EP0881954A1 - Procede pour l'application de peinture en plusieurs couches - Google Patents
Procede pour l'application de peinture en plusieurs couchesInfo
- Publication number
- EP0881954A1 EP0881954A1 EP97903326A EP97903326A EP0881954A1 EP 0881954 A1 EP0881954 A1 EP 0881954A1 EP 97903326 A EP97903326 A EP 97903326A EP 97903326 A EP97903326 A EP 97903326A EP 0881954 A1 EP0881954 A1 EP 0881954A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- basecoat
- coating
- layer
- aqueous
- resins
- 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
- 238000007591 painting process Methods 0.000 title 1
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000004922 lacquer Substances 0.000 claims abstract description 25
- 238000010422 painting Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 75
- 239000011347 resin Substances 0.000 claims description 75
- 239000010410 layer Substances 0.000 claims description 72
- 239000000049 pigment Substances 0.000 claims description 41
- 239000011247 coating layer Substances 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 36
- 239000008199 coating composition Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 208000012641 Pigmentation disease Diseases 0.000 claims description 7
- 230000019612 pigmentation Effects 0.000 claims description 7
- 238000004040 coloring Methods 0.000 claims description 4
- 239000003973 paint Substances 0.000 abstract description 18
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 description 46
- 239000004924 water-based lacquer Substances 0.000 description 25
- 239000000945 filler Substances 0.000 description 20
- 239000004814 polyurethane Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000003431 cross linking reagent Substances 0.000 description 11
- 229920003009 polyurethane dispersion Polymers 0.000 description 11
- 239000004971 Cross linker Substances 0.000 description 9
- 229920006243 acrylic copolymer Polymers 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 125000003010 ionic group Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000005062 Polybutadiene Substances 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
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- -1 antifoams Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 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 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001034 iron oxide pigment Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920003226 polyurethane urea Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- CUSCAMUWVORCCB-UHFFFAOYSA-N 1-methylpyrrole-2,3-dione Chemical compound CN1C=CC(=O)C1=O CUSCAMUWVORCCB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- IWLBIFVMPLUHLK-UHFFFAOYSA-N azane;formaldehyde Chemical compound N.O=C IWLBIFVMPLUHLK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 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
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000000007 visual effect Effects 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
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
Definitions
- the invention relates to a method for producing a multilayer coating, in particular metallic substrates, which is particularly suitable for automotive coating.
- Basecoat / clearcoat topcoat that is applied to an electrophoretically primed body with a filler layer.
- Basecoat and clearcoat are preferably applied wet-on-wet, i.e. after a flash-off time, if necessary with heating, and after subsequent application of a clear coat, the basecoat is baked together with the latter.
- EP-A-0238 037 has disclosed a method for reducing stoving layers, in which a filler and an aqueous metallic basecoat are applied by the wet-on-wet method.
- the example section shows that the filler layer is applied in a dry film thickness of 35 ⁇ m that is customary for filler coatings.
- the object of the invention is to provide a method for producing multi-layer coatings, in particular automotive coatings compared to the prior art to provide a comparable overall level of properties, but a reduced layer thickness of the overall paint structure, which can be carried out with as few baking steps as possible.
- the object is achieved by the method for multi-layer coating of a substrate provided with a baked first electrocoat layer, which is characterized in that on this first electrocoat layer a second coating layer corresponding to a dry layer thickness of 10 to less than 30 microns from a first aqueous , color and / or effect basecoat coating composition containing one or more polyurethane resins is applied, whereupon wet-on-wet a third coating layer corresponding to a dry layer thickness of 7 to 15 microns is applied from a second aqueous, color and / or effect basecoat coating composition and a fourth coating layer of a clear lacquer coating agent is applied to the third coating layer without prior baking and the second, third and fourth coating layers are baked together, a first aqueous basecoat is used berzugsstoff that a higher content of
- Polyurethane resin has as the second basecoat based on the total weight of the respective aqueous basecoat, and the solid resin content in the first basecoat does not deviate by more than 20% from the absolute value of the weight content of solid resin in the second basecoat.
- the process according to the invention makes it possible to apply an aqueous basecoat coating composition directly to a baked-on first coating layer created by electrodeposition, and this layer together with the subsequently applied second coating layer
- ETL electrophoretically depositable coating agent for producing the first coating layer, namely a primer become.
- aqueous coating compositions with a solids content of up to 50% by weight, for example 10 to 20% by weight.
- the solid is formed from binders customary for electrocoating which carry ionic groups or groups which can be converted into ionic groups and, if appropriate, groups capable of chemical crosslinking, and any crosslinking agents which are present.
- the ionic or convertible groups can be anionic or convertible groups, e.g. acidic groups such as COOH groups or cationic or convertible groups, e.g. basic groups such as amino, ammonium, e.g. quaternaries
- Ammonium groups phosphonium and / or sulfonium groups. Binders with basic groups are preferred. Nitrogen-containing basic groups are particularly preferred. These groups can be quaternized or they are at least partially treated with a common neutralizing agent, an acid, e.g. an organic monocarboxylic acid, e.g. Formic acid or acetic acid, converted into ionic groups.
- a common neutralizing agent an acid, e.g. an organic monocarboxylic acid, e.g. Formic acid or acetic acid, converted into ionic groups.
- the electrodeposition coating layer it is possible, for example, to use the usual anodically depositable electrodeposition coating binders and lacquers (ATL) containing anionic groups.
- binders based on polyesters, epoxy resins, poly (meth) acrylates, maleate oils or polybutadiene oils with a weight average molecular weight of, for example, 300 to 10,000 and an acid number of 35 to 300 mg KOH / g.
- the binders carry, for example, -COOH, -S0 3 H and / or -P0 3 H 2 groups. After neutralization of at least some of the acidic groups, the resins can be converted into the water phase.
- the binders can be self-crosslinking or externally crosslinking.
- the lacquers can therefore also contain customary crosslinking agents, for example
- Triazine resins crosslinking agents containing groups capable of transesterification or blocked polyisocyanates.
- Anodically depositable electrodeposition paint binders and paints (ATL) containing anionic groups which can be used according to the invention are described, for example, in DE-A-2824418.
- cathodically depositable electrocoat materials based on cationic or basic binders are preferably used to produce the first coating layer.
- Such basic resins are, for example, resins containing primary, secondary or tertiary amino groups, the amine numbers of which are e.g. are 20 to 250 mg KOH / g.
- the weight average molar mass (Mw) of the base resins is preferably 300 to 10,000.
- base resins examples include amino (meth) acrylate resins, aminoepoxy resins, aminoepoxy resins with terminal double bonds, aminoepoxide resins with primary OH groups, aminopolyurethane resins, amino group-containing polybutadiene resins or modified polybutadiene resins or amino group-containing polybutadiene resins Amine reaction products. This is, amino (meth) acrylate resins, aminoepoxy resins, aminoepoxy resins with terminal double bonds, aminoepoxide resins with primary OH groups, aminopolyurethane resins, amino group-containing polybutadiene resins or modified polybutadiene resins or amino group-containing polybutadiene resins Amine reaction products. This
- Base resins can be self-crosslinking or they are used in a mixture with known crosslinking agents.
- crosslinkers are aminoplast resins, blocked polyisocyanates, crosslinkers with terminal double bonds, polyepoxide compounds or crosslinkers which contain groups capable of transesterification.
- Specific examples of base resins and crosslinking agents which can be used in cathodic dip coating baths are e.g.
- EP-A-0082 291 EP-A-0234 395, EP-A-0 227 975, EP-A-0 178531, EP-A-0333327, EP-A-0310971, EP-A-0456 270, US 3922 253, EP-A-0 261 385, EP-A-0 245786, DE-A-3324211, EP-A-0414 199, EP-A-0476514.
- Non-yellowing CTL systems are preferably used, which prevent yellowing or discoloration of the multi-layer coating when baked.
- KTL systems that crosslink using specially selected blocked polyisocyanates, as described, for example, in EP-A-0265 363.
- the electrocoat material (ETL) coating agent can contain pigments, fillers and / or additives customary in coating.
- the pigments can be dispersed into pigment pastes, e.g. using known paste resins. Resins of this type are familiar to the person skilled in the art. Examples of paste resins that can be used in KTL baths are described in EP-A-0 183 025 and in EP-A-0469497.
- additives as are known in particular for ETL coating agents, are possible as additives.
- these are wetting agents, neutralizing agents, leveling agents, catalysts, corrosion inhibitors, antifoams, solvents, but in particular light stabilizers, if appropriate in combination with antioxidants.
- the usual aqueous, color and / or effect basecoat coating compositions familiar to the person skilled in the art are used for the production of the second and third coating layers, as are used for the production of basecoat / clearcoat two-coat coatings and described in large numbers, for example, in the patent literature become.
- the waterborne basecoats can be physically drying or can be crosslinked to form covalent bonds.
- water-based lacquers that crosslink covalent bonds can be self- or externally crosslinking systems. It can be one- or two-component systems, one-component systems are preferred.
- the waterborne basecoats which can be used in the process according to the invention contain water-dilutable binders. These contain non-ionic and / or ionic groups which impart hydrophilicity to ensure their water dilutability.
- Suitable non-ionically stabilized binders are those binders whose water-dilutability is achieved by incorporating polyether segments into the resin molecule.
- Specific Examples of such stabilized polyurethane or polyurethane acrylate resins are described, for example, in EP-A-0354261, EP-A-0422 357 and EP-A-0424705.
- the water-dilutable, ionic group-containing binders can be cationic or anionic group-containing binders.
- cationically stabilized binders which can be used according to the invention are completely or partially neutralized cationic (meth) acrylic copolymer, polyester,
- Number average molecular weight (Mn) from 500 to 500000, an OH number from 0 to 450, an amine number from 20 to 200 and a glass transition temperature from -50 to + 150 ° C.
- Mn Number average molecular weight
- Specific examples of these binders known to the person skilled in the art are described in DE-A-40 11 633.
- the waterborne basecoats preferably contain binders which are stabilized via anionic groups. These are one or more film-forming resins as are customary in aqueous coating compositions, in particular in aqueous basecoats.
- the film-forming resins can be, for example, polyester, (meth) acrylic copolymer or preferably polyurethane resins. They can be self-curing, cross-linking or physically drying. Specific examples of suitable water-dilutable (meth) acrylic copolymers are e.g. in EP-A-0399427 and EP-A-0287 144.
- suitable water-dilutable polyester resins are e.g. in DE-A-29 26854, DE-A-3832 142 and EP-A-0301 300.
- binders are those in which (meth) acrylic copolymer and polycondensation resin are present covalently or in the form of interpenetrating resin molecules. Examples of such
- the combination is (meth) acrylic copolymer and polyester resin. Specific examples of such a usable combination are, for example in EP-A-0226 171.
- Anionically stabilized polyurethane resins are particularly preferably used.
- Such polyurethane resins are known to the person skilled in the art and are described in great variety in the literature. These are aqueous polyurethane dispersions or solutions or binders in which (meth) acrylic copolymer and polyurethane resin are present in a covalent manner or in the form of interpenetrating resin molecules. Examples of suitable polyurethane dispersions are stable, aqueous dispersions with a solids content of 20 to 50% by weight.
- Weight average molecular weight (Mw) of the resins can vary widely, e.g. from 1000 to 500000.
- the polyurethane resins can contain functional groups such as e.g. Contain hydroxyl groups or blocked isocyanate groups.
- usable polyurethane dispersions are those which can be prepared by chain extension of isocyanate-functional prepolymers with polyamine and / or polyol. They are described for example in EP-A-0089497, EP-A-0228003, DE-A-3628 124 and EP-A-0512 524.
- polyurethane dispersions which can be prepared by chain-extending isocyanate-functional prepolymers with water, such as e.g. described in DE-A-39 15459 and DE-A-4224617.
- Polyurethane dispersions can also be used which are produced by chain extension of polyurethane prepolymers containing polyisocyanates reactive with active hydrogen and containing polyisocyanates, such as e.g. in DE-A-3903804 and DE-A-4001 841.
- anionically stabilized polyurethane (PU) dispersions which can be used are those which can be obtained by chain-extending polyurethane resins containing at least one CH-acidic group in the molecule with compounds which can react with at least two CH-acidic groups. These are special examples polyurethane resin dispersions described in DE-A-42 28510.
- PU dispersions based on polyurethane resins that are chain-extended via siloxane bridges can also be used. Such are e.g. known from DE-A-44 13 562.
- anionically stabilized polyurethane-based binders in which (meth) acrylic copolymer and polyurethane resin are present covalently or in the form of interpenetrating resin molecules are e.g. in EP-A-0 353797, EP-A-0297 576, DE-A-41 22265, DE-A-41 22 266 and WO 95/16004.
- the waterborne basecoats can contain a single aqueous binder, but several aqueous binders can also be present in combination.
- Aqueous binders based on anionically stabilized polyurethanes are preferably present. It may be appropriate if a part, e.g. up to 50 wt .-%, the polyurethane binder is replaced by resins based on a combination of (meth) acrylic copolymer and polyester resin.
- Water-dilutable binders based on cellulose may also be present.
- the customary crosslinkers known to those skilled in the art such as, for example, formaldehyde condensation resins, such as phenol-formaldehyde condensation resins and amine-formaldehyde condensation resins, and free or blocked polyisocyanates can be used.
- the crosslinkers can be used individually or in a mixture.
- the mixing ratio of crosslinker to binder resin is preferably 10:90 to 40:60, particularly preferably 20:80 to 30:70, in each case based on the solids weight.
- the waterborne basecoats used in the process according to the invention contain pigments.
- Pigments include inorganic and / or organic colored pigments and / or effect pigments and any fillers present. All common pigments can be used; Examples are titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, metal pigments, for example made of titanium, aluminum or copper, interference pigments, such as, for example, titanium dioxide-coated aluminum, coated mica, graphite effect pigments, platelet-shaped iron oxide, platelet-shaped copper phthalocyanine pigments, calcium oxide, barium sulfate, barium sulfate.
- first and the second basecoat coating compositions differ in their pigment / volume concentration (PVC) by no more than 30% of the absolute value of the pigment / volume concentration in the second basecoat coating composition.
- PVC pigment / volume concentration
- the pigment / volume concentration of the first basecoat coating composition is preferably below that of the second
- the pigment / volume concentration in a coating agent represents the ratio of pigment volume to pigment volume + binder volume and is calculated using the following equation:
- pigments are preferably used in both basecoat coating compositions, particularly preferably the same pigmentations.
- Pigmentation is understood to mean the relative composition of a pigment mixture, i.e. H. the type of pigments and their respective proportions in the pigment mixture. It is also preferred to use pigmentations with a similar average specific weight in the two basecoat coating compositions (this results from the relative proportions of the individual pigments).
- the average specifics preferably differ
- the coloring absorption pigments (colored pigments) and optionally fillers are generally rubbed into part of the water-dilutable binders. The rubbing can preferably also take place in a special water-thinnable paste resin.
- the paste resins known to the person skilled in the art and suitable for aqueous systems can be used.
- a specific example of a paste resin which can preferably be used and which is based on an anionically stabilized polyurethane resin can be found in DE-A-4000889.
- the grinding is done in conventional units known to those skilled in the art.
- paste resins are present in the waterborne basecoat, they add up to binders plus any crosslinker present. Both binders, crosslinkers and paste resins together result in the solid resin content of the waterborne basecoats.
- the waterborne basecoats may also contain customary auxiliaries, e.g. Catalysts, leveling agents, anti-foaming agents, anti-cratering agents or in particular light stabilizers, if appropriate in combination with antioxidants.
- customary auxiliaries e.g. Catalysts, leveling agents, anti-foaming agents, anti-cratering agents or in particular light stabilizers, if appropriate in combination with antioxidants.
- the waterborne basecoats for example, have a solids content of 10 to 50% by weight, for effect basecoats it is preferably 15-30% by weight, for plain-colored basecoats it is preferably higher, for example 20-45% by weight.
- the ratio of pigment to binder plus optionally crosslinking agent plus optionally paste resin in the waterborne basecoat is, for example, between 0.03: 1 to 3: 1, for effect basecoats, for example, it is preferably 0.06: 1 to 0.6: 1, for monochrome
- Basecoats are preferably higher, for example 0.06: 1 to 2.5: 1, in each case based on the solids weight.
- the first water-based lacquer used to produce the second coating layer preferably has a lower pigment / binder ratio than the second used to produce the third coating layer
- binder includes the binder or binders as such plus any crosslinking agent plus any paste resins present, the sum of these components representing the solid resin content of the water-based paints.
- the first water-based lacquer used to produce the second coating layer is distinguished from the second water-based lacquer used to produce the third coating layer by a higher proportion by weight of polyurethane resins.
- the absolute value of this excess of polyurethane resins in the first waterborne basecoat preferably corresponds to between 5 and 50%, particularly preferably between 10 and 35% of the absolute value of the weight content of solid resin in the second coating agent.
- the preferred absolute value for the polyurethane content in the first basecoat coating agent is calculated as the sum of the polyurethane content X (% by weight) of the second coating agent plus 5 to 50% of 20 % By weight, ie the polyurethane content of the first coating agent is then preferred: X + (1 to 10)% by weight.
- the absolute value of the weight content of solid resin in the first basecoat coating composition does not differ by more than 20% from the absolute value of the weight content of solid resin in the second basecoat coating composition;
- the total solid resin content of the first basecoat coating composition can accordingly be 16 to 24% by weight.
- the solid resin content of the first coating agent is particularly preferably equal to or higher than that of the second basecoat coating agent.
- the first basecoat coating composition can be produced from the second basecoat coating composition by admixing a corresponding amount of polyurethane resin.
- the higher proportion of polyurethane resin can be determined by the same or different polyurethane resins.
- polyurethane resins that can make up the higher proportion in the first water-based lacquer are the polyurethane resins described above as being suitable as binders for water-based lacquers.
- the proportion of polyurethane resin used for the second and third coating layers produced by the process according to the invention can also be different from other water-based lacquers, but preferably similar water-based lacquers.
- the two water-based paints differ only in the above-mentioned distinguishing feature essential to the invention. This is explained in more detail below.
- the first and the second water-based lacquer, apart from the excess polyurethane of the first water-based lacquer have the same solid resin composition, ie the same binders and optionally crosslinking agents and optionally paste resins are present. It is preferred if, taking into account the specifications according to the invention, the quantity of the respective components of the solid resin composition, apart from the excess polyurethane, only have a fluctuation range of less than 30%, particularly preferably less than 20% and particularly preferably less than 15%. In particular, it is preferred if the two waterborne basecoats do not differ in terms of their qualitative or quantitative solid resin composition, with the exception of the distinguishing criterion essential to the invention.
- the waterborne basecoat used to produce the second coating layer has a color tone which is close to or particularly preferably identical to that of the waterborne basecoat used to produce the third coating layer.
- the color difference composed of the difference in brightness, hue and difference in color, between the hues of the second and third coating layers determined in each case with opaque coating and a measurement geometry of (45/0) -fold ⁇ E * (CIELAB) - value does not exceed.
- the ⁇ E * (CIELAB) reference value is the value which results in the CIE-x, y diagram (chromaticity diagram) familiar to the person skilled in the art based on DIN 6175 for the color of the third coating layer, and the following relationship applies:
- all customary clear lacquers or transparent colored or colorless pigmented coating compositions are suitable as clear coating compositions for the production of the fourth and possibly further coating layers.
- These can be single-component or multi-component clear lacquer coating compositions. They can be solvent-free (liquid or as a powder clearcoat), or they can be systems based on solvents, or they can be water-dilutable clearcoats, the binder systems of which are suitable, e.g. anionic, cationic or non-ionic, are stabilized.
- the water-dilutable clear lacquer systems can be water-soluble or water-dispersed systems, for example emulsion systems or powder slurry systems.
- the clear lacquer coating agents harden when stoved to form covalent bonds as a result of chemical crosslinking.
- the clearcoats which can be used in the process according to the invention are the customary clearcoat coating compositions which are known to the person skilled in the art and which contain one or more customary base resins as film-forming binders. If the base resins are not self-crosslinking, they may also contain crosslinking agents. Both the base resin component and the crosslinker component are not subject to any limitation. Polyester, polyurethane and / or (meth) acrylic copolymer resins, for example, can be used as film-forming binders (base resins).
- powder clearcoat systems which can be used as clearcoat in the process according to the invention can be found in EP-A-0 509392, EP-A-0509393, EP-A-0 522648, EP-A-0 544 206, EP-A- 0555 705, DE-A-42 22 194, DE-A-42 27 580.
- the transparent coating can be applied in a single layer or in the form of several layers from the same or from several different transparent coating agents.
- the transparent coating layer is expediently applied as a fourth layer comprising only one clear lacquer coating agent.
- Electrically conductive materials such as metals are suitable as the substrate for the method according to the invention.
- Particularly suitable are e.g. Automobile bodies or parts thereof, they can consist of pretreated or untreated metal, of metal provided with an electrically conductive layer or of electrically conductive or plastic provided with an electrically conductive layer.
- the first coating layer in particular in the form of a
- Corrosion protection primer electrophoretically in the usual way and in a dry layer thickness of usual for ETL primers for example, 15 to 35 microns deposited and baked.
- a dry layer thickness of usual for ETL primers for example, 15 to 35 microns deposited and baked.
- multi-layer coatings are obtained with more than the four coating layers produced according to the invention, but within the scope of the present invention the electrocoat layer applied first in the method according to the invention is referred to as the first coating layer.
- the second coating layer composed of the first coloring and / or effect-imparting water-based lacquer is preferably applied to the substrate provided with the baked ETL layer in one spray pass in one of the
- Coverage of the color tone-dependent dry layer thickness of 10 to less than 30 ⁇ m, for example 10 to 29 ⁇ m, preferably 10 to 25 ⁇ m, particularly preferably 10 to 20 ⁇ m.
- suitable spray application methods are compressed air spraying, airless spraying or electrostatic (ESTA) high-rotation spraying, electrostatic spraying being the preferred application method for applying the first water-based lacquer.
- Waterborne basecoat in one spray pass preferably by compressed air spraying, preferably in a smaller dry layer thickness than the second coating layer, applied from only 7 to 15 ⁇ m and briefly vented, if appropriate at temperatures up to 80 ° C., for example for 1 to 5 minutes, for example by the action of infrared radiation.
- the clear lacquer is applied in a wet-on-wet process.
- the fourth coating layer is overpainted from a customary liquid clear lacquer or powder clear lacquer (in this case it is a dry-in-wet application) in a dry layer thickness customary for clear lacquer layers of, for example, 30 to 80 ⁇ m, preferably 30 to 60 ⁇ m, and together baked with the second and third coating layers.
- a customary liquid clear lacquer or powder clear lacquer in this case it is a dry-in-wet application
- a dry layer thickness customary for clear lacquer layers of, for example, 30 to 80 ⁇ m, preferably 30 to 60 ⁇ m, and together baked with the second and third coating layers.
- the stoving temperature is when the three are stoved together
- the method according to the invention permits the production of four- or multi-layer coatings, in particular automotive coatings with a reduced overall layer thickness and comparable overall property level compared to the prior art, which includes filler layers and / or other intermediate layers. Only two burn-in steps are necessary. It has been shown that excellent properties are achieved by the procedure according to the invention, although this makes it possible to dispense with conventional filler layers.
- Example 1 state of the art, painting with filler layer
- a water-based paint (blue metallic) with a dry layer thickness of 15 ⁇ m is applied by spraying to a customary phosphated body panel pre-coated by cathodic dip painting and with a 30 ⁇ m thick filler layer. After application, the product is briefly flashed off and then predried at 80 ° C. for 10 minutes. It is then overpainted with a commercially available 2K-HS automotive series clear coat (two-component high-solid clear coat based on acrylic resin / polyisocyanate) in a dry layer thickness of 40 ⁇ m and dried for 30 minutes at 130 ° C (object temperature).
- the water-based paint (blue metallic) consisted of the following components:
- the solid resin content (absolute value of the weight content of solid resin) of this water-based lacquer is 13.8% by weight.
- the waterborne basecoat (blue metallic) from Example 1 is applied to a customary phosphated and pre-coated bodywork sheet by cathodic dip coating in a dry layer thickness of 15 ⁇ m. After application, the product is flashed off briefly and then a second layer of the same waterborne basecoat is applied in a dry layer thickness of 10 ⁇ m, likewise by spraying. It is predried at 80 ° C. for 10 minutes. Then the 2K-HS automotive series clearcoat from Example 1 is overpainted in a dry layer thickness of 40 ⁇ m and dried for 30 minutes at 130 ° C (object temperature).
- Example 2 is repeated with the difference that the 15 ⁇ m thick lacquer layer applied to the KTL layer is not applied from the water-based lacquer (blue-metallic) from example 1, but from a modified water-based lacquer (blue-metallic), while the subsequently in 10 ⁇ m dry layer thickness applied lacquer layer as in example 2 is produced from the water-based lacquer (blue-metallic) from example 1.
- the modified waterborne basecoat (blue metallic) is produced by mixing 87 parts of the waterborne basecoat (blue metallic) from Example 1 with 13 parts of an aqueous polyurethane resin adjusted to a solids content of 34% by weight. The following are used as aqueous polyurethane resins:
- Example 4 state of the art, painting with filler layer
- the waterborne basecoat (black) described below is applied to a customary phosphated and pre-coated by cathodic dip painting and pre-coated with a 30 ⁇ m thick filler layer in a dry layer thickness of 20 ⁇ m. After application, the product is briefly flashed off and then predried for 10 minutes at ⁇ o'c.
- Example 2K-HS automotive series clearcoat from Example 1 is overpainted in a dry layer thickness of 40 ⁇ m and dried for 30 minutes at 130'C (object temperature).
- the water-based paint (black) consisted of the following components:
- This waterborne basecoat has a solid resin content of 21.9% by weight.
- Example 5 comparative, painting without filler layer
- the water-based paint (black) from Example 4 is applied to a customary phosphated and pre-coated bodywork sheet by cathodic dip coating in a dry layer thickness of 15 ⁇ m. After application, the product is briefly flashed off and then a second layer of the same waterborne basecoat is applied in a dry layer thickness of 10 ⁇ m, likewise by spraying. It is predried at 80 ° C. for 10 minutes. Subsequently, the 2K-HS automotive series clearcoat from Example 1 is overpainted in a dry layer thickness of 40 ⁇ m and dried for 30 minutes at 13 ° C. (object temperature).
- Example 5 is repeated with the difference that the 15 ⁇ m thick lacquer layer applied to the KTL layer is not applied from the water-based lacquer (black) from example 4, but from a modified water-based lacquer (black), while the one subsequently applied in a 10 ⁇ m dry layer thickness Lacquer layer as in Example 5 is produced from the water-based lacquer (black) from Example 4.
- the modified waterborne basecoat (black) is prepared by mixing 85 parts of the waterborne basecoat (black) from Example 4 with 15 parts of an aqueous polyurethane resin adjusted to a solids content of 34% by weight. The following are used as aqueous polyurethane resins:
- the water-based paints 6a), 6b) and 6c) each have a solid resin content of 23.7% by weight.
- Table 1 summarizes the results of the stone chip tests carried out.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19606716A DE19606716C1 (de) | 1996-02-23 | 1996-02-23 | Verfahren zur Mehrschichtlackierung |
| DE19606716 | 1996-02-23 | ||
| PCT/EP1997/000784 WO1997030795A1 (fr) | 1996-02-23 | 1997-02-19 | Procede pour l'application de peinture en plusieurs couches |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0881954A1 true EP0881954A1 (fr) | 1998-12-09 |
| EP0881954B1 EP0881954B1 (fr) | 1999-08-11 |
Family
ID=7786172
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97903326A Expired - Lifetime EP0881954B1 (fr) | 1996-02-23 | 1997-02-19 | Procede pour l'application de peinture en plusieurs couches |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5976343A (fr) |
| EP (1) | EP0881954B1 (fr) |
| JP (1) | JP4096069B2 (fr) |
| AU (1) | AU1792497A (fr) |
| BR (1) | BR9707608A (fr) |
| DE (2) | DE19606716C1 (fr) |
| ES (1) | ES2140962T3 (fr) |
| WO (1) | WO1997030795A1 (fr) |
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| JPS62216671A (ja) * | 1986-03-17 | 1987-09-24 | Nippon Paint Co Ltd | メタリツク塗装方法 |
| DE3628124A1 (de) * | 1986-08-19 | 1988-03-03 | Herberts Gmbh | Waessriges ueberzugsmittel, verfahren zu seiner herstellung und dessen verwendung |
| DE4000889A1 (de) * | 1990-01-13 | 1991-07-25 | Herberts Gmbh | Bindemittelzusammensetzung zur herstellung von pigmentpasten und waessrige ueberzugsmittel, die diese pigmentpasten enthalten |
| US5326596A (en) * | 1991-12-19 | 1994-07-05 | Kansai Paint Company, Ltd. | Coating method |
| DE4224617A1 (de) * | 1992-07-25 | 1994-01-27 | Herberts Gmbh | Wäßriges Überzugsmittel, Verfahren zu dessen Herstellung und dessen Verwendung bei Verfahren zur Mehrschichtlackierung |
| DE4413562A1 (de) * | 1994-04-19 | 1995-10-26 | Herberts Gmbh | Wäßrige Dispersion von Siloxanbrücken enthaltenden Polyurethanen, deren Herstellung und Verwendung in Überzugsmitteln |
| CA2162210A1 (fr) * | 1994-11-07 | 1996-05-08 | Takumi Kunikiyo | Methode de production d'une pellicule de revetement |
-
1996
- 1996-02-23 DE DE19606716A patent/DE19606716C1/de not_active Expired - Lifetime
-
1997
- 1997-02-19 JP JP52978997A patent/JP4096069B2/ja not_active Expired - Fee Related
- 1997-02-19 DE DE59700330T patent/DE59700330D1/de not_active Expired - Lifetime
- 1997-02-19 WO PCT/EP1997/000784 patent/WO1997030795A1/fr not_active Ceased
- 1997-02-19 US US09/101,271 patent/US5976343A/en not_active Expired - Fee Related
- 1997-02-19 AU AU17924/97A patent/AU1792497A/en not_active Abandoned
- 1997-02-19 EP EP97903326A patent/EP0881954B1/fr not_active Expired - Lifetime
- 1997-02-19 BR BR9707608A patent/BR9707608A/pt not_active IP Right Cessation
- 1997-02-19 ES ES97903326T patent/ES2140962T3/es not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9730795A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59700330D1 (de) | 1999-09-16 |
| EP0881954B1 (fr) | 1999-08-11 |
| JP4096069B2 (ja) | 2008-06-04 |
| WO1997030795A1 (fr) | 1997-08-28 |
| JP2000505352A (ja) | 2000-05-09 |
| ES2140962T3 (es) | 2000-03-01 |
| DE19606716C1 (de) | 1997-08-14 |
| BR9707608A (pt) | 1999-07-27 |
| US5976343A (en) | 1999-11-02 |
| AU1792497A (en) | 1997-09-10 |
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