJBMS-UHFFFAOYSA-N 2-sulfanyldecan-2-ol Chemical compound CCCCCCCCC(C)(O)S XSJHWCBTRSJBMS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- VLDQEHUZQHHLHD-UHFFFAOYSA-N 3-ethenoxypropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCOC=C VLDQEHUZQHHLHD-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
- HQDTVNSMVFOQQF-UHFFFAOYSA-N 4-ethenoxybutan-2-yl(diethoxy)silane Chemical compound C(=C)OCCC([SiH](OCC)OCC)C HQDTVNSMVFOQQF-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
- 101100459438 Caenorhabditis elegans nac-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- STZUMARNGFQGPH-UHFFFAOYSA-N chloromethoxyethene Chemical compound ClCOC=C STZUMARNGFQGPH-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VXCARZYCXKMEDQ-UHFFFAOYSA-N ethenyl 1-methylcyclohexane-1-carboxylate Chemical compound C=COC(=O)C1(C)CCCCC1 VXCARZYCXKMEDQ-UHFFFAOYSA-N 0.000 description 1
- ABTUOFDRTJEXOY-UHFFFAOYSA-N ethenyl 2,2-dimethylbutanoate Chemical compound CCC(C)(C)C(=O)OC=C ABTUOFDRTJEXOY-UHFFFAOYSA-N 0.000 description 1
- MFVRZMIBNINJBB-UHFFFAOYSA-N ethenyl 2,2-dimethylhexanoate Chemical compound CCCCC(C)(C)C(=O)OC=C MFVRZMIBNINJBB-UHFFFAOYSA-N 0.000 description 1
- SSXOSWWUPHFFGN-UHFFFAOYSA-N ethenyl 2,2-dimethylpentanoate Chemical compound CCCC(C)(C)C(=O)OC=C SSXOSWWUPHFFGN-UHFFFAOYSA-N 0.000 description 1
- WGLIYROVGWCUKY-UHFFFAOYSA-N ethenyl 2-ethyl-2-methylbutanoate Chemical compound CCC(C)(CC)C(=O)OC=C WGLIYROVGWCUKY-UHFFFAOYSA-N 0.000 description 1
- ANNAUSOWUNVEIZ-UHFFFAOYSA-N ethenyl 2-ethyl-2-methylpentanoate Chemical compound CCCC(C)(CC)C(=O)OC=C ANNAUSOWUNVEIZ-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- ZLHVSEPPILCZHH-UHFFFAOYSA-N ethenyl 4-tert-butylbenzoate Chemical compound CC(C)(C)C1=CC=C(C(=O)OC=C)C=C1 ZLHVSEPPILCZHH-UHFFFAOYSA-N 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-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
- 238000011160 research Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 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 1
- 239000010959 steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- DJXRIQMCROIRCZ-XOEOCAAJSA-N vibegron Chemical compound C1([C@H]([C@@H]2N[C@H](CC=3C=CC(NC(=O)[C@H]4N5C(=O)C=CN=C5CC4)=CC=3)CC2)O)=CC=CC=C1 DJXRIQMCROIRCZ-XOEOCAAJSA-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
- 239000008096 xylene Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規にして有用なる含ふっ素ビニル系非水重合
体分散液の新規にして有用なる製造方法に関する．
そして、本発明の含ふっ素ビニル系非水重合体分散液は
、とりわけ、塗料用として、接着剤用として、あるいは
、シーリング剤用として利用できるものではあるが、そ
れらのうちでも、塗料用として利用するのが特に望まし
い。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful method for producing a fluorine-containing non-aqueous vinyl polymer dispersion. The fluorine-containing non-aqueous vinyl polymer dispersion of the present invention can be used, among other things, for paints, adhesives, and sealants; among these, it can be used for paints. It is particularly desirable to do so.
近年、溶剤型にして高耐候性をもった塗膜を与える、常
温硬化可能な含ふっ素共重合体が開発され、主として、
塗料用に向けられている。In recent years, room-temperature curable fluorine-containing copolymers have been developed that provide solvent-based coatings with high weather resistance.
Intended for paint.
しかし、かかる溶剤型の含ふっ素共重合体に用いられて
いる溶剤としては、芳香族炭化水素系、エステル系およ
び／またはケトン系などの、いわゆる溶解性の高いもの
が主体になっている。However, the solvents used for such solvent-type fluorine-containing copolymers are mainly those having high solubility, such as aromatic hydrocarbons, esters, and/or ketones.
ところが、こうした溶解性の高い有機溶剤が用いられて
いる塗料は、既設の塗膜（以下、旧塗膜ともいう．）や
、下塗り塗膜の上に塗装して用いられるような場合には
、どうしても、旧塗膜や下塗り塗膜を膨潤し溶解させ、
ひいては、“ちぢみ”や“ふくれ゜゛なとのトラブルが
惹起し易いという致命的な欠点を宿しているし、さらに
、この種の溶剤型含ふっ素共重合体は、通常の溶剤型樹
脂と同様に、分子量が高くなるにつれて、粘度が上昇す
るという必然的な粘度特性を有している処から、塗膜物
性を向上せしめるべく、高分子量タイプの含ふっ素共重
合体を用いて戒る塗料を用いての塗装にさいしては、塗
装可能な粘度のものと為すべく、多量の溶剤による希釈
が必至となり、ひいては、塗装時の不揮発分濃度（不揮
発分含有率）も低くなって、塗装作業性に劣るなどの問
題を抱えている、というのが実状である．
かかる問題に対して、含ふっ素共重合体の非水分散液を
用いることも、特開昭６２−２５１０３号公報や特開昭
６４−６６２７３号公報などに提案されてこそいるもの
の、いずれも専ら、含ふっ素共重合体を分散化安定剤（
分散剤）として用いているというものである．
ところで、非水重合体分散液は、一般に、有機溶剤に不
溶の重合体（以下、分散部分ともいう。）と、有機溶剤
に可溶で、かつ、この分散部分を安定に分散せしめるた
めの、いわゆる分散安定化剤とから構威されるものであ
る．
無論のことながら、分散安定化剤の割合が大きくなれば
、非水重合体分散液の安定性は向上するものの、反面に
おいて、非水分散液の粘度は、著しく高くなる。However, when paints containing highly soluble organic solvents are applied over an existing paint film (hereinafter also referred to as "old paint film") or an undercoat film, By all means, the old paint film and undercoat film will swell and dissolve,
Furthermore, it has the fatal disadvantage of easily causing troubles such as "shrinking" and "swelling."Furthermore, this type of solvent-based fluorine-containing copolymer is similar to ordinary solvent-based resins. In addition, as the molecular weight increases, the viscosity naturally increases, so in order to improve the physical properties of the coating film, paints using high molecular weight type fluorine-containing copolymers have been developed. When painting with paint, it is necessary to dilute it with a large amount of solvent in order to achieve a paintable viscosity, and as a result, the concentration of non-volatile matter (non-volatile content) at the time of painting becomes low, resulting in poor painting workability. The reality is that there are problems such as inferior performance.To solve this problem, it is also possible to use a non-aqueous dispersion of a fluorine-containing copolymer, as disclosed in JP-A No. 62-25103 and JP-A No. 62-25103. 64-66273, etc., but all of them exclusively use fluorine-containing copolymers as dispersion stabilizers (
It is used as a dispersing agent). By the way, a non-aqueous polymer dispersion generally contains a polymer that is insoluble in an organic solvent (hereinafter also referred to as a dispersion portion) and a polymer that is soluble in an organic solvent and that is used to stably disperse the dispersion portion. It is composed of so-called dispersion stabilizers. Needless to say, as the proportion of the dispersion stabilizer increases, the stability of the non-aqueous polymer dispersion improves, but on the other hand, the viscosity of the non-aqueous dispersion increases significantly.
したがって、分散部分としては、一切、含ふっ素共重合
体を含まないで、専ら、かかる分散安定化剤として含ふ
っ素共重合体を用いるという場合には、塗膜の耐久性を
確保しようとして、非水重合体分散液における、ふっ素
含有率を高めようとすると、勢い、分散安定化剤の使用
比率を増大せざるを得なくなるし、その結果、非水分散
液の粘度が高くなる処となるし、結局の処、この種の非
水重合体分散液の重要な特徴点でもある、塗装時の不揮
発分含有率（固形分濃度）が高いという点は、全く、達
成され得なくなるという新たな問題点が、未解決のまま
に残されることとなる。Therefore, if the dispersion part does not contain any fluorine-containing copolymer and the fluorine-containing copolymer is used exclusively as a dispersion stabilizer, non-fluorine-containing copolymers may be used to ensure the durability of the coating film. If you try to increase the fluorine content in the aqueous polymer dispersion, you will have to increase the amount of dispersion stabilizer used, and as a result, the viscosity of the non-aqueous dispersion will increase. As a result, a new problem arises in that the high nonvolatile content (solid content concentration) during coating, which is an important feature of this type of non-aqueous polymer dispersion, cannot be achieved at all. points will be left unresolved.
〔発明が解決しようとする課題〕
しかるに、本発明者らは上述した如き従来技術における
種々の欠点ないしは問題点（未解決課題）の早急なる解
消ないしは解決を図るべく、斬新なる技術に裏打ちされ
た、極めて有用性の高い水性重合体分散液を求めて、鋭
意、研究に着手した。[Problems to be Solved by the Invention] However, the present inventors have developed a novel technology backed by a novel technology in order to promptly eliminate or solve the various drawbacks or problems (unresolved problems) in the prior art as described above. In search of an extremely useful aqueous polymer dispersion, we began intensive research.
したがって、本発明が解決しようとする課題は、一にか
かって、溶剤型含ふっ素共重合体ならびに、従来の非水
分散型含ふっ素共重合体に見られるような塗装作業性な
どの低下という一大弊害から解放された、しかも、耐候
性などの皮膜性能も一段と向上した、極めて有用なる非
水重合体分散液を提供することであり、また、こうした
非水重合体分散液の製造方法を提供することである。Therefore, the problem to be solved by the present invention is to overcome the problem of poor coating workability as seen in solvent-type fluorine-containing copolymers and conventional non-aqueous dispersion-type fluorine-containing copolymers. The object of the present invention is to provide an extremely useful non-aqueous polymer dispersion that is free from major adverse effects and has further improved film performance such as weather resistance, and also to provide a method for producing such a non-aqueous polymer dispersion. It is to be.
そこで、本発明者らは上述した如き発明が解決しようと
する課題に照準を合わせて、鋭意、検討を重ねた結果、
転相分散法という特殊な手段を駆使することによって、
はじめて、分散部分が含ふっ素共重合体からなるもので
あり、とりわけ、耐候性にすぐれ、しかも、塗装作業性
にすぐれるのみならず、旧塗膜や下塗り塗膜などを、何
ら、膨潤させ、溶解させることもない、極めて有用なる
含ふっ素ビニル系非水重合体分散液が得られることを見
い出し、併せて、含ふっ素ビニル系非水重合体分散液の
製造方法をも見い出すに及んで、本発明を完威させるに
到った。Therefore, the inventors of the present invention focused on the problems to be solved by the invention as described above, and as a result of repeated studies,
By making full use of a special method called phase inversion dispersion method,
For the first time, the dispersion part is made of a fluorine-containing copolymer, which not only has excellent weather resistance and painting workability, but also swells the old paint film and undercoat film, etc. We have discovered that an extremely useful fluorine-containing non-aqueous vinyl polymer dispersion that does not require dissolution can be obtained, and have also discovered a method for producing the fluorine-containing vinyl non-aqueous polymer dispersion. He has perfected his invention.
すなわち、本発明はまず、含ふっ素共重合体の存在下に
、ビニル単量体類を重合させ、転相分散せしめて得られ
る含ふっ素ビニル系非水重合体分散液を提供しようとす
るものであり、併せて、重合用有機溶剤中、含ふっ素共
重合体の存在下において、この重合用有機剤に溶解しう
るビニル単量体類を重合させ、次いで、この含ふっ素共
重合体の使用を欠き、専ら、ビニル単量体類を用いて得
られるビニル共重合体は溶解するが、含ふっ素共重合体
は溶解しないような、新たな有機溶剤を加え、しかるの
ち、上記の重合用有機溶剤の一部または全部を除去せし
めることから或る、含ふっ素ビニル系非水重合体分散液
の製造方法を提供しようとするものである。That is, the present invention first aims to provide a fluorine-containing non-aqueous vinyl polymer dispersion obtained by polymerizing vinyl monomers and phase inversion dispersion in the presence of a fluorine-containing copolymer. In addition, in the presence of a fluorine-containing copolymer in an organic solvent for polymerization, vinyl monomers that can be dissolved in this organic agent for polymerization are polymerized, and then the use of this fluorine-containing copolymer is However, a new organic solvent that dissolves the vinyl copolymer obtained using vinyl monomers but does not dissolve the fluorine-containing copolymer is added, and then the above-mentioned organic solvent for polymerization is added. The object of the present invention is to provide a method for producing a fluorine-containing non-aqueous vinyl polymer dispersion by removing part or all of the fluorine-containing vinyl non-aqueous polymer dispersion.
本発明において、上記した「転相分散法」なる用語は、
それぞれ、重合反応時に用いられる溶剤（重合用溶剤）
を、この重合反応が終了した時点で、部分的に、あるい
は全面的に、非水重合体分散液用の溶剤（非水分散用溶
剤）で置き換えるという操作または手段を指称するもの
であり、こうした操作・手段を講じることによって、高
固形分濃度の非水重合体分散液でありながら、分散液の
粘度を、適宜、抑えることができるし、それがために、
塗装作業性の確保も図れるし、しかも、旧塗膜や下塗り
塗膜などを膨潤させたり溶解させたりするという弊害か
らも解放されるというメリットが、もたらさせる。In the present invention, the term "phase inversion dispersion method" mentioned above is
Solvent used during polymerization reaction (polymerization solvent)
It refers to the operation or means of partially or completely replacing the solvent with a solvent for the non-aqueous polymer dispersion (a non-aqueous dispersion solvent) when the polymerization reaction is completed. By taking operations and measures, the viscosity of the dispersion can be appropriately suppressed even though it is a non-aqueous polymer dispersion with a high solid content concentration, and therefore,
This has the advantage of not only ensuring painting workability but also being free from the harmful effects of swelling and dissolving the old paint film, undercoat film, etc.
このさい、上記した重合用溶剤としては、含ふっ素共重
合体それ自体を溶解しうる有機溶剤が用いられるし、他
方、上記した分散用溶剤としては、ビニル共重合体それ
自体を溶解しうる有機溶剤であるが、含ふっ素共重合体
だけは溶解することのないような有機溶剤が用いられる
ということである。At this time, as the above-mentioned polymerization solvent, an organic solvent that can dissolve the fluorine-containing copolymer itself is used, and on the other hand, as the above-mentioned dispersion solvent, an organic solvent that can dissolve the vinyl copolymer itself is used. Regarding the solvent, an organic solvent that does not dissolve the fluorine-containing copolymer is used.
こうした意味合いにおいて、塗装作業性の確保もできる
し、併せて、リフティング現象からの解放も達せられる
ので、「転相分散法」も、本発明が解決しようとする課
題の解決手段としては、まさに、打って付けのものであ
る。In this sense, it is possible to ensure painting workability, and at the same time, it is possible to achieve freedom from the lifting phenomenon, so the "phase inversion dispersion method" is also suitable as a solution to the problems that the present invention aims to solve. It's a given.
ところで、前記した含ふっ素共重合体とは、それぞれ、
後掲される如き含ふっ素ビニル単量体類と該単量体類と
共重合可能な他の単量体類との重合反応によって得られ
るものを指称するものである。By the way, the above-mentioned fluorine-containing copolymers are, respectively,
It refers to a product obtained by a polymerization reaction between fluorine-containing vinyl monomers and other monomers copolymerizable with the monomers as listed below.
かかる含ふっ素ビニル単量体類としては、公知慣用のも
のであれば、いずれも使用しうるが、そのうちでも特に
代表的なもののみを例示するに留めれば、ぶつ化ビニル
、ぶつ化ビニリデン、トリフルオロエチレン、テトラフ
ルオロエチレン、クロロトリフルオロエチレン、プロモ
トリフルオロエチレン、ペンタフルオロプロピレンもし
くは、ヘキサフルオロプロピレンの如き、ふっ素含有一
α−オレフィン類；またはトリフルオロメチルトリフル
オロビニルエーテル、ペンタフルオ口エチルトリフルオ
口ビニルエーテルもしくはヘプタフルオロプ口ピルトリ
フルオロビニルエーテルの如きパーフルオロアルキル・
バーフルオロビニルエーテルなどの、主鎖中に、ふっ素
原子を有する化合物があるが、就中、ぶつ化ビニル、テ
トラフルオロエチレン、クロロトリフルオロエチレン、
ヘキサフルオロプロピレン、またはアルキル基がＣ Ｉ
− Ｃ ＋ ｓなるバーフルオロアルキル・トリフルオ
ロビニルエーテルの使用が望ましい．
これら上掲の含ふっ素ビニル単量体類は単独使用でも、
２種以上の併用でもよいことは勿論である．
また、かかる含ふっ素ビニル単量体類と共重合可能な単
量体類としては、勿論、上掲された如き含ふっ素ビニル
単量体類と共重合可能なものである限りは、ビニル単量
体類であると否とを問わず、いずれも使用できるが、そ
のうちでも特に代表的なもののみを例示するに留めれば
、メチルビニルエーテル、エチルビニルエーテル、ｎ−
プロビルビニルエーテル、イソプロビルビニルエーテル
、ｎ−プチルビニルエーテル、インブチルビニルエーテ
ル、ｔｅｒｔ ７’チルビニルエーテル、ｎ−ペンチ
ルビニルエーテル、ｎ−ヘキシルビニルエーテル、ｎ−
オクチルビニルエーテル、２−エチルヘキシルビニルエ
ーテル、クロロメチルビニルエーテル、クロロエチルビ
ニルエーテル、ペンジルビニルエーテルモシ＜はフェニ
ルエチルビニルエーテルの如きアルキルビニルエーテル
ないしは置換アルキルビニルエーテル類；シクロベンチ
ルビニルエーテル、シクロヘキシルビニルエーテルもし
くはメチルシクロヘキシルビニルエーテルの如きシクロ
アルキルビニルエーテル類；ビニル−２．２−ジメチル
プロバノエート、ビニル−２．２−ジメチルブタノエー
ト、ビニル−２．２−ジメチルペンタノエート、ビニル
−２．２−ジメチルヘキサノエート、ビニル−２−エチ
ル−２−メチルブタノエート、ビニル−２−エチル−２
−メチルペンタノエート、ビニル−３−クロロー２．２
−ジメチルプロバノエート、酢酸ビニル、プロピオン酸
ビニル、ｅＡＭビニル、イソ酪酸ビニル、カプロン酸ビ
ニル、カプリル酸ビニル、カブリン酸ビニル、ラウリン
酸ビニル、Ｃ９の分岐脂肪族カルボン酸ビニル、Ｃ．の
分岐脂肪族カルボン酸ビニル、Ｃ．の分岐脂肪族カルボ
ン酸ビニルもしくはステアリン酸ビニルの如き脂肪族カ
ルボン酸ビニル；シクロヘキサンカルボン酸ビニル、メ
チルシクロヘキサンカルボン酸ビニル、安息香酸ビニル
もしくはｐ一ｔｅｒｔ−ブチル安息香酸ビニルの如き、
環状構造を有するカルボン酸のビニルエステル類；エチ
レン、プロピレンもしくはブテンー１の如きα−オレフ
ィン類；塩化ビニルもしくは塩化ビニリデンの如き、フ
ルオロオレフィンを除く各種ハロゲン化オレフィン類；
スチレン、α−メチルスチレンもしくはビニルトルエン
の如き脂肪族ビニル化合物；メチルアクリレート、エチ
ルアクリレート、プチルアクリレートもしくはシクロヘ
キシルアクリレートの如きアクリル酸エステル類：メチ
ルメタクリレート、エチルメタクリレート、プチルメタ
クリレート、シクロへキシルメタクリレートもしくはペ
ンジルメタクリレートの如きメタクリル酸エステル類；
２−ヒドロキシエチルビニルエーテル、３−ヒドロキシ
プロビルビニルエーテル、２−ヒドロキシプロビルビニ
ルエーテル、４−ヒドロキシプ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−メチルプロビルビニルエーテル、５−ヒドロキシペ
ンチルビニルエーテルもしくは６−ヒドロキシヘキシル
ビニルエーテルの如き水酸基を有するビニルエーテル類
；ビニルトリメトキシシラン、ビニルトリエトキシシラ
ン、ビニルトリプロボキシシラン、ビニルメチルジエト
キシシラン、ビニルトリス（β−メトキシエトキシ）シ
ラン、アリルトリメトキシシラン、トリメトキシシリル
エチルビニルエーテル、トリエトキシシリルエチルビニ
ルエーテル、メチルジメトキシシリルエチルビニルエー
テル、トリメトキシシリルプ口ピルビニルエーテル、ト
リエトキシシリルプロピルビニルエーテル、メチルジエ
トキシシリルプロビルビニルエーテル、ｒ−（メタ）ア
クリロイルオキシプロビルトリメトキシシラン、γ一（
メタ）アクリロイルオキシプロビルトリエトキシシラン
もしくはｒ−（メタ）アクリロイルオキシプロビルメチ
ルジメトキシシランの如き加水分解性シリル基を含有す
る単量体；Ｎ−ジメチルアミノエチル（メタ）アクリル
アξド、Ｎ−ジエチルアミノエチル（メタ）アクリルア
ξド、Ｎ−ジメチルア旦ノプロピル（メタ）アクリルア
ミドもしくはＮ−ジエチルアミノプロピル（メタ）アク
リルアミドの如きアξノ基含有アミド系不飽和単量体；
ジメチルアごノエチル（メタ）アクリレートもしくはジ
ェチルアミノエチル（メタ）アクリレートの如きジアル
キルアミノアルキル（メタ）アクリレー｝１（Ｈ ｔ
ｅｒｔ−ブチルアミノエチル（メタ）アクリレート、ｔ
ｅｒ ｔ−プチルアミノプロビル（メタ）アクリレート
、アジリジニルエチル（メタ）アクリレート、ピロリジ
ニルエチル（メタ）アクリレートもしくはピペリジニル
エチル（メタ）アクリレートの如きアミノ基含有単量体
；または（メタ）アクリル酸、クロトン酸、イタコン酸
、マレイン酸もしくはフマル酸の如きカルボキシル基含
有単量体などである．当該含ふっ素共重合体それ自体の
重合収率を高めるという観点からすれば、アルキルビニ
ルエーテル類、シクロアルキルビニルエーテル類、水酸
基含有ビニルエーテル類およびカルボン酸ビニルエステ
ル類の使用が望ましく、就中、Ｃ．−Ｃ，なるアルキル
基を有するビニルエーテル類、０１〜ｃ３なるアルキル
基を有するカルボン酸ビニルエステル類、および水酸基
含有ビニルエーテル類を用いることが、ｎ−ヘプタンに
対する溶解度（以下、ｎヘブタン・トレランスともいう
。）を２００以下となすためには、特に望ましい。As such fluorine-containing vinyl monomers, any known and commonly used monomers can be used, but among them, only representative ones are exemplified, such as vinyl fluoride, vinylidene fluoride, Fluorine-containing mono-alpha-olefins such as trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, promotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyltrifluorovinyl ether, pentafluoroethyltrifluoroethylene perfluoroalkyl, such as vinyl ether or heptafluoropil trifluorovinyl ether;
There are compounds having a fluorine atom in the main chain, such as barfluorovinyl ether, but among them, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene,
hexafluoropropylene, or the alkyl group is C I
- It is preferable to use barfluoroalkyl trifluorovinyl ether, which is C + s. Even if these fluorine-containing vinyl monomers listed above are used alone,
Of course, two or more types may be used in combination. Furthermore, as monomers copolymerizable with such fluorine-containing vinyl monomers, as long as they are copolymerizable with the above-mentioned fluorine-containing vinyl monomers, vinyl monomers may be used. Any of them can be used, regardless of whether they are a class or not, but to exemplify only the most representative ones, methyl vinyl ether, ethyl vinyl ether, n-
Propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, inbutyl vinyl ether, tert 7' tyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-
Alkyl vinyl ethers or substituted alkyl vinyl ethers such as octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, penzyl vinyl ether; Vinyl ethers; vinyl-2,2-dimethylprobanoate, vinyl-2,2-dimethylbutanoate, vinyl-2,2-dimethylpentanoate, vinyl-2,2-dimethylhexanoate, vinyl-2 -ethyl-2-methylbutanoate, vinyl-2-ethyl-2
-Methylpentanoate, vinyl-3-chloro 2.2
-dimethylprobanoate, vinyl acetate, vinyl propionate, eAM vinyl, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caproate, vinyl laurate, C9 branched aliphatic vinyl carboxylate, C.I. Branched aliphatic vinyl carboxylate of C.I. branched aliphatic vinyl carboxylates, such as branched aliphatic vinyl carboxylates or vinyl stearate; such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate or vinyl p-tert-butylbenzoate;
Vinyl esters of carboxylic acids having a cyclic structure; α-olefins such as ethylene, propylene or butene-1; various halogenated olefins other than fluoroolefins such as vinyl chloride or vinylidene chloride;
Aliphatic vinyl compounds such as styrene, α-methylstyrene or vinyltoluene; acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate or cyclohexyl acrylate: methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate or pendyl Methacrylic acid esters such as methacrylate;
2-Hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3
-Hydroxybutyl vinyl ether, 2-hydroxy-
Vinyl ethers having a hydroxyl group such as 2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether or 6-hydroxyhexyl vinyl ether; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriproxysilane, vinylmethyldiethoxysilane, vinyltris( β-methoxyethoxy) silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyruvinyl ether, triethoxysilylpropyl vinyl ether, methyldiethoxysilylpropyl Vinyl ether, r-(meth)acryloyloxyprobyltrimethoxysilane, γ-(
Monomers containing hydrolyzable silyl groups such as meth)acryloyloxyprobyltriethoxysilane or r-(meth)acryloyloxypropylmethyldimethoxysilane; N-dimethylaminoethyl(meth)acrylamide, N- An amide unsaturated monomer containing an ξ group such as diethylaminoethyl (meth)acrylamide ξ-do, N-dimethylantanopropyl (meth)acrylamide or N-diethylaminopropyl (meth)acrylamide;
dialkylaminoalkyl (meth)acrylate such as dimethylagonoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate}1(H t
ert-butylaminoethyl (meth)acrylate, t
er t-Amino group-containing monomers such as butylaminopropyl (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl (meth)acrylate or piperidinylethyl (meth)acrylate; or (meth) ) Carboxyl group-containing monomers such as acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid. From the viewpoint of increasing the polymerization yield of the fluorine-containing copolymer itself, it is desirable to use alkyl vinyl ethers, cycloalkyl vinyl ethers, hydroxyl group-containing vinyl ethers, and carboxylic acid vinyl esters. The use of vinyl ethers having an alkyl group of -C, carboxylic acid vinyl esters having an alkyl group of 01 to c3, and vinyl ethers containing a hydroxyl group has a high solubility in n-heptane (hereinafter also referred to as n-heptane tolerance). ) is particularly desirable in order to make it 200 or less.
ここにおいて、上記したｎ−ヘプタン・トレランスとは
、該トレランスを求める対象となる生成共重合体の固形
分にｎ−ヘプタンを滴下して行って、この共重合体が白
濁するまでに要するｎ−ヘプタンの量（５リリットル）
を、この測定のために採取した、該共重合体の固形分量
（グラム）で除して１００倍した値である、と定義され
る。Here, the above-mentioned n-heptane tolerance refers to the amount of n-heptane required for the copolymer to become cloudy when n-heptane is added dropwise to the solid content of the copolymer that is the object of determining the tolerance. Amount of heptane (5 liters)
is divided by the solid content (grams) of the copolymer sampled for this measurement and multiplied by 100.
本発明においては、目的含ふっ素ビニル系非水重合体分
散液それ自体の分散安定性などの面からすれば、当該含
ふっ素共重合体のｎ−ヘプタン・トレランスが２００以
下になるように管理されることが、特に望ましい。In the present invention, from the viewpoint of dispersion stability of the target fluorine-containing vinyl non-aqueous polymer dispersion itself, the n-heptane tolerance of the fluorine-containing copolymer is controlled to be 200 or less. It is particularly desirable that
前掲された如き、それぞれ、含ふっ素ビニル単量体類と
共重合可能な他のビニル単量体類とを用いて当該含ふっ
素共重合体を調製するには、ふっ素原子含有率が５〜６
０重量％、好ましくは、ｌＯ〜４０重量％なる範囲内に
入るように管理されるべきである。In order to prepare the fluorine-containing copolymer using the fluorine-containing vinyl monomers and other copolymerizable vinyl monomers as listed above, the fluorine atom content must be 5 to 6.
It should be controlled within a range of 0% by weight, preferably 10 to 40% by weight.
５重量％未満である場合には、得られる皮膜の耐候性な
どが低下するようになり易く、一方、６０重量％を超え
る場合には、皮膜が均一に形威され難くなり易く、ひい
ては、光沢が低下するようにもなるので、いずれの場合
にも好ましくない。If it is less than 5% by weight, the weather resistance of the resulting film tends to deteriorate, while if it exceeds 60% by weight, it tends to be difficult for the film to form a uniform shape, and as a result, the gloss may deteriorate. This is not preferable in either case, since it also causes a decrease in .
また、当該含ふっ素共重合体中にα，β一エチレン性不
飽和二重結合（以下、不飽和基ともいう．を導入せしめ
、それによって、当該含ふっ素共重合体の存在下に、ビ
ニル単量体類を重合させるに当たって、予め、グラフト
化を行なっておくことが、目的含ふっ素ビニル系非水重
合体分散液の分散安定性などの面から、特に望ましい。In addition, α,β-ethylenically unsaturated double bonds (hereinafter also referred to as unsaturated groups) are introduced into the fluorine-containing copolymer, thereby allowing vinyl monomers to form in the presence of the fluorine-containing copolymer. In polymerizing the polymers, it is particularly desirable to carry out grafting in advance from the viewpoint of dispersion stability of the target fluorine-containing non-aqueous vinyl polymer dispersion.
かかる不飽和基を導入せしめる方法としては、たとえば
、当該含ふっ素共重合体中に、予め、反応性極性基（以
下、これを官能基ｒ１ということにする。）を有するビ
ニル単量体類を共重合用単）
量体類（共単量体）の一つとして用いて共重合させ、次
いで、この官能基ｆ＋ と反応性を有する反応性極性基
（以下、これを官能基ｆ２ということにする。）を有す
る不飽和基含有化合物を反応せしめるという方法などが
挙げられる。As a method for introducing such an unsaturated group, for example, vinyl monomers having a reactive polar group (hereinafter referred to as functional group r1) are introduced into the fluorine-containing copolymer in advance. A reactive polar group (hereinafter referred to as functional group f2) that is reactive with this functional group f Examples include a method of reacting an unsaturated group-containing compound having the following.
ここにおいて、特に代表的な官能基ｆ１とｆ２との組み
合わせを挙げるに留めれば、
水酸基一イソシアネート基、
イソシアネート基一水酸基、
エボキシ基一力ルボキシル基、
カルボキシル基一エボキシ基、
水酸基一酸無水基、
酸無水基一水酸基、
アミン基−エポキシ基、
または エボキシ基−アミノ基
などであるが、かかる両反応性極性基の選択、設計は、
反応条件や目的非水重合体分散液の使用目的などによっ
て、適宜、為されることになる。Here, particularly typical combinations of functional groups f1 and f2 are listed: hydroxyl group-isocyanate group, isocyanate group-monohydroxyl group, eboxy group-monocarboxyl group, carboxyl group-mono-epoxy group, hydroxyl group-monoacid anhydride group. , acid anhydride group, monohydroxyl group, amine group-epoxy group, or epoxy group-amino group, etc., but the selection and design of such bireactive polar groups are as follows:
It will be carried out as appropriate depending on the reaction conditions and the intended use of the non-aqueous polymer dispersion.
而して、当該含ふっ素共重合体を調製するには、ラジカ
ル重合開始剤の存在下に、前掲された如き各種の単量体
類を、かかる各種単量体類を溶解しうるような有機溶剤
（重合用有機溶剤）中で、溶液（加圧）重合せしめると
いう方法によるのが、最も簡便であると言えるが、塊状
重合、懸濁重合または乳化重合などの他の公知慣用の重
合方法によることも、勿論、可能であって、そのさいに
は、重合終了後において、固形分を分離して取り出した
のち、有機溶剤（非水分散用有機溶剤）に溶解せしめる
ようにすればよい。Therefore, in order to prepare the fluorine-containing copolymer, various monomers as listed above are added to an organic material capable of dissolving the various monomers in the presence of a radical polymerization initiator. Solution (pressure) polymerization in a solvent (organic solvent for polymerization) is said to be the simplest method, but other known and commonly used polymerization methods such as bulk polymerization, suspension polymerization, or emulsion polymerization can also be used. Of course, this is also possible, and in that case, the solid content may be separated and taken out after the polymerization is completed, and then dissolved in an organic solvent (an organic solvent for non-aqueous dispersion).
かかる重合用有機溶剤としては、勿論、含ふっ素共重合
体、および、目的含ふっ素ビニル系非水重合体を調製す
るにさいして、含ふっ素共重合体の存在下において、ビ
ニル単量体類を重合させて得られる、それぞれ、含ふっ
素共重合体と混合された状態で、あるいは、グラフト化
された状態で、共存する該ビニル単量体類の共重合体（
以下、これをビニル共重合体ということにする。）を溶
解さすことのできるものでさえあれば、いずれも用いる
ことができるが、それらのうちでも特に代表的なものの
みを挙げるに留めれば、トルエン、キシレンもしくは「
ソルベッソＩＯＯＪ （アメリカ国エクソン社製の石
油系溶剤）の如き炭化水素系溶剤；酢酸エチル、酢酸ｎ
−プチルもしくはエチレングリコールモノメチルエーテ
ルアセテートの如きエステル系：アセトン、メチルエチ
ルケトン、メチルイソブチルイソブチルケトン、メチル
アミルケトンもしくはシクロヘキサノンの如きケトン系
：ジメチルホルムアミド、ジメチルアセトアミドもしく
はＮ−メチルピロリドンの如きアミド系；またはメタノ
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、イソプタノール、ｓｅｃ−ブタノ
ール、ｔｅｒ ｔ−ブタノールもしくはエチレングリコ
ールモノアルキルエーテルの如きアルコール系のものが
代表的なものである。Such an organic solvent for polymerization may, of course, be used to add vinyl monomers in the presence of a fluorine-containing copolymer and the desired fluorine-containing vinyl non-aqueous polymer. Copolymers of vinyl monomers coexisting in a mixed state with a fluorine-containing copolymer or in a grafted state obtained by polymerization (
Hereinafter, this will be referred to as a vinyl copolymer. ) can be used as long as it can dissolve it, but to mention only the most representative ones, toluene, xylene or
Hydrocarbon solvents such as Solvesso IOOJ (petroleum solvent manufactured by Exxon, USA); ethyl acetate, acetic acid n
- ester systems such as butyl or ethylene glycol monomethyl ether acetate; ketone systems such as acetone, methyl ethyl ketone, methyl isobutyl isobutyl ketone, methyl amyl ketone or cyclohexanone; amide systems such as dimethylformamide, dimethyl acetamide or N-methylpyrrolidone; or methanol, Alcohols such as ethanol, n-propanol, isopropanol, n-butanol, isoptanol, sec-butanol, tert-butanol or ethylene glycol monoalkyl ether are typical.
かくして得られる含ふっ素共重合体としては、重量平均
分子量が３．０００〜３００ ． ０００なる範囲内に
、とりわけ、５，０００〜２５０．０００なる範囲内に
入るように管理されることが望ましい。The fluorine-containing copolymer thus obtained has a weight average molecular weight of 3.000 to 300. 000, particularly preferably within a range of 5,000 to 250,000.
３．０００未満の場合には、どうしても、皮膜の耐候性
が低下するようになり易く、一方、３００．０００を超
える場合には、どうしても、均一なる皮膜の形或が困難
になり易いためである。If it is less than 3.000, the weather resistance of the film tends to deteriorate, while if it exceeds 300.000, it becomes difficult to form a uniform film. .
次いで、重合用有機溶剤中、含ふっ素共重合体の存在下
に重合させるべきビニル単量体類としては、前掲した含
ふっ素ビニル単量体類に対して共重合可能な他の単量体
類は、いずれも使用しうるが、勿論、この含ふっ素ビニ
ル単量体類もまた、かかるビニル単量体類の一員である
という理由で、同様に使用できる・。Next, as the vinyl monomers to be polymerized in the presence of the fluorine-containing copolymer in the organic solvent for polymerization, other monomers that can be copolymerized with the above-mentioned fluorine-containing vinyl monomers are used. Any of these can be used, but of course, this fluorine-containing vinyl monomer can also be used in the same way because it is a member of such vinyl monomers.
ところで、かかるビニル単量体類を用いるのみで、前述
した含ふっ素共重合体の不存在下において、重合を行な
って得られるビニル共重合体としては、目的含ふっ素ビ
ニル系非水重合体分散液の分散安定性の点からすれば、
ｎ−ヘプタン・トレランスが３００以上となるように管
理されることが望ましい。By the way, the vinyl copolymer obtained by carrying out polymerization using only such vinyl monomers in the absence of the above-mentioned fluorine-containing copolymer can be obtained from the desired fluorine-containing vinyl non-aqueous polymer dispersion. From the point of view of dispersion stability,
It is desirable that the n-heptane tolerance is managed to be 300 or higher.
こうしたｎ−ヘプタン・トレランスを考慮すると、かか
るビニル単量体類としては、含ふっ素ビニル単量体類を
はじめ、０４〜Ｃｌａなるアルキル基を有する脂肪族モ
ノカルボン酸のビニルエステル類、シクロヘキサンカル
ボン酸ビニル、Ｃ３〜ＣＩ８なるアルキル基を有するア
ルキルビニルエーテル類、Ｃ１〜Ｃ．なるアルキル基を
有するシクロアルキルビニルエーテル類、ならびにｎ−
ブチル（メタ）アクリレート、イソブチル（メタ）アク
リレート、２−エチルヘキシル（メタ）アクリレート、
ラウリル（メタ）アクリレートおよびステアリル（メタ
）アクリレートの如きＣ４以上のアルキルアルコールの
（メタ）アクリル酸エステル類よりなる群から選ばれる
少なくとも１種の化合物を主戒分とすることが望ましい
。Considering such n-heptane tolerance, such vinyl monomers include fluorine-containing vinyl monomers, vinyl esters of aliphatic monocarboxylic acids having an alkyl group of 04 to Cla, and cyclohexanecarboxylic acid. vinyl, alkyl vinyl ethers having an alkyl group of C3 to CI8, C1 to C.I. cycloalkyl vinyl ethers having an alkyl group, and n-
Butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
It is desirable that the main component be at least one compound selected from the group consisting of (meth)acrylic acid esters of C4 or higher alkyl alcohols such as lauryl (meth)acrylate and stearyl (meth)acrylate.
かかるビニル単量体類の重合は、前述した含ふっ素共重
合体の調製におけると同様にして、公知慣用の方法で行
なわれるが、本発明において、含ふっ素共重合体とビニ
ル共重合体との存在比率としては、固形分重量比で、９
０／１０〜４０／６０なる範囲内にあることが望ましい
。Polymerization of such vinyl monomers is carried out by a known and commonly used method in the same manner as in the preparation of the fluorine-containing copolymer described above. As for the abundance ratio, the solid content weight ratio is 9
It is desirable that it be within the range of 0/10 to 40/60.
この範囲を超えて、含ふっ素共重合体が余りに多すぎる
場合には、目的含ふっ素ビニル系非水重合体分散液の分
散安定性が低下することになり易く、逆に、余り少なす
ぎる場合には、どうしても、得られる非水重合体分散液
の粘度が高くなり易く、ひいては、塗装作業性が悪くな
るようになるので、いずれの場合も好ましくない。If the amount of the fluorine-containing copolymer exceeds this range and is too large, the dispersion stability of the target fluorine-containing vinyl non-aqueous polymer dispersion tends to decrease; conversely, if it is too small, Either case is unfavorable because the resulting non-aqueous polymer dispersion tends to have a high viscosity, which in turn leads to poor coating workability.
また、本発明の目的重合体分散液、とりわけ、含ふっ素
ビニル系非水重合体分散液を調製するにさいして用いら
れる有機溶剤、つまり、非水分散用溶剤としては、ビニ
ル共重合体の方は溶解するが、含ふっ素共重合体の方は
溶解しないようなものであれば、勿論、いずれも使用で
きるが、得られる重合体分散液の調製のし易さ、あるい
は、分散安定性などの面を考慮して、ヘキサン、ヘプタ
ンもしくはオクタンの如き脂肪族炭化水素類；石油ベン
ジン、石油エーテル、リグロイン、ミネラルスピリット
、石油ナフサもしくはケロシンの如き、沸点が３０〜３
００゜Ｃなる範囲の炭化水素混合物類；またはシクロヘ
キサン、メチルシクロヘキサンもしくはエチルシクロヘ
キサンの如き脂環式炭化水素類などの使用が望ましく、
これらは単独使用でも、２種以上の併用でもよいことは
、勿論である。Furthermore, as the organic solvent used in preparing the object polymer dispersion of the present invention, especially the fluorine-containing non-aqueous vinyl polymer dispersion, that is, as the non-aqueous dispersion solvent, a vinyl copolymer is preferable. Of course, any fluorine-containing copolymer can be used as long as it dissolves while the fluorine-containing copolymer does not, but the ease of preparing the resulting polymer dispersion or the dispersion stability In view of this, aliphatic hydrocarbons such as hexane, heptane or octane; such as petroleum benzene, petroleum ether, ligroin, mineral spirits, petroleum naphtha or kerosene, with a boiling point of 30 to 3
or cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane or ethylcyclohexane;
Of course, these may be used alone or in combination of two or more.
而して、本発明の目的含ふっ素ビニル系非水重合体分散
液を製造するには、たとえば、含ふっ素共重合体の有機
溶剤溶液、つまり、重合用溶剤溶液を仕込んだ反応容器
に、ビニル共重合体を形成するビニル単量体類と、ラジ
カル重合開始剤とを、それぞれ、連続的に、あるいは、
分割して添加するとか、あるいは、含ふっ素共重合体の
重合用溶剤溶液に、ビニル単量体類の一部、および／ま
たは、重合開始剤の一部を仕込んだ反応容器に、残りの
単量体類および開始剤を、それぞれ、連続的に、あるい
は、分割添加するなどの方法によって、溶剤中で、含ふ
っ素共重合体の存在下に、ビニル単量体類を重合せしめ
、次いで、新たな有機溶剤、つまり、上掲した如き非水
分散用溶剤を加えたのち、攪拌下に、先の重合用溶剤の
一部または全部を留去せしめればよい。In order to produce the fluorine-containing vinyl non-aqueous polymer dispersion that is the object of the present invention, for example, a reaction vessel containing a solution of a fluorine-containing copolymer in an organic solvent, that is, a polymerization solvent solution, is charged with vinyl. The vinyl monomers forming the copolymer and the radical polymerization initiator are respectively continuously or
Add the remaining monomers in portions, or add the remaining monomers to a reaction vessel containing a portion of the vinyl monomers and/or a portion of the polymerization initiator to a polymerization solvent solution of the fluorine-containing copolymer. The vinyl monomers are polymerized in the presence of the fluorine-containing copolymer in a solvent by adding polymers and an initiator continuously or in portions, respectively, and then the vinyl monomers are newly added. After adding an organic solvent, that is, a non-aqueous dispersion solvent such as those listed above, part or all of the polymerization solvent may be distilled off while stirring.
さらには、必要に応じて、分散安定性を向上せしめるべ
く、ｎ−ヘプタン・トレランスが３００以上なる重合体
を、含ふっ素共重合体と共に、重合用有機溶剤中に併存
させた状態で、ビニル単量体類を重合せしめるという方
法もまた、採用しうる。Furthermore, in order to improve dispersion stability, if necessary, a polymer having an n-heptane tolerance of 300 or more may be co-existed with a fluorine-containing copolymer in an organic solvent for polymerization, and a vinyl monomer may be added. A method of polymerizing polymers can also be employed.
かかる重合体として特に代表的なもののみを挙げるに留
めれば、アクリル樹脂、アルキド樹脂もしくはアルキル
エーテル化メラミン樹脂、または１２−ヒドロキシステ
アリン酸の如き水酸基含有飽和脂肪酸の自己縮台型ポリ
エステル樹脂などである。Typical examples of such polymers include acrylic resins, alkyd resins, alkyl etherified melamine resins, and self-condensing polyester resins of hydroxyl group-containing saturated fatty acids such as 12-hydroxystearic acid. be.
このさいに用いられるラジカル重合開始剤としては、勿
論、公知慣用のものが挙げられるが、そのうちでも特に
代表的なもののみを例示するに留めれば、アブビスイソ
ブチロニトリルもしくはアゾビスイソバレロニトリルの
如きアブ化合物；またはｔｅｒｔ−プチルバーオキシビ
パレート、ｔｅｒｔ−プチルバーオキシベンゾエート、
ｔｅｒｔ−プチルバーオキシ−２−エチルヘキサノエー
ト、ペンゾイルバーオキサイド、ラウロイルパーオキサ
イド、アセチルバーオキサイド、ジーｔｅｒ ｔ−ブチ
ルパーオキサイド、ジクミルパーオキサイド、クメンハ
イドロパーオキサイド、メチルエチルケトンパーオキサ
イドもしくはジイソブロピルパーオキシヵーボネートの
如き過酸化物などである。As the radical polymerization initiator used in this case, of course, known and commonly used ones can be mentioned, but among them, to exemplify only the most representative ones, abbisisobutyronitrile and azobisisovaleronitrile are mentioned. Ab compounds such as nitriles; or tert-butyl baroxybiparate, tert-butyl baroxybenzoate,
tert-butyl peroxide, 2-ethylhexanoate, penzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxide and peroxides such as oxycarbonates.
かかるラジカル重合開始剤の使用量は、重合開始剤の種
類、重合温度、共重合体の分子量などに応じて、適宜、
決定されるが、概ね、共重合せしめる単量体総量の０．
０１〜ＩＯ重量％程度でよい。The amount of the radical polymerization initiator to be used depends on the type of polymerization initiator, polymerization temperature, molecular weight of the copolymer, etc.
However, it is generally determined that the total amount of monomers to be copolymerized is 0.
It may be about 0.01 to IO% by weight.
また、かかる重合にさいしては、ラウリルメルカブタン
、オクチルメル力ブタン、２一メルヵプトエタノールま
たはα−メチルスチレン・ダイマーなどの連鎖移動剤を
用いて分子量を調節できる。In addition, during such polymerization, the molecular weight can be controlled using a chain transfer agent such as lauryl mercabutane, octyl mercaptoethanol, 2-mercaptoethanol or α-methylstyrene dimer.
かくして得られる含ふっ素ビニル系非水重合体分散液は
、そのままで使用することもできるが、使用目的に応じ
て、さらに、硬化剤、各種の樹脂類、または着色剤など
の各種の添加剤戒分を混合し配合した形で用いることも
できる。The thus obtained fluorine-containing non-aqueous vinyl polymer dispersion can be used as it is, but depending on the purpose of use, it may be added with various additives such as curing agents, various resins, or colorants. It can also be used in a mixed form.
かかる着色剤としては、染料、有ａ＃料、無機顔料また
は金属顔料などが挙げられるし、樹脂類としては、アク
リル樹脂、含ふっ素ビニル樹脂、ニトロセルロースもし
くはセルロースアセテートブチレートの如き繊維素系樹
脂、塩化ビニル・酢酸ビニル共重合樹脂、石油樹脂、ケ
トン樹脂、オイルフリーアルキド樹脂またはエボキシ樹
脂などが挙げられるし、硬化剤としては、アミノ樹脂（
アミノプラスト）、エボキシ樹脂またはポリイソシアネ
ート樹脂などである。Examples of such coloring agents include dyes, alkaline pigments, inorganic pigments, and metal pigments, and examples of resins include cellulose resins such as acrylic resins, fluorine-containing vinyl resins, nitrocellulose, and cellulose acetate butyrate. , vinyl chloride/vinyl acetate copolymer resin, petroleum resin, ketone resin, oil-free alkyd resin, or epoxy resin, and as a curing agent, amino resin (
aminoplast), epoxy resin or polyisocyanate resin.
このようにして得られる本発明の含ふっ素ビニル系非水
重合体分散液は、耐候性にすぐれる皮膜を与えるだけで
なく、旧塗膜や下塗り塗膜を何ら膨潤し溶解させること
もなく、しかも、塗装不揮発分が高い処から、すぐれた
塗装作業性をも有するものである．
とりわけ、旧塗膜や下塗り塗膜などの膨潤、溶解からの
解放と、高塗装不揮発分一塗装作業性の改善とは、本発
明方法における、転相分散ないしは転相分散法という斬
新にして、かつ、有効なる手段の駆使が、もたらす効果
であり、かかる手段の駆使がもたらす一大戒果である．
次に、本発明を参考例、実施例、比較例、応用例および
比較例により、一層、具体的に説明する。The fluorine-containing non-aqueous vinyl polymer dispersion of the present invention obtained in this manner not only provides a film with excellent weather resistance, but also does not swell or dissolve the old paint film or undercoat film. Moreover, it has excellent coating workability due to its high coating non-volatile content. In particular, the release of old paint films and undercoat paint films from swelling and dissolution, and the improvement of high paint non-volatile fraction and painting workability are achieved by using the novel phase inversion dispersion method or phase inversion dispersion method in the method of the present invention. Moreover, it is the effect that can be brought about by making full use of effective means, and the great precept that comes from making full use of such means. Next, the present invention will be explained in more detail using reference examples, examples, comparative examples, applied examples, and comparative examples.
以下において、部および％は特に断わりのない限り、す
べて重量基準であるものとする。In the following, all parts and percentages are based on weight unless otherwise specified.
参考例１（含ふっ素共重合体の調製例）窒素ガスで充分
に置換された、１ｌのステンレス製オートクレープに、
エチルビニルエーテルの１００部、「ベオバ９」 （オ
ランダ国シェル社製の、Ｃ８なるアルキル基を有する分
岐脂肪酸のビニルエステル）の１００部、４−ヒドロキ
シブチルビニルエーテルの５０部、メチルエチルケトン
の２００部、ｔｅｒｔ−プチルパーオキシオクトエート
の５部、アゾビスイソバレロニトリルの５部および１．
２．２．６．６−ペンタメチルピペリジンの１．５部を
仕込んだ。Reference Example 1 (Preparation example of fluorine-containing copolymer) In a 1 liter stainless steel autoclave that was sufficiently purged with nitrogen gas,
100 parts of ethyl vinyl ether, 100 parts of "Beoba 9" (vinyl ester of a branched fatty acid having an alkyl group called C8, manufactured by Shell in the Netherlands), 50 parts of 4-hydroxybutyl vinyl ether, 200 parts of methyl ethyl ketone, tert- 5 parts of butyl peroxyoctoate, 5 parts of azobisisovaleronitrile and 1.
2.2.6.1.5 parts of 6-pentamethylpiperidine was charged.
次いで、液化採取したクロロトリフルオロエチレンの２
００部および、ヘキサフルオ口プロピレンの５０部を圧
入し、攪拌しながら６０℃で、■５時間のあいだ反応さ
せてから、無水メタクリル酸の２部およびメチルエチル
ケトンの３００部を加えて、さらに２時間反応させて、
目的共重合体の溶液を得た。このものの重量平均分子量
は５０，０００で、ふっ素原子含有率は２２％で、かつ
、ｎ−ヘプタン・トレランスは５０であった。Then, 2 of the liquefied and collected chlorotrifluoroethylene
00 parts of methacrylic anhydride and 50 parts of hexafluoropropylene were introduced under pressure and allowed to react at 60°C for 5 hours with stirring, then 2 parts of methacrylic anhydride and 300 parts of methyl ethyl ketone were added and the reaction was continued for another 2 hours. Let me,
A solution of the desired copolymer was obtained. The weight average molecular weight of this product was 50,000, the fluorine atom content was 22%, and the n-heptane tolerance was 50.
参考例２（同上）
参考例１と同様の反応容器に、エチルビニルエーテルの
８０部、酢酸ビニルの１２５部、シクロヘキシルビニル
エーテルの８５部、クロトン酸の１０部、ｔｅｒｔ−プ
チルパーオキシオクトエートの５部、アゾビスイソバレ
ロニトリルの５部、１．２．２，６．６−ペンタメチル
ピペリジンの１．５部および酢酸エチルの２００部を仕
込んだ．次いで、液化採取したクロロトリフルオロエチ
レンの２００部を圧入し、攪拌下に６０゜Ｃで、１５時
間反応させ、しかるのち、酢酸エチルの３００部、アリ
ルグリシジルエーテルの３部およびトリフエニルホスフ
ィンの０．５部を添加し、１１５゜Ｃまで昇温し、同温
度に３時間のあいだ保持して、このアリルグリシジルエ
ーテルの付加反応を行なった．
かくして、不揮発分が５０％なる目的共重合体の溶液が
得られたが、このものの重量平均分子量は６８．０００
で、ふっ素原子含有率は１９％で、かつ、ｎ−ヘプタン
・トレランスは７０であった。Reference Example 2 (same as above) In a reaction vessel similar to Reference Example 1, 80 parts of ethyl vinyl ether, 125 parts of vinyl acetate, 85 parts of cyclohexyl vinyl ether, 10 parts of crotonic acid, and 5 parts of tert-butyl peroxyoctoate were added. , 5 parts of azobisisovaleronitrile, 1.5 parts of 1.2.2,6.6-pentamethylpiperidine, and 200 parts of ethyl acetate. Next, 200 parts of the liquefied chlorotrifluoroethylene was introduced under pressure and reacted at 60°C for 15 hours with stirring, followed by 300 parts of ethyl acetate, 3 parts of allyl glycidyl ether, and 0.0 parts of triphenylphosphine. .5 parts were added, the temperature was raised to 115°C, and the temperature was maintained for 3 hours to carry out the addition reaction of this allyl glycidyl ether. In this way, a solution of the desired copolymer with a nonvolatile content of 50% was obtained, and the weight average molecular weight of this solution was 68.000.
The fluorine atom content was 19%, and the n-heptane tolerance was 70.
参考例３（ビニル共重合体の調製例）
攪拌機、温度計および窒素ガス導入口を備えた四ツロフ
ラスコに、メチルエチルケトンの２００部を仕込み、７
５゜Ｃに昇温し、この温度で、ｎ−プチルメタクリレー
トの９０部、２−エチルへキシルメタクリレートの１０
０部、β−ヒドロキシプロビルメタクリレートのｌＯ部
、ｔｅｒｔ−プチルパーオクトエートの０．８部および
アゾビ・スイソブチロニトリルの０．８部からなる混合
物を、４時間かけて滴下したのち、同温度に約１５時間
のあいだ保持して反応を続行させ、不揮発分が５０％な
る目的共重合体の溶液を得た。このもののｎ−ヘプタン
・トレランスは１．０００であった。Reference Example 3 (Example of Preparation of Vinyl Copolymer) 200 parts of methyl ethyl ketone was charged into a four-way flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet, and 7
The temperature was raised to 5°C, and at this temperature, 90 parts of n-butyl methacrylate and 10 parts of 2-ethylhexyl methacrylate were added.
A mixture of 0 parts of β-hydroxypropyl methacrylate, 0.8 parts of tert-butyl peroctoate, and 0.8 parts of azobisisobutyronitrile was added dropwise over 4 hours, and then The reaction was continued by maintaining the temperature for about 15 hours to obtain a solution of the desired copolymer with a non-volatile content of 50%. The n-heptane tolerance of this product was 1.000.
参考例４（同上〉
窒素で充分に置換された、１ｌのステンレス製オートク
レープに、エチルビニルエーテルのｌｏ０部、「ベオバ
９」の２５０部、酢酸エチルの２００部、ｔｅｒ ｔ−
プチルパーオクトエートの５部およびアゾビスイソバレ
ロニトリルの５部を仕込んだ。Reference Example 4 (same as above) In a 1-liter stainless steel autoclave that was sufficiently purged with nitrogen, 0 parts of ethyl vinyl ether, 250 parts of "Beoba 9", 200 parts of ethyl acetate, and tert-
5 parts of butyl peroctoate and 5 parts of azobisisovaleronitrile were charged.
次いで、液化採取したクロロトリフルオロエチレンの１
５０部を圧入し、攪拌しなから６０゜Ｃでｌ５時間反応
させ目的共重合体の溶液を得た。このもののｎ−ヘプタ
ン・トレランスはＬ ５ ０ ０であった。Next, 1 of the liquefied and collected chlorotrifluoroethylene
50 parts of the copolymer was introduced under pressure and reacted at 60° C. for 15 hours without stirring to obtain a solution of the desired copolymer. The n-heptane tolerance of this product was L500.
実施例１
参考例３と同様の反応容器に、参考例１で得られた含ふ
っ素共重合体溶液の６００部とメチルエチルケトンの２
００部とを仕込んで７５゜Ｃに昇温したのち、既に、参
考例３において、ｎ−ヘプタン・トレランスが３００以
上であることが確認済みとなっているビニル共重合体（
Ｂ）それ自体の調製にさいして用いられた、それぞれ、
ビニル単量体類および重合開始剤をそのまま、すなわち
、同一組威の混合物、つまり、
ｎ−プチルメタクリレート ９０ 部２
−エチルへキシルメタクリレート １００〃β−ヒド
ロキシプ口ピルメタクリレート１０〃ｔｅｒｔ−プチル
パーオキシオクトエート ０．８〃およびアブビスイ
ソブチロニトリル ０．８ ノ／からなる混合物を
、４時間かけて滴下し、滴下終了後も、同温度に１５時
間のあいだ保持して反応を続行させた。Example 1 In a reaction vessel similar to Reference Example 3, 600 parts of the fluorine-containing copolymer solution obtained in Reference Example 1 and 2 parts of methyl ethyl ketone were added.
After charging 00 parts and raising the temperature to 75°C, the vinyl copolymer (which has already been confirmed to have an n-heptane tolerance of 300 or more in Reference Example 3) was prepared.
B) used in its own preparation, respectively;
Vinyl monomers and polymerization initiator as is, i.e., a mixture of the same composition, i.e., n-butyl methacrylate 90 parts 2
A mixture consisting of -ethylhexyl methacrylate 100 β-hydroxybutyl methacrylate 10 tert-butyl peroxyoctoate 0.8 and abbisisobutyronitrile 0.8 was added dropwise over 4 hours. Even after the dropwise addition was completed, the reaction was continued by maintaining the same temperature for 15 hours.
次いで、８０″Ｃに昇温しで、攪拌しながら、減圧下に
メチルエチルケトンの３００部を留去した。Next, the temperature was raised to 80''C, and 300 parts of methyl ethyl ketone was distilled off under reduced pressure while stirring.
しかるのち、「アイソパー ＥＪ （アメリカ国エク
ソン社製の石油系溶剤）の３３０部を仕込んでから、攪
拌しつつ、８０゜Ｃでメチルエチルケトンの２００部を
、減圧下に留去せしめた。Thereafter, 330 parts of Isopar EJ (a petroleum solvent manufactured by Exxon, USA) was charged, and 200 parts of methyl ethyl ketone was distilled off under reduced pressure at 80°C while stirring.
かくして得られた含ふっ素ビニル系非水重合体分散液は
、以下、これをＮＡＤ−１と略記するが、このものは不
揮発分が６０％で、かつ、２５゛Ｃにおけるガードナー
粘度（以下同様）がＤなる、何ら、ブロックの生成の無
い、分散性の良好なものであった。The thus obtained fluorine-containing vinyl non-aqueous polymer dispersion, hereinafter abbreviated as NAD-1, has a non-volatile content of 60% and a Gardner viscosity at 25°C (the same applies hereinafter). was D, indicating that no blocks were generated and the dispersibility was good.
実施例２
窒素ガスで充分に置換された、２２のステンレス製オー
トクレープに、参考例２で得られた含ふっ素共重合体溶
液の７３０部を仕込み、さらに、参考例４において、既
に、ｎ−ヘプタン・トレランスが３００以上であること
が確認済のビニル共重合（Ｂ）の調製にさいして用いら
れたと同様の、それぞれ、含ふっ素ビニル単量体類、ビ
ニル単量体類、溶剤および重合開始剤の混合物をそのま
ま、すなわち、同一組成の混合物、つまり、エチルビニ
ルエーテル
「ベオバ ９」
酢酸エチル
ｔｅｒ ｔ−プチルバーオキシオクトエートおよびアゾ
ビスイソバレロニトリル
よりなる混合物を仕込んだ。Example 2 730 parts of the fluorine-containing copolymer solution obtained in Reference Example 2 was charged into 22 stainless steel autoclaves that had been sufficiently purged with nitrogen gas. The same fluorine-containing vinyl monomers, vinyl monomers, solvent, and polymerization initiator as used in the preparation of vinyl copolymerization (B), which has been confirmed to have a heptane tolerance of 300 or more, respectively. The mixture of agents was charged as such, ie, a mixture of the same composition, ie, a mixture consisting of ethyl vinyl ether "Beova 9", ethyl acetate tert-butylbaroxyoctoate and azobisisovaleronitrile.
次いで、液化採取したクロロトリフルオロエチレンの４
５部を圧人して６０゜Ｃに昇温して重合反応を開始させ
、攪拌しつつ、この温度にｌ５時間のあいだ保持して反
応を続行させた。Then, 4 of the liquefied and collected chlorotrifluoroethylene
5 parts were heated under pressure to 60°C to initiate the polymerization reaction, and this temperature was maintained for 15 hours with stirring to continue the reaction.
しかるのち、攪拌し続けながら、酢酸エチルの２００部
を留去してから、「ロウス（ＬＡＷＳ）Ｊ３０部
７５ 〃
６０〃
１．５〃
１．５〃
（オランダ国シェル社製の石油系溶剤）の３００部を加
え、次いで、攪拌しつつ、６０゜Ｃで酢酸エチルを主或
分とする溶剤の１７０部を、減圧下に、留去せしめた処
、不揮発分が６０％で、かつ、粘度がＣなる、何らのブ
ロックの生或も認められない、分散性の良好な含ふっ素
ビニル系非水重合体水分液が得られた。以下、これをＮ
ＡＤ−２と略記する。Then, while stirring continuously, 200 parts of ethyl acetate was distilled off, and then "LAWS J30 parts 75 60 1.5 1.5 (petroleum solvent manufactured by Shell, Netherlands) Then, while stirring, 170 parts of a solvent mainly composed of ethyl acetate was distilled off under reduced pressure at 60°C. A fluorine-containing vinyl non-aqueous polymer aqueous liquid with good dispersibility, in which no block formation or block formation was observed, was obtained.
It is abbreviated as AD-2.
比較例ｌ
参考例３と同様の反応容器に、「ルξフロンＬＦ−２０
０Ｊ（旭硝子（株）製の含ふっ素共重合体；ふっ素原子
含有率−２５％〕の２１６部、ｎ−ヘプタンの２０４部
および酢酸ｎ−ブチルの１６部を仕込んで８０゜Ｃまで
昇温し、メチルメタクリレートの８０部、メチルアクリ
レートの９０部、β−ヒドロエチルメタクリレートの３
０部およびｔｅｒｔ−プチルパーオキシ−２−エチルヘ
キサノエートの３部からなる混合物を、３時間かけて滴
下し、滴下終了後も、同温度に２時間のあいだ保持して
熟成し、４０部の酢酸エチルを加えた。Comparative Example 1 In a reaction vessel similar to Reference Example 3,
216 parts of 0J (fluorine-containing copolymer manufactured by Asahi Glass Co., Ltd.; fluorine atom content -25%), 204 parts of n-heptane, and 16 parts of n-butyl acetate were charged and heated to 80°C. , 80 parts of methyl methacrylate, 90 parts of methyl acrylate, 3 parts of β-hydroethyl methacrylate
A mixture consisting of 0 parts and 3 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 3 hours, and even after the addition was completed, the mixture was kept at the same temperature for 2 hours to ripen, resulting in 40 parts. of ethyl acetate was added.
得られた対照用の非水重合体分散液は、不揮発分が５０
％で、かつ、粘度がＤであった。以下、これをＮＡＤ−
３と略記する。The control non-aqueous polymer dispersion obtained had a non-volatile content of 50
% and the viscosity was D. Below, this is NAD-
It is abbreviated as 3.
応用例１および２ならびに比較応用例ｌおよび２各実施
例および比較例で得られた含ふっ素ビニル系非水重合体
分散液と、「フルオネー｝ Ｋ−７００Ｊ Ｃ大日
本インキ化学工業（株）製の含ふっ素共重合体〕および
「コロネー｝ＥＨＪ（日本ポリウレタン工業（株）製の
ポリイソシアネート化合物〕とを用いて、第１表に示さ
れるような配合比率に従って、クリヤー塗料を調製した
。Application Examples 1 and 2 and Comparative Application Examples 1 and 2 The fluorine-containing vinyl non-aqueous polymer dispersion obtained in each Example and Comparative Example and "Fluoney" K-700J C manufactured by Dainippon Ink and Chemicals Co., Ltd. A clear paint was prepared using a fluorine-containing copolymer] and Coronet EHJ (a polyisocyanate compound manufactured by Nippon Polyurethane Industries, Ltd.) according to the blending ratios shown in Table 1.
次いで、下塗りとして、中油アルキド樹脂とルチル型酸
化チタンとから調製されたアルキド樹脂系白色塗料を、
予め、塗装しておいた厚さが０．８鵬なる燐酸亜鉛処理
鋼板上に、それぞれのクリヤー塗料を、各別に、エアー
スプレーにより塗装し、室温に７日間のあいだ放置して
乾燥せしめて、各種の硬化塗膜を得た。Next, as an undercoat, an alkyd resin-based white paint prepared from a medium-oil alkyd resin and rutile-type titanium oxide was applied.
Each clear paint was applied separately by air spray onto a pre-coated zinc phosphate-treated steel plate with a thickness of 0.8 mm, and left to dry at room temperature for 7 days. Various cured coating films were obtained.
これらのそれぞれの塗膜について、“ちぢみやふくれ゜
゛などの、いわゆる塗面の状態を目視により評価判定す
ると共に、こうした塗面外観に何らの異常もなかった塗
膜については、さらに、サンシャインウエザオメーター
により、３．０００時間の曝露を行なって、光沢の変化
、つまり、光沢保持率をも比較検討した。For each of these coatings, we visually evaluate the so-called condition of the coating surface, such as "shrinking or blistering," and if there are no abnormalities in the appearance of the coating surface, we further test it with Sunshine Weather. Exposure was performed for 3,000 hours using a meter, and changes in gloss, that is, gloss retention, were also compared and examined.
それらの結果は、まとめて、同表に示す。The results are summarized in the same table.
／
／
／−］
／
第１表からも明らかなように、本発明の含ふっ素ビニル
系非水重合体分散液は、耐候性にすぐれる皮膜を与える
だけでなく、旧塗膜や下塗り塗膜を何ら膨潤し溶解させ
ることもなく、しかも、塗装不揮発分が高い処から、す
ぐれた塗装作業性をも有するものであることも知れる。/ / /-] / As is clear from Table 1, the fluorine-containing vinyl non-aqueous polymer dispersion of the present invention not only provides a film with excellent weather resistance, but also provides a coating that is durable against old paint and undercoat. It is also known that it has excellent coating workability because it does not cause any swelling or dissolution, and has a high coating nonvolatile content.
代 理 人teenager Reason Man
Claims (1)
させ、転相分散せしめて得られる、含ふっ素ビニル系非
水重合体分散液。 ２、前記した含ふっ素共重合体が、５〜６０重量％なる
、ふっ素原子含有率を有し、かつ、３，０００〜３００
，０００なる重量平均分子量を有するものである、請求
項１に記載の含ふっ素ビニル系非水重合体分散液。 ３、まず、重合用有機溶剤中、含ふっ素共重合体の存在
下において、ビニル単量体類を重合させ、次いで、この
含ふっ素共重合体の使用を欠き、このビニル単量体類の
みを用いて得られるビニル共重合体は溶解するが、先の
含ふっ素共重合体は溶解しない、新たな有機溶剤を加え
て、上記重合用有機溶剤の一部または全部を除去せしめ
ることを特徴とする、含ふっ素ビニル系非水重合体分散
液の製造方法。 ４、まず、生成共重合体の固形分にｎ−ヘプタンを滴下
して行って、この共重合体が白濁するまでに要するｎ−
ヘプタン量（ミリリットル）を、この測定のために採取
した、該共重合体の固形分量（グラム）で除して１００
倍した値を以て定義される“ｎ−ヘプタンに対する溶解
度”が２００以下なる含ふっ素共重合体の存在下に、こ
の含ふっ素共重合体の使用を欠き、ビニル単量体類のみ
を用いて得られるビニル共重合体のｎ−ヘプタンに対す
る溶解度が３００以上となるこのビニル単量体類を重合
せしめ、次いで、上記含ふっ素共重合体の使用を欠き、
該ビニル単量体類のみを用いて得られるビニル共重合体
は溶解するが、先の含ふっ素共重合体は溶解しない、新
たな有機溶剤を加えて、上記重合用有機溶剤の一部また
は全部を除去せしめることを特徴とする、含ふっ素ビニ
ル系非水重合体分散液の製造方法。 ５、前記した含ふっ素共重合体が、５〜６０重量％なる
、ふっ素原子含有率を有し、かつ、３，０００〜３００
，０００なる重量平均分子量を有するものである、請求
項３または４に記載の含ふっ素ビニル系非水重合体分散
液の製造方法。 ６、前記した含ふっ素共重合体が、ふっ化ビニリデン、
クロロトリフルオロエチレン、テトラフルオロエチレン
および、ヘキサフルオロプロピレンよりなる群から選ば
れる少なくとも一種の含ふっ素ビニル単量体類と、他の
共重合可能なビニル単量体類との共重合体である、請求
項３または４に記載の含ふっ素ビニル系非水重合体分散
液の製造方法。[Claims] 1. A fluorine-containing non-aqueous vinyl polymer dispersion obtained by polymerizing vinyl monomers in the presence of a fluorine-containing copolymer and performing phase inversion dispersion. 2. The fluorine-containing copolymer described above has a fluorine atom content of 5 to 60% by weight, and 3,000 to 300% by weight.
2. The fluorine-containing vinyl non-aqueous polymer dispersion according to claim 1, which has a weight average molecular weight of ,000. 3. First, vinyl monomers are polymerized in an organic solvent for polymerization in the presence of a fluorine-containing copolymer, and then the fluorine-containing copolymer is omitted and only the vinyl monomers are used. The resulting vinyl copolymer is dissolved, but the fluorine-containing copolymer is not dissolved, and a new organic solvent is added to remove part or all of the organic solvent for polymerization. , a method for producing a fluorine-containing vinyl nonaqueous polymer dispersion. 4. First, add n-heptane dropwise to the solid content of the produced copolymer to measure the amount of n-heptane required for the copolymer to become cloudy.
The amount of heptane (in milliliters) divided by the amount of solids (in grams) of the copolymer sampled for this measurement is 100.
In the presence of a fluorine-containing copolymer that has a "solubility in n-heptane" of 200 or less, which is defined as the value multiplied by the value, it is obtained by omitting the use of this fluorine-containing copolymer and using only vinyl monomers. Polymerizing these vinyl monomers so that the vinyl copolymer has a solubility in n-heptane of 300 or more, then omitting the use of the fluorine-containing copolymer,
The vinyl copolymer obtained using only the vinyl monomers dissolves, but the fluorine-containing copolymer does not dissolve. Adding a new organic solvent, some or all of the above organic solvent for polymerization is added. 1. A method for producing a fluorine-containing non-aqueous vinyl polymer dispersion, the method comprising: removing . 5. The fluorine-containing copolymer described above has a fluorine atom content of 5 to 60% by weight, and 3,000 to 300% by weight.
5. The method for producing a fluorine-containing non-aqueous vinyl polymer dispersion according to claim 3, wherein the dispersion has a weight average molecular weight of ,000. 6. The above-mentioned fluorine-containing copolymer is vinylidene fluoride,
A copolymer of at least one fluorine-containing vinyl monomer selected from the group consisting of chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene and other copolymerizable vinyl monomers, The method for producing a fluorine-containing non-aqueous vinyl polymer dispersion according to claim 3 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30524889A JP2893766B2 (en) | 1989-11-24 | 1989-11-24 | Method for producing fluorovinyl nonaqueous polymer dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30524889A JP2893766B2 (en) | 1989-11-24 | 1989-11-24 | Method for producing fluorovinyl nonaqueous polymer dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03166231A true JPH03166231A (en) | 1991-07-18 |
| JP2893766B2 JP2893766B2 (en) | 1999-05-24 |
Family
ID=17942818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30524889A Expired - Fee Related JP2893766B2 (en) | 1989-11-24 | 1989-11-24 | Method for producing fluorovinyl nonaqueous polymer dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2893766B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006080259A1 (en) * | 2005-01-27 | 2006-08-03 | Kureha Corporation | Vinylidene fluoride based core-shell type polymer and use thereof in nonaqueous electrochemical device |
| CN115260375A (en) * | 2022-08-19 | 2022-11-01 | 江西中氟化学材料科技股份有限公司 | Environment-friendly fluorine-containing copolymer and preparation method thereof |
| CN115449007A (en) * | 2022-08-19 | 2022-12-09 | 江西中氟化学材料科技股份有限公司 | Fluorine-containing copolymer and preparation method thereof |
-
1989
- 1989-11-24 JP JP30524889A patent/JP2893766B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006080259A1 (en) * | 2005-01-27 | 2006-08-03 | Kureha Corporation | Vinylidene fluoride based core-shell type polymer and use thereof in nonaqueous electrochemical device |
| US7851084B2 (en) * | 2005-01-27 | 2010-12-14 | Kureha Corporation | Vinylidene fluoride based core-shell type polymer and use thereof in nonaqueous electrochemical device |
| CN115260375A (en) * | 2022-08-19 | 2022-11-01 | 江西中氟化学材料科技股份有限公司 | Environment-friendly fluorine-containing copolymer and preparation method thereof |
| CN115449007A (en) * | 2022-08-19 | 2022-12-09 | 江西中氟化学材料科技股份有限公司 | Fluorine-containing copolymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2893766B2 (en) | 1999-05-24 |
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