Process for forming a coating composition, a coating composition, and an article comprising the same

Abstract

A process for forming a coating composition includes providing a copolymerizable composition in water. The copolymerizable composition includes 20 wt% or more of ethylenically functionalized silicone polymers and 5 wt% or more of ethylenically unsaturated monomers. A surfactant is provided in an amount of 0.1 to 10 wt%. A copolymerizable organic compound is provided in an amount of 5 to 50 wt%. The copolymerizable organic compound has an ethylenically unsaturated radical and at least one additional functional group. The polymers, monomers, and the copolymerizable organic compound are polymerized in the presence of the surfactant to form an aqueous dispersion of copolymers. The copolymers include at least one additional function group that is not polymerized during polymerization and the copolymers exhibit a glass transition temperature (Tg) of at least 0°C. A crosslinker is mixed with the aqueous dispersion of copolymers. The crosslinker is provided in an amount of at least 10 wt%.

Description

PROCESS FOR FORMING A COATING COMPOSITION,A COATING COMPOSITION, AND AN ARTICLE COMPRISING THE SAMEBACKGROUNDThe invention relates to a process for forming a coating composition, the coating composition, and articles comprising the coating composition.Binders such as those that are used to form coatings can be applied to a substrate. Such coatings are especially useful to protect and enhance metal substrates. Traditional binders have included organic solvents. However, using an organic solvent means that the coating compositions contain a high amount of volatile organic carbon. Such environmental concerns along with the perceived opportunity to save resources and address safety concerns have generated interest in replacing organic solvents with water as the solvent. However, coatings formed with organic solvents have out-performed the known water-based coatings at least with respect to cure time, chemical resistance, mechanical properties, weatherability and / or optical performance over time.Therefore, it would be desirable to provide materials that could be utilized in a coating composition and enable the coating composition to overcome the above-described deficiencies. A process for forming such a coating composition would also be desirable along with the ancillary embodiments thereof.BRIEF SUMMARYEmbodiments of a process for forming a coating composition are provided.In an embodiment, the process comprises providing a copolymerizable composition in water. The copolymerizable composition includes a) 20 wt% or more of ethylenically functionalized silicone polymers, which is based on the total weight of the copolymerizable composition, and b) 5 wt% or more of ethylenically unsaturated monomers, which is based on the total weight of the copolymerizable composition. A surfactant is provided in an amount of 0.1 to 10 wt%, which is based on the total weight of the ethylenically functionalized silicone polymers and the ethylenically unsaturated monomers. A copolymerizable organic compound is provided in an amount of 5 to 50 wt%, which is based on the total weight of the copolymerizable composition. The copolymerizable organic compound has an ethylenically unsaturated radical and at least one additional functional group. The ethylenically functionalized silicone polymers, the ethylenically unsaturated monomers, and the copolymerizable organic compound are polymerized in the presence of the surfactant to form an aqueous dispersion of copolymers. The copolymers comprise at least one additional function group that is not polymerized duringpolymerization. Also, the copolymers exhibit a glass transition temperature (Tg) of at least 0°C, the Tg being determined by differential scanning calorimetry with a heating rate of 10°K per minute according to DIN 53765, pierced crucible. At least one crosslinker is mixed with the aqueous dispersion of copolymers. The at least one crosslinker is provided in an amount of at least 10 wt% based on the total weight of the aqueous dispersion of copolymers.In some embodiments, the process further comprises forming a miniemulsion comprising the ethylenically functionalized silicone polymers, ethylenically unsaturated monomers, copolymerizable organic compound and surfactant.In other embodiments, the process further comprises curing the coating composition by crosslinking the copolymers with the at least one crosslinker by reacting the at least one additional functional group with the at least one crosslinker. In one such embodiment, after 168 hours of curing, a coating formed from the coating composition exhibits a gloss retention of at least 20% after 3000 hours, pendulum hardness (Kdnig method) of 50 or more, solvent resistance of 200 MEK DR or more, and 20° gloss value of 50 or more. In a further embodiment, the coating exhibits a distinctness of image of 50 or more.In other embodiments, the process comprises applying the coating composition to a metal substrate and curing the coating composition.In some embodiments, the surfactant is of the polymerizable variety and is polymerized with the ethylenically functionalized silicone polymers, the ethylenically unsaturated monomers, and the copolymerizable organic compound when forming the aqueous dispersion of copolymers. In one such embodiment, the polymerizable surfactant is selected from the group consisting of anionic surfactants and nonionic surfactants.In other embodiments, the ethylenically functionalized silicone polymers are functionalized utilizing a condensation reaction.In some embodiments, the ethylenically unsaturated monomers are one or more monomers selected from the group consisting of vinyl acetate, vinyl esters of a-branched monocarboxylic acids having 9 to 11 carbon atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n- butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, and 1 ,3-butadiene.In other embodiments, a catalyst is provided to increase the rate of crosslinking.In further embodiments, polymerization occurs at a temperature of 30°C to 70°C.In certain embodiments, the copolymers exhibit a minimum film formation temperature and the minimum film formation temperature is at least 10°C less than the glass transition temperature (Tg) exhibited by the copolymers.Embodiments of a coating composition are also provided. In an embodiment, the coating composition is formed by the process and the coating composition comprises an aqueous dispersion of crosslinkable silicone organic copolymers and at least one crosslinker. In some embodiments, the coating composition further comprises pigment in an amount of 20 to 70 wt%, based on total weight of the coating composition.Embodiments of an article are also provided. In an embodiment, the article comprises the coating composition and a substrate that has the coating composition provided on. The coating composition forms a coating on the substate and, in one embodiment, the coating has a dry film thickness of at least 20 microns and, after curing at about 20°C for 168 hours, exhibits a gloss retention of at least 20% after 3000 hours, pendulum hardness (Kdnig method) of 50 or more, solvent resistance of 200 MEK DR or more, 20° gloss value of 50 or more, and a distinctness of image of 50 or more.BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGThe above, as well as other advantages of the present invention will become readily apparent to those skilled in the art from the following detailed description when considered in the light of the accompanying drawings in which:FIG. 1 is a graph illustrating the differences in curing between embodiments of the coating composition of the present invention.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSIt is to be understood that the invention may assume various alternative orientations and step sequences, except where expressly specified to the contrary. It is also to be understood that the specific processes, compositions, articles, and methods described in the following specification are simply exemplary embodiments of the inventive concepts. Hence, specific properties, conditions, or other physical characteristics relating to the embodiments disclosed are not to be considered as limiting, unless expressly stated otherwise.Further, as used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a method, article, or composition that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such method, article, or composition. Further, unless expressly stated to the contrary, "or" refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).Also, the use of "a" or "an" is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural, or vice versa, unless it is clear that it is meant otherwise. For example, when a single item is described herein, more than one item may be used in place of a single item. Similarly, where more than one item is described herein, a single item may be substituted for that more than one item.In certain embodiments, a process for forming a coating composition is provided. The coating composition can be applied to a wide variety of substrates. For example, the coating composition may be applied to a metal substrate, which are a preferred type of substrate. However, the coating composition is not limited to metal substrate applications and can be utilized on other substrates. For example, the coating composition may be utilized in non-metal substrates like plastics, glass, wood, or leather. Additional substrate embodiments and applications for the coating composition are described below.In an embodiment, the process comprises providing a copolymerizable composition in water. The copolymerizable composition including 20% or more by weight (wt%) of ethylenically functionalized silicone polymers, which is based on the total weight of the copolymerizable composition, and 5 wt% or more of ethylenically unsaturated monomers, which is based on the total weight of the copolymerizable composition. The process comprises providing 0.1 to 10 wt% of a surfactant, which is based on the total weight of the ethylenically functionalized silicone polymers and the ethylenically unsaturated monomers, and 5 to 50% of a copolymerizable organic compound, which is based on the total weight of the copolymerizable composition, the copolymerizable organic compound having an ethylenically unsaturated radical and at least one additional functional group. The ethylenically functionalized silicone polymers, the ethylenically unsaturated monomers, and the copolymerizable organic compound are polymerized in the presence of the surfactant to form an aqueous dispersion of copolymers. At least one additional function group is not polymerized during polymerization. The copolymers exhibit a glass transition temperature (Tg) of at least 0°C, the Tg being determined by differential scanning calorimetry with a heating rate of 10°K per minute according to DIN 53765, pierced crucible. At least one crosslinker is mixed with the aqueous dispersion of copolymers, the at least one crosslinker provided in an amount of at least 10 wt% based on the total weight of the aqueous dispersion of copolymers.In certain embodiments, the copolymerizable composition includes 20 to 95 wt% of the ethylenically functionalized silicone polymers, which is based on the total weight of the copolymerizable composition. Preferably, the copolymerizable composition includes 20 to 70wt% of the ethylenically functionalized silicone polymers, which is based on the total weight of the copolymerizable composition. Even more preferred, the copolymerizable composition includes 25 to 55 wt% of the ethylenically functionalized silicone polymers, which is based on the total weight of the copolymerizable composition.The ethylenically functionalized silicone polymers may be a silicone resin, which is functionalized with ethylenically unsaturated, radically polymerizable groups and comprises siloxane units of the formula[R1p(OR2)zSiO(4-p-z) / 2] (I), where R1is identical or different at each occurrence and is a radical R* or E, where R* is identical or different at each occurrence and is a hydrogen atom or is a hydrocarbon radical which is free from aliphatic multiple C-C bonds, has 1 to 18 carbon atoms, preferably a C1-C18 alkyl, C6-Ci8cycloalkyl or C6-Ci8aryl radical, and may optionally be substituted, andE is an ethylenically unsaturated radical of the formula -(CR52)m-X, preferably -(CH2)3-X, where m is an integer from 1 to 10, preferably 3,R2is identical or different at each occurrence and is a hydrogen atom or a hydrocarbon radical having 1 to 18 carbon atoms, preferably a C Ci8alkyl or C6-Ci8cycloalkyl radical, R5is a hydrogen atom, a C1-C12 alkyl radical or a C6-Ci8aryl radical, preferably a hydrogen atom, andX is an ethylenically unsaturated organic group, and R1is an ethylenically unsaturated radical E in at least 1 mol% and at most 50 mol% of all siloxane units (I), p is 0, 1 , 2 or 3, and z is 0, 1 , 2 or 3, where the sum p + z has a value of 0, 1 , 2 or 3, with the proviso that for at least 20 mol% of all siloxane units of the formula (I) in the silicone polymer, the sum p+z is 1 or 0, with p being 1 or 0 and z being 0,In certain embodiments, a portion of R2can have the same structure as E. In other embodiments, R2can have the same structure as E. In still other embodiments, it may be preferred that at least a portion of the R2can be -(CR52)m-X, most preferably -(CH2)2-X.Particularly preferred silicone polymers are silicone resins for which p and z in the formula [R1p(OR2)zSiO(4-p-z) / 2] (I)have the definition of p = 0 or 1 and z = 0, 1 or 2. Preferably, for at least 20 mol% of all siloxane units of the formula (I), p = 1 and z = 0 or p = 0 and z = 0, this condition being met preferably, for p = 1 and z = 0, for at least 30 mol%, more preferably for at least 35 mol% and more particularly for at least 40 mol%, of all siloxane units of formula (I).It is preferred, moreover, for the siloxane units of formula (I) to contain less than 50 mol% of what are called Q units, for which p = 0 and z = 0.Also suitable, furthermore, are those silicone resins which consist of any desired combination of M units (R3SiOi / 2), D units (R2SiO2 / 2), T units (RSiO3 / 2), and Q units (SiO4 / 2), where R is a radical R1or radical -OR2, and R1and R2have the definition indicated for them above, with the proviso that there are always at least 20 mol% of T units or Q units as per formula (I) for which p = 1 and z = 0 or p = 0 and z = 0.Preferred silicone resins are those which are composed essentially only of T or Q units and D units, with the molar ratio of T / D units being preferably greater than 50 / 50, more particularly greater than 70 / 30, and with particular preference only T units without D units, up to a molar ratio of T / D units of up to 20 / 80. Silicone resins to which maximum preference is given, furthermore, are those which consist predominantly of T units, more particularly those which consist to an extent of at least 80 mol% of T units, very particularly those which consist to an extent of at least 90 mol% of T units. The preferred silicone resins, moreover, are those which carry a small fraction of silicon-bonded alkoxy groups. The synthesis method employed is tolerant toward hydrolyzable alkoxy groups, and so the alkoxy groups are not substantially hydrolyzed; in other words, essentially no hydroxyl groups which are eliminated in the form of water by condensation, leaving behind an Si-O-Si unit, are formed from the alkoxy groups. It is nevertheless preferred for the functional silicone resins used to have a low content of groups of the type R2O, where R2has the definition indicated for it above, in accordance with formula (I). The greater the number of alkoxy groups present, the lower the degree of condensation of the silicone resin. A high degree of condensation is preferred, since for a given substitution pattern it generally corresponds to a higher glass transition temperature. The higher the glass transition temperature, the less the silicone resin components of the copolymer tend to soften, this being an advantage with construction coatings, since in this way a lower soiling propensity can be achieved even in conjunction with relatively high service temperatures. The higher glass transition temperature of the resin is also an advantage when the coating composition is used to form an industrial coating or in another application where properties such as hardness, dirt repellence, and stain resistance are desired.In some embodiments, at least 1 mol%, and preferably at most 50 mol%, more preferably at most 40 mol%, of all siloxane units of the formula (I) comprise as their radical R1an ethylenically unsaturated radical E.In certain embodiments, the radical X may be linear, branched or cyclic. In addition to the double bond, further functional groups may also be present, generally being inert toward an olefinic polymerization, examples being halogen, carboxyl, sulfinato, sulfonato, amino, azido, nitro, epoxy, alcohol, ether, ester, thioether and thioester groups, and also aromatic isocyclic and heterocyclic groups. Preferred examples of radical X are monounsaturated C2to C10 radicals. More preferably, radical X are acrylic radicals, methacrylic radicals, or a combination of acrylic radicals and methacrylic radicals.The hydrocarbon radicals R* free from aliphatic multiple C-C bonds may be, for example, alkyl, cycloalkyl or aryl radicals. Examples of radicals R* are therefore alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tertpentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and isooctyl radicals, such as the 2,2,4- trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n- decyl radical, dodecyl radicals, such as the n-dodecyl radical, hexadecyl radicals, and octadecyl radicals, such as the n-octadecyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl, and phenanthryl radical; alkaryl radicals such as tolyl radicals, xylyl radicals, and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the [3-phenylethyl radical. Particularly preferred radicals R* are the methyl, the isooctyl, the propyl, and the phenyl radical; this recitation is only illustrative and should not be understood as imposing any restriction.If the radicals R* are substituted, they may additionally contain one or more identical or different heteroatoms selected from O, S, Si, Cl, F, Br, P or N atoms.Examples of radicals R* are valid in full for radicals R2.Examples of alkyl radicals R* having 1 to 12 carbon atoms and aryl radicals R* having 6 to 18 carbon atoms are valid in full for C1-C12 alkyl and C6-Ci8aryl radicals R5.In one preferred embodiment there are two different radicals R* present in the silicone resins composed of siloxane units of formula (I). Examples of preferred combinations of radicals R* are the phenyl radical and the methyl radical, the n-butyl radical and the ethyl radical, the n-butyl radical and the methyl radical, the ethyl radical and the methyl radical, the n-octyl radical and the methyl radical, the isooctyl radical and the methyl radical, the isooctyl radical and the phenyl radical, the n-octyl radical and the phenyl radical, the n-octyl radical and the ethyl radical, the phenyl radical and the ethyl radical, the isooctyl radical and theethyl radical; the combination of phenyl radical and methyl radical, ethyl radical and methyl radical, and isooctyl radical and methyl radical, ethyl radical and isooctyl radical, and phenyl radical and isooctyl radical are particularly advantageous. A combination of methyl and isooctyl radicals and of methyl and phenyl radicals as the two different radicals R* has proven to be particularly effective.With these two radical combinations it is possible to best control and set the two properties of compatibility in the polymer matrix and high glass transition temperature. Moreover, they ideally meet the requirements for availability and cost.In some embodiments it has proven to be particularly advantageous that the siloxane units of formula (I) having the more carbon-rich substituent is present at not more than 75 mol% of all siloxane units of the formula (I). This means, for this embodiment, conversely, that the siloxane units of formula (I) having the more carbon-poor substituent is present in not less than 25 mol% of all siloxane units of the formula (I). In one particularly preferred embodiment, the siloxane units of the formula (I) having the more carbon-poor substituent are present in the majority, i.e., at more than 50 mol% of all siloxane units of the formula (I). Thus, in this embodiment, the carbon-richer substituents are present in the minority, i.e., at less than 50 mol% of all siloxane units of the formula (I).Carbon-rich substituents R* are carbon-hydrogen radicals, such as alkyl, cycloalkyl or aryl radicals, having 4 to 18 carbon atoms, preferably 6 to 18 carbon atoms, more preferably the isooctyl radical and the phenyl radical, and carbon-poor substituents R* are alkyl radicals having 1 to 3 carbon atoms, preferably the methyl radical.All ratio figures given are standardized to 100 mol% as the sum of the units of the formula (I) carrying different carbon-rich Si-C bonded radicals.In the case of the combination of isooctyl radicals and methyl radicals it is preferred that there are more siloxane units of the formula (I) which carry methyl radicals than those which carry isooctyl radicals. The ratio of the number of siloxane units of the formula (I) which carry methyl radicals to the number of siloxane units of the formula (I) which carry isooctyl radicals is preferably 51 :49 to 99:1 , more preferably 55:45 to 98:2, more particularly 60:40 to 98:2. Ratios which have proven to be particularly effective are 60:40, 70:30, 90:10, and 95:5. All these figures are standardized to 100 as the sum of the units of the formula (I) that carry methyl groups and that carry isooctyl groups.In the case of the combination of phenyl radicals and methyl radicals, ratios below for the number of siloxane units of the formula (I) which carry methyl radicals to the number of siloxane units of the formula (I) which carry phenyl radicals are preferably 51 :49 to 99:1 , more preferably 55:45 to 98:2, more particularly 60:40 to 98:2. Ratios which have proven to be particularlyeffective are 60:40, 70:30, 80:20, 90:10, and 95:5. All these figures are standardized to 100 as the sum of the units of the formula (I) that carry methyl groups and that carry phenyl groups.The combination of more than two different radicals is also possible when utilizing the process. In that case the preferred ratios stated above for the combination of two different radicals are valid mutatis mutandis if the carbon-richer substituted siloxane units are counted together and are placed in a ratio to the siloxane unit which carries the smallest, or the least carbon-rich, substituent; in this context, a distinction is to be made, in the manner set out above, between combinations involving aromatic substituents and those not involving aromatic substituents.In the case where more than two different siloxane units of the formula (I) are present, also, preferred combinations are those of methyl, n-propyl, phenyl, n-butyl, n-octyl, and isooctyl radicals, more particularly of methyl, n-propyl, phenyl, and isooctyl radicals, and especially preferably of methyl, phenyl, n-propyl, and isooctyl radicals.The ethylenically unsaturated group can be attached to the silicone polymer S through the condensation of a silane of the formula (II) with the silicone polymer S,(R3O)3.n(R4)nSi-(CR52)m-X (II) where R3is a hydrogen atom, a Ci-C6alkyl radical or a C6-Ci8aryl radical, R4is a hydrogen atom, a C1-C12 alkyl radical or a C6-Ci8aryl radical, R5and m have the meaning given above and n is 0, 1 or 2.In some embodiments, the ethylenically unsaturated group can be attached to the silicone polymer S through the condensation of residual alkoxy groups of a silicone resin with the hydroxy group of a hydroxyalkyl acrylate or the hydroxyalkyl methacrylate in the presence of an acid catalyst. In other embodiments, the ethylenically unsaturated group can be attached to the silicone polymer S through the condensation of residual alkoxy groups of a silicone resin with the alkoxy groups of a silane, which also comprises an acrylic or a methacrylic group. Examples of the preparation of the silicone polymer s is disclosed in US2018 / 305576A1 , which is hereby incorporated by reference herein beginning on page 6, paragraph

[0083] through page 7, paragraph

[0089] ,Preferred silanes for functionalizing the silicone polymer include gamma-silanes (m=3), even though such silanes exhibit lower reactivity when compared with the alpha-silanes. It has also been found that small amounts of gamma-silanes can be utilized for functionalizing the silicone polymer. For example, functionalizing the silicone polymer can be achieved with 1 .0 wt%of silane or more, based on the total amount of silicone polymer S used. In other embodiments, it may be advantageous to utilize at least 1 .5 wt% of gamma-silane, preferably at least 2.0 wt%, more preferably at least 2.5 wt% of gamma-silane, and more particularly at least 3.0 wt% of gamma-silane, all of which are based on the total amount of silicone polymer utilized. In still other embodiments, between 4 and 8 wt% of gamma-silane may be utilized, which is based on the total amount of the silicone polymer utilized.Alternatively, functionalizing the silicone polymer can be achieved via another synthesis route. For example, the silicone polymer may be functionalized with an ethylenically unsaturated group by condensation of an ethylenically unsaturated organic molecule onto an alkoxy- or carbinol- or silanol-functional silicone resin species. In one such embodiment, an ethylenically functionalized phenyl silicone resin can be produced by condensation of an ethoxy-functional phenyl silicone resin with 2-hydroxyethyl methacrylate. Alternatively, the additional synthesis routes for functionalizing the silicone polymer may also be utilized in certain embodiments.In certain embodiments, the copolymerizable composition includes 5 to 80 wt% of the ethylenically unsaturated monomers, which is based on the total weight of the copolymerizable composition. In some embodiments, the copolymerizable composition includes 20 to 40 wt% of the ethylenically unsaturated monomers, which is based on the total weight of the copolymerizable composition. In other embodiments, the copolymerizable composition includes 40 to 75 wt% of the ethylenically unsaturated monomers, which is based on the total weight of the copolymerizable composition.Ethylenically unsaturated monomers may be vinyl esters, preferably those of carboxylic acids having 1 to 15 carbon atoms. Preferred are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of a- branched monocarboxylic acids having 9 to 11 carbon atoms, as for example VeoVa9® or VeoValO®, which are sold by Hexion, Inc. A preferred vinyl ester is vinyl acetate.Suitable monomers form the group of acrylic esters or methacrylic esters are esters of unbranched or branched alcohols having 1 to 15 carbon atoms. Preferred methacrylic esters or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate.Preferred vinylaromatics are styrene, alpha-methylstyrene, the isomeric vinyltoluenes and vinylxylenes, and also divinylbenzenes. Particularly preferred is styrene.The vinyl halogen compounds include vinyl chloride, vinylidene chloride, and also tetrafluoroethylene, difluoroethylene, hexylperfluoroethylene, 3,3,3-trifluoropropene, perfluoropropyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene, and vinyl fluoride. Particularly preferred is vinyl chloride.An example of a preferred vinyl ether is methyl vinyl ether.The preferred olefins are ethene, propene, 1 -alkylethenes, and also polyunsaturated alkenes, and the preferred dienes are 1 ,3-butadiene and isoprene. Particularly preferred are ethene and 1 ,3-butadiene.Particularly preferred as monomers are one or more monomers from the group of vinyl acetate, vinyl esters of a-branched monocarboxylic acids having 9 to 11 carbon atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, and 1 ,3-butadiene. Also particularly preferred as comonomers are mixtures of vinyl acetate and ethylene; mixtures of vinyl acetate, ethylene, and a vinyl ester of a-branched monocarboxylic acids having 9 to 11 carbon atoms; mixtures of n-butyl acrylate and 2-ethylhexyl acrylate and / or methyl methacrylate; mixtures of styrene and one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; mixtures of vinyl acetate and one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and optionally ethylene; and mixtures of 1 ,3-butadiene and styrene and / or methyl methacrylate; the stated mixtures may optionally further include one or more of the aforementioned auxiliary monomers.The process comprises providing 0.1 to 10 wt% of a surfactant, which is based on the total weight of the ethylenically functionalized silicone polymers and the ethylenically unsaturated monomers. In certain embodiments, 0.1 to 5 wt% of the surfactant, which is based on the total weight of the ethylenically functionalized silicone polymers and the ethylenically unsaturated monomers, is provided. In certain embodiments, the surfactant may be a mixture of surfactants, which can be chosen from the embodiments described below.Preferably, the surfactant is a polymerizable surfactant, which prevents or minimizes surfactant leaching from the coating composition. Preferred polymerizable surfactants contain at least one radically-polymerizable unsaturated double bond group in its molecule. Examples include, but are not limited to, an anionic polymerizable surfactant and a nonionic polymerizable surfactant.Suitable anionic polymerizable surfactants include, but are not limited to, a hydrocarbon compound having a sulfate group such as ammonium sulfate group (-SO3NH4) and an allyl group (-CH2-CH=CH2), a hydrocarbon compound having a sulfate group such as ammoniumsulfate group (-SO3NH4) and an acrylic ([(-OC(O)-CH=CH2], or methacrylic group [(-OC(O)- C(CH3)=CH2], and an aromatic hydrocarbon compound having a sulfate group such as ammonium sulfate group (-SO3NH4) and a 1 -propenyl group (-CH=CHCH3). Commercially available examples include ELEMI NOL JS-20 and RS-300 (both manufactured by Sanyo Chemical Industries, Ltd.) and surfactants from the HITENOL(R) AR series or the HITENOL(R) KH series or the HITENOL(R) BC series, e.g. HITENOL(R) AR-10, AR-20, KH-05, KH-10, BC- 10, or BC-30). (all manufactured by DKS Co. Ltd.). Further examples are REACTSURF® 2489 & 2490 from Solvay.Suitable nonionic surfactants include, but are not limited to, a hydrocarbon compound or an aromatic hydrocarbon compound having 1-propenyl group (-CH=CHCH3) and a polyoxyethylene group [-(C2H4O)n-H], Examples of the nonionic surfactants include, but are not limited to, Aquaion RN-20, Aquaion RN-2025, Aquaion RN-30, and Aquaion RN-50 (all manufactured by DKS Co. Ltd.) and LATEMUL PD-104, LATEMUL PD-420, LATEMUL PD-430, and LATEMUL PD-450 (all manufactured by Kao Corporation).The copolymerizable organic compound has an ethylenically unsaturated radical and at least one additional functional group which is not free radically polymerized but capable of crosslinking. In some embodiments, the at least one additional functional group comprises two or more functional groups which are not free to radically polymerize but are capable of crosslinking. In some embodiments, the at least one additional functional group comprises three or more functional groups which are not free to radically polymerize but are capable of crosslinking. Preferred functional groups are OH, COOH, amine, and epoxy groups.Preferably, the copolymerizable organic compound is in an amount of 10 to 40 wt%, more preferably in an amount of 10 to 20 wt%, which is based on the total weight of the copolymerizable composition. Examples of preferred copolymerizable organic compounds suitable for use in the process and coating composition include:- ethylenically unsaturated alcohols, preferably hydroxyalkyl (meth)acrylates, more preferably 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, and glycerol 1 -allyl ether;- ethylenically unsaturated monocarboxylic and dicarboxylic acids and their salts, preferably crotonic acid, acrylic acid, methacrylic acid, fumaric acid and maleic acid;- ethylenically unsaturated sulfonic acids and their salts, preferably vinylsulfonic acid and 2- acrylamido-2-methylpropanesulphonic acid;- ethylenically unsaturated primary, secondary or tertiary amines, preferably 2-dimethylaminoethyl methacrylate, 2-tert-butylaminoethyl methacrylate, allyl N-(2-aminoethyl)carbamate hydrochloride, allyl N-(6-aminohexyl)carbamate hydrochloride, allyl N- (3-aminopropyl) hydrochloride, allylamine and vinylpyridine;- ethylenically unsaturated amides, preferably 3-dimethylaminopropylmethacrylamide and 3-trimethylammoniumpropylmethacrylamide chloride;- ethylenically unsaturated phosphonic acids and their salts, preferably vinylphosphonic acid;- ethylenically unsaturated epoxides, preferably glycidyl methacrylate (GMA);- ethylenically unsaturated isocyanates, preferably 1-(isocyanato-1-methyl)-3- (methylethyl)benzene;- ethylenically unsaturated anhydrides, preferably maleic anhydride;- ethylenically unsaturated monomers containing reactive carbonyl groups, for example, acrolein, methacrolein, diacetone acrylamide, diacetone methacrylamide, 2-butanone methacrylate, formyl styrol, diacetone acrylate, diacetone methacrylate, acetonitrile acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate and vinylaceto acetate; and- ethylenically unsaturated organosilanes with reactive groups, preferably methacryloyloxypropyltrimethoxysilane and vinyltrimethoxysilane.Preferably, the copolymerizable organic compounds are ethylenically unsaturated alcohols, more preferably hydroxyalkyl (meth)acrylate, especially 2-hydroxyethyl methacrylate, which is also referred to herein as 2-HEMA, and 2-hydroxyethyl acrylate.The ethylenically functionalized silicone polymers, the ethylenically unsaturated monomers, and the copolymerizable organic compound are polymerized in the presence of the surfactant to form an aqueous dispersion of copolymers.The aqueous dispersion is preferably made by a miniemulsion polymerization. In some embodiments, the miniemulsion polymerization is carried out by preparation in the first step of a solution of at least one silicone polymer in one or more ethylenically unsaturated monomers, which gives a silicone-in-monomer solution. Emulsification in a second step of the resulting silicone-in-monomer solution, using emulsifiers, optionally hydrophobic coemulsifiers, and optionally polymerization inhibitors which prevent premature radical emulsion polymerization, in water in such a way as to give a miniemulsion having z-average particle size of not more than 350 nm, preferably not more than 300 nm, more preferably not more than 250 nm, very preferably not more than 200 nm, with the proviso that the copolymerizable organic compound is added in the first step during the preparation of the silicone-in-monomer solution or in the second step during the emulsification to form the miniemulsion, and subjection in the third step of the resulting miniemulsion to radical emulsion polymerization, where the miniemulsionpolymerization is carried out using water-soluble or oil-soluble, or a mixture of water-soluble and oil-soluble, polymerization initiators.Moreover, in the miniemulsion polymerization, there may optionally also be hydrophobic coemulsifiers present in amounts of up to 3 wt%, based on the total weight of component (A) and of functionalized component (B). In the present case, silicone polymers may often take on the function of the coemulsifier. Further examples of coemulsifiers are hexadecane, cetyl alcohol, oligomeric cyclosiloxanes, such as octamethylcyclotetrasiloxane, for example, or else vegetable oils such as rapeseed oil, sunflower oil or olive oil. Also suitable are organic or inorganic polymers having a number-average molecular weight Mn of less than 10,000. Hydrophobic coemulsifiers particularly preferred in accordance with the invention are the silicone polymers to be polymerized, themselves, and hexadecane.The copolymers are prepared in a heterophase process by the known technique of miniemulsion polymerization. Miniemulsion polymerizations differ in a number of key points from emulsion polymerization. See the following in this regard: Dissertation “Non-aqueous emulsion polymerizations” presented by Kevin Muller, Mainz 2008, pp. 17-20, and references cited therein:In contrast to emulsion polymerization, where the size of the polymer latex particles is determined essentially by kinetic processes and the stability of the lattices, the basis for miniemulsion polymerization is that the monomer even before the polymerization is present completely within micelles and therefore need no longer diffuse from the monomer droplets into the micelles during the polymerization. In other words, therefore, the latex particles formed may be regarded as polymerized copies of the monomer droplets present at the start. A consequence of this is that the size of the latex particles is determined exclusively by the dispersion process and by the stability of the monomer-filled micelles. Since there is no need for transport of monomer through the continuous phase, it is possible in this way to enable the use also of monomers which are absolutely insoluble in the continuous phase. To increase the stability of the monomer droplets it is necessary to suppress Ostwald ripening that takes place. During the miniemulsion polymerization of the dispersed monomer phase, a hydrophobe or, in the case of inverse miniemulsions, a lipophobe is therefore added.Among the species which may act as a hydrophobe, optionally, is a hydrophobic monomer suitable for the purpose, such as, for example, a silicone component.The miniemulsion polymerization differs here from suspension polymerization in two respects: firstly, the resulting polymer particles in the miniemulsion process are much smaller (50-500 nm) than those of the suspension polymerization (1 p-1 mm). Secondly, the number of radicals per growing particle in the suspension polymerization, at 10, is well above those of theminiemulsion polymerization, where, viewed statistically, there is 0.5 radical per growing particle during the reaction.In order to carry out a radical miniemulsion polymerization it is first of all necessary to construct a miniemulsion. For this purpose, the monomer, together with the emulsifier and the hydrophobe, is dispersed in water by input of energy, using, for example, a high-pressure homogenizer or by means of ultrasound. Here, the combination of emulsifier and hydrophobe retards the occurrence of Ostwald ripening and the coalescence of the monomer droplets. In the second stage, the monomer droplets formed in this way are polymerized. This may be triggered either by a water-soluble initiator, which is added after preparation of the stable miniemulsion, or by oil-soluble initiators, which may be present in the monomer phase right from the start, or by a combination of both.The monomer droplets formed in the miniemulsion have, approximately, a size of 50-500 nm. This small size is a consequence of the homogenization of the miniemulsion, achieved through the input of high quantities of energy. The transfer of monomer between the individual droplets is suppressed by the specific type of stabilization.Also, parallel to the small monomer droplets, there are no longer any free micelles present in the miniemulsion. In contrast to the conventional emulsion polymerization, therefore, it is primarily the droplets which are the locus of nucleation (droplet nucleation). During the miniemulsion polymerization, accordingly, there is also only extremely slight diffusion of the monomers observed. Within a miniemulsion polymerization, consequently, each dispersed monomer droplet may be described as an individual reactor operated at a nanoscopic level. As a consequence, a number of advantages result for this method, in contrast to the traditional emulsion and suspension polymerizations, and these advantages are described below.First, because the monomer does not have to be transported through the continuous, usually aqueous phase, it is possible in miniemulsions to polymerize even monomers that are absolutely insoluble in water. The size of the latex particles usually corresponds to that of the monomer droplets formed beforehand and can be adjusted with considerable precision via the nature and amount of the emulsifier used. Each monomer droplet is homogeneous in its composition. Specifically, for copolymerizations, therefore, the monomer ratio in each droplet is the same and is not subject to a difference in diffusion of the monomers. Another advantage of the process is that the amounts of emulsifier used are smaller, at least when compared to traditional polymerization processes, since the miniemulsion is stabilized only kinetically, but not thermodynamically.Preferably, the step of preparing the finely divided miniemulsion, is executed in the process as follows:In the first step, one or more silicone polymers, preferably silicone resins, composed of siloxane units of the formula (I) are dissolved in one or more ethylenically unsaturated monomers, giving a silicone resin-in-monomer solution. Preferably, the silicone resins composed of siloxane units of the formula (I) are soluble in the respective monomer mixture. Insoluble constituents are separated off, as and when appropriate, by filtration. The only silicone resin-in- monomer solutions that are in accordance with the invention are those containing no insoluble silicone constituents. The silicone polymer-in-monomer solution is optionally admixed with a hydrophobic coemulsifier. Examples of hydrophobic coemulsifiers are described above.In certain embodiments of the second step, the silicone polymer-in-monomer solution, preferably, silicone resin-in-monomer solution, is emulsified with water and at least one emulsifier, and optionally with further auxiliaries, such as polymerization inhibitors which prevent the premature radical emulsion polymerization, in such a way, preferably with application of high shearing force, as to obtain emulsions having particle sizes (z-average) of not more than 350 nm, known as miniemulsions. High shearing force in this context may be generated by means of suitable emulsifying equipment, such as conventional rotor-stator systems, or in other ways that are common knowledge, as for example by high-pressure homogenizers, dissolver disks, ultrasound devices or comparable emulsifying technologies allowing a high shearing force to be exerted that permits the generation of small particles of not more than 200 nm, giving miniemulsions having particle sizes (z-average) of not more than 350 nm. In the case of commercial rotor-stator systems, rotary speeds of 4,000 to 12,000 revolutions per minute (rpm), preferably of 5,000 to 11 ,000 rpm, more particularly of 6,000 to 10,000 rpm, have proven to be particularly advantageous. Both continuous and discontinuous embodiments are suitable. In the embodiments where high-pressure homogenizers are utilized to form a miniemulsion, pressures of preferably 300 bar to 1000 bar, more preferably of 350 to 900 bar, more particularly of 400 to 800 bar, have proven to be advantageous. Since the preparations are polymerizable, effective temperature monitoring is important, i.e., the temperatures of the miniemulsions are not to exceed preferably 60°C, more preferably 55°C, more particularly 50°C, and in such an event are to be rapidly cooled back down below these temperatures.In certain embodiments, silicone polymer-in-monomer solutions, preferably, resin-in- monomer solutions, of the process possess viscosities of 2 to 20,000 mPas at 25°C, preferably of 5 to 15,000 mPas at 25°C, more particularly of 7 to 10,000 mPas at 25°C. In some embodiments, the miniemulsions of the process possess viscosities of 2 to 5,000 mPas at 25°C, particularly of 3 to 4,500 mPas at 25°C, more particularly of 5 to 4,000 mPas at 25°C.In other embodiments, the amount of water in the miniemulsions of the process is 80-20 wt%, preferably 75-20, more particularly 70-25 wt%, based on the total weight of the miniemulsion.In some embodiments, the z-average particle size in the miniemulsions is not more than 350 nm, preferably not more than 300 nm, more preferably not more than 250 nm, very preferably not more than 200 nm, and at least 20 nm, preferably at least 30 nm, and more preferably at least 50 nm.The miniemulsions preferably consist of a continuous water phase and a dispersed organic phase.The organic phase of the miniemulsions is polymerized by the process of radical emulsion polymerization. In certain embodiments of a third step, the dispersed silicone polymer- in-monomer solution is subjected to free radical polymerization. This radical emulsion polymerization is preferably executed by metered addition of the miniemulsion to an initial charge comprising water and a portion of catalyst. Further metered feeds comprise the polymerization initiator, which may optionally encompass a plurality of components, each of which is separately metered in or included in the initial charge, according to their mutual interaction and function in the polymerization procedure.When miniemulsion polymerization has been completed, the resulting dispersion, where necessary, is adjusted for the desired pH, optionally filtered, and is then available for the respective use.The reaction temperatures in the miniemulsion polymerization are preferably 0°C to 100°C, more preferably 5°C to 80°C, very preferably 30°C to 70°C.In some embodiments, the pH of the dispersing medium is between 2 and 9, preferably between 4 and 8. In one particularly preferred embodiment, the pH of the dispersing medium is between 4.5 and 7.5. The pH can be adjusted before the start of the reaction by means of hydrochloric acid or aqueous sodium hydroxide solution. The polymerization may be carried out batchwise or continuously, with the inclusion of all or individual constituents of the reaction mixture in the initial charge, with individual constituents of the reaction mixture being included part in the initial charge and part metered in subsequently, or by the metering method without an initial charge. All metered feeds are made preferably at the rate at which the component in question is consumed. It is desired that the polymerization is performed in such a manner that the residual monomeric reaction components in the resulting aqueous dispersion of copolymers is low, preferably below 0.5 wt%, which is based on the total weight of the aqueous dispersion of copolymers.The polymerization is initiated by means of the customary water-soluble initiators or redox-initiator combinations, preferably with the latter. Examples of initiators are the sodium, potassium, and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, potassium peroxodiphosphate, tert-butyl peroxopivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, and azobisisobutyronitrile. The stated initiators are used preferably in amounts of 0.01 to 4.0 wt%, based on the total weight of the monomers. As redox-initiator combinations, initiators identified above are used in conjunction with a reducing agent. Suitable reducing agents are sulfites and bisulfites of monovalent cations, an example being sodium sulfite, or the derivatives of sulfoxylic acid such as zinc or alkali metal formaldehydesulfoxylates, as for example sodium hydroxymethanesulfinate, and ascorbic acid. Preferred reducing agents are sulfinic acid compounds such as 2-hydroxy-2-sulfinato-acetic acid-disodium salt. Reducing agents of this preferred type are sold, for example, under the tradename Bruggolite® FF6 and Bruggolite® FF6 M. The amount of reducing agent is preferably 0.15 to 3 wt% of the monomer amount used. Additionally, small amounts of a metal compound which is soluble in the polymerization medium and whose metal component is redoxactive under the polymerization conditions may be introduced, this compound being based for example on iron or vanadium. One particularly preferred initiator system comprising the aforementioned components is the system tert-butyl hydroperoxide / sodium hydroxymethanesulfinate / Fe(EDTA)2+ / 3+.In certain embodiments, it is also possible to use predominantly oil-soluble initiators, such as cumene hydroperoxide, isopropylbenzene monohydroperoxide, dibenzoyl peroxide or azobisisobutyronitrile. Preferred initiators for miniemulsion polymerizations are potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and dibenzoyl peroxide.The dimensions of the silicone domains within the copolymer after copolymerization has taken place are preferably in the range from 5 nm to 150 nm, more particularly from 10 nm to 140 nm, and especially preferably from 15 nm to 125 nm. The dimensions may be determined, for example, by scanning electron microscopy or transmission electron microscopy on the polymer dispersions or on the polymer films obtained from them.Preferably, the amount of copolymers in the aqueous dispersion, referred to herein as “solids content,” is relatively high. For example, preferably, the solids content of the aqueous dispersion is at least 20 wt%, which is based on the total weight of the aqueous dispersion. In some embodiments, the solids content of the aqueous dispersion is 20 to 70 wt%, which is based on the total weight of the aqueous dispersion. In other embodiments, the solids content of the aqueous dispersion is at least 30 wt%, which is based on the total weight of the aqueousdispersion. In these embodiments, the solids content of the aqueous dispersion is 30 to 70 wt%, which is based on the total weight of the aqueous dispersion.In certain embodiments, the aqueous dispersion of copolymers and the copolymers therein exhibit certain desirable properties which are useful in forming the coating composition of in the use of the coating composition in particular applications. For example, for certain applications, it may be desirable for the aqueous dispersion of copolymers to exhibit a density in a particular range. In one such embodiments, the aqueous dispersion of copolymers may exhibit a density of 0.8 to 1 .1 g / mL. The density can be measured as described below.In other embodiments, the aqueous dispersion of copolymers may have a low volatile organic carbon (VOC) content. In some embodiments, the total VOC of the aqueous dispersion is 6 wt% or less, which is based on the total weight of the aqueous dispersion. In other embodiments, the total VOC of the aqueous dispersion is 5 wt% or less, which is based on the total weight of the aqueous dispersion. In still other embodiments, the total VOC of the aqueous dispersion is 2.5 wt% or less, preferably, 2 wt% or less, which is based on the total weight of the aqueous dispersion.In other embodiments, the aqueous dispersion of copolymers may have a VOC value of 80 grams per liter (g / L) or less. In these embodiments, the aqueous dispersion of copolymers may have a VOC value of 0.01 to 80 g / L. In certain embodiments, the aqueous dispersion of copolymers may have a VOC value of 60 g / L or less. In these embodiments, the aqueous dispersion of copolymers may have a VOC value of 0.01 to 60 g / L. Preferably, the aqueous dispersion of copolymers may have a VOC value of 50 g / L or less, more preferably, 20 g / L or less. The VOC content of the aqueous dispersion can be determined as described below.In still other embodiments, the aqueous dispersion of copolymers may exhibit a viscosity of 5 to 20,000 mPa.s. The viscosity of the aqueous dispersion of copolymers can be determined as described below. For certain applications, it may be desirable for the copolymers to exhibit an average particle size in a particular range. In one such embodiments, the copolymers in the aqueous dispersion of copolymers exhibit a z-average particle size of 20 to 500 nm. The z- average particle size can be measured as described below. In other embodiments, the copolymers in the aqueous dispersion of copolymers exhibit a polydispersity index of 0.01 to 0.7. The polydispersity index of the copolymers can be determined as described below. In other embodiments, the copolymers in the aqueous dispersion may contain a desirable hydroxyl (OH) content. For example, the copolymers may contain an OH content of between 0.5 to 7 wt%, based on the total weight of the copolymers. The OH content of the copolymers can be determined by NMR as described below.In still further embodiments, the aqueous dispersion of copolymers may exhibit excellent stability. Thus, the aqueous dispersion of copolymers can be stored for long period of time such as, for example, 6 months without undergoing any observable phase separation when store at room temperature. In certain embodiments, aqueous dispersion of copolymers are storage stable, meaning, they do not show any sign of layer separation for at least six months at room temperature. In some embodiments, storage stability for the aqueous dispersion of copolymers up to and exceeding two years may be possible. In some embodiments, the storage stability of the aqueous dispersion of copolymers can be imparted to the coating composition, which is also measured by the absence of variation in z-average particle size by more than 20%. Thus, in some embodiments of the coating composition the coating composition does not show variation in z-average particle size by more than 20% over at least a six-month period.The copolymers exhibit a glass transition temperature (Tg) of at least 0°C, the Tg being determined by differential scanning calorimetry with a heating rate of 10°K per minute according to DIN 53765, pierced crucible. In some embodiments, the copolymers exhibit a glass transition temperature (Tg) of 0 to 100°C, the Tg being determined by differential scanning calorimetry with a heating rate of 10°K per minute according to DIN 53765, pierced crucible. The monomer selection or the selection of the weight fractions of the monomers and the copolymerizable organic compound can be made so as to result in general in a glass transition temperature Tg of the copolymers preferably 0°C to 100°C, more preferably 0°C to 80°C, more particularly 0°C to 60°C.In some embodiments, it may be desirable to form copolymers that exhibit a glass transition temperature (Tg) of 45°C, the Tg being determined by differential scanning calorimetry with a heating rate of 10°K per minute according to DIN 53765, pierced crucible. In these embodiments, the monomer selection or the selection of the weight fractions of the monomers and the copolymerizable organic compound can be made so as to result in general in a glass transition temperature Tg of the copolymers preferably 45°C to 100°C. For example, in these embodiments, it may be preferred that at least one of the monomers selected has a homopolymer Tg of 50°C or more. Styrene, methyl methacrylate, isoborynl (meth)acrylate are all examples of monomers with a homopolymer Tg that can be suitably utilized in such embodiments. The advantage of having a glass transition temperature of 45°C or more is even faster drying, short tack-free time and faster curing time for the coating composition. An advantage of having a high or higher glass transition temperature is fast or faster drying, short tack-free time and faster curing time for the coating composition, which is formed after curing with the crosslinker.The glass transition temperature Tg of the polymers can be determined as mentioned above or may also be calculated approximately in advance using the Fox equation. According to Fox T. G., Bull. Am. Physics Soc. 1 , 3, page 123 (1956): 1 / Tg = x1 / Tg1 + x2 / Tg2 + ... + xn / Tgn, where xn is the mass fraction (wt% / 100) of the monomer n, and Tgn is the glass transition temperature in kelvins of the homopolymer of the monomer n. Tg values for homopolymers can be found in numerous literature references and standard works of polymer technology, and in tabular works which can be searched on the Internet, such as, for instance, from Aldrich under the entry “Polymer Properties, Thermal Transitions of Homopolymers” (https: / / www.sigmaaldrich.com / content / dam / sigma- aldrich / docs / Aldrich / General_lnformation / thermal_transitions_of_homopolymers.pdf).The copolymers have at least one additional functional group that is not polymerized during polymerization. The at least one additional functional group is reactive in such a way that a film is formed after application on a substrate by crosslinking through reaction with either the copolymers themselves or with a crosslinker having functional groups capable to react with the at least one functional group of the copolymer. Preferably, the at least one additional function group is one or more hydroxyalkyl groups which are capable for crosslinking. In certain embodiments, the one or more hydroxyalkyl groups are hydroxyethyl or hydroxypropyl groups.Crosslinking may be brought about with or without the help of stimulants such as catalyst or initiator, heat, electronic beam irradiation or UV radiation. Also, drying can activate the crosslinking polymer through changes in pH, oxygen content, evaporation of solvent or carrier, or other changes that causes a reaction to occur.The copolymers can crosslink with themselves if two types of crosslinkable functional monomers are utilized. For example, crosslinkable functional monomers suitable for use in the process include ethylenically unsaturated primary, secondary or tertiary amines, such as, for example, 2-aminoethyl methacrylate, and an ethylenically unsaturated anhydride, such as, for example, methacrylic anhydride; or for example an ethylenically unsaturated epoxides, such as glycidyl methacrylate, and an ethylenically unsaturated anhydride, such as methacrylic anhydride.Preferably, at least one crosslinker is included. The at least one crosslinker is mixed with the aqueous dispersion of copolymers. Preferred crosslinkers have functional groups capable of reacting with the at least one additional function group that was not polymerized during polymerization and formation of the copolymer(s).In certain embodiments, a preferred crosslinker is an organic compound that includes 2 or more isocyanate groups as crosslinkers. Examples for suitable crosslinkers having 2 or more isocyanate groups are diisocyanates and polyisocyanates.Preferred examples for diisocyanates are hexamethylene 1 ,6-diisocyanate, isophorone diisocyanate, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, phenylene 1 ,3-diisocyanate, 4,4’-methylenebis(cyclohexyl isocyanate), 4,4’-methylenebis(phenyl isocyanate) and dimethylphenyl diisocyanate.Examples of polyisocyanates with more than 2 isocyanate groups include polymethylene polyphenylpolyisocyanate and ester of lysine triisocyanate. Mixtures of di / polyisocyanates can be used and also di / polyisocyanates which have been modified by introduction of urethane, allophanate, urea, biuret, uretonimine, urethdion or isocyanurate residues.Suitable isocyanate crosslinkers include the Bayhydur® brand of water-dispersible aliphatic hydrophilically modified polyisocyanate crosslinkers, which are available from Covestro.The chemical structures of copolymers crosslinking and being crosslinked with isocyanate are shown schematically below.Additional examples of suitable crosslinkers are phenolic resins, amino resins, epoxy resins, beta-hydroxy(alkyl)amide resins, alkylated carbamate resins, isocyanates, polyacids, anhydrides, organometallic acid-functional materials, polyamines, polyamides, aminoplasts, and mixtures thereof. Non-limiting examples of suitable aminoplasts include condensates of amines and / or amides with aldehyde. The most common amines or amides are melamine, urea, or benzoguanamine. For example, the condensate of melamine with formaldehyde is a suitable aminoplast. However, condensates with other amines or amides can be used; for example, aldehyde condensates of glycoluril. While the aldehyde used is most often formaldehyde, other aldehydes such as acetaldehyde, crotonaldehyde, and benzaldehyde may be used. The aminoplast contains methylol groups and at least a portion of these groups may be etherified with an alcohol to modify the cure response. Any monohydric alcohol may be employed for this purpose including methanol, ethanol, butanol, and hexanol. Non-limiting examples of commercially available aminoplasts that can be used include CYMELR 303, CYMELR 322, CYMEL(R) 327, CYMEL(R) 380, and CYMEL(R) 1130 (available from CYTEK Industries and / or ALLNEX).Further examples of suitable crosslinkers are polyamine compounds. Particularly suitable compounds of this type are the dihydrazides and trihydrazides of aliphatic and aromatic dicarboxylic acids of 2 to 20 carbon atoms. Representative useful polyamines include ethylene diamine, isophorone diamine, diethylenetriamine and dibutylenetriamine. In one embodiment of this invention it is useful to utilize polyhydrazides as the polyamine compounds. Representative useful polyhydrazides include oxalic dihydrazide, adipic dihydrazide, succinic dihydrazide, malonic dihydrazide, glutaric dihydrazide, phthalic or terephthalic dihydrazide and itaconicdihydrazide. Additionally, water-soluble hydrazines such as ethylene-1 , 2-dihydrazine, propylene- 1 ,3-dihydrazine and butylene-1 ,4-dihydrazine can also be used as a crosslinking agent.Further examples of suitable crosslinkers are polyaziridines; polycarbodiimides; organosilanes, for example, alkoxysilanes that can form crosslinking through condensation reaction with hydroxyl, silanol or carboxylic functionalities of the copolymer; and polyfunctional aldehydes, for example, glyoxal or furaldehydes.The crosslinker need only to be present in an amount necessary to achieve the desired degree of cure. Cuing refers to the process of hardening or setting a coating material after it has been applied to a surface. The goal of curing is to transform the applied coating from a liquid or semi-liquid state into a solid, durable, and stable film that adheres well to the substrate and provides the desired protective, decorative, or functional properties. The crosslinker is preferably used in an amount to provide at least 0.1 equivalent of functional groups in for each equivalent of functional group capable for crosslinking in copolymer. More preferably, the crosslinker is used in an amount to provide between 0.2 to 2.0 equivalent of functional groups in for each equivalent of functional group capable for crosslinking in copolymer.Crosslinking can occur for a predetermined period of time. In certain embodiments, crosslinking may occur over a period of 2 to 30 days. Preferably, crosslinking occurs with the assistance of a catalyst. Catalysts promote the curing reaction and may be tertiary amines, metal compound catalysts, or combinations thereof. Nonlimiting examples of suitable tertiary amine catalysts include triethylamine, N-methylmorpholine, triethylenediamine, pyridine, picoline, and the like. Nonlimiting examples of suitable metal compound catalysts include compounds of lead, zinc, cobalt, titanate, iron, copper, and tin. For example, the metal compound catalyst may be lead 2-ethylhexoate, zinc 2-ethylhexoate, cobalt naphthenate, tetraisopropyl titanate, iron naphthenate, copper naphthenate, dibutyl tin diacetate, dibutyl tin dioctate, dibutyl tin dilaurate, and the like.In certain embodiments, like the one illustrated in FIG. 1 , the presence of the catalyst enables the coating composition to reach a full cure in, for example, 4 to 7 days or less. As referred to herein, the term “full cure” refers to attainment of a pendulum hardness (Kdnig method) of 100 swings, after mixing with the crosslinker. As illustrated by FIG. 1 , the time to cure, measured as pendulum hardness, for the coating composition is significantly improved when a catalyst is utilized when compared with a composition that is cured without a catalyst. In certain embodiments, the coating composition comprises 0.01 to 1 wt% of catalyst, based on the total weight of the coating composition. In other embodiments, the coating composition comprises 0.05 to 0.5 wt% of catalyst, based on the total weight of the coating composition.Preferably, the coating composition comprises 0.1 to 0.3 wt% of catalyst, based on the total weight of the coating composition. In the example illustrated in FIG.1 , the coating composition comprising the catalyst comprised 0.17 wt% of catalyst, based on the total weight of the coating composition.A film on a substrate can be formed after applying the coating composition on a substrate followed by crosslinking.In embodiments where the copolymers formed exhibit a glass transition temperature (Tg) of 45°C or more, it has been surprisingly discovered that a low minimum film formation temperature (MFFT) can still be achieved. It has been observed that having copolymers that exhibit a glass transition temperature (Tg) of 45°C or more often results in poorer film coalescence because such copolymers typically exhibit a high MFFT. An advantage of utilizing copolymers that exhibit a low MFFT in a coating composition is the ability of the coating composition to form a coherent film at room temperature (25°C) or below after mixing with a crosslinker, without the use of any additional coalescing agent as use of a coalescing agent would otherwise increase the VOC of the coating composition. Copolymers that exhibit a glass transition temperature (Tg) of 45°C or more typically have an MFFT greater than 25°C, which results in poorer film coalescence as a lower MFFT is required for better film formation. However, utilizing the process described herein can provide a coating composition with copolymers that exhibit a glass transition temperature (Tg) of 45°C or more and a low MMFT, such as, for example, an MMFT of 25°C or less, can be achieved by incorporating certain functional groups into the copolymer(s) that are capable of hydrogen bonding with water molecules. It has been discovered that when hydrogen bonding occurs between the copolymers and water molecules, the flexibility of the copolymers increases due to hydroplasticization. This is in contrast to the typical decrease is flexibility observed when the Tg of a polymer increases above 45°C.As herein utilized, hydroplasticization refers to the process by which water molecules interact with a polymer, increasing its flexibility. The interacting water acts as a plasticizer, reducing intermolecular forces within the polymer matrix of the copolymer and thereby enhancing its mobility and flexibility. This effect lowers the MFFT of the copolymers formed utilizing the process, facilitating better film coalescence when curing the coating composition. In certain embodiments, the MFFT of the copolymers in the coating composition is at least 10°C lower than the Tg of the copolymers in the coating composition. The minimum film formation temperature can be determined by ASTM D2354 using commercially available devices as described below.Achieving an MFFT for the copolymers in the coating composition being at least 10°C lower than the Tg of the copolymers in the coating composition can be achieved, for example, by selecting monomers having hydrophilic properties. In the present application, monomers that are referred to as having hydrophilic properties or “hydrophilic monomers” are those which exhibit a solubility of at least 6 grams 100 grams of water, with those having at least a solubility of 20 grams per 100 grams of water being preferred. Most preferably, the hydrophilic monomers will have a solubility of 50 grams per 100 grams of water.In certain embodiments, monomers that exhibit hydrophilic properties include the amides and hydroxy alkyl esters of methacrylic acid and acrylic acids, amides and hydroxy alkyl esters of other ethylenically unsaturated acids. Other suitable hydrophilic monomers include ethylenically unsaturated monomers possessing a carboxylic acid group, for example, acrylic acid, methacrylic acid, and itaconic acid. Other examples include the esters of vinyl alcohol such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl versatate. Further examples of monomers that have suitable hydrophilic properties include acrylonitrile, methacrylonitrile, crotonaldehyde, hydroxy-substituted alkyl and aryl acrylates and methacrylates, polyether acrylates and methacrylates, alkyl-phosphato-alkyl acrylates and methacrylates, alkyl-phosphono-alkyl acrylates, methacrylates, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, N-vinyl pyrrolidone, alkyl and substituted alkyl amides of acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, and methacrylamide. In certain embodiments, it may be preferred to utilize methacrylic acid and hydroxyalkyl (meth)acrylates such as HEMA, which includes 2-HEMA.Further, the coating composition can be used as a binder, for example, in the field of industrial coatings or decorative coatings wherein the copolymer dispersions form a film primarily through a crosslinking reaction involving different functional groups.The coating composition can be applied to a wide range of substrates and used in many commercial applications. For example, the coating composition can be applied to automotive substrates, industrial substrates, packaging substrates, wood flooring and furniture, apparel, cookware, bakeware, electronics, including housings and circuit boards, glass and transparencies or sports equipment, including golf balls.In certain embodiments, the coating composition can be used to form an article. The coated article includes a substrate that has the coating composition provided thereon. In these embodiments, the coating composition forms a coating on the substate. The coating has a dry film thickness of at least 25 microns and, after curing at about 20°C for 168 hours, exhibits a gloss retention of at least 20% after 3000 hours, Koenig hardness of 50 or more, solvent resistance of 200 MEK DR or more, and 20° gloss value of 50 or more.In some embodiments, a coating formed by the coating composition exhibits high distinctness-of-lmage(DOI), which indicates the degree of sharpness in a reflected image. In certain embodiments, the coating exhibits a DOI value of at least 50 units after being cured on a substrate. In other embodiments, it may be desired that the coating exhibits a higher DOI. In these embodiments, a coating formed from the coating composition may exhibit a DOI of 75 units or more. DOI can be measured as described below.As described above, suitable substrates can be, for example, metallic or non-metallic. Metallic substrates include, but are not limited to, tin, steel, including electrogalvanized steel, cold rolled steel and hot-dipped galvanized steel, aluminum, aluminum alloys, zinc-aluminum alloys, steel coated with a zinc aluminum alloy, and aluminum plated steel. Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, polyethylene naphthalate), polypropylene, polyethylene, nylon, EVOH, polylactic acid, other “green” polymeric substrates, poly(ethyleneterephthalate) (PET), polycarbonate, polycarbonate acrylobutadiene styrene (PC / ABS), polyamide, wood, veneer, wood composite, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles and leather both synthetic and natural.In certain embodiments, the coating can be applied to a coil. For example, in some of these embodiments, the coating can be applied to a metal coil including, but not limited to, galvanized steel coils and aluminum coils. The coating can be applied by any means standard in the art, such as electrocoating, spraying, electrostatic spraying, dipping, rolling or brushing. The coating can he applied to a dry film thickness of 0.2 to 600 pm, such as from 12 pm to 26 pm, or from 21 pm to 25 pm.The coating composition can also include other optional materials known in the art. For example, the coating composition can also include a colorant or can be free of such materials. As used herein, “colorant” refers to any substance that imparts color and / or other opacity and / or other visual effect to the composition. The colorant can be added to the coating composition in any suitable form, such as discrete particles, dispersions, solutions, and / or flakes. A single colorant or a mixture of two or more colorants can be used in the coating composition. When the coating composition does not include a colorant, then the coating composition may be referred to herein as being a “clear coating” after curing. As a clear coating on an aluminum substrate, for example, an aluminum Q-panel, the coating composition may exhibit 60°gloss values in the range of 148 to 153, which is essentially the value exhibited by the substrate.Examples of colorants include pigments (organic or inorganic), dyes and tints, such as those used in the paint industry and / or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include, for example, a finelydivided solid powder that is insoluble, but wettable, under the conditions of use. A colorant can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants can be incorporated into the coatings by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art.Example of pigments and / or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, diazo, naphthol AS, salt type (flakes), benzimidazolone, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketo pyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, iriarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black, and mixtures thereof. The terms “pigment” and “colored filler” can be used interchangeably.Example of dyes include, but are not limited to, those that are solvent and / or aqueous based, such as phthalo green or blue, iron oxide, bismuth Vanadate, anthraquinone, and perylene and quinacridone.Example of tints include, but are not limited to, pigments dispersed in water-based or water miscible carriers such as AQUA-CHEM 896, commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS, commercially available from Accurate Dispersions Division of Eastman Chemical, Inc.Other examples of materials that can be used with the coating composition include plasticizers, abrasion resistant particles, corrosion resistant particles, corrosion inhibiting additives, fillers including, but not limited to, micas, talc, clays, and inorganic minerals, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow and surface control agents, thixotropic agents, organic cosolvents, reactive diluents, catalysts, reaction inhibitors, and other customary auxiliaries.In certain embodiments, the coating composition includes pigment particles. In an embodiment, the coating composition includes 20 wt% or more pigment particles, which is based on total weight of the coating composition. In other embodiments, the coating composition includes 20 to 70 wt%, or from 30 to 60 wt%, pigment particles, all based on total weight of the coating composition. In some of these embodiments, the pigment particles are inorganic pigment particles.Coatings formed by the coating composition exhibit solvent resistance, corrosion resistance, hardness, flexibility, toughness, durability, gloss, temperature resistance, dirt repellence, UV resistance, microbial resistance, antiblocking properties, chemical resistance, and water repellence. In some embodiments, the coatings formed by the coating compositionexhibit excellent uniformity, gloss retention, hardness, solvent resistance, and 20°gloss value of 50 or more. In an embodiment, the 20° gloss value is in the range from 50 to 200. In certain embodiments, the coating may exhibit a dry film thickness of 20 to 40 microns, a pendulum hardness (Kdnig method) of 118 to 125 swings, MEK double rubs of less than 200, and a Gloss 60° of 143 to 153. As noted above, the dray film thickness can be measured in microns (pm) and using a PosiTector® 6000 paint thickness gage, which uses magnetic and eddy current principles to measure paint thickness. The pendulum hardness, MEK double rubs, and Gloss 60° can all be measured as described below.ExamplesThe following examples, Examples 1-17, are presented solely for the purpose of further illustrating and disclosing the embodiments of the process for forming a coating composition, the coating composition made thereby, and articles made with the coating composition. Comparative Examples, which are not part of the invention, are also described below.In this section, substances are characterized by reporting of data obtained by means of instrumental analysis. The underlying measurements are carried out either in accordance with publicly accessible standards or are determined using specially developed techniques. In order to ensure the clarity of the teaching imparted, the methods used are specified hereinbelow. In all examples, all figures for parts and percentages are given by wt% (by weight), unless otherwise indicated.Viscosity:The viscosities, unless otherwise indicated, are determined by measurement using rotational viscometry in accordance with DIN EN ISO 3219 by using a Brookfield viscometer [spindle LV 1 , 10 rpm]. Unless indicated otherwise, all viscosity figures are for 25°C and atmospheric pressure of 1013 mbar.Molecular compositions:The molecular compositions are determined by nuclear magnetic resonance spectroscopy (regarding terminology see ASTM E 386: 35High-Resolution Nuclear Magnetic Resonance Spectroscopy (NMR): terms and symbols), with measurement of the1H nucleus and the29Si nucleus.Description of 1 H NMR measurement:Solvent: CDCI3, 99.8%dSample concentration: about 50 mg / 1 ml CDCI3 in 5 mm NMR tubesMeasurement without addition of TMS, referencing of spectra with residual CHCI3in CDCI3at7.24 ppm 5Spectrometer: Bruker Avance 400Sample head: 5 mm BBO sample head or SMART sample head (from Bruker)Measurement parameters: 10Pulprog = zg30TD = 64kNS = 64 or 128 (depending on the sensitivity of the sample head)SW = 20.6 ppmAQ = 3.17 s 15D1 = 5 sSFO1 = 500.13 MHzO1 = 6.175 ppmProcessing parameters:SI = 32k 20WDW = EMLB = 0.3 HzAccording to the type of spectrometer used, individual adjustments to the measurement parameters may be required.Description of29Si NMR measurementSolvent: C6D699.8%d / CCI41 :1 v / v with 1 wt% Cr(acac)3as relaxation reagentSample concentration: about 2 g / 1.5 ml solvent in 10 mm NMR 30 tubesSpectrometer: Bruker Avance 400Sample head: 10 mm1H / 13C / 15N / 29Si glass-free QNP sample head (from Bruker)Measurement parameters:Pulprog = zgig60TD = 64kNS = 1024 (depending on the sensitivity of the sample head)SW = 200 ppmAQ = 2.75 sD1 = 4 sSFO1 = 300.13 MHzO1 = -50 ppm 5Processing parameters:SI = 64kWDW = EM LB = 0.3 HzAccording to the type of spectrometer used, individual adjustments to the measurement parameters may be required.Molecular weight distributions:Molecular weight distributions are determined as the weight average Mwand the number average Mn, employing the method of gel permeation chromatography (GPC or size exclusion chromatography (SEC)) with polystyrene standard and a refractive index detector (Rl detector). Unless specified otherwise, THF is used as the eluent and DIN 55672-1 is employed. The polydispersity is the quotient Mw / Mn.Minimum film formation temperature:The minimum film formation temperature is determined by ASTM D2354 using a Rhopoint MFFT 90 bar at 75 pm film thickness.Glass transition temperatures:The glass transition temperature (Tg) is determined by Differential Scanning Calorimetry (DSC) according to DIN 53765, pierced crucible, heating rate 10 K / min.Determination of the particle size:The particle sizes (z-average particle size) were measured by the method of Dynamic Light Scattering (DLS) with a Malvern Zetasizer Nano ZS Particle Size Analyzer. The polydispersity (PDI) of the particle size indicates the width of the size distribution.Application testing of coated films:The aqueous copolymer dispersions were used in an industrial waterborne coating formulation that contains a desired crosslinking agent, also referred to as a hardener. In a typical formulation, the hardener was mixed with the copolymer dispersion with a Cowles blade at 1000 rpm for approximately 30s. Films (approximately between 23-27 pm dry thickness) were evaluated after application of the formulations with a bird bar on Aluminum Q-panels followed by drying at room temperature and 50-55% relative humidity. In some cases, the films were dried at elevated temperature in an oven.The film durability was measured by MEK Double Rub Test (ASTM D5402) after one week of drying. The higher the value the more durable and solvent resistant is the film.The pendulum hardness (Kdnig method) of the film was determined with a BYK Pendulum Hardness Tester (DIN EN ISO 1522). The values are presented as the number of pendulum oscillations.Gloss was measured with an Erichsen Picogloss 503 gloss meter at angles of 20, 60 and 85°. DOI was measured by a Rhopoint IQ 20 / 60 / 85° Haze DOI Meter based on ASTM E430.For accelerated weathering resistance testing, coated Q-panels were subjected to an artificial weathering process through exposure to a fluorescent UV-A light source in a QUV / spray accelerated weathering tester (Q-Lab Products, Cleveland, USA) for 3000 hours in accordance with the EN 927-6 standard. The weathering experiment was conducted by cycles of UV-light irradiation for 8 hours at 60°C, followed by a water spray at 50°C for 4 hours.Example 1Preparation of an ethylenically unsaturated phenyl silicone resin by condensation of an ethoxy-functional phenyl silicone resin with 2-hydroxyethyl methacrylate (2-HEMA)A 3 L four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen inlet, and an overhead stirrer is charged with 931 .34 grams (g) of silicone resin consisting of 60 mol% PhSiO3 / 2 units (TPh units), 36 mol% MeSiO3 / 2 units (T units), and 4 mol% Me2SiO2 / 2units (D units), with 14.2 wt% MeO radicals distributed statistically over the T units, possessing a molecular weight (Mw) of 1800 g / mol and a viscosity of 440 mPa.s at 25 °C and 21 .03 grams of deionized water. 1 .22 grams of 37 wt% Hydrochloric acid was added while stirring the mixture at 200 rpm. These ingredients were mixed and refluxed at 55°C. After the reaction mixture turned clear (after approximately 35 minutes), 31 .74 grams of 2-HEMA was added and the pressure in the flask was reduced to 130 mbar to distill off the volatiles. 76.22 grams of distillate was collected. The ethylynically unsaturated silicone resin (863.62 grams) was collected as a turbid viscous liquid.Viscosity (Brookfield viscometer, L.V. 4 spindle, 10 rpm): 975 mPa.sMolecular Weight and Nonuniformity (toluene used as eluent):Mw= 7305 g / molMn= 1568 g / mol 25Polydispersity = 4.66Molecular Composition from 1-H NMR and 29-Si NMR:Me2SiO2 / 2: 4.70 mol%(Ph)SiO3 / 2: 55.30 mol%MeSiO3 / 2: 40.00 mol%CH2=(CH3)C(O=)CO(CH2)2O-Si: 2.16 wt% MeO-Si: 9.53 wt%HO-Si: 0.84 wt%Example 2Preparation of a compolymerizable composition in water including the silicone resin of Example 1 , ethylenically unsaturated monomers, and a copolymerizable organic compound. In Example 2 the ethylenically unsaturated monomers are butyl methacrylate and butyl acrylate. In Example 2 the copolymerizable organic compound is 2-HEMA and the total amount of 2-HEMA is 16 wt% based on the total weight of the copolymerizable composition.Step 1 : Preparation of miniemulsion:The copolymerizable composition was prepared by forming a mixture of the silicone resin from Example 1 with (meth)acrylic monomers (butyl methacrylate and butyl acrylate) and thecopolymerizable organic compound (2-HEMA, which has a hydroxy group in addition to radically polymerizable methacrylate group), followed by high pressure homogenization. In this example, a IKA® HPH 2000 / 5 high pressure homogenizer was utilized to prepare a miniemulsion, which was formed utilizing the components shown below and according to the following procedure:Components of phase 1 are added to a sealable vessel and mixed on an orbital shaker for 30 minutes.The resulting mixture is combined with a solution of the Phase 2 components and mixed on an orbital shaker for approximately 1 h.The component of Phase 3 is added to the mixture comprising the Phase 1 and Phase 2 components dropwise over 30 minutes while mixed on a magnetic stirrer at 750 rpm; the mixture was subsequently mixed in the mechanical shaker for approximately 30 minutes, where a stable pre-emulsion is formed.The pre-emulsion is passed through the high-pressure homogenizer (IKA® HPH 2000 / 5) at a pressure of 200 bar to obtain a miniemulsion with a Z-average particle size of 165 nm (PDI = 0.12) and Brookfield viscosity (Spindle L.V.4, 10 rpm) of 98 mPa.s.Step 2: PolymerizationThe polymerization of the miniemulsion produced in Step 1 is performed utilizing the components shown below and according to the following procedure:A 3 L polymerization vessel, equipped with an anchor stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, is charged with the reactor water (345.4 grams of RO water), and 121.7 grams of the miniemulsion prepared in Step 1 as the initial charge and heated to 50°C. In one sealable vessel (feed 1), a solution of 10.7 grams of tertiary butyl hydroperoxide (TBHP) in 86.8 grams of RO water is prepared. In a second sealable vessel (feed 2), a solution of 5.48 grams of a formaldehyde-free reducing agent (Bruggolite®FF6 M) in 102.6 grams of deionized water is prepared. In a third vessel (feed 3) is placed 1540 grams of the miniemulsion. Feed 1 and 2 are started at an approximate rate of 0.5 mL / min, followed by the start of feed 3 at an approximate rate of 8.5 mL / min to be continuously metered over a period of 165 minutes. Feeds 1 and 2 are continued for an additional 40 minutes after the completion of feed 3. After cooling to room temperature, the product is adjusted to a pH of 8 by the addition of aqueous ammonia as necessary. Biocide Acticide BW 20 (0.44 grams) is added. The product is then filtered through a 100 pm filter to give a aqueous dispersion of copolymers with the following properties:Specific gravity: 1.055Copolymer glass transition temperature (Tg): 6.7°C Solids content: 42.6%Total remaining free monomer: 670 ppmZ-average particle size: 178 nm (PDI = 0.07)Viscosity (Brookfield, Spindle S.P. 61 , 10 rpm): 12 mPa.sStability: The dispersion prepared according to the above method is stable against any visible separation for >720 days at 25°CExample 2APreparation of a compolymerizable composition in water including the silicone resin of Example 1 , ethylenically unsaturated monomers, and a copolymerizable organic compound. In Example 2A the ethylenically unsaturated monomers are butyl methacrylate and butyl acrylate. In Example 2A the copolymerizable organic compound is 2-HEMA.Step 1 : Preparation of miniemulsion:The copolymerizable composition was prepared by forming a mixture of the silicone resin from Example 1 with (meth)acrylic monomers (butyl methacrylate and butyl acrylate) and the copolymerizable organic compound 2-HEMA, followed by high pressure homogenization. In this example, an IKA® HPH 2000 / 5 high pressure homogenizer was utilized to prepare a miniemulsion, which was formed utilizing the components shown below and according to the following procedure:Components of phase 1 are added to a sealable vessel and mixed on an orbital shaker for 30 minutes.The resulting mixture is combined with a solution of the Phase 2 components and mixed on an orbital shaker for approximately 1 h.The component of Phase 3 is added to the mixture comprising the Phase 1 and Phase 2 components dropwise over 30 minutes while mixed on a magnetic stirrer at 750 rpm; the mixture was subsequently mixed in the mechanical shaker for approximately 30 minutes, where a stable pre-emulsion is formed.The pre-emulsion is passed through the high-pressure homogenizer (IKA® HPH 2000 / 5) at a pressure of 200 bar to obtain a miniemulsion with a Z-average particle size of 160.1 nm (PDI = 0.129) and Brookfield viscosity (Spindle L.V. 61 , 10 rpm) of 129 mPa.s.Step 2: PolymerizationThe polymerization of the miniemulsion produced in Step 1 is performed utilizing the components shown below and according to the following procedure:A 1 L polymerization vessel, equipped with an anchor stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, is charged with the reactor water (105.3 grams of RO water),and 37.4 grams of the miniemulsion prepared in Step 1 as the initial charge and heated to 50°C. In one sealable vessel (feed 1), a solution of 3.23 grams of tertiary butyl hydroperoxide (TBHP) in 26.4 grams of RO water is prepared. In a second sealable vessel (feed 2), a solution of 1 .64 grams of a formaldehyde-free reducing agent (Bruggolite®FF6 M) in 31 .3 grams of deionized water is prepared. In a third vessel (feed 3) is placed 427 grams of the miniemulsion. Feed 1 and 2 are started at an approximate rate of 0.5 mL / min, followed by the start of feed 3 at an approximate rate of 8.5 mL / min to be continuously metered over a period of 165 minutes. Feeds 1 and 2 are continued for an additional 30 minutes after the completion of feed 3. After cooling to room temperature, the product is adjusted to a pH of 8 by the addition of aqueous ammonia as necessary. Biocide Acticide BW 20 (200 ppm) is added. The product is then filtered through a 100 pm filter to give a aqueous dispersion of copolymers with the following properties:Specific gravity: 1.065Copolymer glass transition temperature (Tg): 61.7°C Solids content: 38.53%Z-average particle size: 171 nm (PDI = 0.125)Viscosity (Brookfield, Spindle S.P. 61 , 100 rpm): 9.9 mPa.s Minimum film formation temperature: 7.3°CExample 2BPreparation of a compolymerizable composition in water including the silicone resin of Example 1 , ethylenically unsaturated monomers, and a copolymerizable organic compound. In Example 2B the ethylenically unsaturated monomers are butyl methacrylate and styrene. In Example 2B the copolymerizable organic compound is 2-HEMA.Step 1 : Preparation of miniemulsion:The copolymerizable composition was prepared by forming a mixture of the silicone resin from Example 1 with the ethylenically unsaturated monomers (butyl methacrylate and styrene) and the copolymerizable organic compound 2-HEMA, followed by high pressure homogenization. In this example, a IKA® HPH 2000 / 5 high pressure homogenizer was utilized to prepare a miniemulsion, which was formed utilizing the components shown below and according to the following procedure:Components of phase 1 are added to a sealable vessel and mixed on an orbital shaker for 30 minutes.The resulting mixture is combined with a solution of the Phase 2 components and mixed on an orbital shaker for approximately 1 h.The component of Phase 3 is added to the mixture comprising the Phase 1 and Phase 2 components dropwise over 30 minutes while mixed on a magnetic stirrer at 750 rpm; the mixture was subsequently mixed in the mechanical shaker for approximately 30 minutes, where a stable pre-emulsion is formed. The pre-emulsion is passed through the high-pressure homogenizer (IKA® HPH 2000 / 5) at a pressure of 200 bar to obtain a miniemulsion with a Z-average particle size of 176.6 nm (PDI = 0.132) and Brookfield viscosity (Spindle L.V. 61 , 10 rpm) of 185 mPa.s.Step 2: PolymerizationThe polymerization of the miniemulsion produced in Step 1 is performed utilizing the components shown below and according to the following procedure:A 1 L polymerization vessel, equipped with an anchor stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, is charged with the reactor water (101 grams of RO water), and 35.7 grams of the miniemulsion prepared in Step 1 as the initial charge and heated to 50°C. In one sealable vessel (feed 1), a solution of 3.09 grams of tertiary butyl hydroperoxide (TBHP) in 25.4 grams of RO water is prepared. In a second sealable vessel (feed 2), a solution of 1 .58 grams of a formaldehyde-free reducing agent (Bruggolite®FF6 M) in 31 .3 grams of deionized water is prepared. In a third vessel (feed 3) is placed 462.6 grams of the miniemulsion. Feed 1 and 2 are started at an approximate rate of 0.5 mL / min, followed by the start of feed 3 at an approximate rate of 8.5 mL / min to be continuously metered over a period of 165 minutes. Feeds 1 and 2 are continued for an additional 30 minutes after the completion of feed 3. After cooling to room temperature, the product is adjusted to a pH of 8 by the addition of aqueous ammonia as necessary. Biocide Acticide BW 20 (200 ppm) is added. The product is then filtered through a 100 pm filter to give a aqueous dispersion of copolymers with the following properties:Specific gravity: 1.06Copolymer glass transition temperature (Tg): 49.8°C Solids content: 40.79%Z-average particle size: 147.2 nm (PDI = 0.056)Viscosity (Brookfield, Spindle S.P. 61 , 100 rpm): 9.9 mPa.s Minimum film formation temperature: 9.3°CExample 3Preparation of compolymerizable composition in water including the silicone resin of Example 1 , ethylenically unsaturated monomers, and a copolymerizable organic compound. In Example 3 the ethylenically unsaturated monomers comprise butyl methacrylate. In Example 3 the copolymerizable organic compound is 2-HEMA and the total amount of 2-HEMA is 16 wt% based on the total weight of the copolymerizable composition.Step 1 : Preparation of miniemulsion:The copolymerizable composition was prepared by forming a mixture of the silicone resin from Example 1 with (meth)acrylic monomers (butyl methacrylate) and the copolymerizable organic compound (2-HEMA), followed by high pressure homogenization. In this example, a IKA® HPH 2000 / 5 high pressure homogenizer was utilized to prepare a miniemulsion, which was formed utilizing the components shown below and according to the following procedure:Components of phase 1 are added to a sealable vessel and mixed on an orbital shaker for 30 minutes.The resulting mixture is combined with a solution of the Phase 2 and mixed on an orbital shaker for approximately 1 h.The component of Phase 3 is added to the above mixture dropwise over 30 minutes while mixed on a magnetic stirrer at 750 rpm; the mixture was mixed in the mechanical shaker for approximately 30 minutes by when a stable pre-emulsion is formed.The pre-emulsion is passed through the high-pressure homogenizer at a pressure of 200 bar to obtain a miniemulsion with a z-average particle size of 176 nm (PDI = 0.18).Step 2: PolymerizationThe polymerization of the miniemulsion produced in Step 1 is performed utilizing the components shown below and according to the following procedure:A 1 L polymerization vessel, equipped with an anchor stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, is charged with the reactor water (75.8 g of RO water), and 24.4 grams of the miniemulsion prepared in Step 1 as the initial charge and heated to 50°C. In one sealable vessel (feed 1), a solution of 2.1 grams of tertiary butyl hydroperoxide (TBHP) in 12.1 grams of RO water is prepared. In a second sealable vessel (feed 2), a solution of 0.77 g of a formaldehyde-free reducing agent (Bruggolite®FF6 M) in 14.1 grams of deionized water is prepared. In a third vessel (feed 3) is placed 280.3 grams of the miniemulsion. Feed 1 and 2 are started at an approximate rate of 0.06 mL / min, followed by the start of feed 3 at an approximate rate of 2 mL / min to be continuously metered over a period of 165 minutes. Feeds 1 and 2 are continued for an additional 30 minutes after the completion of feed 3. Biocide Acticide BW 20 (0.15 grams) is added. The product is then filtered through a 100 pm filter to give an aqueous dispersion of copolymers with the following properties:Specific gravity: 1.06Copolymer glass transition temperature (Tg): 37°CSolids content: 39.9%Total remaining free monomer: 980 ppmZ-average particle size: 202 nm (PDI = 0.14)Example 3APreparation of a compolymerizable composition in water including the silicone resin of Example 1 , ethylenically unsaturated monomers, and a copolymerizable organic compound. In Example 3A the ethylenically unsaturated monomer is methyl methacrylate. In Example 3A the copolymerizable organic compound is 2-HEMA.Step 1 : Preparation of miniemulsion:The copolymerizable composition was prepared by forming a mixture of the silicone resin from Example 1 with a (meth)acrylic monomer (methyl methacrylate) and the copolymerizable organic compound 2-HEMA, followed by high pressure homogenization. In this example, a IKA® HPH 2000 / 5 high pressure homogenizer was utilized to prepare a miniemulsion, which was formed utilizing the components shown below and according to the following procedure:Components of phase 1 are added to a sealable vessel and mixed on an orbital shaker for 30 minutes.The resulting mixture is combined with a solution of the Phase 2 components and mixed on an orbital shaker for approximately 1 h.The component of Phase 3 is added to the mixture comprising the Phase 1 and Phase 2 components dropwise over 30 minutes while mixed on a magnetic stirrer at 750 rpm; the mixture was subsequently mixed in the mechanical shaker for approximately 30 minutes, where a stable pre-emulsion is formed.The pre-emulsion is passed through the high-pressure homogenizer (IKA® HPH 2000 / 5) at a pressure of 200 bar to obtain a miniemulsion with a Z-average particle size of 141 .2 nm (PDI = 0.129) and Brookfield viscosity (Spindle L.V. 61 , 50 rpm) of 20 mPa.s.Step 2: PolymerizationThe polymerization of the miniemulsion produced in Step 1 is performed utilizing the components shown below and according to the following procedure:A 1 L polymerization vessel, equipped with an anchor stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, is charged with the reactor water (106.72 grams of RO water), and 40 grams of the miniemulsion prepared in Step 1 as the initial charge and heated to 50°C. In one sealable vessel (feed 1), a solution of 3.27 grams of tertiary butyl hydroperoxide (TBHP) in26.8 grams of RO water is prepared. In a second sealable vessel (feed 2), a solution of 1.67 grams of a formaldehyde-free reducing agent (Bruggolite®FF6 M) in 31.7 grams of deionized water is prepared. In a third vessel (feed 3) is placed 430.8 grams of the miniemulsion. Feed 1 and 2 are started at an approximate rate of 0.5 mL / min, followed by the start of feed 3 at an approximate rate of 8.5 mL / min to be continuously metered over a period of 165 minutes. Feeds 1 and 2 are continued for an additional 30 minutes after the completion of feed 3. After cooling to room temperature, the product is adjusted to a pH of 8 by the addition of aqueous ammonia as necessary. Biocide Acticide BW 20 (200 ppm) is added. The product is then filtered through a 100 pm filter to give a aqueous dispersion of copolymers with the following properties:Specific gravity: 1.08Copolymer glass transition temperature (Tg): 86.7°C Solids content: 33.7%Z-average particle size: 164.4 nm (PDI = 0.144)Viscosity (Brookfield, Spindle S.P. 61 , 100 rpm): 10.7 mPa.sMinimum film formation temperature: 60°CExample 3BPreparation of a compolymerizable composition in water including the silicone resin of Example 1 , ethylenically unsaturated monomers, and a copolymerizable organic compound. In Example 3B the ethylenically unsaturated monomer is iso-butyl methacrylate. In Example 3B the copolymerizable organic compound is 2-HEMA.Step 1 : Preparation of miniemulsion:The copolymerizable composition was prepared by forming a mixture of the silicone resin from Example 1 with a (meth)acrylic monomer (iso-butyl methacrylate) and the copolymerizable organic compound 2-HEMA, followed by high pressure homogenization. In this example, a Hielscher Ultrasonics UP400St ultrasonicator was utilized to prepare a miniemulsion, which was formed utilizing the components shown below and according to the following procedure:Components of phase 1 are added to a sealable vessel and mixed on an orbital shaker for 30 minutes.The resulting mixture is combined with a solution of the Phase 2 components and mixed on an orbital shaker for approximately 1 h.The component of Phase 3 is added to the mixture comprising the Phase 1 and Phase 2 components dropwise over 30 minutes while mixed on a magnetic stirrer at 750 rpm; the mixture was subsequently mixed in the mechanical shaker for approximately 30 minutes, where a stable pre-emulsion is formed. The pre-emulsion is passed through a ultrasonicator (Hielscher Ultrasonics UP400St) using its flow cell attachment at 70% duty cycle for 10 minutes to obtain a miniemulsion with a Z- average particle size of 178 nm (PDI = 0.184).Step 2: PolymerizationThe polymerization of the miniemulsion produced in Step 1 is performed utilizing the components shown below and according to the following procedure:A 1 L polymerization vessel, equipped with an anchor stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, is charged with the reactor water (98.9 grams of RO water), and 34.5 grams of the miniemulsion prepared in Step 1 as the initial charge and heated to 50°C. In one sealable vessel (feed 1), a solution of 3.47 grams of tertiary butyl hydroperoxide (TBHP) in 27.3 grams of RO water is prepared. In a second sealable vessel (feed 2), a solution of 1 .67 grams of a formaldehyde-free reducing agent (Bruggolite®FF6 M) in 32.23 grams of deionized water is prepared. In a third vessel (feed 3) is placed 434 grams of the miniemulsion. Feed 1 and 2 are started at an approximate rate of 0.5 mL / min, followed by the start of feed 3 at an approximate rate of 8.5 mL / min to be continuously metered over a period of 165 minutes. Feeds 1 and 2 are continued for an additional 30 minutes after the completion of feed 3. After cooling to room temperature, the product is adjusted to a pH of 8 by the addition of aqueous ammonia as necessary. Biocide Acticide BW 20 (0.44g) is added. The product is then filtered through a 100 pm filter to give a aqueous dispersion of copolymers with the following properties:Specific gravity: 1.05Copolymer glass transition temperature (Tg): 66.5°C Solids content: 37.96%Z-average particle size: 149 nm (PDI = 0.121) Minimum film formation temperature: 51 °CComparative Example 1Preparation of a compolymerizable composition in water including the silicone resin of Example 1 , ethylenically unsaturated monomers, and a copolymerizable organic compound. In the Comparative Example the ethylenically unsaturated monomers are butyl methacrylate and butyl acrylate. In the Comparative Example the copolymerizable organic compound is 2-HEMA and the total amount of 2-HEMA is 16 wt% based on the total weight of the copolymerizable composition. In the Comparative Example, the copolymers have a Tg<0°C.Step 1 : Preparation of miniemulsion:The copolymerizable composition was prepared by forming a mixture of the silicone resin from Example 1 with (meth)acrylic monomers (butyl methacrylate and butyl acrylate) and the copolymerizable organic compound (2-HEMA, which has a hydroxy group in addition to radically polymerizable methacrylate group), followed by high pressure homogenization. In this example, a IKA® HPH 2000 / 5 high pressure homogenizer was utilized to prepare a miniemulsion, which was formed utilizing the components shown below and according to the following procedure:Components of phase 1 are added to a sealable vessel and mixed on an orbital shaker for 30 minutes.The resulting mixture is combined with a solution of the Phase 2 and mixed on an orbital shaker for approximately 1 h.The component of Phase 3 is added to the above mixture dropwise over 30 minutes while mixed on a magnetic stirrer at 750 rpm; the mixture was mixed in the mechanical shaker for approximately 30 minutes by when a stable pre-emulsion is formed.The pre-emulsion is passed through the high-pressure homogenizer at a pressure of 200 bar to obtain a miniemulsion with a z-average particle size of 169 nm (PDI = 0.14).Step 2: PolymerizationThe polymerization of the miniemulsion produced in Step 1 is performed utilizing the components shown below and according to the following procedure:A 1 L polymerization vessel, equipped with an anchor stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, is charged with the reactor water (98.9 g of RO water), and 33 g of the miniemulsion prepared in Step 1 as the initial charge and heated to 50°C. In one sealable vessel (feed 1), a solution of 2.7 g of tertiary butyl hydroperoxide (TBHP) in 15.4 g of RO water is prepared. In a second sealable vessel (feed 2), a solution of 0.97 g of a formaldehyde-free reducing agent (Bruggolite®FF6 M) in 18.3 g of deionized water is prepared. In a third vessel (feed 3) is placed 359.5 g of the miniemulsion. Feed 1 and 2 are started at an approximate rate of 0.08 mL / min, followed by the start of feed 3 at an approximate rate of 2 mL / min to be continuously metered over a period of 165 minutes. Feeds 1 and 2 are continued for an additional 30 minutes after the completion of feed 3. Biocide Acticide BW 20 (0.15 g) is added. The product is then filtered through a 100 pm filter to give an aqueous dispersion of copolymers with the following properties:Specific gravity: 1 .054;Copolymer glass transition temperature (Tg): -8.3°C;Solids content: 40.4%;Total remaining free monomer: 670 ppmZ-average particle size: 172 nm (PDI = 0.11)Comparative Example 1APreparation of a compolymerizable composition in water including the silicone resin of Example 1 and ethylenically unsaturated monomers, but did not include a copolymerizable organic compound. In Comparative Example 1A the ethylenically unsaturated monomers are butyl methacrylate and butyl acrylate.Step 1 : Preparation of miniemulsion:The copolymerizable composition was prepared by forming a mixture of the silicone resin from Example 1 with (meth)acrylic monomers (butyl methacrylate and butyl acrylate) followed by high pressure homogenization. In this example, a IKA® HPH 2000 / 5 high pressure homogenizer was utilized to prepare a miniemulsion, which was formed utilizing the components shown below and according to the following procedure:Components of phase 1 are added to a sealable vessel and mixed on an orbital shaker for 30 minutes.The resulting mixture is combined with a solution of the Phase 2 components and mixed on an orbital shaker for approximately 1 h.The mixture was subsequently mixed in the mechanical shaker for approximately 30 minutes, where a stable pre-emulsion is formed.The pre-emulsion is passed through the high-pressure homogenizer (IKA® HPH 2000 / 5) twice at a pressure of 200 bar to obtain a miniemulsion with a Z-average particle size of 184.3 nm (PDI = 0.104).Step 2: PolymerizationThe polymerization of the miniemulsion produced in Step 1 is performed utilizing the components shown below and according to the following procedure:A 1 L polymerization vessel, equipped with an anchor stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, is charged with the reactor water (101 grams of RO water), and 30.3 grams of the miniemulsion prepared in Step 1 as the initial charge and heated to 50°C. In one sealable vessel (feed 1), a solution of 2.6 grams of tertiary butyl hydroperoxide (TBHP) in 14.76 grams of RO water is prepared. In a second sealable vessel (feed 2), a solution of 0.92 grams of a formaldehyde-free reducing agent (Bruggolite®FF6 M) in 1 gr7.46 grams of deionized water is prepared. In a third vessel (feed 3) is placed 345 grams of the miniemulsion. Feed 1 and 2 are started at an approximate rate of 0.5 mL / min, followed by the start of feed 3 atan approximate rate of 8.5 mL / min to be continuously metered over a period of 165 minutes. Feeds 1 and 2 are continued for an additional 30 minutes after the completion of feed 3. After cooling to room temperature, the product is adjusted to a pH of 8 by the addition of aqueous ammonia as necessary. Biocide Acticide BW 20 (200 ppm) is added. The product is then filtered through a 100 pm filter to give a aqueous dispersion of copolymers with the following properties:Specific gravity: 1.04Copolymer glass transition temperature (Tg): 18.6°C Solids content: 36.3%Z-average particle size: 168.5 nm (PDI = 0.063)Minimum film formation temperature: 22.2°CExample 4, Example 5, Comparative Example 2, and Comparative Example 3 - Coating CompositionsThe aqueous copolymer dispersions described above and a non-silicone organic polyol dispersion known as BAYHYDROL A 2546, available from Covestro, were used to form coating compositions that contain crosslinker. The crosslinker was a polyisocyanate based hardener called Bayhydur® XP 2655 (polyisocyanate based on hexamethylene diisocyanate, available from Covestro). In some experiments a waterborne tin catalyst (Reaxis C33W50) was added to accelerate crosslinking. For the Examples and Comparative Examples described below, the isocyanate crosslinker was mixed with the aqueous copolymer dispersions with a Cowles blade at 1000-2500 rpm for approximately 30 seconds. Films (approximately between 30 to 50 micron dry thickness) were evaluated after application of the compositions with a bird bar on Aluminum Q-panels followed by drying at room temperature and 50-55 percent relative humidity.The film hardness, gloss and durability were measured after one week. The coating compositions and the test results are shown in Table 1.Table 1Example 6 - Pigmented coating composition including an isocyanate crosslinker1 .20 g of blue pigment 897-7201 Phthalo Blue and 10 g of the aqueous copolymer dispersion of Example 2 were mixed in a FlackTek speed mixer for 2 min at 1600 RPM. 3 g of isocyanate crosslinker Bayhydur XP 2655 was added and mixed for another 2 min at 1600 RPM. The formulation was applied on 3" x 6" A-36 aluminum Q-panels by hand with a drawdown square with 5 mil (127 micron) wet thickness. The formulation was allowed to dry at 20 degree C for at least a week (approximately 25 microns dry thickness was obtained) before measuring hardness, gloss, DOI and MEK double rub numbers.Hardness: 115MEK DR number: >200Gloss (20 ): 70DOI: 82Example 7, Comparative Example 4, and Comparative Example 5 - Coating CompositionsFor Example 7, 10 g of the aqueous copolymer dispersion of Example 2 was mixed by hand with 2.5 g of melamine crosslinker Cymel 385 from Covestro to form a clear coating composition. For Comparative Example 4, 10 g of the copolymer dispersion of Example 2 was utilized to form a coating composition that did not include any crosslinker. For Comparative Example 5, 10 g of a non-silicone organic polyol dispersion known as Allnex VSC 6276w, available from Allnex, was mixed by hand with 2 g of the melamine crosslinker Cymel 385 to form a coating composition.The coating compositions were applied to 3" x 6" A-36 aluminum Q-panels by hand with a drawdown square with 5 mil (127 micron) wet thickness. The coating compositions were allowed to dry at 20° C for about one hour, and then cured in an oven for 30 min at 132° C. The coated panels were characterized for hardness, gloss, and solvent resistance using the MEK double rub method.The coating compositions of Example 7, Comparative Example 4, and Comparative Example 5 and the test results for each are shown in Table 2, below.Table 2Example 8, Example 9, and Comparative Example 6 - Coating Compositions For Example 8, 10 g of the aqueous copolymer dispersion of Example 2 was mixed by hand with 1 .5 g of N-methylol urea crosslinker Cymel 1172 from Covestro to form a clear coating composition. For Example 9, 10 g of the aqueous copolymer dispersion of Example 2 was mixed by hand with 0.5 g of the N-methylol urea crosslinker to form a clear coating composition. For Comparative Example 6, 10 g of the copolymer dispersion of Example 2 was utilized to form a coating composition that did not include any crosslinker.The coating compositions of Example 8, Example 9 and Comparative Example 6 were applied to 3" x 6" A-36 aluminum Q-panels by hand with a drawdown square with 5 mil (127 micron) wet thickness. The formulation was allowed to dry at 20° C for about one hour, and then cured in an oven for 30 min at 136° C. The coated panels were characterized for hardness, gloss, and solvent resistance using the MEK double rub method.The coating compositions and the test results are shown in Table 3.Table 3Example 10, Example 11 , Example 12, Example 13 and Example 14 - Coating CompositionsFor Example 10, the aqueous copolymer dispersion of Example 2A described above was used to form coating composition that contained a crosslinker. The crosslinker was a polyisocyanate based hardener called Bayhydur® XP 2655. For Example 11 , the aqueous copolymer dispersion of Example 2B described above was used to form coating composition that contained the polyisocyanate based hardener called Bayhydur® XP 2655. For Example 12, the aqueous copolymer dispersion of Example 3A described above was used to form coating composition that contained the polyisocyanate based hardener called Bayhydur® XP 2655. For Example 13, the aqueous copolymer dispersion of Example 3B described above was used to form coating composition that contained the polyisocyanate based hardener called Bayhydur® XP 2655. For Example 14, the aqueous copolymer dispersion of Example 2 described above was used to form coating composition that contained the polyisocyanate based hardener called Bayhydur® XP 2655.For Examples 10 through 14, the polyisocyanate based hardener was mixed with the respective aqueous copolymer dispersion using a Cowles blade at 1000-2500 rpm for approximately 30 s to form the coating composition. Films (approximately between 30 to 50 micron dry thickness) were evaluated after application of the formulations with a bird bar on Aluminum Q-panels followed by drying at room temperature and 50-55 percent relative humidity.The cure rate for each coating composition was determined via pendulum hardness (Konig method) of the film measured over a period of seven days, made from coating compositions containing 30 wt% Bayhydur® XP 2655 and 70 wt% of the respective aqueous dispersion. The pendulum hardness (Konig method) of the film was determined with a BYK Pendulum Hardness Tester (DIN EN ISO 1522). As measured by the number of pendulum oscillations or swings, it was observed that as the glass transition temperature of the copolymer in the dispersion increases, the cure rate of the coating composition increases, allowing full cure to be reached before or at 7 days unlike in Example 14, which needed more than 7 days to reach the target hardness of 110-120 Koenig swings.Example 15 - Coating CompositionWhen a tertiary amine catalyst, dimethyl ethanol amine, was added at 0.35 wt%, based on the total weight of the coating composition, to the coating composition of Example 13, the curing time to full cure of the coating composition decreased from ~7days to ~2 days.Example 16 and Example 17 - Coating CompositionsIn addition to cure rate, drying time of a coating composition formed according to the process offers improved performance. The drying time, defined as set-to-touch time and tack- free time, were measured using ASTM D5895-20 and a circular dry time recorder (Gardco Ultracycle RHT Drying Time Recorder), at 23 ± 2 °C and 50 ± 5 % relative humidity. Set-to-touch time is defined as the point at which the coated film has solidified to the point where it no longer lifts off substrate when touched, and tack-free-time is defined as the point at which the film does not adhere to light objects placed on it.The dry time of a coating composition made with the aqueous dispersion of Example 3A and Example 2 were evaluated, each coating composition contained of 30 wt% Bayhydur® XP 2655 and 70 wt% of the respective aqueous dispersion of the Example. The results are shown below in Table 4.Table 4As shown above, the set-to-touch time and tack-free time, increased significantly with the high glass transition temperature copolymers in the coating composition of Example 16, allowing easier and more immediate handling of the resulting films.From the foregoing detailed description, it will be apparent that various modifications, additions, and other alternative embodiments are possible without departing from the true scope and spirit. The embodiments and examples discussed herein were chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to use the invention in various embodiments and with various modifications as are suited to the particular use contemplated. As should be appreciated, all such modifications and variations are within the scope of the invention.

Claims

CLAIMS1. A process for forming a coating composition, comprising: providing a copolymerizable composition in water, the copolymerizable composition including a) 20 wt% or more of ethylenically functionalized silicone polymers, which is based on the total weight of the copolymerizable composition, and b) 5 wt% or more of ethylenically unsaturated monomers, which is based on the total weight of the copolymerizable composition providing 0.1 to 10 wt% of a surfactant, which is based on the total weight of the ethylenically functionalized silicone polymers and the ethylenically unsaturated monomers; providing 5 to 50 wt% of a copolymerizable organic compound, which is based on the total weight of the copolymerizable composition, the copolymerizable organic compound having an ethylenically unsaturated radical and at least one additional functional group; polymerizing the ethylenically functionalized silicone polymers, the ethylenically unsaturated monomers, and the copolymerizable organic compound in the presence of the surfactant to form an aqueous dispersion of copolymers, wherein the copolymers comprise at least one additional function group that is not polymerized during polymerization and the copolymers exhibit a glass transition temperature (Tg) of at least 0°C, the Tg being determined by differential scanning calorimetry with a heating rate of 10°K per minute according to DIN 53765, pierced crucible; and mixing at least one crosslinker with the aqueous dispersion of copolymers, the at least one crosslinker provided in an amount of at least 10 wt% based on the total weight of the aqueous dispersion of copolymers.

2. The process of claim 1 , further comprising forming a miniemulsion comprising the ethylenically functionalized silicone polymers, ethylenically unsaturated monomers, copolymerizable organic compound and surfactant.

3. The process of claim 1 , further comprising curing the coating composition by crosslinking the copolymers with the at least one crosslinker by reacting the at least one additional functional group with the at least one crosslinker.

4. The process of claim 3, wherein, after 168 hours of curing, a coating formed from the coating composition exhibits a gloss retention of at least 20% after 3000 hours, pendulumhardness (Kdnig method) of 50 or more, solvent resistance of 200 MEK DR or more, and 20° gloss value of 50 or more.

5. The process of claim 4, wherein the coating exhibits a distinctness of image of 50 or more.

6. The process of claim 1 , further comprising applying the coating composition to a metal substrate and curing the coating composition.

7. The process of claim 1 , wherein the surfactant is of the polymerizable variety and is polymerized with the ethylenically functionalized silicone polymers, the ethylenically unsaturated monomers, and the copolymerizable organic compound when forming the aqueous dispersion of copolymers.

8. The process of claim 1 , wherein the ethylenically functionalized silicone polymers are functionalized utilizing a condensation reaction.

9. The process of claim 1 , wherein the ethylenically unsaturated monomers are one or more monomers selected from the group consisting of vinyl acetate, vinyl esters of a-branched monocarboxylic acids having 9 to 11 carbon atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n- butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, and 1 ,3-butadiene.

10. The process of claim 1 , further comprising a catalyst to increase the rate of crosslinking.11 . The process of claim 1 , wherein polymerization occurs at a temperature of 30°C to 70°C.

12. The process of claim 1 , wherein the copolymers exhibit a minimum film formation temperature and the minimum film formation temperature is at least 10°C less than the glass transition temperature (Tg) exhibited by the copolymers.

13. The process of claim 7, wherein the polymerizable surfactant is selected from the group consisting of anionic surfactants and nonionic surfactants.

14. A coating composition formed according to the process of claim 1 , the coating composition comprising an aqueous dispersion of crosslinkable silicone organic copolymers and at least one crosslinker.

15. The coating composition of claim 14, further comprising pigment in an amount of 20 to 70 wt%, based on total weight of the coating composition.

16. An article, comprising: the coating composition of claim 14; and a substrate that has the coating composition provided thereon, wherein the coating composition forms a coating on the substate, the coating having a dry film thickness of at least 20 microns and, after curing at about 20°C for 168 hours, exhibiting a gloss retention of at least 20% after 3000 hours, pendulum hardness (Kdnig method) of 50 or more, solvent resistance of 200 MEK DR or more, 20° gloss value of 50 or more, and a distinctness of image of 50 or more.

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