WO1995019400A2 - Additifs, leur production, bains de trempage electrophoretique contenant ces additifs et a precipitation cathodique, ainsi que leur utilisation - Google Patents

Additifs, leur production, bains de trempage electrophoretique contenant ces additifs et a precipitation cathodique, ainsi que leur utilisation Download PDF

Info

Publication number
WO1995019400A2
WO1995019400A2 PCT/EP1995/000078 EP9500078W WO9519400A2 WO 1995019400 A2 WO1995019400 A2 WO 1995019400A2 EP 9500078 W EP9500078 W EP 9500078W WO 9519400 A2 WO9519400 A2 WO 9519400A2
Authority
WO
WIPO (PCT)
Prior art keywords
baths
polymer
additives
mol
ktl
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.)
Ceased
Application number
PCT/EP1995/000078
Other languages
German (de)
English (en)
Other versions
WO1995019400A3 (fr
Inventor
Klausjörg Klein
Matthias Kimpel
Bettina Vogt-Birnbrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Axalta Coating Systems Germany GmbH and Co KG
Original Assignee
Herberts GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Herberts GmbH filed Critical Herberts GmbH
Publication of WO1995019400A2 publication Critical patent/WO1995019400A2/fr
Publication of WO1995019400A3 publication Critical patent/WO1995019400A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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

Definitions

  • the invention relates to the addition of additives to improve the surface in cathodic electrocoating, in particular the addition of anti-cratering agents.
  • anti-cratering agents that can be produced by polymer-analogous implementation. Films are deposited from electrodeposition baths that have been improved in this way; these can be used, for example, as a primer layer in a multilayer coating.
  • Cathodic electrocoating is a process that is frequently used, especially for priming automobile bodies, in which synthetic resins bearing water-dilutable cationic groups are deposited on electrically conductive bodies with the aid of direct current.
  • a workpiece with an electrically conductive surface made of metal or electrically conductive plastic is placed in an aqueous electrodeposition lacquer bath, connected as a cathode to a direct current source and then the lacquer on the surface is coagulated by the flowing current (EP-B-0066859, EP-A- 0 004090, DE-A-32 15 891).
  • the electrocoating bath consists of an aqueous dispersion, e.g. Suspension or emulsion, or from an aqueous solution of one or more binders by at least partial salt formation with organic or inorganic
  • Neutralizing agents are made water-dispersible, from pigments, fillers, additives, solvents and conventional auxiliaries dispersed therein.
  • Corrosion protection greases, seam sealing materials and substances from the pretreatment are Corrosion protection greases, seam sealing materials and substances from the pretreatment.
  • Another class of contaminants are those that are deposited on the non-crosslinked paint film after the electrodeposition coating has been removed from the air, for example silicone-containing aerosols, and lubricants from the transport systems which are necessary for moving the parts to be coated.
  • US-A-4,810,535 describes polyoxyalkylene polyamine-epoxy resin reaction products as an additive to cathodic dipstick systems. This is to avoid craters.
  • EP-A-0 324 951 describes polyoxyalkylenepolyaines as additives to KTL baths in order to obtain trouble-free film surfaces.
  • DE-A-38 30 626 describes modified acrylates as additives for KTL baths, which can be added to the paint material in a way that can be neutralized or not neutralized. In this case too, various types of surface disturbances should be avoided.
  • EP-A-0 301 293 describes cathodic electrocoating baths which contain, as an additive, a homo- or copolymer of an alkyl vinyl ether with a C 2 -C 4 -alkyl radical.
  • the Ho o- or copolymers are prepared by polymerization of an alkyl vinyl ether, optionally together with up to 20 wt .-% of other copolymerizable monomers.
  • the polymers have weight average molecular weights of 500 to 100000 and are in Quantities from 10 to 10000 pp, based on the weight of the finished KTL bath.
  • the disadvantages of the anti-cratering agents listed above also occur here, in particular if the anti-cratering agent is used in the upper quantity range.
  • the object was therefore to provide a surface-improving agent, in particular an anti-crater agent, for KTL systems, which has a good anti-crater effect, has good follow-up layer adhesion, the slipping off of follow-up layers, in particular on the
  • the anti-cratering agent should not have any effect leading to surface defects if its content in KTL baths assumes low values.
  • the invention therefore relates to additives for cathodically depositable aqueous electrodeposition baths in the form of randomly built polymers or copolymers of the schematic formula obtained by polymer-analogous reaction
  • X a substituent different from OR and OR ', preferably halogen, -COOR "or -aryl,
  • R C, - to C 10 alkyl, 0
  • R ' H and / or -C-R "
  • R " C r to C 3 alkyl and the sum of c + d results in at least 1 mol%.
  • random polymer or copolymer or “statistical polymer or copolymer” used in the present description and the patent claims means that individual and / or blocks of the mol% indications a, b, c, d and e labeled molecule portions are statistically distributed over the total molecule of the polymers or copolymers.
  • polymer is used here instead of “polymer or copolymer”.
  • the polymers according to the invention can be produced in various ways. For example, it is possible to prepare the polymers (1) by polymer-analogous conversion of randomly structured polymers of the following schematic formula
  • the reaction can be carried out under various conditions, for example in an organic medium or preferably in the presence of water. For example, it is possible to work under increased pressure and / or with an increase in temperature.
  • a reaction of the polymeric starting material (II) with water and acid such as e.g. organic carboxylic acids and their derivatives.
  • Organic solvents may optionally be present.
  • the acids can be used alone or in a mixture with other catalysts.
  • Halogens are given as examples for the substituent X in the formula (I) and in the formulas (II) and (III) below.
  • Examples of usable halogens are fluorine, chlorine and bromine.
  • Preferred examples of the aryl group in the meaning of X are phenyl and substituted phenyl radicals, such as C 1 -C 4 -alkylated phenyl radicals.
  • the choice of the starting material, the type and amount of acid in the reaction mixture, the proportion of water in the reaction mixture and the choice of reaction conditions have a controlling influence.
  • temperatures below 150 ° C, preferably from 80 to 140 ° C can be used.
  • the pressure is, for example, normal pressure, but it is also possible, for example, to work at higher pressures, up to 6 bar, preferably below 6 bar.
  • inorganic acids such as, for example, hydrogen iodide, hydrogen bromide, hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid
  • organic acids such as, for example, formic acid, acetic acid
  • Oxalic acid, Lactic acid suitable The acids can be used in aqueous solution, but also in organic solution, such as, for example, gaseous acids, such as hydrogen chloride gas, dissolved in an organic solvent.
  • the acids can be used individually or in a mixture.
  • Preferred acids are those which are used as neutralizing agents in conventional KTL baths. It is not necessary to remove such acids from the reaction mixture prior to the use according to the invention of the polymer (I) produced by the polymer-analogous reaction of the polymer (II) in the KTL.
  • examples include acetic acid, formic acid,
  • Lactic acid Lactic acid. Without being bound by theory, it is believed that Lewis acids generally have a catalytic effect and organic acids can act as catalysts and / or also as reactants.
  • the acids are used, for example, in amounts of 0.1 to 100% by weight, based on the weight of the polymer (II), while the amount of water in the reaction mixture is preferably, for example, 5 to 100% by weight, based on the weight of the polymer ( II) is. If the acid is to have a catalytic effect in particular, the proportion of acid in the reaction mixture can be chosen to be low, for example between 0.1 and 10% by weight, based on the weight of the polymer (II). If R 'in the target polymer (I) has the meaning of -COR "in part or in full, this is done by acylation using an organic C 2 -C 4 carboxylic acid, preferably acetic acid. A larger amount of the acid is preferably used, to the
  • acylation reaction for example, 10 to 100% by weight of carboxylic acid, based on the weight of the polymer (II), is used and the amount of water in the reaction mixture is preferably chosen to be low.
  • the polymers (I) produced by polymer-analogous reaction of polymers (II) with water and acid are particularly preferably used in KTL baths.
  • the educt polymers of the schematic formula II used for this purpose are homo- or copolymers of vinyl ethers which can be prepared by free radical or cationic methods in accordance with the usual polymerization methods known to the person skilled in the art. For example, those in the 400
  • a is preferably 0 mol%.
  • the ratio of b: (c + d) in the polymer (I) is preferably 60 to 95 mol% to 5 to 40 mol%.
  • the ratio of b: (c + d) and c: d in the polymer (I) can be influenced by the choice of the process parameters, which can easily be determined by a person skilled in the art on the basis of experiments.
  • the b / (c + d) and the c / d ratio are shifted to low values by measures such as the application of pressure (carrying out the polymer-analog Reaction in an autoclave), increased reaction temperature, long reaction time and shift in the reaction equilibrium due to the removal of reaction products.
  • a volatile alcohol ROH can be removed from the reaction equilibrium by distillation, if appropriate under vacuum.
  • the polymer-analogous reaction of the polymers (II) can be carried out with the aid of phase transfer catalysts or emulsifiers.
  • auxiliaries are preferably not added in the polymer-analogous reaction. It may be appropriate to carry out the polymer-analogous reaction in the absence of oxygen.
  • conventional inhibitors such as hydroquinone, can also be added in order to largely prevent free-radical side reactions.
  • the polymers (I) can alternatively, but less preferably, by polymer-analogous conversion of randomly structured polymers of the schematic formula
  • Organic and / or inorganic bases can be used as bases.
  • bases are organic amines, such as primary, secondary and tertiary amines, and hydroxides, such as alkali metal hydroxides, e.g. Sodium hydroxide and potassium hydroxide.
  • the bases are generally used in catalytic amounts of 0.1 to 10% by weight, based on the weight of the polymer (III), while the amount of water in the reaction mixture is preferably 5 to 10% by weight, based on the weight of the polymer (III) is.
  • the bases should preferably be removed from the reaction mixture before the polymer (I) is used in the KTL according to the invention. This can be done for example by distillation extraction or also by neutralization.
  • the polymers (I) prepared by polymer-analogous reaction are generally obtained as a reaction mixture with catalyst, water and / or organic solvent. It is convenient to organic
  • the polymers (I) which can be used according to the invention as surface-improving agents in KTL baths preferably have an OH number between 0 and 500 mg KOH / g, particularly preferably below 300, particularly preferably below 100.
  • the olefinic double bonds can be isolated and / or conjugated in the polymer (I) available. They can be in teral or distributed along the main chain.
  • the weight average molecular weight (Mw) of the polymers (I) is preferably between 500 and 100,000.
  • the polymers (I) are essentially water-insoluble and become cataphoretic
  • the polymers (I) have no membrane compatibility with regard to an ultrafiltration process coupled with the electrocoating, i.e. the ultrafiltrate is free of them.
  • the polymers (I) act as surface-improving agents if they are used in KTL systems in proportions of, for example, 10 to 10000 ppm, preferably from 100 to 7000 ppm, particularly preferably from 200 to 5000 ppm, based on the finished KTL bath .
  • Another object of the invention are cathodically depositable aqueous electrocoating baths which contain the usual binder systems suitable for cathodic deposition in addition to crosslinking agents, pigments, fillers, solvents and / or customary lacquer additives and additionally contain one or more polymers (I).
  • smooth, crater-free and trouble-free surfaces are formed after baking (for example at temperatures from 110 to 190 ° C.), which do not have any adhesion problems with the usual subsequent layers.
  • the KTL baths show excellent crater resistance.
  • the craters caused by impurities are within wide limits reduced.
  • Amounts of the polymer (I) higher than 10,000 ppm can also be present without the occurrence of interfering effects, such as exudation or disturbances in the subsequent layer adhesion.
  • Cathodic electrocoating baths to which polymers (I) have been added according to the invention are distinguished by an extraordinary resistance to contamination by substances that cause craters.
  • customary electrodeposition coating baths can be used which consist of an aqueous solution or dispersion of cathodically depositable self- or externally crosslinking synthetic resins, optionally crosslinking agents, optionally customary pigments and / or fillers as well as other customary lacquer additives and auxiliaries and optionally organic solvents.
  • the solids content of the KTL baths used according to the invention which is calculated from binders, any crosslinking agent, pigments and / or fillers present, is, for example, 10 to 25% by weight, based on the total bath.
  • the ratio of pigments and fillers to binder (plus any crosslinking agent present) is, for example, 0 to 0.7: 1, based on the weight.
  • the organic solvent content is, for example, up to 10% by weight. If non-self-crosslinking binders that require a crosslinker are used, the ratio of binder / crosslinker is, for example, 90:10 to 60:40, in each case based on the weight of the solid resin.
  • the binders used in the KTL baths contain common basic resins with basic groups, which can contain sulfur, nitrogen or phosphorus. Nitrogen-containing basic groups are preferred. These groups can be quaternized, or they are converted into ionic groups using a conventional neutralizing agent, such as, for example, organic monocarboxylic acids.
  • Basic base resins are, for example, resins containing primary, secondary or tertiary amino groups, the amine numbers of which are, for example, 20 to 250 mg KOH / g.
  • the weight average (Mw) of the molar mass of the base resins is preferably 300 to 10,000.
  • R represents, for example, an alkyl radical having 1 to 4 carbon atoms and the radicals R can be the same or different.
  • Nitrogen-containing basic groups are preferred.
  • the inorganic and / or organic acids theoretically known and used in practice can be used as neutralizing agents which supply anions in the aqueous binder solutions. In practice, monovalent acids are mainly used, which cause the binder to be water-dilutable. Formic acid, acetic acid, lactic acid or alkyl phosphoric acids are preferably used.
  • Base resins are e.g. Amino acrylate resins, amino epoxy resins, amino epoxy resins with terminal double bonds, amino polyurethane resins, amino group-containing polybutadiene resins and modified epoxy resin-carbon dioxide-amine reaction products.
  • 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 and / or amidation.
  • Examples of base resins and crosslinking agents which can be used in cathodic dip coating (KTL) baths and which can be used according to the invention are described in EP-A-0 082 291, EP-A-0 234 395, EP-A-0 209 857, EP -A-0 227 975, EP-A-0 178 531, EP-A-0 333 327, 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, EP-A-0 476 514. These resins can be used alone or in a mixture.
  • the electrocoat materials of the invention can contain pigments.
  • Typical pigments and / or fillers such as carbon black, titanium dioxide, iron oxide red, kaolin, talc or silicon dioxide can be used as pigments for the KTL deposition.
  • the pigments are preferably dispersed and rubbed into conventional pigment paste resins. Such resins are described for example in EP-A-0 469 497.
  • the production of the pigment pastes and the production of the cathodic dip baths are familiar to the person skilled in the art.
  • pigments and / or fillers can be dispersed in customary grinding binders and then ground on a suitable aggregate, for example a bead mill. The pigment paste thus obtained can then be added to the KTL binders in various ways.
  • the KTL coating bath can then be made from this material by diluting it with deionized water.
  • An example of a different procedure first converts the neutralized and thus water-soluble binders or binder mixtures into a dispersion. This is further diluted with deionized water and then the aqueous pigment paste is added.
  • a KTL bath that can be coated is also obtained in this way.
  • Such electrocoat baths contain not only pigments and fillers but also necessary neutralizing agents; They can additionally contain solvents customary for KTL baths and / or further additives or auxiliary substances customary in paint, such as defoamers or catalysts.
  • the surface-improving agent of the formula (I) can be added to the electrocoating baths from the outset during production, or else subsequently directly when used for electrocoating.
  • the anti-crater additive used according to the invention can, for example, be dispersed in the binder mixture before or after neutralization and can be transferred together with the binder into the dispersion phase.
  • An example of another procedure is that after the binder has been transferred into the water phase, the additive is mixed with an auxiliary, such as, for example, part of the dispersible one neutralized resins or neutralized paste resin or a suitable solvent of the dispersion. After thorough homogenization, the additive is stably incorporated.
  • Another possibility is to incorporate the anti-crater additive into any pigment paste used. This is advantageously done before the pigment paste is ground, so as to ensure that the additive is homogeneously distributed in the pigment paste.
  • the pastes thus obtained are stable and show the desired properties after addition to the electrocoating bath.
  • polymer (I) which can be used according to the invention as an anti-cratering agent in cathodic electrocoating materials can also be used in a mixture with one or more other anti-cratering agents which are suitable for use in cathodic electrocoating materials.
  • Examples of such substances which can be used as anti-cratering agents in cathodic electrocoating baths are copolymers of alkyl vinyl ethers, polyesters with beta-hydroxyalkyl groups, polyoxyalkylene polyamines, polyether urethanes with amine groups in the molecule, cationic acrylate resins, cationic microgels, polymer microparticles and / or polyoxyalkylene resin-polyamine-epoxidation products.
  • the sum of the anti-cratering agents used is preferably kept as low as possible, preferably below 2% by weight, based on the finished KTL bath. If the amount is too large, there may be disadvantages in the paint properties.
  • the anti-crater additive it is expediently converted into a water-dilutable form, for example by means of solvents, water-dispersible emulsifiers, water-dilutable binders or water-dilutable paste resins.
  • This procedure is particularly suitable if it has been found that when working with a KTL-Bad surface disturbances occur.
  • Various substrates can be coated under the usual conditions from the electrocoat baths provided with anti-cratering agents according to the invention. After baking, they have a smooth, crater-free surface. Due to the anti-crater additive used according to the invention, other varnish properties, such as e.g. Corrosion protection, stone chip resistance, subsequent layer adhesion, not affected.
  • the polymers (I) can also be used for the aftertreatment of KTL-Fi en according to the procedure of the as yet unpublished application P 4 303 812 by the same applicant.
  • o / w emulsions oil-in-water emulsions
  • Moist, non-crosslinked KTL coatings which have been deposited from KTL baths free of polymers (I) are brought into contact with these emulsions before the subsequent baking.
  • the surface-improving effect when using the polymers (I) as an o / w emulsion, in particular the anti-crater effect, corresponds entirely to that when using the polymers (I) as part of the KTL bath.
  • the adhesion to subsequent layers is perfect and the slipping of plastisols during the gelling process is avoided.
  • the anti-cratering agent used according to the invention is therefore particularly suitable in the motor vehicle sector, for example for priming motor vehicle bodies or motor vehicle body parts, with the subsequent multilayer paint structure.
  • Production of the polymers (I) by polymer-analogous reaction is therefore particularly suitable in the motor vehicle sector, for example for priming motor vehicle bodies or motor vehicle body parts, with the subsequent multilayer paint structure.
  • Example 1 is repeated with the difference that 100 g of glacial acetic acid, 50 g of deionized water and 10 ml of a 41% solution of
  • Boron trifluoride can be used in glacial acetic acid. 132 g of distillate are obtained.
  • Example 1 is repeated with the difference that 50 g of glacial acetic acid and 72 g of deionized water are used. 72 g of distillate are obtained.
  • Example 1 is repeated with the difference that no glacial acetic acid, 50 g of deionized water and 2 ml of the boron trifluoride solution from Example 2 are used.
  • the single-phase system obtained has an iodine number of 53.
  • Example 7a 832 parts of the monocarbonate of an epoxy resin based on bisphenol A (commercial product Epicote 828) are mixed with 830 parts of a commercially available polycaprolactone polyol (commercial product CAPA 205) and 712 parts of diglycol dimethyl ether and at 70 to 140 ° C. with about 0.3% BF 3 etherate reacted until an epoxide number of 0 is reached. 307 parts of a reaction product of 174 parts of tolylene diisocyanate (2.) Are added to this product (solids 70%, 2 equivalents of carbonate) at 40 to 80 ° C in the presence of 0.3% of Zn acetylacetonate as catalyst
  • a crater-forming substance (Anticorrit 15 N-68, from Fuchs Mineralölwerke, Mannheim) are added to the cathodic dip coating from Example 7a and homogeneously distributed overnight.
  • the crater-forming substance can be diluted beforehand with a mixture of xylene and butyl glycol.
  • the PVC materials are common underbody protection materials from Dr. A. Stankiewicz GmbH, Celle and Teroson GmbH, Heidelberg.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne des additifs, leur production et leur utilisation dans des bains aqueux de trempage électrophorétique à précipitation cathodique, notamment comme agents empêchant la formation de cratères et n'entraînant pas d'effets de glissement, ainsi que les bains les contenant. Ces additifs sont des polymères statistiques répondant à la formule schématique (I): -[-(CH2CHX)a (CH2CHOR)b (CH2CHOR')c (CH=CH)d-]-n, dans laquelle a = 0 à 20 % en moles; b = 50 à 99 % en moles; c = 0 à 50 % en moles; d = 0 à 50 % en moles; n = 5 à 1500; X désigne un substituant différent d'OR et d'OR'; R désigne alkyle C1 à C10; R' désigne H et/ou -COR''; R'' désigne alkyle C1 à C3 et la somme c + d s'élève à au moins 1 % en moles.
PCT/EP1995/000078 1994-01-15 1995-01-11 Additifs, leur production, bains de trempage electrophoretique contenant ces additifs et a precipitation cathodique, ainsi que leur utilisation Ceased WO1995019400A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4401045.1 1994-01-15
DE4401045A DE4401045C1 (de) 1994-01-15 1994-01-15 Additive, deren Herstellung und deren Verwendung in kathodisch abscheidbaren Elektrotauchlackbädern

Publications (2)

Publication Number Publication Date
WO1995019400A2 true WO1995019400A2 (fr) 1995-07-20
WO1995019400A3 WO1995019400A3 (fr) 1995-09-08

Family

ID=6507984

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/000078 Ceased WO1995019400A2 (fr) 1994-01-15 1995-01-11 Additifs, leur production, bains de trempage electrophoretique contenant ces additifs et a precipitation cathodique, ainsi que leur utilisation

Country Status (2)

Country Link
DE (1) DE4401045C1 (fr)
WO (1) WO1995019400A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7617049B2 (en) 2007-01-23 2009-11-10 Smith International, Inc. Distance determination from a magnetically patterned target well
US9102784B2 (en) 2011-03-17 2015-08-11 Axalta Coating Systems Ip Co., Llc Acrylic anticrater additive for electrocoats

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3635914A (en) * 1969-12-24 1972-01-18 Gaf Corp Reactive hydroxyl group-containing vinyl chloride terpolymers
AT356779B (de) * 1978-03-13 1980-05-27 Herberts & Co Gmbh Kathodisch abscheidbares waesseriges elektro- tauchlack-ueberzugsmittel
DE3122641A1 (de) * 1981-06-06 1982-12-23 Herberts Gmbh, 5600 Wuppertal Kathodisch abscheidbares waessriges elektrotauchlack-ueberzugsmittel
DE3215891A1 (de) * 1982-04-29 1983-11-03 Basf Farben + Fasern Ag, 2000 Hamburg Selbstvernetzendes, hitzehaertbares bindemittel
AU611925B2 (en) * 1987-07-29 1991-06-27 Basf Lacke & Farben Aktiengesellschaft Aqueous electro-dipcoat baths containing cathodically depositable synthetic resins and process for coating electrically conductive substrates
DE3801787A1 (de) * 1988-01-22 1989-07-27 Basf Lacke & Farben Verfahren zur beschichtung elektrisch leitfaehiger substrate, nach diesem verfahren beschichtete substrate und waessrige elektrotauchlackbaeder
US4810535A (en) * 1988-02-01 1989-03-07 Ppg Industries, Inc. Glycidol-modified polyepoxide-polyoxyalkylenepolyamine adducts
DE3830626A1 (de) * 1988-09-09 1990-03-15 Herberts Gmbh Elektrisch abscheidbarer waessriger tauchlack-ueberzug und verfahren zur herstellung steinschlagfester lackaufbauten
DE3901608A1 (de) * 1989-01-20 1990-07-26 Byk Chemie Gmbh Beschichtungs- und formmassen enthaltend polymerisate von alkylvinylethern und deren verwendung als verlauf- oder antischaummittel
AT392649B (de) * 1989-10-12 1991-05-10 Vianova Kunstharz Ag Verwendung von acrylatcopolymerisaten als additive fuer waessrige kationische lacksysteme
DE4018876A1 (de) * 1990-06-13 1991-12-19 Herberts Gmbh Kathodisch abscheidbare elektrotauchlackbaeder mit additiven zur oberflaechenverbesserung, sowie die verwendung letzterer fuer beschichtungsverfahren
DE4140753A1 (de) * 1991-12-11 1993-06-17 Herberts Gmbh Kathodisch abscheidbare elektrotauchlackbaeder mit additiven zur oberflaechenverbesserung, sowie die verwendung letzterer fuer beschichtungsverfahren

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7617049B2 (en) 2007-01-23 2009-11-10 Smith International, Inc. Distance determination from a magnetically patterned target well
US9102784B2 (en) 2011-03-17 2015-08-11 Axalta Coating Systems Ip Co., Llc Acrylic anticrater additive for electrocoats

Also Published As

Publication number Publication date
WO1995019400A3 (fr) 1995-09-08
DE4401045C1 (de) 1995-07-27

Similar Documents

Publication Publication Date Title
EP0646420B1 (fr) Procédé pour réaliser des revêtements multicouches
DE68925826T2 (de) Elektrobeschichtungszusammensetzung eines polyamin-epoxy-anlagerungsproduktes und beschichtungen
DE3123536A1 (de) Bindemittel fuer kathodisch abscheidbare ueberzugsmassen, verfahren zu ihrer herstellung und ihre verwendung
DE2057799B2 (de) Verfahren zur kathodischen, elektrophoretischen Abscheidung eines Harzes
EP0783548B1 (fr) Procede de production d'un revetement anticorrosion, a forte adherence, et pieces ainsi revetues
EP0036471B1 (fr) Procédé pour le dépôt électrophorétique d'un revêtement sur une pièce conductrice de l'électricité connectée comme cathode
EP0760871A1 (fr) Procede de revetement de substrats metalliques phosphates
EP0279198A1 (fr) Composition pour le trempage électro-phorétique
EP0461566A1 (fr) Bains d'électrodéposition cathodique avec des additifs d'amélioration de surface ainsi que leur utilisation dans des procédés de revêtement
KR20100130194A (ko) 금속-유기 화합물을 함유하는 음극 전착 코팅 물질
DE4401045C1 (de) Additive, deren Herstellung und deren Verwendung in kathodisch abscheidbaren Elektrotauchlackbädern
EP0925334B1 (fr) Produit aqueux de trempage electrophoretique, son utilisation dans des procedes de revetement de substrats electroconducteurs et utilisation d'ions argent et/ou d'argent elementaire dans des produits aqueux de trempage electrophoretique
DE4303787C1 (de) Verfahren zur Herstellung von Elektrotauchlacküberzügen, die frei von Oberflächenstörungen sind und Verwendung von wäßrigen Polyvinylalkohollösungen zur Nachbehandlung von elektrophoretisch abgeschiedenen Überzügen
EP0436135B1 (fr) Procédé de préparation de pâtes catalytiques contenant de l'oxyde de dibutylétain et leur utilisation
DE69210392T2 (de) Reaktionprodukten von einem amindiol mit einem polyfunktionellen verbindung und ihre verwendung in cationischer lackierungzusammensetzungen
DE60305870T2 (de) Kathodische elektro-überzugsmittel
EP0904324A1 (fr) Procede permettant de recouvrir des substrats electroconducteurs
EP0588227B1 (fr) Bains d'électrodéposition cathodique avec des additives contenant du fluor, méthode pour leur préparation et leur usage pour revêtements multicouches
EP0350892B1 (fr) Agents de revêtement thermodurcissables et leur utilisation
DE3932744C2 (fr)
DE3108072C1 (de) Beschichtungsbad für das kataphoretische Beschichten von Oberflächen elektrisch leitfähiger Substrate
EP0230031B1 (fr) Composition aqueuse de revêtement par électrodéposition cathodique et son application au revêtement d'objets
EP0739954B1 (fr) Revêtement par électrodéposition cationique et procédé de revêtement
EP1235951B1 (fr) Procede pour peinture electrophoretique
DE4303812C1 (de) Verfahren zur Herstellung von Elektrotauchlacküberzügen, die frei von Oberflächenstörungen sind und Verwendung von Oberflächenstörungen entgegenwirkenden Mitteln

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

AK Designated states

Kind code of ref document: A3

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase