JPH04180974A - Coating composition excellent in adhesiveness - Google Patents
Coating composition excellent in adhesivenessInfo
- Publication number
- JPH04180974A JPH04180974A JP30862090A JP30862090A JPH04180974A JP H04180974 A JPH04180974 A JP H04180974A JP 30862090 A JP30862090 A JP 30862090A JP 30862090 A JP30862090 A JP 30862090A JP H04180974 A JPH04180974 A JP H04180974A
- Authority
- JP
- Japan
- Prior art keywords
- group
- copolymer
- fluorine
- mol
- formula
- 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
- 239000008199 coating composition Substances 0.000 title claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 52
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 38
- -1 alkyl vinyl ether Chemical compound 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 7
- 125000000962 organic group Chemical group 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 abstract 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 abstract 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 abstract 1
- 125000001188 haloalkyl group Chemical group 0.000 abstract 1
- 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 24
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 239000003973 paint Substances 0.000 description 14
- 239000008096 xylene Substances 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 229920002313 fluoropolymer Polymers 0.000 description 8
- 239000004811 fluoropolymer Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- DASQIKOOFDJYKA-UHFFFAOYSA-N CCIF Chemical compound CCIF DASQIKOOFDJYKA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 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 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- XMJQCVMNFPEJLN-UHFFFAOYSA-N 1-ethenoxy-4-methylpentane Chemical compound CC(C)CCCOC=C XMJQCVMNFPEJLN-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-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
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002923 oximes Chemical group 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-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
- 239000004711 α-olefin 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
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- 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
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RCSBILYQLVXLJG-UHFFFAOYSA-N 2-Propenyl hexanoate Chemical compound CCCCCC(=O)OCC=C RCSBILYQLVXLJG-UHFFFAOYSA-N 0.000 description 1
- PZGMUSDNQDCNAG-UHFFFAOYSA-N 2-Propenyl octanoate Chemical compound CCCCCCCC(=O)OCC=C PZGMUSDNQDCNAG-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
- FLYIRERUSAMCDQ-UHFFFAOYSA-N 2-azaniumyl-2-(2-methylphenyl)acetate Chemical compound CC1=CC=CC=C1C(N)C(O)=O FLYIRERUSAMCDQ-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- JMICBDHJGYAFMU-UHFFFAOYSA-N 3-ethenoxypropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCOC=C JMICBDHJGYAFMU-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- OZYYQTRHHXLTKX-UHFFFAOYSA-N 7-octenoic acid Chemical compound OC(=O)CCCCCC=C OZYYQTRHHXLTKX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- RMZIOVJHUJAAEY-UHFFFAOYSA-N Allyl butyrate Chemical compound CCCC(=O)OCC=C RMZIOVJHUJAAEY-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 102100030500 Heparin cofactor 2 Human genes 0.000 description 1
- 101001082432 Homo sapiens Heparin cofactor 2 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- CBWUNQZJGJFJLZ-UHFFFAOYSA-N [Cl].Cl Chemical compound [Cl].Cl CBWUNQZJGJFJLZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- ZQWPRMPSCMSAJU-UHFFFAOYSA-N cyclohexanecarboxylic acid methyl ester Natural products COC(=O)C1CCCCC1 ZQWPRMPSCMSAJU-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 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
- 230000000694 effects Effects 0.000 description 1
- HJVKTYVDOZVQPA-UHFFFAOYSA-N ethenoxycyclopentane Chemical compound C=COC1CCCC1 HJVKTYVDOZVQPA-UHFFFAOYSA-N 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
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-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
- 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
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 239000011521 glass Substances 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-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
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QNBDJTKBKITRJI-UHFFFAOYSA-N prop-2-enyl 2-methylpropanoate Chemical compound CC(C)C(=O)OCC=C QNBDJTKBKITRJI-UHFFFAOYSA-N 0.000 description 1
- AIPJCMMALQPRMK-UHFFFAOYSA-N prop-2-enyl cyclohexanecarboxylate Chemical compound C=CCOC(=O)C1CCCCC1 AIPJCMMALQPRMK-UHFFFAOYSA-N 0.000 description 1
- DZMOLBFHXFZZBF-UHFFFAOYSA-N prop-2-enyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC=C DZMOLBFHXFZZBF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-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
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-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)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (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
た塗膜を基材に形成するフッ素糸塗料用M成物に関する
ものであり、特に基材に対して付着性が優れているフッ
素塗料用組IIi物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an M composition for fluorine fiber coatings that forms a coating film with excellent weather resistance, chemical resistance, water resistance, water repellency, etc. on a base material. In particular, it relates to a fluorocoat composition IIIi having excellent adhesion to substrates.
(従来技術及び発明が解決しようとする問題、膏)含フ
ッ素共重合体は、け候性、耐水性、i′:I薬品性、撥
水性、低jl!擦性等の各種性質に優れているので、高
m能塗料への応用が期待さ九ている。しかし、含フッ素
共重合体は、通常常温に於いて溶媒不溶性または難錆性
であるため、溶液型塗料としての適用が難しく、基材に
対する付着性が悪いという問題がある。(Prior art and problems to be solved by the invention) Fluorine-containing copolymers have weather resistance, water resistance, i':I drug resistance, water repellency, and low jl! Since it has excellent properties such as abrasion resistance, it is expected to be applied to high performance paints. However, since fluorine-containing copolymers are usually insoluble in solvents or rust-resistant at room temperature, they are difficult to apply as solution-type coatings, and have the problem of poor adhesion to substrates.
ところで、本III呂願人は、含フッ素共重合体のみを
含んで硬化する耐候性塗料用樹脂を開発すべく検討した
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、常
温下で有機溶剤に可溶であること、そして常温硬化する
ことを見い出し、既に提案した(特開昭61−1417
13号公報)。By the way, as a result of studying to develop a resin for weather-resistant coatings that contains only a fluorine-containing copolymer and cures, the authors of this III have developed a fluorine-based ternary compound consisting of a fluoroolefin, a vinyl ether, and a specific organosilicon compound. It was discovered that the copolymer is soluble in organic solvents at room temperature, and that it cures at room temperature.
Publication No. 13).
しかしながら、このような従来の含フッ素共重合体を用
いた塗料は、基材に対する付着性の面で必ずしも満足す
べきものではない。即ち、基材に塗布してすぐのエポキ
シ樹脂下塗り面に形成される塗膜にあってはその付着性
に問題を生じないが、経過時間の長くなったエポキシ樹
脂下塗り面に形成される塗膜においては十分な付着強度
のある塗膜とならないことがある。However, paints using such conventional fluorine-containing copolymers are not necessarily satisfactory in terms of adhesion to substrates. In other words, a coating film formed on the epoxy resin undercoat surface immediately after being applied to the base material will not cause any problems in adhesion, but a coating film formed on the epoxy resin undercoat surface after a long time has elapsed. In some cases, the coating film may not have sufficient adhesion strength.
したがって、本発明の目的は、耐水性、撥水性等の高機
能塗料であって、常温硬化可能な付着性に優れたフッ素
塗料用組成物を提案することにある。Therefore, an object of the present invention is to propose a composition for a fluorine paint that is a highly functional paint with water resistance, water repellency, etc., and is curable at room temperature and has excellent adhesion.
(問題点を解決するための手段)
本発明によれば、 【A〕
(A)フルオロオレフィン
(B)アルキルビニルエーテル
(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、(A)成分乃至(C)成分の合
計モル数量に対して、(A)成分は1乃至30モル%の
範囲で、(B)成分が1乃至95モル%の範囲で。(Means for Solving the Problems) According to the present invention, [A] (A) a fluoroolefin (B) an alkyl vinyl ether (C) an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group; Obtained by polymerization, based on the total molar amount of components (A) to (C), component (A) is in the range of 1 to 30 mol%, and component (B) is in the range of 1 to 95 mol%. .
(C)成分が1乃至30モル%の範囲である含フッ素共
重合体と、
[B) 式 R” −SnX”Y’″y′?(式
中、R′は炭素数4乃至10のアルキル基であり、X゛
は炭素数4乃至10のアルキル基、clまたはOH基で
あり、Y−’、y′2はCl,0COR’ ”、または
OH基であり、これらは同一であ)ても異なっていても
よい。但し、R”はアルキル基、アリール基、アリルア
ルキル基である6 )で表される硬化触媒と、
〔C〕 有機溶媒とからなることを特徴とする塗料用組
成物が提供される。(C) a fluorine-containing copolymer in which the component is in the range of 1 to 30 mol%; group, X' is an alkyl group having 4 to 10 carbon atoms, Cl or OH group, Y-', y'2 are Cl, 0COR''', or OH group, and these are the same). may also be different. Provided is a coating composition characterized by comprising a curing catalyst represented by 6) in which R'' is an alkyl group, an aryl group, or an allylalkyl group, and [C] an organic solvent.
本発明の前記フルオロオレフィン(Alは、式
%式%
(R”、R’、R9は水素原子またはハロゲン原子であ
り、R′は水素原子、ハロゲン原子、アルキル基。The fluoroolefin (Al) of the present invention has the formula % (R'', R', R9 are hydrogen atoms or halogen atoms, and R' is a hydrogen atom, a halogen atom, or an alkyl group.
ハロゲン化アルキル基であり、R′乃至R1の内の1つ
以上にフッ素原子を有する。)で表されることを特徴と
することができる。It is a halogenated alkyl group, and one or more of R' to R1 has a fluorine atom. ).
また、本発明の前記有機珪酸化合物(C)は、Y’−8
i−R@ ・・・ I
暴
Y’−5i−X ・・・ ■
R?
Y’−8i−Y’ ・・・ ■
薯
Y?
(R’、Roはオレフィン性不飽和結合を有し、炭素、
水素、場合によっては酸素からなり、それぞれ同−又は
異なっていてもよい。X゛はオレフィン性不飽和結合を
有しない有機基であり、Y’、Y’、Y9は加水分解す
る基であり、それぞれ同−又は異なっていてもよい。)
の1. n、 叉は■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ことができる。Further, the organic silicate compound (C) of the present invention is Y'-8
i-R@... I vio Y'-5i-X... ■ R? Y'-8i-Y'... ■ 薯Y? (R', Ro have an olefinic unsaturated bond, carbon,
It consists of hydrogen and, in some cases, oxygen, and may be the same or different. X' is an organic group having no olefinic unsaturated bond, and Y', Y', and Y9 are hydrolyzable groups, and may be the same or different. )
1. It can be characterized by being an organosilicon compound (C) represented by either n, or ■.
(作用)
本発明は、樹脂被覆の特性として耐候性、耐水性、耐薬
品性、撥水性、及び低摩擦性に優れるフッ素系重合成分
を一定量に抑え、 かつ前i己アルキルビニルエーテル
及び有機珪素を共重合体として用いて、これを特定の硬
化触媒と共に有機溶媒に溶かすことによって、これが極
めて付着性のある塗料用組成物になるという知見に基づ
くものである。(Function) The present invention suppresses the amount of fluorine-based polymeric components, which have excellent weather resistance, water resistance, chemical resistance, water repellency, and low friction properties as characteristics of the resin coating, to a certain amount, and also contains alkyl vinyl ether and organic silicon. This is based on the knowledge that by using the copolymer as a copolymer and dissolving it in an organic solvent together with a specific curing catalyst, a highly adhesive coating composition can be obtained.
本発明においては、フルオロオレフィンを一定量に抑え
、アルキルビニルエーテル及び有機珪素と共に共重合体
とすることが重要である。フルオロオレフィン成分は共
重合体全体に対して1乃至30モル%、特に5乃至30
モル%であることが望ましい。このよう成分範囲にある
ものは、硬化触媒によ・って基材表面上で速やかに硬化
し、塗布膜は基材と付着性に優れたものとなる。In the present invention, it is important to suppress the amount of fluoroolefin to a certain level and form it into a copolymer with alkyl vinyl ether and organosilicon. The fluoroolefin component is 1 to 30 mol%, especially 5 to 30 mol%, based on the entire copolymer.
It is desirable that it is mol%. A composition within such a range of components is rapidly cured on the surface of the substrate by the curing catalyst, and the coating film has excellent adhesion to the substrate.
本発明においては、アルキルビニルエーテル成分が共重
合体全体に対して1乃至95モル%の範囲、特に50乃
至85モル%の範囲で用いることが望ましく、有機珪素
成分は共重合体全体に対して1乃至30モル%、特に3
乃至25モル%の範囲で用いることが望ましい。また、
有機珪素は、オレフィン性不飽和結合及び加水分解可能
な基を有していることが重要である。オレフィン性不飽
和基は、末端オレフィン性であることが望ましく、特に
末端不飽和の酸エステルであることが望ましい。加水分
解可能な基とは、メトキシ、エトキシなどのアルコキシ
基、ホルミロキシ、アセトキシなどのアシロキシ基、オ
キシムなどが代表的に挙げられるが。In the present invention, the alkyl vinyl ether component is desirably used in a range of 1 to 95 mol%, particularly 50 to 85 mol%, based on the entire copolymer, and the organosilicon component is preferably used in a range of 1 to 95 mol%, based on the entire copolymer. 30 mol% to 30 mol%, especially 3
It is desirable to use it in a range of 25 mol %. Also,
It is important that the organosilicon has an olefinic unsaturated bond and a hydrolyzable group. The olefinically unsaturated group is preferably a terminal olefinic group, and particularly preferably a terminally unsaturated acid ester. Typical hydrolyzable groups include alkoxy groups such as methoxy and ethoxy, acyloxy groups such as formyloxy and acetoxy, and oxime.
アルコキシ基が望ましい。これらの基は組成物が硬化す
るときに大きく影響してくる。Alkoxy groups are preferred. These groups greatly influence when the composition cures.
また、本発明の組成物には有機錫化合物の硬化触媒(B
E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(A1100重重部に対して0.03〜2.0、
特に0.1〜1.5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 (B
It is important to contain E, and its content is 0.03 to 2.0 per 1100 parts by weight of the fluoropolymer (A1100 parts by weight).
In particular, a range of 0.1 to 1.5 parts by weight is desirable. The fluoropolymer is rapidly cured by such a specific curing catalyst.
前記フッ素系重合体[A)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、特に80−12011部の
範囲で使用する組成物が望ましい。When the fluoropolymer [A) and curing catalyst CB] are combined and dissolved in an organic solvent (C),
The resulting coating composition has the excellent properties of a fluororesin, has good adhesion to the substrate, and provides rapid curing. In this case, it is desirable to use a composition in which the fluoropolymer is used in an amount of 40 to 300 parts, particularly 80 to 12,011 parts, per 100 parts by weight of the organic solvent.
(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.
フッ素系重合体の成分[Aコ
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〕アルキルビニルエーテルと(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
有機珪素化合物とを共重合させて得られる共重合体であ
る。Components of Fluorine-based Polymer [A] The fluorine-containing copolymer used in the present invention consists of (A) fluoroolefin, [B] alkyl vinyl ether, and (C)
It is a copolymer obtained by copolymerizing an organic silicon compound having an olefinic unsaturated bond and a hydrolyzable group.
また、本発明においては、目的を損なわない範囲で他の
共重合可能なモノマー、例えば不飽和カルボン酸もしく
はその誘導体、カルボン酸ビニルエステル類、カルボン
酸アリルエステル類、α−オレフィン類、ハロゲン化オ
レフィン類、芳香族ビニル化合物が適宜に共重合されて
いてよい。In addition, in the present invention, other copolymerizable monomers, such as unsaturated carboxylic acids or derivatives thereof, carboxylic acid vinyl esters, carboxylic acid allyl esters, α-olefins, halogenated olefins, may be used to the extent that the purpose is not impaired. or aromatic vinyl compounds may be appropriately copolymerized.
フルオロオレフィン(A)は分子中にψなくとも1以上
のフッ素原子が水素と置換されており、また、場合によ
っては塩素原子、臭素原子等のハロゲン原子が共存して
いてもよい。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、オレフィンのフッ素原子がすべてフ
ッ素原子、塩素原子、及びその他のハロゲン原子が置換
されているペルハロオレフィンが好適である。また、重
合性及び共重合体の性質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。In the fluoroolefin (A), at least one fluorine atom in the molecule ψ is replaced with hydrogen, and in some cases, halogen atoms such as chlorine atoms and bromine atoms may coexist. In the present invention, preferred fluoroolefins (A) are perhaloolefins in which all fluorine atoms in the olefin are substituted with fluorine atoms, chlorine atoms, and other halogen atoms. Further, from the viewpoint of polymerizability and properties of the copolymer, 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、下式で表され。Such olefins are represented by the following formula.
Rさ R′
(R’、R’、R’は水素原子またはハロゲン原子であ
り、R′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′乃至R′の内の1つ以上
にフッ素原子を有する。)
具体的には以下の化合物が用いられる。R'(R',R',R' is a hydrogen atom or a halogen atom, R' is a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, and one of R' to R' (Has at least one fluorine atom.) Specifically, the following compounds are used.
CCl=CF2. CHF=CCl,CH,=CF、
。CCl=CF2. CHF=CCl,CH,=CF,
.
CH2=C)IF 、 CCIF=CF、 、 C)l
c1=cF、。CH2=C)IF, CCIF=CF, , C)l
c1=cF,.
CCl2=CF?、 CCl=CCl?、 CHF
=CCl,。CCl2=CF? , CCl=CCl? , CHF
=CCl,.
CH,=CCIF、 CCl=CCl2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)。Fluoroolefins having 2 carbon atoms (fluoroethylene type) such as CH,=CCIF, CCl=CCl2.
CF、CF=CF2. CF、CF=CHF 、
CF、CHtCF、 。CF, CF=CF2. CF, CF=CHF,
CF, CHtCF, .
CF;CF =CHt 、CF=CF=CHF ICH
FtCF=CHF 。CF; CF=CHt, CF=CF=CHF ICH
FtCF=CHF.
CF、C)l =CH,、CH,CF=CF?、 C
H,C)l=cF、 。CF,C)l=CH,,CH,CF=CF? , C
H, C) l=cF, .
CH,CF =CH,、CF、CCl=CF292 C
F、CCl=CF、 。CH, CF = CH,, CF, CCl = CF292 C
F, CCl=CF, .
CF、CF =CFCI、 CF、CICCl=CF、
、 CF、CCl=CCl?物Cl=CF2
CCIFtCF =cc12. ccl、cF=cp?
、CFtCICCl=CCl?。CF, CF = CFCI, CF, CICCl = CF,
, CF, CCl=CCl? Product Cl=CF2 CCIFtCF =cc12. ccl, cF=cp?
, CFtCICCl=CCl? .
CCl=CCl? CCI□、 CF、CF= Cl
ICl,CCIF、CF= CHCl。CCl=CCl? CCI□, CF, CF= Cl
ICl, CCIF, CF=CHCl.
CF、CCl=C)IcI、 CHF、CCl=CC
l2,CF、CICH=CC]2゜CF2CICC]=
ljlCl,CCI、CH=CCl,CF、ICF=C
F2゜CF2BrCH=CF、 + CF、CBr=C
HBr、 CF、CICBr=C)l、。CF, CCl=C) IcI, CHF, CCl=CC
l2,CF,CICH=CC]2゜CF2CICC]=
ljlCl, CCI, CH=CCl, CF, ICF=C
F2゜CF2BrCH=CF, + CF, CBr=C
HBr, CF, CICBr=C)l,.
CHJrCF =cci、、 CF:CBr=Cl−、
、CF?CH=CHBr。CHJrCF=cci, CF:CBr=Cl-,
,CF? CH=CHBr.
CF2BrCH” CHF 、 CF、BrCF=
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)。CF2BrCH” CHF, CF, BrCF=
Fluoroolefins having 3 carbon atoms (fluoropropene type) such as CF2.
CF、CF、CF=CF、、 CF、CH=CCl
,。CF, CF, CF=CF,, CF, CH=CCl
,.
CF、C)l=cFcF、、 CHF=CCl,C
HCF2゜CF、CF7CF=CH,、CF、C)I=
CHCF、。CF,C)l=cFcF, CHF=CCl,C
HCF2゜CF, CF7CF=CH,, CF, C) I=
CHCF,.
CF?= CFCF2CH9,CF2= CFCHzC
H,。CF? = CFCF2CH9, CF2= CFCHzC
H.
CF、CH,C)I=CH2,CF、CH=C)IcH
,、CF、=CHCH,C)l、。CF,CH,C)I=CH2,CF,CH=C)IcH
,,CF,=CHCH,C)l,.
CH=CFtCH= CHt 、 CFH,2CH
= CHCIII?。CH=CFtCH=CHt, CFH,2CH
=CHCIII? .
CHtCF2CH= CHt 、 CH2= CF
CH2CH=。CHtCF2CH= CHt, CH2= CF
CH2CH=.
CF、(CF2)2CF=CF2 、CF、(CF?
)、CF =CF? 。CF, (CF2)2CF=CF2, CF, (CF?
), CF = CF? .
CF、CCl=CCl? 、 CF2= CF
CFtCCIFt。CF, CCl=CCl? , CF2= CF
CFtCCIFt.
CHF=CCl,CCI、、Cll、=CFCl,CC
l,。CHF=CCl,CCI,,Cll,=CFCl,CC
l,.
CF、(CF2)、CCl=CF、 、 CF、(CL
)、CCl=CF2等の炭素原子数4以上のフルオロオ
レフィン系のもの。CF, (CF2), CCl=CF, , CF, (CL
), fluoroolefins having 4 or more carbon atoms, such as CCl=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(CCIF= CF2)が好適である。Among these, as mentioned above, fluoroethylene and fluoropropene are preferred, and chlorotrifluoroethylene (CCIF=CF2) is particularly preferred.
また本発明において、フルオロオレフィンは、車独で用
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.
アルキルビニルエーテル(B)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(B)は下式の一般式で表される。Alkyl vinyl ether (B) is a compound in which a vinyl group and an alkyl group are bonded via an ether bond. Alkyl vinyl ether (B) is represented by the following general formula.
CH7= CH−0−R”(R”は直鎖状、分岐鞘
状、又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、プロピルビニルエーテル、
イソプロピルビニルエーテル、ブチルビニルエーテル、
tere−ブチルビニルエーテル、ペンチルビニルエー
テル、ヘキシルビニルエーテル、イソヘキシルビニルエ
ーテル、オクチルビニルエーテル、4−メチル−1−ペ
ンチルビニルエーテル等の鎖状アルキルビニルエーテル
類。CH7=CH-0-R"(R" is a linear, branched sheath-like, or cyclic alkyl group.) Specifically, such alkyl vinyl ethers include ethyl vinyl ether, propyl vinyl ether,
Isopropyl vinyl ether, butyl vinyl ether,
Chain alkyl vinyl ethers such as tere-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, and 4-methyl-1-pentyl vinyl ether.
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。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、11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.
有機珪 化合物(C)
有機珪素化合物(C)は分子中にオレフィン系不飽和結
合及び加水分解する基を有する化合物であって具体的に
次の3種の一般式で示すことができる。Organosilicon Compound (C) The organosilicon compound (C) is a compound having an olefinic unsaturated bond and a hydrolyzable group in the molecule, and can be specifically represented by the following three general formulas.
式 %式% (R’、R=はオレフィン性不飽和結合を有し。formula %formula% (R', R= have an olefinic unsaturated bond.
炭素、水素、場合によっては酸素からなり、それぞれ同
−又は異なっていてもよい。X゛はオレフィン性不飽和
結合を有しない有機基であり、Y゛、Y?、Y9は加水
分解する基であり、それぞれ同−又は異なっていてもよ
い。)で表される。It consists of carbon, hydrogen, and in some cases oxygen, and they may be the same or different. X゛ is an organic group having no olefinic unsaturated bond, Y゛, Y? , Y9 are hydrolyzable groups, and may be the same or different. ).
珪素化合# (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、シクロへ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。As the group having an unsaturated bond in silicon compound #(C), vinyl, allyl, butenyl, cyclohexenyl, etc. can be specifically used. As the hydrolyzable group, an alkoxy group, an acyloxy group, an oxime group, etc. can be specifically used.
詳しくは、R7及びR”の不飽和結合基は、ビニル、ア
リル、ブテニル、シクロへキセニル、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、
CH2=C)l−CO01CH2)! −。Specifically, the unsaturated bonding groups of R7 and R'' are vinyl, allyl, butenyl, cyclohexenyl, cyclopentagenyl, etc., and terminal olefinic unsaturated groups are particularly preferable. The unsaturated bond group is
CH2=C)l-CO01CH2), which has an ester bond of a terminally unsaturated acid. −.
C)1.=c(CI、)CO01CH2)! +。C)1. =c(CI,)CO01CH2)! +.
CO3−C(CH=)CO01CH2)20(CTo)
g 。CO3-C(CH=)CO01CH2)20(CTo)
g.
cH2= C(CH,)C00CH,CH,0C)12
CHCH20(CB、)−。cH2= C(CH,)C00CH,CH,0C)12
CHCH20(CB,)-.
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R″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。It can also be a group such as H. Among these, R7
Preferably, R'' to R'' do not contain oxygen and are composed of carbon and hydrogen, and a vinyl group is particularly suitable.
Xl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 hydrocarbon of Xl is a monovalent hydrocarbon group such as methyl, ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl, tolyl, etc., and these groups may also be a halogen-substituted hydrocarbon group. good.
Y’、Y”、Y’は、具体的には、メトキシ。Specifically, Y', Y'', and Y' are methoxy.
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
一〇X= C(CI(す、。Alkoxy groups such as ethoxy, butoxy, methoxyethoxy, alkoxyalkoxy groups, acyloxy groups such as formyloxy, acetoxy-probionoxy, oximes such as 10X=C(CI(su,
一〇入= cncHtctLおよび
−ox= C(CAH9)2などであり、その他任意の
加水分解しうる有機基である。10 = cncHtctL and -ox = C(CAH9)2, etc., and any other hydrolyzable organic group.
本発明では有機珪素化合物は、上記のような一般式、特
に■で表される化合物であることが好ましく、特に基Y
’、Y2.Y’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、y
−y=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
ランなども同様に用いることができる。In the present invention, the organosilicon compound is preferably a compound represented by the above-mentioned general formula, especially a compound represented by the group Y.
', Y2. Organosilicon compounds in which Y' are the same are preferred; among these, R7 is a vinyl group, and y
Particularly preferred are organosilicon compounds in which -y= is an alkoxy group or an alkoxyalkoxy group, such as vinyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(
Methoxyethoxy)silane and the like are preferred. Furthermore, vinylmethyljethoxysilane, vinylphenyldimethoxysilane, etc. can be used similarly.
フッ素共重合体の配合の割合
本発明で用いられるフッ素系重合体のフルオロオレフィ
ン(A)は共重合体中に1乃至30モル%、好ましくは
5乃至30モル%の量で含有していることが望ましい。Blending ratio of fluorine copolymer The fluoroolefin (A) of the fluorine-based polymer used in the present invention is contained in the copolymer in an amount of 1 to 30 mol%, preferably 5 to 30 mol%. is desirable.
フルオロオレフィンがこのような範囲にある場合には、
共重合体は耐候性、耐水性、耐薬品性、撥水性、低摩擦
性が十分に維持されており、高機能塗料になる。また、
アルキルビニルエーテル(B)は1乃至95モル%好ま
しくは50乃至85モル%の量であり、有機珪素化合物
(C)は1乃至30モル%好ましくは3乃至25モル%
の童であり、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、塗料とした
ときの溶媒選択性がよい。また、フルオロオレフィンの
量が前記範囲より少なすぎると充分な耐水性、撥水性、
耐候性などが得られず、多すぎると基材付着性が悪くな
る。また、有機珪素化合物の童があまりに少なすぎると
、硬化後、強靭な塗膜が得られず、あまりに多すぎると
、硬化後、内部応力が増大し塗膜のひび割れの原因とな
り好ましくない。When the fluoroolefins are in this range,
The copolymer maintains sufficient weather resistance, water resistance, chemical resistance, water repellency, and low friction, making it a highly functional paint. Also,
The alkyl vinyl ether (B) is in an amount of 1 to 95 mol%, preferably 50 to 85 mol%, and the organosilicon compound (C) is in an amount of 1 to 30 mol%, preferably 3 to 25 mol%.
When the copolymer is within this range, when the copolymer is used as a coating material, the adhesion to the substrate will be extremely good. Moreover, such a copolymer has good solvent selectivity when used as a coating material. In addition, if the amount of fluoroolefin is too small than the above range, sufficient water resistance, water repellency,
Weather resistance etc. cannot be obtained, and if the amount is too high, adhesion to substrates will deteriorate. Furthermore, if the amount of the organic silicon 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.
の の ムこ い” モノマー
他の共重合可能なモノマーとしては1例えばアクリル酸
、メタアクリル酸、α−エチルアクリル酸、クロトン酸
、4−ペンテン酸、5−ヘキセン酸、6−ヘプテン酸、
7−オクテン酸、8−ノナン酸、9−デカン酸、10−
ウンデシレン酸、マレイン酸、フマール酸、イタコン酸
、シトラコン酸、テ゛トラハイドロフタル側 エンドシ
ス−ビシクロ[2,2,1]ヘプト−5−エン−2,3
−ジカルボン酸等の不飽和カルボン酸、及びそれらのア
ルコール残基の炭素数が1〜20のモノエステルあるい
はジエステル、もしくは無水マレイン酸。Other copolymerizable monomers include acrylic acid, methacrylic acid, α-ethyl acrylic acid, crotonic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid,
7-octenoic acid, 8-nonanoic acid, 9-decanoic acid, 10-
Undecylenic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid endocys-bicyclo[2,2,1]hept-5-ene-2,3
- Unsaturated carboxylic acids such as dicarboxylic acids, monoesters or diesters of these alcohol residues having 1 to 20 carbon atoms, or maleic anhydride.
無水イタコン酸、無水シトラコン酸、無水テトラハイド
ロフタル酸等のオレフィン性酸無水物等の如き不飽和カ
ルボン酸もしくはその誘導体、酢酸ビニル、プロピオン
酸ビニル、酪酸ビニル、イソ酪酸ビニル、カプロン酸ビ
ニル、カプリル酸ビニル、カプリン酸ビニル、ウラリン
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、安息香ビニル、p−t
art−ブチル安息香酸ビニル等の如きカルボン酸ビニ
ルエステル類、!?酸アリル、10ピオン酸アリル、酪
酸アリル、イソ酪酸アリル、カプロン酸アリル、カプリ
ル酸アリル、ウラ、リン酸アリル、シクロヘキサンカル
ボン酸アリル、メチルシクロヘキサンカルボン酸アリル
、安息香酸アリル、p−tert−プチルカロボン酸ア
リルの如きカルボン酸アリルエステル類、エチレン、プ
ロピレン、ブテン−1の如きα−オレフィン類、塩化ビ
ニル、塩化ビニリデン、プロピレン、ブテン−1の如き
ハロゲン化オレフィン顯、スチレン、α−メチルスチレ
ン、ビニルトルエンの如きハロゲン化オレフィン類、ス
チレン、α−メチルスチレン、ビニルトルエンの如き芳
香族ビニル化合物がある。Unsaturated carboxylic acids or derivatives thereof such as olefinic acid anhydrides such as itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, caprylic vinyl acid, vinyl caprate, vinyl urarate, vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, pt
Carboxylic acid vinyl esters such as vinyl art-butylbenzoate,! ? Allyl acid, allyl 10 pionate, allyl butyrate, allyl isobutyrate, allyl caproate, allyl caprylate, ura, allyl phosphate, allyl cyclohexanecarboxylate, allyl methylcyclohexanecarboxylate, allyl benzoate, p-tert-butylcarboxylic acid Carboxylic acid allyl esters such as allyl, α-olefins such as ethylene, propylene, butene-1, halogenated olefins such as vinyl chloride, vinylidene chloride, propylene, butene-1, styrene, α-methylstyrene, vinyltoluene. These include halogenated olefins such as styrene, α-methylstyrene, and aromatic vinyl compounds such as vinyltoluene.
これらの共重合性it体のうち、当該共重合体からなる
塗料の基材との密着性を高めるという観点や、当該共重
合体の重合収率を高めるという観点から、特にマレイン
酸ジアルキルエステル類、カルボン酸ビニルエステル類
の使用が好ましい。Among these copolymerizable IT forms, maleic acid dialkyl esters are particularly preferred from the viewpoint of increasing the adhesion to the base material of the coating material made of the copolymer and from the viewpoint of increasing the polymerization yield of the copolymer. , the use of carboxylic acid vinyl esters is preferred.
これら共重合性単量体を用いて当該共重合体を合成する
に際してはこれら共重合性単重体を1〜70モル%の範
囲内で導入するころが好ましい。When synthesizing the copolymer using these copolymerizable monomers, it is preferable to introduce these copolymerizable monomers within a range of 1 to 70 mol %.
フッ、 重合体の 子愈
また2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
分子量(Mn)が2,000乃至300,000、特に
3.000〜,10,000の範囲内にあることが望ま
しい。In addition, in the fluorine-based polymer according to the present invention, gel and
The number average molecular weight (Mn) measured by permeation chromatography is preferably in the range of 2,000 to 300,000, particularly 3.000 to 10,000.
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R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。If the copolymer has a molecular weight within this range, the solvent selectivity will be improved in conjunction with the above-mentioned combination ratio of each component R, and it will be possible to fully utilize it for applications such as paints.
分子量の測定は1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・ノ(−ミエーションクロマ
トグラフ法(GPC)により測定して求めた数平均分子
ii(Mnlである。The molecular weight is measured using a monodisperse polystyrene having a known molecular weight as a standard substance, and is the number average molecule ii (Mnl) determined by gel nomeation chromatography (GPC).
このようなフッ素系重合体は、具体的に常温において、
たとえはベンゼン、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2 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、[1
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:
Examples include 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.
Dissolves in esters such as ethyl and butyl acetate, and halogenated hydrocarbons such as trichloromethane, dichloroethane, and chlorobenzene.
)・ 、 合 の 法
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)〜(C)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。). , Method of Synthesis The fluorine-containing copolymer as described above can be synthesized by copolymerizing each of the monomers (A) to (C) as described above in the presence of a well-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ter
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(tert−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(tert−ブチルペルオキシ)ヘキサ
ン、 here−ブチルペルベンゾエート、tert
−ブチルペルフェニルアセテート、tert−ブチルペ
ルイソブチレート。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 diter
t-Butyl peroxide, 2,5-dimethyl-2,5-
Di(peroxybenzoate)-hexyne-3,1,4
-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert
tert-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, here-butylperbenzoate, tert
-Butyl perphenylacetate, tert-butyl perisobutyrate.
tert−ブチルペルー5ee−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、t
ert−ブチルペルジエチルアセテートなど、その他ア
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、ジーterL−ブチルペルオキシド
、 2.5−ジメチル−2,5−ジ(tert−ブチル
ペルオキシ)ヘキシン−3、2,5−ジメチル−2,5
−ジ(tert−ブチルペルオキシ)ヘキサン、 1,
4−ビス(tert−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。tert-butylperu 5ee-octoate, tert
t-butyl perbivalate, cumyl perbivalate, t
Other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate, etc. are used, such as ert-butyl perdiethyl acetate. Among these, dicumyl peroxide, di-terL-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5
-di(tert-butylperoxy)hexane, 1,
4-bis(tert-butylperoxyisopropyl)
Dialkyl peroxides such as benzene are preferred.
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−?〜10−’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℃、重合圧力は0−100kg/am’ ・
G、好ましくはO〜50kg/am2 ・Gである。In the copolymerization reaction as described above, the radical initiator is added in the above-mentioned solvent at a molar ratio of 10 to the total number of moles of monomers. The polymerization temperature is preferably 130 to 200°C, preferably 2 to 200°C.
0-100℃, polymerization pressure 0-100kg/am'・
G, preferably 0 to 50 kg/am2.G.
111監亙立皇月
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m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。In the present invention, when producing a fluorine-containing copolymer using a fluoroolefin containing chlorine as a fluoroolefin, the system is It is desirable to have a chlorine scavenger present in the tank.
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) M、 AI、 (OWL−、v−t−(A )
、 ・a H201式中、MはMg、 CaまたはZ
nであり、AはCO,またはHPO□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) M, AI, (OWL-, v-t-(A)
, ・a In formula H201, M is Mg, Ca or Z
n, A is CO, or HPO□, 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).
qgJl?(OH) +うCO7・4H?OMg=Al
t(OH)、、CO,・5H20Mgq^1?(OH)
、、CO,・4H20Mト、A12(OH)t2cO
= ・4H20jgう^1□(O)l)、うHPOj・
4H20Ca−A12(0旧、、CO,−4)120Z
n、A1.(OH)、ecO,・4H,0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Mg2^N0)I
L・3H20のOHの一部がCO,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。qgJl? (OH) + CO7・4H? OMg=Al
t(OH),,CO,・5H20Mgq^1? (OH)
,,CO,・4H20Mt,A12(OH)t2cO
= ・4H20jg ^1□(O)l), うHPOj・
4H20Ca-A12 (0 old, CO, -4) 120Z
n, A1. (OH), ecO, 4H,0 The complex compound represented by (a) may be a compound that is not exactly represented by the above formula, for example, Mg2^N0)I
A compound in which a portion of OH in L.3H20 is replaced with CO may also be used. 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1Mがhであり、Af
ficO,である化合物が好ましい。Among such complex compounds, 1M is h, Af
Compounds that are ficO, are preferred.
(ロ)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MgO、CaO
なとのアルカリ土類金属酸化物、1【(0旧、 、Ca
(OH)pなどのアルカリ土類金属水酸化物、M(CO
3、CaC0,などのアルカリ土類金属炭酸塩などが用
いられる。(b) Basic compounds of alkaline earth metals Examples of basic compounds of alkaline earth metals include MgO, CaO
Alkaline earth metal oxides, 1 [(0 old, , Ca
Alkaline earth metal hydroxides such as (OH)p, M(CO
3, alkaline earth metal carbonates such as CaC0, etc. are used.
上記のようなアルカリ土類金属の塩基性化合物は、(1
gcoす□・Mg(OH)t・5H20などの複塩であ
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 compounds of alkaline earth metals as mentioned above are (1
It may be a double salt such as gcosu□.Mg(OH)t.5H20, 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、
M、含有化合物が好ましい。Among these basic compounds of alkaline earth metals,
Compounds containing M 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
ピ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 polyglycidyl. Aliphatic epoxy compounds such as ether and neopentyl glycol diglycidyl ether are used.
このうちγ−グリシドキシプロピルトリメトキシシラン
などの連索含有エポキシ化合物が好ましい。Among these, epoxy compounds containing continuous chains such as γ-glycidoxypropyltrimethoxysilane are preferred.
上記のような@素捕捉剤のうち、無機化合物である塩素
捕捉剤は、有機化合物である塩素捕Ifl剤と比較して
、塩素(塩酸)との反応が速く、かつ重合系あるいは精
製系に溶解していないため、系外に除去しやすいので好
ましく用いられる。特に(イ)で示した複合化合物が好
ましい。Among the above-mentioned elemental scavengers, chlorine scavengers, which are inorganic compounds, react faster with chlorine (hydrochloric acid) than chlorine scavengers, which are organic compounds, and are suitable for polymerization or purification systems. It is preferably used because it is not dissolved and can be easily removed from the system. Particularly preferred are the composite compounds shown in (a).
上記のような塩素捕捉剤を2重合反応時または得られた
共重合体のW異時あるいはこの両方に存在させることに
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 making the above-mentioned chlorine scavenger present during the double polymerization reaction, during the W phase of the obtained copolymer, or both, coloring of the obtained fluoropolymer can be effectively prevented.
このような塩素捕捉剤を、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塩素原子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1本発明の共重合体に於い
て、共重合体100重量部当たりに対して塩JlllW
I捉剤0.2乃至100!1111のII囲で用いるこ
とが望ましい。When such a chlorine scavenger is used during the polymerization reaction, it is preferably used in an amount of 0.5 to 100 g, preferably 1 to 70 g, per mole of chlorine atoms contained in (A) fluoroolefin. Furthermore, in the copolymer of the present invention, the amount of salt JlllW per 100 parts by weight of the copolymer is
It is desirable to use the I scavenger in the II range of 0.2 to 100!1111.
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.
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乃至10のアルキル基であり+
X’は炭素数4乃至10のアルキル基、 CIま
たはOH基であり、Y”、Y′2はCl,0COR”、
またはOH基であり、これらは同一であっても異なって
いてもよい。但し、R”はアルキル基、アリール基、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。The curing catalyst used in the present invention is 1% (in the formula, R" is an alkyl group having 4 to 10 carbon atoms, and
X' is an alkyl group having 4 to 10 carbon atoms, CI or OH group, Y'', Y'2 is Cl, 0COR'',
or an OH group, which may be the same or different. However, 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、n −C,
H,5n(OH)、Cl、n−C,H,5n(OH)C
l?、n−C,+Ho5nCl,−CJ+−+(OH)
2Cl−CaH,7(0旧CI、、C@H+、5nCl
i、n −C−)1−5n (OH)tOcOc、l(
9,、、n C,H,5n(OH)20COC,+8
2.、n −CJ + 7sn (OH)20COCJ
+ q+n C=HI、5n(OH)?0COC9
,Ht?−n −C−H*5n(OCOC,Hlq)、
、(n−CaHq)tsn(OCOC、、H2,)?(
n−CaHa)Jn(OCOC)l=cHcOOcH,
)2、(n−CjH,)zsn (OCOCH:CHC
OOCH?Ph)を等が用いられる。Specifically, such curing catalysts include n-C,
H, 5n(OH), Cl, n-C, H, 5n(OH)C
l? ,n-C,+Ho5nCl,-CJ+-+(OH)
2Cl-CaH, 7 (0 old CI, , C@H+, 5nCl
i,n -C-)1-5n (OH)tOcOc,l(
9,,,n C,H,5n(OH)20COC,+8
2. , n −CJ + 7sn (OH)20COCJ
+ q+n C=HI, 5n(OH)? 0COC9
,Ht? -n -C-H*5n(OCOC, Hlq),
, (n-CaHq)tsn(OCOC,,H2,)? (
n-CaHa)Jn(OCOC)l=cHcOOcH,
)2, (n-CjH,)zsn (OCOCH:CHC
OOCH? Ph) etc. are used.
このうち特にCaH,5nCl,、
(C,lH*)2Sn(OCOCl−1(2112が好
ましい。Among these, CaH, 5nCl, and (C,lH*)2Sn(OCOCl-1(2112) are particularly preferred.
上記のような含フッ素共重合体と硬化fli!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。Cured with the above fluorine-containing copolymer fli! By using it in combination with a medium, a coating film with excellent adhesion to the substrate and 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(C)に由来する加水分解可能な有機基を有してい
るので、水分と接紬することにより重合体の分子鎖間に
架橋度広が起こり硬化が起こり得る。従って、大気中の
温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こ
とが好ましい。Since the fluorine copolymer used in the present invention has a hydrolyzable organic group derived from the organosilicon compound (C), the degree of crosslinking between the molecular chains of the polymer can be increased by bonding with water. Spreading and hardening may occur. Therefore, as a matter of course, crosslinking can occur due to the temperature in the atmosphere. However, it is preferable to use the above-mentioned curing catalyst 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g
あたり0.03〜2重量部好ましくは0.1〜1.5重
1部の童で用いられる。Such a curing catalyst contains 100 g of fluorine-containing copolymer by weight.
It is used in an amount of 0.03 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight.
1東1五に二
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。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、#
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 acid, 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重重
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#&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III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調製し
てもよい。The fluorine-containing copolymer composition according to the present invention is composed of a fluorine-containing copolymer, a curing agent, and an organic solvent as described above. The solution III, which may contain all of the above-mentioned components, and the solution III 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 are added immediately before use. The above fluorine-containing copolymer composition may be prepared by mixing.
その他の成分
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、硬化触媒及び有機溶剤に加えて、顔
料、染料、脱水剤(オルトギ酸トリメチル)2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)
、γ−シソシアネートプロビルトリメトキシシラン等の
イソシアネート基を有する有機珪素化合物などを含んで
いてもよい。Other components The fluorine-containing copolymer composition according to the present invention contains, in addition to the above-mentioned fluorine-containing copolymer, curing catalyst, and organic solvent, a pigment, a dye, a dehydrating agent (trimethyl orthoformate), a dispersant, and Other paint additives (leveling agents, wetting agents, etc.),
Alkyl silicates and their oligomers as well as their hydrolysates (tetramethyl orthosilicate oligomers, etc.)
, an organosilicon compound having an isocyanate group such as γ-cysocyanatepropyltrimethoxysilane.
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2通常の液体塗料と同じように刷毛、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 coated on bases such as metal, wood, plastic, ceramic, paper, glass, etc. with a brush, spray, roller coater, etc. in the same way as ordinary liquid paints. Can be applied to surfaces. 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
℃)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 at a temperature (°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
エーテルとオレフィン性不飽和結合金有基及び加水分解
す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て、有機溶剤に加え
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塗料となり、しか
も速やかな硬化が達成されて基材との付着性に優れた壷
膜層を形成することができる。(Effects of the Invention) According to the present invention, a fluoropolymer consisting of a fluoroolefin, an alkyl vinyl ether, an olefinically unsaturated gold group and an organosilicon compound having a hydrolyzable group is combined with a specific curing catalyst. By adding this composition to an organic solvent, the composition becomes a coating material with excellent weather resistance, water resistance, chemical resistance, water repellency, and low friction after curing, and also achieves rapid curing and good bonding with the base material. A pot film layer with excellent adhesion can be formed.
(実施例)
以下に本発明に係る塗料用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 coating composition according to the present invention and evaluation of adhesion when used as a coating material were conducted.
尚2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゜
1.5i!にのステンレス製撹#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(T’4VS) 31.1g、エチルビニ
ルエーテル(EVE) 82.2t、 n−プチルヒ
ニルエーテル(BVE) 15.0g、 マレイン2
1 シメf ル(DMM) 108゜1g、合成ハイド
ロタルサイト
(ALa、 *A12(OH)7gcOg ・3..1
)120 )粉末ノ焼成品(SHT) 9.3g、
″JlkIII化ジラウロイル5.輸をベンゼン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) 87.4gをt−トラレー
プ中に導入し、65℃まで異温し。Reference production example 1゜1.5i! After purging the interior of a stainless steel autoclave with a stirrer with nitrogen, under a nitrogen stream, 31.1 g of trimethoxyvinylsilane (T'4VS), 82.2 t of ethyl vinyl ether (EVE), and n-butyl vinyl ether (BVE) were added. ) 15.0g, Malein 2
1 Shimel (DMM) 108°1g, synthetic hydrotalcite (ALa, *A12(OH)7gcOg ・3..1
)120) Powder fired product (SHT) 9.3g,
``JlkIII dilauroyl 5. import benzene 500
It was dissolved in ml and charged all at once. Thereafter, 87.4 g of chlorotrifluoroethylene (CTFE) was introduced into the t-trarepe and heated to 65°C.
8時間反応を行なった。その後、オートクレーブを開放
し、1臀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15 Q g、 メタノールloo
g、 5HT9.4gを加え、50’Cで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400gを加え、再びエバポレー
ターにて減圧下溶媒を留去した。その後、キシレン50
0gを加え、この溶液を直通して SHTを除去し、減
圧濃縮して無色透明な重合体(1)273gを得た。The reaction was carried out for 8 hours. Thereafter, the autoclave was opened, and the reaction solution was taken out into a one-bottle eggplant-shaped flask. To this reaction solution was added 15 Q g of xylene and loo
g, 9.4 g of 5HT was added and heat treated at 50'C for 1.5 hours and then at 60°C for 1.5 hours with stirring,
The residual monomer and solvent were distilled off under reduced pressure using an evaporator, then 400 g of xylene was added, and the solvent was distilled off under reduced pressure using an evaporator again. Then xylene 50
This solution was passed directly through to remove SHT, and concentrated under reduced pressure to obtain 273 g of a colorless and transparent polymer (1).
得られた共重合体のGPCによる数平均分子量は640
0であった。The number average molecular weight of the obtained copolymer by GPC was 640.
It was 0.
また、この重合体の組成分析を元素分析及びNMRを用
いて行なったとコロ、 CTFE/ EVE/ BV
E/DMN/TMVS=26/30/6/30/7 (
モル%)であった。In addition, the composition of this polymer was analyzed using elemental analysis and NMR.
E/DMN/TMVS=26/30/6/30/7 (
(mol%).
参考製造例2゜
1、suのステンレス製撹#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) 31.1 g、エチルビニルエーテ
ル(EVE) 93.0g、 マレイン酸シx−fk
(DEN)206.6g、 合成ハイドロタルサイ
ト(M(4,%^12(0旧、 、CO,・3.5Ht
O)粉末の#!成品(SHT) 9.3g。Reference Production Example 2゜1. After purging the interior of an SU stainless steel autoclave with nitrogen, under a nitrogen stream, 31.1 g of trimethoxyvinylsilane (TMVS), 93.0 g of ethyl vinyl ether (EVE), and maleic acid were added. x-fk
(DEN) 206.6g, synthetic hydrotalcite (M(4,%^12(0 old, , CO, ・3.5Ht
O) Powder #! Finished product (SHT) 9.3g.
過酸化ジラウロイル5.4gをベンゼン500m1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) 35.0 gをオートクレーブ中に
導入し、65℃まで昇温し、8時間反応を行なった。そ
の後、オートクレーブを開放し、1uのナス子型フラス
コに反応液を取り畠した。この反応液にキシレン150
g、 メタノール100g、5H79,4gを加え
、50℃で1.511!?間さらニ60 ”C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4
00gを加え、再びエバポレーターにて減圧上溶媒を留
去した。その後、キシレン500gを加え、この溶液を
濾過して SHTを除去し、減圧濃縮して無色透明な重
合体(II)290gを得た。5.4 g of dilauroyl peroxide was dissolved in 500 ml of benzene and charged all at once. Then, 35.0 g of chlorotrifluoroethylene (CTFE) was introduced into an autoclave, the temperature was raised to 65°C, and reaction was carried out for 8 hours. . Thereafter, the autoclave was opened, and the reaction solution was poured into a 1U eggplant-shaped flask. Add 150 xylene to this reaction solution.
g, 100 g of methanol, 79.4 g of 5H were added, and the temperature was 1.511 at 50°C! ? 1.5 at 60” C
After heat treatment with stirring for a period of time, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then xylene 4
00g was added thereto, and the solvent was distilled off again under reduced pressure using an evaporator. Thereafter, 500 g of xylene was added, the solution was filtered to remove SHT, and concentrated under reduced pressure to obtain 290 g of colorless and transparent polymer (II).
得られた共重合体のGPCによる数平均分子量は4,0
00であった。The number average molecular weight of the obtained copolymer by GPC was 4.0.
It was 00.
また、この重合体の組成分析を元素分析及びNMRを用
いて行なったとコ’5. CTFE/ EVE/ D
EM/TMVS=12/29151/8 (モル%)
テアツf:。In addition, the composition of this polymer was analyzed using elemental analysis and NMR. CTFE/EVE/D
EM/TMVS=12/29151/8 (mol%)
Theatu f:.
参考製造例3゜
1.5*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、 ベンゼン180m
1. エチルビニルエーテル(EVE) 39.4
g、酢酸ビニル(VAc) 108.6 g、トリメト
キシビニルシラン(TMVS) 43.6g、合成ハイ
ドロタルサイト(Mg−、J12(OH)、、co、・
3.58?O)粉末の焼成品(SHT)13.0gを仕
込んだ。その後クロロトリプルオロエチレン(CTFE
) 245 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120m lに溶解し
た開始剤溶液を4時間かけてフィードした。更に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
応を停止した。Reference Production Example 3 After purging the inside of a 1.5* stainless steel autoclave with nitrogen, add 180 m of benzene under a nitrogen stream.
1. Ethyl vinyl ether (EVE) 39.4
g, vinyl acetate (VAc) 108.6 g, trimethoxyvinylsilane (TMVS) 43.6 g, synthetic hydrotalcite (Mg-, J12(OH),, co,.
3.58? O) 13.0 g of fired powder (SHT) was charged. Then chlorotriple oleoethylene (CTFE)
) 245 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. Further 65℃
After the reaction was carried out for 6 hours, the autoclave was cooled with water to stop the reaction.
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、1.5uのナス子型フラスコに反応液を取り出
した。この反応液にキシレン210 g、メタノール1
20g、 S HT 13.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、残留モノ
マー及び溶媒を留去し、次いでキシレン550gを加え
攪拌により均一溶液とした。After cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a 1.5U eggplant type flask. 210 g of xylene and 1 methanol were added to this reaction solution.
20g, SHT 13. Add Og and heat at 50℃ for 1
The mixture was heated at 60° C. for 1.5 hours with stirring. After the treatment, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to form a homogeneous solution.
この溶液を濾過して SHTを除去し、減圧濃縮して無
色透明な重合体(m)288gを得た。This solution was filtered to remove SHT and concentrated under reduced pressure to obtain 288 g of a colorless and transparent polymer (m).
得られた共重合体のGPCによる数平均分子量は21,
000であった。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。The number average molecular weight of the obtained copolymer by GPC was 21,
It was 000. In addition, the composition of this polymer was analyzed using elemental analysis and NMR.
CTFE/ EVE/ VAc/ TMVS= 27/
28/ 39/ 6 (% ル% )であった。CTFE/EVE/VAc/TMVS=27/
It was 28/39/6 (%le%).
比較製造例1
1.5uのステンレス製撹#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) 106 g、 n−ブ
チルビニルエーテル(BVE) 21.0g、 トリ
メトキシビニルシラン(TMVS) 62.2g、
合成ハイドロタルサイト(Mga、5^1t(OH)、
sco、・3.5 H,O)粉末の焼成品(SHT)1
3.0gを仕込んだ、その後クロロトリフルオロエチレ
ン(CTFE)257 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。Comparative Production Example 1 The inside of a 1.5U stainless steel autoclave with a stirrer was replaced with nitrogen, and under a nitrogen flow, 180ml of benzene, 106g of ethyl vinyl ether (EVE), 21.0g of n-butyl vinyl ether (BVE), and trimethoxyvinylsilane were added. (TMVS) 62.2g,
Synthetic hydrotalcite (Mga, 5^1t (OH),
sco, ・3.5 H, O) powder fired product (SHT) 1
After that, 257 g of chlorotrifluoroethylene (CTFE) was introduced into the autoclave, and the temperature was raised to 65°C. To the mixture thus obtained, 7.6 g of dilauroyl peroxide was added to 120 ml of benzene.
An initiator solution dissolved in water was fed over a period of 4 hours.
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。After further reaction at 65°C for 6 hours, the autoclave was cooled with water.
反応を停止させた。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、 1.5XZ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Wj媒を留去し、次いでキシレ
ン550gを加え、撹拌により均一溶液とした。この溶
液をI過してSHTを除去し、減圧濃縮して無色透明な
重合体(IV) 366gを得た。The reaction was stopped. After cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a 1.5XZ eggplant-shaped flask. Add xylene 2 to this reaction solution.
10g, methanol 120g-5HT13°Og
was added and heat treated at 50°C for 1.5 hours and then at 60°C for 1.5 hours with stirring. After the treatment, residual monomers and Wj medium were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to obtain a homogeneous solution. This solution was filtered to remove SHT and concentrated under reduced pressure to obtain 366 g of a colorless and transparent polymer (IV).
得られたポリマーのGPCによる数平均分子量は100
00であった。The number average molecular weight of the obtained polymer by GPC was 100.
It was 00.
また、この重合体の組成分析を元素分析及びNMRを用
いて行なったト、:口、 CTFE/ EVE/ BV
E/TMVS =50/37/6/7 (−Fニル比)
テlhツf:。In addition, the composition analysis of this polymer was performed using elemental analysis and NMR.
E/TMVS =50/37/6/7 (-F nyl ratio)
telhtsuf:.
実施例1
参考製造例1で得られた重合体(1) 38.2重重部
と、テトラメチルオルト珪酸オリゴマー1.9重重部と
、オルトギ酸メチル1.9重重部と、酸化チタン26.
7重量部と、キシレン31.3重1に部とからなる塗料
(1)を調製した。Example 1 Polymer (1) obtained in Reference Production Example 1 38.2 parts by weight, 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) was prepared consisting of 7 parts by weight and 31.3 parts by weight of xylene.
また一方JIS G 3302に規定する亜鉛鋼板+5
PG)にエポキシ塗料マリンSC(三井金属塗料化学■
)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 sheet specified in JIS G 3302 +5
PG) to epoxy paint Marine SC (Mitsui Metal Paint Chemicals)
) was coated and exposed outdoors for 10 days to produce a coating substrate.
また上記のようにして調製した塗料(1)100重量部
に対しn −BuSnCl、の6.3重量%キシレン液
を1.9重重部製合して、塗料用組成物を調製し、この
組成物を上記の塗装基材上に 100μm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、基盤目試験を行なった。Further, a coating composition was prepared by preparing 1.9 parts by weight of a 6.3% by weight xylene solution of n-BuSnCl with respect to 100 parts by weight of the coating material (1) prepared as described above. The product was applied onto the above-mentioned coated substrate using a 100 μm applicator. After the coating film thus obtained was exposed outdoors for one week, a base grain 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)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、基盤目試験を行った。結果を表1に示す。Example 2 A coating film was formed in the same manner as in Example 1 except that the polymer (II) obtained in Reference Production Example 2 was used, and after being exposed outdoors for one week, a base grain test was conducted. The results are shown in Table 1.
実施例3
参考製造例3で得られた重合体(m)を用いた以外は、
実施例1と同様にして塗膜を形成し、#I外に1週間m
g+、、た後、基盤目試験を行った。結果を表1に示す
。Example 3 Except for using the polymer (m) obtained in Reference Production Example 3,
A coating film was formed in the same manner as in Example 1, and left outside #I for 1 week.
After g+, a base test was conducted. 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II造
例1で得られた共重合体(IV)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 A coating film was formed in the same manner as in Example 1, except that the copolymer (IV) obtained in Comparative II Preparation Example 1 was used instead of the polymer (1), After one week of outdoor exposure, a substrate test was conducted.
結果を表1に示す。The results are shown in Table 1.
Claims (3)
A)成分は1乃至30モル%の範囲で、(B)成分が1
乃至95モル%の範囲で、(C)成分が1乃至30モル
%の範囲である含フッ素共重合体と、 〔B〕式R^0^1−SnX^0^1Y^0^1Y^0
^2(式中、R^0^1は炭素数4乃至10のアルキル
基であり、X^1は炭素数4乃至10のアルキル基、C
lまたはOH基であり、Y^0^1、Y^0^2はCl
、OCOR^0^2、またはOH基であり、これらは同
一であつても異なっていてもよい。但し、R^0^2は
アルキル基、アリール基、アリルアルキル基である。)
で表される硬化触媒と、 〔C〕有機溶媒と、からなることを特徴とする付着性に
優れた塗料用組成物。(1) [A] (A) Fluoroolefin (B) Alkyl vinyl ether (C) Obtained by copolymerizing an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group; ) for the total molar quantity of the components (
Component A) is in the range of 1 to 30 mol%, and component (B) is in the range of 1 to 30 mol%.
A fluorine-containing copolymer in which the component (C) is in the range of 1 to 30 mol%, and [B] formula R^0^1-SnX^0^1Y^0^1Y^0
^2 (In the formula, R^0^1 is an alkyl group having 4 to 10 carbon atoms, X^1 is an alkyl group having 4 to 10 carbon atoms, C
l or OH group, and Y^0^1 and Y^0^2 are Cl
, OCOR^0^2, or OH group, which may be the same or different. However, R^0^2 is an alkyl group, an aryl group, or an arylalkyl group. )
A coating composition with excellent adhesion, characterized by comprising a curing catalyst represented by: 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。)で表されること
を特徴とする請求項第1項記載の組成物。(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, The composition according to claim 1, wherein the composition 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. thing.
素、水素、場合によつては酸素からなり、それぞれ同一
叉は異なつていてもよい。X^1はオレフィン性不飽和
結合を有しない有機基であり、Y^1、Y^2、Y^3
は加水分解する基であり、それぞれ同一叉は異なつてい
てもよい。) の I 、II、叉は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項記載の組
成物。(3) The organic silicate compound (C) has the following formula: ▲ 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. ▼… (R ^7 and R^8 have an olefinic unsaturated bond and are composed of carbon, hydrogen, and in some cases oxygen, and may be the same or different. X^1 has an olefinic unsaturated bond It is an organic group that does not have Y^1, Y^2, Y^3
are hydrolyzable groups, and may be the same or different. 2. The composition according to claim 1, wherein the composition is an organosilicon compound (C) represented by any one of I, II, or III.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30862090A JPH04180974A (en) | 1990-11-16 | 1990-11-16 | Coating composition excellent in adhesiveness |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30862090A JPH04180974A (en) | 1990-11-16 | 1990-11-16 | Coating composition excellent in adhesiveness |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04180974A true JPH04180974A (en) | 1992-06-29 |
Family
ID=17983243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30862090A Pending JPH04180974A (en) | 1990-11-16 | 1990-11-16 | Coating composition excellent in adhesiveness |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04180974A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103187321A (en) * | 2011-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Encapsulation die with low adhesion coating film |
-
1990
- 1990-11-16 JP JP30862090A patent/JPH04180974A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103187321A (en) * | 2011-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Encapsulation die with low adhesion coating film |
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