JPS63275678A - Thermoset coating composition - Google Patents
Thermoset coating compositionInfo
- Publication number
- JPS63275678A JPS63275678A JP11036587A JP11036587A JPS63275678A JP S63275678 A JPS63275678 A JP S63275678A JP 11036587 A JP11036587 A JP 11036587A JP 11036587 A JP11036587 A JP 11036587A JP S63275678 A JPS63275678 A JP S63275678A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- meth
- vinyl monomer
- acrylic copolymer
- thermosetting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 24
- 239000008199 coating composition Substances 0.000 title claims description 12
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 29
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 27
- 229920003180 amino resin Polymers 0.000 claims abstract description 16
- -1 acrylic ester Chemical class 0.000 claims abstract description 15
- 239000000049 pigment Substances 0.000 claims abstract description 10
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003973 paint Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 33
- 239000011248 coating agent Substances 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000013007 heat curing Methods 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002537 cosmetic Substances 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 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 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000001530 fumaric acid Substances 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YZBOVSFWWNVKRJ-UHFFFAOYSA-M 2-butoxycarbonylbenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1C([O-])=O YZBOVSFWWNVKRJ-UHFFFAOYSA-M 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 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
- 238000012662 bulk polymerization Methods 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229940072282 cardura Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 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
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- RUZYUOTYCVRMRZ-UHFFFAOYSA-N doxazosin Chemical compound C1OC2=CC=CC=C2OC1C(=O)N(CC1)CCN1C1=NC(N)=C(C=C(C(OC)=C2)OC)C2=N1 RUZYUOTYCVRMRZ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は熱硬化被覆組成物に関し、さらに詳細には自動
車ボディの塗膜といった高度の美粧性と性能とが要求さ
れる塗膜に適した熱硬化被覆組成物に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a thermosetting coating composition, and more particularly to a thermosetting coating composition suitable for coating films that require a high degree of cosmetic properties and performance, such as coatings for automobile bodies. Thermosetting coating compositions.
本発明は、熱硬化被覆組成物において、特定組成のベー
スコート用塗料と特定組成のクリヤーコート用塗料とを
ウェット・オン・ウェット方式で重ね塗りし、加熱硬化
させて形成されているため、
優れた美粧性と性能とを有することができるようにした
ものである。The present invention is an excellent thermosetting coating composition because it is formed by overcoating a base coat paint of a specific composition and a clear coat paint of a specific composition in a wet-on-wet method and curing the composition by heating. It is designed to have both cosmetic properties and performance.
〔従来の技術及び発明が解決しようとする問題点〕自動
車ボディの塗装においては、電着塗装及び中塗塗装を行
った後に、着色顔料及び/又はメタリック顔料を含有し
たベースコート用塗料と上塗のクリヤーコート用塗料と
をウェット・オン・ウェット方式で重ね塗りし、両塗料
を同時に加熱硬化させる、いわゆる2コート・1ベ一ク
方式が一般に行われている。[Prior art and problems to be solved by the invention] In the painting of automobile bodies, after electrodeposition painting and intermediate coating, a base coat paint containing a color pigment and/or metallic pigment and a top clear coat are applied. A so-called 2-coat/1-bake method is generally used, in which a paint is applied wet-on-wet and both paints are heated and cured at the same time.
近年、自動車メーカーの海外進出に伴う国際競争の中で
、美粧性に対する要求がますます強まっている。それゆ
え、美粧性向上のためのクリヤーコートによる改善策と
してクリヤーコートの厚膜化が実施されている。しかし
、この厚膜化は作業性の面で垂直部の塗料のたれの問題
を生じ易く好ましくない。この解決策としてクリヤーコ
ートの2コート化が試みられているが、その場合、工程
の繁雑化、クリヤーコート二層間の剥離等の問題がある
。一方、クリヤーコートを構成するアクリル系共重合体
の低分子量化による美粧性向上も実施されているが、そ
の場合、硬化塗膜の耐溶剤性、耐候性などといった塗膜
性能が低下するという問題が生じる。In recent years, amidst international competition as automakers expand overseas, the demand for cosmetic products has become increasingly strong. Therefore, thickening of the clear coat has been implemented as a measure to improve the cosmetic appearance of the clear coat. However, this thickening is not preferable in terms of workability because it tends to cause the problem of paint dripping on vertical parts. As a solution to this problem, attempts have been made to use two clear coats, but in this case there are problems such as complicated processes and peeling between the two clear coats. On the other hand, attempts have been made to improve cosmetic properties by lowering the molecular weight of the acrylic copolymer that constitutes the clear coat, but in this case, there is a problem that the performance of the cured film, such as solvent resistance and weather resistance, deteriorates. occurs.
本発明の目的は、2コート・1ベ一ク塗装方式において
、前記の問題点が解消され、アクリルアミノ系熱硬化塗
膜の有する耐候性、耐水性等を維持しかつ美粧性に優れ
た熱硬化被覆組成物を提供することである。The object of the present invention is to solve the above-mentioned problems in a 2-coat/1-bake coating method, maintain the weather resistance, water resistance, etc. of an acrylamine thermosetting coating film, and provide a thermal coating with excellent cosmetic properties. An object of the present invention is to provide a cured coating composition.
本発明に従えば、顔料を配合した熱硬化性のベースコー
ト用塗料及び熱硬化性のクリヤーコート用塗料をウェッ
ト・オン・ウェット方式で重ね塗りした後、両塗料を同
時に加熱硬化させることによって形成された熱硬化被覆
組成物において、前記ベースコート用塗料が、
(1)(’a)水酸基含有ビニル七ツマー10〜40重
量%
(b)カルボキシル基含有ビニルモノマー0.2〜10
重量%
(C)一般式(1)
%式%(1)
(式中R1はH又はCH,、、nは1〜4の整数を表わ
す。)
の(メタ)アクリル酸エステル
10〜70重量%
(d)共重合可能な他のビニル系モノマー0〜30重量
%
を共重合させて得られた、水酸基価40〜80mgKO
H/g及び酸価0.5〜25mgK OH/ gのアク
リル系共重合体(I)60〜90重量%及び
(2)アミノ樹脂10〜40重量%からなる組成物に顔
料を配合したものであり、前記クリヤーコート用塗料が
、
(3)(e)t−ブチルメタクリレート15〜50重量
%
(f)一般式(n)
R,0
CHz =CCOC−H2−+I (II)(式中R
2はH又はC’H3、mは8以上の整数を表わす。)
の(メタ)アクリル酸エステル
15〜50重量%
(g)水M!含有ビニルモノマー
10〜50重量%
(h)カルボキシル基含有ビニルモノマー1〜10重量
%
(i)共重合可能な他のビニル系モノマー0〜30重量
%
を共重合させて得られた、水酸基価50〜150mgK
OH/g及び酸価2〜40mgK OH/ gのアクリ
ル系共重合体(II)50〜90重量%及び
(4)アミノ樹脂10〜50重量%からなるものである
ことを特徴とする熱硬化被覆組成物が提供される。According to the present invention, a pigment-containing thermosetting base coat paint and a thermosetting clear coat paint are overcoated in a wet-on-wet manner, and then both paints are heated and cured at the same time. In the thermosetting coating composition, the base coat paint contains (1) ('a) 10 to 40% by weight of a hydroxyl group-containing vinyl monomer (b) 0.2 to 10% by weight of a carboxyl group-containing vinyl monomer.
% by weight (C) 10 to 70% by weight of (meth)acrylic acid ester of general formula (1) % formula % (1) (in the formula, R1 represents H or CH, , n represents an integer of 1 to 4) (d) Hydroxyl value 40-80 mgKO obtained by copolymerizing 0-30% by weight of other copolymerizable vinyl monomers
H/g and an acid value of 0.5 to 25 mgK OH/g, a composition consisting of 60 to 90% by weight of an acrylic copolymer (I) and 10 to 40% by weight of (2) an amino resin, in which a pigment is blended. (3) (e) 15 to 50% by weight of t-butyl methacrylate (f) General formula (n) R,0 CHz = CCOC-H2-+I (II) (in the formula R
2 represents H or C'H3, and m represents an integer of 8 or more. ) (meth)acrylic acid ester 15-50% by weight (g) water M! Containing vinyl monomer 10-50% by weight (h) Carboxyl group-containing vinyl monomer 1-10% by weight (i) Other copolymerizable vinyl monomer 0-30% by weight Obtained by copolymerizing, hydroxyl value 50 ~150mgK
A thermosetting coating comprising 50 to 90% by weight of an acrylic copolymer (II) having an OH/g and an acid value of 2 to 40 mgK OH/g and (4) an amino resin of 10 to 50% by weight. A composition is provided.
本発明において前記ベースコート用塗料に用いるアクリ
ル系共重合体(1)はベースコートとクリヤーコートの
間の層間付着性の観点から水酸基価が40〜80mgK
OH/Hの範囲となるように水酸基含有ビニルモノマー
を含有する。水酸基含有ビニルモノマーが10重量%未
満ではアクリル系共重合体(1)とアミノ樹脂との架橋
反応による硬化塗膜の架橋密度が低く、十分な塗膜性能
が得られず、又、40重量%を越えるとアクリル系共重
合体(I)の溶液粘度が高くなり過ぎ、その上硬化塗膜
の耐水性が低下するので、好ましくない、この水酸基含
有ビニルモノマーの例としてヒドロキシエチル(メタ)
アクリレート、2−ヒドロキシプロピル(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
、4−ヒドロキシブチル(メタ)アクリレート等のヒド
ロキシアルキル(メタ)アクリレート類、[カージュラ
El (シェル化学側製の合成脂肪酸のグリシジルエ
ステル)に代表される、モノエポキシ化合物と(メタ)
アクリル酸、フマル酸又はマレイン酸とのエステル化反
応物、重合性不飽和基を有する低分子量ポリエステル樹
脂等を挙げることができる。In the present invention, the acrylic copolymer (1) used in the base coat paint has a hydroxyl value of 40 to 80 mgK from the viewpoint of interlayer adhesion between the base coat and the clear coat.
Contains a hydroxyl group-containing vinyl monomer so that the OH/H ratio is within the range of OH/H. If the hydroxyl group-containing vinyl monomer is less than 10% by weight, the crosslinking density of the cured coating film due to the crosslinking reaction between the acrylic copolymer (1) and the amino resin will be low, and sufficient coating performance will not be obtained; If the hydroxyl group-containing vinyl monomer is exceeded, the solution viscosity of the acrylic copolymer (I) becomes too high and the water resistance of the cured coating film decreases, which is undesirable.
acrylate, hydroxyalkyl (meth)acrylates such as 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, [Cardura El (synthetic fatty acid manufactured by Shell Chemical)] monoepoxy compounds and (meth) represented by glycidyl esters)
Examples include esterification reaction products with acrylic acid, fumaric acid, or maleic acid, and low molecular weight polyester resins having polymerizable unsaturated groups.
前記(1)(b)項のカルボキシル基含有ビニルモノマ
ーはアクリル系共重合体(1)と顔料との親和性の向上
及びベースコート用塗料が硬化剤を含む場合には、架橋
反応の触媒として重要な役割を果たし、1個又は2個以
上のカルボキシル基を有する重合性単量体、例えばα、
β−モノエチレン型不飽和カルボン酸、具体的にはアク
リル酸、メタクリル酸、イタコン酸、マレイン酸及びフ
マール酸並びにこれらの酸のモノアルキルエステル(例
えばモノメチルエステル、モノエチルエステル、モノブ
チルエステル等)が挙げられる。これらのα、β−モノ
エチレン型不飽和カルボン酸の量が0.2重量%未満で
は上述の効果が不十分であり、又10重量%を越えると
アクリル系共重合体(1)の溶液粘度が高くなり、耐水
性も低下するので好ましくない。この量の好ましい範囲
は0.5〜5重量%である。The carboxyl group-containing vinyl monomer described in (1) and (b) above is important for improving the affinity between the acrylic copolymer (1) and the pigment and as a catalyst for the crosslinking reaction when the base coat paint contains a curing agent. A polymerizable monomer having one or more carboxyl groups, such as α,
β-monoethylenically unsaturated carboxylic acids, specifically acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, and monoalkyl esters of these acids (e.g. monomethyl ester, monoethyl ester, monobutyl ester, etc.) can be mentioned. If the amount of these α,β-monoethylenically unsaturated carboxylic acids is less than 0.2% by weight, the above effects will be insufficient, and if it exceeds 10% by weight, the solution viscosity of the acrylic copolymer (1) will decrease. This is not preferable because it increases the water resistance and reduces water resistance. The preferred range for this amount is 0.5-5% by weight.
前記(1)(c)項に記載の一般式(1)の(メタ)ア
クリル酸エステルは、集鉱性、耐候性、可撓性の点から
必須成分であり、具体例としてメチル(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、n−ブチル(メタ)アクリレート、
イソブチル(メタ)アクリレート、t−ブチル(メタ)
アクリレート等が挙げられる。The (meth)acrylic acid ester of general formula (1) described in item (1)(c) above is an essential component from the viewpoint of mineral collecting property, weather resistance, and flexibility, and specific examples include methyl (meth) Acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate,
Isobutyl (meth)acrylate, t-butyl (meth)
Examples include acrylate.
前記(1)(d)項の共重合可能な他のビニル系モノマ
ーとしてはスチレン、α−メチルスチレン、ビニルトル
エン等のスチレン誘導体;アクリロニトリル、メタクリ
レートリル等の重合性不飽和ニトリル類;酢酸ビニル、
プロピオン酸ビニル等のビニルエステル類;N−メトキ
シメチル(メタ)アクリルアミド、N−エトキシメチル
(メタ)アクリルアミド、N−ブトキシメチル(メタ)
アクリルアミド等のN−アルコキシ置換アミド類;グリ
シジル(メタ)アクリレート、(メタ)アクリルグリシ
ジルエーテル、メタグリシジル(メタ)アクリル酸エス
テル等のエポキシ基含有モノマー;ジメチルアミノエチ
ル(メタ)アクリル酸、ジエチルアミノエチル(メタ)
アクリル酸等の塩基性モノマーを挙げることができ、こ
れらは必要に応じて使用することができる。Other copolymerizable vinyl monomers mentioned in (1) and (d) above include styrene derivatives such as styrene, α-methylstyrene, and vinyltoluene; polymerizable unsaturated nitrites such as acrylonitrile and methacrylate; vinyl acetate;
Vinyl esters such as vinyl propionate; N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)
N-alkoxy-substituted amides such as acrylamide; epoxy group-containing monomers such as glycidyl (meth)acrylate, (meth)acrylic glycidyl ether, and metaglycidyl (meth)acrylic acid ester; dimethylaminoethyl (meth)acrylic acid, diethylaminoethyl ( Meta)
Basic monomers such as acrylic acid can be mentioned, and these can be used as necessary.
本発明においてベースコート用塗料に含まれる前記アク
リル系共重合体(1)は溶液重合法、塊状重合法、乳化
重合法等の公知の何れの方法によっても得ることができ
るが、特に溶液重合法による重合体であることが望まし
い。溶液重合法による場合、有機溶剤及び重合開始剤の
存在下に前記モノマーの混合物を共重合させる。使用す
る有機溶剤はイソプロピルアルコール、n−ブタノール
、トルエン、キシレン等の通常用いられる有機溶剤でよ
く、重合開始剤もアゾビスイソブチロニトリル、過酸化
ベンゾイル、クメンヒドロペルオキシド等の通常用いら
れる重合開始剤でよい。また、必要に応じて2−メルカ
プトエタノール、n−オクチルメルカプタン等の連鎖移
動剤を使用することができる。In the present invention, the acrylic copolymer (1) contained in the base coat paint can be obtained by any known method such as solution polymerization, bulk polymerization, emulsion polymerization, etc., but especially by solution polymerization. Preferably, it is a polymer. In the case of solution polymerization, the mixture of monomers is copolymerized in the presence of an organic solvent and a polymerization initiator. The organic solvent used may be a commonly used organic solvent such as isopropyl alcohol, n-butanol, toluene, or xylene, and the polymerization initiator may be a commonly used polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, or cumene hydroperoxide. A drug is sufficient. Furthermore, a chain transfer agent such as 2-mercaptoethanol or n-octylmercaptan can be used if necessary.
本発明におけるベースコート塗料はアミン樹脂がlO重
重量未満では硬化塗膜の架橋密度が低く、十分なる性能
が得られず、又、40重量%を越えると硬化塗膜の耐水
性、可撓性が低下するので好ましくない。アミノ樹脂の
量の好ましい範囲は15〜30重量%である。このアミ
ノ樹脂は、例えば、アミノトリアジン、尿素、ジシアン
ジアミド又はN、N−エチレン尿素をメチロール化し、
シクロヘキサノール又は炭素数1〜6のアルカノールに
よってアルキルエーテル化して得られ、特にアミノトリ
アジンから得られる、例えばメチルエーテル化メラミン
樹脂、ブチルエーテル化メラミン樹脂等が好適である。In the base coat paint of the present invention, if the amine resin content is less than 10% by weight, the crosslinking density of the cured coating film will be low and sufficient performance will not be obtained, and if it exceeds 40% by weight, the water resistance and flexibility of the cured coating film will deteriorate. This is not preferable because it lowers the temperature. The preferred range for the amount of amino resin is 15-30% by weight. This amino resin is, for example, a methylolated aminotriazine, urea, dicyandiamide or N,N-ethylene urea,
Preferred are melamine resins obtained by alkyl etherification with cyclohexanol or alkanols having 1 to 6 carbon atoms, particularly obtained from aminotriazine, such as methyl etherified melamine resins and butyl etherified melamine resins.
本発明においてクリヤーコート用塗料に用いるアクリル
系共重合体(II)はt−ブチルメタクリレートの量が
15重量%未満では本発明の集糠性向上という特徴を十
分に発揮できない。又、この量が50重量%を越えると
硬化塗膜が脆くなるので好ましくない。t−ブチルメタ
クリレートの量の好ましい範囲は20〜40重量%であ
る。In the acrylic copolymer (II) used in the clear coat paint of the present invention, if the amount of t-butyl methacrylate is less than 15% by weight, the characteristic of improving the bran collectability of the present invention cannot be fully exhibited. Moreover, if this amount exceeds 50% by weight, the cured coating film becomes brittle, which is not preferable. The preferred range for the amount of t-butyl methacrylate is 20-40% by weight.
前記(3)(f)項に記載の一般式(n)の(メタ)ア
クリル酸エステルの例として(メタ)アクリル酸2−エ
チルヘキシル、(メタ)アクリル酸ラウリル、(メタ)
アクリル酸トリデシル、(メタ)アクリル酸ステアリル
等が挙げられる。この(メタ)アクリル酸エステルの量
が15重量%未満では本発明の集糠性向上という特徴が
十分に発揮できず、又、50重量%を越えると硬化塗膜
の硬度、耐溶剤性等が低下する。Examples of the (meth)acrylic ester of general formula (n) described in item (3)(f) above include 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and (meth)acrylate.
Examples include tridecyl acrylate and stearyl (meth)acrylate. If the amount of this (meth)acrylic acid ester is less than 15% by weight, the characteristic of improving the bran collection property of the present invention cannot be fully exhibited, and if it exceeds 50% by weight, the hardness, solvent resistance, etc. of the cured coating film will deteriorate. descend.
前記(3)(g)項の水酸基含有ビニルモノマーはクリ
ヤーコート塗料を構成するアクリル系共重合体(n)の
水酸基価が50〜150曜KOH/g’となる量で含有
され、10重量%未満であるとアクリル系共重合体(n
)とアミノ樹脂との架橋反応による硬化塗膜の架橋密度
が低過ぎて満足できる塗膜性能が得られず、又、50重
量%を越えるとアクリル系共重合体の溶液粘度が高くな
り過ぎ、その上硬化塗膜の耐水性が低下するので好まし
くない。この水酸基含有ビニルモノマーの例としては2
−ヒドロキシエチル(メタ)アクリレート、2−ヒドロ
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、4−ヒドロキシブチル(
メタ)アクリレート等のヒドロキシアルキル(メタ)ア
クリレート類;2−ヒドロキシエチル(メタ)アクリレ
ートとエチレンオキシドとの付加物及び2−ヒドロキシ
エチル(メタ)アクリレートとプロピレンオキシドとの
付加物;2−ヒドロキシエチル(メタ)アクリレートと
γ−ブチロラクトンとの付加物及び2−ヒドロキシエチ
ル(メタ)アクリレートとε−カプロラクトンとの付加
物といった、2−ヒドロキシエチル(メタ)アクリレー
トと有機ラクトン類との付加物を挙げることができる。The hydroxyl group-containing vinyl monomer in item (3) (g) above is contained in an amount such that the hydroxyl value of the acrylic copolymer (n) constituting the clear coat paint is 50 to 150 KOH/g', and is 10% by weight. If it is less than acrylic copolymer (n
) and the amino resin, the crosslinking density of the cured coating film is too low and satisfactory coating performance cannot be obtained, and if it exceeds 50% by weight, the solution viscosity of the acrylic copolymer becomes too high. Moreover, it is not preferable because the water resistance of the cured coating film decreases. Examples of this hydroxyl group-containing vinyl monomer are 2
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (
Hydroxyalkyl (meth)acrylates such as meth)acrylate; adducts of 2-hydroxyethyl (meth)acrylate and ethylene oxide and adducts of 2-hydroxyethyl (meth)acrylate and propylene oxide; ) Adducts of 2-hydroxyethyl (meth)acrylate and organic lactones, such as adducts of acrylate and γ-butyrolactone and adducts of 2-hydroxyethyl (meth)acrylate and ε-caprolactone, can be mentioned. .
本発明のようにメラミン樹脂のような硬化剤を含む場合
、前記(3)(h)項のカルボキシル基含有ビニルモノ
マーは触媒として重要な役割を果たし、アクリル系共重
合体(II)の酸価が2〜40■KOH/gとなる量で
含有される。このカルボキシル基含有ビニルモノマーが
1重量%未満であると上記の硬化が不十分であるため塗
膜性能が低下し、又、10重量%を越えるとアクリル系
共重合体の溶液粘度が高くなり過ぎるため硬化塗膜の美
粧性が低下するとともに耐水性も低下するので好ましく
ない。このカルボキシル基含有ビニルモノマーの具体例
として(メタ)アクリル酸、イタコン酸、フマール酸、
クロトン酸、マレイン酸、イタコン酸モノメチル、イタ
コン酸モノブチル、マレイン酸モノメチル、マレイン酸
モノブチル、2−スルホエチル(メタ)アクリレート等
を挙げることができる。When a curing agent such as a melamine resin is included as in the present invention, the carboxyl group-containing vinyl monomer in item (3) (h) plays an important role as a catalyst, and the acid value of the acrylic copolymer (II) is contained in an amount of 2 to 40 ■KOH/g. If the amount of this carboxyl group-containing vinyl monomer is less than 1% by weight, the above-mentioned curing will be insufficient and the coating performance will deteriorate, and if it exceeds 10% by weight, the solution viscosity of the acrylic copolymer will become too high. Therefore, the cosmetic properties of the cured coating film are reduced and the water resistance is also reduced, which is not preferable. Specific examples of this carboxyl group-containing vinyl monomer include (meth)acrylic acid, itaconic acid, fumaric acid,
Examples include crotonic acid, maleic acid, monomethyl itaconate, monobutyl itaconate, monomethyl maleate, monobutyl maleate, 2-sulfoethyl (meth)acrylate, and the like.
前記(3)(i)項の共重合可能な他のビニル糸上ツマ
−は本発明の特徴である美粧性を損なわない範囲の量で
必要に応じて用いられ、具体例としてスチレン、α−メ
チルスチレン、ビニルトルエン等のスチレン誘導体;ア
クリロニトリル、メタクリロニトリル等の重合性不飽和
ニトリル類;酢酸ビニル、プロピオン酸ビニル等のビニ
ルエステル頻;N−メトキシメチル(メタ)アクリルア
ミド、N−エトキシメチル(メタ)アクリルアミド、N
−ブトキシメチル(メタ)アクリルアミド等のN−アル
コキシ置換アミド類;グリシジル(メタ)アクリレート
、(メタ)アリルグリシジルエーテル、メタグリシジル
(メタ)アクリル酸エステル等のエポキシ基含有モノマ
ー;ジメチルアミノエチル(メタ)アクリル酸、ジエチ
ルアミノエチル(メタ)アクリル酸等の塩基性モノマー
;(メタ)アクリル酸メチル、(メタ)アクリル酸エチ
ル、(メタ)アクリル酸プロピル、(メタ)アクリル酸
ブチル、(メタ)アクリル酸アミル、(メタ)アクリル
酸シクロヘキシル、(メタ)アクリル酸フェニル、(メ
タ)アクリル酸ベンジル等が挙げられる。The other copolymerizable vinyl yarn threads mentioned in item (3)(i) may be used as necessary in an amount within a range that does not impair the cosmetic properties that are a feature of the present invention. Specific examples include styrene, α- Styrene derivatives such as methylstyrene and vinyltoluene; Polymerizable unsaturated nitrites such as acrylonitrile and methacrylonitrile; Vinyl esters such as vinyl acetate and vinyl propionate; N-methoxymethyl (meth)acrylamide, N-ethoxymethyl ( meth) acrylamide, N
-N-alkoxy substituted amides such as butoxymethyl (meth)acrylamide; Epoxy group-containing monomers such as glycidyl (meth)acrylate, (meth)allyl glycidyl ether, metaglycidyl (meth)acrylic acid ester; dimethylaminoethyl (meth) Basic monomers such as acrylic acid, diethylaminoethyl (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate , cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, and the like.
又、前記クリヤーコート用塗料に含まれるアクリル系共
重合体(n)の重合方法としては、前記ベースコート用
塗料に含まれるアクリル系共重合体(1)の重合方法に
準するが、とりわけ溶液重合方法が好ましい。The polymerization method for the acrylic copolymer (n) contained in the clear coat paint is similar to the polymerization method for the acrylic copolymer (1) contained in the base coat paint, but especially solution polymerization. The method is preferred.
本発明における前記クリヤーコート用塗料は、主たる用
途である自動車用塗料における前記品質性能を満足させ
るため、アミノ樹脂を硬化剤として含有する。アミノ樹
脂の世が10重量%未満であると硬化塗膜の架橋密度が
低く、塗膜の耐候性、耐溶剤性、耐水性等が不十分とな
り、又、50重量%を越えると硬化塗膜の光沢窓、メタ
リック惑をはじめ物理的及び化学的性質が悪くなるので
好ましくない。このアミノ樹脂の具体例としては前記ベ
ースコート用塗料に含有されるアミノ樹脂について記載
したものと同じである。The clear coat paint of the present invention contains an amino resin as a curing agent in order to satisfy the quality performance in the automotive paint, which is the main application. If the amount of amino resin is less than 10% by weight, the crosslinking density of the cured coating will be low, resulting in insufficient weather resistance, solvent resistance, water resistance, etc., and if it exceeds 50% by weight, the cured coating will be poor. It is not preferable because it deteriorates the physical and chemical properties such as the glossy window and metallic appearance. Specific examples of this amino resin are the same as those described for the amino resin contained in the base coat paint.
更に、アミノ樹脂を硬化剤として使用する場合には前記
クリヤーコート用塗料に、パラトルエンスルホン酸、ド
デシルベンゼンスルホン酸、ジノニルナフタレンスルホ
ン酸又はそれらのアミン中和物等で代表される外部酸触
媒を使用することができる。Furthermore, when an amino resin is used as a curing agent, an external acid catalyst such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, or their amine neutralized products is added to the clear coat paint. can be used.
本発明におけるベースコート用塗料には、塗料化に際し
て通常用いることができる公知のアルミニウムペースト
、雲母、リン片状酸化鉄、酸化チタン、カーボンブラッ
ク、キナクリドン、シアニンブルー等の顔料が配合され
るが、更にポリエステル系樹脂、エポキシ樹脂、繊維素
樹脂等のアクリル以外の樹脂;及び表面調整剤、紫外線
吸収剤、酸化防止剤、顔料沈降防止剤等の補助的添加剤
を必要に応じて選択し、一般的な配合方法で加えること
ができる。The base coat paint of the present invention contains pigments such as aluminum paste, mica, scaly iron oxide, titanium oxide, carbon black, quinacridone, and cyanine blue, which are commonly used in the preparation of paints. Resins other than acrylic resins such as polyester resins, epoxy resins, and cellulose resins; and auxiliary additives such as surface conditioners, ultraviolet absorbers, antioxidants, and pigment anti-settling agents are selected as necessary, and general It can be added by any combination method.
以下、実施例によって本発明を説明する。 The present invention will be explained below with reference to Examples.
攪拌器、温度制御装置及びコンデンサを備えた容器にト
ルエン40重量部とn−ブタノール10重量部を仕込ん
だ。容器の内容物を攪拌しながら加熱して温度を100
℃に上昇させた。次いで、第1表に示した組成(1)の
溶液を4時間で滴下した後に、過酸化ベンゾイル0.6
重量部とトルエン20重量部とからなる溶液を30分間
で滴下した。反応溶液を100℃でさらに2時間攪拌加
熱して樹脂への転化率を上昇させた後、トルエン30重
量部を添加して反応を終了させた。得られたアクリル系
共重合体溶液(不揮発分50重量%)をアクリル樹脂ワ
ニス(I)とする。このワニスに含まれたアクリル系共
重合体は本発明における前記アクリル系共重合体(1)
の要件を満たしている。この共電体の重量平均分子量は
70,000であった。40 parts by weight of toluene and 10 parts by weight of n-butanol were charged into a container equipped with a stirrer, a temperature control device, and a condenser. Heat the contents of the container while stirring to bring the temperature to 100℃.
The temperature was raised to ℃. Next, a solution of composition (1) shown in Table 1 was added dropwise over 4 hours, and then benzoyl peroxide 0.6
A solution consisting of parts by weight and 20 parts by weight of toluene was added dropwise over 30 minutes. The reaction solution was further stirred and heated at 100° C. for 2 hours to increase the conversion rate to resin, and then 30 parts by weight of toluene was added to terminate the reaction. The obtained acrylic copolymer solution (non-volatile content: 50% by weight) is designated as acrylic resin varnish (I). The acrylic copolymer contained in this varnish is the acrylic copolymer (1) in the present invention.
meets the requirements. The weight average molecular weight of this coelectric material was 70,000.
次に、前記組成(1)の代わりに第1表に示した組成(
2)の溶液を用いて前記と全く同じ手順で反応を行い、
アクリル系共重合体溶液(不揮発分50重量%)を得た
。この溶液をアクリル樹脂ワニス(n)とする。このワ
ニスに含まれたアクリル系共重合体は前記アクリル系共
重合体(1)の要件を満たしていない。この共重合体の
重量平均分子量も70,000であった。Next, in place of the composition (1), the composition shown in Table 1 (
Perform the reaction using the solution of 2) in exactly the same manner as above,
An acrylic copolymer solution (nonvolatile content: 50% by weight) was obtained. This solution is referred to as acrylic resin varnish (n). The acrylic copolymer contained in this varnish does not meet the requirements for the acrylic copolymer (1). The weight average molecular weight of this copolymer was also 70,000.
(以下、余白次頁につづく)
第 1 表
第2表に示す割合の各材料をステンレス容器に入れ、充
分に攪拌した後、希釈用混合溶剤で粘度を調整して、ベ
ースコート用塗料B−1〜B−3を製造した。(The following margins are continued on the next page) 1.Pour each material in the proportions shown in Table 2 into a stainless steel container, stir thoroughly, adjust the viscosity with a diluent mixed solvent, and prepare base coat paint B-1. ~B-3 was produced.
第 2 表
*シェル化学■製の芳香族石油誘導体
クリヤーコート ° 2に4まれるアクリルU第3表に
示した9種類の七ツマー組成を有する各混合物について
、次の手順で重合反応を行った。Table 2 * Aromatic petroleum derivative clear coat manufactured by Shell Chemical ■ Acrylic U listed in Table 2 A polymerization reaction was carried out using the following procedure for each mixture having the nine types of 7-mer compositions shown in Table 3. .
攪拌機、温度制御装置及びコンデンサを備えた容器にま
ずツルペッツ#100(シェル化学01製の芳香族石油
誘導体) 53.3重量部を仕込み、攪拌しながら加熱
して温度を120℃に上昇させた。First, 53.3 parts by weight of Tsurupetz #100 (aromatic petroleum derivative manufactured by Shell Kagaku 01) was charged into a container equipped with a stirrer, a temperature control device, and a condenser, and heated while stirring to raise the temperature to 120°C.
次いで、第3表に記載のモノマー混合物100重量部に
、アゾビスイソブチロニトリル2重量部及びt−ブチル
ペルオキシイソプロピルカーボネート4重量部を添加し
、3時間で滴下させた。次いで、アゾビスイソブチロニ
トリルを0.1重量部づつ30分間隔で4回添加した。Next, 2 parts by weight of azobisisobutyronitrile and 4 parts by weight of t-butylperoxyisopropyl carbonate were added to 100 parts by weight of the monomer mixture listed in Table 3, and the mixture was allowed to drip over 3 hours. Next, 0.1 part by weight of azobisisobutyronitrile was added four times at 30 minute intervals.
120℃でさらに2時間攪拌加熱し、樹脂への転化率を
上昇させた後、n−ブタノール13.3重量部を添加し
て反応を終了させた。得られた9種類のアクリル系共重
合体溶液の粘度と不揮発分及び各アクリル系共重合体の
酸価は第3表に示す通りであった。After further stirring and heating at 120° C. for 2 hours to increase the conversion rate to resin, 13.3 parts by weight of n-butanol was added to terminate the reaction. The viscosity and nonvolatile content of the nine types of acrylic copolymer solutions obtained and the acid value of each acrylic copolymer were as shown in Table 3.
クリヤーコート用塗料の一1浩1
前記9種類のアクリル系共重合体溶液を用い、第3表に
示した塗料配合によりクリヤーコート用塗料P−1〜P
−9を製造した。Clear coat paint P-1 to P-1 using the above nine types of acrylic copolymer solutions and the paint formulations shown in Table 3.
-9 was produced.
これらのクリヤーコート用塗料のうち、そのアクリル系
共重合体が、本発明におけるアクリル系共重合体(II
)の要件を満たしているのは塗料P−1〜P−4である
。Among these clear coat paints, the acrylic copolymer is the acrylic copolymer (II
) The paints P-1 to P-4 meet the requirements.
(以下、余白次頁につづく)
1〜5 び ″ 1〜8
リン酸亜鉛処理された鋼板(30X 45cm)に自動
車用カチオン系電着塗料を塗装し、180℃で30分間
焼付けた。次いで、アルキッド樹脂とアミノ樹脂とから
成る中塗り塗料を塗装し、160℃で30分間焼付けた
後、塗膜をサンディングし、水研し、乾燥した。この塗
膜上に、前記第2表に記載のベースコート用塗料と前記
第3表に記載のクリヤーコート用塗料を第4表の実施例
1〜5に示した組み合わせで、ウェット・オン・ウエン
ト方式により重ね塗りした。この重ね塗りは次のように
して行った。中12膜上にまずベースコート用塗料を乾
燥膜厚が15μmとなるように塗装し、3分間放置した
後、クリヤーコート用塗料を乾燥膜厚が30μmとなる
ように塗装した。未乾燥の重ね塗り塗膜を室温で10分
間放置後、140℃の熱風乾燥機で25分間焼付けて、
実施例1〜5の熱硬化被覆組成物を得た。(Margins continue on next page) 1-5 ″ 1-8 A zinc phosphate-treated steel plate (30 x 45 cm) was coated with an automotive cationic electrodeposition paint and baked at 180°C for 30 minutes. An intermediate paint consisting of an alkyd resin and an amino resin was applied, baked at 160°C for 30 minutes, and the paint film was sanded, water-sanded, and dried. The base coat paint and the clear coat paint listed in Table 3 above were coated in combinations shown in Examples 1 to 5 in Table 4 using a wet-on-wet method.This layer coating was carried out as follows. First, a base coat paint was applied to the medium 12 film to a dry film thickness of 15 μm, and after being left for 3 minutes, a clear coat paint was applied to a dry film thickness of 30 μm. After drying the layered coating film, leave it at room temperature for 10 minutes, then bake it in a hot air dryer at 140°C for 25 minutes.
Thermosetting coating compositions of Examples 1-5 were obtained.
全く同様の手順で、第4表の比較例1〜8に示した組み
合わせで、ベースコート用塗料とクリヤーコート用塗料
を重ね塗りし、比較例1〜8の熱硬化被覆組成物を得た
。Using exactly the same procedure, base coat paints and clear coat paints were overcoated using the combinations shown in Comparative Examples 1 to 8 in Table 4 to obtain thermosetting coating compositions of Comparative Examples 1 to 8.
前記の実施例及び比較例の各熱硬化被覆物の外観及び性
能を評価した結果を第4表に示した。Table 4 shows the results of evaluating the appearance and performance of each of the thermoset coatings of the Examples and Comparative Examples.
この結果から明らかな通り、ベースコートとクリヤーコ
ートのいずれか一方が、本発明におけるアクリル系共重
合体の要件を満たさないアクリル系共重合体を含む場合
には、本発明の目的とする熱硬化被覆組成物を得ること
ができない。As is clear from this result, when either the base coat or the clear coat contains an acrylic copolymer that does not meet the requirements for an acrylic copolymer in the present invention, the thermosetting coating as the object of the present invention Unable to obtain composition.
(以下、余白次頁につづく)
〔発明の効果〕
前記した通り、本発明の熱硬化被覆組成物しよ優れた集
糠性と性能を有するので、特に自動車の車体用塗膜とし
て極めて有用なものとなり得る。(The following margin continues on the next page) [Effects of the Invention] As mentioned above, the thermosetting coating composition of the present invention has excellent bran collection properties and performance, and therefore is extremely useful as a coating film for automobile bodies. It can become a thing.
Claims (1)
化性のクリヤーコート用塗料をウェット・オン・ウェッ
ト方式で重ね塗りした後、両塗料を同時に加熱硬化させ
ることによって形成された熱硬化被覆組成物において、 前記ベースコート用塗料が、 (1)(a)水酸基含有ビニルモノマー 10〜40重量% (b)カルボキシル基含有ビニルモノマー 0.2〜10重量% (c)一般式 ▲数式、化学式、表等があります▼ (式中R_1はH又はCH_3、nは1〜4の整数を表
わす。) の(メタ)アクリル酸エステル 10〜70重量% (d)共重合可能な他のビニル系モノマー 0〜30重量% を共重合させて得られた、水酸基価40〜80mgKO
H/g及び酸価0.5〜25mgKOH/gのアクリル
系共重合体60〜90重量%及び(2)アミノ樹脂10
〜40重量%からなる組成物に顔料を配合したものであ
り、前記クリヤーコート用塗料が、 (3)(e)t−ブチルメタクリレート 15〜50重量% (f)一般式 ▲数式、化学式、表等があります▼ (式中R_2はH又はCH_3、mは8以上の整数を表
わす。) の(メタ)アクリル酸エステル 15〜50重量% (g)水酸基含有ビニルモノマー 10〜50重量% (h)カルボキシル基含有ビニルモノマー 1〜10重量% (i)共重合可能な他のビニル系モノマー 0〜30重量% を共重合させて得られた、水酸基価50〜150mgK
OH/g及び酸価2〜40mgKOH/gのアクリル系
共重合体50〜90重量%及び(4)アミノ樹脂10〜
50重量%からなるものであることを特徴とする熱硬化
被覆組成物。[Scope of Claims] A pigment-containing thermosetting base coat paint and a thermosetting clear coat paint are overcoated in a wet-on-wet manner, and then both paints are heated and cured at the same time. In the thermosetting coating composition, the base coat paint comprises (1) (a) 10 to 40% by weight of a hydroxyl group-containing vinyl monomer (b) 0.2 to 10% by weight of a carboxyl group-containing vinyl monomer (c) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents H or CH_3, and n represents an integer from 1 to 4.) 10 to 70% by weight of (meth)acrylic ester (d) Other copolymerizable Hydroxyl value 40-80mgKO obtained by copolymerizing vinyl monomer 0-30% by weight
H/g and acid value 0.5-25 mgKOH/g acrylic copolymer 60-90% by weight and (2) amino resin 10
A pigment is blended into a composition consisting of ~40% by weight, and the clear coat paint has the following properties: (3) (e) 15 to 50% by weight of t-butyl methacrylate (f) General formula (In the formula, R_2 represents H or CH_3, and m represents an integer of 8 or more.) 15-50% by weight of (meth)acrylic acid ester (g) 10-50% by weight of hydroxyl group-containing vinyl monomer (h) Hydroxyl group value 50-150 mgK obtained by copolymerizing 1-10% by weight of a carboxyl group-containing vinyl monomer (i) 0-30% by weight of another copolymerizable vinyl monomer
OH/g and acid value 2-40 mgKOH/g acrylic copolymer 50-90% by weight and (4) amino resin 10-90% by weight
50% by weight of a thermosetting coating composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62110365A JP2652159B2 (en) | 1987-05-06 | 1987-05-06 | Thermosetting coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62110365A JP2652159B2 (en) | 1987-05-06 | 1987-05-06 | Thermosetting coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63275678A true JPS63275678A (en) | 1988-11-14 |
JP2652159B2 JP2652159B2 (en) | 1997-09-10 |
Family
ID=14533944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62110365A Expired - Lifetime JP2652159B2 (en) | 1987-05-06 | 1987-05-06 | Thermosetting coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2652159B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH072929B2 (en) * | 1988-10-12 | 1995-01-18 | ビーエーエスエフ ラッケ ウント ファルベン アクチエンゲゼルシャフト | Aqueous coating composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53126040A (en) * | 1977-04-11 | 1978-11-02 | Kansai Paint Co Ltd | Method of metallic finish coating |
JPS55159875A (en) * | 1979-05-31 | 1980-12-12 | Kansai Paint Co Ltd | Formation of double-layered paint film |
-
1987
- 1987-05-06 JP JP62110365A patent/JP2652159B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53126040A (en) * | 1977-04-11 | 1978-11-02 | Kansai Paint Co Ltd | Method of metallic finish coating |
JPS55159875A (en) * | 1979-05-31 | 1980-12-12 | Kansai Paint Co Ltd | Formation of double-layered paint film |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH072929B2 (en) * | 1988-10-12 | 1995-01-18 | ビーエーエスエフ ラッケ ウント ファルベン アクチエンゲゼルシャフト | Aqueous coating composition |
Also Published As
Publication number | Publication date |
---|---|
JP2652159B2 (en) | 1997-09-10 |
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