Electrodeposition coating material composition containing composite particles containing a metal-containing catalyst

Abstract

The present invention provides a method for producing a polymeric composite of a cathodically depositable polymer and a polymerizable polymeric composite of a cathodically depositable polymer, comprising: (I) at least one aqueous binder dispersion comprising at least one cathodically depositable polymer (a) and at least one crosslinker component (b); (II) at least one pigment paste containing at least one pigment and / or filler (c) and at least one polymer as grinding resin; The present invention relates to an aqueous cathodically depositable electrodeposition coating material composition comprising: wherein the composition also comprises at least one composite particle (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate polymer (mp).

Description

[Technical Field]

[0001] The present invention relates to an aqueous cathodically depositable electrodeposition coating material composition comprising at least one binder dispersion (I) containing at least one cathodically depositable polymer (a) and at least one crosslinker (b), and at least one pigment paste (II) containing at least one pigment and / or filler (c). The composition also comprises at least one composite particle (p) containing at least one metal-containing catalyst (pc) and at least one (meth)acrylate-based polymer (mp), the polymer (mp) preferably being prepared in the presence of the metal-containing catalyst (pc). The present invention also relates to a method for at least partially coating a conductive substrate by cathodic electrodeposition coating, comprising at least steps (1) to (5), including step (1) of at least partially immersing the substrate in an electrodeposition coating bath containing the electrodeposition coating material composition of the present invention. Furthermore, the present invention relates to a conductive substrate at least partially coated with the calcined electrodeposition coating material composition of the present invention and / or obtainable by the method of the present invention. Finally, the present invention relates to the use of the composite particles (p) to enhance the robustness of electrodeposition coating baths against phosphate contamination. [Background technology]

[0002] In the automotive sector, metal parts used in production usually have to be protected against corrosion. The requirements regarding corrosion protection to be achieved are very strict, especially since manufacturers often offer a guarantee against rust perforation for many years. Such corrosion protection is usually achieved by applying at least one coating suitable for this purpose to the part or to the substrate used in its production.

[0003] To ensure the necessary corrosion inhibition, it is common to apply a phosphate pretreatment composition (e.g., a zinc phosphate-based composition) to metal substrates before applying an electrodeposition coating. Electrocoat materials are coating materials containing a polymer as a binder with a crosslinker, pigments and / or fillers, and often additives. Generally, there are anodically and cathodically depositable electrocoat materials. Anodic electrocoat compositions, particularly those containing metallic effect pigments, are disclosed, for example, in WO 2006 / 117189 A1. However, cathodically depositable materials are most important in industrial coatings, especially automotive finishes. In cathodic electrocoating, the substrate to be coated is immersed in an electrodeposition bath and connected as a cathode. The bath contains an anode as the counter electrode. Particles of the electrodeposition material are stabilized with a positive charge and deposit on the cathode to form a coating. After deposition, the coated substrate is removed from the electrodeposition bath, washed with water, and the coating is baked, i.e., thermally cured. During curing, crosslinking occurs through a chemical reaction between the binder polymer and the crosslinking agent, e.g., between hydroxyl and / or amino groups and isocyanates. To promote effective curing and crosslinking reactions, electrodeposition coating compositions typically contain a respective catalyst, particularly a metal-containing catalyst such as a tin-containing catalyst or a bismuth-containing catalyst.

[0004] Cathodically depositable electrocoat materials are known from the prior art, for example from EP 1 041 125 A1, DE 197 03 869 A1, and WO 91 / 09917 A2.

[0005] As already mentioned above, the primary purpose of cathodically depositable electrocoat materials is corrosion protection of metal substrates. Effective crosslinking and thus film formation is clearly one of the most important factors in obtaining such corrosion protection. Therefore, the presence of a sufficient amount and concentration of a curing catalyst is crucial.

[0006] However, one major problem in this respect is that during normal use of an electrodeposition coating bath filled with the respective electrodeposition coating material composition (i.e., during the coating of a conductive substrate by cathodic electrocoating), the continuous introduction of (and poisoning by) phosphate species is virtually unavoidable. The reason for this is apparently the phosphating pretreatment carried out before immersing the respective substrate in the electrodeposition bath. Phosphates cause catalyst poisoning, i.e., a catalyst degradation process, resulting in no catalytic activity remaining or at least in a significantly reduced inactive species. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] WO 2006 / 117189 A1 [Patent Document 2] EP 1 041 125 A1 [Patent Document 3] DE 197 03 869 A1 [Patent Document 4] WO 91 / 09917 A2 Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, the underlying objective of the present invention was to provide an electrodeposition coating material that overcomes the above-mentioned technical drawbacks, i.e., has high robustness against phosphate contamination. More specifically, the electrodeposition coating material and the respective electrodeposition coating baths filled with the respective electrodeposition coating material compositions should exhibit significantly increased resistance to phosphate contamination. Therefore, the electrodeposition coatings produced by these baths and compositions, respectively, should be properly curable (i.e., crosslinkable) even when a significant amount of phosphate (which would exhibit noticeable phosphate contamination in an industrially realistic scenario) is present in the bath during production. [Means for solving the problem]

[0009] This object has been solved by the subject matter of the present claims and the preferred embodiments thereof disclosed herein, ie the subject matter described herein.

[0010] The first subject of the present invention is (I) at least one aqueous binder dispersion comprising at least one cathodically depositable polymer (a) and at least one crosslinker component (b); (II) at least one pigment paste containing at least one pigment and / or filler (c) and at least one polymer as grinding resin; an aqueous cathodically depositable electrodeposition coating material composition comprising: wherein the composition also comprises at least one composite particle (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate-based polymer (mp).

[0011] The aqueous cathodically depositable electrodeposition coating material composition described above is also referred to as the electrodeposition coating material composition of the present invention or simply as the composition of the present invention.

[0012] A further subject of the present invention is at least steps (1) to (5), i.e. (1) at least partially immersing a conductive substrate in an electrodeposition coating bath containing the electrodeposition coating material composition of the present invention; (2) connecting the substrate as a cathode; (3) depositing the coating film obtained from the electrodeposition coating material composition on a substrate using a direct current; (4) removing the coated substrate from the electrodeposition coating bath; (5) baking the coating film deposited on the substrate; 1. A method for at least partially coating a conductive substrate by cathodic electrodeposition coating, comprising:

[0013] A further subject of the present invention is an electrically conductive substrate at least partially coated with the calcined electrodeposition coating material composition of the present invention and / or obtainable by the method of the present invention.

[0014] Surprisingly, it has been found that the electrodeposition coating material compositions of the present invention enable the production of electrodeposited substrates that maintain the desired properties of these coatings and substrates, even in the presence of significant amounts of phosphate. Thus, the goal of achieving excellent phosphate stain resistance is achieved by maintaining the excellent property profile of electrodeposited coatings produced under conditions involving relatively high phosphate concentrations. DETAILED DESCRIPTION OF THE INVENTION

[0015] In the sense of the present invention, the term "comprises", for example in connection with the electrodeposition coating material composition of the present invention, includes the meaning of "consists of", but does not exclusively mean "consist of". Thus, for example, with respect to the electrodeposition coating material composition of the present invention, the binder dispersion (I) can be comprised therein in addition to components (a), (b) and water, as well as one or more of the further components specified below and optionally included in the electrodeposition coating material composition of the present invention. All components can be present in their preferred embodiments, in each case as specified below. "Consists of" can also be referred to as "comprises only" or "exclusively comprises", i.e., "comprises" is referred to as a general term that includes the specific term "consisting of".

[0016] Electrodeposition coating material composition of the present invention The cathodically depositable aqueous electrodeposition coating material composition of the present invention (hereinafter also referred to as the electrodeposition coating material composition of the present invention or the composition of the present invention) comprises at least one binder dispersion (I) containing at least one cathodically depositable polymer (a) (also referred to as component (a)) and at least one crosslinker (b) (also referred to as component (b)), and at least one pigment paste (II) containing at least one pigment and / or filler. The composition of the present invention also contains water. As used herein, the terms "electrodeposition coating material composition" and "electrodeposition coating composition" are interchangeable.

[0017] The cathodically depositable aqueous electrodeposition coating material composition of the present invention is suitable for at least partially coating a conductive substrate with the electrodeposition coating composition, i.e., suitable for at least partially applying to the substrate surface of the conductive substrate, and such application results in the formation of an electrodeposited coating film on the substrate surface.

[0018] The cathodic deposition electrodeposition coating material composition of the present invention is aqueous. The term "aqueous" in connection with the electrodeposition coating material composition of the present invention is understood for the purposes of the present invention to mean that water as a solvent and / or diluent is present as the major component of all solvents and / or diluents present in the electrodeposition coating material composition, preferably in an amount of at least 35% by weight, based on the total weight of the electrodeposition coating material composition of the present invention. Organic solvents may also be present in smaller proportions, preferably in amounts of less than 20% by weight.

[0019] The electrodeposition coating composition of the present invention preferably comprises a proportion of water of at least 40% by weight, more preferably at least 50% by weight, even more preferably at least 60% by weight, even more preferably at least 65% by weight, particularly preferably at least 70% by weight, and most preferably at least 75% by weight, in each case based on the total weight of the electrodeposition coating composition.

[0020] The electrodeposition coating composition of the present invention preferably contains an organic solvent in a proportion of less than 10% by weight, more preferably 0 to <10% by weight, and very preferably 0 to <7.5% by weight, or 0 to <5% by weight, or 0 to 2% by weight, in each case based on the total weight of the electrodeposition coating composition. Examples of such organic solvents include heterocyclic, aliphatic, or aromatic hydrocarbons, monohydric or polyhydric alcohols, especially methanol and / or ethanol, ethers, esters, ketones, and amides, such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, toluene, xylene, butanol, ethylene glycol, propylene glycol, and butyl glycol ethers and their acetates, butyl diglycol, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetone, isophorone, or mixtures thereof. Representative examples of such organic solvents include ethylene glycol ethers, such as butyl glycol, or propylene glycol ethers, such as butoxypropanol or phenoxypropanol.

[0021] The solids content of the electrodeposition coating material composition of the present invention is preferably 5 to 35% by mass, more preferably 7.5 to 30% by mass, very preferably 10 to 27.5% by mass, more particularly preferably 12.5 to 25% by mass, and most preferably 15 to 22.5% by mass or 15 to 20% by mass, based in each case on the total mass of the electrodeposition coating composition. The solids content, in other words, the nonvolatile content, is determined according to the method described below.

[0022] The electrodeposition coating material composition of the present invention preferably has a pH in the range of 2.0 to 10.0, more preferably in the range of 2.5 to 9.5 or in the range of 2.5 to 9.0, very preferably in the range of 3.0 to 8.5 or in the range of 3.0 to 8.0, more particularly preferably in the range of 2.5 to 7.5 or in the range of 3.5 to 7.0, particularly preferably in the range of 4.0 to 6.5, and most preferably in the range of 3.5 to 6.5 or in the range of 5.0 to 6.0.

[0023] The electrodeposition coating material of the composition preferably contains component (a) in an amount ranging from 15 to 85% by weight, more preferably from 20 to 80% by weight, very preferably from 25 to 77.5% by weight, more particularly preferably from 30 to 75% by weight or from 35 to 75% by weight, and most preferably from 40 to 70% by weight or from 45 to 70% by weight or from 50 to 70% by weight, in each case based on the total solids content of the electrodeposition coating composition. Alternatively, the electrodeposition coating material composition of the present invention preferably contains component (a) in an amount ranging from 1 to 80% by weight, more preferably from 2.5 to 75% by weight, very preferably from 5 to 70% by weight, more particularly preferably from 7.5 to 65% by weight, and most preferably from 8 to 60% by weight or from 10 to 50% by weight, based on the total weight of the electrodeposition coating material composition in each coating bath.

[0024] The electrodeposition coating composition of the present invention further comprises at least one crosslinker component (b), which is present in an amount of preferably 5 to 45% by weight, more preferably 6 to 42.5% by weight, very preferably 7 to 40% by weight, more particularly preferably 8 to 37.5% by weight or 9 to 35% by weight, most preferably 10 to 35% by weight, and particularly preferably 15 to 35% by weight, based in each case on the total solids content of the electrodeposition coating composition. Alternatively, the electrodeposition coating composition of the present invention comprises at least one crosslinker component (b), which is present in an amount of preferably 0.5 to 30% by weight, more preferably 1 to 25% by weight, very preferably 1.5 to 20% by weight, more particularly preferably 2 to 17.5% by weight, most preferably 2.5 to 15% by weight, and particularly preferably 3 to 10% by weight, based on the total weight of the electrodeposition coating composition in each coating bath.

[0025] The weight percent proportions of components (a), (b) and water contained in the electrodeposition coating composition of the present invention, and of any additional components that may be present, are based on the total weight of the electrodeposition coating material composition and add up to 100 weight percent.

[0026] The relative weight ratio of components (a) and (b) to each other in the electrodeposition coating material composition is preferably in the range of 5:1 to 1.1:1, more preferably in the range of 4.5:1 to 1.1:1, very preferably in the range of 4:1 to 1.2:1, and most preferably in the range of 3:1 to 1.5:1.

[0027] The composition of the present invention comprises at least one, preferably exactly one, binder dispersion (I). As known to those skilled in the art, electrodeposition coating compositions typically comprise such binder dispersions, i.e., aqueous dispersions containing at least one polymer as a binder. The composition of the present invention also comprises at least one pigment paste (II). Again, as known to those skilled in the art, electrodeposition coating compositions typically comprise such pigment pastes.

[0028] The different essential and optional components of the composition of the present invention are described below, and the details of the binder dispersion (I) and the pigment paste (II) are also described further below.

[0029] Component (a) Component (a) is at least one cathodically depositable polymer, which preferably functions as at least one binder in the electrodeposition coating material composition of the present invention, and may also function as a grinding resin, as outlined in more detail below.

[0030] Any cathodically depositable polymer is suitable as the binder and thus as component (a). Preferred are poly(meth)acrylates, (meth)acrylate copolymers, and epoxide polymers.

[0031] Preferably, component (a) of the electrodeposition coating composition of the present invention comprises and / or is at least one epoxide-amine adduct.

[0032] For the purposes of the present invention, the epoxide-amine adduct is a reaction product of at least one epoxy resin and at least one amine. The epoxy-amine adduct is hydroxyl-functional, meaning that component (a) is preferably hydroxyl-functional. The epoxy resin used is in particular based on bisphenol A and / or its derivatives. The amine reacted with the epoxy resin is a primary and / or secondary amine or its salt and / or a tertiary amine salt.

[0033] The at least one epoxide-amine adduct used as component (a) is preferably a cationic, epoxide-based, amine-modified resin. The preparation of such cationic, amine-modified, epoxide-based resins is known and is described, for example, in DE 35 18 732, DE 35 18 770, EP 0 004 090, EP 0 012 463, EP 0 961 797 B1, and EP 0 505 445 B1. A cationic, epoxide-based, amine-modified resin is understood to be the reaction product of at least one polyepoxide, preferably having two or more, e.g., three, epoxide groups, with at least one amine, preferably at least one primary and / or secondary amine. Particularly preferred polyepoxides are polyglycidyl ethers of polyphenols prepared from polyphenols and epihalohydrins. The polyphenols used may be, in particular, bisphenol A and / or bisphenol F. Other suitable polyepoxides are polyglycidyl ethers of polyhydric alcohols, such as the polyglycidyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene 1,2-glycol, propylene 1,4-glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol, and 2,2-bis(4-hydroxycyclohexyl)propane. The polyepoxides used may also be modified polyepoxides. Modified polyepoxides are understood to mean polyepoxides in which some of the reactive functional groups have been reacted with at least one modifying compound. Examples of such modified compounds are as follows: i) compounds containing carboxyl groups, such as saturated or unsaturated monocarboxylic acids (e.g., benzoic acid, linseed oil fatty acid, 2-ethylhexanoic acid, versatic acid), aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids of various chain lengths (e.g., adipic acid, sebacic acid, isophthalic acid, or dimer fatty acids), hydroxyalkyl carboxylic acids (e.g., lactic acid, dimethylolpropionic acid), and carboxyl-containing polyesters, or ii) compounds containing amino groups, such as diethylamine or ethylhexylamine or diamines with secondary amino groups, for example N,N'-dialkylalkylenediamines, such as dimethylethylenediamine, N,N'-dialkyl-polyoxyalkyleneamines, such as N,N'-dimethylpolyoxypropylenediamine, cyanoalkylated alkylenediamines, such as bis-N,N'-cyanoethylethylenediamine, cyanoalkylated polyoxyalkylenediamines, such as bis-N,N'-cyanoethylpolyoxypropylenediamine, polyaminoamides, such as Versamides, especially amino-terminated reaction products of diamines (for example hexamethylenediamine), polycarboxylic acids, especially dimeric fatty acids and monocarboxylic acids, more especially fatty acids, or reaction products of one mole of diaminohexane with two moles of monoglycidyl ethers or monoglycidyl esters, especially glycidyl esters of α-branched fatty acids, such as Versatic acid, or iii) compounds containing hydroxyl groups, such as neopentyl glycol, bisethoxylated neopentyl glycol, neopentyl glycol hydroxypivalate, dimethylhydantoin-N,N'-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 hydroxyl group-containing alkyl ketimines, such as aminomethylpropane-1,3-diol methylisobutylketimine or tris(hydroxymethyl)aminomethane cyclohexanone ketimine, and also polyglycol ethers, polyester polyols, polyether polyols, polycaprolactone polyols, polycaprolactam polyols of various functionalities and molecular weights, or iv) Saturated or unsaturated fatty acid methyl esters which are esterified with the hydroxyl groups of the epoxy resin in the presence of sodium methoxide.

[0034] Examples of amines that can be used to prepare component (a) include mono- and dialkylamines, such as methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, methylbutylamine, alkanolamines, such as methylethanolamine or diethanolamine, and dialkylaminoalkylamines, such as dimethylaminoethylamine, diethylaminopropylamine, or dimethylaminopropylamine. Amines that can be used can also contain other functional groups, provided they do not interfere with the reaction of the epoxide groups of the optionally modified polyepoxide with the amine and do not cause gelation of the reaction mixture. Secondary amines are preferably used. The charge required for dilution in water and electrodeposition can be generated by protonation with a water-soluble acid (e.g., boric acid, formic acid, acetic acid, lactic acid, alkylsulfonic acid (e.g., methanesulfonic acid)); preferably, acetic acid and / or formic acid). Another method for introducing cationic groups into the optionally modified polyepoxide is to react the epoxide groups of the polyepoxide with an amine salt.

[0035] The epoxide-amine adducts that can be used as component (a) are preferably reaction products of bisphenol A-based epoxy resins with primary amines and / or secondary amines or salts thereof and / or salts of tertiary amines.

[0036] Ingredient (b) At least one crosslinking agent is present in the electrodeposition coating material composition as component (b), which is preferably selected from the group consisting of blocked polyisocyanates, free polyisocyanates, amino resins, and mixtures thereof, and said component (b) is different from component (a).

[0037] The term "blocked polyisocyanate" is known to those skilled in the art. Usable blocked polyisocyanates are polyisocyanates having at least two isocyanate groups (diisocyanates in the case of exactly two isocyanate groups), but preferably more than two, for example, 3 to 5, isocyanate groups, in which the isocyanate groups are stable at room temperature, i.e., 18 to 23°C, particularly with respect to hydroxyl groups and amino groups, such as primary and / or secondary amino groups, in the resulting blocked polyisocyanate, but react at elevated temperatures, for example, ≥80°C, ≥110°C, ≥130°C, ≥140°C, ≥150°C, ≥160°C, ≥170°C, or ≥180°C, with conversion and formation of urethane and / or urea bonds, respectively.

[0038] In preparing the blocked polyisocyanate, any desired organic polyisocyanate suitable for crosslinking can be used. Preferably used isocyanates are (hetero)aliphatic, (hetero)alicyclic, (hetero)aromatic or (hetero)aliphatic-(hetero)aromatic isocyanates. Preferred polyisocyanates contain 2 to 36, especially 6 to 15, carbon atoms. Preferred examples include ethylene 1,2-ethylene diisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 2,2,4- and (2,4,4)-trimethylhexamethylene 1,6-diisocyanate (TMDI), diphenylmethane diisocyanate (MDI), 1,9-diisocyanato-5-methylnonane, 1,8-diisocyanato-2,4-dimethyloctane, dodecane 1,12-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), cyanate, IPDI), 1,4-diisocyanatomethyl-2,3,5,6-tetramethyl-cyclohexane, decahydro-8-methyl (1,4-methanonaphthalene-2 ​​(or 3), 5-ylenediisocyanate, hexahydro-4,7-methanoindan-1 (or 2), 5 (or 6)-ylenediisocyanate, hexahydro-4,7-methanoindan-1 (or 2), 5 (or 6)-ylenediisocyanate, hexahydrotolylene 2,4- and / or 2,6-diisocyanate (H6-TDI), toluene 2,4- and / or 2,6-diisocyanate (TDI), perhydrodiphenylmethane 2,4'-diisocyanate, perhydrodiphenylmethane 4,4'-diisocyanate (H 12MDI), 4,4'-diisocyanato-3,3',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 mixtures of these compounds. Polyisocyanates of higher isocyanate functionality can also be used, such as trimerized hexamethylene diisocyanate and trimerized isophorone diisocyanate, and more particularly the corresponding isocyanurates. Furthermore, mixtures of polyisocyanates can also be used.

[0039] For blocking polyisocyanates, any suitable aliphatic, alicyclic, or aromatic alkyl monoalcohols can be used. Examples include aliphatic alcohols such as methyl, ethyl, chloroethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, 3,3,5-trimethylhexyl, decyl, and lauryl alcohol; alicyclic alcohols such as cyclopentanol and cyclohexanol; and aromatic alkyl alcohols such as phenylcarbinol and methylphenylcarbinol. Similarly, suitable diols such as ethanediol, 1,2-propanediol, 1,3-propanediol, and / or polyols can also be used for blocking polyisocyanates. Other suitable blocking agents include hydroxylamines such as ethanolamine, oximes such as methyl ethyl ketone oxime, acetone oxime, and cyclohexanone oxime, and amines such as dibutylamine and diisopropylamine.

[0040] Tris(alkoxycarbonylamino)-1,3,5-triazine (TACT) is also known to those skilled in the art. The use of tris(alkoxycarbonylamino)-1,3,5-triazine as a crosslinker in coating material compositions is known. For example, DE 197 12 940 A1 describes the use of such a crosslinker in basecoat materials. U.S. Pat. No. 5,084,541 describes the preparation of corresponding compounds that can be used as component (c). For the purposes of the present invention, such triazines are encompassed by the term "blocked polyisocyanates."

[0041] Amino resins (aminoplast resins) are also known to those skilled in the art. The amino resins used are preferably melamine resins, more particularly melamine-formaldehyde resins, which are also known to those skilled in the art. However, it is preferable not to use amino resins such as melamine-formaldehyde resins as the crosslinking agent (b). Therefore, the electrodeposition coating material composition of the present invention preferably does not contain amino resins such as melamine-formaldehyde resins.

[0042] The electrodeposition coating material composition of the present invention is preferably used as a one-component (1K) coating composition, and therefore preferably does not contain free polyisocyanate.

[0043] Most preferably, at least one component (b) of the inventive composition is selected from blocked polyisocyanates. Preferred blocked polyisocyanates have, for example, an NCO content of 200 to 300 g / eq, more preferably 225 to 275 g / eq (where g / eq means grams of component per mole of NCO in the component).

[0044] The molar ratio of the hydroxyl groups of component (a) to the NCO groups of component (b) is preferably 1.5 to 3.5, more preferably 2.0 to 3.0.

[0045] Pigments and / or fillers (c) The electrodeposition coating material composition of the present invention contains at least one pigment and / or at least one filler (c).

[0046] The term "pigment" is known to those skilled in the art, for example from DIN 55943 (date: October 2001). "Pigments" in the sense of the present invention preferably refer to powder or flake-like components that are substantially, preferably completely, insoluble in the medium that surrounds them, such as the electrodeposition coating material composition of the present invention. Pigments are preferably substances that can be used as pigments due to their coloring and / or magnetic, electrical and / or electromagnetic properties. Pigments preferably differ from "fillers" in their refractive index, which is ≧1.7.

[0047] The term "filler" is known to those skilled in the art, for example from DIN 55943 (dated October 2001). For the purposes of the present invention, a "filler" is preferably a component that is substantially, preferably completely, insoluble in the application medium, such as the electrodeposition coating material composition of the present invention, and is used in particular to increase the volume. A "filler" in the sense of the present invention preferably differs from a "pigment" in its refractive index, the refractive index of the filler being <1.7.

[0048] Any conventional pigment known to those skilled in the art can be used.Examples of suitable pigments are inorganic and organic color pigments.Examples of suitable inorganic color pigments include white pigments such as titanium dioxide, white zinc, zinc sulfide or lithopone; black pigments such as carbon black, iron manganese black or spinel black; chromatic pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt violet and manganese violet, red iron oxide, cadmium sulfoselenide, molybdate red or ultramarine red; brown iron oxide, mixed brown, spinel phase and corundum phase or chrome orange; or yellow iron oxide, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.Other inorganic color pigments are silicon dioxide, aluminum oxide, aluminum oxide hydrate, especially Boehmit, titanium dioxide, zirconium oxide, cerium oxide, and mixtures thereof. Examples of suitable organic colored pigments include monoazo pigments, disazo pigments, anthraquinone pigments, benzimidazole pigments, quinoacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments, thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments or aniline black.

[0049] Any conventional filler known to those skilled in the art can be used. Examples of suitable fillers include kaolin, dolomite, calcite, chalk, calcium sulfate, barium sulfate, graphite, silicates such as magnesium silicates, especially corresponding phyllosilicates such as hectorite, bentonite, montmorillonite, talc and / or mica, silica, especially fumed silica, hydroxides such as aluminum hydroxide or magnesium hydroxide. Examples of kaolin include commercially available products such as ASP 200 (uncalcined kaolin, manufactured by BASF) or KaMin 2000C (calcined kaolin, manufactured by KaMin) (ASP 200 is preferred). Organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or polymer powders can also be used. For further details, see Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 250, "Fillers".

[0050] The content of pigment + filler, based on the total mass of the electrodeposition material coating composition of the present invention, is preferably in the range of 0.1 to 20.0 mass%, more preferably 0.1 to 15.0 mass%, very preferably 0.1 to 10.0 mass%, particularly preferably 0.1 to 5.0 mass%, and more particularly 0.1 to 2.5 mass%.

[0051] The pigment and / or filler are incorporated into the electrodeposition coating material composition in the form of a pigment paste (II). It is possible, and preferred, for one pigment paste (II) to contain both one or more pigments and / or fillers. Such pastes typically contain at least one polymer used as a grinding resin. Therefore, it is preferred that at least one such polymer be used as a grinding resin in the electrodeposition coating material composition of the present invention. It is also possible for at least one polymer (a) used as a binder in the electrodeposition coating material composition to additionally function as a grinding resin in the pigment paste (II). The grinding resin is preferably an epoxide-amine adduct, which can correspond to and / or encompass the definition of component (a) as outlined above. The polymer used as the grinding resin preferably has building blocks that interact with the pigment surface. Therefore, the grinding resin preferably has the effect of an emulsifier. Quaternary ammonium compounds are often incorporated to improve the properties of the grinding resin. In addition to the grinding resin, further customary additives such as wetting agents or dispersants (optional component (d) described below) and solvents (water and organic cosolvents) may be included. The production of the pigment paste involves a grinding / grinding step, whereby the pigment and / or filler are preferably ground together with the grinding resin and further components / solvents to form a pigment paste. To produce the finished electrodeposition coating material composition, this paste is mixed with the remaining components, in particular the binder dispersion (I). The use of a pigment paste advantageously leads to increased flexibility in the electrodeposition coating, since the pigment / filler and binder of the electrodeposition coating material composition can be easily adapted to the practical requirements at any time via the amount of pigment paste.

[0052] As described above, the composition of the present invention comprises at least one binder dispersion (I). The binder dispersion (I) contains at least one component (a) and at least one component (b). The binder dispersion (I) also typically contains a further optional component (d) as described below. In addition to water, further organic cosolvents may also be part of the binder dispersion (I).

[0053] Further optional ingredients (d) Depending on the desired application, the electrodeposition coating material composition of the present invention can contain one or more commonly employed additional additives as one or more optional components (d). Component (d) is different from any of components (a) to (c) and also different from the composite particles (p) described below. Preferably, these additives are selected from the group consisting of wetting agents, emulsifiers, dispersants, surface-active compounds such as surfactants, flow control aids, solubilizers, antifoaming agents, rheology aids, antioxidants, stabilizers, preferably heat stabilizers, process stabilizers, and UV and / or light stabilizers, flexibilizers, plasticizers, and mixtures of the aforementioned additives. The content of the additives can vary widely depending on the intended use. The content of the additives, based on the total weight of the electrodeposition coating material composition of the present invention, is preferably in the range of 0.1 to 20.0% by weight, more preferably 0.1 to 15.0% by weight, very preferably 0.1 to 10.0% by weight, particularly preferably 0.1 to 5.0% by weight, and more particularly 0.1 to 2.5% by weight.

[0054] Composite particles (p) The composition of the present invention comprises at least one type of composite particle (p) as an essential component. Preferably, exactly one type of composite particle is included. The composite particle (p) comprises at least one metal-containing catalyst (pc), preferably exactly one metal-containing catalyst (pc). Quite obviously, the metal-containing catalyst (pc) is a metal-containing catalyst for catalyzing the chemical reaction between the cathodically depositable polymer (a) and the crosslinker component (b).

[0055] In particular, the metal-containing catalyst (pc) is selected from a tin-containing catalyst or a bismuth-containing catalyst. Even more preferably, the catalyst (pc) is a bismuth-containing catalyst, particularly a bismuth(III)-containing catalyst. Particularly preferably, bismuth-containing catalysts, such as bismuth(III) oxide, basic bismuth(III) oxide, bismuth(III) hydroxide, bismuth(III) carbonate, bismuth(III) nitrate, bismuth(III) nitrite (basic bismuth(III) nitrate), bismuth(III) salicylate and / or bismuth(III) salicylate (basic bismuth(III) salicylate), bismuth(III) carboxylates, such as, in particular, bismuth(III) neodecanoate, and mixtures thereof, can be used. Particularly preferred are water-insoluble catalysts, preferably water-insoluble bismuth-containing catalysts. More particularly preferred are bismuth(III) carboxylates, more preferably bismuth(III) neodecanoate.

[0056] The electrodeposition coating material composition of the present invention preferably contains at least one bismuth(III)-containing catalyst in an amount such that the bismuth(III) content, calculated as metallic bismuth, is in the range of 10 ppm to 20,000 ppm, preferably 100 to 15,000 ppm, more preferably 500 to 10,000 ppm, and particularly preferably 1,000 to 5,000 ppm, based on the total mass of the electrodeposition coating material of the present invention. The amount of bismuth, calculated as metallic bismuth, can be determined by inductively coupled plasma-atomic emission spectroscopy (ICP-OES) in accordance with DIN EN ISO 11885 (dated September 2009). Therefore, the amount of composite particles (p) is preferably selected to correspond to the above-specified amount of bismuth, calculated as metallic bismuth.

[0057] The composite particle (p) comprises at least one (meth)acrylate-based polymer (mp), preferably exactly one such polymer (mp).

[0058] (Meth)acrylate-based polymers are generally known to those skilled in the art. Such polymers contain, in reacted form, acrylate-based and / or methacrylate-based monomers, such as (meth)acrylic acid and esters, nitriles, or amides of (meth)acrylic acid. Of course, (meth)acrylate-based polymers can also contain, in reacted form, further olefinically unsaturated monomers, such as vinyl olefinically unsaturated monomers, α-β unsaturated carboxylic acids, and allyl compounds. Thus, although the majority of the monomers, i.e., more than 30% by weight or more than 50% by weight (based in each case on the total weight of the monomers), are in each case acrylate-based and / or methacrylate-based monomers, such polymers may also contain the aforementioned further olefinically unsaturated monomers. Such olefinically unsaturated monomers may be monoolefinically unsaturated or polyolefinically unsaturated. The preparation of these polymers involves, for example, radical polymerization of the aforementioned olefinically unsaturated monomers.

[0059] (Meth)acrylate-based monoolefinically unsaturated monomers include, for example, (meth)acrylic acid and esters, nitriles or amides of (meth)acrylic acid.

[0060] Esters of (meth)acrylic acid are in particular those having a radical R which is not olefinically unsaturated.

[0061] [ka]

[0062] The radical R may be aliphatic or aromatic. Preferably, the radical R is aliphatic. The radical R may be, for example, an alkyl radical or may contain a heteroatom. An example of a radical R containing a heteroatom is an ether. It is preferred to use at least a monomer in which the radical R is an alkyl radical, but this is not necessarily limited thereto.

[0063] When R is an alkyl radical, it may be a linear, branched, or cyclic alkyl radical. In all three cases, the radical may be unsubstituted or substituted with a functional group. The alkyl radical preferably has 1 to 24 carbon atoms, more preferably 1 to 10 carbon atoms.

[0064] Particularly suitable monounsaturated esters of (meth)acrylic acid having unsubstituted alkyl radicals include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, ethylhexyl (meth)acrylate, propylheptyl (meth)acrylate, 3,3,5-trimethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, cycloalkyl (meth)acrylates such as cyclopentyl (meth)acrylate, isobornyl (meth)acrylate, and also cyclohexyl (meth)acrylate, with n- and tert-butyl (meth)acrylate, and methyl methacrylate being particularly preferred.

[0065] Suitable monounsaturated esters of (meth)acrylic acid having a substituted alkyl radical may be substituted with one or more hydroxyl groups, phosphate ester groups, or amino groups, such as primary, secondary, or tertiary amino groups.

[0066] Monounsaturated esters of (meth)acrylic acid having alkyl radicals substituted with one or more hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, with 2-hydroxyethyl (meth)acrylate being particularly preferred.

[0067] A monounsaturated ester of (meth)acrylic acid having a phosphate ester group is, for example, a phosphate ester of polypropylene glycol monomethacrylate, such as Sipomer PAM 200 commercially available from Rhodia.

[0068] Examples of monosaturated esters of (meth)acrylic acid having an amino group include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, 2-aminoethyl (meth)acrylate hydrochloride, 2-N-morpholinoethyl (meth)acrylate, 2-(diisopropylamino)ethyl (meth)acrylate, and 3-(diisopropylamino)propyl (meth)acrylate.

[0069] Amides of (meth)acrylic acid are known to those skilled in the art, and examples thereof include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-butyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-(1-naphthyl)-N-phenyl(meth)acrylamide, N-(triphenylmethyl)methacrylamide, N-[3-(dimethylamino)-propyl]-(meth)acrylamide, N-[3-(diethylamino)-propyl]-(meth)acrylamide, N-[2 [N-(dimethylamino)-ethyl]-(meth)acrylamide, N-[2-(diethylamino)-ethyl]-(meth)acrylamide, 4-(meth)acryloylmorpholine, N-(3-aminopropyl)-(meth)acrylamide hydrochloride, N-(2-aminoethyl)-(meth)acrylamide hydrochloride, diacetone(meth)acrylamide, N-(hydroxymethyl)-(meth)acrylamide, N-(hydroxyethyl)(meth)acrylamide, N-(isobutoxymethyl)(meth)acrylamide, N-(hydroxyethyl)(meth)acrylamide, N-(3-methoxypropyl)(meth)acrylamide, 2-hydroxypropyl(meth)acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, or N-methylol(meth)acrylamide.

[0070] The vinyl monounsaturated monomer may be a monomer having a radical R' in the vinyl group that is not olefinically unsaturated.

[0071] [ka]

[0072] The radical R' may be aliphatic or aromatic, preferably an aromatic radical.

[0073] The radical R' may be a hydrocarbon radical or may contain a heteroatom. Examples of radicals R' containing a heteroatom are ethers, esters, amides, nitriles, and heterocycles. The radical R' is preferably a hydrocarbon radical. When R' is a hydrocarbon radical, it may be unsubstituted or substituted with a heteroatom, with unsubstituted radicals being preferred. The radical R' is preferably an aromatic hydrocarbon radical.

[0074] Preferred vinyl olefinically unsaturated monomers are the vinyl aromatic hydrocarbons, especially vinyl toluene, alpha-methyl styrene, and especially styrene.

[0075] When they contain heteroatoms, olefinically unsaturated monomers such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N,N-dimethylacrylamide, N-[3-(dimethylamino)-propyl]-methacrylamide, vinyl acetate, vinyl propionate, vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylimidazole, and N-vinyl-2-methylimidazoline are preferred.

[0076] Examples of suitable polyolefinically unsaturated monomers include esters of (meth)acrylic acid and allyl ethers of monohydric or polyhydric alcohols having an olefinically unsaturated radical R''. The radical R'' may be an allyl radical or a (meth)acryloyl radical.

[0077] [ka]

[0078] Preferred polyolefinically unsaturated monomers include ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 2,2-propylene glycol di(meth)acrylate, butane-1,4-diol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, and allyl (meth)acrylate.

[0079] Polyolefinically unsaturated compounds further include acrylic and methacrylic acid esters of alcohols having two or more OH groups, such as trimethylolpropane tri(meth)acrylate or glycerol tri(meth)acrylate, but also trimethylolpropane di(meth)acrylate monoallyl ether, trimethylolpropane (meth)acrylate diallyl ether, pentaerythritol tri(meth)acrylate monoallyl ether, pentaerythritol di(meth)acrylate diallyl ether, pentaerythritol (meth)acrylate triallyl ether, triallylsucrose, and pentaallylsucrose.

[0080] Preferably, the (meth)acrylate-based polymer comprises (a) 40 to 98% by weight, preferably 50 to 88% by weight, of C1 to C6 (meth)acrylic acid. 10-alkyl esters, (b) 2 to 45% by weight, preferably 5 to 30% by weight, of a polyolefinically unsaturated monomer, in particular a diolefinically unsaturated monomer, and (c) 0 to 20% by weight, preferably 2 to 10% by weight, of a monoolefinically unsaturated monomer different from monomer (a). The term "polymer composed of a monomer mixture consisting of" is equivalent to the term "applied to the production (i.e., polymerization) of a polymer." Preferably, the (meth)acrylate-based polymer is composed of the aforementioned monomer mixture.

[0081] In a preferred embodiment, the at least one monomer (c) is selected from monomers having at least one, preferably one, amino group. Even more preferably, the monomer (c) is selected from at least one monomer having at least one, preferably one, amino group (i.e., the monomer (c) is composed exclusively of monomers having at least one, preferably one, amino group). This is because such monomers can be protonated and thus transferred to a cationic state, which means that in the cationic electrodeposition coating process, the composite particles are driven to the substrate to be coated to promote the actual deposition (similar to what occurs with component (a) above).

[0082] The (meth)acrylate-based polymer is preferably prepared in the presence of a metal-containing catalyst, and this in situ preparation lends itself very well to the formation of true composite particles, i.e., particles that are a hybrid of both the (meth)acrylate-based polymer and the catalyst.

[0083] Thus, the principle of composite particle production is preferably based on the preparation of the specific monomers and catalysts described above, preferably together with a free radical initiator, in a reaction medium for polymerizing the monomers. Preferably, the preparation is carried out in an oil-in-water emulsion, in which the monomers and preferably the water-insoluble catalyst, and potentially an organic solvent (e.g., n-butyl acetate) for solubilizing the catalyst, form a dispersed phase in the aqueous dispersion medium. A dispersant is preferably included to promote the formation of the dispersion and prevent the particles from flocculating and coagulating. In a preferred embodiment, the addition of the free radical initiator can be delayed until after the dispersion process. Polymerization of the monomers is then induced, for example, by heating, and optionally controlled by further increasing the temperature, resulting in the formation of the composite particles from the polymer and catalyst. Of course, polymerization can also be induced by other known means, such as a redox initiator or ultraviolet radiation. However, increasing the temperature is preferred. Finally, in this embodiment, the composite particles are available in the form of an aqueous dispersion (or emulsion), i.e., particles present in an aqueous medium. After preparation, the composite particles (p) are preferably present in the form of an aqueous dispersion. This is because it can be applied directly into the electrocoat material of the present invention.

[0084] As mentioned above, the production of particles is preferably carried out in the presence of at least one dispersant. Therefore, the aqueous phase usually contains at least one dispersant to stabilize the droplets of the O / W emulsion during its production. Dispersants suitable for stabilizing oil / water emulsions are known and are described, for example, in EP 2794085 and EP 3007815 (also called protective colloids therein), the teachings of which are expressly incorporated by reference. Typical dispersants include polysaccharides, polyvinyl alcohols, polymers with sulfonate groups, polymers with carboxylate groups, polyvinylpyrrolidone, copolymers of vinylpyrrolidone, and inorganic Pickering stabilizers. Suitable dispersants are typically water-soluble organic polymers. Inorganic Pickering systems, such as colloidal silica and colloidal clay minerals, can also be used as dispersants for this purpose. Pickering stabilizers, also called Pickering systems, can be used alone or in combination with water-soluble organic polymers. Dispersing agents from the polysaccharide group include, for example, cellulose derivatives such as hydroxyethyl cellulose, methylhydroxyethyl cellulose, methyl cellulose and carboxymethyl cellulose, methylhydroxypropyl cellulose, lignin sulfonates, and mixtures thereof.

[0085] Among organic water-soluble polymers, particularly preferred are partially hydrolyzed polyvinyl acetates, also known as partially hydrolyzed polyvinyl alcohols (PVA), having a degree of hydrolysis of 70% to 99.9%, particularly 75 to 99%, and more particularly 80 to 95%. Furthermore, PVA copolymers, such as those described in WO 2015 / 165836, are also suitable. The PVA may be, in particular, a carboxy-modified anionic PVA. Such carboxy-modified PVA preferably has a carboxyl group content of 1 to 6 mol%. In particular, carboxy-modified PVA is used as a dispersant, and its 4% by weight aqueous solution preferably has a viscosity in the range of 20.0 to 30.0 mPa*s at 20°C. Particularly preferred among the group of partially hydrolyzed polyvinyl alcohols are those having a degree of hydrolysis of 70% to 99.9%, particularly 75 to 99%, more particularly 80 to 95%, and especially 85 to 95%. Particularly preferred dispersants are carboxy-modified anionic PVAs having 1 to 6 mol % of carboxyl groups based on the amount of repeating units and a degree of hydrolysis in the range of 75 to 99%, particularly 80 to 95%, and especially 85 to 95%. Among these, those having a viscosity of 20.0 to 30.0 mPa*s at 20°C in a 4% by mass aqueous solution are preferred.

[0086] Also preferred dispersants are salt polymers containing sulfonate groups. Such polymers include homopolymers and copolymers of ethylenically unsaturated sulfonic acids, such as 2-acrylamido-2-methylpropanesulfonic acid, optionally with one or more water-soluble monomers such as acrylamide or methacrylamide and their salts. Also included are lignin-based salts of sulfonic acids, also known as lignin sulfonates or lignosulfonates. Suitable lignin sulfonates may include, for example, sodium lignosulfonate, calcium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate, potassium lignosulfonate, or sulfomethylated lignosulfonate. The aforementioned salts are particularly sodium or ammonium salts of polymers containing sulfonate groups.

[0087] Among organic water-soluble polymers, polymers having carboxyl groups are preferred. Typically, such polymers are homopolymers or copolymers of monoethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, or itaconic acid. Polymers having carboxyl groups are usually used in a partially or completely neutralized form, and the carboxyl groups are converted into anionic carboxylate forms. The counter ions are usually selected from sodium and ammonium.

[0088] Typical processes for producing such composite particles are described exemplarily, for example, in DE-A-10 139 171 and applications WO 2011 / 004006, US 2015 / 361227 A1 and WO 2012 / 110443, which are expressly incorporated herein by reference.

[0089] Without wishing to be bound by any particular theory, it is expected that the above preparation process carried out in an oil-in-water emulsion promotes the formation of capsules, i.e. particles having a shell or wall essentially comprising the resulting (meth)acrylate-based polymer (mp) encompassing a preferably water-insoluble catalyst (pc), which is further preferably solubilized in an organic solvent.

[0090] The composite particles preferably have a particle size (d 50 (volume basis, measured by laser diffraction) (d 50 Obviously, the particle sizes given relate to particle sizes measured in the form in which the particles exist after production, ie preferably in the form of an aqueous dispersion (or emulsion).

[0091] The mass ratio (w / w) of the metal-containing catalyst to the (meth)acrylate-based polymer is preferably 98:2 to 20:80, more preferably 97:3 to 50:50, and most preferably 95:5 to 60:40. The mass ratio is calculated taking into account the total mass of monomers applied to produce the polymer and the mass of the metal catalyst applied. Also, the mass ratio (w / w) of the metal in the metal-containing catalyst (i.e., calculated as metal) to the (meth)acrylate-based polymer is preferably 90:10 to 5:95, more preferably 85:15 to 15:85, and most preferably 80:20 to 20:80.

[0092] The composite particles (p) can be introduced into the composition of the present invention by conventional means. For example, the composite particles (and the respective aqueous dispersions (emulsions) of the particles) can be directly applied to the preparation of the composition as individual recipe components. Alternatively, the particles (and the respective aqueous dispersions (emulsions) of the particles) can be, for example, part of the binder dispersion (I).

[0093] In line with the above, the present invention also relates to a method for producing composite particles (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate polymer (mp), wherein the polymer (mp) is prepared in the presence of the metal-containing catalyst (pc), thus the method comprising the following steps: (1) preparing an oil-in-water emulsion in which the monomers and metal-containing catalyst for producing the polymer (mp) are part of or are the dispersed phase in an aqueous medium; (2) polymerizing the monomer in the oil-in-water emulsion of step (1) using an initiator; Includes.

[0094] Preferably, the oil-in-water emulsion of step (1) comprises at least one protective colloid.

[0095] The present invention also relates to composite particles (p) prepared according to the above method.

[0096] The present invention also provides - providing at least one binder dispersion (I) comprising at least one cathodically depositable polymer (a) and at least one crosslinker (b); - providing at least one pigment paste (II) comprising at least one pigment and / or filler and at least one grinding resin; - optionally providing further components different from components (I) and (II); - mixing the binder dispersion (I), the pigment paste (II) and further potential components of the composition; The present invention relates to a method for producing a cathodic deposition electrodeposition coating material composition, comprising: Here, at least one component comprises at least one composite particle (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate-based polymer (mp), and the polymer (mp) is prepared in the presence of the metal-containing catalyst (pc).

[0097] Quite obviously, all essential and preferred features and embodiments described above in the context of the composition of the invention apply equally to the kit of parts and method of manufacture.

[0098] Electrodeposition coating method A further subject of the present invention is at least steps (1) to (5), i.e. (1) at least partially immersing a conductive substrate in an electrodeposition coating bath containing the electrodeposition coating material composition of the present invention; (2) connecting the substrate as a cathode; (3) depositing the coating film obtained from the electrodeposition coating material composition on a substrate using a direct current; (4) removing the coated substrate from the electrodeposition coating bath; (5) baking the coating film deposited on the substrate; 1. A method for at least partially coating a conductive substrate by cathodic electrodeposition coating comprising:

[0099] All preferred embodiments described herein above in relation to the electrodeposition coating material composition of the present invention are also preferred embodiments in relation to the method of the present invention for at least partially coating a conductive substrate by cathodic electrodeposition coating using this electrodeposition coating material composition.

[0100] Preferably, the method includes a step (4.1) between steps (4) and (5) of rinsing the coated substrate, for example with pure water. This step obviously serves to clean the substrate, i.e., to remove any residual coating material that has not been properly deposited on the substrate.

[0101] The method of the present invention is particularly suitable for the electrocoating of automobile bodies or parts thereof, including respective metal substrates. Accordingly, preferred substrates are automobile bodies or parts thereof. Such substrates are, in particular, metal automobile components, such as lateral control arms, spring-loaded control arms, or dampers. Such components may be cast iron parts or may be manufactured by other established methods known in the art. Furthermore, such substrates are metal automobile bodies, for example, automobile bodies that have been partially stamped to cut out specific parts or form specific shapes, and therefore also contain a relatively large number of edges.

[0102] Suitable conductive substrates for use in accordance with the present invention include all commonly used conductive substrates known to those skilled in the art.The conductive substrate for use in accordance with the present invention is preferably a metal substrate, more preferably steel, preferably bare steel, cold-rolled steel (CRS), hot-rolled steel, galvanized steel such as hot-dip galvanized steel (HDG), alloy galvanized steel (e.g., Galvalume, Galvanal, or Galfan), aluminized steel, aluminum, and magnesium, as well as Zn / Mg alloys and Zn / Ni alloys.A particularly suitable substrate is a part of an automobile body or a complete automobile body for production.

[0103] Each conductive substrate is preferably cleaned and / or degreased before being used in step (1) of the method of the present invention.

[0104] The conductive substrate used in accordance with the present invention is preferably a pretreated substrate, for example, pretreated with at least one metal phosphate, such as zinc phosphate. This type of phosphating pretreatment is usually carried out after the substrate has been cleaned and before the substrate is electrocoated in step (1), and is a pretreatment step commonly used, particularly in the automotive industry. However, pretreatment methods other than phosphating are also possible, such as thin-film pretreatments based on zirconium oxide or typical silanes.

[0105] During steps (1), (2), and (3) of the method of the present invention, the electrodeposition coating material composition of the present invention is cathodically deposited onto the region of the substrate immersed in the bath in step (1). In step (2), the substrate is connected as a cathode, and a voltage is applied between the substrate and at least one counter electrode, either located in the deposition bath or separate from the deposition bath, for example, via an anion-exchange membrane permeable to anions. The counter electrode thus functions as an anode. When a current is passed between the anode and the cathode, a firmly adherent coating is deposited on the cathode, i.e., the immersed portion of the substrate. The applied voltage is preferably in the range of 50 to 500 volts. During steps (1), (2), and (3) of the method of the present invention, the electrodeposition coating bath preferably has a bath temperature in the range of 20 to 45°C.

[0106] The calcination temperature in step (5) is preferably in the range of 100 to 210°C, more preferably 120 to 205°C, very preferably 120 to 200°C, more particularly 125 to 195°C or 125 to 190°C, and most preferably 130 to 185°C or 140 to 180°C.

[0107] After step (5) of the method of the present invention is performed, one or more additional coating layers can be applied on the baked coating film obtained after step (5). For example, a primer and / or filler can be applied, followed by a base coat and a clear coat.

[0108] Therefore, the method of the present invention preferably comprises at least one further step (6), i.e. (6) applying at least one additional coating material composition, different from the composition applied in step (1), at least partially onto the fired coating film obtained after step (5). Includes.

[0109] Base material A further object of the present invention is a conductive substrate at least partially coated with the calcined electrodeposition coating material of the present invention, which corresponds to the calcined coating obtained after step (5) of the method of the present invention.

[0110] All preferred embodiments described herein above in relation to the electrodeposition coating material composition of the present invention and the method of the present invention are also preferred embodiments in relation to the at least partially coated substrate of the present invention.

[0111] Of course, the present invention also encompasses a baked electrodeposition coating layer produced from the electrodeposition coating material composition of the present invention.

[0112] method 1. Determination of Nonvolatile Fraction The non-volatile fraction (solids or solid content) is determined according to DIN EN ISO 3251 (date: June 2019). This involves weighing 1 g of sample into a pre-dried aluminum dish, drying the dish with the sample in a drying oven at 180 °C for 30 minutes, cooling in a desiccator, and weighing again. The residue relative to the total amount of sample used corresponds to the non-volatile fraction (unit: % or mass %).

[0113] 2. Glass transition temperature T g Decision Glass transition temperature T g is determined according to DIN 53765:1994-03 using differential scanning calorimetry (DSC) at a heating rate of 10 K / min.

[0114] 3. Determining pH The pH value was determined according to DIN 55659-1 (January 2012).

[0115] 4. Dry Film Thickness Measurement The film thickness was determined according to DIN EN ISO 2808 (date: May 2007), method 12A, using a Fischer Dualscope FM40 device.

[0116] 5. Determination of acetone resistance Acetone resistance is determined using test panels (GB 6800 / OC Chemetall) that have been ED coated and cured according to the five-step procedure described above. The coated panels are rubbed with a hammer-like tool with a head containing a 1 kg weight and acetone-soaked cotton wool. The hammer-like tool and acetone-soaked cotton wool are pushed and pulled across the coating surface without additional pressure, with one back-and-forth in each direction counting as one double rub. 200 double rubs equates to excellent acetone resistance; i.e., the maximum number of double rubs performed in this test is 200. The number of double rubs reported below in the results section corresponds to the number of times that delamination of the cured coating material is observed (in the case of the 200 acetone resistance result, no such delamination occurs).

[0117] 6.Average particle size The particle size distribution of the composite particles was measured by laser diffraction according to ISO 13320 EN:2020-01. A Malvern Mastersizer 2000 was used. The data were processed according to Mie theory by software using the "Universal Model" provided by Malvern Instruments. The parameters of general interest are d n Values, for example, n=10, 50, 90, i.e., d 10 , d 50 and d 90 The value is d 50 The value can be, for example, the volume-based mean median d 50 The particle size. [Example]

[0118] The following examples further illustrate the present invention but are not to be construed as limiting its scope.

[0119] 1. Preparation of the composite particles (p) applied according to the invention Below, we describe a general fabrication protocol, followed by examples of the fabrication of two selected composite particles. Finally, we provide a comprehensive list of composite particles fabricated according to the general fabrication protocol.

[0120] 1.1 General manufacturing protocol Water and a commercially available aqueous polyvinyl alcohol solution (10% by weight) were mixed to obtain Mixture 1. Separately, Mixture 2 was prepared, containing a bismuth neodecanoate catalyst, an optional organic solvent, and the monomers used to prepare the (meth)acrylate-based polymer. Mixture 2 was then emulsified in Mixture 1, for example, using a silent crusher (rotor-stator dispersing tool) at 18,000 rpm for 5 minutes to obtain an oil-in-water emulsion. The temperature was maintained below 35°C using an ice bath during the emulsification process. The emulsion was then transferred to a glass reactor equipped with an anchor stirrer and a water condenser and stirred at 130 rpm. Nitrogen gas was circulated through the reactor throughout the polymerization. A radical initiator (thermal initiator) was then added to the medium, and the temperature was increased: starting from 20°C and reaching 75°C over 60 minutes (linear rate). The temperature was then increased to 85°C within 60 minutes (linear rate) and maintained there for 60 minutes. It was then cooled (linear rate) to room temperature (20°C) over 60 minutes. At the start of the cooling, an initiator (redox initiator partner) was added to the medium over 50 minutes to reduce the residual monomer content.

[0121] The monomers used were: MMA: methyl methacrylate, tBMA: tert-butyl methacrylate, DMAPMA: dimethylaminopropyl methacrylamide, nBA: n-butyl acrylate, BDDA: 1,4-butanediol diacrylate. The organic solvent used was n-butyl acetate (BA). The redox initiator partner system used was Vitamin C (L(+)-ascorbic acid) and tBHP (tert-butyl hydroperoxide).

[0122] 1.2a) Example 1: MMA / tBMA / DMAPMA / BDDA = 60 / 25 / 5 / 10 - K-Kat XK 651 / BA = 75 / 25 The composite particles were prepared by mixing (i) MMA / tBMA / DMAPMA / BDDA in a 60 / 25 / 5 / 10 wt% ratio and (ii) K-Kat XK 651 (King Industries) as the active catalyst and BA as the solvent in a 75 / 25 wt% ratio. The target ratio of metal-containing catalyst to polymer was 90 / 10 wt%. The total active content in the final dispersion was targeted to be 32.15 wt%.

[0123] First, 270.0 g of a 10% by weight aqueous solution of Mowiol 40-88 was diluted with 271.64 g of demineralized water and 2.16 g of a 2.5% by weight aqueous solution of sodium nitrite to prepare an aqueous solution. Next, 364.5 g of K-Kat XK 651, 121.5 g of BA, 32.4 g of MMA, 13.5 g of tBMA, 2.7 g of DMAPMA, and 5.4 g of BDDA were mixed to obtain an oil phase. In a 2 L glass reactor, the oil phase was emulsified into the aqueous phase at 3,500 rpm for 40 minutes using a laboratory dissolver equipped with a 5 cm diameter dissolver disc. The emulsion temperature was maintained below 35°C using an ice bath during the emulsification process. The glass reactor was then equipped with an anchor stirrer and a water condenser and stirred at 130 rpm. Nitrogen gas was purged into the reactor throughout the polymerization. 3.24 g of tert-butyl peroxyneodecanoate was added to the dispersion as a thermal initiator, and the temperature was increased: starting from 20°C and reaching 75°C over 60 minutes (linear rate). The temperature was then increased to 85°C within 60 minutes (linear rate) and held for 60 minutes. The dispersion was then cooled to room temperature (20°C) within 60 minutes (linear rate). At the start of cooling, 15.66 g of a 10 wt. % tBHP solution in water was added within 3 minutes, while 30.94 g of a 10 wt. % Vit C solution in water was added continuously over 50 minutes to reduce the residual monomer content.

[0124] Overall, 1134 g of monodisperse composite particles (d 50 = 1.5 μm, d 90 An aqueous dispersion of the nanoparticles (diameter: 2.3 μm) was obtained.

[0125] 1.2b) Example 2: MMA / DMAPMA / BDDA=80 / 5 / 15-K-Kat XK 651 The composite particles were prepared using (i) MMA / DMAPMA / BDDA in a ratio of 80 / 5 / 15 wt% and (ii) K-Kat XK 651 (King Industries) as the active catalyst. The target ratio of metal-containing catalyst to polymer was 90 / 10 wt%. The total active content in the final dispersion was targeted to be 35.75 wt%.

[0126] First, an aqueous solution was prepared by diluting 405 g of a 10% by weight aqueous solution of Mowiol 40-88 with 160.95 g of demineralized water and 4.32 g of a 2.5% by weight aqueous solution of sodium nitrite. 0.03 g of Tego Foamex 3062 antifoaming agent was added. Next, 486 g of K-Kat XK 651, 43.2 g of MMA, 2.7 g of DMAPMA, and 8.1 g of BDDA were mixed to obtain an oil phase. In a 2 L glass reactor, the oil phase was emulsified into the water phase at 3,500 rpm for 40 minutes using a laboratory dissolver equipped with a 5 cm diameter dissolver disc. The emulsion temperature was maintained below 35°C using an ice bath during the emulsification process. The glass reactor was then equipped with an anchor stirrer and a water condenser and stirred at 130 rpm. 100 g of demineralized water was added. Nitrogen gas was circulated in the reactor throughout the polymerization. 3.24 g of tert-butyl peroxyneodecanoate was added to the dispersion as a thermal initiator, and the temperature was increased: starting from 20 °C and reaching 75 °C over 60 minutes (linear rate). The temperature was then increased to 85 °C within 60 minutes (linear rate) and maintained at that temperature for 60 minutes. The mixture was then cooled to room temperature (20 °C) within 60 minutes (linear rate). At the start of the cooling period, 30.94 g of a 10% by weight aqueous solution of Vit C was added within 3 minutes, while 15.66 g of a 10% by weight aqueous solution of tBHP was added continuously to the medium over 50 minutes to reduce the residual monomer content. Finally, when the temperature reached approximately 20 °C, an additional 100 g of water was added.

[0127] Overall, 1360 g of monodisperse composite particles (d 50 = 1.4 μm, d 90 An aqueous dispersion of the nanoparticles (particle size: 2.2 μm) was obtained.

[0128] 1.3 List of composite particles Table 1 shows a variety of composite particles prepared according to the general procedure outlined in 1.1.

[0129] [Table 1]

[0130] 2. Preparation of aqueous cathodic deposition electrodeposition coating material composition 2.1 Pigment paste (II) A standard pigment paste P1, conventionally used in the preparation of aqueous cathodically depositable electrodeposition coating material compositions, was prepared by (i) mixing the respective components in a dissolver and (ii) grinding the mixture from (i) using a standard mill under conventional conditions.

[0131] Pigment Paste P1 contains an aqueous dispersion of an epoxy-amine adduct as the grinding resin (i.e., a resin meeting the requirements of component (a), with a solids content of 40%, but different from component (a) described below for Binder Dispersion (I)). Paste P1 also contains bismuth(III) nitrite as a catalyst, carbon black as a black pigment and titanium dioxide as a white pigment, and kaolin as a filler. Further components include water and additives customary for aqueous cathodically depositable electrodeposition coating material compositions. The solids content of Pigment Paste P1 was 65%. The amount of bismuth(III), calculated as metallic bismuth, was 4.26% based on the total mass of Pigment Paste P1.

[0132] Pigment paste P2 was prepared in the same way as pigment paste P1, with the same types and amounts of ingredients, except that bismuth(III) nitrite was not applied.

[0133] 2.2 Binder dispersion (I) Two systems (Binder Dispersion (I).1 and Binder Dispersion (I).2) conventionally applied in electrodeposition coating material compositions were used as standard binder dispersions (I). The binder dispersions contained an aqueous dispersion of an epoxy-amine adduct as binder resin (component (a)), a blocked polyisocyanate as crosslinking component (b), and further components such as customary additives, organic cosolvents, and water. The components of the binder dispersions were added in different orders, resulting in different mixing (dissolving) and dispersion steps. The two binder dispersions differed with respect to the type of crosslinking agent (b), i.e., the blocked polyisocyanate, more specifically the blocking agent of the blocked polyisocyanate. This resulted in binder dispersion (I).2 being more reactive (i.e., having a lower deblocking temperature of the blocked polyisocyanate). The solids content of both binder dispersions was 38%.

[0134] 2.3 Electrodeposition coating material composition Electrodeposition coating material compositions were prepared from the pigment pastes and binder dispersions described above. The comparative system was prepared from pigment paste P1 and binder dispersion, while the composition of the present invention was prepared from pigment paste P2, binder dispersion, and also composite particles according to Example 2 above.

[0135] Details of each bath and its ingredients are shown in Table 2. The ingredients in the table were mixed in this order to form an electrodeposition coating material composition for application (item 2. below).

[0136] [Table 2]

[0137] 3. Electrodeposition coating of the substrate The coating films obtained from the electrodeposition coating material composition described above in Section 2.3 were deposited on cathodically connected test panels at a deposition voltage of 200-260 V (the deposition time was appropriately varied to obtain a total charge of about 40-42 As) at a coating bath temperature of 32°C, followed by baking for 15 minutes at a substrate temperature of 175°C, to obtain a coating layer thickness of about 20-22 micrometers. Different amounts of phosphate, i.e., 0 ppm (control), 200 ppm, and 400 ppm, were introduced into the bath before deposition.

[0138] The test panels used cold rolled steel substrates (Gardobond® GB26S 6800 OC) that had been pretreated with a phosphating composition (spray application of a zinc manganese phosphating composition).

[0139] Table 3 provides a list of all the cured coatings that were produced.

[0140] [Table 3]

[0141] 3. Characterization of coated substrate The glass transition temperature T of the cured coating was determined by the above method. g and acetone resistance were investigated.

[0142] Table 4 shows the respective data for the corrosion tests.

[0143] [Table 4]

[0144] The results showed that, due to their high glass transition temperatures and high acetone resistance, the compositions and cured coatings of the present invention exhibit significantly improved film-forming and curing capabilities, respectively, when phosphate poisoning was increased. Specifically, cured Coatings B and C (and H and I) exhibited a significant decrease in film-forming and curing efficiency at phosphate levels of 200 ppm and 400 ppm, respectively, while Systems E and F (and K and L) of the present invention still exhibited optimal film-forming behavior despite phosphate poisoning. Comparison of Coatings B and C with H and I reflects the higher reactivity of Binder Dispersion (I).2 compared to Dispersion (I).1. However, this increased reactivity cannot accommodate phosphate poisoning, and Systems H and I also do not exhibit sufficient film-forming and crosslinking efficiency.

Claims

1. (I) at least one binder dispersion comprising at least one cathodically depositable polymer (a) and at least one crosslinker component (b); and (II) at least one pigment paste containing at least one pigment and / or filler (c) and at least one polymer as grinding resin; An aqueous cathodically depositable electrodeposition coating material composition comprising: An aqueous cathodically depositable electrodeposition coating material composition, wherein the composition also comprises at least one composite particle (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate polymer (mp).

2. 2. The aqueous cathodically depositable electrodeposition coating material composition of claim 1, wherein at least one epoxide-amine adduct is present as the at least one polymer (a).

3. 3. The aqueous cathodically depositable electrodeposition coating material composition according to claim 1, wherein at least a blocked polyisocyanate is present as at least one crosslinker (b).

4. 3. The aqueous cathodically depositable electrodeposition coating material composition according to claim 1 or 2, wherein the metal-containing catalyst (pc) is a bismuth(III)-containing catalyst.

5. The polymer (mp) contains at least (a) 40 to 98 mass % of C of (meth)acrylic acid １ ~C １０ 3. The aqueous cathodic deposition electrodeposition coating material composition according to claim 1, comprising a monomer mixture consisting of (a) an alkyl ester, (b) 2 to 45% by weight of a polyolefinically unsaturated monomer, and (c) 0 to 20% by weight of a monoolefinically unsaturated monomer different from monomer (a).

6. 3. The aqueous cathodically depositable electrodeposition coating material composition according to claim 1 or 2, wherein said polymer (mp) is prepared in the presence of said metal-containing catalyst (pc).

7. A method for producing composite particles (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate polymer (mp), wherein said polymer (mp) is prepared in the presence of said metal-containing catalyst (pc), said method comprising the following steps: (1) preparing an oil-in-water emulsion in which the monomers for producing the polymer (mp) and the metal-containing catalyst are part of or are the dispersed phase in an aqueous medium; (2) polymerizing the monomer in the oil-in-water emulsion of step (1) using an initiator; A method comprising:

8. 8. The method of claim 7, wherein the oil-in-water emulsion of step (1) comprises at least one dispersant.

9. Composite particles (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate polymer (mp) prepared according to the method of claim 7.

10. providing at least one binder dispersion (I) comprising at least one cathodically depositable polymer (a); - providing at least one pigment paste (II) comprising at least one pigment and / or filler; - mixing said binder dispersion (I), said pigment paste (II) and further potential components of the composition; A method for producing a cathodic deposition electrodeposition coating material composition, comprising: A method wherein at least one component of the composition comprises at least one composite particle (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate polymer (mp).

11. At least steps (1) to (5), i.e. (1) at least partially immersing a conductive substrate in an electrodeposition coating bath containing the electrodeposition coating material composition of claim 1; (2) connecting the substrate as a cathode; (3) depositing a coating film obtained from the electrodeposition coating material composition on the substrate using a direct current; (4) removing the coated substrate from the electrodeposition coating bath; (5) firing the coating film deposited on the substrate; 1. A method for at least partially coating a conductive substrate by cathodic electrodeposition coating, comprising:

12. A conductive substrate at least partially coated in a baked form with the electrodeposition coating material composition according to claim 1 and / or the electrodeposition coating material composition produced according to claim 10, and / or at least partially coated by the method according to claim 11.

13. A method for enhancing the phosphate contamination resistance of an aqueous cathodically depositable electrodeposition coating material composition, comprising adding at least one type of composite particle (p) comprising at least one metal-containing catalyst (pc) and at least one (meth)acrylate polymer (mp) to the electrodeposition coating material composition.

14. 14. The method according to claim 13, wherein said polymer (mp) is prepared in the presence of said metal-containing catalyst (pc).

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