JP2017505358A - Aqueous dip coating composition for conductive substrates comprising bismuth and phosphorus containing amine blocked compounds - Google Patents

Abstract

  The present invention comprises at least one cathode depositing binder (A1) and optionally at least one crosslinker (A2) to at least partially coat the conductive substrate with an electrodeposition material. Aqueous coating composition (A) comprising at least 30 ppm bismuth in total with respect to the total mass of (A), and further containing at least one phosphorus blocked with at least one amine of general formula (I) With respect to an aqueous coating composition (A) comprising a compound (P), a method of using (A), a corresponding coating method, and a corresponding method for at least partially coating a conductive substrate with an electrodeposition material The resulting at least partially coated substrate.

Description

  The present invention comprises at least one cathode depositing binder (A1) and optionally at least one crosslinker (A2) to at least partially coat the conductive substrate with an electrodeposition material. Aqueous coating composition (A) comprising at least 30 ppm bismuth in total with respect to the total mass of (A), and further containing at least one phosphorus blocked with at least one amine of general formula (I) With respect to an aqueous coating composition (A) comprising a compound (P), a method of using (A), a corresponding coating method, and a corresponding method for at least partially coating a conductive substrate with an electrodeposition material The resulting at least partially coated substrate.

  A common requirement within the automotive sector is that corrosion of metal parts used in manufacturing must be prevented. The requirements to be realized with respect to corrosion prevention are very strict. The reason is that, in particular, manufacturers often give a long-term guarantee against rust perforation. Such corrosion prevention is usually achieved by coating the part or substrate used in its manufacture with at least one coating suitable for the purpose.

  A disadvantage of known coating methods that particularly affect the known methods used within the automotive industry is that such methods are usually premised on a phosphate pretreatment step. In this process, the substrate for coating is a metal phosphate such as zinc phosphate in the phosphating process to ensure proper corrosion protection after any cleaning process and before the deposition coating process. Is processed. This pretreatment usually involves performing a plurality of in-process steps in a plurality of various dipping tanks that are variously heated. Furthermore, waste sludge is generated during the execution of such pretreatment, which places a burden on the environment and must be disposed of. Therefore, from an environmental and economic standpoint, it is particularly desirable to be able to achieve at least as much corrosion protection as is achieved using known methods, even if such pretreatment steps are omitted.

  Cathode-depositable bismuth-containing coating compositions that can be deposited on a suitable substrate in a one-step coating process are, for example, WO2009 / 021719A2, WO2004 / 018580A1, WO2004 / 018570A2. EP 0 642 558 B2 and WO 95/07319 A1. The bismuth compound used in each case typically functions here as a crosslinking catalyst. However, a drawback of the coating composition disclosed therein is that the resulting coated substrate often lacks sufficient corrosion protection.

  Coating compositions that can be used as a clearcoat or topcoat material and contain a phosphorus-containing amine blocking catalyst are described, for example, in WO 2011/029502 (A1), WO 2010/063332 (A1), US Patent Application This is known from Japanese Patent Publication No. 2009/0087667 (A1), US Patent Application Publication No. 2008/0268256 (A1), and Japanese Patent Application Laid-Open No. 2012-0000568A. The coating composition cured accordingly is notable, for example, in good scratch resistance. The way in which these catalysts are used in electrodeposition systems and, accordingly, improved corrosion protection due to the presence of these catalysts in these systems (such protection is applied to the coated substrate accordingly) Is not listed in any of these documents.

  German Patent 2,658,812 (A1) discloses cathodic depositing electrodeposition materials which contain at least one phosphate of phenol as their crosslinking catalyst. However, a drawback of the coating composition disclosed therein is that the resulting coated substrate often lacks sufficient corrosion protection.

  In particular, from the standpoint of omitting the commonly performed phosphate pretreatment step, it allows for a more economical and environmentally friendly coating method than the conventional coating compositions used, and at least to the same extent to such compositions. There is a need for an electrophoretic depositable coating composition for at least partially coating a conductive substrate with an electrodeposition material that is suitable to achieve the required corrosion protection effect.

International Publication No. 2009 / 021719A2 International Publication No. 2004 / 018580A1 International Publication No. 2004/018570 A2 European Patent Application No. 0642558B2 International Publication No. 95 / 07319A1 International Publication No. 2011/029502 (A1) International Publication No. 2010/063332 (A1) US Patent Application Publication No. 2009/0087667 (A1) US Patent Application Publication No. 2008/0268256 (A1) JP2012-000568A German Patent No. 2658812 (A1)

  Accordingly, it is an object of the present invention to provide a coating composition for at least partially coating a conductive substrate having advantages over coating compositions known in the prior art. In particular, it is an object of the present invention to provide a coating composition that enables a more economical and / or environmentally friendly coating process than the conventional coating compositions used. Furthermore, in particular, the object of the present invention allows for a more economical and / or environmentally friendly coating than conventional coating methods, in other words by metal phosphates in particular before the deposition coating. Although it is possible to omit the phosphating treatment that has to be carried out normally, it is still at least the same as the usual method, and more specifically, an enhanced corrosion protection effect can be realized than the usual method. Is to provide a method.

  This object is achieved by the claimed subject matter and also by preferred embodiments of the subject matter described in the following detailed description.

の少なくとも１種のアミンでブロックされた少なくとも１種のリン含有化合物（Ｐ）を含み、式中、
Ｒ^１およびＲ^２はそれぞれ互いに独立に、Ｃ_１〜１８脂肪族基であるか、Ｃ_３〜１２脂環式基であるか、Ｃ_１〜１０脂肪族基によって架橋されたＣ_３〜１２脂環式基であるか、またはＣ_１〜１０脂肪族基によって架橋されたアリールもしくはヘテロアリール基であり、
Ｒ^３はＨ、Ｃ_１〜１８脂肪族基、Ｃ_３〜１２脂環式基、Ｃ_１〜１０脂肪族基によって架橋されたＣ_３〜１２脂環式基、またはＣ_１〜１０脂肪族基によって架橋されたアリールもしくはヘテロアリール基である、
水性コーティング組成物（Ａ）である。 Accordingly, a first subject of the present invention is to at least partially coat a conductive substrate with an electrodeposition material,
(A1) an aqueous coating composition (A) comprising at least one cathode depositing binder, and (A2) optionally at least one crosslinking agent, relative to the total mass of the coating composition (A) And at least 30 ppm bismuth in total
Formula (I)

At least one phosphorus-containing compound (P) blocked with at least one amine of the formula:
R ¹ and ^{R 2} are each, independently of one _another, or a _{C 1 to 18} aliphatic _group, or a _{C 3 to 12} cycloaliphatic _{radical, C 3 to 12} fat cross-linked by _{C 1 to 10} aliphatic group An aryl or heteroaryl group that is a cyclic group or bridged by a C _1-10 aliphatic group,
R ³ is _{H, C 1 to 18} aliphatic _{radical, C 3 to 12} cycloaliphatic _{radical, C 3 to 12} cycloaliphatic radical cross-linked by _{C 1 to 10} aliphatic group or a _{C 1 to 10} aliphatic group, An aryl or heteroaryl group bridged by
It is an aqueous coating composition (A).

  Accordingly, the aqueous coating composition (A) of the present invention is useful for generating electrodeposition on the substrate surface of a conductive substrate.

  Surprisingly, particularly when used in a method for at least partially coating an electrodeposition material onto a conductive substrate, the aqueous coating composition (A) of the present invention provides a deposition coating, more specifically. Is a conductive process that at least partially coats a metal phosphate such as zinc phosphate to form a metal phosphate layer on the substrate that normally requires implementation prior to electrodeposition. It is possible to omit the step of pretreating the substrate, which makes the coating method in question economically overall, more specifically only in a short time and at a lower cost than conventional methods. It turns out that it becomes possible to become environmentally friendly.

  In particular, it is surprising that the coating composition (A) according to the invention is at least in no way disadvantageous in terms of corrosion protection compared to substrates coated according to conventional methods, in particular Providing a conductive substrate at least partially coated with an electrodeposition material that is advantageous, especially when the substrate used is aluminum that has not undergone any pretreatment such as phosphating It turned out to be possible.

Even more surprisingly, the process (at least through the two-step process (1)) is carried out by a method for at least partially coating a conductive substrate using the coating composition of the present invention. Within 1) it has been found that it is possible to obtain an excellent Bi coating of the substrate via step (1a), in particular a coating of 10 mg / m ² Bi or more. The amount of bismuth here can be determined by fluorescent X-ray analysis by the method described below. Surprisingly, the corrosion protection can be further improved by the amine-blocked phosphorus-containing compound (P) present in (A).

  In one preferred embodiment, the term “comprising” in the sense of the present invention, for example as it relates to the aqueous coating composition (A) of the present invention, has the meaning “consisting of”. With respect to the coating composition (A) according to the invention in this preferred embodiment, it is (A1), with at least one amine-blocking compound (P) and water, in particular in the form of (A3) and / or (A4). In addition to certain bismuth and also optionally (A2), for example, optional components (A5), (A6) and / or (A7) and / or (A8), and also optionally present organic solvents, One or more additional components identified below and optionally present in the coating composition (A) used according to the invention can also be present in the coating composition (A). All of these components identified above and below in the coating composition (A) used according to the invention can each be present in its preferred embodiment.

Substrates Suitable conductive substrates for use in accordance with the present invention are all of the commonly used conductive substrates known to those skilled in the art. The conductive substrate used in accordance with the present invention is preferably plated, such as steel, preferably cold rolled steel, dip galvanized steel, alloy plated steel (eg Galvalume, Galvannealed, or Galfan) and aluminized steel. Selected from the group consisting of steel, aluminum and magnesium selected from the group consisting of steel; plated steel and aluminum are particularly suitable. Particularly preferred are aluminum substrates or substrates having at least one aluminum surface. Also suitable as substrates are hot rolled steel, high strength steel, Zn / Mg alloys and Zn / Ni alloys. Particularly suitable substrates are bodies for automobile production or full body parts. The method of the present invention can also be used for coil coating. Before the conductive substrate is used, the substrate is preferably cleaned and / or degreased.

  The conductive substrate used in accordance with the present invention may be a substrate that has been pretreated with at least one metal phosphate. Furthermore, the conductive substrate used according to the present invention may be a chromate substrate. Such pre-treatment by phosphating or chromate treatment usually performed after the substrate has been cleaned and before dip coating is in particular a routine pre-treatment step within the automotive industry. In this context, it is particularly desirable that the optional pretreatment be designed to be environmentally and / or economically advantageous. Thus, for example, instead of the usual trication phosphating treatment, the nickel component is excluded, and instead a dicationic phosphating treatment (containing zinc and manganese cations and no nickel cations) is applied to the aqueous coating composition (A An optional pretreatment step is possible which is carried out on the conductive substrate used according to the invention before the coating according to).

  However, a specific object of the present invention is to provide such a pre-treatment of the conductive substrate for at least partial coating, for example by phosphating with a metal phosphate such as zinc phosphate or by chromating. It can be omitted. Thus, in one preferred embodiment, the conductive substrate used in accordance with the present invention is not such a phosphate or chromate substrate.

  Prior to being coated with the aqueous coating composition (A) of the present invention, the conductive substrate used according to the present invention is at least one comprising at least one Ti atom and / or at least one Zr atom. An aqueous pretreatment composition comprising at least one water-soluble compound as a fluoride ion source comprising at least one fluorine ion, or at least one Ti atom and / or at least one Aqueous pretreatment composition comprising a water-soluble compound obtainable by reaction of at least one water-soluble compound containing a Zr atom and at least one water-soluble compound as a fluoride ion source containing at least one fluorine ion Can be preprocessed.

At least one Ti atom and / or at least one Zr atom in this case preferably has an oxidation state of +4. For the components that the aqueous pretreatment composition comprises, and more preferably, due to the appropriately selected proportions of such components, the aqueous pretreatment composition is preferably a fluorine complex such as a hexafluorometal salt, That is, in detail, it includes hexafluorotitanate and / or at least one hexafluorozirconate. The pretreatment composition preferably has a total concentration of elemental Ti and / or Zr of 2.5 · 10 ⁻⁴ mol / L or more but not exceeding 2.0 · 10 ⁻² mol / L. The production of such a pretreatment composition and its use in the pretreatment of conductive substrates is known, for example, from WO 2009/115504 A1.

  The pretreatment composition is preferably at least one selected from the group consisting of copper ions, preferably copper (II) ions, and optionally Ca, Mg, Al, B, Zn, Mn and W and also mixtures thereof. One or more water-soluble and / or water-dispersible compounds, including at least one metal ion, preferably at least one aluminosilicate, more particularly at least a 1: 3 atomic ratio of Al to Si. It has what further has. The production of such a pretreatment composition and its use in the pretreatment of conductive substrates is known, for example, from WO 2009/115504 A1. The aluminosilicate is preferably present in the form of nanoparticles having a particle size in the range of 1-100 nm, which can be determined by dynamic light scattering. The average particle size of such nanoparticles in the range of 1-100 nm, which can be determined by dynamic light scattering, is determined according to DIN ISO 13321 (date: 1 October 2004).

  However, in one preferred embodiment, the conductive substrate used in accordance with the present invention is a substrate that has not been pretreated with any of such pretreatment compositions.

Component (A1) and optional component (A2)
The aqueous coating composition (A) used according to the invention comprises at least one cathodic depositing binder as component (A1) and optionally at least one cross-linking agent as component (A2). .

  The term “binder” as part of the coating composition (A) is preferably used in the present invention as a cathode depositing polymeric resin of the aqueous coating composition (A) used according to the present invention. That is, it includes a resin that plays a role in film formation, but none of the existing crosslinking agents are included in the concept of a binder. Thus, a “binder” in the sense of the present invention is a polymeric resin, but none of the existing crosslinking agents are included in the concept of a binder. Furthermore, in particular, any pigments and fillers present are not included in the binder concept. Preferably, furthermore, even if optional component (A5) contains a polymeric complexing agent, that component is not included in the binder concept.

  The coating composition (A) used according to the invention preferably comprises an aqueous dispersion comprising at least one cathodic depositing binder (A1) and optionally at least one crosslinking agent (A2). Or it is prepared using an aqueous solution, more preferably at least one aqueous dispersion. This aqueous dispersion or aqueous solution comprising (A1) and optionally (A2) is preferably in the range of 25-60% by weight, more preferably, based on the total weight in each case of this aqueous dispersion or aqueous solution, A range of 27.5-55% by weight, very preferably, a range of 30-50% by weight, even more preferably a range of 32.5-45% by weight, specifically 35-42.5% by weight. A non-volatile fraction in the range of: solids content.

  Methods for determining the solids content, in particular the solids content of the electrodeposit, are known to those skilled in the art. The solids content is preferably determined by DIN EN ISO 3251 (date: 1 June 2008), in particular by this standard over 180 ° C. for 30 minutes.

  The person skilled in the art is aware of cathode depositing binders (A1). The binder used in the present invention is preferably a binder that is dispersible or soluble in water.

  All conventional cathodic depositing binders known to those skilled in the art are suitable herein as binder component (A1) of the aqueous coating composition (A) used according to the present invention.

  The binder (A1) preferably has a reactive functional group that allows a crosslinking reaction. The binder (A1) herein is a self-crosslinking agent or an external crosslinking agent, preferably an external crosslinking agent. Therefore, in order to enable a crosslinking reaction, the coating composition (A) preferably further comprises at least one crosslinking agent (A2) in addition to at least one binder (A1).

  The binder (A1) present in the coating composition (A) or the optionally present crosslinker (A2) is preferably thermally crosslinkable. The binder (A1) and the optionally present crosslinker (A2) are preferably crosslinkable upon heating to temperatures above room temperature, ie above 18-23 ° C. The binder (A1) and the optionally present crosslinker (A2) are preferably ≧ 80 ° C., more preferably ≧ 110 ° C., very preferably ≧ 130 ° C., particularly preferably ≧ 140. It is crosslinkable only at an oven temperature of ° C. Particularly advantageously, the binder (A1) and the optionally present crosslinker (A2) are crosslinked at 100 to 250 ° C., more preferably 125 to 250 ° C., very preferably 150 to 250 ° C. It is sex.

  The coating composition (A) preferably comprises at least one crosslinking agent (A1) having a reactive functional group that enables a crosslinking reaction, preferably in combination with at least one crosslinking agent (A2).

Any of the conventional crosslinkable and reactive functional groups known to those skilled in the art are contemplated herein. The binder (A1) is preferably an optionally substituted primary amino group, an optionally substituted secondary amino group, a substituted tertiary amino group, a hydroxyl group, a thiol group, a carboxyl group, For example, having a reactive functional group selected from the group consisting of a group having at least one C═C double bond, such as a vinyl group or a (meth) acrylate group, and an epoxide group, the primary and the second In each case, the primary amino group is independently of one another by one or two or three substituents selected from the group consisting of C _1-6 aliphatic groups such as methyl, ethyl, n-propyl or isopropyl. And such C _1-6 aliphatic groups are selected from the group consisting of OH, NH ₂ , NH (C _1-6 alkyl), and N (C _1-6 alkyl) _2. Ru In each case it can be optionally substituted independently of one another by one, two or three substituents. Particularly preferred is at least one binder (A1) having a reactive functional group selected from the group consisting of an optionally substituted primary amino group, an optionally substituted secondary amino group, and a hydroxyl group. 1 or 2 or 3 substituents wherein the primary and secondary amino groups are selected from the group consisting of C _1-6 aliphatic groups such as, for example, methyl, ethyl, n-propyl or isopropyl In each case can be optionally substituted independently of one another, and such C _1-6 aliphatic groups are represented by OH, NH ₂ , NH (C _1-6 alkyl), and N (C _1-6 Alkyl) in each case can be optionally substituted independently of one another by one, two or three substituents selected from the group consisting of ₂ . The reactive functional groups herein, in particular optionally substituted primary and secondary amino groups, can optionally be present at least partially in protonated form.

Particularly preferably, the binding agent (A1) is at least two C ₁ each substituted by a tertiary amino group optionally present in at least partly protonated form, very preferably only at least one hydroxyl group. _{~ 3} alkyl groups in each case independently of one another, more specifically two hydroxyethyl groups, hydroxypropyl groups, or one hydroxypropyl group and one hydroxyethyl group in each case The binder has a tertiary amino group independently and the binder (A1) is preferably at least one polymer resin. Such a binder can be obtained, for example, by the method described in JP2011-057944A.

The binder (A1) present in the coating composition (A1) is preferably at least one acrylate-based polymeric resin and / or at least one epoxide-based polymeric resin, more specifically at least one Some cationic epoxide-based and amine-modified resins. The production of this type of cationic amine-modified epoxide resin is known and is described, for example, in DE 3518732, DE 3518770, EP 040090, EP 0012463, EP 0961797B1, and EP 0505445B1. The cationic epoxide-based amine-modified resin is preferably at least one optionally modified polyepoxide, that is, at least one optionally modified polyepoxide having two or more epoxide groups and at least one preferably Will be understood to be the reaction product of a water soluble amine, preferably with at least one such primary and / or secondary amine. Particularly preferably, the polyepoxide is a polyglycidyl ether of polyphenol and is produced from polyphenol and epihalohydrin. Specific examples of polyphenols that can be used include bisphenol A and / or bisphenol F. Other suitable polyepoxides are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerin, and 2 , A polyglycidyl ether of a polyhydric alcohol such as 2-bis (4-hydroxycyclohexyl) propane. A modified polyepoxide is a polyepoxide in which several reactive functional groups have reacted with at least one modifying compound. Examples of such modifying compounds are as follows:
a) saturated or unsaturated monocarboxylic acids (eg benzoic acid, linseed oil fatty acid, 2-ethylhexanoic acid, versatic acid), aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids with various chain lengths (eg , Adipic acid, sebacic acid, isophthalic acid, or dimer fatty acid), hydroxyalkyl carboxylic acids (eg, lactic acid, dimethylolpropionic acid), and compounds containing carboxyl groups such as carboxyl-containing polyesters, or b) diethylamine or Diamines having ethylhexylamine or secondary amino groups, for example, N, N′-dialkylalkylenediamines such as dimethylethylenediamine, N, N′-dialkylpolyoxyalkyleneamines such as N, N′-dimethylpolyoxypropylenediamine, Bis-N, N ' Cyanalkylated alkylenediamines such as cyanethyl-ethylenediamine, cyanalkylated polyoxyalkyleneamines such as bis-N, N′-cyanethylpolyoxypropylenediamine, polyaminoamides such as versamide, such as in particular diamines (eg hexamethylene Diamines), polycarboxylic acids, especially dimeric fatty acids, and monocarboxylic acids, especially amino-terminated reaction products of fatty acids, or 1 mol of diaminohexane and 2 mol of monoglycidyl ether, or monoglycidyl ester, especially versatic acid, etc. A compound containing an amino group such as a reaction product with a glycidyl ester of an α-branched fatty acid, or c) neopentyl glycol, bisethoxylated neopentyl glycol, neopentyl glycol hydroxypivala , Dimethylhydantoin-NN-diethanol, hexane-1,6-diol, hexane-2,5-diol, 1,4-bis (hydroxymethyl) cyclohexane, 1,1-isopropylidenebis (p-phenoxy) ) -2-propanol, trimethylolpropane, pentaerythritol, or amino alcohols such as triethanolamine, methyldiethanolamine, or aminomethylpropane-1,3-diolmethylisobutylketimine or tris (hydroxymethyl) aminomethanecyclohexanone ketimine Hydroxyl-containing alkyl ketimines and also polyglycol ethers, polyester polyols, polyether polyols, polycaprolactone polyols, polyesters having various functional groups and molecular weights. Compound, or d) sodium saturated or unsaturated fatty acid methyl esters are transesterified with a hydroxyl group in the epoxy resin in the presence of a methoxide containing hydroxyl groups, such as caprolactam polyols.

  Examples of amines that can be used are mono- and dialkylamines such as methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, methylbutylamine, for example alkanolamines such as methylethanolamine or diethanolamine, and for example dimethyl Dialkylaminoalkylamines such as aminoethylamine, diethylaminopropylamine, or dimethylaminopropylamine. The amines that can be used can also contain other functional groups, provided that these groups do not interfere with the reaction of the amine with the epoxide group of the optionally modified polyepoxide and do not result in gelation of the reaction mixture. Under conditions. Secondary amines are preferably used. The charge necessary for dilution with water and electroprecipitation can be generated by protonation with a water-soluble acid (eg boric acid, formic acid, acetic acid, lactic acid, preferably acetic acid). A further possibility for introducing cationic groups into the optionally modified polyepoxide exists in the reaction of epoxide groups in the polyepoxide with amine salts.

  In addition to the at least one cathodic depositing binder (A1), the coating composition (A) preferably comprises at least one cross-linking reaction that allows a crosslinking reaction with the reactive functional groups of the binder (A1). A crosslinking agent (A2) is included.

  Conventional crosslinking agents known to those skilled in the art such as phenolic resins, polyfunctional Mannich bases, melamine resins, benzoguanamine resins, epoxides, free polyisocyanates and / or blocked polyisocyanates, in particular blocked polyisocyanates (A2 ) Can all be used.

  Particularly preferred crosslinking agent (A2) is a blocked polyisocyanate. The blocked polyisocyanates that can be used are any polyisocyanates such as, for example, diisocyanates, in which case the isocyanate groups are reacted with the compound, so that the blocked polyisocyanate formed is At room temperature, i.e. at temperatures between 18 and 23 ° C., in particular stable with respect to hydroxyl and amino groups such as primary and / or secondary amino groups, but for example ≧ 80 ° C., more preferably ≧ 110 ° C., very preferably ≧ 130 ° C., particularly preferably ≧ 140 ° C., or 90 ° C. to 300 ° C., or 100 to 250 ° C., more preferably 125 The reaction is at 250 ° C, very preferably at higher temperatures such as 150-250 ° C.

In preparing the blocked polyisocyanate, any desired organic polyisocyanate suitable for crosslinking can be used. The isocyanate used is preferably a (hetero) aliphatic, (hetero) alicyclic, (hetero) aromatic, or (hetero) aliphatic- (hetero) aromatic isocyanate. Diisocyanates containing 2 to 36, more specifically 6 to 15 carbon atoms are preferred. Preferred examples are 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4 (2,4,4) -trimethyl. 1,6-hexamethylene diisocyanate (TMDI), diphenylmethane diisocyanate (MDI), 1,9-diisocyanato-5-methylnonane, 1,8-diisocyanato-2,4-dimethyloctane, 1,12-dodecane Diisocyanate, ω, ω′-diisocyanatodipropyl ether, cyclobutene 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, 3-isocyanatomethyl-3,5,5 -Trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,4-diisocyanate Natomethyl-2,3,5,6-tetramethylcyclohexane, decahydro-8-methyl-1,4-methanonaphthalene-2 (or 3), 5-ylene dimethylene diisocyanate, hexahydro-4,7-methano- Indan-1 (or 2), 5 (or 6) -ylene methylene diisocyanate, hexahydro-4,7-methanoindan-1 (or 2), 5 (or 6) -ylene diisocyanate, 2,4- And / or 2,6-hexahydrotolylene diisocyanate (H6-TDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), perhydro-2,4′-diphenylmethane diisocyanate, perhydro-4,4'-diphenylmethane diisocyanate _(H 12 MDI), 4,4'- diisocyanato -3, ', 5,5'-tetramethyldicyclohexylmethane, 4,4'-diisocyanato-2,2', 3,3 ', 5,5', 6,6'-octamethyldicyclohexylmethane, ω, ω'-diisocyanato -1,4-diethylbenzene, 1,4-diisocyanatomethyl-2,3,5,6-tetramethylbenzene, 2-methyl-1,5-diisocyanatopentane (MPDI), 2-ethyl-1, 4-diisocyanatobutane, 1,10-diisocyanatodecane, 1,5-diisocyanatohexane, 1,3-diisocyanatomethylcyclohexane, 1,4-diisocyanatomethylcyclohexane, 2,5 (2 , 6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane (NBDI), and also any mixture of such compounds. Polyisocyanates with higher isocyanate functionality can also be used. Examples are trimerized hexamethylene diisocyanate and trimerized isophorone diisocyanate. In addition, mixtures of polyisocyanates can also be utilized. The organic polyisocyanates contemplated as crosslinkers (A2) for the present invention may also be prepolymers derived from polyols including, for example, polyether polyols or polyester polyols. 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate (TDI) and / or 2,4-toluene diisocyanate and 2,6-toluene diisocyanate and / or diphenylmethane diisocyanate Particularly preferred is a mixture of isomers of nart (MDI).

  Preferably, any desired suitable aliphatic, cycloaliphatic or aromatic alkyl monoalcohol can be used for blocking the polyisocyanate. Examples are aliphatic alcohols such as methyl, ethyl, chloroethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, 3,3,5-trimethylhexyl, decyl, and lauryl alcohol; cyclopentanol and cyclohexanol And alicyclic alcohols such as phenyl carbinol and methyl phenyl carbinol. Other suitable blocking agents are hydroxylamines such as ethanolamine, oximes such as methyl ethyl ketone oxime, acetone oxime, and cyclohexanone oxime, and amines such as dibutylamine and diisopropylamine.

  The relative mass ratio of at least one binder (A1) and optionally present at least one crosslinking agent (A2) in the coating composition (A) used according to the invention is determined in each case by the coating. The solid content of the at least one binder (A1) and at least one crosslinker (A2) in the composition (A) is preferably in the range of 4: 1 to 1.1: 1, more preferably Is in the range 3: 1 to 1.1: 1, very preferably in the range 2.5: 1 to 1.1: 1, more specifically 2.1: 1 to 1.1: 1. Range.

  In another preferred embodiment, the relative mass ratio of at least one binder (A1) and optionally present at least one crosslinker (A2) in the coating composition (A) used according to the invention. Is in each case 4: 1 to 1.5: 1 relative to the solids content of at least one binder (A1) and at least one crosslinker (A2) in the coating composition (A) Range, more preferably in the range of 3: 1 to 1.5: 1, very preferably in the range of 2.5: 1 to 1.5: 1, more specifically 2.1: 1 to 1. .5: 1 range.

Coating composition (A)
The aqueous coating composition (A) of the present invention is suitable for at least partially coating a conductive substrate with an electrodeposition material, which means that the composition (A) is a conductive substrate. It means that it is suitable to be applied at least partially in the form of electrodeposition to the substrate surface. Preferably, the entire aqueous coating composition (A) of the present invention is cathodic depositable.

  The aqueous coating composition (A) of the present invention contains water as a liquid diluent.

  The term “aqueous” in connection with the coating composition (A) preferably refers to a liquid coating composition (A) comprising water as the main component of the liquid diluent, ie as a liquid solvent and / or dispersion medium. . However, optionally, the coating composition (A) can contain a small proportion of at least one organic solvent. Examples of such organic solvents are heterocyclic, aliphatic or aromatic hydrocarbons, mono- or polyhydric alcohols, in particular methanol and / or ethanol, ethers, esters, ketones and, for example, N-methylpyrrolidone, N-ethylpyrrolidone Amides such as dimethylformamide, toluene, xylene, butanol, ethyl glycol and butyl glycol and also their acetates, butyl diglycol, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetone, isophorone, or mixtures thereof. The proportion of such organic solvent is preferably not more than 20.0% by weight relative to the total proportion of liquid diluent present in each case in the coating composition (A), ie the liquid solvent and / or the dispersion medium. Preferably 15.0% by weight or less, very preferably 10.0% by weight or less, more specifically 5.0% by weight or less or 4.0% by weight or less or 3.0% by weight or less, and even more Preferably, it is 2.5 mass% or less or 2.0 mass% or less or 1.5 mass% or less, and most preferably 1.0 mass% or less or 0.5 mass% or less.

  % By weight of all components contained in the coating composition (A) of the present invention, in other words, (A1), at least one amine-blocking compound (P) and the total weight of the coating composition (A) and With water, in particular bismuth in the form of (A3) and / or (A4), and also optionally (A2) and optional components (A5), (A6) and / or (A7) and / or (A8), The proportion of organic solvent present optionally and / or preferably is 100% by weight in total.

  The aqueous coating composition (A) is preferably in each case in the range of 5-45% by weight, more preferably in the range of 7.5-35% by weight, based on the total weight of the aqueous coating composition (A), Very preferably in the range of 10-30% by weight, even more preferably in the range of 12.5-25% by weight or in the range of 15-30% by weight or in the range of 15-25% by weight, more specifically, It has a solids content in the range of 17-22% by weight. In particular, methods for determining the solid content of the electrodeposit are known to those skilled in the art. The solids content is preferably determined according to DIN EN IS O3251 (date: June 1, 2008).

  The aqueous coating composition (A) used according to the invention is preferably an aqueous dispersion or solution, preferably an aqueous dispersion.

  The coating composition (A) of the present invention preferably has a pH in the range of 4.0 to 6.5. The aqueous coating composition (A) used according to the invention is particularly preferably in the range of 4.2 to 6.5, more specifically in the range of 4.4 to 6.5 or 4.6 to In the range of 6.5, particularly preferably in the range of 4.8 to 6.4, most preferably in the range of 5.0 to 6.2 or 5.2 to 6.0 or 5.5 to 6.0. has a pH. Methods for adjusting the pH level in aqueous compositions are known to those skilled in the art. The desired pH is preferably set by the addition of at least one acid, more preferably at least one inorganic and / or at least one organic acid. Examples of suitable inorganic acids are hydrochloric acid, sulfuric acid, phosphoric acid and / or nitric acid. Examples of suitable organic acids are propionic acid, lactic acid, acetic acid and / or formic acid. Alternatively or additionally and preferably also, the components described below are suitable for the purpose, i.e. for example having at least one deprotonating functional group such as, for example, a carboxyl group and / or a phenolic OH group. If present, it is also possible to use at least one component (A5) optionally present in the coating composition (A) to adjust the pH level.

Total amount of bismuth and components (A3) and / or (A4) The coating composition (A) comprises a total amount of at least 30 ppm bismuth relative to the total mass of the coating composition (A).

  The total amount of bismuth present in the coating composition (A) is preferably at least 50 ppm or at least 100 ppm or at least 130 ppm or at least 150 ppm or at least 175 ppm or at least 200 ppm, in each case based on the total weight of the coating composition (A). More preferably at least 300 ppm, very particularly preferably at least 500 or at least 750 ppm, more specifically at least 1000 ppm or at least 1500 ppm or at least 2000 ppm. The total amount of bismuth present in the coating composition (A) is preferably in each case not more than 20000 ppm, more preferably not more than 15000 ppm, very preferably in each case relative to the total mass of the coating composition (A). Is 10000 ppm or less or 7500 ppm or less, more specifically 5000 ppm or less or 4000 ppm or less. The total amount of bismuth present in the coating composition (A) is preferably in the range of 30 ppm to 20000 ppm, more preferably in the range of 50 ppm to 15000 ppm, very preferably relative to the total mass of the aqueous coating composition (A). Is in the range of 100 ppm to 10000 ppm or in the range of 130 ppm to 10000 ppm, particularly preferably in the range of 500 ppm to 10000 ppm or in the range of 500 ppm to 20000 ppm or in the range of 1000 ppm to 10000 ppm or in the range of 1000 ppm to 5000 ppm or in the range of 500 ppm to 3000 ppm. The amount of bismuth calculated as metal may be determined by the following method (ICP-OES): the total amount of bismuth and also the function of both (A3) and (A4) can be determined here.

  The term “bismuth” in relation to the total amount of bismuth in the coating composition (A) and optionally optionally in component (A3) and also optionally (A4) It will be understood that it preferably refers to bismuth having an optionally charged, such as, for example, a positively charged cationic bismuth atom. The bismuth in this case may be in the trivalent form (Bi (III)), or alternatively may also be present in other oxidation states. The amount of bismuth is calculated as bismuth metal in each case herein.

  The total amount of bismuth present in the coating composition (A) may contain only bismuth present in solution form (A3) in the coating composition (A). The total amount of bismuth present in the coating composition (A) is alternatively not only in solution form (A3) in the coating composition (A) but also in non-solution form (A4) in the coating composition (A). It may also contain bismuth present in Preferably at least a portion of the total amount of bismuth present in the coating composition (A) is present in solution form (A3) in the coating composition (A).

  The total amount of bismuth present in the coating composition (A) is preferably the sum of (A3) and (A4) in each case. In another preferred embodiment, the total amount of bismuth present in the coating composition (A) corresponds to the amount of component (A3).

  When the coating composition (A) further comprises component (A5), components (A3) and (A5) are preferably in the coating composition (A) a complex of components (A3) and (A5) and / or It is a salt form. Thus, when the total amount of bismuth corresponds to the amount of component (A3), at least 30 ppm of bismuth present in solution form as component (A3) in coating composition (A) is preferably coating composition (A) Present in the form of a bismuth compound in the solution, more specifically in the form of at least one dissolved salt and / or complex of components (A3) and (A5) together with component (A5). Alternatively and / or additionally, for example, component (A3) may also be in the form of hydrated trivalent bismuth.

  As component (A3), preferably at least a part of trivalent bismuth is present. It may in particular be in hydrated form and / or in the form of at least one dissolved salt and / or complex together with (A5).

  The term “in the form present in solution” in connection with component (A3) of the coating composition (A) of the present invention preferably means that component (A3) is this component (A3) in the coating composition (A). At least 95 mol% or at least 97.5 mol%, more preferably at least 99 mol% or at least 99.5 mol%, very preferably at least 99.8 mol% or at least 99.9 mol%, based on the total amount of To the extent that it is present in solution form in the aqueous coating composition (A), more specifically 100 mol%. Therefore, component (A3) is preferably water-soluble. Component (A3) is preferably present in solution form in coating composition (A) at a coating composition (A) temperature in the range of at least 18-40 ° C.

  Component (A3) is preferably selected from the group consisting of oxides of bismuth, basic oxides, hydroxides, carbonates, nitrates, basic nitrates, salicylates, and basic salicylates, and also mixtures thereof Obtained from at least one bismuth compound. At least one such bismuth compound is preferably partially reacted to give component (A3), preferably in the presence of at least one complexing agent (A5), preferably in water.

  In order to produce the aqueous coating composition (A), preferably at least one component (A5) in the form of an aqueous solution is mixed with bismuth oxide, basic oxide, hydroxide, carbonate, nitrate, basic. After reacting with at least one bismuth compound selected from the group consisting of nitrates, salicylates, and basic salicylates, and also mixtures thereof and optionally filtering, the reaction product of (A5) and bismuth compounds An aqueous solution or dispersion or suspension of, preferably a solution, is obtained, and this preferably water-soluble reaction product is used to produce the coating composition (A) used according to the invention.

  Particularly preferably, in order to produce the aqueous coating composition (A), at least one component (A5) selected from the group consisting of lactic acid and dimethylpropionic acid is used in the form of an aqueous solution, among the above bismuth compounds. After reacting with at least one, preferably bismuth (III) oxide and optionally filtering, an aqueous solution or dispersion or suspension, preferably a solution, of the reaction product of (A5) and the bismuth compound is obtained. Preferably water-soluble reaction products are used to produce the coating composition (A) used according to the invention.

In addition to (A3), when the coating composition of the present invention further comprises component (A4), (A) is preferably (A3) coating composition (A) in the form of a solution in coating composition (A) Bismuth of at least 130 ppm relative to the total mass of
Or (A3) at least 30 ppm bismuth in the form of a solution in the coating composition (A) with respect to the total mass of the coating composition (A), and (A4) in the form of a non-solution in the coating composition (A) A total amount of at least 130 ppm bismuth with respect to the total mass of the coating composition (A), including at least 100 ppm bismuth with respect to the total mass of the coating composition (A).

  In this embodiment, at least 100 ppm of bismuth present in non-solution form as component (A4) in the coating composition (A) is preferably in the form of a bismuth compound that is non-solution in the coating composition (A). More specifically, it exists in the form of at least one undissolved bismuth salt, hydroxide and / or oxide.

  The molar proportion of component (A4) within the total amount of bismuth present in the coating composition (A), ie within the total amount of bismuth present in the coating composition (A), is preferably at least 10 mol%, more preferably Is at least 20 mol% or at least 30 mol%, very preferably at least 40 mol% or at least 50 mol% or at least 60 mol% or at least 70 mol%. The proportion of component (A4) in the total amount of bismuth present in the coating composition (A) is preferably in each case 98 mol% or less, very preferably 97 mol% or less or 96 mol% or less, in particular Preferably, it is 95 mol% or less.

  The proportion of mol% of component (A4) in the total amount of bismuth present in the coating composition (A) is preferably greater than the proportion of mol% of component (A3).

  The term “present in non-solution form” in connection with component (A4) of the coating composition (A) of the present invention preferably means that component (A4) is the component (A4) in the coating composition (A) ( At least 95 mol% or at least 97.5 mol%, more preferably at least 99 mol% or at least 99.5 mol%, very particularly preferably at least 99.8 mol% or at least 99.9 mol, based on the total amount of A4) Means in the form of a non-solution in the aqueous coating composition (A) in the order of%, more particularly 100 mol%. Therefore component (A4) is preferably water-insoluble. Component (A4) is preferably present in non-solution form in coating composition (A) at a coating composition (A) temperature in the range of at least 18-40 ° C.

Preferably the coating composition (A) is
(A3) at least 300 ppm bismuth in the form of a solution in the coating composition (A) relative to the total mass of the coating composition (A) or (A3) the coating composition in the form of a solution in the coating composition (A) (A) at least 100 ppm bismuth with respect to the total mass of (A), and (A4) at least 200 ppm bismuth with respect to the total mass of the coating composition (A) in non-solution form in the coating composition (A). The total amount of bismuth is at least 300 ppm relative to the total mass of the coating composition (A).

More preferably, the coating composition (A) is
(A3) at least 400 ppm bismuth in the form of a solution in the coating composition (A) with respect to the total mass of the coating composition (A), and or (A3) the coating in the form of a solution in the coating composition (A) At least 150 ppm bismuth with respect to the total mass of the composition (A), and (A4) at least 250 ppm bismuth with respect to the total mass of the coating composition (A) in non-solution form in the coating composition (A). Including at least 400 ppm of bismuth in total with respect to the total mass of the coating composition (A).

Very preferably the coating composition (A) is
Or (A3) at least 500 ppm bismuth with respect to the total mass of the coating composition (A) in the form of a solution in the coating composition (A), and or (A3) in the form of a solution in the coating composition (A) At least 200 ppm bismuth with respect to the total mass of the coating composition (A), and (A4) at least 300 ppm bismuth with respect to the total mass of the coating composition (A) in non-solution form in the coating composition (A). And a total amount of at least 500 ppm of bismuth with respect to the total mass of the coating composition (A).

The coating composition (A) of the present invention is preferably
Optionally in the presence of at least one component (A6) to (A8), and / or (P) blocked with at least one amine, and optionally in the presence of (A1) and / or (A2) Preferably, at least one selected from the group consisting of oxides of bismuth, basic oxides, hydroxides, carbonates, nitrates, basic nitrates, salicylates, and basic salicylates, and also mixtures thereof Of the water-insoluble bismuth compound at least partially in water by at least partial, preferably complete reaction with at least one at least bidentate complexing agent (A5) suitable for complexing the compound with bismuth. In particular, it is preferably completely converted into at least one water-insoluble bismuth compound (A3), at least a component (A) of the coating composition (A). ) And (A5) and also optionally blocked with components (A4) and / or (A6) to (A8) and / or optionally (A1) and / or (A2) and / or at least one amine Obtaining a mixture comprising at least one of the compounds (P), and
Optionally in the presence of at least one of components (A6) to (A8) and / or at least one compound blocked with at least one amine (P), the product mixture is optionally combined with at least component (A1) and optionally It can be obtained by mixing with (A2) to obtain a coating composition (A).

  The water-insoluble bismuth compound used is optionally part of a pigment paste comprising at least one pigment (A6), especially when (A) comprises component (A4).

  When the total amount of bismuth in (A) corresponds to the amount of component (A3), the aqueous coating composition (A) preferably comprises at least one component (A5) in the form of an aqueous solution, preferably oxidation of bismuth. Reaction with at least one water-insoluble bismuth compound selected from the group consisting of compounds, basic oxides, hydroxides, carbonates, nitrates, basic nitrates, salicylates, and basic salicylates, and mixtures thereof The resulting (A5) and an aqueous solution of the reaction product of this bismuth compound (A3) with at least component (A1) and optionally (A2) and also compound (P) blocked with at least one amine And optionally mixed with at least one of components (A6) to (A8) to obtain an aqueous coating composition (A).

Optional component (A5)
The aqueous coating composition (A) of the present invention preferably comprises at least one at least bidentate complexing agent suitable for complexing bismuth as component (A5), and comprising at least one complexing agent ( A5) is present in the aqueous coating composition (A), preferably in a proportion of at least 5 mol%, based on the total amount of bismuth present in the coating composition (A).

  Component (A5) herein is suitable for complexing both (A3) and (A4). Preferably, the at least one complexing agent (A5) is suitable for forming salts and / or complexes with the component (A3) present in the aqueous coating composition (A).

  Preferably, bismuth in water is in a form (A3) that is soluble in the coating composition (A) at a temperature in the range of 10-90 ° C or in the range of 20-80 ° C, more preferably in the range of 30-75 ° C. Complexing agents that are convertible are particularly suitable as component (A5).

  In the aqueous coating composition (A), the at least one complexing agent (A5) is preferably at least 7.5 mol% relative to the total amount of bismuth present in each case in the coating composition (A). Or a proportion of at least 10 mol%, more preferably a proportion of at least 15 mol% or at least 20 mol%, very preferably a proportion of at least 30 mol% or at least 40 mol%, more particularly at least 50 mol%. % Present. The respective amount of complexing agent (A5) used according to the invention depends, for example, on the hapto number of (A5) and / or the complexing strength of (A5). However, the at least one complexing agent (A5) is present in solution form in the coating composition (A) at least 30 ppm and preferably at least 130 ppm bismuth relative to the total mass of the coating composition (A). However, it exists at a rate that ensures this method.

  The complexing agent (A5) is preferably not the binder component (A1), and in particular is not used to produce the binder (A1).

  The complexing agent (A5) is at least bidentate. Those skilled in the art are familiar with the concept of “hapto number”. The term refers to the number of possible bonds that can be formed by one molecule of complexing agent (A5) with the atom to be complexed, such as the bismuth ion and / or bismuth atom to be complexed. Preferably, (A5) is bidentate, tridentate or tetradentate, more specifically bidentate.

  The complexing agent (A5) can take the form of an anion such as an anion of an organic monocarboxylic acid or polycarboxylic acid.

  The complexing agent (A5) preferably has at least two donor atoms, ie at least two atoms having at least one free electron pair in the valence shell. Preferred donor atoms are selected from the group consisting of N, S, and O atoms, and also mixtures thereof. Particularly preferred complexing agents (A5) are those having at least one oxygen donor atom and at least one nitrogen donor atom, or having at least two oxygen donor atoms. Particularly preferred complexing agents (A5) are those having at least two oxygen donor atoms.

  When O and / or S donor atoms are present in the complexing agent (A5), each of these at least two donor atoms is preferably bound to another carrier atom, such as a carbon atom that is not itself a donor atom. To do. When at least two N donor atoms are present in the complexing agent (A5), each of these at least two N donor atoms is the same carrier that is not itself a donor atom, as in, for example, guanidine or urea. Can be bonded to an atom.

  For example, when O and / or S donor atoms, such as at least two O donor atoms, are present in the complexing agent (A5) and each such at least two donor atoms are carbon atoms that are not themselves donor atoms, etc. These at least two carrier atoms can be directly bonded to each other, ie oxalic acid, lactic acid, bicine (N, N′-bis (2-hydroxyethyl) glycine, for example. ), EDTA, or α-amino acids. The two donor atoms, the two carrier atoms bonded to each other, and the ions and / or atoms to be complexed can then form a five-membered ring. Alternatively, the two carrier atoms can be bridged together via an additional single atom, as in the case of acetylacetone or for example with respect to the phosphorus atom as the carrier atom in 1-hydroxyethane-1,1-diphosphonic acid You can also. In that case, the two donor atoms, the two carrier atoms, the atoms bridging these carrier atoms, and the ions and / or atoms to be complexed can form a six-membered ring. Furthermore, the at least two carrier atoms can be bound to each other by two further atoms, as in the case of maleic acid, for example. If there is a double bond between the two atoms that bind the carrier atoms to each other, then the two carrier atoms will be in contact with each other to allow the formation of a seven-membered ring with the ions and / or atoms to be complexed. Must be in cis position. When two carrier atoms are part of an aromatic system, or when such carrier atoms are linked to each other by up to two further carrier atoms, such as in the case of gallic acid, Tiron, salicylic acid, or phthalic acid, etc. The 1,2- and 1,3-positions in the aromatic system are preferred. Furthermore, the donor atom may also itself be part of an aliphatic or aromatic ring system, such as in the case of 8-hydroxyquinoline.

  Particularly preferred complexing agents (A5) are those having at least two oxygen donor atoms. In this case, at least one oxygen donor atom may have a negative charge, as in, for example, acetylacetonate, or an acid group such as, for example, a carboxylic acid group, a phosphonic acid group, or a sulfonic acid group. It may be a part of Optionally, the oxygen atom of the acid group can similarly or alternatively be negatively charged, such as in the case of deprotonation and formation of a carboxylate group, a phosphonate group, or a sulfonate group.

  If at least one donor atom is an N atom, then the further donor atom is preferably a negatively charged O atom or an acid group (carboxylic acid group, phosphonic acid group, sulfonic acid group, etc.) Is part of.

  If (A5) has only N atoms as donor atoms, this component can also be present as an anion, as in the case of 1,2- or 1,3-dioxime anions, for example. A preferred carrier atom in this case is a C atom. The N atom as the donor atom is preferably in the form of a primary, secondary, or tertiary amino group or is present as an oxime group.

  When (A5) has only S and / or O atoms as donor atoms, then preferred carrier atoms in this case are C atoms, S atoms, and P atoms, more specifically C atoms. O atoms as donor atoms are preferably present at least proportionally in anionic form (eg acetylacetonate) or in the form of carboxylate, phosphonate or sulfonate groups. The S atom as the donor atom is preferably present in the form of a thiol, for example at cysteine.

  The complexing agent (A5) is preferably an organic monocarboxylic acid which is preferably nitrogen-free and preferably at least independently hydroxyl-substituted, an organic polycarboxylic acid which is optionally nitrogen-free and optionally at least independently hydroxyl-substituted, optionally at least alone Hydroxy-substituted aminopolycarboxylic acids, optionally at least solely hydroxyl-substituted amino monocarboxylic acids and sulfonic acids, and also their respective anions, and more preferably, optionally at least solely hydroxyl-substituted monoamines and optional Selected from the group consisting of a polyamine that is at least independently hydroxyl substituted and a compound that contains at least two O donor atoms and is not included in the compounds described in this list, such as 8-hydroxyquinoline and acetylacetone. It is.

  Examples of suitable complexing agents (A5) are at least one organic monocarboxylic acid or polycarboxylic acid which preferably does not contain nitrogen atom (s) and / or their anions.

  The term “polycarboxylic acid” in the sense of the present invention preferably refers to a carboxylic acid having two or more carboxyl groups, for example 2, 3, 4, 5 or 6 carboxyl groups. More preferably, the polycarboxylic acid has 2 or 3 carboxyl groups. The polycarboxylic acid having two carboxyl groups is a dicarboxylic acid, and the polycarboxylic acid having three carboxyl groups is a tricarboxylic acid. The polycarboxylic acids used according to the invention may be aromatic, partially aromatic, alicyclic, partially alicyclic or aliphatic, preferably aliphatic. The polycarboxylic acids used according to the invention are preferably 2 to 64 carbon atoms, more preferably 2 to 36 carbon atoms, more specifically 3 to 18 carbon atoms or 3 to 8 carbon atoms. Have Examples of polycarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, citric acid, mucoic acid, and malic acid.

  The term “monocarboxylic acid” in the sense of the present invention preferably refers to a preferably aliphatic monocarboxylic acid having exactly one C (═O) —OH group. The monocarboxylic acids used according to the invention preferably have 1 to 64 carbon atoms, more preferably 1 to 36, in particular 2 to 18 or 3 to 8 carbon atoms. Have. The monocarboxylic acid herein preferably has at least one hydroxyl group.

  If the complexing agent (A5) used comprises at least one organic monocarboxylic acid or polycarboxylic acid, preferably having no nitrogen (s) and / or anions thereof, at least one organic monocarboxylic acid Or the polycarboxylic acid and / or its anion preferably has at least one carboxyl and / or carboxylate group bonded to an organic group having 1 to 8 carbon atoms, It can be optionally substituted by at least one, preferably at least one or at least two substituents selected from the group consisting of hydroxyl groups, ester groups and ether groups.

  The organic monocarboxylic acid or polycarboxylic acid is preferably one or two alcoholic hydroxyl group (s) in the α-, β-, or γ-position relative to at least one carboxyl group and / or carboxylate group. Or selected from the group consisting of monocarboxylic and polycarboxylic acids having ester group (s) or ether group (s) and / or their anions. Examples of such acids are: glycolic acid (hydroxyacetic acid), lactic acid, γ-hydroxypropionic acid, α-methylolpropionic acid, α, α'-dimethylolpropionic acid, tartaric acid, hydroxyphenylacetic acid, malic acid, citric acid Acids and sugar acids such as, for example, gluconic acid and mucous acid. Cyclic or aromatic carboxylic acids are equally suitable where the placement of hydroxyl, ester or ether groups relative to the carboxyl group allows the formation of a complex. Examples of such are salicylic acid, gallic acid, hydroxybenzoic acid, and 2,4-dihydroxybenzoic acid. Examples of suitable carboxylic acids containing ether or ester groups are methoxyacetic acid, methylmethoxyacetate, isopropylmethoxyacetate, dimethoxyacetic acid, ethoxyacetic acid, propoxyacetic acid, butoxyacetic acid, 2-ethoxy-2-methylpropanoic acid, 3-Ethoxypropanoic acid, butoxypropanoic acid and its esters, butoxybutyric acid, and α- or β-methoxypropionic acid. Arbitrarily active carboxylic acids such as lactic acid can be used in L-type, D-type, or as racemates. Preference is given to using lactic acid (in optically active form, preferably as L-form or as racemate) and / or dimethylolpropionic acid.

  However, it is also possible to use organic monocarboxylic acids or polycarboxylic acids and / or their anions, in particular aminomonocarboxylic acids and / or aminopolycarboxylic acids and / or their anions, as complexing agents (A5) having nitrogen atoms. It is.

  The term “aminopolycarboxylic acid” in the sense of the present invention preferably has two or more carboxyl groups, such as, for example, 2, 3, 4, 5, or 6 carboxyl groups, and also, for example, at least 1 A carboxylic acid having at least one amino group, more specifically at least one or at least two tertiary amino groups, of primary and / or secondary and / or tertiary amino groups Point to. The aminopolycarboxylic acid used according to the invention is preferably 2 to 64 carbon atoms, more preferably 2 to 36 carbon atoms, in particular 3 to 18 carbon atoms or 3 to 8 carbon atoms. Have Examples of aminopolycarboxylic acids are ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), aspartic acid, methylglycidindiacetic acid (MGDA), β-alaninediacetic acid (β-ADA) ), Imidosuccinate (IDS), hydroxyethyleneiminodiacetate (HEIDA), and N- (2-hydroxyethyl) ethylenediamine-N, N, N′-triacetic acid (HEDTA).

  In the sense of the present invention, the term “aminomonocarboxylic acid” preferably has exactly one carboxyl group and, for example, at least one primary and / or secondary and / or primary. It refers to a carboxylic acid having at least one amino group, such as a tertiary amino group, more specifically at least one or at least two tertiary amino groups. The aminomonocarboxylic acid used according to the invention is preferably 2 to 64 carbon atoms, more preferably 2 to 36, more specifically 3 to 18 or 3 to 8 carbons. Has atoms. The amino monocarboxylic acid preferably has at least one hydroxyl group. An example of an amino monocarboxylic acid is bicine (N, N′-bis (2-hydroxyethyl) glycine). Other examples are glycine, alanine, lysine, cysteine, serine, threonine, asparagine, β-alanine, 6-aminocaproic acid, leucine and dihydroxyethylglycine (DHEG) and also pantothenic acid.

  Another example of a suitable complexing agent (A5) is at least one polyamine or monoamine.

  In the sense of the present invention, the term “polyamine” preferably refers to a compound having at least two amino groups, such as primary or secondary or tertiary amino groups. The amino group can also take the form of an oxime group. Overall, however, the polyamine preferably has up to 10 and 10 amino groups, ie at least 2 amino groups plus up to 8 and 8 additional amino groups, ie 1 2, 3, 4, 5, 6, 7, or 8, preferably up to 5 and including 5 additional amino groups, which are preferably primary or secondary A tertiary or tertiary amino group. The polyamine is preferably a diamine or a triamine, more preferably a diamine. The polyamines used according to the invention preferably have 2 to 64 carbon atoms, more preferably 2 to 36, more specifically 3 to 18 or 3 to 8 carbon atoms. . At least one of the carbon atoms is preferably substituted by a hydroxyl group. Accordingly, hydroxyalkyl polyamines are particularly preferred. Examples of polyamines are N, N, N ′, N′-tetrakis-2-hydroxyethylethylenediamine (THEED), N, N, N ′, N′-tetrakis-2-hydroxypropylethylenediamine (Quadrol), guanidine, diethylenetriamine And diphenylcarbazide, and also diacetyldioxime.

  The term “monoamine” in the sense of the present invention preferably has exactly one amino group, such as, for example, exactly one primary or secondary or in particular a tertiary amino group. Preferably it refers to an aliphatic monoamine. The monoamine used according to the invention preferably has 1 to 64 carbon atoms, more preferably 1 to 36, more specifically 2 to 18 or 3 to 8 carbon atoms. . The monoamine preferably has at least one hydroxyl group. An example of a monoamine is triisopropanolamine.

  For example, at least one sulfonic acid is more suitable as complexing agent (A5). Examples of suitable sulfonic acids are taurine, 1,1,1-trifluoromethanesulfonic acid, Tiron, and amidosulfonic acid.

  The molar proportion of any at least one aminopolycarboxylic acid present in the aqueous coating composition (A), more specifically the aminopolycarboxylic acid used as component (A5) is preferably in each case Preferably at least 1/15 or less than 1/20, more preferably at least 1/20 of the total molar amount of bismuth present in the coating composition (A) relative to the total amount of aqueous coating composition (A). Less than 30 or 1/40 or 1/50 or 1/60 or 1/70 or 1/80 or 1/90 or 1/100 or 1/1000. The presence of such acids can result in problems with dipping bath stability and wastewater treatment as a result of the accumulation of such compounds in the dipping bath.

Further optional components of the coating composition (A) Furthermore, depending on the desired application, the aqueous coating composition (A) used according to the invention can comprise at least one pigment (A6).

  This type of pigment (A6) present in the aqueous coating composition (A) is preferably selected from the group consisting of organic and inorganic, colored and extender pigments.

  This at least one pigment (A6) is used to produce the coating composition (A) and may be present as part of an aqueous solution or dispersion comprising component (A1) and optionally (A2). it can.

  The at least one pigment (A6) can alternatively be incorporated into the coating composition (A) in the form of a further aqueous dispersion or solution different from that used. In this embodiment, the corresponding pigment-containing aqueous dispersion or solution may further comprise at least one binder. This type of dispersion or solution preferably further comprises component (A4).

  Examples of suitable inorganic color pigments (A6) are: white pigments such as zinc oxide, zinc sulfide, titanium dioxide, antimony oxide, or lithopone; black pigments such as carbon black, iron manganese black, or spinel black; cobalt green or ultra Chrome pigments such as marine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt violet and manganese violet, red iron oxide, molybdate tread, or ultramarine red; brown iron oxide, mixed brown, spinel phase and Corundum phase; or yellow iron oxide, nickel titanium yellow, or bismuth vanadate. Examples of suitable organic coloring pigments are monoazo pigments, disazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, isoindolinone pigments, isoindolinone pigments, Azomethine pigment, thioindigo pigment, metal complex pigment, perinone pigment, perylene pigment, phthalocyanine pigment, or aniline black. Examples of suitable extender pigments or fillers are chalk, calcium sulfate, barium sulfate, silicates such as talc and kaolin, hydroxides such as silica, aluminum hydroxide and magnesium hydroxide, or textile fibers, cellulose fibers, polyethylene fibers or Organic fillers such as polymer powders; see Roempp Lexikon Racke und Druckfarben, George Thieme Verlag, 1998, 250 ff. See “Fillers”.

  The pigment content of the aqueous coating composition (A) can be varied according to the intended use and nature of the content (A6). The amount is preferably in the range from 0.1 to 30% by weight or in the range from 0.5 to 20% by weight, more preferably in each case based on the total weight of the aqueous coating composition (A). A range of 1.0-15% by weight, very preferably a range of 1.5-10% by weight, more specifically a range of 2.0-5.0% by weight, or 2.0-4. It is the range of 0 mass%, or the range of 2.0-3.5 mass%.

  Depending on the desired application, the coating composition (A) can comprise one or more commonly used additives (A7). Such an additive (A7) is preferably a wetting agent, preferably a surfactant such as an emulsifier, a dispersant, a surfactant, etc. that does not contain the component (A8), a flow control aid, a solubilizer, an antifoaming agent Rheology aids, antioxidants, stabilizers, crystallization inhibitors, preferably heat stabilizers, processing stabilizers, and UV and / or light stabilizers, catalysts, fillers, waxes, flexible agents, plasticizers, and Selected from the group consisting of mixtures of the above additives. The additive content can be varied very widely by intensive use. The amount is preferably 0.1 to 20.0% by weight, more preferably 0.1 to 15.0% by weight, very preferably 0, based on the total weight of the aqueous coating composition (A). 0.1 to 10.0% by mass, particularly preferably 0.1 to 5.0% by mass, and more specifically 0.1 to 2.5% by mass.

  At least one additive (A7) herein is used in producing the coating composition (A) and as part of an aqueous solution or dispersion comprising component (A1) and optionally (A2). Can exist.

  Alternatively, the at least one additive (A7) can also be in an aqueous dispersion or solution containing, for example, at least one pigment (A6) and optionally further at least one binder and further optionally (A4). As such, it can be incorporated into the coating composition (A) in the form of a further aqueous dispersion or solution different from that used.

  In a preferred embodiment, the coating composition (A) used according to the present invention is a cathodic depositing miniemulsion comprising at least one cationic emulsifier (A8). The term “miniemulsion” is, for example, M.M. Grabs et al., Macromol. Symp. From 2009, pages 275-276, 133-141 are familiar to those skilled in the art. Thus, a miniemulsion is an emulsion in which the particles have a range average diameter of 5 to 500 nm. Methods for determining the average diameter of such particles are familiar to those skilled in the art. Such determination of the mean diameter is preferably carried out by the dynamic light scattering method according to DIN ISO 13321 (date: 1 October 2004). Such a type of miniemulsion is known, for example, from WO 82/00148 A1. The at least one cationic emulsifier is preferably an emulsifier having an HLB ≧ 8, which is preferably determined by the Griffin method known to those skilled in the art. The emulsifier can have a reactive functional group. Such reactive functional groups contemplated are the same reactive functional groups that may also have a binder (A1). This emulsifier preferably has a hydrophilic head group, which preferably has four organic, preferably aliphatic groups, for example organic groups having 1 to 10 carbon atoms. It has a bonded quaternary nitrogen atom and a lipophilic tail group. At least one of these organic groups preferably has a hydroxyl group.

Any additional metal ions in (A) The molar proportion of zirconium ions optionally present in the aqueous coating composition (A) is preferably aqueous in each case relative to the total mass of the aqueous composition (A). The total molar amount of bismuth present in the coating composition (A) is preferably at least less than 1/100, preferably at least less than 1/200, more preferably at least 1/300 or 1/400 or 1 / Less than 500 or 1/600 or 1/700 or 1/800 or 1/900 or 1/1000. More particularly preferably, the coating composition (A) does not contain zirconium ions.

Zirconium compounds commonly used in coating compositions to improve corrosion protection are often used in the form of salts or acids containing zirconium ions, more specifically [ZrF ₆ ] ²⁻ ions. However, when bismuth ions are present at the same time, the use of such [ZrF ₆ ] ²⁻ ions results in precipitation of bismuth fluoride. Therefore, the use of zirconium compounds in the coating composition (A) should be avoided.

  Furthermore, preferably the molar proportion of ions optionally present in the aqueous coating composition (A) and selected from the group consisting of ions of rare earth metals is preferably in each case the total mass of the aqueous composition (A). Relative to the total molar amount of bismuth present in the aqueous coating composition (A), at least less than 1/100, very preferably at least 1/200 or 1/300 or 1/400 or 1/500 or Less than 1/600 or 1/700 or 1/800 or 1/900 or 1/1000. Specifically, the coating composition (A) does not contain rare earth metal ions. The presence of such ions makes the method of the present invention more expensive and makes wastewater treatment more difficult. Such ions of the rare earth metal are preferably selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gb, Td, Dy, Ho, Er, Tm, Yb, and Lu. The

の少なくとも１種のアミンでブロックされた少なくとも１種のリン含有化合物（Ｐ）を含み、式中、
Ｒ^１およびＲ^２はそれぞれ互いに独立に、Ｃ_１〜１８脂肪族基であるか、Ｃ_３〜１２脂環式基であるか、Ｃ_１〜１０脂肪族基によって架橋されたＣ_３〜１２脂環式基であるか、またはＣ_１〜１０脂肪族基によって架橋されたアリールもしくはヘテロアリール基であり、好ましくはそれぞれ互いに独立に、Ｃ_１〜１８脂肪族基であるか、またはＣ_１〜１０脂肪族基によって架橋されたアリールもしくはヘテロアリール基であり、
Ｒ^３はＨ、Ｃ_１〜１８脂肪族基、Ｃ_３〜１２脂環式基、Ｃ_１〜１０脂肪族基によって架橋されたＣ_３〜１２脂環式基、またはＣ_１〜１０脂肪族基によって架橋されたアリールもしくはヘテロアリール基であり、好ましくは、Ｈ、Ｃ_１〜１８脂肪族基、またはＣ_１〜１０脂肪族基によって架橋されたアリールもしくはヘテロアリール基である。 Amine-blocking compound The coating composition (A) of the present invention has the general formula (I)

At least one phosphorus-containing compound (P) blocked with at least one amine of the formula:
R ¹ and ^{R 2} are each, independently of one _another, or a _{C 1 to 18} aliphatic _group, or a _{C 3 to 12} cycloaliphatic _{radical, C 3 to 12} fat cross-linked by _{C 1 to 10} aliphatic group An aryl or heteroaryl group which is a cyclic group or bridged by a C _1-10 aliphatic group, preferably each independently of each other a C _1-18 aliphatic group, or a C _1-10 An aryl or heteroaryl group bridged by an aliphatic group,
R ³ is _{H, C 1 to 18} aliphatic _{radical, C 3 to 12} cycloaliphatic _{radical, C 3 to 12} cycloaliphatic radical cross-linked by _{C 1 to 10} aliphatic group or a _{C 1 to 10} aliphatic group, An aryl or heteroaryl group bridged by, preferably an aryl or heteroaryl group bridged by H, a C _1-18 aliphatic group, or a C _1-10 aliphatic group.

  Compound (P) itself contains phosphorus, ie it contains at least one phosphorus atom. Overall, therefore, the compound (P) blocked with at least one amine of the general formula (I) contains phosphorus and nitrogen. It is also possible to use mixtures of two or more different compounds (P), each independently of one another blocked with the same or different amines of the general formula (I).

  Phosphorus-containing compounds (P) which may be used to produce the coating compositions of the invention and which may be amine-blocked, and also methods for producing them are described, for example, in DE 102005045228 (A1). ) Is known to those skilled in the art. Corresponding amine-blocked phosphorus-containing compounds (P) and also processes for their preparation are known to the person skilled in the art, for example in WO 2011/029502 (A1) and WO 2010/063332 (A1).

  The phosphorus-containing compound (P) is preferably selected from the group consisting of phosphonic acid diesters, diphosphonic acid diesters, phosphoric monoesters, and phosphoric diesters, their anions, and also mixtures thereof. Each organic group of these compounds may be acyclic or cyclic, respectively, or may be characterized by a combination of acyclic and cyclic organic groups.

の化合物またはそのアニオンであり、式中、
Ｒ^４およびＲ^５はそれぞれ互いに独立に、
１〜２０個、好ましくは２〜１６個、より詳細には２〜１０個の炭素原子、および任意に、Ｎ、ＮＨ、Ｎ（Ｃ_１〜６アルキル）、Ｏ、およびＳからなる群から選択される１〜４個のヘテロ原子を有する、少なくとも一置換および非置換、好ましくは非置換の（ヘテロ）アルキル基、３〜２０個、好ましくは３〜１６個、より詳細には３〜１０個の炭素原子、および任意に、Ｎ、ＮＨ、Ｎ（Ｃ_１〜６アルキル）、Ｏ、およびＳからなる群から選択される１〜４個のヘテロ原子を有する、少なくとも一置換および非置換、好ましくは非置換の（ヘテロ）シクロアルキル基、ならびに、５〜２０個、好ましくは６〜１４個、より詳細には６〜１０個の炭素原子、および任意に、Ｎ、ＮＨ、Ｎ（Ｃ_１〜６アルキル）、Ｏ、およびＳからなる群から選択される１〜４個のヘテロ原子を有する、少なくとも一置換および非置換、好ましくは非置換の（ヘテロ）アリール基、
少なくとも一置換および非置換の
（ヘテロ）アルキル（ヘテロ）アリール、
（ヘテロ）アリール（ヘテロ）アルキル、
（ヘテロ）アルキル（ヘテロ）シクロアルキル、
（ヘテロ）シクロアルキル（ヘテロ）アルキル、
（ヘテロ）アリール（ヘテロ）シクロアルキル、
（ヘテロ）シクロアルキル（ヘテロ）アリール、
（ヘテロ）アルキル（ヘテロ）シクロアルキル（ヘテロ）アリール、
（ヘテロ）アルキル（ヘテロ）アリール（ヘテロ）シクロアルキル、
（ヘテロ）アリール（ヘテロ）シクロアルキル（ヘテロ）アルキル、
（ヘテロ）アリール（ヘテロ）アルキル（ヘテロ）シクロアルキル、
（ヘテロ）シクロアルキル（ヘテロ）アルキル（ヘテロ）アリール、および
（ヘテロ）シクロアルキル（ヘテロ）アリール（ヘテロ）アルキル
基からなる群から選択され、それらの中に存在する（ヘテロ）アルキル、（ヘテロ）シクロアルキル、および（ヘテロ）アリール基はそれぞれ、上の段落に示す数の炭素原子および任意にヘテロ原子を含有し、
基Ｒ^４およびＲ^５の１個または基Ｒ^４およびＲ^５の両方は、さらに水素であってもよい（部分エステル化）。 Particularly preferred for use as the phosphorus-containing compound (P) is the following general formula (II)

Or an anion thereof, wherein
R ⁴ and R ⁵ are each independently of each other,
1 to 20, preferably 2 to 16, more particularly 2 to 10 carbon atoms, and optionally selected from the group consisting of N, NH, N (C _1-6 alkyl), O, and S At least mono- and unsubstituted, preferably unsubstituted (hetero) alkyl groups, having 1 to 4 heteroatoms, 3 to 20, preferably 3 to 16, more particularly 3 to 10 At least monosubstituted and unsubstituted, preferably having from 1 to 4 heteroatoms selected from the group consisting of N, NH, N (C _1-6 alkyl), O, and S Is an unsubstituted (hetero) cycloalkyl group and 5-20, preferably 6-14, more particularly 6-10 carbon atoms, and optionally N, NH, N (C _{1- 6} alkyl), selected O, and from the group consisting of S Is having 1 to 4 heteroatoms, at least mono-substituted and unsubstituted, preferably unsubstituted (hetero) aryl group,
At least mono- and unsubstituted (hetero) alkyl (hetero) aryl,
(Hetero) aryl (hetero) alkyl,
(Hetero) alkyl (hetero) cycloalkyl,
(Hetero) cycloalkyl (hetero) alkyl,
(Hetero) aryl (hetero) cycloalkyl,
(Hetero) cycloalkyl (hetero) aryl,
(Hetero) alkyl (hetero) cycloalkyl (hetero) aryl,
(Hetero) alkyl (hetero) aryl (hetero) cycloalkyl,
(Hetero) aryl (hetero) cycloalkyl (hetero) alkyl,
(Hetero) aryl (hetero) alkyl (hetero) cycloalkyl,
(Hetero) cycloalkyl (hetero) alkyl (hetero) aryl, and (hetero) cycloalkyl (hetero) aryl (hetero) alkyl selected from the group consisting of and present in (hetero) alkyl, (hetero) Cycloalkyl and (hetero) aryl groups each contain the number of carbon atoms and optionally heteroatoms shown in the above paragraph;
One of the radicals R ⁴ and R ⁵ or both radicals R ⁴ and R ⁵ may also be hydrogen (partial esterification).

Particularly preferred for use as the phosphorus-containing compound (P) is a compound of the general formula (II),
R ⁴ and R ⁵ are each independently 1-20, preferably 2-16, more particularly 2-10 carbon atoms, and optionally N, NH, N (C _1-6 alkyl) At least mono- and unsubstituted, preferably unsubstituted (hetero) alkyl groups, having 1 to 4 heteroatoms selected from the group consisting of, O, and S, 3 to 20, preferably 3 to 16 And more particularly 3 to 10 carbon atoms and optionally ₁ to 4 heteroatoms selected from the group consisting of N, NH, N (C _1-6 alkyl), O, and S. Having at least mono- and unsubstituted, preferably unsubstituted (hetero) cycloalkyl groups, and 5 to 20, preferably 6 to 14, more particularly 6 to 10 carbon atoms, and optionally _{, N, NH, N (C} 1~6 A Kill), O, and having 1-4 heteroatoms selected from the group consisting of S, at least a substituted and unsubstituted, preferably unsubstituted (hetero) aryl group,
Is selected from the group consisting of, one or both radicals R ⁴ and R ⁵ radicals R ⁴ and R ⁵ may also be a hydrogen (partial esterification).

  (Hetero) alkyl groups include alkyl groups and heteroalkyl groups, preferably alkyl groups; (hetero) cycloalkyl groups include cycloalkyl groups and heterocycloalkyl groups, preferably cycloalkyl groups; (hetero) aryl groups are It includes aryl groups and heteroaryl groups, preferably aryl groups.

  In particular, the phosphorus-containing compound (P) is at least one monoalkyl phosphate and / or at least one dialkyl phosphate, in which the alkyl group (s) are independent of one another. Preferably have 1 to 18 carbon atoms. The use of phenyl phosphate is also preferred.

The phosphorus-containing compound (P) is blocked with at least one amine of the general formula (I),
R ¹ and ^{R 2} are each, independently of one _another, or a _{C 1 to 18} aliphatic _group, or a _{C 3 to 12} cycloaliphatic _{radical, C 3 to 12} fat cross-linked by _{C 1 to 10} aliphatic group An aryl or heteroaryl group which is a cyclic group or bridged by a C _1-10 aliphatic group, preferably in each case, independently of each other, a C _1-18 aliphatic group or a C 1 An aryl or heteroaryl group bridged by _{1 to 10} aliphatic groups;
R ³ is _{H, C 1 to 18} aliphatic _{radical, C 3 to 12} cycloaliphatic _{radical, C 3 to 12} cycloaliphatic radical cross-linked by _{C 1 to 10} aliphatic group or a _{C 1 to 10} aliphatic group, An aryl or heteroaryl group bridged by, preferably an aryl or heteroaryl group bridged by H, a C _1-18 aliphatic group, or a C _1-10 aliphatic group.

The expression “C _1-18 aliphatic group” in the sense of the present invention is preferably an acyclic saturated or unsaturated, preferably saturated, aliphatic hydrocarbon group, ie each branched or unbranched, preferably Is branched and optionally unsubstituted or at least monosubstituted, such as disubstituted or trisubstituted, but preferably unsubstituted, 1 to 18, ie 1, 2, 3, 4 C _1-6 aliphatic group having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, ie C _1-18 alkanyl , C _2-18 alkenyl, and C _2-18 alkynyl. Here, alkenyl has at least one C—C double bond and alkynyl has at least one C—C triple bond. Particularly preferably, the C _1-18 aliphatic group is C _1-18 alkanyl, ie C _1-18 alkyl. Very preferably the C _1-18 aliphatic group is a C _2-18 aliphatic group, more particularly a C _3-18 group or a C _4-18 aliphatic group or a C _5-18 aliphatic group, or C _{It is a 6-18} aliphatic group. _C1-18 aliphatic groups are preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl, 2 -Selected from the group comprising ethylhexyl, n-heptyl, n-octyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, n-dodecyl and also isododecyl.

The expression “C _3-12 alicyclic group” for the purposes of the present invention is preferably a cyclic saturated or unsaturated, preferably saturated, alicyclic hydrocarbon group, ie unsubstituted or optionally, for example At least monosubstituted but preferably unsubstituted, such as substituted or trisubstituted, 3 to 12, ie 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 C _3-12 alicyclic groups having the following carbon atoms: C _3-12 cycloalkanyl and C _3-12 cycloalkenyl. Here, cycloalkenyl has at least one C—C double bond. The C _3-12 alicyclic group is more preferably C _3-12 cycloalkanyl, ie, C _3-12 cycloalkyl. Very preferably the C _3-12 alicyclic group is a C _3-12 alicyclic group, more particularly a C _5-6 alicyclic group. The C _3-12 alicyclic group is preferably selected from the group including cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

Preferred aryl groups are C _6-15 aromatic groups, more particularly phenyl groups optionally substituted with at least one C _1-6 aliphatic group. Preferred heteroaryl groups contain at least one heteroatom such as N, S and / or O and / or at least one heteroatom group such as N (C _1-6 alkyl) and / or NH. It has a C _4-15 heteroaromatic group, more specifically a pyridyl group optionally substituted with at least one C _1-6 aliphatic group.

For the purposes of the present invention, the expression “aryl or heteroaryl bridged by a C _1-10 aliphatic group” preferably means that an aryl or heteroaryl group or a C _3-12 alicyclic group is a C _1-10 aliphatic group It means that it is connected to each upper general structure. The C _1-10 aliphatic group is preferably a C _1-10 alkylene group. The C _1-10 aliphatic group may be branched or unbranched and saturated or unsaturated. C _{1 to 10} aliphatic group _{preferably, -CH 2 -, - CH 2} -CH 2 -, - CH (CH 3) -, - CH 2 -CH 2 -CH 2 -, - CH (CH 3) - _{CH 2 -, - CH (CH} 2 CH 3) -, - CH 2 - (CH 2) 2 -CH 2 -, - CH (CH 3) -CH 2 -CH 2 -, - CH 2 -CH (CH 3 _{) -CH 2 -, - CH (} CH 3) -CH (CH 3) -, - CH (CH 2 CH 3) -CH 2 -, - C (CH 3) 2 -CH 2 -, - CH (CH 2 _{CH 2 CH 3) -, -} C (CH 3) (CH 2 CH 3) -, - CH 2 - (CH 2) 3 -CH 2 -, - CH (CH 3) -CH 2 -CH 2 -CH 2 _{-, - CH 2 -CH (CH} 3) -CH 2 -CH 2 -, - CH (CH 3) -CH 2 -CH (CH 3) _{, -CH (CH 3) -CH (} CH 3) -CH 2 -, - C (CH 3) 2 -CH 2 -CH 2 -, - CH 2 -C (CH 3) 2 -CH 2 -, - CH _{(CH 2 CH 3) -CH 2} -CH 2 -, - CH 2 -CH (CH 2 CH 3) -CH 2 -, - C (CH 3) 2 -CH (CH 3) -, - CH (CH 2 _{CH 3) -CH (CH 3)} -, - C (CH 3) (CH 2 CH 3) -CH 2 -, - CH (CH 2 CH 2 CH 3) -CH 2 -, - C (CH 2 CH 2 _{CH 3) -CH 2 -, -} CH (CH 2 CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 -, and CH ₂ - is selected from the group comprising _{- (CH 2) 4 -CH 2} .

Preferably at least one, more preferably at least two, more particularly all three of the radicals R ¹ , R ² and R ³ are each independently of one another C _1-18 aliphatic or C _3-18 aliphatic A group or a C _4-18 aliphatic group, a C _5-18 aliphatic group or a C _6-18 aliphatic group. More preferably, at least one of the groups R ¹ , R ² and R ³ , more preferably at least 2, more particularly all three, in each case independently of one another, a C _1-18 alkyl group or C _3-18 alkyl group or a _{C 4 to 18} alkyl or _{C 5 to 18} alkyl group or _{C having 6 to 18} alkyl group. Very preferably, at least one of the groups R ¹ , R ² and R ³ , more preferably at least 2, more particularly all three, in each case independently of one another, are C _6-18 alkyl groups is there. Particularly preferably, each of the above aliphatic and alkyl groups is a branched or unbranched group of these types, more particularly a branched group.

R ³ is preferably a C _1-18 aliphatic group or an aryl or heteroaryl group bridged by a C _1-10 aliphatic group; in other words, an amine of the general formula (I) is a tertiary It is an amine.

Examples of suitable amines of the general formula (I) in which the phosphorus-containing compound (P) may be blocked are R ¹ and R ² each being an unbranched C _1-18 aliphatic group Unbranched aliphatic amines such as trioctylamine, dioctylamine, octyldimethylamine, dinonylamine, trinonylamine, nonyldimethylamine, tridodecylamine, and dodecyldimethylamine. Examples of suitable amines of the general formula (I) in which the phosphorus-containing compound (P) may be blocked are R ¹ and R ² or one of the radicals R ¹ and R ² each Branched aliphatic amines which are branched C _1-18 aliphatic groups, for example di (isopropanol) amine, diisoamylamine, diisobutylamine, diisononylamine, dodecyldimethylamine, isododecyldimethylamine, tris (2-ethylhexyl) amine , Triisoamylamine, triisononylamine, triisooctylamine, and triisopropylamine. Particularly preferred is tris (2-ethylhexyl) amine.

  Phosphorus-containing compounds (P) used according to the invention and blocked with at least one amine of the general formula (I) are commercially available, for example, as Nacure® products from King Industries.

  The coating composition (A) according to the invention preferably comprises at least one phosphorus-containing compound (P) blocked with at least one amine of the general formula (I) in each case the coating composition (A). 0.05 to 5% by mass or 0.1 to 5% by mass, more preferably 0.1 to 4% by mass or 0.1 to 3% by mass, Preferably in the range of 0.2 to 2.5% by weight, more particularly in the range of 0.2 to 2% by weight, or in the range of 0.3 to 2% by weight, or 0.5 to 1.5% by weight. Including the amount of the range.

  The relative mass ratio of at least one phosphorus-containing compound (P) blocked with at least one amine of the general formula (I) to the total amount of bismuth in the coating composition (A) is preferably 1: 6. Is in the range of ˜1: 1, more preferably in the range of 1: 5 to 1: 1.5, very preferably in the range of 1: 4 to 1: 2.

  The coating composition (A) of the present invention may optionally contain at least one crystallization inhibitor that prevents precipitation of the compound (P) blocked with at least one amine of the general formula (I) as an additive (A7). May be included.

According to the invention, not only blocking the phosphorus-containing compound (P) with only one amine of the general formula (I), but also using a mixture of at least two different amines of the general formula (I) It is also possible to carry out blocking by a mixture of at least one amine of formula (I) and at least one further different amine that does not necessarily have to be included in general formula (I). Thus, for example, in each case a mixture of secondary or tertiary amines of the general formula (I) having unbranched C _1-18 aliphatic groups R ¹ , R ² and / or R ³ , and at least 1 Mixtures of secondary or tertiary amines of general formula (I) having a kind of branched C _1-18 aliphatic groups R ¹ , R ² and / or R ³ may be used. The use of a suitable mixture can likewise prevent possible crystallization. In that case, in particular, the amine of the general formula (I) having at least one branched C _1-18 aliphatic group preferably acts as a crystallization inhibitor. Examples of suitable further amines that are not included in the general formula (I) but may be further present in the coating composition (A) of the present invention are bicyclic amines such as more particularly unsaturated bicyclics. Amines such as 1,5-diazabicyclo [4.3.0] non-5-ene and / or 1,8-diazabicyclo [5.4.0] undec-7-ene.

Method for producing a coating composition (A) A further subject of the present invention is a method for producing an aqueous coating composition (A) according to the invention, which method comprises at least step (0):
(0) optionally at least one water-insoluble bismuth compound, in the presence of at least one of components (A6) to (A8) and optionally (A1) and / or (A2) and / or (B), More preferably, at least one selected from the group consisting of oxides of bismuth, basic oxides, hydroxides, carbonates, nitrates, basic nitrates, salicylates, and basic salicylates, and also mixtures thereof Of the compound at least partially in water by at least partial, preferably complete reaction, of this compound with at least one at least bidentate complexing agent (A5) suitable for the complexation of bismuth. Preferably at least completely converted to at least one water-soluble bismuth compound (A3) to form at least components (A3) and ( 5), optionally component (A4) and also optionally (A1) and / or (A2) and / or (P) blocked with at least one amine of general formula (I), and / or component A step of obtaining a mixture comprising at least one of (A6) to (A8).

  The water-insoluble bismuth compound is preferably part of a pigment paste comprising at least one pigment (A6).

After step (0) has been performed, the method of the present invention optionally comprises the following:
The mixture obtained after carrying out step (0) is optionally blocked with at least component (A1) and optionally with component (A2) and also with at least one amine of general formula (I) (P), At least one further step, such as mixing with at least one of components (A6) to (A8) to obtain a coating composition (A).

  The period of step (0) is preferably at least 2 or at least 4 or at least 6 or at least 8 or at least 10 or at least 12 or at least 14 or at least 16 or at least 18 or at least 20 or at least 22 or at least 24 hours. Step (0) is preferably carried out with stirring at a temperature in the range of 18-23 ° C.

  All of the preferred embodiments described above in connection with the aqueous coating composition (A) of the present invention are also preferred embodiments of the aqueous coating composition (A) used in accordance with the present invention in connection with its production. It is.

Use of Coating Composition (A) A further subject matter of the invention is the coating composition (A) according to the invention, or an electroconductive substrate for electro-coating at least partly with an electrodeposition material. Use of the aqueous coating composition (A) used in the method of the present invention to at least partially coat the dressing.

  All of the preferred embodiments described above in connection with the aqueous coating composition (A) of the present invention are also related to their use for at least partially coating a conductive substrate with an electrodeposition material. It is a preferred embodiment of the aqueous coating composition (A) used according to the invention.

Method for at least partially coating a conductive substrate with a coating composition (A) A further subject matter of the invention is a method for at least partially coating a conductive substrate with an electrodeposition material, in particular If the substrate used is aluminum or a substrate having at least one aluminum surface, at least one step (1):
(1) The process which makes the electroconductive base material connected as a cathode contact with the aqueous coating composition (A) of this invention is included.

In a preferred embodiment, the method of the invention comprises at least one step (1):
(1) A conductive substrate connected as a cathode is applied to the aqueous coating composition (A) of the present invention.
In aqueous coating composition,
Contacting step, wherein step (1) is at least two successive steps (1a) and (1b):
(1a) a stage with an applied voltage in the range of 1-50V, preferably applied for at least 5 seconds, and (1b) a stage with an applied voltage in the range of 50-400V, provided that it is applied in stage (1b) For coating at least partially a conductive substrate with an electrodeposition material, comprising a step carried out at a stage provided that the applied voltage is at least 10V greater than the voltage applied at step (1a) Is the method.

  All of the preferred embodiments described above in connection with the aqueous coating composition (A) of the present invention are also the steps of the method of the present invention for at least partially coating a conductive substrate with an electrodeposition material ( 1 is a preferred embodiment of the aqueous coating composition (A) used according to the invention in connection with its use in 1).

Process (1)
The method of the present invention for at least partially coating a conductive substrate with an electrodeposition material comprises at least one step (1), which comprises an aqueous coating composition comprising a conductive substrate connected as a cathode. This is a step of contacting with (A).

  In the sense of the present invention, the “contacting” step preferably immerses the substrate in the aqueous coating composition (A) used for the purpose of at least partially coating with the coating composition (A). Applying to the substrate, intended to at least partially coat with the coating composition (A), spraying onto the substrate with the intention of coating at least partially with the coating composition (A) The process of rolling. More specifically, the term “contacting” in the sense of the present invention refers to an aqueous coating composition (A) in which the substrate is intended to be at least partially coated with the coating composition (A). ) Refers to the step of immersing in.

  The method of the present invention is preferably a method for at least partially coating a conductive substrate in and / or for automobile manufacturing. The method can be carried out continuously or discontinuously in the form of a strip coating operation, for example in a coil coating process.

  In step (1) of the method of the present invention, the substrate is at least partially coated with the aqueous coating composition (A) of the present invention by electrophoretic deposition of the coating composition onto the substrate surface.

  Step (1) is performed by applying a voltage between the substrate and at least one counter electrode. Step (1) of the method of the present invention is preferably carried out in a dip coating bath. In this case, the counter electrode can be located in the dip coating bath. Alternatively or additionally, the counter electrode can also be present separately from the dip coating bath, eg, via an anion exchange membrane that is permeable to anions. In this case, anions formed during dip coating are transported from the coating material through the membrane and into the anolyte, thereby allowing the pH in the dip coating bath to be adjusted or kept constant. The counter electrode is preferably separate from the dip coating bath.

  In step (1) of the method of the present invention, the substrate is preferably completely coated with the aqueous coating composition (A) by complete electrophoretic deposition onto the entire surface of the substrate.

  Preferably, in step (1) of the method of the invention, the substrate intended for at least partial coating is introduced at least partially, preferably completely, into the dip coating bath, wherein step (1) In the dip coating bath.

  The purpose of step (1) of the method of the present invention is at least partial coating of the substrate by at least partial electrophoretic deposition of the aqueous coating composition (A). The aqueous coating composition (A) in this case is deposited as an electrodeposition material on the substrate surface.

  The aqueous coating composition (A) of the present invention is preferably in contact with a conductive substrate connected as a conductive anode and cathode. Alternatively, the aqueous coating composition (A) is in direct contact with the conductive anode, for example when the anode is present separately from the dip coating bath, for example via an anion exchange membrane that is permeable to anions. There is no need.

  The passage of current between the anode and cathode is accompanied by the deposition of a tightly adhered coating on the cathode, i.e. on the substrate.

  Step (1) of the process according to the invention is preferably in the range from 20 to 45 ° C., more preferably in the range from 22 to 42 ° C., very preferably in the range from 24 to 41 ° C., particularly preferably from 26 to It is carried out at a dip bath temperature in the range of 40 ° C., more particularly preferably in the range of 27-39 ° C., for example in the range of 28-38 ° C. In another preferred embodiment of the method according to the invention, step (1) is carried out at 40 ° C. or lower, more preferably 38 ° C. or lower, very preferably 35 ° C. or lower, particularly preferably 34 ° C. or lower or 33 ° C. or lower. Alternatively, it is carried out at a dip bath temperature of 32 ° C. or lower, 31 ° C. or lower, 30 ° C. or lower, 29 ° C. or lower, or 28 ° C. or lower. In various further preferred embodiments of the method of the present invention, step (1) comprises, for example, ≦ 31 ° C. or ≦ 30 ° C. or ≦ 29 ° C. or ≦ 28 ° C. or ≦ 27 ° C. or ≦ 26 ° C. Or at a dip bath temperature of ≦ 32 ° C. such as ≦ 25 ° C. or ≦ 24 ° C. or ≦ 23 ° C.

  In the step (1) of the method of the present invention, the aqueous coating composition (A) of the present invention preferably has a generated electrodeposition film of 5 to 40 μm, more preferably 10 to 30 μm, particularly preferably 20 to 20 μm. It has a dry film thickness in the range of 25 μm.

Stages (1a) and (1b) in step (1)
Step (1) of the method of the invention comprises at least two successive steps (1a) and (1b) as follows:
(1a) a stage with an applied voltage in the range of 1-50V applied for at least 5 seconds; and (1b) a stage with an applied voltage in the range of 50-400V, but applied in stage (1b) It is carried out in a stage provided that the voltage is at least 10 V greater than the voltage applied in stage (1a).

  Steps (1a) and (1b) within step (1) of the method of the invention are preferably carried out in the dip coating bath used which comprises the coating composition (A).

Stage (1a)
During the execution of step (1a), the corresponding bismuth-enriched layer is formed as a predeposited layer on the conductive substrate, which can be detected and quantified, for example, by X-ray fluorescence analysis. The bismuth herein is preferably in the form of metal bismuth (0), but can alternatively be present in trivalent form and / or other oxidation states. This pre-deposited layer in particular contains little component (A1) and optionally (A2) and / or (A5) and / or (A6) present in the coating composition. Bismuth rich layer which is suitably formed, preferably, exhibits a corrosion preventing effect, excellent property of this effect (in mg of bismuth surface area 1 m ² per) which is proportional to the additional bismuth phase. Preferred additional layer, the surface area 1 m ² per at least 10, or at least 20, or at least 30, more preferably at least 40 or at least 50, and more specifically, it is at least 100, or at least 180mg of bismuth (calculated as metal) .

  Step (1a) is preferably in the range of 1 to 45 V or 1 to 40 V or 1 to 35 V or 1 to 30 V or 1 to 25 V or 1 to 20 V or 1 to 15 V Or it is implemented by the applied voltage of the range of 1-10V or the range of 1-5V. In another preferred embodiment, step (1a) comprises a range of 2 to 45 V or 2 to 40 V or 2 to 35 V or 2 to 30 V or 3 to 25 V or 3 to 20 V or 3 It is carried out with an applied voltage in the range of ~ 15V or in the range of 3-10V or in the range of 3-6V.

  The voltage applied in step (1a) is at least 5 seconds, preferably at least 10 or at least 15 or at least 20 or at least 25 or at least 30 or at least 40 or at least 50 seconds, more preferably at least 60 or at least 70 or Applied over a period of at least 80 or at least 90 or at least 100 seconds, very preferably at least 110 or at least 120 seconds. The period in the present specification is preferably 300 seconds or less, more preferably 250 seconds or less, and more specifically 150 seconds or less. This period refers in each case to the time interval during which the voltage is maintained during the execution of stage (1a).

  In a preferred embodiment, the voltage applied in step (1a) is at least 5 to 500 seconds or 5 to 500 seconds or 10 to 500 seconds or 10 to 300 seconds or at least 20 to 400 seconds or at least 30 to 300 seconds or at least It is applied over a period ranging from 40 to 250 seconds or at least 50 to 200 seconds, more preferably at least 60 to 150 seconds or at least 70 to 140 seconds or at least 80 to 130 seconds.

The voltage in the range of 1-50V applied during the execution of step (1a) for at least 10 seconds can be set constant current (constantly regulated current). Alternatively, this setting can also be carried out at a constant potential (constantly regulated voltage), but step (1a) is a deposition current or a deposition corresponding to a corresponding voltage in the range of 1-50V. It can also be implemented in the current range. This type of deposition current is preferably in the range of 20-400 mA, more preferably in the range of 30-300 mA or in the range of 40-250 mA or in the range of 50-220 mA, more specifically in the range of 55-200 mA. is there. Such a deposition current in step (1a) is preferably used when using a substrate having a surface area in the range of 300-500 cm ² , more specifically 350-450 cm ² or 395-405 cm ² .

The deposition current density of step (1a) is preferably at least 1 A / m ² , more preferably at least 2 A / m ² , more specifically at least 3 A / m ² , but preferably in each case 20 A / M ² or less, more preferably 10 A / m ² or less in each case.

  The deposition current density or the deposition current of step (1a) herein is preferably at least 5 or at least 10 seconds, preferably at least 15 or at least 20 or at least 25 or at least 30 or at least 40 or at least 50 seconds, More preferably, it is applied for at least 60 or at least 70 or at least 80 or at least 90 or at least 100 seconds, very preferably for at least 110 or at least 120 seconds. The period in the present specification is preferably 300 seconds or less, more preferably 250 seconds or less, and more specifically 150 seconds or less. In another preferred embodiment, the deposition current density or deposition current applied in step (1a) is at least 10-500 seconds or at least 20-400 seconds or at least 30-300 seconds or at least 40-250 seconds or at least 50- Applied over a period in the range of 200 seconds, more preferably in the range of at least 60-150 seconds or at least 70-140 seconds or at least 80-130 seconds.

  The voltage or deposition current or deposition current density can be kept constant during the periods described herein. However, alternatively, the voltage or deposition current or deposition current density can take various values during the deposition period in step (1a) within the stated minimum and maximum values in the range of 1-50 V, for example, the minimum To swing up to the maximum deposition voltage, or can be ramped or stepped.

  The setting of the voltage or deposition current or deposition current density during the execution of step (1a) can be carried out “suddenly”, in other words by switching appropriately to a rectifier, for example, Some technically relevant minimum period is required to reach the voltage. Alternatively, the setting is selected in an inclined form, in other words at least approximately continuously and preferably linearly, for example a period of up to 10, 20, 30, 40, 50, 60, 120 or 300 seconds. It can also be carried out for as long as possible. A slope of up to 120 seconds, more preferably up to 60 seconds is preferred. A step-wise voltage increase is also possible here, in which case preferably a certain holding time of, for example, a voltage of 1, 5, 10, or 20 seconds is observed for each of these voltage steps. Is done. A combination of tilt and step is also possible.

  The setting of the voltage or deposition current or deposition current density in step (1a) can also be adjusted in pulse form with no current time or with a voltage below the minimum level between two pulses. The pulse period can be in the range of 0.1 to 10 seconds, for example. Thus, the “period” for deposition is preferably considered to be the sum of the periods when the deposition voltage is within the aforementioned maximum and minimum values when performing step (1a). The slope and pulse can also be matched to each other.

  During the performance of step (1a), the complexing agent (A5) is preferably released again at least partly, more specifically completely. This is because the component (A3) complexed by (A5) is precipitated. In view of the presence of component (A4) in the coating composition (A), the released complexing agent (A5) is used to convert component (A4) at least partially into solution form in (A). Can be utilized, i.e., (A5) can be used to continuously generate (A3) for the purpose of ensuring the presence of adequate storage of (A3).

Stage (1b)
During the execution of step (1b), the actual dip varnish coating is applied after step (1a) by precipitation of the dip varnish component, more specifically (A1) and optionally (A2) and / or (A5). It is formed on the obtained predeposition layer. The coating also includes bismuth, which may be present in trivalent form or alternatively or in other oxidation states. This bismuth can act as a catalyst in any curing step or crosslinking step (6) downstream of the method of the invention. Therefore, in the production of the coating composition (A), it is possible to omit the incorporation of such a catalyst.

  Step (1b) is preferably in the range of 55-400V or 75-400V or 95-400V or 115-390V or 135-370V or 155-350V or 175-330V. Or it is implemented by the applied voltage of the range of 195-310V or the range of 215-290V.

  In step (1b), preferably applied at an interval between the range of 0 to 300 seconds after completion of the execution of step (1a), preferably to the inert counter electrode, but in step (1b) A voltage in the range of 50-400V is applied, provided that this voltage is at least 10V greater than the voltage previously applied in step (1a). While performing step (1b), this voltage is preferably in the range of 50 to 400 V, preferably in the range of 10 to 300 seconds, preferably in the range of 30 to 240 seconds, with the conditions described above. It is maintained above the value.

  The voltage applied in step (1b) is preferably at least 10 seconds or at least 15 or at least 20 or at least 25 or at least 30 or at least 40 or at least 50 seconds, more preferably at least 60 or at least 70 or at least 80 or Applied over a period of at least 90 or at least 100 seconds, very preferably at least 110 or at least 120 seconds. The period in the present specification is preferably 300 seconds or less, more preferably 250 seconds or less, and more specifically 150 seconds or less. This period refers in each case to the time interval during which the voltage is maintained during the execution of stage (1b).

  In one preferred embodiment, the voltage applied in step (1b) is in the range of at least 10 to 500 seconds or at least 20 to 400 seconds or at least 30 to 300 seconds or at least 40 to 250 seconds or at least 50 to 200 seconds; More preferably, it is applied over a period in the range of at least 60-150 seconds or at least 70-140 seconds or at least 80-130 seconds.

  The voltage increase from stage (1a) to stage (1b) can be carried out “suddenly”, in other words by switching corresponding to a rectifier, for example, in order to reach the target voltage. Some kind of technically relevant minimum time is required. Alternatively, the voltage increase is performed in a ramped form, in other words at least approximately continuously, for example over a selectable period such as up to 10, 20, 30, 40, 50, 60, 120, or 300 seconds. You can also. A preferred slope is a maximum of 120 seconds, more preferably a maximum of 60 seconds. A step-wise voltage increase is also possible, in which case preferably a certain holding time of, for example, a voltage of 1, 5, 10, or 20 seconds is observed for each of these voltage steps. A combination of tilt and step is also possible.

  An indication of a period, for example a period in the range of 10 to 300 seconds, for the application of a voltage in step (1b) in the range of 50 to 400 V may mean that this voltage is held constant during the stated period. . However, alternatively, the voltage can also take various values during the deposition period in step (1b) within the stated minimum and maximum values in the range of 50-400V, for example from minimum to maximum deposition voltage. It can swing in a reciprocating manner or can rise in a slope or in steps.

  The voltage in step (1b), ie the deposition voltage, can also be adjusted in pulse form with no current time or with a voltage below the minimum level between two pulses. The pulse period can be in the range of 0.1 to 10 seconds, for example. Therefore, the “period” for deposition is preferably considered to be the sum of the periods when the deposition voltage is within the aforementioned maximum and minimum values when performing step (1b). The slope and pulse can also be matched to each other.

Further optional in-process steps The method of the present invention optionally involves two steps as described above, (1a) and (1b), preferably following step (1) as follows: (2):
(2) The method further includes the step of bringing the substrate coated at least partially with the coating composition (A) into contact with the aqueous sol-gel composition before curing the deposited coating composition (A).

  Those skilled in the art are familiar with the terms “sol-gel composition”, “sol-gel”, and the preparation of sol-gel compositions and sol-gels, see, for example, D.C. Wang et al., Progress in Organic Coatings 2009, 64, 327-338 or S. Wang et al. Zheng et al. Sol-Gel. Sci. Technol. 2010, 54, 174-187.

An aqueous “sol-gel composition” in the sense of the present invention is preferably an aqueous composition prepared by reacting at least one starting compound with water by hydrolysis and condensation, for example M Having at least one metal atom and / or quasi-metal atom such as ¹ and / or M ² , for example having at least two hydrolyzable groups such as two hydrolyzable groups X ¹ , and optionally For example, having at least one non-hydrolyzable organic group such as R ¹ . The at least two hydrolyzable groups herein are preferably each in each case by a single bond to at least one metal atom and / or at least one quasimetal atom present in at least one starting compound. Bond directly to each other. This type of sol-gel composition used in accordance with the present invention because of the presence of non-hydrolyzable organic groups such as R ¹ is also referred to as a “sol-gel hybrid composition”.

The aqueous sol-gel composition used according to the present invention in optional step (2) is preferably
At least one compound Si (X ¹ ) ₃ (R ¹ )
Wherein R ¹ is at least one reactive selected from the group consisting of a primary amino group, a secondary amino group, an epoxide group, and a group having an ethylenically unsaturated double bond. A non-hydrolyzable organic group having a functional group],
More specifically, at least one compound Si (X ¹ ) ₃ (R ¹ )
[Wherein R ¹ is a non-hydrolyzable organic group having at least one epoxide group as a reactive functional group, and X ¹ is a hydrolyzate such as an O—C _1-6 alkyl group, for example. Decomposable group], and
Optionally at least one further compound Si (X ¹ ) ₃ (R ¹ )
[Wherein R ¹ is a non-hydrolyzable organic group having at least one reactive functional group selected from the group consisting of a primary amino group and a secondary amino group, and X ¹ Is, for example, a hydrolyzable group such as an O—C _1-6 alkyl group],
And optionally at least one compound Si (X ¹ ) ₄
[Wherein X ¹ is a hydrolyzable group such as, for example, an O—C _1-6 alkyl group],
And optionally at least one compound Si (X ¹ ) ₃ (R ¹ )
[Wherein R ¹ is a non-hydrolyzable organic group having no reactive functional group such as a C _1-10 alkyl group, and X ¹ is, for example, O—C _1-6. A hydrolyzable group such as an alkyl group],
And optionally at least one compound Zr (X ¹ ) ₄
[Wherein X ¹ is a hydrolyzable group such as an O—C _1-6 alkyl group, for example] and can be obtained by reaction with water.

The method of the present invention preferably follows step (1) or step (2), as follows:
(3) Like a step of rinsing a substrate at least partially coated with the aqueous coating composition (A) obtainable after step (1) or step (2) with water and / or ultrafiltrate The process (3) is further included.

  Specifically, the terms “ultrafiltrate” or “ultrafiltration” in the context of electrodeposition coating are familiar to those skilled in the art, for example, Roempp Lexikon, Racke und Druckfarben, Georg Thiem Verlag 1998. Is defined.

  By performing step (3), excess components of the aqueous coating composition (A) used in the present invention present on the at least partially coated substrate after step (1) are circulated into the dip coating bath. It becomes possible.

The method of the present invention preferably comprises any step (4) following step (1) or (2) or (3),
(4) A substrate at least partially coated with the aqueous coating composition (A) obtainable after step (1) or step (2) or step (3), preferably for 30 seconds up to 1 hour More preferably, the method may further comprise a step (4) of contacting with water and / or ultrafiltrate for 30 seconds up to 30 minutes.

The method of the invention preferably comprises step (1), more specifically any step (4a) following step (1b), or (2) or (3) or (4),
(4a) An aqueous solution or aqueous dispersion of a substrate at least partially coated with the aqueous coating composition (A) obtainable after step (1) or step (2) or step (3) or step (4) Liquid, preferably at least one crosslinking catalyst (V), preferably at least one crosslinking catalyst (V) suitable for crosslinking reactive functional groups of the binder (A1), more specifically May further include a step (4a) of contacting with an aqueous solution of the epoxide polymer resin and / or the acrylate polymer resin used as the binder (A1).

  The aqueous solution of at least one crosslinking catalyst (V) is preferably an aqueous solution of a bismuth compound such as an aqueous solution containing a compound containing trivalent bismuth. During the execution of optional step (4a), the cathode voltage relative to the anode is preferably applied to the conductive substrate used, more preferably in the range of 4V to 100V. By carrying out step (4a), when the amount of component (A3) remains little in the coating composition after carrying out step (1a) of step (1) and cannot be precipitated in step (1b) Effective cross-linking becomes possible.

In a preferred embodiment, the method of the present invention is as follows:
(5) Step (1) and / or (2) and / or (3) and / or (4) and / or (4a) coated at least partially with the aqueous coating composition (A) used in the present invention. Preferably, steps (1) and / or (2) and / or (3) and / or (4) and / or (such as the step of applying at least one further coating film to a subsequently obtainable substrate. Subsequent to 4a), preferably further comprising at least one step (5) performed before optional step (6).

  By step (5), one or more additional coating films are at least partially coated with the aqueous coating composition (A), and steps (1) and / or (2) and / or (3) and / or It can be applied to substrates obtainable after (4) and / or (4a). If more than one coat has to be applied, step (5) can often be repeated appropriately. Examples of further coating films for application are, for example, base coat films, surface films and / or single coat or double coat films. Optionally, after subsequent rinsing with the aqueous sol-gel composition in step (2) and / or any rinsing with water and / or ultrafiltrate (in step (3)) and / or step (4) And / or after performing step (4a), the aqueous coating composition (A) applied by step (1) can be cured, which can be a base coat film, a surface film and / or a single coat or Before a further coat, such as a double coat film, is applied, it is carried out as described below in step (6). However or alternatively, optionally after subsequent rinsing with the aqueous sol-gel composition in step (2) and / or any rinsing with water and / or ultrafiltrate (in step (3)) and / or step After performing (4) and / or step (4a), the aqueous coating composition (A) applied by step (1) may not be cured, but instead, first the base coat film, surface Additional coats such as membranes and / or single coat or double coat membranes can also be applied ("wet-on-wet method"). In this case, following the application of this or these further coat (s), the entire system thus obtained is cured, which is preferably as described below according to step (6). Can be implemented.

In a preferred embodiment, the method of the present invention is as follows:
(6) An aqueous coating composition (at least partially applied to the substrate after step (1) and / or optionally (2) and / or (3) and / or (4) and / or (4a) A), or step (1) and / or optionally (2) and / or (3) and / or (4) and / or (4a) and / or (5) at least partially applied to the substrate It further comprises at least one step (6), such as a step of curing the coated coating.

  Step (6) of the method of the invention is preferably carried out by baking after step (1) or optionally (2) or optionally only after at least one further step (5). Step (6) is preferably performed in an oven. Curing herein is preferably carried out at a substrate temperature in the range of 140 ° C to 200 ° C, more preferably in the range of 150 ° C to 190 ° C, very preferably in the range of 160 ° C to 180 ° C. The Step (6) is preferably carried out over a period of at least 2 minutes to 2 hours, more preferably over at least 5 minutes to 1 hour, very preferably over a period of at least 10 minutes to 30 minutes.

Substrate coated at least partially A further subject of the present invention is a conductive substrate at least partially coated with the aqueous coating composition (A) of the present invention, or at least a conductive substrate with an electrodeposition material. An at least partially coated conductive substrate obtainable by the method of the invention for partially coating.

  The at least partially coated conductive substrate is preferably an aluminum substrate or has at least one aluminum surface.

  A further subject matter of the invention is preferably a metal part or preferably a metal article (product) produced from at least one such substrate.

  Such an article is, for example, a metal piece. Such parts include, for example, body and body parts of vehicles such as cars, trucks, motorcycles, buses, and long distance buses, as well as parts of household electrical appliances, or metallization of equipment, facade metallization, ceilings It may be a metal cladding or other part in the field of window frames.

Method of determination Filiform corrosion according to DIN EN 3665 The determination of filiform corrosion is used to elucidate the corrosion resistance of the coating on the substrate. This determination was made according to DIN EN 3665 (date: August 1, 1997) over 1008 hours for conductive base aluminum (ALU) coated with the coating composition of the present invention or comparative coating composition. Is called. In the course of this time, the coating in question starts with linear damage caused to the coating and is gradually damaged by corrosion taking the form of a line or thread. The average and maximum filament length [mm] may be measured here according to PAPP WT 3102 (Daimler) (date: 21 December 2006) and is a measure of the corrosion resistance of the coating.

2. X-ray fluorescence analysis (XFA) for film mass determination
The film mass (in mg / m ^{2 of} surface area) of the coating under investigation is determined by wavelength dispersive X-ray fluorescence analysis (XFA) according to DIN 51001 (date: August 2003). In this method, for example, the bismuth content of the coating or the bismuth content or the bismuth addition layer such as the coating obtained after step (1a) of step (1) of the method of the invention can be determined. Similarly, the amount of each of the other elements such as zirconium can be determined. The signal obtained when performing X-ray fluorescence analysis is corrected by the value for the separately measured substrate of the uncoated reference sample. A total count (kilocount per second) is determined for each element under analysis, such as bismuth. The total count for each element of the reference sample (uncoated substrate) is subtracted from each total count determined in this way for that sample to obtain the net count for the element under analysis. It is done. These are converted to membrane mass (mg / cm ² ) using element specific conversion functions (obtained from calibration measurements). When multiple coats are applied, the respective film mass is determined after each application. Then, for subsequent coatings, the total count of the preceding film in each case is used as a reference. This determination method is used to determine the bismuth content of the coating obtained after step (1a) of step (1) of the method of the invention.

3. Atomic emission spectroscopy (ICP-OES) for determining the total amount of bismuth present in the coating composition (A)
For example, the amount of certain elements in a sample under analysis, such as bismuth content, is determined using inductively coupled plasma atomic emission spectroscopy (ICP-OES) according to DIN EN ISO 11885 (date: September 2009). The For this purpose, a sample of the coating composition (A) or the comparative composition is taken and the sample is digested by microwave: Here, the sample of the coating composition (A) or the comparative composition is weighed, The volatile constituents of this sample are removed by heating with a linear temperature rise from 18 ° C. to 130 ° C. over 1 hour. A maximum 0.5 g quantity of this product sample is mixed with a 1: 1 mixture of nitric acid (strength 65%) and sulfuric acid (strength 96%) (5 ml of each of the acids). Microwave digestion is then performed using an apparatus from Berghof (Speedwave IV instrument). During decomposition, the sample mixture is heated to a temperature of 250 ° C. over 20-30 minutes, and this temperature is maintained for 10 minutes. After degradation, the residual sample mixture should be a clear solution without the solid fraction. Using ICP-OES according to DIN EN ISO 11885, the total amount of bismuth in the sample is then confirmed. This sample is subjected to thermal excitation in an argon plasma generated by a high frequency field, and the emission for electron transition is visualized as a spectral line of the corresponding wavelength and analyzed using an optical system. There is a linear relationship between the emission intensity and the concentration of the element such as bismuth. Prior to running, calibration measurements are performed as a function of the particular sample under analysis using a known elemental standard (reference standard). Such a calibration can be used to determine the concentration of an unknown solution, such as the concentration of the amount of bismuth in the sample.

  In another measurement of the proportion of bismuth present in solution in each composition, ie, for example, the amount of (A3), the sample used is a sample of ultrafiltrate. In this case, ultrafiltration is performed in 1 hour (ultrafiltration in the circuit; ultrafiltration membrane, Nadir, PVDF, RM-UV 150T), and the sample is taken from the permeate or ultrafiltrate. The amount of (A3) in this sample is then measured by ICP-OES according to DIN EN ISO 11885. Here, it is assumed that the component (A3) present in the form dissolved in (A) is completely transferred into the ultrafiltrate. When the proportion of (A3) measured as outlined above is subtracted from the total amount of bismuth measured in advance, the result is the proportion of component (A4) present in the sample under analysis.

  The examples that follow serve to clarify the invention, but do not impose any limitations.

  Unless otherwise indicated, percentage figures are percentages by weight in each case.

Invention and Comparative Example Inventive Aqueous Coating Composition and Comparative Coating Composition Generation Exemplary BASF CathoGuard® used to produce the following inventive coating compositions Z1 and Z2 and comparative coating composition V1. Trademark) 520 pigment paste contains bismuth nitrate. The person skilled in the art is aware of the preparation of such pigment pastes, for example in DE 102008016220 (A1) (page 7, table 1, variant B).

Comparative coating composition V1
An aqueous dispersion of binder and crosslinker (product CathoGuard® 520, available from BASF Coating GmbH with a solids content of 37.5% by weight) (2130 parts) at room temperature (18-23 ° C.) in small amounts of deionized Mix with water (2497 parts) to give mixture M1. Into this mixture M1, a water-soluble compound containing a pigment paste (a product CathoGuard® 520 with a solid content of 65.0% by weight, commercially available from BASF) (306 parts) and bismuth (III) (67 parts) In addition, the product mixture is mixed by stirring at room temperature (18-23 ° C.) to give a mixture M2. After further stirring for 24 hours at room temperature (18-23 ° C.), the result is a comparative coating composition (V1). The water-soluble compound containing bismuth (III) used is L-(+)-bismuth lactate (Bi1) and has a bismuth content of 11.9% by weight.

  The production of Bi1 is carried out as described below: While introducing and stirring a mixture of L-(+)-lactic acid (strength 88% by weight) (613.64 g) and deionized water (1314.00 g). Heat to 70 ° C. 155.30 g of bismuth (III) oxide may be added to the mixture, during which time the temperature of the product mixture may rise to 80 ° C. After 1 hour, an additional 155.30 g of bismuth (III) oxide may be added to the mixture and the temperature of the product mixture may rise again to 80 ° C. After an additional hour, an additional 155.30 g of bismuth (III) oxide is added to the mixture and the product mixture is stirred for an additional 3 hours. Subsequently, 1003 g of deionized water is added with stirring. After this time, optionally the product mixture is cooled to a temperature in the range of 30-40 ° C if a temperature in the range of 30-40 ° C has not yet been reached. The reaction mixture is then filtered (T1000 depth filter) and the filtrate is used as Bi1. In each case, the part in this sentence represents part by mass.

Coating composition Z1
18. Coating composition Z1 of the present invention is prepared similarly to the preparation of comparative coating composition V1, except that mixture M2 was blocked with amine before further stirring at room temperature (18-23 ° C.) for 24 hours. The difference is that it is further mixed with 5 parts of phosphorus-containing compound (P1). The part here represents part by mass in each case.

  Here, P1 is 119.17 parts of 49.75 parts of di-2-ethylhexyl phosphate (acid number 187.15 mg KOH / g) into a three-necked flask equipped with a stirrer, a temperature probe, and a dropping funnel. Of butyl diglycol and the resulting mixture is stirred at room temperature (18-23 ° C.) for 1 hour. 58.69 parts of tris (2-ethylhexyl) amine are then added dropwise at such a rate that the temperature of the mixture does not exceed 60 ° C. After cooling the mixture at room temperature (18-23 ° C.), stirring is carried out for a further hour and the resulting mixture is used as P1.

Coating composition Z2
The coating composition Z2 of the invention is prepared in the same way as the preparation of the comparative coating composition V1, but 29 parts of the mixture M2 are blocked with amine before further stirring for 24 hours at room temperature (18-23 ° C.) And the phosphorus-containing compound (P) (blocked compound P1). The part here represents part by mass in each case.

  The production of P1 takes place as described in connection with the coating composition Z1.

  Table 1 provides an overview of the resulting inventive aqueous coating compositions Z1 and Z2 and of the aqueous comparative coating composition V1:

2. Production of a conductive substrate coated with the inventive aqueous coating composition Z1 or Z2 or comparative coating composition V1 The aqueous coating composition Z1 or Z2 or comparative coating composition V1 in each case as a dip coating substrate As a metal test panel. Each of compositions Z1 and V1 is applied to the respective substrate after its manufacture as described above.

The metal test panel (T1) used is aluminum (ALU) as an example of a conductive substrate. Each of the two surfaces of each panel used has an area of 10.5 cm · 19 cm and an overall area of about 400 cm ² .

  First, in each case, these panels were placed at a temperature of 62 ° C. for 1.5 to 3 minutes with the commercial products Ridoline 1565-1 (3.0% by weight) and Ridosol 1400-1 (0.3% by weight) from Henkel. ) And also in a bath containing an aqueous solution containing water (96.7% by weight). This is followed by mechanical cleaning (using a fine brush), after which the panel is immersed again in the bath for 1.5 minutes.

  The substrate thus cleaned is subsequently rinsed with water (1 minute) and deionized water (1 minute).

  Immediately thereafter, the aqueous coating composition Z1 or Z2 or comparative coating composition V1 used in the invention is applied to each panel T1, respectively, each panel being one of the compositions Z1, Z2 or V1. Soak in the corresponding dip coating bath containing one. Each of the dip coating baths herein has a temperature of 32 ° C.

  Coating in the dip coating bath is carried out by a two-stage deposition process and a coating process (1), which provides two stages (1a) and (1b), first of all, a voltage 4V 120 Pre-deposit bismuth by applying for a second (corresponding to step (1a)).

  Subsequently, on the substrate obtained after step (1a), step (1b) of step (1) of the method according to the invention is carried out equipotentially by applying a voltage of 4 V, which is caused by the ramp voltage. In each case, it rises continuously and linearly over 30 seconds to a voltage in the range of 160-220V. The respective voltages are then held for 60-180 seconds (holding time).

  Specifically, when coating the substrate T1 with one of the compositions V1 or Z1 or Z2, the following parameters are selected:

V1:
Stage (1a): 4V (equipotentially) over 120 seconds
Stage (1b): Ramp voltage: linear increase to voltage 200V over 30 seconds and hold time at this voltage 180 seconds

Z1:
Stage (1a): 4V (equipotentially) over 120 seconds
Stage (1b): Ramp voltage: linear increase up to voltage 160V over 30 seconds and holding time at this voltage 60 seconds

Z2:
Stage (1a): 4V (equipotentially) over 120 seconds
Stage (1b): Ramp voltage: linear increase up to voltage 160V over 30 seconds and holding time at this voltage 60 seconds

  Subsequent baking steps are performed by baking the resulting coating at 175 ° C. (oven temperature) in each case for 25 minutes. The dry film thickness of the aqueous coating composition of the present invention baked on each substrate is in each case 20 μm.

3. Investigation of the corrosion resistance effect of the coated substrate The substrate T1 coated with one of the coating compositions, V1, Z1 or Z2, is examined.

  All the following tests were carried out according to the aforementioned determination method and / or the corresponding standard. Each value in Table 3 is the mean (including standard deviation) of double or triple determinations.

  As can be seen from Table 3, the substrate coated with the aqueous coating composition of the present invention by the method of the present invention consistently compared to the substrate coated with the comparative coating composition: Shows improved corrosion resistance.

Claims (24)

In order to at least partially coat a conductive substrate with an electrodeposition material,
(A1) an aqueous coating composition (A) comprising at least one cathode depositing binder, and (A2) optionally at least one crosslinking agent, relative to the total mass of the coating composition (A) And at least 30 ppm bismuth in total
Formula (I)

At least one phosphorus-containing compound (P) blocked with at least one amine of the formula:
R ¹ and ^{R 2} are each, independently of one _another, or a _{C 1 to 18} aliphatic _group, or a _{C 3 to 12} cycloaliphatic _{radical, C 3 to 12} fat cross-linked by _{C 1 to 10} aliphatic group An aryl or heteroaryl group that is a cyclic group or bridged by a C _1-10 aliphatic group,
Or R ³ is _H, or a _{C 1 to 18} aliphatic _group, or a _{C 3 to 12} cycloaliphatic _radical, a _{C 3 to 12} cycloaliphatic radical cross-linked by _{C 1 to 10} aliphatic group Or an aryl or heteroaryl group bridged by a C _1-10 aliphatic group,
Aqueous coating composition (A).   The coating composition (A) according to claim 1, having a pH in the range of 4.0 to 6.5.   At least one phosphorus-containing compound (P) blocked with at least one amine of general formula (I) in an amount of 0.05 to 5% by weight, based on the total weight of the coating composition (A) The coating composition (A) according to claim 1 or 2. The coating composition (A) according to any one of claims 1 to 3, wherein at least one of the groups R ¹ , R ² and R ³ is a C _1-18 aliphatic group. The coating composition (A) according to any one of claims 1 to 4, wherein at least one of the groups R ¹ , R ² and R ³ is a C _3-18 alkyl group. Or R ³ is a C _{1 to 18} aliphatic radical, or a C _{1 to 10} aliphatic aryl or heteroaryl group that is bridged by groups, the coating composition according to any one of claims 1 5 (A).   The phosphorus-containing compound (P) is selected from the group consisting of phosphonic diesters, diphosphonic diesters, phosphoric monoesters, and phosphoric diesters, their anions, and mixtures thereof. The coating composition (A) according to one item. The phosphorus-containing compound (P) is
General formula (II) below

Or an anion thereof, wherein
R ⁴ and R ⁵ are each independently of each other,
An unsubstituted ( ₁ ) having ₁ to 20 carbon atoms and optionally ₁ to 4 heteroatoms selected from the group consisting of N, NH, N (C _1-6 alkyl), O, and S Hetero) alkyl groups, 3-20 carbon atoms, and optionally 1-4 heteroatoms selected from the group consisting of N, NH, N (C _1-6 alkyl), O, and S , An unsubstituted (hetero) cycloalkyl group, and 1 to 5 carbon atoms, and optionally 1 selected from the group consisting of N, NH, N (C _1-6 alkyl), O, and S Selected from the group consisting of unsubstituted (hetero) aryl groups having ˜4 heteroatoms;
One of the radicals R ⁴ and R ⁵ or both radicals R ⁴ and R ⁵ may additionally be hydrogen,
The coating composition (A) according to any one of claims 1 to 7.   The bismuth present in the coating composition (A) is present in the coating composition (A) in the form of a solution (A3) and / or in the non-solution form (A4). The coating composition (A) according to one item.   Coating according to any one of the preceding claims, wherein at least part of the total amount of bismuth present in the coating composition (A) is present in the coating composition (A) in the form of a solution (A3). Composition (A).   The coating composition (A) according to any one of claims 1 to 10, wherein the total amount of bismuth present in the coating composition (A) is in the range of at least 30 ppm to 20000 ppm. (A3) at least 100 ppm bismuth, optionally at least 130 ppm bismuth with respect to the total weight of the coating composition (A) in the form of a solution in the coating composition (A),
Or (A3) at least 30 ppm bismuth in the form of a solution in the coating composition (A) with respect to the total mass of the coating composition (A), and (A4) in the form of a non-solution in the coating composition (A) Comprising at least 130 ppm bismuth in a total amount relative to the total mass of the coating composition (A), comprising at least 100 ppm bismuth relative to the total mass of the coating composition (A);
The coating composition (A) according to any one of claims 1 to 11. The coating composition (A) according to any one of claims 1 to 12, further comprising (A5) at least one at least bidentate complexing agent suitable for complexing bismuth.   The at least one complexing agent (A5) is present in the aqueous coating composition (A) in a proportion of at least 5 mol% relative to the total amount of bismuth present in the coating composition (A). The coating composition (A) described in 1.   The binder (A1) is a polymer resin having a tertiary amino group which is at least partially protonated, and the optionally present crosslinking agent (A2) is a block isocyanate. The coating composition (A) according to one item. Coating composition (A) according to claim 15, wherein the tertiary amino groups have, independently of one another, at least two _C1-3 alkyl groups, each of which is at least monosubstituted by a hydroxyl group.   17. A method of using the coating composition (A) according to any one of claims 1 to 16 for at least partially coating a conductive substrate with an electrodeposition material. At least step (1):
(1) contacting the conductive substrate connected as a cathode with the aqueous coating composition (A) according to any one of claims 1 to 16,
A method for at least partially coating a conductive substrate with an electrodeposition material. Step (1) is at least two successive steps (1a) and (1b):
(1a) a stage with an applied voltage in the range of 1-50V applied for at least 5 seconds; and (1b) a stage with an applied voltage in the range of 50-400V, but applied in stage (1b) 19. The method according to claim 18, wherein the method is carried out at a stage provided that the voltage is at least 10V greater than the voltage applied at stage (1a).   20. A method according to claim 18 or 19, wherein the voltage applied in step (1a) is applied over a range of at least 5 to 300 seconds.   The voltage applied in the step (1b) in the range of 50 to 400V is performed at a time interval of 0 to 300 seconds after performing the step (1a), and the voltage within the voltage range of 50 to 400V is 10 to 300. 21. A method according to any one of claims 18 to 20 which is maintained for a range of seconds.   A conductive substrate at least partially coated with the aqueous coating composition (A) according to any one of claims 1 to 16, or obtained by a method according to any one of claims 18 to 21. An electrically conductive substrate at least partially coated.   24. The at least partially coated conductive substrate of claim 22 having at least one surface of aluminum.   21. An article or part produced from at least one substrate according to claim 20.