Coating with improved adhesion

Abstract

Disclosed herein are coating compositions having enhanced adhesion to a variety of different substrates. In some embodiments, the coating may include at least one copolymer derived from a mixture of monomers including tert-butyl acrylate.

Description

Technical Field

[0001] The present invention relates to architectural waterborne coatings having enhanced adhesion to a variety of different substrates, including chalk paints, uncoated wood, alkyd paints, aluminum, galvanized steel, and smooth steel. Background Art

[0002] Water-based emulsions containing polymer particles and pigments are often used as coating compositions. After the coating is applied, the water and any other solvents evaporate, pulling the polymer particles together into a network. The particles then coalesce to form a film or coating. The coating's adhesion to the substrate is related to the degree of particle aggregation and the interaction between the coating and the substrate surface. A coating composition that exhibits good adhesion to one type of surface, such as wood, may not necessarily exhibit good adhesion to other types of surfaces, such as metal or polymer surfaces.

[0003] Titanium dioxide is often used as a pigment in water-based coating compositions such as latex paints. Titanium dioxide provides whiteness and hiding power to the coating. Achieving the desired hiding and whiteness levels generally requires higher levels of titanium dioxide. At higher levels, the statistical distribution of titanium dioxide particles will result in (at least some) titanium dioxide particles being closer together, resulting in the distance between particles being less than the optimal distance for effective light scattering. Therefore, at higher titanium dioxide levels, overcrowding of titanium dioxide particles will reduce the efficiency of the particles in providing whiteness or hiding power. The whiteness of a particular coating can be characterized by the coating's tinting strength. Among other factors, tinting strength depends on the concentration of white pigment and how evenly and optimally it is distributed throughout the coating. While tinting strength can be increased by simply adding additional white pigment to the coating composition, this is impractical from an economic perspective. There remains a need for coating compositions that have generally good adhesion to a variety of substrates. There is also a need for coating compositions that provide a high level of whiteness at concentrations lower than those normally used for titanium dioxide pigments. Summary of the Invention

[0004] Disclosed herein are coating compositions comprising at least one copolymer derived from a monomer mixture comprising t-butyl acrylate. The coating compositions exhibit improved adhesion and tint strength relative to otherwise matched compositions not comprising the copolymer derived from t-butyl acrylate. Furthermore, the combination of t-butyl acrylate and a free radical chain transfer agent as found in the coating compositions described herein synergistically improves adhesion to a variety of substrates.

[0005] The details of one or more embodiments of the invention are set forth in the accompanying description below. Other features, objects, and advantages will be apparent from the description and from the claims. DETAILED DESCRIPTION

[0006] Before disclosing and describing the methods and systems of the present invention, it should be understood that these methods and systems are not limited to specific synthetic methods, specific components or specific compositions. It should also be understood that the terminology used herein is only for the purpose of describing specific embodiments and is not intended to be limiting.

[0007] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" one particular value, and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the from particular value and / or to the other particular value. Similarly, when a value is expressed as an approximation by use of the antecedent "about," it should be understood that the particular value forms another embodiment. It should also be understood that the endpoints of each range are significant both with respect to the other endpoint and independently of the other endpoint.

[0008] "Optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0009] Throughout the description and claims of this specification, the word "comprise" and variations of the word, such as "comprising" and "comprises," mean "including but not limited to," and are not intended to exclude, for example, other additives, components, integers, or steps. "Exemplary" means "an example of," and is not intended to convey an indication of a preferred or ideal embodiment. "Such as" is not used in a limiting sense, but is used for illustrative purposes.

[0010] Disclosed are components that can be used to perform the disclosed methods and systems. These and other components are disclosed herein, and it should be understood that when combinations, subsets, interactions, groups, etc. of these components are disclosed, although specific reference to each of the various individual and collective combinations and arrangements of these components may not be explicitly disclosed, each component is specifically contemplated and described herein for all methods and systems. This applies to all aspects of this application, including but not limited to the steps in the disclosed methods. Therefore, if there are various additional steps that can be performed, it should be understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods.

[0011] The coating compositions disclosed herein exhibit improved adhesion to a variety of substrates including powder coatings, uncoated wood, aluminum, smooth steel, galvanized steel, and alkyd paints. Adhesion testing was performed according to ASTM method D-3359-97.

[0012] The coating compositions disclosed herein include a plurality of particles. The particles can have a particle size of no greater than 5,000 nm, no greater than 4,000 nm, no greater than 3,000 nm, no greater than 2,000 nm, no greater than 1,000 nm, no greater than 750 nm, no greater than 500 nm, no greater than 400 nm, no greater than 300 nm, no greater than 200 nm, or no greater than 100 nm, as determined by light scattering and reported as a volume average particle size. In some embodiments, the particles have a particle size of 10 to 5,000 nm, 10 to 4,000 nm, 10 to 3,000 nm, 10 to 2,000 nm, 10 to 1,000 nm, 10 to 750 nm, 10 to 500 nm, 10 to 400 nm, 10 to 300 nm, 10 to 200 nm, 10 to 100 nm, 10 to 50 nm, 50 to 5,000 nm, 50 to 4,000 nm, A particle size of 50 to 3,000 nm, 50 to 2,000 nm, 50 to 1,000 nm, 50 to 750 nm, 50 to 500 nm, 50 to 400 nm, 50 to 300 nm, 50 to 200 nm, 50 to 100 nm, 100 to 1,000 nm, 100 to 750 nm, 100 to 500 nm, 100 to 400 nm, 100 to 300 nm, or 100 to 200 nm.

[0013] The particles can be prepared by polymerizing a monomer mixture, for example by emulsion polymerization, optionally in the presence of seeds. In some cases, the copolymer can be the product of a single-stage polymerization; such particles can be referred to as single-stage particles. In other embodiments, the particles can include at least two different copolymers (multistage copolymers), such as a first copolymer, a second copolymer, a third copolymer, etc. As used herein, reference to a "first copolymer" does not necessarily require the presence of any other copolymers. In some embodiments, the first copolymer, the second copolymer, etc. can be prepared in separate reaction vessels and then combined. In preferred embodiments, the second copolymer, the third copolymer, etc. are prepared by polymerizing a monomer mixture in the presence of the first copolymer.

[0014] The copolymer particles in the coating compositions disclosed herein can be characterized by a glass transition temperature (T g In some embodiments, the first copolymer may have a T of -10°C to 50°C, -10°C to 35°C, 0°C to 35°C, 5°C to 30°C, 5°C to 25°C, 10°C to 25°C, 12°C to 20°C, or 5°C to 15°C. g When present, the second copolymer may have a T greater than that of the first copolymer as determined by ASTM D 3418-15. g T g For example, the second copolymer may have a Tg A T of at least 10°C, at least 20°C, at least 30°C, at least 40°C, at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 100°C, or at least 110°C higher g In some embodiments, the second copolymer may have a T as determined by ASTM D 3418-15 that is greater than that of the first copolymer. g T g , which is 10°C to 110°C, 10°C to 100°C, 10°C to 90°C, 10°C to 80°C, 10°C to 70°C, 10°C to 60°C, 10°C to 50°C, 10°C to 40°C, 10°C to 30°C, 10°C to 20°C, 20°C to 110°C, 20°C to 70°C, or 30°C to 50°C. In some embodiments, the T of the second copolymer is 0.1°C to 1.0°C, 0.2°C to 1.0°C, 0.3°C to 1.0°C, 0.4°C to 1.0°C, 0.5°C to 1.0°C, 0.6°C to 1.0°C, 0.7°C to 1.0°C, 0.8°C to 1.0°C, 0.9 ...8°C to 1.0°C, 0.9°C to 1.0°C g In comparison, the T of the first copolymer as determined by ASTM D 3418-15 g Less than 300°C, less than 250°C, less than 200°C, less than 175°C, less than 150°C, less than 125°C, less than 100°C, less than 90°C, less than 80°C, less than 70°C or less than 60°C.

[0015] In some embodiments, the first copolymer can have a number average molecular weight of at least 8,000 Da, at least 10,000 Da, at least 15,000 Da, at least 25,000 Da, at least 50,000 Da, at least 100,000 Da, or at least 200,000 Da as determined by gel permeation chromatography. In some cases, the first copolymer can have a number average molecular weight of 8,000 to 500,000 Da, 10,000 to 500,000 Da, 25,000 to 500,000 Da, 50,000 to 500,000 Da, 100,000 to 500,000 Da, 250,000 to 500,000 Da, 8,000 to 250,000 Da, 10,000 to 250,000 Da, 25,000 to 250,000 Da, or 200,000 Da. In some embodiments, the present invention may have a number average molecular weight of between 1,000 to 2,000,000 Da, 50,000 to 250,000 Da, 100,000 to 250,000 Da, 8,000 to 100,000 Da, 10,000 to 100,000 Da, 25,000 to 100,000 Da, 50,000 to 100,000 Da, 8,000 to 500,000 Da, 8,000 to 2,000,000 Da, or 8,000 to 1,000,000 Da.

[0016] The first copolymer can be the product of the polymerization reaction of the first monomer mixture, and wherein the first monomer mixture includes the combination of tert-butyl acrylate monomer or (meth) tert-butyl acrylate monomer.By the gross weight of monomer in the first monomer mixture, tert-butyl (meth) acrylate monomer can be present in the first monomer mixture with the amount of 1 to 65 weight %, 2 to 65 weight %, 5 to 65 weight %, 5 to 40 weight %, 10 to 40 weight %, 5 to 35 weight %, 10 to 35 weight %, 5 to 30 weight %, 10 to 30 weight %, 5 to 25 weight %, 10 to 25 weight %, 15 to 50 weight %, 15 to 40 weight %, 15 to 35 weight %, 15 to 30 weight % or 20 to 30 weight %.In a preferred embodiment, tert-butyl (meth) acrylate monomer is tert-butyl acrylate.

[0017] The first monomer mixture may include n-butyl (meth)acrylate monomer. Based on the total weight of the monomers in the first monomer mixture, the n-butyl (meth)acrylate monomer can be present in the first monomer mixture in an amount of 1 to 55%, 5 to 55%, 10 to 55%, 20 to 55%, 30 to 55%, 40 to 55%, 50 to 55%, 5 to 50%, 10 to 50%, 20 to 50%, 30 to 50%, 40 to 50%, 40 to 55%, or 20 to 40%. In a preferred embodiment, the n-butyl (meth)acrylate monomer is n-butyl acrylate.

[0018] The first monomer mixture can include at least one ethylenically unsaturated acid. According to the total weight of the monomers in the first monomer mixture, the ethylenically unsaturated acid can be present in an amount of 0.1 to 5 weight %, 0.2 to 5 weight %, 0.5 to 5 weight %, 0.5 to 4 weight %, 0.5 to 3 weight %, 0.5 to 2 weight %, 0.5 to 1 weight % or 1 to 2 weight %. As used herein, the ethylenically unsaturated acid includes at least one polymerizable double bond or triple bond and at least one acidic functional group, including carboxylic acid, phosphorous acid and sulfuric acid. Ammonium, alkali metal ions, alkaline earth metal ions and other metal ion salts of these acids can also be used. The ethylenically unsaturated acid can be a monocarboxylic acid, a dicarboxylic acid, a phosphite or sulfuric acid. In some cases, the ethylenically unsaturated acid can have 3 to 15 acidic carbon atoms.

[0019] Suitable ethylenically unsaturated carboxylic acids and their derivatives are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, monoesters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, such as monomethyl maleate, and their metal ions and ammonium salts.

[0020] Suitable sulfuric acid monomers are vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. Suitable styrenesulfonic acid and its derivatives are styrene-4-sulfonic acid and styrene-3-sulfonic acid and their alkali metal ions or alkaline earth metal salts, such as sodium styrene-3-sulfonate and sodium styrene-4-sulfonate.

[0021] The example of phosphorus-containing monomers is vinylphosphonic acid and allylphosphonic acid. Also suitable are monoesters and diesters of phosphonic acid and phosphoric acid and hydroxyalkyl (meth) acrylate, especially monoesters. In addition, suitable monomers are diesters of phosphonic acid and phosphoric acid, which have been esterified once with hydroxyalkyl (meth) acrylate and have also been esterified once with different alcohols (such as alkanols). Suitable hydroxyalkyl (meth) acrylates for these esters are those designated as individual monomers below, more specifically 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Corresponding dihydrogen phosphate monomers include phosphoalkyl (meth) acrylate, such as 2-phosphoethyl (meth) acrylate, 2-phosphopropyl (meth) acrylate, 3-phosphopropyl (meth) acrylate, butyl (meth) acrylate, and 3-phospho-2-hydroxypropyl (meth) acrylate. Also suitable are esters of phosphonic and phosphoric acids with alkoxylated hydroxyalkyl (meth)acrylates, examples being ethylene oxide or propylene oxide condensates of (meth)acrylates, such as H2C═C(CH3)COO(CH2CH2O) n P(OH)2 and H2C═C(CH3)COO(CH2CH2O) n P(═O)(OH)2, wherein n is 1 to 50. More suitable are alkyl phosphates of crotonic acid, alkyl phosphates of maleic acid, alkyl phosphates of fumaric acid, dialkyl phosphates of (meth)acrylates, dialkyl phosphates of crotonic acid, and allyl phosphates. Other unsaturated monomers containing phosphate esters are ethyl (meth)acrylate phosphate ( PAM4000), polypropylene glycol mono(meth)acrylate phosphate ( PAM 200), polyethylene glycol mono(meth)acrylate phosphate ( PAM 100). In some cases, the first monomer mixture can include ethylenically unsaturated acids, such as (meth)acrylic acid and itaconic acid, or a mixture of (meth)acrylic acid and the above-mentioned phosphorus-containing monomers, particularly methacrylic acid and itaconic acid. Alkali or alkaline earth metal ion or ammonia-neutralized salts of the above-mentioned acids, and combinations thereof, can also be used.

[0022] The first monomer mixture may include at least one monomer of formula (1):

[0023]

[0024] wherein R is selected from hydrogen or methyl, X is selected from O or NH, and Y is C 1-6 alkylene, and Z is OH or OC(O)CH2C(O)CH3. In some preferred embodiments, X can be O. In further embodiments, X can be O and R can be methyl. In further embodiments, X can be O, R can be methyl, and Y can be ethylene. In yet further embodiments, X can be O, R can be methyl, Y can be ethylene, and Z can be OC(O)CH2C(O)CH3. The first monomer mixture can include the monomer of formula (1) in an amount of 0.1 to 15 weight %, 0.5 to 15 weight %, 1 to 15 weight %, 2 to 15 weight %, 2 to 10 weight %, 4 to 10 weight % or 4 to 8 weight %, based on the total weight of the monomers in the first monomer mixture.

[0025] The first monomer mixture may include one or more additional monomers in an amount of 5 to 90 weight percent based on the total weight of the monomers in the first monomer mixture, for example, the additional monomers may be selected from α,β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids and C1-C 20 Esters of alkanols, vinyl aromatic compounds, vinyl alcohol and C1-C 30 Esters of monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides, α,β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids with C2-C 30 Esters of alkanediols, α,β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids with C2-C 30 Amides of amino alcohols, primary amides of α,β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N,N-dialkyl derivatives, N-vinyl lactams, open-chain N-vinyl amide compounds, allyl alcohol and C1-C 30 Esters of monocarboxylic acids, esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, amides of α,β-ethylenically unsaturated mono- and dicarboxylic acids with diamines containing at least one primary or secondary amino group, N,N-diallylamine, N,N-diallyl-N-alkylamines, vinyl- and allyl-substituted nitrogen heterocycles, vinyl ethers, C2-C8 monoolefins, non-aromatic hydrocarbons having at least two conjugated double bonds, polyether (meth)acrylates, monomers containing urea groups, and / or mixtures thereof.

[0026] Suitable α,β-ethylenically unsaturated monocarboxylic and dicarboxylic acids are 20Esters of alkanols are methyl (meth)acrylate, methyl ethylacrylate, ethyl (meth)acrylate, ethyl ethylacrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl methacrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 1,1,3,3-tetramethylbutyl (meth)acrylate, ethylhexyl (meth)acrylate, propylheptyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl (meth)acrylate, (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, tetracosyl (meth)acrylate, hexacosyl (meth)acrylate, triacontyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and mixtures thereof.

[0027] Preferred vinylaromatic compounds are styrene, 2-methylstyrene, 4-methylstyrene, 2-(n-butyl)styrene, 4-(n-butyl)styrene, 4-(n-decyl)styrene and particularly preferably styrene.

[0028] Suitable vinyl alcohol and C1-C 30 Esters of monocarboxylic acids are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and mixtures thereof.

[0029] Suitable ethylenically unsaturated nitriles are acrylonitrile, methacrylonitrile and mixtures thereof.

[0030] Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

[0031] Suitable α,β-ethylenically unsaturated monocarboxylic and dicarboxylic acids with C2-C 30 Esters of alkanediols are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethylacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, and the like.

[0032] Suitable primary amides of α,β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N,N-dialkyl derivatives are acrylamide, methacrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-(n-butyl)(meth)acrylamide, N-(tert-butyl)(meth)acrylamide, N-(n-octyl)(meth)acrylamide, N-(1,1,3,3-tetramethylbutyl)(meth)acrylamide, N-ethylhexyl(meth)acrylamide, N-(n-nonyl)(meth)acrylamide, N-(n-decyl)(meth)acrylamide, N-(n-undecyl)(meth)acrylamide, N-tridecaproamide, Alkyl (meth) acrylamide, N-tetradecyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-hexadecyl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-eicosyl (meth) acrylamide, N-docosyl (meth) acrylamide, N-tetracosyl (meth) acrylamide, N-hexacosyl (meth) acrylamide, N-triacontyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide, N,N-dimethyl (meth) acrylamide, N,N-diethyl (meth) acrylamide, morpholinyl (meth) acrylamide.

[0033] Suitable N-vinyllactams and their derivatives are, for example, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, and the like.

[0034] Suitable open-chain N-vinylamide compounds are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide.

[0035] Suitable esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols are N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate and N,N-dimethylaminocyclohexyl (meth)acrylate.

[0036] Suitable amides of α,β-ethylenically unsaturated mono- and dicarboxylic acids containing at least one primary or secondary amino group with diamines are N-[2-(dimethylamino)ethyl]acrylamide, N-[2-(dimethylamino)ethyl]methacrylamide, N-[3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-[4-(dimethylamino)butyl]acrylamide, N-[4-(dimethylamino)butyl]methacrylamide, N-[2-(diethylamino)ethyl]acrylamide, N-[4-(dimethylamino)cyclohexyl]acrylamide, N-[4-(dimethylamino)cyclohexyl]methacrylamide, and the like.

[0037] Suitable other monomers are, among others, N,N-diallylamine and N,N-diallyl-N-alkylamine and their acid addition salts and quaternized products. The alkyl group here is preferably C1-C 24 N,N-diallyl-N-methylamine and N,N-diallyl-N,N-dimethylammonium compounds, such as chlorides and bromides, are preferred.

[0038] Further suitable monomers are vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinyl-2-methylimidazole, and vinyl- and allyl-substituted heteroaromatics, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and salts thereof.

[0039] Suitable C2-C8 monoolefins and non-aromatic hydrocarbons having at least two conjugated double bonds are, for example, ethylene, propylene, isobutylene, isoprene, butadiene, and the like.

[0040] Examples of suitable other monomers containing urea groups are N-vinylurea or N-allylurea or derivatives of imidazolidin-2-one, including N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one, N-(2-(meth)acrylamidoethyl)imidazolidin-2-one.

[0041] Preferred monomers containing urea groups are N-(2-acryloyloxyethyl)imidazolidin-2-one and N-(2-methacryloyloxyethyl)imidazolidin-2-one. Particularly preferred is N-(2-methacryloyloxyethyl)imidazolidin-2-one (2-ureidomethacrylate, UMA).

[0042] Additional monomers may also include crosslinking monomers, examples being monomers carrying keto or aldehyde groups, such as (meth)acrolein, diacetone acrylamide (DAAM), acetoacetoxyethyl methacrylate (AAEM), which may be combined with adipic acid dihydrazide (ADDH) or polyamines, and monomers carrying epoxy groups, such as glycidyl methacrylate (GMA), or monomers carrying alkoxysilane groups, such as vinyltrimethoxysilane, vinyltrimethoxysilane, methacryloxypropyltriethoxysilane and methacryloxypropyltriethoxysilane, or polyethylenically unsaturated compounds, such as allyl (meth)acrylate (AMA), butanediol diacrylate, hexanediol diacrylate and trimethylolpropane tri(meth)acrylate.

[0043] The additional monomers can be present in an amount of 5 to 90%, 10 to 90%, 20 to 90%, 30 to 90%, 40 to 90%, 50 to 90%, 60 to 90%, 70 to 90%, 80 to 90%, 5 to 80%, 10 to 80%, 20 to 80%, 30 to 80%, 40 to 80%, 50 to 80%, 60 to 80%, 70 to 80%, 5 to 70%, 10 to 70%, 20 to 70%, 30 to 7 ... or 10 to 20% is present in the first monomer mixture.

[0044] The first monomer mixture may include one or more free radical chain transfer agents. Suitable free radical chain transfer agents include tert-butyl mercaptan, thioglycolic acid, mercaptoethanol, mercaptopropyltrimethoxysilane, tert-dodecyl mercaptan, 1,8-dimercapto-3,6-dioxaoctane, n-dodecyl mercaptan, n-octyl mercaptan, terpinolene, 2-ethylhexyl thioglycolate, isooctyl 3-mercaptopropionate, α-methylstyrene dimer, cobalt complexes, and combinations thereof. Other suitable compounds herein include essentially aliphatic and / or araliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, dichloromethane, dichloroethane, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds, such as primary, secondary or tertiary aliphatic mercaptans, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-pentanethiol, 2-methylthiophene, 2-methyl-1,2-di ... -2-Propanethiol, n-pentylthiol, 2-pentylthiol, 3-pentylthiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexylthiol, 2-hexylthiol, 3-hexylthiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-methylbutanethiol, 2-ethyl-2-butanethiol, n-heptylthiol and its isomers, n- Heptanethiol and its isomers, n-octanethiol and its isomers, n-decanethiol and its isomers, n-undecanethiol and its isomers, n-dodecanethiol and its isomers, n-tridecanethiol and its isomers, substituted mercaptans such as 2-hydroxyethanethiol, aromatic mercaptans such as benzenethiol, o-, m- or p-methylbenzenethiol, and all other sulfur compounds described in "Polymer Handbook", 3rd edition, 1989, J. Brandrup and EH Immergut, John Wiley & Sons, Part II, pages 133-41, as well as aliphatic and / or aromatic aldehydes such as acetaldehyde, propionaldehyde and / or benzaldehyde, unsaturated fatty acids such as oleic acid, dienes containing non-conjugated double bonds such as divinylmethane or vinylcyclohexane, or hydrocarbons with easily abstractable hydrogen atoms such as toluene. However, mixtures of the aforementioned free-radical chain transfer compounds which are compatible with each other can also be used. The free radical chain transfer agent can be present in an amount of at least 0.25 wt%, at least 0.50 wt%, at least 0.75 wt%, at least 1 wt%, at least 1.25 wt%, at least 1.50 wt%, at least 1.75 wt%, or at least 2.0 wt%, based on the total weight of the monomers in the first monomer mixture. In other embodiments, the free radical chain transfer agent can be present in an amount of no more than 0.6 wt%, no more than 0.5 wt%, or no more than 0.4 wt%, based on the total weight of the monomers in the first monomer mixture.In some embodiments, the free radical chain transfer agent may be present in an amount of 0.25 to 2.0 wt%, 0.50 to 2.0 wt%, 0.75 to 2.0 wt%, 1.0 to 2.0 wt%, 1.25 to 2.0 wt%, 0.25 to 1.5 wt%, 0.50 to 1.5 wt%, 0.75 to 1.5 wt%, or 1.0 to 1.5 wt%.

[0045] The first monomer mixture may include one or more polymerizable surfactants. The polymerizable surfactants included in the copolymer may include ethylenically unsaturated groups that can participate in free radical polymerization. Suitable polymerizable surfactants include those having formula M + —OOC—CH═CHCOOR maleic anhydride half ester, where R is C 6-22 alkyl, and M + Yes + , K + 、Li + NH4 + or protonated or quaternary ammonium.

[0046] In some embodiments, the polymerizable surfactant can be selected from acrylic acid-modified polyoxyethylene alkyl ethers, acrylic acid-modified polyoxyethylene alkylphenyl ethers, allyl acid-modified polyoxyethylene alkyl ethers, allyl acid-modified polyoxyethylene alkylphenyl ethers, allyl acid-modified polyoxyethylene polystyrylphenyl ethers, acrylic acid-modified polyoxyethylene polystyrylphenyl ethers, polyoxyethylene-polyoxypropylene glycol monoacrylates, and mixtures thereof.

[0047] In certain embodiments, the polymerizable surfactant may have Formula 1:

[0048]

[0049] wherein n represents a number from 0 to 1,000. Exemplary polymerizable surfactants may include BC series (Dai-Ichi Kogyo Seiyaku Co., Ltd.), such as DC-10, BC-1025, BC-20, BD-2020, and BC-30.

[0050] In certain embodiments, suitable polymerizable surfactants for use in the copolymer may have Formula 2:

[0051]

[0052] wherein n represents a number from 0 to 1,000. Exemplary polymerizable surfactants may include RN series (Daiichi Kogyo Seiyaku Co., Ltd.), such as RN-10, RN-20, RN-30, RN-40, and RN-5065.

[0053] In certain embodiments, suitable polymerizable surfactants for use in the copolymer may have Formula 3:

[0054]

[0055] where R 1 represents a branched aliphatic hydrocarbon group, a secondary aliphatic hydrocarbon group or a branched aliphatic acyl group, AO and AO' each independently represents an oxyalkylene group having 2 to 4 carbon atoms, R 2 and R 3 Each independently represents a hydrogen atom or a methyl group, x represents a number from 0 to 12, y represents a number from 0 to 1, z represents a number from 1 to 10, X represents a hydrogen atom or an ionic hydrophilic group, m represents a number from 0 to 1,000, and n represents a number from 0 to 1,000. Suitable polymerizable surfactants are described in U.S. Patent No. 6,841,655, which is incorporated herein by reference in its entirety.

[0056] In certain embodiments, the polymerizable surfactant may be provided according to Formula 3a:

[0057]

[0058] where R 1 It is C9-C 15 Alkyl or C7-C 11 Alkyl-phenyl, X is H, SO3NH4 and / or SO3Na, and m is 3 to 50. In some embodiments, R 1 C 10 -C 14 Alkyl, X is H and / or SO3NH4, and m is 5 to 40. In some embodiments, m is 5 to 25, 5 to 20, or 5 to 15 (e.g., m=10). 1 C 10 -C 14 Exemplary polymerizable surfactants of the alkyl group may include the ADEKAREASOAP series ER and SR surfactants (Asahi Denka Co., Ltd.), such as ER-10, ER-20, ER-30, ER-40, SR-10, SR-20, and SR-1025. For example, ADEKAREASOAP SR-10 may be used, which includes an ammonium salt of poly(oxy-1,2-ethanediyl), α-sulfo-ω-[1-(hydroxymethyl)-2-(2-propyleneoxy)ethoxy]-, C11-rich C10-14 branched alkyl ether. Where R 1 C7-C11 Exemplary polymerizable surfactants of the alkyl-phenyl group can include the ADEKA REASOAP series NE and SE surfactants, such as NE-10, NE-20, NE-30, NE-40, NE-50, SE-10N, SE-20N, and SE-1025N.

[0059] Other representative polymerizable surfactants may include MAXEMUL TM 6112、MAXEMUL TM 5011、MAXEMUL TM 5010 (both purchased from Croda Industrial Chemicals) and allyl sulfosuccinate derivatives (such as TREM LT-40 TM (Purchased from Henkel, Germany).

[0060] The polymerizable surfactant may be present in the first monomer mixture in an amount of 0.1 to 5%, 0.2 to 5%, 0.5 to 5%, 1 to 5%, 2 to 5%, 3 to 5%, 4 to 5%, 0.1 to 4%, 0.2 to 4%, 0.5 to 4%, 1 to 4%, 2 to 4%, 3 to 4%, 0.1 to 3%, 0.2 to 3%, 0.5 to 3%, 1 to 3%, 2 to 3%, 0.1 to 2%, 0.2 to 2%, 0.5 to 2%, 1 to 2%, 0.1 to 1%, 0.2 to 1%, 0.5 to 1%, 2 to 5%, 3 to 5%, 4 to 5%, 2 to 4%, 3 to 4%, 2 to 3%, or 1 to 2% by weight of dry surfactant, based on the total weight of monomers in the first monomer mixture. In some embodiments, the first monomer mixture does not include a polymerizable surfactant.

[0061] In some embodiments, the coating composition includes multiple copolymers, for example, two copolymers. The second copolymer can be present in an amount of 1 to 50%, 2 to 40%, 2 to 30%, 2 to 20%, 2 to 10%, 5 to 30%, 5 to 20%, 5 to 15%, or 5 to 10%, based on the total weight of the first copolymer and the second copolymer.

[0062] The second copolymer can be the product of the polymerization reaction of the second monomer mixture. The second copolymer can be the product of the emulsion polymerization of the second monomer mixture, such as the seeded emulsion polymerization of the second monomer mixture. The particles can be the product of two-stage seeded emulsion polymerization, which means that the second monomer mixture is polymerized in the presence of the first copolymer previously synthesized by seeded emulsion polymerization. In certain embodiments, the second monomer mixture does not include tert-butyl acrylate monomer. In other embodiments, the second monomer mixture includes t-butyl(meth)acrylate monomer in an amount of 50 to 100 wt%, 50 to 90 wt%, 50 to 80 wt%, 50 to 70 wt%, 50 to 60 wt%, 1 to 50 wt%, 2 to 50 wt%, 5 to 50 wt%, 5 to 40 wt%, 10 to 40 wt%, 5 to 35 wt%, 10 to 35 wt%, 5 to 30 wt%, 10 to 30 wt%, 5 to 25 wt%, 10 to 25 wt%, 15 to 50 wt%, 15 to 40 wt%, 15 to 35 wt%, 15 to 30 wt%, or 20 to 30 wt%, based on the total weight of monomers in the second monomer mixture. In a preferred embodiment, the t-butyl(meth)acrylate monomer is t-butyl acrylate.

[0063] The second monomer mixture may include n-butyl (meth)acrylate monomer. Based on the total weight of the monomers in the second monomer mixture, the n-butyl (meth)acrylate monomer may be present in the second monomer mixture in an amount of 1 to 90%, 5 to 90%, 10 to 90%, 20 to 90%, 30 to 90%, 40 to 90%, 50 to 90%, 60 to 90%, 70 to 90%, 80 to 90%, 10 to 75%, 20 to 75%, 30 to 75%, 40 to 75%, 50 to 75%, 10 to 50%, 20 to 50%, 30 to 50%, 40 to 50%, 40 to 60% or 20 to 40%. In a preferred embodiment, the n-butyl (meth)acrylate monomer is n-butyl acrylate.

[0064] The second monomer mixture may include at least one ethylenically unsaturated acid as defined above. The ethylenically unsaturated acid may be present in an amount of 0.1 to 5 weight percent, 0.2 to 5 weight percent, 0.5 to 5 weight percent, 0.5 to 4 weight percent, 0.5 to 3 weight percent, 0.5 to 2 weight percent, 0.5 to 1.0 weight percent, or 1 to 2 weight percent, based on the total weight of monomers in the second monomer mixture. Ammonium, alkali metal ion, alkaline earth metal ion, and other metal ion salts of these acids may also be used.

[0065] Suitable ethylenically unsaturated carboxylic acids and their derivatives are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, the monoesters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, such as monomethyl maleate, and the metal and ammonium salts thereof.

[0066] Suitable sulfuric acid monomers are vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. Suitable styrenesulfonic acid and its derivatives are styrene-4-sulfonic acid and styrene-3-sulfonic acid and their alkali metal or alkaline earth metal salts, such as sodium styrene-3-sulfonate and sodium styrene-4-sulfonate.

[0067] The example of phosphorus-containing monomers is vinylphosphonic acid and allylphosphonic acid. Also suitable are monoesters and diesters of phosphonic acid and phosphoric acid and hydroxyalkyl (meth) acrylate, especially monoesters. In addition, suitable monomers are diesters of phosphonic acid and phosphoric acid, which have been esterified once with hydroxyalkyl (meth) acrylate and have also been esterified once with different alcohols (such as alkanols). Suitable hydroxyalkyl (meth) acrylates for these esters are those designated as individual monomers below, more specifically 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Corresponding dihydrogen phosphate monomers include phosphoalkyl (meth) acrylate, such as 2-phosphoethyl (meth) acrylate, 2-phosphopropyl (meth) acrylate, 3-phosphopropyl (meth) acrylate, butyl (meth) acrylate, and 3-phospho-2-hydroxypropyl (meth) acrylate. Also suitable are esters of phosphonic and phosphoric acids with alkoxylated hydroxyalkyl (meth)acrylates, examples being ethylene oxide or propylene oxide condensates of (meth)acrylates, such as H2C═C(CH3)COO(CH2CH2O) n P(OH)2 and H2C═C(CH3)COO(CH2CH2O) n P(═O)(OH)2, wherein n is 1 to 50. More suitable are alkyl phosphates of crotonic acid, alkyl phosphates of maleic acid, alkyl phosphates of fumaric acid, dialkyl phosphates of (meth)acrylates, dialkyl phosphates of crotonic acid, and allyl phosphates. Other unsaturated monomers containing phosphate esters are ethyl (meth)acrylate phosphate ( PAM4000), polypropylene glycol mono(meth)acrylate phosphate ( PAM 200), polyethylene glycol mono(meth)acrylate phosphate ( PAM 100). In some cases, the first monomer mixture can include a mixture of ethylenically unsaturated acids, such as (meth)acrylic acid and itaconic acid, or (meth)acrylic acid and the above-mentioned phosphorus-containing monomers, especially methacrylic acid and itaconic acid. Alkali metal or alkaline earth metal ion or ammonia-neutralized salts of the above-mentioned acids and combinations thereof can also be used. In some cases, the second monomer mixture can include a mixture of ethylenically unsaturated acids, such as (meth)acrylic acid and itaconic acid, or (meth)acrylic acid and the above-mentioned phosphorus-containing monomers, especially methacrylic acid and itaconic acid.

[0068] The second monomer mixture may include at least one monomer of formula (2):

[0069]

[0070] wherein R is selected from hydrogen or methyl, X is selected from O or NH, and Y is C 1-6 alkylene, and Z is OH or OC(O)CH2C(O)CH3. In some preferred embodiments, X can be O. In further embodiments, X can be O and R can be methyl. In further embodiments, X can be O, R can be methyl, and Y can be ethylene. In yet further embodiments, X can be O, R can be methyl, Y can be ethylene, and Z can be OC(O)CH2C(O)CH3. The second monomer mixture can include the monomer of formula (2) in an amount of 0.1 to 15 weight %, 0.5 to 15 weight %, 1 to 15 weight %, 2 to 15 weight %, 2 to 10 weight %, 4 to 10 weight % or 4 to 8 weight %, based on the total monomer weight in the second monomer mixture.

[0071] The second monomer mixture may include one or more additional monomers, for example, which may be selected from α,β-ethylenically unsaturated mono- and dicarboxylic acids and C1-C 20 Esters of alkanols, vinyl aromatic compounds, vinyl alcohol and C1-C 30 Esters of monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides, α,β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids with C2-C 30 Esters of alkanediols, α,β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids with C2-C 30 Amides of amino alcohols, primary amides of α,β-ethylenically unsaturated mono- and dicarboxylic acids and their N-alkyl and N,N-dialkyl derivatives, N-vinyl lactams, open-chain N-vinylamide compounds, allyl alcohol and C1-C 30Esters of monocarboxylic acids, esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, amides of α,β-ethylenically unsaturated mono- and dicarboxylic acids with diamines containing at least one primary or secondary amino group, N,N-diallylamine, N,N-diallyl-N-alkylamines, vinyl- and allyl-substituted nitrogen heterocycles, vinyl ethers, C2-C8 monoolefins, non-aromatic hydrocarbons having at least two conjugated double bonds, polyether (meth)acrylates, monomers containing urea groups, and / or mixtures thereof.

[0072] Suitable α,β-ethylenically unsaturated monocarboxylic and dicarboxylic acids are 20 Esters of alkanols are methyl (meth)acrylate, methyl ethylacrylate, ethyl (meth)acrylate, ethyl ethylacrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, tert-butyl ethylacrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 1,1,3,3-tetramethylbutyl (meth)acrylate, ethylhexyl (meth)acrylate, propylheptyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylate, n-undecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, tetracosyl (meth)acrylate, hexacosyl (meth)acrylate, triacontyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and mixtures thereof.

[0073] Preferred vinylaromatic compounds are styrene, 2-methylstyrene, 4-methylstyrene, 2-(n-butyl)styrene, 4-(n-butyl)styrene, 4-(n-decyl)styrene and particularly preferably styrene.

[0074] Suitable vinyl alcohol and C1-C 30 Esters of monocarboxylic acids are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and mixtures thereof.

[0075] Suitable ethylenically unsaturated nitriles are acrylonitrile, methacrylonitrile and mixtures thereof.

[0076] Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

[0077] Suitable α,β-ethylenically unsaturated monocarboxylic and dicarboxylic acids with C2-C 30 Esters of alkanediols are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethylacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, and the like.

[0078] Suitable primary amides of α,β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N,N-dialkyl derivatives are acrylamide, methacrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-(n-butyl)(meth)acrylamide, N-(tert-butyl)(meth)acrylamide, N-(n-octyl)(meth)acrylamide, N-(1,1,3,3-tetramethylbutyl)(meth)acrylamide, N-ethylhexyl(meth)acrylamide, N-(n-nonyl)(meth)acrylamide, N-(n-decyl)(meth)acrylamide, N-(n-undecyl)(meth)acrylamide, N-tridecyl N-decyl(meth)acrylamide, N-tetradecyl(meth)acrylamide, N-pentadecyl(meth)acrylamide, N-hexadecyl(meth)acrylamide, N-heptadecyl(meth)acrylamide, N-nonadecyl(meth)acrylamide, N-eicosyl(meth)acrylamide, N-docosyl(meth)acrylamide, N-tetracosyl(meth)acrylamide, N-hexacosyl(meth)acrylamide, N-triacontyl(meth)acrylamide, N-stearyl(meth)acrylamide, N-lauryl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and morpholinyl(meth)acrylamide.

[0079] Suitable N-vinyllactams and their derivatives are, for example, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, and the like.

[0080] Suitable open-chain N-vinylamide compounds are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide.

[0081] Suitable esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols are N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate and N,N-dimethylaminocyclohexyl (meth)acrylate.

[0082] Suitable amides of α,β-ethylenically unsaturated mono- and dicarboxylic acids containing at least one primary or secondary amino group with diamines are N-[2-(dimethylamino)ethyl]acrylamide, N-[2-(dimethylamino)ethyl]methacrylamide, N-[3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-[4-(dimethylamino)butyl]acrylamide, N-[4-(dimethylamino)butyl]methacrylamide, N-[2-(diethylamino)ethyl]acrylamide, N-[4-(dimethylamino)cyclohexyl]acrylamide, N-[4-(dimethylamino)cyclohexyl]methacrylamide, and the like.

[0083] Suitable other monomers are N,N-diallylamine and N,N-diallyl-N-alkylamine and their acid addition salts and quaternization products. The alkyl group here is preferably C1-C 24 N,N-diallyl-N-methylamine and N,N-diallyl-N,N-dimethylammonium compounds, such as chlorides and bromides, are preferred.

[0084] Further suitable monomers are vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinyl-2-methylimidazole, and vinyl- and allyl-substituted heteroaromatics, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and salts thereof.

[0085] Suitable C2-C8 monoolefins and non-aromatic hydrocarbons having at least two conjugated double bonds are, for example, ethylene, propylene, isobutylene, isoprene, butadiene, and the like.

[0086] Examples of suitable other monomers containing urea groups are N-vinylurea or N-allylurea or derivatives of imidazolidin-2-one, including N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one, N-(2-(meth)acrylamidoethyl)imidazolidin-2-one.

[0087] Preferred monomers containing urea groups are N-(2-acryloyloxyethyl)imidazolidin-2-one and N-(2-methacryloyloxyethyl)imidazolidin-2-one. Particularly preferred is N-(2-methacryloyloxyethyl)imidazolidin-2-one (2-ureidomethacrylate, UMA).

[0088] Additional monomers may also include crosslinking monomers, examples of which are monomers carrying keto or aldehyde groups, such as (meth)acrolein, diacetone acrylamide (DAAM), acetoacetoxyethyl methacrylate (AAEM), which may be combined with adipic acid dihydrazide (ADDH) or polyamines, and monomers carrying epoxy groups, such as glycidyl methacrylate (GMA), or monomers carrying alkoxysilane groups, such as vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxypropyltriethoxysilane and methacryloxypropyltriethoxysilane, or polyethylenically unsaturated compounds, such as allyl (meth)acrylate (AMA), butanediol diacrylate, hexanediol diacrylate and trimethylolpropane tri(meth)acrylate.

[0089] The additional monomers may be present in an amount of 5 to 90%, 10 to 90%, 20 to 90%, 30 to 90%, 40 to 90%, 50 to 90%, 60 to 90%, 70 to 90%, 80 to 90%, 5 to 80%, 10 to 80%, 20 to 80%, 30 to 80%, 40 to 80%, 50 to 80%, 60 to 80%, 70 to 80%, 5 to 70%, 10 to 70%, 20 to 70%, 30 to 70%, 40 to 80%, 50 to 80%, 60 to 80%, 70 to 80%, 5 to 70%, 10 to 70%, 20 to 70%, 30 to 70%, 40 to 80%, 50 to 90%, 60 to 90%, 70 to 80%, 80 to 90%, 5 to 80%, 10 to 80%, 20 to 80%, 30 to 8 ... or 10 to 20% is present in the second monomer mixture.

[0090] The second monomer mixture may include one or more free radical chain transfer agents. Suitable free radical chain transfer agents include tert-butyl mercaptan, thioglycolic acid, mercaptoethanol, mercaptopropyltrimethoxysilane, tert-dodecyl mercaptan, 1,8-dimercapto-3,6-dioxaoctane, n-dodecyl mercaptan, n-octyl mercaptan, 2-ethylhexyl thioglycolate, isooctyl 3-mercaptopropionate, terpinolene, α-methylstyrene dimer, cobalt complexes, and combinations thereof. Other suitable compounds herein include essentially aliphatic and / or araliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, dichloromethane, dichloroethane, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds, such as primary, secondary or tertiary aliphatic mercaptans, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-pentanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2- Pentanethiol, 4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-methylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomers, n-heptanethiol and its isomers, n-octanethiol and its isomers, n-decanethiol and its isomers, n-undecanethiol and its isomers, n-dodecanethiol and its isomers, n-tridecanethiol and its isomers, substituted mercaptans such as 2-hydroxyethanethiol, aromatic mercaptans such as benzenethiol, o-, m- or p-methylbenzenethiol, and the like in "Polymer Handbook", 3rd edition, 1989, J. Brandrup and E. H. Immergut, John Wiley & Sons, Inc. Wiley & Sons, Part II, pages 133-41, as well as aliphatic and / or aromatic aldehydes such as acetaldehyde, propionaldehyde and / or benzaldehyde, unsaturated fatty acids such as oleic acid, dienes containing non-conjugated double bonds such as divinylmethane or vinylcyclohexane, or hydrocarbons with readily abstractable hydrogen atoms such as toluene. However, mixtures of the above-mentioned free radical chain transfer compounds that are compatible with each other may also be used. The free radical chain transfer agent may be present in an amount of at least 0.25%, at least 0.50%, at least 0.75%, at least 1%, at least 1.25%, at least 1.50%, at least 1.75%, or at least 2% by weight, based on the total weight of the monomers. In other embodiments, the free radical chain transfer agent may be present in an amount of no more than 0.6%, no more than 0.5%, or no more than 0.4% by weight, based on the total weight of the monomers.In some embodiments, the free radical chain transfer agent may be present in an amount of 0.25 to 2.0 wt%, 0.50 to 2.0 wt%, 0.75 to 2.0 wt%, 1.0 to 2.0 wt%, 1.25 to 2.0 wt%, 0.25 to 1.5 wt%, 0.50 to 1.5 wt%, 0.75 to 1.5 wt%, or 1.0 to 1.5 wt%.

[0091] The second monomer mixture may include one or more polymerizable surfactants. Suitable polymerizable surfactants for the second monomer mixture include the compounds described with respect to the first monomer mixture. The polymerizable surfactant may be present in an amount of 0.1 to 5 wt%, 0.2 to 5 wt%, 0.5 to 5 wt%, 1 to 5 wt%, 2 to 5 wt%, 3 to 5 wt%, 4 to 5 wt%, 0.1 to 4 wt%, 0.2 to 4 wt%, 0.5 to 4 wt%, 1 to 4 wt%, 2 to 4 wt%, 3 to 4 wt%, 0.1 to 3 ...2 to 4 wt%, 0.5 to 4 wt%, 1 to 4 wt%, 2 to 4 wt%, 3 to 4 wt%, 0.1 to 3 wt%, 0.2 to 4 wt%, 0.5 to 4 wt%, 1 to 4 wt%, 2 to 4 wt%, 3 to 4 wt%, 0.1 to 3 wt%, 0.2 to 4 wt%, 0.5 to 5 wt%, 1 to 5 wt%, 2 to 5 wt%, 3 to 5 wt%, 4 to 5 wt%, 0.1 to 4 wt%, 0.2 to 4 wt%, 0.5 to 4 wt%, 1 to 4 wt%, 2 to 4 wt%, 3 to 4 wt%, 0.1 to 3 wt%, 0.2 to 4 wt%, 0.5 to 5 wt%, 1 to 5 wt%, 2 to 5 wt%, 3 to 5 wt%, 4 to 5 %, 1 to 3 wt %, 2 to 3 wt %, 0.1 to 2 wt %, 0.2 to 2 wt %, 0.5 to 2 wt %, 1 to 2 wt %, 0.1 to 1 wt %, 0.2 to 1 wt %, 0.5 to 1 wt %, 2 to 5 wt %, 3 to 5 wt %, 4 to 5 wt %, 2 to 4 wt %, 3 to 4 wt %, 2 to 3 wt %, or 1 to 2 wt %. In some embodiments, the second monomer mixture does not include a polymerizable surfactant.

[0092] The coating composition disclosed herein may also include one or more pigments. Suitable pigments include TiO2, calcium carbonate, talc, kaolin, sodium potassium aluminum silicate, barium sulfate, zinc oxide, zinc phosphate, synthetic hollow spherical organic particles containing air (e.g., AQACell HIDE 6299), etc. Other representative pigments include inorganic coloring pigments, such as white pigments, such as zinc white, zinc sulfide, or lithopone; black pigments, such as carbon black, iron manganese black, or spinel black; colored pigments, such as chromium oxide, chromium oxide hydrate green, cobalt green, or ultramarine green, cobalt blue, ultramarine blue, or manganese blue, ultramarine violet, or cobalt violet and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red, or ultramarine red; iron oxide brown, mixed brown, spinel phase, and corundum phase, or chrome orange; or yellow iron oxide, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, zinc cadmium sulfide, chrome yellow, or bismuth vanadate.

[0093] The following monomer mixtures can be used to prepare the polymer particles:

[0094] First monomer mixture (95% to 80% of the total mixture) Composition percentage Itaconic acid 0.5% to 1.5% Methacrylic acid 0.25% to 1.5% n-Butyl acrylate 27% to 50% Methyl methacrylate 10% to 42% tert-Butyl acrylate 5% to 65% Acetoacetoxyethyl methacrylate Up to 7% tert-Dodecyl Mercaptan 0.1% to 2.0% Second monomer mixture (5 to 20% of the total mixture) n-Butyl acrylate 10% to 50% Methyl methacrylate 50% to 90% tert-Dodecyl Mercaptan 0.0% to 2.0%

[0095] Examples

[0096] The following examples are only for the purpose of illustrating the present invention and are not intended to limit the scope of the present invention in any way.

[0097] Procedure 1: Synthesis of polymer dispersions from a monomer mixture

[0098] The polymerization vessel, equipped with a metering device and temperature regulation, carries out the initial charge at 20 to 25°C (room temperature) under a nitrogen atmosphere. The initial charge is heated to 85°C while stirring. When the set temperature is reached, a portion (typically 10%) of feed 1 is added and the mixture is stirred for 5 minutes. Thereafter, feeds 1 and 2 are started; feed 1 is metered in over 2.9 hours and feed 2 is metered in over 2.9 hours. When the feeds are completed, the monomer container is rinsed with feed 3 water. Ten minutes after the end of the feed addition, the temperature is lowered to 80°C and feed 4 is added over 0.25 hours. Five minutes after the end of feed 4, feeds 5 and 6 are metered in parallel over 60 minutes. 30 minutes after the end of these feeds, feed 7 is added over 5 minutes and the batch is cooled to below 40°C. The pH is adjusted to 8.5 using 19% ammonia solution. The solid weight %, pH and particle size of the polymer dispersion are measured.

[0099] Representative examples of polymer dispersions prepared using Procedure 1 are provided in Tables 1 and 2.

[0100] Table 1. Polymer dispersions prepared using Procedure 1 - Examples 1, 2, and 3

[0101]

[0102] Table 2. Polymer dispersions prepared using Procedure 1 - Examples 4, 5, and 6

[0103]

[0104] Representative paint formulations for the polymer dispersions of Examples 1 to 5 are provided in Table 3:

[0105] Table 3. Representative paint formulations prepared from the polymer dispersions of Examples 1 to 5

[0106]

[0107]

[0108] Gloss, adhesion to various substrates, and tint strength data for Paint Examples 1 to 5 are provided in Tables 4 and 5.

[0109] Table 4. Gloss, dry or wet adhesion to various substrates at 1 or 7 day drying time, and tint strength data for paint examples 1 to 3.

[0110]

[0111]

[0112] Table 5. Gloss, dry or wet adhesion to various substrates at 1 or 7 day drying time, dust pick-up resistance, and tint strength data for paint examples 4 and 5.

[0113]

[0114]

[0115] Procedure 2: Synthesis of polymer dispersions from two monomer mixtures

[0116] A polymerization vessel equipped with a metering device and temperature regulation is initially charged under a nitrogen atmosphere at 20 to 25°C (room temperature). The initial charge is heated to 85°C while stirring. When the set temperature is reached, a portion (typically 10%) of feed 1 is added and the mixture is stirred for 5 minutes. Thereafter, feeds 1 and 2 are started; feed 1 is metered in over 3.25 hours and feed 2 is metered in over 2.65 hours. Ten minutes after the end of feed 2, feed 3 is added over 0.5 hours. The monomer vessel is then rinsed with water using feed 4. Ten minutes after the end of the feeds, the temperature is lowered to 80°C and feed 5 is added over 0.25 hours. Five minutes after the end of feed 5, feeds 6 and 7 are metered in parallel over 60 minutes. 30 minutes after the end of these feeds, feed 8 is added and the batch is cooled to below 40°C. The pH of the polymer dispersion is adjusted to 8.5 using 19% ammonia solution. The solid weight %, pH and particle size of the polymer dispersion are measured.

[0117] Representative examples of polymer dispersions prepared using Procedure 2 (Example 6) are provided in Table 6.

[0118] Table 6. Polymer dispersions prepared using Procedure 2 - Example 6

[0119]

[0120]

[0121] A representative paint formulation for the polymer dispersion of Example 6 is provided in Table 7:

[0122] Table 7. Representative paint formulations prepared from the polymer dispersion of Example 6

[0123]

[0124] The gloss, adhesion to various surfaces, and tint strength data for Example 6 are provided in Table 8.

[0125] Table 8. Gloss, dry or wet adhesion to various substrates at 1 or 7 days dry time, and tint strength data for Example 6

[0126] Example 6 Gloss 20° 30.9 Gloss 60° 66.6 Glossiness 85° 87.2 Dry adhesive alkyd resin 1 day 2B Dry Adhesive Alkyd Resin 7 Days 5B Wet Adhesion Alkyd 1 Day 2B Wet Adhesion Alkyd Resin 7 Days 5B Dry adhesive aluminum 1 day 4B Dry Adhesion Aluminum 7 days 5B Wet adhesion aluminum 1 day 4B Wet adhesion aluminum 7 days 5B Dry adhesion to smooth steel 1 day 4B Dry adhesion smooth steel 7 days 5B Wet adhesion smooth steel 1 day 0B Wet adhesion smooth steel 7 days 5B Dry adhesion to galvanized steel 1 day 3B Dry adhesion galvanized steel 7 days 5B Wet adhesion to galvanized steel 1 day 5B Wet adhesion galvanized steel 7 days 5B Dry Adhesive Chalk Paint 1 Day 3B Dry Adhesion Chalk Paint 7 Days 4B Wet Adhesion Chalk Paint 1 Day 0B Wet Adhesion Chalk Paint 7 Days 4B Dry Adhesive Southern Yellow Pine 1 Day 4B Dry Adhesive Southern Yellow Pine 7 Days 5B Wet Adhesion Southern Yellow Pine 1 Day 0B Wet Adhesion Southern Yellow Pine 7 Days 4B Total adhesion 88 Tinting strength 99.92

[0127] Experimental procedures

[0128] Polymer Tg measurement:

[0129] The Tg of the polymers was measured using a differential scanning calorimeter according to ASTM D3418-15. The temperature range of the test was -50 to 125°C with a heating rate of 20°C / min.

[0130] Gloss measurement:

[0131] The paint films were drawn down onto plain white seal paper using a BYK 7-mil Dow latex film caster and the samples were dried for 24 hours at 50% humidity and 76°C. Three gloss measurements were then taken at the top, middle, and bottom of the panel using a BYK Gardner Tri-Glossmeter. The average of these three measurements was reported.

[0132] Cross-hatch adhesion test:

[0133] ASTM D 3559 test method was followed. Metal panels (Q-PANELS, purchased from QLab (3003H14 aluminum, ground, stock number A-612; hot dip galvanized steel G90, stock number SP-105210; smooth finish steel, stock number QD-612) were cleaned with methyl ethyl ketone and dried for 2 hours. The paint was then drawn down using a BYK (A1547) 250 micron drawdown bar and the samples were allowed to dry for 24 hours or 7 days depending on the test requirements. An 11x11 grid pattern was then drawn down with 2 mm spacing between grids. Adhesion was tested as described in ASTM 3559 using polyester / rope-fiber laminate inner tape LA-26 / NAT160 LA-26. For wet adhesion, a paper towel was placed over the drawn grid area and soaked with water for 10 minutes. After 10 minutes, the paper towel was removed and the grid area was blotted with a paper towel to remove moisture. The grid area was allowed to dry for 10 minutes before adhesion was tested using adhesive tape. Alkyd-coated panels were prepared by drawdown coating alkyd paint on a Leneta scrub chart using a 7-mil Dow latex film caster. The drawdown films were cured for 28 days at 50% humidity and 76°C. These cured panels were then drawdown coated with paint formulated with the polymers described herein. The paints were drawndown using a BYK (A1547) 250-micron drawdown bar and cured for either 24 hours or 7 days, depending on the test. Adhesion was tested as described above. To test adhesion to chalk paint, cedar wood with a chalk paint film was used. The painted cedar boards were weathered to a chalk rating of 5 on an exterior natural weather fence. These panels were then painted with the paints described herein using a brush at a natural coverage rate, and the paints were allowed to dry for either 24 hours or 7 days, depending on the test. Dry and wet adhesion were then tested as described above.

[0134] Tinting strength measurement:

[0135] 0.583 grams of EL phthalocyanine blue colorant, sold by BASF Corporation under the name Pure options colorant, was added to a 50 gram paint sample and mixed at 2300 rpm for 2 minutes in a Flack Tek mixing device. Paint was drawn down on an opacity chart using a Gardco 3 mil PGT bird-type film applicator. The paint was air dried at 50% humidity and 76°C for 15 minutes, then dried in an oven at 50°C for 30 minutes. The sample was then cooled to ambient temperature. Tinting strength was measured using an X-rite spectrophotometer. Example 4 was used as a control and was considered to have 100% tinting strength. The tinting strength of the example was compared with that of Example 4. Higher tinting strength indicates better titanium dioxide distribution, as well as better whiteness and better hiding power.

[0136] The scope of the compositions and methods of the appended claims is not limited by the specific compositions and methods described herein, which are intended to illustrate several aspects of the claims, and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. In addition to the compositions and methods shown and described herein, various modifications to the methods are intended to fall within the scope of the appended claims. Further, although only certain representative compositions and method steps disclosed herein are specifically described, other combinations of these compositions and method steps are also intended to fall within the scope of the appended claims, even if not specifically described. Therefore, combinations of steps, elements, components or ingredients may be explicitly mentioned herein, however, fewer other combinations of steps, elements, components and ingredients are included, even if not explicitly stated. As used herein, the term "comprising" and its variants are used synonymously with the term "including" and its variants and are open, non-restrictive terms. Although the terms "comprising" and "including" have been used herein to describe various embodiments, the terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, and are also disclosed. Except in the examples or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and the like used in the specification and claims should at least be understood, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be interpreted in light of the number of significant digits and ordinary rounding techniques.

Claims

1. A coating composition comprising a plurality of polymer particles comprising a first copolymer derived from a first polymerization of a first monomer mixture and a second copolymer derived from a second polymerization of a second monomer mixture, wherein the amount of the first copolymer is 95-80 weight percent based on the total weight of the first copolymer and the second copolymer, and the amount of the second copolymer is 5-20 weight percent based on the total weight of the first copolymer and the second copolymer, and the first monomer mixture comprises: 25 to 65 weight percent of tert-butyl acrylate, based on the total weight of monomers in the first monomer mixture; 5 to 55 weight percent, based on the total weight of monomers in the first monomer mixture, of n-butyl (meth)acrylate; and at least one ethylenically unsaturated acid in an amount of 0.1 to 5 weight percent based on the total weight of monomers in the first monomer mixture; wherein the first monomer mixture comprises a free radical chain transfer agent selected from the group consisting of tert-butyl mercaptan, mercaptoethanol, mercaptopropyltrimethoxysilane, tert-dodecyl mercaptan, 1,8-dimercapto-3,6-dioxaoctane, n-dodecyl mercaptan, n-octyl mercaptan, terpinolene, 2-ethylhexyl thioglycolate, isooctyl mercaptopropionate, α-methylstyrene dimer, cobalt complexes, and combinations thereof; wherein the first monomer mixture comprises a free radical chain transfer agent in an amount of at least 0.25 wt % based on the total weight of monomers in the first monomer mixture; and wherein the second monomer mixture comprises tert-butyl acrylate, styrene, n-butyl (meth)acrylate, methyl methacrylate or a combination thereof, The second monomer mixture comprises at least one ethylenically unsaturated acid in an amount of 0.2 to 5 weight percent based on the total weight of monomers in the second monomer mixture. 2 . The composition of claim 1 , wherein the first monomer mixture comprises t-butyl acrylate in an amount of 10 to 65 wt %, based on the total weight of monomers in the first monomer mixture.

3. The composition of claim 1, wherein the first polymerization is an emulsion polymerization. The composition of claim 1 , wherein the first polymerization is a seeded emulsion polymerization.

5. The composition of claim 1, wherein the first polymer has a T of -10 to 50°C. g , determined by differential scanning calorimetry (DSC) as described in ASTM D3418-15 using the mid-point temperature.

6. The composition of claim 1, wherein the first monomer mixture comprises 5 to 90 weight percent of other polymerizable monomers based on the total weight of monomers in the first monomer mixture.

7. The composition of claim 1, wherein the first monomer mixture comprises styrene, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or a combination thereof.

8. The composition of claim 1, wherein the first monomer mixture comprises styrene.

9. The composition of claim 1, wherein the first monomer mixture comprises methyl methacrylate.

10. The composition of claim 1, wherein the first monomer mixture comprises at least one ethylenically unsaturated acid selected from the group consisting of carboxylic acids, sulfuric acid, phosphorous acid, and combinations thereof.

11. The composition of claim 1 , wherein the first monomer mixture comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, citraconic acid, aconitic acid, 2-ethylacrylic acid, vinylbenzoic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, alkyl methacrylate phosphate or ethyl methacrylate phosphate, phosphate ester of polypropylene glycol monomethacrylate, phosphate ester of polyethylene glycol monomethacrylate, phosphate ester of a mixture of polypropylene glycol and polyethylene glycol monomethacrylate, ammonium salts and metal ion salts of the foregoing acids, or combinations thereof.

12. The composition of claim 1, wherein the first monomer mixture comprises a mixture of methacrylic acid and itaconic acid.

13. The composition of claim 1, wherein the first monomer mixture comprises at least one ethylenically unsaturated acid in an amount of 0.5 to 2 weight percent, based on the total weight of monomers in the first monomer mixture.

14. The composition of claim 1, wherein the first monomer mixture comprises at least one monomer of formula (1): wherein R is selected from hydrogen or methyl, X is selected from O or NH, and Y is C 1-6 alkylene, and Z is OH or OC(O)CH2C(O)CH3.

15. The composition of claim 1, wherein the first monomer mixture comprises the monomer of formula (1) in an amount of 0.1 to 15 weight percent based on the total weight of monomers in the first monomer mixture.

16. The composition of claim 1, wherein the first monomer mixture comprises a monomer of formula (1), wherein X is O.

17. The composition of claim 1, wherein the first monomer mixture comprises a monomer of formula (1), wherein R is methyl.

18. The composition of claim 1, wherein the first monomer mixture comprises a monomer of formula (1) wherein Y is ethylene.

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