Electrodepositable coating composition

Abstract

The present disclosure relates to an electrodepositable coating composition comprising: a cationic salt group-containing film-forming resin dispersed in an aqueous medium, the cationic salt group-containing film-forming resin comprising a reaction product of a reaction mixture comprising: (a) a polyepoxide; (b) at least one polyol comprising an aliphatic substituted phenol, the aliphatic substituted phenol comprising at least two phenolic hydroxyl groups; and (c) a cationic salt group forming agent. The present disclosure also relates to a method of coating a substrate and a coated substrate.

Description

Technical Field

[0001] The present disclosure relates to an electrodepositable coating composition, a coating, a coated substrate, and a method of coating a substrate. Background Art

[0002] Electrodeposition, a coating application method, involves depositing a film-forming composition onto a conductive substrate immersed in an electrodepositable coating composition under the influence of an applied electric potential. Compared to non-electrophoretic coating methods, electrodeposition has gained popularity in the coatings industry due to its higher coating utilization, excellent corrosion resistance, and low environmental impact. Bisphenol A is commonly used as a component of the resin used in electrodepositable coating compositions, but bisphenol A presents health risks. There is a need for an electrodepositable coating composition with reduced bisphenol A content. BRIEF DESCRIPTION OF THE DRAWINGS

[0003] Figure 1 Shown is an isometric view of the box used in the "Nagoya Box Method" referenced in the Examples section.

[0004] Figure 2 A cross-sectional view of the box used in the "Nagoya Box Method" cited in the Examples section is shown. Summary of the Invention

[0005] The present disclosure provides an electrodepositable coating composition, comprising: a film-forming resin containing a cationic salt group, which is dispersed in an aqueous medium, wherein the film-forming resin containing a cationic salt group comprises the reaction product of a reaction mixture, wherein the reaction mixture comprises: (a) a polyepoxide; (b) at least one polyol comprising an aliphatic-substituted phenol, wherein the aliphatic-substituted phenol comprises at least two phenolic hydroxyl groups; and (c) a cationic salt group-forming agent.

[0006] The present disclosure also provides a method for coating a substrate, the method comprising electrophoretically applying an electrodepositable coating composition to at least a portion of the substrate, wherein the electrodepositable coating composition comprises: a film-forming resin containing cationic salt groups, which is dispersed in an aqueous medium, the film-forming resin containing cationic salt groups comprising the reaction product of a reaction mixture, the reaction mixture comprising: (a) a polyepoxide; (b) at least one polyol comprising an aliphatic-substituted phenol, the aliphatic-substituted phenol comprising at least two phenolic hydroxyl groups; and (c) a cationic salt group-forming agent.

[0007] The present disclosure further provides a coated substrate comprising a cured coating film comprising the reaction product of: (1) a film-forming resin containing a cationic salt group dispersed in an aqueous medium, the film-forming resin containing a cationic salt group comprising the reaction product of a reaction mixture comprising: (a) a polyepoxide; (b) at least one polyol comprising an aliphatic-substituted phenol, the aliphatic-substituted phenol comprising at least two phenolic hydroxyl groups; and (c) a cationic salt group-forming agent; and (2) a curing agent. DETAILED DESCRIPTION

[0008] The present disclosure relates to an electrodepositable coating composition comprising: a film-forming resin containing cationic salt groups dispersed in an aqueous medium, the cationic film-forming resin comprising the reaction product of a reaction mixture comprising: (a) a polyepoxide; (b) at least one polyol comprising an aliphatic-substituted phenol, the aliphatic-substituted phenol comprising at least two phenolic hydroxyl groups; and (c) a cationic salt group-forming agent.

[0009] As used herein, the term "electrodepositable coating composition" refers to a composition capable of being deposited onto a conductive substrate under the influence of an electric potential applied between two electrodes immersed in the electrodepositable coating composition, wherein one of the electrodes is the substrate to be coated.

[0010] As used herein, the term "film-forming polymer containing cationic salt groups" refers to a polymer containing at least partially neutralized cationic groups such as sulfonium groups and ammonium groups that impart a positive charge. As used herein, the term "polymer" encompasses, but is not limited to, oligomers and both homopolymers and copolymers.

[0011] As used herein, the term "polyepoxide" refers to a compound or polymer having at least two epoxy functional groups, such as at least three, at least four, or more.

[0012] As used herein, the term "polyol" refers to a compound or polymer having at least two hydroxyl functional groups, such as at least three, at least four, or more.

[0013] As used herein, the term "aliphatic-substituted phenol" refers to a compound comprising at least one phenol comprising at least one alkyl substituent covalently bonded to the phenyl ring (i.e., phenyl group) of the phenol and further comprising at least one hydroxyl functional group (i.e., phenolic hydroxyl group). The at least one alkyl substituent may optionally comprise another phenolic hydroxyl functional group by replacing the alkyl substituent with one or more substituted or unsubstituted phenyl groups, provided that the alkyl substituent is not [—C(R)Ph], wherein each R is independently CH or H if no other alkyl substituent is present on any of the phenyl groups of the aliphatic-substituted phenol. The aliphatic-substituted phenol may optionally further comprise other substituents.

[0014] As used herein, the term "phenolic hydroxyl group" refers to a hydroxyl group covalently bonded as a substituent to a benzene ring (ie, a phenyl group).

[0015] As used herein, the term "alkyl" refers to a hydrocarbon chain substituent corresponding to an alkane minus one hydrogen, and may be saturated or unsaturated. Alkyl substituents may be straight or branched and may contain one or more non-aromatic hydrocarbon rings.

[0016] As used herein, the term "unsaturated aliphatic group" refers to an alkyl group having at least one degree of unsaturation (ie, at least one unsaturated group, [-C(R)=C(R)-], where each R is independently an alkyl group or H).

[0017] As used herein, the term "phenolic lipid" refers to a benzene ring having at least one phenolic hydroxyl functional group and at least one aliphatic substituent comprising at least three carbon atoms covalently bonded to the benzene ring.

[0018] Polyepoxides can include any compound or mixture of compounds having two epoxide groups per molecule.

[0019] The polyepoxide may include an aromatic polyepoxide, an aliphatic polyepoxide, or any combination thereof.

[0020] As used herein, "aromatic polyepoxide" refers to a polyepoxide having at least one aryl group. As used herein, "aryl" refers to a hydrocarbon having a delocalized conjugated π-system having alternating covalent double bonds and covalent single bonds between carbon atoms to form one or more coplanar hydrocarbon rings.

[0021] Non-limiting examples of aromatic polyepoxides include polyglycidyl ethers of aromatic polyphenols, such as diglycidyl ethers of bisphenol A, bisphenol S, bisphenol F, or biphenol. As will be appreciated, such polyepoxides can be produced by etherifying aromatic polyphenols with epichlorohydrin in the presence of a base. Suitable polyphenols that can be used to produce polyepoxides include, but are not limited to, dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)propane; 1,1-bis(4-hydroxyphenyl)isobutane; 2,2-bis(4-hydroxytert-butylphenyl)propane; bis(2-hydroxynaphthyl)methane; 1,5-dihydroxynaphthalene; 1,1-bis(4-hydroxy-3-allylphenyl)ethane; and 4,4-bis(4'-hydroxyphenyl)valeric acid. Another class of useful polyepoxides can similarly be produced by polyphenol resins containing aromatic groups. Additionally, addition polymers containing pendant epoxy groups are prepared by copolymerizing a plurality of polymerizable ethylenically unsaturated monomers, at least one of which is an epoxy-containing monomer and at least one of which has an aromatic group, for example, monovinyl aromatic monomers such as styrene and vinyltoluene.

[0022] The aromatic polyepoxide may include those that do not contain any residues of bisphenol A, bisphenol S, and / or bisphenol F, such that the aromatic polyepoxide and the resulting reaction product are free of residues of bisphenol A, bisphenol S, and / or bisphenol F. Non-limiting examples of aromatic polyepoxides include novolac resins, di- or polyglycidyl ethers of any of the aliphatic-substituted phenols described below, and diglycidyl ethers of dihydroxybenzenes such as catechol, resorcinol, or hydroquinone. For example, the aromatic polyepoxide may include a compound having the following structure:

[0023]

[0024] wherein each R independently comprises hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, and n is an integer from 1 to 3. Another non-limiting example of an aromatic polyepoxide is a compound having the following structure:

[0025]

[0026] Another non-limiting example of an aromatic polyepoxide is a compound having the following structure:

[0027]

[0028] Another non-limiting example of an aromatic polyepoxide is a compound having the following structure:

[0029]

[0030] Another non-limiting example of an aromatic polyepoxide is a compound having the following structure:

[0031]

[0032] As used herein, "aliphatic polyepoxide" refers to a polyepoxide that does not contain aromatic groups.

[0033] Non-limiting examples of aliphatic polyepoxides include addition polymers containing pendant epoxy groups. Such polymers can be prepared by copolymerizing a variety of polymerizable ethylenically unsaturated monomers, at least one of which is an epoxy-containing monomer, such as glycidyl acrylate or glycidyl methacrylate. Any suitable ethylenically unsaturated monomer that does not contain groups reactive with epoxy groups can be used as a comonomer. Exemplary such monomers include α,β-ethylenically unsaturated monomers, such as unsaturated carboxylic acid esters of saturated alcohols having 1 to 8 carbon atoms.

[0034] Other non-limiting examples of aliphatic polyepoxides include polyglycidyl ethers of hydrogenated polyphenols. As will be appreciated, such polyepoxides can be produced by etherifying hydrogenated polyphenols with epichlorohydrin in the presence of a base. Non-limiting examples include hydrogenated diglycidyl ethers of bisphenol A, bisphenol S, or bisphenol F, diglycidyl ethers of glycols (e.g., diglycidyl ethers of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, etc.), and combinations thereof.

[0035] The polyepoxide may have a number average molecular weight (M) of at least 100 g / mol, such as at least 150 g / mol. n The polyepoxide may have a number average molecular weight (M) of not more than 10,000 g / mol, such as not more than 5,000 g / mol, such as not more than 1,000 g / mol. n The polyepoxide may have a number average molecular weight (M) of 100 g / mol to 10,000 g / mol, such as 100 g / mol to 5,000 g / mol, such as 100 g / mol to 1,000 g / mol, such as 150 g / mol to 10,000 g / mol, such as 150 g / mol to 5,000 g / mol, such as 150 g / mol to 1,000 g / mol. n ).

[0036] As used herein, unless otherwise indicated, the term "number average molecular weight (M)" refers to n )" means the number average molecular weight (M) as determined by gel permeation chromatography using the following n): A Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards with molecular weights ranging from approximately 500 g / mol to 900,000 g / mol, dimethylformamide (DMF) with 0.05 M lithium bromide (LiBr) as eluent at a flow rate of 0.5 mL / min, and an Asahipak GF-510HQ column were used for separation.

[0037] The polyepoxide may have an epoxy equivalent weight of at least 50 g / equivalent, such as at least 100 g / equivalent, such as at least 170 g / equivalent. The polyepoxide may have an epoxy equivalent weight of no more than 3,000 g / equivalent, such as no more than 1,500 g / equivalent, such as no more than 1,000 g / equivalent, such as no more than 500 g / equivalent, such as no more than 360 g / equivalent, such as no more than 200 g / equivalent. The polyepoxide may have a weight of 50 g / equivalent to 3,000 g / equivalent, such as 50 g / equivalent to 1,500 g / equivalent, such as 50 g / equivalent to 1,000 g / equivalent, such as 50 g / equivalent to 500 g / equivalent, such as 50 g / equivalent to 360 g / equivalent, such as 50 g / equivalent to 200 g / equivalent, such as 100 g / equivalent to 3,000 g / equivalent, such as 100 g / equivalent to 1,500 g / equivalent, such as 100 g / equivalent to 1,000 g / equivalent. , such as 100 g / equivalent to 500 g / equivalent, such as 100 g / equivalent to 360 g / equivalent, such as 100 g / equivalent to 200 g / equivalent, such as 170 g / equivalent to 3,000 g / equivalent, such as 170 g / equivalent to 1,500 g / equivalent, such as 170 g / equivalent to 1,000 g / equivalent, such as 170 g / equivalent to 500 g / equivalent, such as 170 g / equivalent to 360 g / equivalent, such as 170 g / equivalent to 200 g / equivalent. As used herein, "epoxide equivalent weight" is determined by dividing the theoretical molecular weight of the polyepoxide by the number of epoxide groups present in the epoxy-containing compound. In the case of oligomeric or polymeric epoxy compounds, the epoxy equivalent weight is determined by dividing the average molecular weight of the epoxy compound by the average number of epoxide groups present in the molecule. Epoxide equivalent weight can also be determined by titrating the sample using a Metrohm 808 or 888 Titrando, using a mass of polyepoxide of 0.06 g per 100 g / eq predicted epoxide equivalent weight. The sample is dissolved in 20 mL of dichloromethane (additional solvent can be used to ensure complete dissolution; methanol or tetrahydrofuran can be used as a co-solvent), followed by the addition of 40 mL of glacial acetic acid. One gram of tetraethylammonium bromide is added to the solution prior to titration with 0.1 N perchloric acid.

[0038] Based on the total solid weight of the reaction mixture, the polyepoxide can account for at least 5 weight %, such as at least 20 weight %, such as at least 25 weight %, such as at least 40 weight %, such as at least 50 weight %, such as at least 60 weight %, such as at least 70 weight %, such as at least 80 weight %.Based on the total solid weight of the reaction mixture, the polyepoxide can account for no more than 95 weight %, such as no more than 75 weight %, such as no more than 60 weight %, such as no more than 50 weight %, such as no more than 40 weight %. Based on the total solid weight of the reaction mixture, the polyepoxide may comprise 5% to 95% by weight, such as 5% to 75% by weight, such as 5% to 60% by weight, such as 5% to 50% by weight, such as 5% to 40% by weight, such as 20% to 95% by weight, such as 20% to 75% by weight, such as 20% to 60% by weight, such as 20% to 50% by weight, such as 20% to 40% by weight, such as 25% to 95% by weight, such as 25% to 75% by weight, such as 25% to 60% by weight. %, such as 25% to 50% by weight, such as 25% to 40% by weight, such as 40% to 95% by weight, such as 40% to 75% by weight, such as 40% to 60% by weight, such as 40% to 50% by weight, such as 50% to 95% by weight, such as 50% to 75% by weight, such as 50% to 60% by weight, such as 60% to 95% by weight, such as 60% to 75% by weight, such as 70% to 95% by weight, such as 70% to 75% by weight, such as 80% to 95% by weight. The film-forming resin reaction product containing cationic salt groups can contain the residue of the polyepoxide in the same amount as the residue of the polyepoxide present in the reaction mixture.

[0039] The alkylated phenol may comprise any suitable compound. For example, the aliphatic substituted phenol may comprise a compound having structure (I):

[0040]

[0041] wherein each of A1 to A6 independently comprises a hydroxyl group, hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, wherein at least two of A1 to A6 are hydroxyl groups, and at least one of A1 to A6 is an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group. In a non-limiting example, at least one of A1 to A6 may comprise an alkyl group having at least three carbon atoms. A non-limiting example of an aliphatic-substituted phenol having structure (I) is cardanol.

[0042] Aliphatic substituted phenols may include compounds having structure (II):

[0043]

[0044] wherein each of A1 to A5 independently comprises a hydroxyl group, hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, and at least one of A1 to A5 is a hydroxyl group; each of B1 to B5 independently comprises a hydroxyl group, hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, and at least one of B1 to B5 is a hydroxyl group; and Z comprises a divalent organic linking group and is not [—C(R)—], wherein if four of A1 to A5 and four of B1 to B5 are hydrogen, each R is independently CH or H. For example, one of A1 to A5 comprises an unsaturated aliphatic group, and one of B1 to B5 comprises an unsaturated aliphatic group. For example, wherein one of A1 to A5 comprises an unsaturated aliphatic group containing 3 or more carbon atoms and having a terminal ethylenically unsaturated group, and / or one of B1 to B5 comprises an unsaturated aliphatic group containing 3 or more carbon atoms and having a terminal ethylenically unsaturated group. The divalent organic linking group of Z comprises an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic divalent group having 1 to 50 carbon atoms, such as 1 to 30 carbon atoms, such as 1 to 20 carbon atoms, such as 1 to 15 carbon atoms.

[0045] Non-limiting examples of aliphatic-substituted phenols comprising compounds having structure (II) can include the reaction product of (1) a phenolic lipid comprising an unsaturated aliphatic group and (2) phenol.

[0046] Aliphatic substituted phenols may include cardanol derivatives. As used herein, "cardanol" refers to a meta-substituted phenol ring having a mono-, di-, or tri-unsaturated carbon chain, such as 5 to 25 carbon chains, such as 10 to 20 carbon chains, such as 15 carbon chains, and "cardanol derivatives" are compounds derived from cardanol. Non-limiting examples of cardanol derivatives of aliphatic substituted phenols are compounds having structure (III):

[0047]

[0048] For example, the compound of structure (III) may include the reaction product of cardanol and phenol. Another non-limiting example of a cardanol derivative of an aliphatic substituted phenol is a compound having structure (IV):

[0049]

[0050] wherein each R independently comprises hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, and n is an integer from 1 to 3.

[0051] Aliphatic substituted phenols may also include diallyl bisphenol A. Diallyl bisphenol A has structure (V):

[0052]

[0053] A non-limiting class of aliphatically substituted phenols includes phenolic lipids.

[0054] The aliphatic-substituted phenol may have a theoretical hydroxyl value of at least 50 mg KOH / gram of aliphatic-substituted phenol, such as at least 100 mg KOH / gram, such as at least 150 mg KOH / gram. The aliphatic-substituted phenol may have a theoretical hydroxyl value of no more than 2,000 mg KOH / gram of aliphatic-substituted phenol, such as no more than 700 mg KOH / gram. The aliphatic-substituted phenol may have a theoretical hydroxyl value of 50 mg KOH / gram to 2,000 mg KOH / gram of aliphatic-substituted phenol, such as 50 mg KOH / gram to 700 mg KOH / gram, such as 100 mg KOH / gram to 2,000 mg KOH / gram, such as 100 mg KOH / gram to 700 mg KOH / gram, such as 150 mg KOH / gram to 2,000 mg KOH / gram, such as 150 mg KOH / gram to 700 mg KOH / gram. As used herein, the term "theoretical hydroxyl value" generally refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid absorbed by one gram of a chemical substance containing free hydroxyl groups during acetylation, and is determined herein by theoretically calculating the number of free hydroxyl groups theoretically present in one gram of aliphatic-substituted phenol.

[0055] The aliphatic-substituted phenol may have a number average molecular weight (M) of at least 110 g / mol, such as at least 150 g / mol. n The aliphatic-substituted phenol may have a number average molecular weight (M) of not more than 10,000 g / mol, such as not more than 5,000 g / mol, such as not more than 1,000 g / mol. nThe aliphatic-substituted phenol may have a number average molecular weight (M) of 110 g / mol to 10,000 g / mol, such as 110 g / mol to 5,000 g / mol, such as 110 g / mol to 1,000 g / mol, such as 150 g / mol to 10,000 g / mol, such as 150 g / mol to 5,000 g / mol, such as 150 g / mol to 1,000 g / mol. n ).

[0056] Based on the total solid weight of the reaction mixture, the aliphatic-substituted phenol may account for at least 5 wt %, such as at least 20 wt %, such as at least 25 wt %, such as at least 40 wt %, such as at least 50 wt %, such as at least 60 wt %, such as at least 70 wt %, such as at least 80 wt %. Based on the total solid weight of the reaction mixture, the aliphatic-substituted phenol may account for no more than 95 wt %, such as no more than 75 wt %, such as no more than 60 wt %, such as no more than 50 wt %, such as no more than 40 wt %. Based on the total solid weight of the reaction mixture, the aliphatic-substituted phenol can comprise 5% to 95% by weight, such as 5% to 75% by weight, such as 5% to 60% by weight, such as 5% to 50% by weight, such as 5% to 40% by weight, such as 20% to 95% by weight, such as 20% to 75% by weight, such as 20% to 60% by weight, such as 20% to 50% by weight, such as 20% to 40% by weight, such as 25% to 95% by weight, such as 25% to 75% by weight, such as 25% to 60% by weight. %, such as 25% to 50% by weight, such as 25% to 40% by weight, such as 40% to 95% by weight, such as 40% to 75% by weight, such as 40% to 60% by weight, such as 40% to 50% by weight, such as 50% to 95% by weight, such as 50% to 75% by weight, such as 50% to 60% by weight, such as 60% to 95% by weight, such as 60% to 75% by weight, such as 70% to 95% by weight, such as 70% to 75% by weight, such as 80% to 95% by weight. The film-forming resin reaction product containing cationic salt groups may contain the same amount of aliphatic-substituted phenol residues as the aliphatic-substituted phenol residues present in the reaction mixture.

[0057] The ratio of epoxy functional groups of the polyepoxide to hydroxyl functional groups of the polyol can be 2:0.1 to 2:1.9, such as 10:1 to 1.1:1, such as 5:1 to 1.1:1, such as 3:1 to 1.1:1, such as 2.5:1 to 1.1:1, such as 2.1:1 to 1.9:1, such as 2:1.

[0058] As used herein, the term "cationic salt group forming agent" refers to a material that reacts with epoxy groups and can be acidified before, during, or after reacting with the epoxy groups to form cationic salt groups. Specifically, the cationic salt group forming agent can react with the epoxy groups in the polyepoxide, thereby allowing the cationic salt groups to be incorporated into the film-forming resin containing cationic salt groups. Cationic salt groups can be incorporated into the film-forming resin containing cationic salt groups as follows: the film-forming polymer can react with the cationic salt group forming agent. Examples of suitable materials include amines, such as primary or secondary amines (which can be acidified to form amine salt groups after reacting with the epoxy groups), or tertiary amines (which can be acidified before reacting with the epoxy groups and form quaternary ammonium salt groups after reacting with the epoxy groups. Sulfonium groups can also be formed by the reaction of secondary thiols with epoxides.

[0059] The reaction product may be formed by any suitable method.

[0060] For example, the polyepoxide, (b) the aliphatically substituted phenol, and (c) the cationic salt group forming agent can be reacted in a single step to form the reaction product.

[0061] Alternatively, the reaction product can be formed by reacting (a) the polyepoxide with (b) the aliphatically substituted phenol in a first step to form an intermediate product, and then reacting the intermediate product with (c) the cationic salt group forming agent in a second step.

[0062] The reaction mixture may optionally further comprise other difunctional or polyfunctional chain extenders. For example, the difunctional or polyfunctional chain extender may include a dihydroxy or polyhydroxy functional reactant, a dicarboxylic acid or polycarboxylic acid functional reactant, or a diprimary amine or polyprimary amine functional reactant. The reaction product may also comprise these optional components.

[0063] The dicarboxylic acid functional reactant can include, for example, dimerized fatty acids (such as dimerized fatty acids of oleic acid and / or linoleic acid), alkyl diacids, and combinations thereof.

[0064] As described above, the reaction mixture may optionally further comprise a dihydroxy-functional reactant, including, for example, bisphenol A, bisphenol F, bisphenol S, biphenol, a dihydroxybenzene (such as catechol, resorcinol, or hydroquinone), or a combination thereof. The reaction product may also comprise these optional components.

[0065] The reaction mixture may also optionally contain bisphenol A, bisphenol F, bisphenol S, biphenol, dihydroxybenzene (such as catechol, resorcinol or hydroquinone) or a combination thereof in an amount of 0% to 65% by weight, such as 0% to 40% by weight, such as 0% to 30% by weight, such as 0% to 25% by weight, such as 0% to 20% by weight, such as 0% to 15% by weight, such as 0% to 10% by weight, such as 0% to 5% by weight, the % by weight being based on the total solid weight of the reaction mixture. The film-forming resin reaction product containing cationic salt groups may contain the residue of any of these components in the same amount as the residue of any of these components present in the reaction mixture.

[0066] The reaction mixture may contain less than 65 wt %, such as less than 40 wt %, such as less than 30 wt %, such as less than 25 wt %, such as less than 20 wt %, such as less than 15 wt %, such as less than 10 wt %, such as less than 5 wt %, such as less than 3 wt %, such as less than 1 wt % or less bisphenol A, based on the total solid weight of the reaction mixture. The film-forming resin reaction product containing cationic salt groups may contain the same amount of bisphenol A residues as the residues of bisphenol A present in the reaction mixture.

[0067] The reaction mixture and the resulting reaction product may be substantially free, essentially free, or completely free of bisphenol A. As used herein, the term "substantially free" means that bisphenol A is present in an amount of less than 0.1% by weight, if any, based on the total weight of the resin solids of the reaction mixture or the reaction product. As used herein, "substantially free" means that bisphenol A is present in an amount of less than 0.01% by weight, if any, based on the total weight of the resin solids of the reaction mixture or the reaction product. As used herein, "completely free" means that bisphenol A is absent, i.e., 0.000% by weight, based on the total weight of the resin solids of the reaction mixture or the reaction product.

[0068] The reaction mixture and the resulting reaction product may be substantially free, essentially free, or completely free of bisphenol F. As used herein, the term "substantially free" means that bisphenol F is present in an amount of less than 0.1% by weight, if any, based on the total weight of the resin solids of the reaction mixture or the reaction product. As used herein, "substantially free" means that bisphenol F is present in an amount of less than 0.01% by weight, if any, based on the total weight of the resin solids of the reaction mixture or the reaction product. As used herein, "completely free" means that bisphenol A is absent, i.e., 0.000% by weight of bisphenol F, based on the total weight of the resin solids of the reaction mixture or the reaction product.

[0069] The reaction mixture and the resulting reaction product may be substantially free, essentially free, or completely free of bisphenol S. As used herein, the term "substantially free" means that bisphenol S is present in an amount of less than 0.1% by weight, if any, based on the total weight of the resin solids of the reaction mixture or the reaction product. As used herein, "substantially free" means that bisphenol S is present in an amount of less than 0.01% by weight, if any, based on the total weight of the resin solids of the reaction mixture or the reaction product. As used herein, "completely free" means that bisphenol S is absent, i.e., 0.000% by weight of bisphenol F, based on the total weight of the resin solids of the reaction mixture or the reaction product.

[0070] The reaction mixture may optionally further comprise a lipid phenol. As used herein, a lipid phenol refers to a phenol having at least one saturated or unsaturated, substituted or unsubstituted hydrocarbon substituent containing at least 3 carbon atoms, such as at least 5 carbon atoms, such as at least 6 carbon atoms, such as at least 8 carbon atoms, such as at least 12 carbon atoms. The lipid phenol may optionally further comprise one or more additional phenolic hydroxyl groups, and may optionally comprise other functional groups, such as carboxylic acid groups. The reaction product may also comprise the residue of the lipid phenol.

[0071] The reaction mixture may optionally further comprise a monofunctional active hydrogen-containing component, a monofunctional epoxide-containing component, a monofunctional acid-containing component, or a combination thereof. The reaction product may also comprise these optional components.

[0072] The reaction mixture may optionally further comprise a multifunctional component comprising two or more functional groups, wherein the functional groups comprise carboxylic acid functional groups, anhydrides, hydroxyl functional groups, thiol functional groups, primary amino functional groups, secondary amino functional groups, or any combination thereof. The reaction product may also comprise these optional components.

[0073] The reaction mixture may optionally further comprise a monofunctional group-containing component, including a primary amino group-containing component, a monofunctional thiol group-containing component, a monofunctional carboxylic acid group-containing component, a monofunctional epoxide group-containing component, a monofunctional hydroxyl group-containing component (e.g., phenol), other monofunctional active hydrogen group-containing components, a monofunctional isocyanate group-containing component, and other monofunctional group-containing components. The reaction product may also comprise these optional components.

[0074] The film-forming resin containing cationic salt groups can have a number average molecular weight of at least 400 g / mol, such as at least 1,000 g / mol, such as at least 2,000 g / mol. The film-forming resin containing cationic salt groups can have a number average molecular weight of no more than 50,000 g / mol, such as no more than 20,000 g / mol, such as no more than 5,000 g / mol, such as no more than 3,000 g / mol. The film-forming resin containing cationic salt groups can have a number average molecular weight of 400 g / mol to 50,000 g / mol, such as 400 g / mol to 20,000 g / mol, such as 400 g / mol to 5,000 g / mol, such as 400 g / mol to 3,000 g / mol, such as 1,000 g / mol to 50,000 g / mol, such as 1,000 g / mol to 50,000 g / mol, as measured by gel permeation chromatography using polystyrene standards. The number average molecular weight is 20,000 g / mol, such as 1,000 g / mol to 5,000 g / mol, such as 1,000 g / mol to 3,000 g / mol, such as 2,000 g / mol to 50,000 g / mol, such as 2,000 g / mol to 20,000 g / mol, such as 2,000 g / mol to 5,000 g / mol, such as 2,000 g / mol to 3,000 g / mol.

[0075] The film-forming resin containing cationic salt groups may have a weight average molecular weight of 400 g / mol, such as at least 1,000 g / mol, such as at least 2,000 g / mol. The film-forming resin containing cationic salt groups may have a weight average molecular weight of no more than 200,000 g / mol, such as no more than 50,000 g / mol, such as no more than 20,000 g / mol, such as no more than 5,000 g / mol, such as no more than 3,000 g / mol. The film-forming resin containing cationic salt groups may have a molecular weight as measured by gel permeation chromatography using polystyrene standards of 400 g / mol to 200,000 g / mol, such as 400 g / mol to 50,000 g / mol, such as 400 g / mol to 20,000 g / mol, such as 400 g / mol to 5,000 g / mol, such as 400 g / mol to 3,000 g / mol, such as 1,000 g / mol to 200,000 g / mol, such as 1,000 g / mol to 50,000 g / mol, such as 1,000 g / mol to 50,000 g / mol, Such as a weight average molecular weight of 1,000 g / mol to 20,000 g / mol, such as 1,000 g / mol to 5,000 g / mol, such as 1,000 g / mol to 3,000 g / mol, such as 2,000 g / mol to 200,000 g / mol, such as 2,000 g / mol to 50,000 g / mol, such as 2,000 g / mol to 20,000 g / mol, such as 2,000 g / mol to 5,000 g / mol, such as 2,000 g / mol to 3,000 g / mol.

[0076] The film-forming resin containing cationic salt groups can be the main carrier resin. As used herein, "main carrier resin" refers to a resin component that accounts for more than 50% by weight of the resin solids of the electrodepositable coating composition, excluding curing agent. The main carrier resin is the main film-forming polymer that reacts with the curing agent during the curing of the electrodepositable coating composition. The content of the main carrier resin can be greater than 50% by weight (excluding curing agent) of the resin solids of the electrodepositable coating composition, such as at least 60% by weight, such as at least 70% by weight, such as at least 80% by weight, such as at least 90% by weight, such as at least 95% by weight.

[0077] If present as the primary carrier resin, the film-forming resin containing cationic salt groups may be present in an amount of at least 40% by weight, such as at least 50% by weight, such as at least 60% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. If present as the primary carrier resin, the film-forming resin containing cationic salt groups may be present in an amount of no more than 90% by weight, such as no more than 80% by weight, such as no more than 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. If present as the primary carrier resin, the film-forming resin containing cationic salt groups may be present in an amount of 40% to 90% by weight, such as 40% to 80% by weight, such as 40% to 75% by weight, such as 50% to 90% by weight, such as 50% to 80% by weight, such as 50% to 75% by weight, such as 60% to 90% by weight, such as 60% to 80% by weight, such as 60% to 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.

[0078] The film-forming resin containing a cationic salt group can be an auxiliary resin. As used herein, "auxiliary resin" refers to a resin component that is not the main resin component of the composition and accounts for less than 50% by weight of the resin solids of the electrodepositable coating composition, excluding curing agent. The auxiliary resin can be present in an amount less than 50% by weight (excluding curing agent) of the resin solids of the electrodepositable coating composition, such as less than 40% by weight, such as less than 30% by weight, such as less than 20% by weight, such as less than 10% by weight, such as less than 5% by weight.

[0079] If present as an auxiliary resin, the film-forming resin containing cationic salt groups may be present in an amount of at least 1 wt%, such as at least 3 wt%, such as at least 5 wt%, such as at least 10 wt%, based on the total weight of the resin solids of the electrodepositable coating composition. If present as an auxiliary resin, the film-forming resin containing cationic salt groups may be present in an amount of no more than 39 wt%, such as no more than 25 wt%, such as no more than 15 wt%, such as no more than 10 wt%, such as no more than 5 wt%, based on the total weight of the resin solids of the electrodepositable coating composition. If present as an auxiliary resin, the film-forming resin containing cationic salt groups may be present in an amount of 1 wt % to 39 wt %, such as 1 wt % to 25 wt %, such as 1 wt % to 15 wt %, such as 1 wt % to 10 wt %, such as 1 wt % to 5 wt %, such as 3 wt % to 39 wt %, such as 3 wt % to 25 wt %, such as 3 wt % to 15 wt %, such as 3 wt % to 10 wt %, such as 3 wt % to 5 wt %, such as 5 wt % to 39 wt %, such as 5 wt % to 25 wt %, such as 5 wt % to 15 wt %, such as 5 wt % to 10 wt %, such as 10 wt % to 39 wt %, such as 10 wt % to 25 wt %, such as 10 wt % to 15 wt %.

[0080] As used herein, the term "resin solids" or "resin solids" includes the film-forming resin containing cationic salt groups, the curing agent, the second film-forming resin containing cationic salt groups (if present), and any additional water-dispersible non-pigmented components present in the electrodepositable coating composition.

[0081] Second film-forming resin containing cationic salt groups

[0082] According to the present disclosure, the electrodepositable coating composition may further include a second cationic salt group-containing film-forming resin that is different from the above-mentioned cationic salt group-containing film-forming resin.

[0083] The second film-forming resin containing cationic salt groups can be used in the coating composition of cationic electrodeposition.The second film-forming polymer containing cationic salt groups can comprise active hydrogen functional group.As used herein, term " active hydrogen functional group " refers to those groups that react with isocyanate determined by Zerewitinoff (Zerewitinoff) test described in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, volume 49, page 3181 (1927), and comprises for example hydroxyl, primary amino or secondary amino group and thiol group.The film-forming polymer containing cationic salt groups comprising active hydrogen functional group can be referred to as containing active hydrogen, the film-forming polymer containing cationic salt groups.

[0084] Examples of polymers suitable for use as the second cationic salt group-containing film-forming resin in the present disclosure include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, polyesters, and the like.

[0085] More specific examples of suitable active hydrogen-containing, second cationic salt group-containing film-forming resins include polyepoxide-amine adducts, such as adducts of polyglycidyl ethers of polyphenols (such as bisphenol A) with primary and / or secondary amines, as described in U.S. Pat. No. 4,031,050 at column 3, line 27 to column 5, line 50, U.S. Pat. No. 4,452,963 at column 5, line 58 to column 6, line 66, and U.S. Pat. No. 6,017,432 at column 2, line 66 to column 6, line 26, portions of which are incorporated herein by reference. A portion of the amine reacted with the polyepoxide may be a ketimine of a polyamine, such as described in U.S. Pat. No. 4,104,147 at column 6, line 23 to column 7, line 23, the cited portions of which are incorporated herein by reference. Also suitable are ungelled polyepoxide-polyoxyalkylene polyamine resins such as those described in U.S. Pat. No. 4,432,850 at column 2, line 60 to column 5, line 58, the cited portions of which are incorporated herein by reference. Additionally, cationic acrylic resins such as those described in U.S. Pat. No. 3,455,806 at column 2, line 18 to column 3, line 61 and U.S. Pat. No. 3,928,157 at column 2, line 29 to column 3, line 21, both of which are incorporated herein by reference, may be used.

[0086] In addition to resins containing amine salt groups, resins containing quaternary ammonium salt groups can also be used as the second film-forming resin containing cationic salt groups. Examples of these resins are those formed by reacting organic polyepoxides with tertiary amine acid salts. Such resins are described in U.S. Patent Nos. 3,962,165, column 2, line 3 to column 11, line 7; 3,975,346, column 1, line 62 to column 17, line 25; and U.S. Patent No. 4,001,156, column 1, line 37 to column 16, line 7, portions of which are incorporated herein by reference. Other examples of suitable cationic resins include resins containing ternary sulfonium salt groups, such as those described in U.S. Patent No. 3,793,278, column 1, line 32 to column 5, line 20, portions of which are incorporated herein by reference. Furthermore, it is also possible to employ cationic resins which cure via a transesterification mechanism, as described in European Patent Application No. 12463 B1, page 2, line 1 to page 6, line 25, this part of which is incorporated herein by reference.

[0087] Other suitable second film-forming resins containing cationic salt groups include those film-forming resins that can form an electrodeposited coating composition that resists light degradation. Such polymers include polymers containing cationic amine salt groups, which are derived from side groups and / or terminal amino groups disclosed in U.S. Patent Application Publication No. 2003 / 0054193A1

[0064] to

[0088] paragraphs, and this part of the U.S. Patent Application Publication is incorporated herein by reference. Equally suitable are resins containing active hydrogen, containing second cationic salt groups, derived from polyglycidyl ethers of polyphenols that are substantially free of aliphatic carbon atoms covalently bonded to more than one aromatic group, which are disclosed in U.S. Patent Application Publication No. 2003 / 0054193A1

[0096] to

[0123] paragraphs, and this part of the U.S. Patent Application Publication is incorporated herein by reference.

[0088] Film-forming resins containing cationic salt groups can be made cationic and water-dispersible by at least partially neutralizing with an acid. Suitable acids include organic acids and inorganic acids. Non-limiting examples of suitable organic acids include formic acid, acetic acid, methanesulfonic acid, and lactic acid. Non-limiting examples of suitable inorganic acids include phosphoric acid and sulfamic acid. "Sulfamic acid" means sulfamic acid itself or a derivative thereof having the formula:

[0089]

[0090] wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms. Mixtures of the above-mentioned acids may also be used in the present disclosure.

[0091] The degree of neutralization of the film-forming resin containing cationic salt groups can vary with the specific polymer involved. However, sufficient acid should be used to fully neutralize the film-forming polymer containing cationic salt groups so that the film-forming polymer containing cationic salt groups can be dispersed in the aqueous dispersion medium. For example, the amount of acid used can provide at least 20% of the total theoretical neutralization. It is also possible to use an excess of acid that exceeds the amount required for 100% of the total theoretical neutralization. For example, based on the total amines in the film-forming polymer containing active hydrogen and cationic salt groups, the amount of acid used to neutralize the film-forming polymer containing cationic salt groups can be ≧0.1%. Alternatively, based on the total amines in the film-forming polymer containing active hydrogen and cationic salt groups, the amount of acid used to neutralize the film-forming polymer containing active hydrogen and cationic salt groups can be ≦100%. The range of the total amount of acid used to neutralize the film-forming polymer containing cationic salt groups can be between any combination of the values ​​stated in the preceding sentence (including the stated values). For example, the total amount of acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer can be 20%, 35%, 50%, 60% or 80% based on the total amine in the cationic salt group-containing film-forming polymer.

[0092] The second film-forming resin containing cationic salt groups may be present as a main carrier resin or an auxiliary resin.

[0093] If present as the primary carrier resin, the second film-forming resin containing cationic salt groups may be present in an amount of at least 40% by weight, such as at least 50% by weight, such as at least 60% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. If present as the primary carrier resin, the second film-forming resin containing cationic salt groups may be present in an amount of no more than 89% by weight, such as no more than 80% by weight, such as no more than 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. If present as the primary carrier resin, the second film-forming resin containing cationic salt groups may be present in an amount of 40% to 89% by weight, such as 40% to 80% by weight, such as 40% to 75% by weight, such as 50% to 89% by weight, such as 50% to 80% by weight, such as 50% to 75% by weight, such as 60% to 89% by weight, such as 60% to 80% by weight, such as 60% to 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.

[0094] If present as an auxiliary resin, the second film-forming resin containing cationic salt groups may be present in an amount of at least 1 wt%, such as at least 3 wt%, such as at least 5 wt%, such as at least 10 wt%, based on the total weight of the resin solids of the electrodepositable coating composition. If present as an auxiliary resin, the second film-forming resin containing cationic salt groups may be present in an amount of no more than 39 wt%, such as no more than 25 wt%, such as no more than 15 wt%, such as no more than 10 wt%, such as no more than 5 wt%, based on the total weight of the resin solids of the electrodepositable coating composition. If present as an auxiliary resin, the second film-forming resin containing a cationic salt group may be present in an amount of 1 wt % to 39 wt %, such as 1 wt % to 25 wt %, such as 1 wt % to 15 wt %, such as 1 wt % to 10 wt %, such as 1 wt % to 5 wt %, such as 3 wt % to 39 wt %, such as 3 wt % to 25 wt %, such as 3 wt % to 15 wt %, such as 3 wt % to 10 wt %, such as 3 wt % to 5 wt %, such as 5 wt % to 39 wt %, such as 5 wt % to 25 wt %, such as 5 wt % to 15 wt %, such as 5 wt % to 10 wt %, such as 10 wt % to 39 wt %, such as 10 wt % to 25 wt %, such as 10 wt % to 15 wt %.

[0095] curing agent

[0096] According to the present disclosure, the coating composition of the present disclosure that can be deposited can further include a curing agent. Curing agent reacts with the film-forming polymer containing ionic salt groups. Curing agent can react with the reactive group (such as active hydrogen group) of the film-forming polymer containing ionic salt groups to realize that the coating composition is cured to form a coating. As used herein, the term "curing", "cured" or similar terms used in combination with the coating composition that can be deposited as described herein means that at least a portion of the components of the coating composition that can be deposited are crosslinked to form a coating. In addition, the curing of the coating composition that can be deposited refers to subjecting the composition to curing conditions (such as, elevated temperature), thereby causing the reactive functional group reaction of the components of the coating composition that can be deposited, and causing the components of the composition to be crosslinked and form a coating that is at least partially cured. The non-limiting examples of suitable curing agents are at least partially blocked polyisocyanates, aminoplast resins and phenolic plastic resins, such as phenol formaldehyde condensates, including its allyl ether derivatives.

[0097] Suitable at least partially blocked polyisocyanates include aliphatic polyisocyanates, aromatic polyisocyanates and mixtures thereof. Curing agent can include at least partially blocked aliphatic polyisocyanates. Suitable at least partially blocked aliphatic polyisocyanates include for example fully blocked aliphatic polyisocyanates, such as those described in U.S. Patent number 3,984,299 the 1st hurdle the 57th row to the 3rd hurdle the 15th row, this part of this U.S. Patent is incorporated herein by reference, or comprise the partially blocked aliphatic polyisocyanates reacted with the polymer backbone, as described in U.S. Patent number 3,947,338 the 2nd hurdle the 65th row to the 4th hurdle the 30th row, this part of this U.S. Patent is also incorporated herein by reference. By "blocked" is meant that the isocyanate groups have been reacted with a compound such that the resulting blocked isocyanate groups are stable to active hydrogen at ambient temperature (23° C.), but react with active hydrogen in the film-forming polymer at elevated temperatures, such as between 90° C. and 200° C. The polyisocyanate curing agent may be a fully blocked polyisocyanate having substantially no free isocyanate groups at ambient temperature.

[0098] The polyisocyanate curing agent may include a diisocyanate, a higher functional polyisocyanate, or a combination thereof. For example, the polyisocyanate curing agent may include an aliphatic polyisocyanate and / or an aromatic polyisocyanate. The aliphatic polyisocyanate may comprise (i) alkylene isocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate ("HDI"), 1,2-propylene diisocyanate, 1,2-butene diisocyanate, 2,3-butene diisocyanate, 1,3-butene diisocyanate, ethylene diisocyanate, and butylene diisocyanate, and (ii) cycloalkylene isocyanates such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate) ("HMDI"), the cyclotrimer of 1,6-hexamethylene diisocyanate (also known as the isocyanurate trimer of HDI, available as Desmodur N3300 from Convestro AG commercially available) and m-tetramethylxylylene diisocyanate (can be Commercially available from Allnex SA). Aromatic polyisocyanates can include (i) arylene isocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, and 1,4-naphthalene diisocyanate, and (ii) aralkylene isocyanates such as 4,4′-diphenylmethane (“MDI”), 2,4-tolylene diisocyanate, or 2,6-tolylene diisocyanate (“TDI”), or mixtures thereof, 4,4-toluidine diisocyanate, and xylylene diisocyanate. Triisocyanates such as triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene; tetraisocyanates such as 4,4'-diphenyldimethylmethane-2,2',5,5'-tetraisocyanate; and polymeric polyisocyanates such as tolylene diisocyanate dimer and trimer may also be used. The curing agent may comprise a blocked polyisocyanate selected from polymeric polyisocyanates such as polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, etc. The curing agent may also comprise a blocked trimer of hexamethylene diisocyanate, which may be Desmodur Commercially available from Covestro AG. Mixtures of polyisocyanate curing agents may also be used.

[0099] The blocked polyisocyanate curing agent may include tris(alkoxycarbonylamino)-1,3,5-triazine (TACT). Tris(alkoxycarbonylamino)-1,3,5-triazine may have the following structure:

[0100]

[0101] wherein R1, R2 and R3 each independently comprise a C1-C8 alkyl group, such as a C1-C6 alkyl group, such as a C1-C4 alkyl group. In a non-limiting example, R1 and R2 are each methyl and R3 is n-butyl, or R 1 and R 2 Each is n-butyl and R 3 is methyl. In a non-limiting example, each of the groups R1, R2, and R3 is n-butyl. Examples of suitable tris(alkoxycarbonylamino)-1,3,5-triazines include tris(methoxycarbonylamino)-, tris(butoxycarbonylamino)-, and tris(2-ethylhexyloxycarbonylamino)-1,3,5-triazine, and any combination thereof.

[0102] The polyisocyanate curing agent may be at least partially blocked with at least one blocking agent selected from the group consisting of: 1,2-alkanediols, such as 1,2-propylene glycol; 1,3-alkanediols, such as 1,3-butanediol; benzyl alcohols, such as benzyl alcohol; allyl alcohols, such as allyl alcohol; caprolactam; dialkylamines, such as dibutylamine; and mixtures thereof. The polyisocyanate curing agent may be at least partially blocked with at least one 1,2-alkanediol having three or more carbon atoms (e.g., 1,2-butanediol).

[0103] Other suitable end-capping agents include aliphatic, alicyclic or aromatic alkyl monoalcohols or phenolic compounds, including, for example, lower aliphatic alcohols such as methanol, ethanol and n-butanol; alicyclic alcohols such as cyclohexanol; aromatic alkyl alcohols such as phenylcarbinol and methylphenylcarbinol; and phenolic compounds such as phenol itself and substituted phenols whose substituents do not affect the coating operation, such as cresol and nitrophenol. Glycol ethers and glycol amines can also be used as end-capping agents. Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether. Other suitable end-capping agents include oximes such as methyl ethyl ketone oxime, acetone oxime and cyclohexanone oxime; dialkyl pyrazoles, acetoacetic acid esters; and / or dialkyl malonates.

[0104] The curing agent may include an aminoplast resin. An aminoplast resin is a condensation product of an aldehyde with a substance carrying an amino or amide group. Condensation products obtained from the reaction of an alcohol and an aldehyde with melamine, urea, or benzoguanamine may be used. However, condensation products of other amines and amides may also be used, for example, aldehyde condensates of triazines, diazines, triazoles, guanidines, guanamines, and alkyl- and aryl-substituted derivatives of such compounds, including alkyl- and aryl-substituted ureas and alkyl- and aryl-substituted melamines. Some examples of such compounds are N,N'-dimethylurea, benzourea, dicyandiamide, formaguanamine, acetoguanamine, ammeline, 2-chloro-4,6-diamino-1,3,5-triazine, 6-methyl-2,4-diamino-1,3,5-triazine, 3,5-diaminotriazole, triaminopyrimidine, 2-mercapto-4,6-diaminopyrimidine, 3,4,6-tris(ethylamino)-1,3,5-triazine, etc. Suitable aldehydes include formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal, etc.

[0105] The aminoplast resin may contain hydroxymethyl groups or similar alkyl alcohol groups, and at least a portion of these alkyl alcohol groups may be etherified by reaction with an alcohol to provide a resin soluble in an organic solvent. For this purpose, any monohydric alcohol may be employed, including such alcohols as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and others, as well as benzyl alcohol and other aromatic alcohols, cyclic alcohols such as cyclohexanol, monoethers of ethylene glycol such as cellosolves and carbitols, and halogen-substituted or other substituted alcohols such as 3-chloropropanol and butoxyethanol.

[0106] Non-limiting examples of commercially available aminoplast resins are those sold under the trademark HYDROGEN(R) from Allnex Belgium SA / NV. (such as CYMEL 1130 and 1156) and products from INEOS Melamines under the trademark Aminoplast resins such as those commercially available from RESIMENE 750 and 753. Examples of suitable aminoplast resins also include those described in U.S. Patent No. 3,937,679 at column 16, line 3 to column 17, line 47, this portion of which is hereby incorporated by reference. As disclosed in the preceding portion of the '679 patent, aminoplasts can be used in combination with methanol phenol ethers.

[0107] Phenolic resins are formed by the condensation of aldehydes and phenols. Suitable aldehydes include formaldehyde and acetaldehyde. Methylene releasers and aldehyde releasers (such as paraformaldehyde and hexamethylenetetramine) can also be used as aldehyde releasers. Various phenols can be used, such as phenol itself, cresols, or substituted phenols in which a hydrocarbon group having a linear, branched, or cyclic structure replaces hydrogen in the aromatic ring. Mixtures of phenols can also be used. Some specific examples of suitable phenols are p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol, and unsaturated hydrocarbon-substituted phenols, such as monobutenylphenol containing a butenyl group in the ortho, meta, or para position, and in which double bonds occur at various positions in the hydrocarbon chain.

[0108] As described above, aminoplast resins and phenoplast resins are further described in US Pat. No. 4,812,215 at column 6, line 20 to column 7, line 12, the cited portions of which are incorporated herein by reference.

[0109] By the total weight of the resin solids of the electrodepositable coating composition, the curing agent can be present in the cationic electrodepositable coating composition in an amount of at least 10 wt %, such as at least 20 wt %, such as at least 25 wt %, and can be present in an amount of no more than 60 wt %, such as no more than 59.95 wt %, such as no more than 50 wt %, such as no more than 40 wt %. By the total weight of the resin solids of the electrodepositable coating composition, the curing agent can be present in the cationic electrodepositable coating composition in an amount of 10 wt % to 60 wt %, such as 10 wt % to 59.95 wt %, such as 20 wt % to 50 wt %, such as 25 wt % to 40 wt %.

[0110] Other components of the electrodepositable coating composition

[0111] In addition to the film-forming polymer containing ionic salt groups and the curing agent described above, the electrodepositable coating composition according to the present disclosure may optionally include one or more additional components.

[0112] According to the present disclosure, the coating composition that can be electrodeposited can optionally include a catalyst for catalyzing the reaction between the curing agent and the polymer. Examples of catalysts suitable for cationic electrodepositable coating compositions include, but are not limited to, organotin compounds (e.g., dibutyltin oxide and dioctyltin oxide) and salts thereof (e.g., dibutyltin diacetate); other metal oxides (e.g., oxides of cerium, zirconium, and bismuth) and salts thereof (e.g., bismuth sulfamate and bismuth lactate); or cyclic guanidines as described in U.S. Patent No. 7,842,762, column 1, line 53 to column 4, line 18, and column 16, line 62 to column 19, line 8, the cited portion of which is incorporated herein by reference. During curing, the catalyst can be activated, for example, by heating.

[0113] According to the present disclosure, the electrodepositable coating composition of the present disclosure may optionally include a pit control additive that can be incorporated into the coating composition, such as, for example, a polyalkylene oxide polymer that can include a copolymer of butylene oxide and propylene oxide. According to the present disclosure, the molar ratio of butylene oxide to propylene oxide can be at least 1:1, such as at least 3:1, such as at least 5:1, and in some cases, can be no more than 50:1, such as no more than 30:1, such as no more than 20:1. According to the present disclosure, the molar ratio of butylene oxide to propylene oxide can be from 1:1 to 50:1, such as from 3:1 to 30:1, such as from 5:1 to 20:1.

[0114] The polyalkylene oxide polymer may include at least two hydroxyl functional groups and may be monofunctional, difunctional, trifunctional, or tetrafunctional. As used herein, "hydroxyl functional group" includes -OH groups. For clarity, the polyalkylene oxide polymer may include additional functional groups in addition to hydroxyl functional groups. As used herein, "monofunctional," when used with respect to the number of hydroxyl functional groups included in a particular monomer or polymer, means a monomer or polymer that includes one (1) hydroxyl functional group per molecule. As used herein, "difunctional," when used with respect to the number of hydroxyl functional groups included in a particular monomer or polymer, means a monomer or polymer that includes two (2) hydroxyl functional groups per molecule. As used herein, "trifunctional," when used with respect to the number of hydroxyl functional groups included in a particular monomer or polymer, means a monomer or polymer that includes three (3) hydroxyl functional groups per molecule. As used herein, "tetrafunctional," when used with respect to the number of hydroxyl functional groups included in a particular monomer or polymer, means a monomer or polymer that includes four (4) hydroxyl functional groups per molecule.

[0115] The hydroxyl equivalent weight of the polyalkylene oxide polymer may be at least 100 g / mol, such as at least 200 g / mol, such as at least 400 g / mol, and may be no more than 2,000 g / mol, such as no more than 1,000 g / mol, such as no more than 800 g / mol. The hydroxyl equivalent weight of the polyalkylene oxide polymer may be from 100 g / mol to 2,000 g / mol, such as from 200 g / mol to 1,000 g / mol, such as from 400 g / mol to 800 g / mol. As used herein, with respect to polyalkylene oxide polymers, the "hydroxyl equivalent weight" is determined by dividing the molecular weight of the polyalkylene oxide polymer by the number of hydroxyl groups present in the polyalkylene oxide polymer.

[0116] Alternatively, the z-average molecular weight (M z) can be at least 200 g / mol, such as at least 400 g / mol, such as at least 600 g / mol, and can be no more than 5,000 g / mol, such as no more than 3,000 g / mol, such as no more than 2,000 g / mol. According to the present disclosure, the polyalkylene oxide polymer can have a z-average molecular weight of 200 g / mol to 5,000 g / mol (such as 400 g / mol to 3,000 g / mol, such as 600 g / mol to 2,000 g / mol). As used herein, for polymers having a z-average molecular weight (M) of less than 900,000 z ) of a polyalkylene oxide polymer, the term "z average molecular weight (M z )" means the z-average molecular weight (M) as determined by gel permeation chromatography using the following z ): A Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards with molecular weights ranging from approximately 500 g / mol to 900,000 g / mol, tetrahydrofuran (THF) with 0.05 M lithium bromide (LiBr) at a flow rate of 0.5 mL / min as eluent, and an Asahipak GF-510HQ column were used for separation.

[0117] The polyalkylene oxide polymer may be present in the electrodepositable coating composition in an amount of at least 0.1 wt %, such as at least 0.5 wt %, such as at least 0.75 wt %, based on the total weight of the resin blend solids, and in some cases, in an amount of no more than 10 wt %, such as no more than 4 wt %, such as no more than 3 wt %, based on the total weight of the resin blend solids. The polyalkylene oxide polymer may be present in the electrodepositable coating composition in an amount of 0.1 wt % to 10 wt %, such as 0.5 wt % to 4 wt %, such as 0.75 wt % to 3 wt %, based on the total weight of the resin blend solids.

[0118] The electrodepositable coating composition may be substantially free, essentially free, or completely free of bisphenol A polyoxyethylene ether phosphate. As used herein, the term "substantially free" means that bisphenol A polyoxyethylene ether phosphate (if any) is present in an amount of less than 5% by weight based on the total weight of the resin solids. As used herein, the term "substantially free" means that bisphenol A polyoxyethylene ether phosphate (if any) is present in an amount of less than 1% by weight based on the total weight of the resin solids. As used herein, the term "completely free" means that bisphenol A polyoxyethylene ether phosphate is absent, i.e., 0.00% by weight based on the total weight of the resin solids.

[0119] According to the present disclosure, the coating composition that can be electrodeposited can include other optional ingredients, such as (if desired) various additives, such as fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents or their combinations. Alternatively, the coating composition that can be electrodeposited can be free of any optional ingredients completely, i.e., the optional ingredients are not present in the coating composition that can be electrodeposited. Based on the gross weight of the resin solids of the coating composition that can be electrodeposited, the additives mentioned above can be present in the coating composition that can be electrodeposited in an amount of 0.01 % by weight to 3 % by weight.

[0120] The electrodepositable coating composition may optionally further include a pigment. The pigment may include iron oxide, lead oxide, strontium chromate, carbon black, coal powder, titanium dioxide, talc, barium sulfate, layered silicate pigments, metallic pigments, thermally conductive electrical insulating fillers, flame retardant pigments, and color pigments (such as cadmium yellow, cadmium red, lead chrome yellow, etc.), or any combination thereof.

[0121] The pigment to binder (P:B) ratio described in the present disclosure may refer to the weight ratio of the pigment to the binder in the electrodepositable coating composition, and / or the weight ratio of the pigment to the binder in the deposited wet film, and / or the weight ratio of the pigment to the binder in the dried uncured deposited film, and / or the weight ratio of the pigment to the binder in the cured film. The pigment to binder (P:B) ratio of the pigment to the electrodepositable binder may be at least 0.05:1, such as at least 0.1:1, such as at least 0.2:1, such as at least 0.30:1, such as at least 0.35:1, such as at least 0.40:1, such as at least 0.50:1, such as at least 0.60:1, such as at least 0.75:1, such as at least 1:1, such as at least 1.25:1, such as at least 1.5:1. The pigment to binder (P:B) ratio of the pigment to the electrodepositable binder can be no more than 2.0:1, such as no more than 1.75:1, such as no more than 1.5:1, such as no more than 1.25:1, such as no more than 1:1, such as no more than 0.75:1, such as no more than 0.70:1, such as no more than 0.60:1, such as no more than 0.55:1, such as no more than 0.50:1, such as no more than 0.30:1, such as no more than 0.20:1, such as no more than 0.10:1. The pigment to binder (P:B) ratio of the pigment to the electrodepositable binder may be from 0.05:1 to 2.0:1, such as from 0.05:1 to 1.75:1, such as from 0.05:1 to 1.50:1, such as from 0.05:1 to 1.25:1, such as from 0.05:1 to 1:1, such as from 0.05:1 to 0.75:1, such as from 0.05:1 to 0.70:1, such as from 0.0 5:1 to 0.60:1, such as 0.05:1 to 0.55:1, such as 0.05:1 to 0.50:1, such as 0.05:1 to 0.30:1, such as 0.05:1 to 0.20:1, such as 0.05:1 to 0.10:1, such as 0.1:1 to 2.0:1, such as 0.1:1 to 1.75:1, such as 0.1:1 to 1.50:1, such as 0. 1:1 to 1.25:1, such as 0.1:1 to 1:1, such as 0.1:1 to 0.75:1, such as 0.1:1 to 0.70:1, such as 0.1:1 to 0.60:1, such as 0.1:1 to 0.55:1, such as 0.1:1 to 0.50:1, such as 0.1:1 to 0.30:1, such as 0.1:1 to 0.20:1, such as 0.2:1 to 2.0 :1, such as 0.2:1 to 1.75:1, such as 0.2:1 to 1.50:1, such as 0.2:1 to 1.25:1, such as 0.2:1 to 1:1, such as 0.2:1 to 0.75:1, such as 0.2:1 to 0.70:1, such as 0.2:1 to 0.60:1, such as 0.2:1 to 0.55:1, such as 0.2:1 to 0.50:1, such as 0.2:1 to 0.30:1, such as 0.3:1 to 2.0:1, such as 0.3:1 to 1.75:1, such as 0.3:1 to 1.50:1, such as 0.3:1 to 1.25:1, such as 0.3:1 to 1:1, such as 0.3:1 to 0.75:1, such as 0.3:1 to 0.70:1, such as 0.3:1 to 0.60:1, such as 0.3:1 to 0.55:1, such as 0.3:1 to 0.50:1, such as 0.3:1 to 0.30:1, such as 0.35:1 to 2.0:1, such as 0.35:1 to 1.75:1, such as 0.35:1 to 1.50:1, such as 0.35:1 to 1.25:1, such as 0.35:1 to 1:1, such as 0.35:1 to 0.75:1, such as 0.35:1 to 0.70:1, such as 0.35:1 to 0.60:1, such as 0.35:1 to 0.55:1, such as 0.35:1 to 0.50:1, such as 0.4:1 to 2.0:1, such as 0.4:1 to 1.75:1, such as 0.4:1 to 1.50:1, such as 0.4:1 to 1.25:1, such as 0.4:1 to 1:1, such as 0.4:1 to 0.75:1, such as 0.4:1 to 0.70:1, such as 0.4:1 to 0.60:1, such as 0.4:1 to 0.5 5:1, such as 0.4:1 to 0.50:1, such as 0.5:1 to 2.0:1, such as 0.5:1 to 1.75:1, such as 0.5:1 to 1.50:1, such as 0.5:1 to 1.25:1, such as 0.5:1 to 1:1, such as 0.5:1 to 0.75:1, such as 0.5:1 to 0.70:1, such as 0.5:1 to 0.60:1, such as 0.5:1 to 0.55:1, such as 0.6:1 to 2.0:1, such as 0.6:1 to 1.75:1, such as 0.6:1 to 1.50:1, such as 0.6:1 to 1.25:1, such as 0.6:1 to 1:1, such as 0.6:1 to 0.75:1, such as 0.6:1 to 0.70:1, such as 0.75:1 to 2.0:1, such as 0.75:1 to 1.75:1, such as 0.75:1 to 1.50:1, such as 0.75:1 to 1.25:1, such as 0.75:1 to 1:1, such as 1:1 to 2.0:1, such as 1:1 to 1.75:1, such as 1:1 to 1.50:1, such as 1:1 to 1.25:1, such as 1.25:1 to 2.0:1, such as 1.25:1 to 1.75:1, such as 1.25:1 to 1.50:1, such as 1.50:1 to 2.0:1, such as 1.50:1 to 1.75:1.

[0122] According to the present disclosure, the coating composition that can be electrodeposited can include water and / or one or more organic solvents. Based on the gross weight of the coating composition that can be electrodeposited, water can, for example, be present in an amount of 40 wt % to 90 wt %, such as 50 wt % to 75 wt %. The example of a suitable organic solvent includes an oxygen-containing organic solvent, such as the monoalkyl ether containing 1 to 10 carbon atoms in the alkyl group of ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, such as the monoethyl ether and monobutyl ether of these glycols. Other examples of at least partially water-miscible solvents include alcohols, such as ethanol, isopropyl alcohol, butanol and diacetone alcohol. If used, then based on the gross weight of the coating composition that can be electrodeposited, the organic solvent can generally be present in an amount of less than 10 wt %, such as less than 5 wt %. The coating composition that can be electrodeposited can specifically be provided in the form of a dispersion, such as an aqueous dispersion.

[0123] According to the present disclosure, the total solids content of the electrodepositable coating composition may be at least 1 wt %, such as at least 5 wt %, based on the total weight of the electrodepositable coating composition, and may be no more than 50 wt %, such as no more than 40 wt %, such as no more than 20 wt %. The total solids content of the electrodepositable coating composition may be from 1 wt % to 50 wt %, such as from 5 wt % to 40 wt %, such as from 5 wt % to 20 wt %, based on the total weight of the electrodepositable coating composition. As used herein, "total solids" refers to the non-volatile content of the electrodepositable coating composition, i.e., materials that will not volatilize when heated to 110° C. for 15 minutes.

[0124] The electrodepositable coating composition may have a free bisphenol A content of less than 0.1 wt %, such as less than 0.01 wt %, such as less than 0.001 wt %, based on the total weight of the electrodepositable coating composition, as measured by HPLC or LC-MS. As used herein, "free bisphenol A" refers to an unreacted form of bisphenol A in which none of the hydroxyl groups of the bisphenol A react with a functional group of another molecule.

[0125] The free BPA level of the electrodepositable coating composition can be determined by HPLC.

[0126] The free bisphenol A levels of the electrodepositable coating compositions having free BPA levels of <0.01 as measured by HPLC can be further analyzed by LC-MS to obtain more precise values.

[0127] substrate

[0128] According to the present disclosure, the coating composition that can be electrodeposited can be applied electrophoretically to a conductive substrate. The coating composition that can be electrodeposited can be electrophoretically deposited on any conductive substrate. Suitable substrates include metal substrates, metal alloy substrates and / or metallized substrates, such as nickel-plated plastics. Additionally, the substrate can include non-metallic conductive materials, including composite materials, for example, materials including carbon fibers or conductive carbon. According to the present disclosure, the metal or metal alloy can include cold-rolled steel, hot-rolled steel, stainless steel, steel coated with zinc metal, zinc compounds or zinc alloys, such as electrogalvanized steel, hot-dip galvanized steel, alloyed hot-dip galvanized steel (galvanealed steel) and steel coated with zinc alloys. Aluminum alloys of 2XXX, 3XXX, 4XXX, 5XXX, 6XXX or 7XXX series and composite aluminum alloys and cast aluminum alloys of the A356 series can also be used as substrates. Magnesium alloys of AZ31B, AZ91C, AM60B or EV31A series can also be used as substrates. The substrate used in the present disclosure can also include titanium and / or titanium alloys. Other suitable non-ferrous metals include copper and magnesium and alloys of these materials. Suitable metal substrates for use in the present disclosure include metal substrates commonly used in vehicle body assemblies (such as, but not limited to, doors, body panels, trunk lids, roof panels, hoods, roof and / or stringers, rivets, landing gear components and / or skins used on aircraft), vehicle frames, vehicle parts, motorcycles, wheels, industrial structures and components, such as household appliances including washers, dryers, refrigerators, stoves, dishwashers, etc., agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, lawn furniture, and other articles. As used herein, "vehicle" or variations thereof include, but are not limited to, civil, commercial, and military aircraft and / or land vehicles, such as cars, motorcycles, trucks, tanks, and / or armored cars or trucks. The metal substrate may also be in the form of, for example, metal sheets or prefabricated parts. It should also be understood that the substrate can be pretreated with a pretreatment solution comprising a zinc phosphate pretreatment solution, such as the zinc phosphate pretreatment solutions described, for example, in U.S. Pat. Nos. 4,793,867 and 5,588,989, or a zirconium-containing pretreatment solution, such as those described in U.S. Pat. Nos. 7,749,368 and 8,673,091.

[0129] The substrate may be a multi-metal article. As used herein, the term "multi-metal article" refers to (1) an article having at least one surface comprising a first metal and at least one surface comprising a second metal different from the first metal, (2) a first article having at least one surface comprising a first metal and a second article having at least one surface comprising a second metal different from the first metal, or (3) both (1) and (2). The substrate may include surfaces or components of different substrates that are adjacent or connected together, such as a galvanic assembly.

[0130] Coating method, coating and coated substrate

[0131] The present disclosure also relates to a method for coating a substrate (such as any of the conductive substrates mentioned above). The method may include electrophoretically applying an electrodepositable coating composition as described above to at least a portion of a substrate and curing the coating composition to form an at least partially cured coating on the substrate. The method may include: (a) electrophoretically depositing an electrodepositable coating composition of the present disclosure onto at least a portion of a substrate; and (b) heating the coated substrate to a temperature and for a time sufficient to cure the electrodeposited coating on the substrate. The method may optionally further include: (c) directly applying one or more pigmented coating compositions and / or one or more non-pigmented coating compositions to the at least partially cured electrodeposited coating to form a top coating on at least a portion of the at least partially cured electrodeposited coating; and (d) heating the coated substrate of step (c) to a temperature and for a time sufficient to cure the top coating.

[0132] Can be by the coating composition that cationic electrodeposition is electro-deposited and contact this composition on the conductive substrate with conductive cathode and conductive anode, wherein surface to be coated is negative electrode.After contacting with composition, when having applied enough voltages between electrode, the adhesive film of coating composition is deposited on negative electrode.The condition of carrying out electrodeposition is similar to the condition employed in the electrodeposition of other types of coating usually.The voltage applied can change and can be for example as low as one volt to up to several thousand volts, such as between 50 volts and 500 volts.Current density can be between 0.5 ampere and 15 amperes per square foot, and tends to reduce during electrodeposition, and this shows that insulating film has been formed.

[0133] Once the cationic electrodepositable coating composition is electrodeposited on at least a portion of a conductive substrate, the coated substrate is heated to a temperature and for a period of time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein, the term "at least partially cured" with respect to a coating refers to forming a coating by subjecting the coating composition to curing conditions that chemically react at least a portion of the reactive groups of the components of the coating composition to form a coating. The coated substrate can be heated to a temperature ranging from 250°F to 450°F (121.1°C to 232.2°C), such as 275°F to 400°F (135°C to 204.4°C), such as 300°F to 360°F (149°C to 180°C). Curing time can depend on curing temperature and other variables, for example, the film thickness of the electrodeposited coating, the level and type of the catalyst present in the composition, etc. For the purposes of this disclosure, all that is necessary is that time is sufficient to achieve the curing of the coating on the substrate. For example, the curing time may range from 10 minutes to 60 minutes, such as from 20 minutes to 40 minutes.The thickness of the resulting cured electrodeposited coating may range from 15 microns to 50 microns.

[0134] If desired, the electrodepositable coating compositions of the present disclosure can also be applied to substrates using non-electrophoretic coating application techniques such as flow coating, dipping, spraying, and roller coating. For non-electrophoretic coating applications, the coating compositions can be applied to conductive substrates as well as non-conductive substrates such as glass, wood, and plastic.

[0135] The present disclosure further relates to coatings formed by at least partially curing the electrodepositable coating compositions described herein.

[0136] The present disclosure further relates to a substrate at least partially coated with the electrodepositable coating composition described herein in an at least partially cured state.

[0137] The present disclosure further relates to a coated substrate comprising a cured coating film comprising the reaction product of: (a) a film-forming resin containing cationic salt groups dispersed in an aqueous medium, the film-forming resin containing cationic salt groups comprising the reaction product of a reaction mixture comprising: (a) a polyepoxide; (b) at least one polyol comprising an aliphatic-substituted phenol, the aliphatic-substituted phenol comprising at least two phenolic hydroxyl groups; and (c) a base; and (b) a curing agent.

[0138] Multilayer coating composite materials

[0139] The present disclosure also relates to a method for coating a substrate (such as any of the conductive substrates mentioned above). According to the present disclosure, such a method may include electrophoretically applying an electrodepositable coating composition as described above to at least a portion of the substrate and curing the coating composition to form an at least partially cured coating on the substrate. According to the present disclosure, the method may include (a) electrophoretically depositing an electrodepositable coating composition of the present disclosure onto at least a portion of the substrate; and (b) heating the coated substrate to a temperature and for a time sufficient to cure the electrodeposited coating on the substrate. According to the present disclosure, the method may optionally further include (c) directly applying one or more pigmented coating compositions and / or one or more non-pigmented coating compositions to the at least partially cured electrodeposited coating to form a top coating on at least a portion of the at least partially cured electrodeposited coating, and (d) heating the coated substrate of step (c) to a temperature and for a time sufficient to cure the top coating.

[0140] The electrodepositable coating composition of the present invention may comprise a multilayer coating system. The coating deposited by the composition of the present invention may have one or more additional coatings deposited below and / or above the layer. In a non-limiting example, the coating system may comprise a pretreatment layer, such as a phosphate layer (e.g., a zinc phosphate layer), and the electrodepositable coating composition of the present invention may be deposited on at least a portion of the pretreatment layer; one or more additional coatings may be applied to at least a portion of the electrodeposited coating. In addition to the electrodepositable coating composition of the present invention, the coating system may also include, for example, one or more pretreatment layers, and one or more additional coatings comprising a primer, a basecoat, a color paint, a single coat, a varnish, and / or a topcoat. Suitable additional coatings include any of those known in the art, and each independently may be waterborne, solvent-based, in the form of solid particles (i.e., a powder coating composition) or in the form of a powder slurry. These additional coatings may be cured independently of each other, or alternatively applied and cured simultaneously in a "wet-on-wet" manner. As used herein, "wet-on-wet" refers to a process in which a coating layer (eg, a clearcoat) is applied over a substantially uncured, different coating layer (eg, a basecoat), and both coating layers are then cured simultaneously.

[0141] The coating system may optionally include in any one or more coating layers one or a mixture of two or more of any colorants and / or fillers known to those skilled in the art in an amount sufficient to impart the desired properties, visual and / or color effects.

[0142] The present disclosure further relates to electrodeposited coatings formed by at least partially curing a film from the electrodepositable coating composition described herein.

[0143] The present disclosure also relates to a coated substrate comprising a coating deposited from the electrodepositable coating composition described above.

[0144] The coated substrate can be coated by the methods described herein.

[0145] The coated conductive substrate optionally may not include or may be free of a pretreatment layer between the substrate and the electrodeposited coating.

[0146] The coated conductive substrate optionally may not include any intermediate coating between the substrate and the electrodeposited coating.

[0147] In addition, the topcoat layer can be applied directly to the coating that can be electrodeposited. In other words, the substrate can lack a primer layer. For example, the primer layer can be applied directly to at least a portion of the electrodeposited coating.

[0148] As used herein, the term "residue" refers to the portion of a reactant structure that remains in the reaction product after the reactants undergo a chemical reaction. For example, the residue of a monomer in a polymer refers to the portion of the monomer structure that remains in the polymer after polymerization.

[0149] As used herein, unless otherwise defined, the term "substantially free" means that a component, if any, is present in an amount of less than 5 weight percent, based on the total weight of the slurry composition.

[0150] As used herein, unless otherwise defined, the term "substantially free" means that the component, if any, is present in an amount of less than 1 wt %, based on the total weight of the slurry composition.

[0151] As used herein, unless otherwise defined, the term "completely free" means that the component is not present in the slurry composition, ie, 0.00 wt %, based on the total weight of the slurry composition.

[0152] For the purpose of this detailed description, it should be understood that, except where expressly stated otherwise, the present disclosure may take alternative variations and step sequences. In addition, except in any operating examples, or where otherwise indicated, all figures expressing, for example, the amount of the ingredients used in this specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters set forth in the following description and the appended claims are approximate values ​​that can be changed according to the desired properties to be obtained by the present disclosure. At least, and not attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in accordance with the number of reported significant figures and by applying usual rounding techniques.

[0153] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0154] Furthermore, it should be understood that any numerical range described herein is intended to include all subranges subsumed therein. For example, a range of "1 to 10" is intended to include all subranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0155] As used herein, "comprising," "containing," and similar terms are understood in the context of this application to be synonymous with "including" and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, ingredients, or method steps. However, they also include the more restrictive terms "consisting of" and "consisting essentially of." As used herein, "consisting of" is understood in the context of this application to exclude the presence of any unspecified elements, ingredients, or method steps. As used herein, "consisting essentially of" is understood in the context of this application to include the specified elements, materials, ingredients, or method steps "as well as those elements, materials, ingredients, or method steps that do not materially affect the basic and novel characteristics of what is described."

[0156] As used herein, the terms "on," "onto," "applied on," "applied onto," "formed on," "deposited on," or "deposited onto" mean formed on, covered on, deposited on, or disposed on a surface but not necessarily in contact with the surface. For example, a composition "deposited onto" a substrate does not preclude the presence of one or more other intermediate coating layers of the same or different composition positioned between the electrodepositable coating composition and the substrate.

[0157] In this application, unless otherwise specifically stated, the use of the singular includes the plural, and the plural encompasses the singular. For example, although "a" film-forming polymer containing an ionic salt group, "a" aliphatic-substituted phenol, and "a" cationic salt group-forming agent are mentioned herein, combinations (i.e., multiples) of these components may be used. In addition, in this application, unless otherwise specifically stated, the use of "or" means "and / or", even if "and / or" may be explicitly used in some cases.

[0158] While specific aspects of the present disclosure have been described in detail, those skilled in the art will appreciate that various modifications and alternatives to those details can be developed based on the overall teachings of the present disclosure. Therefore, the particular arrangements disclosed are intended to be illustrative only and not limiting of the scope of the present disclosure, which is to be given by the full scope of the appended claims and any and all equivalent forms thereof.

[0159] The following examples illustrate the present disclosure, which, however, should not be considered to limit the disclosure to its details.Unless otherwise indicated, all parts and percentages in the following examples and throughout the specification are by weight.

[0160] Examples

[0161] Example 1: Electrodepositable Coating Composition Containing an Auxiliary Resin Containing an Aliphatic Substituted Phenol

[0162] Preparation of blocked polyisocyanate crosslinking agent 1.1 g of dibutyltin dilaurate, 177.4 g of methyl isobutyl ketone, 567 g of diethylene glycol monobutyl ether, 118 g of ethylene glycol monobutyl ether, and 176 g of methanol were stirred and mixed in a flask set to total reflux under nitrogen. The mixture was heated to a temperature of 35°C, and 1340 g of polymeric phenylene diisocyanate (LUPRANATE M20, commercially available from BASF) was added dropwise, allowing the temperature to rise due to the exothermic reaction and remaining below 100°C. After the addition was complete, a temperature of 100°C was established in the reaction mixture, and the reaction mixture was held at this temperature until no residual isocyanate was detected by IR spectroscopy. 136 g of methyl isobutyl ketone was then added, and the reaction mixture was stirred at 100°C for 30 minutes, then removed from the flask and cooled to ambient temperature.

[0163] Preparation of Jeffamine Adducts : To a round bottom flask, 1300 g of DER732 (liquid aliphatic diepoxy resin: the reaction product of epichlorohydrin and polypropylene glycol with an epoxy equivalent weight of 310 to 330 g / equivalent, available from sources such as Dow Chemical), 752 g of Epon TM880 (diglycidyl ether of bisphenol A with an epoxy equivalent weight of 188, available from Hexion) and 684 g of bisphenol A. The flask was equipped with a stirrer and a temperature measuring probe and purged with nitrogen. The mixture was heated to 130° C. and 3 g of benzyldimethylamine was added. The mixture was allowed to exotherm, after which the mixture was allowed to cool to 150° C. The temperature was maintained until the epoxy equivalent weight reached 1370. After adding 360 g of bis(2-(2-butoxyethoxy)ethoxy)methane and 94 g of methoxypropanol, the temperature was cooled to 100° C., and then 63 g of diethanolamine and 5 g of N-methylethylamine were added. The mixture was stirred for 30 minutes. 440 g of Jeffamine D400 (an amine-terminated polyethylene glycol (polyetheramine) commercially available from Huntsman) was added, the mixture was allowed to exotherm, and then heated at 100° C. until the viscosity stabilized. The mixture was then poured into a mixture of 3426 g of deionized water and 81 g of acetic acid. The mixture was stirred at ambient temperature for 40 minutes and 1372 g of deionized water were added.

[0164] Preparation of additive resin : A 3-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. 705.37 g of DER were added to the 3-liter flask. TM 732, 170.14g bisphenol A and 11.46g bis(2-(2-butoxyethoxy)ethoxy)methane. The flask was heated to 130°C. Then, a mixture of 1.65g benzyldimethylamine (BASF) and 0.92g bis(2-(2-butoxyethoxy)ethoxy)methane was added to the flask and heated to 135°C. The reaction mixture was then kept at 135°C until the EEW was 1230. Then 54.99g bis(2-(2-butoxyethoxy)ethoxy)methane was added to the flask and the reaction temperature was reduced to 100°C. At 100°C, 179.78g Jeffamine D400 and 6.89g bis(2-(2-butoxyethoxy)ethoxy)methane were added to the reaction mixture and kept at 90°C to 95°C for 4 hours until the viscosity stabilized. After the viscosity stabilized, 22.47g Epon TM 880 and 5.05 g of bis(2-(2-butoxyethoxy)ethoxy)methane were added to the flask. The reaction mixture was kept at 90°C to 95°C until the viscosity stabilized.

[0165] Preparation of standard main film-forming resin ("standard main resin") : A 12-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. 676.1 g of Epon was added to the 3-liter flask. TM880, 206.8 g bisphenol A, 46.5 g cyclohexylamine, 56.1 g ethoxylated bisphenol A polyol, 30.5 g methyl isobutyl ketone, and 0.3 g EtPPBr (ethyltriphenylphosphonium bromide) were premixed in an Erlenmeyer flask. The flask was heated to 130°C and the reaction exothermed to 145°C. The reaction mixture was then held at 145°C for 2 hours. After this holding period, 88.4 g methyl isobutyl ketone, 28.6 g ethoxylated bisphenol A polyol, and 84.2 g ARCOL polyol PPG 725 (available from Covestro LLC) were added, followed by 592.9 g of the blocked polyisocyanate described above, while cooling to 105°C. At 105°C, 49.0 g of diketimine (the reaction product of diethylenetriamine and methyl isobutyl ketone, 73% solids in methyl isobutyl ketone) was added, followed by 44.7 g of N-methylethanolamine, and the reaction was allowed to exotherm to 120°C. The reaction mixture was then held at 120°C for 1 hour. After the 1 hour, 1904 g of this resin mixture was added to a mixture of 27 g of 90% formic acid, 110 g of deionized water, and 213 g of the above-described Jeffamine adduct and mixed for 30 minutes. 1455 g of deionized water was added to the reaction mixture and mixed for 30 minutes. An additional 1100 g of deionized water was added, and the solvent was removed by vacuum distillation.

[0166] Preparation of comparative auxiliary resin A A 3-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. 511.5 g of Epon premixed in the conical flask was added to the 3-liter flask. TM 880, 214.8 g bisphenol A, 0.2 g Tetronic 150R1 (a tetrafunctional block copolymer with a surfactant containing terminal secondary hydroxyl groups, commercially available from BASF), 52.7 g bis(2-(2-butoxyethoxy)ethoxy)methane, and 98.0 g ethoxylated bisphenol A polyol. The flask was heated to 60°C, at which temperature 62.1 g aminopropyldiethanolamine, 3.9 g ethanolamine, and 40.3 g diethanolamine were added to the flask, and the reaction was allowed to exotherm to 180°C. The reaction mixture was then held at 170°C for 1 hour. After holding, 6.8 g methyl isobutyl ketone and 20.5 g Dowanol were added. TM PM, while cooling to 145 ° C. At 145 ° C, add 17.7g Epon TM After holding at 880°C for 1 hour, 600.2 g of blocked polyisocyanate crosslinker was added to the reaction mixture while cooling to 110°C. 21.3 g of acetic acid was added and mixed for 15 minutes. After 60 minutes, 836.0 g of deionized water was added and stirred for an additional 30 minutes.

[0167] Preparation of experimental auxiliary resin 1 A 3-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. 273.5 g of Epon premixed in an Erlenmeyer flask were added to the 3-liter flask. TM 880, 57.4g bisphenol A, 154.1g NX-4005 (aliphatic substituted phenol: cardanol derivative according to structure (IV) with a hydroxyl equivalent weight of 316 g / equivalent), 0.1 g Tetronic 150R1, 26.5 g bis(2-(2-butoxyethoxy)ethoxy)methane, and 52.4 g ethoxylated bisphenol A polyol. The flask was heated to 60°C, at which temperature 33.2 g aminopropyldiethanolamine, 2.1 g ethanolamine, and 21.5 g diethanolamine were added to the flask, and the reaction was allowed to exotherm to 180°C. The reaction mixture was then held at 170°C for 1 hour. After holding, 3.7 g methyl isobutyl ketone and 10.9 g Dowanol were added. TM PM (propylene glycol methyl ether, commercially available from Dow Chemical Company) while cooling to 145°C. At 145°C, 8.9 g of Epon TM After holding at 880°C for 1 hour, 279.6 g of a blocked polyisocyanate crosslinker was added to the reaction mixture while cooling to 110°C. 11.4 g of acetic acid was added and mixed for 15 minutes. 804.3 g of this resin mixture was then added to 1196 g of deionized water.

[0168] Preparation of experimental auxiliary resin 2 A 3-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. 210.3 g of Epon premixed in the conical flask was added to the 3-liter flask. TM 880, 236.3g NX-4005, 0.1g Tetronic 150R1, 26.1g bis(2-(2-butoxyethoxy)ethoxy)methane and 40.3g ethoxylated bisphenol A polyol. The flask was heated to 60°C, at which temperature 25.6g aminopropyldiethanolamine, 1.6g ethanolamine and 16.6g diethanolamine were added to the flask, and the reaction was allowed to exotherm to 180°C. The reaction mixture was then kept at 170°C for 1 hour. After the incubation period, 2.8g methyl isobutyl ketone and 8.4g Dowanol were added. TM PM, while cooling to 145 ° C. At 145 ° C, add 8.7g Epon TMAfter holding at room temperature for 1 hour, 353.5 g of a blocked polyisocyanate crosslinker was added to the reaction mixture while cooling to 110°C. 8.8 g of acetic acid was added and mixed for 15 minutes. 807.5 g of this resin mixture was then added to 1,192 g of deionized water.

[0169] Preparation of experimental auxiliary resin 3 : A 3-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. 291.0 g of Epon premixed in the Erlenmeyer flask was added to the 3-liter flask. TM 880, 61.1 bisphenol A, 105.8 g NX-5266 (aliphatic substituted phenol: cardanol derivative according to structure (III)), 0.09 g Tetronic 150R1, 28.2 g bis(2-(2-butoxyethoxy)ethoxy)methane and 55.7 g ethoxylated bisphenol A polyol. The flask was heated to 60°C, at which temperature 35.4 g aminopropyldiethanolamine, 2.2 g ethanolamine and 22.9 g diethanolamine were added to the flask and the reaction was allowed to exotherm to 180°C. The reaction mixture was then kept at 170°C for 1 hour. After the incubation period, 3.9 g methyl isobutyl ketone and 232.8 g Dowanol were added. TM PM, while cooling to 145 ° C. At 145 ° C, add 9.4g Epon TM After holding at 880°C for 1 hour, 297.4g of blocked polyisocyanate crosslinker was added to the reaction mixture while cooling to 110°C. 12.1g of acetic acid was added and mixed for 15 minutes. 995.8g of this resin mixture was then added to 1,000g of deionized water and stirred for an additional 30 minutes.

[0170] Preparation of experimental auxiliary resin 4 : A 3-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. 291.0 g of Epon premixed in the Erlenmeyer flask was added to the 3-liter flask. TM 880, 61.1g bisphenol A, 105.8g NX-5266, 0.09g Tetronic 150R1, 28.2g bis(2-(2-butoxyethoxy)ethoxy)methane and 55.7g ethoxylated bisphenol A polyol. The flask was heated to 60°C, at which temperature 35.4g aminopropyldiethanolamine, 2.2g ethanolamine and 22.9g diethanolamine were added to the flask and the reaction was allowed to exotherm to 180°C. The reaction mixture was then kept at 170°C for 1 hour. After the holding time, 3.9g methyl isobutyl ketone and 232.8g butyl cellosolve (2-butoxyethanol) were added while cooling to 145°C. At 145°C, 9.4g Epon was added. TM After holding at 880°C for 1 hour, 297.4g of the blocked polyisocyanate crosslinker described above was added to the reaction mixture while cooling to 110°C. 12.1g of acetic acid was added and mixed for 15 minutes. 995.8g of this resin mixture was then added to 1,000g of deionized water and stirred for an additional 30 minutes.

[0171] Preparation of electrodepositable coating compositions :In a container suitable for electrodeposition, each component in the table below was added under stirring. The relevant resins used and the final DI water added varied slightly based on the difference in solid and water content of each resin added, but each final composition contained the same solid and resin content. The solid content of the final composition was 25%. After mixing, the mixture was then ultrafiltered (20% reconstituted with deionized water) before electrodeposition. Each composition contained an equal amount (less than 1 wt %, wt % based on resin solid weight) of catalyst.

[0172] Electrodepositable coating compositions

[0173]

[0174] 1 Bis(2-(2-butoxyethoxy)ethoxy)methane, available from BASF Corporation.

[0175] 2 As described in paragraphs

[0185] to

[0187] of Example 2 of U.S. Patent Publication No. 2021 / 0324209A1, the cited portion of which is incorporated herein by reference.

[0176] 3 Commercially available from Dow Chemical Company.

[0177] 4 Pigment paste, solids content 60 wt. % and pigment to binder ratio 2.36.

[0178] The substrate was immersed in a stirred bath containing an electrodepositable coating composition heated to 90°F (32.2°C), with the cathode of a DC rectifier connected to the substrate and the anode of the rectifier connected to a stainless steel tube for circulating cooling water to control the bath temperature. The voltage was increased from 0V to a set point voltage of 190V over a period of 30 seconds, and then maintained at this voltage for another 20 to 120 seconds to deposit the desired film thickness. This combination of time, temperature, and voltage deposited a coating of approximately 18 microns after curing. After electrodeposition, the panel was removed from the bath, rinsed vigorously with deionized water, and cured for 20 minutes at 165°C in a Despatch LFD 1-42 electric oven. This process was performed on electrogalvanized steel substrates (EZG) or cold rolled steel (CRS) that had been phosphated ((EZG / C700, ACT test panel product #31611 or CRS / C700, ACT test panel product #28630)) or pretreated with ZIRCOBOND 1.5 (pretreated panels are referred to as "Zb 1.5" in the table below), which is commercially available from PPG Industries. For EZG and CRS panels pretreated with ZIRCOBOND 1.5 pretreatment, the panels were cleaned and pretreated according to the method described in Example 2 of International Publication No. WO 2018 / 039462 A1 using the "standard cleaner" described in paragraphs

[0271] to

[0279] .

[0179] The coated panels were tested for appearance (Ra), throwability, cure, flexibility (mandrel bend), impact resistance, and corrosion resistance. The test procedures and results are provided below.

[0180] Appearance (surface roughness) test procedure: Surface roughness was evaluated according to the following method: an electrodepositable coating composition was electrodeposited onto a metal panel and cured by baking in an electric oven. The coating texture was then evaluated over a specified length of the panel using a profilometer. The roughness profile was filtered using an Lc parameter of 2.5 mm and an Ls parameter of 8 μm according to ISO 4287-1997 3.1.6, and the Ra metric, hereinafter referred to as Ra, was summarized according to ISO 4287-1997 4.2.1. The specific test procedure was as follows: the electrodepositable coating composition was electrodeposited onto a metal panel measuring 4 × 6 × 0.032 inches, and the coating was cured by baking in an electric oven at 175°C for 25 minutes. The coating texture was evaluated using a Mitutoyo Surftest SJ-402 non-slip stylus profilometer equipped with a 4 mN detector and a diamond stylus tip with a 90° taper and a 5 μm tip radius. The scan length, measurement speed, and data sampling interval were 48 mm, 1 mm / s, and 5 μm, respectively. The raw data was first filtered into a roughness profile using the Lc parameter of 2.5 mm and the Ls parameter of 8 μm according to ISO 4287-1997 3.1.6, and then summarized into the Ra metric according to ISO 4287-1997 4.2.1. This test is referred to herein as the surface roughness test method.

[0181] Throwing power :according to Figure 1 and Figure 2The "Nagoya box method" shown is used to evaluate throwing power. The Nagoya box 10 has four parallel metal panels 1, 2, 3 and 4, each of which has a size of 6.9 cm (w) × 15.2 cm (I), a plate spacing of 20 mm, and is sealed at the bottom and sides. A through-hole 5 with a diameter of 1.6 cm is located at the center 5 cm from the bottom edge of the metal panels 1, 2 and 3 (but not 4). The box 10 is immersed in an electrodeposition paint container 20 filled with a cathodic electrodeposition paint. In this case, the cathodic electrodeposition paint flows into the box 10 only through each through-hole 5. While stirring the cathodic electrodeposition paint, the metal panels 1 to 4 are electrically connected, and a counter electrode 21 is set at a distance of 150 mm from the metal panel 1. A voltage is applied to the metal panels 1 to 4 as the negative electrode and the counter electrode 21 as the positive electrode to perform cathodic electrodeposition coating. The box 10 is immersed in an electrodepositable composition (ED 7000Z from PPG Industries) heated to 32° C. and magnetically stirred. Each panel is used as a cathode, which is electrically connected to a counter electrode spaced 150mm from the first panel. Voltage is applied to the panel for a period of time, with an initial 30-second voltage ramp applied to rise to 190V. After reaching 190V, the voltage is maintained for 180 seconds. After coating is complete, the coated panel is thoroughly rinsed in deionized water and placed in an electric oven heated to 175°C for 25 minutes. The thickness and uniformity of the coating on each panel face are evaluated in 4 areas located at right angles to the center holes on panels 1, 2, and 3, which are spaced 1mm apart. These locations are also checked on the face of panel 4, which does not contain holes. In order to evaluate the throwing power of the electrodepositable composition, the film thickness on the G face is divided by the film thickness on the A face and multiplied by 100%.

[0182] Mandrel bend test method : The flexibility of the coatings (and hence the lifting or cracking of the coatings) was evaluated using the mandrel bend test method according to ASTM D 522 (December 2010) and the results are reported in mm.

[0183] Reverse shock test method : The impact resistance of the coatings was evaluated using the reverse impact test method performed according to ASTM D 2794-93(2019) and the results were reported in inch-pounds.

[0184] Corrosion resistance was evaluated by hot water salt immersion and the GMW14782 test method described below.

[0185] Hot Water Salt Dip (HSD) Corrosion Test Panels were tested for scratch creep and blistering using a hot salt immersion test. Scratch creep was measured from the affected coating on the left side of the scratch to the affected coating on the right side. An X-shaped scratch was made on the cured coating before being placed in an immersion chamber for 10 days. The immersion solution was a 5% NaCl salt solution at 55°C.

[0186] GMW14782 corrosion test The coated panels were subjected to the GM cyclic corrosion test GMW 14872 (November 2022), in which the panels were scratched by cutting through the coating system to the metal substrate (a 10.2 cm vertical line in the middle). The panels were exposed to condensing humidity (8 hours at 25°C and 45% humidity, then 8 hours at 49°C and 100% humidity, followed by 8 hours at 60°C and 30% humidity) for 40 days. At the end of the test, the panels were rated by measuring the coating loss (creep) at the scratch and the maximum creep (on both sides) of each panel in millimeters.

[0187] a Experimental composition 4 was tested only for appearance, since it was similar to experimental composition 3 except for the solvent used.

[0188]

[0189] These results indicate that the experimental electrodepositable coating compositions provide satisfactory performance in all measured properties. Example 2: A film-forming resin comprising a primary film-forming resin containing an aliphatic substituted phenol and optionally an auxiliary film-forming resin containing an aliphatic substituted phenol Resin electrodepositable coating composition

[0190] Preparation of experimental main resin 1 A primary film-forming electrophoretic coating resin was prepared by replacing 50% of the BPA in the standard primary resin of Example 1 with the aliphatic substituted phenol diallyl bisphenol A by the following steps: A 12-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. To the 3-liter flask was added 676.1 g of Epon premixed in the Erlenmeyer flask. TM880, 103.4 g bisphenol A, 139.7 g diallyl bisphenol A (BX-o-DABPA: commercially available from Bimax), 46.5 g cyclohexylamine, 56.1 g ethoxylated bisphenol A polyol, 31.6 g methyl isobutyl ketone, and 0.28 g EtPPBr (ethyltriphenylphosphonium bromide). The flask was heated to 130°C and the reaction was allowed to exotherm to 145°C. The reaction mixture was then held at 145°C for 2 hours. After holding, 92.1 g methyl isobutyl ketone, 28.6 g ethoxylated bisphenol A polyol, and 84.2 g ARCOL Polyol PPG 725 (available from Covestro LLC) were added, followed by 613 g of blocked polyisocyanate while cooling to 105°C. At 105°C, 49.0 g of diketimine (the reaction product of diethylenetriamine and methyl isobutyl ketone, 73% solids in methyl isobutyl ketone) was added, followed by 44.7 g of N-methylethanolamine, and the reaction was allowed to exotherm to 120°C. The reaction mixture was then held at 120°C for 1 hour. After the 1 hour, 1670.4 g of this resin mixture was added to a mixture of 23.1 g of 90% formic acid, 972.8 g of deionized water, and 186.8 g of the above-described Jeffamine adduct and mixed for 30 minutes. 1276.4 g of deionized water was added to the reaction mixture, and the mixture was mixed for 30 minutes. An additional 1100.0 g of deionized water was added, and the solvent was removed by vacuum distillation.

[0191] Preparation of experimental main resin 2 A primary film-forming electrophoretic coating resin was prepared by replacing 100% of the BPA in the standard primary resin of Example 1 with the aliphatic substituted phenol diallyl bisphenol A by the following steps: A 12-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. To the 3-liter flask was added 676.1 g of Epon premixed in the Erlenmeyer flask. TM880, 279.3 g of diallyl bisphenol A (BX-o-DABPA: commercially available from Bimax), 46.5 g of cyclohexylamine, 56.1 g of ethoxylated bisphenol A polyol, 32 g of methyl isobutyl ketone, and 0.28 g of EtPPBr (ethyltriphenylphosphonium bromide). The flask was heated to 130°C and the reaction was allowed to exotherm to 145°C. The reaction mixture was then held at 145°C for 2 hours. After this holding period, 95.8 g of methyl isobutyl ketone, 28.6 g of ethoxylated bisphenol A polyol, and 84.2 g of ARCOL Polyol PPG 725 (available from Covestro LLC) were added, followed by 633 g of blocked polyisocyanate while cooling to 105°C. At 105°C, 49.0 g of diketimine (the reaction product of diethylenetriamine and methyl isobutyl ketone, 73% solids in methyl isobutyl ketone) was added, followed by 44.7 g of N-methylethanolamine, and the reaction was allowed to exotherm to 120°C. The reaction mixture was then held at 120°C for 1 hour. After the 1 hour, 1722.4 g of this resin mixture was added to a mixture of 23.1 g of 90% formic acid, 1002.6 g of deionized water, and 192.5 g of the above-described Jeffamine adduct and mixed for 30 minutes. 1315.6 g of deionized water was added to the reaction mixture and mixed for 30 minutes. An additional 1100.0 g of deionized water was added, and the solvent was removed by vacuum distillation.

[0192] Preparation of experimental auxiliary resin 5 Experimental auxiliary resin 5 was prepared by replacing 50% of the bisphenol A in comparative auxiliary resin A with diallyl bisphenol A. Auxiliary resin 5 was prepared by the following method: A 3-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. 302.1 g of Epon premixed in an Erlenmeyer flask was added to the 3-liter flask. TM 880, 63.4 g bisphenol A, 85.7 g diallyl bisphenol A (BX-o-DABPA: commercially available from Bimax), 0.09 g Tetronic 150R1, 29.2 g bis(2-(2-butoxyethoxy)ethoxy)methane, and 57.9 g ethoxylated bisphenol A polyol. The flask was heated to 60°C, at which point 36.7 g aminopropyldiethanolamine, 2.3 g ethanolamine, and 23.8 g diethanolamine were added to the flask, and the reaction was allowed to exotherm to 180°C. The reaction mixture was then held at 170°C for 1 hour. After holding, 4.0 g methyl isobutyl ketone and 12.1 g Dowanol were added. TM PM, while cooling to 145 ° C. At 145 ° C, add 9.8g Epon TMAfter holding at 880°C for 1 hour, 308.8g of a blocked polyisocyanate crosslinker was added to the reaction mixture while cooling to 110°C. 12.6g of acetic acid was added and mixed for 15 minutes. 806.2g of this resin mixture was then added to 1,000g of deionized water and stirred for an additional 30 minutes.

[0193] Preparation of experimental auxiliary resin 6 Experimental auxiliary resin 6 was prepared by replacing 100% of bisphenol A in comparative auxiliary resin A with diallyl bisphenol A. Auxiliary resin 6 was prepared by the following method: A 3-liter flask was equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen inlet, and a heating mantle with a thermometer connected by a temperature feedback control device. To the 3-liter flask was added 272.8 g of Epon premixed in an Erlenmeyer flask. TM 880, 154.8 g of diallyl bisphenol A (BX-o-DABPA: commercially available from Bimax), 0.08 g of Tetronic 150R1, 29.3 g of bis(2-(2-butoxyethoxy)ethoxy)methane, and 52.2 g of ethoxylated bisphenol A polyol. The flask was heated to 60°C, at which temperature 33.1 g of aminopropyldiethanolamine, 2.08 g of ethanolamine, and 21.5 g of diethanolamine were added to the flask, and the reaction was allowed to exotherm to 180°C. The reaction mixture was then held at 170°C for 1 hour. After holding, 3.6 g of methyl isobutyl ketone and 10.9 g of Dowanol were added. TM PM, while cooling to 145 ° C. At 145 ° C, add 9.8g Epon TM After holding at 880°C for 1 hour, 349.0 g of blocked polyisocyanate was added to the reaction mixture while cooling to 110°C. 11.3 g of acetic acid was added and mixed for 15 minutes. 808 g of this resin mixture was then added to 1,200 g of deionized water and stirred for an additional 30 minutes.

[0194] Preparation of electrodepositable coating compositions In a container suitable for electrodeposition, each component listed in the table below was added with stirring. The solids content was 25%. After mixing, the mixture was ultrafiltered (20% reconstituted with deionized water) before electrodeposition. Each composition contained an equal amount (less than 1% by weight, wt% based on resin solids) of catalyst. Comparative composition A was the same as above.

[0195] Electrodepositable coating compositions

[0196]

[0197] 1 Bis(2-(2-butoxyethoxy)ethoxy)methane, available from BASF Corporation.

[0198] 2 As described in paragraphs

[0185] to

[0187] of Example 2 of U.S. Patent Publication No. 2021 / 0324209A1, the cited portion of which is incorporated herein by reference.

[0199] 3 Commercially available from Dow Chemical Company.

[0200] 4 Pigment paste, solids content 60 wt. % and pigment to binder ratio 2.36.

[0201] The substrate was immersed in a stirred bath containing an electrodepositable coating composition heated to 90°F (32.2°C), and the cathode of a DC rectifier was connected to the substrate, and the anode of the rectifier was connected to a stainless steel pipe for circulating cooling water to control the bath temperature. The voltage was increased from 0V to a set point voltage of 190V over a period of 30 seconds, and then maintained at this voltage for another 20 to 120 seconds to deposit the required film thickness. This combination of time, temperature, and voltage deposited a coating of approximately 18 microns after curing. After electrodeposition, the panel was removed from the bath, vigorously rinsed with deionized water, and cured for 20 minutes at 165°C in a Despatch LFD 1-42 electric oven. This process was performed on electrogalvanized steel substrates (EZG) and cold rolled steel substrates (CRS) (bare or pre-treated as described above) as described above.

[0202] The coated panels were tested for appearance (Ra), throwability, cure, flexibility (mandrel bend), impact resistance, and corrosion resistance. The testing procedures were the same as in Example 1, and the results are provided below.

[0203]

[0204] These results indicate that the experimental electrodepositable coating compositions provide satisfactory performance in all measured properties.

[0205] Those skilled in the art will appreciate that, based on the foregoing disclosure, many modifications and variations are possible without departing from the broad inventive concepts described and exemplified herein. Therefore, it should be understood that the foregoing disclosure is merely illustrative of various illustrative aspects of the present application, and that those skilled in the art can readily make many modifications and variations within the spirit and scope of the present application and the appended claims.

Claims

1. An electrodepositable coating composition comprising: A film-forming resin containing cationic salt groups, dispersed in an aqueous medium, the film-forming resin containing cationic salt groups comprising the reaction product of a reaction mixture comprising: (a) polyepoxide; (b) at least one polyol comprising an aliphatic-substituted phenol comprising at least two phenolic hydroxyl groups; and (c) Cationic salt group-forming agent.

2. The electrodepositable coating composition of claim 1 , wherein the polyepoxide comprises 5 to 95 wt %, such as 20 to 75 wt %, and the polyol comprises 5 to 95 wt %, such as 25 to 80 wt %, the wt % being based on the total solids weight of the reaction mixture.

3. The electrodepositable coating composition of claim 1 or 2, wherein the reaction mixture further comprises bisphenol A, bisphenol F, bisphenol S, a diphenol, a dihydroxybenzene such as catechol, resorcinol, or hydroquinone, or a combination thereof.

4. The electrodepositable coating composition of claim 3, wherein bisphenol A comprises 0 wt% to 65 wt%, such as 0 wt% to 40 wt%, the wt% being based on the total solids weight of the reaction mixture.

5. The electrodepositable coating composition of any one of the preceding claims, wherein the reaction mixture further comprises a monofunctional active hydrogen-containing component, a monofunctional epoxide-containing component, a monofunctional acid-containing component, or a combination thereof.

6. The electrodepositable coating composition of any one of the preceding claims, wherein the aliphatic-substituted phenol comprises a compound having structure (I): wherein A1 to A6 each independently comprises a hydroxyl group, hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, wherein at least two of A1 to A6 are hydroxyl groups, and at least one of A1 to A6 is an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group.

7. The electrodepositable coating composition of any one of the preceding claims, wherein the aliphatic-substituted phenol comprises a compound having structure (II): wherein each of A1 to A5 independently comprises a hydroxyl group, hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, and at least one of A1 to A5 is a hydroxyl group; each of B1 to B5 independently comprises a hydroxyl group, hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, and at least one of B1 to B5 is a hydroxyl group; and Z comprises a divalent organic linking group and is not [—C(R)—], wherein if four of A1 to A5 and four of B1 to B5 are hydrogen, each R is independently CH or H.

8. The electrodepositable coating composition of claim 7, wherein at least one of A1 to A5 comprises an unsaturated aliphatic group and / or at least one of B1 to B5 comprises an unsaturated aliphatic group.

9. The electrodepositable coating composition according to claim 7 or 8, wherein at least one of A1 to A5 comprises an unsaturated aliphatic group containing 3 or more carbon atoms and having a terminal ethylenically unsaturated group, and / or at least one of B1 to B5 comprises an unsaturated aliphatic group containing 3 or more carbon atoms and having a terminal ethylenically unsaturated group.

10. The electrodepositable coating composition of any one of claims 7 to 9, wherein the divalent organic linking group of Z comprises an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic divalent group having 1 to 50 carbon atoms, such as 1 to 30 carbon atoms, such as 1 to 20 carbon atoms, such as 1 to 15 carbon atoms.

11. The electrodepositable coating composition of any one of claims 7 to 10, wherein the aliphatic-substituted phenol has a hydroxyl value of 50 mg KOH / gram to 2,000 mg KOH / gram of aliphatic-substituted phenol, such as 50 mg KOH / gram to 700 mg KOH / gram, such as 150 mg KOH / gram to 700 mg KOH / gram.

12. The electrodepositable coating composition of any one of claims 7 to 11, wherein the aliphatic-substituted phenol has a number average molecular weight (Mw) of 110 to 10,000 g / mol, such as 150 to 5,000 g / mol, such as 150 to 1,000 g / mol, as measured by gel permeation chromatography using polystyrene standards.

13. The electrodepositable coating composition of any one of the preceding claims, wherein the aliphatically substituted phenol comprises a cardanol derivative.

14. The electrodepositable coating composition of any preceding claim, wherein the aliphatic-substituted phenol comprising the compound having structure (II) comprises the reaction product of (1) a phenolic lipid comprising an unsaturated aliphatic group and (2) phenol.

15. The electrodepositable coating composition of any one of the preceding claims, wherein the aliphatic-substituted phenol comprises a compound having structure (III):

16. The electrodepositable coating composition of any one of the preceding claims, wherein the aliphatic-substituted phenol comprises a compound having structure (IV): wherein each R independently comprises hydrogen, an unsubstituted or substituted, branched or linear, saturated or unsaturated, cyclic, acyclic or partially cyclic aliphatic, aromatic or arylaliphatic group, and n is 1 to 3.

17. The electrodepositable coating composition of any one of claims 7 to 12, wherein the aliphatic-substituted phenol comprises diallyl bisphenol A.

18. The electrodepositable coating composition of claim 16, wherein the diallyl bisphenol A has structure (V):

19. The electrodepositable coating composition of any preceding claim, wherein the aliphatically substituted phenol comprises a phenolic lipid.

20. An electrodepositable coating composition according to any preceding claim, wherein the polyepoxide has an epoxy equivalent weight of 50 to 500, such as 100 to 360, such as 170 to 200.

21. An electrodepositable coating composition according to any one of the preceding claims, wherein the ratio of epoxy functional groups of the polyepoxide to hydroxyl functional groups of the polyol is from 2:0.1 to 2:1.9, such as from 10:1 to 1.1:1, such as from 5:1 to 1.1:1, such as from 3:1 to 1.1:1, such as from 2.5:1 to 1.1:1, such as from 2.1:1 to 1.9:

1.

22. The electrodepositable coating composition of any one of the preceding claims, wherein the polyepoxide comprises an aromatic polyepoxide, an aliphatic polyepoxide, or any combination thereof.

23. The electrodepositable coating composition of claim 22, wherein the aromatic polyepoxide comprises diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of biphenol, diglycidyl ether of dihydroxybenzene, or any combination thereof.

24. The electrodepositable coating composition of claim 22 or 23, wherein the aliphatic polyepoxide comprises a hydrogenated diglycidyl ether of bisphenol A, a diglycidyl ether of a diol, or any combination thereof.

25. The electrodepositable coating composition of any preceding claim, wherein the polyepoxide comprises a polyglycidyl ether of any one of the aliphatic-substituted phenols of claims 1 and 6 to 19.

26. The electrodepositable coating composition of any one of the preceding claims, wherein the cationic salt group forming agent comprises an amine, a sulfur-containing base, or any combination thereof.

27. An electrodepositable coating composition according to any one of the preceding claims, wherein the film-forming resin containing cationic salt groups is the primary carrier resin.

28. An electrodepositable coating composition according to any one of the preceding claims, wherein the film-forming resin containing cationic salt groups is an auxiliary resin.

29. The electrodepositable coating composition of any preceding claim, wherein (a) the polyepoxide, (b) the aliphatically substituted phenol, and (c) the cationic salt group forming agent react in a single step to form the reaction product.

30. The electrodepositable coating composition of any one of claims 1 to 28, wherein the reaction product is formed by reacting (a) the polyepoxide with (b) the aliphatic-substituted phenol in a first step to form an intermediate product, and subsequently reacting the intermediate product with (c) the cationic salt group-forming agent in a second step.

31. An electrodepositable coating composition according to any one of the preceding claims, wherein the film-forming resin containing cationic salt groups has a number average molecular weight of 400 g / mol to 50,000 g / mol, such as 400 g / mol to 20,000 g / mol, such as 1,000 g / mol to 5,000 g / mol, such as 2,000 g / mol to 3,000 g / mol as measured by gel permeation chromatography using polystyrene standards.

32. An electrodepositable coating composition according to any preceding claim, wherein the film-forming resin containing cationic salt groups has a weight average molecular weight of 4,000 to 200,000 g / mol as measured by gel permeation chromatography using polystyrene standards.

33. An electrodepositable coating composition according to any one of the preceding claims, wherein the reaction mixture further comprises a multifunctional component comprising two or more functional groups, wherein the functional groups comprise carboxylic acid functional groups, anhydrides, hydroxyl functional groups, thiol functional groups, primary amino functional groups, secondary amino functional groups, or any combination thereof.

34. The electrodepositable coating composition of any one of the preceding claims, wherein the reaction mixture further comprises a monofunctional component comprising a primary amino functional group-containing component, a monofunctional thiol group-containing component, a monofunctional carboxylic acid group-containing component, a monofunctional epoxy group-containing component, a monofunctional hydroxyl group-containing component (e.g., phenol), other monofunctional active hydrogen group-containing components, a monofunctional isocyanate group-containing component, or a combination thereof.

35. The electrodepositable coating composition of any preceding claim, wherein the reaction product is substantially free, essentially free, or completely free of bisphenol A.

36. The electrodepositable coating composition of any preceding claim, wherein the reaction product is substantially free, essentially free, or completely free of bisphenol F.

37. The electrodepositable coating composition of any preceding claim, wherein the reaction product is substantially free, essentially free, or completely free of bisphenol S.

38. An electrodepositable coating composition according to any one of the preceding claims, wherein the electrodepositable coating composition has a free bisphenol A content of less than 0.1 wt %, such as less than 0.01 wt %, such as less than 0.001 wt %, based on the total weight of the electrodepositable coating composition as measured by HPLC or LC-MS.

39. The electrodepositable coating composition of any one of the preceding claims, wherein the electrodepositable coating composition further comprises a second film-forming resin containing cationic salt groups dispersed in the aqueous medium, wherein the second film-forming resin containing cationic salt groups is different from the film-forming resin containing cationic salt groups.

40. The electrodepositable coating composition of any preceding claim, further comprising a curing agent.

41. The electrodepositable coating composition of any preceding claim further comprising a catalyst.

42. The electrodepositable coating composition of any preceding claim further comprising a pigment.

43. The electrodepositable coating composition of claim 39, wherein the ratio of pigment to binder is from 0.05:1 to 2:

1.

44. The electrodepositable coating composition of any one of the preceding claims, wherein the electrodepositable coating composition is substantially free, essentially free, or completely free of bisphenol A polyoxyethylene ether phosphate.

45. A method of coating a substrate, the method comprising electrophoretically applying the electrodepositable coating composition of any preceding claim to at least a portion of the substrate.

46. ​​A coated substrate comprising a cured coating film comprising the reaction product of: (a) a film-forming resin containing cationic salt groups, dispersed in an aqueous medium, the film-forming resin containing cationic salt groups comprising the reaction product of a reaction mixture comprising: (a) a polyepoxide; (b) at least one polyol comprising an aliphatic-substituted phenol, the aliphatic-substituted phenol comprising at least two phenolic hydroxyl groups; and (c) a cationic salt group-forming agent; and (b) Curing agent.

47. A coated substrate according to claim 46, wherein the coating is deposited from an electrodepositable coating composition according to any one of the preceding claims 1 to 44.

48. The coated substrate of claim 46 or 47, wherein the coating is applied by electrophoretically applying the electrodepositable coating composition to at least a portion of the substrate.

49. The coated substrate of any one of claims 46 to 48, wherein the substrate comprises a vehicle body, a vehicle frame, a vehicle part, a motorcycle, a wheel, an industrial structure and component, agricultural equipment, lawn and garden equipment, an air conditioning unit, a heat pump unit, lawn furniture, a packaging container, or any combination thereof.

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