WO1982002397A1 - Thermosetting acrylic enamel stabilized against weathering by addition of ultraviolet light stabilizer - Google Patents
Thermosetting acrylic enamel stabilized against weathering by addition of ultraviolet light stabilizer Download PDFInfo
- Publication number
- WO1982002397A1 WO1982002397A1 PCT/US1980/001756 US8001756W WO8202397A1 WO 1982002397 A1 WO1982002397 A1 WO 1982002397A1 US 8001756 W US8001756 W US 8001756W WO 8202397 A1 WO8202397 A1 WO 8202397A1
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- WO
- WIPO (PCT)
- Prior art keywords
- weight
- composition according
- ultraviolet light
- coating
- light stabilizer
- Prior art date
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- 239000004611 light stabiliser Substances 0.000 title claims abstract description 41
- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229920001187 thermosetting polymer Polymers 0.000 title abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- -1 glycidyl ester Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 239000000470 constituent Substances 0.000 claims description 17
- 239000008199 coating composition Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000049 pigment Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000004185 ester group Chemical group 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical group OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- NJIDLJRHMJCJIV-UHFFFAOYSA-N C.C(CC)(=O)O Chemical compound C.C(CC)(=O)O NJIDLJRHMJCJIV-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 2
- 239000012964 benzotriazole Substances 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 2
- 150000002430 hydrocarbons Chemical group 0.000 claims 2
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 claims 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 1
- 125000002837 carbocyclic group Chemical group 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000004925 Acrylic resin Substances 0.000 abstract description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000178 Acrylic resin Polymers 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000012963 UV stabilizer Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229940072282 cardura Drugs 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 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 4
- 150000002148 esters Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940043232 butyl acetate Drugs 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000008096 xylene Substances 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
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229920006397 acrylic thermoplastic Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
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- 238000006552 photochemical reaction Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- FLYXGBNUYGAFAC-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(2-hydroxyphenyl)methanone Chemical class OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1O FLYXGBNUYGAFAC-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- XQFFPRQMEMRTBL-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl-methylcarbamodithioic acid Chemical compound C(C)(C)(C)C=1C=C(CN(C(S)=S)C)C=C(C1O)C(C)(C)C XQFFPRQMEMRTBL-UHFFFAOYSA-N 0.000 description 1
- NPYKRXUXPUDWEU-UHFFFAOYSA-N (3,5-ditert-butylphenyl)-(2,4-dihydroxyphenyl)methanone Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C(=O)C=2C(=CC(O)=CC=2)O)=C1 NPYKRXUXPUDWEU-UHFFFAOYSA-N 0.000 description 1
- SUQGLJRNDJRARS-UHFFFAOYSA-N (3-benzoyloxyphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C=1)=CC=CC=1OC(=O)C1=CC=CC=C1 SUQGLJRNDJRARS-UHFFFAOYSA-N 0.000 description 1
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- BZVKNZLGFQSCCJ-UHFFFAOYSA-N 2-(3-methyl-5-propan-2-ylphenyl)-1-benzofuran-6-ol Chemical class CC(C)C1=CC(C)=CC(C=2OC3=CC(O)=CC=C3C=2)=C1 BZVKNZLGFQSCCJ-UHFFFAOYSA-N 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001354 dialkyl silanes Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 230000035620 dolor Effects 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZTTRRULOZHQYCR-UHFFFAOYSA-N ethyl 3-[4-hydroxy-3,5-bis(2-methylpentan-2-yl)phenyl]prop-2-enoate Chemical compound CCCC(C)(C)C1=CC(C=CC(=O)OCC)=CC(C(C)(C)CCC)=C1O ZTTRRULOZHQYCR-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- ANAHIDIYOHYVRY-UHFFFAOYSA-N methyl 3-(3,5-dibutyl-4-hydroxyphenyl)propanoate Chemical compound CCCCC1=CC(CCC(=O)OC)=CC(CCCC)=C1O ANAHIDIYOHYVRY-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- HKLPOBRVSAUJSG-UHFFFAOYSA-N n-(4-anilinophenyl)prop-2-enamide Chemical compound C1=CC(NC(=O)C=C)=CC=C1NC1=CC=CC=C1 HKLPOBRVSAUJSG-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- LYDRKKWPKKEMNZ-UHFFFAOYSA-N tert-butyl benzoate Chemical compound CC(C)(C)OC(=O)C1=CC=CC=C1 LYDRKKWPKKEMNZ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/32—Modified amine-aldehyde condensates
Definitions
- This invention relates to coating compositions and to coated articles having a color coat overlaid with a clear coat.
- it is directed toward thermosetting acrylic enamels containing ultraviolet light stabilizers, which enamels give a high quality weather resistant coating, especially useful for coating the exterior of automobile and truck bodies.
- the enamels are prepared as disclosed in United States Patent 3,622,651 - Vasta issued November 23, 1971, incorporated herein by reference.
- the addition of one or more ultraviolet light stabilizers serves to diminish the degradation effects of the ultraviolet radiation in the sunlight.
- the enamels also contain one or more antioxidants.
- Sunlight is composed of electromagnetic radiation with energy in the infrared, visible, and ultraviolet portions of the spectrum.
- the energy may be partially or wholly absorbed by the coating.
- the energy absorbed initiates a photochemical reaction which causes discoloration and/or physical failure of the coating.
- Pigimented surface coatings also suffer from ultraviolet degradation.
- the inclusion of an ultraviolet light stabilizer can increase the useful life of both clear and pigmented coatings. Ultraviolet light stabilizers protect the coatings by absorbing the destructive, high energyultraviolet rays and converting such energy into nondestructive heat energy.
- Antioxidants are useful in preventing the oxidation of polymers, or for inhibiting oxidation already begun by oxygen, air, ozone, or oxidizing agents of many types.
- the rate of thermal oxidation of the polymeric systems used in coating compositions is normally rather slow, i.e., a reaction that occurs over weeks, months, or years under ordinary conditions. However, even though the reaction is often slow, pronounced effects may be readily observable very early in the degradation reaction. Furthermore, more rapid oxidative degradation occurs in the presence of ultraviolet radiant energy.
- Antioxidants can assist ultraviolet light stabilizers in effectively retarding this degradation.
- Thermosetting acrylic enamel finishes are widely used on the exterior of automobiles and trucks.
- Ultraviolet light stabilizers have traditionally been used only in those coating compositions which are utilized as topcoats. The problem with this procedure has been the tendency of the stabilizers to leach out of the topcoat and escape into the atmosphere, leaving the topcoat susceptible to weathering.
- the composition of this invention containing ultraviolet light stabilizer and, optionally, antioxidant, has a preferred utility of being used as a clear coat/color coat finish and particularly as the clear coat of such a finish. It is theorized that the ultraviolet light stabilizer will migrate from the color coat into the clear coat, thereby protecting the clear coat against weathering.
- the preferred finish is one in which both the clear coat and the color coat contain as additives one or more ultraviolet light stabilizers and one or more antioxidants. Some of the additives will be consumed from the clear surface through leaching, evaporation, and photochemical reaction. A high concentration of additives in the color coat will serve as a reservoir and replenish the lost additives through diffusion from the color coat to the clear coat.
- Thermosetting acrylic enamels prepared according to the teachings of United States Patent 3,622,651 - Vasta can be used to provide clear coats of increased flexibility and durability.
- Substrates are coated with first a color coat then a clear coat containg thermosetting acrylic enamels prepared according to the teachings of united States Patent 3,622,651 - Vasta and at least one ultraviolet light stabilizer.
- the invention also provides a liquid coating composition consisting essentially of solvents and (a) 95-50%, byweight, of a polymer having a backbone of polymerized ethylenically unsaturated monomers and having ester groups attached directly to its backbone, said ester groups comprising about 10 to 75 percent of the total weight of the polymer and consisting essentially of Ester Group (A) 0-C-O-P ⁇ -OH and Ester Group (B) selected from the group consisting of
- Ester Group (3) is from about 1:1.5 to 1:2.5;
- R 1 is a saturated hydrocarbon radical containing
- R 2 is selected from the group consisting of alkylene, vinylene, aromatic carbocyclic and heteroradicals
- R 3 is selected from the group consisting of a saturated aliphatic hydrocarbon radical having one to 26 carbon atoms and an ethylenically unsaturated aliphatic hydrocarbon radical having 12 to 18 carbon atoms; (b) 5-50% by weight, based on the weight of the polymer, of a melamine formaldehyde resin which has been at least partially reacted with an aliphatic monohydric alcohol having from 1-4 carbon atoms; and (c) at least one ultraviolet light stabilizer.
- These enamels preferably contain about 1-20% by weight, based on the weight of the filmforming constituents, of ultraviolet light stabilizer.
- they also contain about 0.1-5% by weight of antioxidant, wherein the weight ratio of ultraviolet light stabilizer to antioxidant is about 1:1 to about 50:1. More preferably, about 5-8% by weight of ultraviolet light stabilizer is used, optionally with about 0.1-1% by weight of antioxidant, wherein the weight ratio of ultraviolet light stabilizer to antioxidant is about 10:1.
- the specified percentages of ultraviolet light stabilizer or antioxidant may be obtained by combining two or more ultraviolet light stabilizers or two or more antioxidants as well as by utilizing such additives singularly.
- the acrylic polymer is prepared by conventional polymerization techniques in which the monomer constituents are blended with solvents and a polymerization catalyst and heated to 75-150°C. for about 2-6 hours to form a polymer that has a relative viscosity of about 1.04-1.10 and preferably about 1.06-1.09.
- Typical solvents and diluents which are used to prepare the acrylic polymer and the coating composition of this invention are toluene, xylene, butyl acetate, acetone, methyl isobutyl ketone, methyl ethyl ketone, butyl alcohol, and other aliphatic, cycloaliphatic and aromatic hydrocarbons, esters, ethers, ketones, and alcohols, such as are conventionally used in coating compositions.
- a polymerization catalyst is used to prepare the acrylic polymer.
- Typical catalysts are di-t-butyl peroxide, cumene hydroperoxide, azobisisobutyronitrile and the like.
- Typical ultraviolet light stabilizers which are useful in this, invention are as follows:
- Benzophenones such as hydroxydodecycloxybenzophenone, 2,4-dihydroxybenzophenone, hydroxybenzophenones containing sulfonic acid groups, 2,4- dihydroxy-3',5'-di-t-butylbenzophenone, 2,2',4'- trihydroxybenzophenone esters of dicarboxylic acids, 2-hydroxy-4-acryloxyethoxybenzophenone, aliphatic monoesters of 2,2',4-t ihydroxy-4'-alkoxybenzophenone, 2- hydroxy-4-methoxy-2'-carboxybenzophenone;
- Triazoles such as 2-phenyl-4-(2'-4'-dihydroxybenzoyl) triazoles, substituted benzotriazoles such as hydroxyphenyltriazoles such as 2-(2'-hydroxy-5'- methylphenyl)benzotriazole, 2-(2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-octylphenyl) naphthotriazole; Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine, sulfur-containing derivatives of diallyl-4-hydroxyphenyltriazines, hydroxyphenyl1,3,5-triazines and such triazines containing sulfonic acid groups, aryl-1,3,5-triazines, orthohydroxyaryl-s- triazine;
- Benzoates such as dibenzoate of diphenylolpropane, t-butyl benzoate of diphenylolpropane, nonyl ph ⁇ nyl benzoate, octyl phenyl benzoate, resorcinol dibenzoate.
- ultraviolet light stabilizers that can be used include lower alkyl thiomethylene-containing phenols, substituted benzenes such as 1,3-bis(2' hydroxybenzoyl) benzene, metal derivatives of 3,5,-di-tbutyl-4-hydroxyphenylpro ⁇ ionic acid, asymmetrical oxalic acid diarylamides, alkylhydroxyphenylthioalkanoic acid esters, dialkylhydroxyphenylalkanoic acid esters of di- and tri- pentaerythritol, phenyl- and naphthlenesubstituted oxalic acid diamides, methyl- ⁇ -(3,5-di-1butyl-4-hydroxyphenyl)propionate, ⁇ , ⁇ '-bis(2-hydroxy phenyl) diisopropylbenzene, 3,5'-dibromo-2'-hydroxy- acetophenone, ester derivatives of 4,4-bis(4'-hydroxyphen
- Typical antioxidants are as follows: tetrakisalkylene dialkylhydroxyaryl alkyl ester alkanes such as tetrakismethylene-3-(3',5'-dibutyl-4'-hydroxyphenyl) propionate methane, the reaction product of p-aminodiphenylamine and glycidyl methacrylate, the reaction product of n-hexyl-N'-phenyl-p-phenylene diamine and glycidyl methacrylate, pentaerythritol tetrakis (thioglycolate), trimetlxylolpropane tris (thioglycolauc, trimethylolethane tris(thioglycolate), N-(4-anilinophenyl) acrylamide, N-(4-anilinophenyl)maleamic acid, N-(4-anilinophenyl)maleimide, alkylhydroxy
- Plasticizers can be used in the novel coating composition of this invention in amounts of up to 20% by weight of the film-forming material. Preferably, about 3-8% by weight of a plasticizer is used.
- Functional polymeric plasticizers which react with the constituents in the coating composition can be used, such as epoxidized soya bean oil, oil-free and oil-modified alkyIs and polyesters, such as polyorthophthalate esters, polyalkylene adipate esters or polyarylene adipate esters. Volatile non-functional monomeric plasticizers can also be used.
- the enamel contains pigment in the amount of 0.1-20.0% pigment volume concentration. Preferably, a pigment volume concentration of about 0.3-6.0% is used.
- the enamel may contain one or more transparent pigments , i . e . , pigments having the same or similar refractive index as the binder of the clear coat with a small particle size of about 0.015-50 microns.
- iron pyrophosphate and finely divided silica are particularly useful additives for both the color coat and clear coat.
- iron pyrophosphate and finely divided silica Up to about 10% by weight of iron pyrophosphate and up to about 15% by weight of silica, based on the weight of the film-forming constituents, can be used.
- the addition of iron pyrophosphate and silica will improve the overall durability and performance of the finish.
- iron pyrophosphate creates a synergistic effect with ultraviolet light stabilizers and antioxidants, yielding a period of outdoor weatherability surpassing that which would cumulatively be expected from a combination of the three types of additives .
- Thermosetting acrylic enamels prepared in the manner described and containing about 1-20% by weight, and preferably about 5-8% by weight, based on the weight of the film-forming constituents, of ultraviolet light stabilizer prove particularly useful in clear coat/color coat finishes.
- Such enamels may also contain about 0.1-5% by weight, and preferably about 0.1-1% by weight, of antioxidant. Where an antioxidant is used, the weight ratio of ultraviolet light stabilizer to antioxidant ranges from about 1:1 to about 50:1 and is preferably about 10:1.
- novel coating compositions of this invention can be applied to a variety of substrates, e.g., metal, wood, glass, and plastics such as polypropylene, styrene, and copolymers of styrene, by any of the usual application methods, e.g., spraying, electrostatic spraying, dipping, brushing, flow coating, and the like.
- the coating composition is applied over a suitably primed metal substrate.
- These coatings can be air dried or can be baked to minimize the drying period.
- the resulting coating is about 1-5 mils thick, preferably 1-3 mils thick, and can be rubbed or polished in accordance with conventional techniques, if desired, to improve smoothness or apparent gloss or both.
- the coating preferably is cured at about 125-175oC. for about 15-30 minutes.
- conventional catalyst to the novel composition, the curing temperature can be reduced to 80-110°C.
- Typical catalysts that can be used are butyl acid phosphate, paratoluene sulfonic acid and the like.
- EXAMPLE A steel substrate is coated with a chip-resistant primer and a primer surfacer which is sanded as appropriate to obtain the desired finish. Then the base coat or color coat is sprayed thereon, to a thickness of 15 ⁇ m and allowed to dry a few minutes until it is dry to the touch. Than the clear coat is sprayed on to a dry film thickness of 40-45 ⁇ m, let stand for 10 minutes, then baked 20 minutes at 130oC.
- compositions known in the art can be used for the chip resistant primer and the primer surface. Although the same is true for the color coat, preferably it is made by blending the following ingredients by known techniques and reacting them at reflux:
- Wax 6.84 The color coat is reduced 70-100% with butylacetate to facilitate spraying.
- the clear coat includes an acrylate resin by blending the following ingredients and reacting them by heating I to reflux, about 650°C, then adding II and refluxing for 8 hours.
- the acrylate resin at 60% solids is then blended with melamine and solvents as follows:
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The weatherability and durability of finishes derived from thermosetting acrylic enamels can be significantly increased by adding to the enamel, before it is applied, one or more ultraviolet light stabilizers and, optionally, one or more antioxidants. The flexibility and durability of the clear coat in a color coat/clear coat system can be improved by using an acrylic resin containing phthalic anhydride reacted with a glycidyl ester.
Description
TITLE Thermosetting Acrylic Enamel Stabilized Against Weathering by Addition of Ultraviolet Light Stabilizer BACKGROUND OF THE INVENTION
This invention relates to coating compositions and to coated articles having a color coat overlaid with a clear coat. In particular, it is directed toward thermosetting acrylic enamels containing ultraviolet light stabilizers, which enamels give a high quality weather resistant coating, especially useful for coating the exterior of automobile and truck bodies. The enamels are prepared as disclosed in United States Patent 3,622,651 - Vasta issued November 23, 1971, incorporated herein by reference. The addition of one or more ultraviolet light stabilizers serves to diminish the degradation effects of the ultraviolet radiation in the sunlight. Optionally, the enamels also contain one or more antioxidants.
Sunlight is composed of electromagnetic radiation with energy in the infrared, visible, and ultraviolet portions of the spectrum. When the ultraviolet portion of sunlight falls upon a clear surface coating, the energy may be partially or wholly absorbed by the coating. In many instances, the energy absorbed initiates a photochemical reaction which causes discoloration and/or physical failure of the coating. Pigimented surface coatings also suffer from ultraviolet degradation. The inclusion of an ultraviolet light stabilizer can increase the useful life of both clear and pigmented coatings. Ultraviolet light stabilizers protect the coatings by absorbing the destructive, high energyultraviolet rays and converting such energy into nondestructive heat energy.
Antioxidants are useful in preventing the oxidation of polymers, or for inhibiting oxidation already begun by oxygen, air, ozone, or oxidizing agents of many types. The rate of thermal oxidation of the polymeric systems used in coating compositions is normally rather slow, i.e., a reaction that occurs over weeks, months, or years under ordinary conditions. However, even though the reaction is often slow, pronounced effects may be readily observable very early in the degradation reaction. Furthermore, more rapid oxidative degradation occurs in the presence of ultraviolet radiant energy. Antioxidants can assist ultraviolet light stabilizers in effectively retarding this degradation. Thermosetting acrylic enamel finishes are widely used on the exterior of automobiles and trucks. It has been found that an excellent appearance along with depth of color and metallic glamour can be obtained by applying a clear or transparent coat over the conventional colored or pigmented coat. However, the weatherability and durability of these clear coats have been found to be poor. Checking, cracking, and flaking of the clear coat occur after relatively short periods of exposure to outdoor weathering, giving the automobile or truck an unsightly appearance. Eefinishing of these weathered clear coats is difficult and expensive, since the clear coat must be sanded to remove cracked and flaked clear coat before a refinish coat can be applied. In an effort to retard or substantially reduce checking, cracking and flaking of the clear coat, conventional ultraviolet light stabilizers have been added to the clear coat. Also , the combination of a transparent pigment and an ultraviolet light screener has been added to the clear coat, as suggested by
LaBerge United States Patent 3,407,156 issued October
22, 1968. In each of the above cases, the durability and weatherability of the clear coat was increased for a relatively small length of time but not to the extent required for a practical automotive or truck finish. There exists a felt need for acrylic enamels effectively stabilized against ultraviolet radiation for use in a clear coat/dolor coat system.
Ultraviolet light stabilizers have traditionally been used only in those coating compositions which are utilized as topcoats. The problem with this procedure has been the tendency of the stabilizers to leach out of the topcoat and escape into the atmosphere, leaving the topcoat susceptible to weathering.
The composition of this invention, containing ultraviolet light stabilizer and, optionally, antioxidant, has a preferred utility of being used as a clear coat/color coat finish and particularly as the clear coat of such a finish. It is theorized that the ultraviolet light stabilizer will migrate from the color coat into the clear coat, thereby protecting the clear coat against weathering. The preferred finish is one in which both the clear coat and the color coat contain as additives one or more ultraviolet light stabilizers and one or more antioxidants. Some of the additives will be consumed from the clear surface through leaching, evaporation, and photochemical reaction. A high concentration of additives in the color coat will serve as a reservoir and replenish the lost additives through diffusion from the color coat to the clear coat. Thermosetting acrylic enamels prepared according to the teachings of United States Patent 3,622,651 - Vasta can be used to provide clear coats of increased flexibility and durability.
SUMMARY OF THE INVENTION Substrates are coated with first a color coat then a clear coat containg thermosetting acrylic enamels prepared according to the teachings of united States Patent 3,622,651 - Vasta and at least one ultraviolet light stabilizer. The invention also provides a liquid coating composition consisting essentially of solvents and (a) 95-50%, byweight, of a polymer having a backbone of polymerized ethylenically unsaturated monomers and having ester groups attached directly to its backbone, said ester groups comprising about 10 to 75 percent of the total weight of the polymer and consisting essentially of Ester Group (A) 0-C-O-P^-OH and Ester Group (B) selected from the group consisting of
O 0 0 OH ιι ι it >5 ii i
-C-O-R -0-C-R -C-0-CH--C-H 0
*• I
CH2-0-C-R"
0 0 0 H OH
II 1 II 2 n t »
-C-O-R -O-C-R -C-O-C-CH¬
CH^-O-C-R" or mixtures thereof, wherein the molar ratio of Ester Group (A) to
Ester Group (3) is from about 1:1.5 to 1:2.5;
R1 is a saturated hydrocarbon radical containing
2-10 carbon atoms;
R2 is selected from the group consisting of alkylene, vinylene, aromatic carbocyclic
and heteroradicals, and R3 is selected from the group consisting of a saturated aliphatic hydrocarbon radical having one to 26 carbon atoms and an ethylenically unsaturated aliphatic hydrocarbon radical having 12 to 18 carbon atoms; (b) 5-50% by weight, based on the weight of the polymer, of a melamine formaldehyde resin which has been at least partially reacted with an aliphatic monohydric alcohol having from 1-4 carbon atoms; and (c) at least one ultraviolet light stabilizer.
These enamels preferably contain about 1-20% by weight, based on the weight of the filmforming constituents, of ultraviolet light stabilizer. Optionally, they also contain about 0.1-5% by weight of antioxidant, wherein the weight ratio of ultraviolet light stabilizer to antioxidant is about 1:1 to about 50:1. More preferably, about 5-8% by weight of ultraviolet light stabilizer is used, optionally with about 0.1-1% by weight of antioxidant, wherein the weight ratio of ultraviolet light stabilizer to antioxidant is about 10:1. The specified percentages of ultraviolet light stabilizer or antioxidant may be obtained by combining two or more ultraviolet light stabilizers or two or more antioxidants as well as by utilizing such additives singularly.
DETAILED DESCRIPTION OF THE INVENTION It has been found that clear coats of the invention using acrylics with the glycidyl ester "Cardura E" made by Shell Chemical Co. are more flexible and have surprisingly much lower
viscosity than those with similar acrylics but without the "Cardura E". In one test, at about a 60% solids level the polymer of the invention gave a Gardner Holdt viscosity of J while one without the Cardura E gave a viscosity of Z4.
The acrylic polymer is prepared by conventional polymerization techniques in which the monomer constituents are blended with solvents and a polymerization catalyst and heated to 75-150°C. for about 2-6 hours to form a polymer that has a relative viscosity of about 1.04-1.10 and preferably about 1.06-1.09.
Typical solvents and diluents which are used to prepare the acrylic polymer and the coating composition of this invention are toluene, xylene, butyl acetate, acetone, methyl isobutyl ketone, methyl ethyl ketone, butyl alcohol, and other aliphatic, cycloaliphatic and aromatic hydrocarbons, esters, ethers, ketones, and alcohols, such as are conventionally used in coating compositions.
About 0.1-4% by weight, based on the weight of the monomer, of a polymerization catalyst is used to prepare the acrylic polymer. Typical catalysts are di-t-butyl peroxide, cumene hydroperoxide, azobisisobutyronitrile and the like.
Typical ultraviolet light stabilizers which are useful in this, invention are as follows:
Benzophenones such as hydroxydodecycloxybenzophenone, 2,4-dihydroxybenzophenone, hydroxybenzophenones containing sulfonic acid groups, 2,4- dihydroxy-3',5'-di-t-butylbenzophenone, 2,2',4'- trihydroxybenzophenone esters of dicarboxylic acids, 2-hydroxy-4-acryloxyethoxybenzophenone, aliphatic monoesters of 2,2',4-t ihydroxy-4'-alkoxybenzophenone, 2- hydroxy-4-methoxy-2'-carboxybenzophenone;
Triazoles such as 2-phenyl-4-(2'-4'-dihydroxybenzoyl) triazoles, substituted benzotriazoles such as hydroxyphenyltriazoles such as 2-(2'-hydroxy-5'- methylphenyl)benzotriazole, 2-(2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-octylphenyl) naphthotriazole; Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine, sulfur-containing derivatives of diallyl-4-hydroxyphenyltriazines, hydroxyphenyl1,3,5-triazines and such triazines containing sulfonic acid groups, aryl-1,3,5-triazines, orthohydroxyaryl-s- triazine;
Benzoates such as dibenzoate of diphenylolpropane, t-butyl benzoate of diphenylolpropane, nonyl phεnyl benzoate, octyl phenyl benzoate, resorcinol dibenzoate. Other ultraviolet light stabilizers that can be used include lower alkyl thiomethylene-containing phenols, substituted benzenes such as 1,3-bis(2' hydroxybenzoyl) benzene, metal derivatives of 3,5,-di-tbutyl-4-hydroxyphenylproρionic acid, asymmetrical oxalic acid diarylamides, alkylhydroxyphenylthioalkanoic acid esters, dialkylhydroxyphenylalkanoic acid esters of di- and tri- pentaerythritol, phenyl- and naphthlenesubstituted oxalic acid diamides, methyl-β-(3,5-di-1butyl-4-hydroxyphenyl)propionate, α , α '-bis(2-hydroxy
phenyl) diisopropylbenzene, 3,5'-dibromo-2'-hydroxy- acetophenone, ester derivatives of 4,4-bis(4'-hydroxyphenyl)pentanoic acid wherein there is at least one unsubstituted position ortho to the aromatic hydroxyl groups, organophosphorus sulfides such as bis (diphenylphosphinothioyl)monosulfide and bis (diphenylphosphinothioyl) disulfide, 4-benzoyl-6-(dialkylhydroxybenzyl) resorcinol, bis(3-hydroxy-4-benzoylphenoxy)diphenylsilane, bis(3-hydroxy-4-benzoylphenoxy)dialkylsilane, 1,8-naphthalimides, α-cyano-β,β-diphenylaerylic acid derivatives, bis (2-benzoxazolyl)alkanes, bis (2-napthoxazolyl)alkanes, methylene malonitriles containing aryl and heterocyclic substitutes, alkylenebis (dithio) carbamate, 4-benzoyl-3-hydroxyphenoxyethyl aerylate, 4-benzoyl-3-hydroxyphenoxyethyl methacrylate, aryl- or alkyl-substituted acrylonitriles, 3-methyl-5-isopropylphenyl-6-hydroxycoumarone.
Particularly useful ultraviolet light stabilizers that can be used are hindered amines of bipiperidyl derivatives such as those disclosed in Murayama et al., U.S. Patent 4,061,616, issued December 6, 1977, column 2, line 65, through column 4, line 2, and nickel compounds such as [1-phenyl-3-methyl-4-decanoylpyrazolate
(5)]-Ni, bis[phenyldithiocarbamato]-Ni(II), and others listed in the above patent, column 8, line 44 through line 55. Among the available ultraviolet light stabilizers, including screeners and absorbers, it is preferred to use "Tinuvin" 900 absorber and "Tinuvin"
292 hindered amine light stabilizer (free radical scavenger) both produced by Ciba Geigy.
Typical antioxidants are as follows: tetrakisalkylene dialkylhydroxyaryl alkyl ester alkanes such as tetrakismethylene-3-(3',5'-dibutyl-4'-hydroxyphenyl) propionate methane, the reaction product of p-aminodiphenylamine and glycidyl methacrylate, the reaction
product of n-hexyl-N'-phenyl-p-phenylene diamine and glycidyl methacrylate, pentaerythritol tetrakis (thioglycolate), trimetlxylolpropane tris (thioglycolauc, trimethylolethane tris(thioglycolate), N-(4-anilinophenyl) acrylamide, N-(4-anilinophenyl)maleamic acid, N-(4-anilinophenyl)maleimide, alkylhydroxyphenyl groups bonded through carboalkoxy linkages to the nitrogen atom of a heterocyclic nucleus containing an imidocarbonyl group or an imidodithiocarbonyl group, 3,5-di-t-butyl4-hydroxycinnamonitrile, ethyl-3,5-di-t-hexyl-4-hydroxycinnamate, substituted benzyl esters of β-substituted hydroxyphenylpropionic acids, bis (hydroxyphenylalkylene) alkyl isocyanurate compounds, tetrakishydroxybenzylphosphonium halides alone or in combination with a dialkylthiodialkanoate, thiodimethylidyne tetrakisphenols alone or in combination with a dialkyl thiodialkanoate or phosphite or phosphonate, dihydrocarbylhydroxyphenylaryl or -alkyl phosphonites or phosphonates or phosphates or phosphites or phosphinates or phosphinites or phosphorothionates or phosphinothionates, diphenylbis (3,5-di-tbutyl-4-hydroxyphenoxy) silane, hydrocarbylhydroxyphenyldihydrocarbyldithiocarbamates such as 3,5-di-t-butyl-4-hydroxyphenyldimethyldithiocarbamate and aminobenzylthioether.
Plasticizers can be used in the novel coating composition of this invention in amounts of up to 20% by weight of the film-forming material. Preferably, about 3-8% by weight of a plasticizer is used. Functional polymeric plasticizers which react with the constituents in the coating composition can be used, such as epoxidized soya bean oil, oil-free and oil-modified alkyIs and polyesters, such as polyorthophthalate esters, polyalkylene adipate esters or polyarylene adipate esters. Volatile non-functional monomeric plasticizers can also be used.
In the color coat, the enamel contains pigment in the amount of 0.1-20.0% pigment volume concentration. Preferably, a pigment volume concentration of about 0.3-6.0% is used. Examples of the great variety of pigments which are used in the novel coating composition of this invention are metallic oxides (preferably titanium dioxide, zinc oxide, and the like), metal hydroxides, metal flakes, metal powders, chromates (such as lead chromate), sulfides, sulfates, carbonates, carbon black, silica, talc, china clay, iron blues, organic reds, maroons, organic dyes, lakes, and the like. If the enamel is to be employed as a clear coat, it may contain one or more transparent pigments , i . e . , pigments having the same or similar refractive index as the binder of the clear coat with a small particle size of about 0.015-50 microns.
Two particularly useful additives for both the color coat and clear coat are iron pyrophosphate and finely divided silica. Up to about 10% by weight of iron pyrophosphate and up to about 15% by weight of silica, based on the weight of the film-forming constituents, can be used. The addition of iron pyrophosphate and silica will improve the overall durability and performance of the finish. Although applicant does not wish to be bound by the following theory, it is believed that iron pyrophosphate creates a synergistic effect with ultraviolet light stabilizers and antioxidants, yielding a period of outdoor weatherability surpassing that which would cumulatively be expected from a combination of the three types of additives .
''
Thermosetting acrylic enamels prepared in the manner described and containing about 1-20% by weight, and preferably about 5-8% by weight, based on the weight of the film-forming constituents, of ultraviolet light stabilizer prove particularly useful in clear coat/color coat finishes. Such enamels may also contain about 0.1-5% by weight, and preferably about 0.1-1% by weight, of antioxidant. Where an antioxidant is used, the weight ratio of ultraviolet light stabilizer to antioxidant ranges from about 1:1 to about 50:1 and is preferably about 10:1.
The novel coating compositions of this invention can be applied to a variety of substrates, e.g., metal, wood, glass, and plastics such as polypropylene, styrene, and copolymers of styrene, by any of the usual application methods, e.g., spraying, electrostatic spraying, dipping, brushing, flow coating, and the like. Preferably, the coating composition is applied over a suitably primed metal substrate. These coatings can be air dried or can be baked to minimize the drying period. The resulting coating is about 1-5 mils thick, preferably 1-3 mils thick, and can be rubbed or polished in accordance with conventional techniques, if desired, to improve smoothness or apparent gloss or both.
After the novel coating composition is applied, the coating preferably is cured at about 125-175ºC. for about 15-30 minutes. By the addition of conventional catalyst to the novel composition, the curing temperature can be reduced to 80-110°C. Typical catalysts that can be used are butyl acid phosphate, paratoluene sulfonic acid and the like.
EXAMPLE A steel substrate is coated with a chip-resistant primer and a primer surfacer which is sanded as appropriate to obtain the desired finish. Then the base coat or color coat is sprayed thereon, to a thickness of 15 μm and allowed to dry a few minutes until it is dry to the touch. Than the clear coat is sprayed on to a dry film thickness of 40-45 μm, let stand for 10 minutes, then baked 20 minutes at 130ºC.
Compositions known in the art can be used for the chip resistant primer and the primer surface. Although the same is true for the color coat, preferably it is made by blending the following ingredients by known techniques and reacting them at reflux:
Weight Parts Dynopol M700 polyester 13.80
Maprenal M650 melamine 4.45 Cellulose acetate butyrate solution (CAB) 29.32
Isobutylacetate 5.26
Uresin B polymeric platicizer
(Hoechst) 2.00 Tinuvin 900 UV stabilizer
(Ciba Geigy) 0.2
Tinuvin 292 UV stabilizer 0.2
EVA Wax 6.53
Aluminum flake millbase 16.86 Butyl cellosolve acetate 4.00
(and desired colorants) This gives a solids content for the color coat of 25% solids of:
Polyester 46.9
Melamine 11.33
CAB 33.83
Wax 6.84 The color coat is reduced 70-100% with butylacetate to facilitate spraying.
The clear coat includes an acrylate resin by blending the following ingredients and reacting them by heating I to reflux, about 650°C, then adding II and refluxing for 8 hours.
Weight Parts I Solvesso 100 (Exxor. Chemicals) 35.00
Phthalic anhydride 3.60
II Cardura E (Shell Chemical) 6.00 Styrene 6.00
Methyl methacrylate 7.80.
Butyl methacrylate 12.00
Hydroxy ethyl acrylate 11.10
Ethyl hexyl acrylate 12.00 Phthalic anhydride 1.50
Acrylic acid 1.50
Solvesso 100 5.00
Tertiary butyl perbenzoate 2.77 to give a solids content of 60.19% and a GardnerHoldt viscosity of J.
The acrylate resin at 60% solids is then blended with melamine and solvents as follows:
Weight Parts Acrylate resin 43.43 Luwipal 015 melamine resin (BASF) 23.04 Tinuvin 900 UV stabilizer 0.2
Tinuvin 292 UV stabilizer 0.2
Solvents:
Butyl acetate 4.73
Xylene 4.55
Butanol 1.20 Solvesso 100 4.35
Butyl cellosolve acetate 2.70 Cellulose acetate 4. 00 and these diluted with xylene 10.00
Claims
CLAIMS 1. A liquid coating composition consisting essentially of solvents and
(a) 95-50%, by weight, of a polymer having a backbone of polymerized ethylenically unsaturated monomers and having ester groups attached directly to its backbone, said ester groups comprising about 10 to 75 percent of the total weight of the polymer and consisting essentially of Este Group (A)
Ester Group (B) selected from the group consisting of
Ester Group (3) is from about 1:1.5 to 1:2.5; and wherein
R1 is a saturated hydrocarbon radical containing
2-10 carbon atoms;
R1 is selected from the group consisting of alkylene, vinylene, aromatic, carbocyclic and heteroradicais, and
R3 is selected from the group consisting of a saturated aliphatic hydrocarbon radical having one to 26 carbon atoms and an ethylenically unsaturated aliphatic hydrocarbon radical having 12 to 18 carbon atoms;
OMPI (b) 5-50% by weight, based on the weight of the polymer, of a melamine formaldehyde resin which has been at least partially reacted with an aliphatic monohydric alcohol having from 1-4 carbon atoms; and
(c) at least one ultraviolet light stabilizer.
2. The composition of claim 1 wherein the backbone consists essentially of styrene and an acrylic ester selected from the group consisting of an alkyl methacrylate, an alkyl acrylate and mixture thereof in which the alkyl group contains
1-12 carbon atoms; in which
R1 is a saturated hydrocarbons group having 2-4 carbon atoms,
R2 is an aromatic radical, and
R3 is a tertiary hydrocarbon group having eight through ten carbon atoms.
3. A composition according to claim 1 which contains about 1-20% by weight, based on the weight of the film-forming constituents, of ultraviolet light stabilizer.
4. A composition according to claim 3 wherein the ultraviolet light stabilizer is a benzopnenone or a substituted benzotriazole.
5. A composition according to claim 3 which contains about 0.1-5% by weight, based on the weight of the film-forming constituents, of antioxidant, wherein the weight ratio of ultraviolet light stabilizer to antioxidant is about 1:1 to about 50:1.
6. A composition according to claim 3 which contains about 5-8% by weight, based on the weight of the film-forming constituents, of ultraviolet light stabilizer.
-AJ
7. A composition according to claim 6 wherein the ultraviolet light stabilizer is 2-(2'-hydroxyphenyl)- benzotriazole.
8. A composition according to claim 5 which contains about 0.1-1% by weight, based on the weight of the film-forming constituents, of antioxidant, wherein the weight ratio of ultraviolet light stabilizer to antioxidant is about 10:1.
9. A composition according to claim 8 which contains up to about 10% by weight, based on the weight of the film-forming constituents, of iron pyrophosphate and up to about 15% by weight of finely divided silica.
10. A composition according to claim 7 wherein the antioxidant is tetrakismethylene-3-(3',5'-dibutyl4'-hydroxyphenyl) propionate methane.
11. A composition according to claim 1 also containing plasticizer.
12. A composition according to claim 1 whichcontains pigment in the amount of 0.1-20.0% pigment volume concentration.
13. A composition according to claim 1 where- in the acrylic polymer consists essentially of 10-18% by weight styrene, 25-30% by weight methyl methacrylate,
38-42% by weight butyl acrylate, 10-16% by weight hydroxyethyl acrylate, and 1-3% by weight acrylic acid.
14. A composition according to claim 13 which contains about 5-8% by weight, based on the weight of the film-forming constituents, of ultraviolet light stabilizer and about 0.1-1% by weight of antioxidant.
15. A composition according to claim 14 which contains up to about 10% by weight, based on the weight of the film-forming constituents, of iron pyrophosphate and up to about 15% by weight of finely divided silica.
16. A composition according to claim 14 where in the ultraviolet light stabilizer is 2-(2'-hydroxyphenyl)benzotriazole.
17. A composition according to claim 14 wherein the antioxidant is tetrakismethylene-3-(3',5'-dibutyl-4'-hydroxyphenyl)propionate methane.
18. A composition according to claim 17 which contains about 5-8% by weight, based on the weight of the film-forming constituents, of ultraviolet light stabilizer and about 0.1-1% by weight of antioxidant.
19. A composition according to claim 18 which contains up to about 10% by weight, based on the weight of the film-forming constituents, of iron pyrophosphate and up to about 15% by weight of finely divided silica.
20. A composition according to claim 18 wherein the ultraviolet light stabilizer is 2-(2'-nydroxyphenyl)benzotriazole.
21. A composition according to claim 18 wherein the antioxidant is tetrakismethylene-3-(3',5'- dibutyl-4'-hydroxyphenyl)propionate methane.
22. A coated article consisting essentially of a substrate, a first coating on said substrate, said first coating consisting essentially of the film-forming constituents containing pigment in the amount of 0.1-20.0% pigment volume concentration, and a transparent second coating over said first coating, said second coating consisting essentially of the coating composition of claim 1.
23. A coated article according to claim 22 wherein the first coating is about 1.0 mil thick and the second coating is about 1.0-1.3 mils thick.
24. A coated article according to claim 23 wherein both the first and second coating contain ultraviolet light stabilizer.
25. A coated article according to claim 22 wherein both the first and second coating consist essentially of the composition of claim 7.
26. A process for producing an acrylic enamel finish having excellent aesthetic properties and outstanding weatherability and durability, which comprises:
A. depositing on a substrate a first coating consisting essentially of:
(1) the film-forming constituents
(2) pigment in the amount of 0.1-20.0% pigment volume concentration, and
(3) volatile organic solvent for said filmforming constituents;
B. allowing said substrate to air dry for about 10 minutes;
C. depositing over said first coating a transparent second coating of the coating composition of claim 1; and
D. heating the resultant multilayer coating at a temperature in the range of from about 125ºC to about 175ºC. for about 15 minutes to 30 minutes.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1980/001756 WO1982002397A1 (en) | 1980-12-31 | 1980-12-31 | Thermosetting acrylic enamel stabilized against weathering by addition of ultraviolet light stabilizer |
EP19810901404 EP0067989A1 (en) | 1980-12-31 | 1980-12-31 | Thermosetting acrylic enamel stabilized against weathering by addition of ultraviolet light stabilizer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
WOUS80/01756801231 | 1980-12-31 | ||
PCT/US1980/001756 WO1982002397A1 (en) | 1980-12-31 | 1980-12-31 | Thermosetting acrylic enamel stabilized against weathering by addition of ultraviolet light stabilizer |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1982002397A1 true WO1982002397A1 (en) | 1982-07-22 |
Family
ID=22154716
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1980/001756 WO1982002397A1 (en) | 1980-12-31 | 1980-12-31 | Thermosetting acrylic enamel stabilized against weathering by addition of ultraviolet light stabilizer |
Country Status (2)
Country | Link |
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EP (1) | EP0067989A1 (en) |
WO (1) | WO1982002397A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4576977A (en) * | 1983-08-09 | 1986-03-18 | Asahi Glass Company Ltd. | Curable resin composition |
US4775707A (en) * | 1984-11-01 | 1988-10-04 | Ciba-Geigy Corporation | Coatings materials stabilized against the action of light |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3407156A (en) * | 1964-06-03 | 1968-10-22 | Du Pont | Weatherable transparent coating composition for wood substrates |
US3622651A (en) * | 1969-12-01 | 1971-11-23 | Du Pont | Novel polymer having pendent ester groups for low temperature bake coatings |
US3823205A (en) * | 1965-11-22 | 1974-07-09 | Du Pont | Lacquers based on acrylic polymer blends |
US4104432A (en) * | 1975-06-30 | 1978-08-01 | Toyoda Gosei Kabushiki-Kaisha (Toyoda Synthetics Co., Ltd.) | Plastic articles having on the surface thereof a protected metal film |
US4208465A (en) * | 1978-05-03 | 1980-06-17 | E. I. Du Pont De Nemours And Company | Clear coat/color coat finish containing an antioxidant and an ultraviolet light stabilizer |
-
1980
- 1980-12-31 WO PCT/US1980/001756 patent/WO1982002397A1/en unknown
- 1980-12-31 EP EP19810901404 patent/EP0067989A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3407156A (en) * | 1964-06-03 | 1968-10-22 | Du Pont | Weatherable transparent coating composition for wood substrates |
US3823205A (en) * | 1965-11-22 | 1974-07-09 | Du Pont | Lacquers based on acrylic polymer blends |
US3622651A (en) * | 1969-12-01 | 1971-11-23 | Du Pont | Novel polymer having pendent ester groups for low temperature bake coatings |
US4104432A (en) * | 1975-06-30 | 1978-08-01 | Toyoda Gosei Kabushiki-Kaisha (Toyoda Synthetics Co., Ltd.) | Plastic articles having on the surface thereof a protected metal film |
US4208465A (en) * | 1978-05-03 | 1980-06-17 | E. I. Du Pont De Nemours And Company | Clear coat/color coat finish containing an antioxidant and an ultraviolet light stabilizer |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4576977A (en) * | 1983-08-09 | 1986-03-18 | Asahi Glass Company Ltd. | Curable resin composition |
US4775707A (en) * | 1984-11-01 | 1988-10-04 | Ciba-Geigy Corporation | Coatings materials stabilized against the action of light |
Also Published As
Publication number | Publication date |
---|---|
EP0067989A1 (en) | 1983-01-05 |
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