JPH0247175A - Chipping-resistant acrylic base coating composition - Google Patents
Chipping-resistant acrylic base coating compositionInfo
- Publication number
- JPH0247175A JPH0247175A JP19715588A JP19715588A JPH0247175A JP H0247175 A JPH0247175 A JP H0247175A JP 19715588 A JP19715588 A JP 19715588A JP 19715588 A JP19715588 A JP 19715588A JP H0247175 A JPH0247175 A JP H0247175A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- meth
- acrylic
- paint
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 51
- 239000000126 substance Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 229920000877 Melamine resin Polymers 0.000 abstract description 4
- 239000004640 Melamine resin Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 abstract description 3
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 abstract 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- -1 Blenmar PP-1000 Chemical compound 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920003180 amino resin Polymers 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 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 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 210000004417 patella Anatomy 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 2
- 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
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 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
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101150096839 Fcmr gene Proteins 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- JTDWCIXOEPQECG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC(C)(C)C Chemical compound N=C=O.N=C=O.CCCCCC(C)(C)C JTDWCIXOEPQECG-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
- 229920000297 Rayon Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 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
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 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
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 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
- 125000005442 diisocyanate group Chemical group 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
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-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
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical class OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- 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、自動車のような美粧性および長期の耐候性の
要求される塗料組成物に関し、更に詳しくはメタリック
粉末や着色顔料等の着色剤を配合したベース塗料とクリ
ヤー塗料とを用いて２コート・１ベ一ク方式により塗膜
を形成する際のべ一ス塗料として使用するのに好適で、
かつ耐チッピング性に優れた塗膜の得られるアクリル系
ベース塗料組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to coating compositions that require cosmetic properties and long-term weather resistance, such as those used in automobiles. Suitable for use as a base paint when forming a paint film using a two-coat/one-bake method using a base paint and clear paint containing
The present invention also relates to an acrylic base coating composition that provides a coating film with excellent chipping resistance.
〔従来の技術１
アクリル系塗料組成物は、その塗膜物性、特に光沢性、
耐候性、耐薬品性、耐汚染性に優れているため、自動車
ボディの塗装に重用されている。[Prior art 1] Acrylic paint compositions are characterized by their physical properties, especially gloss,
Because it has excellent weather resistance, chemical resistance, and stain resistance, it is heavily used for painting automobile bodies.
しかしながら、従来のアクリル系塗料組成物には以下の
問題点があり、その改善が望まれていた。However, conventional acrylic paint compositions have the following problems, and improvements have been desired.
すなわち、走行中の自動車が、小石が飛びはねることに
より車体の塗膜が瞬間的に破損される現象、所謂チッピ
ングにより、自動車塗膜が損傷を受け、ボディが腐食さ
れるという問題点があった。In other words, when a car is running, the paint film on the car body is momentarily damaged by flying pebbles, which is called chipping, which causes damage to the car paint film and corrodes the body. .
通常、自動車の塗装系は、化成処理、電着ブライマー、
中塗り塗装および上塗り塗装の各工程から構成されてお
り、耐チッピング性は、特開昭６２−１４３９７８号公
報および特開昭６３−５９３７５号公報に開示されるよ
うに、中塗り塗膜により確保される例が多い。Automotive paint systems usually include chemical conversion treatment, electrodeposition brimer,
It consists of each process of intermediate coating and top coating, and chipping resistance is ensured by the intermediate coating as disclosed in JP-A-62-143978 and JP-A-63-59375. There are many examples.
本発明のような上塗り塗膜においても、チッピングを防
止するためには、衝撃により発生するエネルギーを途中
の塗膜に吸収させ、素地金属まで伝達しないようにする
という中塗り塗膜と同じ発想による改良も検討された。In order to prevent chipping in the top coat film of the present invention, it is based on the same idea as the intermediate coat film, which is to absorb the energy generated by impact into the intermediate paint film and prevent it from being transmitted to the base metal. Improvements were also considered.
しかしながら、上塗り塗膜は、美粧性の付与と耐候性な
どの塗膜品質の達成を目的としているので、耐チッピン
グ性の付与との両立は従来技術では困難であった。However, since the top coat is intended to provide cosmetic properties and achieve coating film quality such as weather resistance, it has been difficult with conventional techniques to simultaneously provide chipping resistance.
本発明は、かかる従来の問題点を解決すべく鋭意検討の
結果完成されたもので、本発明の目的は、アクリル系塗
料組成物本来の光沢性、塗膜性能並びにメタリック粉末
や着色顔料を含有する場合の美粧性を損うことなく、塗
膜の耐チッピング性が改善されたアクリル系ベース塗料
を提供することにある。The present invention was completed as a result of intensive studies in order to solve these conventional problems, and the purpose of the present invention is to improve the inherent glossiness and coating performance of acrylic paint compositions, as well as the inclusion of metallic powders and coloring pigments. To provide an acrylic base paint with improved chipping resistance of the paint film without impairing its cosmetic properties.
すなわち、本発明のベース塗料組成物は、着色剤を配合
したベース塗料を塗装し、次いでクリヤー塗料を重ね塗
りした後、加熱硬化させ塗膜を得る塗装系に用いるベー
ス塗料において、該ベース塗料が、
（ａ）下記一般式（Ｉ）または（ＩＴ）（式中、Ｒ１、
Ｒ２およびＲ３はそれぞれ独立して水素原子またはメチ
ル基を示し、ｍは３〜５の整数、ｎは１〜６の整数、ｐ
は２〜７の整数である。）
で表わされる水酸基含有（メタ）アクリル酸エステル
１０〜６０重量％（ｂ）上記一般
式（Ｉ）または（１’Ｉ）以外の水酸基含有ビニルモノ
マー ０〜２０重量％（Ｃ） α、β−モノエ
チレン性不飽和カルボン酸０．２〜ｌＯ重量％
（ｄ）炭素原子数が１〜４のアルキル基を有する（メタ
）アクリル酸エステル ３０〜８０重量％および
（ｅ）上記（ａ）〜（ｄ）成分と共重合可能な他のビニ
ルモノマー ０〜５０重量％を共重
合して得られる水酸基価が２０〜１００ｍｇＫｏ）Ｉ／
ｇでガラス転移温度が４０〜−３０’Ｃであるアクリル
系共重合体（Ａ） ５０〜９５重量％と、硬化剤（Ｂ）
５〜５０重量％とから成るものである。That is, the base paint composition of the present invention is a base paint used in a coating system in which a base paint containing a colorant is applied, then a clear paint is overcoated, and then the base paint is cured by heating to form a coating film. , (a) The following general formula (I) or (IT) (wherein R1,
R2 and R3 each independently represent a hydrogen atom or a methyl group, m is an integer of 3 to 5, n is an integer of 1 to 6, p
is an integer from 2 to 7. ) Hydroxyl group-containing (meth)acrylic acid ester
10-60% by weight (b) hydroxyl group-containing vinyl monomer other than the above general formula (I) or (1'I) 0-20% by weight (C) α,β-monoethylenically unsaturated carboxylic acid 0.2-1O % by weight (d) 30-80% by weight of (meth)acrylic acid ester having an alkyl group having 1 to 4 carbon atoms, and (e) other vinyl monomer copolymerizable with the above components (a) to (d). The hydroxyl value obtained by copolymerizing 0 to 50% by weight is 20 to 100 mgKo)I/
50 to 95% by weight of an acrylic copolymer (A) having a glass transition temperature of 40 to -30'C and a curing agent (B)
5 to 50% by weight.
本発明のベース塗料組成物に使用されるアクリル系共重
合体（Ａ）は、前記した特定の構造のモノマー（ａ）〜
（ｆ）を、特定の比率で共重合させて得られるもので、
かつ水酸基価が２０〜１００ｍｇＫＯｆ（／ｇでガラス
転移温度が４０〜−３０℃のものでなければならない。The acrylic copolymer (A) used in the base coating composition of the present invention includes monomers (a) to
It is obtained by copolymerizing (f) at a specific ratio,
In addition, it must have a hydroxyl value of 20 to 100 mg KOf (/g) and a glass transition temperature of 40 to -30°C.
前記一般式（Ｉ）または（ＩＴ）で表わされるモノマー
（ａ）は、塗膜の耐チッピング性の向上に著しい効果を
発揮する成分であり、またベース塗料組成物に含まれる
アミノ樹脂、イソシアネートプレポリマーのような硬化
剤（Ｂ）との架橋反応にも寄与する成分である。モノマ
ー（ａ）の使用量は、ｌＯ〜６０重量％程度が適当であ
る。使用量が１０重量％未満の場合には、目的とする耐
チッピング性の改良効果が十分でなく、６０重量゛％を
越えると塗膜の耐水性、光沢性、メタリック感が低下し
好ましくない。耐チッピング性と他の塗膜物性のバラン
スを考慮すると、使用量のより好ましい範囲は２０〜４
０重量％である。The monomer (a) represented by the general formula (I) or (IT) is a component that exhibits a remarkable effect on improving the chipping resistance of the coating film, and is also a component that exhibits a remarkable effect on improving the chipping resistance of the coating film. It is a component that also contributes to the crosslinking reaction with the curing agent (B) such as a polymer. The appropriate amount of monomer (a) to be used is about 10 to 60% by weight. If the amount used is less than 10% by weight, the intended effect of improving chipping resistance will not be sufficient, and if it exceeds 60% by weight, the water resistance, gloss, and metallic feel of the coating film will deteriorate, which is undesirable. Considering the balance between chipping resistance and other coating film properties, the more preferable range of usage is 20 to 4.
It is 0% by weight.
前記一般式（１）で表わされるモノマー（ａ）の具体例
としては、２−ヒドロキシエチルメタクリレートのＣ−
カプロラクトン１モル付加物、２−ヒドロキシエチルメ
タクリレートのε−カプロラクトン２モル付加物、２−
ヒドロキシエチルアクリレートのε−カプロラクトン１
．Ｉｌ−ル付加物、２−ヒドロキシエチルアクリレート
のε−カプロラクトン２モル付加物等の２−ヒドロキシ
（メタ）アクリレートと有機ラクトン類の付加物が挙げ
られる。A specific example of the monomer (a) represented by the general formula (1) is C- of 2-hydroxyethyl methacrylate.
1 mole adduct of caprolactone, 2 mole adduct of ε-caprolactone of 2-hydroxyethyl methacrylate, 2-
ε-caprolactone of hydroxyethyl acrylate 1
．． Examples include adducts of 2-hydroxy (meth)acrylate and organic lactones, such as Il-yl adduct and 2-mol adduct of ε-caprolactone of 2-hydroxyethyl acrylate.
また、前記一般式（ＴＩ）で表わされるモノマー（ａ）
の具体例としては、ブレンマーＰＰ−１０００、ブレン
マーＰＥ−３５０、ブレンマーＰＥ−２００、ブレンマ
ーＰＥ−９０（以上商品名、日本油脂側製）のようなメ
タクリル酸へのプロピレンオキシドまたはエチレンオキ
シドの付加物が挙げられる。In addition, the monomer (a) represented by the general formula (TI)
Specific examples include adducts of propylene oxide or ethylene oxide to methacrylic acid such as Blenmar PP-1000, Blenmar PE-350, Blenmar PE-200, and Blenmar PE-90 (all trade names, manufactured by NOF). Can be mentioned.
水酸基含有ビニルモノマー（ｂ）の具体例としては、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、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Ｅ（シェル化学社製の
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、フマール酸、マレ
イン酸とのエステル化反応物：等が挙げられる。Specific examples of the hydroxyl group-containing vinyl monomer (b) include 2
-Hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Cardura E (glycidyl ester of synthetic fatty acids manufactured by Shell Chemical Co., Ltd.) Examples include esterification reaction products of representative monoepoxy compounds with (meth)acrylic acid, fumaric acid, and maleic acid.
モノマー（ｂ）は、得られるアクリル系共重合体（Ａ）
のＯＨ価が２０〜１００ｍｇＫＯ）１／ｇとなるように
、モノマー（ａ）との関係で使用される。Monomer (b) is the resulting acrylic copolymer (A)
It is used in relation to monomer (a) such that the OH number of the monomer (a) is 20 to 100 mg KO)1/g.
α、β−モノエチレン性不飽和カルボン酸（Ｃ）は、主
としてアクリル系共重合体（Ａ）と硬化剤（Ｂ）の架橋
反応を促進する触媒として重要な役割を果す成分であり
、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、フマール酸；およびイタコン酸、マレイ
ン酸、フマール酸等をアルコール（例えばメタノール、
エタノール、ブタノール等）で変性したモノアルキルエ
ステル等が挙げられる。The α,β-monoethylenically unsaturated carboxylic acid (C) is a component that plays an important role as a catalyst that mainly promotes the crosslinking reaction between the acrylic copolymer (A) and the curing agent (B). acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid;
Examples include monoalkyl esters modified with ethanol, butanol, etc.).
これらのα、β−モノエチレン性不飽和カルボン酸の使
用量は、アクリル系共重合体中に０．２〜１０重量％含
まれることが必要である。０．２重量％未満では上述の
効果が不十分であり、また１０重量％を越えると塗膜の
光沢性、メタリック感、更には耐水性等も低下し好まし
くない。より好ましい使用料の範囲は、硬化剤（Ｂ）と
してアミノ樹脂を用いる場合には１〜５重量％であり、
イソシアネートプレポリマーを用いる場合には０．２〜
３重量％である。The amount of these α,β-monoethylenically unsaturated carboxylic acids used must be 0.2 to 10% by weight in the acrylic copolymer. If it is less than 0.2% by weight, the above-mentioned effects will be insufficient, and if it exceeds 10% by weight, the gloss, metallic feel, and water resistance of the coating film will deteriorate, which is not preferable. A more preferable range of usage is 1 to 5% by weight when using an amino resin as the curing agent (B),
When using isocyanate prepolymer, 0.2~
It is 3% by weight.
本発明に用いる炭素原子数が１〜４のアルキル基を有す
る（メタ）アクリル酸エステル（ｄ）は、メタリック感
、光沢感の付与に寄与すると共に、塗膜の耐溶剤性、耐
薬品性、耐候性等も向上させる特性を有する。具体例と
しては、メチルメタクリレート、エチルメタクリレート
、プロピルメタクリレート、ｎ−ブチルメタクリレート
、ｉ−ブチルメタクリレート、ｔ−ブチルメタクリレー
ト、メチルアクリレート、エチルアクリレート、プロピ
ルアクリレート、ｎ−ブチルアクリレート、ｉ−ブチル
アクリレートおよびｔ−ブチルアクリレートが挙げられ
る。千ツマ−（ｄ）の使用量は３０〜８０重量％が適当
である。３０重量％未満では前記効果が不十分であり、
８０重量％を越えると塗膜の耐薬品性、耐溶剤性が低下
し好ましくない。The (meth)acrylic acid ester (d) having an alkyl group having 1 to 4 carbon atoms used in the present invention contributes to imparting a metallic feel and a glossy feeling, and also improves solvent resistance, chemical resistance, and It also has properties that improve weather resistance. Specific examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate and t-butyl acrylate. Butyl acrylate is mentioned. The appropriate amount of Chizuma (d) used is 30 to 80% by weight. If it is less than 30% by weight, the above effect is insufficient,
If it exceeds 80% by weight, the chemical resistance and solvent resistance of the coating film will decrease, which is not preferable.
本発明に用いる上記（ａ）〜（ｄ）成分と共重合可能な
他のとニルモノマー（ｅ）としては、ラウリル（メタ）
アクリレート、シクロヘキシル（メタ）アクリレート、
２−エチルヘキシル（メタ）アクリレート、フェニル（
メタ）アクリレート、ベンジル（メタ）アクリレート、
フェネチル（メタ）アクリレート等の（メタ）アクリル
酸エステル類；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子ツマー等が挙げられる。この
モノマー（ｅ）は、本発明の主たる用途である自動車用
塗料等における品質性能、例えば耐候性、美粧性、耐薬
品性、耐溶剤性、耐水性、可とう性、付着性等に影響を
与えるため、これらの性能を損わない範囲で適宜選択し
て使用される。モノマー（ｅ）の使用範囲は０〜５０重
量％であるが、更に好ましくは３０重量％以下である。Other monomers (e) copolymerizable with the above components (a) to (d) used in the present invention include lauryl (meth)
Acrylate, cyclohexyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, phenyl (
meth)acrylate, benzyl(meth)acrylate,
(meth)acrylic esters such as phenethyl (meth)acrylate; styrene derivatives such as styrene, α-methylstyrene, and vinyltoluene; polymerizable unsaturated nitriles such as acrylonitrile and methacrylate; vinyl acetate, vinyl propionate, etc. Vinyl esters: N-alkoxy substituted amides such as N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide;
Epoxy group-containing monomers such as glycidyl (meth)acrylate, (meth)allyl glycidyl ether, metaglycidyl (meth)acrylic acid ester; basic monomers such as dimethylaminoethyl (meth)acrylic acid, diethylaminoethyl (meth)acrylic acid, etc. can be mentioned. This monomer (e) affects the quality performance of automotive paints, etc., which are the main uses of the present invention, such as weather resistance, cosmetic properties, chemical resistance, solvent resistance, water resistance, flexibility, and adhesion. Therefore, these materials are appropriately selected and used within a range that does not impair their performance. The usage range of monomer (e) is 0 to 50% by weight, more preferably 30% by weight or less.
本発明におけるベース塗料用アクリル系共重合体（Ａ）
の重合方法としては、溶液重合法、塊状重合法、乳化重
合法等の公知の何れの重合法でもよいが、とりわけ溶液
重合法による重合体であることが好ましい。溶液重合法
による場合、有機溶剤および重合開始剤の存在下に、前
記千ツマ−の混合物を共重合させる。有機溶剤としては
、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が使用でき、ま
た、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
れる重合開始剤が使用できる。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。本発明のアクリル
系共重合体（Ａ）は水酸基価が２０〜１００ｍｇＫＤＨ
／ｇであるが、水酸基価が２０ｍｇＫＯＨ／ｇ未満であ
ると硬化塗膜の架橋密度が低く、耐溶剤性が低下し、ま
たクリヤー塗膜との眉間密着性も低下する。また、１０
０ｍｇＫＯ）１／ｇを越えると、塗膜の耐水性が低下し
好ましくない。アクリル系共重合体（ＡＪのガラス転移
温度は４０〜−３０℃の範囲であるが、ガラス転移温度
は４０℃を越えるとベースコート塗膜が硬く脆くなり、
耐チッピング性が低下し、−３０℃未満では耐溶剤性が
低下し好ましくない。Acrylic copolymer (A) for base paint in the present invention
As the polymerization method, any known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. may be used, but it is particularly preferable to use a solution polymerization method. In the case of the solution polymerization method, the mixture of 1,000 polymers is copolymerized in the presence of an organic solvent and a polymerization initiator. As the organic solvent, commonly used organic solvents such as isopropyl alcohol, n-butanol, toluene, and xylene can be used, and as the polymerization initiator, commonly used organic solvents such as azobisisobutyronitrile, benzoyl peroxide, and cumene hydroperoxide can be used. Polymerization initiators can be used. Also, if necessary, 2-
Chain transfer agents such as mercaptoethanol and n-octylmercaptan can be used. The acrylic copolymer (A) of the present invention has a hydroxyl value of 20 to 100 mgKDH.
/g, but if the hydroxyl value is less than 20 mgKOH/g, the crosslinking density of the cured coating film will be low, the solvent resistance will be reduced, and the glabella adhesion with the clear coating film will also be reduced. Also, 10
If it exceeds 0mgKO)1/g, the water resistance of the coating film will decrease, which is not preferable. The glass transition temperature of acrylic copolymer (AJ) is in the range of 40 to -30°C, but when the glass transition temperature exceeds 40°C, the base coat film becomes hard and brittle.
Chipping resistance decreases, and if it is lower than -30°C, solvent resistance decreases, which is not preferable.
本発明のベース塗料組成物は、本発明の主たる用途であ
る自動車用塗料等に於ける前記品質性能を満足させるた
め、硬化剤（Ｂ）を含有する。硬化剤（Ｂ）としては、
例えばアミノ樹脂、イソシアネートプレポリマー、ブロ
ックトポリイソシアネート、シランカップリング剤、ア
ルミニウムキレート系硬化剤が使用できる。The base coating composition of the present invention contains a curing agent (B) in order to satisfy the above-mentioned quality performance in automotive coatings and the like, which are the main uses of the present invention. As the curing agent (B),
For example, amino resins, isocyanate prepolymers, blocked polyisocyanates, silane coupling agents, and aluminum chelate curing agents can be used.
硬化剤（Ｂ）の使用量は、５〜５０重量％である。The amount of curing agent (B) used is 5 to 50% by weight.
硬化剤の使用量が５重量％未満では塗膜の耐候性、耐溶
剤性、耐水性等が不十分であり、５０重量％を越えると
塗膜の光沢性、メタリック感を始め、物理性能、化学性
能全般に劣り、好ましくない。If the amount of curing agent used is less than 5% by weight, the weather resistance, solvent resistance, water resistance, etc. of the coating film will be insufficient, and if it exceeds 50% by weight, the glossiness, metallic feel, physical performance, etc. of the coating film will be deteriorated. Poor overall chemical performance and unfavorable.
アミン樹脂の具体例としては、アミノトリアジン、尿素
、ジシアンジアミド、Ｎ、Ｎ−エチレン尿素のメチロー
ル化物をシクロヘキサノールまたは炭素原子数が１〜６
のアルカノールでアルキルエーテル化したものであり、
特にアミノトリアジンより得られたもの、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。Specific examples of amine resins include aminotriazine, urea, dicyandiamide, N,N-ethylene urea methylol, cyclohexanol, or carbon atoms of 1 to 6.
is alkyl etherified with alkanol,
Particularly suitable are those obtained from aminotriazine, such as methyl etherified melamine resin and butyl etherified melamine resin.
アミノ樹脂を硬化剤として使用する場合には、ベース塗
料組成物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、ナフタレンスルホン酸またはそれらのアミ
ン中和物等で代表される外部触媒を添加することができ
る。When using an amino resin as a curing agent, an external catalyst such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, or their amine neutralized products can be added to the base coating composition. .
本発明にいうイソシアネートプレポリマーとは、１分子
中に遊離またはブロックされたインシアネート基を２個
以上含有する化合物であり、具体的には、テトラメチレ
ンジイソシアネート、ヘキサメチレンジイソシアネート
、トリメチルヘキサンジイソシアネート等の脂肪族イソ
シアネート類、イソホロンジイソシアネート、４，４゛
−メチレンビス（シクロヘキシルイソシアネート）等の
脂環族系ジイソシアネート類、キシリレンジイソシアネ
ート、トリレンジイソシアネート等の芳香族ジイソシア
ネート類、その他インシアネートへのエチレングリコー
ル、プロピレングリコール、ネオペンチルグリコール、
トリメチロールプロパン等の多価アルコール付加物や、
イソシアネート基と反応する官能基を有する低分子量の
ポリエステル樹脂または水等の付加物またはビユレット
体、ジイソシアネート同志の重合体、更に低級１価アル
コール、メチルエチルケトオキシム等公知のブロック化
剤でこれら化合物のイソシアネート基をブロックしたも
の等が挙げられる。The isocyanate prepolymer referred to in the present invention is a compound containing two or more free or blocked incyanate groups in one molecule, and specifically includes tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexane diisocyanate, etc. Aliphatic isocyanates, isophorone diisocyanate, alicyclic diisocyanates such as 4,4゛-methylenebis(cyclohexyl isocyanate), aromatic diisocyanates such as xylylene diisocyanate, tolylene diisocyanate, and other incyanates such as ethylene glycol and propylene. glycol, neopentyl glycol,
Polyhydric alcohol adducts such as trimethylolpropane,
A low molecular weight polyester resin having a functional group that reacts with an isocyanate group, an adduct of water or the like, a biuret form, a polymer of diisocyanates, and a known blocking agent such as a lower monohydric alcohol or methyl ethyl ketoxime can be used to remove the isocyanate group of these compounds. Examples include those that are blocked.
イソシアネートプレポリマーを使用する場合についても
、ジブチルチンジラウレート、トリエチルアミン等の外
部触媒を添加することができる。Even when using isocyanate prepolymers, external catalysts such as dibutyltin dilaurate, triethylamine, etc. can be added.
本発明のベース塗料組成物は、基本的には上記アクリル
系共重合体（Ａ）と硬化剤（Ｂ）とからなるが、これら
以外に本発明の目的とする塗膜の優れた耐チッピング性
を損なわない範囲で、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系以外の樹脂を含有させる
ことができる。通常、これら樹脂の使用量は、ベース塗
料組成物に対して３０重重量未満である。３０重量％を
越えると加熱硬化後のクリヤー塗膜との付着性が低下し
たり、耐候性が低下する場合がある。The base coating composition of the present invention basically consists of the above-mentioned acrylic copolymer (A) and curing agent (B), but in addition to these, it also provides excellent chipping resistance of the coating film, which is the object of the present invention. Resins other than acrylic resins, such as polyester resins, epoxy resins, and cellulose resins, can be contained within a range that does not impair the properties. Typically, the amount of these resins used is less than 30 weight by weight based on the base coating composition. If it exceeds 30% by weight, the adhesion to the clear coating film after heat curing may be reduced, and the weather resistance may be reduced.
なお、本発明のベース塗料組成物は、塗料として用いる
に際し、従来公知の下記成分を含有することができる。The base coating composition of the present invention, when used as a coating material, can contain the following conventionally known components.
すなわち、アルミニウムペースト、雲母、リン片状酸化
鉄等の光輝剤；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；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系以外の樹脂
；表面調整剤、紫外線吸収剤、酸化防止剤、顔料沈降防
止剤、揺変性付与剤等の補助的添加剤；等が挙げられる
。Namely, brightening agents such as aluminum paste, mica, and flaky iron oxide; pigments such as titanium oxide, carbon black, quinacridone, and cyanine blue; non-acrylic resins such as polyester resins, epoxy resins, and cellulose resins; Auxiliary additives such as regulators, ultraviolet absorbers, antioxidants, pigment antisettling agents, and thixotropy imparting agents are included.
本発明のベース塗料用組成物は、前記した各成分を一般
的な配合方法により配合して製造される。ベース塗料と
して使用するに際しては、各種の希釈溶剤を用いてフォ
ードカップＮｏ、４による２０℃における粘度力月０〜
２０秒の範囲内となるように調整して、これを基材に対
して乾燥膜厚カ月０〜３０μｍとなるように直接塗装す
るか、あるいは予め基材上にブライマー塗膜を形成させ
た所へ、乾燥膜厚が１０〜３０μｍとなるように塗装す
る。The base coating composition of the present invention is produced by blending the above-mentioned components using a common blending method. When used as a base paint, the viscosity at 20°C according to Ford Cup No. 4 using various diluting solvents should be
Adjust the coating time to within 20 seconds and apply it directly to the base material to a dry film thickness of 0 to 30 μm, or pre-form a brimer coating on the base material. The coating is applied so that the dry film thickness is 10 to 30 μm.
次いで常温下に数分間放置した後、例えばアクリル系樹
脂／アミノ樹脂系やアクリル系樹脂／イソシアネートプ
レポリマーをビヒクルとし、必要に応じて紫外線吸収剤
、光安定剤、垂れ防止剤等の補助的添加剤等を配合して
なる熱硬化性クリヤー塗料を希釈溶剤でフォードカップ
Ｎ０１４による２０℃の粘度が１３〜４０秒の範囲内と
なるように調整し、これをベース用塗膜の上に、乾燥膜
厚が２０〜５０μｍとなるよう重ね塗りし、常温下に数
分間放置する。しかる後、硬化剤としてアミノ樹脂を用
いた場合には６０℃〜１８０℃なる温度範囲で、またイ
ソシアネートプレポリマーを用いた場合には常温〜１４
０℃の温度範囲で１０〜４０分間で硬化させる。このよ
うにして耐チッピング性に優れた２コート・１ベ一ク方
式の硬化塗膜を形成することができる。Next, after being left at room temperature for several minutes, for example, acrylic resin/amino resin or acrylic resin/isocyanate prepolymer is used as a vehicle, and if necessary, auxiliary additions such as ultraviolet absorbers, light stabilizers, anti-sag agents, etc. A thermosetting clear paint made by blending agents etc. is adjusted with a diluting solvent so that the viscosity at 20°C according to Ford Cup No. 014 is within the range of 13 to 40 seconds, and this is applied onto the base paint film and dried Coating is repeated so that the film thickness is 20 to 50 μm, and left at room temperature for several minutes. Thereafter, the temperature range is 60°C to 180°C when an amino resin is used as the curing agent, or from room temperature to 14°C when an isocyanate prepolymer is used.
Curing is performed in a temperature range of 0° C. for 10 to 40 minutes. In this way, a two-coat, one-bake cured coating film with excellent chipping resistance can be formed.
以下、本発明を実施例および比較例により具体的に説明
するが、部および％は特に断りのない限り、全て重量基
準による。Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, and all parts and percentages are based on weight unless otherwise specified.
くベース塗料用アクリル系共重合体Ｂ−１−８−５の合
成〉
第１表に示した組成の溶剤を９０℃に加熱した後、第１
表に示した組成のモノマーおよび重合開始剤の混合物を
４時間で滴下し、更に３時間同温度で重合させ、ベース
塗料用アクリル系共重合体Ｂ−１−Ｂ−５を合成した。Synthesis of acrylic copolymer B-1-8-5 for base paint> After heating the solvent having the composition shown in Table 1 to 90°C,
A mixture of monomers and a polymerization initiator having the composition shown in the table was added dropwise over a period of 4 hours, and the mixture was further polymerized at the same temperature for 3 hours to synthesize acrylic copolymers B-1-B-5 for base coatings.
くクリヤー塗料用共重合体Ｃ−を及びＣ−２の合成〉第
２表に示した組成の溶剤を１３０℃に加熱した後、第２
表に示した組成のモノマーおよび重合開始剤の混合物を
４時間で滴下し、更に２時間同温度で重合させ、クリヤ
ー塗料用共重合体Ｃ−１およびＣ−２を合成した。Synthesis of copolymers C- and C-2 for clear paints After heating the solvent having the composition shown in Table 2 to 130°C,
A mixture of monomers and a polymerization initiator having the composition shown in the table was added dropwise over 4 hours, and polymerization was further carried out at the same temperature for 2 hours to synthesize copolymers C-1 and C-2 for clear coatings.
実施例１および比較例１
ソリッドカラー ベース の
下記配合のソリッドカラー用ベース塗料ＢＰ−１および
ＢＰ−２を調製した。Example 1 and Comparative Example 1 Solid color base paints BP-1 and BP-2 having the following formulations were prepared.
アクリル系共重合体
（Ｂ−１またはＢ−２） １６０重量部ニ
ーパン２０ＳＥ” ３Ｑ ／／ル
ビクロン５００ＲＧ” ２ ／／キ
シレン ２０〃セロソルブアセ
テート ２０〃＊ｌ ブチル化メラミン樹脂
（三井東圧化学■製）峠 赤色顔料（トーソー側製）
クリヤー ；の礼１
下記配合合のクリヤー塗料ＣＰ−１を調製した。Acrylic copolymer (B-1 or B-2) 160 parts by weight Kneepan 20SE" 3Q // Rubicron 500RG" 2 // Xylene 20〃Cellosolve Acetate 20〃*l Butylated melamine resin (manufactured by Mitsui Toatsu Chemicals) Pass Red Pigment (manufactured by Toso) Clear; Norei 1 A clear paint CP-1 having the following formulation was prepared.
クリヤー塗料用共重合体Ｃ−１１１７重量部ニーパン２
０ＳＥ ５０ ｔｔツルペッツ
＃１５０″３２０ ／／
ｎ−ブタノール ５ 〃チヌビン３
２Ｂ” Ｑ、７ ／／サノールＬ
Ｓ−７７０ｆｉＳＱ、４ ／／モダフロー”
０，２ ／／＊３ 芳香族石油誘導体
（エッソ社製）孝４ 紫外線吸収剤（チバガイギー側製
）傘５ 光安定剤（三共■製）
傘６ レベリング剤（モンサント社製）ｌ又試１
リン酸亜鉛で化成処理した０、 ８ｍｍｘ ９０ｍｍＸ
３０ｍｍのダル鋼板に、カチオン電着、中塗塗膜を施
し、サンディングして得たテストピース上に、トルエン
：酢酸エチル：ツルペッツ＃１５０を４：３：３（重量
）の割合で混合した溶剤を用いてＮ０９４フオードカツ
プで１４秒になるように粘度調整したソリッドカラー用
ベース塗料を２ステージで２０μｍになるように塗装し
た。３分間室温で放置した後、ツルペッツ５１００：ツ
ルペッツ＃１５０を２＝１（重量）の割合で混合した溶
剤を用い、Ｎ００４フオードカツプで２８秒になるよう
粘度調整したクリヤー塗料を３５μｍになるように塗装
し、１０分間室温で放置した後、 ！４０℃Ｘ３０分間
焼付を行った。耐チッピング性および他の塗膜性能の評
価結果を第３表に示した。Copolymer C-1117 for clear paints Part by weight Kneepan 2
0SE 50 tt Tsurpets #150″320 // n-butanol 5 Tinuvin 3
2B” Q, 7 // Sanor L
S-770fiSQ, 4 //Modaflow”
0,2 //*3 Aromatic petroleum derivative (manufactured by Esso) 4 Ultraviolet absorber (manufactured by Ciba Geigy) Umbrella 5 Light stabilizer (manufactured by Sankyo ■) Umbrella 6 Leveling agent (manufactured by Monsanto) 1 Rin 0.8mm x 90mmx treated with acid zinc
A 30 mm dull steel plate was coated with a cationic electrodeposition and an intermediate coating, and then sanded. A solvent containing a mixture of toluene: ethyl acetate: Tsurupetz #150 in a ratio of 4:3:3 (by weight) was applied to the test piece. A solid color base paint whose viscosity was adjusted to 14 seconds with a N094 Ford Cup was applied in two stages to a thickness of 20 μm. After leaving it at room temperature for 3 minutes, use a solvent mixed with Tsurupetz 5100 and Tsurupetz #150 in a ratio of 2=1 (by weight), and apply a clear paint to a thickness of 35 μm using a N004 food cup to adjust the viscosity to 28 seconds. After leaving it at room temperature for 10 minutes, ! Baking was performed at 40°C for 30 minutes. Table 3 shows the evaluation results of chipping resistance and other coating film performances.
表から明らかなように、実施例１の場合には、耐チッピ
ング性および他の塗膜性能が良好な２コート・１ベーク
系塗膜が形成できたのに対し、比較例１の場合には、ベ
ース塗膜と中塗り塗膜の間で眉間剥離が多く見られ、耐
チッピング性は低位であった。As is clear from the table, in the case of Example 1, a 2-coat, 1-bake coating film with good chipping resistance and other coating properties could be formed, whereas in the case of Comparative Example 1, , A lot of glabellar peeling was observed between the base paint film and the intermediate paint film, and the chipping resistance was low.
実施例２〜４および比較例２
メタ１ツク ベース の
下記配合で、メタリック用ベース塗料ＢＰ−３〜ＢＰ−
６を調製した。Examples 2 to 4 and Comparative Example 2 Metallic base paints BP-3 to BP- were prepared using the following formulations of metallic base paints.
6 was prepared.
アクリル系共重合体
（Ｂ−３〜Ｂ−６’） １６０重量
部ニーパン２０ＳＥ ３３ ／
／アルペーストｌＩ０９ＭＡ” １５
／／キシレン ２０〃＊７ ア
ルミニウムペースト（東洋アルミ側製）クリヤー塗料に
は、前記ＣＰ−１を使用した。Acrylic copolymer (B-3 to B-6') 160 parts by weight Knee pants 20SE 33 /
/Alpaste lI09MA” 15
//Xylene 20〃*7 Aluminum paste (manufactured by Toyo Aluminum) The above-mentioned CP-1 was used as the clear paint.
かくして得られたメタリック用ベース塗料およびクリヤ
ー塗料を、前記のソリッドカラー用の場合と同様の工程
により２コート・ｌベーク系塗膜を形成した。評価結果
を第４表に示した。Using the metallic base paint and clear paint thus obtained, a 2-coat/1-bake paint film was formed using the same process as for the solid color paint. The evaluation results are shown in Table 4.
実施例２〜４の場合には、耐チッピング性、他の塗膜性
能ともに良好な２コート・１ベーク系塗膜が形成できた
のに対し、比較例２では耐チッピング性が低位であった
。In Examples 2 to 4, two-coat, one-bake coatings with good chipping resistance and other coating properties were formed, whereas in Comparative Example 2, chipping resistance was low. .
実施例５および比較例３
メタリックベース の
下記配合で、メタリック用ベース塗料ＢＰ−７およびＢ
Ｐ−８を調製した。Example 5 and Comparative Example 3 Metallic base paints BP-7 and B were prepared using the following formulation of metallic base.
P-8 was prepared.
アクリル系共重合体
（Ｂ−７またはＢ−８） １６０重量部ス
ミジュールＮ−７５” ２５ ／／ア
ルペーストｌ１０９ＭＡ １５ ／／
キシレン ２０〃峠 イソシア
ネートプレポリマー（住友化学■製）
２亙ｊ：」１１Δ匪１
下記配合のクリヤー塗料ＣＰ−２を調製した。Acrylic copolymer (B-7 or B-8) 160 parts by weight Sumidur N-75” 25 // Alpaste l109MA 15 //
Xylene 20〃Touge Isocyanate prepolymer (manufactured by Sumitomo Chemical ■) 2㎙j:〃11Δ匪1 A clear paint CP-2 having the following formulation was prepared.
クリヤー塗料用共重合体Ｃ−２１２０重量部スミジュー
ルＮ−７５３６／／
キシレン ２０〃チヌビン３２
１１ ０．７ ／１サノールＬＳ
７７０ ０．４ １１モグフロ−〇、
２〃
このようにして得たメタリック用ベース塗料およびクリ
ヤー塗料を、前記テストピース上に、トルエンニ酢酸エ
チル：ソルベツソ＃１５０を６＝３二１ （重量）の割
合で混合した溶剤にて、Ｎｏ、 ４フオードカツプで１
３秒に粘度調整したメタリックベース塗料を２ステージ
で２０μｍになるように塗装した。３分間室温で放置し
た後、トルエン：キシレン：酢酸ｎ−ブチル＝３：５：
２（重量）の割合で混合した溶剤にて、Ｎｏ、 ４フオ
ードカツプで１５秒となるように粘度調整したクリヤー
塗料を３５μｍとなるよう塗装し、１０分間室温で放置
した後、８０℃×３０分間焼付を行った。耐チッピング
性、他の塗膜性能の評価結果を第５表に示した。Copolymer for clear paint C-2120 parts by weight Sumidur N-7536 // Xylene 20〃Tinuvin 32
11 0.7 /1 Sanol LS
770 0.4 11 Mogflow〇,
2. The metallic base paint and clear paint thus obtained were coated on the test piece with a solvent containing ethyl toluene diacetate: Solbetsuso #150 in a ratio of 6=321 (by weight). 4 food cups in 1
A metallic base paint whose viscosity was adjusted to 3 seconds was applied in two stages to a thickness of 20 μm. After standing at room temperature for 3 minutes, toluene: xylene: n-butyl acetate = 3:5:
A clear paint with a viscosity adjusted to 35 μm was applied using a solvent mixed at a ratio of 2 (by weight) using a No. 4 food cup for 15 seconds, and after being left at room temperature for 10 minutes, it was heated at 80°C for 30 minutes. Burning was performed. Table 5 shows the evaluation results of chipping resistance and other coating film performances.
実施例５では、耐チッピング性、他の塗膜性能共に良好
な２コート・１ベーク系塗膜が形成できたのに対し、比
較例３の塗膜では、耐チッピング性が低位となった。In Example 5, a two-coat, one-bake coating film with good chipping resistance and other coating properties was formed, whereas in Comparative Example 3, the coating film had low chipping resistance.
第
表
“１石油製芳香族系炭化水素
２ 日石レギュラーガソリン 室温×２４時間浸漬、引
上後外観判定
３１０％）１２Ｓ０４スポツト 室温×２４時間後、外
観判定
″４５０℃温水 ２週′間浸漬、引上後外観判定″５
サンシャインＷ−０−Ｍ ２０００時間後、５０℃、
９８％ＲＨにて耐湿２４０時間経過後の外観”６ °５
の条件後、ゴバン目セロテープ剥離試験を行い、付着率
を表示
尚、表中の記号は次の意味を有する。Table 1: Petroleum-made aromatic hydrocarbons 2: Nisseki regular gasoline, immersed at room temperature for 24 hours, appearance judgment after pulling up: 310%) 12S04 spot: Room temperature x 24 hours, appearance judgment: immersed in 450°C hot water for 2 weeks, Appearance judgment after pulling up ``5
Sunshine W-0-M 2000 hours later, 50°C,
Appearance after 240 hours of humidity resistance at 98% RH "6 °5
After the above conditions, a cross-cut Cellotape peel test was conducted and the adhesion rate was shown.The symbols in the table have the following meanings.
Ｏ非常に良好 Ｏ良好 Δ不良
×極めて不良
第
表
飛石試験ＩＩ （ＪＡ−４００型、スガ試験機側製）を
用い、−３０℃の恒温槽内で、３ｋｇ／ｒｎ２のエヤー
圧で７号細石（５００ｇ）を塗膜に対して４５℃の角度
より衝突させ、剥離の状況を目視にて判定。O Very good O Good Δ Poor x Extremely poor No. 7 fine stone using a stepping stone test II (JA-400 type, manufactured by Suga Test Instruments) in a thermostatic chamber at -30°C with an air pressure of 3 kg/rn2 (500g) was caused to collide with the coating film at an angle of 45°C, and the state of peeling was visually determined.
第 表 第３表中の耐チツピング性評価法と同一である。No. table This is the same as the chipping resistance evaluation method in Table 3.
日石レギュラーガソリン 室温×２４時間浸漬、引上後
外観判定
°３１０％Ｈ２ＳＯ４スポット 室温×２４時間後、外
観判定
″４５０℃温水 ２週間浸漬、引上後外観判定″５ サ
ンシャインＷ−０−Ｍ ２０００時間後、５０℃、９
８％ＲＨにて耐湿２４０時間経過後の外観″６ “５の
条件後、ゴバン目セロテープ剥離試験を行い、付着率を
表示
第５表
”１ 第３表中の耐チツピング性評価方法と同一である
。Nisseki Regular Gasoline Room temperature x 24 hours immersion, appearance judgment after pulling °310% H2SO4 spot Room temperature x 24 hours, appearance judgment ``450℃ hot water 2 weeks immersion, appearance judgment after pulling'' 5 Sunshine W-0-M 2000 After hours, 50℃, 9
Appearance after 240 hours of humidity resistance at 8% RH ``6'' After the conditions of 5, a cross-cut Cellotape peel test was performed and the adhesion rate was shown Table 5 ``1 Same as the chipping resistance evaluation method in Table 3. be.
”２ 白石レギュラーガソリン 室温×２４時間浸漬、
引上後外観判定
３ 同％Ｈ２ＳＯ４スポット 室温Ｘ２４時間後、外観
判定
″４５０℃温水 ２週間浸漬、引上後外観判定８５
サンシャインＷ−０−Ｍ ２０００時間後、５０℃、
９８％ＲＨにて耐湿２４０時間経過後の外観“６５の条
件後、ゴバン目セロテープ剥離試験を行い、付着率を表
示
Ｃ発明の効果〕
以上の実施例からも明らかなように、本発明のアクリル
系ベース塗料用組成物を用いて２コート・１ベ一ク方式
で積層塗膜を形成すると、優れた美粧性、塗膜性能を保
持しながら耐チッピング性が改善された塗膜が得られる
。”2 Shiraishi regular gasoline soaked at room temperature for 24 hours,
Appearance judgment after pulling 3 Same % H2SO4 spot Room temperature x 24 hours later, appearance judgment ``450℃ warm water immersion for 2 weeks, appearance judgment after pulling 85
Sunshine W-0-M 2000 hours later, 50°C,
Appearance after 240 hours of humidity resistance at 98% RH After the conditions of 65, a cross-cut Cellotape peel test was conducted and the adhesion rate was shown. When a laminated coating film is formed using a two-coat/one-bake method using the base coating composition, a coating film with improved chipping resistance while maintaining excellent cosmetic properties and coating performance can be obtained.
特許出願人 三菱レイヨン株式会社Patent applicant: Mitsubishi Rayon Co., Ltd.
Claims (1)
塗料を重ね塗りした後、加熱硬化させ塗膜を得る塗装系
に用いるベース塗料において、該ベース塗料が （ａ）下記一般式（ I ）または（II） ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＾１、Ｒ＾２およびＲ＾３はそれぞれ独立し
て水素原子またはメチル基を示し、ｍは３〜５の整数、
ｎは１〜６の整数、ｐは２〜７の整数である。） で表わされる水酸基含有（メタ）アクリル酸エステル１
０〜６０重量％ （ｂ）上記一般式（ I ）または（II）以外の水酸基含
有ビニルモノマー０〜２０重量％ （ｃ）α，β−モノエチレン性不飽和カルボン酸０．２
〜１０重量％ （ｄ）炭素原子数が１〜４のアルキル基を有する（メタ
）アクリル酸エステル３０〜８０重量％および （ｅ）上記（ａ）〜（ｄ）成分と共重合可能な他のビニ
ルモノマー０〜５０重量％ を共重合して得られる水酸基価が２０〜１００ｍｇＫＯ
Ｈ／ｇでガラス転移温度が４０〜−３０℃であるアクリ
ル系共重合体（Ａ）５０〜９５重量％と、 硬化剤（Ｂ）５〜５０重量％とから成るベース塗料組成
物。[Scope of Claims] A base paint used in a coating system in which a base paint containing a coloring agent is applied, then a clear paint is overcoated, and then a coating film is obtained by heating and curing the base paint, wherein the base paint is (a) one of the following general Formula (I) or (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, R^2 and R^3 are Each independently represents a hydrogen atom or a methyl group, m is an integer of 3 to 5,
n is an integer of 1 to 6, and p is an integer of 2 to 7. ) Hydroxyl group-containing (meth)acrylic acid ester 1
0 to 60% by weight (b) 0 to 20% by weight of a hydroxyl group-containing vinyl monomer other than the above general formula (I) or (II) (c) α,β-monoethylenically unsaturated carboxylic acid 0.2
-10% by weight (d) 30-80% by weight of a (meth)acrylic acid ester having an alkyl group having 1 to 4 carbon atoms and (e) other copolymerizable components with the above components (a) to (d). The hydroxyl value obtained by copolymerizing 0 to 50% by weight of vinyl monomer is 20 to 100 mg KO.
A base coating composition comprising 50 to 95% by weight of an acrylic copolymer (A) having a glass transition temperature of 40 to -30°C in H/g and 5 to 50% by weight of a curing agent (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19715588A JPH0247175A (en) | 1988-08-09 | 1988-08-09 | Chipping-resistant acrylic base coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19715588A JPH0247175A (en) | 1988-08-09 | 1988-08-09 | Chipping-resistant acrylic base coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0247175A true JPH0247175A (en) | 1990-02-16 |
Family
ID=16369682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19715588A Pending JPH0247175A (en) | 1988-08-09 | 1988-08-09 | Chipping-resistant acrylic base coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0247175A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008013290A1 (en) * | 2006-07-25 | 2008-01-31 | Kansai Paint Co., Ltd. | Aqueous coating composition |
| JP2008202038A (en) * | 2007-01-22 | 2008-09-04 | Mitsubishi Rayon Co Ltd | Thermoset coating resin composition |
| CN102907326A (en) * | 2012-11-07 | 2013-02-06 | 云南农业大学 | Tissue culture propagation method for Medicagao Sativa L. |
| WO2022075269A1 (en) * | 2020-10-05 | 2022-04-14 | 日本ペイント・オートモーティブコーティングス株式会社 | Base coating material composition and coated article |
| JP2022060948A (en) * | 2020-10-05 | 2022-04-15 | 日本ペイント・オートモーティブコーティングス株式会社 | Coating method for double-layer coating film on molding for automobile component |
-
1988
- 1988-08-09 JP JP19715588A patent/JPH0247175A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008013290A1 (en) * | 2006-07-25 | 2008-01-31 | Kansai Paint Co., Ltd. | Aqueous coating composition |
| JPWO2008013290A1 (en) * | 2006-07-25 | 2009-12-17 | 関西ペイント株式会社 | Water-based paint composition |
| US8404354B2 (en) | 2006-07-25 | 2013-03-26 | Kansai Paint Co., Ltd. | Water-based paint compositions |
| JP5430935B2 (en) * | 2006-07-25 | 2014-03-05 | 関西ペイント株式会社 | Water-based paint composition |
| JP2008202038A (en) * | 2007-01-22 | 2008-09-04 | Mitsubishi Rayon Co Ltd | Thermoset coating resin composition |
| CN102907326A (en) * | 2012-11-07 | 2013-02-06 | 云南农业大学 | Tissue culture propagation method for Medicagao Sativa L. |
| WO2022075269A1 (en) * | 2020-10-05 | 2022-04-14 | 日本ペイント・オートモーティブコーティングス株式会社 | Base coating material composition and coated article |
| JP2022060948A (en) * | 2020-10-05 | 2022-04-15 | 日本ペイント・オートモーティブコーティングス株式会社 | Coating method for double-layer coating film on molding for automobile component |
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