JPH0655913B2 - Fluorocarbon resin-containing electrodeposition paint - Google Patents
Fluorocarbon resin-containing electrodeposition paintInfo
- Publication number
- JPH0655913B2 JPH0655913B2 JP62128730A JP12873087A JPH0655913B2 JP H0655913 B2 JPH0655913 B2 JP H0655913B2 JP 62128730 A JP62128730 A JP 62128730A JP 12873087 A JP12873087 A JP 12873087A JP H0655913 B2 JPH0655913 B2 JP H0655913B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- electrodeposition coating
- acrylate
- acrylic acid
- methacrylic acid
- 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.)
- Expired - Lifetime
Links
- 238000004070 electrodeposition Methods 0.000 title claims description 43
- 229920005989 resin Polymers 0.000 title claims description 26
- 239000011347 resin Substances 0.000 title claims description 26
- 239000003973 paint Substances 0.000 title description 12
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 20
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- -1 Hydroxyalkyl ester Chemical class 0.000 claims description 15
- 239000008199 coating composition Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 36
- 239000011248 coating agent Substances 0.000 description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 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 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- DFVPUWGVOPDJTC-UHFFFAOYSA-N 2,2,3,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)C(F)(F)F DFVPUWGVOPDJTC-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007739 conversion coating 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
- 230000007547 defect Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、フツ素含有電着塗料に関し、更に詳しくは、
低摩擦性であつて、均一な塗膜厚を容易に得ることがで
きるフツ素樹脂含有電着塗料関する。TECHNICAL FIELD The present invention relates to a fluorine-containing electrodeposition coating composition, and more specifically,
The present invention relates to a fluororesin-containing electrodeposition coating composition having low friction and capable of easily obtaining a uniform coating film thickness.
従来の技術 従来の電着塗料にはアクリル−メラミン系、アルキド−
メラミン系、エポキシ−メラミン系、アクリル−ウレタ
ン系、エポキシ−ウレタン系、不飽和ポリエステル等の
熱硬化性樹脂が用いられている。ポリブタジエン、エポ
キシ−ウレタン等は、自動車の下塗用として多用され、
今や必須の工程となつている。特にアクリル−メラミン
系は、外観および塗膜性能が優れる点から、上塗り、ワ
ンコート電着塗料としてすでに各種分野で実用化されて
いる。Conventional technology Conventional electrodeposition paints include acrylic-melamine-based, alkyd-
Thermosetting resins such as melamine-based, epoxy-melamine-based, acrylic-urethane-based, epoxy-urethane-based, and unsaturated polyester are used. Polybutadiene, epoxy-urethane, etc. are often used as undercoats for automobiles,
It is now an essential process. In particular, the acrylic-melamine type has already been put to practical use in various fields as a top coat and a one-coat electrodeposition coating composition because of its excellent appearance and coating film performance.
しかし素材が錆びやすい鉄などにおいては、耐食性の点
でワンコート電着塗料は不利である。その原因は、下地
塗装工程における複数回の塗装による防錆処理ができな
い点が大きい。しかし亜鉛めつき、ニツケルめつき、ク
ロムめつき等の電気めつき、リン酸鉛処理等の化成皮膜
などによつて、耐食性は近年屋外等においても問題のな
いレベルまで向上されている。However, the one-coat electrodeposition coating is disadvantageous in terms of corrosion resistance when the material is rusty iron. The main reason is that the rust prevention treatment cannot be performed by coating multiple times in the base coating process. However, in recent years, corrosion resistance has been improved to a level at which there is no problem even outdoors, etc., due to zinc plating, nickel plating, electric plating such as chromium plating, and chemical conversion coating such as lead phosphate treatment.
一方、耐食性の悪い下地、例えば鉄等においては、耐食
性の良い塗膜が必要とされるが、これらに対してはフツ
素塗料およびシリコン塗料などが近年実用化されてい
る。しかしフツ素樹脂を用いた電着塗装方法はまだ充分
に開発されておらず、金属の潤滑化表面処理法（特開昭
５７−１０４６８８）および高耐候性電着塗料組成物
（特開昭６１−９７７６５）において用いられている
が、これらにおいてはフツ素樹脂の特性が充分に生かさ
れているとは言え難い。On the other hand, a coating having good corrosion resistance is required for a substrate having poor corrosion resistance, such as iron, and fluorine coating and silicon coating have been put into practical use in recent years. However, an electrodeposition coating method using a fluorine resin has not been sufficiently developed, and a metal lubricated surface treatment method (JP-A-57-104688) and a high weather-resistant electrodeposition coating composition (JP-A-61-61). -97765), it is difficult to say that the characteristics of fluorine resin are fully utilized in these.
発明が解決しようとする問題点 フツ素塗料およびシリコン塗料などの開発が従来の塗料
技術の大きな改良をもたらし、さらに高度な各種技術の
開発や特殊な用途の拡大に伴つて、フツ素樹脂含有の電
着塗料の開発が要求されている。しかしフツ素樹脂粉末
は、水溶性電着塗料に対する分散性が悪く、界面活性剤
を使用していたが、外観不良が生じ電着塗装の特性が充
分生かされないという問題がある。Problems to be Solved by the Invention The development of fluorine coatings and silicone coatings has brought about great improvements in conventional coating technology, and with the development of various advanced technologies and the expansion of special applications, fluorine resin-containing materials have been developed. Development of electrodeposition paint is required. However, the fluororesin powder has a poor dispersibility in a water-soluble electrodeposition coating and a surfactant has been used, but there is a problem that the appearance is poor and the characteristics of the electrodeposition coating are not fully utilized.
本発明の目的は、優れた塗膜をもつフツ素樹脂含有電着
塗料を提供するものである。本発明にかかる電着塗料を
用いて完成した塗膜は、フツ素樹脂特有の低摩擦性、非
粘着性、耐絶縁性、揆水性揆油性等を示す。しかも、同
塗料を用いれば均一な膜厚の塗膜を一回の電着塗膜によ
り容易に得ることができる。An object of the present invention is to provide a fluorine resin-containing electrodeposition coating composition having an excellent coating film. A coating film completed by using the electrodeposition coating composition according to the present invention exhibits low friction property, non-adhesion property, insulation resistance, water-repellent oil-oil property and the like peculiar to fluorine resin. Moreover, if the same paint is used, a coating film having a uniform film thickness can be easily obtained by a single electrodeposition coating film.
問題点を解決するための手段 本発明は、下記のＡ成分とＢ成分とを、その固形分比が
１：２〜３：１で含有することを特徴とするフツ素樹脂
含有電着塗料である。MEANS FOR SOLVING THE PROBLEMS The present invention provides a fluororesin-containing electrodeposition coating composition comprising the following components A and B in a solid content ratio of 1: 2 to 3: 1. is there.
Ａ成分：フツ素樹脂１００重量部に対して、下記のａ〜
ｄ成分を含有する共重合体の１０〜５０重量部を含有す
る分散液と、該分散液をｐＨ７〜１０に調整するアンモ
ニアまたは有機アミン中和剤。Component A: For 100 parts by weight of fluorine resin, the following a to
A dispersion containing 10 to 50 parts by weight of a copolymer containing the component d, and an ammonia or organic amine neutralizing agent for adjusting the pH of the dispersion to 7 to 10.
ａ アクリル酸もしくはメタクリル酸のフツ化アルキル
エステル１０〜８０重量％ ｂ アクリル酸もしくはメタクリル酸またはそれらの遊
離カルボキシ基を含有する誘導体５〜３０重量％ ｃ アクリル酸もしくはメタクリル酸のヒドロキシアル
キルエステルまたはそれらの誘導体０〜３０重量％ ｄ スチレンまたはアクリル酸もしくはメタクリル酸の
アルキルエステル０〜３０重量％ Ｂ成分：水溶性電着塗料。a Fluorinated alkyl ester of acrylic acid or methacrylic acid 10 to 80% by weight b Acrylic acid or methacrylic acid or a derivative thereof containing a free carboxy group 5 to 30% by weight c Hydroxyalkyl ester of acrylic acid or methacrylic acid or their Derivative 0-30% by weight d Styrene or alkyl ester of acrylic acid or methacrylic acid 0-30% by weight B component: Water-soluble electrodeposition coating composition.
作 用 本発明に従えば、フツ素樹脂含有電着塗料は、フツ素樹
脂と、分散液と、中和剤と、水溶性電着塗料とを含有す
る。Operation According to the present invention, the fluororesin-containing electrodeposition coating contains a fluororesin, a dispersion, a neutralizing agent, and a water-soluble electrodeposition coating.
フツ素樹脂としては、４フツ化エチレン樹脂（ＰＴＦ
Ｅ）、４フツ化エチレン−６フツ化プロピレン共重合樹
脂（ＦＥＰ）、４フツ化エチレン−パーフロロアルキル
ビニルエーテル共重合樹脂（ＰＦＡ）、４フツ化エチレ
ン−エチレン共重合樹脂（ＥＴＦＥ）、３フツ化塩化エ
チレン樹脂（ＰＣＴＦＥ）、フツ化ビニリデン樹脂（Ｐ
ＶｄＦ）等の微粉末が単独でまたは２種以上混合して用
いられる。As fluorocarbon resin, tetrafluoroethylene resin (PTF
E), 4 fluorinated ethylene-6 fluorinated propylene copolymer resin (FEP), 4 fluorinated ethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), 4 fluorinated ethylene-ethylene copolymer resin (ETFE), 3 ft Chlorinated ethylene resin (PCTFE), vinylidene fluoride resin (P
Fine powders such as VdF) may be used alone or in admixture of two or more.
分散液としては、下記のａ〜ｄ成分を含む共重合体（平
均分子量５０００〜８００００、好ましくは２００００
〜５００００）が用いられる。特にａ成分は、フツ素を
含有するので、従来用いられていた界面活性剤のような
塗装面の外観不良の発生もなく、フツ素樹脂を良好に分
散させる。As the dispersion liquid, a copolymer containing the following components a to d (average molecular weight 5,000 to 80,000, preferably 20,000)
˜50000) is used. In particular, since the component a contains fluorine, the fluororesin is satisfactorily dispersed without causing the appearance defect of the coated surface unlike the conventionally used surfactant.
ａ 下記の一般式で表わされるアクリル酸もしくはメタ
クリル酸のフツ化アルキルエステル１０〜８０重量％、
好ましくは４０〜６０重量％、 式中Ｒ1＝ＨまたはＣＨ３ Ｒ2＝フロロアルキル基 ｂ アクリル酸もしくはメタクリル酸または遊離のカル
ボキシ基を有するアクリル酸もしくはメタクリル酸の誘
導体５〜３０重量％、好ましくは５〜１０重量％、 ｃ アクリル酸もしくはメタクリル酸のヒドロキシアル
キルエステルまたはアクリル酸もしくはメタクリル酸誘
導体のヒドロキシアルキルエステル０〜３０重量％、好
ましくは２０〜３０重量％、 ｄ スチレンまたはアクリル酸もしくはメタクリル酸の
アルキルエステル０〜３０重量％、好ましくは２０〜３
０重量％ 次に上記ａ〜ｄの各成分について具体的に記載する。a 10 to 80% by weight of a fluorinated alkyl ester of acrylic acid or methacrylic acid represented by the following general formula,
Preferably 40-60% by weight, In the formula, R 1 = H or CH 3 R 2 = fluoroalkyl group b acrylic acid or methacrylic acid or a derivative of acrylic acid or methacrylic acid having a free carboxy group 5 to 30% by weight, preferably 5 to 10% by weight, c Acrylic acid or methacrylic acid hydroxyalkyl ester or acrylic acid or methacrylic acid derivative hydroxyalkyl ester 0-30% by weight, preferably 20-30% by weight d Styrene or acrylic acid or methacrylic acid alkyl ester 0-30% by weight , Preferably 20 to 3
0% by weight Next, the components a to d will be specifically described.
ａ アクリル酸もしくはメタクリル酸のフツ化アルキル
エステルであり、具体例として、上記一般式においてＲ
１がＣＨ3、Ｒ２が−ＣＨ2ＣＦ3、−ＣＨ2ＣＦ2ＣＦ2Ｈ
または−ＣＨ2ＣＦ2ＣＦＨＣＦ３の化合物があげられ、
これら化合物は市販されている。a a fluorinated alkyl ester of acrylic acid or methacrylic acid, and as a specific example, R in the above general formula
1 is CH 3, R2 is -CH 2 CF 3, -CH 2 CF 2 CF 2 H
Or a compound of —CH 2 CF 2 CFHCF 3 ;
These compounds are commercially available.
ｂ アクリル酸、メタクリル酸、イタコン酸、マレイン
酸、フマル酸、クロトン酸等のカルボキシ基をもつ化合
物が用いられ、５％重量以下の配合比では分散剤自体の
水溶化が生じ難く、過剰に加えると電着膜の外観が悪く
なる。b A compound having a carboxy group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid is used, and the compounding ratio of 5% by weight or less makes it difficult for the dispersant itself to be water-solubilized and is added excessively. And the appearance of the electrodeposition film deteriorates.
ｃ 具体的化合物としては、２−ヒドルキシエチル(メ
タ)アクリレート、２−ヒドルキシプロピル(メタ)アク
リレート、３−ヒドロキシプロピル（メタ）アクリレー
ト、２−ヒドロキシブチル(メタ)アクリレート、３−ヒ
ドロキシブチル(メタ)アクリレート、４−ヒドロキシブ
チル(メタ)アクリレート、５−ヒドロキシペンチル(メ
タ)アクリレート、６−ヒドロキシヘキシル(メタ)アク
リレート等があげられ、水中での安定性、電着塗料との
架橋のため、０〜３０重量％好ましくは２０〜３０重量
％を用いる。c Specific examples of the compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate. ) Acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and the like, which are stable in water and cross-linked with the electrodeposition coating composition. -30% by weight, preferably 20-30% by weight is used.
ｄ 具体例としては、スチレン、メチル(メタ)アクリレ
ート、エチル(メタ)アクリレート、n−プロピル(メタ)
アクリレート、イソプロピル(メタ)アクリレート、n−
ブチル(メタ)アクリレート、sec−ブチル(メタ)アクリ
レート、t−ブチル(メタ)アクリレート、イソブチル(メ
タ)アクリレート、n−ヘキシル(メタ)アクリレート、２
−エチルヘキシル(メタ)アクリレート、n−オクチル(メ
タ)アクリレート、ラウリル(メタ)アクリレート、トリ
デシル(メタ)アクリレート、ステアリル(メタ)アクリレ
ート等が、塗料と金属との密着性の改善、ポリマーのＴ
ｇの調整、可とう性の付与のために含有される。d As specific examples, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth)
Acrylate, isopropyl (meth) acrylate, n-
Butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc. improve adhesion between paint and metal, T of polymer
It is contained for adjusting g and imparting flexibility.
上記a〜dの成分を従来法に従つて共重合体させる。共重
合の方法としては、例えば塊重合、溶液重合が用いうる
が後者の方法が簡便である。The above-mentioned components a to d are copolymerized by a conventional method. As the copolymerization method, for example, bulk polymerization or solution polymerization can be used, but the latter method is simple.
具体的な合成方法は、重合開始剤にベンゾインパーオキ
サイド、t−ブチルパーベンゾエート、t−ブチルパーオ
キサイド、ヒドロパーオキサイド、クメンヒドロパーオ
キサイド、ジ−ｔ−ブチルパーオキサイドなどの有機過
酸化物、アゾビスイソブチロニトリル、アゾイン酪酸ニ
トリルなどのアゾ化合物を使用し、溶剤として水に可溶
なアセトン、メチルエチルケトン、メタノール、エタノ
ール、n−プロパノール、イソプロパノール、n−ブタノ
ール、イソブタノール、エチレングリコールモノメチル
エーテル、エチレングリコールモノエチルエーテル、エ
チレングリコールモノブチルエーテルなどを使用する。Specific synthesis method, benzoin peroxide, t-butyl perbenzoate, t-butyl peroxide, hydroperoxide, cumene hydroperoxide, organic peroxides such as di-t-butyl peroxide as a polymerization initiator, Azo compounds such as azobisisobutyronitrile and azoinbutyric acid nitrile are used, and water-soluble acetone, methyl ethyl ketone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol monomethyl ether are used as a solvent. , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc. are used.
重合は約５０〜１６０℃で約２〜２４時間、残存モノマ
ーが無くなるまで行なう。The polymerization is carried out at about 50 to 160 ° C. for about 2 to 24 hours until the residual monomer is exhausted.
本発明にかかる電着塗料は、フツ素樹脂１００重量部に
対し上記方法により製造された分散液１０〜５０重量部
および中和剤１〜３重量部を添加して得たフツ素樹脂分
散液に、水溶性電着塗料の固形分比が約１：２〜３：１
になるよう混和することにより製造される。具体的には
フツ素樹脂１００部に対し上記分散液１０〜５０重量部
を加えてよく混練し、次に中和剤を加えてｐＨを７〜１
０に調整する。このために必要な中和剤の量は、１〜３
重量部となる。このときフイビリル化は起きない。ここ
へ徐々に水、好ましくは純水を加えてフツ素樹脂を水中
に分散させる。得られたフツ素樹脂分散液と水溶性電着
塗料を攪拌下に混ぜてフツ素樹脂と水溶性電着塗料の固
形分比が約１：２〜３：１になるようにすると、本発明
にかかる電着塗料が得られる。The electrodeposition coating composition according to the present invention is a fluororesin dispersion obtained by adding 10 to 50 parts by weight of the dispersion prepared by the above method and 1 to 3 parts by weight of a neutralizing agent to 100 parts by weight of the fluororesin. In addition, the solid content ratio of the water-soluble electrodeposition paint is about 1: 2 to 3: 1.
It is manufactured by mixing so that. Specifically, 10 to 50 parts by weight of the above dispersion liquid is added to 100 parts of a fluorine resin and kneaded well, and then a neutralizing agent is added to adjust the pH to 7-1.
Adjust to 0. The amount of neutralizing agent required for this is 1 to 3.
Parts by weight. At this time, fibrillation does not occur. Water, preferably pure water, is gradually added to this to disperse the fluorine resin in water. When the obtained fluororesin dispersion liquid and the water-soluble electrodeposition coating are mixed under stirring so that the solid content ratio of the fluororesin and the water-soluble electrodeposition coating becomes about 1: 2 to 3: 1, the present invention An electrodeposition coating composition can be obtained.
上記の中和剤としては、アンモニアまたは有機アミンが
用いられる。有機アミンは、ジメチルアミン、トリメチ
ルアミン、ジエチルアミン、トリエチルアミン、ジイソ
プロピルアミン、ブチルアミン、モノエタノールアミ
ン、ジエタノールアミン、トリエタノヘルアミン、モノ
イソプロパノールアミン、ジイソプロパノールアミン、
トリイソプロパノールアミン、Ｎ−メチルエタノールア
ミン、Ｎ−アミノエチルエタノールアミン、Ｎ−メチル
ジエタノールアミン、ポリグリコールアミン等が例示さ
れる。Ammonia or an organic amine is used as the neutralizing agent. Organic amines include dimethylamine, trimethylamine, diethylamine, triethylamine, diisopropylamine, butylamine, monoethanolamine, diethanolamine, triethanohelamine, monoisopropanolamine, diisopropanolamine,
Examples include triisopropanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, polyglycolamine and the like.
水溶性電着塗料には、アニオン型およびカチオン型の電
着塗料が含まれ、アクリル系、ポリエステル系、ポリイ
ミド系のものが好ましい。具体的には、アクリル系とし
てエレコートＡＭ（商品名、(株)シミズ製）またはエレ
コートＡＭ２(同前)などがアニオン型電着塗料として、
またエレコートＣＭ(同前)がカチオン型電着塗料として
例示される。またポリエステル系、ポリイミド系の電着
塗料は、水溶性の耐熱ワニスをイオン交換することによ
つて、均一な膜厚で電着塗装できる種類がある。The water-soluble electrodeposition paint includes anion type and cation type electrodeposition paints, and acrylic type, polyester type and polyimide type paints are preferable. Specifically, Elecoat AM (trade name, manufactured by Shimizu Co., Ltd.) or Elecoat AM2 (same as above) as an acrylic type is used as an anionic electrodeposition coating,
Elecoat CM (same as above) is exemplified as a cationic type electrodeposition paint. There are some types of polyester-based or polyimide-based electrodeposition coatings that can be electrodeposited with a uniform film thickness by ion-exchange of a water-soluble heat-resistant varnish.
なお上記分散剤にシリコン樹脂を加えてシリコン変性さ
せて、高耐熱性を付加してもよい。High heat resistance may be added by adding silicon resin to the dispersant to modify the silicon.
本発明にかかる電着塗料は、通常の電着塗装法に準じて
用いられる。すなわち、通電圧、通電時間、温度等は常
法に従えばよい。電着塗装後の焼付をフツ素樹脂の融点
以上に加熱することにより行えば、樹脂が溶融して連続
フイルム化し、耐食性を飛躍的に増大させることができ
る。The electrodeposition coating composition according to the present invention is used according to a usual electrodeposition coating method. That is, the applied voltage, energization time, temperature, etc. may be in accordance with ordinary methods. If the baking after electrodeposition coating is carried out by heating above the melting point of the fluorine resin, the resin is melted to form a continuous film, and the corrosion resistance can be dramatically increased.
実施例 Ａ)分散剤の合成 ジムロート還流器をそなえた３００mlの４ツ口フラスコ
にイソプロピルアルコール４０g を加え、水浴上で加熱
還流下攪拌をおこなう。次にイソプロピルアルコール４
０gにアクリル酸１２g、２−ヒドロキシエチルアクリレ
ート４０g、n−ブチルアクリレート１２g、２−エチル
ヘキシルアクリレート２８g およびトリフロロエチルメ
タクリレート５６gと２，２，３，４，４，４−ヘキサ
フロロブチルメタクリレート１２g ならびに重合開始剤
としてアゾビスイソブチロニトリル２g を添加し混ぜた
のち、滴下ロートに移す。前述の４ツ口フラスコに滴下
ロートを付け、攪拌モータで攪拌をおこない、イソプロ
ピルアルコールの還流下、上記モノマーの混合物を八分
割し、１０分間隔で滴下を行なう。反応温度７０〜８０
℃で約５時間反応させモノマー臭がなくなるまで行な
う。Example A) Synthesis of Dispersant 40 g of isopropyl alcohol was added to a 300 ml four-necked flask equipped with a Dimroth reflux condenser, and the mixture was stirred on a water bath with heating under reflux. Then isopropyl alcohol 4
0 g of acrylic acid 12 g, 2-hydroxyethyl acrylate 40 g, n-butyl acrylate 12 g, 2-ethylhexyl acrylate 28 g and trifluoroethyl methacrylate 56 g and 2,2,3,4,4,4-hexafluorobutyl methacrylate 12 g and polymerization 2 g of azobisisobutyronitrile was added as an initiator, mixed, and then transferred to a dropping funnel. The dropping funnel is attached to the 4-necked flask described above, and the mixture is stirred with a stirring motor. Under reflux of isopropyl alcohol, the mixture of the above monomers is divided into eight, and the mixture is added dropwise at intervals of 10 minutes. Reaction temperature 70-80
React at room temperature for about 5 hours until the monomer odor disappears.
Ｂ)電着塗料の製造 ＰＴＦＥ微粉末５０ｇ（商品名ルブロンＬ−２、ダイキ
ン工業社製）にＡ項の分散剤２０ｇを加え、少量の純水
とともにトリエチルアミン１ccをさらに加え、混合す
る。徐々に純水を加え、フツ素樹脂を分散させ５００ml
とする。別途に水溶性耐熱ワニス(商品名アクアネル６
００、日本触媒製)１００gとイオン交換水４００gを加
えて攪拌したのち、イオン交換処理によつて精製し、雑
イオンを取りのぞく。両者を混合１とし、２５℃の浴
温でＳＶＳ３０４を陰極として１５０Ｖ２分間アニオン
電極を行なうと、フツ素樹脂含有の電着塗膜が得られ
た。B) Production of electrodeposition paint To 50 g of PTFE fine powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.), 20 g of the dispersant of the section A is added, and 1 cc of triethylamine is further added together with a small amount of pure water and mixed. Pure water is gradually added to disperse the fluorine resin and 500 ml.
And Separately water-soluble heat-resistant varnish (trade name AQUANEL 6
(00, manufactured by Nippon Shokubai Co., Ltd.) and 400 g of ion-exchanged water are added and stirred, and then purified by ion-exchange treatment to remove miscellaneous ions. Both were mixed, and anion electrode was carried out at a bath temperature of 25 ° C. with SVS304 as a cathode for 150 V for 2 minutes to obtain a fluorine resin-containing electrodeposition coating film.
さらに３６０℃１０分間電気炉中焼付けると、ＰＴＦＥ
と電着塗料の塗膜が連続フイルム化した。When baked in an electric furnace at 360 ° C for 10 minutes, PTFE
And the coating film of electrodeposition paint became a continuous film.
Ｃ)特性試験 Ｂ項で得られたフツ素樹脂コーテイング片（以下、本件
試験片と記す）について下記の試験を行なつた。C) Characteristic test The following test was performed on the fluororesin coating piece (hereinafter referred to as the present test piece) obtained in the section B.
a)非粘着性試験 試験片をエタノールで洗浄後、セキスイセロテープ(幅
１８mm)を貼り、２mm／sのスピードで引き上げたときの
荷重を測定し、下記の結果を得た。a) Non-tackiness test After the test piece was washed with ethanol, a Sekisui Cellotape (width: 18 mm) was attached, and the load when pulled up at a speed of 2 mm / s was measured, and the following results were obtained.
b)摩擦性試験 試験台上に塗装面が対峙するように３cm角の試験片をお
いて、同３cm角の試験片上に５００g のおもりをのせて
横方向に移動させて荷重を測定する。なお、試験片の表
面は試験毎にエタノールで毎回洗浄した。結果を第２表
および第３表に示す。 b) Friction test Place a 3 cm square test piece on the test stand so that the coated surfaces face each other. Place a 500 g weight on the 3 cm square test piece and move it laterally to measure the load. The surface of the test piece was washed with ethanol for each test. The results are shown in Tables 2 and 3.
発明の効果 本発明にかかる電着塗料を用いて電着塗装を行なうと、
電着塗膜にフツ素樹脂微粉末が含有されているために、
フツ素樹脂の融点以上に加熱して焼付することによりフ
ツ素樹脂が溶融し連続フイルム化する。このフイルム化
により塗膜による耐食性が著しく増大し、さらにフツ素
樹脂特有の低摩擦性、耐薬品性、揆水性揆油性等の機能
性を有する塗膜が形成される。しかも、同塗膜はワンコ
ートで均一な膜厚のものとして得られる。 Effects of the Invention When electrodeposition coating is performed using the electrodeposition coating material according to the present invention,
Because the electrodeposited coating contains fluorine resin fine powder,
The fluororesin is melted to form a continuous film by heating it to a temperature above the melting point of the fluororesin and baking it. Due to this film formation, the corrosion resistance of the coating film is remarkably increased, and further a coating film having functionality such as low friction property, chemical resistance, and water / oil repellent characteristic of fluororesin is formed. Moreover, the same coating film can be obtained with one coat and having a uniform film thickness.
一方、本発明にかかる電着塗料は、水溶性分散剤とし
て、界面活性剤の代わりに含フツ素分散液を用いるの
で、ランニング中の取扱い、保管が容易である。また界
面活性剤による外観不良も発生せず、分散液中のフツ素
がフツ素樹脂粉末とともに電着塗膜に含有され、焼付時
にこれらが一体化する。また、界面活性剤による焼付時
の他の樹脂分の劣化という現象も生じない。さらに本発
明では、容易に入手しうるフツ素樹脂の微粉末を用いる
ため、モノマーよりフツ素樹脂を合成する必要がなく経
済的に有利である。On the other hand, in the electrodeposition coating composition according to the present invention, since the fluorine-containing dispersion liquid is used as the water-soluble dispersant instead of the surfactant, handling and storage during running are easy. Further, the appearance of the surface is not deteriorated by the surfactant, and the fluorine in the dispersion liquid is contained in the electrodeposition coating film together with the fluorine resin powder, and these are integrated at the time of baking. Also, the phenomenon of deterioration of other resin components during baking due to the surfactant does not occur. Further, in the present invention, since fine powder of fluorocarbon resin that is easily available is used, there is no need to synthesize the fluorocarbon resin from the monomer, which is economically advantageous.
したがつて本発明にかかる電着塗料は、化学工業、電子
電気工業、機械工業、食品工業はもとより、宇宙開発、
海洋開発から一般家庭にいたるまで広い分野で利用され
うる。Therefore, the electrodeposition coating material according to the present invention can be applied to the chemical industry, the electrical and electronic industry, the mechanical industry, the food industry, space development,
It can be used in a wide range of fields from ocean development to ordinary households.
Claims (1)
が１：２〜３：１で含有することを特徴とするフツ素樹
脂含有電着塗料。 Ａ成分：フツ素樹脂１００重量部に対して、下記のａ〜
ｄ成分を含有する共重合体の１０〜５０重量部を含有す
る分散液と、該分散液をｐＨ７〜１０に調整するアンモ
ニアまたは有機アミン中和剤。 ａ アクリル酸もしくはメタクリル酸のフツ化アルキル
エステル１０〜８０重量％ ｂ アクリル酸もしくはメタクリル酸またはそれらの遊
離カルボキシ基を含有する誘導体５〜３０重量％ ｃ アクリル酸もしくはメタクリル酸のヒドロキシアル
キルエステルまたはそれらの誘導体０〜３０重量％ ｄ スチレンまたはアクリル酸もしくはメタクリル酸の
アルキルエステル０〜３０重量％ Ｂ成分：水溶性電着塗料。1. A fluororesin-containing electrodeposition coating composition comprising the following components A and B in a solid content ratio of 1: 2 to 3: 1. Component A: For 100 parts by weight of fluorine resin, the following a to
A dispersion containing 10 to 50 parts by weight of a copolymer containing the component d, and an ammonia or organic amine neutralizing agent for adjusting the pH of the dispersion to 7 to 10. a Fluorinated alkyl ester of acrylic acid or methacrylic acid 10 to 80% by weight b Acrylic acid or methacrylic acid or a derivative thereof containing a free carboxy group 5 to 30% by weight c Hydroxyalkyl ester of acrylic acid or methacrylic acid or their Derivative 0-30% by weight d Styrene or alkyl ester of acrylic acid or methacrylic acid 0-30% by weight B component: Water-soluble electrodeposition coating composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62128730A JPH0655913B2 (en) | 1987-05-26 | 1987-05-26 | Fluorocarbon resin-containing electrodeposition paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62128730A JPH0655913B2 (en) | 1987-05-26 | 1987-05-26 | Fluorocarbon resin-containing electrodeposition paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63291966A JPS63291966A (en) | 1988-11-29 |
| JPH0655913B2 true JPH0655913B2 (en) | 1994-07-27 |
Family
ID=14992033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62128730A Expired - Lifetime JPH0655913B2 (en) | 1987-05-26 | 1987-05-26 | Fluorocarbon resin-containing electrodeposition paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655913B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2505285B2 (en) * | 1989-07-17 | 1996-06-05 | シャープ株式会社 | Electrodeposition coating composition |
| JPH07102196A (en) * | 1993-10-01 | 1995-04-18 | Nitto Denko Corp | Electrodeposition coating agent and electrodeposition coating method |
| JP4533476B2 (en) * | 1999-07-07 | 2010-09-01 | 株式会社シミズ | Fluorine resin-containing cationic electrodeposition coating and production method |
| JP2001294815A (en) * | 2000-04-13 | 2001-10-23 | Jsr Corp | Aqueous dispersion for forming low dielectric constant insulating film, low dielectric constant insulating film, and electronic component |
| JP4623689B2 (en) * | 2000-05-22 | 2011-02-02 | 神東塗料株式会社 | Anionic electrodeposition paint and electrodeposition coating method thereof |
| JP4667564B2 (en) * | 2000-07-28 | 2011-04-13 | 株式会社シミズ | Cationic electrodeposition coating composition |
-
1987
- 1987-05-26 JP JP62128730A patent/JPH0655913B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63291966A (en) | 1988-11-29 |
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