EP0386132A1 - Procede de revetement de substrats electroconducteurs, substrats revetus selon ce procede et bains aqueux de trempage electrophoretique - Google Patents

Procede de revetement de substrats electroconducteurs, substrats revetus selon ce procede et bains aqueux de trempage electrophoretique

Info

Publication number
EP0386132A1
EP0386132A1 EP89900242A EP89900242A EP0386132A1 EP 0386132 A1 EP0386132 A1 EP 0386132A1 EP 89900242 A EP89900242 A EP 89900242A EP 89900242 A EP89900242 A EP 89900242A EP 0386132 A1 EP0386132 A1 EP 0386132A1
Authority
EP
European Patent Office
Prior art keywords
electrocoating
group
amine
weight
chr
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.)
Pending
Application number
EP89900242A
Other languages
German (de)
English (en)
Inventor
Günther OTT
Udo Reiter
Walter Jouck
David J. Santure
Dieter RÜHL
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.)
BASF Farben und Fasern AG
Original Assignee
BASF Lacke und Farben AG
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 BASF Lacke und Farben AG filed Critical BASF Lacke und Farben AG
Publication of EP0386132A1 publication Critical patent/EP0386132A1/fr
Pending 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
    • 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
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1444—Monoalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1483—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
    • 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 method for coating electrically conductive substrates, in which
  • the substrate is immersed in an aqueous electrocoating bath, the aqueous electrocoating bath containing a cationic amine-modified epoxy resin which can be obtained by reacting
  • components (A) and (B) being used in a molar ratio of 10: 1 to 1: 1, preferably 4: 1 to 1.5: 1.0, and the positive charges by protonation of the reaction product and / or use of amine salts are introduced as a (C) component.
  • the substrate is switched as a cathode, 5 (3) a film is deposited on the substrate by direct current,
  • the invention also relates to substrates coated by the process according to the invention and to the electrocoating baths used in the process according to the invention.
  • the above-described cathodic electrodeposition coating is a coating method which is frequently used primarily for priming and is used in particular for priming automobile bodies.
  • a method according to the preamble of claim 1 is known from the German laid-open documents DE-OS-35 18732, DE-OS-3409 188 and DE-OS-35 18770.
  • the object on which the present invention is based is to provide a new method 5 according to the preamble of claim 1, with which lacquer films can be produced which, compared to the lacquer films of the prior art, have fewer and / or less pronounced surface defects 10 and in overpainted lacquer layers do not cause damage due to liability problems.
  • this object is achieved by a method
  • the electrocoating bath is at least 7.5% by weight of a polyoxyalkylene polyamine or a mixture of several polyoxyalkylene polyamines with
  • ⁇ U contains different chemical structures, the% by weight indicating that contained in the electrocoating bath
  • US Pat. No. 3,975,250 discloses cationic reactive plasticizers which can be used in electrocoating baths and which are prepared by reacting partially blocked polyisocyanates with polyoxypropylene diamines.
  • An average specialist standing before the task on which the present invention is based, however, can find no information on solving the problem in US Pat. No. 3,975,250.
  • US Pat. No. 4,423,166 discloses an electrocoating process which is characterized in that the electrocoating bath contains an adduct of a polyoxyalkylene polyamine and a polyepoxide as an anti-scratch agent. In the method disclosed in US Pat. No. 4,423,166, however, no electrocoating baths are used in accordance with the preamble of patent claim 1.
  • Electrocoating baths for cathodic electrocoating are preferably produced by first preparing an aqueous dispersion which contains a cationic resin, optionally a crosslinking agent and other customary additives, such as e.g. Defoamer
  • a pigment paste is then incorporated into this aqueous dispersion.
  • the pigment paste consists of a rubbing resin and pigments and / or fillers.
  • the pigment paste can also contain other additives such as Contain plasticizers, wetting agents, antioxidants, etc.
  • pigments or fillers that may be contained in the pigment paste are mentioned: titanium dioxide, antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate, barium carbonate, porcelain, clay, calcium carbonate, aluminum silicate, silicon dioxide, _ 5 Magnesium carbonate, magnesium silicate, cadmium yellow, cadmium red, carbon black, phthalocyanine blue, chrome yellow, toluidyl red and hydrated iron oxide.
  • the pigment paste is added to the aqueous dispersion described above in such an amount that the Finished electrocoating bath has the properties required for the deposition.
  • the weight ratio between pigment or filler and the total amount of cationic resin contained in the electrocoating bath is 0.05 to 0.5.
  • the electrocoating baths used according to the invention contain a cationic amine-modified epoxy resin which can be obtained by reacting
  • components (A) and (B) are used in a molar ratio of 10: 1 to 1: 1, preferably 4: 1 to 1.5: 1, and the positive charges are obtained by protonating the reaction product and / or use of amine salts as (C) component.
  • Cationic amine-modified epoxy resins of the type described above are disclosed in German Offenlegungs ⁇ DE-OS-34 09 188, DE-0S-35 18 732 and DE-OS-35 18 770.
  • all compounds which contain two reactive epoxy groups and have an epoxy equivalent weight which is less than 2000, preferably less than 1000, particularly preferably less than 500 can be used as component (A).
  • diepoxide compounds which can be used as component (A) are diglycidyl ethers of polyphenols, diglycidyl ethers of dialcohols and diglycidyl esters of dicarboxylic acids.
  • Diglycidyl ethers of polyphenols in particular diglycidyl ethers of bisphenol A, are very particularly preferably used as component (A).
  • Diglycidyl ethers of polyphenols can be obtained by reacting epihalohydrins with polyphenols.
  • component (A) Mixtures of different diepoxide compounds can of course also be used as component (A).
  • component (B) in the molecule all components which react monofunctionally to epoxy groups and contain an alcoholic OH group reactive towards epoxy groups, a phenolic OH group reactive towards epoxy groups or an SH group reactive towards epoxy groups can be used as component (B) in the molecule become.
  • Water-soluble amines are preferably used as the (C) component.
  • usable amines are mono- and dialkylamines, such as methylamine, ethylamine, propyl amine, 'butylamine, dimethylamine, diethylamine, dipropylamine, methylbutylamine, etc. mentioned.
  • Alkanolamines such as, for example, methylethanolamine and diethanolamine, can also be used as (C) components.
  • Ketimines of polyamines with primary and secondary amino groups can also be used as (C) components.
  • Dialkylaminoalkylamines such as, for example, dimethylaminoethylamine, diethylaminopropylamine and dimethylaminopropylamine, are also useful as (C) components.
  • component (C) In many cases, several different amines are used as component (C).
  • the cationic amine-modified epoxy resin in question can be produced by producing, in a first stage, an intermediate product containing components having a molecular weight of 400 to 5000 from components (A) and (B). This reaction is preferably carried out in an inert organic solvent at reaction temperatures from 100 ° to 190 ° C. in the presence of suitable catalysts (e.g. tertiary amines) and checked by means of epoxy equivalent weight determinations.
  • suitable catalysts e.g. tertiary amines
  • the epoxy groups of the intermediate product thus obtained are then at least partially reacted with component (C).
  • This reaction is also used in cases where no amine salts are used as (C) components preferably carried out in an organic solvent.
  • the reaction between amines and compounds containing epoxide groups often starts when the reactants are mixed. Depending on the desired course of the reaction - especially to complete the reaction - it is advisable to raise the reaction temperature to 50 to 150 ° C.
  • the corresponding reaction is preferably carried out in a water-containing reaction medium.
  • modifying compounds are: a) compounds containing carboxyl groups, such as saturated or unsaturated monocarboxylic acids (eg benzoic acid, linseed oil fatty acid, 2-ethylhexanoic acid, versatic acid), aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids of various chain lengths (eg adipic acid, Sebacic acid, isophthalic acid or dimeric fatty acids), hydroxyalkylcarboxylic acids (eg lactic acid, dimethylolpropionic acid) and carboxyl-containing esters or b) compounds containing amino groups, such as diethylamine or ethylhexylamine or diamines with secondary amino groups, eg N, N'-dialkylalkylenediamine, such as dim, N, N'-dialkyl-polyoxyalkylene amine, such as N, N'-dimethyl-polyoxy propylene diamine, cyanoalkyl
  • hydroxyl groups such as neopentyl glycol, bis-ethoxylated neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, dimethylhydantoin-N, N'-diethanol, 1,6-hexanediol, 2,5-hexanediol, 1,4-bis (hydroximethyl) - cyclohexane, 1, l-isopropylidene-bis- (p-phenoxy) -2-propanol, trimethylolpropane, pentaerythritol or amino alcohols, such as triethanolamine, methyldiethanolamine or hydroxyl-containing alkylketimines, such as aminomethylpropanediol-1,3-methyl-isobutylketimine or tris ( hydroximethyl) -aminomethane-cyclohexanone-ketimine as well as polyglycol ethers
  • hydroxyl groups
  • the positive charges required for water dilutability and electrical separability can be introduced into the binder molecules by protonation with water-soluble acids (eg boric acid, formic acid, lactic acid, preferably acetic acid) and / or by using amine salts as (C) components become.
  • water-soluble acids eg boric acid, formic acid, lactic acid, preferably acetic acid
  • amine salts as (C) components become.
  • the cationic amine-modified epoxy resins used in accordance with the invention are essentially epoxy group- free, ie their epoxy group content is so low that crosslinking reactions via epoxy groups cannot occur either before or after the deposition of the lacquer film. 5
  • the cationic amine-modified epoxy resins used according to the invention preferably contain no free epoxy groups.
  • the cationic amine-modified epoxy resin used in the electrocoat • LO baths used according to the invention can be converted by chemical modification into a self-crosslinking cationic resin.
  • a self-crosslinking cationic resin can be obtained, for example, by reacting the cationic amine-modified epoxy resin or a precursor of the cationic amine-modified epoxy resin with a partially blocked polyisocyanate, which on average contains one free isocyanate group per molecule.
  • crosslinking agents are phenoplasts, polyfunctional Mannich bases, melamine resins, benzoguanas, blocked polyisocyanates and compounds which contain at least two groups of the general formula R -0-C0-. 0 1 The remainder R means:
  • R 1 R -0-C0-CH--, R 3 -CH0H-CH 2 -, R 4 -CH0R 5 -CH0H-CH_-
  • R 2 alkyl 5
  • R 3 H, alkyl, R 6 -0-CH or R 6 -C0-0-CH ⁇ -
  • R 4 H or alkyl
  • R 5 H, alkyl or aryl
  • R alkyl, cycloalkyl or aryl
  • Examples of compounds which contain at least two groups of the general formula R -0-C0- are bis (carbalkoxymethyl) azelate, bis (carbalkoxymethyl) sebacate, bis (carbalkoxymethyl) adipate, bis (carbalkoxymethyl) decanate, bis (carbalkoxymethyl) terephthalate, bis (2-hydroxybutyl) acelate and bis (2-hydroxyethyl) terephthalate.
  • Electrodeposition baths which contain the cationic amine-modified epoxy resin in question as an externally crosslinking cationic resin in combination with a blocked polyisocyanate as a crosslinking agent are particularly preferably used in the process according to the invention.
  • Any polyisocyanates in which the isocyanate groups have been reacted with a compound can be used as blocked polyisocyanates, so that the blocked polyisocyanate formed is resistant to hydroxyl and amino groups at room temperature, at elevated temperatures, generally in the range from about 90 ° C to about 300 ° C, but reacts.
  • Any organic polyisocyanates suitable for crosslinking can be used in the production of the blocked polyisocyanates. Isocyanates which something "3 to 36, more preferably about 8 to about 15 Kohlenstoff ⁇ atoms.
  • diisocyanates examples include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and l-isocyanatomethyl-5-isocyanato- 1 are preferred , 3,3-trimethylcyclohexane
  • Polyisocyanates with higher isocyanate functionality can also be used, examples being trimerized hexamethylene diisocyanate and trimerized isophorone diisocyanate you can also use mixtures of polyisocyanates.
  • the organic polyisocyanates which are suitable as crosslinking agents in the invention can also be prepolymers which are derived, for example, from a polyol, including a polyether polyol or a polyester polyol.
  • Any suitable aliphatic, cycloaliphatic or aromatic alkyl mono alcohols can be used to block the polyisocyanates.
  • suitable aliphatic, cycloaliphatic or aromatic alkyl mono alcohols can be used to block the polyisocyanates.
  • aliphatic alcohols such as methyl, ethyl, chloroethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, 3,3,5-trimethylhexyl, decyl and lauryl alcohol
  • cycloaliphatic alcohols such as cyclopentanol and cyclohexanol
  • aromatic alkyl alcohols such as. Phenylcarbinol and methylphenylcarbinol.
  • blocking agents are hydroxylamines, w h e ethanolamine, oximes such as methyl ethyl ketone oxime, acetone oxime and cyclohexanone oxime, or amines such as dibutylamine and diisopropylamine.
  • oximes such as methyl ethyl ketone oxime, acetone oxime and cyclohexanone oxime
  • amines such as dibutylamine and diisopropylamine.
  • the suitable polyisocyanates and blocking agents can also be used, in suitable proportions, for the preparation of the above-mentioned partially blocked polyisocyanates.
  • the crosslinking agent is generally used in an amount of 5 to 60% by weight, preferably 20 to 40% by weight, based on the total amount of crosslinkable cationic resin contained in the electrocoating material.
  • the proportion of the cationic amine-modified epoxy resin described in the preamble of patent claim 1 in the total amount of binders contained in the electrocoating bath is preferably 90 to 40, particularly preferably 75, in the cases in which the cationic amine-modified epoxy resin is present as an externally crosslinking resin up to 60% by weight, and in cases where the cationic amine-modified epoxy resin is present as a self-crosslinking resin, the proportion is preferably 100 to 70% by weight.
  • electrocoating baths containing at least 7.5% by weight of a polyoxyalkylene polyamine are used in the process according to the invention, the% by weight relating to the total amount of binders contained in the electrocoating bath .
  • Polyoxyalkylene polyamines are understood to mean compounds which contain both oxyalkylene groups and at least two amino groups, preferably at least two primary amino groups.
  • the polyoxyalkylene polyamines should have a number average molecular weight of about 137 to 3600, preferably 400 to 3000, particularly preferably 800 to 2500.
  • the polyoxyalkylene polyamines should have an amine equivalent weight of about 69 to about 1800, preferably 200 to 1500, particularly preferably 400 to 1250.
  • Polyoxyalkylene polyamines used with preference have a chemical structure according to the general formula (I)
  • R H or alkyl radical with 1 to 6 carbon atoms, preferably
  • polyoxyalkylene polyamines which contain different oxyalkylene groups
  • polyoxyalkylene polyamines which have a chemical structure in accordance with the general formula (II):
  • polyoxyalkylene polyamine derivatives which can be obtained by reacting the polyoxyalkylene polyamines described in US Pat. No. 3,236,895 in column 2, lines 40-72 with acrylonitrile and subsequent hydrogenation of the reaction product. These derivatives have a chemical structure according to the general structural formula (III):
  • the polyoxyalkylene polyamines or polyoxyalkylene polyamine mixtures can be incorporated into the electrocoating baths at any time during production and also after the electrocoating baths have been completed.
  • the polyoxyalkylene polyamines or polyoxyalkylene polyamine mixtures are preferably an aqueous dispersion or a precursor of the aqueous dispersion which contains the cationic amine-modified epoxy resin described in the preamble of claim 1, optionally crosslinking agents and other customary additives (see p. 5, Lines 5 to 10), or to the pigment paste or to a precursor of the pigment paste (see p. 5, lines 15 ff.).
  • the polyoxyalkylene polyamine molecules are most likely protonated by the acid contained in the aqueous dispersion or pigment paste.
  • the corresponding polyoxyalkylene polyamine or polyoxyalkylene polyamine mixture in protonated form can be added to the aqueous dispersion in question or to a precursor of this dispersion or to the pigment paste or to a precursor of the pigment paste.
  • the protonated polyoxyalkylene polya in or polyoxyalkylene polyamine mixture can be obtained by simply adding a Bronsted acid to the corresponding polyoxyalkylene polyamine or polyoxyalkylene polyamine mixture.
  • the total amount of Bronsted acid contained in the finished electrocoating bath is to be selected so that the pH of the electrocoating bath is between 4 and 8, preferably between
  • the amount of polyoxyalkylene polyamine or polyoxyalkylene polyamine mixture contained in the electrocoating baths used in accordance with the invention is at least 7.5% by weight, the weight 96 being based on the total amount of binders contained in the electrocoating bath .
  • the electrocoating baths used according to the invention must contain at least 7.5 parts by weight of polyoxyalkylene polyamine or polyoxyalkylene polyamine mixture per 100 parts by weight of binder.
  • the upper limit of the amount of polyoxyalkylene polyamine or polyoxyalkylene polyamine mixture contained in the electrocoating baths used according to the invention is determined by the plasticizing effect of the added polyoxyalkylene polyamine or polyoxyalkylene polyamine mixture and is generally 20 to 40% by weight, the weight .-% - refers to the total amount of binders contained in the electrocoating bath.
  • the electrocoating baths used according to the invention preferably contain 8 to 18, particularly preferably 10 to 15,% by weight of polyoxyalkylene polyamine or polyoxyalkylene polyamine mixture, the percentages by weight being based on the total amount of binders contained in the electrocoating bath.
  • the total amount of binders contained in the electrocoating bath is determined by the amount of cationic amine-modified epoxy resin contained in the electrocoating bath of the type described in the preamble of claim 1, which may be present in the electrocoating bath Amount of crosslinking agents, the amount of rubbing resin contained in the electrocoating bath and the amount of resins which crosslink under the baking conditions, if any, are also present in the electrocoating bath.
  • the solids content of the electrocoating baths used according to the invention is preferably 7 to 35 parts by weight, particularly preferably 12 to 25 parts by weight.
  • the electrocoating bath is brought into contact with an electrically conductive anode and with the electrically conductive substrate connected as a cathode.
  • electrical current passes between the anode and cathode, a firmly adhering lacquer film is deposited on the cathode.
  • the temperature of the electrocoating bath should be between 15 to 35 ° C., preferably between 20 to 30 ° C.
  • the applied voltage can vary over a wide range and can e.g. are between two and a thousand volts. Typically, however, voltages between 50 and
  • the current density is usually
  • the coated object is rinsed off and is ready for baking.
  • the deposited lacquer films are generally baked at temperatures of 130 to 200 ° C. for a period of 10 to 60 minutes, preferably at 150 to 180 ° C. for a period of 15 to 30 minutes.
  • the method according to the invention can be used for coating any electrically conductive substrates, but in particular for coating metals such as steel, aluminum, copper and the like.
  • the invention is explained in more detail in the following examples. All parts and percentages are by weight unless expressly stated otherwise.
  • the resin has a solids content of 70.2% and a base content of 0.97 milliequivalents / gram.
  • the resulting aqueous dispersion is freed from low-boiling solvents in a vacuum distillation and then diluted to a solids content of 33% with deionized water.
  • the procedure is as under 1.3.1, with the difference that no polyoxypropylenediamine is used. To set the solids of 33 96, less deionized water is added after the vacuum distillation.
  • Electrocoating bath 1 dispersion according to 1.3.1 with paste according to 2.2
  • Polyoxypropylenediamine content (based on the total amount of binders): 11.9% by weight
  • Electrocoating bath 2 dispersion according to item 1.3.2 with paste according to item 2.2 polyoxypropylenediamine content (based on the total amount of binders): 6.0% by weight
  • Electrocoating bath 3 dispersion according to point 1.3.3 with
  • Liability 1 0.5 0.5 0.5

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Molecular Biology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Paints Or Removers (AREA)
  • Conductive Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

On utilise selon un procédé cathodique de trempage électrophorétique des bains de trempage électrophorétique qui contiennent une résine époxyde cationique aminomodifiée obtenue par conversion: (A) d'un composé diépoxyde avec un poids équivalent d'époxyde inférieur à 2000, (B) d'un composé porteur d'un groupe alcoolique OH, d'un groupe phénolique OH ou d'un groupe SH qui réagit de manière monofonctionnelle avec des groupes époxydes, (C) d'une amine. Les composants (A) et (B) présentent un rapport molaire mutuel compris entre 10:1 et 1:1, de préférence entre 4:1 et 1,5:1, et les charges positives sont introduites par protonisation et/ou par l'utilisation en tant que composants (C) de sels aminés. Ces bains de trempage électrophorétique se caractérisent par le fait qu'ils contiennent au moins 7,5 % en poids d'une polyoxyalkylènepolyamine, par rapport à la teneur totale en liants du bain de trempage électrophorétique.
EP89900242A 1988-01-22 1988-12-15 Procede de revetement de substrats electroconducteurs, substrats revetus selon ce procede et bains aqueux de trempage electrophoretique Pending EP0386132A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3801786A DE3801786A1 (de) 1988-01-22 1988-01-22 Verfahren zur beschichtung elektrisch leitfaehiger substrate, nach diesem verfahren beschichtete substrate und waessrige elektrotauchlackbaeder
DE3801786 1988-01-22

Publications (1)

Publication Number Publication Date
EP0386132A1 true EP0386132A1 (fr) 1990-09-12

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EP89900242A Pending EP0386132A1 (fr) 1988-01-22 1988-12-15 Procede de revetement de substrats electroconducteurs, substrats revetus selon ce procede et bains aqueux de trempage electrophoretique
EP19880120995 Expired - Lifetime EP0324950B1 (fr) 1988-01-22 1988-12-15 Procédé de revêtement des substrats électroconducteurs, substrats revêtus par ce procédé et bains aqueux d'électrodéposition

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US (1) US5380412A (fr)
EP (2) EP0386132A1 (fr)
JP (1) JPH02503572A (fr)
KR (1) KR930008748B1 (fr)
CN (1) CN1043065C (fr)
AT (1) ATE73162T1 (fr)
AU (1) AU619237B2 (fr)
BR (1) BR8807878A (fr)
CA (1) CA1338228C (fr)
DE (2) DE3801786A1 (fr)
ES (1) ES2030146T3 (fr)
WO (1) WO1989006672A1 (fr)
ZA (1) ZA89249B (fr)

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DE19631370A1 (de) * 1996-08-02 1998-02-05 Hoechst Ag Härtungsmittel für Epoxidharz-Systeme
US5789468A (en) * 1997-03-27 1998-08-04 E. I. Du Pont De Nemours And Company Internal anticratering agent for cathodic electrocoating compositions
US6417292B1 (en) * 2000-04-07 2002-07-09 Ppg Industries Ohio, Inc. Electrodepositable coating compositions including ungelled reaction products of epoxy functional polyesters and amines coated substrates and methods of electrocoating using the same
JP3490991B2 (ja) * 2001-09-17 2004-01-26 関西ペイント株式会社 カチオン性塗料組成物
FR2860523B1 (fr) * 2003-10-01 2006-01-13 Commissariat Energie Atomique Procede de formation d'un film polymere sur une surface conductrice ou semi-conductrice de l'electricite par electro-greffage, surfaces obtenues et applications
CN104685012B (zh) * 2012-10-02 2016-12-14 关西涂料株式会社 阳离子电沉积涂料组合物
CN103304773B (zh) * 2013-06-24 2016-01-20 浩力森涂料（上海）有限公司 离子型固化剂及其制备方法
KR102341535B1 (ko) * 2017-03-10 2021-12-22 주식회사 케이씨씨 양이온 전착수지 조성물
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Also Published As

Publication number Publication date
CN1036048A (zh) 1989-10-04
CN1043065C (zh) 1999-04-21
ES2030146T3 (es) 1992-10-16
AU619237B2 (en) 1992-01-23
EP0324950B1 (fr) 1992-03-04
WO1989006672A1 (fr) 1989-07-27
DE3868914D1 (en) 1992-04-09
JPH02503572A (ja) 1990-10-25
KR900700551A (ko) 1990-08-16
ATE73162T1 (de) 1992-03-15
US5380412A (en) 1995-01-10
DE3801786A1 (de) 1989-07-27
KR930008748B1 (ko) 1993-09-13
EP0324950A1 (fr) 1989-07-26
CA1338228C (fr) 1996-04-02
ZA89249B (en) 1989-10-25
AU2799689A (en) 1989-08-11
BR8807878A (pt) 1990-10-09

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