EP0437453A1 - Procede de fabrication d'un revetement multicouches a base de compositions aqueuses de revetement - Google Patents
Procede de fabrication d'un revetement multicouches a base de compositions aqueuses de revetementInfo
- Publication number
- EP0437453A1 EP0437453A1 EP89910428A EP89910428A EP0437453A1 EP 0437453 A1 EP0437453 A1 EP 0437453A1 EP 89910428 A EP89910428 A EP 89910428A EP 89910428 A EP89910428 A EP 89910428A EP 0437453 A1 EP0437453 A1 EP 0437453A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- weight
- copolymerizable
- monomers
- free
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 title claims abstract description 13
- 239000011248 coating agent Substances 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 41
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 239000008199 coating composition Substances 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000003791 organic solvent mixture Substances 0.000 claims description 14
- 229920000058 polyacrylate Polymers 0.000 claims description 14
- -1 acrylic ester Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 9
- 229920003180 amino resin Polymers 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 description 12
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000004922 lacquer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 101150038956 cup-4 gene Proteins 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 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
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003472 neutralizing effect Effects 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
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000010586 diagram Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
-
- 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
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
Definitions
- the invention relates to a method for producing a multilayer protective and / or decorative coating on a substrate surface, in which
- a suitable pigmented basecoat composition is applied to the substrate surface
- a transparent aqueous top coating composition containing a water-dilutable polyacrylate resin as a binder and an aminoplast resin as a crosslinking agent is applied to the base layer and then
- the invention also relates to aqueous coating compositions, water-thinnable polyacrylate resins and a process for the production of water-thinnable polyacrylate resins.
- the method according to the preamble of claim 1 is known. It is used in particular for the production of automotive metal effect coatings (cf. e.g.
- aqueous top coating compositions for economic and ecological reasons, it is desirable to use aqueous top coating compositions in stage (3) of the so-called “base coat clear coat” process described above.
- top coating compositions must be sprayable using automatic painting equipment. For this purpose, they have to have such a high solids content at spray viscosity that lacquer films with a sufficient layer thickness are obtained with one to two spray coats (cross coats), and they have to deliver baked lacquer films that have a good appearance (good flow, high gloss, good top coat level ... ) demonstrate.
- the aqueous top coating composition disclosed in Example 2 of EP-A-38127 does not meet all of the above requirements.
- the object on which the present invention is based is to provide aqueous top coating compositions which meet the above-mentioned requirements.
- top coating compositions which contain a water-dilutable polyacrylate resin as a binder, which is available is by
- (a2) an ethylenically unsaturated monomer copolymerizable with (a1), (a3), (b1) and (b2), which carries at least one hydroxyl group per molecule and is essentially free of carboxyl groups, or a mixture of such monomers and optionally
- Polyacrylate resin is at least partially neutralized and dispersed in water, the sum of the parts by weight of (b1) and (b2) always giving 100% by weight and (a1), (a2), (a3), (b1) and (b2) be selected in type and amount so that the polyacrylate resin has a hydroxyl number of 40 to 200, preferably 60 to 140, an acid number of 20 to 100, preferably 25 to 50 and a glass transition temperature (T G ) of -40 ° C to + 60 ° C, preferably -20 ° C to + 40 ° C.
- step (1) of the process according to the invention are well known (see e.g. US-A-3, 639, 147, EP-A-38127, DE-A-33 33 072 and EP-A-279813).
- step (1) base coating compositions containing metal pigments, in particular aluminum pigments, are preferably used. In this way, metallic effect coatings are obtained.
- the phrase "essentially free of carboxyl groups" is intended to express that components (a1), (a2) and (a3) have a low carboxyl group content (but at most so much that one of components (a1), (a2) and (a3 ) produced polyacrylate resin has an acid number of at most 10). However, it is preferred that the carboxyl group content of components (a1), (a2) and (a3) be kept as low as possible. Carboxyl-free (a1), (a2) and (a3) components are particularly preferably used.
- component (a1) which can be copolymerized with (a2), (a3), (b1) and (b2) and is essentially carboxyl-free ester of (meth) acrylic acid or a mixture of such (meth) acrylic acid esters become.
- examples include alkyl acrylates and alkyl methacrylates with up to 20 carbon atoms in the alkyl radical, e.g. Methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate and methacrylate and cycloaliphatic (meth) acrylic acid esters, e.g.
- Cyclohexyl (meth) acrylate called.
- Mixtures of alkyl acrylates and / or alkyl methacrylates are preferably used as (al) components, which consist of at least 25% by weight of n-butyl and / or t-butyl acrylate
- component (a2) all with (a1), (a3), (b1) and (b2) copolymerizable ethylenically unsaturated monomers which carry at least one hydroxyl group per molecule and are essentially free of carboxyl groups, or a mixture of such monomers is used.
- Hydroxylalkyl esters of acrylic acid, methacrylic acid or another ⁇ , ⁇ -ethylenically unsaturated carboxylic acid are mentioned as examples. These esters can be derived from an alkylene glycol esterified with the acid, or they can be obtained by reacting the acid with an alkylene oxide.
- component (a2) preference is given to hydroxyalkyl esters of acrylic acid and methacrylic acid in which the hydroxyalkyl group contains up to 4 carbon atoms, reaction products of cyclic esters, such as, for example, ⁇ -caprolactone and these hydroxyalkyl esters, or mixtures of these hydroxyalkyl esters or ⁇ -caprolactone-modified hydroxyalkyl esters used.
- cyclic esters such as, for example, ⁇ -caprolactone and these hydroxyalkyl esters, or mixtures of these hydroxyalkyl esters or ⁇ -caprolactone-modified hydroxyalkyl esters used.
- hydroxyalkyl esters examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.
- esters of other unsaturated acids such as. B. Ethacrylic acid, crotonic acid and similar acids with up to about 6 carbon atoms per molecule can also be used.
- Component (a3) which can be used is all copolymerizable with (a1), (a2), (b1) and (b2), essentially carboxyl-free ethylenically unsaturated monomers or mixtures of such monomers.
- Vinylaromatic hydrocarbons such as styrene, ⁇ -alkylstyrene and vinyltoluene, are preferably used as component (a3).
- Components (a1), (a2) and optionally (a3) are optionally mixed in a suitable organic solvent and added to an organic solvent or solvent mixture and polymerized there in the presence of at least one polymerization initiator.
- the organic solvents and polymerization initiators used are the solvents and polymerization initiators customary for the production of polyacrylate resins and suitable for the production of aqueous dispersions.
- Examples of useful solvents are butyl glycol, 2-methoxypropanol, n-butanol, methoxybutanol, n-propanol, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
- Ethylene glycol monobutyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether and 3-methyl-3-methoxybutanol.
- Free-radical initiators such as benzoyl peroxide, azobisisobutyronitrile and t-butyl perbenzoate are cited as examples of useful polymerization initiators.
- the polymerization is carried out at a temperature of 80 to 160 ° C, preferably 120 to 160 ° C.
- the mixture of (a1), (a2) and optionally (a3) is added to the organic solvent or solvent mixture within 2 to 8 hours, preferably within 3 to 6 hours, and is polymerized there in the presence of at least one free radical initiator.
- step (II) After at least 80% by weight, preferably 100% by weight, of the mixture consisting of (a1), (a2) and optionally (a3) has been added, in step (II)
- component (b1) in stage (II) It is preferred to use 100% by weight of component (b1) in stage (II). In other words: it is preferred to use component (b1) in stage (II) without admixing component (b2).
- component (b1) it is possible to use any ethylenically unsaturated monomer carrying at least one carboxyl group per molecule and copolymerizable with (a1), (a2) and (a3) or a mixture of such monomers.
- Acrylic acid and / or methacrylic acid are preferably used as components (b1).
- other ethylenically unsaturated acids with up to 6 carbon atoms in the molecule can also be used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
- Maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester can also be used as component (b1).
- any (a1), (a2), (a3) and (b1) copolymerizable ethylenically unsaturated monomer or a mixture of such monomers can be used as component (b2).
- component (b2) As Kompo ⁇ Entente (b2) all monomers listed in the description of components (a1), (a2) and (a3) can be used.
- Components (b1) and optionally (b2) are preferably added within 10 to 60 minutes, particularly preferably within 15 to 45 minutes.
- the components (a1), (a2), (a3), (b1) and (b2) are selected in their type and amount so that the reaction product has a hydroxyl number of 40 to 200, preferably 60 to 140, an acid number of 20 to 100 , preferably 25 to 50 and a glass transition temperature (T G ) of -40 ° C to + 60 ° C, preferably -20 ° C to + 40 ° C.
- the glass transition temperatures of polyacrylate resins can be calculated using the following formula:
- W n weight fraction of the nth monomer
- T Gn glass transition temperature of the homopolymer
- the amount and rate of addition of the initiator is preferably chosen so that a polyacrylate resin having a number average molecular weight of 2500 to 20,000 is obtained. It is preferred to start the initiator addition at the same time as the addition of the mixture of components (a1), (a2) and optionally (a3) and about half an hour after the addition of component (b1) and optionally (b2) has ended has been ending.
- the initiator is preferably added in a constant amount per unit of time. After the addition of the initiator has ended, the reaction mixture is kept at the polymerization temperature (as a rule about 11/2 hours) until all of the monomers used have essentially been completely reacted.
- Substantially completely converted is intended to mean that preferably 100% by weight of the monomers used have been reacted, but it is also possible that a low residual monomer content of at most up to about 0.5% by weight, based on the Weight of the reaction mixture can remain unreacted.
- the polyacrylate resins according to the invention are produced by adding 40 to 87.5% by weight, preferably 55 to 80% by weight of component (a1), 10 to 45% by weight, preferably 12 to
- component (a2) 35% by weight of component (a2), 0 to 25% by weight, preferably 8 to 18% by weight of component (a3), 2.5 to 15% by weight, preferably 3 to 7% by weight component (b1) and 0 to
- component (b2) 6% by weight are used, the sum of the parts by weight of (a1), (a2), (a3), (b1) and (b2) always giving 100% by weight.
- the polyacrylate resin obtained is at least partially neutralized and in water dispersed.
- Both organic bases and inorganic bases such as ammonia and hydrazine can be used for neutralization.
- Primary, secondary and tertiary amines e.g. Ethylamine, propylamine, dimethylamine, dibutylamine, cyclohexylamine, benzylamine, morpholine, piperidine and triethanolamine are used.
- Tertiary amines are particularly preferably used as neutralizing agents, in particular dimethylethanolamine.
- Triethylamine, tripropylamine and tributylamine are particularly preferably used as neutralizing agents, in particular dimethylethanolamine.
- the neutralization reaction is generally carried out by
- the neutralizing base with the polyacrylate resin is carried out.
- Sufficient base is preferably used so that the top coating composition has a pH of 7-8.5, preferably 7.2 to 7.8.
- the partially or completely neutralized polyacrylate resin is then dispersed by adding water. This creates an aqueous polyacrylate resin dispersion. If necessary, part or all of the organic solvent can be distilled off.
- the polyacrylate resin dispersions according to the invention contain polyacrylate resin particles whose average particle size is preferably between 60 and 250 nm (measurement method: laser light separation, measuring device:
- aqueous polyacrylate resin dispersions obtained in this way are coated according to the invention by generally known methods by admixing an aminoplast resin and, if appropriate, further additives, such as flow control agents, UV stabilizers, transparent pigments, etc. received compositions.
- top coating compositions according to the invention preferably contain so much aminoplast resin that the weight ratio between polyacrylate resin solid and aminoplast resin solid is 60:40 to 90:10, particularly preferably 70:30 to 85:15.
- all aminoplast resins that can be processed into a stable top coating composition with the polyacrylate resin according to the invention can be used as crosslinking agents.
- Melamine-formaldehyde resins which are partially or completely etherified with aliphatic alcohols, which preferably contain 1 to 4 carbon atoms per molecule, are preferably used as crosslinking agents.
- top coating compositions according to the invention are sprayed on (generally 20 to 40 seconds. Run-out time from DIN cup 4 (DIN 53 211 (1974)) and a pH of 7.0 to 8.5, preferably 7.2 to 7 , 8 set.
- the top coating compositions according to the invention have a high solids content (20 to 45% by weight, preferably 32 to 40% by weight) at a peak viscosity that with one or two spray coats (cross coats), lacquer films with a sufficient layer thickness (the thickness of the stoved lacquer film should be preferably between 25 and 45 ⁇ m) are obtained and - deliver baked lacquer films with a very good appearance (good flow, high gloss, good top coat level ...) and good mechanical-technological properties and - have a relatively low proportion of organic cosolvents (less than 35% by weight, based on the Total solids content of binders and crosslinking agents).
- top coating compositions according to the invention are used together with water-thinnable base coating compositions for the production of metallic effect coatings, then metallic effect coatings are obtained in which the transparent top layer adheres particularly well to the base layer.
- the top coating compositions according to the invention can also contain crosslinked polymer microparticles such as those e.g. are disclosed in EP-A-38127 and / or other compatible resins such as e.g. contain water-dilutable or water-soluble polyacrylate resins, polyester resins, alkyd resins or epoxy resin esters. and they can also be pigmented.
- the resin solution thus obtained is neutralized with dimethylethanolamine at approx. 95 ° C. to a degree of neutralization of 80%. Then enough water is added that the solids content of the dispersion is about
- transparent top coating compositions are prepared and sprayed with a 10% strength aqueous dimethylethanolamine solution and distilled water
- top coat compositions contain
- a water-thinnable base coating composition pigmented with aluminum flakes according to EP-A-279813 is applied to a phosphated steel sheet coated with a commercially available electrodeposition coating and a commercially available filler so that a
- the monomers (a1), (a2), (a3) and (b1) used to produce the polyacrylate resin P2 according to the invention are mixed and polymerized.
- the polymerization conditions are the same as in the production of the polyacrylate resin P2 according to the invention.
- component (b1) is not only added after the addition of the mixture of (a1), (a2) and (a3), but already together with (a1), (a2) and (a3) is added.
- An aqueous top coating composition prepared from the polyacrylate resin V according to B prepared in this way only has a viscosity of 24 DIN seconds (run-out time from DIN cup 4 (DIN 53 211 (1974)) and a pH of 7.4 to 7.5 a solids content of 24.1% by weight.
- the following diagram shows the viscosity of the polyacrylate resin dispersion P2 prepared according to A and diluted with water as a function of the solids content of the dispersion in comparison with an analogous dispersion of the polyacrylate resin V (pH of the two dispersions: 7, 8). It is clear that the viscosity of the polyacrylate resin dispersion P2 according to the invention at solids contents of 25 to about 53% by weight is lower than the viscosity of the comparable dispersion of the polyacrylate resin V.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Medicinal Preparation (AREA)
Abstract
L'invention concerne un procédé de fabrication d'un revêtement multicouches, dans lequel la composition aqueuse de revêtement de finition renferme une résine de polyacrylate diluable à l'eau, présentant un indice d'hydroxyle de 40 à 200, un indice d'acide de 20 à 100 et une température de transition vitreuse (TG) de -40°C à +60°C, préparée en ajoutant, à un solvant organique un mélange (I) composé d'un ester d'acide (méth)acrylique et d'un monomère copolymérisable contenant des groupes hydroxyles, et en le polymérisant sur le radical; ensuite, on ajoute en outre au mélange (I) un monomère contenant des groupes carboxyles que l'on polymérise encore.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3832826 | 1988-09-28 | ||
| DE3832826A DE3832826A1 (de) | 1988-09-28 | 1988-09-28 | Verfahren zur herstellung eines mehrschichtigen ueberzugs, waessrige beschichtungszusammensetzungen, wasserverduennbare polyacrylatharze und verfahren zur herstellung von wasserverduennbaren polyacrylatharzen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0437453A1 true EP0437453A1 (fr) | 1991-07-24 |
Family
ID=6363836
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89114904A Expired - Lifetime EP0365775B1 (fr) | 1988-09-28 | 1989-08-11 | Procédé de préparation d'une revêtement multicouche par utilisation de compositions de revêtement aqueux |
| EP89910428A Pending EP0437453A1 (fr) | 1988-09-28 | 1989-08-11 | Procede de fabrication d'un revetement multicouches a base de compositions aqueuses de revetement |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89114904A Expired - Lifetime EP0365775B1 (fr) | 1988-09-28 | 1989-08-11 | Procédé de préparation d'une revêtement multicouche par utilisation de compositions de revêtement aqueux |
Country Status (9)
| Country | Link |
|---|---|
| EP (2) | EP0365775B1 (fr) |
| JP (2) | JPH0688014B2 (fr) |
| AT (1) | ATE86149T1 (fr) |
| AU (1) | AU616059B2 (fr) |
| BR (1) | BR8907677A (fr) |
| CA (1) | CA1329303C (fr) |
| DE (2) | DE3832826A1 (fr) |
| WO (1) | WO1990003229A1 (fr) |
| ZA (1) | ZA896542B (fr) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2872710B2 (ja) * | 1989-10-27 | 1999-03-24 | 三井化学株式会社 | 合成樹脂エマルション及びその製造方法 |
| DE4143688B4 (de) | 1991-03-30 | 2007-03-29 | Basf Coatings Ag | Verwendung eines Mischsystems sowie Verfahren zur Herstellung von Wasserbasislacken und von wasserverdünnbaren Überzugsmitteln |
| DE4132430A1 (de) * | 1991-09-28 | 1993-04-01 | Basf Lacke & Farben | Waessrige lacke und verfahren zur herstellung von automobildecklackierungen |
| DE4222194A1 (de) * | 1992-07-07 | 1994-01-13 | Basf Lacke & Farben | Verfahren zur Herstellung einer zweischichtigen Lackierung und für dieses Verfahren geeignete Pulverlacke |
| DE19528878A1 (de) * | 1995-08-05 | 1997-02-06 | Herberts Gmbh | Wäßrige Überzugsmittel unter Verwendung von Polyalkylenglykoldialkylethern und Verfahren zur Mehrschichtlackierung |
| DE19602555A1 (de) | 1996-01-25 | 1997-08-07 | Basf Lacke & Farben | Wäßrige Bindemittellösungen und -dispersionen |
| US6025449A (en) * | 1997-03-05 | 2000-02-15 | Kansai Paint Co., Ltd. | Water-soluble acrylic resin, resin composition containing the same for use in water-based coating composition, water-based coating composition and coating method by use of the same |
| DE19714577A1 (de) | 1997-04-09 | 1998-10-15 | Basf Coatings Ag | Mischsystem zur Herstellung wasserverdünnbarer Überzugsmittel |
| DE19730890C2 (de) * | 1997-07-18 | 2001-07-05 | Basf Coatings Ag | Verfahren zur Herstellung mehrschichtiger Überzüge und mit diesen beschichtete Substrate |
| DE19903391A1 (de) * | 1999-01-29 | 2000-08-03 | Bayer Ag | Wäßriges Überzugsmittel, Verfahren zu seiner Herstellung und seine Verwendung |
| JP2002241681A (ja) * | 2001-02-14 | 2002-08-28 | Mitsubishi Rayon Co Ltd | 水性被覆組成物および水性塗料 |
| DE10237576A1 (de) * | 2002-08-16 | 2004-02-26 | Bayer Ag | Wässrige Bindemittel-Dispersionen als Überzugsmittel |
| WO2007013684A2 (fr) * | 2005-07-29 | 2007-02-01 | Kansai Paint Co., Ltd. | Composition de revetement transparente aqueuse et procede de formation de film de finition multicouche |
| DE102005050823A1 (de) * | 2005-10-24 | 2007-04-26 | Basf Coatings Ag | Von organischen Lösemitteln im Wesentlichen oder völlig freie, strukturviskose, härtbare, wässrige Pulverdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung |
| EP2143743A1 (fr) | 2008-07-08 | 2010-01-13 | Akzo Nobel Coatings International B.V. | Utilisation de dérivés de dianhydrohexitol dans la préparation de résines |
| KR100958078B1 (ko) * | 2009-12-28 | 2010-05-13 | 재단법인 구미전자정보기술원 | 채색유리판용 유기 프라이머 조성물 |
| CN118638469B (zh) * | 2024-06-19 | 2025-12-16 | 松井新材料集团股份有限公司 | 一种水性玻璃喷涂油墨及其制备方法和应用 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4413037A (en) * | 1981-06-17 | 1983-11-01 | Mobil Oil Corporation | Acrylic modified anionic water dispersible styrene hydroxyethyl (meth)acrylate copolymers |
| DE3543361A1 (de) * | 1985-12-07 | 1987-06-11 | Basf Ag | Verfahren zur herstellung waessriger polymerdispersionen und deren verwendung |
| DE3631826A1 (de) * | 1986-09-19 | 1988-03-31 | Roehm Gmbh | Herstellung eines methylmethacrylat-copolymerisats |
-
1988
- 1988-09-28 DE DE3832826A patent/DE3832826A1/de not_active Ceased
-
1989
- 1989-08-11 EP EP89114904A patent/EP0365775B1/fr not_active Expired - Lifetime
- 1989-08-11 AU AU43152/89A patent/AU616059B2/en not_active Ceased
- 1989-08-11 BR BR898907677A patent/BR8907677A/pt not_active IP Right Cessation
- 1989-08-11 EP EP89910428A patent/EP0437453A1/fr active Pending
- 1989-08-11 AT AT89114904T patent/ATE86149T1/de not_active IP Right Cessation
- 1989-08-11 WO PCT/EP1989/000949 patent/WO1990003229A1/fr not_active Ceased
- 1989-08-11 JP JP1509744A patent/JPH0688014B2/ja not_active Expired - Lifetime
- 1989-08-11 DE DE8989114904T patent/DE58903658D1/de not_active Expired - Fee Related
- 1989-08-28 ZA ZA896542A patent/ZA896542B/xx unknown
- 1989-09-27 CA CA000613737A patent/CA1329303C/fr not_active Expired - Fee Related
-
1996
- 1996-03-12 JP JP8055163A patent/JP2680294B2/ja not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9003229A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0688014B2 (ja) | 1994-11-09 |
| JP2680294B2 (ja) | 1997-11-19 |
| JPH03503740A (ja) | 1991-08-22 |
| DE3832826A1 (de) | 1990-04-05 |
| DE58903658D1 (de) | 1993-04-08 |
| EP0365775B1 (fr) | 1993-03-03 |
| EP0365775A1 (fr) | 1990-05-02 |
| ZA896542B (en) | 1990-06-27 |
| AU4315289A (en) | 1990-04-18 |
| WO1990003229A1 (fr) | 1990-04-05 |
| AU616059B2 (en) | 1991-10-17 |
| CA1329303C (fr) | 1994-05-03 |
| BR8907677A (pt) | 1991-07-30 |
| JPH08318219A (ja) | 1996-12-03 |
| ATE86149T1 (de) | 1993-03-15 |
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