Coating composition for coating substrate comprising binder component

Abstract

The present invention relates to a coating composition for coating a substrate comprising a binder component. Provided herein are coating compositions for coating a substrate. The coating composition includes a first polymer including a first polymer binding moiety having an acid functional group or a derivative thereof. The coating composition also includes a second polymer including a second polymer binding moiety having an amine functional group. The coating composition also includes a solvent. The first polymer is substantially free of amine functional groups and the second polymer is substantially free of acid functional groups, or derivatives thereof. The acid functional group and the amine functional group are substantially reactive with each other at least after application of the coating composition to the substrate.

Description

[0001] This application is a divisional application of an invention patent application with an application date of December 28, 2017, application number 201711460293.1, and title “Coating composition comprising an adhesive component for coating a substrate”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to U.S. Provisional Application No. 62 / 440,121 filed on December 29, 2016 and U.S. Patent Application No. 15 / 804,557 filed on November 6, 2017, which are hereby incorporated by reference in their entirety.

[0004] FIELD OF THE INVENTION

[0002] The present invention relates generally to coating compositions for coating a substrate comprising a first polymer and a second polymer. Background Art

[0005] Coating compositions are used to form coatings, such as primer layers, basecoat layers, and clearcoat layers, for protective and decorative purposes. These coating compositions can be used in automotive OEM and refinishing surface coating applications and provide a protective layer for the underlying substrate and can also have aesthetically pleasing value. Currently, automotive coatings are typically multi-layer coating systems, including a clearcoat layer overlying a basecoat layer, wherein the basecoat layer is overlying one or more additional layers, such as a primer layer and an electrocoat layer.

[0006] In finishing surface coating applications, customers expect high productivity and excellent performance. In order to achieve the desired productivity, the coating composition is preferably able to dry at ambient temperature or slightly elevated temperature in a relatively short period of time. However, many current quick-drying coating compositions do not meet the desired performance requirements, such as excellent stone-chip resistance, moisture resistance, interlayer and intralayer adhesion, and appearance. In addition, if the coating (e.g., basecoat) is not fully dried before the clearcoat composition covering the basecoat is subsequently applied to form a clearcoat, the application of the topcoat composition will interfere with the basecoat, and the appearance of the basecoat will be adversely affected. For example, the flake control and metallic appearance (i.e., "angle flash color (downflop)") of the basecoat composition containing special effect pigments (e.g., metal and pearlescent flake pigments) will be impaired due to the mixing of the basecoat and the clearcoat at the interface between them interfering with the flake pigment.

[0007] Therefore, it is desirable to provide a coating composition having a short drying time and excellent performance.Furthermore, other desirable features and characteristics will become apparent from the subsequent detailed description and the appended claims, taken in conjunction with this background. Summary of the invention

[0008] Provided herein is a coating composition for coating a substrate. The coating composition comprises a first polymer, the first polymer comprising a first polymer binding portion having an acid functional group or a derivative thereof. The coating composition further comprises a second polymer, the second polymer comprising a second polymer binding portion having an amine functional group. The coating composition further comprises a solvent. The first polymer is substantially free of amine functional groups, and the second polymer is substantially free of acid functional groups or derivatives thereof. The acid functional group and the amine functional group are substantially reactive with each other at least after the coating composition is applied to the substrate. DETAILED DESCRIPTION

[0009] The following detailed description is merely exemplary in nature and is not intended to limit the coating compositions as described herein. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.

[0010] Provided herein is a coating composition for coating a substrate. The coating composition can be used to coat any type of substrate known in the art. In some embodiments, the substrate is a vehicle, an automobile, or a motor vehicle. "Vehicle" or "automobile" or "motor vehicle" includes automobiles, such as sedans, vans, minivans, buses, SUVs (sports utility vehicles); trucks; semi-trailers (semi trucks); tractors; motorcycles; trailers; ATVs (all terrain vehicles); pickup trucks; heavy duty movers, such as bulldozers, mobile cranes (mobile cranes) and earthmoving machinery (earth movers); airplanes; ships; ships; and other modes of transportation. The coating composition can also be used to coat substrates in industrial applications, such as buildings, fences, fixed structures, bridges, pipelines, cellulosic materials such as wood, paper, fibers, etc.

[0011] The coating composition comprises the first polymer, the second polymer and a solvent. In some embodiments, the first polymer and the second polymer are considered to be a part of an adhesive polymer component. The term "adhesive polymer component" refers to the film-forming component of the coating composition. Generally, the adhesive polymer component can include polymers, oligomers, and combinations thereof, which are necessary for forming a coating with desired properties (such as hardness, protection, adhesion, etc.). The term "adhesive polymer component" may not include other components, such as solvents, pigments, catalysts, rheology modifiers, antioxidants, UV stabilizers and absorbents, leveling agents, defoamers, anti-cratering agents or other conventional additives, unless any of these other components is the film-forming component of the coating composition. One or more of these other components may be included in the coating composition. In certain embodiments, the "adhesive polymer component" does not include pigments and solvents at least. In some embodiments, and as described in more detail below, the coating composition also includes other components, such as non-functional polymers, pigments and additives. The coating composition may also include a crosslinking agent as described herein.

[0012] The first polymer comprises a first polymer binding portion having an acid functional group or a derivative thereof. The derivative of the acid functional group may include any acid functional group formed by another compound in one or more steps, such as by blocking the acid functionality of the acid functional group or by replacing hydrogen atoms with alkyl and acyl groups. The second polymer comprises a second polymer binding portion having an amine functional group. The acid functional group and the amine functional group are substantially reactive to each other at least after the coating composition is applied to the substrate. The term "substantially" about the reactivity of the acid functional group and the amine functional group to each other means that based on the acid functional group and the amine functional group with a lower molar concentration respectively, at least 60%, or at least 75%, or at least 85%, or at least 90%, or at least 95%, or alternatively at least 99% of the acid functional group and the amine functional group can be used for reactivity (that is, reaction degree) to each other. The acid functional group and the amine functional group can interact by non-covalent bonding (such as ionic bonding). In some embodiments, when the first and second polymers are dissolved in a solvent (e.g., a polar solvent), the ionic interactions between the acid functional groups and the amine functional groups are minimized, thereby resulting in a coating composition that exhibits minimal gelation. In some additional embodiments, after the solvent evaporates, such as after the coating composition is applied to a substrate, the ionic interactions between the acid functional groups and the amine functional groups are maximized, thereby forming a coating having improved coating properties (e.g., adhesion) after curing.

[0013] The first polymer is substantially free of amine functional groups, and the second polymer is substantially free of acid functional groups. In some embodiments, the amount of amine 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 remaining amine functional groups of the first polymer. In some embodiments, the amount of acid functional groups in the second polymer is minimized to reduce the occurrence of intramolecular interactions between the amine functional groups of the second polymer and any remaining acid functional groups of the second polymer. The term "substantially free" about the presence of amine functional groups in the first polymer means that the mixture for forming the first polymer contains less than 0.1% by weight, or less than 0.05% by weight, or less than 0.01% by weight, or less than 0.005% by weight, or alternatively less than 0.001% by weight of amine functional groups based on the gross weight of the mixture. The term "substantially free" with respect to the presence of acid functional groups in the second polymer means that the mixture used to form the second polymer contains less than 0.1 wt%, or less than 0.05 wt%, or less than 0.01 wt%, or less than 0.005 wt%, or alternatively less than 0.001 wt% acid functional groups based on the total weight of the mixture.

[0014] Based on the gross weight of the adhesive polymer component of the coating composition, the first polymer can be used in the coating composition in an amount of about 1 wt % to about 90 wt %, or about 5 wt % to about 90 wt %, or about 5 wt % to about 80 wt %, or alternatively about 5 wt % to about 60 wt %.Based on the gross weight of the adhesive polymer component of the coating composition, the second polymer can be used in the coating composition in an amount of about 1 wt % to about 90 wt %, or about 5 wt % to about 90 wt %, or about 5 wt % to about 80 wt %, or about 5 wt % to about 60 wt %.In some embodiments, the acid functional group of the first polymer and the amine functional group of the second polymer are used in the coating composition in an amount of about 10:1 to about 1:10, or about 5:1 to about 1:5, or alternatively about 4:1 to about 1:4 with a molar ratio of acid functional group to amine functional group.

[0015] The first polymer comprises a first polymer binding portion having an acid functional group or a derivative thereof. The first polymer binding portion can be at least a portion of the backbone of the first polymer, can be a side chain of the first polymer, can be grafted to the first polymer, or a combination thereof. The first polymer may comprise more than one first polymer binding portion, wherein the polymer binding portion is at any position of the first polymer. In certain embodiments, the first polymer binding portion is a first polymer. The first polymer binding portion may be formed by an acid functional monomer, an acid functional oligomer, an acid functional macromer, or a combination thereof. In an embodiment, for example, in an embodiment where the first polymer is an acrylic-based polymer, the monomer, oligomer, or macromer comprises a polymerizable double bond, such as an ethylenically unsaturated double bond. However, it should be understood that the first polymer may be a polyester-based polymer or a polyurethane-based polymer as described below. In some 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 linear or branched.

[0016] The acid functional group or its derivative may be a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an anhydride group, or a combination thereof. The first polymer binding portion may have more than one type of acid functional group or its derivative. In certain embodiments, the acid functional group or its derivative is a carboxylic acid group.

[0017] In some embodiments, the first polymer binding portion is polymerized by a first polymer monomer mixture comprising an acid-functional monomer. In certain embodiments, the acid-functional monomer is selected from the following group: acrylic acid, methacrylic acid, crotonic acid, oleic acid, cinnamic acid, glutaconic acid, muconic acid, undecylenic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and combinations thereof. In some embodiments, the first polymer monomer mixture may include an anhydride of any acid-functional monomer. Suitable anhydrides include maleic anhydride and itaconic anhydride. In these embodiments, anhydride monomers may be hydrolyzed to form corresponding carboxyl groups. It should be understood that the first polymer monomer mixture may include acid-functional monomers and anhydride monomers. After the first polymer is polymerized, after the first polymer is formulated into a coating composition, or after the coating composition is applied to a substrate, the anhydride groups of the first polymer may be hydrolyzed to form acid-functional groups.

[0018] In some embodiments, the first polymer monomer mixture comprises an acid-functional monomer or derivative thereof in an amount of about 0.1 wt % to about 12 wt %, or about 0.5 wt % to about 10 wt %, or about 0.5 wt % to about 8 wt %, or alternatively about 1 wt % to about 5 wt %, based on the gross weight of the first polymer monomer mixture. Without being bound by theory, it is believed that polymers polymerized from a polymer monomer mixture comprising an acid-functional monomer in an amount greater than 12 wt % will result in a coating composition having moisture sensitivity and resulting in gelation of the coating composition due to reactivity with the second polymer. Without being bound by theory, it is also believed that polymers polymerized from a polymer monomer mixture comprising an acid-functional monomer in an amount less than 0.1 wt % will result in a polymer that does not react sufficiently with the second polymer.

[0019] The weight average molecular weight of the first polymer may be from about 2,000 to about 200,000, or from about 8,000 to about 200,000, or alternatively from about 10,000 to about 200,000. Unless otherwise specified, the "molecular weight" disclosed herein can be determined by gel permeation chromatography (GPC) using polystyrene as a standard. The polydispersity of the first polymer may be from about 1.05 to about 10.0, or from about 1.2 to about 8, or alternatively from about 1.5 to about 5. The Tg of the first polymer may be from about -50°C to about 100°C, or from about -30°C to about 100°C, or from about -5°C to about 100°C, or from about 0°C to 80°C, or alternatively from about 10°C to about 60°C. "Tg" means the glass transition temperature of the polymer and can be measured by differential scanning calorimetry (DSC) or can be calculated as described by Fox in Bull. Amer. Physics Soc., 1, 3, p. 123 (1956). It should be understood that the Tg of the first polymer may depend on the type of polymer used, for example, the Tg of a polyester-based polymer may be from about -50°C to about 40°C, the Tg of an acrylic-based polymer may be from about -5°C to about 100°C, and the Tg of a polyurethane polymer may be from -50°C to about 100°C. Without being bound by theory, it is believed that the first polymer having the above weight average molecular weight provides a coating composition that exhibits minimal gelation and improved coating properties (e.g., improved adhesion). In particular, a polymer having a weight average molecular weight of less than 2,000 may be separated from the coating composition before reacting and curing with the second polymer, thereby resulting in a coating having poorer properties. In addition, even if the polymer having a weight average molecular weight of less than 2,000 is not separated from the coating composition, the polymer may not substantially contribute to the formation of a coating film. In contrast, polymers having a weight average molecular weight greater than 200,000 may result in a coating composition having a viscosity that is not suitable for spray application of the coating composition. The first polymer may include one or more polymers each having at least an acid functional group or a derivative thereof. Each polymer may have more than one type of acid functional group or a derivative thereof.

[0020] The second polymer comprises a second polymer binding portion having an amine functional group. The amine functional group may be a primary amine, a secondary amine, or a tertiary amine. The second polymer binding portion may be at least a portion of the backbone of the second polymer, may be a side chain of the second polymer, may be grafted to the second polymer, or a combination thereof. The second polymer may comprise more than one second polymer binding portion, wherein the polymer binding portion is at any position of the second polymer. In certain embodiments, the second polymer binding portion is a second polymer. The second polymer binding portion may be formed by an amine functional monomer, an amine functional oligomer, an amine functional macromer, or a combination thereof. In an embodiment, for example, in an embodiment where the second polymer is an acrylic-based polymer, the monomer, oligomer, or macromer comprises a polymerizable double bond, such as an ethylenically unsaturated double bond. However, it should be understood that the second polymer may be a polyester-based polymer or a polyurethane-based polymer as described below. In an embodiment, 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 linear or branched.

[0021] In some embodiments, the second polymer binding portion can be polymerized by a second polymer monomer mixture comprising an amine functional monomer, a carboxyl functional monomer, or a combination thereof. In one embodiment, the second polymer binding portion can be polymerized by a second polymer monomer mixture comprising an amine functional monomer. The amine functional monomer can be selected from the group consisting of tert-butylaminoethyl methacrylate (t-BAEMA), N,N-dimethylaminoethyl acrylate (DMAEA), and a combination thereof. In another embodiment, the second polymer binding portion is polymerized by a second polymer monomer mixture comprising a carboxyl functional monomer. The carboxyl functional monomer can be methacrylic acid. In an embodiment where the second polymer is polymerized by a carboxyl functional monomer (e.g., methacrylic acid), the second polymer is reacted with an imine compound (e.g., propylene imine) to form a primary amine functional group. The secondary amine functional group can be polymerized by t-BAEMA. Alternatively, the secondary amine functional group can be polymerized by a polymer comprising an epoxy functional group and an amine compound (e.g., a primary amine). The tertiary amine functional groups may be polymerized from N,N-dialkylaminoalkyl acrylates (e.g., N,N-dimethylaminoethyl acrylate and N,N-diethylaminoethyl acrylate) and N,N-dialkylaminoalkyl methacrylates (e.g., N,N-dimethylaminoethyl methacrylate and N,N-diethylaminoethyl methacrylate). It should be understood that the amine functional groups of the second polymer may include protecting groups that cooperate with the amine functional groups to selectively inhibit the amine functionality of the amine functional groups, such as when the second polymer is in a dissolved state before application and / or before curing. However, it should be understood that the protecting groups are separated from the amine functional groups before use to allow the amine functionality of the amine functional groups, such as before application, after application, or after curing.

[0022] In some embodiments, the second polymer monomer mixture comprises an amine functional monomer in an amount of about 0.1 wt % to about 15 wt %, or about 0.5 wt % to about 12 wt %, or about 0.5 wt % to about 10 wt %, or alternatively about 1 wt % to about 7 wt %, based on the total weight of the second polymer monomer mixture. Without being bound by theory, it is believed that polymers polymerized from a polymer monomer mixture comprising an amine functional monomer in an amount greater than 15 wt % will result in gelation of the coating composition due to reactivity with the first polymer. Without being bound by theory, it is also believed that polymers polymerized from a polymer monomer mixture comprising an amine functional monomer in an amount less than 0.1 wt % will result in a polymer that does not react sufficiently with the first polymer.

[0023] The weight average molecular weight of the second polymer may be from about 2,000 to about 200,000, or from about 8,000 to about 200,000, or alternatively from about 10,000 to about 200,000. The polydispersity of the second polymer may be from about 1.05 to about 10.0, or from about 1.2 to about 8, or from about 1.5 to about 5. The Tg of the second polymer may be from about -50°C to about 100°C, or from about -30°C to about 100°C, or from about -5°C to about 100°C, or from about 0°C to 80°C, or alternatively from about 10°C to about 60°C. It should be understood that the Tg of the second polymer may depend on the type of polymer used, for example, the Tg of a polyester-based polymer may be from about -50°C to about 40°C, the Tg of an acrylic-based polymer may be from about -5°C to about 100°C, and the Tg of a polyurethane polymer may be from -50°C to about 100°C. Without being bound by theory, it is believed that the second polymer with the above-mentioned weight average molecular weight provides a coating composition that exhibits minimal gelation and improved coating properties (e.g., improved adhesion). In particular, a polymer with a weight average molecular weight of less than 2,000 can be separated from the coating composition before reacting and curing with the first polymer, thus resulting in a coating with poor performance. Examples of polymers with a weight average molecular weight of less than 2,000 and therefore not suitable as the second polymer of the coating composition include, but are not limited to, small amine-containing molecules, such as triethylamine and propylamine. In addition, even if the polymer with a weight average molecular weight of less than 2,000 is not separated from the coating composition, the polymer may not substantially contribute to the formation of a coating film. In contrast, a polymer with a weight average molecular weight greater than 200,000 can result in a coating composition with a viscosity that is not suitable for spray application of the coating composition. The second polymer may include one or more polymers each having at least an amine functional group. Each polymer may have more than one type of amine functional group.

[0024] In some embodiments, the first polymer, the second polymer, or both the first polymer and the second polymer have crosslinkable functional groups, such as isocyanate reactive groups. The term "crosslinkable functional groups" refers to functional groups located in oligomers, functional groups in polymers, functional groups in polymer backbones, functional groups in pendant groups of polymer backbones, functional groups located at the ends of polymer backbones, or combinations thereof, wherein these functional groups are capable of crosslinking with crosslinking functional groups (during the curing step) to produce a coating in the form of a crosslinked structure.

[0025] Typical crosslinkable functional groups may include hydroxyl, thiol, isocyanate, thioisocyanate, acetoacetoxy, carboxyl, primary amine, secondary amine, epoxy, anhydride, ketimine, aldimine, or a feasible combination thereof. Some other functional groups, such as orthoesters, orthocarbonates, or cyclic amides that can generate hydroxyl or amine groups once the ring structure is opened, may also be suitable as crosslinkable functional groups.

[0026] 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 with hydroxyl functional groups can be polymerized by a first polymer monomer mixture also comprising a hydroxyl functional monomer. The second polymer with hydroxyl functional groups can be polymerized by a second polymer monomer mixture also comprising a hydroxyl functional monomer. Non-limiting examples of hydroxyl functional monomers for forming primary hydroxyl groups include 2-hydroxyethyl methacrylate (HEMA) and 2-hydroxyethyl acrylate (HEA). Non-limiting examples of hydroxyl functional monomers for forming secondary hydroxyl groups include hydroxypropyl methacrylate (HPMA) and hydroxypropyl acrylate (HPA). In certain embodiments, hydroxyl functional monomers are selected from the group of 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and combinations thereof. It should be understood that the selection of the hydroxyl functional groups of the first polymer is independent of the selection of the hydroxyl functional groups of the second polymer, and vice versa. In other embodiments, the crosslinkable functional group is a thiol functional group. In various embodiments, the amine functional groups of the second polymer are the only crosslinkable functional groups of the second polymer because the amine functional groups are available to react with the acid functional groups of the first polymer and are reactive to crosslink with isocyanates.

[0027] In some embodiments, the first polymer, the second polymer, or both the first polymer and the second polymer are polymerized from additional monomers other than monomers containing acid functional groups and amine functional groups, such as any acrylic monomer known in the art and any ethylenically unsaturated monomers known in the art. Non-limiting examples of these additional monomers include unsubstituted or substituted alkyl acrylates, such as alkyl acrylates having 1 to 20 carbon atoms in the alkyl group; alkyl methacrylates, such as alkyl methacrylates having 1 to 20 carbon atoms in the alkyl group; alicyclic acrylates; alicyclic methacrylates; aryl acrylates; aryl methacrylates; other ethylenically unsaturated monomers, such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, N,N-dialkyl acrylamide, N,N-dialkyl methacrylamide; vinyl aromatic compounds, such as styrene, and combinations thereof. Other non-limiting 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, etc. Other non-limiting examples include other ethylenically unsaturated monomers, such as vinyl aromatic compounds. Non-limiting examples of vinyl aromatic compounds include styrene, α-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 by additional monomers selected from the following group: styrene, methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, and combinations thereof. It should be 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.

[0028] 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.Styrene can be used in an amount of about 10 wt % to about 50 wt %, or about 20 wt % to about 40 wt %, or alternatively about 25 wt % to about 35 wt %, each based on the gross weight of the first polymer.Butyl acrylate can be used in an amount of about 10 wt % to about 50 wt %, or about 20 wt % to about 40 wt %, or alternatively about 25 wt % to about 35 wt %, each based on the gross weight of the first polymer.Isobornyl acrylate can be used in an amount of about 1 wt % to about 40 wt %, or about 10 wt % to about 30 wt %, or alternatively about 15 wt % to about 25 wt %, each based on the gross weight of the first polymer. 2-Hydroxyethyl methacrylate can be used in an amount of about 0.1 wt % to about 30 wt %, or about 1 wt % to about 20 wt %, or alternatively about 3 wt % to about 12 wt %, each based on the gross weight of the first polymer. Hydroxypropyl methacrylate can be used in an amount of about 0.1 wt % to about 30 wt %, or about 1 wt % to about 20 wt %, or alternatively about 3 wt % to about 12 wt %, each based on the gross weight of the first polymer. Methacrylic acid can be used in an amount of about 0.1 wt % to about 12 wt %, or about 1 wt % to about 9 wt %, or alternatively about 3 wt % to about 7 wt %, each based on the gross weight of the first polymer.

[0029] In another exemplary embodiment, the first polymer comprises the reaction product of methyl methacrylate, butyl methacrylate, ethylhexyl acrylate, 2-hydroxyethyl methacrylate and methacrylic acid.Methyl methacrylate can be used in an amount of about 10 wt % to about 50 wt %, or about 20 wt % to about 40 wt %, or alternatively about 25 wt % to about 35 wt %, each based on the gross weight of the first polymer.Butyl methacrylate can be used in an amount of about 5 wt % to about 45 wt %, or about 15 wt % to about 35 wt %, or alternatively about 20 wt % to about 30 wt %, each based on the gross weight of the first polymer.Ethylhexyl acrylate can be used in an amount of about 5 wt % to about 45 wt %, or about 15 wt % to about 35 wt %, or alternatively about 20 wt % to about 30 wt %, each based on the gross weight of the first polymer. 2-Hydroxyethyl methacrylate can be used in an amount of about 0.1 wt % to about 40 wt %, or about 10 wt % to about 30 wt %, or alternatively about 15 wt % to about 25 wt %, each based on the total weight of the first polymer. Methacrylic acid can be used in an amount of about 0.1 wt % to about 12 wt %, or about 0.1 wt % to about 8 wt %, or alternatively about 0.1 wt % to about 4 wt %, each based on the total weight of the first polymer.

[0030] In another exemplary embodiment, the first polymer comprises styrene, methyl methacrylate, butyl methacrylate, ethylhexyl acrylate, 2-hydroxyethyl methacrylate and acrylic acid reaction product.Styrene can be used in an amount of about 1 wt % to about 50 wt %, or about 10 wt % to about 30 wt %, or alternatively about 15 wt % to about 25 wt %, each based on the gross weight of the first polymer.Methyl methacrylate can be used in an amount of about 1 wt % to about 50 wt %, or about 10 wt % to about 40 wt %, or alternatively about 20 wt % to about 30 wt %, each based on the gross weight of the first polymer.Butyl methacrylate can be used in an amount of about 1 wt % to about 50 wt %, or about 10 wt % to about 30 wt %, or alternatively about 15 wt % to about 25 wt %, each based on the gross weight of the first polymer. Ethylhexyl acrylate can be used in an amount of about 1 wt % to about 50 wt %, or about 10 wt % to about 40 wt %, or alternatively about 20 wt % to about 30 wt %, each based on the gross weight of the first polymer. 2-Hydroxyethyl methacrylate can be used in an amount of about 0.1 wt % to about 40 wt %, or about 5 wt % to about 20 wt %, or alternatively about 5 wt % to about 15 wt %, each based on the gross weight of the first polymer. Acrylic acid can be used in an amount of about 0.1 wt % to about 12 wt %, or about 0.1 wt % to about 8 wt %, or alternatively about 0.1 wt % to about 4 wt %, each based on the gross weight of the first polymer.

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

[0032] In another exemplary embodiment, the second polymer comprises the reaction product of methyl methacrylate, ethyl acrylate and tert-butylaminoethyl methacrylate.Methyl methacrylate can be used in an amount of about 60 % by weight to about 90 % by weight, or about 70 % by weight to about 85 % by weight, or about 75 % by weight to about 81 % by weight, each based on the gross weight of the second polymer.Ethyl acrylate can be used in an amount of about 5 % by weight to about 25 % by weight, or about 10 % by weight to about 20 % by weight, or alternatively about 12 % by weight to about 18 % by weight, each based on the gross weight of the second polymer.Tertiary butylaminoethyl methacrylate can be used in an amount of about 0.1 % by weight to about 12 % by weight, or about 3 % by weight to about 10 % by weight, or alternatively about 5 % by weight to about 9 % by weight, each based on the gross weight of the second polymer.

[0033] In another exemplary embodiment, the second polymer comprises the reaction product of methyl methacrylate, butyl acrylate and N,N-dimethylaminoethyl acrylate.Methyl methacrylate can be used in an amount of about 60% by weight to about 90% by weight, or about 70% by weight to about 85% by weight, or alternatively about 75% by weight to about 81% by weight, each based on the gross weight of the second polymer.Butyl acrylate can be used in an amount of about 5% by weight to about 25% by weight, or about 10% by weight to about 20% by weight, or alternatively about 12% by weight to about 18% by weight, each based on the gross weight of the second polymer.N,N-dimethylaminoethyl acrylate can be used in an amount of about 0.1% by weight to about 12% by weight, or about 3% by weight to about 10% by weight, or alternatively about 5% by weight to about 9% by weight, each based on the gross weight of the second polymer.

[0034] In another exemplary embodiment, the second polymer comprises the reaction product of methyl methacrylate, ethyl acrylate, and the reaction product of methacrylic acid and propylene imine.Methyl methacrylate can be used in an amount of about 65 wt % to about 95 wt %, or about 73 wt % to about 87 wt %, or alternatively about 77 wt % to about 83 wt %, each based on the gross weight of the second polymer.Ethyl acrylate can be used in an amount of about 5 wt % to about 25 wt %, or about 10 wt % to about 20 wt %, or alternatively about 12 wt % to about 18 wt %, each based on the gross weight of the second polymer.Methacrylic acid can be used in an amount of about 0.1 wt % to about 12 wt %, or about 1 wt % to about 7 wt %, or alternatively about 2 wt % to about 6 wt %, each based on the gross weight of the second polymer.Propylene imine can be used in an amount of about 0.1 wt % to about 12 wt %, or about 1 wt % to about 7 wt %, or alternatively about 1 wt % to about 5 wt %, each based on the gross weight of the second polymer.

[0035] In another exemplary embodiment, the second polymer comprises the reaction product of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate and N,N-dimethylaminoethyl acrylate.Methyl methacrylate can be used in an amount of about 60% by weight to about 90% by weight, or about 70% by weight to about 85% by weight, or alternatively about 75% by weight to about 81% by weight, each based on the gross weight of the second polymer.Butyl acrylate can be used in an amount of about 0.1% by weight to about 15% by weight, or about 1% by weight to about 15% by weight, or alternatively about 3% by weight to about 8% by weight, each based on the gross weight of the second polymer.2-Hydroxyethyl acrylate can be used in an amount of about 0.1% by weight to about 25% by weight, or about 1% by weight to about 17% by weight, or alternatively about 7% by weight to about 13% by weight, each based on the gross weight of the second polymer. N,N-dimethylaminoethyl acrylate may be used in an amount of about 0.1 wt % to about 12 wt %, or about 1 wt % to about 10 wt %, or alternatively about 4 wt % to about 10 wt %, each based on the total weight of the second polymer.

[0036] The first polymer, the second polymer, or both the first polymer and the second polymer are independently selected from linear or branched acrylic polymers, linear or branched polyester polymers, polyurethane polymers, or combinations thereof. "Acrylic polymer" means a polymer comprising polymerized "(meth)acrylates" (which means acrylates and / or methacrylates), optionally copolymerized with other ethylenically unsaturated monomers, such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and vinyl aromatic compounds such as styrene.

[0037] In some embodiments, the first polymer, the second polymer, or both the first polymer and the second polymer are polyester polymers. The polyester polymer can be linear 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 should be understood that the selection of the polyester for the first polymer is independent of the selection of the polyester for the second polymer, and vice versa.

[0038] The non-limiting examples of suitable alicyclic polycarboxylic acids are tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tricyclodecanedicarboxylic acid, endethylenehexahydrophthalic acid, camphoric acid, cyclohexanetetracarboxylic acid and cyclobutanetetracarboxylic acid.Alicyclic polycarboxylic acids can be used not only with their cis-form, but also with their trans-form and as a mixture of two forms. Other non-limiting examples of suitable polycarboxylic acids can include aromatic and aliphatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, halogenated phthalic acid (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 polycarboxylic acids and alicyclic polycarboxylic acids, may be suitable. Combinations of polyols may also be suitable. If desired, monoacids (e.g., benzoic acid) may also be included to control molecular weight. It should be understood that although polyesters and polyols having more than two functional groups may be used to generate more branching points, the amount of functional groups resulting from branching should be controlled to prevent gelation.

[0039] Non-limiting suitable polyols include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanedimethanol, trimethylpentanediol, ethylbutylpropylene glycol, ditrimethylolpropane, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, polyethylene glycol and polypropylene glycol. If desired, monohydric alcohols (e.g., butanol, octanol, lauryl alcohol), ethoxylated or propoxylated phenols and polyols may also be included to control molecular weight.

[0040] The non-limiting examples of suitable polyesters include branched copolyester polymers. The branched copolyester polymers and production methods described in U.S. Patent No. 6,861,495 (which is incorporated herein by reference) may be suitable. Monomers with multifunctional groups such as AxBy (x, y independently = 1 to 3) types may be used, including monomers with one carboxyl and two hydroxyls, two carboxyls and one hydroxyl, one carboxyl and three hydroxyls, or three carboxyls and one hydroxyl to produce branched structures. The non-limiting 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, etc.

[0041] Branched copolyester polymers can be conventionally polymerized from a monomer mixture comprising a chain extender selected from the group of hydroxycarboxylic acids, lactones of hydroxycarboxylic acids, and combinations thereof, and one or more branching monomers. Some suitable hydroxycarboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxypentanoic acid, and hydroxypivalic acid (pyvalic acid). Some suitable lactones include caprolactone, valerolactone; and corresponding lactones of hydroxycarboxylic acids (e.g., 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxypentanoic acid, and hydroxypivalic acid). In certain embodiments, caprolactone can be used. In some embodiments, a branched copolyester polymer can be produced by polymerizing a monomer mixture comprising a chain extender and a hyperbranched monomer in a single step, or by first polymerizing a hyperbranched monomer and then polymerizing a chain extender. It should be understood that the branched copolyester polymer can be formed from an acrylic core and the above-mentioned extension monomers.

[0042] In embodiments where the first polymer is a polyester polymer (also referred to herein as an "acid functional polyester"), the first polymer may be produced by using an excess of a diacid or anhydride with a polyol in the synthesis or other methods known to those skilled in the art to ensure that the polymer chain terminates with an acid functional group in a linear or branched structure. Alternatively, a polyester having a hydroxyl group at the terminal position of the polymer chain may be post-reacted with a diacid or anhydride to form an acid functional group.

[0043] In embodiments when the second polymer is a polyester polymer (also referred to herein as an "amine functional polyester"), the second polymer may be produced by including an amine functional polyol, such as a tertiary amine functional polyol, in the synthesis with the polyacid and polyol or other methods known to those skilled in the art. Non-limiting examples of monomers having only one reactive group capable of condensing with an acid or anhydride and placing the tertiary amine functional group at a terminal position in the 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-limiting examples of polyols having tertiary amine groups that may place amine functional groups along the polymer chain include simple compounds such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N,N-dibutylethanolamine, triethanolamine, triisopropanolamine, and the like sold under the trade names N-methyldiethanolamine, N-ethyldiethanolamine, N-butyl ... (a tertiary amine nitrogen atom) and (two tertiary amine nitrogen atoms) A compound commercially available from Akzo Nobel NV of Amsterdam, Netherlands. The second polymer may also be subjected to post-polymerization, for example by reacting the above carboxylic acid-containing polyester polymer with a suitable amine compound such as propylene imine.

[0044] In some embodiments, the first polymer, the second polymer or both the first polymer and the second polymer are polyurethane polymers. Polyurethane can be produced by polyols and polyisocyanates. Polyols can be polymers or oligomers organic species and mixtures thereof with at least two hydroxyl functional groups or two thiol functional groups. Polyesters and polycarbonates with terminal hydroxyl groups can be effectively used as diols.

[0045] In some embodiments, the production of polyurethane polymer is well known to those skilled in the art, and in particular, polyurethane polymer can be produced by reacting excessive polyisocyanates with polyols. In certain embodiments, polyurethane polymer is formed by utilizing low molar mass polyols (e.g., polyols) limited by experience and structural formula. The limiting examples of polyols include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, trimethylpentanediol, ethylbutylpropylene glycol, ditrimethylolpropane, trimethylolethane, trimethylolpropane, glycerine, pentaerythritol, dipentaerythritol, polyethylene glycol and polypropylene glycol. In other embodiments, polyurethane polymer is formed by utilizing number-average molar mass to be, for example, oligomeric or polymeric polyols of at most 8000, or at most 5000, or at most 2000 and / or, for example, corresponding hydroxyl-functional polyethers, polyesters or polycarbonates.

[0046] Non-limiting examples of suitable polyisocyanates include aromatic, aliphatic or alicyclic diisocyanates, triisocyanates or tetraisocyanates, including polyisocyanates with isocyanurate structural units, such as isocyanurates of hexamethylene diisocyanate and isocyanurates of isophorone diisocyanate; adducts of 2 molecules of diisocyanate (e.g., hexamethylene diisocyanate) and diols (e.g., ethylene glycol); uretdione of hexamethylene diisocyanate; uretdione of isophorone diisocyanate or isophorone diisocyanate; adducts of trimethylolpropane and meta-tetramethylxylene diisocyanate. Other polyisocyanates disclosed herein may also be suitable for producing polyurethanes.

[0047] In certain embodiments, diols and diisocyanates are used to form polyurethane polymers to avoid crosslinking and forming a network that will cause polymer gelation. Chain extenders such as diamines can be used to increase molecular weight. Small amounts of monomers with higher functionality levels (e.g., triols or triisocyanates) can be used to create branching points and branched structures. However, the concentration of these monomers with higher functionality levels may need to be low enough not to cause polymer crosslinking and gelation.

[0048] In embodiments where the first polymer is a polyurethane polymer (also referred to herein as an "acid-functional polyurethane"), the first polymer can be effectively produced by reacting any acid-group-containing diol as part of a diol mixture at an expected acid group concentration level with a polyisocyanate. 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. In addition, acid functional groups can be produced at terminal positions by using low levels of acid-containing monomers having only one functional group that can react with polyisocyanates and terminate the polymer chain. In a staged synthesis, an excess of polyisocyanates is used to ensure that the polymer chain is first terminated with an isocyanate group. The terminal isocyanate group is in turn treated with an acid-containing monomer having only one functional group that can potentially react with polyisocyanates. Examples of such monomers include 2-hydroxypropionic acid, 3-hydroxypropionic acid, 3-mercaptopropionic acid, and the like.

[0049] Acid functional polyurethanes can also be prepared by reacting one or more polyols with one or more polyisocyanates, wherein low levels of diacids or anhydrides, such as aliphatic or aromatic dicarboxylic acid anhydride diols (depending on the desired acid group concentration) are included in the diol mixture. Similarly, in a staged synthesis, linear or branched polyurethanes having terminal hydroxyl or thiol groups can be post-treated with diacids and / or anhydrides to produce terminal acid functional groups.

[0050] In some embodiments, when the second polymer is a polyurethane polymer (also referred to herein as an "amine-functional polyurethane"), the second polymer may have a tertiary amine group. Amine-functional polyurethanes having tertiary amine groups can be produced by using a low concentration (depending on the desired molecular weight and degree of branching) of a polymer, oligomer or simple compound having one or more tertiary amine functional groups and one or more functional groups capable of reacting with isocyanate groups in the synthesis. Non-limiting examples of monomers having only one reactive group capable of reacting with an isocyanate group and placing the tertiary amine functional group at the terminal position of the 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-limiting examples of polyols having tertiary amine groups that can place amine functionality along the polymer chain include simple compounds such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N,N-dibutylethanolamine, triethanolamine, triisopropanolamine, and those sold under the trade names (a tertiary amine nitrogen atom) and (two tertiary amine nitrogen atoms) A compound commercially available from Akzo Nobel N.V. of Amsterdam, Netherlands.

[0051] Amine functional polyurethanes with primary amine groups can be produced by post-reacting the acid groups of an acid functional polyurethane (e.g., the acid functional polyurethanes described above) with an imine compound (e.g., propylene imine). Alternatively, a polyurethane polyol can be reacted with an excess of polyisocyanate to ensure that the polymer chain is terminated with isocyanate groups in a linear or branched structure. These isocyanate groups can then be hydrolyzed to form primary amine groups, thereby forming an amine functional polyurethane.

[0052] As mentioned above, the coating composition also includes a solvent. In some embodiments, the solvent is an organic solvent. The organic solvent can be a liquid carrier to disperse and / or dilute the above-mentioned ingredients and form a coating composition with desired properties. The solvent or solvent blend is generally selected from the following group: aromatic hydrocarbons, such as naphtha or xylene; 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 the organic solvent added depends on the desired solid content, the desired rheological (e.g., spraying) properties, and the desired VOC amount of the coating composition. Based on the gross weight of the coating composition, the solvent can be present in an amount of about 10% by weight to about 95% by weight, or about 20% by weight to about 95% by weight, or alternatively about 40% by weight to about 95% by weight.

[0053] The total solids content of the coating composition may be in an amount from about 5 wt % to about 90 wt %, or from about 5 wt % to about 80 wt %, or alternatively from about 5 wt % to about 60 wt %, based on the total weight of the coating composition.

[0054] In some embodiments, the coating composition is a solvent-containing coating composition. In certain embodiments, the coating composition is substantially free of water. The term "substantially free" with respect to the amount of water in the coating composition means that the coating composition comprises less than 5 wt %, or less than 3 wt %, or less than 2 wt %, or less than 1 wt %, or less than 0.1 wt % of water based on the gross weight of the coating composition.

[0055] As also described above, the coating composition may also include a non-functional polymer. The non-functional polymer may include a linear or branched acrylic polymer, a linear or branched polyester polymer, a polyurethane polymer, or a combination thereof. The term "non-functional polymer" refers to a polymer that is substantially free of acid functional groups and amine functional groups. The term "substantially" used herein with respect to the non-functional polymer being substantially free of acid functional groups and amine functional groups means that the non-functional polymer comprises less than 0.1% by weight of acid functional groups and amine functional groups. The non-functional polymer may have other functional groups that are not acid functional groups or amine functional groups.

[0056] As also introduced above, the coating composition may further include a crosslinking agent, which may react with the crosslinkable functional groups of the first polymer, the second polymer, or both the first polymer and the second polymer to form a crosslinked polymer network (referred to herein as a crosslinked network). Although it is understood that the coating composition provides improved coating properties, particularly interlayer adhesion, without crosslinking with a crosslinking agent, a crosslinking agent may be used in the coating composition to further improve coating properties.

[0057] The term "crosslinking agent" refers to a component having a "crosslinking functional group", which is a functional group located in each molecule of a compound, oligomer, polymer, a functional group located in a polymer backbone, a functional group of a side group of a polymer backbone, a functional group located at the end of a polymer backbone, or a combination thereof, wherein these functional groups are capable of crosslinking (during the curing step) with a crosslinkable functional group to produce a coating in the form of a crosslinked structure. Those of ordinary skill in the art will recognize that certain combinations of crosslinking functional groups and crosslinkable functional groups will be excluded because they cannot crosslink and produce a film-forming crosslinked structure. The coating composition may include more than one type of crosslinking agent with the same or different crosslinking functional groups. Typical crosslinking functional groups may include hydroxyl, thiol, isocyanate, thioisocyanate, acetoacetoxy, carboxyl, primary amine, secondary amine, epoxy, anhydride, ketimine, aldimine, orthoester, orthocarbonate, cyclic amide, or a combination thereof.

[0058] In some embodiments, polyisocyanates with isocyanate functional groups can be used as crosslinking agents to react with crosslinkable functional groups such as hydroxyl functional groups and amine functional groups. In certain embodiments, only primary amine and secondary amine functional groups can react with isocyanate functional groups. Suitable polyisocyanates can have an average of 2 to 10, or 2.5 to 8, or alternatively 3 to 8 isocyanate functional groups. Typically, the ratio of the isocyanate functional groups on the polyisocyanate of the coating composition to the crosslinkable functional groups (e.g., hydroxyl and / or amine groups) of the first polymer, the second polymer, or both the first polymer and the second polymer is about 0.25: 1 to about 3: 1, or about 0.8: 1 to about 2: 1, or alternatively about 1: 1 to about 1.8: 1. In other embodiments, melamine compounds with melamine functional groups can be used as crosslinking agents to react with crosslinkable functional groups.

[0059] Examples of suitable polyisocyanates include any conventionally used aromatic, aliphatic or alicyclic diisocyanates, triisocyanates or tetraisocyanates, including polyisocyanates having isocyanurate structural units, for example, isocyanurate of hexamethylene diisocyanate and isocyanurate of isophorone diisocyanate; adducts of 2 molecules of diisocyanate (for example, hexamethylene diisocyanate, uretdione of hexamethylene diisocyanate, uretdione of isophorone diisocyanate or isophorone diisocyanate, isocyanurate of meta-tetramethylxylene diisocyanate) and diols (for example, ethylene glycol).

[0060] It is also possible to use polyisocyanate functional adducts having isocyanurate structural units, for example, an adduct of two molecules of diisocyanate (e.g., hexamethylene diisocyanate or isophorone diisocyanate) and a diol (e.g., ethylene glycol); an adduct of three molecules of hexamethylene diisocyanate and one molecule of water (available under the trade name N is commercially available from Bayer Corporation of Pittsburgh, Pennsylvania); an adduct of 1 molecule of trimethylolpropane and 3 molecules of toluene diisocyanate (available under the trade name L is commercially available from Bayer Corporation of Pittsburgh, Pennsylvania); an adduct of 1 molecule of trimethylolpropane and 3 molecules of isophorone diisocyanate or a compound such as 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene; and an adduct of 1 molecule of pentaerythritol and 4 molecules of toluene diisocyanate.

[0061] As also described above, the coating composition may also include a pigment. Any pigment known in the art for use in coating compositions may be used in the coating composition. Non-limiting examples of suitable pigments include metal oxides; metal hydroxides; effect pigments, including metal flakes, chromates (e.g., lead chromate), sulfides, sulfates, carbonates, carbon black, silica, talc, china clay, phthalocyanine blue and green, organic reds, organic maroons, pearlescent pigments; other organic pigments and dyes; and combinations thereof. If desired, chromate-free pigments may also be used, such as barium metaborate, zinc phosphate, aluminum triphosphate, and combinations thereof.

[0062] Additional non-limiting examples of suitable effect pigments include bright aluminum flakes, very 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-limiting examples of suitable colored pigments include titanium dioxide, zinc oxide, iron oxide, carbon black, mono azo red toner, red iron oxide, quinacridone red brown, transparent red oxide, di Azinecarbazole violet, iron blue, indanthrene blue, chromium titanate, titanium yellow, monoazo permanent orange, iron yellow, monoazobenzimidazolone yellow, transparent yellow oxide, isoindoline yellow, tetrachloroisoindoline yellow, anthraquinone orange, lead chrome yellow, phthalocyanine green, quinacridone red, perylene red brown, quinacridone violet, pre-deepened chrome yellow, thioindigo red, transparent red oxide flakes, molybdenum orange, molybdenum orange red, and combinations thereof.

[0063] Also as described above, the coating composition may further include additives such as catalysts, UV stabilizers and other additives. The coating composition may further include a catalyst to reduce the curing time and allow the coating composition to cure at ambient temperature. Ambient temperature generally refers to a temperature in the range of 18°C ​​to 35°C. Typical 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; triphenylboron, tetraisopropyl titanate, triethanolamine titanate chelate, dibutyltin dioxide, dibutyltin dioctoate, tin octoate, aluminum titanate, aluminum chelates, zirconium chelates, hydrocarbons; Halides such as ethyltriphenylphosphine Iodide and other such Salts, and other catalysts known to those skilled in the art, or combinations thereof.

[0064] The coating composition may also include an ultraviolet light stabilizer. Non-limiting examples of such ultraviolet light stabilizers include ultraviolet light absorbers, screeners, quenchers, and hindered amine light stabilizers. Antioxidants may also be added to the coating composition. Typical ultraviolet light stabilizers may include benzophenones, triazoles, triazines, benzoates / salts, hindered amines, and mixtures thereof. Blends of hindered amine light stabilizers may be used, such as 328 and 123, all under the trade name Commercially available from Ciba Specialty Chemicals of Tarrytown, New York.

[0065] Non-limiting examples of suitable ultraviolet light absorbers include hydroxyphenylbenzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amyl-phenyl)-2H-benzotriazole, 2[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, the reaction product of 2-(2-hydroxy-3-tert-butyl-5-methylpropionate)-2H-benzotriazole and a polyethylene ether glycol having a weight average molecular weight of 300, 2-(2-hydroxy-3-tert-butyl-5-iso-octylpropionate)-2H-benzotriazole; hydroxyphenyl s-triazines, such as 2-[4(( 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 UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone and 2-hydroxy-4-dodecyloxybenzophenone.

[0066] Non-limiting examples of suitable hindered amine light stabilizers include N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-dodecylsuccinimide, N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecylsuccinimide, N-(2-hydroxyethyl)-2,6,6,6-tetramethylpiperidin-4-ol-succinic acid copolymer, 1,3,5-triazine-2,4,6-triamine, N,N"'-[1,2 -ethylenediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propylenediyl]]bis[N,N"'-dibutyl-N',N"'-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)], poly-[[6-[1,1,3,3-tetramethylbutyl]-amino]-1,3,5-triazine-2,4-diyl][2,2 ,6,6-tetramethylpiperidinyl)-imino]-1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl)-imino]), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate 1-dimethyl-2-nitro-3-oxo-7-oxa-3,20-diazabispiro(5.1.11.2)heneicosane-20-yl)propanoate.

[0067] Non-limiting 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 phenylpropionic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester. In certain embodiments, the antioxidant includes a hydroperoxide decomposer, such as HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), triphenyl phosphate, and other organophosphorus compounds, such as PH-10 from Ciba Specialty Chemicals TNPP, from Ciba Specialty Chemicals 168. From GE Specialty Chemicals 626, Mark PEP-6 from Asahi Denka, Mark HP-10 from Asahi Denka, P-EPQ, Ethanox 398 from Albemarle, Weston 618 from GE Specialty Chemicals, 12. Ciba Specialty Chemicals 38. From GE Specialty Chemicals 641, and from Dover Chemicals S-9228.

[0068] The coating composition may also contain other additives known in the art for coating compositions. Examples of such additives may include wetting agents, leveling agents and flow control agents, for example, those sold under the respective trade names of S (polybutyl acrylate), 320 and 325 (high molecular weight polyacrylate), 347 (polyether-modified siloxane); leveling agents based on (meth)acrylic homopolymers; rheology control agents; thickeners, such as partially crosslinked polycarboxylic acids or polyurethanes; and defoamers. The additives can be used in conventional amounts familiar to those skilled in the art.

[0069] Depending on the type of crosslinker, the coating composition of the present invention can be formulated as a one-pack (1K) or two-pack (2K) coating composition. The one-pack coating composition can be an air-dry coating or an unactivated coating. The term "air-dry coating" or "unactivated coating" refers to a coating that dries primarily by solvent evaporation and does not require crosslinking to form a coating film with the desired properties. If a polyisocyanate with free isocyanate groups is used as a crosslinker, the coating composition can be formulated as a two-pack coating composition, wherein the crosslinker is mixed with the other components of the coating composition only immediately before the coating is applied. If, for example, a blocked polyisocyanate is used as a crosslinker, the coating composition can be formulated as a one-pack (1K) coating composition. The coating composition can be further adjusted to a spray viscosity with an organic solvent determined by a person skilled in the art before application.

[0070] "Two-pack coating composition" or "two-component coating composition" means a thermosetting coating composition comprising two components stored in separate containers, which are usually sealed to increase the shelf life of the components of the coating composition. The components are mixed to form a pot mix prior to use. The pot mix is ​​applied as a layer of desired thickness to a substrate surface (e.g., an automobile body or body part). After application, the layer is cured under ambient conditions or bake-cured at an elevated temperature to form a coating having desired coating properties (e.g., high gloss, smooth appearance, and durability) on the substrate surface.

[0071] In some embodiments, the coating composition is a one-pack coating composition. As described above, the amount of acid functional groups in the first polymer and the amount of amine functional groups in the second polymer and the molecular weight of the first and second polymers have been formulated to provide a one-pack coating composition that exhibits minimal gelation and improved coating properties (e.g., improved adhesion). In some embodiments, a crosslinking agent may be used in the coating composition, thereby making the coating composition a two-pack coating composition. However, it should be understood that in a two-pack coating composition, the first polymer and the second polymer are contained in the same package and are exposed to each other.

[0072] The coating composition can be used to form a coating on a substrate. The coating can be used as a base coat, a clear coat, a color coat, a top coat, a single-stage coat, a midcoat, a primer, a sealer, or a combination thereof. In certain embodiments, the coating composition is used to form a base coat coating.

[0073] The term "base coat" refers to a coating that is opaque and provides most of the protection, color, hiding (also referred to as "opaque"), and visual appearance. The base coat typically contains color pigments, effect pigments such as metal flake pigments, rheology control agents, UV absorbers, and other coating additives. The term "base coat coating composition" refers to a coating composition that can be used to form a base coat. The term "base coat" refers to a coating formed by a base coat coating composition. The base coat can be formed by applying one or more layers of the same or different base coat coating compositions. In automotive coatings, the substrate is typically coated with a primer layer for protection and adhesion, then the base coat is applied on the primer layer, optionally a sealer is applied on the primer for most of the protection, color, and most of the visual appearance, and then a clear coat is applied on the base coat for further protection and visual appearance. Sometimes, a single coating referred to as a "top coat" can be used to provide the functions of both the base coat and the clear coat. Additional coatings can also be used. For example, before applying the primer layer, the metal substrate can be treated with a phosphate material and coated with an electrocoat.

[0074] The term "midcoat" or "intermediate coating" refers to a colored opaque coating located between a basecoat and a clearcoat in a multilayer coating system. In order to obtain some unique and attractive colors or visual effects, the automotive industry and other coating end-use applications may use a multilayer coating system with three or more coatings instead of the traditional "basecoat and clearcoat" two-layer system. The multilayer system may generally include at least a first colored and opaque basecoat, a second transparent color coating deposited on at least a portion of the basecoat, and a third clear coating deposited on at least a portion of the second transparent color coating. The second transparent color coating is generally referred to as an intermediate coating, which contains a colored pigment. The intermediate coating is generally formulated to be transparent so that the color of the underlying basecoat can be visible through the intermediate coating.

[0075] As described above, the amount of acid functional groups in the first polymer and the amount of amine functional groups in the second polymer, as well as the molecular weights of the first and second polymers, have been formulated to provide a coating composition that exhibits minimal gelation. Gelation can be evaluated by measuring the change in viscosity of the coating composition over time. Without being bound by theory, it is believed that compositions containing polymers having an amount of functional groups greater than the amount of functional groups described herein for the first polymer and the second polymer will exhibit an undue increase in viscosity over time, thereby causing the composition to gel.

[0076] In some embodiments, a coating formed from a coating composition comprising both acid and amine functional groups has improved adhesion to a substrate according to ASTM D3359 B and ASTM D6677 described below, compared to a coating formed from a coating composition that does not comprise both acid and amine functional groups.

[0077] In some embodiments, the coating composition comprising both acid functional groups and amine functional groups has an improved drying time after application to a substrate compared to a coating composition that does not comprise both acid functional groups and amine functional groups. The term "dry" means that the resulting finished product is physically dry to the touch in a relatively short period of time to minimize dirt pick-up and, in the case of a basecoat, to allow the application of a subsequent clearcoat. In embodiments when the coating composition is used as a basecoat composition, applying a clearcoat composition to the basecoat composition before drying the basecoat composition can result in reduced flake control and metallic appearance (i.e., "goniochromaticity") of basecoat compositions containing special effect pigments (e.g., metallic and pearlescent flake pigments) due to interfering flake pigments due to mixing of the basecoat composition and the clearcoat composition at the interface therebetween. "Goniochromaticity" refers to a phenomenon associated with metallic effect coatings in which the color changes with viewing angle to provide a three-dimensional metallic effect on the surface of a vehicle.

[0078] Coating system is also provided herein.Coating system can comprise the primer layer covering on substrate, the base coat covering on primer layer and the clear coat covering on base coat.Should be appreciated that coating system can comprise one or more other layers, for example any in the above-mentioned coating, wherein other layer is arranged between primer layer, base coat and / or the clear coat, any position above or below.In some embodiments, coating composition can be used for forming primer layer, base coat, clear coat or its combination.In certain embodiments, coating composition is used to form base coat.

[0079] Also provided herein is a method for coating a substrate using a coating composition. The method includes applying a first coating composition including the above-mentioned coating composition to at least a portion of the substrate to form a first wet coating. The method may also include curing or drying the first wet coating at a temperature of 18°C ​​(64°F) to 180°C (356°F) to form a first dry coating on the substrate. The first wet coating may be cured or dried for an amount of time of about 10 minutes to 3 days. The method may also include a step of flashing the first wet coating. The method may also include applying a second coating composition to the substrate to form a multilayer coating. In certain embodiments, the second coating composition may be applied to the first wet coating to form a second wet coating, and the first and second wet coatings may be cured together to form a multilayer coating, wherein the second coating composition is the same or different from the first coating composition. In other embodiments, the second coating composition is applied to the first dry coating to form a second wet coating and the second wet coating is cured to form a multilayer coating, wherein the second coating composition is the same or different from the first coating composition. In multiple embodiments, the first coating composition is a primer composition, and the second coating composition is a clear coating composition. In some embodiments, the applying step may include spraying, electrocoating, brushing, rolling, dipping, laminating, and the like.

[0080] Example

[0081] The following Examples 1-8 and 14 describe the preparation of various first polymers (acid functional) and various second polymers (amine functional) of the present disclosure. The following Examples 9-13 and 15 describe exemplary and comparative coating compositions comprising the first polymer and / or the second polymer of Examples 1-8 and 14. The following Examples 9-13 and 15 further describe the formation of coatings from the coating compositions, and the testing of these coatings.

[0082] Example 1

[0083] Preparation of 78 / 15 / 7 wt% MMA / BA / t-BAEMA polymer

[0084] Example 1 describes the preparation of a polymer having secondary amine groups (second polymer) that can be used in an exemplary coating composition. A 5-liter flask was equipped with a thermometer, stirrer, additional funnel, heating mantle, reflux condenser, and a device to maintain a nitrogen blanket over the reactants. The flask was maintained under a positive nitrogen pressure and the following ingredients were used (Table 1).

[0085] Table 1.

[0086]

[0087] Charge part 1 mixture into a flask. Heat the mixture to reflux temperature and reflux for about 10 minutes. Feed part 2 into the flask over 180 minutes. Simultaneously feed part 4 into the flask over 360 minutes. At the end of the feed, rinse part 2 into the flask using part 3. Maintain the reaction mixture at reflux temperature throughout the feed and reflux the reaction mixture for an additional 30 minutes. Rinse part 4 using part 5 at the end of the feed. Maintain the reaction mixture at reflux temperature throughout the feed and reflux the reaction mixture for an additional 120 minutes. Allow the resin solution to cool to about 50°C before adding part 6. Fill out the finished product.

[0088] The obtained polymer solution was a light yellow transparent polymer solution with a solid content of about 40.1% and a Gardner-Holtz viscosity of U+1 / 2.

[0089] Example 2

[0090] Preparation of 78 / 15 / 7 wt% MMA / EA / t-BAEMA polymer

[0091] Example 2 describes the preparation of another polymer (second polymer) having secondary amine groups that can be used in the exemplary coating composition. The resin solution was prepared using the procedure described in Example 1, except that EA (ethyl acrylate) monomer was used instead of BA monomer.

[0092] The obtained polymer solution was a light yellow transparent polymer solution with a solid content of about 39.5% and a Gardner-Holtz viscosity of X+1 / 2.

[0093] Example 3

[0094] Preparation of 78 / 15 / 7 wt% MMA / BA / DMAEA polymer

[0095] Example 3 describes the preparation of a polymer having tertiary amine groups (second polymer) that can be used in an exemplary coating composition. A resin solution was prepared using the procedure described in Example 1, except that DMAEA (N,N-dimethylaminoethyl acrylate monomer) was used instead of t-BAEMA monomer.

[0096] The resulting polymer solution was a light yellow transparent polymer solution having a solid content of about 39.4% and a Gardner-Holtz viscosity of U+1 / 4. Based on gel permeation chromatography using polymethyl methacrylate as a standard, the polymer had 77,620 Mw and 42,379 Mn.

[0097] Example 4

[0098] Preparation of 81 / 14.6 / 4.4 / 2.91 wt% MMA / EA / MAA (PI) polymer

[0099] Example 4 describes the preparation of a polymer (second polymer) with primary amine groups that can be used in an exemplary coating composition. The steps described in Example 1 were used to prepare an MMA / EA / MAA (81 / 14.6 / 4.4 wt%) resin solution, except that t-BAEMA monomer was replaced with MAA (methacrylic acid monomer) in a solvent blend of isopropanol, ethyl acetate, and toluene. After the polymer solution was cooled to about 55° C., a stoichiometric amount of propylene imine was added to the reaction mixture to react with the carboxylic acid groups. The reaction mixture was gradually heated to 70° C. and maintained at this temperature for 1 hour to ensure that the reaction was completed before cooling.

[0100] The resulting polymer solution was a light yellow transparent polymer solution having a solid content of about 40.1% and a Gardner-Holtz viscosity of Z+1 / 4. Based on gel permeation chromatography using polymethyl methacrylate as a standard, the polymer had 104,104 Mw and 37,348 Mn.

[0101] Example 5

[0102] Preparation of 78 / 5 / 10 / 7 wt% MMA / BA / HEA / DMAEA polymer

[0103] Example 5 describes the preparation of a polymer (second polymer) having a tertiary amine group and a hydroxyl group that can be used in an exemplary coating composition. The resin solution was prepared using the steps described in Example 1, except that DMAEA (N,N-dimethylaminoethyl acrylate monomer) was used instead of t-BAEMA monomer, and 2-hydroxyethyl acrylate (HEA) was added to the monomer blend. Methyl isobutyl ketone was used as a solvent.

[0104] The resulting polymer solution was a light yellow transparent polymer solution having a solid content of about 43% and a Gardner-Holtz viscosity of Z 1. Based on gel permeation chromatography using polymethyl methacrylate as a standard, the polymer had 103,791 Mw and 28,582 Mn.

[0105] Example 6

[0106] Preparation of 29 / 31 / 20 / 7.5 / 7.5 / 5 wt% Sty / BA / IBOA / HEMA / HPMA / MAA polymer

[0107] Example 6 describes the preparation of a polymer (first polymer) having carboxylic acid groups that can be used in an exemplary coating composition. A 5-liter flask was equipped with a thermometer, agitator, an addition funnel, a heating mantle, a reflux condenser, and a device to maintain a nitrogen blanket over the reactants. The flask was maintained under a positive nitrogen pressure and the following ingredients (Table 2) were used.

[0108] Table 2.

[0109]

[0110] Charge the portion 1 mixture to the flask. Heat the mixture to reflux temperature and reflux for about 10 minutes. Feed portion 2 to the flask over 195 minutes. Simultaneously feed portion 4 to the flask over 200 minutes. At the end of the feed, rinse portion 2 into the flask using portion 3. Maintain the reaction mixture at reflux temperature throughout the feed. Rinse portion 4 using portion 5 at the end of the feed. Maintain the reaction mixture at reflux temperature throughout the feed and reflux the reaction mixture for an additional 120 minutes. Allow the resin solution to cool to about 50°C before adding portion 6. Saturate the finished product.

[0111] The resulting polymer solution was a light yellow transparent polymer solution having a solid content of about 40.1% and a Gardner-Holtz viscosity of U+1 / 2. Based on gel permeation chromatography using polymethyl methacrylate or polystyrene as a standard, the polymer had 28,875 Mw and 5,714 Mn.

[0112] Example 7

[0113] Preparation of MMA / BMA / EHA / HEMA / MAA (30.29 / 26.65 / 23.11 / 18.55 / 1.40 wt %)

[0114] Example 7 describes the preparation of another polymer (first polymer) having carboxylic acid groups that can be used in the exemplary coating composition. A resin solution was prepared using a similar procedure as described in Example 6 in a solvent blend of xylene, butyl acetate, and n-butanol with the monomers and their weight ratios listed above.

[0115] The resulting polymer solution was a light yellow transparent polymer solution having a solid content of about 54.34% and a Gardner-Holtz viscosity of X+1 / 2. Based on gel permeation chromatography using polymethyl methacrylate or polystyrene as a standard, the polymer had 31,982 Mw and 10,530 Mn.

[0116] Example 8

[0117] 20 / 24 / 20 / 23.3 / 10.5 / 2.2 wt% Sty / MMA / BMA / EHA / HEMA / acrylic acid (AA) polymer preparation

[0118] Example 8 describes the preparation of another polymer (first polymer) having carboxylic acid groups that can be used in the exemplary coating composition. A resin solution was prepared using a similar procedure as described in Example 6 in butyl acetate with the monomers and their weight ratios as listed above.

[0119] The resulting polymer solution was a clear polymer solution with a solids content of about 58.35% and a Gardner-Holtz viscosity of Z+1 / 2. The polymer had a Mw of 38,026 and a Mn of 9,537 based on gel permeation chromatography using polymethyl methacrylate or polystyrene as standards.

[0120] Example 9

[0121] Example 9 describes the coating properties that can be achieved by using both a first polymer (acid functional) and a second polymer (amine functional) in an exemplary coating composition. Example 9 specifically focuses on the second polymer having primary amine functional groups. The results show that the adhesion properties of the coating formed by the exemplary coating composition are improved compared to the coating formed by the comparative coating composition. The improvement in adhesion properties is demonstrated by 3 colors: silver, bright red, and metallic red.

[0122] Example 9.1: Silver coating composition with aluminum flakes:

[0123] The sample coating compositions are generally described as follows:

[0124] C1 is a comparative coating composition comprising the polymer having primary amine functional groups of Example 4 (second polymer); C5 is another comparative coating composition comprising the polymer having acid functional groups of Example 6 (first polymer); E1 is an exemplary coating composition comprising both the polymer of Example 4 (second polymer) and the polymer of Example 6 (first polymer); E2 is another exemplary coating composition comprising both the polymer of Example 4 (second polymer) and the polymer having acid functional groups of Example 7 (first polymer).

[0125] Preparation of coating composition:

[0126] In Table 3 below, the ingredients from Part 1 and Part 2 below were added to a metal container and mixed thoroughly using an air mixer. Part 3 was added to the container and mixed for an additional 30 minutes. Parts 4 and 5 were then added to the container in sequence and mixed for an additional 15 minutes.

[0127] Table 3.

[0128]

[0129] In Table 3, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is an aluminum paste in a mixture of aliphatic and aromatic solvents; the CAB-20 solution is 15 wt % cellulose acetate butyrate ("CAB") in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone, which is CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee); the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; and PGMEA is propylene glycol monomethyl ether acetate.

[0130] Example 9.2: Bright red coating composition:

[0131] The sample coating compositions are generally described as follows:

[0132] C6 is a comparative coating composition comprising the polymer having primary amine functional groups of Example 4 (second polymer); E9 is an exemplary coating composition comprising both the polymer of Example 4 (second polymer) and the polymer of Example 6 (first polymer); E10 is another exemplary coating composition comprising both the polymer of Example 4 (second polymer) and the polymer having acid functional groups of Example 7 (first polymer).

[0133] Preparation of coating composition:

[0134] Coating compositions were prepared using the same procedures as above with the ingredients listed in Table 4 below.

[0135] Table 4.

[0136]

[0137] 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 a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; and PGMEA is propylene glycol monomethyl ether acetate.

[0138] Example 9.3: Metallic red coating composition with aluminum flakes:

[0139] The sample coating compositions are generally described as follows:

[0140] C9 is a comparative coating composition comprising the polymer having primary amine functional groups of Example 4 (second polymer); E15 is an exemplary coating composition comprising both the polymer of Example 4 (second polymer) and the polymer of Example 6 (first polymer); E16 is another exemplary coating composition comprising both the polymer of Example 4 (second polymer) and the polymer having acid functional groups of Example 7 (first polymer).

[0141] Preparation of coating composition:

[0142] Coating compositions were prepared using the same procedures as above with the ingredients listed in Table 5 below.

[0143] Table 5.

[0144]

[0145] 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 866J (manufactured by Axalta Coating Systems, Philadelphia PA); CAB-20 solution is 15 wt % CAB-381-20 (from Eastman Chemical Co., Kingsport, Tenn.essee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tenn.essee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; PGMEA is propylene glycol monomethyl ether acetate.

[0146] Example 9: Formation of a coating from a coating composition

[0147] Commercial Primer-Sealer 42440S TM (manufactured by Axalta Coating Systems, Philadelphia, PA) was sprayed on the electroplated metal panels. The basecoat sample (coating composition) was mixed with a commercially available reducing agent reducer 7175S TM (manufactured by Axalta Coating Systems, Philadelphia, PA) were mixed in a 1:1 volume ratio. The reduced basecoat sample was sprayed on the dried sealer according to the technical data sheet. The commercial clearcoat 74500S was then sprayed TM (manufactured by Axalta Coating Systems, Philadelphia, PA), and baked the panels in an oven at 160° F. for 15 minutes. The panels were cured for 3 days under ambient conditions to form the coating.

[0148] Example 9: Adhesion test of coating

[0149] Each coating of Example 9 was tested for adhesion. In particular, dry and wet adhesion tests were performed using the Cross-Hatch Adhesion Testing and the X-Hatch Adhesion Testing. The boards were tested for dry adhesion on the 3rd, 5th, and 7th day after the boards were baked. The boards were then kept in a humidity chamber for 96 hours. The boards were tested for wet adhesion immediately after the boards were removed from the humidity chamber and 4 hours after they were removed. The boards were tested for 24 hours recovery 24 hours after the boards were removed from the humidity chamber.

[0150] To perform the cross-hatch adhesion test (grid adhesion), parallel cuts are made at appropriate intervals on the test area of ​​the coating using a cutting guide or a special cross-hatch cutter with multiple preset blades. The tape is then applied to the test area of ​​the coating and subsequently peeled off. The test area is then inspected and rated. The standard method for the application and execution of this test is given by ASTM D3359 B.

[0151] To perform the X-scribe adhesion test, a sharp razor blade, scalpel, knife or other cutting device is used to create two cuts in the coating, with the legs at an angle of 30-45 degrees between and deep into the substrate, which cross to form an "X" on the test area of ​​the coating. A steel or other hard metal ruler is used to ensure straight cuts. The tape is then applied to the test area of ​​the coating and subsequently peeled off. The test area is then inspected and rated. The standard method for the application and execution of this test is given by ASTM D6677.

[0152] Adhesion can be rated on a sliding scale from 0 (no adhesion, ie, complete failure) to 10 (complete adhesion, ie, complete success). The adhesion results are given in Table 6 below.

[0153] Table 6.

[0154]

[0155] The adhesion test results of the coating of Example 9 clearly show that the exemplary coating compositions (Samples E1, E2, E9, E10, E15 and E16) formed coatings with improved adhesion compared to the coatings of the comparative coating compositions (Samples C1, C5, C6 and C9) in all types of adhesion tests including cross-hatch adhesion, X-line adhesion, dry adhesion, wet adhesion and 24-hour recovery adhesion. The results also show that the exemplary coating compositions can be used to form coatings with improved adhesion for a wide range of color families and different classes of pigment chemistries.

[0156] Example 10

[0157] Example 10 also describes the coating properties that can be achieved by using both a first polymer (acid functional) and a second polymer (amine functional) in an exemplary coating composition. Example 10 specifically focuses on the second polymer having secondary amine functional groups. The results show that the adhesion properties of the coating formed by the exemplary coating composition are improved compared to the coating formed by the comparative coating composition. The improvement in adhesion properties is evidenced by the silver color.

[0158] Example 10.1: Silver coating composition with aluminum flakes:

[0159] The sample coating compositions are generally described as follows:

[0160] C2 is a comparative coating composition comprising the polymer having secondary amine functional groups of Example 1 (second polymer); C5 is another comparative coating composition comprising the polymer having acid functional groups of Example 6 (first polymer); E3 is an exemplary coating composition comprising both the polymer of Example 1 (second polymer) and the polymer of Example 6 (first polymer); E4 is another exemplary coating composition comprising both the polymer of Example 1 (second polymer) and the polymer having acid functional groups of Example 7 (first polymer).

[0161] Preparation of coating composition:

[0162] The coating compositions were prepared using the same procedure described in Example 9 with the ingredients listed in Table 7 below. The coating compositions were sprayed and tested in the same manner as in Example 9.

[0163] Table 7.

[0164]

[0165] In Table 7, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is an 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 a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; and PGMEA is propylene glycol monomethyl ether acetate.

[0166] Example 10: Coating Adhesion Test

[0167] Each coating of Example 10 was tested for adhesion in the same manner as in Example 9. Adhesion can be rated on a floating scale from 0 (no adhesion, i.e., complete failure) to 10 (complete adhesion, i.e., complete success). The adhesion results are given in Table 8 below.

[0168] Table 8.

[0169]

[0170] The adhesion test results of the coating of Example 10 clearly show that the exemplary coating compositions (Samples E3 and E4) formed coatings with improved adhesion compared to the coatings of the comparative coating compositions (Samples C2 and C5) in all types of adhesion tests including cross-hatch adhesion, X-line adhesion, dry adhesion, wet adhesion, and 24-hour recovery adhesion.

[0171] Embodiment 11

[0172] Example 11 also describes the coating properties that can be achieved by using both a first polymer (acid functional) and a second polymer (amine functional) in an exemplary coating composition. Example 11 specifically focuses on a second polymer having a secondary amine functional group that is different from the secondary amine functional group of Example 10. The results show that the adhesion properties of the coating formed from the exemplary coating composition are improved compared to the coating formed from the comparative coating composition. The improvement in adhesion properties is demonstrated by 3 colors: silver, bright red, and metallic red.

[0173] Example 11.1: Silver coating composition with aluminum flakes:

[0174] The sample coating compositions are generally described as follows:

[0175] C3 is a comparative coating composition comprising the polymer having secondary amine functional groups of Example 2 (second polymer); C5 is another comparative coating composition comprising the polymer having acid functional groups of Example 6 (first polymer); E5 is an exemplary coating composition comprising both the polymer of Example 2 (second polymer) and the polymer of Example 6 (first polymer); E6 is another exemplary coating composition comprising both the polymer of Example 2 (second polymer) and the polymer having acid functional groups of Example 7 (first polymer).

[0176] Preparation of coating composition:

[0177] The coating compositions were prepared using the same procedures described in Example 9 with the ingredients listed in Table 9 below. The coating compositions were sprayed and tested in the same manner as in Example 9.

[0178] Table 9.

[0179]

[0180] In Table 9, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is an 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 a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; and PGMEA is propylene glycol monomethyl ether acetate.

[0181] Example 11.2: Bright red coating composition:

[0182] The sample coating compositions are generally described as follows:

[0183] C7 is a comparative coating composition comprising the polymer having secondary amine functional groups of Example 2 (second polymer); E11 is an exemplary coating composition comprising both the polymer of Example 2 (second polymer) and the polymer of Example 6 (first polymer); E12 is another exemplary coating composition comprising both the polymer of Example 2 (second polymer) and the polymer having acid functional groups of Example 7 (first polymer).

[0184] Preparation of coating composition:

[0185] The coating compositions were prepared using the same procedure described in Example 9 with the ingredients listed in Table 10 below. The coating compositions were sprayed and tested in the same manner as in Example 9.

[0186] Table 10.

[0187]

[0188] In Table 10, the first red dispersion is a 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 a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; and PGMEA is propylene glycol monomethyl ether acetate.

[0189] Example 11.3: Metallic red coating composition with aluminum flakes:

[0190] The sample coating compositions are generally described as follows:

[0191] C10 is a comparative coating composition comprising the polymer having secondary amine functional groups of Example 2 (second polymer); E17 is an exemplary coating composition comprising both the polymer of Example 2 (second polymer) and the polymer of Example 6 (first polymer); E18 is another exemplary coating composition comprising both the polymer of Example 2 (second polymer) and the polymer having acid functional groups of Example 7 (first polymer).

[0192] Preparation of coating composition:

[0193] The coating compositions were prepared using the same procedure described in Example 9 with the ingredients listed in Table 11 below. The coating compositions were sprayed and tested in the same manner as in Example 9.

[0194] Table 11.

[0195]

[0196] In Table 11, 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 866J (manufactured by Axalta Coating Systems, Philadelphia PA); CAB-20 solution is 15 wt % CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; PGMEA is propylene glycol monomethyl ether acetate.

[0197] Example 11: Coating Adhesion Test

[0198] Each coating of Example 11 was tested for adhesion in the same manner as in Example 9. Adhesion can be rated on a floating scale from 0 (no adhesion, i.e., complete failure) to 10 (complete adhesion, i.e., complete success). The adhesion results are given in Table 12 below.

[0199] Table 12.

[0200]

[0201] The adhesion test results of the coating of Example 11 clearly show that the exemplary coating compositions (Samples E5, E6, E11, E12, E17 and E18) formed coatings with improved adhesion compared to the coatings of the comparative coating compositions (Samples C3, C5, C7 and C10) in all types of adhesion tests including cross-hatch adhesion, X-line adhesion, dry adhesion, wet adhesion and 24-hour recovery adhesion. The results also show that the exemplary coating compositions can be used to form coatings with improved adhesion for a wide range of color families and different classes of pigment chemistries.

[0202] Example 12

[0203] Example 12 also describes the coating properties that can be achieved by using both a first polymer (acid functional) and a second polymer (amine functional) in an exemplary coating composition. Example 12 specifically focuses on the second polymer having a tertiary amine functional group. The results show that the adhesion properties of the coating formed by the exemplary coating composition are improved compared to the coating formed by the comparative coating composition. The improvement in adhesion properties is demonstrated by 3 colors: silver, bright red, and metallic red.

[0204] Example 12.1: Silver coating composition with aluminum flakes:

[0205] The sample coating compositions are generally described as follows:

[0206] C4 is a comparative coating composition comprising the polymer having a tertiary amine functional group of Example 3 (second polymer); C5 is another comparative coating composition comprising the polymer having an acid functional group of Example 6 (first polymer); E7 is an exemplary coating composition comprising both the polymer of Example 3 (second polymer) and the polymer of Example 6 (first polymer); E8 is another exemplary coating composition comprising both the polymer of Example 3 (second polymer) and the polymer having an acid functional group of Example 7 (first polymer).

[0207] Preparation of coating composition:

[0208] The coating compositions were prepared using the same procedure described in Example 9 with the ingredients listed in Table 13 below. The coating compositions were sprayed and tested in the same manner as in Example 9.

[0209] Table 13.

[0210]

[0211] In Table 13, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is an 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 a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; and PGMEA is propylene glycol monomethyl ether acetate.

[0212] Example 12.2: Bright red coating composition:

[0213] The sample coating compositions are generally described as follows:

[0214] C8 is a comparative coating composition comprising the polymer having a tertiary amine functional group of Example 3 (the second polymer); E13 is an exemplary coating composition comprising both the polymer of Example 3 (the second polymer) and the polymer of Example 6 (the first polymer); E14 is another exemplary coating composition comprising both the polymer of Example 3 (the second polymer) and the polymer having an acid functional group of Example 7 (the first polymer).

[0215] Preparation of coating composition:

[0216] The coating compositions were prepared using the same procedure described in Example 9 with the ingredients listed in Table 14 below. The coating compositions were sprayed and tested in the same manner as in Example 9.

[0217] Table 14.

[0218]

[0219] In Table 14, the first red dispersion is a 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 a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; and PGMEA is propylene glycol monomethyl ether acetate.

[0220] Example 12.3: Metallic red coating composition with aluminum flakes:

[0221] The sample coating compositions are generally described as follows:

[0222] C11 is a comparative coating composition comprising the polymer having a tertiary amine functional group of Example 3 (the second polymer); E19 is an exemplary coating composition comprising both the polymer of Example 3 (the second polymer) and the polymer of Example 6 (the first polymer); and E20 is another exemplary coating composition comprising both the polymer of Example 3 (the second polymer) and the polymer having an acid functional group of Example 7 (the first polymer).

[0223] Preparation of coating composition:

[0224] The coating compositions were prepared using the same procedure described in Example 9 with the ingredients listed in Table 15 below. The coating compositions were sprayed and tested in the same manner as in Example 9.

[0225] Table 15.

[0226]

[0227] In Table 15, 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 866J (manufactured by Axalta Coating Systems, Philadelphia PA); CAB-20 solution is 15 wt % CAB-381-20 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; PGMEA is propylene glycol monomethyl ether acetate.

[0228] Example 12: Coating Adhesion Test

[0229] Each coating of Example 12 was tested for adhesion in the same manner as in Example 9. Adhesion can be rated on a floating scale from 0 (no adhesion, i.e., complete failure) to 10 (complete adhesion, i.e., complete success). The adhesion results are given in Table 16 below.

[0230] Table 16.

[0231]

[0232] The results of the adhesion testing of the coating of Example 12 clearly show that the exemplary coating compositions (Samples E7, E8, E13, E14, E19, and E20) formed coatings with improved adhesion compared to the coatings of the comparative coating compositions (Samples C4, C5, C8, and C11) in all types of adhesion tests including cross-hatch adhesion, X-line adhesion, dry adhesion, wet adhesion, and 24-hour recovery adhesion. The results also show that the exemplary coating compositions can be used to form coatings with improved adhesion for a wide range of color families and different classes of pigment chemistries.

[0233] Embodiment 13

[0234] Example 13 also describes the coating properties that can be achieved by using both a first polymer (acid functional) and a second polymer (amine functional) in an exemplary coating composition. Example 13 specifically focuses on the use of a polyisocyanate as a crosslinking agent. The results show that the adhesion properties of the coating are further improved when a crosslinking agent is used. The improvement in adhesion properties is demonstrated by 2 colors: silver and bright red.

[0235] Example 13.1: Silver coating composition with aluminum flakes:

[0236] The sample coating compositions are generally described as follows:

[0237] E21 is an exemplary coating composition comprising both the polymer having a tertiary amine functional group and a hydroxyl functional group of Example 5 (the second polymer) and the polymer having an acid functional group and a hydroxyl functional group of Example 7 (the first polymer); E22 is another exemplary coating composition comprising the polymer of Example 5 (the second polymer) and the polymer having an acid functional group of Example 7 (the first polymer) and a polyisocyanate (cross-linking agent).

[0238] Preparation of coating composition:

[0239] In Table 17 below, the ingredients from Part 1 and Part 2 were added to a metal container and mixed thoroughly using an air mixer. Part 3 was added to the container and mixed thoroughly for another 30 minutes. Part 4 and Part 5 were then added in sequence and allowed to mix thoroughly for 15 minutes. After reduction (before spraying), Activator 12305S was added at a rate of 1 oz / quart. TM (manufactured by Axalta Coating Systems, Philadelphia PA) was added to sample E22. The coating composition was sprayed and tested in the same manner as in Example 9.

[0240] Table 17.

[0241]

[0242] In Table 17, the anti-settling dispersion is a Bentone dispersion; the aluminum paste is an 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 a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; PGMEA is propylene glycol monomethyl ether acetate; the activator 12305S TM Axalta® is a polyisocyanate activator commercially available from Axalta Coating Systems, Philadelphia, PA.

[0243] Example 13.2: Bright red coating composition:

[0244] The sample coating compositions are generally described as follows:

[0245] E23 is an exemplary coating composition comprising both the polymer having tertiary amine functional groups and hydroxyl functional groups of Example 5 (second polymer) and the polymer having acid functional groups and hydroxyl functional groups of Example 7 (first polymer); E24 is another exemplary coating composition comprising the polymer of Example 5 (second polymer) and the polymer having acid functional groups of Example 7 (first polymer) and a polyisocyanate (cross-linking agent).

[0246] Preparation of coating composition:

[0247] In Table 18 below, the ingredients from Part 1 and Part 2 were added to a metal container and mixed thoroughly using an air mixer. Part 3 was added to the container and mixed thoroughly for another 30 minutes. Parts 4 and 5 were then added in sequence and mixed thoroughly for 15 minutes. After reduction (before spraying), Activator 12305S was added at a rate of 1 oz / quart. TM Added to sample E24. The coating composition was sprayed and tested in the same manner as in Example 9.

[0248] Table 18.

[0249]

[0250] In Table 18, the anti-settling dispersion is a Bentone dispersion; the first red dispersion is a 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 a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; the CAB-1 solution is 15 wt % CAB-531-1 (from Eastman Chemical Co., Kingsport, Tennessee) in a 7:3 weight ratio of butyl acetate and methyl ethyl ketone; PGMEA is propylene glycol monomethyl ether acetate; activator 12305S TM is a polyisocyanate activator commercially available from Axalta Coating Systems, Philadelphia, PA.

[0251] Example 13: Adhesion test of coating Each coating of Example 13 was tested for adhesion in the same manner as in Example 9. Adhesion can be rated on a floating scale of 0 (no adhesion, i.e., complete failure) to 10 (complete adhesion, i.e., complete success). The adhesion results are given in Table 19 below.

[0252] Table 19.

[0253]

[0254] The adhesion test results of the coating of Example 13 clearly show that the exemplary coating compositions (Samples E21, E22, E23 and E24) form coatings with improved adhesion in all types of adhesion tests including cross-hatch adhesion, X-line adhesion, dry adhesion, wet adhesion and 24-hour recovery adhesion. The further cross-linking of the first and second polymers with polyisocyanates exhibits comparable and possibly improved cross-hatch and X-line adhesion in wet adhesion tests compared to coating compositions that are not further cross-linked with polyisocyanates. The results also show that the exemplary coating compositions can be used to form coatings with improved adhesion for a wide range of color families and different classes of pigment chemistries.

[0255] Embodiment 14

[0256] Preparation of 20 / 20 / 20 / 15 / 10 / 15 wt% Sty / BA / MMA / EHA / HEMA / MAA polymer

[0257] 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 some embodiments, the use of an acid functional monomer in an amount greater than 12 wt % can result in gelation of the coating composition. A resin solution was prepared in butyl acetate solvent using the monomers and their weight ratios as listed above using a similar procedure as described in Example 6.

[0258] The resulting polymer solution was an extremely viscous, transparent polymer solution having a solid content of 52.92% and a Gardner-Holtz viscosity of Z 7. Based on gel permeation chromatography using polymethyl methacrylate or polystyrene as a standard, the polymer had 38,017 Mw and 11,549 Mn.

[0259] Embodiment 15

[0260] Testing of polymer blends

[0261] In Table 20 below, the ingredients are combined according to the molar ratio of the acid functional groups of the first polymer to the amine functional groups of the second polymer. The resulting solution is a clear light yellow polymer solution. The viscosity of the polymer solution is then measured on a Brookfield viscometer using spindle #3 at 20 rpm.

[0262] Table 20.

[0263]

[0264] Compared with the viscosity of the standard polymer solutions S1, S2 and S3 containing only the first polymer or the second polymer, the exemplary polymer solutions E25, E27 and E28 containing the first polymer and the second polymer formed by 15 wt % MAA show increased viscosity. In contrast, the exemplary polymer solutions E26 and E29 containing less than 12 wt % MAA show a viscosity similar to the viscosity of the standard polymer solutions S1, S2 and S3. The viscosity test results clearly show that the interaction between the first polymer and the second polymer of the exemplary polymer solutions E26 and E29 is minimized before the application and curing of the coating composition, as demonstrated by the similar viscosity of the exemplary polymer solutions E26 and E29 and the standard polymer solutions S1, S2 and S3. It is believed that the first polymer formed by the MAA of an amount not greater than 12 wt % shows a minimized interaction with the second polymer when in a dissolved state (e.g., before applying the coating composition). Such an interaction will be amplified during drying to provide enhanced film properties.

[0265] In contrast, exemplary polymer solutions E25, E27, and E28 experience an increase in solution viscosity compared to the viscosity of standard polymer solutions S1, S2, and S3, which is evidence of increased interaction between the first polymer and the second polymer prior to application and curing of the coating composition due to the higher amount of MAA used to form the first polymer. In addition to paint properties, the higher viscosity of these polymer solutions can have a negative impact on the spray application of coating compositions containing these polymer solutions, thereby limiting the scope of the coating composition.

[0266] Although at least one exemplary embodiment has been presented in the foregoing detailed description, it should be understood that there are multiple variations. It should also be understood that one or more exemplary embodiments are merely examples and are not intended to limit the scope, applicability, or configuration in any way. On the contrary, the foregoing detailed description will provide a convenient route for those skilled in the art to implement the exemplary embodiments. It should be understood that the functions and arrangements of the elements described in the exemplary embodiments may be changed in a variety of ways without departing from the scope set forth in the appended claims.

[0267] Embodiment 1. A coating composition for coating a substrate, comprising:

[0268] a first polymer comprising a first polymer-binding portion having an acid functional group or a derivative thereof;

[0269] a second polymer comprising a second polymer-binding portion having an amine functional group; and

[0270] Solvents;

[0271] wherein the first polymer is substantially free of amine functional groups and the second polymer is substantially free of acid functional groups or derivatives thereof; and

[0272] wherein the acid functional groups and the amine functional groups are substantially reactive with each other at least after the coating composition is applied to the substrate.

[0273] Embodiment 2. The coating composition of embodiment 1, wherein the solvent is present in an amount of 10 wt % to 95 wt % based on the total weight of the coating composition.

[0274] Embodiment 3. The coating composition of embodiment 1, wherein the coating composition is substantially free of water.

[0275] Embodiment 4. The coating composition of embodiment 1, wherein each of the first polymer and the second polymer independently has a weight average molecular weight in an amount of about 2,000 to about 200,000.

[0276] Embodiment 5. The coating composition of embodiment 1, wherein the first polymer binding moiety is polymerized from a first polymer monomer mixture comprising an acid functional monomer.

[0277] Embodiment 6. The coating composition of embodiment 5, wherein the acid functional monomer is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, oleic acid, cinnamic acid, glutaconic acid, muconic acid, undecylenic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and combinations thereof.

[0278] Embodiment 7. The coating composition according to embodiment 5, wherein the first polymer monomer mixture comprises the acid functional monomer or its derivative in an amount of 0.1 wt % to 12 wt % based on the total weight of the first polymer monomer mixture.

[0279] Embodiment 8. The coating composition of Embodiment 5, wherein the first polymer has hydroxyl functional groups, wherein the first polymer monomer mixture further comprises a hydroxyl functional monomer.

[0280] Embodiment 9. The coating composition of embodiment 8, wherein the hydroxyl functional monomer is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and combinations thereof.

[0281] Embodiment 10. The coating composition of embodiment 5, wherein the first polymer monomer mixture further comprises an additional monomer selected from the group consisting of styrene, methyl (meth)acrylate, butyl (meth)acrylate, ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, and combinations thereof.

[0282] Embodiment 11. The coating composition of embodiment 1, wherein the second polymer is polymerized from a second polymer monomer mixture comprising an amine-functional monomer, a carboxyl-functional monomer, or a combination thereof.

[0283] Embodiment 12. The coating composition of embodiment 11, wherein the amine functional monomer is selected from the group consisting of tert-butylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, and combinations thereof.

[0284] Embodiment 13. The coating composition of embodiment 11, wherein the carboxyl functional monomer is methacrylic acid.

[0285] Embodiment 14. The coating composition of embodiment 11, wherein the second polymer polymerized from the carboxyl functional monomer is reacted with an imine compound to form an amine functional group.

[0286] Embodiment 15. A coating composition according to embodiment 11, wherein the second polymer monomer mixture comprises the amine functional monomer, the carboxyl functional monomer, or a combination thereof in an amount of 0.1 wt % to 15 wt % based on the total weight of the second polymer mixture.

[0287] Embodiment 16. The coating composition of embodiment 11, wherein the second polymer has hydroxyl functional groups, wherein the second polymer monomer mixture further comprises a hydroxyl functional monomer.

[0288] Embodiment 17. The coating composition of embodiment 16, wherein the hydroxyl functional monomer is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and combinations thereof.

[0289] Embodiment 18. The coating composition of embodiment 11, wherein the second polymer monomer mixture further comprises an additional monomer selected from the group consisting of styrene, methyl (meth)acrylate, butyl (meth)acrylate, ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, and combinations thereof.

[0290] Embodiment 19. The coating composition of Embodiment 1, wherein the coating formed from the coating composition has improved adhesion to the substrate compared to a coating formed from a coating composition that does not include both the acid functional group and the amine functional group.

[0291] Embodiment 20. The coating composition of embodiment 1, further comprising one or more non-functional polymers, crosslinkers, pigments, additives, or combinations thereof.

Claims

1. A solvent-containing coating composition for coating a substrate, comprising: a first polymer comprising a first polymer-binding portion having an acid-functional group or a derivative thereof, wherein the first polymer-binding portion is polymerized from a first polymer monomer mixture comprising 0.5 wt % to 8 wt % of the acid-functional monomer based on the total weight of the first polymer monomer mixture; a second polymer comprising a second polymer-binding moiety having an amine functional group, wherein the second polymer-binding moiety is polymerized from a second polymer monomer mixture comprising from 0.5 wt % to 10 wt % of the amine functional monomer based on the total weight of the second polymer monomer mixture; and an organic solvent, wherein the organic solvent is selected from the group consisting of naphtha, xylene, methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, acetone, butyl acetate, hexyl acetate, propylene glycol monomethyl ether acetate, isopropyl alcohol, butanol, and combinations thereof, the organic solvent is present in an amount of 40 wt % to 95 wt % based on the total weight of the solvent-containing coating composition, and the solvent-containing coating composition is substantially free of water, and; wherein the first polymer is substantially free of amine functional groups and the second polymer is substantially free of acid functional groups or derivatives thereof; wherein the amine functional group is a tertiary amine functional group; wherein the acid functional group and the amine functional group are substantially reactive with each other at least after the solvent-containing coating composition is applied to the substrate, wherein the acid functional monomer is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, oleic acid, cinnamic acid, glutaconic acid, muconic acid, undecylenic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and combinations thereof; wherein the amine functional monomer is selected from tert-butylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, and combinations thereof; and wherein the acid functional groups of the first polymer and the amine functional groups of the second polymer are used in the coating composition in a molar ratio of the acid functional groups to the amine functional groups of 4:1 to 1:4, and Wherein, the total solid content of the coating composition is in an amount of 5 wt % to 60 wt % based on the total weight of the coating composition. 2 . The solvent-borne coating composition of claim 1 , wherein each of the first polymer and the second polymer independently has a weight average molecular weight in an amount of 2,000 to 200,000.

3. The solvent-containing coating composition according to claim 1, wherein: The first polymer has a hydroxyl functional group, and the first polymer monomer mixture further comprises a hydroxyl functional monomer, wherein the hydroxyl functional monomer is selected from 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and a combination thereof.

4. The solvent-containing coating composition of claim 1, wherein the second polymer is polymerized from the second polymer monomer mixture, the second polymer monomer mixture comprising: An amine functional monomer selected from the group consisting of tert-butylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, and combinations thereof; a carboxyl functional monomer selected from methacrylic acid; or Its combination. 5 . The solvent-borne coating composition according to claim 4 , wherein the second polymer polymerized from the carboxyl functional monomer is reacted with an imine compound to form an amine functional group.

6. The solvent-containing coating composition according to claim 4, wherein: The second polymer has a hydroxyl functional group, and the second polymer monomer mixture further comprises a hydroxyl functional monomer, wherein the hydroxyl functional monomer is selected from 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and a combination thereof.

7. The solvent-borne coating composition according to claim 1, wherein the solvent-borne coating composition is a one-pack solvent-borne coating composition.

8. The solvent-borne coating composition of claim 1, further comprising one or more non-functional polymers, crosslinkers, pigments, additives, or combinations thereof.

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