EP1192226B1 - Elektrotauchlackbad mit wasserlöslichen polyvinylalkohol(co)polymeren - Google Patents
Elektrotauchlackbad mit wasserlöslichen polyvinylalkohol(co)polymeren Download PDFInfo
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- EP1192226B1 EP1192226B1 EP00945845A EP00945845A EP1192226B1 EP 1192226 B1 EP1192226 B1 EP 1192226B1 EP 00945845 A EP00945845 A EP 00945845A EP 00945845 A EP00945845 A EP 00945845A EP 1192226 B1 EP1192226 B1 EP 1192226B1
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- Prior art keywords
- polyvinyl alcohol
- parts
- polymer
- electrodeposition bath
- groups
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/901—Electrodepositable compositions
Definitions
- the invention relates to a new use of water-soluble Polyvinyl alcohol (co) polymers, containing a polyvinyl alcohol (co) polymer Electrocoating bath and a process for the production of coated Substrates using the electrodeposition bath.
- Electrocoating is a well-known method of coating the surface of electrically conductive objects (compare for example: Glasurit manual paints and paints, Curt R. Vincentz Verlag, Hanover, 1984, Pages 374 to 384 and pages 457 to 462, as well as DE-A-35 18 732, DE-A-35 18 770, EP-A-0 040 090, EP-A-0 012 463, EP-A-0 259 181, EP-A-0 433 783 and EP-A-0 262 069).
- the process is used to coat objects made of metal, especially for priming automobile bodies, or for Coating of conductive plastic used.
- the paints used in electrodeposition coating generally contain synthetic resins containing amino groups or carboxyl groups as binders, the neutralization of the amino or carboxyl groups achieving water dispersibility.
- Special grinding resins and optionally other non-water-dispersible constituents such as polymers, plasticizers, pigments, fillers, additives and auxiliaries can be further constituents of the electrodeposition paints.
- the crosslinking agents used in the electrodeposition paints are either not water-dispersible or can be water-dispersible, the electrodeposition paints being externally crosslinking, or also self-crosslinking or curable with condensation.
- the properties of the paint are influenced.
- electrodeposition paints are known in which the addition of polymer microparticles or suspended or dispersed polymer powders is intended to favorably influence the protection against corrosion, especially on edges.
- EP-A-0 259 181 recommends that the edges of the coated substrate be closed observed increased susceptibility to corrosion due to an inadequate to fix thick lacquer layer by adding polymer microgels, e.g. Poly (meth) acrylate copolymers in combination with ethylenically unsaturated Vinyl compounds can be part of such microgels.
- polymer microgels e.g. Poly (meth) acrylate copolymers in combination with ethylenically unsaturated Vinyl compounds can be part of such microgels.
- microgel dispersions based on epoxy-amine adducts are characterized by their good tolerance and high efficacy as Edge protection additives from, as described in EP 0626 000.
- the particle sizes of such Plastic powder can significantly reduce the particle sizes of the water-dispersible synthetic resins of known electrodeposition paints exceed: the average particle diameter in JP-A-0624820 is 1 to 50 Micrometers, in DE-A-39 40 782 and EP-A-0 433 783 at 0.1 to 100 Micrometer.
- EP-A-0 259 181, DE-B-26 50 611, EP-A-0 052 831, EP-A-0 433 783, SU-A-436890, JP-A-53094346, JP-A-79028410 and JP-A-0624820 polymer particles described leads to aqueous electrodeposition paints in some Cases to improve the edge coverage.
- Disadvantageous side effects of adding plastic powder are one Deterioration of the wrap around the electrocoat, the adhesion to the substrate and / or to subsequent coatings, such as overcoated paint layers or PVC underbody protection, deterioration in mechanical properties, such as Flexibility, ductility, breaking and impact resistance, poorer flow properties and a drastic deterioration in the course.
- the stability disadvantages of the paints are eliminated by incorporating copolymers with vinyl acetal, vinyl alcohol and ethylene units directly into the resins, for example. by grafting reaction, as described in DE 196 18 379.
- the proportion is more than 10% by weight. of polymer resin is necessary to achieve adequate edge coverage.
- the incorporation of plastic powder or microgels requires proportions in the percentage range, whereby the flow is in some cases drastically impaired.
- im Electrodeposition paints are water-soluble cellulose ethers, such as hydroxyethyl cellulose, (EP 0640 700). The effectiveness is not permanent, however, because of the degradation of the polymer takes place.
- Polyvinyl alcohols are widely used in paints, especially as Suspension stabilizers in the polymerization of vinyl monomers.
- Polyvinyl alcohols as complexing agents and suspension stabilizers in the pre-treatment of iron, steel, zinc and aluminum sheets in combination with chromates or fluorine compounds is known (J 73008702, WO 9627034), in particular the electrophoretic deposition of metal suspensions, such as Aluminum (SU 738334, J-A-111201), metal oxide suspensions, such as bsw.
- Electrocoating indicate which coatings result in all requirements in terms of edge protection and resistance to contamination, especially towards Oiling is sufficient and at the same time can be produced with little effort and has long-term stability are.
- the invention teaches the use of a water soluble polyvinyl alcohol (co) polymers or a mixture of Polyvinyl alcohol (co) polymers as an additive in aqueous electrocoating baths.
- Aqueous electrocoating baths contain little or no organic Solvent.
- the term water soluble means a real dissolution process in water and not a dispersion of particulate units at the supermolecular level.
- the polyvinyl alcohol (co) polymer is preferably used as an additive in aqueous solution prepared, if necessary with conventional paint additives, and the aqueous solution dem Electrocoating bath added.
- additive defines that the Polyvinyl alcohol (co) polymer as a molecularly independent unit in Electrocoating bath is present and in particular not reactive in a binder, resin or the like is involved. Of course, this definition does not conclude from that the polyvinyl alcohol (co) polymer is reactive in a deposited coating is incorporated into the other components of the deposited coating.
- polyvinyl alcohol (co) polymer denotes a random copolymer or block copolymer which contains polymer units of the general formula I, or a homopolymer which consists of polymer units of the general formula I, the polyvinyl alcohol copolymers being advantageous according to the invention, and therefore are preferred.
- the polymer building blocks I be linked head-to-head or head-to-tail.
- the polymer building blocks I are advantageously to a far predominant extent Head and tail linked.
- variable R 1 stands for hydrogen atoms or for substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals.
- alkyl radicals examples include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.
- Suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.
- alkylcycloalkyl radicals examples include methylenecyclohexane, Ethylene cyclohexane or propane-1,3-diyl-cyclohexane.
- Suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, - Propyl- or -butylcyclohex-1-yl.
- Suitable aryl radicals are phenyl, naphthyl or biphenylyl.
- alkylaryl radicals examples include benzyl, ethylene or propane-1,3-diylbenzene.
- Suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl.
- Suitable arylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or -Butylphen-1-yl.
- Suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.
- radicals R 1 described above can be substituted.
- electron-withdrawing or electron-donating atoms or organic radicals can be used.
- Suitable substitutes are halogen atoms, especially chlorine and Fluorine, nitrile groups, nitro groups, partially or fully halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and Arylcycloalkyl radicals, including those mentioned above by way of example, in particular tert-butyl; Aryloxy, alkyloxy and cycloalkyloxy radicals, in particular phenoxy, Naphthoxy, methoxy, ethoxy, propxy, butyloxy or cyclohexyloxy; Arylthio, Alkylthio and cycloalkylthio radicals, in particular phenylthio, naphthylthio, Methylthio, ethylthio, propylthio, butyl
- the radicals R 1 are predominantly hydrogen atoms, that is to say that the other radicals R 1 are only present in a minor proportion.
- the term “subordinate portion” denotes a portion which advantageously varies the application properties profile of the polyvinyl alcohol (co) polymers, in particular their water solubility, and does not deteriorate or even completely change them.
- Special advantages result if they change the radicals R 1 are exclusively hydrogen atoms, that is to say that the polymer building blocks I are derived from the hypothetical polyvinyl alcohol. Accordingly, polyvinyl alcohol (co) polymers which contain these polymer building blocks I are used with particular preference.
- polyvinyl alcohol copolymers to be used according to the invention also contain, in particular, polymer building blocks of the general formula II. - [- C (R 1 ) 2 -C (R 1 ) (OC (O) R 2 ) -] - (II)
- the radicals R 1 have the meaning given above, hydrogen atoms also being of particular advantage here and therefore being used with particular preference.
- the radicals R 2 represent alkyl radicals with one to ten carbon atoms, preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl, particularly preferably methyl.
- the particularly preferred polymer building blocks II are derived from vinyl acetate.
- the polymer building blocks II can be linked head-to-head or head-to-tail.
- the polymer building blocks II are by far predominantly head-to-tail linked.
- these monomers are also used, they are to be used according to the invention using polyvinyl alcohol copolymers only in a minor proportion included, this term also here in the sense explained above is applied.
- the acyclic olefins offer in particular ethylene and propylene, in particular ethylene, particular advantages and are therefore preferably used if necessary.
- Polyvinyl alcohol (co) polymers have a degree of polymerization of 100 to 20,000, preferably 200 to 15,000, particularly preferably 300 to 12,000 and in particular 400 up to 10,000.
- the content of polymer building blocks I is advantageously in the Polyvinyl alcohol copolymers at 50 to 99.9, preferably 60 to 99.9, especially preferably 70 to 99 and in particular 80 to 99 mol%.
- the polyvinyl alcohol copolymers offer the particularly advantageous polymer building blocks I and II contain very special ones Advantages and are therefore used very particularly preferably according to the invention. These polyvinyl alcohol copolymers are also known in the art for short Called polyvinyl alcohols.
- polyvinyl alcohols are not by direct Polymerization processes are accessible, but are based on polymer analogs Reactions produced by hydrolysis of polyvinyl acetate.
- Particularly advantageous Commercial polyvinyl alcohols have molecular weights of 10,000 to 500,000 Daltons, preferably 15,000 to 320,000 Daltons and especially 20,000 to 300,000 daltons.
- Very particularly advantageous, commercially available polyvinyl alcohols have a degree of hydrolysis of 98 to 99 or 87 to 89 mol%.
- the vinyl alcohol content can be determined, for example, indirectly via the DIN ester number 53401 determine, namely by the remaining proportion of vinyl acetate after the Hydrolysis is determined by means of the ester number.
- ATL anodic
- KTL cathodic
- ETL electrodeposition paint baths
- Electroposition baths are aqueous coating materials (ETL) with a Solids content of in particular 5 to 30% by weight.
- crosslinking agents (B) and / or their functional groups (b1) ready in the binder (A) incorporated one speaks of self-crosslinking.
- the binders (A) come as complementary functional groups (a2) preferably thio, amino, hydroxyl, carbamate, allophanate, carboxy, and / or (meth) acrylate groups, but in particular hydroxyl groups, and as complementary functional groups (b1) preferably anhydride, carboxy, Epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, amino, Hydroxy and / or beta-hydroxyalkylamide groups, but especially blocked Isocyanate groups into consideration.
- complementary functional groups (a2) preferably thio, amino, hydroxyl, carbamate, allophanate, carboxy, and / or (meth) acrylate groups, but in particular hydroxyl groups
- complementary functional groups (b1) preferably anhydride, carboxy, Epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, amino, Hydroxy and / or beta-hydroxyalkylamide groups,
- the binders (A) with functional groups (a11) are in cathodic separable electrodeposition paints (KTL) are used, whereas the binders (A) with functional groups (a12) used in anodic electrodeposition paints (ATL) will.
- Suitable functional groups (a11) to be used according to the invention those by neutralizing agents and / or quaternizing agents in cations are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, especially tertiary ones Amino groups or secondary sulfide groups.
- Suitable cationic groups to be used according to the invention (a11) are primary, secondary, tertiary or tertiary sulfonium groups or quaternary Phosphonium groups, preferably quaternary ammonium groups or quaternary Ammonium groups, tertiary sulfonium groups, but especially quaternary groups Ammonium groups.
- Suitable functional groups (a12) to be used according to the invention which can be converted into anions by neutralizing agents Carboxylic acid, sulfonic acid or phosphonic acid groups, in particular Carboxylic acid groups.
- Suitable anionic groups to be used according to the invention (a12) are carboxylate, sulfonate or phosphonate groups, in particular Carboxylate groups.
- the selection of the groups (a11) or (a12) is to be made so that no disturbing Reactions with the functional groups (a2) with the crosslinking agents (B) can react, are possible.
- the person skilled in the art can therefore make the selection in a simpler manner Wise, based on their expertise.
- Suitable neutralizing agents for functional ones convertible to cations Groups (a11) are inorganic and organic acids such as sulfuric acid, Hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, Dimethylolpropionic acid or citric acid, especially formic acid, acetic acid or lactic acid.
- Suitable neutralizing agents for convertible into anions functional groups (a12) are ammonia, ammonium salts such as, for example
- Ammonium carbonate or ammonium hydrogen carbonate as well as amines, e.g. Trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, Triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, Triethanolamine and the like.
- amines e.g. Trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, Triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, Triethanolamine and the like.
- the amount of neutralizing agent is chosen so that 1 to 100 equivalents, preferably 50 to 90 equivalents of the functional Groups (a11) or (a12) of the binder (b1) are neutralized.
- Suitable binders (A) for ATL are from patent DE-A-2824 418 known. These are preferably polyester, epoxy resin ester, Poly (meth) acrylates, maleic oils or polybutadiene oils with a weight average Molecular weight from 300 to 10,000 Daltons and an acid number from 35 to 300 mg KOH / g.
- KTL examples of suitable KTL can be found in the patents EP-A-0 082 291, EP-A-0 234 395, EP-A-0 227 975, EP-A-0 178 531, EP-A-333 327, EP-A-0 310 971, EP-A-0 456 270, US-A-3,922,253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A-0 414 199 or EP-A-476 514 known.
- These are preferably primary, secondary, tertiary or quaternary amino or ammonium groups and / or resins (A) containing tertiary sulfonium groups and having amine numbers preferably between 20 and 250 mg KOH / g and a weight average Molecular weight from 300 to 10,000 daltons.
- A tertiary sulfonium groups and having amine numbers preferably between 20 and 250 mg KOH / g and a weight average Molecular weight from 300 to 10,000 daltons.
- KTL and the corresponding electrodeposition baths preferably used.
- the EDL preferably contain crosslinking agents (B).
- Suitable crosslinking agents (B) are blocked organic ones Polyisocyanates, in particular blocked so-called paint polyisocyanates, with aliphatically, cycloaliphatically, araliphatically and / or aromatically bound, blocked isocyanate groups.
- Polyisocyanates with 2 to 5 isocyanate groups are preferred for their preparation per molecule and with viscosities from 100 to 10,000, preferably 100 to 5000 and in particular 100 to 2000 mPas (at 23 ° C) are used.
- the Polyisocyanates in the customary and known manner are hydrophilic or hydrophobic be modified.
- polyisocyanates examples include, for example, in "Methods of organic chemistry ", Houben-Weyl, Volume 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, and by W. Siefken, Liebigs Annalen der Chemie, Volume 562, pages 75 to 136.
- the Polyurethane prepolymers containing isocyanate groups, which are produced by the reaction of polyols can be prepared with an excess of polyisocyanates and the are preferably of low viscosity.
- polyisocyanates are isocyanurate, biuret, allophanate, Iminooxadiazinedione, urethane, urea and / or uretdione groups
- polyisocyanates containing urethane groups are, for example by reacting part of the isocyanate groups with polyols, e.g.
- Trimethylolpropane and glycerol are preferably aliphatic or cycloaliphatic polyisocyanates, especially hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, Dicyclohexylmethane-2,4'-diisocyanate, Dicyclohexylmethane-4,4'-diisocyanate or 1,3-bis (isocyanatomethyl) cyclohexane (BIC), diisocyanates derived from dimer fatty acids such as those under the The trade name DDI 1410 is sold by the Henkel company, 1,8-diisocyanato-4-isocyanatomethyl octane, 1,7-diisocyanato-4-isocyanatomethylheptane or 1-isocyanato-2- (3
- suitable crosslinking agents (B) are all known aliphatic and / or cycloaliphatic and / or aromatic polyepoxides, for example based on bisphenol-A or bisphenol-F.
- Suitable as polyepoxides are, for example, also those commercially available under the names Epikote® der Shell, Denacol® from Nagase Chemicals Ltd., Japan Polyepoxides, such as Denacol EX-411 (pentaerythritol polyglycidyl ether), Denacol EX-321 (trimethylolpropane polyglycidyl ether), Denacol EX-512 (polyglycerol polyglycidyl ether) and Denacol EX-521 (polyglycerol polyglycidyl ether).
- TACT alkoxycarbonylamino triazines
- B crosslinking agents
- tris (alkoxycarbonylamino) triazines (B) examples are in the US-A-4,939,213, US-A-5,084,541 or EP-A-0 624 577 are described.
- methyl-butyl mixed esters and the butyl-2-ethylhexyl mixed esters are advantageous and the butyl esters. These have the advantage over the pure methyl ester better solubility in polymer melts and also less prone to Crystallize.
- crosslinking agents (B) are amino resins, for example melamine, guanamine, benzoguanamine or urea resins. Included The customary and known amino resins are also suitable, their Methylol and / or methoxymethyl groups e.g. T. by means of carbamate or Allophanate groups are defunctionalized. Crosslinking agents of this type are used in US-A-4 710 542 and EP-B-0 245 700 and in the article by B. Singh et al. "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry "in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193-207.
- crosslinking agents (B) are beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide.
- suitable crosslinking agents (B) are compounds with on average at least two groups capable of transesterification, for example Reaction products of malonic acid diesters and polyisocyanates or of esters and partial esters of polyhydric alcohols of malonic acid with monoisocyanates, such as them European Patent EP-A-0 596 460;
- the amount of crosslinking agents (B) in the coating material of the invention or ETL can vary widely and is based in particular on the one hand Functionality of the crosslinking agent (B) and on the other hand according to the number of im Binder (A) existing crosslinking functional groups (a2) and after the network density that you want to achieve.
- the skilled person can therefore determine the amount the crosslinking agent (B) on the basis of his general technical knowledge, if appropriate determine with the help of simple, orienting experiments.
- the crosslinking agent (B) in the coating material of the invention in one Amount of 5 to 60% by weight, particularly preferably 10 to 50% by weight and in particular 15 to 45 wt .-%, each based on the solids content of the coating material according to the invention contain.
- crosslinking agent (B) and binder (A) it is recommended to use the further to choose the amounts of crosslinking agent (B) and binder (A) so that in the coating material of the invention the ratio of functional Groups (b1) in the crosslinking agent (B) and functional groups (a2) in Binder (A) between 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1.5, especially preferably 1.2: 1 to 1: 1.2 and in particular 1.1: 1 to 1: 1.1.
- the invention finally teaches a method for painting electrically conductive Substrates in which (1) the electrically conductive substrate in an electrodeposition bath is immersed as described above, (2) the substrate as a cathode or anode, preferably as a cathode, is switched on, (3) by direct current Film is deposited on the substrate, (4) the painted substrate from the Electrodeposition paint bath is removed, (5) the deposited paint film is baked and, (6) optionally, following step (5) a filler, a stone chip protection paint and a solid top coat or, alternatively, a base coat and a clear coat are applied and are baked, the basecoat and the clearcoat preferably after Wet-on-wet process can be applied and baked.
- the temperature is kept at 60 ° C. for a further 60 minutes and is reduced NCO equivalent weight of 1120 g / eq determined (based on solids).
- NCO equivalent weight 1120 g / eq determined (based on solids).
- 933 parts are melted Trimethylolpropane added at such a rate that a Product temperature of 100 ° C is not exceeded.
- the end of the addition one leaves react for a further 60 min. There are no NCO groups in the subsequent control more verifiable. It is cooled to 65 ° C. and diluted at the same time 965 parts of n-butanol and 267 parts of methyl isobutyl ketone.
- the solids content is 70.1% (1 h at 130 ° C.).
- the temperature is kept at 60 ° C. for a further 60 minutes and is reduced NCO equivalent weight of 887 g / eq determined (based on solids).
- NCO equivalent weight 887 g / eq determined (based on solids).
- 1293 parts are melted Trimethylolpropane added at such a rate that a Product temperature of 100 ° C is not exceeded.
- the solids content is 80.5% (1 h at 130 ° C).
- K2000 polyether, Byk Chemie / Germany
- Plastilit® 3060 75 minutes after the addition of the amine, 903 parts of Plastilit® 3060 are used (Propylene glycol compound, BASF / Germany), diluted with 522 parts Propylene glycol phenyl ether (mixture of 1-phenoxy-2-propanol and 2-phenoxy-1-propanol, BASF / Germany), and at the same time cools down rapidly to 95 ° C. After 10 minutes, 14821 parts of the reaction mixture are placed in a dispersing vessel convicted. There, 474 parts of lactic acid (88% in Water), dissolved in 7061 parts of deionized water. Then 20 min homogenized before using a further 12600 parts of deionized water in small Portions being further diluted.
- the volatile solvents are removed by distillation in vacuo and then replaced in the same amount by deionized water.
- the dispersion (A / B1) has the following key figures: Solids content 33.8% (1 hour at 130 ° C) 29.9% (1/2 hour at 180 ° C) Base content 0.71 milliequivalents / g solid (130 ° C) Acidity 0.36 milliequivalents / g solid (130 ° C) pH 6.3 Particle size 116 nm (Mass mean from photon correlation spectroscopy)
- binder dispersion (A / B2) is produced in a completely analogous manner to Binder dispersion (A / B1), however, are used immediately after dilution with Propylene glycol phenyl ether 378 parts of K-KAT® XP 348 (bismuth 2-ethylhexanoate; 25% bismuth, King Industries, USA) with stirring in the organic stage mixed in. After cooling, completely analogous to (A / B1) 14821 parts of the Reaction mixture dispersed:
- the dispersion (A / B2) has the following key figures: Solids content 33.9% (1 hour at 130 ° C) 30.1% (1/2 hour at 180 ° C) Base content 0.74 milliequivalents / g solid (130 ° C) Acidity 0.48 milliequivalents / g solid (130 ° C) pH 5.9 Particle size 189 nm (Mass mean from photon correlation spectroscopy)
- reaction mixture After 10 minutes, the entire reaction mixture is transferred to a dispersing vessel. There, 609 parts of lactic acid (88% in water) and 152 parts of emulsifier mixture (mixture of 1 part butyl glycol and 1 part of a tertiary acetylene glycol (Surfynol 104, Air Products / USA)), dissolved in 30266 parts of deionized, are added in portions with stirring Water, too.
- lactic acid 88% in water
- emulsifier mixture mixture of 1 part butyl glycol and 1 part of a tertiary acetylene glycol (Surfynol 104, Air Products / USA)
- the volatile solvents are removed by distillation in vacuo and then replaced in the same amount by deionized water.
- the dispersion (A / B3) has the following key figures: Solids content 37.0% (1 hour at 130 ° C) 34.1% (1/2 hour at 180 ° C) Base content 0.53 milliequivalents / g solid (130 ° C) Acidity 0.32 milliequivalents / g solid (130 ° C) pH 6.6 Particle size 150 nm (Mass mean from photon correlation spectroscopy)
- the viscous solution is stabilized against bacterial attack with 9 parts of Parmetol® K40 (Schülke and Mayr / Germany).
- the solids content of the solution is 5.0% (1 h at 130 ° C.).
- the product formed was characterized: Poly (vinyl alcohol-co-vinyl acetate-co-ethylene): Weight average molar mass 215,000 daltons Polyvinyl alcohol content 83.3% Polyvinyl acetate content 9.5% Polyethylene content 7.2%
- the solids content of the solution is 5.0% (1 h at 130 ° C.).
- an organic-aqueous grinding resin solution is used prepared by placing 2598 Parts of bisphenol A diglycidyl ether (epoxy equivalent weight (EEW) 188 g / eq), 787 Parts of bisphenol-A, 603 parts of dodecylphenol and 206 parts of butylglycol in Presence of 4 parts triphenylphosphine at 130 ⁇ C up to an EEW of 865 g / eq can react.
- EW epoxy equivalent weight
- the resin solution is used directly for paste production.
- a pigment paste PI which is stable to segregation is obtained. Solids content 60.0% (1/2 hour at 180 ° C)
- An organic-aqueous sulfonium grating resin solution is prepared by in the first stage in a stainless steel reaction vessel 2632 parts of bisphenol A diglycidyl ether (Epoxy equivalent weight (EEW) 188 g / eq), 985 parts bisphenol-A, 95 parts of nonylphenol in the presence of 1 part of triphenylphosphine at 130 ° C to reacts to an EEW of 760 g / eq.
- EW epoxy equivalent weight
- 985 parts bisphenol-A 985 parts of nonylphenol in the presence of 1 part of triphenylphosphine at 130 ° C to reacts to an EEW of 760 g / eq.
- 996 Share 2-butoxypropanol the temperature is lowered to 80 ° C.
- the reaction is complete when the acid number is less than 5 (mg KOH per g Solid). Then 10541 parts of deionized water are gradually added.
- the resin solution is used directly for paste production.
- the acid number is less than 1 (mg KOH per g of solid), it is 1457 parts Butyl glycol dissolved.
- the resin solution is used directly for paste production.
- a pigment paste (P2) which is stable to segregation is obtained. Solids content 61.5% (1/2 hour at 180 ° C)
- Electroposition paints consist of mixtures of an aqueous dispersion (A / B) and deionized water. The resulting mixtures are added to the pigment paste (P) added with stirring in designated cases.
- the aqueous solutions of polyvinyl alcohol (co) polymers (D) can be incorporated by adding to the binder dispersion (A / B) or pigment paste (P) with stirring, or by subsequent addition to the binder-paste mixture, as in the present case.
- Gray pigmented electrodeposition paints based on the binder dispersion (A / B1) and the pigment paste (P1) Electrodeposition paint Comparative experiment V1 example 1
- Example 2 Polyvinyl alcohol (co) polymer 0 ppm 600 ppm 600 ppm Parts by weight (parts) Binder disp. (A / B1) 491 491 491 Pigment paste (P1) 120 120 120 Deion. water 389 377 377 Solution of the polyvinyl alcohol (co) polym.
- the deposited paint film is rinsed off with deionized water and 20 min Baked in for a long time at 180 ° C. The baked paint films thus obtained were checked.
- the specified layer thicknesses are to be understood as dry film thicknesses.
- Test results of electrocoating baths based on the binder dispersions (A / B1) and (A / b2) with and without pigment paste (P1) Electrocoating baths Pigmented gray Unpigmented (clear coat) Examples (see Point 6; Tab. 1 and 2) V1 1 2 V2 3 4th Binder dispersion (A / B1) dito dito (STARTING AT 2)*) dito dito Pigment paste (P1) dito dito - - - PVAl-CP solution (1) - (D1) (D2) - (D1) (D2) Go PVAI copolymes. in bath (2), ppm 0 600 600 0 2000 2000 Deposition on zinc phosphate. Steel tested.
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Chemically Coating (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
Durch Modifikation der Bindemittel, Auswahl der Vernetzer und Variation der Zusammensetzung der Bestandteile des Elektrotauchlacks werden die Eigenschaften der Lackierung, wie z.B. Korrosionsschutz, Haftung und Verlauf beeinflußt. So sind insbesondere Elektrotauchlacke bekannt, bei denen durch Zusatz von PolymerMikroteilchen oder suspendierten bzw. eindispergierten Polymerpulvern der Korrosionsschutz, speziell an Kanten, der Verlauf günstig beeinflußt werden soll.
Dabei ist ein Anteil über 10 Gew.-%. von Polymerharz notwendig, um eine ausreichende Kantenabdeckung zu erzielen.
Die Einarbeitung von Kunststoffpulver oder Mikrogelen erfordert Anteile im Prozentbereich, wobei der Verlauf z.T. drastisch verschlechtert wird.
- im wesentlichen säuregruppenfreien (Meth)acrylsäureester,
- Monomere, welche mindestens eine Hydroxylgruppe pro Molekül tragen und im wesentlichen säuregruppenfrei sind, wie Hydroxyalkylester der Acrylsäure, Methacrylsäure oder einer anderen alpha,beta-olefinisch ungesättigten Carbonsäure, die sich von einem Alkylenglykol ableiten, das mit der Säure verestert ist, oder die durch Umsetzung der alpha,beta-olefinsich ungesättigten Carbonsäure mit einem Alkylenoxid erhältlich sind,
- Monomere, welche mindestens eine Säuregruppe, die in die entsprechende Säureaniongruppe überführbar ist, pro Molekül tragen,
- Vinylester von in alpha-Stellung verzweigten Monocarbonsäuren mit 5 bis 18 Kohlenstoffatomen im Molekül,
- Umsetzungsprodukte aus Acrylsäure und/oder Methacrylsäure mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül,
- cyclische und/oder acyclische Olefine wie Ethylen, Propylen, But-1-en, Pent-1-en, Hex-1-en, Cyclohexen, Cyclopenten, Norbonen, Butadien, Isopren, Cylopentadien und/oder Dicyclopentadien, insbesondere Ethylen,
- (Meth)Acrylsäureamide
- Epoxidgruppen enthaltende Monomere wie die Glycidylester ethylenisch ungesättigter Carbonsäuren,
- vinylaromatische Kohlenwasserstoffe,
- Nitrile,
- Vinylverbindungen, insbesondere Vinyl- und/oder Vinylidendihalogenide, N-Vinylpyrrolidon oder Vinylether,
- Allylverbindungen, insbesondere Allylether und -ester.
oder
- organische und/oder anorganische Pigmente, Korrosionsschutzpigmente und/oder Füllstoffe wie Calciumsulfat, Bariumsulfat, Silikate wie Talk oder Kaolin, Kieselsäuren, Oxide wie Aluminiumhydroxid oder Magnesiumhydroxid, Nanopartikel, organische Füllstoffe wie Textilfasern, Cellulosefasern, Polyethylenfasern oder Holzmehl, Titandioxid, Ruß, Eisenoxid, Zinkphosphat oder Bleisilikat; diese Additive können auch über Pigmentpasten in die erfindungsgemäße ETL eingearbeitet werden, wobei als Reibharze die vorstehend beschriebenen Bindemittel (A) in Betracht kommen;
- Radikalfänger;
- organische Korrosionsinhibitoren;
- Katalysatoren für die Vernetzung wie anorganische und organische Salze und Komplexe des Zinns, Bleis, Antimons, Wismuts, Eisens oder Mangans, vorzugsweise organische Salze und Komplexe des Wismuts und des Zinns, insbesondere Wismutlactat, -ethylhexanoat oder -dimethylolpropionat, Dibutylzinnoxid oder Dibutylzinndilaurat;
- Slipadditive;
- Polymerisationsinhibitoren;
- Entschäumer;
- Emulgatoren, insbesondere nicht ionische Emulgatoren wie alkoxylierte Alkanole und Polyole, Phenole und Alkylphenole oder anionische Emulgatoren wie Alkalisalze oder Ammoniumsalze von Alkancarbonsäuren, Alkansulfonsäuren, und Sulfosäuren von alkoxylierten Alkanolen und Polyolen, Phenolen und Alkylphenole;
- Netzmittel wie Siloxane, fluorhaltige Verbindungen, Carbonsäurehalbester, Phosphorsäureester, Polyacrylsäuren und deren Copolymere oder Polurethane;
- Haftvermittler;
- Verlaufmittel;
- filmbildende Hilfsmittel wie Cellulose-Derivate;
- Flammschutzmittel;
- organische Lösemittel;
- niedermolekulare, oligomere und hochmolekulare Reaktivverdünner, die an der thermischen Vernetzung teilnehmen können, insbesondere Polyole wie Tricyclodecandimethanol, dendrimere Polyole, hyperverzweigte Polyester, Polyole auf der Basis von Metatheseoligomeren oder verzweigten Alkanen mit mehr als acht Kohlenstoffatomen im Molekül;
- Antikratermittel;
Eine halbe Stunde danach werden 211 Teile Butylglykol und 1210 Teile Isobutanol zugesetzt.
Feststoffgehalt | 33,8 % (1 Std. bei 130°C) |
29,9 % (1/2 Std. bei 180°C) | |
Basengehalt | 0,71 Milliequivalente/g Festkörper(130°C) |
Säuregehalt | 0,36 Milliequivalente/g Festkörper(130°C) |
pH | 6,3 |
Teilchengröße | 116 nm |
(Massemittel aus Photonen-Korrelations-Spektroskopie) |
Feststoffgehalt | 33,9 % (1 Std. bei 130°C) |
30,1 % (1/2 Std. bei 180°C) | |
Basengehalt | 0,74 Milliequivalente/g Festkörper(130°C) |
Säuregehalt | 0,48 Milliequivalente/g Festkörper(130°C) |
pH | 5,9 |
Teilchengröße | 189 nm |
(Massemittel aus Photonen-Korrelations-Spektroskopie) |
Nach 10 min wird die gesamte Reaktionsmischung in ein Dispergiergefäß überführt. Dort gibt man portionsweise unter Rühren 609 Teile Milchsäure (88%ig in Wasser) und 152 Teile Emulgatormischung (Mischung aus 1 Teil Butylglykol und 1 Teil eines tertiären Acetylenglykols (Surfynol 104, Fa. Air Products / USA)), gelöst in 30266 Teilen entionisiertem Wasser, zu.
Feststoffgehalt | 37,0 % (1 Std. bei 130°C) |
34,1 % (1/2 Std. bei 180°C) | |
Basengehalt | 0,53 Milliequivalente/g Festkörper(130°C) |
Säuregehalt | 0,32 Milliequivalente/g Festkörper(130°C) |
pH | 6,6 |
Teilchengröße | 150 nm |
(Massemittel aus Photonen-Korrelations-Spektroskopie) |
Mowiol® 47-88, Fa. Clariant / Deutschland | |
Gewichtsmittlere Molmasse | 228 000 Dalton |
Polyvinylalkohol-Gehalt | 89,2% |
Polyvinylacetat-Gehalt | 10,8% |
Nach Erreichen von 80°C wird das Gemisch unter Rühren zwei Stunden gehalten, wobei das Polymer vollständig gelöst ist. Darauf erfolgt Abkühlung auf 35°C.
Der Feststoffgehalt der Lösung liegt bei 5,0 % (1 h bei 130°C).
Laborprodukt, Fa. BASF AG, Deutschland | |
Gewichtsmittlere Molmasse | 239 000 Dalton |
Polyvinylacetat-Gehalt | 92,8% |
Polyethylen-Gehalt | 7,2% |
Poly(vinylalkohol-co-vinylacetat-co-ethylen): | |
Gewichtsmittlere Molmasse | 215 000 Dalton |
Polyvinylalkohol-Gehalt | 83,3% |
Polyvinylacetat-Gehalt | 9,5% |
Polyethylen-Gehalt | 7,2% |
Feststoffgehalt | 60,0 % (1/2 Std. bei 180°C) |
Feststoffgehalt | 61,5 % (1/2 Std. bei 180°C) |
Grau pigmentierte Elektrotauchlacke auf Basis der Bindemittel-Dispersion (A/B1) und der Pigmentpaste (P1) | |||
Elektrotauchlack | Vergleichsversuch | ||
V1 | Beispiel 1 | Beispiel 2 | |
Polyvinylalkohol-(co)polymer | 0 ppm | 600 ppm | 600 ppm |
Gewichtsanteile (Teile) | |||
Bindemittel-Disp. (A/B1) | 491 | 491 | 491 |
Pigmentpaste (P1) | 120 | 120 | 120 |
Deion. Wasser | 389 | 377 | 377 |
Lsg des Polyvinyl-Alkohol(co)polym. (D1) | 12 | ||
(D2) | 12 | ||
SUMME | 1000 | 1000 | 1000 |
Unpigmentierte Elektrotauchlacke (Klarlack) auf Basis der Bindemittel-Dispersion (A/B2) | |||
Elektrotauchlack | Vergleichsversuch | ||
V2 | Beispiel 3 | Beispiel 4 | |
Polyvinylalkohol-(co)polymer | 0 ppm | 1500 ppm | 600 ppm |
Gewichtsanteile (Teile) | |||
Bindemittel-Disp.(A/B2) | 498 | 498 | 498 |
Deion. Wasser | 502 | 462 | 462 |
Lsg des Polyvinyl-Alkohol(co)polym. (D1) | 40 | ||
(D2) | 40 | ||
SUMME | 1000 | 1000 | 1000 |
Grau pigmentierte Elektrotauchlacke auf Basis der Bindemittel-Dispersion (A/B3) und der Pigmentpaste (P2) | |||
Elektrotauchlack | Vergleichsversuch | ||
V3 | Beispiel 5 | Beispiel 6 | |
Polyvinylalkohol-Copolymer | 0 ppm | 600 ppm | 600 ppm |
Gewichtsanteile (Teile) | |||
Bindemittel-Disp.(A/B3) | 416 | 416 | 416 |
Pigmentpaste (P2) | 105 | 105 | 105 |
Deion. Wasser | 479 | 467 | 467 |
Lsg des Polyvinyl-Alkohol(co)polym. (D1) | 12 | ||
(D2) | 12 | ||
SUMME | 1000 | 1000 | 1000 |
Prüfergebnisse von Elektrotauchlackbäder auf Basis der Bindemittel- Dispersionen (A/B1) und (A/b2) mit und ohne Pigmentpaste (P1) | ||||||
Elektrotauchlackbäder | Grau pigmentiert | Unpigmentiert (Klarlack) | ||||
Beispiele (s. Pkt. 6; Tab. 1 u.2) | V1 | 1 | 2 | V2 | 3 | 4 |
Bindemittel-Dispersion | (A/B1) | dito | dito | (A/B2)*) | dito | dito |
Pigmentpaste | (P1) | dito | dito | - | - | - |
PVAl-CP -Lösung (1) | - | (D1) | (D2) | - | (D1) | (D2) |
Geh. PVAI-Copolym. im Bad (2), ppm | 0 | 600 | 600 | 0 | 2000 | 2000 |
Abscheidung auf zinkphosphat. Stahlprüft. (3) Schichtdicke, µm | 20,7 | 20,9 | 20,2 | 20,6 | 19,2 | 19,3 |
Spannung, V | 300 | 310 | 300 | 320 | 320 | 320 |
Elektrische Gütezahl (4) als Maß für die Kantenbedeckung, % | 6 | 100 | 97 | 8 | 88 | 73 |
Verlauf (5) | 2 | 3 | 3 | 2 | 2 | 3 |
Korrosionsschutz nach 10 | ||||||
Zyklen Klimawechseltest (6) | ||||||
Unterwanderung am Ritz, mm (7) | 2,3 | 2,1 | 2,1 | 2,3 | 2,1 | 2,3 |
Flächenrost (8) | 1 | 1 | 1 | 1 | 1 | 1 |
Kantenrost (9) | 3 | 1 | 1 | 4 | 1 | 2 |
Korrosionsschutz nach Kantenbeschichtungsprüfungder Ford-Prüfmethode BI 127-01 (10) | ||||||
Zahl der Rostpunkte auf einer Klingenscheide (10) | >80 | 19 | 21 | >80 | 29 | 35 |
Ölspritzerverträglichkeit (11) nach BASF-Prüfmethode MEB0123A Verkraterte Fläche pro Gesamtfl: in % (11) | >80 | ≤10 | ≤10 | >80 | ≤10 | ≤10 |
Prüfergebnisse von Elektrotauchlackbäder auf Basis der Bindemittel-Dispersion (A/B3) mit Pigmentpaste (P2) | |||
Elektrotauchlackbäder | Grau pigmentiert | ||
Beispiele (s. Pkt. 6; Tab.3) | V3 | 5 | 6 |
Bindemittel-Dispersion | (A/B3) | dito | dito |
Pigmentpaste | (P2) | dito | dito |
PVAI-CP-Lösung | - | (D1) | (D2) |
Gehalt PVA1-Copolym. im Bad in ppm | 0 | 600 | 600 |
Abscheidung auf zinkphosphatierten Stahlprüftafeln | |||
Schichtdicke in µm | 20,2 | 19,9 | 20,3 |
Spannung in V | 310 | 310 | 310 |
Elektrische Gütezahl als Maß für die Kantenbedeckung in % | 12 | 99 | 95 |
Verlauf | 2 | 3 | 3 |
Korrosionsschutz nach 10 Zyklen Klimawechseltest Unterwanderung am Ritz in mm | 2,6 | 2,4 | 2,4 |
Flächenrost | 1 | 1 | 1 |
Kantenrost | 3 | 1 | 1 |
Korrosionsschutz nach Kantenbeschichtungsprüfung der Ford-Prüfmethode BI 127-01 Zahl der Rostpunkte auf einer Klingenscheide | >80 | 22 | 24 |
Ölspritzerverträglichkeit nach BASF-Prüfmethode MEB0123A Verkraterte Fläche pro Gesamtfläche in % | >80 | ≤10 | ≤10 |
Claims (7)
- Verwendung eines wasserlöslichen Polyvinylalkohol(co)polymers oder einer Mischung von Polyvinylalkohol(co)polymeren als Additiv in wäßrigen kathodischen Elektrotauchlackbädem, wobei der Anteil an Polyvinylalkohol(co)polymer in dem Elektrotauchlackbad 2 bis 10.000 ppm, bezogen auf das Gesamtgewicht des Elektrotauchbades, beträgt.
- Verwendung nach Anspruch 1, wobei das Polyvinylalkohol(co)polymer ein Copolymer aus Vinylalkohol und ethylenisch ungesättigten Monomeren, vorzugsweise einem ethylenisch ungesättigten Monomer oder mehreren ethylenisch ungesättigten Monomeren, insbesondere Vinylacetat, Vinylacetal, Ethylen und/oder Propylen.
- Verwendung nach Anspruch 1 oder 2, wobei das Polyvinylalkohol(co)polymer einen Vinylalkohol-Anteil von 50 bis 99,9, vorzugsweise 60 bis 99,9, besonders bevorzugt 70 bis 99 und insbesondere 80 bis 99 Mol-%, aufweist.
- Verwendung nach einem der Ansprüche 1 bis 3, wobei die gewichtsmittlere Molekularmasse des Polyvinylalkohol(co)polymeren 10. 000 bis 500.000, vorzugsweise 15.000 bis 320.000 und insbesondere 20.000 bis 300.000 Dalton, beträgt.
- Verwendung nach einem der Ansprüche 1 bis 4, wobei der Anteil an Polyvinylalkohol(co)polymer in dem Elektrotauchlackbad 20 bis 5000 ppm und insbesondere 300 bis 1500 ppm, jeweils bezogen auf das Gesamtgewicht des Elektrotauchbades, beträgt.
- Wäßriges kathodisches Elektrotauchlackbad enthaltend(A) ein kathodisch abscheidbares Bindemittel,(B) optional ein Vemetzungsmittel,(C) optional lackübliche Zusatzstoffe sowie(D) ein gelöstes Polyvinylalkohol(co)polymer gemäß einem der Ansprüche 2 bis 5, wobei der Anteil an Polyvinylalkohol(co)polymer in dem Elektrotauchlackbad 2 bis 10.000 ppm, bezogen auf das Gesamtgewicht des Elektrotauchbades, beträgt.
- Verfahren zum Lackieren elektrisch leitfähiger Substrate, bei dem(1) das elektrisch leitfähige Substrat in ein Elektrotauchlackbad gemäß Anspruch 6 getaucht wird,(2) das Substrat als Kathode geschaltet wird,(3) durch Gleichstrom ein Film auf dem Substrat abgeschieden wird,(4) das lackierte Substrat aus dem Elektrotauchlackbad entfernt wird,(5) der abgeschiedene Lackfilm eingebrannt wird und,(6) optional, anschließend an die Stufe (5) ein Füller und/oder ein Steinschlagschutzlack und ein Unidecklack oder alternativ ein Basislack und Klarlack appliziert und eingebrannt werden, wobei der Basislack und der Klarlack insbesondere nach dem Naß-in-naß-Verfahren appliziert und eingebrannt werden.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19930060 | 1999-06-30 | ||
DE19930060A DE19930060A1 (de) | 1999-06-30 | 1999-06-30 | Elektrotauchlackbad mit wasserlöslichem Polyvinylalkohol(co)polymeren |
PCT/EP2000/006035 WO2001002498A1 (de) | 1999-06-30 | 2000-06-29 | Elektrotauchlackbad mit wasserlöslichen polyvinylalkohol(co)polymeren |
Publications (2)
Publication Number | Publication Date |
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EP1192226A1 EP1192226A1 (de) | 2002-04-03 |
EP1192226B1 true EP1192226B1 (de) | 2005-06-15 |
Family
ID=7913117
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00945845A Expired - Lifetime EP1192226B1 (de) | 1999-06-30 | 2000-06-29 | Elektrotauchlackbad mit wasserlöslichen polyvinylalkohol(co)polymeren |
Country Status (9)
Country | Link |
---|---|
US (1) | US6951602B1 (de) |
EP (1) | EP1192226B1 (de) |
JP (1) | JP5527915B2 (de) |
AT (1) | ATE297967T1 (de) |
AU (1) | AU5979800A (de) |
BR (1) | BR0012095B1 (de) |
DE (2) | DE19930060A1 (de) |
ES (1) | ES2243279T3 (de) |
WO (1) | WO2001002498A1 (de) |
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-
1999
- 1999-06-30 DE DE19930060A patent/DE19930060A1/de not_active Ceased
-
2000
- 2000-06-29 AU AU59798/00A patent/AU5979800A/en not_active Abandoned
- 2000-06-29 DE DE50010568T patent/DE50010568D1/de not_active Expired - Lifetime
- 2000-06-29 BR BRPI0012095-2A patent/BR0012095B1/pt not_active IP Right Cessation
- 2000-06-29 JP JP2001508277A patent/JP5527915B2/ja not_active Expired - Lifetime
- 2000-06-29 US US10/009,161 patent/US6951602B1/en not_active Expired - Lifetime
- 2000-06-29 AT AT00945845T patent/ATE297967T1/de not_active IP Right Cessation
- 2000-06-29 WO PCT/EP2000/006035 patent/WO2001002498A1/de active IP Right Grant
- 2000-06-29 ES ES00945845T patent/ES2243279T3/es not_active Expired - Lifetime
- 2000-06-29 EP EP00945845A patent/EP1192226B1/de not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019072774A1 (de) | 2017-10-09 | 2019-04-18 | Basf Coatings Gmbh | Elektrotauchlacke enthaltend wenigstens eine triazin-verbindung |
US11692105B2 (en) | 2017-10-09 | 2023-07-04 | Basf Coatings Gmbh | Electrocoats containing at least one triazine compound |
WO2023117951A1 (en) | 2021-12-21 | 2023-06-29 | Basf Se | Apparatus for generating a digital access element |
WO2023117937A1 (en) | 2021-12-21 | 2023-06-29 | Basf Se | Environmental attributes for coating materials |
Also Published As
Publication number | Publication date |
---|---|
EP1192226A1 (de) | 2002-04-03 |
DE50010568D1 (de) | 2005-07-21 |
AU5979800A (en) | 2001-01-22 |
US6951602B1 (en) | 2005-10-04 |
JP5527915B2 (ja) | 2014-06-25 |
ES2243279T3 (es) | 2005-12-01 |
WO2001002498A1 (de) | 2001-01-11 |
BR0012095B1 (pt) | 2010-11-03 |
ATE297967T1 (de) | 2005-07-15 |
BR0012095A (pt) | 2002-04-02 |
DE19930060A1 (de) | 2001-01-11 |
JP2003504448A (ja) | 2003-02-04 |
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