TW593598B - High solids clear coating composition - Google Patents
High solids clear coating composition Download PDFInfo
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- TW593598B TW593598B TW089104967A TW89104967A TW593598B TW 593598 B TW593598 B TW 593598B TW 089104967 A TW089104967 A TW 089104967A TW 89104967 A TW89104967 A TW 89104967A TW 593598 B TW593598 B TW 593598B
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- 239000008199 coating composition Substances 0.000 title claims abstract description 49
- 239000007787 solid Substances 0.000 title claims description 29
- 238000000576 coating method Methods 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 30
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 6
- -1 dimethyl-fluorenyl-1-propanol Chemical group 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000004611 light stabiliser Substances 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 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 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000035800 maturation Effects 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 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 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- RAADJDWNEAXLBL-UHFFFAOYSA-N 1,2-di(nonyl)naphthalene Chemical compound C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 RAADJDWNEAXLBL-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 229960002887 deanol Drugs 0.000 claims 1
- ZLXMDTDPTCRLKU-UHFFFAOYSA-N dibutyl-(dibutyl-$l^{3}-stannanyl)oxytin Chemical compound CCCC[Sn](CCCC)O[Sn](CCCC)CCCC ZLXMDTDPTCRLKU-UHFFFAOYSA-N 0.000 claims 1
- 239000012972 dimethylethanolamine Substances 0.000 claims 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims 1
- 229940070765 laurate Drugs 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229920003270 Cymel® Polymers 0.000 description 7
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920000180 alkyd Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical class OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- CFGGNXFNDNQZKD-UHFFFAOYSA-N 2-(9H-fluoren-1-yl)prop-2-enoic acid Chemical compound C1C2=CC=CC=C2C2=C1C(C(=C)C(=O)O)=CC=C2 CFGGNXFNDNQZKD-UHFFFAOYSA-N 0.000 description 3
- 241000006479 Cyme Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
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- 239000003085 diluting agent Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- OUGJKAQEYOUGKG-UHFFFAOYSA-N ethyl 2-methylidenebutanoate Chemical compound CCOC(=O)C(=C)CC OUGJKAQEYOUGKG-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
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- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- JKJJSJJGBZXUQV-UHFFFAOYSA-N methyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OC JKJJSJJGBZXUQV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
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- HAUVRGZOEXGUJS-UHFFFAOYSA-N 2-methyl-4-(oxiran-2-yl)but-2-enoic acid Chemical compound OC(=O)C(C)=CCC1CO1 HAUVRGZOEXGUJS-UHFFFAOYSA-N 0.000 description 1
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- UDVRROYKHLBOPZ-UHFFFAOYSA-N 3,3-dihydroxy-2-methylpropanoic acid Chemical compound OC(O)C(C)C(O)=O UDVRROYKHLBOPZ-UHFFFAOYSA-N 0.000 description 1
- NKKWYENCEXCGLD-UHFFFAOYSA-N 4,4-dimethylpentane-1,2-diol Chemical compound CC(C)(C)CC(O)CO NKKWYENCEXCGLD-UHFFFAOYSA-N 0.000 description 1
- PEAOADVZXHOLJJ-UHFFFAOYSA-N 4-ethenyl-n-methylbenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=C(C=C)C=C1 PEAOADVZXHOLJJ-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Description
593598
7X /4 五、發明說明(l) έ ί :明ΐ常關於高固體,低voc (揮發性有機"、、 組合物,更尤指適於汽車 ==份)塗料 塗層之低VOC透明塗料組合物。磨先應用中所使用多層 頃發現在汽車磨光市場 系統:頃持續努力以在經常較高應用透明,料 觀,最上塗層透明I,和使這 整體外 頃進一步努力發展I彻νΩ 一 系、、充4化之扰性。亦 a 低v〇c之塗料組合物。對於為 具有卓越性能特徵平衡之透明途料對於在應择用後 要,尤指在高固體含I t j 4 : =依…、存在持 '績性需 胺/丙烯酸系多元醇交二 / U鄭又%或二聚虱胺自身縮合塗料 如,可以提供具有可接受損耗之塗料,但此類塗料 f體含量具有不良抗酸腐㈣和外觀降低。另-方面2 鼠酸鹽/丙烯酸系多元醇基底2K胺甲酸酯塗料通常提供可、 接受之抗腐蝕性,但此類塗料具有不良抗損耗性。因/此, 依然存在不僅提供可接受之抗損耗性和抗酸腐蝕性,而且 在儘可能最低之VOC提供高光澤和DO I塗料的需要。 個由尼δ午海拉(Ntsihlele)和庇茲(Pizzi)在標題為 “由異氰酸鹽-甲氧曱基三聚氰胺系統共反應之交聯塗料 (Cross-Linked Coatings by Co-Reaction of
Isocyanate-Methoxymethyl Melamine System)” 之文件 (應用聚合物科學刊物(Journal of Applied Polymer Science),第55冊,第153 - 161頁,1995年)中敘述之研 究,提供將芳香族二異氰酸鹽與曱氧曱基三聚氰胺反應。 593598 五、發明說明(2) 明塗料組合物之需要, 黃或變脆且提供高光澤 然而,依然持續存在對於高固體透 當長時間曝露於陽光時彼等不會變 和 D Ο I 〇 發明敘述 氰酸鹽 其中該 之脂肪 生透明 環族碳 鹽組份 氰酸鹽 之組份 的搁置 該 >丨 本發明係關於一種包括異 胺組份之透明塗料組合物, 平均2至6個異氰酸鹽官能度 本發明亦關於在基材上產 塗佈一層包括異氰酸鹽, 塗料組合物,其中該異氰酸 氰酸鹽官能度之脂肪族聚異 將該層熟化為透明塗層。 一個本發明之優點在於其 署(EPA)目前之標準。 另一優點在於由本發明塗 抗腐餘性。 而另一優點在於從本發明 度和高度光澤。 按照此處所使用: “二包裝塗料組合物”表 包括二種貯存於個別容器内 封,以提高塗料組合物組份 前混合以形成適用混合物。 為數分鐘(15分鐘至45分鐘) ,環族破酸酯和三聚氰 異氰酸鹽組份包括具有 族聚異氰酸鹽。 塗料之方法,其包括: 酸酯和三聚氰胺之透明 包括具有平均2至6個異 ,和 低VOC,其顯著低於美國環保 料組合物產生之塗層的損耗和 塗料組合物產生之塗層的透明 示一種熱固性塗料組合物,其 。這些容器典型上密 哥命。將該組份在使用 物之有限適用期典型上 至數小時(4小時至6小時)。將
第6頁 593598 ------ 五、發明說明(3) 混合物以所需厚度應用 S^ 以在基材料表面上熱化,或在 ^車體。 出、、1 >」 打成具有所需舍〇 /JE2L极烤孰乂 l 單ίϊ;性和抗環靡性。質之塗層,二声 早包裝塗料組合物,,表八一 如巧度 包括二個貯存於同_容器;::種熱固性塗科 隔以避免早期交聯。將該單包裝匕“ ’將其 :,;;士將該層曝露於…ί::合物應用於基:: 將该層在南溫供烤熟化以在基村表^且隔之叙份。=上 性質之塗層’如高光澤’抗性面2形成具有:二 性。 和對於環境腐麵料 “低VOC塗料組合物”表示—種冷 " 包括〇至〇.4 72公斤有機溶劑y每物,其=升 二公升組合物0. 118 (每加余⑷至〇 . 178公斤有上容佳為 (定皆加侖1.5磅),按照在ASTM D3 9 6 〇中提供之步驟下測^ ‘‘高固體組合物”表示一種塗料組合物,其固 65至1〇〇百分比之間,較佳大於7〇百分比,全部為以***均分子量”和“Gpc數量平均分子量” 重量平均分子量和數量平均分子量,其分別藉由】用凝: 第7頁 593598 五、發明說明(4) --- 滲透層析法測量。使用由加州(CaUf〇nia)修立特帕可 (Hewlett-Packard);帕羅亞托(Pal〇 AU〇)提供之高性能 液體層析法(HPLC)。除非特別指出,使用之液相為四氫呋 喃,標準為聚曱基丙烯酸甲酿。 工 “聚合物粒子大小”表示藉由使用由紐約哈茲維爾 . (Holtsville),布魯克海芬儀器公司(Br〇〇khaven -
Instruments Corporation)提供之布魯克海芬型號^ —⑽ 粒子篩分機所測量之聚合物粒子直徑。該篩分機使用準彈 性光散射技術測量聚合物粒子之大小。散射強度為粒子大 小之函數。使用根據強度加重平均之直徑。此技術係於由暹> 偉納(Weiner) et al.所著之美國化學學會論集(American
Chemical Society Symposium)系列 1987 年版,標題為光 天凝聚光譜於粒子篩選之用途與矛盾(Uses and Abuses of Photon Correlation Spectroscopy in Particle Sizing),第48-61頁,第3章中敘述。 χκ合物固體或組合物固體”表示乾燥態之聚合物 或組合物。 此處使用之“脂肪族”包括脂肪族和環脂肪族物質。 可交聯”表示加成物之個別組份包含一些官能度,其& 在本發明之組合物中反應以得到良好外觀,持久性,硬度 和抗損耗性之塗層。 抗酸腐餘性”表示由塗佈表面提供相對於由環境作用 之化學腐蝕之抗性,例如酸雨。 - 抗損耗性 表示塗層對於機械磨擦之抗性,例如,塗
第8頁 593598 五、發明說明(5) 佈表面之磨擦,如汽車車體,其典型上在、、主、 表面期間發生。 ^洗和清潔塗佈 專利申请者思外地發現,與典型熱固性塗 用之傳統研究相反,即涉及聚合物和交聯組=組合物中使 常可用之路徑為結合傳統上將被認定為用以=者,一種非 VOC高固體透明塗料組合物之交聯劑,其產生產特定低 料性質之塗料,如透明度,損耗和抗腐蝕性。具有優良塗 更意外地發現,藉由在透明塗料組合物中包'^利申請者 酯,固體含量能夠進一步提高而不犧牲抗S餘^族碳酸 光澤,DO I,和其它希望之塗料性質。咸相作0和損耗性, 係作為典型上在塗料組合物中使用之溶劑,°且^^旨組份 應以產生安定且可熟化之交聯結構。因此,所=热化時反 合物之黏度能夠實質上降低而不犧牲塗料性質。生塗料組 該透明塗料組合物包括異氰酸鹽,環族碳=能和二取— 胺組份。該異氰酸鹽組份包括具有平均2至6個, 至6個,更佳3至4個異氰酸鹽官能度之脂肪族聚異Χ氛&酸· 鹽。該塗料組合物包括3 〇 %至7 0 %脂肪聚異氰酸赜, 35%至55%,最佳為40%至50%,該百分比為以組;物她 重量為基準之重量百分比。 _… 適當脂肪族聚異氰酸鹽實例包括脂肪族或環脂肪族一 ,三-或四-異氰酸鹽類,其可以是乙烯系不飽^或=^一 是,如1,2-伸丙基二異氰酸鹽,三亞甲基二異氰酸趟,四 亞曱基二異氰酸鹽,2, 3-伸丁基二異氰酸鹽,六亞甲美一 異氰酸鹽,八亞甲基二異氰酸鹽,2, 2, 4-三甲其 一 1恭亞甲基
第9頁 593598 五、發明說明(6) 二異氰酸鹽,2, 4, 4-三曱基六亞曱基二異氰酸鹽,十二亞 曱基二異氰酸鹽,ω -二丙醚二異氰酸鹽,1,3-環戊烷二 異氰酸鹽,1,2-環己烷二異氰酸鹽,1,4-環己烷二異氰酸 鹽,異佛爾酮二異氰酸鹽,4-甲基-1,3 -二異氰酸基環己 烷,反亞乙烯基二異氰酸鹽,二環己基甲烷-4, 4’ -二異氰 酸鹽,3, 3’ -二曱基-二環己基甲烷4, 4’ -二異氰酸鹽,偏-四曱基苯二曱基二異氰酸鹽,具異三聚氰酸鹽結構單位之 聚異氰酸鹽類,如六亞曱基二異氰酸鹽之異三聚氰酸鹽, 和異佛爾酮二異氰酸鹽之二異三聚氰酸鹽,2分子二異氰 酸鹽之加成物,如六亞曱基二異氰酸鹽,六亞曱基二異氰 酸鹽之脲駄酮(uretidiones),異佛爾酮二異氰酸鹽之脲 駄酮(uretidiones)或異佛爾酮二異氰酸鹽,和如乙二醇 之^二醇,3分子六亞曱基二異氰酸鹽和1分子水之加成物 (可自潘西維尼亞(Pennsylvania),匹茲堡 (Pittsburgh),拜耳公司(Bayer Corporation)取得,商 標名稱為Desmodur N)。 芳香族聚異氰酸鹽並不適用於本發明,因為由彼等所產 生之透明塗料太過於光敏性並易於隨熟化而變黃,且當長 時間曝露於陽光時便破裂。結果此類透明塗料並不对久。 倘若需要,則聚異氰酸鹽之異氰酸鹽官能度可以以單體 醇封端以避免單包裝組合物内之過早交聯。許多適當之單 體醇類包括甲醇,乙醇,丙醇,丁醇,異丙醇,異丁醇, 己醇,2-乙基己醇和環己醇。 塗料組合物之三聚氰胺組份包括適當之單體或聚合物三
第10頁 593598 五、發明說明(7) 聚氰胺或其結合物。烷氧基單體三聚氰胺較佳。塗料組合 物包括10%至4 5%三聚氰胺,較佳2〇%至4〇%,最佳2 5%至 3 5% ’該百分比為以組合物固體總重量為基準之重量百分 比。 在本發明之文中,“烷氧基單體三聚氰胺,,表示低分子 量三聚氰胺,其包含平均3個或多個羥曱基,其每個三畊 核以個元醉鱗化之經甲基’如曱醇,n~* 丁醇,異 丁醇或其類似物,且平均縮合度達約2,較佳為約1 · 1至約 1 · 8,且單核物種比例不大於約5 〇 %重量比。該聚合物三聚 氰胺之平均縮合度大於1.9。 許多此類適當之單體三聚氰胺包括高度烷化之三聚氰 胺’如曱基化’ 丁基化,異丁基化三聚氰胺和其混合物。 尤其較佳為六經曱基三聚氰胺,三羥曱基三聚氰胺,部份 曱基化之六羥曱基三聚氰胺,且五甲氧曱基三聚氰胺較 佳。六羥甲基三聚氰胺和部份曱基化之六羥曱基三聚氰胺 更佳,六羥曱基三聚氰胺最佳。 許多這些適當單體三聚氰胺係商業上可取得。例如,新 澤西州(New Jersey),西佩德森(Wes1: Patters〇n)之西達 克工業公司(Cytec Industries Inc·)供應 Cymel® 301 (聚合度1· 5,95%曱基和5%羥甲基),Cyme 1® 35 0 (聚合度 1. 6,84%甲基和16%羥曱基),3 0 3,325,327和370,其全 部為單體二聚氰胺。適當聚合物三聚氰胺包括已知為 Resimene^ BMP55 0 3之高胺基(部份烷基化,—N,—H)三聚 氰胺(分子量690,聚分散度ι· 98,56% 丁基,44%胺基),
第11頁 593598 五、發明說明(8) 其由米蘇里州(Missouri),聖路易市(St. Louis)之索路 堤亞公司(Solutia Inc·)銷售,或由新澤西州,西佩德森 之西達克工業公司供應之Cymel® 1158。 西達克工業公司亦銷售Cymel® 1130 @ 80%固體(聚合度 2. 5),Cyme 1® 1 1 33 ( 48% 曱基,4% 羥曱基和48°/。丁基),其 皆為聚合物三聚氰胺。 該塗料組合物較佳包括一種或多種觸媒以提高組份當熟 化時之交聯。通常,該塗料組合物包括觸媒為0 · 1 %至5 %, 較佳0· 1%至2%,更佳〇· 5%至2%,最佳〇· 5%至1· 2%,該百分 比為以組合物固體總重量為基準之重量百分比。 許多適當觸媒包括傳統酸觸媒,如芳香族續酸,例如十 二基苯磺酸,對甲苯磺酸和二壬基萘磺酸,無論是否以胺 阻隔,如二甲基四氫曙唑和2-胺基-2-曱基一1—丙醇,n,n一 二曱基乙醇胺和其結合物。其它能夠使用之酸觸媒為強 酸’如碌酸’尤指苯基酸填酸鹽’其可以以胺阻隔或否。 除了以上,該塗料組合物較佳包括少量一種或多種有機 錫觸媒,如二丁基錫二月桂酸鹽,二丁基錫二乙酸鹽,辛 酸錫,和二丁基錫氧化物。二丁基錫二月桂酸鹽較佳。有 機錫觸媒之添加量通常為〇· 001%至0.5%,較佳0 Q5%至 0 · 2%,更佳0 · 1 %至0. 1 5%,該百分比為以組合物固體總重 罝為基準之重量百分比。 這些觸媒較佳添加於三聚氰胺組份。 塗料組合物之碳酸酯組份包括五元或六元環族碳酸g旨戍 其結合物。六元環族碳酸酯較佳。該塗料組合物包括5 %至
593598 五、發明說明(11) 胺與含環族碳酸酯之多環反應而製備之六元環族碳酸酯官 能化聚胺曱酸屬亦適用於本發明。 本發明之塗料組合物,其係調配於高固體塗料系統中, 其更包含至少一種典型上擇自有芳香族烴構成之族群之有 機溶劑,如石油腦或二曱苯;酮類,如曱基戊基酮,甲基 _ 異丁基酮,曱基乙基酮或丙酮;酯類,如乙酸丁酯或乙酸 · 己酯;和乙二醇醚酯類,如丙二醇單甲基醚乙酸酯。有機 溶劑之添加量取決於所需固體含量以及所需之組合物VOC 量。倘若需要,則有機溶劑可以添加於黏合劑之二組份。 本發明之塗料組合物亦可以包含傳統添加劑,如安定 劑,和流變控制劑,流動劑,和動化劑。理所當然,此類 額外添加劑將取決於塗料組合物之用途。將不包括任何將 對於熟化塗料透明度將不利影響之添加劑,因為該組合物 係用以作為透明塗料。可以擇一或兼具添加以上添加劑, 視塗料組合物之用途而定。 本發明之透明塗料組合物可以以二包裝塗料組合物之形 式銷售,其中第一包裝包括聚異氰酸鹽組份,第二包裝包 括三聚氰胺組份。通常第一和第二包裝係貯存於個別容器 並在使用前混合。容器較佳密封不透氣以避免貯存期間劣 ¥ 化。混合可以例如在混合喷嘴或於容器内完成。 或者,當聚異氰酸鹽之異氰酸鹽官能度被阻隔時,塗料 組合物組份二者皆能夠以單包裝塗料組合物之形式貯存於 同一容器内。 ^ 為了改良塗料組合物透明磨光之耐候性,可以添加約
第15頁 593598 五、發明說明(12) O '. 1至5 %重量比紫外光安定劑或紫外光安定劑和吸收劑之 結合物,以組·合物固體之重量為基準。這些安定劑包括紫 外線吸收劑,遮蔽劑,消化體和特定受阻胺光安定劑。同 時,能夠添加約0. 1至5%重量比抗氧化劑,以組合物固體 重量為基準。有用之代表性紫外光安定劑包括二苯基酮 類,如羥十二環二苯基酮,2,4 -二羥基二苯基酮;*** 類,如2 -苯基-4 - ( 2 ’ - 4 ’ -二經苯甲基)三σ坐;和三哄類, 如三哄和三。坐之3,5 -二烧基-4 -羥苯基衍生物,如2 -(苯並 ***-2 -基)-4,6 -雙(曱乙基-1-苯乙基)酚,2-(3 -羥基-3’,5’ -二-三級戊苯基)苯並***,2-(3,,5’-雙(1,1-二曱 丙基)_2’_羥苯基)-2Η-苯並***,苯丙酸,3-(2Η-苯並三 唑-2 -基)-5-(1,1-二甲乙基)-4-羥基-C7_9-支鏈烷基酯, 和2-(3’,5’-雙(1-曱基-1-苯乙基)-2’-羥苯基)苯並三 口坐 〇 代表性受阻胺光安定劑為雙(2,2,6,6 _四曱基六氫吡啶 基)癸二酸鹽,雙(N-曱基-2, 2, 6, 6-四甲基六氫吡啶基)癸 二酸鹽和雙(N -辛氧基-2, 2, 6,6-四曱基哌啶炔基)癸二酸 鹽。一種紫外光吸收劑和受阻胺光安定劑之有用摻和物為 雙(N -辛氧基_2, 2, 6, 6 -哌啶炔基)癸二酸鹽和苯丙酸, 3 -(2H-苯並***-2 -基)-5-(1,1-二甲乙基)-4 -羥基-C7_9-支鏈烷基醋。另一有用之紫外光吸收劑和受阻胺光安定劑 之推和物為2_(3’,5’ -雙(1-曱基-1-苯乙基)-2’ -經苯基) 苯並***和癸二酸,雙(2, 2, 6, 6 -四曱基-4-六氫吡啶) 酯,皆由紐約州,泰銳鎮(Tarrytown),西霸特殊化學品
第16頁 593598 五、發明說明(13) — 公司(Ciba Specialty Chemicals)銷售,商標名稱分別為 hnuvin® 9 0 0 和Tlnuvin® 123。 ^發明之塗料組合物視需要可以包含流動調整樹脂為 〇^1%至40% ’較佳為5°/。至35%,更佳為1〇%至30% ,如非水性 分散劑(NAD ),所有百分比係以組合物固體總重量為基 準。流動調整樹脂之平均分子量通常於2 〇,〇 〇 〇至丨〇 〇,〇 〇 〇 範圍内變化,較佳為25, 0 0 0至8 0, 0 0 0,更佳為3 〇, 〇〇〇至 50,000。 ’ 非水性分散液形式樹脂係藉由在聚合物分散液安定劑和 有機溶劑存在下,將至少一種乙烯單體分散聚合而製備。 該聚合物分散液安定劑可以是任何非水性分散液中常用之 已知安定劑,且可以包括以下物質(1)至(9 )作為實例: 〜(1)在分子内具有約1 · 0個可聚合雙鍵之聚酯巨分子,如 同ϊ將丙稀酸縮水甘油酯或甲基丙稀酸縮水甘油醋添加於 如1 2-羥基硬脂酸之含羥基脂肪酸之自動縮合聚酯時便可 得到般。 (2 ) —種梳式聚合物,其藉由將所述之聚§旨巨分子在(1) 下與甲基丙烯酸甲酯和/或其它(甲基)丙烯酸酯或乙烯單 體共聚合而製備。 (3) —種聚合物,可藉由將所述之聚合物在(2 )下與少量 (甲基)丙稀酸縮水甘油酯共聚合,其後,於其縮水甘油基 添加(曱基)丙烯酸,所以植入雙鍵之步驟而得到。 (4) 一種含羥基丙烯酸共聚物·,其藉由將至少2 〇 %重量比 含4個或多個碳原子之一元醇的(甲基)丙烯酸酯共聚物而
第17頁 593598 五、發明說明(14) 製備。 (5) —種丙烯酸共聚物,其可藉由在(4)下,以其數量平 均分子量為基準,將每分子至少0.3個雙鍵植入所述之共 聚物中而得到。一種植入雙鍵之方法,例如,可以包括將 丙烯酸聚合物與少量(曱基)丙烯酸縮水甘油酯共聚合,其 後於該縮水甘油基添加(丙稀酸)。 (6) —種烷基三聚氰胺,對於礦油精具有高耐性。 (Ό 一種醇酸樹脂,其油長度不低於丨5%和/或〆種可藉 由將可聚合雙鍵植入醇酸樹脂而得到之樹脂。植入雙鍵之 方法,例如,包括(甲基)丙烯酸縮水甘油酯於醇酸樹脂内|| 之魏基之加成反應。 (8 ) —種對於礦油精呈右古+ e ^ y 顶,、有问耐性之無油聚酯樹脂,和油 長、又低於1 5 %之醇酸樹脂,和/或可择由 樹脂而得到之樹脂。由將雙鍵植人該醇酸 (9) 一種乙酸纖維素丁酸酯 。植入雙鍵之實例方法包括 添加於乙酸纖維素丁酸酯。 於其中植入可聚合之雙 將異氰酸基乙基甲基丙烯酸 为放液安定劑可g依 j j以早獨或結合使用 在上述分散液安定劑t,為;::便用。
:低極性溶劑如脂肪族烴為能夠溶, 某些程度。作為能夠符合 ;:::性能需求心 之丙烯酸共聚物在(4)和(下二=之刀政液安定劑,月 整分子量,玻璃轉移溫 2 土在於其不僅有助方 刀 包含平均約〇 593598 五、發明說明(15) 至約1 . 2個可聚合雙鍵之丙烯酸共聚物更佳,其可與分散 粒子接枝共聚合。 根據本發明使用之非水性分散液形式樹脂,能夠藉由在 上述聚合物分散液安定劑和有機溶劑存在下,分散聚合至 少一個乙烯單體簡單地製備,其主要包含脂肪族烴。該分 散液安定劑和乙烯單體可溶於有機溶劑中。然而,由乙烯 單體形成之聚合物粒子不溶於溶劑中。 形成適於作為聚合物分散液安定劑之丙烯酸共聚物之單 體組份,和形成分散粒子之乙烯單體事實上可以任何反應 基可聚合之不飽和單體。對於該目的能夠使用各種單體。 此類單體之代表性實例包括以下。 (a)丙烯酸或甲基丙烯酸之酯類,例如,丙烯酸或甲基 丙稀酸之Ci_18烧基酯類,如丙稀酸曱酯,丙稀酸乙酯,丙 稀酸丙醋,丙烯酸異丙醋,丙稀酸丁酯,丙稀酸己酷,丙 烯酸辛酯,丙烯酸月桂酯,丙烯酸硬脂酯,曱基丙烯酸甲 醋,曱基丙烯酸乙酯,曱基丙烯酸丙酯,曱基丙烯酸異丙 醋,曱基丙烯酸丁酯,甲基丙烯酸己酯,曱基丙烯酸辛 ,曱基丙烯酸月桂酯,和甲基丙烯酸硬脂酯;丙烯酸縮 水甘油酯和甲基丙稀酸縮水甘油自旨;丙稀酸或甲基丙稀酸 之C2_8烯基S旨類,如丙稀酸稀丙§旨,曱基丙烯酸稀丙醋, 丙浠酸或曱基丙稀酸之C2_8羥烧基醋類,如丙稀酸經乙 S旨,曱基丙稀酸經乙酯,如丙稀酸經丙醋,甲基丙烯酸經 丙醋;以及丙稀酸或曱基丙稀酸之C3_18烯氧烧基醋類,如 丙烯酸烯氧乙酯,和曱基丙稀酸稀氧乙酯。
593598 五、發明說明(16) _(b)乙烯芳香族化合物,例如苯乙烯,α -甲基苯乙烯, 乙烯曱苯,ρ -氣苯乙烯和乙烯吡啶。 (c) a , /3 -乙稀系不飽和酸,如丙稀酸,甲基丙烯酸, 分解烏頭酸和巴豆酸。 (d) 丙烯酸和甲基丙烯酸之醯胺類,如丙烯醯胺,甲基 丙烯醯胺,η - 丁氧甲基丙烯醯胺,N -羥曱基丙烯醯胺,n-丁氧曱基丙烯醯胺,和N -羥曱基曱基丙烯醯胺。 (e) 其它:例如,丙烯腈,曱基丙稀腈,曱基異丙烯基 酮,乙酸乙稀酯,Veo Va單體(殼牌化學品公司(Shell Chemicals Co., Ltd.)之產品;為含10個碳原子之高分枝 結構合成飽和單羧酸的混合乙烯酯類),丙酸乙烯酯,三 曱基乙酸乙烯酯,曱基丙烯酸異氰酸乙基酯,(曱基)丙烯 酸^全氟環己酯,ρ-苯乙烯磺醯胺,N-甲基-ρ-苯乙烯磺醯 胺,和7 -甲基丙烯醯氧基三甲氧矽烷。 上述單體中,以下物質能夠特別有利地用以製備用以作 為分散液安定劑之丙烯酸系共聚物: 以相當長鏈,低極性單體為基礎之混合單體,如η-曱基 丙烯酸丁酯,2_乙基曱基丙烯酸己酯,甲基丙烯酸十二 S旨,曱基丙烯酸月桂酯,和甲基丙烯酸硬脂酯,視需要補 充苯乙烯,(曱基)丙烯酸曱酯,甲基丙烯酸乙酯,2-羥基 (甲基)丙烯酸乙酯,(曱基)丙烯酸丙酯,和(甲基)丙烯 酸。該分散液安定劑可以藉由將(甲基)丙烯酸縮水甘油酯 或曱基丙烯酸異氰酸乙酯添加於用以植入可聚合雙鍵之單 體的共聚物而製備。
第20頁 593598 五、發明說明(17) 用以作為分散液安定劑之丙烯酸系共聚物能夠根據已知 之溶液聚合方法,使用反應基聚合引發劑而製備。 分散液安定劑之數目平均分子量較佳為約1,0 0 0至約 5 0,0 0 0,然為了較佳結果,為約3,0 0 0至約2 0,0 0 0。 上述單體中,用以形成分散聚合物粒子之尤其較佳乙烯 單體主要包含相當高極性之單體,如(曱基)丙烯酸曱酯, (曱基)丙烯酸乙酯,η-(曱基)丙烯酸丁 S旨,和丙烯腈,視 需要補充(曱基)丙烯酸,和2 -羥基(曱基)丙烯酸乙酯,亦 能夠如分子内交聯般提供凝膠粒子,其藉由共聚合少量多 官能單體,如二乙烯苯,和乙二醇二曱基丙烯酸酯,藉由 共聚合許多具有互相反應性官能基之單體,如曱基丙烯酸 縮水甘油酯和甲基丙稀酸,或藉由共聚合自動反應性單 體,如Ν-烷氧甲基化丙烯醯胺,和r -甲基丙烯醯氧丙基 三甲氧基矽烷。 於進行分散液聚合中,分散液安定劑與形成分散粒子乙 烯單體之比例擇自約5/95至約8 0 / 2 0重量比之範圍,較佳 約1 0 / 9 0至約6 0 / 4 0重量比,該分散液聚合能夠在反應基聚 合物引發劑存在下以已知步驟進行。 而所產生非水性分散液形式丙烯酸樹脂的粒子大小通常 為約0 . 0 5微米至約2微米,從薄膜之擱置壽命安定性和光 澤,平滑度和耐候性,約0. 1微米至約0. 7微米之範圍較 佳。 使用時,將二包裝塗料組合物中包含聚異氰酸鹽之第一 包和包含三聚氰胺及環族碳酸酯之第二包恰於使用前,或
第21頁 593598 五、發明說明(18) 在使用前約5至3 0分鐘混合,以形成適用混合物,其有限 適用壽命為約1 0分鐘至約6小時。其後’彼等變成太黏而 不能容許經由傳統塗佈系統應用,如喷霧。適用混合層典 型上係以傳統技術塗佈於基質,如喷霧,靜電噴霧,輥塗 佈’液浸或塗刷。通常’將厚度為2 5微米至7 5微米之透明 塗層塗佈於金屬基材上’如汽車車體,其常以其它塗料層 預塗佈’如電塗佈’底漆和基底塗料。當應用時該二包裝 塗料組合物可以在約8 〇 °C至1 β 〇烘烤約6 〇至1 〇分鐘。 當使用包含阻隔聚異氰酸鹽之單包裝組合物時,將其使 用上述應用技術塗佈之層,在8〇至2〇〇範圍内之烘烤 溫度热化,較佳為8 〇 °c至1 6 0 °C,持續約6 〇至1 〇分鐘。頃 了解真貫烘烤溫度將視觸媒和其用量,欲熟化之層厚度, 阻隔異氰酸鹽官能度和塗料組合物中使用之三聚1胺二 疋。在OEM (原設備製造)環境下使用前述烘烤步驟尤其有 用0 / 本發明之透明塗料組合物適於在各種基材上提供透明塗 。曰FM ::金府屬’木材和水泥基材。本組合物尤適於在汽車 OEM或再磨光應用中提供透明塗層。這些組合物亦適於在 工業和維修塗料應用中作為透明塗料層。
第22頁 593598 五、發明說明(19) 測試步驟 使用以下步驟產生在以下實例中提出之數據: 測^~ _ 測試方法 乾燥薄膜厚庶 ASTMD1400 接受之最低程度),不良 ASTM D523,視覺 2〇^ltW~ 至少80之評比(可接受之最低程度) ASTM D523 DOI ' - 至少80之評比(可接受之最低程度) ASTM D5767 多肯(Tukon)厚度 ASTMD1474 MEK磨擦 ASTM D5402 抗損耗性(乾燥,濕潤及平台頂洗車) 見以下 抗酸腐蝕性(梯度棒) 見以下 固體百分比65% (可接受之最低程度) ASTM D2369 ' 1拉克計(Crockme ter ) -乾燥抗損耗性 、將在黑色基底塗層上具有熟化透明塗料之嵌片塗佈一層 由米蘇里(M i s s〇u r i),坎薩司市(K a n s a s C i t y)之佛特列 斯殿粉/朋阿米公司(Faultless Starch/Bon Ami Corporation)銷售之朋阿米研磨劑。該透明塗料之乾燥塗 層居度為5 0被米。其後測試該微片’ 1 〇雙重磨擦相對於 A · A · T · C · C ·庫拉克計(伊利諾州(Illinois),芝加哥市 (Chicago),亞特拉斯電子設備公司(Atlas Electric Devices Corporation),型號CM-1 )綠色毛說包裹之指尖 之損耗。以測量該塗佈嵌片損耗面積相對於未損耗面積之 2 0 °光澤,將該乾燥抗損耗性記錄為光澤滯留之百分比。 皇拉克計-濕潤抗損乾 使用類似以上庫拉克計-乾燥抗損耗性中之步驟測試濕
第23頁 593598 五、發明說明(20) 潤抗損耗性,除了使用之磨擦介質為濕潤氧化鋁漿液而非 朋阿米磨擦劑。該濕潤氧化鋁漿液如下: 去離子水(DI) 294克 ASE-60®稠化劑1 21克 AMP-95% (於DI水中之10%溶液)2 25克 氧化鋁(120#粗礫)3 7克 由潘西維尼亞州(pennSylVania),費城(Philadelphia) ’維姆哈斯公司(R 〇 h m a n d H a s s C〇m p a n y )銷售之相關稠 化劑 由威斯康辛州(Wisconsin),威克奇市(Milwaukee),亞 is、¼ 克化學公司(A 1 d r i c h C h e m i c a 1 s )銷售 3由潘西維尼亞州,費城,MDC工業公司(MDC industries) 銷、售之磨擦劑 將聚液之p Η維持7 · 6 - 8 · 0,黏度維持於1 2 5 ± 1 0泊 (P〇^se)(l〇 rpm之布魯克費#4針)。為了 測试,潤抗損耗性,於其上具有熟化透明塗料之黑色基底 ί層肷片上塗佈〇 · 7毫升漿液。該透明塗料乾燥厚度為4 0 铽米其後將该嵌片具有漿液之部份測試1 0雙重磨擦相對 KA.A.T.C,C· Crockmeter(伊利諾州,芝加哥市,亞特拉 斯電子設備公司,型號CM — n綠色毛說包裹之指尖之損 2二以測量該塗佈敌片損耗面積相對於未損耗面積之2〇。 光澤,將該乾燥抗損耗性記錄為光澤滯留之百分比。 ‘備具有以下配方之合成雨配方:
π% 溶液 I刃内序 35.7 克 95%氫氧化飼 95%氫氧化納 85%氫氧化鉀 10.5 克 12.6 克 1·2克 於以上添加去離子水,以產生ι_克陽離子溶液 陰離子溶液
ί 子水:以產生㈣0克陰離子溶液。 合成5 ?4 η、加於陽離子溶液’直到得到ρη 1以產生 。成雨。24小時後,將pH再調整至1。 括將約0.2毫升合成雨滴置於先以黑色基底塗料 ς 々I塗佈表面上[5〇8公分χ 5〇8公分(2英叶X 2 崔册、反。其後將該板置於8 0 X:之梯度爐中3 0分鐘。以 式輪廓計(由伊利諾(Inin〇is),羅林草地(Ramng eadows) ’泰勒哈布森公司(Tayl〇r H〇bsori inc·)銷售之 surtronic 3P輪廓計)測量測試塗層之腐蝕深度,以12個 數據點平均。 於以下實例說明本發明: 實例 實例1 將下表1中所列之組份稱入裝置閘,混合器和冷凝器之5 < 公升燒甑中。以氮清掃燒瓶並在反應期間維持於氮包覆
第25頁 593598 五、發明說明(22) 下。將稱入物加熱至丨4 ο X:,開始蒸除蒸餾液,其主要為 反應期間產生之乙醇。將稱入物保持於丨4 0艺4小時,並 回收鶴液。逐漸將稱入物之溫度提高至丨6 〇。〇以終止並回 收748. 8克餾液。冷卻相期間添加η克甲基戊基酮(MAK)溶 劑’以產生包含9 5 %環族碳酸酯之透明液體。 表1 三羥曱基丙烷 363.43 克 新戊基乙二醇 452.9 ^ 1,6-己二醇 碳酸二乙酯 960〇Χ~- 二丁基錫二月桂酯 iTX~- 移除之餾液 (74U) …· 實例2
將下表2中步驟1所列之組份稱入裝置間,混合器 二2公升燒瓶内。以氮清掃燒瓶並在反應期間維持於氮 包覆下。將稱入物加熱至8 0 C。將下夺?也 份預先混合,並以30分鐘逐漸添加於^步驟2所列之組 境下任由溫度提高至1 〇 〇 °c,並將稱入你冉入物。在放熱環 時。採取稱入物之紅外吸收光譜以確定呆持於100 °c 1小 加之異氰酸鹽已消•毛。其1,任由稱入:驟2期間全部添 包含90. 17體積比GPC重量平均分子量為令卻以產生一種 透明液體。 ' 以之環族碳酸酉旨 表2
第26頁 593598 五、發明說明(23) 1由德州奥斯丁( A u s t i η),漢斯曼公司(H u n s t m a η Corporation)銷售 2由潘西維尼亞,艾倫鎮(ah ent〇wn)氣體產品公司(Air
Products Corporation)銷售 3由潘西維尼亞,匹茲堡(Pi ttsburgh)拜 C〇rp〇ratir〇銷售 拜耳公司(Bayer 添 和6之塗料組合 使用貫例1和2之環族組份產生本發明之塗合 加下表3中所列之材料以產生實例3,$, 、 ° 物:
❶
第27頁 593598 五、發明說明(24)
Cyme 1® 1 158,32 7,3 5 0三聚氰胺係由新泽 森之西達克工業公司銷售。 肌^
Tinuvin® 2 9 2和384光安定劑係由紐約州,主力》古 殊化學品公司銷售。 泰銳鎮西霸特 B Y K ® 3 0 1流動添加劑係由康乃迪卡,威林佛濟 (Wallingford) BYK化學品(BYK Chemie)销隹仏 聚醋多元醇係1莫耳二羥甲基丙酸,2莫耳已=内酯,〇·4ι 耳異戊四醇之反應產物,其1 0, 0 0 0 GPC重量平均分子旦、 @,8 0% η· V. 。 f
二丁基錫二月桂酯係由潘西維尼亞,艾倫鎮氣體產品 銷售。 J
Desmodur® N 33 0 0係由潘西維尼亞,匹茲堡拜耳公司 售。 本基酸填酸鹽係由康乃狄卡州(Connecticut),諾瓦克市 (Norwalk)金恩工業公司(King Industries)銷售。 將來自貫例3 ’ 4,5和6塗料組合物之層喷霧塗佈於電 塗佈並以磷酸化塗底漆之鋼鐵上,其預先塗佈強迫乾燥'水 生基底塗料,並在1 4 0 °C烘烤熟化3 0分鐘,以形成其上+ 具 有厚度4 0微米薄膜之塗層。為了比較,亦相同方式擊備來 自由達樂威(Delaware),威明頓(Wilmington)枉邦公司 (DuPont Company)銷售之傳統商用2 -包裝塗料組合物 (Imron® ES聚胺基曱酸酯)之塗層。 測試來自實例3,4,5,6和對照實例1 (C ◦ m p · e χ工) 之塗料的薄膜性質。結果於下表4中敘述:
593598 五、發明說明(25) 表4 性質 實例3 實例4 實例5 實例6 Comp. Ex. 1 固體(%非揮發性物) 85.3 87.5 87.7 85.1 53 多肯硬度(Knoops) 10.1 14.3 4.1 20.9 14.3 20°光澤 94 94 92 94 89 DOI 93 98 95 98 98 光澤滯留%之濕潤耗損 97 98 99 99 82 光澤滯留%之乾燥耗損 95 93 92 97 60 微米深度之抗酸腐蝕性 0.87 0.5 0.2 0.25 1.57 從上表4能夠看到本發明之透明塗料組合物不僅提供高 固體含量之透明塗料組合物,亦提供優良物理性質,如硬 度和抗溶劑性。 專利申請者意外地發現,從添加下表5中所列之材料製 備之實例7和對照實例2 ( C 〇 m ρ · E X. 2 )之塗料性質能夠看 到,當將環族碳酸酯添加於三聚氰胺/異氰酸鹽組份組合 物時,塗層性質戲劇性地改良。 表5 材料 用途 實例7 Comp. Ex. 2 碳酸伸丁酯 反應性稀釋劑 11克 實例1 反應性稀釋劑 15克 Cymel® 1158 聚合物三聚氰胺 20.56 克 20.25 克 Cymel® 327 聚合物三聚氰胺 7.8克 0.0 Tinuvin® 292/384 摻合物 光安定劑 7.5克 7.5克 10%BYK® 301 流動添加劑 0.68 克 0.68 克 聚酯樹脂 薄膜形成劑 9·38 克 二丁基錫二月桂酯 觸媒 1克 酸溶液#1 觸媒 2克 酸溶液#2 觸媒 2.42 克 Tolonate® HDT LV 聚異氰酸鹽 40克 80.8 克
第29頁 593598 五、發明說明(26) 碳酸伸丁酯係由德州奥斯丁,漢斯曼公司銷售。 Cymel® 1158和Cymel® 32 7係由新澤西州,西佩德森之$ 達克工業公司銷售。 ^ T i nuv i η® 2 9 2 / 3 8 4溶液係由紐約州,泰銳鎮西霸特殊 品公司銷售(13.3%1^111^;[1^ 2 9 2 和 2 6.67%1^1111\^® 於溶劑中之溶液)。 化學 384 酯樹脂係1莫耳二羥曱基丙酸,2莫耳Ε-己内酯 異戊四醇之縮合產物 ·
Tolonate® HDTLV係來自德州 公司(Rhodia Co.)。 由港(Freeport),羅迪亞 酉欠〉谷液# 1為2 5 %笨基酸碟酸鹽 酸溶液#2為由康乃狄卡州,諾 叫胺基-2—甲基醇胺阻;:;:、; =銷售 將實例7之塗層測試薄膜性質。對::=酸。 2)不能測試,因為太厚而 …'、 j2 (C〇mP. Ex 述: 贺務。結果於下表e中敘
性質 固體(%非揮 ~黏度(#4 ~~ 2〇° - D〇T__ Autospe^TP^ _光澤滯留 ]>澤滯留。/Q^ggl
Comp. Ex. 2 —-------- 87.8 霧) X) 從以上結果-L--ώ_ 碳酸醋組份對於形成笔有到添加同固體含量(87.8%)之 ⑽,塗料外觀和塗料性質具有戲劇 593598
第31頁
Claims (1)
- 593598 案號j 891Q4967 六、申請專利範圍 1 . 一種包含異氰酸鹽 料組合物,其中該組合 百分比以組合物固體總 氰酸鹽組份包括具有平 異氰酸鹽,且該環族碳 多個五元或六元環之環 2 .根據申請專利範圍 官能度係藉由將該官能 3 .根據申請專利範圍 一種脂肪族醇。 4.根據申請專利範圍 更包括一種或多種有機 5 .根據申請專利範圍 媒係擇自由二丁基錫二 丁基錫氧化物,辛酸錫 6 .根據申請專利範圍 擇自由十二基苯磺酸, 磺酸,苯基酸磷酸鹽, 酸鹽,以胺阻隔之苯基 酸,和其結合物構成之 7. 根據申請專利範圍 基四氫卩琴唑,2 -胺基-2 或其結合物。 8. 根據申請專利範圍 π 曰 補充 、環族碳酸酯和三聚氰胺之透明塗 物包括5 %至4 0 %該碳酸酯組份(所有 重量為基準之重量百分比),該異 均2至6個異氰酸鹽官能度之脂肪族 酸S旨組份包括至少一個具有一個或 碳酸酯。 第1項之組合物,其中該異氰酸鹽 度與單體醇反應而阻隔。 第2項之組合物,其中該單體醇為 第1或2項之組合物,其_該組合物 錫或酸觸媒。 第4項之組合物,其中該有機錫觸 月桂酸鹽,二丁基錫二乙酸鹽,二 ,和其結合物構成之族群。 第4項之組合物,其中該酸觸媒係 以胺阻隔之十二基苯磺酸,對甲苯 以胺阻隔之對甲苯磺酸,苯基酸磷 酸磷酸鹽,以胺阻隔之二壬基萘磺 族群。 第6項之組合物,其中該胺為二甲 -曱基-1-丙醇,η,η -二甲基乙醇胺 第4項之組合物,其中該組合物包O:\63\63054-910628.ptc 第32頁 593598 _案號89104967 f/年6月曰 修正_ 六、申請專利範圍 括0 . 0 0 1%至5 . 0 %該觸媒,所有百分比為以組合物固體總重 量為基準之重量百分比。 9 .根據申請專利範圍第1項之組合物,其中該聚異氰酸 鹽包括一種或多種六亞甲基二異氰酸鹽,異佛爾酮二異氰 酸鹽,偏四甲基苯二曱基二異氰酸鹽,或其結合物的三聚 1 0 .根據申請專利範圍第1或2項之組合物,其包括3 0 %至 7 0 %該聚異氰酸鹽,所有百分比為以組合物固體總重量為 基準之重量百分比。 1 1 .根據申請專利範圍第1 ,2或9項之組合物,其中該聚 異氰酸鹽具有平均2 . 5至6個異氰酸鹽官能度。 1 2 .根據申請專利範圍第1項之組合物,其中該三聚氰胺 組份包括單體三聚氰胺,聚合物三聚氰胺或其結合物。 1 3 .根據申請專利範圍第1或1 2項之組合物,其包括1 0 °/〇 至4 5 %該三聚氰胺,其中所有百分比為以組合物固體總重 量為基準之重量百分比。 1 4.根據申請專利範圍第1項之組合物,其更包括一種流 動調整樹脂。 1 5 .根據申請專利範圍第1項二包裝組合物形式之組合 物,其中該二包裝組合物之第一包裝包括該聚異氰酸鹽組 份,且該二包裝組合物之第二包裝包括該三聚氰胺和環族 碳酸i旨組份。 1 6 .根據申請專利範圍第1項之組合物,其中該組合物之 VOC係在每公升組合物0. 0公斤至0. 4 7 2公斤有機溶劑範圍O:\63\63054-910628.ptc 第33頁 593598 _案號89104967_Ϋ /年G月曰 修正_ 六、申請專利範圍 内變4匕。 1 7.根據申請專利範圍第1項之透明塗料組合物,其中從 該組合物所產生基材上之透明塗層具有D Ο I評比為至少 80 0 1 8 .根據申請專利範圍第1項之組合物,其更包括紫外光 安定劑,光吸收劑或其結合物。 1 9 . 一種在基材上產生透明塗層之方法,其包括:塗佈 一層包括異氰酸鹽,環族碳酸酯和三聚氰胺組份之透明塗 料組合物,其中該組合物包括5 %至4 0 %該碳酸酯組份(所有 百分比以組合物固體總重量為基準之重量百分比),該異 氰酸鹽組份包括具有平均2至6個異氰酸鹽官能度之脂肪族 聚異氰酸鹽,且該環族碳酸酯組份包括至少一個具有一個 或多個五元或六元環之環碳酸酯;且 將該層熟化為該透明塗層。 2 0 .根據申請專利範圍第1 9項之方法,其中該塗層之DO I 評比為至少8 0。 2 1 .根據申請專利範圍第1 9項之方法,其中該塗層之 2 0 °光澤為至少8 0。 2 2 .根據申請專利範圍第1 9項之方法,其中該聚異氰酸 鹽之異氰酸鹽官能度係藉由將該聚異氰酸鹽與單體醇反應 而阻隔。 2 3.根據申請專利範圍第2 2項之方法,其中該層之熟化 係在8 0 °C至1 6 0 °C高烘烤溫度發生。O:\63\63054-910628.ptc 第34頁
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- 2000-03-16 WO PCT/US2000/006962 patent/WO2000055263A1/en not_active Application Discontinuation
- 2000-03-16 CN CN00805130A patent/CN1344301A/zh active Pending
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- 2000-03-16 JP JP2000605685A patent/JP2002539318A/ja active Pending
- 2000-03-16 NZ NZ514218A patent/NZ514218A/en unknown
- 2000-03-16 AU AU38901/00A patent/AU761107B2/en not_active Ceased
- 2000-03-16 AT AT00918021T patent/ATE308591T1/de not_active IP Right Cessation
- 2000-03-16 EP EP00918021A patent/EP1169396B1/en not_active Expired - Lifetime
- 2000-03-17 TW TW089104967A patent/TW593598B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ES2251369T3 (es) | 2006-05-01 |
AU3890100A (en) | 2000-10-04 |
WO2000055263A1 (en) | 2000-09-21 |
NZ514218A (en) | 2003-05-30 |
BR0010383A (pt) | 2002-02-05 |
DE60023675D1 (de) | 2005-12-08 |
KR20020001773A (ko) | 2002-01-09 |
EP1169396B1 (en) | 2005-11-02 |
US6544593B1 (en) | 2003-04-08 |
JP2002539318A (ja) | 2002-11-19 |
CA2361327A1 (en) | 2001-09-21 |
CN1344301A (zh) | 2002-04-10 |
DE60023675T2 (de) | 2006-09-07 |
AU761107B2 (en) | 2003-05-29 |
EP1169396A1 (en) | 2002-01-09 |
ATE308591T1 (de) | 2005-11-15 |
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