Coating compositions and related methods

Abstract

The present invention discloses a polyaspartic acid composition comprising an asymmetric polyaspartic acid resin. The asymmetric polyaspartic acid resin is a reaction product of an asymmetric aspartic acid composition and an isocyanate chain extender. The asymmetric aspartic acid composition is a reaction product of a multifunctional acrylate component, at least one butenedioic acid dialkyl ester, and a multifunctional primary amino compound. Also disclosed is a multi-resin form of a polyaspartic acid composition. The multi-resin polyaspartic acid compositions include at least two different asymmetric polyaspartic acid resin variants. Also disclosed are a method of preparing the polyaspartic acid composition, as well as a coating composition comprising the polyaspartic acid composition, a method of preparing a coated article using the coating composition, and a coated article prepared thereby.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 387,810, filed on December 16, 2022, the entire content of which is incorporated herein by reference. Technical Field

[0003] In general, the present disclosure relates to polyaspartic acid coating compositions, and more particularly, to compositions, curable coatings, and coated articles based on asymmetric polyaspartic acid resins, and methods of making and using the same. Background Art

[0004] Performance coatings based on isocyanate chemistry are well - known and widely used in various industries. For example, in the field of vehicle manufacturing and repair, polyurethane coatings are widely used in primers, basecoats, and clearcoats in original equipment manufacturer (OEM) coatings and refinish coatings for vehicles. Common components of such coatings (e.g., polyisocyanates, polyols, etc.) are readily available and can be used to prepare coatings with good abrasion resistance, chemical resistance, corrosion resistance, heat resistance, or mechanical impact resistance.

[0005] Unfortunately, the chemicals used to impart unique beneficial properties to performance coatings for a particular application often have technical drawbacks, poor performance, and / or low productivity in other applications. For example, depending on the specific application, two - component coatings utilizing aspartate esters are widely used due to their low viscosity, high - solids - level tolerance, fast cure rate, and potential for good appearance. However, many curable aspartate ester compositions used to prepare such coatings have numerous defects. For example, most aspartate esters having a suitable pot life for vehicle coatings have a low functionality (functionality = 2, i.e., each molecule has two NH groups), forming coatings with a low cross - link density, which can affect the scratch resistance and durability of the coating. Adding high - functionality polyol resins to coating compositions containing aspartate esters and polyisocyanates significantly shortens the pot life. It is well - known that pigmented high - gloss polyaspartate ester coatings have appearance defects such as reduced gloss under high - temperature / high - humidity conditions and may exhibit fogging and color change during the normal life of the coated product. Unfortunately, conventional aspartate ester coatings formulated to improve scratch resistance also have poor appearance and low productivity problems. Therefore, there remains an opportunity to develop improved coating chemicals to achieve an optimal balance of properties such as pot life, appearance, productivity, adhesion, scratch resistance, and durability. Summary of the Invention

[0006] The present invention provides a polyaspartate ester composition. The polyaspartate ester composition comprises an asymmetric polyaspartate ester resin, which is a reaction product of an asymmetric aspartate ester composition and an isocyanate chain extender. The asymmetric aspartate ester composition is a reaction product of a polyfunctional acrylate component that on average contains at least two acrylate groups per molecule and is substantially free of monofunctional acrylate compounds, at least one dialkyl fumarate, and a polyfunctional primary amino compound.

[0007] The present invention also provides a multi-resin form of a polyaspartic acid composition or a poly-polyaspartic acid composition. The poly-polyaspartic acid composition comprises at least two of the asymmetric polyaspartate resins, each of which independently is a reaction product of a form of the asymmetric aspartic acid composition and an isocyanate chain extender.

[0008] The present invention also provides a method for preparing a polyaspartate ester composition. The method includes: reacting a polyfunctional acrylate component, the at least one dialkyl fumarate, and a polyfunctional primary amino compound to obtain an asymmetric aspartate ester composition; and reacting the asymmetric aspartate ester composition with an isocyanate chain extender to form an asymmetric polyaspartate resin and obtain a polyaspartate composition. In one embodiment, the method includes preparing at least two different variants of the asymmetric polyaspartate resin and then combining these variants together to obtain a poly-polyaspartic acid composition.

[0009] The present invention also provides a coating composition that comprises a curable polyaspartate ester component. The curable polyaspartate ester component comprises the polyaspartate ester composition or the poly-polyaspartate ester composition.

[0010] The present invention also provides a method for preparing a coated article using the coating composition, and a coated article prepared by the method and / or using the coating composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 Graph showing Amtec scratch performance results for various single-resin and multi-resin coating compositions prepared in examples according to embodiments of the present invention.

[0012] Figure 2 Graph showing Amtec scratch performance results for various other single-resin and multi-resin coating compositions prepared in examples according to embodiments of the present invention.

[0013] Figure 3 Graph showing Amtec scratch performance results for various single-resin and multi-resin comparative coating compositions prepared in examples. DETAILED DESCRIPTION

[0014] The following specific embodiments are exemplary only and are not intended to limit the composition or method. In addition, there is no intention to be bound by any theory presented in the foregoing background art or the following specific embodiments. For the sake of brevity, conventional techniques related to the compositions, methods, processes, and portions thereof described herein may not be described in detail. To be better known and more easily understood by those skilled in the art, the various tasks and process steps described herein may be incorporated into a more comprehensive program or process having additional steps or functions not described in detail herein. Thus, for the sake of brevity, these conventional steps may only be mentioned briefly or may be omitted entirely without providing well-known process details.

[0015] The present invention provides a polyaspartic acid composition comprising at least one asymmetric polyaspartic acid resin. The asymmetric polyaspartic acid resin enables a coating chemistry with improved properties and scratch resistance without the defects or performance degradation in terms of appearance and productivity exhibited by conventional polyaspartic acid coatings. Accordingly, high-performance coating compositions based on the polyaspartic acid ester composition are also provided herein, as well as methods for preparing the compositions, preparing their coatings, and preparing coated articles therewith. As demonstrated herein, the coating compositions of the embodiments of the present invention can be formulated to exhibit balanced drying performance in terms of a sufficiently long pot life at a rapid curing time and to impart excellent mechanical properties (including scratch resistance) to the coatings.

[0016] The asymmetric polyaspartic acid resin is an asymmetric aspartic acid composition chain-extended with an isocyanate, i.e., the reaction product of (I) an asymmetric aspartic acid composition and (II) an isocyanate chain extender. Thus, the asymmetric polyaspartic acid resin is best understood in view of the components of the chain extension reaction and thus in view of its components.

[0017] The asymmetric aspartic acid ester composition (I) comprises, consists essentially of, or is the reaction product of the following three main components: (A) a polyfunctional acrylate component; (B) at least one dialkyl fumarate; and (C) a polyfunctional primary amino compound. These components will be further detailed below.

[0018] Component (A) comprises (or is) a polyfunctional acrylate compound. In this sense, the polyfunctional acrylate component (A) typically contains on average at least two acrylate functional groups (such as acryloyloxy and / or methacryloyloxy) per molecule of acrylate compound. In this way, the polyfunctional acrylate component (A) comprises (or is) a polyacrylate compound, which may also be described as polyacrylates, polyacrylate esters, etc. The term "acrylate" when used for component (A) generally refers to a reactive / reactable acrylate group (i.e., the presence of an acryloyloxy functional group), rather than a post-reacted acrylate. In this sense, the term "polyacrylate compound" is preferred, although given the definitions herein, the mention of "polyacrylates" should also be understood to have the same meaning. In addition, the term "acrylate" with respect to a functional group encompasses both acryloyloxy and substituted acryloyloxy, such as methacryloyloxy, etc. The polyfunctional acrylate component (A) may contain the same or different types of such acrylate groups, as will be understood from the description herein.

[0019] Examples of suitable polyacrylate compounds include difunctional acrylates, trifunctional acrylates, and higher functional acrylates suitable for the reaction chemistries described herein. Such compounds can be prepared or otherwise obtained for embodiments of the present invention, and the preparation methods are known in the art and the specific compounds are also known and commercially available, as exemplified and further detailed herein.

[0020] In some embodiments, the polyfunctional acrylate component (A) includes difunctional acrylates (i.e., diacrylate compounds). Examples of such diacrylate compounds include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tricyclodecane dimethanol diacrylate, etc., as well as combinations, derivatives, and / or variants thereof. It should be understood that derivatives and / or variants of such diacrylate compounds listed in the form of methacryloxy substitution include their acryloxy variants. Specifically, according to the foregoing listing, examples of diacrylate compounds suitable for the polyfunctional acrylate component (A) should be understood to also include ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, cyclohexanedimethanol diacrylate, etc., and combinations thereof, as well as combinations with the above methacrylate variants.

[0021] In some embodiments, the polyfunctional acrylate component (A) includes trifunctional acrylates (i.e., triacrylate compounds). Examples of such triacrylate compounds include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, glycerol triacrylate, etc., as well as combinations, derivatives, and / or variants thereof.

[0022] Other examples of polyacrylate compounds suitable for use in or as the polyfunctional acrylate component (A) include tetraacrylates such as pentaerythritol tetra(meth)acrylate; pentaacrylates; hexaacrylates such as dipentaerythritol hexa(meth)acrylate, etc., as well as combinations, derivatives, and / or variants thereof.

[0023] In some embodiments, the polyfunctional acrylate component (A) comprises at least one of bifunctional acrylates and trifunctional acrylates, or consists essentially of at least one of bifunctional acrylates and trifunctional acrylates, or is at least one of bifunctional acrylates and trifunctional acrylates. In some such embodiments, the bifunctional acrylates are selected from linear alkyl glycol diacrylates such as 1,6 - hexanediol diacrylate (HDDA) and 1,4 - butanediol diacrylate (BDDA). In these or other such embodiments, the trifunctional acrylates are selected from trimethylolpropane triacrylate (TMPTA) and trimethylolpropane ethoxylated triacrylate (TMPEOTA).

[0024] In specific embodiments, the polyfunctional acrylate component (A) comprises trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylated triacrylate (TMPEOTA), 1,6 - hexanediol diacrylate (HDDA), 1,4 - butanediol diacrylate (BDDA) or a combination thereof. In certain embodiments, the polyfunctional acrylate component (A) is trimethylolpropane triacrylate (TMPTA). In other certain embodiments, the polyfunctional acrylate component (A) is 1,6 - hexanediol diacrylate (HDDA).

[0025] Generally, the polyfunctional acrylate component contains on average at least two acrylate groups per molecule. However, the polyfunctional acrylate component (A) can contain any number of polyfunctional acrylate compounds, and thus a component (A) with an average of more than 2 or more than 2.5 acryloxy functional groups per molecule can be used. It should also be understood that the polyfunctional acrylate component (A) can contain acrylate - functional polymers or oligomers, or can be an acrylate - functional polymer or oligomer, such as a methacrylate - capped polyurethane oligomer, etc.

[0026] Typically, component (A) is substantially free of monofunctional acrylate compounds. That is, in certain embodiments, component (A) does not contain acrylate components having only one acryloxy group, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate, etc. In the same way, the asymmetric aspartate ester composition (I) is typically prepared in the absence or non - presence of monofunctional acrylates in the reaction mixture of (A) - (C). However, as understood from the description of the polyaspartic resin composition below, in certain embodiments, the asymmetric aspartate ester composition (I) so prepared can be combined with one or more other asymmetric aspartate ester compositions that do not contain monofunctional acrylates.

[0027] Component (B) includes at least one dialkyl maleate. Dialkyl maleates can be equivalently described as dialkyl malates and dialkyl fumarates, and both of these esters can be used in component (B) or serve as component (B). Generally, dialkyl malates are selected as further detailed below.

[0028] Generally, the dialkyl maleate has the following formula: R 1 O(O)CCH=CHC(O)OR 2 , where R 1 and R 2 each independently selected from alkyl groups. Examples of alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, heptyl, octyl (e.g., n-octyl, 2-ethylhexyl, etc.), lauryl, etc., as well as combinations, derivatives, and / or variants thereof. Such derivatives and / or variants thereof should be understood to include other linear, branched, and / or cyclic hydrocarbon groups, including isomers of those above, those with more than 6 carbon atoms, cyclic forms of those above, etc. For example, cycloalkyl groups such as cyclohexyl, di-tert-butylcyclohexyl, etc. are also included.

[0029] Examples of specific dialkyl maleates include dialkyl malates such as dimethyl maleate, diethyl maleate, dibutyl maleate, dipentyl maleate, dioctyl maleate, dilauryl maleate, dicycloalkyl maleates (e.g., dicyclohexyl maleate, di-tert-butylcyclohexyl maleate, etc.), etc., as well as combinations, derivatives, and / or variants thereof (e.g., di-n-butyl maleate, diisobutyl maleate, di-tert-butyl maleate, etc.). It should be understood that such compounds can be referred to and / or described in different ways without departing from the scope of the embodiments of the present invention. For example, the compound di(2-ethylhexyl) maleate is commonly referred to as dioctyl maleate (DOM), which illustrates a variant of the dialkyl maleates applicable herein. Examples of specific dialkyl maleates also include dialkyl fumarates, which include fumarate forms of any of the above maleates (e.g., dimethyl fumarate, diethyl fumarate, dioctyl fumarate, dipentyl fumarate, dilauryl fumarate, etc.), dicyclohexyl fumarate, etc.

[0030] Generally, component (B) includes (or is) a dialkyl maleate. However, it should be understood that such dialkyl maleates may isomerize under normal conditions (e.g., before and / or during use), so any actual option used in component (B) or serving as component (B) may contain a mixture of maleate and fumarate isomers of the same dialkyl maleate compound.

[0031] Component (B) may comprise only one or more than one dialkyl maleate. In some specific embodiments, component (B) consists essentially of only one dialkyl maleate. However, in general embodiments, component (B) may comprise at least one, at least two, at least three or at least four dialkyl maleates. In specific embodiments, component (B) comprises at least two dialkyl maleates. When more than one dialkyl maleate is used, dialkyl maleates, dialkyl fumarates or combinations thereof may be used in or as component (B).

[0032] In some embodiments, component (B) comprises at least one of dibutyl maleate (DBM), dioctyl maleate (DOM) and combinations thereof.

[0033] In certain embodiments, component (B) comprises at least two different dialkyl maleates. In some such embodiments, at least one dialkyl maleate is selected from diethyl maleate (DEM), dibutyl maleate (DBM) and dioctyl maleate (DOM). In specific such embodiments, each of the different dialkyl maleates is selected from diethyl maleate (DEM), dibutyl maleate (DBM) and dioctyl maleate (DOM).

[0034] It should be understood that more than two dialkyl maleates may also be used in or as component (B), so the above specific examples are not exhaustive. Instead, the examples included herein illustrate different available dialkyl maleates in terms of molecular properties (such as chain length, hydrophobicity / hydrophilicity, solubility, etc.) and performance characteristics of the resulting resins (such as Tg, Mw, etc.). Thus, it will be readily understood by those skilled in the art that different combinations and ratios of dialkyl maleates may be used in component (B) to achieve the same or different results as other combinations and / or ratios.

[0035] Component (C) comprises (or is) a polyfunctional primary amino compound. In typical embodiments, the polyfunctional primary amino compound (C) is an organic diamine having two primary amine groups. However, other polyamino compounds such as organic triamines, polyaminosiloxanes, etc. may also be used. Similarly, mixtures of polyfunctional primary amino compounds may be used in or as component (C).

[0036] Suitable polyfunctional primary amino compounds generally contain two or more primary amino groups (i.e., -NH2). In some embodiments, the polyfunctional primary amino compound is selected from organic diamines. Examples of such organic diamines include aliphatic diamines such as ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, diethylenetriamine, triethylenetetramine, 2-methyl-1,5-pentanediamine, 2-[2-(2-aminoethoxy)ethoxy]ethylamine, 3-[2-(3-aminopropoxy)ethoxy]propylamine, 3-[3-(3-aminopropoxy)propoxy]propylamine, 3-[4-(3-aminopropoxy)butoxy]propylamine, 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine, and alicyclic diamines such as monocyclic or bicyclic alicyclic diamines, and / or aralkyl diamines such as 1,3- and 1,4-cyclohexanediamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine (i.e., "isophorone diamine" (IPDA)), norbornanediamine, 2,4- and 2,6-hexahydrotoluenediamine, 2,4'- and 4,4'-diamino-dicyclohexylmethane and 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 1,3- and 1,4-benzenedimethanamine, tetramethylbenzenedimethanamine, and combinations thereof.

[0037] In some embodiments, the polyfunctional primary amino compound is an alicyclic diamine such as a monocyclic or bicyclic alicyclic diamine. Examples of these diamines include isophorone diamine (i.e., 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA)), norbornyldiamine, 2,4'- and 4,4'-diaminodicyclohexylmethane (PACM) and 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane (such as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 3,3'-diethyl-4,4'-diaminodicyclohexylmethane) and mixtures thereof.

[0038] In some embodiments, the polyfunctional primary amino compound is a polyether diamine having the following formula:

[0039] H2N-D 2 -O-D 1 -O-D 3 -NH2,

[0040] where D 1 、D 2 and D 3Independently represents a hydrocarbyl linking group having 2 to 15, or 2 to 8, or 2 to 6, or 2 to 4 carbon atoms. Examples of such compounds include 2-[2-(2-aminoethoxy)ethoxy]ethylamine (e.g., Jeffamine XTJ-504, available from Huntsman), 3-[2-(3-aminopropoxy)ethoxy]propylamine (e.g., Etheramine NDPA 10, available from Tomah Products), 3-[3-(3-aminopropoxy)propoxy]propylamine (e.g., Etheramine NDPA 11, available from Tomah Products), 3-[4-(3-aminopropoxy)butoxy]propylamine (e.g., Etheramine NDPA 12, available from Tomah Products), and 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine (e.g., Etheramine DPA-DEG, available from Tomah Products; or BASF TTD, available from BASF).

[0041] In a specific embodiment, the polyfunctional primary amino compound (C) is isophorone diamine (IPDA). In some such embodiments, component (C) consists essentially of isophorone diamine (IPDA), or consists of isophorone diamine (IPDA).

[0042] In certain embodiments, the polyfunctional acrylate component (A) includes trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), 1,6-hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), or a combination thereof; the at least one dialkyl fumarate (B) includes dibutyl maleate (DBM), dioctyl maleate (DOM), or a combination thereof; and / or the asymmetric polyfunctional primary amino compound (C) includes isophorone diamine (IPDA). In some such embodiments, the at least one dialkyl fumarate (B) further includes diethyl maleate (DEM).

[0043] It should be understood that those skilled in the art can make specific selections of components (A)-(C) according to the embodiments of the present invention to improve the properties and / or performance of the resulting resin and coatings prepared therefrom, including increased crosslink density, improved flexibility, and improved scratch resistance.

[0044] The mixture of (A)-(C) of the reaction product from which the asymmetric aspartic acid composition (I) is obtained will be selected according to the desired use of the aspartic acid composition, the resin, and the coating, as well as the desired final properties. Thus, the ratio of (A):(B) can vary widely. For example, the polyfunctional acrylate component (A) and the at least one dialkyl maleate (B) can react in a stoichiometric ratio of (A):(B) from about 0.1:99.9 to about 50:50 to form the asymmetric aspartic acid composition (I). It should be understood that such a stoichiometric ratio will be based on the reactive functional groups involved in the preparation of the aspartic acid composition (I), such as the acrylate groups of component (A), the double bonds in component (B), the reactive amino groups in component (C), etc.

[0045] Regarding the ratio of (A):(B), in typical embodiments, the components will react at a ratio of (A):(B) from about 5:95 to about 50:50, such as from about 5:95 to about 30:70, or at a ratio of (A):(B) from about 10:90 to about 30:70, or about 10:90 to about 25:75. Depending on the specific conditions employed, the ratio of (A):(B) can also be selected outside of these ranges. However, those skilled in the art should understand that an amount of component (A) exceeding a certain limit may lead to increased gelation and thus be detrimental to the reaction.

[0046] The ratio of (C) is generally selected based on the total amount and functionality of (A) and (B) (i.e., the total functional equivalents). For example, the polyfunctional primary amino compound (C) can be reacted together in a stoichiometric ratio of (C):(A)(B) from about 0.95:1 to about 1.5:1 to form the asymmetric aspartic acid composition (I). In this case, the ratio (C):(A)(B) represents the number of reactive primary amine groups -NH2 of component (C) to the total number of reactive functional groups of components (A) and (B) (i.e., reactive acrylate groups + reactive enoate groups). Thus, it should be understood that component (C) with simple stoichiometric equivalents (i.e., the ratio (C):(A)(B) is 1:1) can be used, or a slightly excessive amount of component (A) and / or (B) can be used (e.g., the ratio (C):(A)(B) is 0.95:1), or an excessive amount of component (C) can be used (e.g., the ratio (C):(A)(B) is 1.5:1). Those skilled in the art will select the specific ratio according to the desired functionality of the asymmetric aspartic acid composition (I).

[0047] Typically, the goal is to have the ratio (C):(A)(B) be 1:1 to minimize the remaining free reactive groups from all three components in the asymmetric aspartic acid composition (I). In a specific embodiment, the amount of component (C) is selected such that the stoichiometric ratio of the components (C):(A)(B) is from about 0.95:1 to about 1.4:1, or from about 0.98:1 to about 1.3:1; or from about 0.99:1 to about 1.25:1, or from about 1:1 to about 1.2:1.

[0048] For the above stoichiometric ratios, those skilled in the art should understand that molar ratios can also be used to represent the specific ratios of the components (A)-(C) used, as they are essentially related to the stoichiometric ratios related to the molar amounts of the components used multiplied by the number of functional groups present. Such amounts (e.g., loadings by mass) will be elaborated in detail by the specific embodiments given in the following examples.

[0049] As described above, the asymmetric polyaspartate resin is the reaction product of the asymmetric aspartic acid ester composition (I) and an isocyanate chain extender (II). In this way, it should be understood that the reaction product of (A)-(C) in the asymmetric aspartic acid ester composition (I) has isocyanate reactivity, specifically, the NH functionality imparted by component (C). Therefore, the isocyanate chain extender (II) is not particularly limited and can be selected from any isocyanate (e.g., a compound containing multiple isocyanate functional groups) capable of chain-extending the aspartic acid reaction product of (A)-(C) to obtain the asymmetric polyaspartate resin.

[0050] The isocyanate chain extender (II) can be or include any type of organic polyisocyanate compound, i.e., an organic compound having two or more free isocyanate groups bonded in an aliphatic, cycloaliphatic, araliphatic, and / or aromatic manner. It should be understood that due to the presence of at least two free isocyanate groups, the isocyanate chain extender (II) can be referred to as a "polyisocyanate" in some cases. However, in the context of the present disclosure, the term "polyisocyanate" refers to dimers, trimers, or other oligomeric forms of isocyanate compounds, while the terms "polyisocyanate compound" and "polyfunctional isocyanate" are used herein to refer to compounds based on the number of free isocyanate groups (i.e., regardless of whether such polyisocyanate compounds can be used in dimer, trimer, or other oligomeric forms). Given the description and examples herein, those skilled in the art will readily understand the specific types and classes of polyisocyanate compounds suitable for use in or as the isocyanate chain extender (II). In some embodiments, the isocyanate chain extender (II) is liquid at room temperature or becomes liquid by adding an organic solvent compatible with the reaction of (I) and (II).

[0051] In some embodiments, the isocyanate chain extender (II) has an average NCO functionality of 1.5 to 6.0, or 1.8 to 4.0, or about 2.0.

[0052] In some embodiments, the isocyanate chain extender (II) can be selected from 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1,5-pentane diisocyanate, 4,4'-diisocyanatocyclohexylmethane, the cyclo-trimer of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, urethdione dimer and / or biuret, hexamethylene diisocyanate (HDI) and its derivatives, 1,1',6,6'-tetramethylhexamethylene diisocyanate, p- or m-tetramethylxylylene diisocyanate, 2,2',5-trimethylhexane diisocyanate, aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate; and combinations thereof.

[0053] Generally, the isocyanate chain extender (II) comprises (or is) an alkyl diisocyanate, an aryl diisocyanate, an alkaryl diisocyanate, or a combination thereof. In a specific embodiment, for example, the isocyanate chain extender (II) is selected from isophorone diisocyanate (IPDI), 1,5-pentane diisocyanate (PDI), 4,4'-diisocyanatodicyclohexylmethane (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI), and combinations thereof. In a specific embodiment, the isocyanate chain extender (II) is isophorone diisocyanate (IPDI).

[0054] In order to obtain an asymmetric polyaspartic acid resin with balanced drying properties, mechanical properties, and optical properties, it is generally desirable to prepare an asymmetric polyaspartic acid resin that does not contain isocyanate groups. In addition, it is desirable to prepare an asymmetric polyaspartic acid resin having an NH equivalent weight of about 300 to about 5,000 g, or about 500 to about 2,500 g. Accordingly, the asymmetric aspartic acid composition (I) is typically reacted (i.e., chain-extended) with an isocyanate chain extender (II) in a stoichiometric ratio of (II):(C) of about 0.05:1 to about 0.9:1, where this stoichiometric ratio is defined by the reactive functional groups participating in the chain extension, i.e., the ratio of the number of NCO groups of the isocyanate chain extender (II) to the number of reactive primary or secondary amine (NH) groups of the polyfunctional primary amine compound (C) in the mixture of (A)-(C) of the reaction product from which the asymmetric aspartic acid composition (I) is obtained. For example, in some embodiments, the asymmetric polyaspartic acid resin is formed by chain-extending the asymmetric aspartic acid composition (I) with an isocyanate chain extender (II) in a stoichiometric ratio of (II):(C) of about 0.1:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1. In some such embodiments, the asymmetric polyaspartic acid resin prepared is substantially free of free / unreacted isocyanate groups. In these or other embodiments, the amine value of the asymmetric polyaspartic acid resin is about 50 to about 100, such as about 55 to about 90, or about 60 to about 90, or about 60 to about 80.

[0055] Embodiments of the present invention provide a polyaspartic resin composition according to the foregoing description. That is, the polyaspartic resin composition may comprise two or more asymmetric polyaspartic resins prepared according to the foregoing embodiments. In a specific embodiment, the polyaspartic resin composition comprises a first asymmetric polyaspartic resin (1) and a second asymmetric polyaspartic resin (2) different from the first asymmetric polyaspartic resin (1). In such an embodiment, the first asymmetric polyaspartic resin is a reaction product of an (I-1) asymmetric aspartic acid composition and an (II-1) isocyanate chain extender, wherein the asymmetric aspartic acid composition (I-1) comprises a reaction product of a mixture of: (A1) a polyfunctional acrylate component having an average of at least two acrylate groups per molecule, (B1) at least one dialkyl fumarate, and (C1) an asymmetric polyfunctional primary amino compound. The second asymmetric polyaspartic resin is a reaction product of an (I-2) asymmetric aspartic acid composition and an (II-2) isocyanate chain extender, wherein the asymmetric aspartic acid composition (I-2) comprises a reaction product of a mixture of: (A2) a polyfunctional acrylate component having an average of at least two acrylate groups per molecule, (B2) at least one dialkyl fumarate, and (C2) an asymmetric polyfunctional primary amino compound.

[0056] In such embodiments, each of components (A1) and (A2) is independently selected according to the parameters of component (A) above. Similarly, each of components (B1) and (B2) is independently selected according to the parameters of component (B) above, and each of components (C1) and (C2) is independently selected according to the parameters of component (C) above. In the same manner, the isocyanate chain extenders (II-1) and (II-2) are also selected according to the parameters of the isocyanate chain extender (II) above.

[0057] In certain embodiments, the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) each independently comprise difunctional acrylates, trifunctional acrylates, or a combination thereof. Generally, at least one of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) is substantially free of monofunctional acrylate compounds, as described in further detail below. In some embodiments, both the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) are substantially free of monofunctional acrylate compounds.

[0058] In some embodiments, the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) are each independently selected from dialkyl maleates. In these or other embodiments, the asymmetric polyfunctional primary amino compound (C1) and the asymmetric polyfunctional primary amino compound (C2) are each independently selected from organic diamines having two primary amine groups. In these or other embodiments, the isocyanate chain extender (II-1) and the isocyanate chain extender (II-2) are each independently selected from alkyl diisocyanates, aryl diisocyanates, alkaryl diisocyanates, and combinations thereof.

[0059] In some embodiments, the polyaspartic acid composition is obtained as described above, wherein the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) are each independently selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylated triacrylate (TMPEOTA), 1,6-hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof; the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) are each independently selected from di(C1-C 10 )alkyl maleates (i.e., dialkyl maleates wherein each alkyl group has 1 to 10 carbon atoms); at least one of the asymmetric polyfunctional primary amino compound (C1) and the asymmetric polyfunctional primary amino compound (C2) comprises isophorone diamine (IPDA); and / or the isocyanate chain extender (II-1) and the isocyanate chain extender (II-2) are each independently selected from isophorone diisocyanate (IPDI), 1,5-pentane diisocyanate (PDI), 4,4'-diisocyanatodicyclohexylmethane (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI), and combinations thereof.

[0060] The first asymmetric polyaspartic resin (1) and the second asymmetric polyaspartic resin (2) are independently selected to be different from each other and compatible in the polyaspartic composition. For example, in certain embodiments, one of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) comprises trifunctional acrylates selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylated triacrylate (TMPEOTA), and combinations thereof; the other of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) comprises linear alkyl glycol diacrylates, or difunctional acrylates selected from 1,6 - hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof. In this way, the functionality of the asymmetric polyaspartic resins varies, such that the polyaspartic composition has unique properties superior to those of any one resin used alone. In other such embodiments, at least two trifunctional acrylates or at least two difunctional acrylates are used as components (A1) and (A2), respectively. For example, in some embodiments, the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) each comprise trifunctional acrylates selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylated triacrylate (TMPEOTA), or combinations thereof. In other embodiments, each of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) independently comprises linear alkyl glycol diacrylates, or difunctional acrylates selected from 1,6 - hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof.

[0061] In some embodiments, the polyaspartic acid composition is obtained as described above, wherein one of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) comprises trifunctional acrylates selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), and combinations thereof, and the other of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) comprises difunctional acrylates selected from linear alkyl glycol diacrylate, or 1,6 - hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof; wherein each of the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B - 2) independently comprises dibutyl maleate (DBM), dioctyl maleate (DOM), diethyl maleate (DEM), or combinations thereof; wherein each of the asymmetric polyfunctional primary amino compound (C1) and the asymmetric polyfunctional primary amino compound (C2) independently comprises isophorone diamine (IPDA); and each of the isocyanate chain extender (II - 1) and the isocyanate chain extender (II - 2) independently comprises isophorone diisocyanate (IPDI).

[0062] In some embodiments, the polyaspartic ester composition is obtained as described above, wherein one of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) is trimethylolpropane triacrylate (TMPTA), and the other of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) is 1,6 - hexanediol diacrylate (HDDA); wherein each of the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) comprises dibutyl maleate (DBM), dioctyl maleate (DOM), diethyl maleate (DEM), or combinations thereof; wherein each of the asymmetric polyfunctional primary amino compound (C1) and the asymmetric polyfunctional primary amino compound (C2) is isophorone diamine (IPDA); and each of the isocyanate chain extender (II - 1) and the isocyanate chain extender (II - 2) is isophorone diisocyanate (IPDI).

[0063] The preparation of the polyaspartic acid composition and its components is generally the same as that of the polyaspartic acid composition described above. For example, in some embodiments, the mixture of (A1)-(C1) of the reaction product from which the asymmetric aspartic acid composition (I-1) is obtained contains a polyfunctional acrylate component (A1) and the at least one dialkyl maleate (B1) present in a stoichiometric ratio of (A1):(B1) of about 0.1:99.9 to about 50:50, or (A1):(B1) of about 5:95 to about 50:50, such as about 5:95 to about 30:70, or (A1):(B1) of about 10:90 to about 30:70, or about 10:90 to about 25:75; and an asymmetric polyfunctional primary amino compound (C1) present in a stoichiometric ratio of (C1):(A1)(B1) of about 0.95:1 to about 1.5:1, such as about 0.95:1 to about 1.4:1, or about 0.98:1 to about 1.3:1; or (C1):(A1)(B1) of about 0.99:1 to about 1.25:1, or about 1:1 to about 1.2:1. In these or other embodiments, the mixture of (A2)-(C2) of the reaction product from which the asymmetric aspartic acid composition (I-2) is obtained contains a polyfunctional acrylate component (A2) and at least one dialkyl maleate (B2) present in a stoichiometric ratio of (A2):(B2) of about 0.1:99.9 to about 50:50, or about 5:95 to about 50:50, such as about 5:95 to about 30:70, or (A2):(B2) of about 10:90 to about 30:70, or about 10:90 to about 25:75; and an asymmetric polyfunctional primary amino compound (C2) present in a stoichiometric ratio of (C2):(A2)(B2) of about 0.95:1 to about 1.5:1, such as about 0.95:1 to about 1.4:1, or about 0.98:1 to about 1.3:1; (C2):(A2)(B2) of about 0.99:1 to about 1.25:1, or about 1:1 to about 1.2:1.

[0064] It should be understood that the polyaspartate ester composition of the embodiments of the present invention may comprise only one asymmetric polyaspartate ester resin prepared from the above components (A)-(C), and at least one polyaspartate ester resin with unrestricted selection. For example, although the single resin composition described herein is prepared from component (A) substantially free of monofunctional acrylate compounds, the polyaspartate ester composition may comprise a resin prepared in the absence of monofunctional acrylate compounds (i.e., from the asymmetric aspartate ester composition (I)) and a second asymmetric aspartate ester composition, or a third and / or fourth asymmetric aspartate ester composition, which comprises an asymmetric polyaspartate ester resin that is a reaction product of components (A)-(C) and a monofunctional acrylate compound (such as methyl acrylate). Such monofunctional acrylate compounds, which are characterized by having only one acrylate functional group, are known in the art and are unrestricted with respect to the second, third, fourth, etc. asymmetric polyaspartate ester resins of the polyaspartate ester composition. However, it should be understood that in all embodiments of the polyaspartate ester composition, there is at least one asymmetric polyaspartate ester resin described herein that is free of monoacrylate, or a combination of at least two asymmetric polyaspartate ester resins described herein that are free of monoacrylate.

[0065] The polyaspartic acid composition and the polyaspartate ester composition described herein can be used in the curable polyaspartate component of a coating composition or as the curable polyaspartate component of a coating composition. Accordingly, there is also provided herein a coating composition comprising a curable polyaspartate component, wherein the curable polyaspartate component comprises a polyaspartic acid composition according to the foregoing embodiments. In some embodiments, the curable polyaspartate component comprises a polyaspartate ester composition according to the foregoing embodiments and thus comprises two different variants of asymmetric polyaspartate resins.

[0066] The coating composition is generally a liquid coating composition comprising a liquid carrier. In some embodiments, the coating composition is substantially free of water and uses an organic carrier. An organic solvent-based coating composition is a coating composition that uses an organic solvent as a solvent or diluent during the preparation and / or application of the coating composition. Typically, a solvent-based coating composition contains, for example, 20 to 90% by weight of an organic solvent based on the total amount of the coating composition.

[0067] Organic solvents are commonly used solvents in coating technology. These organic solvents may come from the preparation of the binder or be added separately. Examples of suitable solvents are typically aprotic solvents such as ethers, ketones, esters, etc. Specific examples include polar and non-polar aprotic solvents such as glycol ethers or esters, N-alkylpyrrolidones (such as N-methylpyrrolidone and N-ethylpyrrolidone), ketones (such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone), aromatic or aliphatic hydrocarbons (such as toluene, xylene, linear or branched aliphatic C6-C12 hydrocarbons, aliphatic hydrocarbons such as hexane, heptane and dodecane), mineral spirits, esters (such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and hexyl acetates, propionates and / or butyrates), ethers (such as tetrahydrofuran, methylal, acetal, butyral, diethyl ether, dibutyl ether, etc.), ether-ester solvents (such as ethylene glycol monobutyl ether acetate, monoethyl ether acetate), etc. and combinations thereof. Exemplary solvents are esters such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and hexyl acetates, propionates and / or butyrates, and ether-esters such as ethylene glycol monobutyl ether acetate, monoethyl ether acetate, etc. In a typical embodiment, butyl acetate is used as the solvent / organic carrier. It should be understood that solventless coating systems can also be employed. Similarly, for example, for environmental and / or regulatory reasons, the coating composition may be free of specific solvents.

[0068] Typically, the coating composition comprises a curing agent as detailed below. The coating composition can be in the form of a one-component coating composition or a two-component coating composition. To prevent premature curing and facilitate processing, the composition can be in the form of a two-component curable composition having a first component (Part A) and a second component (Part B), the first component comprising a polyaspartate component and the second component comprising a curing agent. In other words, to avoid premature reaction, the components that will react with each other (i.e., the polyaspartate component and the curing agent) must be stored separately before application. Typically, the polyaspartate component and the curing agent are only mixed together shortly before application. The term "shortly before application" is well known to those skilled in the art. The time at which a ready-to-use coating composition can be prepared before actual use / application depends, for example, on the pot life of the coating composition. Coating compositions with a very short pot life can be applied by a two-component spray gun where the reactive components are fed separately into a static mixer and then applied directly.

[0069] In some embodiments, the polyaspartate component and the curing agent are formulated together in one composition.

[0070] Typically, the curing agent is an isocyanate curing agent, i.e., a curing agent having free isocyanate groups and reactive isocyanate groups. Alternatively, the curing agent can comprise two or more curing agents, typically at least one of which has free and reactive isocyanate groups. The isocyanate curing agent can be a polyisocyanate or a polyisocyanate mixture, e.g., those isocyanate curing agents exclusively having isocyanate groups bonded in an aliphatic and / or cycloaliphatic manner, such as those having an average NCO functionality of 1.5 to 6.0, or 1.8 to 4.0. General and specific examples of suitable curing agents (including isocyanate and polyisocyanate curing agents) are listed in U.S. Patent No. 10,519,336, which is incorporated herein by reference.

[0071] Examples of suitable isocyanate curing agents include the polyisocyanate forms of the isocyanate compounds described above with respect to the isocyanate chain extender (II). Thus, it should be understood that in some embodiments, the same isocyanate compound can be present or otherwise used or employed as the isocyanate chain extender (II) and the curing agent. However, in some embodiments, the isocyanate chain extender (II) is selected from non-oligomeric isocyanates, while in the same embodiments, the isocyanate curing agent is selected from oligomeric isocyanates (e.g., the trimerized form of the isocyanate also used for the isocyanate chain extender (II)).

[0072] Those skilled in the art will understand that diisocyanates can be converted to higher functionality compounds by conventional methods, e.g., by trimerization or by reaction with water or a polyol (such as trimethylolpropane or glycerol). Thus, the at least one curing agent having free isocyanate groups can also be used in the form of reaction products, such as isocyanate-modified resins or isocyanate-functional prepolymers. Such curing agents can be selected from isophorone diisocyanate (IPDI), 1,5-pentane diisocyanate (PDI), methylene diphenyl diisocyanate (MDI), 4,4'-methylenebis(cyclohexyl isocyanate) (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI), combinations thereof, and polyol-modified derivatives thereof.

[0073] Typically, the isocyanate curing agent can include or be selected from: isocyanurates, uretidinediisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane groups, polyisocyanates containing allophanate groups, polyisocyanates containing polyesters and polyethers, polyisocyanates containing polyacrylic acids, polyisocyanates containing carbodiimide groups, and polyisocyanates containing acylurea groups. In addition, the isocyanate groups of the curing agent can be completely or partially blocked. Low molecular weight compounds containing active hydrogen for blocking the NCO groups are known in the art and include aliphatic or cycloaliphatic alcohols, dialkylamino alcohols, oximes, lactams, imides, hydroxyalkyl esters and esters, and malonic or acetoacetic acids of 5- and 6-membered nitrogen-containing heterocycles such as imidazole and pyrazole.

[0074] The coating composition generally comprises a curable polyaspartate component and a polyisocyanate curing agent in a stoichiometric ratio of NCO:NH of about 0.8 to about 2, or about 0.9 to about 2, or about 1 to about 1.5, or about 1.1 to about 1.5, based on the total number of free isocyanate groups (NCO) and the total number of free amino groups (NH) of the polyisocyanate curing agent in the polyaspartate composition. The NCO groups in excess of the NH groups in the coating composition typically react with moisture from the environment, solvents, or residual moisture carried by other components.

[0075] The coating composition generally comprises an additive component, which includes any number of available additives known in the coating art. Typically, for example, the additive component includes curing catalysts, UV absorbers and / or light stabilizers, rheology modifiers, adhesion promoters, dehumidifiers, wetting agents, chain extenders, binders, leveling and / or flow promoters, or combinations thereof. However, it should be understood that the coating composition can be substantially free of any one or more of these additives and can equally contain additives not specifically mentioned above. Specific additives, selection criteria, and their available amounts have been set forth in US2020031982A1, the entire content of which is incorporated herein by reference. The addition amounts of the additives can be conventional amounts familiar to those skilled in the art. Pigments, fillers, and additives commonly used in paints can be used in one and / or both components of the two-component system.

[0076] Additives can be used in part A, part B, or both, as described above for the two-component form of the coating composition. For example, in some embodiments, a curing catalyst (e.g., dibutyltin dilaurate, in an amount of about 0 to about 1500 ppm based on total binder solids) is used and formulated into part B of the composition. In these or other embodiments, at least one UV absorber and / or light stabilizer, rheology modifier, wetting agent, leveling and / or flow promoter, or a combination thereof is used in the coating composition and formulated into part A. In these or other embodiments, at least one adhesion promoter, dehumidifying agent, chain extender, binder, or a combination thereof is used in the coating composition and formulated into part B.

[0077] In typical embodiments, part A and part B each contain an organic solvent or a mixture of organic solvents as the liquid carrier. For example, in some embodiments, n-butyl acetate is used as the solvent in part A and part B. In other embodiments, one or both of part A and part B are substantially free of organic solvents.

[0078] According to the present disclosure, the coating composition may further comprise pigments, fillers, and / or common coating additives. All organic or inorganic coloring pigments used in paints and / or pigments that impart special effects are suitable for the pigments. Examples of inorganic or organic coloring pigments are titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone pigments, or pyrrolopyrrole pigments. Examples of special effect pigments include metallic pigments (e.g., metallic pigments made of aluminum or copper), interference pigments (e.g., aluminum coated with titanium dioxide, mica coated), and graphite effect pigments. Examples of fillers are silica, barium sulfate, talc, aluminum silicate, and magnesium silicate.

[0079] As can be seen from the following examples, in some embodiments, the coatings prepared from the coating composition exhibit certain performance metrics. For example, the coating may exhibit an AMTEC gloss retention of at least about 70%, or at least about 75%, or at least about 80% after reflow (60 °C). In a specific embodiment, the coating composition comprises a polyaspartate ester composition, and the AMTEC gloss retention exhibited by the prepared coating after reflow (60 °C) is at least about 3% higher than the expected value based on the performance of a comparative single polyaspartate ester composition (i.e., a coating prepared from only one polyaspartate ester resin). These and other performance metrics will be described in more detail below.

[0080] The present invention also provides a method for coating a substrate with the coating composition. Specifically, the method includes: coating at least a part of a substrate (e.g., a bare or pre-coated metal and / or plastic substrate) with the coating composition; and curing the coating composition to form a coating on the substrate, thereby preparing a coated article.

[0081] In some embodiments, curing of the coating composition is carried out by heat energy and / or chemical reaction.

[0082] The substrate can be metal or plastic. The metal substrate can be any industrial article to be coated with a one-component or two-component coating. In some embodiments, the two-component coating component is, for example, a two-component polyurethane coating composition. Exemplary metal substrates are vehicle bodies and vehicle body parts. Metal substrates that can be used are, for example, various materials used in industrial coatings and vehicle construction, such as metals, such as iron, zinc, aluminum, magnesium, stainless steel, or their alloys.

[0083] The plastic substrate can be any industrial article to be coated with a one-component or two-component coating. In some embodiments, the two-component coating composition is, for example, a two-component polyurethane coating composition. Exemplary plastic substrates are vehicle bodies and vehicle body parts. Plastic substrates that can be used are, for example, various materials used in industrial coatings and vehicle construction, such as polypropylene (PP), polyethylene (PE), polyurethane (PU), polyester (PES), polyamide (PA), poly(meth)acrylate, thermoplastic olefins (such as blends of polypropylene (PP) and ethylene / propylene-diene rubber (EPDM)), polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), and their blends (such as blends of acrylonitrile-butadiene-styrene (ABS) and polycarbonate (PC) or blends of polycarbonate (PC) and polybutylene terephthalate (PBT)), sheet molding compounds (SMC), blends of polyphenylene ether (PPO) and polyamide (PA), and their mixtures.

[0084] The coating composition can be applied by conventional application methods. Examples of application methods are brushing, roll coating, knife coating, dip coating, and spraying. Spraying is exemplary. After an optional flash drying stage, the coating can subsequently be cured and / or the next coating can be applied. In a specific embodiment, the coating composition is applied in a two-coat process.

[0085] In some embodiments, the applied coating composition cures at a temperature, for example, of from about -30 to about 75 °C, such as from about -25 to about 70 °C, or from about -18 to about 65 °C, or from about -12 to about 60 °C, or from about 0 to about 60 °C. Generally, the curing temperature used is from about ambient temperature to about 65 °C. In some embodiments, for example, ambient temperature curing is employed, provided that it is about ambient temperature (e.g., room temperature ± about 10 °C, or ± about 5 °C). In other embodiments, elevated temperatures are used. For example, in a specific embodiment, the applied coating composition is baked at from about 37 to about 70 °C (such as from about 43 to about 60 °C).

[0086] In a specific embodiment, curing is humidity-sensitive and the cure rate can be fine-tuned by varying the drying temperature under a given humidity condition. For example, when the absolute humidity given by the temperature and relative humidity is high, air drying is typically employed. When the absolute humidity is low, baking is typically used to cure the coating, for example, to accelerate curing. It should be understood that the pot life of the coating composition may also be affected by temperature and / or humidity, and thus the pot life can be extended beyond the scope described herein by controlling the storage and / or application environment. However, those skilled in the art should understand that it may be difficult to control temperature and humidity on an industrial scale, and thus different techniques or solutions may be required in small-scale and large-scale setups to achieve such control.

[0087] In some embodiments, the method includes applying a multi-layer coating composition to at least a portion of a metal or plastic substrate. In this regard, it should be understood that at least one layer (in some embodiments, one layer) of the multi-layer contains the coating composition of the present invention. Thus, the other layers of the multi-layer may also contain the coating composition of the present invention or a coating composition different from the coating composition of the present invention. Accordingly, the coating composition of the present invention can be adjacent to a metal or plastic substrate, or to an optional primer coat, or to an intermediate coat (or interlayer) of a multi-layer structure, or to the outer layer of the multi-layer.

[0088] In some embodiments, the multi-layer coating is applied by the wet-on-wet method or by applying one layer of the multi-layer, curing it first, and then applying the next layer. If the multi-layer coating is applied by applying one layer of the multi-layer, curing it first, and then applying the next layer, then in some embodiments, the one layer is cured at a sufficient temperature for a sufficient time before applying the next layer. Regarding the curing temperature, refer to the temperatures set forth above when defining the curing temperature of the applied coating composition.

[0089] It should be understood that the coating compositions of the present disclosure are characterized by balanced drying properties, i.e., having a rapid curing time within a sufficient pot life, which is at least 30 minutes at room temperature and ambient humidity in some embodiments; mechanical properties such as scratch resistance, adhesion, and interlayer adhesion in a multi-layer structure; chemical and corrosion resistance; and optical properties such as coating appearance (smoothness and gloss).

[0090] According to the present disclosure, the coating compositions and the methods are applicable to automotive and industrial coatings. In the automotive coating industry, the coating compositions and the methods can be used to coat vehicle bodies and body parts in vehicle production line painting and vehicle repair (e.g., in-line or in a separate paint booth), or to paint spare parts (such as on-line, in-line or off-line). They can also be used to coat large vehicles and transportation vehicles such as trucks, buses, and train carriages, where the curing temperature used can be -20 to 150 °C, can be -10 to 150 °C in some embodiments, can be more 0 to 150 °C in some embodiments, and can be mostly 10 to 150 °C in some embodiments, such as 10 to 140 °C. Most typically, the coating compositions and the methods can be used for vehicle and vehicle part repair. For repair, the curing temperature used is, for example, -10 to 80 °C, 0 to 80 °C in some embodiments, and mostly 10 to 70 °C in some embodiments, such as 10 to 60 °C. In addition, the coating compositions and the methods can be used to coat any industrial product other than motor vehicles.

[0091] The present disclosure will be explained in more detail based on the following examples.

[0092] Examples

[0093] The following examples illustrate embodiments of the present disclosure and are intended to illustrate rather than limit the invention.

[0094] Unless otherwise indicated, all parts and percentages are recorded based on weight. Where provided, the molecular weights (number-average molecular weight and weight-average molecular weight) mentioned herein can be determined by conventional methods known in the art. For example, the molecular weight of the polyaspartic acid resin can be determined by gel permeation chromatography (GPC) using, for example, polystyrene standards and a tetrahydrofuran (THF) eluent. Unless otherwise indicated, the molecular weights are recorded as weight-average molecular weight (Mw).

[0095] Measurement method

[0096] The following measurement methods are used to evaluate the parameters given in the examples and claims.

[0097] Viscosity:The viscosity of the activated coating solution is determined according to the method based on ASTM D 4212. Measurements are carried out using a Zahn No. 2 flow cup at room temperature (20 ± 3 °C) and at a relative humidity of approximately 30%.

[0098] Pot life: The pot life is determined by the increase in the solution viscosity over time (e.g., using a Zahn No. 2 flow cup). The pot life is defined as the time required for the viscosity to reach 1.5 times the initial value and represents the elapsed time during which the coating composition remains easily sprayable.

[0099] Hardness: Samples are prepared by applying a coating on a glass plate to obtain a dry film with a thickness of approximately 50 μm. The Martens hardness is measured using a Fischer hardness tester (FisherScope HM2000S) equipped with a Vickers indenter (indentation hardness, ASTM E2546). The maximum load used is 5 mN and the loading time is 5 seconds. The results are in MPa. The hardness is measured 2 hours, 24 hours, and 7 days after the coating is applied (sprayed) and air-dried.

[0100] Solid content: The weight percentage of solids in the resin is determined according to the method based on DIN EN ISO 3251. A weighed resin sample (approx. 1 g) is loaded into an aluminum dish with a diameter of 75 mm equipped with a paper clip. The aluminum dish loaded with the sample is placed in an oven at approximately 105 °C (±1 °C) for approximately 1 hour and weighed again. The weight percentage of solids is calculated using Equation (I):

[0101] % solids = 100 % × (weight of residue / weight of sample) (I)

[0102] The recorded solids content is determined by measuring two samples and taking the average result.

[0103] Amine value: The amine value is determined using a defined solution according to the method based on DIN 53176 and is expressed in equivalents (mg KOH / g). The sample is diluted in methoxypropanol and then titrated with perchloric acid. The amine value (AV) is calculated according to Equation (II):

[0104]

[0105] where V is the volume of perchloric acid used (mL) with a concentration of C (e.g., 0.1 mol / L).

[0106] Adhesion:The coating adhesion of an electrophoretic coating panel (4 inches x 12 inches) with a primer layer applied adjacent to the electrophoretic coating layer, a basecoat (such as a waterborne basecoat) applied adjacent to the primer layer, and then a clearcoat applied on top was evaluated. This test method is based on ASTM D2247-92 and ASTM D3359-92A. Dry and wet adhesion was evaluated using cross-cut (X-hatch) and grid-cut (#-hatch) tape tests. In the X-hatch test, two cuts were made in the coating, each cut being approximately 40 mm long and intersecting at a small angle (between 30 and 45 degrees) near the middle. In the #-cut test, grid scratches were made using a manual cross-cut tester with the lines spaced 1 mm apart from each other. The panel was gently brushed to remove any detached coating debris. To ensure good contact with the film, clear tape (Scotch tape) was placed on the X-shaped cuts and grid areas and rubbed with an eraser to ensure good contact. Within 60 to 120 seconds after applying the tape, it was pulled back quickly by grasping the free end at an angle as close to 180 degrees as possible.

[0107] The dry adhesion was rated from 0 (complete failure) to 10 (no failure) according to the degree of damage, which can be evaluated by visual comparison with a standard (such as an actual sample, photo, chart, etc.).

[0108] The wet adhesion was evaluated using the same method, but the panel was placed in a humidity cabinet at 100% RH and 40 °C for 10 days. After pulling the panel out of the humidity cabinet, the adhesion of the coating was evaluated at 1 hour and 24 hours. Similar to the dry adhesion, the wet adhesion was rated from 0 (complete failure) to 10 (no failure) according to the degree of damage. After the humidity treatment, the visible blisters on each panel (4 inches x 12 inches) were also counted and measured. The diameter of the largest blister on each panel (in millimeters) was recorded. In addition to the cross-cut (X-hatch) and grid-cut (#-hatch) tape tests, the formation of large blisters is also an indication of weak wet adhesion.

[0109] Gloss: The glossiness of the coated sample was measured one day after spraying. The glossiness was measured using a Mini TRI glossmeter from Byk Gardner GmbH, Germany, with a measurement angle of 0° for the reflected light.

[0110] Distinctness of Image (DOI) and dullness (du) : One day after spraying, the distinctness of image (DOI) and dullness (du) of the coating sample were measured. The sample was evaluated using a Wavescan-DOI instrument from Byk Gardner GmbH, Germany, which uses a CCD camera to measure the diffused light caused by fine (such as < 1 mm) and very fine (such as < 0.1 mm) surface structures and record the DOI and du values.

[0111] The DOI can also be described in terms of, e.g., brightness, sharpness or clarity. The DOI decreases due to fine structures close to the human eye resolution (i.e., smaller than 1 mm). A higher DOI value is better.

[0112] Structures smaller than 0.1 mm affect visual perception and are used to determine a parameter of the coating called “dullness”. The dullness (du) value is preferably low, with a minimum value of 1.

[0113] Material: Unless otherwise specified, all solvents, substrates and reagents were purchased from various commercial suppliers (BASF, Covestro, Evonik, Sigma-Aldrich, VWR, Alfa Aesar, etc.) or otherwise obtained and used as received (i.e., without further purification) or in a form conventionally used in the art.

[0114] Isophorone diamine (IPDA) was obtained from Evonik Industries in Germany, BASF SE in Germany or DKSH in Switzerland / China.

[0115] Isophorone diisocyanate (IPDI) was obtained from Evonik Industries in Germany and Covestro AG in Germany.

[0116] Dialkyl maleate compounds (e.g., dialkyl maleates), including diethyl maleate (DEM), dibutyl maleate (DBM) and bis(2-ethylhexyl) maleate (i.e., dioctyl maleate, DOM), were obtained from numerous commercial sources, including DSM Fine Chemicals in Austria and Polynt S.p.A. in Italy.

[0117] Arylate compounds including 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA) and methyl acrylate were obtained from numerous commercial sources, including BASF SE in Germany, ECEM in the Netherlands and DOW Benelux in the Netherlands.

[0118] Solvent / diluent 1 was butyl acetate (i.e., n-butyl acetate) and was obtained from BASF SE in Germany, Celanese in the United States or Oxea GmbH in Germany.

[0119] Solvent / diluent 2 was propylene glycol monomethyl ether acetate (PGMEA) and was obtained from BASF SE in Germany, Dow Chemical Company in the United States or Lyondell Basell in Germany.

[0120] The solvent / diluent 3 is butylene glycol diacetate (BGA), which can be purchased from BASF SE or Ineos Oxide in Germany.

[0121] The solvent / diluent 4 is an aromatic fluid (such as Aromatic 100 Fluid), which can be purchased from numerous sources.

[0122] The UV additives include benzotriazole UV absorbers (such as Tinuvin 384-2) and UV stabilizers (such as Tinuvin 292), which can be purchased from BASF SE.

[0123] The S / A additives include silicone and acrylic type additives, which can be purchased from Byk Chemie GmbH in Germany (such as Byk 315, Byk 361), and Baysilone OL17 from OMG Borchers.

[0124] The curing agent 1 is an aliphatic polyisocyanate (HDI trimer) (such as Desmodur N 3300A).

[0125] The adhesion promoter 1 is a silane composition (such as Silquest A187).

[0126] The moisture scavenger 1 is p-toluenesulfonyl isocyanate (pTSI).

[0127] The catalyst 1 is dibutyltin dilaurate (DBTDL) in butyl acetate (10% by weight).

[0128] It should be understood that the various materials described above and used in the following examples are identified by technical names and / or trade names and illustrate the components of the embodiments described herein. For example, 1,6-hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA) represent specific choices suitable for use as the polyfunctional acrylate component (A); diethyl maleate (DEM), dibutyl maleate (DBM), and bis(2-ethylhexyl) maleate (i.e., dioctyl maleate, DOM) represent specific choices suitable for use as the dialkyl maleate (B); isophorone diamine (IPDA) represents a specific choice suitable for use as the polyfunctional primary amino compound (C); and isophorone diisocyanate (IPDI) represents a specific choice suitable for use as the isocyanate chain extender (II). It should also be understood that in contrast to component (A), the comparative compound includes methyl acrylate (MA) as a monofunctional acrylate component.

[0129] Preparation example

[0130] In the following Examples 1-5, various aspartic acid compositions were prepared, and other parameters and details are further listed in Table 1 below.

[0131] Example 1A: Bis-aspartate of isophorone diamine, bis(2-ethylhexyl) maleate and trimethylolpropane triacrylate (Aspartate Composition 1)

[0132] In a reactor equipped with a propeller stirrer, thermocouple, condenser and feed funnel, 349.06 g of isophorone diamine (IPDA), 5.03 g of 2,6-di-tert-butyl-4-methylphenol and 26.49 g of n-butyl acetate were loaded under a nitrogen blanket. The mixture was heated to 35 °C. 349.51 g of bis(2-ethylhexyl) maleate (DOM) was added to the reactor contents while maintaining the temperature below 75 °C. After 5 minutes, the temperature of the reaction contents was set to 50 °C and maintained for 1.5 hours. In the second step, 349.51 g of bis(2-ethylhexyl) maleate (DOM) was added to the reactor contents while maintaining the temperature below 75 °C. After 5 minutes, the temperature of the reaction contents was set to 60 °C and maintained for 1.5 hours. In the third step, 349.51 g of bis(2-ethylhexyl) maleate (DOM) and 101.39 g of trimethylolpropane triacrylate (TMPTA) were added to the reactor contents while maintaining the temperature below 75 °C. After a rinse step with 69.51 g of n-butyl acetate, the reactor temperature was maintained at 70 °C for 30 hours.

[0133] Example 1B: Reaction product of Example 1A chain-extended with isophorone diisocyanate (Resin 1)

[0134] 780.00 g of the reaction product of Example 1A (Aspartate Composition 1) was loaded into a reactor equipped with a propeller stirrer, thermocouple, condenser and feed funnel. The reaction contents were heated to 50 °C, followed by a dilution step with 160.00 g of n-butyl acetate. Then, 77.23 g of isophorone diisocyanate (IPDI) was slowly added to the reactor while maintaining the temperature of the reaction contents below 60 °C. After a rinse step with 19.16 g of n-butyl acetate, the reactor contents were maintained at 70 °C for 2 hours. In the dilution step, 117.27 g of n-butyl acetate was added to the reactor. The product resin, Resin 1, will be mentioned and used in the following other examples.

[0135] Example 2A: Bis-aspartate of isophorone diamine, bis(2-ethylhexyl) maleate and 1,6-hexanediol diacrylate (Aspartic Acid Composition 2)

[0136] In a reactor equipped with a propeller stirrer, a thermocouple, a condenser, and a feed funnel, 345.66 g of isophorone diamine (IPDA), 5.03 g of 2,6-di-tert-butyl-4-methylphenol, and 26.49 g of n-butyl acetate were loaded under a nitrogen blanket. The mixture was heated to 35 °C. 346.10 g of bis(2-ethylhexyl) maleate (DOM) was added to the reactor contents while maintaining the temperature below 75 °C. After 5 minutes, the temperature of the reaction contents was set to 50 °C and maintained for 1.5 hours. In the second step, 346.10 g of bis(2-ethylhexyl) maleate (DOM) was added to the reactor contents while maintaining the temperature below 75 °C. After 5 minutes, the temperature of the reaction contents was set to 60 °C and maintained for 1.5 hours. In the third step, 346.10 g of bis(2-ethylhexyl) maleate (DOM) and 115.00 g of 1,6-hexanediol diacrylate (HDDA) were added to the reactor contents while maintaining the temperature below 75 °C. After a rinse step with 69.51 g of n-butyl acetate, the reactor temperature was maintained at 70 °C for 30 hours.

[0137] Example 2B: Reaction product of Example 2A (resin 2) extended with isophorone diisocyanate

[0138] In a reactor equipped with a propeller stirrer, a thermocouple, a condenser, and a feed funnel, 762.00 g of the reaction product of Example 2A (aspartate ester composition 2) was loaded and heated to 50 °C in the reactor, followed by a dilution step with 156.31 g of n-butyl acetate. Then, 74.72 g of isophorone diisocyanate (IPDI) was slowly added to the reactor while maintaining the reaction temperature below 60 °C. Next, 18.53 g of n-butyl acetate was added, and the reactor contents were maintained at 70 °C for 2 hours. In the dilution step, 114.47 g of n-butyl acetate was added to the reactor. The product resin, i.e., resin 2, will be mentioned and used in other examples below.

[0139] Example 3: Bis(aspartate ester) of isophorone diamine, bis(2-ethylhexyl) maleate, and 1,6-hexanediol diacrylate extended with isophorone diisocyanate

[0140] In a reactor equipped with a propeller stirrer, a thermocouple, a condenser, and a feed funnel, 278.92 g of isophorone diamine (IPDA), 3.32 g of 2,6-di-tert-butyl-4-methylphenol, and 17.49 g of n-butyl acetate were charged under a nitrogen blanket. The mixture was heated to 35 °C. 224.68 g of dibutyl maleate (DBM) was added to the reactor contents while maintaining the temperature below 75 °C. After 5 minutes, the temperature of the reaction contents was set to 50 °C and maintained for 1.5 hours. In the second step, 224.68 g of dibutyl maleate (DBM) was added to the reactor contents while maintaining the temperature below 75 °C. After 5 minutes, the temperature of the reaction contents was set to 60 °C and maintained for 1.5 hours. In the third step, 224.68 g of dibutyl maleate (DBM) and 37.12 g of 1,6-hexanediol diacrylate (HDDA) were added to the reactor contents while maintaining the temperature below 75 °C. After a flushing step with 45.92 g of n-butyl acetate, the reactor temperature was maintained at 70 °C for 30 hours, then cooled to 50 °C and the reaction contents were diluted with 216.78 g of n-butyl acetate. Then, 126.59 g of isophorone diisocyanate (IPDI) was slowly added to the reactor while maintaining the reaction temperature below 60 °C. Next, 35.70 g of n-butyl acetate was added and the reactor temperature was maintained at 70 °C for 2 hours. In the dilution step, 164.11 g of n-butyl acetate was added to the reactor. The product resin, i.e., Resin 3, will be mentioned and used in other examples below.

[0141] Comparative Example 1A: Bis-aspartate of isophorone diamine, bis(2-ethylhexyl) maleate, and methyl acrylate (Aspartate Composition 4)

[0142] In a reactor equipped with a propeller agitator, a thermocouple, a condenser, and a feed funnel, 352.12 g of isophorone diamine (IPDA), 5.03 g of 2,6-di-tert-butyl-4-methylphenol, and 26.49 g of n-butyl acetate were loaded under a nitrogen blanket. The mixture was heated to 35 °C. 352.57 g of bis(2-ethylhexyl) maleate (DOM) was added to the reactor contents while maintaining the temperature below 75 °C. After 5 minutes, the temperature of the reaction contents was set to 50 °C and maintained for 1.5 hours. In the second step, 352.57 g of bis(2-ethylhexyl) maleate (DOM) was added to the reactor contents while maintaining the temperature below 75 °C. After 5 minutes, the temperature of the reaction contents was set to 60 °C and maintained for 1.5 hours. In the third step, 352.57 g of bis(2-ethylhexyl) maleate (DOM) and 89.14 g of methyl acrylate (MA) were added to the reactor contents while maintaining the temperature below 75 °C. After a rinsing step with 69.51 g of n-butyl acetate, the reactor temperature was maintained at 70 °C for 30 hours.

[0143] Comparative Example 1B: Reaction product of Comparative Example 1A chain-extended with isophorone diisocyanate (Resin 4)

[0144] In a reactor equipped with a propeller agitator, a thermocouple, a condenser, and a feed funnel, 777.00 g of the reaction product of Comparative Example 1A (aspartate composition 4) was loaded. The reaction contents were heated to 50 °C, followed by a dilution step with 159.39 g of n-butyl acetate. Then, 77.61 g of isophorone diisocyanate (IPDI) was slowly added to the reactor while maintaining the temperature of the reaction contents below 60 °C. After a rinsing step with 19.27 g of n-butyl acetate, the temperature of the reactor contents was maintained at 70 °C for 2 hours. In the dilution step, 116.91 g of n-butyl acetate was added to the reactor. The product resin, i.e., Resin 4, will be mentioned and used in other examples below.

[0145] Comparative Example 2A: Bis-aspartate of isophorone diamine and diethyl maleate (aspartate composition 5)

[0146] In a reactor equipped with a propeller agitator, a thermometer, a condenser, and a feed system, 204.91 g of isophorone diamine (IPDA) and 34.44 g of n-butyl acetate were loaded. The mixture was heated to 30 °C. 414.99 g of diethyl maleate (DEM) and 10.33 g of n-butyl acetate were added to the reactor over about 4 hours, followed by a rinsing step with 10.33 g of n-butyl acetate. The reactor temperature was maintained at a maximum of 50 °C during the addition and for 46 hours after the addition was complete.

[0147] Comparative Example 2B: Reaction product of Comparative Example 2A chain-extended with isophorone diisocyanate (Resin 5)

[0148] The reaction product of Comparative Example 2A (aspartate ester composition 5), weighing 688.78 g, was diluted with 151.62 g of n-butyl acetate and heated to 40 °C in a reactor. 80.82 g of isophorone diisocyanate (IPDI) mixed with 16.89 g of n-butyl acetate was added to the reactor over 1 hour while maintaining the reactor at a temperature not exceeding 50 °C. After a rinse step with 16.89 g of n-butyl acetate, the reactor contents were maintained at 50 °C until no NCO functional groups were detectable by infrared spectroscopy. 45 g of n-butyl acetate was added to the reactor during the dilution step.

[0149] Additional information regarding the above aspartate composition 5 and Resin 5 is reported in U.S. Patent No. 10,519,336, the content of which is incorporated herein by reference.

[0150] The product resin of Comparative Example 2B, i.e., Resin 5, is mentioned and used in the other examples below.

[0151] Table 1. Asymmetric aspartic resins of Examples 1-3 and Comparative Examples 1-2

[0152]

[0153] Formulation Example 1: General Procedure

[0154] In one exemplary embodiment, a varnish composition is formed by mixing Part A and Part B together to form a homogeneous solution. Part A contains one or two polyaspartate ester resins, solvents, UV absorbers and stabilizers, flow and leveling additives. Part B contains polyisocyanates, silane additives, moisture scavengers, catalysts and solvents. Parts A and B of the curable coatings 1-16 and comparative curable coatings 1-6 in different spray forms are prepared according to the above general method, as shown in Tables 2-5 below.

[0155] Table 2. Coating compositions using Resins 1 and 5

[0156]

[0157] Table 3. Coating compositions using Resins 2 and 5

[0158]

[0159] Table 4. Comparative coating compositions using Comparative Resin 4 and 5

[0160]

[0161] Table 5. Coating compositions using Resins 1 and 3

[0162]

[0163] The comparative curable coating (CCE1) shown in the table above contains only Resin 5 as a curable resin and is used to demonstrate the endpoints of the weight percentage ranges for Resin 5 based on the solids of each resin in the resin mixtures of Resin 1 / Resin 5, Resin 2 / Resin 5, and Resin 4 / Resin 5.

[0164] Coating Examples and Performance Analysis

[0165] Electrophoretic coating panels (4 inches x 12 inches) were used to prepare coatings comprising a primer layer, a basecoat layer, and a clearcoat layer using a clearcoat composition for appearance and performance testing. The same clearcoat was also sprayed on a glass plate to determine the Martens hardness. Specifically, coating compositions 1-17 were prepared as shown in the following table: First, the binder part A and the activator part B of the curable composition (CC) 1-16 and the comparative curable composition (CCE) 1-6 were mixed together to form a uniform solution. The uniform solution was then sprayed onto the electrophoretic coating panel with a spray gun, wherein each electrophoretic coating panel had a primer layer adjacent to the electrophoretic coating and a basecoat layer (e.g., a water-based basecoat layer) disposed on the primer layer. Spraying was performed using a double coating process with a flash-off time of about 5 minutes between coatings. After spraying, the clearcoat layer was air-dried under ambient conditions. The coated panel was dried overnight and its appearance was measured. The Martens hardness was measured after air-drying for 2 hours, 24 hours, and 7 days. The coated panels were then aged at room temperature for at least five days and in a low temperature oven at 50°C for 64 hours to accelerate the aging process. After aging, the coated panels were tested for scratch resistance as further described below. The thickness of the substantially fully cured varnish layer was about 50 µm.

[0166] The coated panels were tested for scratch resistance using the Amtec test in accordance with DIN EN ISO 20566, using an Amtec laboratory car wash machine from Amtec Kistler GmbH, Prittriching, Germany, which simulates a car wash. According to the Amtec test, the coated panels were scratched with a plastic brush in the presence of the slurry. The panels with the scratched coating were then subjected to a 2-hour baking process at approximately 60°C for recovery. The gloss values of the coating before the Amtec test and after scratch recovery (reflow) were determined. The gloss retention after reflow was calculated by dividing the gloss after scratch reflow by the gloss before the Amtec test as an indicator of how much gloss can be retained. The ideal gloss retention level of the scratched coating after reflow depends on the original equipment manufacturer (OEM), but in general, a gloss retention of 75% or more after reflow is very ideal.

[0167] The results of the performance and appearance tests are listed in Table 6-9 below.

[0168] Table 6. Performance analysis of Coating Compositions 1-6

[0169]

[0170] Table 7. Performance analysis of Coating Compositions 7-11

[0171]

[0172] Table 8. Performance analysis of Coating Compositions 12-17

[0173]

[0174] Table 9. Performance analysis of Coating Compositions 18-23

[0175]

[0176] In Table 6-9, the actual observed values (indicated by an asterisk "*") of the single resin compositions are used as endpoints for generating the linear property predictions of the multi-resin compositions, as described in further detail below.

[0177] As shown in Table 6-9 above, the polyaspartate ester compositions of the embodiments of the present invention employing the asymmetric polyaspartate ester resins described herein exhibit properties superior to those of conventional compositions employing conventional aspartate ester resins. Specifically, as can be seen from Exemplary Coating Compositions 1-11 and 18-23, compared to the benchmarks set by Comparative Coatings 12-17 prepared from Comparative Curable Compositions CCE1-CCE6 comprising Comparative Resin 4 and / or 5, the asymmetric polyaspartate ester resins 1-3 used to prepare Curable Compositions CC1-CC16 significantly improve the Amtec scratch resistance while maintaining the appearance. These excellent results apply to both the single-resin and multi-resin compositions (i.e., multi-resin compositions comprising at least one of the asymmetric polyaspartate ester resins described herein) of the embodiments of the present invention.

[0178] Also as shown in Table 6-9 above, in the mixture of Resin 1 and Resin 5, the gloss retention rate after Amtec reflux is higher than that predicted by the linear response (cumulative effect) of the properties of Resin 1 and Resin 5 based on the endpoints (i.e., 0% and 100% resin content of the given resin in the mixture). The synergy factor is calculated by the relative increase in the gloss retention rate after reflux relative to the value predicted by the linear relationship:

[0179] Synergy factor = (GRAR 测试 - GRAR 预测 ) / GRAR 预测 ,

[0180] where GRAR 测试 is the gloss retention after reflux obtained from Amtec testing. GRAR 预测 is the gloss retention after reflux predicted or expected by a linear function established from the gloss retention values after reflux at two endpoints (i.e., 0% and 100% resin content of a given resin in the mixture).

[0181] When the synergistic factor is higher than 3% (which is the Amtec test error for the same test (testing multiple panels simultaneously)), a synergistic effect is considered to exist. In this set of mixtures, there is a strong synergistic effect because the synergistic factor is as high as 28%. Similarly, in the mixture of Resin 2 and Resin 5 shown in Table 7 above, the gloss retention after reflux is higher than the value predicted by the linear response based on the properties of Resin 2 and Resin 5. The synergistic factor is as high as 22%. In the mixture of Resin 3 and Resin 1 shown in Table 9 above, the gloss retention after Amtec scratching reflux is higher than the value predicted by the linear response based on the properties of Resin 3 and Resin 1. The synergistic factor is as high as 11%. In contrast, as shown in Table 8 above, the coatings 12 - 17 prepared from the comparative curable compositions 1 - 6 did not exhibit consistent synergistic properties. Instead, as shown by the mixture of comparative resins 4 / 5 in coatings 13 - 16, when the comparative resins are used together in amounts similar to those in the above examples, a decrease in their performance compared to the single resin endpoints is typically observed.

[0182] The linear prediction results and the observed Amtec performance values for these examples are as Figures 1-3 shown, where Figure 1 a graph of the Amtec test results for the Resin 1 / Resin 5 and Resin 2 / Resin 5 mixtures (i.e., from Tables 6 - 7) is provided, Figure 2 a graph of the Amtec test results for the Resin 3 / Resin 1 mixture (i.e., from Table 9) is provided, Figure 3 a graph of the Amtec test results for the comparative Resin 4 / Resin 5 mixture (i.e., from Table 8) is provided. As shown, compared to the comparative mixtures of conventional aspartic resins, the asymmetric aspartic resins according to the embodiments of the present invention have improved synergistic properties. As Figure 3 shown, the comparative resin mixtures did not exhibit consistent improvements in scratch resistance in terms of synergistic properties.

[0183] Durability is evaluated by an accelerated exposure / weathering test using an irradiance - controlled xenon arc (i.e., xenon quartz / boron exposure test) according to SAE International Standard SAE J2527 (September 2017 Edition), which is a performance - based accelerated weathering standard that uses a xenon arc as a light source to simulate outdoor exposure to sunlight (e.g., ultraviolet light) in an accelerated manner, and this standard is incorporated herein by reference.

[0184] The gloss (20°) was measured before exposure (initial) and after exposure according to the foregoing procedure. The gloss retention rate was calculated by dividing the gloss value of the varnish after exposure by the initial gloss value. The initial gloss, gloss after exposure, and gloss retention rate of coating compositions 1-16 are listed in Tables 10-12 below.

[0185] Table 10. Durability and gloss retention of Coating Compositions 1-6

[0186]

[0187] Table 11. Durability and gloss retention of Coating Compositions 7-11

[0188]

[0189] Table 12. Durability and gloss retention of Coating Compositions 12-17

[0190]

[0191] As shown, the exemplary resin compositions of the embodiments of the present invention provide durable coatings with a gloss retention rate of at least 50% after 4000 hours, such as at least about 55%, or at least about 60%, or at least about 70%. In a specific embodiment, the gloss retention rate of the exemplary coating composition after 2000 hours is at least about 95%, or at least about 98%, or at least about 99%. In these or other embodiments, the gloss retention rate of the coating composition after 3000 hours is at least about 90%, or at least about 95%, or at least about 98%, or at least about 99%. In these or other embodiments, the gloss retention rate of the coating composition after 4000 hours is at least about 70%, or at least about 75%, or at least about 80%, or at least about 85%, or at least about 90%.

[0192] It should be noted that the endpoints of the ranges shown in the above table and Figures 1-3 the illustrations represent a single resin composition of the embodiments of the present invention. As demonstrated by the Amtec test results, the asymmetric aspartic resin exhibits better scratch resistance than conventional aspartic resins (represented by those shown at the endpoints of the resin 4 / resin 5 comparative mixture). As shown, the asymmetric aspartic resins of the embodiments of the present invention exhibit good or excellent performance in Amtec properties (i.e., higher than 70%, or higher than 75%). Although not quantified in the above embodiments, it is reported that coating compositions containing resins 1-3 (alone and various mixtures of the embodiments of the present invention) all maintain good spray viscosity, appearance, productivity, and pot life, thus providing improved performance without affecting other desirable performance characteristics.

[0193] Although at least one exemplary embodiment has been presented in the foregoing detailed description, it should be understood that a vast number of variations exist. It should also be understood that the at least one exemplary embodiment is presented only as an example and is not intended to limit the scope, applicability, or configuration in any way. On the contrary, the foregoing detailed description is intended to provide a convenient roadmap for those skilled in the art to implement the exemplary embodiments.

[0194] Aspects of embodiments of the present invention are provided below to further illustrate its various features.

[0195] Aspect 1. A polyaspartic acid composition comprising an asymmetric polyaspartic acid resin, which is a reaction product of (I) and (II):

[0196] (I) An asymmetric aspartic acid composition, which is a reaction product of a mixture of (A), (B), and (C):

[0197] (A) A polyfunctional acrylate component that on average contains at least two acrylate groups per molecule and is substantially free of monofunctional acrylate compounds,

[0198] (B) At least one dialkyl maleate, and

[0199] (C) A polyfunctional primary amino compound; and

[0200] (II) An isocyanate chain extender.

[0201] Aspect 2. The polyaspartic acid composition according to Aspect 1, wherein the polyfunctional acrylate component (A) includes: (i) difunctional acrylates; (ii) trifunctional acrylates; or (iii) both (i) and (ii).

[0202] Aspect 3. The polyaspartic acid composition according to Aspect 1 or 2, wherein the polyfunctional acrylate component (A) includes trifunctional acrylates selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylate triacrylate (TMPEOTA), and combinations thereof.

[0203] Aspect 4. The polyaspartic acid composition according to any one of Aspects 1 - 3, wherein the polyfunctional acrylate component (A) includes difunctional acrylates selected from linear alkyl diol diacrylates, or selected from 1,6 - hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof.

[0204] Aspect 5. The polyaspartic acid composition according to any one of Aspects 1-4, wherein the polyfunctional acrylate component (A) comprises: (i) trimethylolpropane triacrylate (TMPTA); (ii) 1,6-hexanediol diacrylate (HDDA); or (iii) both (i) and (ii).

[0205] Aspect 6. The polyaspartic acid composition according to any one of Aspects 1-5, wherein the at least one dialkyl maleate (B) comprises a dialkyl maleate.

[0206] Aspect 7. The polyaspartic acid composition according to any one of Aspects 1-6, wherein the at least one dialkyl maleate (B) comprises: (i) dibutyl maleate (DBM); (ii) dioctyl maleate (DOM); or (iii) both (i) and (ii).

[0207] Aspect 8. The polyaspartic acid composition according to any one of Aspects 1-6, wherein the at least one dialkyl maleate (B) comprises at least two different dialkyl maleates.

[0208] Aspect 9. The polyaspartic acid composition according to Aspect 8, wherein the at least two different dialkyl maleates comprise diethyl maleate (DEM), dibutyl maleate (DBM), dioctyl maleate (DOM), or a combination thereof.

[0209] Aspect 10. The polyaspartic acid composition according to any one of Aspects 1-9, wherein the polyfunctional primary amino compound (C) is an organic diamine having two primary amine groups.

[0210] Aspect 11. The polyaspartic acid composition according to any one of Aspects 1-10, wherein the polyfunctional primary amino compound (C) comprises isophorone diamine (IPDA).

[0211] Aspect 12. The polyaspartic acid composition according to any one of Aspects 1-11, wherein the isocyanate chain extender (II) comprises an alkyl diisocyanate, an aryl diisocyanate, an alkylaryl diisocyanate, or a combination thereof.

[0212] Aspect 13. The polyaspartic acid composition according to any one of Aspects 1-12, wherein the isocyanate chain extender (II) is selected from isophorone diisocyanate (IPDI), 1,5-pentane diisocyanate (PDI), 4,4'-diisocyanatodicyclohexylmethane (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI), and combinations thereof.

[0213] Aspect 14. The polyaspartic acid composition according to any one of Aspects 1-13, wherein the isocyanate chain extender (II) comprises isophorone diisocyanate (IPDI), and wherein in the mixture of (A)-(C) of the reaction product from which the asymmetric aspartic acid composition (I) is obtained:

[0214] (i) The polyfunctional acrylate component (A) comprises trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), 1,6-hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), or a combination thereof;

[0215] (ii) The at least one dialkyl maleate (B) comprises dibutyl maleate (DBM), dioctyl maleate (DOM), or a combination thereof;

[0216] (iii) The polyfunctional primary amino compound (C) comprises isophorone diamine (IPDA); or

[0217] (iv) Any combination of (i)-(iii).

[0218] Aspect 15. The polyaspartic acid composition according to any one of Aspects 1-14, wherein the mixture of (A)-(C) of the reaction product from which the asymmetric aspartic acid composition (I) is obtained comprises:

[0219] (i) The polyfunctional acrylate component (A) and the at least one dialkyl maleate (B) present in a stoichiometric ratio of (A):(B) of about 5:95 to about 50:50, or (A):(B) of about 5:95 to about 30:70, or about 10:90 to about 30:70, or about 10:90 to about 25:75;

[0220] (ii) The polyfunctional primary amino compound (C) present in a stoichiometric ratio of (C):(A)(B) of about 0.95:1 to about 1.5:1, or (C):(A)(B) of about 0.95:1 to about 1.4:1, or about 0.98:1 to about 1.3:1, or about 0.99:1 to about 1.25:1, or about 1:1 to about 1.2:1; or

[0221] (iii) Both (i) and (ii).

[0222] Aspect 16. The polyaspartic acid composition according to any one of Aspects 13-15, wherein the asymmetric polyaspartic acid resin:

[0223] (i) Formed by chain-extending an asymmetric aspartic acid composition (I) with an isocyanate chain extender (II) at a stoichiometric ratio of (II):(C) of about 0.05:1 to about 0.9:1, or at a stoichiometric ratio of (II):(C) of about 0.1:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1, based on the number of functional equivalent numbers of the polyfunctional primary amino compound (C) in the mixture of (A)-(C) of the reaction product from which the asymmetric aspartic acid composition (I) is obtained;

[0224] (ii) Formed by chain-extending an asymmetric aspartic acid composition (I) with an isocyanate chain extender (II) at a stoichiometric ratio of (NCO):(NH) of about 0.05:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1, based on the number of free isocyanate groups (NCO) in the isocyanate chain extender (II) and the total number of free amino groups (NH) in the asymmetric aspartic acid composition (I);

[0225] (iii) Substantially free of isocyanate groups;

[0226] (iv) Having an amine value of about 60 to about 80; or

[0227] (v) Any combination of (i)-(iv).

[0228] Aspect 17. A polyaspartic acid composition, comprising:

[0229] (1) A first asymmetric polyaspartic acid resin, which is a reaction product of (I-1) and (II-1):

[0230] (I-1) An asymmetric aspartic acid composition, which is a reaction product of a mixture of (A1), (B1) and (C1):

[0231] (A1) A polyfunctional acrylate component, which on average contains at least two acrylate groups per molecule,

[0232] (B1) At least one dialkyl maleate, and

[0233] (C1) A polyfunctional primary amino compound, and

[0234] (II-1) An isocyanate chain extender; and

[0235] (2) A second asymmetric polyaspartic acid resin, which is different from the first asymmetric polyaspartic acid resin (1), and is a reaction product of (I-2) and (II-2):

[0236] (I-2) Asymmetric aspartic acid composition, comprising the reaction product of a mixture of (A2), (B2), and (C2):

[0237] (A2) A polyfunctional acrylate component, which on average contains at least two acrylate groups per molecule,

[0238] (B2) At least one dialkyl maleate, and

[0239] (C2) A polyfunctional primary amino compound, and

[0240] (II-2) An isocyanate chain extender.

[0241] Aspect 18. The polyaspartic acid composition according to aspect 17, wherein:

[0242] (i) The polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) each independently comprise bifunctional acrylates, trifunctional acrylates, or a combination thereof;

[0243] (ii) The at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) each independently are selected from dialkyl maleates;

[0244] (iii) The polyfunctional primary amino compound (C1) and the polyfunctional primary amino compound (C2) each independently are selected from organic diamines having two primary amine groups;

[0245] (iv) The isocyanate chain extender (II-1) and the isocyanate chain extender (II-2) each independently are selected from alkyl diisocyanates, aryl diisocyanates, alkaryl diisocyanates, and combinations thereof; or

[0246] (v) Any combination of (i)-(iv).

[0247] Aspect 19. The polyaspartic acid composition according to aspect 17 or 18, wherein:

[0248] (i) The polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) each independently are selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), 1,6-hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof;

[0249] (ii) The at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) each independently are selected from di(C1-C 10 ) alkyl maleates;

[0250] (iii) At least one of the polyfunctional primary amino compound (C1) and the polyfunctional primary amino compound (C2) comprises isophorone diamine (IPDA);

[0251] (iv) The isocyanate chain extender (II-1) and the isocyanate chain extender (II-2) are each independently selected from isophorone diisocyanate (IPDI), 1,5-pentane diisocyanate (PDI), 4,4'-diisocyanatodicyclohexylmethane (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI), and combinations thereof; or

[0252] (v) Any combination of (i)-(iv).

[0253] Aspect 20. The polyaspartic acid composition according to any one of Aspects 17-19, wherein:

[0254] (i) One of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) comprises trifunctional acrylates selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), and combinations thereof, and the other of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) comprises linear alkyl glycol diacrylates, or difunctional acrylates selected from 1,6-hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof;

[0255] (ii) At least one of the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) comprises dibutyl maleate (DBM), dioctyl maleate (DOM), diethyl maleate (DEM), or combinations thereof, provided that at least one of (B1) and (B2) does not contain diethyl maleate (DEM);

[0256] (iii) The polyfunctional primary amino compound (C1) and the polyfunctional primary amino compound (C2) each independently comprise isophorone diamine (IPDA);

[0257] (iv) The isocyanate chain extender (II-1) and the isocyanate chain extender (II-2) each independently comprise isophorone diisocyanate (IPDI); or

[0258] (v) Any combination of (i)-(v).

[0259] Aspect 21. The polyaspartic acid composition according to any one of Aspects 17-20, wherein:

[0260] (i) One of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) is trimethylolpropane triacrylate (TMPTA), and the other of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) is 1,6 - hexanediol diacrylate (HDDA);

[0261] (ii) Each of the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) includes dibutyl maleate (DBM), dioctyl maleate (DOM) or a combination thereof; wherein each of the polyfunctional primary amino compound (C1) and the polyfunctional primary amino compound (C2) is isophorone diamine (IPDA); and

[0262] (iii) Each of the isocyanate chain extender (II - 1) and the isocyanate chain extender (II - 2) is isophorone diisocyanate (IPDI).

[0263] Aspect 22. The polyaspartic acid composition according to any one of Aspects 17 - 21, wherein:

[0264] (i) The mixture of (A1)-(C1) of the reaction product from which the asymmetric aspartic acid composition (I - 1) is obtained contains the polyfunctional acrylate component (A1) and the at least one dialkyl maleate (B1) present in a stoichiometric ratio of (A1):(B1) of about 5:95 to about 50:50, or (A1):(B1) of about 5:95 to about 30:70, or about 10:90 to about 30:70, or about 10:90 to about 25:75, and the polyfunctional primary amino compound (C1) present in a stoichiometric ratio of (C1):(A1)(B1) of about 0.1:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1;

[0265] (ii) The mixture of (A2)-(C2) of the reaction product from which the asymmetric aspartic acid composition (I - 2) is obtained contains the polyfunctional acrylate component (A2) and the at least one dialkyl maleate (B2) present in a stoichiometric ratio of (A2):(B2) of about 5:95 to about 50:50, or (A2):(B2) of about 5:95 to about 30:70, or about 10:90 to about 30:70, or about 10:90 to about 25:75, and the polyfunctional primary amino compound (C2) present in a stoichiometric ratio of (C2):(A2)(B2) of about 0.1:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1; or

[0266] (iii) Both (i) and (ii).

[0267] Aspect 23. A coating composition comprising a curable polyaspartic acid component, wherein the curable polyaspartic acid component comprises:

[0268] The polyaspartic acid composition according to any one of Aspects 1-16; and / or

[0269] The polyaspartic acid composition according to any one of Aspects 17-22.

[0270] Aspect 24. The coating composition according to Aspect 23, further comprising an isocyanate curing agent.

[0271] Aspect 25. The coating composition according to Aspect 24, wherein the isocyanate curing agent comprises a polyisocyanate selected from the group consisting of oligomeric forms of isophorone diisocyanate (IPDI), 1,5-pentane diisocyanate (PDI), methylene diphenyl diisocyanate (MDI), 4,4'-methylenebis(cyclohexyl isocyanate) (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI), and polyol-modified derivatives thereof and combinations thereof.

[0272] Aspect 26. The coating composition according to any one of Aspects 23-25, further comprising an additive component, wherein the additive component comprises a curing catalyst, a UV absorber and / or a light stabilizer, a rheology modifier, an adhesion promoter, a dehumidifying agent, a wetting agent, a chain extender, a binder, a leveling and / or flow promoter, or a combination thereof.

[0273] Aspect 27. The coating composition according to any one of Aspects 23-26, wherein the curable polyaspartic acid ester component comprises a polyaspartic acid ester composition, and wherein:

[0274] (i) A first asymmetric polyaspartic acid resin (1) and a second asymmetric polyaspartic acid resin (2) are present in the curable polyaspartic acid component in a ratio of (1):(2) of about 95:5 to about 5:95 (weight / weight), or in a ratio of (1):(2) of about 90:10 to about 10:90;

[0275] (ii) The coating composition comprises a curable polyaspartic acid ester component and a polyisocyanate curing agent in a stoichiometric ratio of NCO:NH of about 1.1 to about 1.5, based on the total number of free isocyanate groups (NCO) in the polyisocyanate curing agent and the total number of free amino groups (NH) in the polyaspartic acid ester composition; or

[0276] (iii) Both (i) and (ii).

[0277] Aspect 28. The coating composition according to any one of aspects 23 - 27, which is in the form of a two - part curable composition and comprises:

[0278] A first part, which comprises a polyaspartic acid component, and

[0279] A second part, which comprises a curing agent.

[0280] Aspect 29. The coating composition according to aspect 28, wherein in the two - component curable composition:

[0281] (i) The first part further comprises a UV absorber and / or a light stabilizer, a rheology modifier, a wetting agent, a leveling and / or flow promoter, or a combination thereof;

[0282] (ii) The second part further comprises a curing catalyst, an adhesion promoter, a dehumidifying agent, a chain extender, a binder, or a combination thereof; or

[0283] (iii) Both (i) and (ii).

[0284] Aspect 30. The coating composition according to any one of aspects 23 - 29, wherein the curable polyaspartic ester component comprises the polyaspartic ester composition, wherein the coating composition further comprises a polyisocyanate curing agent, and wherein the coating prepared from the coating composition exhibits synergistic Amtec properties that are higher than the expected Amtec properties of a substantially similar theoretical coating calculated from the linear relationship of coating compositions each comprising only one polyaspartic ester resin in the polyaspartic ester composition.

[0285] Aspect 31. The coating composition according to aspect 30, wherein the synergistic Amtec properties exhibited by the coating are at least about 3% higher than the expected Amtec properties of a substantially similar theoretical coating.

[0286] Aspect 32. A method of preparing a coated article, which comprises:

[0287] a) Coating at least a portion of a substrate with a coating composition; and

[0288] b) Curing the coating composition to form a coating on the substrate, thereby preparing a coated article;

[0289] wherein the coating composition is the coating composition according to any one of aspects 23 - 31.

[0290] Aspect 33. A coated article prepared by the method according to aspect 32.

[0291] It should be understood that various changes can be made to the functions and arrangements of the elements described in the above exemplary embodiments without departing from the scope set forth in the appended claims. In addition, all combinations of the above components, compositions, method steps, formulation steps, etc. are expressly contemplated for use in the various non-limiting embodiments described herein, even if such combinations are not expressly described in the same or similar paragraphs.

[0292] For any Markush group relied upon when describing specific features or aspects of the various embodiments herein, different, special, and / or unexpected results can be obtained from each member of the corresponding Markush group independent of all other Markush members. Each member of the Markush group can be relied upon individually or in combination, and each member of the Markush group provides adequate support for specific embodiments within the scope of the appended claims.

[0293] In addition, any ranges and sub-ranges relied upon in describing various embodiments of the present invention, whether independently or jointly, fall within the scope of the appended claims and are understood to describe and cover all ranges, including integral and / or fractional values therein, even if such values are not explicitly recited herein. Those skilled in the art will readily recognize that the ranges and sub-ranges recited herein are sufficient to describe and implement the various embodiments of the present invention, and these ranges and sub-ranges can be further divided into relevant halves, thirds, quarters, fifths, etc. For example, for the range "from 0.1 to 0.9", this range can be further divided into the lower third (i.e., from 0.1 to 0.3), the middle third (i.e., from 0.4 to 0.6), and the upper third (i.e., from 0.7 to 0.9), and these thirds, either individually or jointly, are within the scope of the appended claims and can be relied upon either individually or jointly and provide sufficient support for specific embodiments within the scope of the appended claims. Further, for the terms defining or modifying a range, such as "at least", "greater than", "less than", "not exceeding", etc., it should be understood that such terms include sub-ranges and / or upper or lower limits. As another example, the range "at least 10" inherently includes sub-ranges from at least 10 to 35, from at least 10 to 25, from 25 to 35, etc., and each sub-range can be relied upon either individually or jointly and provide sufficient support for specific embodiments within the scope of the appended claims. Individual values within the disclosed ranges can be relied upon and provide sufficient support for specific embodiments within the scope of the appended claims. For example, the range "1 to 9" includes various individual integers such as 3, and individual values (or fractions) including a decimal point such as 4.1, and these values can be relied upon and provide sufficient support for specific embodiments within the scope of the appended claims. Finally, it should be understood that the term "about" in any specific numerical value and range described herein is used to specify a value within the standard error, as understood by those skilled in the art in the relevant conventional techniques and processes associated with formulating and / or applying blends and compositions such as those described herein for equivalent functions, potencies, end loads, etc. Thus, "about" can specify a value of ±10%, or 5%, or 1%, or 0.5%, or 0.1% of the recited value or range.

[0294] Although this disclosure is described with respect to its specific embodiments, it will be apparent to those skilled in the art that many other forms and modifications exist. The appended claims and this disclosure are to be construed generally to cover all such apparent forms and modifications, which are within the true scope of this disclosure.

Claims

1. A polyaspartic acid composition comprising an asymmetric polyaspartic acid resin, said asymmetric polyaspartic acid resin being the reaction product of (I) and (II): (I) An asymmetric aspartic acid composition, which is the reaction product of a mixture of (A), (B) and (C): (A) A polyfunctional acrylate component that on average contains at least two acrylate groups per molecule and is substantially free of monofunctional acrylate compounds, (B) At least one dialkyl maleate, and (C) A polyfunctional primary amino compound; and (II) An isocyanate chain extender.

2. The polyaspartic acid composition according to claim 1, wherein: (i) The polyfunctional acrylate component (A) includes bifunctional acrylates and / or trifunctional acrylates; (ii) The at least one dialkyl maleate (B) includes dialkyl maleates; (iii) The polyfunctional primary amino compound (C) is an organic diamine having two primary amine groups; or (iv) Any combination of (i)-(iii).

3. The polyaspartic acid composition according to claim 1 or 2, wherein: (i) The polyfunctional acrylate component (A) includes trifunctional acrylates selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA) and combinations thereof; (ii) The polyfunctional acrylate component (A) includes linear alkyl diacrylates or bifunctional acrylates selected from 1,6 - hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA) and combinations thereof; (iii) The at least one dialkyl maleate (B) includes at least two different dialkyl maleates, optionally each selected from diethyl maleate (DEM), dibutyl maleate (DBM), dioctyl maleate (DOM) and combinations thereof; (iv) The polyfunctional primary amino compound (C) includes isophorone diamine (IPDA); (v) The isocyanate chain extender (II) includes alkyl diisocyanates, aryl diisocyanates, alkaryl diisocyanates or combinations thereof; or (vi) Any combination of (i)-(v).

4. The polyaspartic acid composition according to claim 1 or 2, wherein: (i) The polyfunctional acrylate component (A) includes trimethylolpropane triacrylate (TMPTA) and / or 1,6 - hexanediol diacrylate (HDDA); (ii) The at least one dialkyl maleate (B) includes dibutyl maleate (DBM) and / or dioctyl maleate (DOM); (iii) The isocyanate chain extender (II) is selected from isophorone diisocyanate (IPDI), 1,5 - pentane diisocyanate (PDI), 4,4'-diisocyanatodicyclohexylmethane (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI) and combinations thereof; or (iv) Any combination of (i)-(iii).

5. The polyaspartic acid composition according to claim 1, wherein the isocyanate chain extender (II) comprises isophorone diisocyanate (IPDI), and wherein in the mixture of (A)-(C) of the reaction product from which the asymmetric aspartic acid composition (I) is obtained: (i) The polyfunctional acrylate component (A) comprises trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), 1,6 - hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), or a combination thereof; (ii) The at least one dialkyl maleate (B) comprises dibutyl maleate (DBM), dioctyl maleate (DOM), or a combination thereof; (iii) The polyfunctional primary amino compound (C) comprises isophorone diamine (IPDA); or (iv) Any combination of (i)-(iii).

6. The polyaspartic acid composition according to claim 1, wherein the mixture of (A)-(C) of the reaction product from which the asymmetric aspartic acid composition (I) is obtained comprises: (i) The polyfunctional acrylate component (A) and the at least one dialkyl maleate (B) present in a stoichiometric ratio of (A):(B) of about 5:95 to about 50:50, or (A):(B) of about 5:95 to about 30:70, or about 10:90 to about 30:70, or about 10:90 to about 25:75; (ii) The polyfunctional primary amino compound (C) present in a stoichiometric ratio of (C):(A)(B) of about 0.95:1 to about 1.5:1, or (C):(A)(B) of about 0.95:1 to about 1.4:1, or about 0.98:1 to about 1.3:1, or about 0.99:1 to about 1.25:1, or about 1:1 to about 1.2:1; or (iii) Both (i) and (ii).

7. The polyaspartic acid composition according to claim 5 or 6, wherein the asymmetric polyaspartic acid resin: (i) Is formed by chain - extending the asymmetric aspartic acid composition (I) with an isocyanate chain extender (II) in a stoichiometric ratio of (II):(C) of about 0.05:1 to about 0.9:1, or (II):(C) of about 0.1:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1, based on the number of functional equivalents of the polyfunctional primary amino compound (C) in the mixture of (A)-(C) of the reaction product from which the asymmetric aspartic acid composition (I) is obtained; (ii) formed by chain-extending the asymmetric aspartic acid composition (I) with an isocyanate chain extender (II) at a stoichiometric ratio of (NCO):(NH) of about 0.05:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1, based on the number of free isocyanate groups (NCO) in the isocyanate chain extender (II) and the total number of free amino groups (NH) in the asymmetric aspartic acid composition (I); (iii) substantially free of isocyanate groups; (iv) having an amine value of about 60 to about 80; or (v) any combination of (i)-(iv).

8. A polyaspartic acid composition comprising: (1) a first asymmetric polyaspartic acid resin, which is a reaction product of (I-1) and (II-1): (I-1) an asymmetric aspartic acid composition, which is a reaction product of a mixture of (A1), (B1) and (C1): (A1) a polyfunctional acrylate component, which on average contains at least two acrylate groups per molecule, (B1) at least one dialkyl maleate, and (C1) a polyfunctional primary amino compound, and (II-1) an isocyanate chain extender; and (2) a second asymmetric polyaspartic acid resin, which is different from the first asymmetric polyaspartic acid resin (1) and is a reaction product of (I-2) and (II-2): (I-2) an asymmetric aspartic acid composition, which is a reaction product of a mixture of (A2), (B2) and (C2): (A2) a polyfunctional acrylate component, which on average contains at least two acrylate groups per molecule, (B2) at least one dialkyl maleate, and (C2) a polyfunctional primary amino compound, and (II-2) an isocyanate chain extender.

9. The polyaspartic acid composition according to claim 8, wherein: (i) the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) each independently comprise bifunctional acrylates, trifunctional acrylates or a combination thereof; (ii) the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) each independently are selected from dialkyl maleates; (iii) the polyfunctional primary amino compound (C1) and the polyfunctional primary amino compound (C2) each independently are selected from organic diamines having two primary amine groups; (iv) the isocyanate chain extender (II-1) and the isocyanate chain extender (II-2) each independently are selected from alkyl diisocyanates, aryl diisocyanates, alkylaryl diisocyanates and combinations thereof; or (v) any combination of (i)-(iv).

10. The polyaspartic acid composition according to claim 8 or 9, wherein: (i) The polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) are each independently selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), 1,6 - hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof; (ii) The at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) are each independently selected from di(C1-C 10 ) alkyl maleates; (iii) At least one of the polyfunctional primary amino compound (C1) and the polyfunctional primary amino compound (C2) includes isophorone diamine (IPDA); (iv) The isocyanate chain extender (II - 1) and the isocyanate chain extender (II - 2) are each independently selected from isophorone diisocyanate (IPDI), 1,5 - pentane diisocyanate (PDI), 4,4'-diisocyanatodicyclohexylmethane (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI), and combinations thereof; or (v) Any combination of (i)-(iv).

11. The polyaspartic acid composition according to claim 8 or 9, wherein: (i) One of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) includes trifunctional acrylates selected from trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), and combinations thereof, and the other of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) includes linear alkyl glycol diacrylates or difunctional acrylates selected from 1,6 - hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), and combinations thereof; (ii) At least one of the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) includes dibutyl maleate (DBM), dioctyl maleate (DOM), diethyl maleate (DEM), or combinations thereof, provided that at least one of (B1) and (B2) does not contain diethyl maleate (DEM); (iii) The polyfunctional primary amino compound (C1) and the polyfunctional primary amino compound (C2) each independently include isophorone diamine (IPDA); (iv) The isocyanate chain extender (II - 1) and the isocyanate chain extender (II - 2) each independently include isophorone diisocyanate (IPDI); or (v) Any combination of (i)-(v).

12. The polyaspartic acid composition according to claim 8 or 9, wherein: (i) One of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) is trimethylolpropane triacrylate (TMPTA), and the other of the polyfunctional acrylate component (A1) and the polyfunctional acrylate component (A2) is 1,6 - hexanediol diacrylate (HDDA); (ii) Each of the at least one dialkyl maleate (B1) and the at least one dialkyl maleate (B2) comprises dibutyl maleate (DBM), dioctyl maleate (DOM) or a combination thereof; wherein each of the polyfunctional primary amino compound (C1) and the polyfunctional primary amino compound (C2) is isophorone diamine (IPDA); and (iii) Each of the isocyanate chain extender (II-1) and the isocyanate chain extender (II-2) is isophorone diisocyanate (IPDI).

13. The polyaspartic acid composition according to claim 8 or 9, wherein: (i) The mixture of (A1)-(C1) of the reaction product from which the asymmetric aspartic acid composition (I-1) is obtained comprises a polyfunctional acrylate component (A1) and the at least one dialkyl maleate (B1) present in a stoichiometric ratio of (A1):(B1) of about 5:95 to about 50:50, or (A1):(B1) of about 5:95 to about 30:70, or about 10:90 to about 30:70, or about 10:90 to about 25:75, and a polyfunctional primary amino compound (C1) present in a stoichiometric ratio of (C1):(A1)(B1) of about 0.95:1 to about 1.5:1, or about 0.1:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1; (ii) The mixture of (A2)-(C2) of the reaction product from which the asymmetric aspartic acid composition (I-2) is obtained comprises a polyfunctional acrylate component (A2) and the at least one dialkyl maleate (B2) present in a stoichiometric ratio of (A2):(B2) of about 5:95 to about 50:50, or (A2):(B2) of about 5:95 to about 30:70, or about 10:90 to about 30:70, or about 10:90 to about 25:75, and a polyfunctional primary amino compound (C2) present in a stoichiometric ratio of (C2):(A2)(B2) of about 0.1:1 to about 0.9:1, or about 0.1:1 to about 0.75:1, or about 0.1:1 to about 0.5:1, or about 0.2:1 to about 0.4:1; or (iii) Both (i) and (ii).

14. A coating composition comprising a curable polyaspartate component, wherein the curable polyaspartate component comprises: The polyaspartic acid composition according to claim 1 or 2 or the polyaspartic acid composition according to claim 8 or 9; And Optionally, further comprises: (i) An isocyanate curing agent, optionally selected from isophorone diisocyanate (IPDI) in oligomeric form, 1,5-pentane diisocyanate (PDI), methylene diphenyl diisocyanate (MDI), 4,4'-methylenebis(cyclohexyl isocyanate) (HMDI), hexamethylene diisocyanate (HDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI), and their polyol-modified derivatives, and combinations thereof; (ii) An additive component, optionally including a curing catalyst, a UV absorber and / or a light stabilizer, a rheology modifier, an adhesion promoter, a moisture dehumidifier, a wetting agent, a chain extender, a binder, a leveling and / or flow promoter, or combinations thereof; or (iii) Both (i) and (ii).

15. A coating composition comprising a curable polyaspartate component, the curable polyaspartate component comprising the polyaspartate composition according to claim 8 or 9, wherein: (i) The first asymmetric polyaspartic resin (1) and the second asymmetric polyaspartic resin (2) are present in the curable polyaspartate component in a ratio of (1):(2) of about 95:5 to about 5:95 (weight / weight), or in a ratio of (1):(2) of about 90:10 to about 10:90; (ii) The coating composition comprises a curable polyaspartate component and a polyisocyanate curing agent in a stoichiometric ratio of NCO:NH of about 1.1 to about 1.5, based on the total number of free isocyanate groups (NCO) in the polyisocyanate curing agent and the total number of free amino groups (NH) in the polyaspartate composition; or (iii) Both (i) and (ii).

16. A two-component curable composition comprising: A first part comprising a curable polyaspartate component, the curable polyaspartate component comprising the polyaspartate composition according to claim 1 or 2 or the polyaspartate composition according to claim 8 or 9; and A second part comprising a curing agent.

17. The coating composition according to claim 16, wherein in the two-component curable composition: (i) The first part further comprises a UV absorber and / or a light stabilizer, a rheology modifier, a wetting agent, a leveling and / or flow promoter, or combinations thereof; (ii) The second part further comprises a curing catalyst, an adhesion promoter, a moisture dehumidifier, a chain extender, a binder, or combinations thereof; or (iii) Both (i) and (ii).

18. The coating composition according to claim 16, wherein the curable polyaspartate component comprises the polyaspartate composition, wherein the coating composition further comprises a polyisocyanate curing agent, and wherein a coating prepared from the coating composition exhibits synergistic Amtec properties that are higher than the expected Amtec properties of a substantially similar theoretical coating calculated from the linear relationship of coating compositions each comprising only one of the polyaspartate resins in the polyaspartate composition, optionally wherein the synergistic Amtec properties exhibited by the coating are at least about 3% higher than the expected Amtec properties of the substantially similar theoretical coating.

19. A method of preparing a coated article, comprising: a) coating at least a portion of a substrate with the coating composition according to claim 14; and b) curing the coating composition to form a coating on the substrate, thereby preparing a coated article.

20. A coated article prepared by the method according to claim 19.

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