JPH03263474A - Fluorine-based polymer composition for coating material - Google Patents
Fluorine-based polymer composition for coating materialInfo
- Publication number
- JPH03263474A JPH03263474A JP6112590A JP6112590A JPH03263474A JP H03263474 A JPH03263474 A JP H03263474A JP 6112590 A JP6112590 A JP 6112590A JP 6112590 A JP6112590 A JP 6112590A JP H03263474 A JPH03263474 A JP H03263474A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- group
- copolymer
- compound
- 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.)
- Pending
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 43
- 239000011737 fluorine Substances 0.000 title claims abstract description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title abstract description 27
- 229920000642 polymer Polymers 0.000 title abstract description 20
- 239000011248 coating agent Substances 0.000 title abstract description 16
- 238000000576 coating method Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 title abstract 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 53
- -1 vinyl compound Chemical class 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 239000002516 radical scavenger Substances 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 239000003054 catalyst Substances 0.000 abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- 150000003377 silicon compounds Chemical class 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 abstract description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003606 tin compounds Chemical class 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000758 substrate Substances 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- 229920002313 fluoropolymer Polymers 0.000 description 14
- 239000004811 fluoropolymer Substances 0.000 description 14
- 239000008096 xylene Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 9
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical compound CCCCCOC=C IOSXLUZXMXORMX-UHFFFAOYSA-N 0.000 description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound 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
- 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 2
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- DASQIKOOFDJYKA-UHFFFAOYSA-N CCIF Chemical compound CCIF DASQIKOOFDJYKA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013142 basic testing Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000003544 oxime group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- XMJQCVMNFPEJLN-UHFFFAOYSA-N 1-ethenoxy-4-methylpentane Chemical compound CC(C)CCCOC=C XMJQCVMNFPEJLN-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
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- IUGFLBOXRUKMEN-UHFFFAOYSA-N 2-hept-6-enyloxirane Chemical compound C=CCCCCCC1CO1 IUGFLBOXRUKMEN-UHFFFAOYSA-N 0.000 description 1
- FCZHJHKCOZGQJZ-UHFFFAOYSA-N 2-oct-7-enyloxirane Chemical compound C=CCCCCCCC1CO1 FCZHJHKCOZGQJZ-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 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
- 229910014265 BrCl Inorganic materials 0.000 description 1
- 229910014813 CaC2 Inorganic materials 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical group [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CBWUNQZJGJFJLZ-UHFFFAOYSA-N [Cl].Cl Chemical compound [Cl].Cl CBWUNQZJGJFJLZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HJVKTYVDOZVQPA-UHFFFAOYSA-N ethenoxycyclopentane Chemical compound C=COC1CCCC1 HJVKTYVDOZVQPA-UHFFFAOYSA-N 0.000 description 1
- YOZWCVVCWGZSSF-UHFFFAOYSA-N ethenyl(ethyl)silicon Chemical compound CC[Si]C=C YOZWCVVCWGZSSF-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
- IJNRGJJYCUCFHY-UHFFFAOYSA-N ethenyl-dimethoxy-phenylsilane Chemical compound CO[Si](OC)(C=C)C1=CC=CC=C1 IJNRGJJYCUCFHY-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
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 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
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (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、耐候性、耐薬品性、耐水性、撥水性等に優れ
た塗膜を形成する塗料用フッ素系重合体組成物に関する
ものであり、有機溶剤に溶解し。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a fluoropolymer composition for paint that forms a coating film with excellent weather resistance, chemical resistance, water resistance, water repellency, etc. Yes, soluble in organic solvents.
常温で速やかに硬化させることができ、さらに詳しくは
基材との密着性に優れた塗膜を形成し得る塗料用フッ素
共重合体組成物に関する。The present invention relates to a fluorine copolymer composition for paints that can be rapidly cured at room temperature and, more particularly, can form a coating film with excellent adhesion to a substrate.
(従来技術及び発明が解決しようとする問題点)建築物
、車両、船舶、航空機等の外装分野には、耐候性、耐水
性、撥水性の優れた塗料が要求され、ポリエステル系ま
たはアクリル系の高級外装塗料が利用されている。しか
しながら上述の高級塗料でさえ屋外耐用年数は短く数年
で美観と基材保護作用を失う。(Prior art and problems to be solved by the invention) Paints with excellent weather resistance, water resistance, and water repellency are required for the exterior of buildings, vehicles, ships, aircraft, etc., and polyester-based or acrylic-based paints are required. High-quality exterior paint is used. However, even the above-mentioned high-quality paints have a short outdoor service life and lose their beauty and substrate protection effect within a few years.
一方、含フッ素共重合体は耐候性、耐水性、耐薬品性、
撥水性、低摩擦性等に優れ、高機能塗料3−
4−
への応用が期待されている。しかしながら含フッ素重合
体は、溶剤に溶解し難く、また基材に対する付着性が悪
いという問題が見られる。これらの問題点を解決した含
フッ素重合体は既に提案され、特公昭60−21686
号に開示されている。しかしながら、この共重合体を常
温硬化させるには。On the other hand, fluorine-containing copolymers have weather resistance, water resistance, chemical resistance,
It has excellent water repellency and low friction properties, and is expected to be applied to high-performance paints. However, fluorine-containing polymers have problems in that they are difficult to dissolve in solvents and have poor adhesion to substrates. Fluorine-containing polymers that solved these problems have already been proposed and published in Japanese Patent Publication No. 60-21686
Disclosed in the issue. However, to cure this copolymer at room temperature.
メラミン系硬化剤や尿素樹脂系硬化剤が必要であって、
その分だけ耐候性が劣るという問題点かある。A melamine-based hardening agent or a urea resin-based hardening agent is required.
The problem is that the weather resistance is correspondingly inferior.
また本願出願人は、超耐候性塗料用樹脂として、加水分
解性基と結合した珪素基を硬化部として用いる含フッ素
共重合体を開発すべく検討を重ねた結果、フルオロオレ
フィン、ビニルエーテル及び特定の有機珪素化合物とか
らなるフッ素系3元共重合体が、硬化触媒以外の硬化成
分を必要とすることなく常温硬化することを見い出し、
既に提案した(特開昭61−1.41713号)。In addition, as a result of repeated studies to develop a fluorine-containing copolymer that uses a silicon group bonded to a hydrolyzable group as a curing moiety as a resin for ultra-weather-resistant paints, the applicant found that fluoroolefins, vinyl ethers, and specific We have discovered that a fluorine-based ternary copolymer consisting of an organosilicon compound can be cured at room temperature without requiring any curing components other than a curing catalyst,
This has already been proposed (Japanese Unexamined Patent Publication No. 61-1.41713).
しかし、このフッ素系重合体を用いた塗料も基材に対す
る塗膜付着性が不十分であった。However, paints using this fluoropolymer also had insufficient film adhesion to substrates.
よって、本発明の目的は、上記のような問題点を解決し
ようとするものであって、耐候性、耐水性、耐薬品性、
撥水性、低摩擦性等を十分に有しつつ、基材との付着性
に優れた塗膜を得え、且つ多様な有機溶媒の選択が可能
で速やかな硬化が期待できる塗料用フッ素系重合体組成
物を提供することにある。Therefore, an object of the present invention is to solve the above-mentioned problems, and to improve weather resistance, water resistance, chemical resistance,
A fluorine-based polymer for paints that has sufficient water repellency, low friction, etc., and can be used to obtain a coating film with excellent adhesion to the substrate, and allows for the selection of a variety of organic solvents and is expected to cure quickly. The object of the present invention is to provide a combined composition.
(問題点を解決する為の手段) 本発明に係る含フッ素共重合体によれば。(Means for solving problems) According to the fluorine-containing copolymer according to the present invention.
〔A〕(^)フルオロオレフィン
(B)エポキシ基含有ビニル化合物
(C)オレフィン性不飽和結合及び加水分解可能な基を
有する有機珪素化合物
を共重合させて得られる含フッ素共重合体と、CH3式
R’ −3n、X’X2Y〔式中、R′は炭素数
4〜10のアルキル基であり、X1、X2はClまたは
OH基であり同一であっても異なっていてもよく、Yは
Clまたは0COR”(R″はアルキル基、アリール基
、またはアリルアルキル基である)〕
で表わされる硬化触媒と、
(C) 有機溶媒とからなることを特徴とする塗料用
フッ素系重合体組成物が提供される。[A] (^) Fluoroolefin (B) An epoxy group-containing vinyl compound (C) A fluorine-containing copolymer obtained by copolymerizing an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group, and CH3 Formula R'-3n, Cl or 0COR"(R" is an alkyl group, an aryl group, or an allyl alkyl group)]; and (C) an organic solvent. is provided.
本発明においてフルオロオレフィン(A)は、式
%式%
(R1、R2、R3は水素原子またはハロゲン原子であ
り、R4は水素原子、ハロゲン原子、アルキル基。In the present invention, the fluoroolefin (A) has the formula % (R1, R2, R3 are hydrogen atoms or halogen atoms, and R4 is a hydrogen atom, a halogen atom, an alkyl group.
ハロゲン化アルキル基であり、R1乃至R4の内の1つ
以上にフッ素原子を有する。)で表され、通常のオレフ
ィンの炭素に結合した水素を少なくとも1a以上フッ素
原子と置換したものである。フルオロオレフィン(A)
にはフッ素原子の他に塩素原子、臭素原子等が水素と置
換してあっても良く、炭素数2ないし6のフルオロオレ
フィン(A)が具体的なものとして使用できる。It is a halogenated alkyl group, and one or more of R1 to R4 has a fluorine atom. ), and is an ordinary olefin in which at least 1a or more of the hydrogens bonded to the carbon atoms are replaced with fluorine atoms. Fluoroolefin (A)
In addition to fluorine atoms, chlorine atoms, bromine atoms, etc. may be substituted with hydrogen, and fluoroolefins (A) having 2 to 6 carbon atoms can be specifically used.
エポキシ基含有ビニル化合物(B)は、式
%式%
(Nは0叉は1であり、R5はアルキレン、オキシアル
キレン、叉はジオキシアルキレンであり、R6は水素原
子又はメチル基である。)で表され。The epoxy group-containing vinyl compound (B) has the formula % (N is 0 or 1, R5 is alkylene, oxyalkylene, or dioxyalkylene, and R6 is a hydrogen atom or a methyl group). It is expressed as.
化合物中に少なくとも1個以上のエポキシ基が存在する
ビニル化合物で、エポキシ基とビニル基の間には、エー
テル結合、ポリエステル結合等が介在してもよい。In a vinyl compound in which at least one epoxy group is present in the compound, an ether bond, a polyester bond, etc. may be interposed between the epoxy group and the vinyl group.
有機珪素化合物(C)は、不飽和結合を有する基及び加
水分解する基が共に珪素に少なくとも1以上績合してい
るものであり、具体的に次の3種の一般式で示すことが
できる。The organosilicon compound (C) has at least one unsaturated bond-containing group and one hydrolyzable group combined with silicon, and can be specifically represented by the following three general formulas. .
式
%式%
(R7はオレフィン系不飽和結合を有する基で、R6、
R9はオレフィン系不飽和結合を有する基または炭化水
素基で、Y1、Y2、Y3は加水分解する基である。)
で表される。珪素化合物(C)の不飽和結合を有する基
として、 ビニル、アリル、ブテニル、シクロヘキセニ
ル等が具体的に使用できる。加水分解する基としては、
具体的にアルコキシ基、アシロキシ基、オキシム基等が
具体的に使用できる。Formula % Formula % (R7 is a group having an olefinic unsaturated bond, R6,
R9 is a group having an olefinically unsaturated bond or a hydrocarbon group, and Y1, Y2, and Y3 are groups that undergo hydrolysis. ). As the group having an unsaturated bond in the silicon compound (C), vinyl, allyl, butenyl, cyclohexenyl, etc. can be specifically used. As a group to be hydrolyzed,
Specifically, an alkoxy group, an acyloxy group, an oxime group, etc. can be used.
また1本発明の好ましいアルキルビニルエーテル(D)
は、 式
%式%
(R10は直鎖状、分岐鎖状、又は環状アルキル基であ
る。)で表され Rloは直鎖状アルキル。In addition, one preferable alkyl vinyl ether (D) of the present invention
is represented by the formula % (R10 is a linear, branched, or cyclic alkyl group), and Rlo is a linear alkyl group.
分岐鎖状アルキル及びシクロアルキルであり、炭素数が
2乃至10のアルキル基を有するアルキルビニルエーテ
ル(D)が具体的なものとして使用できる。An alkyl vinyl ether (D) which is a branched alkyl or cycloalkyl and has an alkyl group having 2 to 10 carbon atoms can be specifically used.
(作用)
本発明者等は、含フッ素重合体が耐候性、耐水性、耐薬
品性、撥水性、及び低摩擦性に優れていることに着目す
ると共に、含フッ素重合単量体を組み合わせた前記(A
)乃至(C)の成分からなる共重合体が前記特性を維持
しながら、各種の有機溶媒に可溶で、特定の硬化触媒に
よって極めて硬化が速く起こり、その硬化膜が基材に対
する付着性を極めて有していることを見出したものであ
る。(Function) The present inventors have focused on the fact that fluoropolymers have excellent weather resistance, water resistance, chemical resistance, water repellency, and low friction, and have combined fluoropolymer monomers. Said (A
) to (C) are soluble in various organic solvents while maintaining the above properties, and cure extremely quickly with a specific curing catalyst, and the cured film has excellent adhesion to the substrate. This is what we found to be extremely effective.
本発明においてはフッ素系重合体(A)が前記(A)乃
至(C)成分であることが重要であり、このような3成
分を組み合わせた共重合体は有機溶媒に可溶であり、加
水分解可能な基の存在によって硬化が可能である。硬化
したこのような共重合体は耐候性、耐水性、耐薬品性、
撥水性、低摩擦性に優れた塗膜を形成し、しかも基材に
対する付着性に優れたものとなる。また、前記3成分に
、アルキルビニルエーテル(D)を加えることが望まし
く、(D)成分を加えることのよって溶媒選択性が更に
広がる傾向(ごある、。In the present invention, it is important that the fluoropolymer (A) is the above-mentioned components (A) to (C), and a copolymer that is a combination of these three components is soluble in organic solvents and Curing is possible due to the presence of degradable groups. These cured copolymers are weather resistant, water resistant, chemical resistant,
Forms a coating film with excellent water repellency and low friction, and also has excellent adhesion to substrates. Furthermore, it is desirable to add an alkyl vinyl ether (D) to the above three components, and adding component (D) tends to further broaden the solvent selectivity.
また、本発明の組成物には有機錫化合物の硬化触媒〔J
3]を含有させることが重要であり、その含有量はフッ
素重合体〔A〕10O重景部に対して0゜0:3〜30
、特に0.1−10重量部の範囲であることが望ましい
。このような特定の硬化触媒によって、前記フッ素系重
合体は速やかな硬化を起こす。The composition of the present invention also contains an organotin compound curing catalyst [J
3] is important, and its content is 0°0:3-30 relative to the fluoropolymer [A] 10O heavy area.
, particularly preferably in the range of 0.1-10 parts by weight. The fluoropolymer is rapidly cured by such a specific curing catalyst.
このように前記フッ素系重合体CA)と硬化触媒CB)
とを組み合わせ、 しかもこれらを有機溶媒〔C〕で溶
解させると、フッ素系樹脂の優れた特性を有しながら基
材に対する密着性がよく、速やかな硬化をもたらす塗料
の組成物となる。尚、この場合、有機溶媒100重量部
に対してフッ素系重合体を40〜300、特1.m 8
0−120重量部の範囲で使用する組成物が望ましい。In this way, the fluoropolymer CA) and the curing catalyst CB)
When these are combined and dissolved in an organic solvent [C], a coating composition that has the excellent properties of a fluororesin, has good adhesion to a substrate, and quickly cures can be obtained. In this case, the amount of the fluoropolymer is 40 to 300 parts by weight, especially 1. m 8
It is desirable to use a composition in the range of 0-120 parts by weight.
(発明の好ましい実施態様)
以下、本発明に係る塗料用フッ素系重合体組成物につい
て具体的に説明する。(Preferred Embodiments of the Invention) The fluoropolymer composition for paint according to the present invention will be specifically described below.
フッ 4 の A
本発明で用いられる含フッ素共重合体は(A)フルオロ
オレフィンと (B)エポギシ基含有ビごル化合物 と
(C)オレフィン性不飽和結合及び加水分解用能な基を
有する有機珪素化合物とを共重合8セて得られる共重合
体である。また、場合によフては(D)アルキルビニル
エーテルを成分どすることが望ましい。Fluorine-containing copolymer used in the present invention comprises (A) a fluoroolefin, (B) an epoxy group-containing Vigor compound, and (C) an organic compound having an olefinic unsaturated bond and a hydrolyzable group. It is a copolymer obtained by copolymerizing with a silicon compound. In some cases, it is desirable to add (D) alkyl vinyl ether as a component.
1オー仄−すヤ乙並−ン
フルオロオレフィン(A)は分子・中に少なくとも1以
1−のフッ素原子が水素ど置換されており、また、場合
によっては塩素原子、臭素原子等が共存していてもよい
。Fluoroolefins (A) have at least one or more fluorine atoms substituted with hydrogen or the like in the molecule, and in some cases chlorine atoms, bromine atoms, etc. coexist. You can leave it there.
本発明において好ましいフルオロオレフィン(A)とし
ては、フッ素原子が50%以」−1特に70%以り一水
素と置換しているものであり、中でもベルハロオロオレ
フインが好適である。Preferred fluoroolefins (A) in the present invention are those in which 50% or more of fluorine atoms, especially 70% or more, are substituted with monohydrogen, and among these, berhalooloolefins are preferred.
また、重合性の観点から炭素原子数が2乃至6特に2ま
たは3のフルオロオレフィンが好ましい。Further, from the viewpoint of polymerizability, fluoroolefins having 2 to 6 carbon atoms, particularly 2 or 3 carbon atoms, are preferred.
このようなオレフィン類としては、 ド式で表され、
11−
12−
RW R4
(R1,R2、R3は水素原子またはハロゲン原r−で
あり、R4は水素原子、ハロゲン原子、アルキル基、ハ
ロゲン化アルキル基であり、R1乃至R4の内の1つ以
上にフッ素原子を有する。)
具体的には以Fの化合物が用いられる。Such olefins are represented by the formula: 11-12-RW R4 (R1, R2, R3 are hydrogen atoms or halogen atoms r-, R4 is hydrogen atoms, halogen atoms, alkyl groups, halogenated (It is an alkyl group, and one or more of R1 to R4 has a fluorine atom.) Specifically, the following compounds are used.
CF2” CF2 HCHF= CF2 + CO3
−CF2 g CH2=ClIP 、 C(、IF=
CF2. CCl5CF=CGIP=CClF、 C
l(F=CCl2,Cl(2=CC]、F、 CCl、
=CClF等の炭素原子数2のフルオロオレフィン(フ
ルオロエチレン系)。CF2” CF2 HCHF= CF2 + CO3
-CF2 g CH2=ClIP, C(, IF=
CF2. CCl5CF=CGIP=CCIF, C
l(F=CCl2, Cl(2=CC], F, CCl,
=Fluoroolefin having 2 carbon atoms (fluoroethylene type) such as CClF.
CF、CF=CF、、 CF、CF3CCl,CF、
ClI=CF、。CF, CF=CF,, CF, CF3CCl, CF,
ClI=CF,.
CF3CF ”CH2、CF3CClCHF 、 CH
F2CF=ClIP 。CF3CF”CH2, CF3CClCHF, CH
F2CF=ClIP.
CF、ClI =ClI、 、 Cl1、CF=CF
、 、 Cl1、CH=CF、 。CF, ClI = ClI, , Cl1, CF=CF
, , Cl1, CH=CF, .
CH,CFFCH,、CF、ClCF=CF、 、
Cl73ccl=cF2゜CFICF =CFCl,C
F2ClCCl=CF2. CF2ClCF=CFC]
、。CH, CFFCH,, CF, ClCF=CF, ,
Cl73ccl=cF2゜CFICF=CFCl,C
F2ClCCl=CF2. CF2ClCF=CFC]
,.
CFCl、CF =CF7. CF3CCl=CClF
、 CF3CCl,=CC]ハCClF2CF =C
Cl2,CCl、、CF3CCl,CF3CCC]、=
CCl,。CFCl, CF = CF7. CF3CCl=CCIF
, CF3CCl,=CC] CClF2CF =C
Cl2, CCl,, CF3CCl, CF3CCC], =
CCl,.
CFClzCCl=CCl2,CFsCF=Cl(Cl
,CClF2CF=ClCl,−CF、CC]=Cl+
(:1. CllF2CCl=CCl2,CF、C
lClI =CCl2゜CF2ClCCl= CHC
lI CCl5CF= CtlC]、CF3CClCF
2 。CFClzCCl=CCl2, CFsCF=Cl(Cl
, CClF2CF=ClCl, -CF, CC]=Cl+
(:1. CllF2CCl=CCl2, CF, C
lClI = CCl2゜CF2ClCCl= CHC
lI CCl5CF= CtlC], CF3CClCF
2.
CF 2 BrCl(=CF 21 CF 3CBr
== CHRrr CF 2 Cl,Cll r−
Cl+2 tCJBrCF = CCl,2,CF=
CBr= ClI2 、 cp、co= ClIl
r。CF 2 BrCl (=CF 21 CF 3CBr
== CHRrr CF 2 Cl, Cll r-
Cl+2 tCJBrCF = CCl,2,CF=
CBr= ClI2, cp, co= ClIl
r.
CF2BrC)l =ClIP 、 CF2BrCF
=CF2等の炭素原子数3のフルオロオレフィン(フル
オロプロペン系)。CF2BrC)l = ClIP, CF2BrCF
=Fluoroolefin having 3 carbon atoms such as CF2 (fluoropropene type).
CF3CClCF= CF2 、 CF3CClCF
CFs −CF3CCl=CFCF3− CF2=
CFCF2CHCFハCF、CF、CF= CH2゜C
F3CCl= CHCF3. CF2= CFCF2C
H3,CF、= CFC[12CH3゜CF3CClC
l= ClI2.CF3Cl1= ClCl3 、CF
2= CHCJCH3、Cl13CF2CH=CH2,
CF3CClC)ICFH2−CH3CF2Cl=CJ
、CH2=C,FC)12CJ、 CF3(CF2
)2CF=CF2 。CF3CClCF= CF2, CF3CClCF
CFs −CF3CCl=CFCF3− CF2=
CFCF2CHCF CF, CF, CF= CH2゜C
F3CCl=CHCF3. CF2= CFCF2C
H3, CF, = CFC[12CH3°CF3CClC
l=ClI2. CF3Cl1= ClCl3, CF
2=CHCJCH3, Cl13CF2CH=CH2,
CF3CClC)ICFH2-CH3CF2Cl=CJ
, CH2=C,FC)12CJ, CF3(CF2
)2CF=CF2.
CF3(CF2)3CF =CF2 、 CF3CCl
=CFCF3 、 CF3CClニCClF2.
CFz=CFCl2CCl3+ Cl12=CFCl2
CCl3、CF3(CF2)2CC]、=CF2 、C
F3(CF2)3CCl,=CF2等の炭素原子数4以
上のフルオロオレフィン系。CF3(CF2)3CF=CF2, CF3CCl
=CFCF3, CF3CCl2CClF2.
CFz=CFCl2CCl3+ Cl12=CFCl2
CCl3, CF3(CF2)2CC], =CF2, C
Fluoroolefins having 4 or more carbon atoms such as F3(CF2)3CCl,=CF2.
これらの中では、上記のようにフルオロエチレン及びフ
ルオロプロペン系が好ましく、特にクロロトリフルオロ
エチレン(CClP=CF2)が好適である。Among these, as mentioned above, fluoroethylene and fluoropropene are preferred, and chlorotrifluoroethylene (CClP=CF2) is particularly preferred.
また本発明において、フルオロオレフィンは、単独で用
いてもよく、また2種以上を混合して用いてもよい。Further, in the present invention, the fluoroolefins may be used alone or in combination of two or more.
エボ シ ビニル Δ B
エポキシ基含有ビニル化合物(B)は、−形式が下式で
表される。Evocy vinyl ΔB The epoxy group-containing vinyl compound (B) is represented by the following formula.
が用いられる。このうち特にグリシジルビニルエーテル
、グリシジルアリルエーテル等が好ましい。is used. Among these, particularly preferred are glycidyl vinyl ether, glycidyl allyl ether, and the like.
ム C
有機珪素化合物(C)は不飽和結合を有する基及び加水
分解する基が共に珪素に少なくとも1以上結合している
ものであり、具体的に次の3種の一般式で示すことがで
きる。M C The organosilicon compound (C) is a compound in which at least one group having an unsaturated bond and a hydrolyzable group are both bonded to silicon, and can be specifically represented by the following three general formulas. .
CJ=C(Coo) N−R’−CH−CH2(Nは0
叉は1であり R5はアルキレン、オキシアルキレン、
叉はジオキシアルキレンであり、R6は水素原子叉はメ
チル基である。)具体的には、グリシジルビニルエーテ
ル、グリシジルアリルエーテル、ビニルオキシラン、
1.2−エポキシ−4−ペンテン、 1.2−エポキシ
−5−ヘキセン、 1.2−エポキシ−6−ヘプテン。CJ=C(Coo) N-R'-CH-CH2 (N is 0
is 1 and R5 is alkylene, oxyalkylene,
or dioxyalkylene, and R6 is a hydrogen atom or a methyl group. ) Specifically, glycidyl vinyl ether, glycidyl allyl ether, vinyl oxirane,
1.2-epoxy-4-pentene, 1.2-epoxy-5-hexene, 1.2-epoxy-6-heptene.
2−エポキシ−7−オクテン、 1,2−エポキシ−8
−ノネン、 1,2−エポキシ−9−デセン、グリシジ
ルアクリレート、グリシジルメタクリレート等1゜
式
%式%
(R7はオレフィン性不飽和結合を有する基で、15−
・1B−
R♂、R9はオレフィン性不飽和結合を有する基または
炭化水素基で、炭素、水素、場合によっては酸素を含む
もので、それぞれ同−叉は異なっていてもよい。Y1、
Y1、Y3は加水分解する基であり、それぞれ同−叉は
異なっていてもよい。)で表される。2-epoxy-7-octene, 1,2-epoxy-8
-nonene, 1,2-epoxy-9-decene, glycidyl acrylate, glycidyl methacrylate, etc. A group having an unsaturated bond or a hydrocarbon group containing carbon, hydrogen, and in some cases oxygen, which may be the same or different.Y1,
Y1 and Y3 are hydrolyzable groups, and may be the same or different. ).
珪素化合物(C)の不飽和結合を有する基として、ビニ
ル、アリル、ブテニル、シクロヘキセニル等が具体的に
使用できる。加水分解する基としては、具体的にアルコ
キシ基、アシロキシ基、オキシム基等が具体的に使用で
きる。Vinyl, allyl, butenyl, cyclohexenyl, etc. can be specifically used as the group having an unsaturated bond in the silicon compound (C). As the hydrolyzable group, an alkoxy group, an acyloxy group, an oxime group, etc. can be specifically used.
詳しくは、R7乃至R9の不飽和結合基は、ビニル、ア
リル、ブテニル、シクロヘキセニル、シクロペンタジェ
ニルなどであり、特に末端オレフィン性不飽和基である
ことが好ましい。またR7乃至R9の不飽和結合基は、
末端不飽和酸のエステル結合を有する。Specifically, the unsaturated bonding groups R7 to R9 are vinyl, allyl, butenyl, cyclohexenyl, cyclopentagenyl, etc., and terminal olefinic unsaturated groups are particularly preferred. Furthermore, the unsaturated bonding groups of R7 to R9 are
It has a terminal unsaturated acid ester bond.
CH2= CH−C00(CLh
C)12=C(CH5)Coo(CHzh −Clh
= C(CH3)C00(CH2)2 −0(CH2)
3 ’Cl12= C(CHs)C00CH2CH2
0ClhCHCH20(Clls)−H
などの基であることもできる。これらのなかでは、R7
乃至R9が酸素を含まず炭素と水素とから構成されてい
ることが好ましく、特にビニル基が最適である。CH2= CH-C00(CLh C)12=C(CH5)Coo(CHzh-Clh
= C(CH3)C00(CH2)2 -0(CH2)
3'Cl12= C(CHs)C00CH2CH2
It can also be a group such as 0ClhCHCH20(Clls)-H. Among these, R7
Preferably, R9 to R9 do not contain oxygen and are composed of carbon and hydrogen, and a vinyl group is particularly suitable.
R6及びR9の炭化水素は、具体的には、1価の炭化水
素基であるメチル、エチル、プロピル、テトラデシル、
オクタデシル、フェニル、ベンジル、トリルなどであり
、またこれらの基は、ハロゲン置換炭化水素基でもよい
。Specifically, the hydrocarbons of R6 and R9 include monovalent hydrocarbon groups such as methyl, ethyl, propyl, tetradecyl,
These groups include octadecyl, phenyl, benzyl, tolyl, etc., and these groups may also be halogen-substituted hydrocarbon groups.
YI 、Yl 、Y3は、具体的には、メトキシ、エト
キシ、ブトキシ、メトキシエトキシ、などのアルコキシ
基、アルコキシアルコキシ基、ホルミロキシ、アセトキ
シ、プロビオノキシなどのアシロキシ基、オキシムたと
えば
−ON = e(CJh 。YI, Yl, and Y3 are, for example, alkoxy groups such as methoxy, ethoxy, butoxy, and methoxyethoxy, alkoxyalkoxy groups, acyloxy groups such as formyloxy, acetoxy, and probionoxy, and oximes, such as -ON=e(CJh).
−ON= CHlj12C2H5および−ON= C(
C6H5)2などであり、その他任意の加水分解しろる
有機基である。-ON= CHlj12C2H5 and -ON= C(
C6H5)2, etc., and any other hydrolyzable organic group.
本発明では有機珪素化合物は5,1−記のような一般式
で表わさiする化合物であることが好ましく、特に基Y
l 、Y2 、Y3が同一である有機珪素化合物である
ことが好ましい、これらの中でもR7がビニル基であり
、YI−Y3がアルコキシ基またはアルコキシアルコキ
シ基である有機珪素化合物が特に好ましく、たとえばビ
ニロキシプロピルトリメトキシシラン、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
ス(メトキシエトキシ)シランなどが好ましい。またビ
ニルメチルジェトキシシラン、ビニルフエニルジメトキ
シシランなども+iqwに用いることができる。In the present invention, the organosilicon compound is preferably a compound represented by the general formula i such as 5,1-, and particularly the group Y
Organosilicon compounds in which 1, Y2, and Y3 are the same are preferred.Among these, organosilicon compounds in which R7 is a vinyl group and YI-Y3 is an alkoxy group or an alkoxyalkoxy group are particularly preferred; for example, vinyloxy Preferred are propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(methoxyethoxy)silane, and the like. Vinylmethyljethoxysilane, vinylphenyldimethoxysilane, etc. can also be used for +iqw.
アルキルビニルエー−ル(D)
アルキルビニルエーテル(D)はビニル基とアルキル基
とがエーテル結合を介して結合した化合物である。アル
キルビニルエーテル(1))はF式で表さ九る。
C)I、= CH−0−h?、”(R50は直鎖状、分
岐鎖状、叉は環状アルキル基である。)
このようなアルキルビニルエーテルとしては、具体的に
は、エチルビニルエーテル、ブし1ピルビニルエーテル
、イソプロピルビニルニーデル、ブチルビニルエーテル
、tert−ブチルビニルエーテル2 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等の鎖状アルキルビニルエー
テル類、シクロペンチルビニルエーテル、シクロヘキシ
ルビニルエーテル等のシクロアルキルビニルエーテル類
が用いられる。このうち特にエチルビニルエーテル、プ
ロピルビニルエーテル、ブチルビニルエーテル等が好ま
しい。Alkyl vinyl ether (D) Alkyl vinyl ether (D) is a compound in which a vinyl group and an alkyl group are bonded via an ether bond. Alkyl vinyl ether (1)) is represented by the formula F.
C) I, = CH-0-h? ," (R50 is a linear, branched, or cyclic alkyl group.) Examples of such alkyl vinyl ether include ethyl vinyl ether, butyl vinyl ether, isopropyl vinyl needle, butyl Vinyl ether, tert-butyl vinyl ether 2 Pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1
- Chain alkyl vinyl ethers such as pentyl vinyl ether, and cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether are used. Among these, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and the like are particularly preferred.
上記のようなアルキルビニルエーテルは、単独で用いて
もよく、また2種以上を混合して用いてもよい。The above alkyl vinyl ethers may be used alone or in combination of two or more.
フッ 共重合体の配合の割合
本発明で用いられるフッ素糸重合体ノフルオロオレフィ
ン(A)は共重合体中に25〜60モル%、好ましくは
30〜55モル%の量で含有していることが望ましい。Blending ratio of fluorine copolymer The fluorine thread polymer nofluoroolefin (A) used in the present invention should be contained in the copolymer in an amount of 25 to 60 mol%, preferably 30 to 55 mol%. is desirable.
フルオロオレフィンがこのよう19−
20−
な範囲にある場合には、共重合体は耐候性、耐水性、*
薬品性、撥水性、低摩擦性が優れており。When the fluoroolefin is in this 19-20- range, the copolymer has weather resistance, water resistance, *
It has excellent chemical properties, water repellency, and low friction properties.
高級塗料剤等になる、また、エポキシ基含有ビニル化合
物(B)は0,5〜60モル%好ましくは1.0〜50
モル%の量であり、有機珪素化合物(C)はO,5〜2
5モル%好ましくは1.0〜20モル%の量であり、こ
のような範囲にある場合には、共重合体を塗料として使
用した時に基材に対する付着性が極めて良好となる。し
かもこのような共重合体は。The epoxy group-containing vinyl compound (B) is preferably 0.5 to 60 mol %, preferably 1.0 to 50
The amount is mol%, and the organosilicon compound (C) is O,5~2
The amount is 5 mol %, preferably 1.0 to 20 mol %, and within this range, when the copolymer is used as a paint, the adhesion to the substrate will be extremely good. Moreover, such a copolymer.
塗料としたときの溶媒選択性がよく、特に、アルキルビ
ニルエーテル(D)を50モル%以下、好ましくは10
〜40モル%の量で用いるど更によい。It has good solvent selectivity when used as a paint, especially when the alkyl vinyl ether (D) is 50 mol% or less, preferably 10
It is even better to use it in an amount of ˜40 mol %.
また、フルオロオレフィンの量が前記範囲より余りに少
なすぎると充分な耐候性が得られず、多すぎると溶剤に
対し不溶性或いは溶解可能な溶剤が限られたものとなる
ため、含フッ素共重合体を塗料用どして用いる場合には
、取扱いが困難になり好ましくない。また、有機珪素化
合物の量があまりに少なすぎると、硬化後、強靭な塗膜
が得られず、あまりに多1ぎると、硬化後、内部応力が
増太し塗膜のひび割れの原因となり好ましくない。Furthermore, if the amount of fluoroolefin is too small from the above range, sufficient weather resistance will not be obtained, and if it is too large, the solvents that can be dissolved or dissolved in the solvent will be limited, so the fluorine-containing copolymer When used as a paint, it becomes difficult to handle, which is undesirable. Furthermore, if the amount of the organosilicon compound is too small, a tough coating film cannot be obtained after curing, and if it is too large, internal stress increases after curing, which is undesirable, causing cracks in the coating film.
11皇洪1i1然豆ヱ1
また、本発明に係るフッ素系重合体においては、ゲル・
パーミションクロマトグラフ法によって測定した数平均
分P;t(Mt+)が2,000乃至300,000゜
特に3,000〜100,000の範囲内にあることが
望ましい。共重合体がこうのような分子量範囲にあれば
、前述した各成分配合比と相まって溶媒選択性が良くな
り、塗料等の用途に十分な活用が可能となる。11 Huanghong 1i1 Natural Bean 1 In addition, in the fluoropolymer according to the present invention, gel,
The number average fraction P;t(Mt+) measured by permeation chromatography is preferably in the range of 2,000 to 300,000°, particularly 3,000 to 100,000. If the copolymer has a molecular weight in this range, the solvent selectivity will be improved in combination with the above-mentioned blending ratio of each component, and it will be possible to fully utilize it for applications such as paints.
分子量の測定は、分子量既知の単分散ポリスチレンを標
準物質として用いて、ゲル・パーミェーションクロマト
グラフ法(GPC)により測定して求めた数平均分子l
t(Mn)である。Molecular weight is measured using monodisperse polystyrene of known molecular weight as a standard substance and determined by gel permeation chromatography (GPC).
t(Mn).
このようなフッ素系重合体は、具体的に常温において、
たとえばベンゼン、 トルエン、キシレンなどの芳香族
炭化水素類、アセトン、メチルエチルケトンなどのケト
ン類、ジエチルエーテル、ジプロピルエーテル、メチル
セロソルブ、エチルセロソルブなどのエーテル類、酢酸
エチル、酢酸ブチルなどのエステル類、 トリクロロメ
タン、ジクロロエタン、クロロベンゼン等のハロゲン化
炭化水素類などに溶解する。Specifically, such fluorine-based polymers have the following properties at room temperature:
For example, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, dipropyl ether, methyl cellosolve, and ethyl cellosolve, esters such as ethyl acetate and butyl acetate, and trichloro. Dissolves in halogenated hydrocarbons such as methane, dichloroethane, and chlorobenzene.
フ・ ム の ・
上記のような含フッ素共重合体は、上記のような各モノ
マー(A)〜(D)を周知のラジカル開始剤の存在下共
重合することによって合成することができる。Fluorine-containing copolymers as described above can be synthesized by copolymerizing each of the monomers (A) to (D) as described above in the presence of a known radical initiator.
このようなラジカル開始剤として、公知の種々のものが
使用できる。具体的には有機ペルオキシド、有機ペルエ
ステルであるベンゾイルペルオキシド、ジクロルベンゾ
イルペルオキシド、ジクミルペルオキシド、ジーtar
t−ブチルペルオキシド、2.5−ジメチル−2,5−
ジ(ペルオキシベンゾエート)−ヘキシン−3、1,4
−ビス(tart−ブチルペルオキシイソプロビル)ベ
ンゼン、ラウロイルペルオキシド、tert−ブチルペ
ルアセテート、2.5−ジメチル−2,5−ジ(ter
t−ブチルペルオキシ)ヘキシン−3、2,5−ジメチ
ル−2,5−ジ(tart−ブチルペルオキシ)ヘキサ
ン、 te+rt−ブチルペルベンゾエート
アセテート
しert−ブチルペルーseaーオクトエート、ter
t −ブチルペルビバレート、クミルペルビバレート、
tert−ブチルペルジエチルアセテートなど、その化
アゾ化合物たとえばアゾビスイソブチロニトリル、ジメ
チルアゾイソブチレートなどが用いられる。このうちジ
クミルペルオキシド
プチルペルオキシド、2,5−ジメチル−2,5−ジ(
tart−ブチルペルオキシ)ヘキシン−3、 2,5
−ジメチル−2,5−ジ(七er七ープチルペルオキシ
ヘキサン、 1,4−ビス( tart−ブチルペルオ
キシイソプロビル)ベンゼンなどのジアルキルペルオキ
シドが好ましい。Various known radical initiators can be used as such radical initiators. Specifically, organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, and di-tar
t-Butyl peroxide, 2,5-dimethyl-2,5-
Di(peroxybenzoate)-hexyne-3,1,4
-bis(tart-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert)
tert-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tart-butylperoxy)hexane, te+rt-butylperbenzoate acetate, ert-butylperu sea-octoate, ter
t-butyl perbivalate, cumyl perbivalate,
Tert-butyl perdiethyl acetate and its azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate are used. Of these, dicumyl peroxide butyl peroxide, 2,5-dimethyl-2,5-di(
tart-butylperoxy)hexyne-3, 2,5
Dialkyl peroxides such as -dimethyl-2,5-di(7er7-butylperoxyhexane, 1,4-bis(tart-butylperoxyisopropyl)benzene) are preferred.
上記のような共重合反応は、有機溶媒からなる反応媒体
中で行なわれることが好ましい。このような有機溶媒と
しては、ベンゼン、 トルエン、キシレンなどの芳誉族
炭化水素、クロロベンゼン。The copolymerization reaction as described above is preferably carried out in a reaction medium consisting of an organic solvent. Examples of such organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, and chlorobenzene.
ブロモベンゼン、ヨードベンゼン、などのハロゲン化芳
香族炭化水素、n−ヘキサン、シクロヘキサン、n−へ
ブタン等の脂肪族炭化水素、などを23−
・24−
用いることができる。Halogenated aromatic hydrocarbons such as bromobenzene and iodobenzene, aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-hebutane, and the like can be used.
上記のような共重合反応は、上記のような溶媒中でラジ
カル開始剤をモノマーの合計モル数に対して、モル比で
10−2〜10−3の範囲で添加して行なうことが好ま
しい.また重合温度は一30〜200℃、好ましくは2
0〜100’C、重合圧力はo〜100kg/a112
・G、好ましくはO−5 0kg/an” ・Gである
。The above copolymerization reaction is preferably carried out in the above solvent by adding a radical initiator in a molar ratio of 10-2 to 10-3 based on the total number of moles of monomers. The polymerization temperature is -30 to 200°C, preferably 2
0~100'C, polymerization pressure is o~100kg/a112
・G, preferably O-5 0 kg/an'' ・G.
11夏罠崖亘亘1
本発明では,フルオロオレフィンとして塩素を含むフル
オロオレフィンを用いて含フッ素共重合体を製造するに
際しては、重合反応時および/または得られた共重合体
の精製時に、系内に塩素捕捉剤を存在させておくことが
望ましい。11 Summer Tragai Wataru 1 In the present invention, when producing a fluorine-containing copolymer using a fluoroolefin containing chlorine as the fluoroolefin, it is necessary to It is desirable to have a chlorine scavenger present.
このような塩素捕捉剤としては、以下のような化合物を
用いることができる。As such a chlorine scavenger, the following compounds can be used.
(イ) MXAl, (OR)z−+3y−z− (A
) − ・a [20(式中、MはKg. Caまた
はZnであり、AはCO,またはHPO4であり、x.
y. zは整数であり,aは0または整数である
。)で示される複合化合物。(A) MXAl, (OR)z-+3y-z- (A
) − ·a [20 (wherein M is Kg. Ca or Zn, A is CO or HPO4, x.
y. z is an integer, and a is 0 or an integer. ) complex compound.
(イ)で示される複合化合物としては,具体的には下記
のような化合物が用いられる。Specifically, the following compounds are used as the composite compound represented by (a).
にに6Alz(OR)+aCOs・4H20HKaAh
(OH)26cO3 ・5H20にg5A12(OH)
+4C03・4H20Hii。Ah(OHhzCOs・
48.01’1g6Alz(OB)t6HPo4・4H
,OCa6A12(OH)tacOs ・4HzOZn
6A16(OH)t6cO3 4 4H20この(イ)
で示される複合化合物は、上記のような式で正確に示さ
れない化合物であってもよく、たとえばにz2A1(O
H)、・3H20の0■の一部がCO3で置換された化
合物であってもよい。またこれらの化合物は結晶水が除
去されていてもよい。Nini6Alz(OR)+aCOs・4H20HKaAh
(OH)26cO3 ・5H20 to g5A12(OH)
+4C03・4H20Hii. Ah(OHhzCOs・
48.01'1g6Alz(OB)t6HPo4・4H
,OCa6A12(OH)tacOs・4HzOZn
6A16(OH)t6cO3 4 4H20 this (a)
The complex compound represented by may be a compound that is not exactly represented by the above formula, for example, z2A1(O
H), .3H20 may be a compound in which part of 0■ is replaced with CO3. Further, water of crystallization may be removed from these compounds.
このような複合化合物のうちでは、MがMgであり、A
がCO,である化合物が好ましい。In such a complex compound, M is Mg and A
Compounds in which is CO, are preferred.
(口)アルカリ土類金属の塩基性化合物アルカリ土類金
属の塩基性化合物としては、具体的にはM.O、CaO
などのアルカリ土類金属酸化物、)Lg(OHh、Ca
(OH) 2などのアルカリ土類金属水酸化物、Mg
CO3、CaCLなどのアルカリ土類金属炭酸私などが
用いられる。(Example) Basic compounds of alkaline earth metals Examples of basic compounds of alkaline earth metals include M. O, CaO
Alkaline earth metal oxides such as )Lg(OHh, Ca
Alkaline earth metal hydroxides such as (OH) 2, Mg
Alkaline earth metal carbonates such as CO3 and CaCL are used.
上記のようなアルカリ土類金属の叡基性化合物は、(M
にC03)4・Mg(01():i・511 、0なと
の複塩であってもよく、また、これらの化合物は結晶水
が除去されていてもよい。The basic compound of alkaline earth metal as mentioned above is (M
It may be a double salt of C03)4.Mg(01():i.511, 0), and the water of crystallization may be removed from these compounds.
これらのアルカリ土類金属の塩基性化合物のうちでは、
にg含有化合物が好ましい。Among these basic compounds of alkaline earth metals,
Compounds containing g are preferred.
(ハ)エポキシ基含有化合物
エポキシ基含有化合物としては、γ−グリシドキシプロ
ビルトリメトキシシラン、 β−(3,4−エポキシシ
クロヘキシル)エチルトリメトキシシランなどの珪素含
有エポキシ化合物、トリメチロールプロパンポリグリシ
ジルエーテル、ネオペンチルグリコールジグリシジルエ
ーテルなどの脂肪族エポキシ化合物などが用いられる。(c) Epoxy group-containing compounds Examples of epoxy group-containing compounds include silicon-containing epoxy compounds such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and trimethylolpropane polysilane. Aliphatic epoxy compounds such as glycidyl ether and neopentyl glycol diglycidyl ether are used.
この)ちγ−グリシドキシプロビルトリメトキシシラン
などの珪素含有エポキシ化合物が好ましい。Of these, silicon-containing epoxy compounds such as γ-glycidoxypropyltrimethoxysilane are preferred.
上記のような塩素捕捉剤のうち、無機化合物である塩素
捕捉剤は、有機化合物eある塩素捕捉剤と比較し7て、
塩素(塩酸)との反応が速く、かつ重合系あるいは精製
系に溶解(1,ていないため、系外に除去しやすいので
好ましく用いられる。特に(イ)で示したη自体合物が
好ましい。Among the above-mentioned chlorine scavengers, chlorine scavengers that are inorganic compounds are compared to chlorine scavengers that are organic compounds.
It is preferably used because it reacts quickly with chlorine (hydrochloric acid) and is not dissolved in the polymerization or purification system, making it easy to remove from the system. Particularly preferred is the η itself compound shown in (a).
」−記のような塩素捕捉剤を、重合反応時または得られ
た共重合体の精製時あるいはこの両方〔ごイf在させる
ことによって、得られるフッ素系重合体の着色を効果的
に防止することができる。By adding a chlorine scavenger such as the following during the polymerization reaction, during purification of the resulting copolymer, or both, coloring of the resulting fluoropolymer can be effectively prevented. be able to.
このような塩素捕捉剤を1重合反応時に用いる場合には
、 (a)フルオロオレフィンに含まれる駄素原7−1
モルに対して0.5〜100g好ましくは1〜70gの
量で用いることが好ましい。また。When such a chlorine scavenger is used in a monopolymerization reaction, (a) the chlorine scavenger 7-1 contained in the fluoroolefin;
It is preferred to use it in an amount of 0.5 to 100 g, preferably 1 to 70 g, based on mole. Also.
本発明の共重合体に於いて、共重合体1. OO重量部
当たりに対して塩素捕捉剤0.2乃至1,00重量部の
範囲で用いることが望ましい。In the copolymer of the present invention, copolymer 1. It is desirable to use the chlorine scavenger in a range of 0.2 to 1,00 parts by weight per part by weight of OO.
硬化触媒(B)
本発明に係る組成物では、上記のようなフッ素系重合体
の硬化反応を促進するため、硬化触媒が用いられる。Curing Catalyst (B) In the composition according to the present invention, a curing catalyst is used in order to accelerate the curing reaction of the fluoropolymer as described above.
27−
28−
本発明で用いられる硬化触媒は1式
%式%
〔式中、R′は炭素数4〜10のアルキル基であり+、
X1. X、2はClまたは0)1基であり同〜であ
っても異な−】でいてもよく、YはClまたは0COR
”(R″はアルキル基、アリール基、またはアリルアル
キル基である)〕
で表わされる有機錫化合物である。27- 28- The curing catalyst used in the present invention is 1 formula% formula% [wherein R' is an alkyl group having 4 to 10 carbon atoms, +
X1. X and 2 are Cl or 0)1 group and may be the same or different -], Y is Cl or 0COR
"(R" is an alkyl group, an aryl group, or an allylalkyl group)].
このような硬化触媒としては、具体的には。Specifically, such a curing catalyst includes:
n −C4H,,5n(Oil)2c1、n −C4H
g5n(OH)Cl2、n −C4Hg5nCl3、C
a1tt(OH)2c]、CaC2(0)1)Cl2、
C6H17SnClg、n −C4t1gSn(OH)
20cOc7H+s、n、 C411Jn(OH)2
0COC+14123、n C6J7Sn(OH)2
,0COC7H1s、n−C6H17Sn(011>2
0COClJ23、等が用いられる。n -C4H,,5n(Oil)2c1,n -C4H
g5n(OH)Cl2,n-C4Hg5nCl3,C
a1tt(OH)2c], CaC2(0)1)Cl2,
C6H17SnClg, n-C4t1gSn(OH)
20cOc7H+s,n, C411Jn(OH)2
0COC+14123,n C6J7Sn(OH)2
,0COC7H1s,n-C6H17Sn(011>2
0COClJ23, etc. are used.
このうち特に
C4Hg5nCl3、C411,+5n(OH)、0c
Oc7Htsが好ましい。Among these, especially C4Hg5nCl3, C411, +5n(OH), 0c
Oc7Hts is preferred.
上記のような含フッ素共重合体と硬化触媒とを組み合わ
せて用いることによって、基材との密着性および耐候性
に優れた塗膜を得ることができる。By using a combination of a fluorine-containing copolymer and a curing catalyst as described above, a coating film having excellent adhesion to a substrate and excellent weather resistance can be obtained.
なお本発明で用いられるフッ素共重合体は、有機珪素化
合物(D)に由来する加水分解可能な有機基を有してい
るので、水分と接触することにより重合体の分子鎖間に
架橋反応が起こり硬化する。従って、大気中の湿気によ
っても当然のことながら架橋が起こり得る。しかしなが
ら基材に塗布された含フッ素共重合体の皮膜が迅速に硬
化するように上記のような硬化触媒を用いる。Since the fluorine copolymer used in the present invention has a hydrolyzable organic group derived from the organosilicon compound (D), a crosslinking reaction occurs between the molecular chains of the polymer when it comes into contact with moisture. occurs and hardens. Therefore, as a matter of course, moisture in the atmosphere can also cause crosslinking. However, the above-mentioned curing catalyst is used so that the fluorine-containing copolymer film applied to the substrate is rapidly cured.
このような硬化触媒は、含フッ素共重合体100重量部
あたり0.03〜30重量部好ましくは0.1〜10重
量部の量で用いられる。Such a curing catalyst is used in an amount of 0.03 to 30 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the fluorine-containing copolymer.
有 C−
本発明では、上記のようなフッ素系重合体、硬化触媒と
を溶解して均一な溶液とし塗料として用いるため、含フ
ッ素共重合体を溶解し得る有機溶剤が用いられる。Yes C- In the present invention, an organic solvent capable of dissolving the fluorine-containing copolymer is used in order to dissolve the above-mentioned fluorine-containing polymer and curing catalyst to form a uniform solution and use it as a paint.
このような有機溶剤としては、 トルエン、キシレン、
酢酸ブチル、イソブチルメチルケトン、メチルセルソル
ブ、エチルセルソルブあるいはこれらの混合物が用いら
れる。Such organic solvents include toluene, xylene,
Butyl acetate, isobutyl methyl ketone, methyl cellosolve, ethyl cellosolve, or a mixture thereof is used.
上記のような有機溶剤は、含フッ素共重合体100重量
部あたり40〜300重量部好ましくは80〜120重
量部の量で用いられる。The organic solvent as described above is used in an amount of 40 to 300 parts by weight, preferably 80 to 120 parts by weight, per 100 parts by weight of the fluorine-containing copolymer.
本発明に係る含フッ素共重合体組成物は、上記のように
含フッ素共重合体、硬化触媒および有機溶剤を含んで構
成されているが、この含フッ素共重合体組成物は、予め
上記のような各成分を全部含んでいてもよく、また含フ
ッ素共重合体を有機溶剤に溶解してなる第1溶液と、硬
化触媒を有機溶剤に溶解してなる第2溶液とを使用直前
に混合して上記の含フッ素共重合体組成物をm製しても
よい。The fluorine-containing copolymer composition according to the present invention contains the fluorine-containing copolymer, the curing catalyst, and the organic solvent as described above. The first solution prepared by dissolving the fluorine-containing copolymer in an organic solvent and the second solution prepared by dissolving the curing catalyst in an organic solvent may be mixed immediately before use. The above fluorine-containing copolymer composition may be manufactured by m.
11口19」1分
本発明に係る含フッ素共重合体組成物は、上記のような
含フッ素共重合体、炭素原子に直接結合したイソシアネ
ート基を有する有機珪素化合物、硬化触媒及び有機溶剤
に加えて、原料、染料、脱水剤(オルトギ酸トリメチル
)、分散剤およびその他の塗料添加剤(レベリング剤、
湿潤剤等)、アルキルシリケート及びそのオリゴマーさ
らにはそれらの加水分解物(テトラメチルオルト珪酸オ
リゴマー等)などを含んでいてもよい。The fluorine-containing copolymer composition according to the present invention contains, in addition to the above-mentioned fluorine-containing copolymer, an organosilicon compound having an isocyanate group directly bonded to a carbon atom, a curing catalyst, and an organic solvent. raw materials, dyes, dehydrating agents (trimethyl orthoformate), dispersants and other paint additives (leveling agents,
Wetting agents, etc.), alkyl silicates and oligomers thereof, and further hydrolyzed products thereof (tetramethyl orthosilicate oligomers, etc.).
本発明に係る含フッ素共重合体組成物は、塗料として用
いることができ、通常の液体塗料と同じように刷頂、ス
プレー、ローラコータ等で金属、木、プラスチック、セ
ラミック、紙、ガラスなどの基剤表面に塗布することが
できる。硬化後の皮膜は、耐候性、耐薬品性、耐溶剤性
、耐水性、耐熱性、低摩擦性に優れ、さらに透明性、伸
び性にも優れている。The fluorine-containing copolymer composition according to the present invention can be used as a paint, and can be applied to metals, wood, plastics, ceramics, paper, glass, etc. by printing, spraying, roller coater, etc. in the same way as ordinary liquid paints. Can be applied to the surface of the agent. The cured film has excellent weather resistance, chemical resistance, solvent resistance, water resistance, heat resistance, and low friction, as well as excellent transparency and elongation.
このような本発明に係る含フッ素共重合体組成物の硬化
反応(架橋反応)は、常温すなわち室温付近(0〜40
’C)で十分進行するが、必要に応じて加熱下で反応を
行わしめてもよい。The curing reaction (crosslinking reaction) of the fluorine-containing copolymer composition according to the present invention is carried out at room temperature, that is, around room temperature (0 to 40
Although the reaction proceeds satisfactorily in 'C), the reaction may be carried out under heating if necessary.
(発明の効果)
本発明によれば、フルオロオレフィンとアルキルビニル
エーテルとエポキシ基含有ビニル化合物とオレフィン性
不飽和結合金有基及び加水分解す31−
32−
る基を有する有機珪素化合物とから成るフッ素系重合体
と特定の硬化触媒とを組み合わせることにより、該組成
物が硬化後耐候性、耐水性、耐薬品性、撥水性、及び低
摩擦性に優れたものとなり。(Effects of the Invention) According to the present invention, a fluorine compound comprising a fluoroolefin, an alkyl vinyl ether, a vinyl compound containing an epoxy group, and an organosilicon compound having an olefinically unsaturated bonded gold group and a hydrolyzable group. By combining the system polymer and a specific curing catalyst, the composition becomes excellent in weather resistance, water resistance, chemical resistance, water repellency, and low friction after curing.
しかも速やかな硬化が達成され基材との付着性に優れる
ため、塗料用として実用性の高い組成物になる。Moreover, it achieves rapid curing and has excellent adhesion to substrates, making it a highly practical composition for paint applications.
(実施例)
以下に本発明に係る塗料用フッ素系重合体組成物の実施
例及びそれを塗料としたときの付着性の評価を行った。(Example) Below, Examples of the fluoropolymer composition for paint according to the present invention and evaluation of adhesion when used as a paint were conducted.
尚、本発明はこれら実施例に限定されるものではない。Note that the present invention is not limited to these examples.
参考製造例1゜
1.51のステンレス製撹拌機つきオートクレーブ内を
窒素置換した後、窒素気流下に、 トリメトキシビニル
シラン(TMVS) 15.5 g、エチルビニルニー
9ル(EVE)30.3g、グリシジルビニルエーテル
(GVE)22.5g、合成ハイドロタルサイト(1,
5A1□(OH)、5COs・3.5B20)粉末の焼
成品(SHT)4.7g、 過酸化ジラウロイル2.
7gをベンゼン250m1に溶解し一括して仕込んだ。Reference Production Example 1 After purging the inside of an autoclave with a 1.5 mm stainless steel stirrer with nitrogen, under a nitrogen stream, 15.5 g of trimethoxyvinylsilane (TMVS), 30.3 g of ethyl vinyl silane (EVE), Glycidyl vinyl ether (GVE) 22.5g, synthetic hydrotalcite (1,
5A1□(OH), 5COs/3.5B20) powder calcined product (SHT) 4.7g, dilauroyl peroxide 2.
7 g was dissolved in 250 ml of benzene and charged all at once.
その後クロロトリフルオロエチレン(CTPE)91.
8gをオートクレーブ中に導入し、65℃まで昇温し、
7.5時間反応を行なった。その後。Then chlorotrifluoroethylene (CTPE) 91.
8g was introduced into an autoclave, the temperature was raised to 65°C,
The reaction was carried out for 7.5 hours. after that.
オートクレーブを水冷し反応を停止させ、冷却後未反応
モノマーを追い出し、オートクレーブを開放し、11の
ナス形フラスコに反応液を取り出した。この反応液にキ
シレン75g、メタノール50g、 5H74,7
gを加え、50’Cl’1.5時間さらに 60℃で1
.5時間撹拌下に加熱処理した後、エバポレーターにて
減圧下、残留モノマー及び溶媒を留去し、次いでキシレ
ン200gを加え、再びエバポレーターにて減圧下溶媒
を留去した。The autoclave was cooled with water to stop the reaction, and after cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a No. 11 eggplant-shaped flask. To this reaction solution, 75 g of xylene, 50 g of methanol, 5H74,7
g and 50'Cl' for 1.5 hours at 60°C.
.. After heat treatment with stirring for 5 hours, the residual monomer and solvent were distilled off under reduced pressure using an evaporator, then 200 g of xylene was added, and the solvent was distilled off under reduced pressure using an evaporator again.
その後、キシレン250gを加え、この溶液を減退して
SHTを除去し、減圧濃縮して無色透明な重合体(1
)93.8gを得た。Thereafter, 250 g of xylene was added, the solution was reduced to remove SHT, and concentrated under reduced pressure to obtain a colorless and transparent polymer (1
) 93.8g was obtained.
得られた共重合体のGPCによる数平均分Pikは1.
0000であった。The number average Pik of the obtained copolymer by GPC is 1.
It was 0000.
また、この重合体の組成分析を元素分析及びNMRを用
イテ行なツタトコ口、CTFE/ E V E /GV
E/TMVS=47/36/12/fi (P/1、%
)であ−)だ。In addition, the composition of this polymer was analyzed using elemental analysis and NMR, CTFE/EVE/GV.
E/TMVS=47/36/12/fi (P/1,%
) de-) desu.
参考製造例2゜
1.51のステンレス製撹拌機つきオートクレーブ内を
窒素置換【、5た後、窒素気流下に、 トリメトキシビ
ニルシラン(TMVS) 31.1 g、エチルビニル
エーテルfル(EVE)82.2g、グリシジJv7’
)ルエーテル(GAE)17.1g、合成ハイドロタル
サイト(ME<、 5A12(OH)+5CO3+ 3
.51420 )粉末の焼成品(S HT) 9.3
g、 過酸化ジラウロイル5.4gをベンゼン500
m1に溶解し一括して仕込んだ。その後クロロトリフル
オロエチレン(CTFE) 183゜5gをオートクレ
ーブ中に導入し、65℃まで昇温し、7.5時間反応を
行なった。その後、オートクレーブを水冷し反応を停止
さセ、冷却後未反応モノマーを追い出し、オートクレー
ブを開放し、1」−のナス形フラスコに反応液を取り出
した。この反応液にキシレン150g、メタノール10
0g、5HT9.4gを加え、50℃で1.5時間さら
に 60’Cで1゜5時間撹拌Fに加熱処理した後、エ
バポレーターにて減圧五、残留千ツマ・・及び溶媒を留
去し、次いでキシレン4. OOgを加え、再びエバポ
レーターに゛C減圧下溶媒を留去シ、7た。その後、キ
シレン500 gを加λ、この溶液を濾過して S H
Tを除去し2、減圧濃縮して無色透明な重合体(II)
220gを得た。Reference Production Example 2 After purging the inside of a 1.51 mm stainless steel autoclave with a stirrer with nitrogen, under a nitrogen stream, 31.1 g of trimethoxyvinylsilane (TMVS), 82 g of ethyl vinyl ether (EVE) were added. 2g, Grishiji Jv7'
) ether (GAE) 17.1g, synthetic hydrotalcite (ME<, 5A12(OH)+5CO3+ 3
.. 51420) Powder fired product (SHT) 9.3
g, 5.4 g of dilauroyl peroxide and 500 g of benzene
It was dissolved in ml and charged all at once. Thereafter, 183.5 g of chlorotrifluoroethylene (CTFE) was introduced into the autoclave, the temperature was raised to 65° C., and a reaction was carried out for 7.5 hours. Thereafter, the autoclave was cooled with water to stop the reaction, and after cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a 1'' eggplant-shaped flask. This reaction solution contains 150 g of xylene and 10 g of methanol.
0 g and 9.4 g of 5HT were added, and the mixture was heated at 50° C. for 1.5 hours and then at 60° C. for 1.5 hours with stirring. Then xylene 4. OOg was added, and the solvent was again distilled off under reduced pressure using an evaporator. Then, add 500 g of xylene, filter this solution, and
Remove T2 and concentrate under reduced pressure to obtain a colorless and transparent polymer (II)
220g was obtained.
得られた共重合体のG P Cによる数I+1均分子−
量は11000であった。The number I+1 homogeneous molecule of the obtained copolymer by GPC is -
The amount was 11,000.
また、この重合体の組成分析を元素分析及びNMRを用
いて行なったところ、CTFE/ E V E /GA
E/TMVS=50/41/415 (モル%) であ
った。In addition, when the composition of this polymer was analyzed using elemental analysis and NMR, it was found that CTFE/EVE/GA
E/TMVS=50/41/415 (mol%).
比較製造例1
1.51のステンレス製撹拌機つきオートクレーブ内を
窒素置換し、窒素気流下にベンゼン180m1. エ
チルビニルエーテル(EVE) 121.1g、シク
ロヘキシルビニルエーテル(CyHVE ) 15.9
g、 トリメトキシビニルシラン(TにVS)43.
6g、合成ハイドロタルサイト(Jigイ、、 5A1
2(OH>(5COs ・3.5 H2O)粉末の焼成
品(SHT)13.0gを仕込35−
36−
んだ。その後クロロトリフルオロエチレン(CTFE)
256.9 gをオートクレーブ中に導入し、65℃ま
で昇温した。このようにして得られた混合物に、過酸化
ジラウロイル7.6gをベンゼン120m1に溶解させ
た開始剤溶液を4時間かけてフィードした。さらに65
℃で6時間反応を行なった後、オートクレーブを水冷し
、反応を停止させた8 冷却後、未反応上ツマ−を追い
出し、オートクレーブを開放し、1..51のナス形フ
ラスコに反応液を取り出した。この反応液にキシレン2
10 g、メタノール120g、5HT13.Ogを加
え、50℃で1.5時間さらに60℃で1.5時間撹拌
下に加熱処理した、処理後、エバポレーターにて減圧下
に残留モノマー及び溶媒を留去し、次いでキシレン55
0 K、を加え、撹拌により均一溶液とした。Comparative Production Example 1 The inside of a 1.51 stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and 180 ml of benzene was added under a nitrogen stream. Ethyl vinyl ether (EVE) 121.1g, cyclohexyl vinyl ether (CyHVE) 15.9g
g, trimethoxyvinylsilane (VS to T) 43.
6g, synthetic hydrotalcite (Jigii, 5A1
13.0 g of a calcined product (SHT) of 2(OH>(5COs ・3.5 H2O) powder) was charged. After that, chlorotrifluoroethylene (CTFE) was added.
256.9 g was introduced into an autoclave, and the temperature was raised to 65°C. An initiator solution of 7.6 g of dilauroyl peroxide dissolved in 120 ml of benzene was fed to the mixture thus obtained over a period of 4 hours. 65 more
After the reaction was carried out at ℃ for 6 hours, the autoclave was cooled with water to stop the reaction.8 After cooling, the unreacted upper part was expelled, the autoclave was opened, and 1. .. The reaction solution was taken out into a No. 51 eggplant-shaped flask. Add 2 xylene to this reaction solution.
10 g, methanol 120 g, 5HT13. After the treatment, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then xylene 55
0 K, and stirred to form a homogeneous solution.
この溶液を濾過してS HTを除去し、減圧濃縮して無
色透明な重合体(I[N) 351.3 gを得た。This solution was filtered to remove S HT and concentrated under reduced pressure to obtain 351.3 g of a colorless and transparent polymer (I[N).
得られたポリマーのGPCによる数平均分子量は120
00であったわ
また。この重合体の組成分析を元素分析及びNMRI用
イテ行なったとコロ、CTFE/ E V E /Cy
HVE /TMVS= 51 / 39 /4/ 6
(−eル比)であった。The number average molecular weight of the obtained polymer by GPC was 120.
It was 00 again. The compositional analysis of this polymer was carried out for elemental analysis and NMRI, CTFE/EVE/Cy.
HVE/TMVS=51/39/4/6
(-e ratio).
実施例1
参考製造例1で得られた重合体(1)38.2重量部と
、テトラメチルオルト珪酸オリゴマー1.9重量部と、
オルトギ酸メチル149重量部と、酸化チタン26,7
重量部と、キシレン31゜3重量部とからなる塗料(1
)を調製した。Example 1 38.2 parts by weight of the polymer (1) obtained in Reference Production Example 1, 1.9 parts by weight of tetramethyl orthosilicate oligomer,
149 parts by weight of methyl orthoformate and 26.7 parts by weight of titanium oxide
paint (1 part by weight) and 31°3 parts by weight of xylene.
) was prepared.
また一方JIS G 3302ニ規定する亜鉛画板(S
PG)にエポキシ塗料マリンSC(三片金属塗料化学■
)を塗布し、屋外暴露期間を10日として塗装用基材を
製作した。On the other hand, zinc drawing boards (S
PG) to epoxy paint Marine SC (Mikata Metal Paint Chemical)
) was coated and exposed outdoors for 10 days to produce a coating substrate.
また上記のようにしてll製した塗料(1) 1.0
0重量部に対しn −BuSnClgの6.3重量%キ
シレン液を3.8重量部混合して含フッ素共重合体組成
物を調製し、この組成物を上記の塗装基材上に10。Also, paint (1) prepared as above 1.0
A fluorine-containing copolymer composition was prepared by mixing 3.8 parts by weight of a 6.3% by weight xylene solution of n-BuSnClg with respect to 0 parts by weight, and this composition was coated on the above-mentioned coating substrate.
μmのアプリケーターを用いて塗布した。このようにし
て得られた懐膜を屋外に1週間暴露した後、基盤目試験
を行なった。It was applied using a μm applicator. After exposing the membrane thus obtained outdoors for one week, a base eye test was conducted.
結果を表1に示す。The results are shown in Table 1.
実施例2
参考製造例2で得られた重合体(II) 38.2重量
部と、テトラメチルオルト珪酸オリゴマー1.9重量部
と、オルトギ酸メチル1.9重量部と、酸化チタン26
.7重量部と、キシレン31.3重量部とからなる塗料
(1)をEll製した。Example 2 38.2 parts by weight of the polymer (II) obtained in Reference Production Example 2, 1.9 parts by weight of tetramethyl orthosilicate oligomer, 1.9 parts by weight of methyl orthoformate, and 26 parts by weight of titanium oxide.
.. A paint (1) consisting of 7 parts by weight and 31.3 parts by weight of xylene was manufactured by Ell.
また一方JIS G 3302に規定する亜鉛鋼板(S
PG)にエポキシ塗料マリンSC(三片金属塗料化学■
)を塗布し、屋外暴露期間を10日として塗装用基材を
製作した。On the other hand, galvanized steel sheets (S
PG) to epoxy paint Marine SC (Mikata Metal Paint Chemical)
) was coated and exposed outdoors for 10 days to produce a coating substrate.
また上記のようにしてlEl製した塗料(II) 1
00重量部に対しn−3uSnC]4の6.3重量%キ
シレン液を3.8重量部混合して含フッ素共重合体組成
物をm製し、この組成物を上記の塗装基材上に100μ
mのアプリケーターを用いて塗布した。このようにして
得られた塗膜を屋外に1週間暴露した後。In addition, paint (II) made from lEl as described above 1
A fluorine-containing copolymer composition was prepared by mixing 3.8 parts by weight of a 6.3% by weight xylene solution of n-3uSnC]4 with respect to 00 parts by weight, and this composition was applied onto the above coating substrate. 100μ
It was applied using a m applicator. After exposing the coating thus obtained outdoors for one week.
基盤目試験を行なった。A basic test was conducted.
結果を表1に示す。The results are shown in Table 1.
比較例1
実施例1において、重合体(1)の代わりに比較製造例
1で得られた共重合体(m)を用いた以外は、実施例1
と同様にして塗膜を形成し、屋外に1週間暴露した後、
基盤目試験を行なった。Comparative Example 1 Example 1 except that the copolymer (m) obtained in Comparative Production Example 1 was used instead of the polymer (1).
After forming a coating film in the same manner as above and exposing it outdoors for one week,
A basic test was conducted.
結果を表1に示す。The results are shown in Table 1.
表 1Table 1
Claims (4)
R’−SnX^1X^2Y 〔式中、R’は炭素数4〜10のアルキル基であり、X
^1、X^2はClまたはOH基であり同一であつても
異なつていてもよく、YはClまたはOCOR”(R”
はアルキル基、アリール基、またはアリルアルキル基で
ある)〕 で表わされる硬化触媒と、 〔C〕有機溶媒とからなることを特徴とする塗料用フッ
素系重合体組成物。(1) [A] (A) Fluoroolefin (B) Vinyl compound containing an epoxy group (C) Fluorine-containing copolymer obtained by copolymerizing an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group and [B] formula R'-SnX^1X^2Y [wherein, R' is an alkyl group having 4 to 10 carbon atoms, and
^1 and X^2 are Cl or OH groups and may be the same or different, and Y is Cl or OCOR"(R"
is an alkyl group, an aryl group, or an allyl alkyl group)]; and [C] an organic solvent.
子であり、R^4は水素原子、ハロゲン原子、アルキル
基、ハロゲン化アルキル基であり、R^1乃至R^4の
内の1つ以上にフッ素原子を有する。)で表され、前記
エポキシ基含有ビニル化合物(B)は、式 ▲数式、化学式、表等があります▼ (Nは0又は1であり、R^5はアルキレン、オキシア
ルキレン、又はジオキシアルキレンであり、R^6は水
素原子又はメチル基である。)で表され、前記有機珪酸
化合物(C)は、 式 ▲数式、化学式、表等があります▼・・・ I ▲数式、化学式、表等があります▼・・・II ▲数式、化学式、表等があります▼・・・III (R^7はオレフィン系不飽和結合を有する基で、R^
8、R^9は不飽和結合を有する基または炭化水素基で
、Y^1、Y^2、Y^3は加水分解する基である。)
の I 、II、又はIIIのいずれかで表される有機珪素化合
物(C)であることを特徴とする請求項第1項記載の含
フッ素共重合体。(2) The fluoroolefin (A) has the following formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (R^1, R^2, R^3 are hydrogen atoms or halogen atoms, R^4 is a hydrogen atom, is a halogen atom, an alkyl group, or a halogenated alkyl group, and has a fluorine atom in one or more of R^1 to R^4. There are mathematical formulas, chemical formulas, tables, etc. ▼ (N is 0 or 1, R^5 is alkylene, oxyalkylene, or dioxyalkylene, and R^6 is a hydrogen atom or methyl group.) The organic silicate compound (C) has the following formulas: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... I ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・...III (R^7 is a group having an olefinic unsaturated bond, R^
8. R^9 is a group having an unsaturated bond or a hydrocarbon group, and Y^1, Y^2, and Y^3 are hydrolyzable groups. )
The fluorine-containing copolymer according to claim 1, wherein the fluorine-containing copolymer is an organosilicon compound (C) represented by any one of I, II, or III.
ルキルビニルエーテル(D)を加え、該共重合体を構成
する(A)、(B)、(C)、(D)から導かれる構成
単位の合計モル数に対して(D)成分を50モル%以下
で含有させることを特徴とする請求項第1項記載の含フ
ッ素共重合体。(3) The copolymer is made by adding alkyl vinyl ether (D) to the components (A) to (C), and from (A), (B), (C), and (D) constituting the copolymer. The fluorine-containing copolymer according to claim 1, characterized in that the component (D) is contained in an amount of 50 mol% or less based on the total number of moles of the derived structural units.
て、該共重合体の重合時或いは重合後に、共重合体10
0重量に対して塩素捕捉剤0.2乃至100重量で塩素
除去処理してなる含フッ素共重合体。(4) In the copolymer according to claim 1 or 3, during or after polymerization of the copolymer, copolymer 10
A fluorine-containing copolymer obtained by removing chlorine with a chlorine scavenger of 0.2 to 100% by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6112590A JPH03263474A (en) | 1990-03-14 | 1990-03-14 | Fluorine-based polymer composition for coating material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6112590A JPH03263474A (en) | 1990-03-14 | 1990-03-14 | Fluorine-based polymer composition for coating material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03263474A true JPH03263474A (en) | 1991-11-22 |
Family
ID=13162047
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6112590A Pending JPH03263474A (en) | 1990-03-14 | 1990-03-14 | Fluorine-based polymer composition for coating material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03263474A (en) |
-
1990
- 1990-03-14 JP JP6112590A patent/JPH03263474A/en active Pending
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