EP1087843A1 - Verfahren zur mehrschichtlackierung - Google Patents
Verfahren zur mehrschichtlackierungInfo
- Publication number
- EP1087843A1 EP1087843A1 EP00909361A EP00909361A EP1087843A1 EP 1087843 A1 EP1087843 A1 EP 1087843A1 EP 00909361 A EP00909361 A EP 00909361A EP 00909361 A EP00909361 A EP 00909361A EP 1087843 A1 EP1087843 A1 EP 1087843A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- irradiation
- radiation
- filler
- layer
- nir radiation
- 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
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 239000003973 paint Substances 0.000 title description 16
- 238000004519 manufacturing process Methods 0.000 title description 2
- 230000005855 radiation Effects 0.000 claims abstract description 56
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 13
- 238000010422 painting Methods 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 8
- 230000008439 repair process Effects 0.000 claims description 5
- 238000004040 coloring Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 description 33
- 239000010410 layer Substances 0.000 description 32
- 239000002904 solvent Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008199 coating composition Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 7
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
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- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
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- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LMFOAVVKMLWZOS-UHFFFAOYSA-N (1-acetyloxy-2-oxo-2-phenylethyl) acetate Chemical compound CC(=O)OC(OC(C)=O)C(=O)C1=CC=CC=C1 LMFOAVVKMLWZOS-UHFFFAOYSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- JLBXCKSMESLGTJ-UHFFFAOYSA-N 1-ethoxypropan-1-ol Chemical compound CCOC(O)CC JLBXCKSMESLGTJ-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Chemical class 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 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 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium 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
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004924 water-based lacquer Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0263—After-treatment with IR heaters
-
- 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
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
Definitions
- the invention relates to a method for multi-layer painting with in particular
- Water-based paints which are used in particular in the field of vehicle refinishing.
- the developed water-based paints have already reached a quality level that makes them equal to the solvent-based paints in a number of properties.
- some properties have not yet reached the quality level of solvent-based paints.
- insufficient grindability is found.
- the object of the invention was therefore to provide a process for multi-layer coating, in particular for vehicle refinishing, which also makes it possible to use water-based filler coating compositions
- the uniform quality of the coating should also be ensured, in particular, under strongly varying environmental conditions during application, such as, for example, the air humidity. Uniform coating quality should also be provided at critical points such as sikken or edges. Furthermore, the filler layers obtained should be easy and quick to sand. It has been shown that this object can be achieved if a filler layer applied to an optionally precoated substrate is irradiated with NIR radiation. The invention therefore relates to the use of NIR radiation for irradiating filler layers in the multi-layer coating of substrates.
- the NIR radiation (near infrared) used according to the invention is short-wave infrared radiation in the wavelength range from approximately 760 to approximately 1500 nm, preferably 760 to 1200 nm.
- Another object of the invention is a process for multi-layer coating, in which a surface coating agent is applied to an optionally precoated substrate and then cured, a top coat layer comprising a coloring and / or effect-imparting base coat and a clear coat coating agent or a pigmented coat is applied to the filler layer obtained
- Single-coat topcoat is applied and cured, which is characterized in that after application of the filler coating agent, the not yet cured filler layer is irradiated with NIR radiation in the wavelength range from 800 to 1500 nm.
- an aqueous surface coating agent is applied.
- solvent-based coating agents it is also possible to use solvent-based coating agents.
- the filler layer which has not yet hardened can optionally be subjected to a flash-off phase.
- the irradiation with NIR radiation is carried out to dry the, in particular, aqueous filler layer.
- the aqueous filler layer (final hardening) can be hardened using a suitable Häraingsclar. For example, it can be forced at room temperature higher temperatures, by irradiation with UV or IR or NIR radiation. Final curing is preferably carried out using UV or NIR radiation.
- NIR radiation in general for drying paints and varnishes is known.
- the following areas of application are mentioned, for example: printing industry, film drying, pipe drying, wood coatings, powder coatings.
- the particular advantages of NIR technology are the very rapid drying, especially with water-based paints, and the gentle drying through low heating of the substrate. None is known about possible applications of this technology in vehicle painting, in particular vehicle refinishing.
- the object of the present invention can be achieved by using NIR radiation for drying and curing, in particular, water-based filler layers in a multilayer structure. It was equally surprising that the filler could be dried directly with NIR radiation. On account of the high layer thickness and the filler surface that closes quickly due to the radiation, it was rather to be expected that a considerable gradient of properties would arise from the film surface to the interface with the substrate with regard to hardness, grindability and adhesion.
- the irradiation with NIR radiation carried out in the method according to the invention can be carried out with a customary high-energy NIR radiator.
- NIR emitters are commercially available (for example from Industrie SerVis). These are, for example, high-performance halogen lamps with a radiation density of generally more than 1 W / cm 2 , preferably more than 10 W / cm 2 , for example up to 15 MW / m 2 .
- the emitters reach one, for example
- Radiator surface temperature of over 2000 K, for example from 2000 to 3000 K.
- Suitable radiators have, for example, an emission spectrum a maximum between 750 and 1200 nm.
- a flash-off phase can be switched on before irradiation with NIR radiation.
- the flash-off phase can be carried out in the usual way, for example by letting it stand in the air or by inflating air e.g. at
- the coating compositions which can be used in the process according to the invention are conventional water-based fillers known to those skilled in the art, such as are used in the field of vehicle painting, in particular vehicle refinishing.
- the coating compositions contain water-dilutable binders.
- the water-dilutable binders are the customary binders known to those skilled in the art for this purpose. For example, it can be a one-component or two-component water-dilutable binder system.
- one-component binder systems are those based on polyurethane, polyacrylate, polyester and / or epoxy resins.
- the one-component binder systems can e.g. be physically or oxidatively drying.
- two-component crosslinkable binder systems are those based on hydroxy-functional binders, such as e.g. Polyurethane, polyester urethane and / or polyacrylate polyols, and polyisocyanates, based on epoxy / polyamide systems, based on acetoacetyl-functional and (meth) acryloyl-functional binders, and on the basis of acryloyl-functional or acryloyl- and glycidyl-functional binders and polyamines.
- hydroxy-functional binders such as e.g. Polyurethane, polyester urethane and / or polyacrylate polyols, and polyisocyanates, based on epoxy / polyamide systems, based on acetoacetyl-functional and (meth) acryloyl-functional binders, and on the basis of acryloyl-functional or acryloyl- and glycidyl-functional binders and polyamines.
- Water-thinnable ones with high energy content can also be used.
- UV radiation at least partially curable binders.
- These are preferably free-radically curable binders.
- Both preferred free-radically curing binders can be prepolymers, such as poly- or oligomers, which have free-radically polymerizable olefinic double bonds, in particular in the form of (meth) acryloyl groups in the molecule.
- the prepolymers can be in combination with reactive diluents, ie reactive liquid monomers.
- prepolymers or oligomers are (meth) acryloyl-functional (meth) acrylic copolymers, epoxy resin (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, polymethane (meth) acrylates, unsaturated polyesters, unsaturated polyurethanes or silicone (meth) acrylates with mediators
- Mn Molecular masses (Mn) preferably in the range from 200 to 10,000, particularly preferably from 500 to 3000 and with an average of 2 to 20, preferably 3 to 10, free-radically polymerizable, olefinic double bonds per molecule.
- reactive diluents are used in amounts of 1 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of prepolymers and reactive diluents. These are defined low-molecular compounds that can be mono-, di- or polyunsaturated. Examples of such reactive diluents are: (meth) acrylic acid and its esters, maleic acid and its half esters, vinyl acetate, vinyl ether, substituted vinyl ureas, ethylene and
- UV-curable binders are e.g. those described in DE-A-41 33 290.
- binder systems mentioned here for coating compositions are merely an exemplary list.
- the binder systems can also be modified further, and so can different crosslinking mechanisms can be combined with one another, for example curing with UV radiation can be combined with a further crosslinking mechanism. Examples of the latter combination are described in the as yet unpublished German patent application by the same applicant P 198 187 35 and in WO-A-9800452 and DE-A-197 09 560.
- the coating compositions which can be used in the process according to the invention contain fillers and / or pigments. These are the usual fillers and organic or inorganic coloring and / or anti-corrosion pigments that can be used in the paint industry. Examples of coloring
- Pigments are titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone or pyrrolopyrrole pigments.
- Zinc phosphate is an example of an anti-corrosion pigment.
- fillers are silicon dioxide, aluminum silicate, barium sulfate, calcium carbonate and talc.
- the coating compositions can furthermore contain water and small amounts of organic solvents and additives customary in paint.
- the organic solvents which may be present in the filler coating compositions are customary paint solvents. These can originate from the production of the binders or are added separately. They are preferably water-miscible solvents.
- suitable solvents are monohydric or polyhydric alcohols, e.g. Propanol, butanol, hexanol; Glycol ethers or esters, e.g. Diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, each with Cl to C6 alkyl, ethoxypropanol, butyl glycol; Glycols, e.g. Ethylene glycol, propylene glycol and their oligomers, N-methylpyrrolidone and ketones, e.g. Methyl ethyl ketone,
- the coating compositions can furthermore contain customary paint additives.
- customary paint additives are leveling agents, rheology-influencing agents, such as highly disperse silica or polymeric urea compounds, thickeners, such as crosslinked polycarboxylic acid or polyurethanes, defoamers, wetting agents,
- Anti-cratering agent and hardening accelerator are used in customary amounts known to the person skilled in the art.
- the coating compositions additionally contain photoinitiators, e.g. in amounts from 0.1 to 5
- % By weight, preferably from 0.5 to 3% by weight, based on the sum of free-radically polymerizable prepolymers, reactive diluents and photoinitiators.
- photoinitiators are benzoin and derivatives, acetophenone and derivatives, e.g. 2,2-diacetoxyacetophenone, benzophenone and derivatives, thioxanthone and derivatives, anthraquinone, 1-benzoylcyclohexanol, organophosphorus compounds such as e.g.
- the photoinitiators can be used alone or in combination.
- the binder components which are reactive with one another must be stored separately and can only be used shortly before
- spray viscosity can be adjusted with water or organic solvents before application.
- the application of the coating compositions in the process according to the invention can be carried out by customary methods, preferably by means of spray application.
- Suitable substrates are metal and plastic substrates, in particular the substrates known in the automotive industry, such as Iron, zinc, aluminum,
- the filler layers can optionally be pretreated Substrates are applied as such or to customary primers, for example on bare steel sheet, sanded, on polyvinyl butyral primer, 2K epoxy primers, sanded factory or old paintwork.
- Irradiation with NIR radiation takes place for 5 to 15 minutes at room temperature.
- the irradiation can be carried out, for example, in a conveyor system equipped with an NIR emitter or with an NIR emitter that is positioned in front of the object to be irradiated or the location to be irradiated.
- the first option is available e.g. when refinishing individual parts, whereby the belt speed and thus the irradiation time can be varied.
- belt speeds of 1.0 to 7.0 m / min can be set, which can correspond, for example, to irradiation times of 2 to 20 s.
- the distance between the NIR emitter and the object surface can e.g. 10 to 60 cm.
- the NIR radiator is positioned directly in front of the object or location to be irradiated.
- the exposure time can e.g. 1 to 300 s, the object distance e.g. 5 to 70 cm.
- object temperatures can be set. For example, object temperatures of 80 to 150 ° C can be set.
- the final hardening can then take place in accordance with the preferred embodiment.
- the final hardening can e.g. at room temperature, by means of
- Heat for example in an oven or with IR or NIR radiation, or with high-energy radiation, preferably UV radiation. You can also use different methods can be combined with each other. Final curing is preferably carried out using a further NIR irradiation step or, if using binders curable by means of high-energy radiation, using UV radiation.
- the irradiation can be carried out in a similar manner as described above, i.e. a further irradiation phase or a further band pass follows.
- the irradiation times can be varied as required. For example, they can range from 1 to 300 seconds.
- the filler layer can preferably be irradiated with UV radiation sources with emissions in the wavelength range from 180 to 420 nm, in particular from 200 to 400 nm.
- UV radiation sources are e.g. High-pressure, medium-pressure and low-pressure mercury lamps as well as doped lamps such as iron or
- UV radiation sources are gas discharge tubes, e.g. Xenon low pressure lamps, UV lasers, UV spot lamps, e.g. UN-emitting diodes and black light tubes.
- discontinuous UN radiation sources can also be used. These are preferably so-called high-energy flash devices (in short: UV flash lamps).
- the exposure time to UN radiation when using UN flash lamps as the UV radiation source can be, for example, in the range from 1 millisecond to 400 seconds, preferably from 4 to 160 seconds, depending on the number of flash discharges selected.
- the flashes can be triggered, for example, every 4 s.
- the hardening can, for example, by. 1 to 40 successive lightning discharges.
- the radiation duration can be, for example, in the range from 1 millisecond to from a few seconds to about 5 minutes, preferably less than 5 minutes.
- the distance between the UV radiation sources and the substrate surface to be irradiated can be, for example, 5 to 60 cm.
- UV radiation sources and UN technology are known to the person skilled in the art. It is also possible, but less preferred, to carry out the drying and curing of the filler layer using a single NIR irradiation step. The irradiation times can then be, for example, 5 to 300 seconds.
- the topcoat layer can be pigmented single-layer topcoats or a basecoat / clearcoat two-layer structure. It can be painted over with solvent-based or water-based coating agents.
- Color and / or effect basecoats which can be used for the basecoat / clearcoat topcoat are all suitable in vehicle painting, especially refinishing, and solvent-based or water-based basecoats known to those skilled in the art.
- solvent-based basecoats are those based on
- waterborne basecoats are those based on physically drying polyurethane, polyurethane / urea, polyester, polyester urethane and / or polyacrylate resins and their modifications, such as acrylated or silicon-modified polyurethane and / or polyester resins.
- waterborne basecoats come from chemically crosslinking binder components, e.g. from binders containing hydroxyl groups and polyisocyanate crosslinkers.
- the basecoat film can be cured at room temperature or forced at, for example, 40 to 80 ° C. However, the basecoat film can also be coated wet-on-wet, if necessary after a short flash-off phase, with a clear coat and then cured together with the clear coat.
- Clearcoats which can be used for the basecoat / clearcoat topcoat are all suitable for vehicle painting, in particular repair painting, and solvent-based or water-based clearcoats known to those skilled in the art. Examples of these are solvent-based or aqueous clear lacquers based on binders containing hydroxyl groups and / or amino groups and Polyisocyanatvemetz ⁇ r and based on amino group-containing and acryloyl group-containing binders.
- Pigmented single-layer topcoats which can be used for the topcoat are all customary in vehicle painting, in particular repair painting
- Suitable solvent-based or water-based single-layer topcoats known to those skilled in the art. Examples of these are solvent-based or aqueous single-layer topcoats based on binders containing hydroxyl groups and / or amino groups and polyisocyanate crosslinkers and on binders based on binders containing amino groups and acryloyl groups.
- topcoat layers can for example be used over a longer period of time, e.g. be dried within 18 hours (overnight) at room temperature. However, you can also, if necessary after a flash-off time of about 10 to 30 minutes, dry at higher temperatures
- Temperatures e.g. for 20 to 50 minutes at e.g. 40 to 60 ° C, are subjected.
- topcoat layers by using high-energy radiation, preferably UV radiation, if appropriate binders are used.
- high-energy radiation preferably UV radiation
- binders to be used here are the binders already mentioned above, which are at least partially curable by means of high-energy radiation.
- the inventive method is preferably used in vehicle and
- Vehicle parts painting especially in vehicle refinishing. However, it can also be used in vehicle series painting, in particular for repair painting in vehicle series painting.
- Filler layers produced with the method according to the invention can be ground very well wet and dry after curing. There will be a uniform, reproducible quality of the fuller layer Interlayer adhesion and surface quality also achieved under varying external conditions, in particular with very harmless atmospheric humidity. Likewise, a uniform quality of the coating, especially with regard to appearance and flow, is also guaranteed at critical points such as sikken or edges. Of course, the extremely short drying time, which is achieved with the method according to the invention, is also advantageous. If the final hardening is also carried out with NIR radiation or also with UV radiation, this process step is also extremely shortened. The throughput times, for example in a repair shop, can thereby be significantly reduced, which improves the overall profitability of the workshop.
- the room temperature was irradiated with an NIR radiator (500 W / cm 2 ) to dry the fillers.
- the distance between the lamp and the object was 10 cm, the irradiation time 10 s.
- the fillers were finally cured after 5 minutes with a second NIR irradiation step under the same conditions, but with an irradiation time of 15 s each.
- a water-based lacquer (produced in accordance with DE-A-196 43 802, position example 4) was applied to the hardened filler layers in a resulting dry film layer thickness of 13 to 15 ⁇ m. After a flash-off phase of 25 minutes at room temperature, a solvent-based clear coat (base
- a filler was produced on the basis of a binder system curable by means of UN radiation.
- the following components were mixed with one another and homogenized for a few minutes using a high-speed stirrer (all information relates to the weight):
- the filler was prepared for one with a customary one
- Dry film thickness of around 60 ⁇ m at 40% and at 70% relative
- Spotlight / object was 10 cm, the irradiation time was 10 s each.
- the fenders coated with the filler according to Examples 1 and 2 show a uniform surface quality both at 40% relative air humidity and at 70% relative air humidity on the entire object, including beads and edges.
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Soil Working Implements (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19913446 | 1999-03-25 | ||
| DE19913446A DE19913446C2 (de) | 1999-03-25 | 1999-03-25 | Verfahren zur Mehrschichtlackierung |
| PCT/EP2000/002231 WO2000058026A1 (de) | 1999-03-25 | 2000-03-14 | Verfahren zur mehrschichtlackierung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1087843A1 true EP1087843A1 (de) | 2001-04-04 |
| EP1087843B1 EP1087843B1 (de) | 2004-12-22 |
Family
ID=7902304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00909361A Revoked EP1087843B1 (de) | 1999-03-25 | 2000-03-14 | Verfahren zur mehrschichtlackierung |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6432491B1 (de) |
| EP (1) | EP1087843B1 (de) |
| AT (1) | ATE285300T1 (de) |
| DE (2) | DE19913446C2 (de) |
| WO (1) | WO2000058026A1 (de) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19857045C2 (de) * | 1998-12-10 | 2001-02-01 | Industrieservis Ges Fuer Innov | Beschichtung von Gegenständen |
| DE10009822C1 (de) * | 2000-03-01 | 2001-12-06 | Basf Coatings Ag | Verfahren zur Herstellung von Beschichtungen, Klebschichten oder Dichtungen für grundierte oder ungrundierte Substrate und Substrate |
| AU2001293853A1 (en) * | 2000-09-29 | 2002-04-08 | Advanced Photonics Technologies Ag | Method and arrangement for producing a coated thermosensitive article or container with thermosensitive contents |
| DE10048361C1 (de) * | 2000-09-29 | 2002-06-06 | Advanced Photonics Tech Ag | Verfahren zur Herstellung eines beschichteten wärmeempfindlichen Artikels oder Behälters mit wärmeempfindlichem Inhalt |
| DE60017146T2 (de) * | 2000-10-24 | 2006-03-23 | Usinor S.A. | Verfahren zur Herstellung von lackierten Metallblechen |
| DE10064277B4 (de) * | 2000-12-22 | 2013-01-03 | Advanced Photonics Technologies Ag | Verfahren zum Erzeugen einer Beschichtung auf einem Substrat |
| AU2002223671A1 (en) * | 2000-11-08 | 2002-05-21 | Adphos Advanced Photonics Technologies Ag | Method for generating a coating on a substrate |
| DE10055549A1 (de) * | 2000-11-09 | 2002-05-29 | Basf Coatings Ag | Farb- und/oder effektgebende Mehrschichtlackierung, Verfahren zu ihrer Herstellung und ihre Verwendung |
| US6432490B1 (en) | 2001-02-12 | 2002-08-13 | E. I. Du Pont De Nemours And Company | Process for coating substrates |
| DE10106890B4 (de) * | 2001-02-14 | 2006-10-05 | Advanced Photonics Technologies Ag | Verfahren und Anordnung zur Herstellung eines quasi-endlosen beschichteten, wickelfähigen Bleches |
| US6541078B2 (en) | 2001-05-09 | 2003-04-01 | E. I. Du Pont De Nemours And Company | Process for coating substrates |
| DE10242810A1 (de) * | 2002-09-14 | 2004-03-25 | Volkswagen Ag | Antenne bzw. Antennenanordnung für ein Kraftfahrzeug |
| US20040254257A1 (en) * | 2003-06-10 | 2004-12-16 | Laginess Thomas J. | Coating composition curable with ultraviolet radiation |
| DE102004016093A1 (de) * | 2004-04-01 | 2005-10-20 | Volkswagen Ag | Verfahren zur Trocknung wenigstens einer Lackschicht auf einem Substrat |
| US20070116866A1 (en) * | 2005-11-18 | 2007-05-24 | Basf Corporation | Quick method for repairing damage to a finish on a substrate |
| DK1854552T3 (da) * | 2006-05-11 | 2009-01-26 | Du Pont | Fremgangsmåde til reparationslakering af köretöjer |
| WO2009057054A2 (en) * | 2007-10-31 | 2009-05-07 | Greenkote (Israel) Ltd. | Method of applying phosphate coatings to object-surfaces |
| DE102008042635A1 (de) * | 2008-10-07 | 2010-04-08 | Airbus Deutschland Gmbh | Verfahren zur beschleunigten Trocknung von Polymeren sowie Vorrichtung |
| US9126228B2 (en) | 2008-10-07 | 2015-09-08 | Airbus Operations Gmbh | Method for accelerated drying of polymers and device |
| FR2961718B1 (fr) * | 2010-06-29 | 2012-08-17 | Plastic Omnium Cie | Procede et cabine de peinture d'une piece de carrosserie de vehicule automobile |
| DE102011106196A1 (de) * | 2011-06-07 | 2012-12-13 | Oerlikon Trading Ag, Trübbach | Lackieranlage |
| JP6444987B2 (ja) * | 2013-04-18 | 2018-12-26 | エリコン サーフェス ソリューションズ アーゲー、 プフェフィコン | 金属光沢仕上げを有するコンポーネントの製造方法 |
| US20260049227A1 (en) * | 2023-08-24 | 2026-02-19 | Swimc Llc | Radiation curable vinyl primer system and ink-receptive coatings formed therefrom |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3806257A1 (de) * | 1988-02-27 | 1989-08-31 | Audi Ag | Verfahren zum lackieren von kraftfahrzeugkarosserien oder deren teilen |
| DE8817101U1 (de) * | 1988-05-02 | 1992-10-22 | Wu, Ching-Shun, Tainan/T'ai-nan | Vorrichtung zum Einbrennen von flüssigen und pulverförmigen Lacken in einem Brennofen |
| DE4027259A1 (de) | 1990-08-29 | 1992-03-05 | Herberts Gmbh | Bindemittelzusammensetzung, deren herstellung, diese enthaltende ueberzugsmittel und deren verwendung |
| DE4123860A1 (de) | 1991-07-18 | 1993-01-21 | Herberts Gmbh | Waessriges ueberzugsmittel und dessen verwendung |
| US5418040A (en) * | 1991-08-05 | 1995-05-23 | Honda Giken Kogyo Kabushiki Kaisha | Automobile fuel tank with damper layer and method of manufacturing such damper layer |
| DE4137613A1 (de) | 1991-11-15 | 1993-05-19 | Herberts Gmbh | Bindemittelzusammensetzung, diese enthaltende ueberzugsmittel und deren verwendung |
| DE4226270A1 (de) | 1992-08-08 | 1994-02-10 | Herberts Gmbh | Wasserverdünnbares Beschichtungsmittel auf Basis von Polyacrylaten und Polyisocyanaten |
| DE4226243A1 (de) | 1992-08-08 | 1994-02-10 | Herberts Gmbh | Wasserverdünnbares Überzugsmittel auf Polyol- und Polyisocyanatbasis, Verfahren zu dessen Herstellung und seine Verwendung |
| SE506983C2 (sv) | 1996-07-02 | 1998-03-09 | Akzo Nobel Nv | Ortoesterbaserad polymer, förfarande för dess framställning och användning därav |
| DE19643802A1 (de) | 1996-10-30 | 1998-05-07 | Herberts Gmbh | Wäßrige Bindemitteldispersion für physikalisch trocknende Überzugsmittel und deren Verwendung |
| ES2182500T3 (es) * | 1998-03-16 | 2003-03-01 | Advanced Photonics Tech Ag | Procedimiento para el lacado con material en polvo. |
| DE19818735A1 (de) | 1998-04-27 | 1999-10-28 | Herberts Gmbh | Strahlungshärtbare Beschichtungsmittel und deren Verwendung |
-
1999
- 1999-03-25 DE DE19913446A patent/DE19913446C2/de not_active Expired - Lifetime
-
2000
- 2000-03-14 DE DE50009004T patent/DE50009004D1/de not_active Revoked
- 2000-03-14 WO PCT/EP2000/002231 patent/WO2000058026A1/de not_active Ceased
- 2000-03-14 AT AT00909361T patent/ATE285300T1/de not_active IP Right Cessation
- 2000-03-14 EP EP00909361A patent/EP1087843B1/de not_active Revoked
- 2000-03-14 US US09/700,650 patent/US6432491B1/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0058026A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US6432491B1 (en) | 2002-08-13 |
| WO2000058026A1 (de) | 2000-10-05 |
| EP1087843B1 (de) | 2004-12-22 |
| DE19913446A1 (de) | 2000-09-28 |
| DE19913446C2 (de) | 2002-10-31 |
| ATE285300T1 (de) | 2005-01-15 |
| DE50009004D1 (de) | 2005-01-27 |
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