CN101218316B - 涂漆组合物及上漆物品 - Google Patents
涂漆组合物及上漆物品 Download PDFInfo
- Publication number
- CN101218316B CN101218316B CN2006800253418A CN200680025341A CN101218316B CN 101218316 B CN101218316 B CN 101218316B CN 2006800253418 A CN2006800253418 A CN 2006800253418A CN 200680025341 A CN200680025341 A CN 200680025341A CN 101218316 B CN101218316 B CN 101218316B
- Authority
- CN
- China
- Prior art keywords
- component
- paint film
- molecular weight
- composition
- paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003973 paint Substances 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 238000004383 yellowing Methods 0.000 claims abstract description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 6
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 19
- 208000034189 Sclerosis Diseases 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000005406 washing Methods 0.000 abstract description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009477 glass transition Effects 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 23
- -1 isocyanate compound Chemical class 0.000 description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- 238000010422 painting Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- 239000002966 varnish Substances 0.000 description 11
- 239000002421 finishing Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000037452 priming Effects 0.000 description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical class NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- UBYWYEGPDNYPHZ-UHFFFAOYSA-N 2-hydroxyethyl but-2-enoate Chemical compound CC=CC(=O)OCCO UBYWYEGPDNYPHZ-UHFFFAOYSA-N 0.000 description 1
- GWSQQDUFKKYTCA-UHFFFAOYSA-N 2-hydroxypropyl but-2-enoate Chemical compound CC=CC(=O)OCC(C)O GWSQQDUFKKYTCA-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- FKMPFWRSYRKMSI-UHFFFAOYSA-N 3-hydroxypropyl but-2-enoate Chemical compound CC=CC(=O)OCCCO FKMPFWRSYRKMSI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XWWRMFGLNKSHQW-UHFFFAOYSA-N CC=CC(=O)O.OCC(C)(CO)C Chemical compound CC=CC(=O)O.OCC(C)(CO)C XWWRMFGLNKSHQW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- NKKMVIVFRUYPLQ-UHFFFAOYSA-N but-2-enenitrile Chemical compound CC=CC#N NKKMVIVFRUYPLQ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- PJJDTHSONOWIIH-UHFFFAOYSA-N dodecyl but-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C=CC PJJDTHSONOWIIH-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000010410 layer 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 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
- 229910000165 zinc phosphate Inorganic materials 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
- C08G18/6233—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols the monomers or polymers being esterified with carboxylic acids or lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6237—Polymers of esters containing glycidyl groups of alpha-beta ethylenically unsaturated carboxylic acids; reaction products thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
本发明提供了一种能形成具有优良的耐洗车机刮擦性、防尘-耐污性和耐候性的漆膜的涂漆组合物以及上漆物品。本发明提供了一种包含(A)组分和(B)组分的清漆组合物,其中(A)组分为包含35-50质量%(以该树脂的固体级分计)ε-己内酯结构单元的丙烯酸类共聚物(羟值为200-340毫克KOH/克,重均分子量为5000-15000),(B)组分为不泛黄型多异氰酸酯化合物。组合物中包括每1当量(A)组分的羟基对应0.5-2当量的比例的(B)组分的异氰酸酯基团,由所述涂漆组合物形成的硬化漆膜的杨氏模量不高于1.5帕,固化漆膜的交联的分子量(Mc)不高于350克/摩尔,以及硬化漆膜的玻璃化转变温度(Tg)为至少65℃。
Description
技术领域
本发明涉及可用于需要形成具有优良的耐刮性、耐候性和防尘—耐污性的漆膜的领域中的涂漆组合物以及涂有所述涂漆的物品。
背景技术
需要适应于车辆(如汽车、摩托车)用的油漆,在车辆上形成的漆膜应具有优良的耐溶剂性、耐汽油性以及耐候性而又不降低涂膜的硬度或又不影响外观。具体地说,为适应自动洗车设备对漆膜耐刮性的要求,具有高耐刮性的油漆近来已变得很重要。
包含10-50质量%由异氰酸酯化合物与已内酯多羟基化合物相反应而制得的氨基甲酸酯多羟基化合物(重均分子量为1500-4000,羟值为50-180毫克KOH/克),30-80质量%氟化树脂共聚物(其中氟-烯烃作为主要原材料已经参与反应,羟值为50-150毫克KOH/克)和10-40重量%交联剂的涂漆组合物是已知为能赋予漆膜耐刮性,并能使漆膜具有初始拒水性的涂漆组合物(例如所引述专利1)。然而,这类涂漆组合物存在一个因氟化树脂共聚物的拒水性而使水基底涂层的润湿性变低的缺点。
此外,还有一种其特征为包含下列组分的油漆组合物也已知为是能形成具有优良的耐酸、耐候和耐刮性涂层的汽车涂漆用面层油漆:90-50重量%作为可硬化树脂的组分(A)-由苯乙烯单体与丙烯酸酯单体构成的丙烯酸类共聚物(羟值为60-140毫克KOH/克,重均分子量为3000-30000),其中丙烯酸酯单体包括作为含羟基基团的丙烯酸单酯单体的,丙烯酸1,4-丁二醇单酯单体和/或ε-己内酯改性的丙烯酸酯单体,以及含4-24个碳原子的伯醇的丙烯酸酯单体,所述苯乙烯单体含量为45-55重量%;和10-50重量%组分(B)-氨基树脂和/或(封端的)多异氰酸酯化合物(例如所引述专利2)。然而,这类涂漆 组合物存在一个由于丙烯酸1,4-丁二醇单酯单体的用量只是满足了耐刮性要求,而漆膜的玻璃化转变温度(Tg)低,因而使防尘-耐污性能低的缺点。
此外,还有一种包含下列组分的紫外线硬化型涂漆组合物也已知为是具有优良的耐刮性、极好的外观、优良的粘附性和耐汽油性(例如所引述专利3)的涂层的紫外线可硬化涂漆:(A)官能度为至少4、数均分子量为300-2000、一个分子中有至少4个(甲基)丙烯酰基基团的紫外线可固化的多官能(甲基)丙烯酸酯;(B)内酯改性的多元醇(甲基)丙烯酸单酯聚合物,其中含20-60质量%开环的ε-己内酯加合物(源自内酯改性的羟值为100-180毫克KOH/克);(C)不泛黄型多异氰酸酯化合物;其中相对于(A)、(B)和(C)组分的总量计,(A)组分的用量为10-50质量%,(B)+(C)组分的用量为90-50质量%,(B)组分与(C)组分的比例为(B)组分中一个当量羟基对应(C)组分中0.5-1.5当量的异氰酸酯基团;还可包含组分(D)光稳定剂和(E)光聚合引发剂,该组合物的特征在于由所述紫外线硬化型涂漆组合物形成的硬化漆膜的努氏硬度为10-18,硬化漆膜交联键间的分子量为150-300。
然而,这些涂漆组合物在进行硬化反应时存在必须采用紫外辐射照射的缺点。
此外,大家都知道,(A)由脂族二异氰酸酯或脂环族二异氰酸酯与数均分子量为500-1500的聚己内酯二醇和/或三醇相反应,然后经除去未反应的脂族二异氰酸酯或脂环族二异氰酸酯后而制得的含双官能和/或三官能端NCO基团的预聚合物和(B)羟基值为10-150毫克KOH/克(以树脂计)、玻璃化转变温度为30-100℃的丙烯酸类多羟基化合物,当NCO/OH当量比为0.5-2.0时已知能形成对丙烯酸类模制品具有优良耐刮性的双—液型聚氨酯漆膜(例如所引述专利4)。然而,这些涂漆组合物由于形成其涂膜是可延伸的,因而漆膜存在发粘的缺点。
[所引述专利1]
Japanese Unexamined Patent Application Laid Open H5-051556
[所引述专利2]
Japanese Unexamined Patent Application Laid Open H5-320562
[所引述专利3]
Japanese Unexamined Patent Application Laid Open2003-277684
[所引述专利4]
Japanese Unexamined Patent Application Laid OpenH11-042746
发明内容
本发明的目的是提供能形成具有优良的耐洗车损伤性、防尘-耐污性和耐候性的漆膜的涂漆组合物以及经涂漆的物品。
通过对上述问题的研究,本发明者业已发现,上述目的可通过采用包含具有特定量的开环ε-己内酯加合物和不泛黄型多异氰酸化合物的丙烯酸类共聚物的涂漆组合物来达到,本发明基于这些研究结果而实现。
这就是说,本发明是一种包含(A)组分和(B)组分的涂漆组合物,其中(A)组分为包含35-50质量%(以树脂的固体级分计)ε-己内酯结构单元的丙烯酸类共聚物(羟值为200-340毫克KOH/克,重均分子量为5000-15000),(B)组分为不泛黄型多异氰酸酯化合物。所形成的清漆组合物的特征在于:组合物中包括每1当量(A)组分的羟基对应0.5-2当量的比例的(B)组分的异氰酸酯基团,由所述涂漆组合物形成的硬化漆膜的杨氏模量不高于1.5帕,固化涂层的交联的分子量(Mc)不高于350克/摩尔,以及硬化漆膜的玻璃化转变温度(Tg)为至少65℃。
此外,本发明提供了用上述清漆组合物涂敷得到的上漆物品。
本发明的油漆组合物可形成具有优良的耐刮性、良好的耐候性及防尘-耐污性的漆膜。
具体实施方式
用于本发明的(A)组分丙烯酸类共聚物优选包含35-50质量%(以树脂的固体级分计)的ε-己内酯结构单元并且其羟值为200-340毫克KOH/克。在这样情况下,当ε-己内酯结构单元含量低于35质量%时,则耐刮性会变差,当ε-己内酯结构单元含量高于50质量%时,则防尘-耐污性和耐候性会变差。此外,如果(A)组分丙烯酸类共聚物的羟值低于200毫克KOH/克,则防尘-耐污性和耐候性会变差,如果羟值超过340毫克KOH/克,则耐刮性与(B)组分不泛黄型多异氰酸酯化合物的相容性会变差。
(A)组分中开环ε-己内酯加成物的含量理想地为37-47质量%,最理想地为39-45质量%。
此外,(A)组分丙烯酸类共聚物的羟值范围优选为220-320毫克KOH/克。
(A)组分丙烯酸类共聚物的重均分子量范围优选为5000-15000,较理想的为7000-13000。当重均分子量低于5000时,则防尘-耐污性和耐候性会变差,当超过15000时,则与(B)组分不泛黄型多异氰酸酯化合物的相容性会变差。
可用于(A)组分丙烯酸类共聚物中的含羟基基团的可自由基聚合的单体的实例包括(甲基)丙烯酸2-羟乙基酯、(甲基)丙烯酸2-羟丙基酯、(甲基)丙烯酸3-羟丙基酯、(甲基)丙烯酸4-羟丁基酯、(甲基)丙烯酸聚乙二醇单酯、(甲基)丙烯酸聚丙二醇单酯、(甲基)丙烯酸新戊二醇单酯以及(甲基)丙烯酸甘油单酯。所用含羟基基团的可自由基聚合的单体可以为单独一种类型,也可以两种或多种类单体混合使用。
可用于(A)组分丙烯酸类共聚物中的其它可共聚合的乙烯基单体的实例包括:(甲基)丙烯酸及它们的烷基取代形式,(甲基)丙烯酸烷基酯(如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁醋、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂基酯以及(甲基)丙烯酸硬脂基酯),二元酸的酯(如衣康酸、马来酸及富马酸的酯),苯乙烯和环取代的苯乙烯(如乙烯基甲苯、二甲基苯乙烯及乙基苯乙 烯),(甲基)丙烯腈,(甲基)丙烯酰胺,醋酸乙烯酯以及氯乙烯。所用该其它可共聚合的乙烯基单体可以为单独一种类型,或可以两种或多种类单体混合使用。
在(A)组分丙烯酸类共聚物中实施ε-己内酯开环加成的方法的实例包括:方法(1)使ε-己内酯与上述含羟基基团的可自由基共聚合的单体经历开环加成,然后可作为己内酯改性的可进行自由基聚合的单体用于共聚合中;方法(2)在共聚合反应期间或反应后,将ε-己内酯开环加成到含羟基基团的可自由基聚合的单体与其它乙烯基单体的共聚物中;方法(3)将ε-己内酯开环加成到二羟甲基链烷酸(如2,2-二羟甲基丁酸)中,然后与含环氧基团的(甲基)丙烯酸单酯(如(甲基)丙烯酸缩水甘油酯)的均聚物进行加成反应,或该(甲基)丙烯酸单酯与其它可共聚合乙烯基单体的共聚物与其进行加成反应。
此外,Praxel FA-1(商品名,由1摩尔ε-己内酯与1摩尔丙烯酸2-羟乙基酯开环加成的单体,Daicel Chemical Industries Co.制造),Praxel FM-1D,Praxel FM-2D,Praxel FM-3和Praxel FM-4(都是商品名,分别为由1、2、3或4摩尔ε-己内酯与1摩尔甲基丙烯酸2-羟乙基酯开环加成的单体,Daicel Chemical Industries Co.制造),都可用作可自由基聚合单体,它们都是可商购作为可自由基聚合单体,其中ε-己内酯已与含羟基基团的甲基丙烯酸酯开环加成。
在由上述单体制备(A)组分丙烯酸类共聚物的共聚反应中通常采用聚合引发剂。聚合引发剂的实例包括基于有机过氧化物的聚合引发剂和偶氮基聚合引发剂。对聚合引发剂的使用量没有特别的限制,但0.5-15质量%(相对于单体的总量)是优选的。
此外,适用于制备本发明(A)组分的有机溶剂的实例包括:脂环烃(如环己烷和乙基环己烷),芳烃溶剂(如甲苯、二甲苯、乙基苯和芳烃油),酮基溶剂(如丙酮、甲乙酮、甲基异丁酮、环己酮和异佛尔酮),酯基溶剂(如乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸3-甲氧基丁酯和己二酸双(2-乙基己酯)),醚基溶剂(如二丁基醚、四氢呋喃、1,4-二烷和1,3,5-三烷),以及含氮溶剂(如乙腈、戊腈、N,N-二甲基甲酰胺和N,N-二乙基甲酰胺)。有机溶剂可以为单独一种类型或可以是包含两种或两种以上类型的混合溶剂。在这种情况下,含羟基基团的树脂的固含量可在不影响树脂分散液稳定性的条件下任意选择,但通常为10-70重量%的固含量。
优选用作本发明(B)组分的不泛黄型多异氰酸酯化合物是脂族和脂环族多异氰酸酯化合物。其典型实例包括六亚甲基二异氰酸酯和/或异佛尔酮二异氰酸酯与多元醇和/或低分子量聚酯多羟基化合物的反应产物,异氰脲酸酯(为六亚甲基二异氰酸酯和/或异佛尔酮二异氰酸酯的聚合物)以及缩二脲化合物(由上述化合物再与氨基甲酸酯键反应得到的)。
此外,这些聚合物中的异氰酸酯基团经具有羟基基团的化合物掩蔽的封端异氰酸酯也是优选采用的。各种不泛黄型多异氰酸酯化合物如除上述以外的二异氰酸酯化合物的聚合物也可采用。所用该不泛黄型多异氰酸酯化合物可以为单独一类,或可以两种或两种以上类型混合使用。
本发明中(A)组分与(B)组分的比例是:每1当量(A)组分的羟基对应0.2-2当量,优选0.5-1.5当量,最理想0.6-1.2当量的(B)组分的异氰酸酯基团。当1当量(A)组分羟基基团所对应的(B)组分异氰酸酯基团的当量低于0.5时,则硬化性能不能令人满意,如果用量超过2当量时,则耐刮性能会下降。
本发明的清漆组合物可根据需要添加有机溶剂和各种添加剂,如紫外线吸收剂,光稳定剂,抗氧化剂,表面活性剂,表面调节剂,硬化反应催化剂,抗静电剂,香料,除水剂以及流变调节剂(如聚乙烯蜡、聚酰胺蜡)以及例如细小的内交联树脂颗粒。
可通过调整上述组分使本发明清漆组合物形成的硬化漆膜的杨氏模量不高于1.5帕,优选0.01-1.2帕,最优选0.1-1.0帕,固化涂膜的交联的分子量(Mc)不高于350克/摩尔,优选300-350克/摩尔,硬化漆膜的玻璃化转变温度(Tg)为至少65℃,优选65-90℃。在那些硬化漆膜的杨氏模量低于0.01帕的情况下,漆膜的防尘-耐污性和 耐候性很差,而在杨氏模量超过1.5帕的那些情况下,耐刮性会变差。此外,在硬化漆膜的交联间的分子量低于300的那些情况下,耐刮性很差,而分子量超过350的情况下,防尘-耐污性和耐候性会变差。此外,在玻璃化转变温度(Tg)低于65℃的情况下,防尘-耐污性和耐候性差,而玻璃化转变温度超过90℃则耐刮性会变差。
本发明中杨氏模量的测定方法是通过采用拉伸试验机(商品名为Tensilon/UTM-III-200,Toyo Baldwin Co.制造)在20℃下以每分钟10%的样品长度伸长率测定分离的漆膜试样得到的曲线算得的。这就是说,在分离的漆膜试样为40毫米的情况下,漆膜以每分钟拉伸4毫米的方式伸长。测得的模量值较大说明较硬。
固化涂膜的交联的分子量(Mc)是通过采用强迫伸缩振动型粘度测定装置(商品名为Rheovibron DDV-II-EA,Toyo Baldwin Co.制造),在110赫兹的振动频率和2℃/分钟的升温速率下,测定分离的漆膜试样在橡胶区域的动态刚性模量所得到的数值,并按下式表示:
Mc=293×ρ/(log10G′-7)
式中Mc为交联间的分子量(克/摩尔),ρ是漆膜的密度(克/立方厘米),G′为橡胶区域的动态刚性模量(E′/3(10-9牛/平方米)),E′为在橡胶区域的动态弹性模量(10-9牛/平方米)。
玻璃化转变温度(Tg)是通过采用强迫伸缩振动型粘度测定装置(商品名为Rheovibron,DDV-II-EA,Toyo Baldwin Co.制造),在110赫兹的振动频率、2℃/分钟的升温速率下,测定分离漆膜试样的Tanδ的最大点数值得到的。
适用于本发明清漆组合物的涂装方法是,例如二涂一烤涂装法,在该方法中,将着色的底涂层涂在基材上,然后将所述清漆组合物以未交联的清漆涂在该底涂层上;或是罩面涂装法,在该方法中将着色的底涂层涂在基材上,然后将未交联清漆涂敷在底涂层上,经烘烤后,其上再涂一层所述清漆组合物作为罩面清漆并烘烤;还有其它一些涂装法,其中在上述罩面涂装法中的清漆层上,涂一层透明底漆以保证与下层透明涂层的粘附性,再将所述清漆组合物作为未交联的罩面清 漆涂在该底漆上。
先根据需要,通过加热或添加有机溶剂或反应性稀释剂将上述着色的底漆、清漆、罩面清漆和透明底漆的粘度调节至指定的要求,然后采用常用类型的涂装器械(如空气喷涂器、静电空气喷涂器、辊涂机、流涂机或浸涂系统)来实施涂装,或者采用刷涂、线绕棒刮涂器或涂膜器进行涂装。这些方法中喷涂是优选的。
此外,其上涂敷本发明清漆组合物的基材的实例包括有机材料和无机材料如木材,玻璃,金属,布料,塑料,泡沫材料,弹性体,纸,陶瓷,混凝土和石膏板。这些基材可以是预先经表面处理过的材料,或者表面上预先已形成有漆膜的材料。
上面已经提出了一些涂装方法的实例,但涂装本发明清漆组合物的方法不仅限于这些方法。
对本发明清漆组合物涂敷的漆膜厚度没有特别的限制,但是,通常干燥后的漆膜厚度优选为10-150微米,更理想为10-100微米。
可采用本发明清漆组合物进行涂敷得到涂敷物品的实例包括:结构,木制品,金属制品,塑料制品,橡胶制品,加工纸,陶瓷制品及玻璃制品。实际上,这类物品包括:汽车,汽车部件(例如车体、保险杠、阻流板、后视镜、车轮、内装饰件及各种材料制的部件),金属板材如钢板,自行车,自行车部件,道路设施(例如护栏、交通信号和消声墙),隧道设施(例如侧壁板材),船舶,铁路车辆,飞机,家具,乐器,家具电器,建筑材料,容器,办公设备,运动器具以及玩具等。
说明性实施例
下面将通过说明性实施例对本发明作更实用性的说明,但本发明不限于这些说明性实施例。此外,由本发明清漆组合物形成的漆膜的性能是通过下述方法测定的。
(1)对汽车清洗机的耐刮性
耐刮性:用刷子将泥浆水(JIS Z-8901-84,以10/99/1的8型尘土/水/中性洗涤剂的混合物)刷涂在试片上,然后用自动汽车清洗机 中的洗车刷以150rpm转速转动洗刷10秒钟,其后用流动水漂洗试片。对以上步骤重复10次,然后用色差计(CR-331,Minolta Camera Co.制造)通过测量L*值来测定试片表面的刮擦程度。所测数值低的为好。
(2)防尘-耐污性
将尘土水(JIS Z-8901-84,以1.3/98/0.5/0.2的8型尘土/水/炭黑/赫黄颜料)涂敷在试片上,然后在50℃下干燥10分钟,经这样八次反复处理后,用抛光布以固定用力清洁漆膜,同时用水冲洗,并用目视评定污斑,按下列标准作出评价:
○:无污斑
△:部分保留沾污物质
×:全部表面上保留有沾污物质
(3)耐候性
采用日光型碳弧灯加速耐候试验机(JIS K-5400(1990)9.8.1)对漆膜照射3000小时,以目视评定漆膜的状况。
制备实施例1和3-6
含羟基基团涂漆的树脂溶液A-1和A-3-A-6的制备
将表1所列组合物中的二甲苯导入装置有温度计、回流冷凝器、搅拌器和滴液漏斗的四颈烧瓶中,同时在氮气流下搅拌并加热,使温度保持在140℃。接着,将表1中所列的组合物的单体混合物和聚合引发剂(滴加的成分)从滴液漏斗于140℃温度下在2小时内匀速滴加。滴完后继续保持140℃温度1小时,然后将反应温度降至110℃。随后加入表1所列组合物的聚合引发剂溶液(辅助催化剂),在110℃保温2小时后,导入表1所列用量的ε-己内酯,于150℃下保温3小时以完成反应,于是制得了含羟基基团油漆的树脂溶液A-1。此外,含羟基基团油漆的树脂溶液A3-A6的制备,除按表1所列加入的原材料数量不同外,A3-A6的制备步骤与A-1相同。
表1
制备实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
含羟基树脂溶液 | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | |
最先导入 | 二甲苯 | 36.8 | 36.6 | 36.7 | 36.7 | 33.0 | 37.3 | 36.4 | 36.2 |
2,2-二羟甲基丁 酸 | - | 16.5 | - | - | - | - | 12.8 | 20.1 | |
单体 | 丙烯酸丁酯 | 2.7 | 3.3 | 11.0 | 8.7 | 2.7 | 2.7 | 1.4 | - |
甲基丙烯酸2-羟 乙酯 | 33.3 | - | 25.0 | 33.3 | 33.3 | 33.3 | - | - | |
甲基丙烯酸缩水 甘油酯 | - | 16.2 | - | - | - | - | 12.8 | 20.1 | |
叔丁基过氧-2-乙 基己酸酯 | 1.2 | 1.4 | 1.2 | 1.2 | 5.0 | 0.7 | 1.5 | 1.5 | |
辅助催化剂 | 叔丁基过氧-2-乙 基己酸酯 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
二甲苯 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
辅助组分 | ε-己内酯 | 24.0 | 24.0 | 24.0 | 18.0 | 24.0 | 24.0 | 33.0 | 33.0 |
二甲苯 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
总计 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | |
树脂的羟值(mgKOH/g) | 240 | 310 | 180 | 240 | 240 | 240 | 240 | 369 | |
非挥发性物质(质量%) | 61 | 61 | 61 | 61 | 65 | 61 | 62 | 62 | |
重均分子量 | 9.100 | 9.300 | 8.900 | 9.000 | 3.200 | 17,10 0 | 9,100 | 9,300 | |
在树脂的固体部分中ε-己内酯含 量(质量%) | 39.3 | 39.3 | 39.3 | 29.5 | 36.9 | 39.3 | 53.2 | 32.3 |
制备实施例2、7和8
含羟基基团涂漆的树脂溶液A-2、A-7和A-8的制备
将表1所列组合物中的二甲苯和2,2-二羟甲基丁酸导入装置有温度计、回流冷凝器、搅拌器和滴液漏斗的四颈烧瓶中,同时在氮气 流下搅拌并加热,使温度保持在140℃。接着,将表1中所列组合物的单体混合物和聚合引发剂(滴加的组分)从滴液漏斗在140℃温度下在2小时内匀速滴加。滴完后继续在140℃温度下保温1小时,然后将反应温度降至110℃。随后加入表1所列组合物的聚合引发剂溶液(辅助催化剂),在110℃保温2小时后,导入表1所列的ε-己内酯,于150℃下保温3小时以完成反应,于是制得了含羟基基团涂漆的树脂溶液A-2、A-7和A-8。
制备实施例9-20
清漆CC-1-CC-12的制备
依次将表2和表3中原材料进行混合并搅拌以得到均匀的混合物,制成清漆。
表2
制备实施例 | 9 | 10 | 11 | 12 | |
清漆 | CC-1 | CC-2 | CC-3 | CC-4 | |
含羟基基团的丙烯酸类树脂 | A-1 | 35.4 | - | 44.2 | 25.0 |
A-2 | - | 30.7 | - | - | |
A-3 | - | - | - | - | |
A-4 | - | - | - | - | |
A-5 | - | - | - | - | |
A-6 | - | - | - | - | |
A-7 | - | - | - | - | |
A-8 | - | - | - | - | |
交联剂(Sumidure HT-1) | 29.3 | 33.1 | 22.0 | 37.3 | |
紫外光吸收剂溶液2) | 1.5 | 1.5 | 1.5 | 1.5 | |
光稳定剂溶液3) | 1 | 1 | 1 | 1 | |
表面调节剂溶液4) | 0.4 | 0.4 | 0.4 | 0.43 | |
Solvesso 1005) | 32.4 | 33.3 | 30.9 | 34.8 | |
总计 | 100.0 | 100.0 | 100.0 | 100.0 | |
(B)组分的NCO基团与(A)组分的羟基基团的 当量比 | 1.0 | 1.0 | 0.6 | 1.8 |
表3
制备实施例 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | |
清漆 | CC-5 | CC-6 | CC-7 | CC-8 | CC-9 | CC-10 | CC-11 | CC-12 | |
含羟基基团的丙烯酸类 树脂 | A-1 | - | - | - | - | - | - | 54.7 | 20.0 |
A-2 | - | - | - | - | - | - | - | - | |
A-3 | 40.0 | - | - | - | - | - | - | - | |
A-4 | - | 35.4 | - | - | - | - | - | - | |
A-5 | - | - | 35.4 | - | - | - | - | - | |
A-6 | - | - | - | 35.4 | - | - | - | - | |
A-7 | - | - | - | - | 35.3 | - | - | - | |
A-8 | - | - | - | - | - | 28.6 | - | - | |
交联剂HT 1) | 24.8 | 29.3 | 29.3 | 29.3 | 29.5 | 34.8 | 13.6 | 41.4 | |
紫外光吸收剂溶液2) | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | |
光稳定剂溶液3) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
表面调节剂溶液4) | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | |
Solvesso 1005) | 32.3 | 32.4 | 32.4 | 32.4 | 32.3 | 33.7 | 28.8 | 35.7 | |
总计 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | |
(B)组分的NCO基团与(A) 组分的羟基基团的当量比 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 0.3 | 2.5 |
上表的附注
1)Sumidure HT:商品名,液态HDI的缩二脲型树脂(不挥发馏分75质量%,NCO含量为13质量%),由Sumika Beyer Urethane Co.制造
2)Tinuvin 900:商品名,20质量%二甲苯溶液,Ciba SpecialtyChemicals Co.制造
3)Tinuvin 292:商品名,20质量%二甲苯溶液,Ciba SpecialtyChemicals Co.制造
4)BYK-300:商品名,10质量%二甲苯溶液,Bikkukemi Co.制造
5)Solvesso 100:商品名,芳烃油,Esso Co.制造
实施例1-4
试样的制备和漆膜性能的研究
将阳离子电沉积漆Aqua No.4200(商品名,BASF Coatings JapanCo.制造)以电沉积法涂敷在经磷酸锌处理过的中碳钢板上,使经175℃烘烤25分钟后的干膜厚度为20微米,然后以空气喷涂法涂敷中间涂层漆HS-H300(商品名,BASF Coatings Japan Co.制造),使经140℃烘烤30分钟后的干膜厚度为30微米。然后,用空气喷涂法涂敷溶剂基底漆Belcoat No.6000黑(商品名,BASF Coatings Japan Co.制造,涂漆颜色:黑),以使干膜厚度为15微米,在20℃下固定3分钟后,用Sorbesso 100(商品名,Esso Co.制造,芳烃油)将清漆CC-1或CC-2稀释至涂敷粘度(No.4 Ford杯,20℃下25秒),用具有湿碰湿体系的空气喷涂法进行涂敷使干膜厚度为40微米,并经140℃烘烤30分钟制得试样。
然而,实施例1-实施例4的耐污试验的试片中以Belcoat No.6000白(商品名,BASF Coatings Japan Co.制造,涂漆颜色:白)代替底漆。
漆膜性能列于表4中,在所有情况中都没有产生涂漆浊度,得到的漆膜具有均匀光泽,这些漆膜具有优良的耐洗车损伤性、耐污性和耐候性。
对照实施例1-8
试样的制备和漆膜性能的研究
除清漆是CC-5-CC-12外,其余按照与实施例1相同的方法制备试样。漆膜性能列于表5中,对照实施例1、3和5的耐污性和耐候性较差,而对照实施例2的耐洗车损伤性很差。此外,对照实施例4和6中A和B组分的相容性很差。
此外,在异氰酸酯含量低的对照实施例7中,防尘-耐污性和耐候性很差,异氰酸酯含量过量的对照实施例8中,耐刮性降低。
表4
实施例1 | 实施例2 | 实施例3 | 实施例4 | ||
清漆 | CC-1 | CC-2 | CC-3 | CC-4 | |
(B)组分的NCO基团与(A)组分的羟基基团的当 量比 | 1.0 | 1.0 | 0.6 | 1.8 | |
树脂的羟值(mgKOH/g) | 240 | 310 | 240 | 240 | |
ε-己内酯含量(质量%) | 39 | 39 | 39 | 39 | |
(A)组分重均分子量 | 9100 | 9300 | 9100 | 9100 | |
A组分与B组分的相容性 | ○ | ○ | ○ | ○ | |
硬化的漆膜性能 | 杨氏膜量 | 0.43 | 0.5 | 0.3 | 1.3 |
固化漆膜的交联的分子量 | 316 | 311 | 340 | 320 | |
漆膜Tg | 66.2 | 76.2 | 66 | 75 | |
对汽车清洗机的耐刮擦性 | 0.2 | 0.8 | 0.3 | 1.2 | |
防尘-耐污性 | ○ | ○ | ○ | ○ | |
耐候性 | 正常 | 正常 | 正常 | 正常 |
表5
对照实施例 1 | 对照实施例 2 | 对照实施例 3 | 对照实施例 4 | 对照实施例 5 | 对照实施例 6 | 对照实施例 7 | 对照实施例 8 | ||
清漆 | CC-5 | CC-6 | CC-7 | CC-8 | CC-9 | CC-10 | CC-11 | CC-12 | |
(B)组分的NCO基团与(A)组分的羟基 基团的当量比 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 0.3 | 2.5 |
树脂的羟值(mgKOH/g) | 180 | 240 | 240 | 240 | 240 | 350 | 240 | 240 | |
ε-己内酯含量(质量%) | 39 | 30 | 37 | 39 | 53 | 32 | 39 | 39 | |
(A)组分重均分子量 | 8900 | 9000 | 3200 | 17100 | 9100 | 9300 | 9100 | 9100 | |
A组分与B组分的相容性 | ○ | ○ | ○ | × | ○ | × | ○ | ○ | |
硬化的漆 膜性能 | 杨氏模量 | 0.45 | 7.5 | 0.43 | - | 0.32 | - | 0.1 | 2 |
固化漆膜的交联的分子量 | 389 | 313 | 335 | - | 346 | - | 400 | 370 | |
漆膜Tg | 60.1 | 68.5 | 62.3 | - | 58.6 | - | 55 | 95 | |
对汽车清洗机的耐刮擦性 | 0.2 | 7.5 | 0.1 | - | 0.1 | - | 1.3 | 8 | |
防尘-耐污性 | × | ○ | × | - | × | - | × | ○ | |
耐候性 | 水斑 | 正常 | 水斑 | - | 水斑 | - | 水斑 | 正常 |
工业应用前景
本发明的清漆组合物可用于各种领域中,具体地说,可用作车辆如汽车、摩托车用涂漆。
Claims (2)
1.一种包含(A)组分和(B)组分的清漆组合物,其中(A)组分为包含以树脂的固体级分计35-50质量%的ε-己内酯结构单元的丙烯酸类共聚物,该丙烯酸类共聚物的羟值为200-340毫克KOH/克和重均分子量为5000-15000,(B)组分为不泛黄型多异氰酸酯化合物,该组合物的特征在于:组合物中包括每1当量(A)组分的羟基对应0.5-2当量的比例的(B)组分的异氰酸酯基团,由所述漆组合物形成的硬化漆膜的杨氏模量不高于1.5帕,固化漆膜的交联的分子量(Mc)不高于350克/摩尔,以及硬化的漆膜的玻璃化转变温度(Tg)为至少65℃。
2.用权利要求1公开的漆组合物涂漆得到的上漆物品。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP202990/2005 | 2005-07-12 | ||
JP2005202990A JP5279984B2 (ja) | 2005-07-12 | 2005-07-12 | 塗料組成物及び塗装物品 |
PCT/IB2006/001853 WO2007007146A2 (en) | 2005-07-12 | 2006-07-03 | Paint compositions and painted objects |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101218316A CN101218316A (zh) | 2008-07-09 |
CN101218316B true CN101218316B (zh) | 2011-03-09 |
Family
ID=36954825
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2006800253418A Active CN101218316B (zh) | 2005-07-12 | 2006-07-03 | 涂漆组合物及上漆物品 |
Country Status (8)
Country | Link |
---|---|
US (1) | US8536274B2 (zh) |
EP (1) | EP1907493B1 (zh) |
JP (1) | JP5279984B2 (zh) |
KR (1) | KR101284204B1 (zh) |
CN (1) | CN101218316B (zh) |
AT (1) | ATE472581T1 (zh) |
DE (1) | DE602006015196D1 (zh) |
WO (1) | WO2007007146A2 (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5362324B2 (ja) * | 2008-10-31 | 2013-12-11 | 日産自動車株式会社 | 塗料組成物、塗装仕上げ方法及び塗装物品 |
ITMI20100440A1 (it) * | 2010-03-18 | 2011-09-19 | Dow Global Technologies Inc | Processo per la preparazione di poliuretani rinforzati con fibre lunghe che contengono riempitivi particolati |
EP2495292B1 (de) * | 2011-03-04 | 2013-07-24 | FFT EDAG Produktionssysteme GmbH & Co. KG | Fügeflächenvorbehandlungsvorrichtung und Fügeflächenvorbehandlungsverfahren |
US9190039B2 (en) * | 2013-03-14 | 2015-11-17 | D'addario & Company, Inc. | Radiation curable drumhead membrane |
DE102013219060A1 (de) * | 2013-09-23 | 2015-03-26 | Lankwitzer Lackfabrik Gmbh | Verkehrsmittel mit elastifiziertem Lack |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1542068A (zh) * | 2003-03-28 | 2004-11-03 | ������������ʽ���� | 涂膜的形成方法 |
CN1572856A (zh) * | 2003-05-20 | 2005-02-02 | 拜尔材料科学股份公司 | 用于抗划伤面漆的高固含量粘合剂组合物 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06220397A (ja) * | 1993-01-25 | 1994-08-09 | Mazda Motor Corp | 二液型ウレタン塗料組成物 |
JP3329049B2 (ja) * | 1994-01-24 | 2002-09-30 | 日本油脂ビーエーエスエフコーティングス株式会社 | 自動車用上塗塗料のクリヤーコート用熱硬化被覆組成物 |
US6436531B1 (en) * | 1998-07-20 | 2002-08-20 | 3M Innovative Properties Company | Polymer blends and tapes therefrom |
US6652971B1 (en) * | 2000-10-30 | 2003-11-25 | E. I. Du Pont De Nemours And Company | Hydroxy-functional (meth)acrylic copolymers and coating composition |
US6894124B2 (en) * | 2000-11-01 | 2005-05-17 | Kansai Paint Co., Ltd. | High solid paint compositions |
US6605669B2 (en) * | 2001-04-03 | 2003-08-12 | E. I. Du Pont De Nemours And Company | Radiation-curable coating compounds |
JP2003119410A (ja) | 2001-10-10 | 2003-04-23 | Kansai Paint Co Ltd | 塗料組成物及びそれを用いた塗膜形成方法 |
JP2003181368A (ja) * | 2001-12-13 | 2003-07-02 | Kansai Paint Co Ltd | 複層塗膜形成方法 |
WO2003080745A1 (fr) * | 2002-03-22 | 2003-10-02 | Basf Nof Coatings Co., Ltd. | Composition de revetement pouvant etre sechee sous uv et articles revetus |
JP2003313493A (ja) * | 2002-04-23 | 2003-11-06 | Nippon Yushi Basf Coatings Kk | 上塗り塗料組成物、塗装仕上げ方法及び塗装物品 |
AU2003276847A1 (en) * | 2002-08-09 | 2004-02-25 | Carnegie Mellon University | Polymers, supersoft elastomers and methods for preparing the same |
JP2004256679A (ja) * | 2003-02-26 | 2004-09-16 | Dainippon Ink & Chem Inc | ウレタン系塗料およびウレタン系塗料用硬化剤組成物 |
JP4259278B2 (ja) * | 2003-10-27 | 2009-04-30 | Basfコーティングスジャパン株式会社 | 熱硬化性塗料組成物 |
US7288290B2 (en) * | 2004-05-26 | 2007-10-30 | Ppg Industries Ohio, Inc. | Process for applying multi-component composite coatings to substrates to provide sound damping and print-through resistance |
-
2005
- 2005-07-12 JP JP2005202990A patent/JP5279984B2/ja not_active Expired - Fee Related
-
2006
- 2006-07-03 AT AT06779826T patent/ATE472581T1/de not_active IP Right Cessation
- 2006-07-03 DE DE602006015196T patent/DE602006015196D1/de active Active
- 2006-07-03 US US11/995,405 patent/US8536274B2/en not_active Expired - Fee Related
- 2006-07-03 CN CN2006800253418A patent/CN101218316B/zh active Active
- 2006-07-03 WO PCT/IB2006/001853 patent/WO2007007146A2/en not_active Application Discontinuation
- 2006-07-03 EP EP06779826A patent/EP1907493B1/en not_active Not-in-force
- 2006-07-03 KR KR1020077030582A patent/KR101284204B1/ko not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1542068A (zh) * | 2003-03-28 | 2004-11-03 | ������������ʽ���� | 涂膜的形成方法 |
CN1572856A (zh) * | 2003-05-20 | 2005-02-02 | 拜尔材料科学股份公司 | 用于抗划伤面漆的高固含量粘合剂组合物 |
Also Published As
Publication number | Publication date |
---|---|
EP1907493A2 (en) | 2008-04-09 |
DE602006015196D1 (de) | 2010-08-12 |
JP2007023069A (ja) | 2007-02-01 |
ATE472581T1 (de) | 2010-07-15 |
KR101284204B1 (ko) | 2013-07-09 |
WO2007007146A2 (en) | 2007-01-18 |
US20080227915A1 (en) | 2008-09-18 |
US8536274B2 (en) | 2013-09-17 |
JP5279984B2 (ja) | 2013-09-04 |
WO2007007146A3 (en) | 2007-05-18 |
CN101218316A (zh) | 2008-07-09 |
KR20080027796A (ko) | 2008-03-28 |
EP1907493B1 (en) | 2010-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4368395B2 (ja) | 塗料組成物、塗装仕上げ方法及び塗装物品 | |
CN101218316B (zh) | 涂漆组合物及上漆物品 | |
US5985463A (en) | Coating containing hydroxy containing acrylosilane polymer to improve mar and acid etch resistance | |
JP4894190B2 (ja) | 塗料組成物、塗装仕上げ方法及び塗装物品 | |
JP2006517251A (ja) | 耐擦傷性および耐酸エッチング性を改善するためのアクリロシランポリマーを含むコーティング | |
KR19990008255A (ko) | 내스크래치성 코팅 조성물 | |
JP5362324B2 (ja) | 塗料組成物、塗装仕上げ方法及び塗装物品 | |
JP4595639B2 (ja) | 塗料組成物、塗装仕上げ方法及び塗装物品 | |
JP4961727B2 (ja) | 塗料組成物、塗装仕上げ方法及び塗装物品 | |
US20080107904A1 (en) | Hydroxyl-Containing Resin Composition for Coating Materials, Coating Composition, Coating Finishing Method, and Coated Article | |
JP2020516734A (ja) | 構造化表面を作製するコーティング材料 | |
MXPA00011525A (en) | Coating containing hydroxy containing acrylosilane polymer to improve mar and acid etch resistance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |