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US20050234149A1 - Aqueous electrodeposition paints, use thereof in methods for coating electrically conductive substrates, and use of bismuth compounds in said aqueous electrodeposition paints - Google Patents

Aqueous electrodeposition paints, use thereof in methods for coating electrically conductive substrates, and use of bismuth compounds in said aqueous electrodeposition paints Download PDF

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Publication number
US20050234149A1
US20050234149A1 US10/521,343 US52134305A US2005234149A1 US 20050234149 A1 US20050234149 A1 US 20050234149A1 US 52134305 A US52134305 A US 52134305A US 2005234149 A1 US2005234149 A1 US 2005234149A1
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Prior art keywords
bismuth
groups
pigments
reactive functional
electrocoat
Prior art date
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Abandoned
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US10/521,343
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English (en)
Inventor
Karl-Heinz Grosse-Brinkhaus
Gunther Ott
Hardy Reuther
Hans-Otto Koebert
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BASF Coatings GmbH
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BASF Coatings GmbH
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Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Assigned to BASF COATINGS AG reassignment BASF COATINGS AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GROSSE-BRINKHAUS, KARL- HEINZ, KOEBBERT, HANS- OTTO, OTT, Günther, REUHER, HARDY
Publication of US20050234149A1 publication Critical patent/US20050234149A1/en
Priority to US11/416,909 priority Critical patent/US7504444B2/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/025—Preservatives, e.g. antimicrobial agents

Definitions

  • the present invention relates to aqueous electrocoat (EC) materials comprising bismuth compounds, to their use in processes for coating electrically conductive substrates, and the use of bismuth compounds in aqueous electrocoat materials.
  • EC aqueous electrocoat
  • aqueous coating materials and the aqueous components used to prepare these coating materials such as binder dispersions, pigment pastes, and the like, for example, there is a desire from the standpoint of the environment in particular for a very low solvent content. Besides the desired effect of a reduced burden on the environment, however, the reduction in solvent content also leads to problems. For example, the problem of bacterial and/or fungal infestation of these aqueous systems occurs to an increased extent (see Wolfgang Siegert in Park+Lack, Vol. 99, No. 1, 1992, pages 37 to 39).
  • the bacterial resistance can be increased, for example, by replacing the lactic acid commonly used to neutralize the binder by acids which are less readily biodegradable, such as acetic acid, formic acid or inorganic acids, for example. Frequently, however, this change of acid is insufficient to eliminate the problems caused by the bacterial or fungal infestation. It is also possible to add biocidal additives, such as formaldehyde or isothiazolinones, to the electrocoat materials (cf. the paper by Siegfried Kuhpal, “Mikrobielle sidewalk in der Elektrotauchlacktechnik (ETL)” [Microbial Problems in Electrocoating], ADVANCES IN COATINGS, 2 nd Symposium, Nov.
  • biocidal additives such as formaldehyde or isothiazolinones
  • Patent EP-A 0 925 334 discloses the addition of silver or silver ions to electrocoat materials as a bactericide. In this case, however, silver may be deposited colloidally, and these deposits may in turn detract from the stability of the binders and/or electrocoat materials.
  • Patent EP 0 509 437 B1 describes the use of bismuth compounds or zirconium compounds alongside dialkyltin carboxylates for the purpose of improving corrosion protection. No reference to a bactericidal effect can be inferred.
  • Patent EP 0 642 558 B1 describes catalyzed cationic paint binders which comprise bismuth salts of lactic acid and/or of dimethylolpropionic acid. No reference to a bactericidal effect can be inferred from this patent.
  • European patent application EP 0 690 106 A1 discloses compositions which comprise water-soluble bismuth compounds, which are suitable as catalysts for the curing of EC materials. They include an epoxy-amine adduct in an amount such that the ratio of the number of bismuth atoms to the number of beta-hydroxyamine groups in the epoxy-amine adduct is from 1:10 to 10:1.
  • the acid used for preparing the bismuth compounds is employed in an amount such that there are between 0.1 and less than 2 mol of dissociable protons per mole of bismuth. In the examples, only a bismuth salt of dimethylolpropionic acid is used. There are no references to a bactericidal effect.
  • German patent DE 43 30 002 C1 discloses the use of bismuth salts of organic carboxylic acids as catalysts for an electrocoat material whose use allows a simplified process for producing a corrosion protection coating by means of electrocoating. Apart from the bismuth compounds, no other catalysts are used. Moreover, details of any bactericidal effect of bismuth compounds are again lacking here.
  • German patent application DE 44 34 593 A1 describes the use of bismuth salts of organic carboxylic acids in an electrocoat material which, in combination with a nickel-free and/or chromium-free pretreatment, permits a corrosion protective coating where toxic ingredients are largely avoided. References to a bactericidal effect cannot be inferred from the patent.
  • EC electrocoat
  • the invention accordingly provides the novel electrocoat (EC) materials comprising bismuth compounds, comprising
  • the EC materials of the invention were easy to prepare, were stable on storage, featured an optimum particle size of the dispersed constituents, possessed very good filterability, and were outstandingly resistant to infestation by microorganisms.
  • Their electrophoretic deposition on electrically conductive substrates was easy and trouble-free.
  • the resultant electrocoats were very even, were free from surface defects and inhomogeneities, and afforded outstanding corrosion protection and edge protection.
  • the deposited but uncured or only part-cured films of the EC materials of the invention could be overcoated wet on wet with aqueous coating materials, such as waterborne primers or waterborne surfacers, without defects or problems and then baked together with said aqueous coating materials.
  • the present invention further provides for the use of at least one bismuth compound, preferably selected from the group consisting of bismuth carboxylates, in electrocoat materials for increasing the resistance of said materials to infestation by microorganisms, and provides for the use of the bismuth compound, preferably selected from the group consisting of bismuth carboxylates, as a bactericide for electrocoat materials (EC materials).
  • at least one bismuth compound preferably selected from the group consisting of bismuth carboxylates
  • bismuth carboxylates are formed from carboxylic acids selected from the group consisting of aliphatic carboxylic acids which other than the carboxylic acid preferably contain no further functional groups and of aromatic carboxylic acids.
  • the bismuth carboxylates are employed preferably in an amount of from 0.05 to 4% by weight, based on the solids of the electrocoat material.
  • a process for preparing electrocoat materials with increased resistance to infestation by microorganisms which comprises adding at least one bismuth compound, preferably selected from the group consisting of bismuth carboxylates, to a conventional electrocoat material.
  • the EC materials of the invention preferably have a solids content of from 5 to 50% by weight, more preferably from 5 to 35% by weight. Solids here are the fraction of a EC material which makes up the electrocoat produced from it.
  • the EC materials of the invention comprise at least one binder (A).
  • the binders (A) may be self-crosslinking and/or externally crosslinking.
  • Self-crosslinking binders (A) contain reactive functional groups which are able to undergo thermal crosslinking reactions with themselves and/or with complementary reactive functional groups in the self-crosslinking binders (A).
  • Externally crosslinking binders (A) contain reactive functional groups which are able to undergo thermal crosslinking reactions with complementary reactive functional groups in crosslinking agents (B).
  • At least one externally crosslinking binder (A) in combination with at least one crosslinking agent (B).
  • the binder (A) contains potentially cationic and/or cationic groups. Binders (A) of this kind are used in cathodically depositable electrocoat materials.
  • Suitable potentially cationic groups which can be converted into cations by neutralizing agents and/or quaternizing agents are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, especially tertiary amino groups or secondary sulfide groups.
  • Suitable cationic groups are primary, secondary, tertiary or quaternary ammonium groups, tertiary sulfonium groups or quaternary phosphonium groups, preferably quaternary ammonium groups or tertiary sulfonium groups, but especially quaternary ammonium groups.
  • Suitable neutralizing agents, for the potentially cationic groups are inorganic and organic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, sulfonic acids, such as amidosulfonic acid or methanesulfonic acid, for example, formic acid, acetic acid, lactic acid, dimethylolpropionic acid or citric acid, especially formic acid, acetic acid or lactic acid.
  • inorganic and organic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, sulfonic acids, such as amidosulfonic acid or methanesulfonic acid, for example, formic acid, acetic acid, lactic acid, dimethylolpropionic acid or citric acid, especially formic acid, acetic acid or lactic acid.
  • binders (A) for cathodically depositable electrocoat materials are known from documents EP 0 082 291 A1, EP 0 234 395 A1, EP 0 227 975 A1, EP 0 178 531 A1, EP 0 333 327, EP 0 310 971 A1, EP 0 456 270 A1, U.S. Pat. No.
  • amine numbers preferably between 20 and 250 mg KOH/g and a weight-average molecular weight of from 300 to 10 000 daltons.
  • amino (meth)acrylate resins amino epoxy resins, amino epoxy resins with terminal double bonds, amino epoxy resins with primary and/or secondary hydroxyl groups, amino polyurethane resins, amino-containing polybutadiene resins or modified epoxy resin-carbon dioxide-amine reaction products.
  • Suitable potentially anionic groups which can be converted into anions by neutralizing agents are carboxylic, sulfonic or phosphonic acid groups, especially carboxylic acid groups.
  • Suitable anionic groups are carboxylate, sulfonate or phosphonate groups, especially carboxylate groups.
  • Suitable neutralizing agents for the potentially nonionic groups are ammonia, ammonium salts, such as ammonium carbonate or ammonium hydrogen carbonate, for example, and also amines, such as trimethylamine, triethylamine, tributylamine, dimethyl-aniline, diethylaniline, triphenylamine, dimethyl-ethanolamine, diethylethanolamine, methyldiethanol-amine, triethanolamine, and the like.
  • binders (A) for anodically depositable electrocoat materials are known from German patent application DE 28 24 418 A1. They are preferably polyesters, epoxy resin esters, poly(meth)acrylates, maleate oils or polybutadiene oils having a weight-average molecular weight of from 300 to 10 000 daltons and an acid number of from 35 to 300 mg KOH/g.
  • the amount of neutralizing agent is generally chosen such that from 1 to 100 equivalents, preferably from 30 to 90 equivalents, as the potentially cationic or potentially anionic groups of a binder (A) are neutralized.
  • Suitable reactive functional groups are hydroxyl groups, thiol groups, and primary and secondary amino groups, especially hydroxyl groups.
  • Suitable complementary reactive functional groups are blocked isocyanate groups, hydroxymethylene and alkoxymethylene groups, preferably methoxymethylene and butoxymethylene groups, and especially methoxymethylene groups. Preference is given to using blocked isocyanate groups.
  • suitable blocking agents are those described below.
  • the EC materials used are preferably cathodic.
  • the amount of the above-described binders (A) in the EC materials of the invention is guided in particular by their solubility and their dispersibility in the aqueous medium and by their functionality with regard to the crosslinking reactions with themselves or with the constituents (B), and may therefore be determined readily by the skilled worker on the basis of his or her general art knowledge, where appropriate with the assistance of simple preliminary tests.
  • Suitable crosslinking agents (B) include all customary and known crosslinking agents which contain suitable complementary reactive functional groups.
  • the crosslinking agents (B) are preferably selected from the group consisting of blocked polyisocyanates, melamine-formaldehyde resins, tris(alkoxycarbonyl-amino)triazines, and polyepoxides.
  • the crosslinking agents (B) are more preferably selected from the group consisting of blocked polyisocyanates and highly reactive melamine-formaldehyde resins. With particular preference the blocked polyisocyanates are used.
  • the blocked polyisocyanates (B) are prepared from customary and known paint polyisocyanates containing aliphatically, cycloaliphatically, araliphatically and/or aromatically attached isocyanate groups.
  • paint polyisocyanates having from 2 to 5 isocyanate groups per molecule and having viscosities of from 100 to 10 000, preferably from 100 to 5 000, and in particular from 100 to 2 000 mPas (at 23° C.).
  • the paint polyisocyanates may have been given a conventional hydrophilic or hydrophobic modification.
  • paint polyisocyanates are described, for example, in “Methoden der organischen Chemie”, Houben-Weyl, Volume 14/2, 4 th edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, and by W. Siefken, Liebigs Annalen der Chemie, Volume 562, pages 75 to 136.
  • paint polyisocyanates are polyisocyanates containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and/or uretdione groups, which are obtainable from customary and known diisocyanates.
  • diisocyanates it is preferred to use hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexyl-methane 2,4′-diisocyanate, dicyclohexylmethane 4,4′-diisocyanate or 1,3-bis(isocyanatomethyl)cyclohexane (BIC), diisocyanates derived from dimer fatty acids, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,7-diiso-cyanato-4-isocyanatomethylheptane, 1-isocyanato-2-(3-isocyanatopropyl)cyclohexane, 2,4- and/or 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate or mixtures
  • crosslinking agents (B) in the EC materials of the invention is guided in particular by their functionality with regard to the crosslinking reaction with the constituents (A) and may therefore readily be determined by the skilled worker on the basis of his or her art knowledge, where appropriate with the assistance of simple preliminary tests.
  • the EC materials comprise at least one bismuth compound (C).
  • bismuth carboxylates are employed.
  • the bismuth carboxylates which can be employed are preferably formed from carboxylic acids selected from the group consisting of aliphatic carboxylic acids which besides the carboxylic acid preferably contain no further functional group and of aromatic carboxylic acids.
  • One preferred bismuth compound is bismuth ethylhexanoate. This is sold, for example, by King Industries under the designation K-Kat 348 in the form of a solution.
  • Another preferred bismuth compound (C) is the water-insoluble bismuth subsalicylate of empirical formula C 7 H 5 O 4 Bi. It has a bismuth content of from 56 to 60% by weight.
  • Bismuth subsalicylate (C) is a commercial compound and is sold, for example, by MCP HEK GmbH, Lubeck, Germany.
  • the EC materials of the invention contain preferably from 0.05 to 4%, more preferably from 0.1 to 3.5%, and in particular from 0.15 to 3% by weight of bismuth compound (C).
  • One advantage of the EC materials of the invention is that the various possible bismuth compounds which may be employed in accordance with the invention can be incorporated either solid or else as liquids (in solution and/or dispersion) into binders or binder dispersions and/or grinding resins or grinding resin dispersions.
  • the EC materials of the invention may further comprise at least one customary and known additive (D) selected from the group consisting of catalysts other than bismuth compound (C); pigments; anticrater additives; polyvinyl alcohols; thermally curable reactive diluents; molecularly dispersely soluble dyes; light stabilizers, such as UV absorbers and reversible free-radical scavengers (HALS); antioxidants; low-boiling and high-boiling (“long”) organic solvents; devolatilizers; wetting agents; emulsifiers; slip additives; polymerization inhibitors; thermolabile free-radical initiators; adhesion promoters; leveling agents; film-forming auxiliaries; flame retardants; corrosion inhibitors; flow aids; waxes; siccatives; biocides, and flatting agents, in effective amounts.
  • D customary and known additive
  • Pigments are preferably used as additives (D).
  • the pigments (D) are preferably selected from the group consisting of customary and known color pigments, effect pigments, electrically conductive pigments, magnetically shielding pigments, fluorescent pigments, extender pigments, and anticorrosion pigments, organic and inorganic.
  • the EC materials of the invention are prepared by mixing and homogenizing the above-described constituents using customary and known mixing techniques and apparatus such as stirred tanks, stirred mills, extruders, kneading apparatus, Ultraturrax, inline dissolvers, static mixers, micromixers, toothed-gear dispersers, pressure relief nozzles and/or microfluidizers.
  • the pigments are incorporated preferably in the form of pigment pastes or pigment preparations into the EC materials (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Pigment preparations”, page 452).
  • bismuth compounds (C) brings about an extremely high resistance of the EC materials of the invention to infestation by microorganisms. This high resistance is retained even in the case of intensive operation of the electrocoating baths of the invention, where large quantities of fresh EC material and thus further nutrient for the microorganisms are supplied.
  • the EC materials of the invention are applied conventionally by immersing an electrically conductive substrate in an electrocoating bath of the invention, connecting the substrate as the cathode or anode, preferably as the cathode, depositing a EC material film on the substrate using direct current, removing the coated substrate from the electrocoating bath, and subjecting the deposited EC material film to conventional thermal curing (baking).
  • the resulting electrocoat can then be overcoated with a surfacer or with an antistonechip primer and a solid-color topcoat material or, alternatively, with a basecoat material and a clearcoat material by the wet-on-wet technique.
  • the surfacer film or antistonechip primer film and also the solid-color topcoat film are preferably each baked individually.
  • the basecoat film and the clearcoat film are preferably baked together. This procedure results in multicoat paint systems having outstanding performance properties.
  • multicoat paint systems by the wet-on-wet technique wherein the deposited EC material film is not cured or is only partly cured thermally and is immediately overcoated with the other coating materials, especially aqueous coating materials, after which it is baked together with at least one of the films of the coating materials (EC material film+surfacer film; EC material film+surfacer film+solid-color topcoat film; EC material film+surfacer film+basecoat film, or EC material film+surfacer film+basecoat film+clearcoat film).
  • the resulting multicoat paint systems have outstanding performance properties, the production processes being particularly economic and energy-saving. In the course of these processes it is found that the EC material films of the invention lend themselves particularly well to undisrupted overcoating by the wet-on-wet technique.
  • electrocoats of the invention are obtained which exhibit very good leveling, are free from surface defects and inhomogeneities, and afford outstanding corrosion protection and edge protection.
  • the polyurethane crosslinker is prepared in analogy to the preparation of the polyurethane crosslinker from Example 1 in DE 196 37 559, from an isomer and relatively highly functional oligomer based on 4,4′-diphenylmethane diisocyanate, having an NCO equivalent weight of 135 g/eq (Lupranat® M 20 S from BASF) by first reacting 4.3 moles of a total of 6 moles of isocyanate with 4.3 moles of butyl diglycol and then reacting the remaining 1.7 moles of isocyanate with trimethylolpropane.
  • the crosslinker is present in an 80% strength solution in methyl isobutyl ketone and isobutanol (weight ratio 9:1).
  • K-Cat 348 commercial bismuth ethylhexanoate solution
  • a reactor equipped with a stirrer, reflux condenser, internal thermometer and inert gas inlet is charged with 1 084 parts of isomers and relatively highly functional oligomers based on 4,4′-diphenylmethane diisocyanate, having an NCO equivalent weight of 135 (Basonat® A270 from BASF), under a nitrogen atmosphere.
  • 0.6 part of dibutyltin dilaurate is added and 1 314 parts of butyl diglycol are added dropwise at a rate such that the product temperature remains below 70° C. Cooling may be necessary. The temperature is held at 70° C. for a further 120 minutes. In the course of the subsequent check, NCO groups can no longer be detected.
  • the product is cooled to 70° C. Solids content is >97%.
  • Example 1.3 a grinding resin is prepared which for greater ease of handling is additionally neutralized and diluted with 2.82 parts of glacial acetic acid and 13.84 parts of DI water. The original solids content is thus reduced to 60%.
  • the mixture is subsequently dispersed in a stirred laboratory mill for 1-2 hours to a Hegman fineness of 12 ⁇ m and where appropriate is adjusted with further water to the desired processing viscosity.
  • the pigment paste 2 is prepared, with the further addition to the mixture of 1.1 parts of bismuth ethylhexanoate (Bi content 26%).
  • the binder dispersions of the invention (diluted to 15% solids) and the electrocoating baths of the invention were exposed to adapted microbes from contaminated cathodic electrocoat bath material. To this end 100 ml of each sample were inocculated with 0.1 ml of Burkholderia cepacia suspension.
  • the samples are agitated on a circular shaker.
  • the material is coated out and the microbe count is determined.
  • Electrocoat 3 >10

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US10/521,343 2002-08-08 2003-07-17 Aqueous electrodeposition paints, use thereof in methods for coating electrically conductive substrates, and use of bismuth compounds in said aqueous electrodeposition paints Abandoned US20050234149A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/416,909 US7504444B2 (en) 2002-08-08 2006-05-03 Aqueous electrocoat materials, their use in processes for coating electrically conductive substrates, and the use of bismuth compounds in these aqueous electrocoat materials

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10236347.1 2002-08-08
DE10236347A DE10236347A1 (de) 2002-08-08 2002-08-08 Wäßrige Elektrotauchlacke, ihre Verwendung in Verfahren zur Beschichtung elektrisch leitfähiger Substrate sowie die Verwendung von Bismutverbindungen in diesen wäßrigen Elektrotauchlacken
PCT/EP2003/007747 WO2004018570A2 (fr) 2002-08-08 2003-07-17 Peinture aqueuse electrophoretique par immersion, son utilisation dans un procede de revetement de substrats electroconducteurs et utilisation de composes bismuth dans ces peintures aqueuses electrophoretiques par immersion

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US11/416,909 Continuation US7504444B2 (en) 2002-08-08 2006-05-03 Aqueous electrocoat materials, their use in processes for coating electrically conductive substrates, and the use of bismuth compounds in these aqueous electrocoat materials

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US20050234149A1 true US20050234149A1 (en) 2005-10-20

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US10/521,343 Abandoned US20050234149A1 (en) 2002-08-08 2003-07-17 Aqueous electrodeposition paints, use thereof in methods for coating electrically conductive substrates, and use of bismuth compounds in said aqueous electrodeposition paints
US11/416,909 Expired - Lifetime US7504444B2 (en) 2002-08-08 2006-05-03 Aqueous electrocoat materials, their use in processes for coating electrically conductive substrates, and the use of bismuth compounds in these aqueous electrocoat materials

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US (2) US20050234149A1 (fr)
EP (1) EP1525272B2 (fr)
JP (1) JP2005534796A (fr)
AT (1) ATE353093T1 (fr)
AU (1) AU2003250083A1 (fr)
BR (1) BR0313295A (fr)
CA (1) CA2494874A1 (fr)
DE (2) DE10236347A1 (fr)
ES (1) ES2280832T3 (fr)
MX (1) MXPA05000838A (fr)
WO (1) WO2004018570A2 (fr)

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US20100065210A1 (en) * 2006-11-03 2010-03-18 Henkel Corporation Flowable non-sagging adhesive compositions
US8980078B2 (en) 2011-09-07 2015-03-17 Nippon Paint Co., Ltd. Electrodeposition coating composition
CN107667150A (zh) * 2015-05-21 2018-02-06 威士伯采购公司 用于涂料组合物的抗微生物剂
CN109952030A (zh) * 2016-11-03 2019-06-28 宣伟投资管理有限公司 涂料和涂饰用的抗微生物剂
US10435805B2 (en) 2013-11-18 2019-10-08 Basf Coatings Gmbh Two-stage method for dip-coating electrically conductive substrates using a Bi (III)-containing composition
RU2822390C1 (ru) * 2020-05-25 2024-07-04 БАСФ Коатингс ГмбХ Содержащий висмут материал для нанесения покрытия электроосаждением с улучшенной каталитической активностью

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JP5623423B2 (ja) 2008-12-29 2014-11-12 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 水性の電着コーティング組成物、リン酸塩前処理の代用法を含む金属の自動車車体をコーティングするための方法、及び、該水性の電着コーティング組成物の製造方法
JP5325610B2 (ja) * 2009-03-02 2013-10-23 日本パーカライジング株式会社 金属表面処理用組成物、これを用いた金属表面処理方法およびこれらを用いた金属表面処理皮膜
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AU2003250083A1 (en) 2004-03-11
EP1525272B2 (fr) 2011-11-30
ES2280832T3 (es) 2007-09-16
MXPA05000838A (es) 2005-04-19
CA2494874A1 (fr) 2004-03-04
AU2003250083A8 (en) 2004-03-11
US7504444B2 (en) 2009-03-17
WO2004018570A2 (fr) 2004-03-04
DE10236347A1 (de) 2004-02-19
EP1525272B1 (fr) 2007-01-31
US20070027238A1 (en) 2007-02-01
JP2005534796A (ja) 2005-11-17
DE50306437D1 (de) 2007-03-22
ATE353093T1 (de) 2007-02-15
EP1525272A2 (fr) 2005-04-27
WO2004018570A3 (fr) 2004-06-17

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