Coating compositions for coating substrates, which include binder components

Abstract

Coating composition for coating a substrate, comprising: a first polymer comprising a first polymer-bound part having an acid-functional group or a derivative thereof; wherein the first polymer-bound part is polymerized from a first polymer monomer mixture comprising acid-functional monomers in an amount of 0.1 to 12 wt.% based on the total weight of the first polymer monomer mixture; a second polymer comprising a second polymer-bound part having an amino-functional group; wherein the second polymer-bound part is polymerized from a second polymer monomer mixture comprising amino-functional monomers in an amount of 0.1 to 15 wt.%, based on the total weight of the second polymer monomer mixture; and an organic solvent; wherein the first polymer includes less than 0.1 wt% of amino functional groups and the second polymer includes less than 0.1 wt% of acid functional groups or derivatives thereof; and where the acid functional groups and the amino functional groups are essentially reactive with each other, at least after the coating composition has been applied to the substrate, the coating composition is essentially free of water.

Description

Technical area

[0001] The technical field generally concerns coating compositions that include a first polymer and a second polymer for coating substrates. background

[0002] Coating compositions are used to form coating layers, such as primer, basecoat, and clearcoat, for protective and decorative purposes. These coating compositions can be used in automotive OEM and refinish applications, providing a protective layer for the underlying substrate and potentially offering aesthetic value. Currently, automotive coatings are typically multilayer coating systems that include a clearcoat layer over a basecoat layer, with the basecoat layer over one or more additional layers, such as a primer and an electrocoat.

[0003] In refinishing applications, customers demand high productivity and excellent performance. To achieve the desired productivity, coating compositions are preferably able to dry relatively quickly at room temperature or slightly elevated temperatures. However, many of today's fast-drying coating compositions do not meet the desired performance requirements, such as excellent stone chip resistance, moisture resistance, adhesion between and within layers, and appearance. Furthermore, if the coating layer, such as a basecoat, has not dried sufficiently before the subsequent application of a clearcoat composition over the basecoat to form a clear layer, the application of the clearcoat composition will disrupt the basecoat layer and adversely affect its appearance.For example, flake control and metallic appearance (i.e., “downflop”) of basecoat compositions containing special effect pigments, such as metallic and pearlescent flake pigments, will suffer due to the disruption of the flake pigments caused by mixing the basecoat and clearcoat layers at the interface between them.

[0004] EP 3 176 234 A1 relates to a coating material for a gas barrier comprising a polycarboxylic acid, a polyamine compound, a multivalent metal compound and a base, wherein the following condition applies: (number of moles of -COO groups contained in the polycarboxylic acid) / (number of moles of amino groups contained in the polyamine compound) = 100 / 20 to 100 / 90.

[0005] US 2013 / 0165525A1 concerns compositions and treatment methods using compositions containing polyelectrolyte complexes, wherein the compositions comprise a water-soluble first polyelectrolyte that carries or is capable of developing a net cation charge and a water-soluble second polyelectrolyte that carries or is capable of developing a net anion charge.

[0006] Accordingly, it is desirable to provide coating compositions that exhibit a short drying time and excellent performance. Furthermore, other desirable features and properties will become apparent from the detailed description below and the accompanying claims in conjunction with this background. Brief summary

[0007] A coating composition for coating a substrate is provided herein. The coating composition includes a first polymer comprising a first polymer-bound part having an acid-functional group or a derivative thereof, wherein the first polymer-bound part is polymerized from a first polymer monomer mixture comprising acid-functional monomers in an amount of 0.1 to 12 wt% based on the total weight of the first polymer monomer mixture. The coating composition further includes a second polymer comprising a second polymer-bound part having an amino-functional group, wherein the second polymer-bound part is polymerized from a second polymer monomer mixture comprising amino-functional monomers in an amount of 0.1 to 15 wt% based on the total weight of the second polymer monomer mixture.The coating composition further includes an organic solvent. The first polymer contains less than 0.1 wt% of amino functional groups, and the second polymer contains less than 0.1 wt% of acid functional groups or derivatives thereof. The acid functional groups and the amino functional groups are substantially reactive with each other, at least after application of the coating composition to the substrate. The coating composition is substantially free of water. Detailed description

[0008] The following detailed description is merely exemplary and is not intended to limit coating compositions such as those described herein. Furthermore, there is no intention of being bound to any theory presented in the preceding background or in the following detailed description.

[0009] A coating composition for coating a substrate is provided herein. The coating composition can be used to coat any type of substrate known to the prior art. In embodiments, the substrate is a vehicle, automobile, or motor vehicle. "Vehicle" or "automobile" or "motor vehicle" includes automobiles such as cars; vans; minivans; buses; SUVs (sport utility vehicles); trucks; semi-trailer trucks; tractors; motorcycles; trailers; ATVs (all-terrain vehicles); pickup trucks; heavy-duty machinery such as bulldozers, mobile cranes, and earthmoving equipment; aircraft; boats; ships; and other means of transportation. The coating composition can also be used to coat substrates in industrial applications such as buildings; fences; stationary structures; bridges; pipes; and cellulose-based materials (e.g., wood, paper, fibers, etc.).

[0010] The coating composition includes a first polymer, a second polymer, and a solvent. In embodiments, the first and second polymers are characterized as part of a binder polymer component. The term "binder polymer component" refers to film-forming components of a coating composition. Typically, a binder polymer component can include polymers, oligomers, and combinations thereof that are essential for the formation of a coating exhibiting desired properties, such as hardness, protection, adhesion, and others.Additional components, such as solvents, pigments, catalysts, rheology modifiers, antioxidants, UV stabilizers and absorbers, leveling agents, antifoaming agents, anti-crater agents, or other common additives, may not be included in the term "binder polymer component" unless any of these additional components are film-forming components of the coating composition. One or more of these additional components may be included in the coating composition. In certain embodiments, the "binder polymer component" excludes at least pigments and solvents. In embodiments, and as described in more detail below, the coating composition further includes other components, such as non-functional polymers, pigments, and additives.The coating composition may also include a crosslinking agent as described herein.

[0011] The first polymer includes a first polymer-bound part comprising an acid functional group or a derivative thereof, wherein the first polymer-bound part is polymerized from a first polymer monomer mixture containing acid functional monomers in an amount of 0.1 to 12 wt%, based on the total weight of the first polymer monomer mixture. Derivatives of the acid functional group may include any acid functional group formed from another compound in one or more steps, such as by blocking the acid functionality of the acid functional group or by replacing a hydrogen atom with an alkyl and acyl group. The second polymer includes a second polymer-bound part comprising an amino functional group, wherein the second polymer-bound part is polymerized from a second polymer monomer mixture containing amino functional monomers in an amount of 0.1 to 15 wt%.-% comprises, based on the total weight of the second polymer monomer mixture, that is polymerized. The acid functional group and the amino functional group are substantially reactive with each other, at least after application of the coating composition to the substrate. The terminology "substantially" with respect to the reactivity of the acid functional group and the amino functional group with each other means that at least 60%, alternatively at least 75%, alternatively at least 85%, alternatively at least 90%, alternatively at least 95%, or alternatively at least 99% of the acid functional groups and the amino functional groups are available for mutual reactivity (i.e., degree of reactivity) based on the first polymer or the second polymer having the lower molar concentration of acid functional groups or amino functional groups, respectively.The acid and amino functional groups can interact via non-covalent bonding, such as ionic bonding. In embodiments, when the first and second polymers are dissolved in a solvent, such as a polar solvent, ionic interactions between the acid and amino functional groups are minimized, resulting in a coating composition that exhibits minimal gelation. Furthermore, in embodiments, after solvent evaporation, such as after application of the coating composition to the substrate, the ionic interactions between the acid and amino functional groups are maximized, forming a coating layer that, after curing, exhibits improved coating performance, such as adhesion.

[0012] The first polymer is essentially free of amino functional groups, and the second polymer is essentially free of acid functional groups. In embodiments, the amount of amino functional groups in the first polymer is minimized to reduce the occurrence of intramolecular interactions between the acid functional groups of the first polymer and any other amino functional groups of the first polymer. Similarly, in embodiments, the amount of acid functional groups in the second polymer is minimized to reduce the occurrence of intramolecular interactions between the amino functional groups of the second polymer and any other acid functional groups of the second polymer. The term "essentially free" with respect to the presence of amino functional groups in the first polymer means that the mixture used to form the first polymer contains less than 0.1 wt.-%, alternatively less than 0.05 wt%, alternatively less than 0.01 wt%, alternatively less than 0.005 wt%, or alternatively less than 0.001 wt% amino functional groups, based on the total weight of the mixture. The terminology "essentially free" with respect to the presence of acid functional groups in the second polymer means that the mixture used to form the second polymer includes less than 0.1 wt%, alternatively less than 0.05 wt%, alternatively less than 0.01 wt%, alternatively less than 0.005 wt%, or alternatively less than 0.001 wt% acid functional groups, based on the total weight of the mixture.

[0013] The first polymer can be used in the coating composition in an amount of approximately 1 to approximately 90 wt.%, or alternatively, approximately 5 to approximately 90 wt.%, or alternatively, approximately 5 to approximately 80 wt.%, or alternatively, approximately 5 to approximately 60 wt.%, based on the total weight of the binder polymer component of the coating composition. The second polymer can be used in the coating composition in an amount of approximately 1 to approximately 90 wt.%, or alternatively, approximately 5 to approximately 90 wt.%, or alternatively, approximately 5 to approximately 80 wt.%, or alternatively, approximately 5 to approximately 60 wt.%, based on the total weight of the binder polymer component of the coating composition.In embodiments, the acid functional groups of the first polymer and the amino functional groups of the second polymer are used in the coating composition in a molar ratio of acid functional groups to amino functional groups of about 10:1 to about 1:10, alternatively of about 5:1 to about 1:5, or alternatively of about 4:1 to about 1:4.

[0014] The first polymer includes a first polymer-bound part comprising an acid-functional group or a derivative thereof. The first polymer-bound part may be at least part of the backbone of the first polymer, a side chain of the first polymer, grafted onto the first polymer, or a combination thereof. The first polymer may include more than one first polymer-bound part with the polymer-bound units located at any position within the first polymer. In certain embodiments, the first polymer-bound part is the first polymer itself. The first polymer-bound part may be composed of an acid-functional monomer, an acid-functional oligomer, an acid-functional macromonomer, or combinations thereof.In some embodiments, the monomer, oligomer, or macromonomer includes a polymerizable double bond, such as an ethylene unsaturated double bond, for example, in embodiments where the first polymer is an acrylic-based polymer. However, it is understood that the first polymer may be a polyester-based or polyurethane-based polymer, as described below. In other embodiments, the first polymer is a copolymer. The copolymer may be a random copolymer, an alternating copolymer, a periodic copolymer, a statistical copolymer, a block copolymer, or a graft copolymer. The copolymer may be straight-chain or branched.

[0015] The acid functional group, or a derivative thereof, can be a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group, or combinations thereof. The first polymer-bound part can have more than one type of acid functional group or derivative thereof. In certain embodiments, the acid functional group, or a derivative thereof, is a carboxylic acid group.

[0016] In embodiments, the first polymer-bound part is polymerized from a first polymer monomer mixture comprising acid-functional monomers. In certain embodiments, the acid-functional monomers are selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, oleic acid, cinnamic acid, glutaconic acid, muconic acid, undecenic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and combinations thereof. In embodiments, the first polymer monomer mixture may include acid anhydrides of any of the acid-functional monomers. Suitable acid anhydrides include maleic anhydride and itaconic anhydride. In these embodiments, the acid anhydride monomers may be hydrolyzed to form the corresponding carboxyl groups. It is understood that the first polymer monomer mixture may include acid-functional monomers and acid anhydride monomers.The acid anhydride group of the first polymer can be hydrolyzed to form an acid functional group after polymerization of the first polymer, after the first polymer has been formulated into a coating composition, or after the coating composition has been applied to a substrate.

[0017] According to the invention, the first polymer monomer mixture includes the acid-functional monomers or derivatives thereof in an amount of 0.1 to 12 wt.%, preferably about 0.5 to about 10 wt.%, alternatively about 0.5 to about 8 wt.%, or alternatively about 1 to about 5 wt.%, based on the total weight of the first polymer monomer mixture. Without being bound to any theory, it is assumed that a polymer polymerized from a polymer monomer mixture containing acid-functional monomers in an amount greater than 12 wt.% results in a coating composition that is sensitive to moisture and leads to gelation of the coating composition due to reactivity with the second polymer. Without being bound to any theory, it is also assumed that a polymer polymerized from a polymer monomer mixture containing acid-functional monomers in an amount less than 0.1 wt.% results in a coating composition that is sensitive to moisture and leads to gelation of the coating composition due to reactivity with the second polymer.Including -% leads to a polymer that does not react sufficiently with the second polymer.

[0018] The first polymer may have a weight-average molecular weight of 2,000 to 200,000, alternatively of about 8,000 to about 200,000, or alternatively of about 10,000 to about 200,000. The “molecular weights” disclosed herein may be determined by gel permeation chromatography (GPC) using polystyrene as a standard, unless otherwise specified. The first polymer may have a polydispersity of about 1.05 to about 10.0, alternatively of about 1.2 to about 8, or alternatively of about 1.5 to about 5. The first polymer can have a Tg of approximately -50 °C to approximately 100 °C, alternatively from approximately -30 °C to approximately 100 °C, alternatively from approximately -5 °C to approximately 100 °C, alternatively from approximately 0 °C to 80 °C, or alternatively from approximately 10 °C to approximately 60 °C. "Tg" stands for glass transition temperature of the polymer and can be measured by differential scanning calorimetry (DSC) or, as described by Fox in Bull. Amer. Physics Soc.,The Tg can be calculated as described in , 1, 3, page 123 (1956). It is understood that the Tg for the first polymer may depend on the type of polymer used. For example, polyester-based polymers may have a Tg of about -50 °C to about 40 °C, acrylic-based polymers may have a Tg of about -5 °C to about 100 °C, and polyurethane polymers may have a Tg of about -50 °C to about 100 °C. Without being bound to any theory, it is assumed that the first polymer exhibiting the weight-average molecular weight described above will provide a coating composition that shows minimal gelling and improved coating performance, such as improved adhesion.In particular, polymers with a weight-average molecular weight of less than 2000 may separate from the coating composition before reacting with the second polymer, resulting in a coating with inferior properties upon curing. Furthermore, even if polymers with a weight-average molecular weight of less than 2000 do not separate from the coating composition, they may not contribute significantly to forming the coating film. Conversely, polymers with a weight-average molecular weight greater than 200,000 may result in a coating composition with a viscosity unsuitable for spray application. The first polymer may include one or more polymers, each containing at least one acid functional group or a derivative thereof.Each of the polymers can have more than one type of acid functional group or a derivative thereof.

[0019] The second polymer includes a second polymer-bound part containing an amino-functional group. The amino-functional group can be a primary amine, a secondary amine, or a tertiary amine. The second polymer-bound part can be at least part of the backbone of the second polymer, a side chain of the second polymer, a graft onto the second polymer, or a combination thereof. The second polymer can include more than one second polymer-bound part, with the polymer-bound units located at any position within the second polymer. In certain embodiments, the second polymer-bound part is the second polymer itself. The second polymer-bound part can be composed of an amino-functional monomer, an amino-functional oligomer, an amino-functional macromonomer, or combinations thereof.In some embodiments, the monomer, oligomer, or macromonomer includes a polymerizable double bond, such as an ethylene unsaturated double bond, for example, in embodiments where the second polymer is an acrylic-based polymer. However, it is understood that the second polymer may be a polyester-based or polyurethane-based polymer, as described below. In other embodiments, the second polymer is a copolymer. The copolymer may be a random copolymer, an alternating copolymer, a periodic copolymer, a statistical copolymer, a block copolymer, or a graft copolymer. The copolymer may be straight-chain or branched.

[0020] In embodiments, the second polymer-bound part can be polymerized from a second polymer monomer mixture comprising amino-functional monomers, carboxyl-functional monomers, or a combination thereof. In one embodiment, the second polymer-bound part can be polymerized from a second polymer monomer mixture comprising amino-functional monomers. The amino-functional monomers can be selected from the group consisting of t-butylaminoethyl methacrylate (t-BAEMA), N,N-dimethylaminoethyl acrylate (DMAEA), and combinations thereof. Secondary amino-functional groups can be polymerized from t-BAEMA. Alternatively, secondary amino-functional groups can be polymerized from a polymer comprising epoxide-functional groups and an amino compound, such as a primary amine.Tertiary amino-functional groups can be polymerized from N,N-dialkylaminoalkyl acrylates, such as N,N-dimethylaminoethyl acrylate and N,N-diethylaminoethyl acrylate, and N,N-dialkylaminoalkyl methacrylate, such as N,N-dimethylaminoethyl methacrylate and N,N-diethylaminoethyl methacrylate. It is understood that the amino-functional groups of the second polymer may include protecting groups that interact with the amino-functional groups to selectively block their amino functionality, for example, when the polymer is in solution prior to application and / or curing. However, it is understood that... The protecting groups detach from the amino-functional groups before use in order to release the amino functionality of the amino-functional groups, for example before application, after application or after hardening.

[0021] According to the invention, the second polymer monomer mixture includes the amino-functional monomers in an amount of 0.1 to 15 wt.%, preferably about 0.5 to about 12 wt.%, alternatively about 0.5 to about 10 wt.%, or alternatively about 1 to about 7 wt.%, based on the total weight of the second polymer monomer mixture. Without being bound to any theory, it is assumed that a polymer polymerized from a polymer monomer mixture containing amino-functional monomers in an amount greater than 15 wt.% will lead to gelation of the coating composition due to reactivity with the first polymer. Without being bound to any theory, it is also assumed that a polymer polymerized from a polymer monomer mixture containing amino-functional monomers in an amount less than 0.1 wt.% will result in a polymer that does not react sufficiently with the first polymer.

[0022] The second polymer can have a weight-average molecular weight of 2,000 to 200,000, or alternatively, of approximately 8,000 to 200,000, or alternatively, of approximately 10,000 to 200,000. The second polymer can have a polydispersity of approximately 1.05 to 10.0, or alternatively, of approximately 1.2 to 8, or alternatively, of approximately 1.5 to 5. The second polymer can have a Tg of approximately -50 °C to 100 °C, or alternatively, of approximately -30 °C to 100 °C, or alternatively, of approximately -5 °C to 100 °C, or alternatively, of approximately 0 °C to 80 °C, or alternatively, of approximately 10 °C to 60 °C. It is understood that the Tg for the second polymer may depend on the type of polymer used. For example, polyester-based polymers can have a Tg of about -50 °C to about 40 °C, acrylic-based polymers can have a Tg of about -5 °C to about 100 °C, and polyurethane polymers can have a Tg of about -50 °C to about 100 °C.Without being bound to any theory, it is assumed that the second polymer, which has the weight-average molecular weight described above, provides a coating composition that exhibits minimal gelation and improved coating performance, such as enhanced adhesion. In particular, polymers with a weight-average molecular weight of less than 2000 may separate from the coating composition prior to reacting with the first polymer, resulting in a coating with inferior properties upon curing. Examples of polymers with a weight-average molecular weight of less than 2000, and therefore unsuitable as the second polymer for the coating composition, include, but are not limited to, small amino-containing molecules such as triethylamine and propylamine.Furthermore, even if polymers with a weight-average molecular weight of less than 2000 do not separate from the coating composition, they cannot substantially contribute to the formation of the coating film. In contrast, polymers with a weight-average molecular weight greater than 200,000 can result in a coating composition with a viscosity unsuitable for spray application. The second polymer may include one or more polymers, each possessing at least one amino functional group. Each of the polymers may possess more than one type of amino functional group.

[0023] In embodiments, the first polymer, the second polymer, or both the first and second polymers have a crosslinkable functional group, such as an isocyanate group. The term "crosslinkable functional group" refers to functional groups located in the oligomer, in the polymer, in the polymer backbone, in a side group of the polymer, at the end of the polymer backbone, or combinations thereof, wherein these functional groups are capable of crosslinking with crosslinking functional groups (during the curing step) to form a coating in the form of crosslinked structures.

[0024] Typical crosslinkable functional groups can include hydroxyl, thiol, isocyanate, thioisocyanate, acetacetoxy, carboxyl, primary amine, secondary amine, epoxide, anhydride, ketimine, aldimine, or any executable combination thereof. Some other functional groups, such as orthoesters, orthocarbonates, or cyclic amides that can generate hydroxyl or amino groups once the ring structure is opened, may also be suitable as crosslinkable functional groups.

[0025] In certain embodiments, the crosslinkable functional group is a hydroxyl functional group. The hydroxyl functional group can be a primary hydroxyl group, a secondary hydroxyl group, or a combination thereof. The first polymer containing the hydroxyl functional group can be polymerized from the first polymer monomer mixture, which further includes hydroxyl functional monomers. The second polymer containing the hydroxyl functional group can be polymerized from the second polymer monomer mixture, which further includes hydroxyl functional monomers. Non-restrictive examples of hydroxyl functional monomers used to form primary hydroxyl groups include 2-hydroxyethyl methacrylate (HEMA) and 2-hydroxyethyl acrylate (HEA).Non-restrictive examples of hydroxyl-functional monomers used to form secondary hydroxyl groups include hydroxypropyl methacrylate (HPMA) and hydroxypropyl acrylate (HPA). In certain embodiments, the hydroxyl-functional monomers are selected from the group consisting of 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, and combinations thereof. It is understood that the selection of hydroxyl-functional groups for the first polymer is independent of the selection of hydroxyl-functional groups for the second polymer, and vice versa. In other embodiments, the crosslinkable functional group is a thiol-functional group.In various embodiments, the amino-functional group of the second polymer is the only crosslinkable functional group of the second polymer, since the amino-functional group is available for reaction with the acid-functional group of the first polymer and is reactive for crosslinking with isocyanates.

[0026] In embodiments, the first polymer, the second polymer, or both the first polymer and the second polymer are polymerized from additional monomers, such as any acrylic monomer known in the prior art, and any ethylene unsaturated monomer known in the prior art, which are present in addition to the monomers that include the acid functional groups and amino functional groups.Non-restrictive examples of these additional monomers include unsubstituted or substituted alkyl acrylates, such as those with 1 to 20 carbon atoms in the alkyl group; alkyl methacrylates, such as those with 1 to 20 carbon atoms in the alkyl group; cycloaliphatic acrylates; cycloaliphatic methacrylates; aryl acrylates; aryl methacrylates; other ethylene unsaturated monomers, such as acrylonitriles, methacrylonitriles, acrylamides, methacrylamides, N-alkylacrylamides, N-alkylmethacrylamides, N,N-dialkylacrylamides, N,N-dialkylmethacrylamides; vinyl aromatics, such as styrene, and combinations thereof.Other non-restrictive examples include non-functional acrylic monomers, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylonitrile, and the like. Further non-restrictive examples include other ethylene unsaturated monomers, such as vinyl aromatics. Non-restrictive examples of vinyl aromatics include styrene, alpha-methylstyrene, tert-butylstyrene, and vinyltoluene. In certain embodiments, the first polymer, the second polymer, or both the first polymer and the second polymer are polymerized from further monomers from the group consisting of styrene, methyl(meth)acrylate, butyl(meth)acrylate, ethylhexyl(meth)acrylate, isobornyl(meth)acrylate, and combinations thereof.It is understood that the selection of additional monomers for the first polymer is independent of the selection of additional monomers for the second polymer, and vice versa.

[0027] In an exemplary embodiment, the first polymer comprises the reaction product of styrene, butyl acrylate, isobornyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and methacrylic acid. The styrene can be used in an amount of about 10 to about 50 wt.%, alternatively about 20 to about 40 wt.%, or alternatively about 25 to about 35 wt.%, in each case based on the total weight of the first polymer. The butyl acrylate can be used in an amount of about 10 to about 50 wt.%, alternatively about 20 to about 40 wt.%, or alternatively about 25 to about 35 wt.%, in each case based on the total weight of the first polymer. The isobornyl acrylate can be used in an amount of about 1 to about 40 wt.%, alternatively about 10 to about 30 wt.%, or alternatively about 15 to about 25 wt.%, in each case based on the total weight of the first polymer. 2-Hydroxyethyl methacrylate can be present in amounts ranging from 0.1 to approximately 30 wt.The hydroxypropyl methacrylate may be used in an amount of approximately 0.1 to 30% by weight, or alternatively, approximately 1 to 20% by weight, or alternatively, approximately 3 to 12% by weight, each based on the total weight of the first polymer. The methacrylic acid may be used in an amount of approximately 0.1 to 12% by weight, or alternatively, approximately 1 to 9% by weight, or alternatively, approximately 3 to 7% by weight, each based on the total weight of the first polymer.

[0028] In another exemplary embodiment, the first polymer includes the reaction product of methyl methacrylate, butyl methacrylate, ethylhexyl acrylate, 2-hydroxyethyl methacrylate, and methacrylic acid. The methyl methacrylate can be used in an amount of about 10 to about 50 wt.%, alternatively about 20 to about 40 wt.%, or alternatively about 25 to about 35 wt.%, in each case based on the total weight of the first polymer. The butyl methacrylate can be used in an amount of about 5 to about 45 wt.%, alternatively about 15 to about 35 wt.%, or alternatively about 20 to about 30 wt.%, in each case based on the total weight of the first polymer. The ethylhexyl acrylate can be used in an amount of about 5 to about 45 wt.%, alternatively about 15 to about 35 wt.%, or alternatively about 20 to about 30 wt.%, in each case based on the total weight of the first polymer.The 2-hydroxyethyl methacrylate can be used in an amount of approximately 0.1 to approximately 40 wt%, or alternatively approximately 10 to approximately 30 wt%, or alternatively approximately 15 to approximately 25 wt%, in each case based on the total weight of the first polymer. The methacrylic acid can be used in an amount of approximately 0.1 to approximately 12 wt%, or alternatively approximately 0.1 to approximately 8 wt%, or alternatively approximately 0.1 to approximately 4 wt%, in each case based on the total weight of the first polymer.

[0029] In another exemplary embodiment, the first polymer includes the reaction product of styrene, methyl methacrylate, butyl methacrylate, ethylhexyl acrylate, 2-hydroxyethyl methacrylate, and acrylic acid. The styrene can be used in an amount of about 1 to about 50 wt.%, alternatively about 10 to about 30 wt.%, or alternatively about 15 to about 25 wt.%, in each case based on the total weight of the first polymer. The methyl methacrylate can be used in an amount of about 1 to about 50 wt.%, alternatively about 10 to about 40 wt.%, or alternatively about 20 to about 30 wt.%, in each case based on the total weight of the first polymer. The butyl methacrylate can be used in an amount of about 1 to about 50 wt.%, alternatively about 10 to about 30 wt.%, or alternatively about 15 to about 25 wt.%, in each case based on the total weight of the first polymer. Ethylhexyl acrylate can be present in amounts ranging from approximately 1 to approximately 50 wt.-%, alternatively from about 10 to about 40 wt% or alternatively from about 20 to about 30 wt%, in each case based on the total weight of the first polymer. The 2-hydroxyethyl methacrylate can be used in an amount of about 0.1 to about 40 wt%, alternatively from about 5 to about 20 wt% or alternatively from about 5 to about 15 wt%, in each case based on the total weight of the first polymer. The acrylic acid can be used in an amount of about 0.1 to about 12 wt%, alternatively from about 0.1 to about 8 wt% or alternatively from about 0.1 to about 4 wt%, in each case based on the total weight of the first polymer.

[0030] In an exemplary embodiment, the second polymer includes the reaction product of methyl methacrylate, butyl acrylate, and tert-butylaminoethyl methacrylate. The methyl methacrylate can be used in an amount of about 60 to about 90 wt.%, alternatively about 70 to about 85 wt.%, or alternatively about 75 to about 81 wt.%, in each case based on a total weight of the second polymer. The butyl acrylate can be used in an amount of about 5 to about 25 wt.%, alternatively about 10 to about 20 wt.%, or alternatively about 12 to about 18 wt.%, in each case based on a total weight of the second polymer. The tert-butylaminoethyl methacrylate can be used in an amount of about 0.1 to about 12 wt.%, alternatively about 3 to about 10 wt.%, or alternatively about 5 to about 9 wt.%, in each case based on a total weight of the second polymer.

[0031] In another exemplary embodiment, the second polymer includes the reaction product of methyl methacrylate, ethyl acrylate, and tert-butylaminoethyl methacrylate. The methyl methacrylate can be used in an amount of about 60 to about 90 wt.%, alternatively about 70 to about 85 wt.%, or alternatively about 75 to about 81 wt.%, in each case based on a total weight of the second polymer. The ethyl acrylate can be used in an amount of about 5 to about 25 wt.%, alternatively about 10 to about 20 wt.%, or alternatively about 12 to about 18 wt.%, in each case based on a total weight of the second polymer. The tert-butylaminoethyl methacrylate can be used in an amount of about 0.1 to about 12 wt.%, alternatively about 3 to about 10 wt.%, or alternatively about 5 to about 9 wt.%, in each case based on a total weight of the second polymer.

[0032] In another exemplary embodiment, the second polymer includes the reaction product of methyl methacrylate, butyl acrylate, and N,N-dimethylaminoethyl acrylate. The methyl methacrylate can be used in an amount of about 60 to about 90 wt.%, alternatively about 70 to about 85 wt.%, or alternatively about 75 to about 81 wt.%, in each case based on a total weight of the second polymer. The butyl acrylate can be used in an amount of about 5 to about 25 wt.%, alternatively about 10 to about 20 wt.%, or alternatively about 12 to about 18 wt.%, in each case based on a total weight of the second polymer. The N,N-dimethylaminoethyl acrylate can be used in an amount of about 0.1 to about 12 wt.%, alternatively about 3 to about 10 wt.%, or alternatively about 5 to about 9 wt.%, in each case based on a total weight of the second polymer.

[0033] In another exemplary embodiment, the second polymer includes the reaction product of methyl methacrylate, ethyl acrylate, and the reaction product of methacrylic acid and propyleneimine. The methyl methacrylate can be used in an amount of about 65 to about 95 wt.%, alternatively about 73 to about 87 wt.%, or alternatively about 77 to about 83 wt.%, in each case based on a total weight of the second polymer. The ethyl acrylate can be used in an amount of about 5 to about 25 wt.%, alternatively about 10 to about 20 wt.%, or alternatively about 12 to about 18 wt.%, in each case based on a total weight of the second polymer. The methacrylic acid can be used in an amount of about 0.1 to about 12 wt.%, alternatively about 1 to about 7 wt.%, or alternatively about 2 to about 6 wt.%, in each case based on a total weight of the second polymer. Propylenimine can be found in amounts ranging from approximately 0.1 to approximately 12 grams by weight.-%, alternatively from about 1 to about 7 wt.% or alternatively from about 1 to about 5 wt.%, each based on a total weight of the second polymer, may be used.

[0034] In another exemplary embodiment, the second polymer includes the reaction product of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, and N,N-dimethylaminoethyl acrylate. The methyl methacrylate can be used in an amount of about 60 to about 90 wt.%, alternatively about 70 to about 85 wt.%, or alternatively about 75 to about 81 wt.%, in each case based on a total weight of the second polymer. The butyl acrylate can be used in an amount of about 0.1 to about 15 wt.%, alternatively about 1 to about 15 wt.%, or alternatively about 3 to about 8 wt.%, in each case based on a total weight of the second polymer. The 2-hydroxyethyl acrylate can be used in an amount of about 0.1 to about 25 wt.%, alternatively about 1 to about 17 wt.%, or alternatively about 7 to about 13 wt.%, in each case based on a total weight of the second polymer.The N,N-dimethylaminoethyl acrylate can be used in an amount of about 0.1 to about 12 wt%, alternatively from about 1 to about 10 wt% or alternatively from about 4 to about 10 wt%, in each case based on a total weight of the second polymer.

[0035] The first polymer, the second polymer, or both the first and second polymers are independently selected from a straight-chain or branched acrylic polymer, a straight-chain or branched polyester polymer, a polyurethane polymer, or combinations thereof. "Acrylic polymer" means that a polymer comprises polymerized "(meth)acrylate(s)," which means acrylates and / or methacrylates, optionally copolymerized with other ethylene unsaturated monomers, such as acrylamides, methacrylamides, acrylonitriles, methacrylonitriles, and vinyl aromatics, such as styrene.

[0036] In embodiments, the first polymer, the second polymer, or both the first and second polymers can be polyester polymers. The polyester polymer can be straight-chain or branched. Useful polyesters can include esterification products of aliphatic or aromatic dicarboxylic acids, polyols, diols, aromatic or aliphatic cyclic anhydrides, and cyclic alcohols. It is understood that the choice of polyester for the first polymer is independent of the choice of polyester for the second polymer, and vice versa.

[0037] Non-restrictive examples of suitable cycloaliphatic polycarboxylic acids include tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, endoethylenehexahydrophthalic acid, camphoric acid, cyclohexanetetracarboxylic acid, and cyclobutanetetracarboxylic acid. These cycloaliphatic polycarboxylic acids can be used not only in their cis form, but also in their trans form and as a mixture of both. Other non-restrictive examples of suitable polycarboxylic acids may include aromatic and aliphatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, halogenated phthalic acids, such as tetrachloro- or tetrabromophthalic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, trimellitic acid and pyromellitic acid.Combinations of polyacids, such as a combination of polycarboxylic acids and cycloaliphatic polycarboxylic acids, can be suitable. Combinations of polyols can also be suitable. If desired, monoacids, such as benzoic acid, can also be included to influence the molecular weight. It is understood that, although polyesters and polyols exhibiting more than two functionalities can be used to create more branching points, the number of functionalities should be controlled due to the branching effect to prevent gelation.

[0038] Non-restrictive, suitable polyhydric alcohols include ethylene glycol, propanediols, butanediols, hexanediols, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanedimethanol, trimethylpentanediol, ethylbutylpropanediol, ditrimethylolpropane, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, polyethylene glycol, and polypropylene glycol. If desired, monohydric alcohols, such as butanol, octanol, lauryl alcohol, ethoxylated or propoxylated phenols, may also be included with polyhydric alcohols to control the molecular weight.

[0039] Non-restrictive examples of suitable polyesters include a branched copolyester polymer. The branched copolyester polymer and process for its preparation as described in U.S. Patent No. 6,861,495, hereby incorporated by reference, may be suitable. Monomers with multifunctional groups such as AxBy (x,y = 1 to 3, independent of each other), including those having one carboxyl group and two hydroxyl groups, two carboxyl groups and one hydroxyl group, one carboxyl group and three hydroxyl groups, or three carboxyl groups and one hydroxyl group, may be used to generate branched structures. Non-restrictive examples of such monomers include 2,3-dihydroxypropionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-dihydroxypropionic acid, 2,2-bis(hydroxymethyl)propionic acid, and the like.

[0040] The branched copolyester polymer can typically be polymerized from a monomer mixture containing a chain extender selected from the group consisting of hydroxycarboxylic acids, a lactone of a hydroxycarboxylic acid, and a combination thereof; and one or more branching monomers. Some suitable hydroxycarboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxypivalic acid. Some suitable lactones include caprolactone, valerolactone, and lactones of the corresponding hydroxycarboxylic acids, such as 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and hydroxypivalic acid. In certain embodiments, caprolactone is used.In embodiments, the branched copolyester polymer can be produced in one step by polymerizing the monomer mixture, which includes the chain extender and hyperbranched monomers, or by first polymerizing the hyperbranched monomers followed by polymerizing the chain extenders. It is understood that the branched copolyester polymer can be formed from an acrylic core with elongating monomers, as described above.

[0041] In embodiments where the first polymer is a polyester polymer (hereinafter also referred to as an "acid-functional polyester"), the first polymer can be produced by using excess amounts of diacids or anhydrides with polyols during synthesis or by other methods known to those skilled in the art to ensure that the polymer chains are terminated with acid-functional groups in a straight-chain or branched structure. Alternatively, the polyesters with hydroxyl groups at the terminal positions of the polymer chain can be further reacted with a diacid or anhydride to form acid-functional groups.

[0042] In embodiments where the second polymer is a polyester polymer (hereinafter also referred to as an "amino-functional polyester"), the second polymer can be prepared by using an amino-functional polyol, such as a tertiary amino-functional polyol, with polyacids and polyols in synthesis, or by other methods known to those skilled in the art. Non-limiting examples of monomers having only one reactive group capable of condensing with acids or anhydrides and positioning the tertiary amino group at the terminal position of a polymer chain include N,N-dimethylethanolamine, N,N-diethylethanolamine, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, and the like.Non-restrictive examples of polyhydroxyl with tertiary amino groups that can position the amino functional groups along the polymer chains include simple compounds such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N,N-dibutylethanolamine, triethanolamine, triisopropanolamine, and compounds traded by Akzo Nobel NV, Amsterdam, Netherlands under the trade name Ethomeen. ® (a tertiary amine nitrogen atom) and ethoduomeen ® (two tertiary amine nitrogen atoms) are available. The second polymer can also undergo post-polymerization, for example by reacting carboxylic acid-containing polyester polymers as described above with suitable amino compounds, such as propyleneimine.

[0043] In embodiments, the first polymer, the second polymer, or both the first and second polymers are polyurethane polymers. Polyurethanes can be prepared from polyols and polyisocyanates. Polyols can be polymeric or oligomeric organic species with at least two hydroxyl functionalities or two mercapto functionalities, and mixtures thereof. Polyesters and polycarbonates with terminal hydroxyl groups can be effectively used as the diols.

[0044] In certain embodiments, the preparation of polyurethane polymers is known to those skilled in the art; in particular, polyurethane polymers can be prepared by reacting polyisocyanate(s) with polyol(s) in excess. In certain embodiments, low-molecular-weight polyols defined by an empirical and structural formula, such as polyhydric alcohols, are used to form the polyurethane polymer. Non-restrictive examples of polyhydric alcohols include ethylene glycol, propanediols, butanediols, hexanediols, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanedimethanol, trimethylpentanediol, ethyl butylpropanediol, ditrimethylolpropane, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, polyethylene glycol, and polypropylene glycol.In other embodiments, oligomeric or polymeric polyols with number-average molar masses of, for example, up to 8000, alternatively up to 5000, alternatively up to 2000, and / or, for example, corresponding hydroxyl-functional polyethers, polyesters or polycarbonates are used to form the polyurethane polymer.

[0045] Non-restrictive examples of suitable polyisocyanates include aromatic, aliphatic, or cycloaliphatic di-, tri-, or tetraisocyanates, including polyisocyanates containing isocyanurate structural units, such as the isocyanurate of hexamethylene diisocyanate and the isocyanurate of isophorone diisocyanate; the adduct of two molecules of a diisocyanate, such as hexamethylene diisocyanate, and a diol, such as ethylene glycol; uretidiols of hexamethylene diisocyanate; uretidiols of isophorone diisocyanate or isophorone diisocyanate; and the adduct of trimethylolpropane and meta-tetramethylxylene diisocyanate. Other polyisocyanates disclosed herein may also be suitable for the production of polyurethanes.

[0046] In certain embodiments, diols and diisocyanates are used to form the polyurethane polymer in order to prevent crosslinking and network formation, which would lead to polymer gelation. Chain extenders such as diamines can be used to increase the molecular weight. A small amount of monomers with higher functional content, such as triols or triisocyanates, can be used to create branch points and branched structures. However, the concentration of these higher-functionality monomers must be low enough to prevent polymer crosslinking and gelation.

[0047] In embodiments where the first polymer is a polyurethane polymer (hereafter referred to as "acid-functional polyurethanes"), the first polymer can be effectively prepared by reacting any acid-containing diols, as part of the diol mixtures, with polyisocyanates in an amount corresponding to the desired concentrations of acid groups. Examples of such monomers include 2,3-dihydroxypropionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-dihydroxypropionic acid, and 2,2-bis(hydroxymethyl)propionic acid. Alternatively, acid-functional groups can be generated at the terminal positions by using a small amount of acid-containing monomers with only one functional group, which can react with polyisocyanates and terminate polymer chains. In a multi-step synthesis, polyisocyanate is used in excess to ensure that the polymer chains are terminated with isocyanate groups first.The terminal isocyanate groups are then treated with acidic monomers that possess only one functional group capable of reacting with polyisocyanates. Examples of such monomers include 2-hydroxypropionic acid, 3-hydroxypropionic acid, 3-mercaptopropionic acid, and the like.

[0048] Acid-functional polyurethanes can also be prepared by reacting one or more polyols with one or more polyisocyanates, incorporating a small amount of diacids or anhydrides, such as aliphatic or aromatic dicarboxylic anhydrides, depending on the desired acid group concentration in the diol mixtures. Similarly, in a multi-step synthesis, straight-chain or branched polyurethanes with terminal hydroxy or thiol groups can be post-treated with diacids and / or anhydrides to generate a terminal acid-functional group.

[0049] In embodiments where the second polymer is a polyurethane polymer (hereinafter also referred to as "amino-functional polyurethane"), the second polymer may contain tertiary amino groups. The amino-functional polyurethane containing tertiary amino groups can be prepared, depending on the desired molecular weight and degree of branching, using low concentrations of a polymer, oligomer, or simple compound having one or more tertiary amino-functional groups together with one or more functional groups capable of reacting with isocyanate groups in synthesis.Non-restrictive examples of monomers possessing only one reactive group capable of reacting with isocyanates and positioning the tertiary amino group at the terminal position of a polymer chain include N,N-dimethylethanolamine, N,N-diethylethanolamine, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, and the like. Non-restrictive examples of polyhydroxyls with tertiary amino groups capable of positioning the amino functional groups along the polymer chains include simple compounds such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N,N-dibutylethanolamine, triethanolamine, triisopropanolamine, and compounds marketed by Akzo Nobel NV, Amsterdam, The Netherlands, under the trade name Ethomeen. ® (a tertiary amine nitrogen atom) and ethoduomeen ® (two tertiary amine nitrogen atoms) are available, one.

[0050] Amino-functional polyurethanes with primary amino groups can be prepared by further reacting the acid groups of acid-functional polyurethanes, such as those described above, with imine compounds, such as propyleneimine. Alternatively, a polyurethane polyol can be reacted with an excess of polyisocyanates to ensure that the polymer chains are terminated with isocyanate groups in a straight-chain or branched structure. These isocyanate groups can then be hydrolyzed to form primary amino groups, thus creating amino-functional polyurethanes.

[0051] As introduced above, the coating composition further includes an organic solvent. The organic solvent can act as the carrier liquid to disperse and / or dilute the above components and form a coating composition exhibiting the desired properties. The solvent or solvent mixtures are typically selected from the group of aromatic hydrocarbons, such as petroleum naphtha or xylenes; ketones, such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, or acetone; esters, such as butyl acetate or hexyl acetate; glycol ether esters, such as propylene glycol monomethyl ether acetate; and alcohols, such as isopropanol and butanol, and combinations thereof. The amount of organic solvent added depends on the desired solids content, the desired rheological properties (e.g.,The amount of solvent depends on the spray properties and the desired amount of VOC in the coating composition. The solvent can be present in an amount of approximately 10 to approximately 95 wt.%, alternatively approximately 20 to approximately 95 wt.%, or alternatively approximately 40 to approximately 95 wt.%, based on the total weight of the coating composition.

[0052] The total solids content of the coating composition can be in a quantity of approximately 5 to approximately 90 wt.%, alternatively in a quantity of approximately 5 to approximately 80 wt.%, or alternatively in a quantity of approximately 5 to approximately 60 wt.%, based on the total weight of the coating composition.

[0053] The coating composition is a solvent-based coating composition. The coating composition is essentially free of water. The term "essentially free" with regard to the amount of water in the coating composition means that the coating composition contains less than 5% by weight, alternatively less than 3% by weight, alternatively less than 2% by weight, alternatively less than 1% by weight, or alternatively less than 0.1% by weight of water, based on the total weight of the coating composition.

[0054] As also introduced above, the coating composition may further include non-functional polymers. The non-functional polymers may include straight-chain or branched acrylic polymers, straight-chain or branched polyester polymers, polyurethane polymers, or combinations thereof. The term "non-functional polymer" refers to a polymer that is essentially free of acid functional groups and amino functional groups. The term "essentially" as used herein in relation to the non-functional polymer that is essentially free of acid functional groups and amino functional groups means that the non-functional polymer contains less than 0.1 wt% of acid functional groups and amino functional groups. The non-functional polymers may contain other functional groups besides acid functional groups or amino functional groups.

[0055] As also introduced above, the coating composition may further include a crosslinking agent that can react with the crosslinkable functional group of the first polymer, the second polymer, or both the first and second polymers to form a crosslinked polymeric network, referred to herein as the crosslinked network. Although it is understood that the coating composition provides, in particular, improved coating performance, especially adhesion between layers, without crosslinking using a crosslinking agent, a crosslinking agent may be used in the coating composition to further enhance the coating performance.

[0056] The term "crosslinking agent" refers to a component that contains "crosslinking functional groups." These functional groups are present in every molecule of the compound, in the oligomer, in the polymer, in the polymer backbone, in the polymer side chain, at the end of the polymer backbone, or a combination thereof. These functional groups are capable of crosslinking with crosslinkable functional groups (during the curing step) to form a coating in the form of crosslinked structures. An average person would recognize that certain combinations of crosslinking and crosslinkable functional groups are excluded because they do not crosslink and therefore do not produce the film-forming crosslinked structures. The coating composition may include more than one type of crosslinking agent, which may or may not contain the same or different crosslinking functional groups.Common crosslinking functional groups can include hydroxyl, thiol, isocyanate, thioisocyanate, acetacetoxy, carboxyl, primary amine, secondary amine, epoxide, anhydride, ketimine, aldimine, orthoester, orthocarbonate, cyclic amide or combinations thereof.

[0057] In embodiments, polyisocyanates containing isocyanate functional groups can be used as the crosslinking agent to react with crosslinkable functional groups, such as hydroxyl and amino functional groups. In certain embodiments, only primary and secondary amino functional groups can react with the isocyanate functional groups. Suitable polyisocyanate can have an average of 2 to 10, alternatively 2.5 to 8, or alternatively 3 to 8 isocyanate functional groups. Typically, the coating composition has a ratio of isocyanate functional groups on the polyisocyanate to crosslinkable functional groups (e.g., hydroxyl and / or amino groups) of the first polymer, the second polymer, or both the first and second polymers of approximately 0.25:1 to approximately 3:1, alternatively approximately 0.8:1 to approximately 2:1, or alternatively approximately 1:1 to approximately 1.8:1.In other embodiments, melamine compounds with melamine functional groups can be used as the crosslinking agent to react with the crosslinkable functional groups.

[0058] Examples of suitable polyisocyanates include any of the commonly used aromatic, aliphatic, or cycloaliphatic di-, tri-, or tetraisocyanates, including polyisocyanates containing isocyanurate structural units, such as the isocyanurate of hexamethylene and the isocyanurate of isophorone diisocyanate; the adduct of two molecules of a diisocyanate, such as hexamethylene diisocyanate; uretidiols of hexamethylene diisocyanate; uretidiols of isophorone diisocyanate or isophorone diisocyanate; isocyanurate of meta-tetramethylxylylene diisocyanate; and a diol, such as ethylene glycol.

[0059] Polyisocyanate functional adducts containing isocyanurate structural units can also be used, for example, the adduct of 2 molecules of a diisocyanate, such as hexamethylene diisocyanate or isophorone diisocyanate, and a diol, such as ethylene glycol; the adduct of 3 molecules of hexamethylene diisocyanate and 1 molecule of water (commercially available from Bayer Corporation of Pittsburgh, Pennsylvania, under the trade name Desmodur). ® N); the adduct of 1 molecule of trimethylolpropane and 3 molecules of toluene diisocyanate (commercially available from Bayer Corporation in Pittsburgh, Pennsylvania under the trade name Desmodur ® L); the adduct of 1 molecule of trimethylolpropane and 3 molecules of isophorone diisocyanate or compounds such as 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene; and the adduct of 1 molecule of pentaerythritol and 4 molecules of toluene diisocyanate.

[0060] As also introduced above, the coating composition may further include a pigment. Any pigment known in the field for use in coating compositions may be used in the coating composition. Non-restrictive examples of suitable pigments include metal oxides, metal hydroxides, effect pigments including metal flakes, chromates such as lead chromate, sulfides, sulfates, carbonates, carbon black, silicon dioxide, talc, china clay, phthalocyanine blue and green, organo reds, organo maroons, pearlescent pigments, other organic pigments and dyes, and combinations thereof. If desired, chromate-free pigments such as barium metaborate, zinc phosphate, aluminum triphosphate, and combinations thereof may also be used.

[0061] Other non-restrictive examples of suitable effect pigments include bright aluminum flakes, extremely fine aluminum flakes, medium particle size aluminum flakes and bright medium-coarse aluminum flakes; mica flakes coated with titanium dioxide pigment, also known as pearl pigments; and combinations thereof. Non-restrictive examples of suitable colored pigments include titanium dioxide, zinc oxide, iron oxide, carbon black, mono-azo red toner, red iron oxide, quinacridone maroon, transparent red oxide, dioxazinecarbazole violet, iron blue, indanthrone blue, chromium titanate, titanium yellow, monoazopermanene orange, ferrite yellow, monoazobenzimidazolone yellow, transparent yellow oxide, isoindoline yellow, tetrachloroisoindoline yellow, anthanthrone orange, lead chromate yellow, phthalocyanine green, quinacridone red, perylene brown, quinacridone violet, pre-darkened chrome yellow, thio-indigo red, transparent red oxide chip, molybdate orange red, and combinations thereof.

[0062] As also mentioned above, the coating composition may include additives such as catalysts, UV light stabilizers, and other additives. The coating composition may also contain a catalyst to reduce the curing time and enable curing at ambient temperatures. Ambient temperatures are typically defined as temperatures in the range of 18°C ​​to 35°C.Common catalysts include organic metal salts, such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dichloride, dibutyltin dibromide, zinc naphthenate; compounds containing tertiary amino groups, such as triethylamine; triphenylborone, tetraisopropyl titanate, triethanolamine titanate chelate, dibutyltin dioxide, dibutyltin dioctoate, zinn octoate, aluminum titanate, aluminum chelates, zirconium chelate, hydrocarbon phosphonium halides, such as ethyltriphenylphosphonium iodide and other such phosphonium salts, and other catalysts or combinations thereof known to those skilled in the art.

[0063] The coating composition may also include an ultraviolet light stabilizer. Non-restrictive examples of such ultraviolet light stabilizers include ultraviolet absorbers, screeners, quenchers, and hindered amine light stabilizers. An antioxidant may also be added to the coating composition. Typical ultraviolet light stabilizers may include benzophenones, triazoles, triazines, benzoates, hindered amines, and mixtures thereof. A mixture of hindered amine light stabilizers, such as tinuvin, is also an example. ® 328 and Tinuvin ® 123, all traded by Ciba Specialty Chemicals of Tarrytown, New York, under the trade name Tinuvin ® available, can be used.

[0064] Non-restrictive examples of suitable ultraviolet light absorbers include hydroxyphenylbenzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert.amylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, a reaction product of 2-(2-hydroxy-3-tert.butyl-5-methylpropionate)-2H-benzotriazole and polyethylene ether glycol, which has a weight-average molecular weight of 300, 2-(2-hydroxy-3-tert.butyl-5-isooctylpropionate)-2H-benzotriazole; Hydroxyphenyl-s-triazines, such as 2-[4-((2-hydroxy-3-dodecyloxy / tridecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4(2-Hydroxy-3-(2-ethylhexyl)oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4-octyloxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; Hydroxybenzophenone UVAbsorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone and 2-hydroxy-4-dodecyloxybenzophenone.

[0065] Nicht einschränkende Beispiele für geeignete gehinderte Amin-Lichtstabilisatoren schließen N-(1,2,2,6,6-Pentamethyl-4-piperidinyl)-2-dodecylsuccinimid, N-(1-Acetyl-2,2,6,6-Tetramethyl-4-piperidinyl)-2-dodecylsuccinimid, N-(2-Hydroxyethyl)-2,6,6,6-Tetramethylpiperidin-4-ol-Bernsteinsäure-Copolymer, 1,3,5-Triazin-2,4,6-Triamin, N,N'''-[1,2-Ethandiylbis[[[4,6-bis[butyl-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-dibutyl-bis(1,2,2,6,6-pentamethyl-4-Piperidinyl)], Poly-[[6-[1,1,3,3-tetramethylbutyl)-amino]-1,3,5-triazin-2,4-diyl][2,2,6,6-tetramethylpiperidinyl)imino]-1,6-hexandiyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]), Bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacat, Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacat, Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacat, Bis (1,2,2,6,6-pentamethyl-4-piperidinyl)[3,5-bis(1,1-dimethylethyl-4-hydroxyphenyl)methyl]butylpropandioat, 8-Acetyl-3-dodecyl-7,7,9,9,-tetramethyl-1,3,8-triazaspiro(4,5)decan-2,4-dione and dodecyl / tetradecyl-3-(2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazal-dispiro(5.1.11.2)-henicosan-20-yl)propionate.,

[0066] Non-restrictive examples of suitable antioxidants include tetrakis[methylene(3,5-di-tert-butylhydroxyhydrocinnamate)]methane, octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tris(2,4-di-tert-butylphenyl)phosphite, 1,3,5-tris(3,5-di-tert-butyl)-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9-branched alkyl esters. In certain embodiments, the antioxidant includes hydroperoxide decomposers such as Sanko. ® HCA (9,10-Dihydroxy-9-Oxa-10-phosphenanthrene-10-oxide), triphenyl phosphate and other organophosphorus compounds, such as irgafos ® TNPP from Ciba Specialty Chemicals, Irgafos ® 168 from Ciba Specialty Chemicals, Ultranox ®626 from GE Specialty Chemicals, Mark PEP-6 from Asahi Denka, Mark HP-10 from Asahi Denka, Irgafos ® P-EPO from Ciba Specialty Chemicals, Ethanox 398 from Albemarle, Weston 618 from GE Specialty Chemicals, Irgafos ® 12 from Ciba Specialty Chemicals, Irgafos ® 38 from Ciba Specialty Chemicals, Ultranox ® 641 from GE Specialty Chemicals and Doverphos ® S-9228 from Dover Chemicals.

[0067] The coating compositions may also include other additives known in the field for use in coating compositions. Examples of such additives include wetting agents, leveling agents, and self-leveling agents, for example, Resiflow. ® S (Polybutyl acrylate), BYK ® 320 and 325 (high molecular weight polyacrylates), BYK ®347 (polyether-modified siloxane) under the corresponding trade names, leveling agents based on (meth)acrylic homopolymers; rheology aids; thickeners, such as partially cross-linked polycarboxylic acid or polyurethanes; and antifoaming agents. The additives may be used in conventional quantities familiar to those skilled in the field.

[0068] Depending on the type of crosslinking agent, the coating composition of this invention can be formulated as a one-component (1K) or two-component (2K) coating composition. One-component coating compositions can be air-drying or non-activated coatings. The terms "air-drying coating" or "non-activated coating" refer to a coating that dries primarily by solvent evaporation and does not require crosslinking to form a coating film exhibiting the desired properties. When polyisocyanates with free isocyanate groups are used as the crosslinking agent, the coating composition can be formulated as a two-component coating composition by mixing the crosslinking agent with the other components of the coating composition only shortly before application.For example, if blocked polyisocyanates are used as the crosslinking agent, the coating compositions can be formulated as a one-component (1K) coating composition. The coating composition can further be adjusted to spray viscosity with organic solvents determined by experts in the field prior to application.

[0069] "Two-pack coating composition" or "two-component coating composition" refers to a thermosetting coating composition that comprises two components stored in separate containers. These containers are typically sealed to enhance the shelf life of the coating composition components. The components are mixed before use to form a pot mixture. The pot mixture is applied as a layer of the desired thickness to a substrate surface, such as an automotive body or body panels. After application, the layer is cured at ambient conditions or at elevated temperatures to form a coating on the substrate surface that exhibits desired coating properties such as high gloss, a smooth appearance, and durability.

[0070] In embodiments, the coating composition is a one-component coating composition. As described above, the amounts of acid functional groups in the first polymer and the amounts of amino functional groups in the second polymer, together with the molecular weights of the first and second polymers, were formulated to provide a one-component coating composition that exhibits minimal gelation and improved coating performance, such as enhanced adhesion. In embodiments, the crosslinking agent can be used in the coating composition, making it a two-component coating composition. However, it is understood that the first and second polymers are contained in the same package and are exposed to each other in the two-component coating composition.

[0071] The coating composition can be used to form a coating layer on the substrate. This coating layer can be used as a basecoat, clearcoat, colored lacquer, topcoat, one-stage lacquer, intermediate lacquer, primer, sealer, or combinations thereof. In certain embodiments, the coating composition is used to form a basecoat coating layer.

[0072] The term "basecoat" refers to a coating that is opaque and provides much of the protection, color, coverage (also known as "opacity"), and visual appearance. A basecoat typically contains color pigments, effect pigments such as metallic flake pigments, rheology aids, UV absorbers, and other coating additives. The term "basecoat composition" refers to a coating composition that can be used to form a basecoat. The term "basecoat layer" refers to a coating layer formed from a basecoat composition. A basecoat layer can be formed by applying one or more layers of the same or different basecoat compositions.Automotive coatings typically involve coating a substrate with a primer for protection and adhesion, followed by a basecoat over the primer, optionally with a sealer applied over the primer for the majority of the protection, color, and appearance, and finally a clearcoat over the basecoat for further protection and appearance. Sometimes a single coating layer, referred to as a "topcoat," can be used to provide the function of both the basecoat and clearcoat. An additional coating layer may also be used. For example, a metal substrate may be treated with a phosphate material and then coated with an electrocoat before the primer is applied.

[0073] The term "intermediate coat" or "intermediate coating layer" refers to a non-opaque coating located between a base coat and a clear coat in a multi-layer coating system. To achieve some unique and attractive colors or visual effects, the automotive industry and other end users of coating applications may use a multi-layer coating system that has three or more coating layers instead of the traditional "base coat and clear coat" two-layer system. The multi-layer system may typically include at least a first colored and opaque base coat layer, a second non-opaque colored coating layer applied to at least some area of ​​the base coat layer, and a third clear coat layer applied to at least some area of ​​the second non-opaque colored coating layer.The second non-opaque color coat is usually referred to as an intermediate coat containing color pigments. The intermediate coat is typically formulated to be non-opaque, allowing the color of the underlying base coat to show through.

[0074] As described above, the amounts of acid functional groups in the first polymer and the amounts of amino functional groups in the second polymer, along with the molecular weights of the first and second polymers, were formulated such that a coating composition exhibits minimal gelation. Gelation can be determined by measuring the change in viscosity of the coating composition over time. Without being bound to any theory, it is assumed that a composition including polymers exhibiting functionalities in greater quantities than those described herein for the first and second polymers will show an unsuitable increase in viscosity over time, causing the composition to gel.

[0075] In embodiments, the coating layer formed from the coating composition that includes both the acid functional group and the amino functional group exhibits improved adhesion to the substrate compared to a coating layer formed from a coating composition that does not include both the acid functional group and the amino functional group, as described below in ASTM D3359 B and ASTM D6677.

[0076] In embodiments, the coating composition, which includes both the acid functional group and the amino functional groups, exhibits an improved drying time after application to the substrate compared to a coating composition that does not include both an acid functional group and the amino functional group. The term "dry" means that the resulting coating is physically touch-dry after a relatively short time to minimize dirt ingress and, in the case of a basecoat, to allow the application of the subsequent clearcoat. In embodiments where the coating composition is used as a basecoat composition, applying a clearcoat composition to the basecoat composition before the basecoat composition has dried may result in reduced flake control and a diminished metallic appearance (i.e., a less pronounced metallic sheen).Down-flopping occurs in the basecoat composition, which contains special effect pigments such as metallic and pearlescent flake pigments. This is due to the disruption of the flake pigments caused by mixing the basecoat and clearcoat compositions at the interface between them. "Down-flop" refers to a phenomenon associated with metallic effect coatings where the color changes with the viewing angle to provide a three-dimensional metallic effect on the vehicle's surface.

[0077] A coating system is also provided herein. The coating system may include a primer layer applied over the substrate, a basecoat layer applied over the primer layer, and a clearcoat layer applied over the basecoat layer. It is understood that the coating system may include an additional layer or additional layers, such as any of the coating layers described above, wherein the additional layers are arranged in any position between, above, or below the primer layer, the basecoat layer, and / or the clearcoat layer. In embodiments, the coating composition may be used to form the primer layer, the basecoat layer, the clearcoat layer, or combinations thereof. In certain embodiments, the coating composition is used to form the basecoat layer.

[0078] A method for coating a substrate using the coating composition is also provided herein. The method includes the step of applying a first coating composition, which includes the coating composition described above, to at least one area of ​​the substrate to form a first wet coating layer. The method may further include the step of curing or drying the first wet coating layer at a temperature in the range of 18 °C (64 °F) to 180 °C (356 °F) to form a first dry coating layer on the substrate. The first wet coating layer may be cured or dried for a period of about 10 minutes to 3 days. The method may further include the step of flashing the first wet coating layer.The process can further include the step of applying a second coating composition to the substrate to form a multilayer coating. In certain embodiments, the second coating composition can be applied over the first wet coating layer to form a second wet coating layer, and the first and second wet coating layers can be cured together to form the multilayer coating, wherein the second coating composition is the same as or different from the first coating composition.In other embodiments, the second coating composition is applied over the first dry coating layer to form a second wet coating layer, and the second wet coating layer is cured to form the multilayer coating, wherein the second coating composition is the same as or different from the first coating composition. In various embodiments, the first coating composition is a basecoat composition and the second coating composition is a clearcoat composition. In embodiments, the application steps may include spraying, electroplating, brushing, rolling, dipping, laminating, and the like. EXAMPLES

[0079] Examples 1-8 and 14 below describe the preparation of various first polymers (acid-functional) and various second polymers (amino-functional) from this disclosure. Examples 9-13 and 15 below describe exemplary and comparative coating compositions that include the first polymers and / or the second polymers of Examples 1-8 and 14. Examples 9 to 13 and 15 below further describe the formation of coating layers from the coating compositions and the testing of these coating layers. EXAMPLE 1: Production of an MMA / BA / t-BAEMA polymer, 78 / 15 / 7 wt%

[0080] Example 1 describes the preparation of a polymer with secondary amino groups (the second polymer) that can be used in an exemplary coating composition. A 5-liter flask was equipped with a thermometer, stirrer, additional funnels, heating jacket, reflux condenser, and a device to maintain a nitrogen blanket over the reactants. The flask was kept under nitrogen pressure, and the following components were used (Table 1). Table 1. Weight (grams) Part 1 Ethyl acetate 449,6 Butyl acetate 352 Part 2 Methyl methacrylate (MMA) 1058,8 Butyl acrylate (BA) 203,6 t-Butylaminoethyl methacrylate (t-BAEMA) 95 Ethyl acetate 25,4 toluene 16,9 Part 3 toluene 21,9 Part 4 2,2'-Azobis(methylbutyronitrile) (Vazo® 67 from DuPont Co., Wilmington, DE) 10,8 Ethyl acetate 84,9 toluene 389,4 Part 5 toluene 13 Part 6 Isopropanol 254,5 acetone 424,2 In total 3400

[0081] The mixture of Part 1 was placed in the flask. The mixture was heated to reflux temperature and boiled under reflux for approximately 10 minutes. Part 2 was added to the flask over 180 minutes. Part 4 was added to the flask concurrently over 360 minutes. Portion 3 was used to flush Part 2 into the flask at the end of the addition. The reaction mixture was maintained at reflux temperature throughout the entire addition process and heated under reflux for an additional 30 minutes. Part 5 was used to flush Part 4 at the end of the addition process. The reaction mixture was maintained at reflux temperature throughout the entire addition process and heated under reflux for an additional 120 minutes. The resin solution was cooled to approximately 50 °C before the addition of Part 6. The finished product was filled into containers.

[0082] The resulting polymer solution was a pale yellow, clear polymer solution with a solids content of about 40.1% and a Gardner-Holtz viscosity of U + 1 / 2. EXAMPLE 2 Production of an MMA / EA / t-BAEMA polymer, 78 / 15 / 7 wt%

[0083] Example 2 describes the preparation of another polymer with secondary amino groups (the second polymer) that can be used in an exemplary coating composition. The resin solution was prepared using the procedure described in Example 1, except that the BA monomer was replaced by EA (ethyl acrylate) monomer.

[0084] The resulting polymer solution was a pale yellow clear polymer solution with a solids content of about 39.5% and a Gardner-Holtz viscosity of X + 1 / 2. EXAMPLE 3 Production of an MMA / BA / DMAEA polymer, 78 / 15 / 7 wt%

[0085] Example 3 describes the preparation of a polymer with tertiary amino groups (the second polymer) that can be used in an exemplary coating composition. The resin solution was prepared using the procedure described in Example 1, except that the t-BAEMA monomer was replaced by DMAEA (N,N-dimethylaminoethyl acrylate monomer).

[0086] The resulting polymer solution was a pale yellow, clear polymer solution with a solids content of approximately 39.4% and a Gardner-Holtz viscosity of U + 1 / 4. The polymer had a Mw of 77620 and a Mn of 42379, based on gel permeation chromatography using polymethyl methacrylate as a standard. EXAMPLE 4 Production of an MMA / EA / MAA(PI) polymer, 81 / 14.6 / 4.4 / 2.91 wt%

[0087] Example 4 describes the preparation of a polymer with primary amino groups (the second polymer) that can be used in an exemplary coating composition. The MMA / EA / MAA (81 / 14.6 / 4.4 wt%) resin solution was prepared using a similar procedure to that described in Example 1, except that the t-BAEMA monomer was replaced by MAA (methacrylic acid monomer) in a solvent mixture of isopropanol, ethyl acetate, and toluene. After cooling the polymer solution to about 55 °C, a stoichiometric amount of propyleneimine was added to the reaction mixture to react with the carboxylic acid groups. The reaction mixture was gradually heated to 70 °C and held at that temperature for one hour to ensure complete reaction before cooling.

[0088] The resulting polymer solution was a pale yellow, clear polymer solution with a solids content of approximately 40.1% and a Gardner-Holtz viscosity of Z + 1 / 4. The polymer had a Mw of 104104 and a Mn of 37348, based on gel permeation chromatography using polymethyl methacrylate as a standard. EXAMPLE 5 Production of an MMA / BA / HEA / DMAEA polymer, 78 / 5 / 10 / 7 wt%

[0089] Example 5 describes the preparation of a polymer with tertiary amino groups and hydroxyl groups (the second polymer) that can be used in an exemplary coating composition. The resin solution was prepared using the procedure described in Example 1, except that the t-BAEMA monomer was replaced by DMAEA (N,N-dimethylaminoethyl acrylate monomer) and 2-hydroxyethyl acrylate (HEA) was added to the monomer mixture. Methyl isobutyl ketone was used as the solvent.

[0090] The resulting polymer solution was a pale yellow, clear polymer solution with a solids content of approximately 43% and a Gardner-Holtz viscosity of Z1. The polymer had a Mw of 103791 and a Mn of 28582, based on gel permeation chromatography using polymethyl methacrylate as a standard. EXAMPLE 6 Production of a Sty / IBOA / HEMA / HPMA / MAA polymer, 29 / 31 / 20 / 7.5 / 5 wt.%

[0091] Example 6 describes the preparation of a polymer with carboxylic acid groups (the first polymer) that can be used in an exemplary coating composition. A 5-liter flask was equipped with a thermometer, a stirrer, additional funnels, a heating jacket, a reflux condenser, and a device to maintain a nitrogen blanket over the reactants. The flask was kept under positive nitrogen pressure, and the following components were used (Table 2). Table 2. Weight (grams) Part 1 Methyl amyl ketone 560,04 Part 2 Styrene (Sty) 592,34 Butyl acrylate (BA) 633,16 Isobornyl acrylate (IBOA) 408,56 2-Hydroxyethyl methacrylate (HEMA) 153,15 Hydroxypropyl methacrylate (HPMA) 153,15 Methacrylic acid (MAA) 102,14 Part 3 Methyl amyl ketone 33,21 Part 4 Di-t-butyl peroxide 11,22 Methyl amyl ketone 331,88 Part 5 Methyl amyl ketone 24,87 Part 6 Methyl amyl ketone 240,28 In total 3244

[0092] The mixture of Part 1 was placed in the flask. The mixture was heated to reflux temperature and heated under reflux for approximately 10 minutes. Part 2 was added to the flask over 195 minutes. Part 4 was added to the flask concurrently over 200 minutes. Part 3 was used to flush Part 2 into the flask at the end of the addition. The reaction mixture was maintained at reflux temperature throughout the entire addition process. Part 5 was used to flush Part 4 at the end of the addition process. The reaction mixture was maintained at reflux temperature throughout the entire addition process and heated under reflux for a further 120 minutes. The resin solution was cooled to approximately 50 °C before the addition of Part 6. The finished product was filled into the flask.

[0093] The resulting polymer solution was a pale yellow, clear polymer solution with a solids content of approximately 40.1% and a Gardner-Holtz viscosity of U + 1 / 2. The polymer had a Mw of 28875 and a Mn of 5714, based on gel permeation chromatography using either polymethyl methacrylate or polystyrene as a standard. EXAMPLE 7 Production of an MMA / BMA / EHA / HEMA / MAA polymer, 30.29 / 26.65 / 23.11 / 18.55 / 1.40 wt.%

[0094] Example 7 describes the preparation of another polymer with carboxylic acid groups (the first polymer) that can be used in an exemplary coating composition. The resin solution was prepared using the same procedure as described in Example 6, wherein the monomers and their weight ratios, as listed above, were contained in a solvent mixture of xylene, butyl acetate, and n-butanol.

[0095] The resulting polymer solution was a pale yellow, clear polymer solution with a solids content of approximately 54.34% and a Gardner-Holtz viscosity of X + 1 / 2. The polymer had a Mw of 31982 and a Mn of 10530, based on gel permeation chromatography using either polymethyl methacrylate or polystyrene as a standard. EXAMPLE 8 Production of a Sty / MMA / BMA / EHA / HEMA / Acrylic acid (AA) polymer, 20 / 24 / 20 / 23.3 / 10.5 / 2.2 wt%

[0096] Example 8 describes the preparation of another polymer with carboxylic acid groups (the first polymer) that can be used in an exemplary coating composition. The resin solution was prepared using the same procedure as described in Example 6, with the monomers and their weight ratios being used as listed above in butyl acetate.

[0097] The resulting polymer solution was a clear polymer solution with a solids content of approximately 58.35% and a Gardner-Holtz viscosity of Z + 1 / 2. The polymer had a Mw of 8026 and a Mn of 9537, based on gel permeation chromatography using either polymethyl methacrylate or polystyrene as a standard. EXAMPLE 9

[0098] Example 9 describes the coating properties that can be achieved by using both the first polymers (acid-functional) and the second polymers (amino-functional) in exemplary coating compositions. Example 9 focuses specifically on the second polymers, which possess primary amino-functional groups. The results demonstrate the improved adhesion performance of coating layers formed from the exemplary coating compositions compared to coating layers formed from reference coating compositions. The improvement in adhesion performance is demonstrated for three colors: silver, bright red, and metallic red. Example 9.1: Silver coating compositions with aluminum flakes:

[0099] Sample coating compositions are generally described as follows: C1 is a comparison coating composition that includes the polymer from Example 4, which has a primary amino functional group (the second polymer); C5 is another comparison coating composition that includes the polymer from Example 6, which has an acid functional group (the first polymer); E1 is an exemplary coating composition that includes both the polymer from Example 4 (the second polymer) and the polymer from Example 6 (the first polymer); and E2 is another exemplary coating composition that includes both the polymer from Example 4 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0100] Production of the coating compositions: In Table 3 below, the components of Part 1 and Part 2 were placed in a metal container and thoroughly mixed using an air mixer. Part 3 was added to the container and mixed for a further 30 minutes. Part 4 and Part 5 were then added to the container one after the other and mixed for a further 15 minutes. Table 3. Example 9.1 - : Silver coating compositions C5 C1 El E2 Part 1 Acrylic polyol resin 17,54 17,76 6,86 Resin from example 4 10,05 10,08 9,61 Resin from example 6 6,30 10,93 Resin from example 7 21,46 Part 2 Wax dispersion 33,17 33,57 33,69 34,26 Anti-settling dispersion 3,97 3,97 3,97 1,59 Part 3 Aluminum paste 7,25 7,25 7,25 7,25 Part 4 CAB-20 solution 8,27 8,37 8,40 8,55 CAB-1 solution 8,53 8,63 8,67 8,81 Part 5 PGMEA 2,52 2,52 2,52 2,52 Butyl acetate 12,46 7,90 7,64 6,00

[0101] In Table 3, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is aluminum paste in a mixture of aliphatic and aromatic solvents; the CAB-20 solution is 15 wt% cellulose acetate butyrate (“CAB”), which is CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee), in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 9.2: Bright red coating compositions:

[0102] Sample coating compositions are generally described as follows: C6 is a comparison coating composition that includes the polymer from Example 4, which has a primary amino functional group (the second polymer); E9 is an exemplary coating composition that includes both the polymer from Example 4 (the second polymer) and the polymer from Example 6 (the first polymer); and E10 is another exemplary coating composition that includes both the polymer from Example 4 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0103] Production of the coating compositions: Coating compositions were produced using the same procedure described above with the components listed in Table 4 below. Table 4. Example 9.2 - Bright red coating compositions C6 E9 E10 Part 1 Acrylate resin 11,11 Resin from example 4 10,22 10,24 7,57 Resin from example 6 11,09 Resin from example 7 14,78 Part 2 Wax dispersion 27,59 27,64 27,71 Part 3 First red dispersion 17,46 17,46 17,46 Part 4 CAB-20 solution 6,88 6,89 6,91 CAB-1 solution 7, 10 7,11 7,13 Part 5 PGMEA 2,5 2,5 2,5 Butyl acetate 17,14 17,07 15,97

[0104] In Table 4, the first red dispersion is Commercial Power Tint: PT-165 (manufactured by Axalta Coating Systems, Philadelphia, PA); the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 9.3: Metallic red coating composition with aluminum flakes:

[0105] Sample coating compositions are generally described as follows: C9 is a comparison coating composition that includes the polymer from Example 4, which has a primary amino functional group (the second polymer); E15 is an exemplary coating composition that includes both the polymer from Example 4 (the second polymer) and the polymer from Example 6 (the first polymer); and E16 is another exemplary coating composition that includes both the polymer from Example 4 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0106] Production of the coating compositions: Coating compositions were produced using the same procedure described above with the components listed in Table 5 below. Table 5. Example 9.3 - Metallic red coating compositions C9 E15 E16 Part 1 Acrylic polyol resin 15,46 4,60 Resin from example 4 10 10 8,78 Resin from example 6 10,84 Resin from example 7 18,77 Part 2 Wax dispersion 33,37 33,4 33,67 Anti-settling dispersion 1,59 1,59 1,59 Part 3 Aluminum paste 6,52 6,52 6,52 Second red dispersion 4,73 4,73 4,73 Part 4 CAB-20 solution 8,32 8,33 8,4 CAB-1 solution 8,58 8,59 8,66 Part 5 PGMEA 2,50 2,50 2,50 Butyl acetate 8,95 8,9 6,39

[0107] In Table 5, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is an aluminum paste in a mixture of aliphatic and aromatic solvents; the second red dispersion is Chromabase. ® 866J (manufactured by Axalta Coating Systems, Philadelphia, PA); the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 9: Formation of coating layers from coating compositions

[0108] Commercially available primer-sealer 42440S (manufactured by Axalta Coating Systems, Philadelphia, PA) was sprayed onto electroplated metal plates. Basecoat samples (coating compositions) were mixed at a 1:1 volume ratio with commercially available thinner 7175S (manufactured by Axalta Coating Systems, Philadelphia, PA). The diluted basecoat samples were sprayed onto the dried sealer according to the technical data sheet. Commercially available clearcoat 74500S™ (manufactured by Axalta Coating Systems, Philadelphia, PA) was then sprayed on, and the plates were heat-treated in an oven at 160°F for 15 minutes. The plates were left to cure at ambient conditions for 3 days to form the coating layers. Example 9: Adhesion test of coating layers

[0109] Adhesion testing was performed on each of the coating layers of Example 9. Specifically, dry and wet adhesion tests were conducted using the cross-hatch and X-hatch adhesion tests. The dry adhesion test was performed on the panels on days 3, 5, and 7 after heat treatment. The panels were then stored in a humidity chamber for 96 hours. The wet adhesion test was performed immediately on the panels and again 4 hours after removal from the humidity chamber. A 24-hour recovery test was performed on the panels 24 hours after removal from the humidity chamber.

[0110] To perform the cross-hatch adhesion test, a cutting guide or a special cross-hatch cutter with multiple preset blades is used to make parallel incisions at appropriate intervals on a test area of ​​a coating layer. Adhesive tape is then applied to the test area of ​​the coating and subsequently removed. The test area is then inspected and evaluated. A standard method for applying and performing this test is provided in ASTM D3359 B.

[0111] To perform the X-hatch adhesion test, two cuts intersecting to form an "X" on a test area of ​​a coating layer are made into the coating layer using a sharp razor blade, scalpel, knife, or other cutting device at an angle of 30 to 45 degrees between the cuts and downwards to the substrate. A steel or other carbide ruler is used to ensure straight cuts. Adhesive tape is then applied to the test area of ​​the coating and subsequently removed. The test area is then inspected and evaluated. A standard method for applying and performing this test is provided in ASTM D6677.

[0112] Liability can be assessed on a sliding scale ranging from 0 (no liability, i.e., total failure) to 10 (complete liability, i.e., total success). The liability results are shown in Table 6 below. Table 6. Example 9.1: Silver coating compositions Example 9.2: Bright red coating compositions Example 9.3: Metallic red coating compositions Dry adhesion - Day 3 Dry adhesion - Day 3 Dry adhesion day 3 sample C5 C1 E1 E2 C6 E9 E10 C9 E15 E16 Grid 5 4 7 8 3 7 9 6 9 9 X Hatch 10 9 10 10 10 10 10 6 10 10 Dry adhesion - Day 5 Dry adhesion - Day 5 Dry adhesion - Day 5 sample C5 C1 E1 E2 C6 E9 E10 C9 E15 E16 Grid 7 4 8 8 5 7 7 6 9 9 X Hatch 10 10 10 9 10 9 10 10 10 10 Dry adhesion - Day 7 Dry adhesion - Day 7 Dry adhesion - Day 7 sample C5 C1 E1 E2 C6 E9 E10 C9 E15 E16 Grid 2 3 7 8 4 7 7 4 9 8 X Hatch 10 10 10 10 10 9 10 10 10 10 Wet adhesion - Instant Wet adhesion - Instant Wet adhesion - Instant sample C5 C1 E1 E2 C6 E9 E10 C9 E15 E16 Grid 7 2 8 8 5 3 3 8 8 8 X Hatch 10 10 9 10 10 10 10 10 10 10 Wet adhesion - 4 hours Wet adhesion -4 hours Wet adhesion -4 hours sample C5 C1 E1 E2 C6 E9 E10 C9 E15 E16 Grid 5 2 8 8 4 3 6 8 8 8 X Hatch 8 8 10 10 10 10 10 10 10 10 24-hour recovery Recovery -24 hours Recovery -24 hours sample C5 C1 E1 E2 C6 E9 E10 C9 E15 E16 Grid 7 2 8 9 1 3 3 4 8 8 X Hatch 9 8 9 10 10 10 10 10 9 10

[0113] The results of the adhesion tests of the coating layers from Example 9 clearly show that the exemplary coating compositions (samples E1, E2, E9, E10, E15, and E16) form coating layers exhibiting improved adhesion compared to coating layers made from the reference coating compositions (samples C1, C5, C6, and C9) in all types of adhesion tests, including grid adhesion, X-hatch adhesion, dry adhesion, wet adhesion, and the 24-hour recovery adhesion test. The results also show that the exemplary coating compositions can be used to form coating layers exhibiting improved adhesion for a wide range of color families with different types of pigment chemistries. EXAMPLE 10

[0114] Example 10 also describes the coating properties that can be achieved by using both the first polymers (acid-functional) and the second polymers (amino-functional) in exemplary coating compositions. Example 10 focuses specifically on the second polymers, which possess secondary amino-functional groups. The results show an improvement in the adhesion performance of coating layers formed from the exemplary coating compositions compared to coating layers formed from reference coating compositions. The improvement in adhesion performance is demonstrated for silver. Example 10.1: Silver coating compositions with aluminum flakes:

[0115] Sample coating compositions are generally described as follows: C2 is a comparison coating composition that includes the polymer from Example 1, which has a secondary amino functional group (the second polymer); C5 is another comparison coating composition that includes the polymer from Example 6, which has an acid functional group (the first polymer); E3 is an exemplary coating composition that includes both the polymer from Example 1 (the second polymer) and the polymer from Example 6 (the first polymer); and E4 is another exemplary coating composition that includes both the polymer from Example 1 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0116] Production of the coating compositions: Coating compositions were prepared using the same procedure described in Example 9, with the components listed in Table 7 below. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 7. Example 10.1 - : Silver coating compositions C5 C2 E3 E4 Part 1 Acrylic polyol resin 17,54 15,70 4,81 Resin from example 1 13,35 13,37 12,69 Resin from example 6 6,30 10,89 Resin from example 7 18,98 Part 2 Wax dispersion 33,17 33,49 33,54 33,94 Anti-settling dispersion 3,97 3,97 3,97 1,59 Part 3 Aluminum paste 7,25 7,25 7,25 7,25 Part 4 CAB-20 solution 8,27 8,35 8,36 8,46 CAB-1 solution 8,53 8,61 8,62 8,73 Part 5 PGMEA 2,52 2,52 2,52 2,52 Butyl acetate 12,46 6,76 6,68 5,80

[0117] In Table 7, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is aluminum paste in a mixture of aliphatic and aromatic solvents; the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 10: Adhesion test of coating layers

[0118] An adhesion test was performed on each of the coating layers of Example 10 in the same manner as in Example 9. Adhesion can be assessed on a sliding scale ranging from 0 (no adhesion, i.e., total failure) to 10 (complete adhesion, i.e., total success). The adhesion results are given in Table 8 below. Table 8. Example 10.1: Silver coating compositions Dry adhesion - Day 3 sample C5 C2 E3 E4 Grid 5 3 7 8 X Hatch 10 7 10 9 Dry adhesion - Day 5 sample C5 C2 E3 E4 Grid 7 2 7 8 X Hatch 10 10 10 10 Dry adhesion - Day 7 sample C5 C2 E3 E4 Grid 2 3 7 8 X Hatch 10 6 8 10 Wet adhesion - Instant upper C5 C2 E3 E4 Grid 7 1 4 7 X Hatch 10 10 10 10 Wet adhesion -4 hours sample C5 C2 E3 E4 Grid 5 1 4 7 X Hatch 8 6 10 9 Wet adhesion - 24 hours sample C5 C2 E3 E4 Grid 7 3 6 8 X Hatch 9 7 9 9

[0119] The results of the adhesion tests of the coating layers from Example 10 clearly show that the exemplary coating compositions (samples E3 and E4) form coating layers exhibiting improved adhesion compared to coating layers from the reference coating compositions (samples C2 and C5) in all types of adhesion tests, including grid adhesion, X-hatch adhesion, dry adhesion, wet adhesion and the 24-hour recovery test for adhesion. EXAMPLE 11

[0120] Example 11 also describes the coating properties that can be achieved by using both the first polymers (acid-functional) and the second polymers (amino-functional) in exemplary coating compositions. Example 11 focuses specifically on the second polymers, which have secondary amino-functional groups that differ from those in Example 10. The results demonstrate the improved adhesion performance of coating layers formed from the exemplary coating compositions compared to coating layers formed from reference coating compositions. The improved adhesion performance is demonstrated for three colors: silver, bright red, and metallic red. Example 11.1: Silver coating compositions with aluminum flakes:

[0121] Sample coating compositions are generally described as follows: C3 is a comparison coating composition that includes the polymer from Example 2, which has a secondary amino functional group (the second polymer); C5 is another comparison coating composition that includes the polymer from Example 6, which has an acid functional group (the first polymer); E5 is an exemplary coating composition that includes both the polymer from Example 2 (the second polymer) and the polymer from Example 6 (the first polymer); and E6 is another exemplary coating composition that includes both the polymer from Example 2 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0122] Production of the coating compositions: Coating compositions were prepared using the same procedure as described in Example 9, with the components listed in Table 9 below. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 9. Example 11.1 - Silver coating compositions C5 C3 E5 E6 Part 1 Acrylic polyol resin 17,54 15,70 4,81 Resin from example 2 13,35 13,37 12,69 Resin from example 6 6,30 10,89 Resin from example 7 18,98 Part 2 Wax dispersion 33,17 33,49 33,54 33,94 Anti-settling dispersion 3,97 3,97 3,97 1,59 Part 3 Aluminum paste 7,25 7,25 7,25 7,25 Part 4 CAB-20 solution 8,27 8,35 8,36 8,46 CAB-1 solution 8,53 8,61 8,62 8,73 Part 5 PGMEA 2,52 2,52 2,52 2,52 Butyl acetate 12,46 6,76 6,68 5,80

[0123] In Table 10, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is aluminum paste in a mixture of aliphatic and aromatic solvents; the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 11.2: Bright red coating compositions:

[0124] Sample coating compositions are generally described as follows: C7 is a comparative coating composition that includes the polymer from Example 2, which has a secondary amino functional group (the second polymer); E11 is an exemplary coating composition that includes both the polymer from Example 2 (the second polymer) and the polymer from Example 6 (the first polymer); and E12 is another exemplary coating composition that includes both the polymer from Example 2 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0125] Production of the coating compositions: Coating compositions were prepared using the same procedure described in Example 9, with the components listed in Table 10 below. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 10. Example 11.2 - Bright red coating compositions C7 E11 E12 Part 1 Acrylic polyol resin 10,03 Resin from example 2 12,20 12,11 9,22 Resin from example 6 9,86 Resin from example 7 13,53 Part 2 Wax dispersion 27,67 27,47 27,57 Part 3 First red dispersion 17,46 17,46 17,46 Part 4 CAB-20 solution 6,9 6,85 6,88 CAB-1 solution 7,12 7,06 7,09 Part 5 PGMEA 2,5 2,5 2,5 Butyl acetate 16,13 16,69 15,8

[0126] In Table 10, the first red dispersion is Commercial Power Tint: PT-165 (manufactured by Axalta Coating Systems, Philadelphia, PA); the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 11.3: Metallic red coating composition with aluminum flakes:

[0127] Sample coating compositions are generally described as follows: C10 is a comparative coating composition that includes the polymer from Example 2, which has a secondary amino functional group (the second polymer); E17 is an exemplary coating composition that includes both the polymer from Example 2 (the second polymer) and the polymer from Example 6 (the first polymer); and E18 is another exemplary coating composition that includes both the polymer from Example 2 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0128] Production of the coating compositions: Coating compositions were prepared using the same procedure described in Example 9, with the components listed in Table 11 below. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 11. Example 11.3 - Metallic red coating compositions C10 E17 E18 Part 1 Acrylic polyol resin 13,40 2,58 Resin from example 2 13,25 13,27 10,77 Resin from example 6 10,81 Resin from example 7 17,32 Part 2 Wax dispersion 33,25 33,28 33,53 Anti-settling dispersion 1,59 1,59 1,59 Part 3 Aluminum paste 6,52 6,52 6,52 Second red dispersion 4,73 4,73 4,73 Part 4 CAB-20 solution 8,29 8,3 8,36 CAB-1 solution 8,55 8,56 8,62 Part 5 PGMEA 2,50 2,50 2,50 Butyl acetate 7,92 7,87 6,09

[0129] In Table 11, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is aluminum paste in a mixture of aliphatic and aromatic solvents; the second red dispersion is Chromabase. ®866J (manufactured by Axalta Coating Systems, Philadelphia, PA); the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 11: Adhesion test of coating layers

[0130] An adhesion test was performed on each of the coating layers of Example 11 in the same manner as in Example 9. Adhesion can be assessed on a sliding scale ranging from 0 (no adhesion, i.e., total failure) to 10 (complete adhesion, i.e., total success). The adhesion results are given in Table 12 below. Table 12. Example 11.1: Silver coating compositions Example 11.2: Bright red coating compositions Example 11.3: Metallic red coating compositions Dry adhesion - Day 3 Dry adhesion - Day 3 Dry adhesion - Day 3 sample C5 C3 E5 E6 C7 E11 E12 C10 E17 E18 Grid 5 3 7 8 8 8 8 7 10 9 X Hatch 10 10 8 10 10 10 10 10 10 10 Dry adhesion - Day 5 Dry adhesion - Day 5 Dry adhesion - Day 5 sample C5 C3 E5 E6 C7 E11 E12 C10 E17 E18 Grid 7 5 7 8 8 7 8 6 9 9 X Hatch 10 10 10 10 10 10 10 10 9 10 Dry adhesion - Day 7 Dry adhesion - Day 7 Dry adhesion - Day 7 sample C5 C3 E5 E6 C7 E11 E12 C10 E17 E18 Grid 2 2 7 7 7 7 8 7 9 8 X Hatch 10 10 10 10 10 10 10 10 10 10 Wet adhesion - Instant Wet adhesion - Instant Wet adhesion - Instant sample C5 C3 E5 E6 C7 E11 E12 C10 E17 E18 Grid 7 2 4 7 4 7 3 6 8 8 X Hatch 10 4 9 10 10 10 10 10 10 10 Wet adhesion -4 hours Wet adhesion -4 hours Wet adhesion -4 hours sample C5 C3 E5 E6 C7 E11 E12 C10 E17 E18 Grid 5 2 7 8 4 7 4 7 5 9 X Hatch 8 10 10 10 10 10 10 10 10 10 24-hour recovery Recovery -24 hours Recovery -24 hours sample C5 C3 E5 E6 C7 E11 E12 C10 E17 E18 Grid 7 2 7 8 3 6 7 4 8 8 X Hatch 9 7 9 10 10 8 9 10 10 10

[0131] The adhesion test results of the coating layers from Example 11 clearly show that the exemplary coating compositions (samples E5, E6, E11, E12, E17, and E18) form coating layers exhibiting improved adhesion compared to coating layers from the reference coating compositions (samples C3, C5, C7, and C10) in all types of adhesion tests, including grid adhesion, X-hatch adhesion, dry adhesion, wet adhesion, and the 24-hour adhesion recovery test. The results also demonstrate that the exemplary coating compositions can be used to form coating layers exhibiting improved adhesion for a wide range of color families with different types of pigment chemistries. EXAMPLE 12

[0132] Example 12 also describes the coating properties that can be achieved by using both the first polymers (acid-functional) and the second polymers (amino-functional) in exemplary coating compositions. Example 12 focuses specifically on the second polymers, which possess tertiary amino-functional groups. The results demonstrate the improved adhesion performance of coating layers formed from the exemplary coating compositions compared to coating layers formed from reference coating compositions. The improvement in adhesion performance is demonstrated for three colors: silver, bright red, and metallic red. Example 12.1: Silver coating compositions with aluminum flakes:

[0133] Sample coating compositions are generally described as follows: C4 is a comparison coating composition that includes the polymer from Example 3, which has a tertiary amino functional group (the second polymer); C5 is another comparison coating composition that includes the polymer from Example 6, which has an acid functional group (the first polymer); E7 is an exemplary coating composition that includes both the polymer from Example 3 (the second polymer) and the polymer from Example 6 (the first polymer); and E8 is another exemplary coating composition that includes both the polymer from Example 3 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0134] Production of the coating compositions: Coating compositions were prepared using the same procedure as described in Example 9, with the components listed in Table 13 below. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 13. Example 12.1 - Silver coating compositions C5 C4 E7 E8 Part 1 Acrylic polyol resin 17,54 17,51 6,68 Resin from example 3 10,25 10,26 9,80 Resin from example 6 6,30 10,83 Resin from example 7 21,09 Part 2 Wax dispersion 33,17 33,31 33,35 33,91 Anti-settling dispersion 3,97 3,97 3,97 1,59 Part 3 Aluminum paste 7,25 7,25 7,25 7,25 Part 4 CAB-20 solution 8,27 8,31 8,32 8,46 CAB-1 solution 8,53 8,57 8,58 8,72 Part 5 PGMEA 2,52 2,52 2,52 2,52 Butyl acetate 12,46 8,32 8,25 6,68

[0135] In Table 13, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is aluminum paste in a mixture of aliphatic and aromatic solvents; the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 12.2: Bright red coating compositions:

[0136] Sample coating compositions are generally described as follows: C8 is a comparative coating composition that includes the polymer from Example 3, which has a tertiary amino functional group (the second polymer); E13 is an exemplary coating composition that includes both the polymer from Example 3 (the second polymer) and the polymer from Example 6 (the first polymer); and E14 is another exemplary coating composition that includes both the polymer from Example 3 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0137] Production of the coating compositions: Coating compositions were prepared using the same procedure described in Example 9, with the components listed in Table 14 below. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 14. Example 12.2 - Bright red coating compositions C8 E13 E14 Part 1 Acrylic polyol resin 10,92 Resin from example 3 10,34 10,36 7,69 Resin from example 6 10,92 Resin from example 7 14,61 Part 2 Wax dispersion 27,39 27,44 27,57 Part 3 First red dispersion 17,46 17,46 17,46 Part 4 CAB-20 solution 6,83 6,84 6,88 CAB-1 solution 7,05 7,06 7,09 Part 5 PGMEA 2,5 2,5 2,5 Butyl acetate 17,51 17,44 16,25

[0138] In Table 14, the first red dispersion is Commercial Power Tint: PT-165 (manufactured by Axalta Coating Systems, Philadelphia, PA); the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 12.3: Metallic red coating composition with aluminum flakes:

[0139] Sample coating compositions are generally described as follows: C11 is a comparison coating composition that includes the polymer from Example 3, which has a tertiary amino functional group (the second polymer); E19 is an exemplary coating composition that includes both the polymer from Example 3 (the second polymer) and the polymer from Example 6 (the first polymer); and E20 is another exemplary coating composition that includes both the polymer from Example 3 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer).

[0140] Production of the coating compositions: Coating compositions were prepared using the same procedure described in Example 9, with the components listed in Table 15 below. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 15. Example 12.3 - Metallic red coating compositions C11 E19 E20 Part 1 Acrylic polyol resin 15,27 4,47 Resin from example 3 10,22 10,23 8,95 Resin from example 6 10,79 Resin from example 7 18,62 Part 2 Wax dispersion 33,21 33,25 33,54 Anti-settling dispersion 1,59 1,59 1,59 Part 3 Aluminum paste 6,52 6,52 6,52 Second red dispersion 4,73 4,73 4,73 Part 4 CAB-20 solution 8,28 8,29 8,36 CAB-1 solution 8,54 8,55 8,63 Part 5 PGMEA 2,50 2,50 2,50 Butyl acetate 9,15 9,08 6,58

[0141] In Table 15, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is aluminum paste in a mixture of aliphatic and aromatic solvents; the second red dispersion is Chromabase. ®866J (manufactured by Axalta Coating Systems, Philadelphia, PA); the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; and PGMEA is propylene glycol monomethyl ether acetate. Example 12: Adhesion test of coating layers

[0142] An adhesion test was performed on each of the coating layers of Example 12 in the same manner as in Example 9. Adhesion can be assessed on a sliding scale ranging from 0 (no adhesion, i.e., total failure) to 10 (complete adhesion, i.e., total success). The adhesion results are given in Table 16 below. Table 16. Table 16. Example 12.1: Silver coating compositions Example 12.2: Bright red coating compositions Example 12.3: Metallic red coating compositions Dry adhesion - Day 3 Dry adhesion - Day 3 Dry adhesion - Day 3 sample C5 C4 E7 E8 C8 E13 E14 C11 E19 E20 Grid 5 3 7 8 7 8 10 8 9 10 X Hatch 10 7 10 10 10 10 10 10 10 10 Dry adhesion - Day 5 Dry adhesion - Day 5 Dry adhesion - Day 5 sample C5 C4 E7 E8 C8 E13 E14 C11 E19 E20 Grid 7 5 7 8 7 7 9 6 9 9 X Hatch 10 10 10 10 10 8 10 10 10 10 Dry adhesion - Day 7 Dry adhesion - Day 7 Dry adhesion - Day 7 sample C5 C4 E7 E8 C8 E13 E14 C11 E19 E20 Grid 2 4 8 8 7 7 8 4 8 8 X Hatch 10 10 10 10 10 10 10 7 10 10 Wet adhesion - Instant Wet adhesion - Instant Wet adhesion - Instant sample C5 C4 E7 E8 C8 E13 E14 C11 E19 E20 Grid 7 5 8 9 1 2 5 7 9 10 X Hatch 10 10 10 10 2 6 10 10 10 10 Wet adhesion -4 hours Wet adhesion -4 hours Wet adhesion -4 hours sample C5 C4 E7 E8 C8 E13 E14 C11 E19 E20 Grid 5 6 7 9 2 3 6 8 10 10 X Hatch 8 8 9 10 5 7 10 10 10 10 24-hour recovery Recovery -24 hours Recovery -24 hours sample C5 C4 E7 E8 C8 E13 E14 C11 E19 E20 Grid 7 6 7 9 5 6 6 5 8 8 X Hatch 9 9 8 10 9 8 10 10 10 10

[0143] The adhesion test results of the coating layers from Example 12 clearly show that the exemplary coating compositions (samples E7, E8, E13, E14, E19, and E20) form coating layers exhibiting improved adhesion compared to coating layers made from the reference coating compositions (samples C4, C5, C8, and C11) in all types of adhesion tests, including grid adhesion, X-hatch adhesion, dry adhesion, wet adhesion, and the 24-hour adhesion recovery test. The results also demonstrate that the exemplary coating compositions can be used to form coating layers exhibiting improved adhesion for a wide range of color families with different types of pigment chemistries. EXAMPLE 13

[0144] Example 13 also describes the coating properties that can be achieved by using both the first polymers (acid-functional) and the second polymers (amino-functional) and a crosslinking agent in exemplary coating compositions. Example 13 focuses on the use of polyisocyanates as the crosslinking agent. The results show the improvement in the adhesion performance of coating layers when the crosslinking agent is used. The improvement in adhesion performance is demonstrated for two colors: silver and bright red. Example 13.1: Silver coating compositions with aluminum flakes:

[0145] Sample coating compositions are generally described as follows: E21 is an exemplary coating composition that includes both the polymer from Example 5, which has a tertiary amino functional group and a hydroxyl functional group (the second polymer), and the polymer from Example 7, which has an acid functional group and a hydroxy functional group (the first polymer); and E22 is another exemplary coating composition that includes both the polymer from Example 5 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer), and a polyisocyanate (crosslinking agent).

[0146] Production of the coating compositions: In Table 17 below, the components of Part 1 and Part 2 were placed in a metal container and thoroughly mixed using an air mixer. Part 3 was added to the container and thoroughly mixed for an additional 30 minutes. Parts 4 and 5 were then added sequentially and thoroughly mixed for 15 minutes. Activator 12305S (manufactured by Axalta Coating Systems, Philadelphia, PA) was added to sample E22 after dilution (prior to spraying) at a ratio of 1 ounce per quart. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 17. Example 13.1 - Silver coating compositions E21 E22 Part 1 Resin from example 5 8,9 8,9 Resin from example 5 20,83 20,83 Part 2 Wax dispersion 33,9 33,9 Anti-settling dispersion 1,58 1,58 Part 3 Aluminum paste 7,14 7,14 Part 4 CAB-20 solution 8,46 8,46 CAB-1 solution 8,72 8,72 Part 5 PGMEA 2,52 2,52 Butyl acetate 7,96 7,96 Part 6 Activator 12305S™ 1 ounce / RTS quart

[0147] In Table 18, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is aluminum paste in a mixture of aliphatic and aromatic solvents; the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; PGMEA is propylene glycol monomethyl ether acetate; and the activator 12305S™ is a commercially available polyisocyanate activator from Axalta Coating Systems, Philadelphia, PA. Example 13.2: Bright red coating compositions:

[0148] Sample coating compositions are generally described as follows: E23 is an exemplary coating composition that includes both the polymer from Example 5, which has a tertiary amino functional group and a hydroxyl functional group (the second polymer), and the polymer from Example 7, which has an acid functional group and a hydroxy functional group (the first polymer); and E24 is another exemplary coating composition that includes both the polymer from Example 5 (the second polymer) and the polymer from Example 7, which has an acid functional group (the first polymer), and a polyisocyanate (crosslinking agent).

[0149] Production of the coating compositions: In Table 18 below, the components of Part 1 and Part 2 were placed in a metal container and thoroughly mixed using an air mixer. Part 3 was added to the container and thoroughly mixed for a further 30 minutes. Parts 4 and 5 were then added sequentially and thoroughly mixed for 15 minutes. Activator 12305S was added to sample E24 after dilution (prior to spraying) at a ratio of 1 ounce per quart. The coating compositions were sprayed and tested in the same manner as in Example 9. Table 18. Example 13.2 - Bright red coating compositions E23 E24 Part 1 Resin from example 5 6,97 6,97 Resin from example 7 14,4 14,4 Part 2 Wax dispersion 27,61 27,61 Part 3 Red dispersion 17,45 17,45 Part 4 CAB-20 solution 6,89 6,89 CAB-1 solution 7,1 7,1 Part 5 PGMEA 2,52 2,52 Butyl acetate 17,05 17,05 Part 6 Activator 12305S™ 1 ounce / RTS quart

[0150] In Table 18, the anti-settling dispersion is a Bentone dispersion; the first red dispersion is Commercial Power Tint: PT-165 (manufactured by Axalta Coating Systems, Philadelphia, PA); the CAB-20 solution is 15 wt% CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; the CAB-1 solution is 15 wt% CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in butyl acetate and methyl ethyl ketone in a weight ratio of 7:3; PGMEA is propylene glycol monomethyl ether acetate; and the activator 12305S™ is a commercially available polyisocyanate activator from Axalta Coating Systems, Philadelphia, PA. Example 13: Adhesion test of coating layers

[0151] An adhesion test was performed on each of the coating layers of Example 13 in the same manner as in Example 9. Adhesion can be assessed on a sliding scale ranging from 0 (no adhesion, i.e., total failure) to 10 (complete adhesion, i.e., total success). The adhesion results are given in Table 19 below. Table 19 Example 13.1: Silver coating compositions Example 13.2: Bright red coating compositions Dry adhesion - Day 7 Dry adhesion - Day 7 sample E21 E22 E23 E24 Grid 10 10 10 10 X Hatch 10 10 9 10 Wet adhesion - Instant Wet adhesion - Instant sample E21 E22 E23 E24 Grid 8 10 8 10 X Hatch 10 10 10 10 Wet adhesion - 4 hours Wet adhesion - 4 hours sample E21 E22 E23 E24 Grid 10 10 10 10 X Hatch 10 10 10 10 24-hour recovery Recovery -24 hours sample E21 E22 E23 E24 Grid 9 10 10 9 X Hatch 10 9 10 9

[0152] The results of the adhesion tests of the coating layers from Example 13 clearly show that the exemplary coating compositions (samples E21, E22, E23, and E24) form coating layers exhibiting improved adhesion compared to coating layers made from the reference coating compositions (samples C4, C5, C8, and C11) in all types of adhesion tests, including lattice adhesion, X-hatch adhesion, dry adhesion, wet adhesion, and the 24-hour adhesion recovery test. Further crosslinking of the first and second polymers with polyisocyanates shows comparable and potentially improved lattice and X-hatch adhesion in the wet adhesion test compared to the coating compositions that were not further crosslinked with polyisocyanates.The results also show that the exemplary coating compositions can be used to form coating layers that exhibit improved adhesion for a wide range of color families with different types of pigment chemistries. EXAMPLE 14 Production of a Sty / BA / MMA / EHA / HEMA / MAA polymer, 20 / 20 / 20 / 15 / 10 / 15 wt%

[0153] Example 14 describes the preparation of another polymer from a reaction mixture containing an acid-functional monomer in an amount of 15 wt%, based on the total weight of the reaction mixture. As described above, in embodiments, the use of the acid-functional monomer in an amount greater than 12 wt% can lead to gelation of the coating composition. The resin solution was prepared using the same procedure as described in Example 6, with the monomers and their weight ratios being used as listed above in butyl acetate.

[0154] The resulting polymer solution was an extremely viscous, clear polymer solution with a solids content of approximately 52.92% and a Gardner-Holtz viscosity of Z7. The polymer had a Mw of 38017 and a Mn of 11549, based on gel permeation chromatography using either polymethyl methacrylate or polystyrene as a standard. EXAMPLE 15 Testing of polymer mixtures

[0155] Table 20 below shows the components combined according to the molar ratios of the acid functional groups of the first polymer and the amino functional groups of the second polymer. The resulting solutions are clear, pale yellow polymer solutions. The viscosities of the polymer solutions are then measured using a Brookfield viscometer at 20 rpm with spindle No. 3. Table 20. S1 S2 S3 E25 E26 E27 E28 E29 First polymer from example 14 (15 wt% MAA) 147,5 - - 9,7 - 32,3 78,0 - First polymer from example 7 (1.4 wt% MAA) - 149,5 - - 64,2 - - 138,1 Second polymer from example 5 (wt% DMAEA) - - 189,0 176,6 107,8 147,6 88,9 14,5 Butyl acetate 177,5 175,5 136,0 138,7 153,0 145,1 158,0 172,4 In total 325,0 325,0 325,0 325,0 325,0 325,0 325,0 325,0 Solid % 25 25 25 25 25 25 25 25 Molar ratio of functional groups n / a n / a n / a 1 / 4 1 / 4 1 / 1 4 / 1 4 / 1 Viscosity (cps) 158 21 116 218 66 855 2440 33

[0156] The exemplary polymer solutions E25, E27, and E28, which include the first polymer formed from 15 wt% MAA and the second polymer, exhibit increased viscosities compared to the viscosities of the standard polymer solutions S1, S2, and S3, which include only either the first polymer or the second polymer. In contrast, the exemplary polymer solutions E26 and E29, which include less than 12 wt% MAA, show viscosities similar to those of the standard polymer solutions S1, S2, and S3. The viscosity test results clearly demonstrate that interactions between the first and second polymers of the exemplary polymer solutions E26 and E29 are minimized prior to application and curing of the coating compositions, as evidenced by the similar viscosities of the exemplary polymer solutions E26 and E29 and the standard polymer solutions S1, S2, and S3.It is assumed that the first polymers, formed from MAA in an amount of no more than 12 wt%, exhibit minimal interactions with the second polymer when in solution (e.g., before application of the coating composition). Such interactions intensify upon drying to produce the improved film properties.

[0157] In contrast, the exemplary polymer solutions E25, E27, and E28 suffer from an increase in viscosity compared to the standard polymer solutions S1, S2, and S3. This indicates an increase in interactions between the first and second polymers prior to application and curing of the coating compositions, due to the higher amount of MAA used in the formation of the first polymer. The higher viscosities of these polymer solutions can negatively affect the spray application of the coating compositions containing these polymer solutions, as well as the color properties, thus limiting the application range of the coating composition.

[0158] Although at least one exemplary embodiment has been presented in the preceding detailed description, it should be understood that a large number of variations exist. It should also be understood that the exemplary embodiment or embodiments are merely examples and are not intended to limit the scope, applicability, or configuration in any way. Rather, the preceding detailed description will provide those skilled in the art with a practical plan for implementing an exemplary embodiment. It is understood that various modifications to the function and arrangement of elements described in an exemplary embodiment can be made without deviating from the scope as set forth in the appended claims.

Claims

[1] A coating composition for coating a substrate, comprising: a first polymer comprising a first polymer-bound portion having an acid-functional group or a derivative thereof; wherein the first polymer-bound portion is polymerized from a first polymer monomer mixture comprising acid-functional monomers in an amount of 0.1 to 12 wt.%, based on the total weight of the first polymer monomer mixture; a second polymer comprising a second polymer-bound portion having an amino-functional group; wherein the second polymer-bound portion is polymerized from a second polymer monomer mixture comprising amino-functional monomers in an amount of 0.1 to 15 wt.%, based on the total weight of the second polymer monomer mixture; and an organic solvent; wherein the first polymer includes less than 0.1 wt% of amino functional groups and the second polymer includes less than 0.1 wt% of acid functional groups or derivatives thereof; and wherein the acid functional groups and the amino functional groups are substantially reactive with each other, at least after application of the coating composition to the substrate, wherein the coating composition is substantially free of water. [2] Coating composition according to claim 1, wherein: the organic solvent is present in an amount of 10 to 95 wt.%, based on the total weight of the coating composition. [3] A coating composition according to any one of the preceding claims, wherein the first polymer and the second polymer independently have a weight average molecular weight in an amount of 2000 to 200000. [4] Coating composition according to any one of the preceding claims, wherein the acid functional monomers are selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, oleic acid, cinnamic acid, glutaconic acid, muconic acid, undecenoic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and combinations thereof. [5] Coating composition according to claim 4, wherein: the first polymer has a hydroxyl-functional group, the first polymer monomer mixture further comprises hydroxyl-functional monomers, and the hydroxyl-functional monomers are preferably selected from the group of 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and combinations thereof. [6] A coating composition according to any one of the preceding claims, wherein the second polymer is selected from a second polymer monomer mixture comprising: amino-functional monomers selected from the group of t-butylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate and combinations thereof. [7] Coating composition according to any one of the preceding claims, wherein: the second polymer has hydroxyl-functional groups, the second polymer monomer mixture further comprises hydroxyl-functional monomers, and the hydroxyl-functional monomers are preferably selected from the group of 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and combinations thereof. [8] A coating composition according to any one of the preceding claims, wherein a coating layer formed from the coating composition has improved adhesion to the substrate compared to a coating layer formed from a coating composition that does not comprise both the acid functional group and the amino functional group. [9] Coating composition according to any one of the preceding claims, further comprising one or more non-functional polymers, crosslinking agents, pigments, additives or combinations thereof.