CN1154392A - 粉末涂料 - Google Patents
粉末涂料 Download PDFInfo
- Publication number
- CN1154392A CN1154392A CN96122025.2A CN96122025A CN1154392A CN 1154392 A CN1154392 A CN 1154392A CN 96122025 A CN96122025 A CN 96122025A CN 1154392 A CN1154392 A CN 1154392A
- Authority
- CN
- China
- Prior art keywords
- acid
- glycidyl ester
- formula
- methyl
- paint compositions
- 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.)
- Granted
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- 239000000843 powder Substances 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title abstract description 33
- 239000011248 coating agent Substances 0.000 title abstract description 30
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 20
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 36
- 239000003973 paint Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- -1 glycidyl ester Chemical class 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003351 stiffener Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- WKJICCKTDQDONB-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCC1OC1 WKJICCKTDQDONB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- XIEXCYRSJCCMDZ-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)-2-oxoacetic acid Chemical compound OC(=O)C(=O)OCC1CO1 XIEXCYRSJCCMDZ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 7
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 239000008199 coating composition Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000004848 polyfunctional curative Substances 0.000 abstract description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 229920005646 polycarboxylate Polymers 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QNAJAJLBHMMOJB-UHFFFAOYSA-N oxiran-2-ylmethyl propanoate Chemical compound CCC(=O)OCC1CO1 QNAJAJLBHMMOJB-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000037452 priming Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- JEBXNNPMFYXVHS-UHFFFAOYSA-N cyclohexane-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1C(O)=O JEBXNNPMFYXVHS-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000113 methacrylic resin Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-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
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002987 primer (paints) Substances 0.000 description 2
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 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 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LINJIWJIUXFXHS-UHFFFAOYSA-N 2-ethylhexyl but-2-enoate Chemical compound CCCCC(CC)COC(=O)C=CC LINJIWJIUXFXHS-UHFFFAOYSA-N 0.000 description 1
- AILDTIZEPVHXBF-UHFFFAOYSA-N Argentine Natural products C1C(C2)C3=CC=CC(=O)N3CC1CN2C(=O)N1CC(C=2N(C(=O)C=CC=2)C2)CC2C1 AILDTIZEPVHXBF-UHFFFAOYSA-N 0.000 description 1
- PGVOAQFJGQYAIR-UHFFFAOYSA-N C(C1CO1)OC(C1(C(C(=O)O)CC(CC1)C)C)=O Chemical compound C(C1CO1)OC(C1(C(C(=O)O)CC(CC1)C)C)=O PGVOAQFJGQYAIR-UHFFFAOYSA-N 0.000 description 1
- HCBGKRRZBJSDAA-UHFFFAOYSA-N C(C1CO1)OC(C1C(C(=O)O)(CCCC1)C)=O Chemical compound C(C1CO1)OC(C1C(C(=O)O)(CCCC1)C)=O HCBGKRRZBJSDAA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000016594 Potentilla anserina Nutrition 0.000 description 1
- 244000308495 Potentilla anserina Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006208 butylation Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PWYYERNADDIMJR-UHFFFAOYSA-N pentyl but-2-enoate Chemical compound CCCCCOC(=O)C=CC PWYYERNADDIMJR-UHFFFAOYSA-N 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000035935 pregnancy 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
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/934—Powdered coating composition
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Charge And Discharge Circuits For Batteries Or The Like (AREA)
Abstract
粉末涂料组合物，该组合物包含一种或多种具有自由羧基的聚(甲基)丙烯酸树脂作为基料，和一种或多种分子量至多为1500的环氧树脂作为上述聚(甲基)丙烯酸树脂的硬化剂，其中该环氧树脂包含至少70％(重量)的选自脂族和环脂族多羧酸多缩水甘油酯的缩水甘油酯。所述粉末涂料甚至在低温下施用时仍具有特别良好的流动性。
Description
本发明涉及粉末涂料组合物，该组合物是基于具有自由羧基的固体聚(甲基)丙烯酸树脂，即基于通过聚合含丙烯酸单体和/或甲基丙烯酸单体的一些单体而得到的树脂，此外，还涉及该组合物作为汽车用漆的应用。
每当希望使用这种高耐候性和高硬度的粉末涂料组合物，而用其它通常用于粉末涂料的基料体系例如聚酯又不能达到时，常使用基于聚(甲基)丙烯酸树脂的粉末涂料组合物。含有特定连续羧基的聚(甲基)丙烯酸树脂，通常例如以粉末涂料用的基料在市场上销售，该树脂主要是用异氰脲酸三缩水甘油酯固化，且所生产的粉末涂料具有下文所援引的特性(Johnson Wax Speciality Chem-icals Product Application Bulletin，Powder Coatings)。然而，这类粉末涂料只能在高于160℃的温度下使用，因为在低于上述温度下它们的流动性很差，导致产生显著的桔皮效应。虽然它们的耐候性较好，但是却不适于制备汽车用漆，因为在这种情况下，为了不致在涂覆于其上的末道涂料组合物的硬化过程中使底漆的涂层受到有害的影响，该涂料组合物要求在最高140-150℃的温度下固化。
本发明通过提供特制的基于聚(甲基)丙烯酸树脂的粉末涂料，提出了解决上述问题的方法，该粉末涂料在140-150℃的温度下硬化迅速而完全，甚至在这样的较低温度下仍然具有良好的流动性以及优良的耐候性。这是通过使用分子量低于1500的环氧树脂作为基于具有自由羧基的聚(甲基)丙烯酸树脂的粉末涂料的硬化剂而实现的，该环氧树脂含有至少70％(重量)的脂族和/或环脂族的多羧酸多缩水甘油酯。
因此，本发明涉及一种粉末涂料组合物，该组合物包括一种或多种具有自由羧基的聚(甲基)丙烯酸树脂作为基料，以及一种或多种分子量至多为1500的环氧树脂作为聚(甲基)丙烯酸树脂的硬化剂，在该粉末涂料组合物中，环氧树脂含有至少70％(重量)的选自脂族和环脂族多羧酸多缩水甘油酯的缩水甘油酯。
除了它们极好的流动性之外，本发明的粉末涂料组合物在室温或适度的较高温度例如10-40℃下还具有良好的可贮存性，因此，它们也具有良好的反应性/稳定性比率。
具有自由羧基的聚(甲基)丙烯酸树脂可以通过共聚丙烯酸单体和/或甲基丙烯酸单体得到，这些单体是例如，C1-C12(甲基)丙烯酸烷基酯，通常是(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸(2-乙基己基)酯、(甲基)丙烯酸癸酯以及(甲基)丙烯酸十二酯，C1-C4(甲基)丙烯酸烷基酯是优选的，或具有丙烯酸和/或甲基丙烯酸的(甲基)丙烯酰胺，和任选其它另外的乙烯属不饱和共聚单体，通常是乙烯基芳族类，例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯或也可是β-卤化苯乙烯。所述共聚可以根据已知的方法进行，例如通过将单体溶于适宜的有机溶剂中，并在可溶于溶剂的适宜引发剂例如过氧化二枯基以及适宜的链转移反应剂例如巯基乙酸(溶液聚合)的存在下加热使其反应，或通过将单体混合物与有机溶剂中的引发剂在水中一起进行悬浮聚合，或也可以通过用表面活性剂例如十二烷基硫酸钠将该单体混合物在水中乳化，并在水溶性的聚合引发剂例如K2S2O8(乳液聚合)存在下使其反应。然后将制得的呈固体形式的聚(甲基)丙烯酸树脂与溶剂或水分离。例如根据JP-A-SHo53-140395中所述，该反应也可以不采用溶剂或水进行。适宜的聚(甲基)丙烯酸树脂在室温(15-25℃)下是固体的。它们通常具有的分子量为1000-50000(中等分子量Mw)，优选5000-20000。采用DSC(加热速率：10℃/min)测定的聚(甲基)丙烯酸树脂的Tg值(玻璃化温度)优选为40-75℃。该树脂的酸值(以每克聚(甲基)丙烯酸树脂KOH的毫克当量表示)优选为30-160，更优选35-80。
脂族多羧酸多缩水甘油酯优选的是含有2-50个碳原子、特别优选2-20个碳原子的脂族多羧酸多缩水甘油酯，除了羧基之外，它也可以含其它的官能团。适宜的脂族多羧酸的典型实例是草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、或癸二酸。适用于本发明的硬化剂是下式(I)给出的脂族多缩水甘油酯，式中，X1、X2、X3、X4、X5和X6各自相互独立地为氢原子、C1-C4烷基或下式(II)给出的基团，式(II)中的A是含2-4个碳原子的亚烷基，优选乙烯基，Y是氢原子或甲基：式(I)的多缩水甘油酯是在EP-A-0 506 617中特别公开的。具体的实例是缩水甘油基丙酮-1，1，3，3-四丙酸酯和缩水甘油基戊酮-(3)-2，2，4，4-四丙酸酯。
优选的脂族多羧酸多缩水甘油酯是草酸二缩水甘油酯、琥珀酸二缩水甘油酯、己二酸二缩水甘油酯、癸二酸二缩水甘油酯以及壬二酸二缩水甘油酯。
在本说明书中，环脂族多羧酸多缩水甘油酯通常可理解为是基于含一个或多个环脂族环的碳主链、且不含C-C重键或属于芳基的多羧酸多缩水甘油酯。单独的环脂族环可以含一种或多种取代基，通常是C1-C6烷基、氯代、溴代或羟基取代基且优选含5-10个碳原子。如果多羧酸含两个或多个环脂族环，那么这些环可以是稠合的或通过适宜的原子团连接，特别是通过直链或支链的具有例如1-30个碳原子的2-6价脂族基团连接，这些基团也可以含一个或多个杂原子，通常是硫原子、氮原子或优选氧原子，以及一些取代基例如氯代、溴代或羟基取代基。这类连接基的典型实例是下式的连接基
式中，Q是优选含2-15个碳原子且不含C-C双键的2-6价有机基团。适用于本发明的环脂族多羧酸多缩水甘油酯的具体实例是六氢化邻苯二甲酸二缩水甘油酯、六氢化间苯二酸二缩水甘油酯、六氢化对苯二酸二缩水甘油酯、甲基六氢化邻苯二甲酸二缩水甘油酯、2，5-二甲基六氢化邻苯二甲酸二缩水甘油酯、桥亚甲基六氢化邻苯二甲酸二缩水甘油酯、1，8-，2，3-和2，6-十氢化萘二羧酸二缩水甘油酯、环己烷三羧酸三缩水甘油酯，例如六氢化半苯六甲酸三缩水甘油酯或优选六氢化苯三酸三缩水甘油酯以及六氢化偏苯三酸三缩水甘油酯、六氢化苯偏四甲酸四缩水甘油酯(环己烷-1，2，3，4-四羧酸)或六氢化均苯四酸四缩水甘油酯(环己烷-1，2，4，5-四羧酸)。环己烷多羧酸多缩水甘油酯，例如1，2，4-或1，3，5-环己烷三羧酸三缩水甘油酯，也可以通过例如常规的方法由相应的环己烷多羧酸与环氧氯丙烷反应而得到。在市场上不能买到的情况下，环己烷多羧酸可以例如根据US-A-3 444 237通过水合相应的苯多甲酸制备。
在DE-A-23 19 815和EP-A-0 506 617中公开的环脂族多缩水甘油酯也非常适用于本发明的粉末涂料。它们具有下式(III)，式中n是2-9、优选2-3的整数，X1、X2、X3和X4各自相互独立地为氢原子、C1-C4烷基或上述式(II)的基团：这种类型的化合物的说明性实例是环戊酮-2，2，5，5-四(丙酸缩水甘油酯)、环己酮-2，2，6，6-四(丙酸缩水甘油酯)或环辛酮-2，2-二(丙酸缩水甘油酯)。
其它适用于本发明的环脂族多缩水甘油酯是下式给出的二缩水甘油酯，它们也公开在EP-A-0 506 617中，式中X7是含2-30个碳原子的m价的脂族或环脂族基团，其碳链可以被一个或多个杂原子，通常是氮原子、硫原子或优选氧原子间断，且是未取代的或取代的，可以特别含羟基、氯代或溴代取代基，其中m是2-6的整数，X8和X9各自独立地为氢、氯或溴原子、C1-C4烷基或X8或X9中的一个是下式(V)给出的基团，另一个具有上述意义之一：
X7优选的是由含有2-10个碳原子的脂族多元醇衍生的二-四价基团，它们通常可以从乙二醇、甘油、三羟甲基丙烷或双(三羟甲基丙烷)低聚，或通过从聚醚多元醇中除去2-4个羟基，或是具有以下分子结构的二-四价、优选二价的基团
其中，X10和X11各自独立地为氢原子、C1-C4烷基或环己基。X10和X11特别优选氢原子或甲基。特别优选的这种结构的化合物具有式(G-CH2)3C-C2H5、(G-CH2)2C(C2H5)-CH2-O-CH2-(C2H5)C(CH2-G)2、(G-CH2)2CH(OH)以及G-(C6H4)-C(CH3)2-(C6H4)-G，其中，在所有情况下G相当于式(VI)的基团，而X8是氢原子或上式(V)的基团：
含六氢化对苯二酸二缩水甘油酯、1，2，4-环己烷三羧酸三缩水甘油酯(六氢化偏苯三酸三缩水甘油酯)、1，3，5-环己烷三羧酸三缩水甘油酯(六氢化苯三酸三缩水甘油酯)或上式(III)或(IV)的多缩水甘油基化合物的粉末涂料是优选的。
本发明的粉末涂料当然也可以包括一些脂族和/或环脂族多羧酸多缩水甘油酯的混合物。然而，这种新型的粉末涂料组合物也可以另外含其它固体和/或液体的环氧树脂化合物，如果它们的量不超过所述粉末涂料组合物中环氧树脂总量的30％(重量)的话。这也特别适用于EP-A-0 506 617和EP-A-0 536 085中公开的环氧树脂化合物，该两说明书中所述的环氧树脂化合物可以认为是本说明的成分，且据称是作为基于酸性聚酯和含芳基的粉末涂料的硬化剂，特别是作为其中所述的在分子中含芳基的多缩水甘油酯的硬化剂，例如用于芳族多羧酸多缩水甘油酯，如邻苯二甲酸二缩水甘油酯、间苯二酸二缩水甘油酯或对苯二酸二缩水甘油酯或用于苯三酸三缩水甘油酯或偏苯三酸三缩水甘油酯的硬化剂。
然而，本发明粉末涂料的特别有利的实施方案是，其中环氧树脂仅仅是选自脂族和环脂族多羧酸多缩水甘油酯的缩水甘油酯的组合物。
在室温(10-25℃)下是液体的环氧树脂优选呈固体混合相(固溶体)的形式使用，如EP-A-0 536 085中所述，该固体混合相是由室温下是固体的液体环氧树脂形成的。
本发明的粉末涂料组合物优选环氧树脂的含量能使聚(甲基)丙烯酸树脂的羧基与环氧树脂基团之比为0.5∶1至2∶1。
本发明的粉末涂料也可以另外含其它常用于涂料工业中的改性剂，通常是光稳定剂、固化促进剂、染料、颜料(例如二氧化钛颜料)、除气剂(例如苯偶姻)和/或流动性控制剂。适宜的流动性控制剂通常是聚乙烯醇缩醛类例如聚乙烯醇缩丁醛、聚乙二醇、聚乙烯基吡咯烷酮、甘油、丙烯酸共聚物(例如，可按商标Modaflow或Acrylron买到的)。如EP-A-0 462 053所公开，如果不必利用上述固溶体的形成使液体环氧树脂固化，则本发明的粉末涂料也可以含由脲或蜜胺和甲醛组成的固态胶体缩聚物。
本发明的粉末涂料可以采用在球磨机中将各组分简便地混合进行制备。另一种更优选的合适的方法包括将各组分在一起熔融、混合和均化，优选在挤出机例如Buss Ko-捏和机中进行，然后将产物冷却和粉碎。该粉末涂料组合物优选具有的粒度为0.015-500μm，更优选10-75μm。在某些情况下，有利的方法是，首先用一部分基料、环氧树脂和任选的其它组分制备母料，然后在第二个步骤中将其与其余的基料和其余的组分混合和均化，以制成粉末涂料组合物成品。
在涂覆到被涂覆的物件上之后，使该粉末涂料在不低于约100℃、优选120-140℃的温度下硬化。通常，硬化约需5-60分钟。适于涂覆的材料是在固化所需的温度下稳定的所有材料，特别是陶瓷材料和金属。衬底上可以事先涂覆了一种或多种与该粉末涂料相容的底漆涂层。
本发明的组合物优选的应用领域是汽车用漆，它是作为最顶层喷涂在首先涂覆到汽车上的一种或多种底漆的涂层之上。因此，本发明还涉及上述粉末涂料组合物作为汽车用漆的应用。
实施例：
具有下列成分的单体混合物：
-甲基丙烯酸(MAA) 15
-苯乙烯(St) 15
-甲基丙烯酸甲酯(MMA) 30
-甲基丙烯酸丁酯(BuMA) 40
-过氧化二枯基(引发剂) 1.5
-巯基乙酸(链转移剂) 1.75
被给入由下列成分组成的反应剂装料中：
-甲苯 30毫升
-过氧化二枯基(引发剂) 1.5克
-巯基乙酸(链转移剂) 1.75克在EP-A-0 697 440的实施例1中作了详细说明。如该实施例中所述，进一步加工导致生成甲基丙烯酸树脂A。
下表中援引的粉末涂料组合物(其量以克计)是在挤出机(实验室用挤出机，由PRISM，The Old Stables，England供应)中于60-80℃的温度下均化的。将冷却后的挤出物研磨到具有粒度为约40μm的成品粉末涂料。将每种粉末涂料组合物静电喷涂在预涂了银色金属底漆(VWL 97A BASF)的铝板上，该底漆涂层为40μm。粉末涂料的涂层厚度如表中所示。该涂料的重要特性也示于下表中。
表
(1)：羧基官能团的丙烯酸树脂，由SC Johnson Wax供应；酸值：75mg KOH/g物质；ICI熔融粘度：在200℃下为6000MPas；分子量(中等分子量Mw)：17000(2)：异氰脲酸三缩水甘油酯(3a)：六氢化邻苯二甲酸二缩水甘油酯(Araldit PY 284)(3b)：六氢化偏苯三甲酸三缩水甘油酯(4)：基于丁基化聚丙烯酸酯的流动性控制剂(5)：HALS(聚烷基哌啶化合物)(6)：紫外线吸收剂(7)：实验等级从0(差)到10(很好)
| 粉末涂料编号 | 1 | 2 | 3 |
| 甲基丙烯酸树脂A | - | - | 74.81 |
| Joncryl SCX 819(1) | 87 | 87 | - |
| TGIC(2) | 13 | - | |
| 1，2 CHDA DGE(3a) | 13 | — | |
| HHTMLATGE(3b) | 20.79 | ||
| 苯偶姻 | 0.3 | 0.3 | 0.29 |
| Modaflow M 2000(4) | 0.3 | 0.3 | 0.29 |
| Tinuvin 144(5) | 1.4 | 1.4 | 1.31 |
| Tinuvin 900(6) | 2.6 | 2.6 | 2.51 |
| 挤出条件 | PRISM Extruder 250rpm | ||
| 60-80℃ | 70℃ | ||
| 胶凝时间140℃(s) | 250 | 570 | 248 |
| 烘烤条件 | 30min/140℃ | ||
| 粉末涂料厚度 | 60μm | 60μm | 45μm |
| 光泽(20°) | 80 | 80 | 47 |
| 光泽(60°) | 100 | 100 | 91 |
| 流动性(目测)(7) | 1 | 7 | 6 |
| 流动性LW(8) | 61.5 | 42.3 | 35 |
| 流动性SN(9) | 153.7 | 92 | 93 |
| Tg℃粉末(10) | 37 | 32 | 32 |
| Tg℃硬化体系 | 46 | 55 | 55 |
流动性的测定采用″Wave Scan″表面光度仪(Byk供应)(8)：参数″Long Wave″：从＞60(差)到＜30(很好)(9)：参数″Subnote″：从＞150(差)到＜50(很好)(10)：该表中的Tg值采用DSC(加热速率：10℃/min)测定。上表特别说明，2号和3号新型粉末涂料的流动性能显著地优于采用相同基料但是用常规的粉末涂料硬化剂异氰脲酸三缩水甘油酯的粉末涂料(粉末涂料1)。
Claims (8)
1.一种粉末涂料组合物，该组合物包括一种或多种具有自由羧基的聚(甲基)丙烯酸树脂作为基料，和一种或多种分子量至多为1500的环氧树脂作为上述聚(甲基)丙烯酸树脂的硬化剂，该环氧树脂含有至少70％(重量)的选自脂族和环脂族多羧酸多缩水甘油酯的缩水甘油酯。
2.根据权利要求1的粉末涂料组合物，其中采用DSC(加热速率为每分钟10℃)测定的具有自由羧基的聚(甲基)丙烯酸树脂的Tg值为40-75℃。
3.根据权利要求1或2的粉末涂料组合物，其中具有自由羧基的聚(甲基)丙烯酸树脂的酸值为30-160。
4.根据权利要求1-3中任一项的粉末涂料组合物，该组合物包括含有2-50个碳原子的脂族多羧酸多缩水甘油酯。
5.根据权利要求4的粉末涂料组合物，该组合物包括草酸二缩水甘油酯、琥珀酸二缩水甘油酯、己二酸二缩水甘油酯、癸二酸二缩水甘油酯、壬二酸二缩水甘油酯。
6.根据权利要求1-5中任一项的粉末涂料组合物，该组合物包括六氢化邻苯二甲酸二缩水甘油酯、六氢化对苯二酸二缩水甘油酯、1，2，4-环己烷三羧酸三缩水甘油酯、1，3，5-环己烷三羧酸三缩水甘油酯或式(III)或式(IV)的多缩水甘油基的化合物，式(III)中的n是2-9的整数，X1、X2、X3和X4各自相互独立地为氢原子、C1-C4烷基或式(II)的基团，式(II)中的A是含2-4个碳原子的亚烷基，式(IV)中X7是含2-30个碳原子的m价脂族或环脂族基团，其碳链可以被一个或多个杂原子，通常是氮原子或硫原子或特别是氧原子间断，且可以是未取代的或可以被一个或多个羟基、氯代或溴代取代基取代，m是2-6的整数，X8和X9各自独立地为氢、氯或溴原子或C1-C4烷基或X8和X9之一是式(V)的基团，另一个是氢、氯或溴原子或C1-C4烷基：
7.根据权利要求1-6中任一项的粉末涂料组合物，该组合物包括仅选自脂族和环脂族的多羧酸多缩水甘油酯的缩水甘油酯作为环氧树脂。
8.根据权利要求1-7中任一项的汽车用漆。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3013/95 | 1995-10-25 | ||
| CH301395 | 1995-10-25 | ||
| US73328996A | 1996-10-17 | 1996-10-17 | |
| US09/298,572 US6433084B1 (en) | 1995-10-25 | 1999-04-23 | Powder coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1154392A true CN1154392A (zh) | 1997-07-16 |
| CN1078903C CN1078903C (zh) | 2002-02-06 |
Family
ID=27174079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96122025A Expired - Fee Related CN1078903C (zh) | 1995-10-25 | 1996-10-24 | 粉末涂料 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6433084B1 (zh) |
| EP (1) | EP0770650B1 (zh) |
| JP (1) | JP4337010B2 (zh) |
| CN (1) | CN1078903C (zh) |
| BR (1) | BR9605229A (zh) |
| DE (1) | DE59610452D1 (zh) |
| ES (1) | ES2198471T3 (zh) |
| TW (1) | TW432100B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228242B (zh) * | 2005-06-23 | 2011-02-16 | Ppg工业俄亥俄公司 | 粉末涂料组合物，中等光泽范围涂层，相关方法和基材 |
| CN103980787A (zh) * | 2014-04-30 | 2014-08-13 | 张家港江南粉末涂料有限公司 | 一种罩光用丙烯酸透明粉末涂料及其制备方法 |
| CN105694683A (zh) * | 2016-04-28 | 2016-06-22 | 佛山市恒学科技服务有限公司 | 一种透明粉末涂料 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6437045B1 (en) | 1999-11-10 | 2002-08-20 | Vantico Inc. | Powder coating of carboxyl polyester or (poly)methacrylate and cycloaliphatic polyepoxide |
| US20040236037A1 (en) * | 2003-05-19 | 2004-11-25 | December Timothy S. | Particulate coatings having improved chip resistance, UV durability, and color stability |
| KR20070097076A (ko) * | 2004-12-24 | 2007-10-02 | 디에스엠 아이피 어셋츠 비.브이. | 하나 이상의 수지 및 하나 이상의 분산제를 포함하는, 분말코팅 조성물에 적합한 조성물 |
| JP4796322B2 (ja) * | 2005-03-30 | 2011-10-19 | 阪本薬品工業株式会社 | 新規な熱硬化性樹脂組成物 |
| CA2751671A1 (en) * | 2009-02-09 | 2010-08-12 | Huntsman Advanced Materials (Switzerland) Gmbh | Powder coating composition |
| JP5849963B2 (ja) * | 2010-11-15 | 2016-02-03 | 日産化学工業株式会社 | 多官能エポキシ化合物 |
| AU2012328817B2 (en) * | 2011-10-25 | 2015-07-30 | 3M Innovative Properties Company | Corrosion, chip and fuel resistant coating composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3444237A (en) | 1966-03-23 | 1969-05-13 | Grace W R & Co | Esters of cyclohexane-1,2,4-tricarboxylic acid |
| US3859314A (en) * | 1967-06-29 | 1975-01-07 | Celanese Coatings Co | Process for preparing glycidyl esters of polycarboxylic acids |
| US3758633A (en) * | 1971-08-16 | 1973-09-11 | Ford Motor Co | Crosslinking agents and flow control agents powdered coating compositions of carboxy containing copolymers epoxy |
| CH571511A5 (zh) | 1972-04-21 | 1976-01-15 | Ciba Geigy Ag | |
| US4255553A (en) * | 1975-05-21 | 1981-03-10 | Toyo Boseki Kabushiki Kaisha | Powder coating composition |
| CH619218A5 (en) | 1975-12-03 | 1980-09-15 | Ciba Geigy Ag | Process for the preparation of polyglycidyl polycarboxylates |
| JPS5950165B2 (ja) * | 1977-05-14 | 1984-12-06 | 日本合成化学工業株式会社 | アクリル系樹脂の製造法 |
| EP0462053B1 (de) | 1990-06-05 | 1997-01-15 | Ciba SC Holding AG | Pulverförmige frei fliessende Epoxidharzzusammensetzungen |
| EP0506617B1 (de) | 1991-03-27 | 1996-08-21 | Ciba-Geigy Ag | Vernetzungsmittel für Pulverlacke auf Basis von Polyestern |
| TW282486B (zh) | 1991-10-03 | 1996-08-01 | Ciba Geigy Ag | |
| TW289044B (zh) | 1994-08-02 | 1996-10-21 | Ciba Geigy Ag |
-
1996
- 1996-10-05 TW TW085112183A patent/TW432100B/zh active
- 1996-10-16 DE DE59610452T patent/DE59610452D1/de not_active Expired - Lifetime
- 1996-10-16 ES ES96810696T patent/ES2198471T3/es not_active Expired - Lifetime
- 1996-10-16 EP EP96810696A patent/EP0770650B1/de not_active Expired - Lifetime
- 1996-10-24 BR BR9605229A patent/BR9605229A/pt not_active Application Discontinuation
- 1996-10-24 CN CN96122025A patent/CN1078903C/zh not_active Expired - Fee Related
- 1996-10-25 JP JP28379496A patent/JP4337010B2/ja not_active Expired - Fee Related
-
1999
- 1999-04-23 US US09/298,572 patent/US6433084B1/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228242B (zh) * | 2005-06-23 | 2011-02-16 | Ppg工业俄亥俄公司 | 粉末涂料组合物，中等光泽范围涂层，相关方法和基材 |
| CN103980787A (zh) * | 2014-04-30 | 2014-08-13 | 张家港江南粉末涂料有限公司 | 一种罩光用丙烯酸透明粉末涂料及其制备方法 |
| CN105694683A (zh) * | 2016-04-28 | 2016-06-22 | 佛山市恒学科技服务有限公司 | 一种透明粉末涂料 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW432100B (en) | 2001-05-01 |
| EP0770650A1 (de) | 1997-05-02 |
| JPH09165534A (ja) | 1997-06-24 |
| DE59610452D1 (de) | 2003-06-26 |
| JP4337010B2 (ja) | 2009-09-30 |
| US6433084B1 (en) | 2002-08-13 |
| BR9605229A (pt) | 1998-07-21 |
| ES2198471T3 (es) | 2004-02-01 |
| EP0770650B1 (de) | 2003-05-21 |
| CN1078903C (zh) | 2002-02-06 |
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