CN1048033C - 可用环状碳酸酯固化的涂层组合物 - Google Patents
可用环状碳酸酯固化的涂层组合物 Download PDFInfo
- Publication number
- CN1048033C CN1048033C CN94119559A CN94119559A CN1048033C CN 1048033 C CN1048033 C CN 1048033C CN 94119559 A CN94119559 A CN 94119559A CN 94119559 A CN94119559 A CN 94119559A CN 1048033 C CN1048033 C CN 1048033C
- Authority
- CN
- China
- Prior art keywords
- resin
- coating composition
- primary amine
- epoxy
- weight
- 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.)
- Expired - Fee Related
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 38
- 125000004122 cyclic group Chemical group 0.000 title description 2
- 239000011347 resin Substances 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 75
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 150000005676 cyclic carbonates Chemical group 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 11
- 239000012736 aqueous medium Substances 0.000 claims abstract description 8
- 239000004593 Epoxy Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 235000013824 polyphenols Nutrition 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 239000002609 medium Substances 0.000 claims 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 16
- 150000003141 primary amines Chemical group 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- -1 vibrin Polymers 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000004070 electrodeposition Methods 0.000 description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000002118 epoxides Chemical group 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 150000003335 secondary amines Chemical group 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical group CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-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
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 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
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 description 1
- LHXNVCCLDTYJGT-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)propan-2-ol Chemical compound CC(O)COCC1CO1 LHXNVCCLDTYJGT-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- LDMZRDUOPRQABF-UHFFFAOYSA-N C(C1CO1)OCCCC1=CC=C(C=C1)CC Chemical compound C(C1CO1)OCCCC1=CC=C(C=C1)CC LDMZRDUOPRQABF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- XVEUJTIZHZIHJM-UHFFFAOYSA-N a828782 Chemical compound CCOC(N)=O.CCOC(N)=O XVEUJTIZHZIHJM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion 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
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 125000003367 polycyclic group Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004383 yellowing 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
- C09D5/4496—Cathodic paints characterised by the nature of the curing agents
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4453—Polyepoxides characterised by the nature of the curing agent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
- Polyesters Or Polycarbonates (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
描述了一种涂层组合物，该组合物在水相介质中包含：
A)一种具有许多伯胺基团的树脂和，
B)一种具有许多环状碳酸酯基团的固化剂。
Description
本发明总的来说涉及涂层组合物，尤其涉及适于阴极电沉积的组合物。
现在工业上广泛使用电沉积涂层组合物及电沉积方法。在电沉积过程中，通过如下方法将带离子电荷的较低分子量的树脂沉积到导体基材上：将基材浸入分散有带电荷树脂的电涂浴中，在基材和相反电荷的一极(通常为盛装电涂浴液的容器壁)之间施加电压。这样就在基材上产生较柔软的低分子量树脂的涂层。该涂层一般经过使树脂固化或交联而转变成坚硬的高分子量涂层。
一种固化机理是在可电沉积的涂层组合物中使用密胺甲醛树脂固化剂，使之与被电沉积树脂上的羟官能基反应。这一固化方法可在较低温度(例如132℃)下获得良好固化，但交联键含有不希望有的醚键，所得涂层的全面耐腐蚀性差，且片状和环状腐蚀(chip andcyclic corrosion)及片状和环状耐腐蚀性差。
为了解决密胺交联的电涂层的某些问题，许多用户使用聚异氰酸酯交联剂与被电沉积树脂上的羟官能基反应。这一固化方法可获得预期的氨基甲酸乙酯交联键，但仍然带来几种不利。为了防止可电沉积涂层组合物的早期胶凝，必须封阻固化剂中的高度反应性的异氰酸酯基团(如用肟或醇)。然而被封阻的聚异氰酸酯要求在高温(例如150℃或更高)下解封阻，从而开始固化反应。所得电涂层还可能易于泛黄。此外，在固化过程中释放的挥发性封阻剂对各种涂层性能具有不利影响，并增加VOC。因此对于可电沉积涂层组合物需要一种能得到预期氨基甲酸乙酯交联键，但又避免伴随封阻的聚异氰酸酯固化剂的使用所产生的问题的技术。此外，因为用于羟官能树脂的密胺和聚异氰酸酯固化剂还被用于许多电涂层以外的涂层组合物中，而且仍然带来同样缺点，因此整个涂层领域也有此需要。
本发明的目的是提供一种适于阴极电沉积的组合物，该组合物无需密胺交联就可以固化且不会随后将挥发性有机化合物释放到环境中。
业已发现可用在水相介质中包含如下成分的涂层组合物得到含有预期氨基甲酸乙酯交联键的耐久性涂层：
A)一种具有许多伯胺基的树脂，和
B)一种具有许多环状碳酸酯基团的固化剂。
当树脂(A)中的伯胺基为用酸盐化的阳离子伯胺基团时，该涂层组合物尤其可用于阴极电沉积。
含伯胺基的树脂(A)可以是本领域公知的许多树脂中的任一种。许多此类已知树脂包括环氧树脂，丙烯酸系树脂，聚酯树脂，聚醚树脂，聚氨酯树脂，聚酰胺树脂，聚丁二烯树脂和酚醛树脂。
在一个优选实施方案中，该树脂为环氧树脂，亦称作聚环氧化物树脂或聚缩水甘油醚。该优选的聚缩水甘油醚为双酚A及相似多元酚的聚缩水甘油醚。有用的环氧树脂的重均分子量(按GPC测定)可为3000-6000。环氧当量可为500-1900，优选870-1200。环氧树脂可通过，例如在碱存在下用表卤代醇(如表氯醇)醚化多元酚而制备。
氨基可通过多元酚的聚缩水甘油醚与含伯胺的多元胺的反应而引入。反应时胺应过量，以得到胺端基树脂。在一个优选实施方案中，缩水甘油醚上的环氧基团与含一个仲胺基团和至少一个，优选两个被酮亚胺封阻的潜在伯胺基团的化合物反应。本发明所用的树脂优选具有的伯胺当量为300-3000，更优选8501300。使某些反应性环氧基团与改性物质，如多元醇或多元羧酸反应也是有利的，这样可改善膜性能。
丙烯酸系聚合物在本领域是众所周知的，可由单体如丙烯酸甲酯，丙烯酸，甲基丙烯酸，甲基丙烯酸甲酯，甲基丙烯酸丁酯，甲基丙烯酸环己基酯等制备。还可以使用取代的丙烯酸酯和甲基丙烯酸酯，如丙烯酸羟乙酯，丙烯酸羟丁酯，丙烯酸2-乙基己酯和丙烯酸正丁酯。也可将可共聚的烯属不饱和共聚单体如苯乙烯引入聚合物中。可通过含氨基丙烯酸系单体(如甲基丙烯酰胺或丙烯酰胺)的共聚将伯氨基团引入丙烯酸系聚合物中。
聚酯也可用作本发明组合物中的树脂。此类聚酯在本领域是众知的，且可通过用含伯或仲羟基的有机多元醇(例如乙二醇，丁二醇，新戊二醇)对有机多元羧酸(例如邻苯二甲酸，六氢化邻苯二甲酸，己二酸，马来酸)或它们的酐进行多元酯化而制备。伯氨基团可通过羧酸官能基聚酯与过量1摩尔的伯胺预聚体反应而引入聚酯中。
聚氨酯可在本发明中用作树脂。在本领域中聚氨酯是众知的，通过聚异氰酸酯和多元醇的反应而制备。有用的聚异氰酸酯的实例包括六亚甲基二异氰酸酯，甲苯二异氰酸酯，MDI，异佛尔酮二异氰酸酯及这些二异氰酸酯的缩二脲和三异氰脲酸盐。有用的多元醇的实例包括低分子量脂族多元醇，聚酯多元醇，聚醚多元醇，脂肪族醇等。伯胺基团可通过用过量的含伯胺的多胺或用含有一个仲胺基团和至少一个用酮亚胺封阻的潜在伯胺基团的化合物使聚氨酯封端而引入聚氨酯中。
聚醚可在本发明中用作树脂。有用聚醚的实例是以环氧丙烷和/或聚氧乙烯为基础的聚醚。正如本领域所公知的，这些聚醚可制成端基为环氧或伯胺基，从而引入双酚A基的环氧树脂中。
环氧改性的线型酚醛可在本发明中用作树脂。环氧线型酚醛可用一种含有一个仲胺基团和至少一个用酮亚胺封阻的伯胺基团的化合物封端。
聚丁二烯，聚异戊二烯，或其他环氧改性的橡胶基聚合物可在本发明中用作树脂。可用一种含有一个仲胺基团和至少一个用酮亚胺封阻的潜在伯胺基团的化合物对环氧橡胶封端。
在上述任一树脂上包含其他官能基团(如羟基)是有利的。这些官能基团可用作与任选的辅助交联剂如氨基塑料树脂反应的反应部位。引入此类基团的技术在本领域是众知的。
在一个优选实施方案中，伯胺基团用诸如乙酸，乳酸或柠檬酸之类的酸成盐。这对要求树脂的水溶性或分散性的水相涂层组合物来说是特别有用的。它对阴极电涂组合物也特别有用，在该组合物中，树脂必须带有阳电荷，以使之电沉积到电沉积池的阴极上。
本发明的涂层组合物还包括组分(B)，该组分为带有许多环状碳酸酯基团的固化剂。组分(B)化合物可用下式表示：
其中R代表有机基团，n为2-8，优选2-6，更优选3-4。
可用作组分(B)的化合物很容易通过聚环氧化物与二氧化碳反应而把环氧基团转变成环状碳酸酯基团而制备。聚环氧化物在本领域是众知的。可用于制备组分(B)化合物的聚环氧化物可以是三环氧化物。该三环氧化物可以为三元醇与表卤代醇的反应产物，例如已通过与表卤代醇反应而环氧化的三羟甲基丙烷。聚环氧化物还包括环氧线型酚醛。还可以使用聚环氧化物低聚体或聚合物，如含有甲基丙烯酸缩水甘油酯或环氧基封端的聚缩水甘油醚的丙烯酸系聚合物或低聚体。还可以使用其他聚环氧化物，如环氧线型酚醛。与其他聚环氧化物一样，环氧线型酚醛可与二氧化碳反应而形成环状碳酸酯交联剂。
也可以使用官能度大于3的环状碳酸酯。例如，在诸如异佛尔酮二异氰酸酯的二异氰酸酯上的异氰酸酯基团可与诸如三羟甲基丙烷的多元醇加合而产生四官能醇，可用表卤代醇使该四官能醇环氧化而得到四官能聚环氧化物，而该聚环氧化物再与二氧化碳反应形成四官能环状碳酸酯。其他高官能度聚环氧化物，如四(4-缩水甘油氧基苯基)乙烷也可与CO2反应形成聚环状碳酸酯。
在本发明的涂层组合物中可任意使用一种溶剂。尽管本发明的组合物可以以基本为固体粉末或分散体的形式使用，但通常希望该组合物基本为液体状态，该液体状态可通过使用溶剂而达到。该溶剂应同时是伯胺官能聚合物(A)和组分(B)的溶剂。一般来说，取决于组分(A)和(B)的溶解特性，溶剂可以是任何有机溶剂和/或水。本发明组合物中溶剂的量为约0.01％(重量)-约99％(重量)，优选约10％(重量)-约60％(重量)，更优选为约30％(重量)-约50％(重量)。有用溶剂的实例包括甲基乙基酮，甲基异丁基酮，乙酸正戊酯，乙二醇丁醚乙酸酯，丙二醇单甲醚乙酸酯，二甲苯，N-甲基吡咯烷酮，或芳香烃混合物。在另一个优选实施方案中，溶剂为水或水与少量水相共溶剂的混合物。
涂层组合物可以用本领域公知的许多技术中的任一种而涂覆在制品上。这些技术包括喷涂，浸涂，辊涂，幕涂等。对汽车主板优选喷涂。
在一个优选实施方案中，本发明的涂层组合物处于水相介质中，且树脂组分(A)上的胺基被酸化成盐，从而赋予树脂水分散性。此种组合物对阴极电沉积特别有用，因为树脂的电沉积除去了树脂伯胺基团上的阳电荷，从而使它们能与固化剂(B)上的环状碳酸酯基团反应。
如果希望在非电涂应用中使用本发明的水相涂层组合物，则优选通过引入阴离子或非离子基团而使树脂对水稳定，因为使伯氨基成盐将降低它们与环状碳酸酯基团的反应性。然而此类体系可能具有太高的反应性，需要以双组分(即2K)涂层组合物的形式使用。另一方面，通过使用反应改性剂，如丙二醇甲醚乙酸酯，有可能使用单组分水相涂层组合物。
对在阴极电沉积中使用的水可分散树脂的中和程度应足以防止未成盐氨基与组分(B)上的环状碳酸酯基团的早期反应，以免给涂层浴的性能带来不利影响(一般至少为80％，更优选90-100％)。
为了提高各种膜性能，通常以乳液形式使用水可分散的树脂，在乳液中，水可分散树脂构成连续相，而任选的不具有可带电荷的亲水基团的水不溶性树脂(如环氧丙烯酸酯树脂)构成分散相。
将可电沉积的涂层组合物分散在水相介质中。在本发明范围内使用的术语“分散体”被认为是两相透明或不透明的水相树脂体系，其中树脂为分散相，水为连续相。树脂相的平均粒径为约0.1-10微米，优选小于5微米。树脂产品在水相介质中的浓度一般并无严格要求，但一般来说水分散体的大部分为水。水分散体通常含有约3-50％，优选10-40％(重量)固体树脂。待用水进一步稀释的水相树脂浓缩物一般总固体为10-30％(重量)。
将以上组分均匀分散于含有酸的水相介质中，酸的含量足以中和足量胺基而赋予树脂水分散性。有用酸的实例包括磷酸，乙酸，丙酸，柠檬酸和乳酸。
除水之外，电涂组合物的水相介质还可含有一种聚结溶剂。有用的聚结溶剂包括烃类，醇类，酯类，醚类和酮类。优选的聚结溶剂包括醇类，多元醇类和酮类。具体的聚结溶剂包括乙二醇单丁基和单己基醚，及丙烯的苯基醚，乙二醇乙基溶纤剂，丙基溶纤剂，丁基溶纤剂，乙二醇二甲醚或双丙酮醇。还可将少量和水不混溶的有机溶剂如二甲苯，甲苯，甲基异丁基酮或2-乙基己醇加入水和与水混溶的有机溶剂的混合物中。聚结溶剂的量并无严格限制，以固体树脂总重量计，一般为约0-15％(重量)，优选约0.5-5％(重量)。
电沉积涂层组合物可进一步含有常规颜料，如二氧化钛，氧化铁，炭黑，硅酸铝，沉淀硫酸钡，磷钼酸铝，铬酸锶，碱性硅酸铅或铬酸铅。颜料对树脂的重量比很重要，优选小于50∶100，更优选小于40∶100，一般为约20-40∶100。还发现，较高的颜料/固体树脂重量比对聚结和流动不利。
电沉积涂层组合物可含有任选的成分，如润湿剂，表面活性剂，消泡剂，抗氧化剂，紫外线吸收剂，光稳定剂等。表面活性剂和润湿剂的实例包括烷基咪唑啉，如可从Ciba-Geigy IndustrialChemicals以Amine C购得的烷基咪唑啉，可从Air Productsand Chemicals以Surfynol104购得的炔醇。存在这些任选的成分时，它们占树脂固体的约0-20％(重量)。增塑剂是任选的成分，因为它们能促进流动。实例是高沸点、与水不混溶的物质，如壬基酚或双酚A的环氧乙烷或环氧丙烷加合物。可以使用增塑剂，且如果使用的话，其含量一般为树脂固体的约0-15％(重量)。
一般来说，要加入足量的水以使分散体的固体含量大于20％(重量)，优选大于30％(重量)。
电沉积涂层组合物的电导率为0.1-5毫西门子/厘米(mS/cm)，优选0.5-3mS/cm。当该值太低时，难以得到具有预期保护功能和其他功能的膜厚。相反，如果组合物导电性太好，可能会引起基材或反电极在浴中的溶解、膜厚不均匀或耐水性或耐腐蚀性差等问题。
电沉积涂层组合物可通过电沉积涂覆方法以10-25％(重量)的不挥发含量和15-35毫米的干燥膜厚涂覆到导电基材上。涂覆完成后，可在室温或高温下固化涂层，这取决于具体的碱性树脂的性质。
本发明的涂层制剂的电沉积可以用本领域熟练者公知的许多方法中的任一种进行。沉积在所有导电基材上进行，例如在金属如钢，铜，铝等上。
可将着色的树脂涂层及任选的一透明涂层施于包括电涂底层的底层上。在汽车应用中，着色的树脂层常称为底层或着色底层。着色的树脂层中的树脂可以是本领域公知的许多树脂。例如，树脂可以是丙烯酸系树脂，聚氨酯树脂，或聚酯树脂。典型的着色树脂涂层制剂在美国专利4791168，4414357和4546046中有描述，这些公开结合入本文作参考。在一个优选实施方案中，如美国专利4720528所述，树脂为ε-己内酯改性的丙烯酸系树脂，该公开结合入本文作参考。着色树脂可用任一种已知机理和固化剂固化，如密胺多元醇反应(例如，羟官能丙烯酸系树脂的密胺固化)。
用于此类复合涂层的其他着色底层组合物在本领域是已知的，在这里不需作详细说明。在本领域已知的、在底层组合物中有用的聚合物包括丙烯酸系聚合物，乙烯基聚合物，聚氨酯，聚碳酸酯，聚酯，醇酸树脂和聚硅氧烷。优选聚合物包括丙烯酸系聚合物和聚氨酯。底层聚合物优选是可交联的，因此含有一种或多种可交联官能基团。此类基团包括，例如羟基，异氰酸酯，胺，环氧，丙烯酸酯，乙烯基，硅烷和乙酰乙酸酯基团。这些基团可被掩蔽或封阻，以使它们在预期固化条件下(一般为高温)解封阻并能参与交联反应。有用的可交联官能基团包括羟基，环氧，酸，酐，硅烷和乙酰乙酸酯基团。优选的可交联官能基团包括羟官能基和氨官能基。
底层聚合物可以是自交联的，或需要单独的交联剂，该交联剂可与聚合物的官能基团反应。例如，当聚合物含羟官能基团时，交联剂可以是氨基塑料树脂，异氰酸酯和封阻的异氰酸酯(包括异氰脲酸酯)，及酸或酐官能交联剂。
制品用上述涂层涂覆后，对组合物进行处理以使涂覆层固化。尽管可使用包括在室温条件下固化在内的多种固化方法，但热固化是优选的，因为它具有附加的好处，如从涂层组合物中驱除残留水或溶剂。一般来说，热固化通过使被涂制品暴露于高温而进行，而高温一般是由辐射热源提供的。固化温度随交联剂中使用的具体封阻基团而改变，但通常为90-200℃，优选121-162℃，最优选121-141℃。固化时间随使用的具体组分，物理参数(如涂层厚度)而改变，但一般固化时间为15-60分钟。
本发明由下列实施例进一步描述。制备1-伯胺官能树脂
将1504重量份(4摩尔)双酚A二缩水甘油醚，684份(3摩尔)双酚A和243份二甲苯加到5升四颈圆底烧瓶中。将混合物加热到130℃，加入2.2份三苯基膦。然后将反应加热到150℃并保持90分钟。加入308份二甲苯和154份乙二醇单丁醚，使反应冷却到100℃。然后加入571.5份二亚乙基三胺的二酮亚胺(4.5当量氮)和37.6份甲基乙醇胺(0.5摩尔)。然后将温度在110℃保持1小时。氮的毫克当量(Meq)为1.36Meq N/g固体树脂，胺当量为735g/当量氮。制备2-颜料研磨树脂
将下列物质加到一个12升烧瓶中：2125g双酚A的二缩水甘油醚，644g双酚A，370g十二烷基苯酚和162g二甲苯。将混合物加热到1250℃，加入3.1g三苯基膦。反应温度升到130℃，并维持3小时。通过加入795g乙二醇单丁醚和1907g丙二醇缩水甘油醚使反应冷却。剩余的环氧通过加入218g 2-氨基乙氧基乙醇和173g二甲氨基丙胺而封端。温度在110℃保持4小时。然后将温度降至70℃，加入164g乙酸和1439g去离子水。在一个单独容器中，用6000g去离子水稀释得到的树脂。制备3-颜料研磨糊
将下列物质加到合适容器中：10700g研磨树脂，325g炭黑，542g二丁基氧化锡，379g硅酸铅，1625g粘土，8504g二氧化钛和2574g去离子水。在高剪切下混合这些成分，然后碾碎。然后用2000g去离子水稀释该糊。制备4-碳酸酯交联剂
将500g三羟甲基丙烷三缩水甘油醚溶于200g异丁醇中，加入10g四正丁基溴化铵催化剂。混合物加热到100℃，使二氧化碳的稳定气流鼓泡通过反应混合物。用红外光谱和环氧化物滴定同时检测反应程度。当反应进行到大于95％(按滴定测定)时，使气流停止。这样得到三(环状碳酸酯)交联剂。制备5-碳酸酯交联剂
将500g三羟甲基丙烷三缩水甘油醚溶于200g异丁醇中，加入10g四正丁基溴化铵催化剂。混合物加热到100℃，用稳定的二氧化碳气流清洗反应器。10-20分钟后，封闭该体系，并导入二氧化碳气体直到压力为130磅/平方英寸。在整个反应期间保持该压力。用红外光谱和环氧化物滴定同时检测反应程度。当反应进行到大于98％(按滴定测定)时，冷却该体系，并使之达到大气压力。这样得到三(环状碳酸酯)交联剂。实施例1-2
用15.3重量份乙酸中和264重量份制备1得到的胺官能树脂。然后加入55重量份制备4(实施例1)或制备5(实施例2)的碳酸酯交联剂和21份聚环氧丙烷与对甲苯酚的加合物并使之混合。此外，加入2份聚乙烯烷基醚和1份非离子表面活性剂消泡剂。将这种成盐的树脂混合物保持在高搅拌下，同时慢慢加入577份去离子水以完成乳化。乳液的pH值为6.0，粒径为162nm。
将343份这种乳液和106份去离子水混合，然后加入52份来自制备3的颜料糊制得一电涂浴。该浴固体为20％。pH值为6.67，电导率为4670μS。
将一块试验钢板浸入电涂浴中，施加电流电沉积15μm涂层。在110℃下固化该涂层30分钟，得到坚硬的耐久电涂底层。
本发明已参照其具体实施方案而得到详细描述。应当理解，在本发明的要旨和范围内可作修改和变更。
Claims (13)
1.一种涂层组合物，其特征在于它在一种介质中包含：
A)一种具有许多伯胺基团的树脂，和
B)一种具有许多环状碳酸酯基团的固化剂。
2.根据权利要求1的一种涂层组合物，其特征在于树脂(A)为环氧树脂。
3.根据权利要求1的一种涂层组合物，其特征在于树脂(A)为下列两种物质的反应产物：
a)一种聚环氧化物树脂和
b)一种含有一个仲胺基团和至少一个被酮亚胺封阻的潜在伯胺基团的化合物。
4.根据权利要求3的一种涂层组合物，其特征在于聚环氧化物树脂为多元酚的聚缩水甘油醚。
5.根据权利要求3的一种涂层组合物，其特征在于化合物(b)具有一个仲胺基团和两个被酮亚胺封阻的潜在伯胺基团。
6.根据权利要求2的一种涂层组合物，其特征在于环氧树脂的环氧当量为500-1900。
7.根据权利要求3或4的一种涂层组合物，其特征在于聚环氧化物树脂的环氧当量为500-1900。
8.根据权利要求1，2，3，4，5或6的一种涂层组合物，其特征在于树脂(A)的伯胺当量为300-3000。
9.根据权利要求1，2，3，4，5或6的一种涂层组合物，其特征在于固化剂(B)为聚环氧化物与二氧化碳的反应产物。
10.根据权利要求9的一种涂层组合物，其特征在于聚环氧化物为三环氧化物。
11.根据权利要求10的一种涂层组合物，其特征在于三环氧化物为三元醇与表卤代醇的反应产物。
12.根据权利要求1，2，3，4，5或6的一种涂层组合物，其特征在于介质为水相介质。
13.根据权利要求1，2，3，4，5或6的一种涂层组合物，其特征在于树脂(A)上的伯胺基团为用酸盐化的阳离子伯胺基团。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17132093A | 1993-12-21 | 1993-12-21 | |
| US171,320 | 1993-12-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1127284A CN1127284A (zh) | 1996-07-24 |
| CN1048033C true CN1048033C (zh) | 2000-01-05 |
Family
ID=22623318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94119559A Expired - Fee Related CN1048033C (zh) | 1993-12-21 | 1994-12-21 | 可用环状碳酸酯固化的涂层组合物 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5856382A (zh) |
| EP (1) | EP0661355B2 (zh) |
| JP (1) | JP3604434B2 (zh) |
| KR (1) | KR100333114B1 (zh) |
| CN (1) | CN1048033C (zh) |
| AT (1) | ATE177463T1 (zh) |
| AU (1) | AU691210B2 (zh) |
| BR (1) | BR9405205A (zh) |
| CA (1) | CA2138637C (zh) |
| DE (1) | DE69416984T3 (zh) |
| ES (1) | ES2131623T5 (zh) |
| GR (1) | GR3030427T3 (zh) |
| MX (1) | MX197341B (zh) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5431791A (en) * | 1993-12-21 | 1995-07-11 | Basf Corporation | Cathodic electrodeposition method utilizing cyclic carbonate-curable coating composition |
| DE19504947C2 (de) * | 1994-06-20 | 2003-07-03 | Bollig & Kemper Gmbh & Co Kg | Mehrschichtlackierung |
| DE19530225C1 (de) * | 1995-08-17 | 1996-06-13 | Herberts Gmbh | Einbrennüberzugsmittel und Verwendung desselben |
| US5902473A (en) * | 1997-06-30 | 1999-05-11 | Basf Corporation | Cathodic electrodeposition coating with carbamate-functional crosslinking agents |
| DE19746379A1 (de) | 1997-10-21 | 1999-04-22 | Bayer Ag | Einbrennüberzugsmittel und seine Verwendung |
| DE19843835A1 (de) * | 1998-09-24 | 2000-03-30 | Herberts Gmbh | Wäßrige Beschichtungsmittel auf Epoxid/Amin-Basis und ihre Verwendung bei Mehrschichtlackierungen |
| US6048443A (en) * | 1998-12-21 | 2000-04-11 | Basf Corporation | Low bake cathodic electrocoat having dual cure mechanism |
| AT409633B (de) * | 1999-01-18 | 2002-09-25 | Solutia Austria Gmbh | Bindemittel für ''soft-feel''-lacke |
| US6916877B2 (en) * | 2000-06-16 | 2005-07-12 | Basf Corporation | Coating composition including a water-based copolymer cross-linking with a water-dispersible cross-linking agent, method of preparing the same, and a cured film thereof |
| US6881791B2 (en) * | 2000-06-16 | 2005-04-19 | Basf Corporation | Poly-electrolyte free block copolymers and their use in crosslinking coatings applications |
| US6699943B2 (en) | 2000-06-16 | 2004-03-02 | Basf Corporation | Water-based coating composition having carbamate-melamine cross-linking, method of preparing the same, and a cured film thereof |
| DE10029803A1 (de) | 2000-06-16 | 2002-01-03 | Basf Coatings Ag | Copolymerisate und Copolymerisatdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung |
| US6607646B2 (en) | 2001-09-12 | 2003-08-19 | E. I. Du Pont De Nemours And Company | Cathodic electrocoating compositions containing hydroxyl-carbonate blocked polyisocyanate crosslinking agent |
| US7049387B2 (en) | 2001-10-16 | 2006-05-23 | Georgia-Pacific Resins, Inc. | Cure accelerator system for phenolic resins |
| US20040192876A1 (en) * | 2002-11-18 | 2004-09-30 | Nigel Hacker | Novolac polymer planarization films with high temparature stability |
| EP1649322A4 (en) * | 2003-07-17 | 2007-09-19 | Honeywell Int Inc | PLANARIZATION FILMS FOR ADVANCED MICRO-ELECTRONIC APPLICATIONS AND EQUIPMENT AND METHOD FOR THE PRODUCTION THEREOF |
| DE102007012229A1 (de) * | 2007-03-12 | 2008-09-18 | Basf Se | Verfahren zur Herstellung von Produkten |
| EP2397474A1 (de) * | 2010-06-17 | 2011-12-21 | Construction Research & Technology GmbH | 2-Oxo-1,3-dioxolan-4-carbonsäureester, ihre Herstellung und Verwendung |
| US20140256874A1 (en) | 2013-03-05 | 2014-09-11 | Ppg Industries Ohio, Inc. | Curable solid particulate compositions |
| CN103333323B (zh) * | 2013-06-13 | 2015-09-02 | 武汉市科达云石护理材料有限公司 | 高韧性高活性环氧树脂固化剂及其制备方法 |
| CN103952058A (zh) * | 2014-04-16 | 2014-07-30 | 广德县中银化工有限责任公司 | 一种电泳涂料 |
| US10501572B2 (en) | 2015-12-22 | 2019-12-10 | Carbon, Inc. | Cyclic ester dual cure resins for additive manufacturing |
| WO2017156132A1 (en) * | 2016-03-08 | 2017-09-14 | 3D Systems, Incorporated | Non-isocyanate polyurethane inks for 3d printing |
| CN108424536A (zh) * | 2018-01-27 | 2018-08-21 | 嘉兴立新材料有限公司 | 一种改性环氧树脂材料的制备方法 |
| CN108485194A (zh) * | 2018-01-27 | 2018-09-04 | 嘉兴立新材料有限公司 | 一种改性环氧树脂材料 |
| CN108485196A (zh) * | 2018-01-27 | 2018-09-04 | 嘉兴立新材料有限公司 | 一种环氧树脂浇注材料的制备方法 |
| CN108546389A (zh) * | 2018-01-27 | 2018-09-18 | 嘉兴立新材料有限公司 | 一种改性环氧树脂体系 |
| CN108485201A (zh) * | 2018-01-27 | 2018-09-04 | 嘉兴立新材料有限公司 | 一种改性环氧树脂复合材料的制备方法 |
| CN108485197A (zh) * | 2018-01-27 | 2018-09-04 | 嘉兴立新材料有限公司 | 一种改性环氧树脂体系的制备方法 |
| CN108440908A (zh) * | 2018-01-27 | 2018-08-24 | 嘉兴立新材料有限公司 | 一种环氧树脂浇注材料 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0120466A1 (de) * | 1983-03-30 | 1984-10-03 | BASF Lacke + Farben AG | Hitzehärtbare Überzugsmittel und deren Verwendung |
| EP0149156A2 (en) * | 1983-12-16 | 1985-07-24 | Ppg Industries, Inc. | A novel process of curing compositions with the reaction product of polyprimary amines and organic carbonates |
| US4588783A (en) * | 1983-12-16 | 1986-05-13 | Ppg Industries, Inc. | Amide-containing polyhydroxyethyl carbamates |
| US5132458A (en) * | 1987-08-08 | 1992-07-21 | Hoechst Ag | Curable compounds |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923842A (en) * | 1974-06-28 | 1975-12-02 | Phillips Petroleum Co | Preparation of oxirane compound from the corresponding olefin via the cyclic carbonate ester |
| US4122069A (en) * | 1977-04-11 | 1978-10-24 | Texaco Development Corporation | Polyether dihydroxyalkyl carbamate epoxy additive for epoxy resins |
| JPS59155470A (ja) * | 1983-02-23 | 1984-09-04 | Kansai Paint Co Ltd | 熱硬化性塗料用樹脂組成物 |
| JPS60105607A (ja) * | 1983-11-02 | 1985-06-11 | G C Dental Ind Corp | 低粉塵性粉末状歯科用アルギン酸塩印象材 |
| US4484994A (en) * | 1984-02-17 | 1984-11-27 | American Cyanamid Company | Hydroxyalkyl carbamate-containing resins for cathodic electrodeposition and method of making the same |
| JPS6136319A (ja) * | 1984-07-30 | 1986-02-21 | Kansai Paint Co Ltd | 熱硬化性樹脂塗料用硬化剤、その製造方法及びその塗装方法 |
| DE3529263A1 (de) * | 1985-08-16 | 1987-02-19 | Hoechst Ag | Verfahren zur herstellung von 2-oxo-1,3-dioxolanen |
| US4746447A (en) * | 1986-01-10 | 1988-05-24 | Chevron Research Company | Carbonate treated hydrocarbyl-substituted polyamines |
| DE3624454A1 (de) * | 1986-02-13 | 1987-08-20 | Hoechst Ag | Aminourethane, verfahren zu ihrer herstellung und ihre verwendung |
| DE3644370A1 (de) * | 1986-12-24 | 1988-07-07 | Hoechst Ag | Aminourethane, verfahren zu ihrer herstellung aus polyaminen und ihre verwendung |
| DE3644373A1 (de) * | 1986-12-24 | 1988-07-07 | Hoechst Ag | Aminogruppenhaltige polymerisate, ihre herstellung und ihre verwendung |
| DE3711947A1 (de) * | 1987-04-09 | 1988-10-20 | Hoechst Ag | Haertungskomponente fuer kunstharze und deren verwendung |
| US5001210A (en) * | 1988-09-30 | 1991-03-19 | Medtronic, Inc. | Method for producing polyurethanes from poly-(hydroxyalkyl urethanes) |
| US5202383A (en) * | 1991-07-19 | 1993-04-13 | Ppg Industries, Inc. | High throw power electrodeposition system |
| US5431791A (en) * | 1993-12-21 | 1995-07-11 | Basf Corporation | Cathodic electrodeposition method utilizing cyclic carbonate-curable coating composition |
-
1994
- 1994-12-16 EP EP94119908A patent/EP0661355B2/en not_active Expired - Lifetime
- 1994-12-16 AT AT94119908T patent/ATE177463T1/de not_active IP Right Cessation
- 1994-12-16 DE DE69416984T patent/DE69416984T3/de not_active Expired - Fee Related
- 1994-12-16 ES ES94119908T patent/ES2131623T5/es not_active Expired - Lifetime
- 1994-12-20 CA CA002138637A patent/CA2138637C/en not_active Expired - Fee Related
- 1994-12-21 BR BR9405205A patent/BR9405205A/pt not_active IP Right Cessation
- 1994-12-21 KR KR1019940035529A patent/KR100333114B1/ko not_active Expired - Fee Related
- 1994-12-21 AU AU81659/94A patent/AU691210B2/en not_active Ceased
- 1994-12-21 JP JP31882494A patent/JP3604434B2/ja not_active Expired - Fee Related
- 1994-12-21 CN CN94119559A patent/CN1048033C/zh not_active Expired - Fee Related
-
1995
- 1995-01-02 MX MX9500113A patent/MX197341B/es unknown
-
1996
- 1996-10-03 US US08/725,692 patent/US5856382A/en not_active Expired - Fee Related
-
1999
- 1999-06-04 GR GR990401511T patent/GR3030427T3/el unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0120466A1 (de) * | 1983-03-30 | 1984-10-03 | BASF Lacke + Farben AG | Hitzehärtbare Überzugsmittel und deren Verwendung |
| EP0149156A2 (en) * | 1983-12-16 | 1985-07-24 | Ppg Industries, Inc. | A novel process of curing compositions with the reaction product of polyprimary amines and organic carbonates |
| US4588783A (en) * | 1983-12-16 | 1986-05-13 | Ppg Industries, Inc. | Amide-containing polyhydroxyethyl carbamates |
| US5132458A (en) * | 1987-08-08 | 1992-07-21 | Hoechst Ag | Curable compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69416984D1 (de) | 1999-04-15 |
| GR3030427T3 (en) | 1999-09-30 |
| DE69416984T2 (de) | 1999-10-28 |
| EP0661355A1 (en) | 1995-07-05 |
| AU691210B2 (en) | 1998-05-14 |
| MX197341B (es) | 2000-07-05 |
| ES2131623T3 (es) | 1999-08-01 |
| AU8165994A (en) | 1995-06-29 |
| ES2131623T5 (es) | 2006-08-01 |
| JP3604434B2 (ja) | 2004-12-22 |
| EP0661355B2 (en) | 2006-01-25 |
| CA2138637C (en) | 2004-03-09 |
| EP0661355B1 (en) | 1999-03-10 |
| BR9405205A (pt) | 1995-08-08 |
| CN1127284A (zh) | 1996-07-24 |
| US5856382A (en) | 1999-01-05 |
| CA2138637A1 (en) | 1995-06-22 |
| KR100333114B1 (ko) | 2002-11-30 |
| JPH07252441A (ja) | 1995-10-03 |
| DE69416984T3 (de) | 2007-06-21 |
| KR950018337A (ko) | 1995-07-22 |
| ATE177463T1 (de) | 1999-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1048033C (zh) | 可用环状碳酸酯固化的涂层组合物 | |
| KR100368477B1 (ko) | 하나이상의폴리에테르세그먼트및다수의환형카르보네이트를사용한캐쏘드전착방법과이방법에사용하기위한조성물 | |
| CN1374991A (zh) | 有改良外观、改良边角遮盖力和减少焊缝的阴极电涂组合物 | |
| US4686249A (en) | Heat-hardenable binder mixture of amino resin and hydroxy epoxides | |
| EP0612818B1 (en) | Electrodeposition coating composition comprising crosslinked microparticles | |
| CN1048043C (zh) | 利用环碳酸酯可固化的涂料组合物的阴极电沉积方法 | |
| EP0576943B1 (en) | Process for coating a metal substrate | |
| KR20010101313A (ko) | 음극 전기피복 코팅 조성물 | |
| DE3741161A1 (de) | Hitzehaertbares waessriges ueberzugsmittel fuer die kathodische elektrotauchlackierung | |
| CA2099602C (en) | Polyol extended cathodic electrodeposition resins | |
| CN1045269A (zh) | 用酸质子化后可用水稀释的聚合反应产物 | |
| JPS6141274B2 (zh) | ||
| JPH1143630A (ja) | カチオン型電着塗料組成物 | |
| JPH10265720A (ja) | 電着塗料組成物及び電着塗料組成物の製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20000105 Termination date: 20101221 |