Hydrophobic coating composition

Abstract

To provide a coating composition exhibiting hydrophobicity, anti-graffiti, anti-icing, anti-fouling, anti-fingerprint, anti-stain, anti-fogging and / or easy stain removal, and to provide a method for producing the same.SOLUTION: There is provided a coating composition comprising (I) an organic binder and (ii) a polyorganosiloxane of formula (I), Z1 - L1 {[Si (R) (R ') O] p-SiR " 2} m-Si (R) - L2 - Z2 (I).SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Application No. 62 / 966,219, filed January 27, 2020, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to coating compositions comprising an organic binder and a polyorganosiloxane that can be used in architectural and / or industrial applications. [Background technology]

[0003] Coating compositions based on organic binders are common in architectural and industrial applications. The binder is a key component of a coating composition and can be dispersed in molecular form (in water or organic solvents to form a true solution) or as a colloidal dispersion (emulsion or sol). The binder forms a continuous film of polymer (resin) on the substrate surface, helping the coating adhere to the substrate. Coating compositions can be part of a one-component system containing a binder or a two-component system containing a binder and a hardener. Coating compositions can be either one-component or two-component systems and can be converted into functional coating systems by including additives. Coating compositions can have varying degrees of hydrophobicity, easy removal of stains and graffiti, microbial resistance, durability, or other related benefits, which can depend on the binder chemistry, filler type and loading, and the presence of other additives.

[0004] Graffiti damage is a growing concern. Today, most people view graffiti damage not as an art form, but as a form of vandalism and property destruction when the graffiti is unwanted. Graffiti is primarily found on facilities such as schools, public and private buildings, cars, trucks, trains, vehicles, and public restrooms, as well as open areas such as bridge support walls, building interior walls, and park structures. Most graffiti is created with oil-based paints such as enamel, epoxy, lacquer, and urethane, applied with spray cans. Traditionally, removal of unwanted graffiti has been accomplished by sandblasting it from the substrate. However, this method is expensive and hazardous to health due to the release of potentially carcinogenic particles. Furthermore, this method damages the coating surface. This method does not provide a long-term solution, and the surface may be repainted with new damaging graffiti.

[0005] Another commonly used method is by treating the substrate with chemicals. This is generally dangerous because the chemicals often destroy the surface and require handling highly corrosive solutions. The search for more environmentally friendly solutions is highly desirable. On the other hand, stain removal for home and exterior architectural coatings is typically achieved by soap and water or high-pressure washing with water. To reduce maintenance needs, it is desirable for such coatings to have built-in stain-resistant or easy-to-clean properties.

[0006] Some stains can be resisted by increasing hydrophobicity, and one way to enhance this is to add silicone-based compounds / additives to coatings. One example, U.S. Patent No. 4,833,187, uses silicones for the same purpose. These silicones, based on functionalized polydimethylsiloxane (PDMS) or PDMS-organic hybrids, generally do not react with organic binders (the functional groups of PDMS cannot chemically react with those of binders). As a result, they suffer from several drawbacks, including blooming and surface leaching, which can cause oily spots and stickiness in the coating, resulting in inconsistent and durable coating performance. Therefore, these silicones have only seen limited acceptance as compounds incorporated into architectural or industrial coatings. Summary of the Invention

[0007] The present inventors have surprisingly discovered that the coating compositions of the present invention exhibit hydrophobicity, anti-graffiti, anti-icing, anti-smudge, anti-fingerprint, anti-stain, anti-tarnish, and / or easy stain removal. The coating compositions comprise (i) an organic binder, as described herein, and (ii) a compound of formula (I)Z 1 -L 1 {[Si(R)(R')O] p -SiR'''2} m -L 2 -Z 2 The polyorganosiloxanes include:

[0008] In the polyorganosiloxane of formula (I), the subscript p>9; the subscript m is an integer from 1 to 5; each of R, R', or R'' is a saturated hydrocarbon substituent selected from the group consisting of monovalent alkyl containing 1 to 22 carbon atoms, optionally substituted with F or -OH groups, aryl containing 6 to 22 carbon atoms, polycyclic aryl containing 8 to 22 carbon atoms, alkylaryl containing 7 to 23 carbon atoms, and arylalkyl containing 7 to 22 carbon atoms, and H or L. 1 -Z 1 or L2 -Z 2 and each of R, R', and R'' may be the same or different; 1 or L 2 Each of the is a single bond, L 1 or L 2 -O-, -NR bonded to the silicon atom of each siloxy unit of polyorganosiloxane (I) through a carbon atom of 3 -C(O)- and / or -NR 3 -, -OC(O)NR 3 -, -NR 3 -C(O)-NR 3 - moieties and optionally substituted by one or more OH groups, or a trivalent group, 1 and L 2 may be the same or different, and where R 3 is hydrogen, Me3Si- or alkyl containing 1 to 8 carbon atoms; Z 1 or Z 2 are independently R, R', R'', and R 1 , alkylarylalkyl containing 8 to 22 carbon atoms, arylether containing 6 to 22 carbon atoms, cycloalkyl containing 6 to 22 carbon atoms, cycloalkylalkylene containing 7 to 22 carbon atoms, bicycloalkyl containing 7 to 22 carbon atoms, cyclothioalkyl containing 6 to 12 carbon atoms, aryl containing 5 to 12 carbon atoms and a heteroatom selected from the group consisting of -N, -O, and -S, alkylaldehyde containing 1 to 20 carbon atoms, and alkylarylaldehyde containing 7 to 20 carbon atoms, and wherein Z 1 or Z 2 is optionally substituted by alkyl of 1 to 8 carbon atoms; and each R 1is a monovalent unsaturated, unsubstituted or substituted alkenyl or alkynyl group selected from the group consisting of alkenyl containing 2 to 22 carbon atoms, cycloalkenyl containing 6 to 22 carbon atoms, bicycloalkenyl alkylene containing 7 to 22 carbon atoms, acrylate group, methacrylate group, alkynyl containing 2 to 22 carbon atoms, and each R 1 Oxiranyl and carbonate derivatives of the group, and oxiranyl groups containing 3 to 22 carbon atoms, carbonate groups containing 4 to 23 carbon atoms, Cl, Br, I, -SH, -SR, -OH, -OR, -CN, -NCO, and blocked -NCO, (X) x (Y) 3-x Si-, R 6 x R' 3-x and ionic groups derived from Si-, polyether groups, carboxy (-COOH), diacids, diesters, polyester groups, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and esters of carboxylic acids, S or P acids, phosphines, amino groups, primary amines, secondary amines, tertiary amines, keto groups, and betaines, and =R is as defined above, the subscript x is an integer from 1 to 3, and X and Y are each selected from the group consisting of OH, OR', -N(R')2, R'O(O)-O-, and R', where R' is as defined above, and X and Y may be the same or different, and where each R 6 is an aryl containing 6 to 10 carbon atoms, an arylalkyl containing 7 to 12 carbon atoms, a cycloalkyl containing 6 to 12 carbon atoms, a bicycloalkyl containing 7 to 16 carbon atoms, an epoxyalkyl containing 3 to 12 carbon atoms, an epoxycycloalkyl containing 6 to 12 carbon atoms, an epoxybicycloalkyl containing 7 to 16 carbon atoms, a thiocycloalkyl containing 6 to 12 carbon atoms, an aryl containing 5 to 12 carbon atoms and containing one or more heterosubstitutions of -N, -O, and -S- atoms.

[0009] The coating composition exhibits increased hydrophobicity, anti-graffiti properties, and / or ease of stain removal compared to a coating formulation without the additive.

[0010] In another embodiment, there is provided a method for preparing a coating composition comprising combining an organic binder (i) and a polyorganosiloxane (ii) of formula (I). DETAILED DESCRIPTION OF THE INVENTION

[0011] In one embodiment herein, all ranges herein are understood to include all subranges therebetween. In another specific embodiment herein, it is understood that any listing of members of a group can further include combinations of any two or more of the members of said group.

[0012] In the specification and claims, the following terms and phrases should be understood as indicated.

[0013] The singular forms "a," "an," and "the" include plurals, and references to numerical values ​​include at least that particular value unless the context clearly dictates otherwise. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes cases where the event occurs and cases where it does not occur.

[0014] Approximate terms used throughout this specification and claims may be applied to modify any quantitative expression that can vary within acceptable limits without causing a change in the relevant basic function. Thus, values ​​modified by terms such as "about" should not be limited to the exact value specified. In some cases, the approximation language may correspond to the precision of the instrument used to measure the value.

[0015] All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "etc.") provided herein is intended merely to better illustrate the invention and does not limit the scope of the invention unless otherwise claimed.

[0016] No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0017] The terms "comprising," "including," "containing," "characterized by," and their grammatical equivalents are inclusive or open-ended terms that do not exclude additional, unrecited elements or method steps, but are understood to include the more restrictive terms "consisting of" and "consisting essentially of."

[0018] Additionally, it is understood to include each and every individual representative and combination of any compound, material, or group of substances explicitly or implicitly disclosed and / or claimed in the specification as belonging to a group of structurally, compositionally, and / or functionally related compounds, materials, or substances.

[0019] The term "alkyl" as used herein means any monovalent saturated straight-chain, branched, or cyclic hydrocarbon group. Examples of alkyl include methyl, ethyl, propyl, and isobutyl.

[0020] As used herein, the term "aliphatic radical" refers to an organic group having at least one valence and consisting of a linear or branched array of atoms that is not cyclic. Aliphatic radicals are defined as containing at least one carbon atom. The array of atoms comprising an aliphatic radical may include heteroatoms such as nitrogen, sulfur, silicon, selenium, and oxygen, or may be composed exclusively of carbon and hydrogen. For convenience, the term "aliphatic radical" is defined herein to encompass a wide range of functional groups, such as alkyl, alkenyl, haloalkyl, conjugated dienyl, alcohol, ether, aldehyde, ketone, carboxylic acid, acyl (e.g., carboxylic acid derivatives such as esters and amides), amine, and nitro groups, as part of the "linear or branched array of atoms that is not cyclic." For example, the 4-methylpent-1-yl radical is a C6 aliphatic radical containing a methyl group, where the methyl group is the alkyl functional group. Similarly, the 4-nitrobut-1-yl radical is a C4 aliphatic radical containing a nitro functional group, where the nitro group is the functional group. The aliphatic radical may be a haloalkyl group containing one or more halogen atoms, which may be the same or different. Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine. Aliphatic radicals containing one or more halogen atoms include alkyl halides such as trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, bromodichloromethyl, bromoethyl, and 2-bromotrimethylene (e.g., —CHCHBrCH—).Further examples of aliphatic radicals include allyl, aminocarbonyl (e.g., -CONH), carbonyl, 2,2-dicyanoisopropylidene (i.e., -CHC(CN)CH-), methyl (i.e., -CH), methylene (i.e., -CH-), ethyl, ethylene, formyl (i.e., -CHO), hexyl, hexamethylene, hydroxymethyl (i.e., -CHOH), mercaptomethyl (i.e., -CHSH), methylthio (i.e., -SCH), methylthiomethyl (i.e., -CHSCH), methoxy, methoxycarbonyl (i.e., CHOCO-), nitromethyl (i.e., -CHNO), thiocarbonyl, trimethylsilyl (i.e., (CH)Si-), t-butyldimethylsilyl, 3-trimethyoxysilylpropyl (i.e., (CHO)SiCHCHCH-), vinyl, vinylidene, and the like. By way of further example, a C1-C10 aliphatic radical contains at least one but no more than 10 carbon atoms. A methyl group (i.e., CH3-) is an example of a C1 aliphatic radical. A decyl group (i.e., CH3(CH2)9-) is an example of a C10 aliphatic radical.

[0021] As used herein, the term "alicyclic radical" refers to a radical that has at least one valence and contains an arrangement of atoms that is cyclic but not aromatic. As defined herein, "alicyclic radical" does not include aromatic groups. An "alicyclic radical" may contain one or more acyclic elements. For example, a cyclohexylmethyl group (CH 11CH2-) is an alicyclic radical containing a cyclohexyl ring (a cyclic but non-aromatic arrangement of atoms) and a methylene group (a non-cyclic element). An alicyclic radical may contain heteroatoms such as nitrogen, sulfur, selenium, silicon, and oxygen, or may be composed exclusively of carbon and hydrogen. For convenience, the term "alicyclic radical" is defined herein to encompass a wide range of functional groups, such as alkyl, alkenyl, alkynyl, haloalkyl, conjugated dienyl, alcohol, ether, aldehyde, ketone, carboxylic acid, acyl (e.g., carboxylic acid derivatives such as esters and amides), amine, and nitro groups. For example, the 4-methylcyclopent-1-yl radical is a C6 alicyclic radical containing a methyl group, where the methyl group is the alkyl group functional group. Similarly, the 2-nitrocyclobut-1-yl radical is a C4 alicyclic radical containing a nitro group, where the nitro group is the functional group. An alicyclic radical may contain one or more halogen atoms, which may be the same or different. Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine. Alicyclic radicals containing one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene-2,2-bis(cyclohex-4-yl) (i.e., —CH 10 C(CF3)2C6H 10 -), 2-chloromethylcyclohex-1-yl, 3-difluoromethylenecyclohex-1-yl, 4-trichloromethylcyclohex-1-yloxy, 4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl, 2-bromopropylcyclohex-1-yloxy (e.g., CH3CHBrCH2CH 10 Further examples of alicyclic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (i.e., H2C6H 10-), 4-aminocarbonylcyclopent-1-yl (i.e., NH2COC5H8-), 4-acetyloxycyclohex-1-yl, 2,2-dicyanoisopropylidenebis(cyclohex-4-yloxy) (i.e., -OC6H 10 C(CN)2C6H 10 O-), 3-methylcyclohex-1-yl, methylenebis(cyclohex-4-yloxy) (i.e., -OCH 10 CH2C6H 10 O-), 1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-tetrahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl, hexamethylene-1,6-bis(cyclohex-4-yloxy) (i.e., -OCH 10 (CH2)6C6H 10 O-), 4-hydroxymethylcyclohex-1-yl (i.e., 4-HOCH2C6H 10 -), 4-mercaptomethylcyclohex-1-yl (i.e., 4-HSCH2C6H 10 -), 4-methylthiocyclohex-1-yl (i.e., 4-CH3SC6H 10 -), 4-methoxycyclohex-1-yl, 2-methoxycarbonylcyclohex-1-yloxy (2-CH3OCOC6H 10 O-), 4-nitromethylcyclohex-1-yl (i.e., NO2CH2C6H 10 -), 3-trimethylsilylcyclohex-1-yl, 2-t-butyldimethylsilylcyclopent-1-yl, 4-trimethoxysilylethylcyclohex-1-yl (i.e., (CHO)SiCHCHCHH 10 -), 4-vinylcyclohexen-1-yl, vinylidenebis(cyclohexyl), and the like. The term "C3-C10 cycloaliphatic radical" includes cycloaliphatic radicals containing at least 3 but not more than 10 carbon atoms. The cycloaliphatic radical 2-tetrahydrofuranyl (C4H7O-) represents a C4 cycloaliphatic radical. The cyclohexylmethyl radical (C6H 11 CH2-) represents a C7 cycloaliphatic radical.

[0022] As used herein, the term "aromatic" or "aromatic radical" refers to an array of atoms having at least one valence that includes at least one aromatic group. The array of atoms having at least one valence that includes at least one aromatic group may include heteroatoms such as nitrogen, sulfur, selenium, silicon, and oxygen, or may be composed exclusively of carbon and hydrogen. As used herein, the term "aromatic radical" includes, but is not limited to, phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl radicals. As noted, an aromatic group includes at least one aromatic group. An aromatic group is always a cyclic structure with 4n+2 "delocalized" electrons, where "n" is an integer of one or more, as illustrated by phenyl (n=1), thienyl (n=1), furanyl (n=1), naphthyl (n=2), azulenyl (n=2), anthracenyl (n=3), and the like. An aromatic radical may also include non-aromatic elements. For example, a benzyl group is an aromatic radical containing a phenyl ring (the aromatic group) and a methylene group (the non-aromatic element). Similarly, a tetrahydronaphthyl radical is an aromatic radical containing an aromatic group (CH) bonded to a non-aromatic element, -(CH). For convenience, the term "aromatic radical" is defined herein to encompass a wide range of functional groups, such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (e.g., carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like. For example, a 4-methylphenyl radical is a C aromatic radical containing a methyl group, where the methyl group is the alkyl group functional group. Similarly, a 2-nitrophenyl group is a C aromatic radical containing a nitro group, where the nitro group is the functional group.Aromatic radicals include halogenated aromatic radicals such as 4-trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-1-yloxy) (i.e., -OPhC(CF3)2PhO-), 4-chloromethylphen-1-yl, 3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-1-yl (i.e., 3-CCl3Ph-), 4-(3-bromoprop-1-yl)phen-1-yl (i.e., 4-BrCH2CH2CH2Ph-), and the like. Further examples of aromatic radicals include 4-allyloxyphen-1-oxy, 4-aminophen-1-yl (i.e., 4-HNPh-), 3-aminocarbonylphen-1-yl (i.e., NHCOPh-), 4-benzoylphen-1-yl, dicyanomethylidenebis(4-phen-1-yloxy) (i.e., -OPhC(CN)PhO-), 3-methylphen-1-yl, methylenebis(4-phen-1-yloxy) (i.e., -OPhCHPhO-), 2-ethylphen-1-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl, hexamethylene-1,6-bis(4-phen-1-yloxy), and the like. Examples of suitable aromatic radicals include 4-hydroxymethylphen-1-yl (i.e., -OPh(CH2)6PhO-), 4-hydroxymethylphen-1-yl (i.e., 4-HOCH2Ph-), 4-mercaptomethylphen-1-yl (i.e., 4-HSCH2Ph-), 4-methylthiophen-1-yl (i.e., 4-CH3SPh-), 3-methoxyphen-1-yl, 2-methoxycarbonylphen-1-yloxy (e.g., methylsalicyl), 2-nitromethylphen-1-yl (e.g., 2-NO2CH2Ph), 3-trimethylsilylphen-1-yl, 4-t-butyldimethylsilylphen-1-yl, 4-vinylphen-1-yl, vinylidenebis(phenyl), and the like. The term "C3-C10 aromatic radical" includes aromatic radicals containing at least three but not more than ten carbon atoms. The aromatic radical 1-imidazolyl (C3H2N2-) represents a C3 aromatic radical. The benzyl radical (C7H7-) represents a C7 aromatic radical.

[0023] As used herein, the term "non-hydrolyzable" refers to a group that cannot be easily cleaved by the addition of water, hydroxide anions, or, similarly, by the addition of alcohols or alkoxide anions. In the case of water or alcohols, the group is not easily cleaved, especially under acidic or basic conditions. The term "non-hydrolyzable" indicates that the group is preferably bonded to the silicon atom by a C-Si bond, and thus the non-hydrolyzable group is preferably an organyl group.

[0024] As used herein, the term "hydrolyzable" refers to a group that can be easily cleaved by the addition of water, hydroxide anion, alcohol, or alkoxide anion. In the case of water or alcohol, the group is easily cleavable, especially under acidic or basic conditions. The term "hydrolyzable" refers to a group that is bonded to a silicon atom by an Si-X bond, where X is Cl, Br, or I, rather than a C-Si bond, such as in the case of hydroxy, hydrocarbylcarbonyloxy, and hydrocarbyloxy groups, Si-O, Si-N, Si-S, or Si-H bonds.

[0025] Provided herein is a coating composition comprising (i) an organic binder and (ii) a polyorganosiloxane. In one or more embodiments, the coating composition exhibits increased hydrophobicity, anti-graffiti, anti-icing, anti-smudge, anti-fingerprint, anti-fogging, and / or ease of stain removal compared to a coating that does not contain the additive.

[0026] In some embodiments of the coating composition, the polyorganosiloxane is hydrolyzable or has been hydrolyzed. In these embodiments, the polyorganosiloxane can be alkoxy-functionalized ("hydrolyzable" or "partially hydrolyzed") and / or silanol-functionalized silicone ("fully hydrolyzed") and / or a combination. In other words, the coating composition of the present invention contains an alkoxy-functional silicone, a silanol-functional silicone, or a mixture thereof. As used herein, the term "alkoxy-functionalized and / or silanol-functionalized silicone" refers to a silicone containing an alkoxy-functional group, -OR, and / or a hydroxy-functional group, -OH, where R is an alkyl or aryl group, and where the -OH or -OR group is directly bonded to the silicon atom (i.e., -SiOH or -Si(OR)). In some embodiments, the alkoxy-functional group and / or the hydroxy-functional group can be hydrolyzed at least to some extent, up to 100%.

[0027] In some embodiments, a coating composition is provided that exhibits high hydrophobicity, anti-graffiti, anti-icing, anti-fouling, anti-fingerprint, anti-stain, anti-fog, and / or easy soil resistance properties. In such embodiments, the coating composition comprises (i) an organic binder, and (ii) a polyorganosiloxane of Formula I: Z 1 -L 1 {[Si(RR')O] p -SiR'''2} m -L 2 -Z 2 (I) wherein subscript p>9, and wherein subscript m is an integer from 1 to 5, and wherein each of R, R', or R'' is a saturated hydrocarbon substituent selected from the group consisting of monovalent alkyl containing 1 to 22 carbon atoms, optionally substituted with an F or -OH group, aryl containing 6 to 22 carbon atoms, polycyclic aryl containing 8 to 22 carbon atoms, alkylaryl containing 7 to 23 carbon atoms, and arylalkyl containing 7 to 22 carbon atoms, and H or L 1 -Z1 or L 2 -Z 2 where each of R, R', or R'' can be the same or different.

[0028] In Equation 1, L 1 or L 2 is a single bond, a divalent or trivalent group, and L 1 or L 2 can be selected from the group consisting of divalent alkylene groups having at least two carbon atoms. Optionally, the divalent alkylene group can be selected from the group consisting of L 1 or L 2 one or more -O-, -NR bonded to the silicon atom of the siloxy unit of the polyorganosiloxane (I) through a carbon bond of 3 -C(O)-, -NR 3 -, -OC(O)NR 3 - and / or -NR 3 -C(O)-NR 3 -part, where R 3 is hydrogen, Me3Si- or C1-C8-alkyl. Furthermore, the divalent alkenyl group is substituted by one or more OH groups. In some preferred embodiments, L 1 or L 2 is a divalent C2-C12-alkylene group, a divalent C2-C4 alkylene group. In some embodiments, L 1 or L 2 is —(CH)— and / or —(CH)—. In all such embodiments, L 1 and L 2 may be the same or different.

[0029] Z in Equation 1 1 or Z 2 are R, R', R'', R 1, monovalent unsubstituted or substituted C1-C30 hydrocarbons, C8-C22-alkylarylalkyl, C6-C22-arylether, C6-C22-cycloalkyl, C7-C22-cycloalkylalkylene, C7-C22 bicycloalkyl, C6-C12-cyclothioalkyl, C5-C12-hetero-N,-O,-S-aryl, C1-C20-alkylaldehydes and C7-C20-alkylarylaldehydes, optionally containing C1-C8-alkyl, OH, Cl, or Br, and silyl ether groups R 1 3Si—O—substituted with 1 is a monovalent unsaturated, unsubstituted or substituted alkenyl or alkynyl group selected from the group consisting of alkenyl, including C2-C22-alkenyl, C6-C22-cycloalkenyl, C7-C22-bicycloalkenylalkylene, C2-C22-alkynyl, and each R 1 oxiranyl and carbonate derivatives of C3-C22-oxiranyl groups, C4-C23-carbonate compounds, or groups selected from Cl, Br, I, -SH, -SR, -OH, -OR, -CN, -NCO, blocked NCO, or R 1 is (X) x (Y) 3-x Si-, or (R'X) x R' 3-x Si-, R 6 x R' 3-x a group selected from Si-, a polyether group, a carboxy (-COOH), a diacid, a diester, a polyester group, a nitro-alkyl-, a cyano-alkyl-, an acyl- or an alkylsulfonylfluoride- group, and an ionic group derived from an ester of a carboxylic acid or a sulfonic acid or a phosphonic acid, a phosphonate, a phosphine, an amine, a keto group, and a betaine, and wherein R' is as defined above, the subscript x is an integer from 1 to 3, and X and Y are each selected from the group consisting of OH, OR', -N(R')2, R'O(O)-O-, and R', where R' is as defined above, and X and Y may be the same or different, and wherein each R6 is aryl containing 6 to 10 carbon atoms, arylalkyl containing 7 to 12 carbon atoms, cycloalkyl containing 6 to 12 carbon atoms, bicycloalkyl containing 7 to 16 carbon atoms, epoxyalkyl containing 3 to 12 carbon atoms, epoxycycloalkyl containing 6 to 12 carbon atoms, epoxybicycloalkyl containing 7 to 16 carbon atoms, thiocycloalkyl containing 6 to 12 carbon atoms, and aryl containing 5 to 12 carbon atoms, wherein the aryl, alkylaryl, or cycloalkyl contains one or more heterosubstitutions of -N, -O, and -S- atoms.

[0030] As mentioned above, R 1 represents an ester of a carboxylic acid or a sulfonic acid or a phosphonic acid, for example, —C(O)——OR 3 , (R 3 O)2-P(O)-O-, (R 3 O)2-P(O)-, phosphonate (R 3 -O)2-P-, phosphines, amines, betaines, e.g., -NHR 3 -CH2-COOH, -NHR 3 -CH2-OS(O)2(OH), -SS(O)2(OR3), and primary, secondary, and tertiary amines -N(R 3 )2, or phosphine-P(R 3 )2, and acid addition salts of amines or phosphines, preferably quaternary -N + R 2 3 or -P + R 2 R is a group selected from salts having three groups, and ionic groups derived from alkyl or aryl enamines. 3 is hydrogen, C1-C8 alkyl, a single bond or L 1 or L 2 is a C2-C8 alkenyl bonded to a silicon atom of a siloxy unit of polyorganosiloxane (I) through a carbon bond of

[0031] In one embodiment, R 1 is -C(O)-OR 3 , (R 3O)2-P(O)-O-, (R 3 O)2-P(O)-, phosphonate (R 3 -O)2-P-, -NR 3 -CH2-COOH, -NR 3 -CH2-OS(O)2(OH), -SS(O)2(OR3),-N(R 3 )2, -P(R 3 )2, Acid addition salts of amines, quaternary-N + R 2 3 or -P + R 2 a salt having three groups, an alkyl or aryl enamine of formula (II), [ka] where R 3 is hydrogen or alkyl of 1 to 8 carbon atoms, and a single bond or L 1 or L 2 and the alkenyl contains from 2 to 8 carbon atoms bonded to the silicon atom of each siloxy unit of the polyorganosiloxane (I) through a carbon bond of

[0032] In one or more embodiments, Z of formula (I) as defined herein 1 or Z 2 is optionally -O-, -NH-, -C(O)-, -C(S)-, a tertiary amino group [ka] and quaternary ammonium groups [ka] and organosilyl groups. In some embodiments, Z as defined herein may include one or more groups selected from 1 or Z 2 is an alkyl of 1 to 8 carbon atoms, OH, Cl, or Br, and a silyl ether group R 1 3Si—O—, where R1 is as defined above for formula (I), and wherein R 1 is preferably an alkyl group of 1 to 8 carbon atoms, most preferably Me, and Z 1 or Z 2 may be terminated with OH-, oxyalkyl- of 1 to 8 carbon atoms, or oxycarbonylalkyl of 1 to 8 carbon atoms, poly-C2-C4-alkylene oxide, vinyl, allyl, hexenyl, octenyl, allyloxypropyl, -CH2C≡CH, -C(O)C≡CH, -C(O)(CH2)8CH=CH2, cyclohexenylethyl, limonyl, norbornenylethyl, vinylphenylethyl, allyloxyphenyloxypropyl, -(OCH2CHO) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OCH=CH2, or -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OH, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-Alkyl containing 1 to 4 carbon atoms, or -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OC(O)- alkyl of 1 to 4 carbon atoms, where a, b, and c are 0 to 20 and a+b+c=1 to 20, -[-Si(CH3)2OSi(CH3)2]CH=CH2, and [ka] (X) x (Y) 3-x Si-, or (R'X) x R' 3-xSi-, where R' is as defined above and the subscript x is an integer from 1 to 3, and X and Y are each selected from the group consisting of OH, OR', -N(R')2, R'C(O)-O-, and an unsubstituted or substituted oxyphenyl moiety of the formula: [ka] where R 10 and R 14 are hydrogen or R as defined above. 1 and R 11 , R 12 , R 13 is selected from -OR, where R=H or alkyl of 1 to 8 carbon atoms, where the group R 11 From R 13 at least one of which is OH, and eugenol, bisphenol ether, cumylphenol ether, glycidyl propyl ether, epoxy limonyl, epoxy cyclohexyl, epoxy norbornyl, [ka] and carbonate derivatives of these epoxides, tetrahydro-2H-thiopyranyl, carbazole, indole, trisphenylsilyl, and R 6 MeSi-, where R 6is as defined herein and is optionally substituted by alkyl of 1 to 8 carbon atoms, OH, Cl, CN, and the silyl ether group RSi—O—, and groups selected from Cl, —SH, —NCO, blocked NCO, and ionizable groups derived from esters of carboxylic acids, phenyl, phenylpropyl, styryl, naphthyl, eugenol, bisphenol ether, cumylphenol ether, norbornyl, vinyl, allyl, allyloxypropyl, hexenyl, norbornenyl, cyclohexenylethyl, limonyl, and glycidyl propyl ether, epoxylimonyl, epoxycyclohexenyl, epoxynorbornyl, and carbonate derivatives of these epoxides; (X) x (Y) 3-x Si-, or (R'X) x R' 3-x Si-, R 6 x R' 3-x Si-, where x, X and Y are as defined above, and where R 6 In one embodiment, may be selected from phenyl, naphthyl, phenylethyl, phenylpropyl, eugenol, limonyl, epoxylimonyl, glycidyl propyl ether epoxycyclohexylethyl, norbornenylethyl, epoxynorbornenylethyl, carbazole, and indole.

[0033] Further, in some embodiments, Z 1 or Z 2can specifically represent an unsubstituted alkyl group containing 1 to 24 carbon atoms, specifically a straight-chain alkyl group containing 1 to 24 carbon atoms; a poly(alkylene oxide) group having 2 to 24 carbon atoms, wherein the alkylene oxide units are ethylene oxide units, propylene oxide units, or a combination of these units; an oxycarbonyl hydrocarbyl group containing 2 to 24 carbon atoms, specifically an oxycarbonyl alkyl group containing 2 to 24 carbon atoms, an oxyalkyl group containing 1 to 24 carbon atoms, an alkanoyl group containing 1 to 24 carbon atoms, or an alkanoyl ester group containing 1 to 24 carbon atoms, wherein the alkoxide group of the alkanoyl ester group is an alkoxide group of 1 to 24 carbon atoms.

[0034] In some embodiments, Z 1 or Z 2 specifically represents an unsubstituted alkyl group containing 1 to 24 carbon atoms and is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl groups.

[0035] According to the present invention, the group Z 1 or Z 2 When represents a poly(alkylene oxide) group having 2 to 24 carbon atoms, it preferably represents a poly(ethylene oxide) group containing 3 to 12 ethylene oxide repeating units or a poly(propylene oxide) group containing 3 to 8 propylene oxide repeating units.

[0036] Base Z 1 or Z 2If represents an oxycarbonylalkyl group containing 2 to 24 carbon atoms, it is preferred according to the invention if the alkyl group of the oxycarbonyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl groups, branched alkyl groups containing 3 to 22 carbon atoms, such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl groups, and cyclic alkyl groups containing 3 to 22 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups. It is also preferred according to the invention if the alkyl group of the oxycarbonylalkyl group is attached to the oxycarbonyl group by a carbon atom substituted with three alkyl substituents, each containing 1 to 8 carbon atoms.

[0037] Base Z 1 or Z 2 represents an oxyalkyl group of 1 to 24 carbon atoms, according to the present invention, the alkyl group of the oxyalkyl group containing 1 to 24 carbon atoms is preferably selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-hexyl, n-heptyl or n-octyl groups, branched alkyl groups containing 3 to 22 carbon atoms, such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl groups, and cyclic alkyl groups containing 3 to 22 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups.

[0038] Base Z 1 or Z 2represents an alkanoyl group containing 1 to 24 carbon atoms, according to the present invention, the alkanoyl group containing 1 to 24 carbon atoms is preferably a carboxylate, -COOH, -CH2CO2H, -(CH2)2CO2H, -(CH2)3CO2H, -(CH2)4CO2H, -(CH2)5CO2H, -(CH2)6CO2H, -(CH2)7CO2H, -(CH2)7CO2H, -(CH2)9CO2H, or -(CH2) 10 COH.

[0039] Base Z 1 or Z 2 represents an alkanoyl ester group of 1 to 24 carbon atoms, where the alkoxide group of the alkanoyl ester group is an alkoxide group, and according to the present invention the alkanoyl group is preferably a carboxylate, -COOH, -CH2CO2H, -(CH2)2CO2H, (CH2)3CO2H, (CH2)4CO2H, (CH2)5CO2H, (CH2)6CO2H, (CH2)7CO2H, (CH2)7CO2H, (CH2)9CO2H, or (CH2) 10 COH, and the alkoxide group of the ester is preferably selected from methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy or n-hexoxy groups. Particularly preferred alkanoyl ester groups according to the present invention are selected from the group consisting of -COOMe, -COOEt, -COOtBu, -CH2CO2Me, -CH2CO2Et, CH2CO2tBu, -(CH2)2CO2Me, -(CH2)2CO2Et, -(CH2)2CO2-tBu, -(CH2)3CO2Me, -(CH2)3CO2Et, -(CH2)3CO2tBu, -(CH2)4CO2Me, -(CH2)4CO2Et, -(CH2)4CO2tBu, -(CH2)5CO2Me, -(CH2)5CO2Et, -(CH2)5CO2tBu, -(CH2)6CO2Me, -(CH2)6CO2Et, and -(CH2)6CO2tBu. Preferably, the hydrocarbyl radical Z 1 or Z 2The substituents in the formula -C are hydroxyl groups, alkoxy groups, in particular methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butyoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy, n-hexoxy, cyclopentoxy or cyclohexoxy groups, siloxy groups, in particular -SiMe2-O-, CH=CH2, -OSiMe3, -OSiEt3, -OSi(iPr)3, -OSiPh3, -OSi(cyHex)3, -OSi(tBu)Me2, -OSi(tBu)Ph2, perfluoroalkyl groups, in particular trifluoromethyl, groups of the general formula -C with x=2 to 24. x F 2x+1 linear perfluoroalkyl groups of the formula -COOMe, -COOEt, -COOtBu, -CH2CO2Me, -CH2CO2Et, CH2CO2tBu, (CH2)2CO2Me, (CH2)2CO2Et, (CH2)2CO2tBu, -(CH2)3CO2Me, (CH2)3CO2Et, (CH2)3CO2tBu, (CH2)4CO2Me, (CH2)4CO2Et, (CH2)4CO2tBu, -(CH2)5CO2Me, -(CH2)5CO2Et, (CH2)5CO2tBu, (CH2)6CO2Me, (CH2)6CO2Et, and (CH2)6CO2tBu, and ester groups, in which the alkoxy group is derived from a tertiary alkoxide containing 1 to 25 carbon atoms, and -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OH, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-Alkyl of 1 to 4 carbon atoms, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OC(O)- alkyl of 1 to 4 carbon atoms, and -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c-O-SiR3, where R is alkyl of 1 to 8 carbon atoms, a, b, c are 0 to 20, and a+b+c=1 to 20; more preferably, the hydrocarbyl radical Z 1 or Z 2 simultaneously contains both a polyether group and a terminal hydroxyl group, a polyether group and a terminal alkoxy group, or a polyether group and a terminal siloxy group, as defined above.

[0040] In one or more embodiments, Z in formula (I) 1 or Z 2 further comprises at least one moiety selected from the group consisting of polyether moieties, ester moieties, and coating matrix reactive moieties, such as alkenyl, epoxy, acrylate, methacrylate, thiolate, hydroxyl, alkoxy, carboxy (—COOH), amino, alkoxysilyl, and isocyanate, ketone, diketone, 1,3 diketone, diacid, 1,3 diacid, diester, 1,3 diester, CH—, nitro-alkyl-, cyano-alkyl-, acyl-, and alkylsulfonyl fluoride-groups adjacent to a carbonyl group, and donor and acceptor groups in a Michael addition reaction. In some particular embodiments, Z of formula (I) 1 or Z 2 contains a polyether moiety. The polyether moiety is -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OH, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-Alkyl of 1 to 4 carbon atoms, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OC(O)- alkyl of 1 to 4 carbon atoms, and -(OCH2CH2) a -(OCH2CH(CH3))b -(OCH2CH2CH(CH3)) c -O-SiR3, where R is alkyl of 1 to 8 carbon atoms, a, b, c are 0 to 20, and a+b+c=1 to 20, and the formula -(OCH2CH2) 3-10 , -(OCH2CH2) 3-10 -OH, and -(OCH2CH(CH3)) 3-10、 -(OCH2CH(CH3)) 3-10 A group represented by —OH is more preferred.

[0041] In some embodiments, Z of formula (I) of the coating composition 1 or Z 2 is selected from vinyl esters of linear or branched chain carboxylic acids. In one or more embodiments, Z in formula (I) 1 or Z 2 is selected from vinyl esters of linear carboxylic acids. In one or more embodiments, Z in formula (I) of the coating composition 1 or Z 2 is selected from vinyl esters of branched chain carboxylic acids.

[0042] In some embodiments, Z of formula (I) 1 or Z 2 may be selected from vinyl esters of neopentanoic acid, vinyl esters of neodecanoic acid, or vinyl esters of neononanoic acid. In some embodiments, Z in formula (I) 1 or Z 2 may be selected from vinyl esters of neodecanoic acid or vinyl esters of neononanoic acid.

[0043] In one or more embodiments, Z of Formula 1 of the coating composition 1 Or Z 2 , or Z 1 and Z 2 In some embodiments, both of Z in formula (I) of the coating composition are selected from vinyl esters of neodecanoic acid or vinyl esters of neononanoic acid. 1 or Z2 In some other embodiments, Z in formula (I) of the coating composition is selected from vinyl esters of neononanoic acid. 1 or Z 2 is selected from vinyl esters of neodecanoic acid.

[0044] As noted above, in some embodiments, Z in formula (I) 1 and Z 2 is a vinyl ester of neodecanoic acid or neononanoic acid, wherein Z does not represent a vinyl ester of neodecanoic acid or neononanoic acid. 1 or Z 2 may be a crosslinker (crosslinking agent, crosslinker). The crosslinker may be a reactive functional group. In one or more embodiments, the reactive functional group of the crosslinker functions as a binder or a curing agent (cured product). In such embodiments, Z in formula (I) 1 is a vinyl ester of neodecanoic acid or neononanoic acid, Z 2 is selected from crosslinkers that are reactive functional groups that react with the coating matrix. In some embodiments, the crosslinker functions as a binder or a curing agent. In other embodiments, Z in formula (I) 2 is a vinyl ester of neodecanoic acid or neononanoic acid, then Z 1 is selected from crosslinkers, which are reactive functional groups that react with the coating matrix.

[0045] In one embodiment, R 1 is -C(O)-OR 3 , (R 3 O)2-P(O)-O-, (R 3 O)2-P(O)-, phosphonate (R 3 -O)2-P-, -NR 3 -CH2-COOH, -NR 3 -CH2-OS(O)2(OH), -SS(O)2(OR3), -N(R 3 )2, -P(R 3 )2, Acid addition salts of amines, quaternary-N + R2 3 or -P + R 2 a salt having three groups, an alkyl or aryl enamine of formula (II), [ka] where R 3 is hydrogen or alkyl of 1 to 8 carbon atoms, and a single bond or L is bonded to the silicon atom of each siloxy unit of the polyorganosiloxane (I). 1 or L 2 is an alkenyl containing 2 to 8 carbon atoms attached via a carbon bond.

[0046] As used herein, a crosslinker refers to a reactive functional group that forms a covalent bond with an organic binder or curing agent present in a coating composition. In some embodiments, the reactive functional group of the crosslinker forms a covalent bond with the binder of the coating composition. In some other embodiments, the reactive functional group of the crosslinker forms a covalent bond with the curing agent of the coating composition. The reactive group depends on the type of functional group and the type of binder and / or curing agent.

[0047] In some embodiments of the coating composition, Z 1 or Z 2 is selected from the group consisting of alkoxy, hydroxyalkyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, ketone, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction. In some embodiments, Z in formula (I) 1 is a vinyl ester of neononanoic or neodecanoic acid, Z 2is selected from the group consisting of alkoxy, hydroxyalkyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction. 2 is a vinyl ester of neononanoic or neodecanoic acid, Z 1 is selected from the group consisting of alkoxy, hydroxyalkyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl- or alkylsulfonylfluoride-groups, and donor and acceptor groups in a Michael addition reaction.

[0048] In some other embodiments of the coating composition, the polyorganosiloxane is represented by the general formula (IIA): [ka] Here Z 1 , Z 2 , Z 3 , and Z 4 may be the same or different, where subscript n is 0 or an integer from 1 to 20, subscript m is 0 or an integer from 1 to 20, and subscript o is 0 or an integer from 1 to 20.

[0049] In formula (IIA), R or R' is a saturated hydrocarbon substituent selected from the group consisting of monovalent alkyl containing 1 to 22 carbon atoms, optionally substituted with F; aryl containing 6 to 22 carbon atoms, polycyclic aryl containing 8 to 22 carbon atoms, alkylaryl containing 7 to 22 carbon atoms, arylalkyl containing 7 to 22 carbon atoms, and H; or L 1 -Z 1 , L 2 -Z 2 , L 3 -Z 3 , or L 4 -Z 4 and where R and R' may be the same or different.

[0050] In formula (IIA), Z in formula (IIA) 1 , Z 2 , Z 3 or Z 4 are R, R', and R 1 , alkylarylalkyl containing 8 to 22 carbon atoms, aryl ether containing 6 to 22 carbon atoms, cycloalkyl containing 6 to 22 carbon atoms, cycloalkylalkylene containing 7 to 22 carbon atoms, bicycloalkyl containing 7 to 22 carbon atoms, cyclothioalkyl containing 6 to 12 carbon atoms, aryl containing 5 to 12 carbon atoms and a heteroatom selected from the group consisting of -N, -O, and -S, alkylaldehyde containing 1 to 20 carbon atoms, and alkylarylaldehyde containing 7 to 20 carbon atoms, each of which groups optionally contains an alkyl of 1 to 8 carbon atoms, OH, Cl, or Br, and a silyl ether group R 1 3Si—O—, which may be substituted with Si—O—.

[0051] In formula (IIA), R 1is a monovalent unsaturated, unsubstituted or substituted alkenyl or alkynyl group selected from the group consisting of alkenyl containing 2 to 22 carbon atoms, cycloalkenyl containing 6 to 22 carbon atoms, bicycloalkenyl alkylene containing 7 to 22 carbon atoms, acrylate group, methacrylate group, alkynyl containing 2 to 22 carbon atoms, and each R 1 Oxiranyl and carbonate derivatives of the group, oxiranyl groups containing 3 to 22 carbon atoms, carbonate groups containing 4 to 23 carbon atoms, Cl, Br, I, -SH, -SR, -OH, -OR, -CN, -NCO, and blocked -NCO, (X) x (Y) 3-x Si-, R 6 x R' 3-x Ionic groups derived from Si-, polyether groups, carboxy (-COOH), diacids, diesters, polyester moieties, nitro-alkyl-, cyano-alkyl-, acyl- or alkylsulfonylfluoride-groups, and esters of carboxylic acids, S or P acids, phosphines, amino groups, primary amines, secondary amines, tertiary amines, keto groups, and betaines.

[0052] In formula (IIA), Z 1 , Z 2 , Z 3 and Z 4 may be the same or different.

[0053] In formula (IIA), L 1 , L 2 , L 3 and L 4 Each of the is a single bond, L 1 , L 2 , L 3 and L 4 -O-, -NR bonded to the silicon atom of each siloxy unit of polyorganosiloxane (IIA) through a carbon bond of 3 -C(O)- and / or -NR 3 -, -OC(O)NR 3 -, -NR 3 -C(O)-NR3 - or a trivalent group, wherein L is selected from the group consisting of a divalent alkylene group having at least two carbon atoms, optionally interrupted by one or more - moieties and optionally substituted with one or more OH groups, 1 and L 2 may be the same or different, and where R 3 is hydrogen, Me3Si- or alkyl containing 1 to 8 carbon atoms, and wherein L 1 , L 2 , L 3 , and L 4 may be the same or different.

[0054] In one or more embodiments, Z in formula (IIA) 1 , Z 2 , Z 3 or Z 4 comprises at least one moiety selected from the group consisting of polyether moieties, ester moieties, and coating matrix reactive moieties such as alkenyl, alkoxy, hydroxyalkyl, alkoxysilyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, ketone, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction.

[0055] In some specific embodiments, Z of formula (IIA) 1 , Z 2 , Z 3 or Z 4 contains a polyether moiety. The polyether moiety is -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OH, -(OCH2CH2) a -(OCH2CH(CH3)) b-(OCH2CH2CH(CH3)) c -O-Alkyl of 1 to 4 carbon atoms, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OC(O)- alkyl of 1 to 4 carbon atoms, and -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-SiR, where R is alkyl of 1 to 8 carbon atoms, a, b, c are 0 to 20, and a+b+c=1 to 20, and may include alkyl groups of the formula -(OCHCH) 3-10 , -(OCH2CH2) 3-10 -OH, and -(OCH2CH(CH3)) 3-10、 -(OCH2CH(CH3)) 3-10 A group represented by —OH is more preferred.

[0056] In some embodiments, Z of formula (IIA) of the coating composition 1 , Z 2 , Z 3 or Z 4 is selected from vinyl esters of linear or branched chain carboxylic acids. 1 , Z 2 , Z 3 or Z 4 is selected from vinyl esters of linear carboxylic acids. In one or more embodiments, Z of formula (IIA) of the coating composition 1 , Z 2 , Z 3 or Z 4 is selected from vinyl esters of branched chain carboxylic acids.

[0057] In one or more embodiments, Z of formula (IIA) of the coating composition 1 , Z 2 , Z 3 or Z 4 , or Z 1 and Z 3 or Z2 and Z 4 or Z 1 and Z 4 or Z 2 and Z 4 or Z 3 and Z 4 or Z 1 and Z 2 or Z 1 and Z 3 and Z 4 In some embodiments, both of Z in Formula (IIA) are selected from vinyl esters of neodecanoic acid or vinyl esters of neononanoic acid. 1 , Z 2 , Z 3 or Z 4 At least one of Z in formula (IIA) of the coating composition is a vinyl ester of neodecanoic acid or neononanoic acid. 1 , Z 2 , Z 3 or Z 4 is selected from vinyl esters of neononanoic acid containing 9 carbon atoms in the acid moiety, an example of which is VeoVa 9™ available from Hexion Inc. In some embodiments, Z of formula (IIA) 1 , Z 2 , Z 3 or Z 4 In some embodiments, at least one of Z in formula (IIA) of the coating composition is VeoVa9. 1 , Z 2 , Z 3 or Z 4 is selected from vinyl esters of neodecanoic acid containing 10 carbon atoms in the acid moiety, which is also known as VeoVa 10™ and is available from Hexion Inc. In some embodiments, Z of formula (IIA) 1 , Z 2 , Z 3 or Z 4 At least one of the is a vinyl ester of neodecanoic acid.

[0058] As noted above, in embodiments of the polyorganosiloxane of formula (IIA), Z1 , Z 2 , Z 3 or Z 4 is selected from vinyl esters of neodecanoic acid or neononanoic acid, for example, Z 1 is selected from vinyl esters of neodecanoic acid. 1 , Z 2 , Z 3 and Z 4 At least one of the remaining groups is selected from crosslinkers (coating matrix reactive groups), e.g., Z 2 is selected from crosslinkers. In some of these embodiments, Z 1 , Z 2 , Z 3 and Z 4 The remainder of, for example, Z 3 In such an exemplary embodiment, Z of the polyorganosiloxane of formula (II) is a vinyl ester of neodecanoic acid. 1 , Z 2 , Z 3 and Z 4 two groups selected from represent vinyl esters of neodecanoic acid, and Z 1 , Z 2 , Z 3 and Z 4 represents a crosslinker, wherein in one embodiment, Z 1 or Z 2 can be a vinyl ester of neodecanoic acid (pendant position), and Z 3 or Z 4 can be a vinyl ester of neodecanoic acid (terminal position). 3 and Z 4 can be a vinyl ester of neodecanoic acid (wherein the vinyl ester of neodecanoic acid occupies all terminal positions). 1 , Z 2 , Z 3 and Z 4 two groups are crosslinkers, and at least one of the remaining groups is a vinyl ester of neodecanoic acid. 1or Z 2 can be a cross-linker (pendant position), and Z 3 or Z 4 In another embodiment, Z 3 and Z 4 can be a crosslinker (where the crosslinker occupies all terminal positions).

[0059] As noted above, in some embodiments, Z in formula (IIA) 1 , Z 2 , Z 3 or Z 4 at least one of Z is a vinyl ester of neodecanoic acid, wherein the remaining Z does not represent a vinyl ester of neodecanoic acid; 1 , Z 2 , Z 3 or Z 4 may be a crosslinker. The crosslinker may be a reactive functional group that reacts with the coating matrix. In such an embodiment, Z in formula (IIA) 1 or Z 2 is a vinyl ester of neodecanoic acid, then Z 3 and Z 4 In another embodiment, at least one or both of Z in formula (IIA) is selected from crosslinkers that are reactive functional groups that react with the coating matrix. 3 or Z 4 or if both are vinyl esters of neodecanoic acid, then Z 1 or Z 2 The crosslinker is selected from crosslinkers in which one or both of the functional groups is a reactive functional group. As used herein, a crosslinker refers to a reactive functional group that forms a covalent bond with an organic binder or curing agent present in the coating composition. In some embodiments, the reactive functional group of the crosslinker forms a covalent bond with the binder of the coating composition. In some other embodiments, the reactive functional group of the crosslinker forms a covalent bond with the curing agent of the coating composition. The reactivity depends on the type of functional group and the type of binder and / or curing agent.

[0060] In some embodiments of the coating composition, Z 1 , Z 2 , Z 3 or Z 4 is selected from the group consisting of alkenyl, alkoxy, hydroxyalkyl, alkoxysilyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, ketone, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction. In some embodiments, the four Z in Formula (IIA) 1 , Z 2 , Z 3 or Z 4 is a vinyl ester of neodecanoic acid, then Z 1 , Z 2 , Z 3 or Z 4 At least one of the remaining groups is selected from the group consisting of alkenyl, alkoxy, hydroxyalkyl, alkoxysilyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, ketone, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction. The vinyl ester of neodecanoic acid in such embodiments can be a vinyl ester of neononanoic acid or a vinyl ester of neodecanoic acid. In some other embodiments, Z of Formula (IIA) 1 or Z 2 or Z if both are vinyl esters of neodecanoic or neononanoic acid. 3 or Z 4or both are selected from the group consisting of alkenyl, alkoxy, hydroxyalkyl, alkoxysilyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, ketone, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction.

[0061] In some embodiments of the coating composition, Z of formula (IIA) 1 , Z 2 , Z 3 or Z 4 at least one but not more than three of Z are selected from vinyl esters of neodecanoic acid or neononanoic acid; 1 , Z 2 , Z 3 or Z 4 The remaining groups are trimethoxysilyl groups.

[0062] In some embodiments of the coating composition, Z of formula (IIA) 1 , Z 3 and Z 4 is selected from vinyl esters of neodecanoic or neononanoic acid, where Z 2 is a trimethoxysilyl group.

[0063] In some embodiments of the coating composition, Z of formula (IIA) 1 and optionally Z 2 is selected from vinyl esters of neodecanoic or neononanoic acid, 3 and Z 4 , and optionally Z 2 is a trimethoxysilyl group.

[0064] In some embodiments, Z of formula (IIA) of the coating composition 1 , Z 2 , Z 3or Z 4 represents a polyether moiety, e.g., -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OH, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-Alkyl of 1 to 4 carbon atoms, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OC(O)- alkyl of 1 to 4 carbon atoms, and -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c —O—SiR3, where R is alkyl of 1 to 8 carbon atoms, a, b, c are 0 to 20, and a+b+c=1 to 20. In one or more embodiments, Z of formula (IIA) of the coating composition is selected from: 1 , Z 2 , Z 3 or Z 4 is the formula -(OCH2CH2) 3-10 , -(OCH2CH2) 10 -OSi(CH3) 3-10 , -(OCH2CH2) 3-10 -OH, -(OCH2CH(CH3)) 3-10 , and -(OCH2CH(CH3)) 3-10 The group is selected from groups represented by -OH.

[0065] In one or more embodiments, Z of formula (IIA) of the coating composition 1 , Z 2 , Z 3 or Z 4 , or Z 1 and Z 3 or Z 2 and Z 4 or Z 1 and Z 4 or Z 2 and Z4 In some embodiments, both of Z in Formula (IIA) are selected from polyether groups. 1 , Z 2 , Z 3 or Z 4 In some embodiments, at least one of Z in formula (IIA) of the coating composition is a polyether. 1 , Z 2 , Z 3 or Z 4 is the formula -(OCH2CH2) 7,5 In some embodiments, the Z of formula (IIA) is selected from polyethers represented by the formula: 1 , Z 2 , Z 3 or Z 4 At least one of the groups has the formula -(OCH2CH2) 3-10 -OSi(CH3)3 or -(OCH2CH2) 3-10 It is a polyether represented by —OH.

[0066] As noted above, in embodiments of the polyorganosiloxane of formula (IIA), Z 1 , Z 2 , Z 3 or Z 4 One or more of Z is selected from polyethers, e.g., Z 1 In these embodiments, Z is selected from polyethers. 1 , Z 2 , Z 3 and Z 4 At least one of the remaining is selected from cross-linkers, e.g., Z 2 is selected from crosslinkers. In some of these embodiments, Z 1 , Z 2 , Z 3 and Z 4 The remainder of, for example, Z 3 is another polyether. In such an exemplary embodiment, Z of the polyorganosiloxane of formula (IIA) 1 , Z 2 , Z 3 and Z 4 two groups selected from represent a polyether, and Z1 , Z 2 , Z 3 and Z 4 represents a crosslinker, where in one embodiment, Z 3 or Z 4 can be a polyether (terminal position), and Z 1 or Z 2 In another embodiment, Z 3 and Z 4 can be a polyether (the polyether occupies all terminal positions). In yet another embodiment, Z 1 , Z 2 , Z 3 and Z 4 two groups are crosslinkers and at least one of the remaining groups is a polyether, wherein in one embodiment, Z 3 or Z 4 can be a cross-linker (pendant position), and Z 1 or Z 2 In another embodiment, Z 3 and Z 4 can be a crosslinker (crosslinkers occupy all terminal positions).

[0067] As noted above, in some embodiments, Z of Formula II 1 , Z 2 , Z 3 or Z 4 at least one of Z is a polyether, and the remaining Z not representing a polyether 1 , Z 2 , Z 3 or Z 4 may be a crosslinker. The crosslinker may be a reactive functional group that reacts with the coating matrix. In one or more embodiments, the reactive functional group of the crosslinker functions as a binder or curing agent. In such embodiments, Z of Formula II 1 or Z 2 is a polyether, then Z 3 and Z 4In another embodiment, at least one or both of Z in Formula II is selected from crosslinkers that are reactive functional groups that react with the coating matrix. 3 or Z 4 or if both are polyethers, then Z 1 or Z 2 In some embodiments, the reactive functional group of the crosslinker forms a covalent bond with the binder of the coating composition. In other embodiments, the reactive functional group of the crosslinker forms a covalent bond with the curing agent of the coating composition. The reactivity depends on the type of functional group and the type of binder and / or curing agent.

[0068] In some embodiments of the coating composition, Z 1 , Z 2 , Z 3 or Z 4 is selected from the group consisting of alkenyl, alkoxy, hydroxyalkyl, alkoxysilyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, ketone, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction. In some embodiments, the four Z in Formula II are 1 , Z 2 , Z 3 or Z 4 If at least one but not more than three of Z are polyethers, then Z 1 , Z 2 , Z 3 or Z 4wherein at least one of the remaining groups is selected from the group consisting of alkenyl, alkoxy, hydroxyalkyl, alkoxysilyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, ketone, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction. The polyethers of such embodiments have the formula —(OCHCH) 7,5 -OCH3 or -(OCH2CH2) 10 -OSi(CH3)3 or -(OCH2CH2) 10 In some other embodiments, Z in formula (IIA) can be represented by —OH. 1 or Z 2 or if both are polyethers, Z 3 or Z 4 or both are selected from the group consisting of alkenyl, alkoxy, hydroxyalkyl, alkoxysilyl, trialkoxysilyl, isocyanate, acrylate, methacrylate, epoxy, thiolate, hydroxyl, carboxy (—COOH), amino, ketone, diketone, 1,3-diketone, diacid, 1,3-diacid, diester, 1,3-diester, nitro-alkyl-, cyano-alkyl-, acyl- or alkylsulfonyl fluoride-groups, and donor and acceptor groups in a Michael addition reaction.

[0069] In some embodiments of the coating composition, Z of formula (IIA) 1 , Z 2 , Z 3 or Z 4 Up to three groups of the formula -(OCH2CH2) 7,5 -OCH3, or -(OCH2CH2) 10 -OSi(CH3)3, or -(OCH2CH2) 10 -OSi(CH3)3, wherein Z is selected from polyethers represented by 1 , Z2 , Z 3 or Z 4 The remaining groups are 1,3-diesters of the formula -O(CO)CH2(COOCH3).

[0070] In some embodiments of the coating composition, Z of formula (IIA) 1 , Z 3 and Z 4 is the formula -(OCH2CH2) 7,5 -OCH3, and -(OCH2CH2) 10 -OSi(CH3)3, wherein Z is selected from the group of polyethers represented by 2 is a 1,3-diester with the formula -O(CO)CH2(COOCH3).

[0071] In some embodiments of the coating composition, Z of formula (IIA) 1 and optionally Z 2 is the formula -(OCH2CH2) 7,5 -OCH3, and -(OCH2CH2) 10 -OSi(CH3)3, wherein Z is selected from polyethers represented by 3 and Z 4 , and optionally Z 2 is a 1,3-diester with the formula -O(CO)CH2(COOCH3).

[0072] In some embodiments, the polyorganosiloxane is selected so that the final silicone-based coating product has a weight average molecular weight of silicone ranging from about 100 to about 10,000, from about 600 to about 10,000, or from about 800 to about 5,000. In some embodiments, the polyorganosiloxane is selected so that the viscosity of the silicone in the silicone-based coating is from about 2 cps to about 2,500 cps, preferably from about 2 cps to about 1,800 cps, more preferably from about 5 cps to about 1,700 cps, and most preferably from about 10 cps to about 1,600 cps. As described herein, viscosity is measured using a rotational viscometer at a shear rate of 10 s -1Measured at 25°C.

[0073] In certain embodiments, the aforementioned polyorganosiloxane selected from the group of compounds of formula (I) or (IIA) is present in the coating composition in an amount ranging from about 0.01 to about 30 weight percent, for example, from about 0.02 to about 20 weight percent, or in some cases, from about 0.05 to about 15 weight percent, where the weight percent is based on the total weight of the coating / coating composition.

[0074] The organic binder of the coating compositions described herein can be one or more organic binders, preferably a polymeric organic binder. In the broadest aspect, it is contemplated that any polymeric binder can be used. The binder imparts properties such as gloss, durability, flexibility, and toughness. The organic binder (a) can be an organic binder selected from the group consisting of acrylic resins, hydroxyacrylate resins, vinyl acrylic resins, vinyl acetate / ethylene (VAE), alkyd resins, polyurethanes (urethane resins), epoxy resins, latex, asphalt, polyesters, melamine formaldehyde, phenol formaldehyde, polyamides, isocyanates, synthetic or natural resins, such as alkyds, melamine resins, such as melamine alkyds, and combinations thereof. Preferred acrylic binders are formed from monoethylenically unsaturated acid-free monomers, including C1-C4 alkyl esters of acrylic or methacrylic acid, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, and ethylhexyl acrylate; hydroxyalkyl esters of acrylic or methacrylic acid, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamides and alkyl-substituted acrylamides, such as acrylamide, methacrylamide, N-tertiary butyl acrylamide, N-methacrylamide, and N,N-dimethacrylamide, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate; acrylonitrile, and methacrylonitrile. The monoethylenically unsaturated acid-free monomers may include the vinyl monomer styrene to form copolymers, or may be formed solely from styrene.

[0075] Examples of acid-free monomers for the organic binder include butyl acrylate, methyl methacrylate, ethylhexyl acrylate, styrene, vinyl toluene, acrylonitrile, vinyl acetate, acrylic acid, vinyl esters of neodecanoic or neononanoic acid, silane-containing monomers, and combinations thereof.

[0076] In some embodiments, the organic binder is an organic solvent-based epoxy resin, such as a phenol-formaldehyde epoxy resin, which can be further reacted with a hardener component such as a polyamine or reacted with itself via ring-opening polymerization.

[0077] In one or more embodiments, the coating system is a solvent-based system, in which the organic binder can be an alkyd resin, which can be a complex branched and crosslinked polyester with unsaturated fatty acid residues. The organic binder can also be a polyurethane binder, where such urethane resin binders typically include the reaction product of a polyisocyanate and a polyol. In one embodiment, the organic binder can be a polyol-based acrylate, such as a hydroxyacrylate or hydroxymethacrylate polymer or oligomer. The free hydroxyl groups are further reacted with a crosslinker / hardener containing two or more isocyanate groups. The crosslinker / hardener can be a polymer, oligomer, or monomer containing free isocyanate groups to form a polyurethane polymer. The hydroxyacrylate or hydroxymethacrylate prepolymer or oligomer can be derived from the homopolymerization or copolymerization of hydroxyalkyl acrylates and methacrylates, including 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and their corresponding alkyl derivatives, such as propyl and butyl derivatives. Also included are the monomethacrylates and monoacrylates of diethylene glycol, glycerol, trimethylolpropane, and pentaerythritol. Further examples include the di- and triacrylates and methacrylates of the aforementioned glycols, provided that at least one free hydroxyl group remains for reaction with the isocyanate functionality. Additional hydroxyacrylates include N-hydroxymethyl methacrylamide and N-hydroxymethyl acrylamide.Furthermore, the hydroxyacrylate or hydroxymethacrylate prepolymer or oligomer may be a copolymer obtained by reacting a hydroxyacrylate or hydroxymethacrylate with a mono-, di-, tri-, or oligoethylenically unsaturated acid-free monomer, such as a monomer containing a C1-C4 alkyl ester of acrylic acid or methacrylic acid, for example, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethylhexylhexyl acrylate; a hydroxyalkyl ester of acrylic acid or methacrylic acid, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamide and alkyl-substituted acrylamide, for example, acrylamide, methacrylamide, N-tertiary butylacrylamide, N-methacrylamide, and N,N-dimethacrylamide, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acrylonitrile, and methacrylonitrile. The monoethylenically unsaturated acid-free monomer may include the vinyl monomer styrene.

[0078] In one embodiment, the polyol used to form the binder polyurethane can be selected from the group of polyoxyalkylenes, such as polyoxyethylene and polyoxypropylene, and copolymers thereof. Further examples include hydroxyl-functional polyesters or aliphatic or aromatic diols or polyols.

[0079] The organic binder can be present in the coating composition in an amount of from about 5% to about 99% by weight, preferably from about 7% to about 95% by weight, more preferably from about 10% to about 90% by weight, and even more preferably from about 15% to about 80% by weight, where the weight percentages are based on the total weight of the coating composition.

[0080] In one or more embodiments, the coating composition further comprises one or more curing agents. In such embodiments, it may be necessary to combine the binder with a curing agent to enable film formation. As used herein, the term "curing agent" refers to a reactive compound having two or more functional groups. The functional groups crosslink with the binder, but are not limited to reacting with the binder. In some embodiments, the functional groups can also react with other auxiliary components of the composition, such as fillers or additives. In some other embodiments, the functional groups can self-polymerize to form oligomers. The primary purpose of the curing agent is, but is not limited to, crosslinking with the binder to cure the coating. In one embodiment, the curing agent can be selected from the group of polyamines, including aromatic or aliphatic diamines or oligoamines, such as 1,2-diaminocyclohexane, 4,4'-diaminodiphenyl sulfone, 1,5-diamino-2-methylpentane, diethylenetriamine, hexamethylenediamine, isophoronediamine, and triethylenetetramine.

[0081] In one embodiment, the crosslinker / curing agent can be a polyisocyanate with free isocyanate groups that can react with polyols included in the coating formulation to form polyurethane compounds and aid in bonding the coating. In another embodiment, curing agents such as aromatic, aliphatic, and cycloaliphatic diisocyanates or polyisocyanates and mixtures of two or more can react with water, polyols, or polyamines to crosslink binders such as polyurethane or polyurea or biuret oligomers or polymers, or combinations thereof.

[0082] Examples of di- or polyisocyanate curing agents include toluene-2,4-diisocyanate, m-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthylene diisocyanate and 1,4-xylylene diisocyanate, or isophorone diisocyanate.

[0083] The coating compositions described herein can further include one or more auxiliary ingredients selected from the group consisting of fillers or pigments, water, and solvents. In addition to the three main categories of ingredients, coatings can have a wide variety of additives, which are typically added in small amounts but have a significant impact on the product and its application or handling. Some examples include additives such as surfactants to modify surface tension, dispersants, defoamers to control foaming, flocculants, opacifying polymers, colorants, antistatic agents, flow improvers, agents to improve finished appearance, agents to increase wet edge, pigment stability improvers, agents to impart antifreeze properties, agents to control skinning, catalysts, thickeners, stabilizers, emulsifiers, conditioners, adhesion promoters, UV stabilizers, flatteners (matt agents), biocides to combat bacterial growth, silicone-based adhesion promoters, and the like, and combinations thereof.

[0084] In one embodiment, the coating composition can include a filler, which can include a particulate solid. Fillers are typically incorporated to impart toughness, texture, or special properties to the coating, and / or to reduce the cost of the coating. In some embodiments, the filler can be selected from the group consisting of titanium dioxide, clay, nanoclay, organoclay, ground calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, calcium carbonate treated with compounds containing stearate moieties or stearic acid, fumed silica, precipitated silica, crushed quartz, ground quartz, finely ground quartz, alumina, aluminum hydroxide, ceramic and glass spheres, titanium hydroxide, kaolin, bentonite, montmorillonite, diatomaceous earth, iron oxide, carbon black, graphite, talc, mica, pumice, wollastonite, dolomite, feldspar, color pigments, and combinations thereof.

[0085] In another embodiment, the coating composition includes one or more solvents. The solvent may be selected from the group consisting of alcohols, glycols, ketones, esters, ethers, carbonates, aliphatic, cycloaliphatic, aromatic, heteroaromatic, heteroaliphatic, heteroalicyclic, amides, sulfoxides, water, and combinations thereof. In some embodiments, the solvent may be mineral spirits, acetone, turpentine, naphtha, toluene, methyl ethyl ketone, dimethylformamide, 2-butoxyethanol, glycol ethers, ethylbenzene, xylene, n-butyl acetate, butanol, pyridine, dimethyl carbonate, dimethyl sulfoxide, and combinations thereof.

[0086] In one embodiment, the coating composition includes an additive such as an organic surfactant to modify the surface tension of the coating, for example, the surfactant used in the dispersions containing the coating compositions described herein. Surfactants are also used to stabilize the dispersion of polymer particles during emulsion polymerization in coatings and other applications. The mechanical stability, freeze-thaw stability, and shelf life of the coating are all improved by the addition of surfactants. The addition of surfactants to the coating also increases the wetting of the solution, allowing the coating to coat the surface more easily. The surfactant can be one or more of anionic, cationic, nonionic, or amphoteric surfactants. In one particular embodiment, the surfactant is a nonionic surfactant. Anionic surfactants can optionally be used in the context of the present invention. Examples include surfactants such as alkali metal salts of sulfonic acids or alkyl sulfates of aromatic hydrocarbon-based acids, and preferred nonionic surfactants are polyoxyethylenated alkylphenols or polyoxyethylenated fatty alcohols. The amount of surfactant that can be used is that typically used for emulsification. Nonionic (preferably), ionic, or amphoteric surfactants can be used alone or mixed together. In practice, dispersions according to the present invention contain from about 30 to about 90% by weight, preferably from about 30 to about 60% by weight, of water per weight of from about 70 to about 10% by weight, preferably from about 70 to about 40% by weight, of the non-aqueous phase.

[0087] The coating composition may further comprise a dispersant. The dispersant used herein may comprise a phosphate and / or a polyacrylic.

[0088] The flocculants that can be used herein can preferably be selected from glycols and / or aliphatic petroleum fractions.

[0089] The thickener herein may preferably be selected from acrylic cellulose thickeners, polyurethanes, natural gums and mixtures thereof.

[0090] In certain embodiments, the coating composition of the present invention includes a colorant. As used herein, the term "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 in any suitable form, such as discrete particles, dispersions, solutions, and / or flakes. The coating composition of the present invention can use a single colorant or a mixture of two or more colorants.

[0091] Examples of colorants include pigments, dyes, and tints, such as those used in the paint industry and / or listed by the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. Colorants can include, for example, finely divided solid powders that are insoluble but wettable under the conditions of use. Colorants can be organic or inorganic, and can be agglomerated or non-agglomerated. Colorants can be incorporated into coating compositions by using grinding vehicles, such as acrylic grinding vehicles, the use of which will be familiar to those skilled in the art.

[0092] Examples of pigments and / or pigment compositions include, but are not limited to, carbazole dioxazine crude pigments, azo, monoazo, disazo, naphthol AS, salt-type, benzimidazolone, condensed, metal complex, isoindolinone, isoindoline, and polycyclic phthalocyanines, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketopyrrolopyrrole red ("DPPBO red"), titanium dioxide, carbon black, and mixtures thereof. The terms "pigment" and "colored filler" may be used interchangeably.

[0093] Examples of dyes include, but are not limited to, solvent and / or aqueous based dyes such as phthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum, and quinacridone.

[0094] Examples of tints include, but are not limited to, pigments dispersed in water-based or water-miscible carriers, such as AQUA-CHEM 896 available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS available from the Accurate Dispersions division of Eastman Chemical, Inc.

[0095] As noted above, the colorant may be in the form of a dispersion, including, but not limited to, a nanoparticle dispersion, which may include one or more highly dispersed nanoparticle colorants and / or colorant particles that produce a desired visible color and / or opacity and / or visual effect.

[0096] In one or more embodiments, the coating compositions herein can be used in any coating, varnish, lacquer, shellac, or stain. In one embodiment, the coating compositions are used in paints, and in certain embodiments, organic paints.

[0097] In one embodiment herein, the coating composition has synergistic properties compared to compositions in which the polyorganosiloxane additive is used in combination with an organic binder. In more specific embodiments, the coating composition herein has a water surface contact angle of from about 5 to about 80, from about 40 to about 80, or from about 80 to about 120, or from about 120 to about 180.

[0098] In one or more embodiments, the coating composition exhibits properties including, but not limited to, hydrophobicity, low surface energy, durability, anti-graffiti, stain resistance / easy cleaning, and resistance to water, UV radiation, chemicals, temperature, or microorganisms. In some embodiments, the coating composition is resistant to graffiti and may be referred to as an anti-graffiti coating. In some embodiments, the coating composition may be a non-sacrificial coating.

[0099] In some embodiments, the coating composition forms a paint.

[0100] In one embodiment, any of the foregoing coating compositions can be applied to a substrate, including, but not limited to, metal (including bare or pre-coated metal), plastic, wood, concrete, glass, paper, cement, clay, rock, stone, fabric, ceramic, synthetic foam, plaster, plaster of Paris, putty, stucco, or composites. In some aspects, an additional primer can be coated on the substrate before applying the coating.

[0101] In one embodiment, the coating on the substrate can have a thickness of about 1 to 1000 μm. The final coating composition, whether freshly prepared or after storage, can be applied to the facade by a variety of techniques, such as immersion techniques, including dip-drain and dip-spin procedures, curtain coating, brush coating, or roller coating, and combinations of the above. Spray techniques, as well as combinations such as spray and spin and spray and brush techniques, are also contemplated. High-temperature coated articles can be coated with the coating compositions described herein. Possible treatments include primers, precoats, and / or overcoats. A primer is a preparatory coating applied to a material before the coating or paint itself is applied. A primed surface improves the adhesion of the coating or paint, thereby increasing the durability of the coating and providing improved protection for the painted surface. A suitable primer can also block and seal stains or hide the color of the overcoat.

[0102] In some embodiments, a primer is used before coating the substrate, where the primer is fully or partially cured. Before coating the substrate, it may be necessary to apply a precoat to prepare the surface and help the coating adhere properly. In such embodiments, the desired coating can be achieved by simply applying the primer and allowing it to dry fully or partially before applying the desired coating for the final finish. A primer and sealer can be selected for the precoat to achieve the best possible uniform finish. This type of precoat can hide any color of the new drywall and create a uniform finish for the final coat.

[0103] In yet another embodiment, a method for producing a coating composition is provided. The method includes combining (i) an organic binder; and (ii) a polyorganosiloxane of Formula (I) and / or (IIA), where the organic binder (i) and the polyorganosiloxane of Formula (I) and (IIA) are described herein. In some embodiments, the method further includes adding a curing agent.

[0104] The term "combination" in the phrase "a combination of (i) an organic binder and (ii) a polyorganosiloxane of formula (I) and / or (IIA)" is non-limiting with respect to the composition and preparation of the combination; i.e., components (i) and (ii) can be present / mixed together before, during, or after the addition of the curing agent, or one of components (i) and (ii) can be added separately to the curing agent followed by the other component. [Example]

[0105] The vinyl ester of neodecanoic acid is referred to herein as VeoVa™ 10 (Hexion Inc.), and the vinyl ester of neononanoic acid is referred to herein as VeoVa™ 9 (Hexion Inc.). VeoVa™ 10-based hydrolyzable PDMS was used in this study to prepare polyorganosiloxanes of general formulas (III), (IV), (V), and (VI) as described below. Polyorganosiloxanes of formulas (III), (IV), (V), and (VI) were synthesized and characterized for further study. In the polyorganosiloxanes of formulas (III), (IV), (V), and (VI), R 1 and R 2 represents alkyl-substituted VeoVa™ (Hexion Inc.).

[0106] Example 1 Synthesis of trimethoxy-functionalized siloxane 100.0 g of Si-H terminated polydimethylsiloxane (M) with an average D unit chain length of 11 H -D 11 -M H ) and 175 ppm of Wilkinson's catalyst (tris-triphenyl-rhodium chloride) were mixed in xylene and heated to 80°C. Vinyltrimethoxysilane (16.0 g) was added dropwise to the above mixture, which was then vigorously stirred at 80°C for 9 hours to form a Si-H terminated trimethoxy-functionalized polydimethylsiloxane. Excess Si-H terminated polydimethylsiloxane (M H -D 11 -M H ) was removed in vacuo (130° C., <1 mbar) to yield 113.0 g of intermediate product, which was used further in the subsequent reaction step without further characterization.

[0107] Example 2 Synthesis of VeoVa10™ and Trimethoxysilyl-Functionalized Siloxanes VeoVa10™ [Hexion] (40.0 g) was added dropwise to a vigorously stirred mixture of the Si-H terminated trimethoxy-functionalized polydimethylsiloxane obtained by Example 1 (above) at 80°C to form a mixture. Lamoreaux-Pt catalyst (10 ppm, as a 3.3 wt.% Pt solution in octanol) was further added to the above mixture (VeoVa10™ and Si-H terminated trimethoxy-functionalized polydimethylsiloxane) under a N2 atmosphere, and the Pt-catalyzed mixture was maintained at 80°C for 5 hours. Subsequently, volatile components were removed in vacuo (65°C, <1 mbar). A pure product, the acid ester of trimethoxy-functionalized siloxane (Structure III), was obtained as a brownish fluid (139.0 g, 97.0% yield based on the amount of starting materials used). [ka]

[0108] Example 3 Synthesis of polyether and malonate functionalized PDMS(IV) 24.6 g of allyl / methyl terminated polyether with an average ethylene oxide chain length of 7.5 was dissolved in 9.4 g mmol of Si-H terminated polydimethylsiloxane (M H D5D H 6M H The mixture was added dropwise to a vigorously stirred mixture of 2.1 g of allyl glycidyl ether (2.1 g) and 2.1 g of methyl malonate (2.1 g) at 80°C for 17 hours. 2.1 g of triethylamine and 2.1 g of methyl hydrogen malonate were added, and the mixture was stirred at 120°C for 5 hours. Subsequently, volatile components were removed in vacuo (100°C, <5 mbar). [ka]

[0109] Tabletop Example 4: Synthesis of vinyl esters of neodecanoic acid and hydroxy-functionalized PDMS(V) VeoVa10™ [Hexion] is added dropwise to a vigorously stirred mixture of Si-H terminated polydimethylsiloxane with an average D unit chain length of 12 in xylene at 80°C. Lamoreaux-Pt catalyst (3.3 wt.% Pt solution in octanol) is further added to the above mixture under N2 atmosphere, and the mixture is kept at 80°C. Excess Si-H terminated polydimethylsiloxane (M H -D 12 -M H The volatile components were removed under vacuum (130°C, <1 mbar) to give the intermediate product, which was used in the subsequent reaction step without further characterization. A solution of the intermediate product, allyl glycidyl ether, and Lamoreaux-Pt catalyst (3.3 wt.% Pt solution in octanol) was heated to 100°C under a N2 atmosphere. After the Si-H conversion was complete, triethylamine and VeoVa10™ [Hexion] were added, and the mixture was stirred at 120°C for 5 hours. Subsequently, the volatile components were removed under vacuum (100°C, <1 mbar). [ka]

[0110] Prophetic Example 5: Synthesis of VeoVa™ and Hydroxy-Functionalized PDMS (VI) 10 mmol of allyl glycidyl ether was dissolved in 10 mmol of Si-H terminated polydimethylsiloxane (M H D6D H 6M H) at 80 °C. Lamoreaux-Pt catalyst (3.3 wt.% Pt solution in octanol) is further added to the above mixture under N2 atmosphere, and the mixture is maintained at 80 °C to obtain an intermediate product, which is further used in the subsequent reaction step without further characterization. The intermediate product, 70 mmol of VeoVa10 [Hexion], and a solution of Lamoreaux-Pt catalyst (3.3 wt.% Pt solution in octanol) are heated to 120 °C under N2 atmosphere. After complete Si-H conversion, triethylamine and 10 mmol of VeoVa10™ [Hexion] are added, and the mixture is stirred at 120 °C for 5 h. Subsequently, volatile components are removed in vacuo (100 °C, <1 mbar). [ka]

[0111] Prophetic Example 6: Synthesis of VeoVa™ and trimethoxysilyl-functionalized PDMS (VII) 60 mmol of VeoVa10™ [Hexion] was dissolved in 10 mmol of Si-H terminated polydimethylsiloxane (M H D6D H 6M H ) at 80 °C. Lamoreaux-Pt catalyst (3.3 wt.% Pt solution in octanol) is further added to the above mixture under N2 atmosphere, and the mixture is maintained at 120 °C to obtain an intermediate product, which is further used in the subsequent reaction step without further characterization. A solution of the intermediate product, 20 mmol of vinyltrimethoxysilane, and Lamoreaux-Pt catalyst (3.3 wt.% Pt solution in octanol) is heated to 100 °C under N2 atmosphere. [ka]

[0112] Example 7: Anti-graffiti testing Anti-graffiti performance refers to the ease of removing graffiti by hand with a wooden spatula without damaging the substrate. Two ratings were given: a rating of 1 (high) corresponds to the graffiti being very easy to remove (very little force required from the hand), and a rating of 2 (low) means that the graffiti is difficult or impossible to remove (strong force required from the hand).

[0113] A polyurethane-based clear coating (2K colorless gloss clear coating) was obtained from one of the industry benchmarks (Benchmark I) and was used as a base formulation as a control sample for reference. As a commercial reference for the anti-graffiti coating, a 2K PUR anti-graffiti coating was used from another standard industry benchmark (Benchmark II).

[0114] Preparation of control sample: Formulation 1 was prepared by hand mixing 3 g of Benchmark I sample with 1 g of Desmodur N75 (hardener I) and coating onto a metal plate. The coating was allowed to dry at room temperature for 7 days. In this study, Benchmark I sample was used as the hydroxyacrylate binder.

[0115] Test Sample Preparation: Formulation 2 was prepared by hand mixing 3 g of Benchmark I sample, 1 g of Desmodur N75 (curing agent), and 0.4 g of VeoVa silane-terminated hydrolyzable polysiloxane (13 D units) as described in the specification and coated onto a metal plate. The coating was dried at room temperature for 3 days, followed by 2 days at 60°C. Desmodur N75, used herein as the curing agent component of polyurethane coating systems, is an aliphatic polyisocyanate, HDI biuret.

[0116] Preparation of a control sample: Formulation 3 was prepared by mixing 5 g of Benchmark II sample (a two-component polyurethane paint containing an additive that provides non-stick properties for subsequent graffiti removal) and 1 g of a standard commercial hardener (Hardener II), mixed by hand, and coated onto a metal plate. The commercial hardener used in this example was compatible with the Benchmark II sample. The coating was allowed to dry at room temperature for 7 days.

[0117] Anti-graffiti test: A commercially available acrylic resin spray was applied to the coated surface. E-Coll's red, commercially available solvent-based acrylic spray paint was applied to the coated surface as graffiti. The paint was allowed to dry for at least one day. Then, adhesive tape from Tesa Tape 7475 was applied and pressed onto the dried paint by rolling the brayer and a 2300g weight five times over the tape to measure the anti-graffiti properties. After one day, the adhesive tape was removed and the anti-graffiti performance was evaluated. A passing cycle refers to the complete removal of the graffiti paint.

[0118] The use of VeoVa silane-terminated hydrolyzable polysiloxane (13D units) in a two-component polyurethane gloss clear coating demonstrated superior effectiveness over commercially available two-component polyurethane-based anti-graffiti coatings. Example Formulation 2 demonstrated the best performance of all formulations, removing graffiti more than four times. [Table 1]

[0119] While the invention has been described with reference to particular embodiments, those skilled in the art will recognize that various changes can be made and equivalents can be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but rather to include all embodiments falling within the scope of the appended claims.

Claims

1. (i) an organic binder, and (ii) a polyorganosiloxane of formula (I), Z １ -L １ {[Si(R)(R’)O] ｐ -SiR’’ ２ } ｍ -L ２ -Z ２ (I) where subscript p>9, where the subscript m is an integer from 1 to 5; wherein each of R, R', or R'' is a saturated hydrocarbon substituent selected from the group consisting of monovalent alkyl containing 1 to 22 carbon atoms, optionally substituted with an F or -OH group, aryl containing 6 to 22 carbon atoms, polycyclic aryl containing 8 to 22 carbon atoms, alkylaryl containing 7 to 23 carbon atoms, and arylalkyl containing 7 to 22 carbon atoms, and H, or L １ -Z １ or L ２ -Z ２ and wherein each of R, R', or R'' can be the same or different; Here, L １ or L ２ each of is selected from the group consisting of a single bond, a divalent alkylene group having at least two carbon atoms, and a trivalent group; optionally, two carbon atoms of the divalent alkylene group are joined by a bond such as L １ or L ２ -O-, -NR bonded to the silicon atom of each siloxy unit of the polyorganosiloxane (I) through a carbon bond of the formula ３ -C(O)-, -NR ３ -, -OC(O)NR ３ - and / or -NR ３ —C(O)—NR ３ - moieties, and wherein R ３ is hydrogen, Me ３ Si—, or alkyl containing 1 to 8 carbon atoms, optionally a divalent alkylene group substituted with one or more OH groups, and wherein L １ and L ２ may be the same or different, Here, Z １ or Z ２ are R, R', R'', R １ cycloalkyl containing 6 to 22 carbon atoms; cycloalkyl alkylene containing 7 to 22 carbon atoms; bicycloalkyl containing 7 to 22 carbon atoms; cyclothioalkyl containing 6 to 12 carbon atoms; aryl containing 5 to 12 carbon atoms and a heteroatom selected from the group consisting of -N, -O, and -S; alkylaldehyde containing 1 to 20 carbon atoms; and alkylarylaldehyde containing 7 to 20 carbon atoms, and wherein Z １ or Z ２ is optionally substituted by alkyl of 1 to 8 carbon atoms; Here, each R １ is a monovalent unsaturated, unsubstituted or substituted alkenyl or alkynyl group selected from the group consisting of alkenyl containing 2 to 22 carbon atoms; cycloalkenyl containing 6 to 22 carbon atoms; bicycloalkenyl alkylene containing 7 to 22 carbon atoms; acrylate group; methacrylate group; alkynyl containing 2 to 22 carbon atoms; and each R １ Oxiranyl and carbonate derivatives of the group; and oxiranyl groups containing 3 to 22 carbon atoms; carbonate groups containing 4 to 23 carbon atoms; Cl, ​​Br, I, —SH, —S—R, —OH, —O—R, —CN, —NCO, and blocked —NCO, (X) ｘ (Y) ３－ｘ Si-, R ６ ｘ R' ３－ｘ Si-: polyether groups, carboxy (-COOH), diacid, diester, polyester groups, nitro-alkyl-, cyano-alkyl-, acyl- or alkylsulfonylfluoride- groups, and ionic groups derived from esters of carboxylic or sulfonic or phosphonic acids, phosphonates, phosphines, amines, keto groups, and betaines; where R is as defined above, and the subscript x is an integer from 1 to 3, and X and Y are each independently OH, OR', -N(R'), ２ , R'O(O)-O-, and R', where R' is as defined above, X and Y may be the same or different, and where each R ６ is aryl containing 6 to 10 carbon atoms, arylalkyl containing 7 to 12 carbon atoms, cycloalkyl containing 6 to 12 carbon atoms, bicycloalkyl containing 7 to 16 carbon atoms, epoxyalkyl containing 3 to 12 carbon atoms, epoxycycloalkyl containing 6 to 12 carbon atoms, epoxybicycloalkyl containing 7 to 16 carbon atoms, thiocycloalkyl containing 6 to 12 carbon atoms, and aryl containing 5 to 12 carbon atoms, wherein the aryl, arylalkyl, or cycloalkyl contains one or more heterosubstitutions of -N, -O, and -S- atoms; 1. A coating composition comprising:

2. R １ is -C(O)-O-R ３ , (R ３ O) ２ -P(O)-O-, (R ３ O) ２ -P(O)-, phosphonate (R ３ -O) ２ -P-, -NHR ３ -CH ２ -COOH, -NHR ３ -CH ２ -O-S(O) ２ (OH), -SS(O) ２ (OR ３ ), -N(R ３ ) ２ , -P(R ３ ) ２ , acid addition salts of amines, quaternary-N ＋ R ２ ３ or -P ＋ R ２ ３ a salt having a group, an alkyl or aryl enamine of formula (II), 【Chemistry 1】 Here, R ３ is hydrogen or alkyl of 1 to 8 carbon atoms, and a single bond or L is bonded to the silicon atom of each siloxy unit of the polyorganosiloxane (I). １ or L ２ 2. The coating composition of claim 1, wherein the alkyl group is an alkenyl group having from 2 to 8 carbon atoms attached through a carbon bond of the formula:

3. L １ or L ２ 10. The coating composition of claim 1, wherein is a divalent alkylene group of 2 to 12 carbon atoms.

4. Z in formula (I) １ and Z ２ One of Z is a vinyl ester of neodecanoic acid or a vinyl ester of neononanoic acid, and the remaining Z １ or Z ２ is alkenyl, alkoxy, hydroxyalkyl, (X) ｘ (Y) ３－ｘ 2. The coating composition of claim 1, wherein the group is selected from the group consisting of Si—, where X, Y, and x are as defined, —NCO, acrylate, methacrylate, epoxy containing 3 to 22 carbon atoms, —SR, where R is as defined, hydroxyl, carboxy (—COOH), amino, keto group, diacid, diester, nitro-alkyl-, cyano-alkyl-, acyl-, or alkylsulfonyl fluoride group, donor and acceptor groups in a Michael addition reaction.

5. 10. The coating composition of claim 1, wherein the polyorganosiloxane of Formula I is present in an amount of about 0.01 to about 30 weight percent, based on the total weight of the coating composition.

6. 10. The coating composition of claim 1, wherein the polyorganosiloxane of Formula I is present in an amount of about 0.02 to about 20 weight percent, based on the total weight of the coating composition.

7. 10. The coating composition of claim 1, wherein the organic binder is selected from the group consisting of acrylic resins, hydroxyacrylate resins, vinyl acrylic resins, vinyl acetate / ethylene (VAE), alkyd resins, polyurethanes, epoxy resins, latex, asphalt, polyester, melamine formaldehyde, phenol formaldehyde, polyamides, isocyanates, alkyds, melamine resins, silanes, siloxanes, monoalkoxysilanes, dialkoxysilanes, trialkoxysilanes, and combinations thereof.

8. 8. The coating composition of claim 7, wherein the organic binder is an acrylic binder comprising one or more monomers selected from the group consisting of butyl acrylate, methyl methacrylate, ethylhexyl acrylate, styrene, vinyl toluene, acrylonitrile, vinyl acetate, acrylic acid, vinyl ester of neodecanoic acid, or vinyl ester of neononanoic acid, and silane-containing monomers.

9. 8. The coating composition of claim 7, wherein the organic binder is selected from an epoxy resin binder or a siloxane binder.

10. 8. The coating composition of claim 7, wherein the organic binder is a polyurethane binder based on an aliphatic or aromatic polyol.

11. The coating composition of claim 1 , wherein the organic binder is present in an amount of from about 5 wt % to about 99 wt %, based on the total weight of the coating composition.

12. 12. The coating composition of claim 11, wherein the organic binder is present in an amount of about 7% to about 95% by weight, based on the total weight of the coating composition.

13. The coating composition of claim 1 further comprising one or more curing agents.

14. 10. The coating composition of claim 1, further comprising at least one adjunct ingredient selected from the group consisting of fillers, water, solvents, surfactants, dispersants, defoamers, flocculants, thickeners, opaque polymers, biocides, colorants, antistatic agents, silicone-based additives, and combinations thereof.

15. 15. The coating composition of claim 14, wherein the filler is selected from the group consisting of titanium dioxide, clay, nanoclay, organoclay, ground calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, calcium carbonate treated with compounds containing stearate moieties or stearic acid, fumed silica, precipitated silica, crushed quartz, crushed quartz, alumina, aluminum hydroxide, ceramic and glass spheres, titanium hydroxide, kaolin, bentonite montmorillonite, diatomaceous earth, iron oxide, carbon black, graphite, talc, mica, pumice, wollastonite, dolomite, feldspar, color pigments, and combinations thereof.

16. 15. The coating composition of claim 14, wherein the solvent is selected from the group consisting of mineral spirits, acetone, turpentine, naphtha, toluene, methyl ethyl ketone, dimethylformamide, 2-butoxyethanol, glycol ethers, ethylbenzene, xylene, n-butyl acetate, butanol, and combinations thereof.

17. A paint, varnish, lacquer, shellac or stain comprising the coating composition of claim 1.

18. 10. A coated article having a coating comprising the coating composition of claim 1 disposed on a substrate, wherein the coating has a surface contact angle with water of from about 5 degrees to about 180 degrees as determined by ASTM D7334.

19. 20. The coated article of claim 18, wherein the substrate comprises metal, plastic, wood, concrete, glass, paper, brick, cement, clay, rock, stone, fabric, ceramic, synthetic foam, gypsum, plaster of Paris, putty, stucco, or a composite.

20. (i) an organic binder; and (ii) a polyorganosiloxane of formula (IIA): 【Chemistry 2】 Here, Z １ , Z ２ , Z ３ , and Z ４ may be the same or different, wherein subscript n is 0 or an integer from 1 to 20, subscript m is 0 or an integer from 1 to 20, and subscript o is 0 or an integer from 1 to 20; wherein R or R' is a saturated hydrocarbon substituent selected from the group consisting of monovalent alkyl containing 1 to 22 carbon atoms, optionally substituted by F, aryl containing 6 to 22 carbon atoms, polycyclic aryl containing 8 to 22 carbon atoms, alkylaryl containing 7 to 22 carbon atoms, arylalkyl containing 7 to 22 carbon atoms, and H; or L １ -Z １ , L ２ -Z ２ , L ３ -Z ３ or L ４ -Z ４ and where R and R' may be the same or different; wherein Z of formula (IIA) １ , Z ２ , Z ３ or Z ４ are R, R', and R １ aryl containing 5 to 12 carbon atoms and a heteroatom selected from the group consisting of -N, -O, and -S; alkylaldehyde containing 1 to 20 carbon atoms; and alkylarylaldehyde containing 7 to 20 carbon atoms, each group being an alkyl of 1 to 8 carbon atoms, OH, Cl, or Br, or a silyl ether group R １ ３ is a monovalent radical selected from the group consisting of: Here, R １ is a monovalent unsaturated, unsubstituted or substituted alkenyl or alkynyl group selected from the group consisting of alkenyl containing 2 to 22 carbon atoms, cycloalkenyl containing 6 to 22 carbon atoms, bicycloalkenyl alkylene containing 7 to 22 carbon atoms, acrylate group, methacrylate group, alkynyl containing 2 to 22 carbon atoms, and each R １ Oxiranyl and carbonate derivatives of the group, and oxiranyl groups containing 3 to 22 carbon atoms, carbonate groups containing 4 to 23 carbon atoms, Cl, Br, I, -SH, -S-R, -OH, -O-R, -CN, -NCO, and blocked -NCO, (X) ｘ (Y) ３－ｘ Si-, R ６ ｘ R' ３－ｘ Si—, polyether groups, carboxy (—COOH), diacids, diesters, polyester moieties, nitro-alkyl-, cyano-alkyl-, acyl- or alkylsulfonylfluoride- groups, and ionic groups derived from esters of carboxylic, sulfonic or phosphonic acids, phosphines, amino groups, primary amines, secondary amines, tertiary amines, keto groups and betaines; and where R is as defined, and the subscript x is an integer from 1 to 3, and X and Y are each independently OH, OR', -N(R'), ２ , R'O(O)-O-, and R', where R' is as defined above, and X and Y may be the same or different, and where each R ６ is aryl containing 6 to 10 carbon atoms, arylalkyl containing 7 to 12 carbon atoms, cycloalkyl containing 6 to 12 carbon atoms, bicycloalkyl containing 7 to 16 carbon atoms, epoxyalkyl containing 3 to 12 carbon atoms, epoxycycloalkyl containing 6 to 12 carbon atoms, epoxybicycloalkyl containing 7 to 16 carbon atoms, thiocycloalkyl containing 6 to 12 carbon atoms, and aryl containing 5 to 12 carbon atoms, wherein the aryl, arylalkyl, or cycloalkyl contains one or more heterosubstitutions of -N, -O, and -S- atoms; And here Z １ , Z ２ , Z ３ , and Z ４ may be the same or different; and Here, L １ , L ２ , L ３ and L ４ each of is selected from the group consisting of a single bond, a divalent alkylene group having at least two carbon atoms, and a trivalent group; optionally, two carbon atoms of the divalent alkylene group are joined by a bond such as L １ or L ２ -O-, -NR bonded to the silicon atom of each siloxy unit of the polyorganosiloxane (I) through a carbon bond of the formula ３ -C(O)-, -NR ３ -, -OC(O)NR ３ - and / or -NR ３ —C(O)—NR ３ - moieties, and wherein R ３ is hydrogen, Me ３ Si— or alkyl containing 1 to 8 carbon atoms, optionally a divalent alkylene group substituted with one or more OH groups; And here L １ , L ２ , L ３ , and L ４ may be the same or different, 1. A coating composition comprising:

21. R １ is -C(O)-O-R ３ , (R ３ O) ２ -P(O)-O-, (R ３ O) ２ -P(O)-, phosphonate (R ３ -O) ２ -P-, -NHR ３ -CH ２ -COOH, -NHR ３ -CH ２ -O-S(O) ２ (OH), -SS(O) ２ (OR ３ ), -N(R ３ ) ２ , -P(R ３ ) ２ , acid addition salts of amines, quaternary-N ＋ R ２ ３ or -P ＋ R ２ ３ a salt having a group, an alkyl or aryl enamine of formula (II), 【Transformation 3】 Here, R ３ is hydrogen or alkyl of 1 to 8 carbon atoms, and a single bond or L １ , L ２ , L ３ or L ４ 21. The coating composition of claim 20, wherein the alkyl group is an alkenyl containing 2 to 8 carbon atoms bonded to the silicon atoms of the siloxy units of the polyorganosiloxane (IIA) through a carbon bond of the formula:

22. L １ , L ２ , L ３ or L ４ 21. The coating composition of claim 20, wherein is a divalent alkylene group containing from 2 to 12 carbon atoms.

23. Z in formula (IIA) １ , Z ２ , Z ３ or Z ４ 21. The coating composition of claim 20, wherein at least one of is a crosslinker.

24. Z in formula (IIA) １ , Z ２ , Z ３ or Z ４ 21. The coating composition of claim 20, wherein is at least one moiety selected from the group consisting of a polyether moiety and an ester moiety.

25. Z １ , Z ２ , Z ３ or Z ４ 25. The coating composition of claim 24, wherein at least one of is a polyether moiety.

26. Z in formula (IIA) １ and optionally Z ２ is represented by the formula -(OCH ２ CH ２ ) ７，５ -OCH ３ and -(OCH ２ CH ２ ) １０ -OSi(CH ３ ) ３ wherein Z is selected from the group consisting of polyethers represented by ３ , Z ４ and optionally Z ２ are each represented by the formula -O(CO)CH ２ (COOCH ３ 25. The coating composition of claim 24, wherein the ester is a 1,3-diester represented by the formula:

27. Z of Formula II １ , Z ３ and Z ４ Each of the formula -(OCH ２ CH ２ ) ７，５ -OCH ３ and -(OCH ２ CH ２ ) １０ -OSi(CH ３ ) ３ wherein Z is selected from the group consisting of polyethers represented by ２ is represented by the formula -O(CO)CH ２ (COOCH ３ The coating composition according to claim 24, wherein the 1,3-diester is a 1,3-diester represented by the formula:

28. The polyether portion is -(OCH ２ CH ２ ) ａ -(OCH ２ CH (CH ３ )) ｂ -(OCH ２ CH ２ CH (CH ３ )) ｃ -OH, -(OCH ２ CH ２ ) ａ -(OCH ２ CH (CH ３ )) ｂ -(OCH ２ CH ２ CH (CH ３ )) ｃ —O—C1-C4 alkyl, —(OCH ２ CH ２ ) ａ -(OCH ２ CH (CH ３ )) ｂ -(OCH ２ CH ２ CH (CH ３ )) ｃ —O—C(O)—C1-C4 alkyl, and —(OCH ２ CH ２ ) ａ -(OCH ２ CH (CH ３ )) ｂ -(OCH ２ CH ２ CH (CH ３ )) ｃ —O—SiR ３ wherein R is alkyl containing 1 to 8 carbon atoms; a, b, and c are each independently 0 to 20; and a+b+c=1 to 20.

29. The polyether portion is -(OCH ２ CH ２ ) ３－１０ , -(OCH ２ CH ２ ) ３－１０ -OH, (OCH ２ CH (CH ３ )) ３－１０ , and (OCH ２ CH (CH ３ )) ３－１０ 26. The coating composition of claim 25, wherein the alkyl group is selected from the group consisting of —OH.

30. 26. The coating composition of claim 25, wherein the polyether moiety is a vinyl ester of a linear or branched chain carboxylic acid.

31. Z in formula (IIA) １ , Z ２ , Z ３ or Z ４ and up to three groups of the formula -(OCH ２ CH ２ ) ７，５ -OCH ３ , -(OCH ２ CH ２ ) １０ -OSi(CH ３ ) ３ , -(OCH ２ CH ２ ) １０ -OSi(CH ３ ) ３ , or -(OCH ２ CH ２ ) １０ 26. The coating composition of claim 25, wherein the polyether moieties are individually selected from polyether moieties represented by -OH.

32. Z １ , Z ２ , Z ３ or Z ４ At least one of the groups (X) is alkenyl, alkoxy, hydroxyalkyl, ｘ (Y) ３－ｘ 21. The coating composition of claim 20, wherein the group is selected from Si-, where X, Y, and x are as defined, -NCO, acrylate, methacrylate, epoxy containing 3 to 22 carbon atoms, -SR, where R is as defined, hydroxyl, carboxy (-COOH), amino, keto group, diacid, diester, nitro-alkyl-, cyano-alkyl-, acyl- or alkylsulfonyl fluoride- group, or a donor or acceptor group in a Michael addition reaction.

33. 21. The coating composition of claim 20, wherein the polyorganosiloxane of Formula (IIA) is present in an amount of about 0.01 to about 30 weight percent, based on the total weight of the coating composition.

34. 21. The coating composition of claim 20, wherein the polyorganosiloxane of Formula (IIA) is present in an amount of from about 0.02 to about 20 weight percent, or from about 0.05 to about 15 weight percent, based on the total weight of the coating composition.

35. 21. A coated article having a coating comprising the coating composition of claim 20 disposed on a substrate, wherein the coating composition forms a coating having a surface contact angle with water of from about 5 to about 180 degrees.

36. (i) an organic binder; and (ii) a polyorganosiloxane of formula (I) Z １ -L １ {[Si(R)(R’)O] ｐ -SiR’’ ２ } ｍ -L ２ -Z ２ (I) where subscript p>9, where the subscript m is an integer from 1 to 5; wherein each of R, R', or R'' is a saturated hydrocarbon substituent selected from the group consisting of monovalent alkyl containing 1 to 22 carbon atoms, optionally substituted with an F or -OH group, aryl containing 6 to 22 carbon atoms, polycyclic aryl containing 8 to 22 carbon atoms, alkylaryl containing 7 to 23 carbon atoms, and arylalkyl containing 7 to 22 carbon atoms, and H, or L １ -Z １ or L ２ -Z ２ and wherein each of R, R', and R'' can be the same or different; Here, L １ or L ２ each of which is a single bond, optionally L １ or L ２ -O-, -NR bonded to the silicon atom of each siloxy unit of the polyorganosiloxane (I) through a carbon bond of the formula ３ -C(O)- and / or -NR ３ -, -OC(O)NR ３ -, -NR ３ —C(O)—NR ３ - moieties and optionally substituted with one or more OH groups, or is a trivalent group, and wherein L １ and L ２ may be the same or different, and where R ３ is hydrogen, Me ３ Si— or alkyl containing 1 to 8 carbon atoms, Here, Z １ or Z ２ are R, R', R'', R １ , alkylarylalkyl containing 8 to 22 carbon atoms, arylether containing 6 to 22 carbon atoms, cycloalkyl containing 6 to 22 carbon atoms, cycloalkylalkylene containing 7 to 22 carbon atoms, bicycloalkyl containing 7 to 22 carbon atoms, cyclothioalkyl containing 6 to 12 carbon atoms, aryl containing 5 to 12 carbon atoms and a heteroatom selected from the group consisting of -N, -O, and -S, alkylaldehyde containing 1 to 20 carbon atoms, and alkylarylaldehyde containing 7 to 20 carbon atoms, and wherein Z １ or Z ２ is optionally substituted by alkyl of 1 to 8 carbon atoms; Here, each R １ is a monovalent unsaturated, unsubstituted or substituted alkenyl or alkynyl group selected from the group consisting of alkenyl containing 2 to 22 carbon atoms; cycloalkenyl containing 6 to 22 carbon atoms; bicycloalkenyl alkylene containing 7 to 22 carbon atoms; acrylate group; methacrylate group; alkynyl containing 2 to 22 carbon atoms; and each R １ Oxiranyl and carbonate derivatives of the group; and oxiranyl groups containing 3 to 22 carbon atoms; carbonate groups containing 4 to 23 carbon atoms; Cl, ​​Br, I, —SH, —S—R, —OH, —O—R, —CN, —NCO, and blocked —NCO, (X) ｘ (Y) ３－ｘ Si-, R ６ ｘ R' ３－ｘ Si—; polyether groups, carboxy (—COOH), diacid, diester, polyester groups, nitro-alkyl-, cyano-alkyl-, acyl- or alkylsulfonylfluoride- groups and esters of carboxylic or sulfonic or phosphonic acids, phosphonates, phosphines, amines, keto groups and ionic groups derived from betaines, where R is as defined above, and the subscript x is an integer from 1 to 3, and X and Y are each independently OH, OR', -N(R'), ２ , R'O(O)-O-, and R', where R' is as defined above, and X and Y may be the same or different, and where each R ６ is aryl containing 6 to 10 carbon atoms, arylalkyl containing 7 to 12 carbon atoms, cycloalkyl containing 6 to 12 carbon atoms, bicycloalkyl containing 7 to 16 carbon atoms, epoxyalkyl containing 3 to 12 carbon atoms, epoxycycloalkyl containing 6 to 12 carbon atoms, epoxybicycloalkyl containing 7 to 16 carbon atoms, thiocycloalkyl containing 6 to 12 carbon atoms, and aryl containing 5 to 12 carbon atoms, wherein the aryl, arylalkyl, or cycloalkyl contains one or more heterosubstitutions of -N, -O, and -S- atoms; A method of making a coating composition comprising combining

37. (i) an organic binder; and (ii) a polyorganosiloxane of formula (IIA): 【Chemistry 4】 Here, Z １ , Z ２ , Z ３ , and Z ４ may be the same or different, wherein subscript n is 0 or an integer from 1 to 20, subscript m is 0 or an integer from 1 to 20, and subscript o is 0 or an integer from 1 to 20; wherein R or R' is a saturated hydrocarbon substituent selected from the group consisting of monovalent alkyl containing 1 to 22 carbon atoms, optionally substituted by F, aryl containing 6 to 22 carbon atoms, polycyclic aryl containing 8 to 22 carbon atoms, alkylaryl containing 7 to 22 carbon atoms, arylalkyl containing 7 to 22 carbon atoms, and H; or L １ -Z １ , L ２ -Z ２ , L ３ -Z ３ or L ４ -Z ４ and where R and R' may be the same or different; wherein Z of formula (IIA) １ , Z ２ , Z ３ or Z ４ are R, R', and R １ cycloalkyl containing from 6 to 22 carbon atoms; cycloalkyl alkylene containing from 7 to 22 carbon atoms; bicycloalkyl containing from 7 to 22 carbon atoms; cyclothioalkyl containing from 6 to 12 carbon atoms; aryl containing from 5 to 12 carbon atoms and a heteroatom selected from the group consisting of -N, -O, and -S; alkyl aldehyde containing from 1 to 20 carbon atoms; and alkyl aryl aldehyde containing from 7 to 20 carbon atoms, each of which optionally contains an alkyl of 1 to 8 carbon atoms, OH, Cl, or Br, or a silyl ether group R １ ３ may be substituted with Si—O—, Here, R １ is a monovalent unsaturated, unsubstituted, or substituted alkenyl or alkynyl group selected from the group consisting of alkenyl containing 2 to 22 carbon atoms, cycloalkenyl containing 6 to 22 carbon atoms, bicycloalkenyl alkylene containing 7 to 22 carbon atoms, acrylate group, methacrylate group, alkynyl containing 2 to 22 carbon atoms, and each R １ Oxiranyl and carbonate derivatives of the group, and oxiranyl groups of 3 to 22 carbon atoms, carbonate groups of 4 to 23 carbon atoms, Cl, Br, I, —SH, —S—R, —OH, —O—R, —CN, —NCO, and blocked —NCO, (X) ｘ (Y) ３－ｘ Si-, R ６ ｘ R' ３－ｘ Si—, polyether groups, carboxy (—COOH), diacids, diesters, polyester moieties, nitro-alkyl-, cyano-alkyl-, acyl- or alkylsulfonylfluoride- groups, and ionic groups derived from esters of carboxylic, sulfonic or phosphonic acids, phosphines, amino groups, primary amines, secondary amines, tertiary amines, keto groups and betaines; where R is as defined above, and the subscript x is an integer from 1 to 3, and X and Y are each independently OH, OR', -N(R'), ２ , R'O(O)-O-, and R', where R' is as defined above, and X and Y may be the same or different, and where each R ６ is aryl containing 6 to 10 carbon atoms, arylalkyl containing 7 to 12 carbon atoms, cycloalkyl containing 6 to 12 carbon atoms, bicycloalkyl containing 7 to 16 carbon atoms, epoxyalkyl containing 3 to 12 carbon atoms, epoxycycloalkyl containing 6 to 12 carbon atoms, epoxybicycloalkyl containing 7 to 16 carbon atoms, thiocycloalkyl containing 6 to 12 carbon atoms, and aryl containing 5 to 12 carbon atoms, wherein the aryl, arylalkyl, or cycloalkyl contains one or more heterosubstitutions of -N, -O, and -S- atoms; And here Z １ , Z ２ , Z ３ , and Z ４ may be the same or different; and Here, L １ , L ２ , L ３ and L ４ each of is selected from the group consisting of a single bond, a divalent alkylene group having at least two carbon atoms, and a trivalent group; optionally, two carbon atoms of the divalent alkylene group are joined by a bond such as L １ or L ２ -O-, -NR bonded to the silicon atom of each siloxy unit of the polyorganosiloxane (I) through a carbon bond of the formula ３ -C(O)-, -NR ３ -, -OC(O)NR ３ - and / or -NR ３ —C(O)—NR ３ - moieties, and wherein R ３ is hydrogen, Me ３ Si—, or alkyl containing 1 to 8 carbon atoms, wherein the divalent alkylene group is optionally substituted with one or more OH groups; And here L １ , L ２ , L ３ , and L ４ may be the same or different, A method of making a coating composition comprising combining

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