WO1986001217A1 - Weatherable abrasion resistant etherified aminoplast derived coating for plastic substrates - Google Patents
Weatherable abrasion resistant etherified aminoplast derived coating for plastic substrates Download PDFInfo
- Publication number
- WO1986001217A1 WO1986001217A1 PCT/US1985/001527 US8501527W WO8601217A1 WO 1986001217 A1 WO1986001217 A1 WO 1986001217A1 US 8501527 W US8501527 W US 8501527W WO 8601217 A1 WO8601217 A1 WO 8601217A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polycaprolactone polyol
- solvent
- molecular weight
- protective coating
- coating composition
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 27
- 229920003180 amino resin Polymers 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 title claims description 26
- 239000011248 coating agent Substances 0.000 title claims description 18
- 238000005299 abrasion Methods 0.000 title abstract description 19
- 229920003023 plastic Polymers 0.000 title description 12
- 239000004033 plastic Substances 0.000 title description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 40
- 150000003077 polyols Chemical class 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 29
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000011253 protective coating Substances 0.000 claims abstract description 20
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 13
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 16
- 239000008199 coating composition Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012815 thermoplastic material Substances 0.000 claims 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 230000003993 interaction Effects 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 14
- -1 caprolactone polyol Chemical class 0.000 description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 13
- 239000004417 polycarbonate Substances 0.000 description 13
- 229920000515 polycarbonate Polymers 0.000 description 13
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 11
- 229920003270 Cymel® Polymers 0.000 description 11
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012963 UV stabilizer Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 3
- 229940044613 1-propanol Drugs 0.000 description 3
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229960005335 propanol Drugs 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LHWAQPXNRDXYJW-UHFFFAOYSA-N (2,3-dihydroxyanthracen-1-yl)-phenylmethanone Chemical class OC=1C(O)=CC2=CC3=CC=CC=C3C=C2C=1C(=O)C1=CC=CC=C1 LHWAQPXNRDXYJW-UHFFFAOYSA-N 0.000 description 1
- HKCCRRDTILVMHH-UHFFFAOYSA-N (2-chlorophenyl)-(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1Cl HKCCRRDTILVMHH-UHFFFAOYSA-N 0.000 description 1
- GZXPAMLBWRKEEF-UHFFFAOYSA-N (4-ethoxy-2-hydroxyphenyl)-(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OCC)=CC=C1C(=O)C1=CC=C(OC)C=C1O GZXPAMLBWRKEEF-UHFFFAOYSA-N 0.000 description 1
- QIZJTIBDFGGTBF-UHFFFAOYSA-N (4-ethoxy-2-hydroxyphenyl)-(4-propoxyphenyl)methanone Chemical compound C1=CC(OCCC)=CC=C1C(=O)C1=CC=C(OCC)C=C1O QIZJTIBDFGGTBF-UHFFFAOYSA-N 0.000 description 1
- JBESZWSJUKQSDM-UHFFFAOYSA-N (5-amino-2-hydroxyphenyl)-phenylmethanone Chemical compound NC1=CC=C(O)C(C(=O)C=2C=CC=CC=2)=C1 JBESZWSJUKQSDM-UHFFFAOYSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- AZUXKVXMJOIAOF-UHFFFAOYSA-N 1-(2-hydroxypropoxy)propan-2-ol Chemical compound CC(O)COCC(C)O AZUXKVXMJOIAOF-UHFFFAOYSA-N 0.000 description 1
- HDRZKABGOGYHPC-UHFFFAOYSA-N 10,10-dihydroxyanthracen-9-one Chemical class OC1(O)C2=CC=CC=C2C(=O)C2=CC=CC=C12 HDRZKABGOGYHPC-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-UHFFFAOYSA-N 0.000 description 1
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 1
- OGYSYXDNLPNNPW-UHFFFAOYSA-N 4-butoxy-4-oxobutanoic acid Chemical class CCCCOC(=O)CCC(O)=O OGYSYXDNLPNNPW-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 0 Cc1nc(*)nc(*)n1 Chemical compound Cc1nc(*)nc(*)n1 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 150000004891 diazines Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000011179 visual inspection Methods 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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Abstract
A protective coating composition containing a polycaprolactone polyol and an aminoplast derivative is applied to a thermoplastic substrate to produce a thermoformable article having abrasion resistance, solvent resistance and weatherability.
Description
"WEATHERABLE ABRASION RESISTANT ETHERIFIED AMINOPLAST DERIVED COATING FOR PLASTIC SUBSTRATES"
This invention relates to coatings for thermoplastic surfaces, to a method for the use of such coatings, and to the articles so coated. More particularly, this invention relates to protective coatings having good adhesion and thermoformability and their use to impart to plastic surfaces abrasion resistance, chemical solvent resistance, and weatherabilit . These protective coatings may be formulated from an aminoplast derivative and polycaprolactone polyols.
Background In the past years, plastics have become commercially vital materials used in a wide range of applications. Particularly, plastics may be applied as transparent articles, as translucent articles, or to opaque surfaces to provide texture, shine, and durability. Generally, these applications require a high degree of abrasion resistance in addition to other required properties, for example, impact strength, tensile strength, or elongation.
To date, no plastic exists which can be made to possess all desirable properties in the desirable proportions. Therefore, a coatings technology has developed which allows the joining of plastic materials and thereby a joining of their desirable properties. For example, the coatings technology may be used to join a substrate possessing high impact resistance, tensile strength, non-opacity, and elongation resistance, such as for example, a polycarbonate substrate, with an outer surface coating possessing high abrasion resistance, and low susceptibility to attack by solvents such as for example, an etherified aminoplast derived coating to produce a single article possessing the structural
strength of the polycarbonates and the resistance to surface attack of the etherified aminoplast derivatives.
Coatings suitable for use on plastic substrates must also possess other secondary properties which render them useable. For example, a coating applied for abrasion resistance must also be compatible with the substrate, have good adhesion to the substrate and preferably, be weather resistant, thermoformable, and solvent resistant. It is often in secondary properties that a particular coating may be judged unsuitable for use in any particular application. Therefore, it is in the secondary properties that much effort for improvement is directed. U.S. Pat. No. 4,197,392, assigned to the same assignee as the present invention, discloses a UV resistant transparent coating for plastic materials containing a melamine, a polyol, and a benzophenone. This coating has both weather resistance and thermoformability, however a greater degree of these two properties is desirable.
U.S. Pat. No. 4,096,125 discloses water-borne polycaprolactone coatings wherein polycaprolactone polyols are reacted with a polycarboxylic anhydride and subsequently with hexamethoxymethylmela ine. This coating has insufficient weather resistance and thermoformability.
U.S. Patent No. 3994851 discloses a water-borne abrasion resistant coatings containing the reaction products of hexamethoxymethylmelamine and polycaprolactone polyols having a molecular weight less than about 850. Those coatings lack sufficient levels of adhesion and thermoformability.
It is therefore, an object of the present invention to provide protective coating compositions which may be applied to plastic substrates, particularly polycarbonate substrates to impart
abrasion resistance, solvent resistance and weather resistance.
It is another object of the present invention to provide a protective coating for plastic substrates, particularly polycarbonate substrates, which will continue to adhere and weather well subsequent to a thermoforming process.
It is another object of the present invention to provide a method for protecting sensitive thermoplastic sheet from abrasion and solvent attack, even after prolonged weathering or thermoforming.
It is yet another object of the present invention to provide an abrasion resistant and solvent resistant coated thermoplastic article which will, withstand thermoforming and prolonged weathering.
Various other objects and advantages of this invention will become apparent to those skilled in the art from the accompanying description and disclosure. Description of the Invention In the broad scope of the present invention there are provided protective coating compositions for thermoplastic substrates containing polycaprolactone polyols of controlled polycaprolactone chain length, an aminoplast derivative, a solvent, a catalyst and optionally a UV stabilizer and reaction stabilizer. This protective coating composition may be applied to any thermoplastic substrate, but preferably a polycarbonate substrate, to impart abrasion resistance, solvent resistance, and weatherability. The parent polycaprolactone polyol which is reacted with the aminoplast derivative as described herein is provided by the reaction of an epsilon-caprolactone in the presence of a polyhydric initiator having at least two reactive hydrogen atoms present as hydroxyl. The epsilon-caprolactone monomers have the general formula.
where R* is hydrogen or lower alkyl, that is, a linear or branched alkyl group having from 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl. Usually at least six of the R* groups are hydrogen and the remaining three are hydrogen, methyl or any combination thereof. The caprolactone polyol has a hydroxyl functionality corresponding to that of the polyhydric initiator and contains oxycaproyl units, that is units of.
Preferably, the average number of such units is no less than about 3 for any single chain.
More specifically, the caprolactone polyol reactants are prepared by the reaction of the aforesaid epsilon-caprolactone monomers with a y-functional polyhydric initiator where y has a value of at least two and is usually no more than six, employing a monomer to initiator mole ratio of greater than about 6:1. The preparation of the parent caprolactone polyols is illustrated by the following equation which is specific to the preferred monomer, epsilon-caprolactone:
O
R"«0H)y + R"-.0«C«CH2f50fχ-H]y
where R" denotes the residue of a polyhydric alcohol after subtracting y number of -OH groups, y preferably being 2 or 3 and x has an average value of from 3 to about 20 and preferably no less than 5. Though higher values of x are suitable, the high melting points and low solubility of such compounds may require the use
of aggressive solvents for dissolution which would damage the plastic substrate to which the coating is applied.
Though polyhydric initiators with higher functionality are suitable, preferred polyhydric initiators encompassed by R" (OH) are those wherein y is 2 such as for example glycol, dimethylolethane, dimethylolpropane, 1,4-butanediol, 1,6 hexanediol, diethylene glycol, di-1,2-propylene glycol, oxyethylated and/or oxypropylated adducts of such compounds such as, for example, ethylene oxide adducts of dimethylolpropane, and mixtures of any of the aforesaid initiators. It is evident, therefore, that R" is a saturated, aliphatic radical having at least two carbon atoms and consists of carbon and hydrogen, or carbon, hydrogen and oxygen where oxygen is present solely as ether oxygen, as in diethylene glycol or the aforementioned oxyalkylated adducts. The more commonly employed initiators have no more than 10 carbon atoms.
The class of caprolactone polyols suitable for use herein are the epsilon-caprolactone diols having an average molecular weight of from about 1000 to about 6000. Preferred are the diols having an average molecular weight of about 1250 or greater.
TONE Polyols are caprolactone based multifunctional polyols which are commercially available from Union Carbide Corporation. These polyols have a maximum acid number of 0.25 mg. KOH/g polyol and a maximum water content of 0.03%.
Following are specific polyols and their properties:
Table 1
Aver. Hydrox. Melting Vise. Spec.
Mol. No.mg. Point Cent. Grav.
Wt. KOH/g Rng.°C 55°C 55/20
°C
Difunctional
TONE 0200 530 212 30-40 88 1.073
TONE 0210 830 135 35-45 167 1.072
TONE 0230 1250 90 40-50 284 1.071 TONE 0240 2000 56.1 45-55 635 1.071
TONE 0260 3000 37.4 50-60 1490 1.070
Trifunctional
TONE 0301 300 560 0 225 1.084
TONE 0305 540 310 15-20 200 1.072 TONE 0310 900 187 27-32 270 1.073
The parent caprolactone polyols which are reacted with aminoplast derivatives as described herein are - prepared by methods known to the art such as those described in U.S. Pat. No. 3169,945, the teachings of which are incorporated herein by reference. It is generally preferred that the reaction between the polyhydric initiator and monomer be effected at a temperature between about 130°C. in the presence of a catalyst such as stannous octoate or the other catalysts disclosed in said patent.
The aminoplasts for use herein are amine-aldehyde reaction products, i.e., aldehyde condensation products of amine compounds. Preferably, the aldehyde employed is formaldehyde, although the products can be made from other aldehydes, such as acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural and others. Suitable amines for use herein are for example, those of melamine, urea, triazines, diazines, triazoles, guanidines, guanamines, and alkyl and aryl substituted derivatives of such compounds including alkyl and aryl substituted melamine provided at least two amino groups are present.
These aminoplasts contain methylol or similar alkylol groups, the structure of the alkylol group depending upon the particular aldehyde employed. At least a portion, i.e., all or part, of these alkylol groups should be etherified by reaction with an alcohol. Any monohydric alcohol can be employed for this purpose, including aliphatic alcohols such as methanol, ethanol, propanol, butanol, and other alkanols, usually having up to about 6 carbon atoms; aromatic alcohols; such as benzyl alcohol cyclic alcohols such as cyclohexanol; monoethers of glycols such as the Cello-Solves and Carbitols; and halogen-substituted or other substituted alcohols such as 3-chloropropanol. Though the above amines, aldehydes, and alcohols are suitable, the preferred aminoplast derived component of the coating composition of this invention is an amine-aldehyde-alcohol of the general formula:
wherein R' * * is independently selected from H, -CH2OH, and -CH20(CH2) H, wherein β is an integer from 1 to 6, and Riv is selected from H, -OH, -CH, and -N(R,,,)-J. iv Preferably, RiV is -N(R",)2 and all R« " are an alkoxymethy1, particularly, methoxymethyl. The aminoplast derived component is produced in a manner well known in the art using acidic or basic catalyst and varying conditions of time and temperature in accordance with conventional practice.
The aldehyde is often employed as a solution in water or alcohol and the condensation, etherification, and polymerization reactions may be carried out either sequentially or simultaneously.
i
CYMEL 301 hexamethoxymethylmelamine is commercially available from American Cyanamid Company. This aminoplast derivative is a clear liquid with a specific gravity of 1.2, refractive index of 1.515-1.520, a free formaldehyde percent maximum of 0.30, a low free methylol content, an equivalent weight of 130-190, and a vapor pressure, 180βC, mm of 0.02-0.03.
The solvent used in the preparation of the coating composition includes alcohols, ketones, esters, ethers, alkoxy alkanols, halogenated compounds, carboxylic acids, aromatic compounds, or the like, which may be used alone or in a combination of two or more thereof. Particularly suitable examples of the solvent are lower alcohols (e.g. methanol, ethanol, propanol or butanol) and alkoxy alkanols (e.g. methyl cellosolve, ethyl cellosolve or butyl cellosolve) .
The solvent employed must not injure the substrate to which the coating composition is applied, that is, it must be nonagressive yet it must be capable of dissolving the aminoplast derivative and in particular the polycaprolactone polyol. Preferably, the solvent should be of such a volatility that it can be easily evaporated and removed from the coating composition at temperatures below cure temperature. A suitable, nonagressive solvent for a given substrate and a given polycaprolactone polyol may be readily determined by one skilled in the art. The preferred solvent is butyl cellosolve.
Suitable catalysts are alkyl acid phosphates, such as monomethyl acid phosphate, monoethyl acid phosphate, monopropyl acid phosphate and monobutyl acid phosphate, as well as the corresponding dialkyl compounds, such as 'dibutyl acid phosphate. A mixture of mono- and dialkyl phosphates is often utilized. In addition to the alkyl acid phosphates, examples of
other acid catalysts which can be used include phosphoric acid, maleic acid and anhydride, fumaric acid, chloromaleic acid and anhydride, alkyl acid phthalates such as methyl, ethyl, propyl and butyl acid phthalates, monoalkyl succinates and aleates such as methyl, ethyl, propyl and butyl succinates and maleates and others having sufficient solubility to permit them to be dissolved in the coating composition at the desired proportion. Catalysts which have been found to be particularly suitable are compounds such as the sulfonic acids and derivatives thereof including, for example, p-toluene sulfonic acid, methyl-p-sulfonic acid and the like.
Protective coating compositions which are to be prepared in advance of or stored prior to application and cure require reaction stabilizers or stabilizers to deactivate the catalyst until cure. It is within the skill of the art to determine a suitable stabilizer for use with a given catalyst. The preferred, catalyst of the instant invention, p-toluene sulfonic acid as well as others may be stabilized with equimolar amounts of a suitable amine stabilizer, for example, methylaminoethanol, triethylamine, 2 amino - 2 methyl- 1 propanol but preferably the stabilizer is triethylamine.
Any suitable ultraviolet stabilizer may be used in the present invention at any concentration effective to protect the thermoplastic substrate from the degradative effects of light. Suitable ultraviolet absorbers are for example benzophenone derivatives, including: 2,2*4,4'-tetrahydroxybenzophenone;
2,2'-dihydroxy-4-methoxy-4'-ethoxybenzophenone;2-hydr- oxy-4,4• ,5•-trimethoxybenzophenone; 2-hydroxy-4-propoxy-4' ,6*-dichlorobenzophenone;
2-hydroxy-4-methoxy-4•-methylbenzophenone; 2-hydroxy-4-methoxy-2'-chlorobenzophenone;
2-hydroxy-4,4' ,5*-trimethoxybenzophenone; 2-hydroxy-4-ethoxy-4*-methoxybenzophenone; 2-hydroxy-4-ethoxy-4'-propoxybenzophenone; and the like. Suitable benzotriazole derivatives may also be employed including 2-(2'-hydroxy-5,-methylphenyl) -benzotriazole, 2-(2•-hydroxy-3'-methyl-5*-tert- butylphenyl)-benzotriazole, 2-(2*-hydroxy-3*-di-tert -butylphenyl)-benzotriazole and derivatives of crotonic acid such as a-cyano-b methyl-b-(p-methoxyphenyl)-crotonic acid methyl ester, a-cyano-b-N-(2-methyl-indolinyl)crotonic acid methyl ester, substituted acrylates such as 2 ethyl-hexyl-2-cyano-3,3-diphenyl acrylate as well as malonic acid esters such as, for example, the dimethyl, diethyl, dipropyl and the like esters of malonic acid and the like and mixtures thereof. Most preferred are the dihydroxybenzophenones such as: 2,4-dihydroxybenzophenone,2,2*-dihydroxybenzophenone, 2-hydroxy-5-aminobenzophenone, 2,2' ,4,4*-tetrahydroxybenzophenone, 2,2* ,5,5*-tetrahydroxybenzophenone, dihydroxyanthrophenones, dihydroxyanthrones, etc.
Although the protective coating herein is intended for application to any thermoplastic substrate, the preferred substrate is polycarbonate. The polycarbonate or polycarbonate blend can be prepared by an suitable process including those outlined in U.S. Pats. 3,028,365; 2,999,846; 3,248,414; 3,153,008; 3,215,668; 3,187,065; 2,964,974; 2,970,137; 2,991,273; 2,999,835; 3,014,891; 3,030,331; 3,431,224; 3,290,412 and the like.
The protective coating composition may be blended by mixing an aminoplast derived component, a polycaprolactone polyol, an appropriate, nonagressive solvent, a catalyst, and optionally, a reaction stabilizer and UV stabilizer. Preferably the weight ratio of aminoplast derived component to
polycaprolactone polyol ranges from about 3/1 to about 1/2 and most preferably, from about 7/3 to about 2/3. The solvent should be added in sufficient amount to produce from about 15% to about 75% solids. The amount of catalyst, reaction stabilizer, and UV stabilizer which should be added is well within the determination of one skilled in the art.
The protective coating composition may be applied to the thermoplastic substrate by any of the well known means. Spraying, dipping, roll coating, and the like are appropriate coating techniques. The parameters of the coating technique chosen should be adjusted so as to produce a cured protective coating having a thickness of from about 0.05 to about 1 mil. Preferably the thickness should be about 0.2 mils. The preferred method of curing the applied coating composition is by heat curing. The coated substrate may be heated in ovens by infrared radiation, by microwave, etc. Preferably the solvent used in the coating composition should be substantially evaporated before the reaction or cure temperature of the coating is reached.
The following examples further demonstrate specific embodiments of the instant invention. They are intended to be illustrative and are not to be construed as placing a limitation on the scope of the invention herein disclosed.
Tests Cross Hatch Adhesion Test (Adhesion Test) The sample is tested in accordance with the procedure of ASTM D-3359 Method B. Samples which attain a rating of 5B in the ASTM standard are given a "Pass". Samples which show any flaking or detachment of the squares in the lattice are given a "Fail".
Taber Abrasion Test (Abrasion Test)
The sample is tested in accordance with the procedure of ASTM D-1044-78 using a CS-10F wheel, 500g load, and 100 cycles. The reported figure is the percentage of transmitted light that is scattered by the abraded specimens. Thermoform Test
The sample is heated to forming temperature and formed around a 1"radius mandrel. The sample is rated "Fail" if upon visual inspection any cracking, flaking, or detachment of the coating is observed. Watersoak Test The sample is tested in accordance with the above Cross Hatch Adhesion Test and immersed in a 65°C water bath. The reported figure is the number of days which the sample is soaked before any flaking or detachment of the squares in the lattice^ is observed in subsequent adhesion tests. Example 1-4 The following polyols were combined with CYMEL 301, butyl cellosolve, and a catalyst mixture having 20% by weight p-toluenesulfonic acid and 80% by weight 2-propanol in the gram weight proportions shown below. The resulting coating composition was dip coated onto a 1/8" BPA polycarbonate panel and cured to a noncritical thickness of less than 1 mil at a temperature of 130°C for 2 hours.
Table 2 1
CYMEL 301 192 192 192 192
1,4-butanediol 48
1,6-hexanediol - 48
Neopentylglycol - 48
Trimethylolpropane - - - - 48
Butyl Cellosolve 3 36600 360 360 360
Catalyst mixture 1 122 12 12 12
Adhesion Test F Faaiill Fail Fail Fail
Abrasion Test 4 4..88 3.5 6.4 4.7
Thermoform Test F Faaiill Fail Fail Fail
Watersoak Test 1 1 1 1 1
Examples 5-12
The following TONE Polyols were combined with CYMEL 301, butyl cellosolve, and a catalyst mixture having 20% by weight p-toluenesulfonic acid and 80% by weight 2-propanol in the gram weight proportions show below. The resulting coating composition was dip coated on to an 1/8" BPA-polycarbonate panel and cured to a non critical thickness of less than 1 mil of a temperature of 130°C for 2 hours.
Table 3 7 8 10 11 12
CYMEL 301 120 120 120 120 120 120 120 120 TONE 200 120 - - - - - - TONE 210 - 120 - - - - - - TONE 230 - - 120 - - - - - TONE 240 - - - 120 - - - - TONE 260 - - - - 120 - - - TONE 301 - - - - - 120 - - TONE 305 - - - - - - 120 - TONE 310 - - - - - - - 120 Butyl 360 360 360 360 360 360 360 360
Cellosolve Catalyst 12 12 12 12 12 12 12 12
Mixture Adhesion Pass Pass Pass Pass Pass Pass Pass Pass Test
Abrasion 5.5 6.2 7.4 7.6 6.3 3.6 1.7 4.2 Test Thermoform Pass Pass Pass Pass Pass Fail Pass Pass
Test Watersoak 3 3-5 5 14-21 19-22 1 3 1-4
Test
Examples 13-17 TONE 0230 was combined with CYMEL 301, butyl cellosolve, a UV stabilizer, a reaction stabilizer mixture of 95% by weight 2-amino, 1-methyl, 1-propanol and 5% by weight water, and a catalyst mixture having 20% by weight p-toluene-sulfonic acid and 80% by weight 2-propanol in the gram weights shown below. The resulting coating composition was dip coated onto an 1/8" BPA-polycarbonate panel and cured to a noncritical thickness of less than 1 mil at a temperature of 130°C for 2 hours.
Table 4
13 14 15 16 17
CYMEL 301 168 144 120 96 72
TONE 0230 72 96 120 144 168
Butyl cellosolve 360 360 360 360 360
Dihydroxybenzophenone 12 12 12 12 12
Reaction Stabilizer 6 6 6 6 6
Mixture
Catalyst Mixture 10 10 10 10 10
Adhesion Test Pass Pass Pass Pass Pass
Abrasion Test 8.2 9.6 14.6 25.2 28.8
Thermoform Test Pass Pass Pass Pass Pass
Watersoak Test 21-27 14-21 14-21 7-14 27-35
Examples 18-22
TONE 0240 was combined with CYMEL 301, butyl cellosolve, a UV stabilizer, a reaction stabilizer mixture of 95% by weight 2-amino, 1-methyl, 1-propanol and 5% by weight water, and a catalyst mixture having 20% by weight p-toluene-sulfonic acid and 80% by weight 2-propanol in the gram weights shown below. The resulting coating composition was dip coated onto an 1/8" BPA-polycarbonate panel and cured to a noncritical thickness of less than 1 mil at a temperature of 130°C for 2 hours.
Table 5
18 19 20 21 22
CYMEL 301 168 144 120 96 72 TONE 0240 72 96 120 144 168 Butyl Cellosolve 360 360 360 360 360
Dihydroxybenzophenonιee 12 12 12 12 12 Reaction Stabilizer 6 6 6 6 6
Mixture Catalyst Mixture 10 10 10 10 10 Adhesion Test Pass Pass Pass Pass Pass Abrasion Test 9 12.2 17.6 20.6 28 Thermoform Test Pass Pass Pass Pass Pass Watersoak Test 50 14-21 50 50 28-35
Examples 23-27 TONE 0260 was combined with CYMEL 301, butyl cellosolve, a UV stabilizer, a reaction stabilizer mixture of 95% by weight 2-amino, 1-methyl, 1-propanol and 5% by weight water, and a catalyst mixture having 20% by weight p-toluene-sulfonic acid and 80% by weight 2-propanol in the gram weights shown below. The resulting coating composition was dip coated onto an 1/8" BPA-polycarbonate panel and cured to a noncritical thickness of less than 1 mil at a temperature of 130°C for 2 hours.
Table 6
23 24 25 26 27
CYMEL 301 168 144 120 96 72
TONE 0260 72 96 120 144 168
Butyl Cellosolve 360 360 360 360 360
Dihydroxybenzophenone 12 12 12 12 12
Reaction Stabilizer 6 6 6 6 6
Mixture
Catalyst Mixture 10 10 10 10 10
Adhesion Test Pass Pass Pass Pass Pass
Abrasion Test 6.0 8.5 10.5 15.3 25.1
Thermoform Test Fail - Pass «. Pass
Watersoak Test 23-30 50 50 50 28-35
Claims
(1) A protective coating on a thermoplastic substrate consisting essentially of the reaction products of:
(i) an aminoplast derived compound; and (ii) polycaprolactone polyol of the general formula:
(2) The protective coating of Claim 1 wherein said x is on average no less than 5.
(3) A protective coating on a thermoplastic substrate consisting essentially of the reaction products of:
(i) an aminoplast derived compound of the general formula:
-CH-0(CH,) H, z is an integer from 1 to 6 iv and R is selected from the group consisting of H, -OH, -CH- and -N(R,")2; and
(ii) a polycaprolactone polyol of the general formula:
O R"-_0-frC II-CH2CH2CH2CH2CH2-0>χ-H]
wherein R" is a residue of a polyhydric alcohol, y is 2 or 3, and x is on average 5 or greater but less than the value at which an aggressive solvent is required for dissolution, and said polycaprolactone polyol has a molecular weight of about 1250 or greater.
(4) The protective coating of claim 3 wherein R' ' * is -CH2OCH3 and R1V is -N(R,")2
(5) A curable protective coating composition for thermoplastic materials consisting essentially of (i) an aminoplast derived compound;
(ii) polycaprolactone polyol of the general formula:
R" 0-( IC-CH2CH2CH2CH2CH2-O χ-H] wherein R" is a residue of a polyhydric alcohol; y is 2 or 3; x is on average greater than 3 but less than the value at which said polycaprolactone polyol is insoluble in a nonagressive solvent, and said polycaprolactone polyol has a molecular weight greater than 1000. (iii)a solvent.
(6) The coating composition of claim 5 which further contains a catalyst and reaction stabilizer.
(7) A curable protective coating composition for thermoplastic materials consisting essentially of:
(i) an aminoplast derived compound of the general formula:
NtR'"),
-CH,0(CH,)_H, z is an integer from 1 to 6 and Riv is selected from the group consisting of H, -OH, -CH3 and -N(R'» ,)2;
(ii) polycaprolactone polyol of the general formula:
0
R"- HC-CH2CH2CH2CH2CH2-Ofχ-H] wherein R" is a residue of a polyhydric alcohol; y is 2 or 3; x is on average greater than 3 but less than the value at which said polycaprolactone polyol is insoluble in a nonagressive solvent, and said polycaprolactone polyol has a molecular weight greater than 1000; (iii)a solvent; (iv) a reaction catalyst; and (v) a reaction stabilizer.
(8) The curable coating composition of claim 7 wherein x is on average greater than about 5 and said polycaprolactone polyol has a molecular weight greater than about 1250.
(9) A method for protecting a thermoplastic substrate from harmful interaction with its environment comprising the steps of:
(i) coating said thermoplastic substrate with a protective coating composition consisting essentially of an aminoplast derived compound, a polycaprolactone polyol having a molecular weight greater than about 1000, and a solvent; and (ii) curing said coating composition to a hard protective coating.
(10) The method of claim 9 wherein said coating step further requires that said polycaprolactone polyol be of the general formula:
(11) The method of claim 10 wherein said coating step further requires that said x be on average greater than about 5 and said polycaprolactone polyol has a molecular weight greater than about 1250.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP50382585A JPH0611807B2 (en) | 1984-08-17 | 1985-08-13 | Weather resistant and abrasion resistant etherified aminoplast derivative coating for plastic substrates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US641,914 | 1984-08-17 | ||
US06/641,914 US4552936A (en) | 1984-08-17 | 1984-08-17 | Weatherable abrasion resistant etherified aminoplast derived coating for plastic substrates |
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WO1986001217A1 true WO1986001217A1 (en) | 1986-02-27 |
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PCT/US1985/001527 WO1986001217A1 (en) | 1984-08-17 | 1985-08-13 | Weatherable abrasion resistant etherified aminoplast derived coating for plastic substrates |
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US (1) | US4552936A (en) |
EP (1) | EP0190326A1 (en) |
JP (1) | JPH0611807B2 (en) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988000218A1 (en) * | 1986-07-02 | 1988-01-14 | General Electric Company | Melamine based protective coatings for thermoplastic substrates |
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US5045396A (en) * | 1988-11-23 | 1991-09-03 | Ppg Industries, Inc. | UV resistant primer |
US5199979A (en) * | 1988-11-25 | 1993-04-06 | Ppg Industries, Inc. | UV resistant, abrasion resistant coatings |
US5385964A (en) * | 1990-10-02 | 1995-01-31 | Ppg Industries, Inc. | Silica-free UV-absorbing abrasion resistant coatings |
US5693422A (en) * | 1990-10-02 | 1997-12-02 | Ppg Industries, Inc. | Silica-free UV-absorbing abrasion resistant coatings |
US6040009A (en) * | 1994-06-23 | 2000-03-21 | Mazda Motor Corporation | Low solvent content type-resin composition, coating composition containing such resin composition and process for coating such coating composition |
US6352778B1 (en) | 1999-12-20 | 2002-03-05 | General Electric Company | Coating compositions containing silylated aroylresorcinols, method, and articles coated therewith |
US7960031B2 (en) * | 2004-06-30 | 2011-06-14 | Sabic Innovative Plastics Ip B.V. | Coated sheet, method of formation thereof, and articles derived therefrom |
KR20070084142A (en) | 2004-10-12 | 2007-08-24 | 에스디씨 코우팅스 인코포레이티드 | Coating compositions, articles, and methods of coating articles |
CA2647709A1 (en) | 2006-03-31 | 2007-10-11 | Sdc Technologies, Inc. | Coating compositions, articles, and methods of coating articles |
US9181451B2 (en) | 2013-08-30 | 2015-11-10 | Sdc Technologies, Inc. | Formable aminoplast resin-based coating compositions |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4101603A (en) * | 1976-05-26 | 1978-07-18 | Union Carbide Corporation | High solids coating compositions |
US4197392A (en) * | 1978-08-21 | 1980-04-08 | General Electric Company | Melamine coatings |
US4246376A (en) * | 1979-09-10 | 1981-01-20 | Henkel Corporation | Curing agents |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1308697A (en) * | 1969-05-02 | 1973-02-21 | Amicon Corp | Coating compositions |
US3806480A (en) * | 1971-10-26 | 1974-04-23 | Cook Paint & Varnish Co | Esters of melamine resins |
US3994851A (en) * | 1972-10-26 | 1976-11-30 | Ppg Industries, Inc. | High solids polyester coating composition |
US4096125A (en) * | 1976-05-26 | 1978-06-20 | Union Carbide Corporation | Polycaprolactone derivatives and coating compositions thereof |
US4218355A (en) * | 1978-07-21 | 1980-08-19 | Ppg Industries, Inc. | Low organic solvent-containing polyester coating compositions |
US4425466A (en) * | 1981-09-09 | 1984-01-10 | Monsanto Company | Coating compositions comprising a methylated methylolated melamine |
US4440913A (en) * | 1981-12-25 | 1984-04-03 | Kansai Paint Co., Ltd. | Coating composition for pliable substrates |
-
1984
- 1984-08-17 US US06/641,914 patent/US4552936A/en not_active Expired - Lifetime
-
1985
- 1985-06-21 CA CA000484893A patent/CA1280246C/en not_active Expired - Fee Related
- 1985-08-13 JP JP50382585A patent/JPH0611807B2/en not_active Expired - Lifetime
- 1985-08-13 EP EP85904316A patent/EP0190326A1/en not_active Withdrawn
- 1985-08-13 WO PCT/US1985/001527 patent/WO1986001217A1/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4101603A (en) * | 1976-05-26 | 1978-07-18 | Union Carbide Corporation | High solids coating compositions |
US4197392A (en) * | 1978-08-21 | 1980-04-08 | General Electric Company | Melamine coatings |
US4246376A (en) * | 1979-09-10 | 1981-01-20 | Henkel Corporation | Curing agents |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988000218A1 (en) * | 1986-07-02 | 1988-01-14 | General Electric Company | Melamine based protective coatings for thermoplastic substrates |
Also Published As
Publication number | Publication date |
---|---|
JPS61503037A (en) | 1986-12-25 |
EP0190326A1 (en) | 1986-08-13 |
JPH0611807B2 (en) | 1994-02-16 |
CA1280246C (en) | 1991-02-12 |
US4552936A (en) | 1985-11-12 |
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