MXPA00011525A - Coating containing hydroxy containing acrylosilane polymer to improve mar and acid etch resistance - Google Patents
Coating containing hydroxy containing acrylosilane polymer to improve mar and acid etch resistanceInfo
- Publication number
- MXPA00011525A MXPA00011525A MXPA/A/2000/011525A MXPA00011525A MXPA00011525A MX PA00011525 A MXPA00011525 A MX PA00011525A MX PA00011525 A MXPA00011525 A MX PA00011525A MX PA00011525 A MXPA00011525 A MX PA00011525A
- Authority
- MX
- Mexico
- Prior art keywords
- weight
- alkyl
- group
- binder
- coating composition
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 17
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 42
- 239000008199 coating composition Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 229920001228 Polyisocyanate Polymers 0.000 claims abstract description 20
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 20
- 125000004432 carbon atoms Chemical group C* 0.000 claims abstract description 19
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 17
- 150000004756 silanes Chemical class 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000969 carrier Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 229910000077 silane Inorganic materials 0.000 claims description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-Dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N Isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N Hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- FWEOQOXTVHGIFQ-UHFFFAOYSA-N 8-Anilinonaphthalene-1-sulfonic acid Chemical compound C=12C(S(=O)(=O)O)=CC=CC2=CC=CC=1NC1=CC=CC=C1 FWEOQOXTVHGIFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 11
- 239000003849 aromatic solvent Substances 0.000 description 10
- 238000009500 colour coating Methods 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000004611 light stabiliser Substances 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 239000002987 primer (paints) Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N 2-cyanopropene-1 Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- PFVOFZIGWQSALT-UHFFFAOYSA-M 5-ethoxypentanoate Chemical compound CCOCCCCC([O-])=O PFVOFZIGWQSALT-UHFFFAOYSA-M 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N Aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- MZNDIOURMFYZLE-UHFFFAOYSA-N CCCCO.CCCCO Chemical compound CCCCO.CCCCO MZNDIOURMFYZLE-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N Cyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920001225 Polyester resin Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N Titanium isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007590 electrostatic spraying Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002650 habitual Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 2
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229940113165 trimethylolpropane Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- APAUNQLFVGBQQW-UHFFFAOYSA-N (1,2,2-trimethylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1(C)C APAUNQLFVGBQQW-UHFFFAOYSA-N 0.000 description 1
- CLHPBURJMZXHFZ-UHFFFAOYSA-N (1,2,2-trimethylcyclohexyl) prop-2-enoate Chemical compound CC1(C)CCCCC1(C)OC(=O)C=C CLHPBURJMZXHFZ-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 1
- WVWYODXLKONLEM-UHFFFAOYSA-N 1,2-diisocyanatobutane Chemical compound O=C=NC(CC)CN=C=O WVWYODXLKONLEM-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- UFXYYTWJETZVHG-UHFFFAOYSA-N 1,3-diisocyanatobutane Chemical compound O=C=NC(C)CCN=C=O UFXYYTWJETZVHG-UHFFFAOYSA-N 0.000 description 1
- LTIKIBFTASQKMM-UHFFFAOYSA-N 1-[bis(4-isocyanatophenyl)methyl]-4-isocyanatobenzene Chemical compound C1=CC(N=C=O)=CC=C1C(C=1C=CC(=CC=1)N=C=O)C1=CC=C(N=C=O)C=C1 LTIKIBFTASQKMM-UHFFFAOYSA-N 0.000 description 1
- KDLIYVDINLSKGR-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanatophenoxy)benzene Chemical compound C1=CC(N=C=O)=CC=C1OC1=CC=C(N=C=O)C=C1 KDLIYVDINLSKGR-UHFFFAOYSA-N 0.000 description 1
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-Dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2,6-dimethylheptan-4-one Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N 2-Heptanone Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXBOKASTQKMONI-UHFFFAOYSA-N 2-methyl-5-(2-methylphenoxy)benzenesulfonic acid Chemical compound CC1=CC=CC=C1OC1=CC=C(C)C(S(O)(=O)=O)=C1 FXBOKASTQKMONI-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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N Azobisisobutyronitrile Chemical compound N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Benzyl butyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N COCCO[SiH3] Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K Iron(III) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229940119545 Isobornyl methacrylate Drugs 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N Methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N Sec-Butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 210000001138 Tears Anatomy 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N Toluene diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H Zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1R,3R,4R)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 1
- RGPOEMJHEZPRID-UHFFFAOYSA-N [N-]=C=O.[N-]=C=O Chemical compound [N-]=C=O.[N-]=C=O RGPOEMJHEZPRID-UHFFFAOYSA-N 0.000 description 1
- AJMJSPWGPLXRSJ-UHFFFAOYSA-N [SiH3]OC(=O)CC=C Chemical class [SiH3]OC(=O)CC=C AJMJSPWGPLXRSJ-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 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
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M caproate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000001627 detrimental Effects 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- QSHZUFRQHSINTB-UHFFFAOYSA-L dibutyltin(2+);dibromide Chemical compound CCCC[Sn](Br)(Br)CCCC QSHZUFRQHSINTB-UHFFFAOYSA-L 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N dodecyl prop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- DNPFOADIPJWGQH-UHFFFAOYSA-N octan-3-yl prop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C=C DNPFOADIPJWGQH-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- CNRZQDQNVUKEJG-UHFFFAOYSA-N oxo-bis(oxoalumanyloxy)titanium Chemical compound O=[Al]O[Ti](=O)O[Al]=O CNRZQDQNVUKEJG-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 238000000518 rheometry Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 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
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
Abstract
A coating composition particularly useful as a clear coating used over a pigmented base coat that has improved resistance to marring and to acid etching when exposed to natural weathering conditions containing 40-70%by weight of film forming binder and 30-60%by weight of a volatile liquid carrier for the binder;wherein the binder contains (a) 50-90%by weight, based on the weight of the binder, of an acrylosilane polymer of polymerized monomers from the following group:an alkyl methacrylate, an alkyl acrylate, each having 1-12 carbon atoms in the alkyl group, cycloaliphatic alkyl methacrylate, cycloaliphatic alkyl acrylate, styrene or any mixture of these monomers;hydroxy containing monomers from the following group:hydroxy alkyl methacrylate, hydroxy alkyl acrylate each having 1-4 carbon atoms in the alkyl group, or any mixtures of these monomers;and a mono-ethylenically unsaturated silane monomer;and the polymer having a weight average molecular weight of 1,000-15,000 determined by gel permeation chromatography. (b) 10-50%by weight, based on the weight of the binder of an organic polyisocyanate;and wherein the ratio of isocyanate groups of the organic polyisocyanate to hydroxy groups of the acrylosilane polymer is about 0.4:1 to 1.3:1.
Description
COATING CONTAINING HYDROXY, WHICH CONTAINS A POLYMER OF ACRYLOSILA OR TO IMPROVE THE RESISTANCE TO USUAL WEAR AND RESISTANCE TO THE ATTACK OF THE ACIDS
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is directed to coating compositions, in particular to a clear coating composition used as a clear coating on a color coating or base coat of a motor vehicle having improved resistance to the usual wear and tear of acids.
2. Description of the Previous Technique
Acid rain and other air pollutants have caused problems of water staining and the acid attack of the finishes used on cars and trucks. The selection finish that is currently used on the exterior of automobiles and trucks is a clear coating / color coating finish in which a clear Ref.124768 coating is applied over a color coating or clear coating which is pigmented to provide protection to the color coating and improve the appearance of the overall finish such as brightness and clarity or sharpness of the image. Another problem is the usual wear resistance of the clear coating. Finishing damage can be caused by mechanical washing procedures used in a typical commercial car wash or by other mechanical damage to the finish. A number of clear coatings containing acrylosilane polymers have been used as clear coatings as shown in Hazan et al., U.S. Pat. No. 5,066,698 issued November 19, 1991, Nordstrom et al., U.S. Pat. No. 5,532,027 issued July 2, 1996 and Lewin et al., U.S. Pat. No. 5,684,084 issued November 4, 1997. However, none of the compositions shown in the above patents have the necessary combination of properties that include the costs that are desirable for an automotive OEM clear coating composition (original equipment manufacture). . There is a need for clear OEM coating compositions that will form finishes that are resistant to acid attack and water stains caused by acid rain and that are resistant to the usual damage.
Brief Description of the Invention
A coating composition containing 40-70% by weight of a film-forming binder ^ 30-60% by weight of a volatile liquid carrier for the binder; wherein the binder contains a. 50-90% by weight, based on the weight of the binder, of an acrylosilane polymer of the polymerized monomers of the following group; an alkyl methacrylate, an alkyl acrylate, each having 1-12 carbon atoms in the alkyl group, the cycloaliphatic alkyl methacrylate, the cycloaliphatic alkyl acrylate, the styrene or any mixture of these monomers; the hydroxy-containing monomers of the following group: hydroxyalkyl methacrylate, hydroxyalkyl acrylate each having 1-4 carbon atoms in the alkyl group, or any mixtures of these monomers; and a monoethylenically unsaturated silane monomer, and the polymer having a weight average molecular weight of 1,000-15,000 determined by gel permeation chromatography;
b. 10-50% by weight, based on the weight of the binder, of an organic polyisocyanate; and wherein the ratio or proportion of the isocyanate groups of the organic polyisocyanate to the hydroxy groups of the acrylosilane polymer is from 0.4: 1 to 1.3: 1.
Detailed description of the invention
The coating composition of this invention is generally used as a clear coating composition which is applied over a base coat which is a pigmented coating composition. The clear coating / color coating finishes are conventionally used on the exterior of automobiles and trucks. The coating composition of this invention forms a clear finish, has improved resistance against usual wear, improved resistance against attack by acids, and improved resistance against the formation of water spots. For a typical car or truck body, metal foil or plastic is used or a composite material can be used. If the steel is used, it is first treated with an oxidation-proof, inorganic compound, such as zinc or iron phosphate and then a primer coating is applied by electrodeposition. Typically, these electrodeposition primers are epoxy modified resins crosslinked with a polyisocyanate and are applied by a;? cathodic electrodeposition process. Optionally, a primer can be applied onto the primer electrodeposited usually by spraying to provide a better appearance and / or improved adhesion of the base coat to the primer. Then a pigmented basecoat or a color coating is applied. A typical color coating comprises a pigment which may include metallic flake pigments such as aluminum flake or flake-flake pigments, a film-forming binder the which may be a polyurethane, an acrylourethane, an acrylic polymer or a silane polymer, and contains a crosslinking agent such as an aminoplast, typically, an alkylated formaldehyde melamine crosslinking agent or a polyisocyanate. The base coat may be carried by a solvent or by water and may be in the form of a dispersion or a solution. A clear coating or topcoat is then applied to the color coating or basecoat before the basecoat is fully cured or hardened and the basecoat and clearcoat are then fully cured in the usual manner by baking at 100-150 °. C for 15-45 minutes. The base coat and clear coat preferably have a dry coating thickness of 2.5-75 microns and 25-100 microns, respectively. The clear coating composition of this invention contains 40-70% by weight of a film-forming binder and 30-60% of a volatile organic liquid carrier which is usually a solvent for the binder and volatilizes at 35 ° C and above this value. The clear coating can also be in a dispersion form. The film-forming binder of the clear coating composition contains 50-90% by weight of an acrylosilane polymer having reactive hydroxyl and silane groups and 10-50% by weight of an organic polyisocyanate crosslinking agent. The acrylosilane polymer comprises polymerized n-silane containing monomers of alkyl methacrylates, alkyl acrylate, each having 1-12 carbon atoms in the alkyl groups, cycloaliphatic alkyl methacrylate, cycloaliphatic alkyl acrylate, styrene or mixtures of any of the previous monomers. The polymer contains polymerized hydroxy which contains monomers such as hydroxy alkyl methacrylate, hydroxy alkyl acrylate each having 1-4 carbon atoms in the alkyl group or a mixture of these monomers and contains polymerized ethylenically monounsaturated silane monomers . The acrylosilane polymer has a weight average molecular weight of 1,000-15,000. All molecular weights described herein are determined by gel permeation chromatography (GPC). Preferred acrylosilane polymers contain 35-75% by weight of the polymerized alkyl or styrene alkyl acrylate or styrene monomers or mixtures thereof, 20-40% by weight of polymerized hydroxy alkyl acrylate or methacrylate monomers or mixtures thereof and 5-25% by weight of the ethylenically monounsaturated silane monomer. A preferred acrylosilane polymer is the product of the polymerization of 35-75% by weight of the non-silane monomers of an alkyl methacrylate, an alkyl acrylate having each of 1-8 carbon atoms in the alkyl group, styrene or mixtures of styrene of these monomers; 20-40% by weight of the hydroxy alkyl methacrylate having 1-4 carbon atoms in the alkyl group; and 5-25% by weight of a monomer containing silane, ethylenically monounsaturated.
Typically the useful ethylenically unsaturated silane-containing monomers are alkyl acrylates, alkyl methacrylates wherein the alkyl groups have 1-12 carbon atoms such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate butyl, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, and lauryl acrylate. Alkyl cycloaliphatic alkyl acrylates and methacrylates, for example, such as cyclohexyl methacrylate, cyclohexyl acrylate, trimethylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, isobutyl methacrylate, t-butyl cyclohexyl acrylate, methacrylate t -butyl cyclohexyl, isobornyl methacrylate, isobornyl acrylate and the like. The aryl acrylate and the aryl methacrylates can also be used, for example, such as benzyl acrylate and benzyl methacrylate. Mixtures of two or more of the monomers mentioned above are useful in the formulation of the polymer with the desired characteristics.
In addition to the alkyl acrylates or methacrylates, other polymerizable monomers which do not contain silane, in amounts of up to 50% by weight of the polymer, can be used in a silane polymer for the purpose of achieving the desired physical properties such as hardness, appearance, and resistance to habitual wear. Examples of such other monomers are styrene, methyl styrene, acrylamide, acrylonitrile, and methacrylonitrile. Styrene can be used in the range of 0-50% by weight. The hydroxy-functional monomers can be incorporated into the silane polymer to produce a polymer having a hydroxy number of 20 to 200. Typically, the useful hydroxy-functional monomers are hydroxy alkyl acrylates and methacrylates such as methacrylate. of hydroxy ethyl, hydroxy propyl methacrylate, hydroxy butyl methacrylates, hydroxy isobutyl methacrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate, and hydroxy butyl acrylate. Typical commercial hydroxy-functional monomers may contain up to 1% acrylic or methacrylic acid. During polymerization, the acid may cause side reactions involving the silane monomers that extend or expand the molecular weight distribution of the acrylic polymer which will have detrimental effects on the solids content of the paint, the stability of the paint and still cause the gelation during the preparation of the copolymer. Preferably, the acid content of these hydroxy monomers should be limited to about 0.1%. A suitable silane-containing monomer useful in the formation of an acrylosilane polymer is a silane having the following structural formula:
wherein R is either CH3, CH3CH2, CH30, or CH3CH20; R1 and R2 are CH3 or CH3CH2; R3 is either H, CH3, or CH3CH2; and n is 0 or a positive integer from 1 to 10. Preferably, R is CH30 or CH3CH20 and n is 1. Typical examples of such silanes are acrylate alkoxy silanes, such as gamma acryloxypropyltrimethoxy silane and methacrylate alkoxy silanes, such as gamma-methacryloxypropyltrimethoxy silane or gamma trimethoxy silyl propyl methacrylate, and gamma-methacryloxypropyltris (2-methoxyethoxy) silane. Other suitable silane monomers have the following structural formula:
wherein R, R1 and R2 are as described above and n is a positive integer from 1 to 10. Examples of such silanes are vinylalkoxy silanes, such as vinyltrimethoxy silane, vinyltriethoxy silane, and vinyltris (2-methoxyethoxy) silane . Other monomers containing silane, useful, are acyloxysilanes, including acrylate, silanes, methacrylate, silanes, and vinylacetoxy silanes, such as vinylmethyl diacetoxy silane, acrylatepropyltriacetoxy silane, and methacrylatepropylthiacetoxy silane. Mixtures of the silane-containing monomers mentioned above are also suitable. Consistent with the aforementioned components of the acrylosilane polymer, the following are an example of an acrylosilane polymer useful in the coating composition of this invention which contains the following constituents: 15-30% by weight styrene, 30-50% by weight weight of isobutyl methacrylate, 15-30% by weight of hydroxyethyl methacrylate, and 15-30% by weight of methacryloxypropyl trimethoxy silane.
Typical polymerization catalysts used to form the acrylosilane polymer are the azo-type catalysts such as azo-bis-isobutyronitrile, acetate catalysts such as t-butyl peracetate, di-t-butyl peroxide, t-butyl perbenzoate. -butyl, and t-butyl peroctoate. Typical solvents that can be used to polymerize the monomers and to form the coating composition are ketones such as methyl amyl ketone, isobutyl ketone, methyl ethyl ketone, aromatic hydrocarbon solvents such as toluene, xylene, aromatic solvent "Solvesso" 100, ethers, esters, alcohols, acetates and mixtures of the above. The coating composition may contain from 1-20% by weight of a polyester resin which is the esterification product of an aliphatic dicarboxylic acid, a polyol having at least three reactive hydroxyl groups, a diol, a cyclic anhydride and a cyclic alcohol and having a number average molecular weight of 500-4,000. A preferred polyester resin is the esterification product of adipic acid, trimethylol propane, hexandiol, hexahydrophthalic anhydride and dicyclohexanedimethanol.
Also, the coating composition may contain from 1-20% by weight of an acrylic resin with hydroxy function (without the functionality of the silane). The coating composition also contains an organic polyisocyanate crosslinking agent. Any of the adducts with aromatic, aliphatic, cycloaliphatic, isocyanate, trifunctional and isocyanate isocyanate, conventional, polyol and diisocyanate functions can be used. Typically, the useful diisocyanates are hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-bisphenylene diisocyanate, toluene diisocyanate, biscyclohexyl diisocyanate, tetramethylene xylene diisocyanate, ethyl ethylene diisocyanate, 2,3-dimethyl ethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-dicyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-phenylene diisocyanate, 1,3-diisocyanate, naphthalene, bis- (4-isocyanatocyclohexyl) -methane, and 4,4'-diisocyanatodiphenyl ether. Typical trifunctional isocyanates that may be used are triphenylmethane triisocyanate, 1,3-benzene triisocyanate, and 2,4,6-toluene triisocyanate. The trimers of the diisocyanates can also be used. These trimers may be biurets or isocyanurates. The examples are sold under the registered names of "Desmodur" N3300 or "Tolonate" HDT. These trimers also contain higher oligomers such as pentamers, heptamers, etc., which are; generated during the process of preparing these trimers. A useful isocyanurate is the isocyanurate of isophorone diisocyanate. The isocyanate-functional adducts which are formed from an organic polyisocyanate and a polyol can be used. Any of the polyisocyanates mentioned above can be used with a polyol to form an adduct. Polyols such as trimethylol alkanes similar to trimethyl propane or ethane can be used. A useful adduct is the product of the reaction of tetramethylxylidene diisocyanate and trimethylolpropane and is sold under the trade name "Cythane" 3160. Curing or hardening catalysts are generally used in the coating composition in amounts of 0.1-5. % by weight, based on the weight of the binder, for the catalysis of the crosslinking between the silane portions and the hydroxy portions of the acrylosilane polymer with the isocyanate portions of the polyisocyanate. A mixture of a blocked sulphonic acid catalyst and an alkyl or aryl acid phosphate catalyst such as butyl acid phosphate or phenylic acid phosphate is preferred. Typical blocked acid catalysts are dodecyl benzene sulphonic acid blocked with an amine such as amino methyl propanol. The blocked toluene sulphonic acid can also be used. In a two component composition where component A contains the acrylosilane polymerThe blocked acid catalyst is added to this component and the acid phosphate catalyst is added to the component B which contains the crosslinking agent of the polyisocyanate. Just before application, components A and B are mixed together and applied: usually by spraying or electrostatic spraying. Other catalysts can be used and include dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dichloride, dibutyl tin dibromide, tenyl boron, tetraisopropyl titanate, triethanolamine titanate chelate, dioxide dibutyl tin, dibutyl tin dioctoate, tin octoate, aluminum titanate, aluminum chelates, zirconium chelate, and other such catalysts or mixtures thereof known to those skilled in the art. Tertiary amines and acids or combinations thereof are also useful for catalyzing the silane bond. Other silane curing catalysts are described in U.S. Pat. No. 4,923,945, column 15 to column 17, incorporated herein by reference. To improve the environmental resistance of the clear coating, the ultraviolet light stabilizers or a combination of the ultraviolet light stabilizers can be added to the clear coating composition in the amount of 0.1-10% by weight, based on the weight of the binder. Such stabilizers include the absorbed, filtered, ultraviolet light absorbers and light stabilizers of specified hindered amines. An antioxidant may also be added, in the amount of 0.1-5% by weight, based on the weight of the binder. Typical ultraviolet light stabilizers that are useful include benzophenones, triazoles, triazines, benzoates, hindered amines and mixtures thereof. Specific examples of ultraviolet light stabilizers are described in U.S. Pat. No. 4,591,533, the complete descion of which is incorporated herein for reference. For its good durability, a mixture of "Tinuvin" 1130, "Tinuvin" 384 and "Tinuvin" 123 (hindered amine), all commercially available from Ciba-Geigy, is preferred. The clear coating composition may also include other additives of conventional formulation such as flow control agents, for example, such as Resiflow® S (polybutyl acrylate), BYK® 320 and 325 (high molecular weight polyacrylates); and agents for the control of rheology; such as smoky silica. The conventional solvents and diluents described above are used to disperse and / or dilute the aforementioned polymers of the clear coating composition. Typical base coatings used in combination with the clear coating composition comprise as the film-forming binder a polyurethane, an acrylourethane, a silane resin, an acrylic resin and a crosslinking agent such as a polyisocyanate or a melamine resin rented. The base coat can be a solution transported by water or a solution or dispersion based on a solvent. The basecoat contains pigments such as those conventionally used, including metallic flake pigments such as aluminum flakes.
Both the base coat and the clear coat are applied by conventional techniques such as spraying, electrostatic spraying, submersion, brush application, and flow coating. The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise indicated. Molecular weights are determined by GPC (Gel Permeation Chromatography) using polymethyl methacrylate as the standard.
EXAMPLE 1
A polymeric solution of acrylosilane was prepared by copolymerization in the presence of a mixture of butanol / Solvesso Aromatic Solvent 2/1 of 134 parts by weight of styrene (S), 134 parts by weight of hydroxyethyl methacrylate (HEMA), 134 parts by weight. weight of methacryloxypropyl trimethoxy silane (MAPTS) and 268 parts by weight of isobutyl methacrylate (IBMA) in the presence of 53.6 parts by weight of Vazo®674. The resulting polymer solution had a solids content of 67% and a viscosity of X-Y on the Gardner Holdt scale measured at 25 ° C. The polymer composition is 20% S / 20% HEMA / 20% MAPTS / 40% IBMA and has an average molecular weight of 4800.
A coating composition was formulated by mixing together the following ingredients:
Portion A Parts by Weight Acrylosilane Polymer Solution (Prepared previously) 80. 0 Amine Light Stabilizers 4. 3 Stored and UV (HALS) 19.7% Tinuvin® 11301, 16.7% Tinuvin® 3841, 4.1% Tinuvin® 1231 and 14.7% Tinuvin® 0791 in 44.8% Solvent Solvent Solvent 100) "Resiflow" S2 (50% Solids one agent of 0.2 control of the polybutyl acrylate flow in Solvesso Aromatic Solvent 100) Solution of the Dodecylbenzene Sulphonic Acid (at 33.3% solids in methanol and blocked with amino methyl propanol) Aromatic solvent Solvesso 100 10. 0 3-Ethoxy Propionate of Ethyl 12. 0 Portion B Solution of Hexa Diisocyanate Trimer24. 0 methylene (at 72% solids Desmodur® 33003 in a 50/35/15 mixture by weight of n-butanol and aromatic hydrocarbon solvent) Total 131. 8 Sources of the above constituents are: 1. Product of Ciba Specialty Chemical Company 2. Product of King Industries Inc. 3. Product of Bayer Corp. 4. Product of E. I. du Pont de Nemours and Company
Portion A is loaded into a mixing vessel and mixed and then Portion B is added and mixed to form the coating composition containing 76% by weight of the acrylosilane polymer by weight and 24% by weight of the isocyanate. The coating composition was reduced to a spray viscosity of 35 seconds measured on a # 2 Fisher apparatus with ethyl 3-ethoxy propionate. The steel panels electrically coated with a conventional primer were spray-coated with an acrylic melamine basecoat modified with water-borne polyester, black and after 10 minutes of waiting it was pre-baked for 10 minutes at 83 ° C and then the The clear coating composition prepared above was sprayed to provide a 0.00508 cm (2 mil) film when cured and then the panels were baked at 120 ° C for 30 minutes to form a clear base coat / coating that has a higher gloss of 80 on a 20 ° brightness meter and a hardness of 12 knoop units measured with a Tukon Hardness Machine.
EXAMPLE 2
A polymer solution (B) of acrylosilane was prepared by copolymerizing 108 parts of a monomer / initiator mixture (20 parts of styrene, 30 parts of hydroxyethyl methacrylate, 10 parts of gamma-methacryloxypropyl trimethoxy silane, 28 parts of isobutyl methacrylate, 12 parts of ethylhexyl acrylate, 8 parts of Vazo® 67) in 60 parts of a 2/1 reflux mixture of 100 / n-butanol aromatic solvent. The resulting resin solution was 66% solids, had a Gardner-Holt viscosity of X +, and a MW of 5100 as determined by CPG. A coating composition was formulated by mixing the following ingredients:
Portion To Parts in Weight
Acrylosilane polymer B 100,. 0 UV / HALS solution (described in Ex. 1) 5. . 4 Resifluow S 0. , 3 Solution of Dodecylbenzene Sulphonic Acid 1. , 7 (described in Ex. 1) Aromatic Solvent 100 12.5 Ethyl 3-Ethoxy Propionate 15.0 Portion B Desmodur® 3300 solution (72% solids 37.5 described in Ex. 1) Phenyl acid phosphate Albright® PA-75 0.6
Total 173.0
A clear coating was prepared and sprayed on a black water-borne base coat, in the same manner as described in Example 1. The base coat / clear coat was baked at 1305 for 30 minutes. The results of the test are shown in the
Table I.
Comparative Example 3
This example illustrates a clear two-component urethane coating that does not contain silane with good resistance to acid attack but poor resistance to usual wear. An acrylic polymer solution with function of; hydroxyl (C) was prepared by copolymerizing 104 parts of a monomer / initiator mixture (25 parts of styrene, 32 parts of hydroxyethyl acrylate, 43 parts of n-butyl methacrylate, 4 parts of Vazo® 67) in 60 parts of a reflux mixture 9/1 aromatic solvent 100 / n-butyl acetate solvent. The resulting resin solution was 66% solids, had a Gardner-Holt viscosity of Y-, and a MW of 5300 as determined by CPG. A clear coating was prepared by mixing 2.6 parts of Portion A (bottom) with 1 part of Portion B (bottom):
Portion To Parts in Weight
Acrylic polymer C (described above) 100, 0 UV / HALS solution (see Example 1) 1. 2 Xylene solution 50% Resifluow S 0. 4 75% solution of phenyl or 0 phenyl phosphate. , 5 in butanol n-butanol 10.0 Aromatic Solvent 100 20.1 3-Ethoxy Ethyl Propionate 13.4 Portion B Desmodur® 3300 39.4 Solution 3 of Desmodur® 4470 39.2 Aromatic Solvent 100 2.2 Butyl Acetate 7.7 Ethyl 3-Ethoxy Propionate 6.0 Xylene 5.5
A clear coating was sprayed onto a: waterborne basecoat, black, in the same manner as described in Example 1. E.L basecoat / clearcoat was baked at 130 ° C for 30 minutes. The test results are shown in the Table
I.
Comparative Example 4
This example illustrates a clear coating of 2K urethane which does not contain silane with good wear resistance but poor resistance to attack by the acid. A clear coating was prepared by combining 2. (5 parts of Portion A (bottom) with 1 part of Portion B (bottom).
Portion To Parts in Weight
Acrylic Polymer C (described in Example 3) 100.0 UV / HALS Solution (described in Example 1) 7.3 50% Xylene Solution of Resifluow S 0.4
Butyl Benzyl Phthalate 6.0
75% solution of 0.1 phenyl phosphate in butanol n-butanol 10.0
3-Ethoxy Ethyl Propionate 18.3 Portion B Desmodur® 3300 72.0 n-butanol 14.0 Xylene 10.0
Aromatic Solvent 100 4.0
A clear coating was prepared and sprayed on a water-borne, black base coat, in the same manner as described in Example 1.
The basecoat / clearcoat was baked at 130
° C for 30 minutes. The results of the test are shown in Table I.
Table I
Note 1 Lowest temperature (° C) where the acid attack occurs on the test in the gradual furnace
Note 2 Damage generated on the Benchtop Car Wash (5 = good, 10 = poor).
Test Methods
Acid Attack Resistance Panels, which have a clear, cured coating on the black base coatings, are placed over a gradual temperature furnace with a surface temperature ranging from 45 to 85 ° C. The panels were stained (200 microliters) with an acid solution of pH 1 along the gradient. After 30 minutes of exposure, the stains are removed by washing with deionized water.
Resistance to Habitual Wear
A Benchstop car wash machine is used to inflict damage on the cured panels with the clear coating on the black basecoat. The method is described in the GM 9707P Standard Specification Test of General Motors Engineering.
It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates.
Having described the invention as above, property is claimed as contained in the following
Claims (11)
1. A coating composition comprising 40-70% by weight of a film-forming binder and 30-60% by weight of a volatile liquid carrier for the binder; characterized in that the binder consists essentially of: a. 50-90% by weight, based on the weight of the binder, of an acrylosilane polymer consisting essentially of the polymerized monomers of the following group; an ethylenically monounsaturated silane monomer; monomers selected from the group consisting of an alkyl methacrylate, an alkyl acrylate, each having 1-12 carbon atoms in the alkyl group, cycloaliphatic alkyl methacrylate, the cycloaliphatic alkyl acrylate, the styrene or any mixture of these monomers; the hydroxy-containing monomers selected from the group consisting of hydroxyalkyl methacrylate, hydroxyalkyl acrylate each having 1-4 carbon atoms in the alkyl group or any mixtures of these monomers; and the polymer having a weight average molecular weight of 1,000-15,000 determined by gel permeation chromatography; b. 10-50% by weight, based on the weight of the binder of an organic polyisocyanate; and wherein the ratio or proportion of the isocyanate groups of the organic polyisocyanate to the hydroxy groups of the acrylosilane polymer is from 0.4: 1 to 1.3: 1.
2. The coating composition according to claim 1, characterized in that the ethylenically monounsaturated silane monomer has the following structural formula: wherein: R is selected from the group consisting of CH3, CH3CH2, CH30, or CH3CH20; R1 and R2 are individually selected from the group consisting of CH3, or CH3CH2; and R3 is selected from the group consisting of H, CH3, or CH3CH2 and n is 0 or a positive integer from 1 to 10.
3. The coating composition according to claim 2, characterized in that the silane monomer is selected from the group consisting; of gamma trimethoxy silyl propyl methacrylate and gamma trimethoxy silyl propyl acrylate.
. The coating composition according to claim 2, characterized in that the acrylosilane polymer consists essentially of 35-75% by weight, based on the weight of the acrylosilane polymer, of the polymerized monomers selected from the group consisting of alkyl acrylates. , alkyl methacrylates having each 1-8 carbon atoms in the alkyl and styrene group, 20-40% by weight, based on the weight of the acrylosilane polymer, of the polymerized monomers selected from the group consisting of methacrylates. hydroxy alkyl and hydroxy alkyl acrylates each having 1-4 carbon atoms in the alkyl groups and 5-25% by weight of the ethylenically monounsaturated silane monomer.
5. The coating composition according to claim 4, characterized in that the organic polyisocyanate is the trimer of the hexamethylene diisocyanate or the trimer of the isophorone diisocyanate.
6. The coating composition according to claim 5, characterized in that it contains 0.1-5% by weight, based on the weight of the binder, of a mixture of the catalysts of a blocked sulfonic acid catalyst and the acid phosphate of aryl or alkyl .
7. The coating composition according to claim 6, characterized in that the blocked acid catalyst is a blocked dodecyl benzene sulphonic acid and the aryl acid phosphate is the phenyl acid phosphate.
8. The coating composition according to claim 2, characterized in that it contains about 1-10% by weight, based on the weight of the binder, of ultraviolet light absorbers.
9. The coating composition of; according to claim 2, characterized in that the acrylosilane polymer consists essentially; of 35-75% by weight, based on the weight of the polymer of; acrylosilane, of the polymerized monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates each having 1-4 carbon atoms in the alkyl and styrene group, 20-40% by weight, based on the weight of the polymer of acrylosilane, of the polymerized monomers selected from the group consisting of hydroxy alkyl methacrylates and hydroxy alkyl ds acrylates each having 1-4 carbon atoms in the alkyl groups and 5-25% by weight of the ethylenically monounsaturated silane monomer and the organic polyisocyanate is the trimer of hexamethylene diisocyanate or the trimer of isophorone diisocyanate and the coating composition contains 0.1 - 5% by weight, based on the weight of the binder, of a mixture of catalysts of a sulphonic acid catalyst blocked and aryl or alkyl acid phosphate.
10. A two-component coating composition, characterized in that it comprises: Component A of an acrylosilane polymer consisting essentially of 35-75% by weight, based on the weight of the acrylosilane polymer, of the polymerized monomers selected from the group consisting of of alkyl acrylates, alkyl methacrylates each having 1-4 carbon atoms in the alkyl and styrene group, 20-40% by weight, based on the weight of the acrylosilane polymer, of the polymerized monomers selected from the group consisting of of hydroxy alkyl methacrylates and hydroxy alkyl acrylates each having 1-4 carbon atoms in the alkyl groups and 5-25% by weight, of the ethylenically monounsaturated silane monomer and containing 0.1-2% by weight, based on in the weight of component A, of "a blocked dodecylbenzene sulphonic acid and Component B consists of an organic polyisocyanate of the trimer of hexamethylene diisocyanate or the trimer of isophorone diisocyanate and containing 0.1-2% by weight, based on the weight of Component B, of an aryl acid phosphate catalyst; wherein the components A and B are completely mixed together to form a coating composition before application.
11. A substrate, characterized in that it has a base coat layer of a composition of; coating pigmented and coated on the top with the coating composition in accordance with claim 1. ACRYLOSILAN POLYMER TO IMPROVE THE RESISTANCE TO USUAL WEAR AND RESISTANCE TO THE ATTACK OF THE ACIDS SUMMARY OF THE INVENTION The present invention relates to a coating composition particularly useful as a clear coating used on a pigmented base coat having improved resistance to usual wear and an improved resistance to attack by the acid when exposed to environmental conditions. , which contains 40-70% by weight of a film-forming binder and 30-60% by weight of a volatile liquid carrier for the binder; wherein the binder contains: (a) 50-90% by weight, based on the weight of the binder, of an acrylosilane polymer of the polymerized monomers of the following group; an alkyl methacrylate, an alkyl acrylate, each having 1-12 carbon atoms in the alkyl group, cycloaliphatic alkyl methacrylate, the cycloaliphatic alkyl acrylate, the styrene - or any mixture of these monomers; the hydroxy-containing monomers of the following group: hydroxyalkyl methacrylate, hydroxyalkyl acrylate each having 1-4 carbon atoms in the alkyl group or any mixtures of these monomers; and an ethylenically monounsaturated silane monomer, and the polymer having a weight average molecular weight of 1,000-15,000 determined by gel permeation chromatography. (b) 10-50% by weight, based on the weight of the binder of an organic polyisocyanate; and wherein the ratio or proportion of the isocyanate groups of the organic polyisocyanate to the hydroxy groups of the acrylosilane polymer is from 0.4: 1 to 1.3: 1.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09103852 | 1998-06-24 |
Publications (1)
Publication Number | Publication Date |
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MXPA00011525A true MXPA00011525A (en) | 2001-11-21 |
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