Composition for preparing a release coating

Abstract

A composition for forming a release coating comprises (A) an organosilicon compound having only one silicon-bonded functional group X, the silicon-bonded functional group X being present in an M siloxy unit of formula (XR1 2SiO1 / 2), where X is the silicon-bonded functional group, and each R1 is an independently selected hydrocarbyl group free of ethylenic unsaturation. The composition also comprises (B) an organopolysiloxane including an average of at least two silicon-bonded functional groups X per molecule. Further, the composition comprises (C) an organopolysiloxane including at least two independently selected silicon-bonded groups Y.

Description

COMPOSITION FOR PREPARING A RELEASE COATINGCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and all advantages of U.S. Provisional Patent Application No.63 / 561 ,579 filed on 5 March 2024, the content of which is incorporated herein by reference.TECHNICAL FIELD

[0002] The subject disclosure generally relates to a composition and, more specifically, to a composition for preparing a release coating and related methods.BACKGROUND

[0003] Silicone compositions are known in the art and utilized in myriad industries and end use applications. One such end use application is to form release coatings or liners from which adhesives can be removed. For example, silicone compositions may be utilized to coat various substrates, such as paper, to give release liners for laminating pressure sensitive adhesives (e.g. tapes). Such silicone compositions are typically addition-curable.

[0004] Conventional release liners are typically formed by addition reacting (or hydrosilylating) an organopolysiloxane having an unsaturated hydrocarbon group and an organohydrogenpolysiloxane in the presence of a hydrosilylation reaction catalyst. It’s generally desirable to extend bathlife of compositions for preparing release liners to extend working life and minimize premature cure. As such, inhibitors are typically included in conventional compositions for preparing release liners. However, inhibitors and hydrosilylation reaction catalysts also have compatibility issues that influence bathlife and influence performance properties of the resulting release coatings.BRIEF SUMMARY

[0005] A composition for forming a release coating is disclosed. The composition comprises (A) an organosilicon compound having only one silicon-bonded functional group X, the silicon- bonded functional group X being present in an M siloxy unit of formula (XR^SiOf^), where X is the silicon-bonded functional group, and each R1is an independently selected hydrocarbyl group free of ethylenic unsaturation. The composition also comprises (B) an organopolysiloxane including an average of at least two silicon-bonded functional groups X per molecule. Further, the composition comprises (C) an organopolysiloxane including at least two silicon-bonded groups Y, optionally present in D siloxy units independently of formula (YR1SiO2 / 2), where each R1is an independently selected hydrocarbyl group free of ethylenic unsaturation, and each Y is an independently selected silicon-bonded group. In addition, the composition comprises (D) a hydrosilylation-reaction inhibitor, (E) a catalyst, and optionally (F), an organic solvent. When the composition is solventless and free from the organic solvent (F), component (A) is present in anamount of at least 30 wt.% based on the total weight of components (A)-(E). When the composition includes the organic solvent (F), component (A) is present in a wt / wt ratio of from 8:1 to 100:1 relative to component (B) in the composition. The silicon-bonded functional group X is an independently selected silicon-bonded aliphatically unsaturated group or a silicon-bonded hydrogen atom, and when each X is the silicon-bonded aliphatically unsaturated group, each Y is H, and when each X is a silicon-bonded hydrogen atom, each Y is an independently selected silicon-bonded aliphatically unsaturated group.

[0006] A method of preparing the composition is also disclosed. In addition, a release coating formed by curing the composition, a method of preparing a coated substrate comprising a release coating disposed on a substrate, as well as the coated substrate formed in accordance with the method, are disclosed.DETAILED DESCRIPTION

[0007] A composition for forming a release coating is disclosed. The composition and release coating formed therefrom have excellent performance properties. For example, the composition can be utilized to prepare release coatings having desirable low release force and excellent compatibility with silicone-based pressure-sensitive adhesives. However, the composition is not so limited, and can be utilized in other diverse end-use applications.

[0008] The composition comprises (A) an organosilicon compound having only one silicon- bonded functional group X. The silicon-bonded functional group X (referred to as “X” for brevity) is present in an M siloxy unit of formula (XR^SiOf^), where X is the silicon-bonded functional group, and each R1is an independently selected hydrocarbyl group free of ethylenic unsaturation.

[0009] In general, hydrocarbyl groups suitable for R1may independently be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups encompass aryl groups as well as saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. One example of a combination of a linear and cyclic hydrocarbyl group is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, and the like, as well as derivatives, modifications, and combinations thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g. iso-propyl and / or n-propyl), butyl (e.g. isobutyl, n- butyl, tert-butyl, and / or sec-butyl), pentyl (e.g. isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, as well as branched saturated hydrocarbon groups having from 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycyloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethyl phenyl. R1 is free of ethylenic unsaturation, and thus each R1 is not analkenyl group or an alkynyl group. In addition, each R1is free of halogenated substitution, and thus free from fluorine atoms.

[0010] In specific embodiments, each R1 is independently selected from alkyl groups having from 1 to 32, alternatively from 1 to 28, alternatively from 1 to 24, alternatively from 1 to 20, alternatively from 1 to 16, alternatively from 1 to 12, alternatively from 1 to 8, alternatively from 1 to 4, alternatively 1 , carbon atoms.

[0011] X is a group capable of undergoing hydrosilylation. Because component (A) includes only one X, component (A) is not cross-linkable. In one embodiment, X is an ethylenically unsaturated group. In a different embodiment, X is H. When X is the ethylenically unsaturated group, component (A) is free from any other ethylenically unsaturated groups and silicon-bonded hydrogen atoms. When X is H, component (A) is free from silicon-bonded ethylenically unsaturated groups and any other silicon-bonded hydrogen atoms.

[0012] When X is an ethylenically unsaturated group, X can be an alkenyl group or an alkyl group, and X typically has from 2 to 32, alternatively from 2 to 28, alternatively from 2 to 24, alternatively from 2 to 20, alternatively from 2 to 16, alternatively from 2 to 12, alternatively from 2 to 8, alternatively from 2 to 4, alternatively 2, carbon atoms. "Alkenyl" means an acyclic, branched or unbranched, monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples thereof include vinyl groups, allyl groups, hexenyl groups, and octenyl groups. "Alkynyl" means an acyclic, branched or unbranched, monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples thereof include ethynyl, propynyl, and butynyl groups. Various examples of ethylenically unsaturated groups include CH2=CH — , CH2=CHCH2— , CH2=CH(CH2)4— , CH2=CH(CH2)6— , CH2=C(CH3)CH2— , H2C=C(CH3)— , H2C=C(CH3)— , H2C=C(CH3)CH2— , H2C=CHCH2CH2— , H2C=CHCH2CH2CH2— , HC=C— , HC CCH2— , HC CCH(CH3)— , HC CC(CH3)2— , and HC CC(CH3)2CH2— . Typically, when R1is an ethylenically unsaturated group, the aliphatic unsaturation is terminal in R1. As understood in the art, ethylenic unsaturation may be referred to as aliphatic unsaturation.

[0013] Component (A) also comprises D siloxy units of formula (R12SiO2 / 2), where each R1is independently selected and defined above. In one embodiment, component (A) is linear and consists essentially of, alternatively consists of, only D siloxy units and M siloxy units. Because component (A) includes only one X, when component (A) is linear and includes two M siloxy units, the other M siloxy unit is generally of formula (R^3SiO -| / 2) , where each R1 is independently selected and defined above. For example, in some such embodiments, the component (A) can be an organosiloxane of formula (I):XSiR12O(SiR12O)eSiR13(I):wherein each X and each R1is independently selected and defined above, and subscript e is from 2 to 3,000, alternatively from 2 to 2,800, alternatively from 2 to 2,600, alternatively from 2 to 2,400, alternatively from 2 to 2,200, alternatively from 2 to 2,000, alternatively from 2 to 1 ,800, alternatively from 2 to 1 ,600, alternatively from 2 to 1 ,400, alternatively from 2 to 1 ,200, alternatively from 2 to 1 ,000, alternatively from 2 to 800, alternatively from 2 to 600, alternatively from 2 to 400. In a specific embodiment, the M unit not including X includes two methyl groups and an alkyl group having at least 2, alternatively at least 3, alternatively 4, carbon atoms, e.g. the M unit is a dimethylbutylsiloxy unit.

[0014] In other embodiments, component (A) may be branched or partly-branched. When component (A) is branched or partly-branched, component (A) may include one or more, e.g. up to 200, T siloxy units of formula (R1SiO3 / 2), where each R1is independently selected and defined above. In these embodiments, component (A) can be an organopolysiloxane of formula (II):(XR12SiO-| / 2)(R13SiO-| / 2)b(Rl2SiO2 / 2)c(Rl SiO3 / 2)d(II) wherein each X and each R1is independently selected and defined above, and subscript b, c, and d represent the number of corresponding siloxy units present in component (A). Subscripts b, c, and are not mole fractions, but normalized integers based on there being one M unit of formula (XR12SiO-| / 2). Subscript c is typically from 2 to 3,000, alternatively from 2 to 2,800, alternatively from 2 to 2,600, alternatively from 2 to 2,400, alternatively from 2 to 2,200, alternatively from 2 to 2,000, alternatively from 2 to 1 ,800, alternatively from 2 to 1 ,600, alternatively from 2 to 1 ,400, alternatively from 2 to 1 ,200, alternatively from 2 to 1 ,000, alternatively from 2 to 800, alternatively from 2 to 600, alternatively from 2 to 400. Subscript d is from 1 to 200, alternatively from 1 to 190, alternatively from 1 to 180, alternatively from 1 to 170, alternatively from 1 to 160, alternatively from 1 to 150, alternatively from 1 to 140, alternatively from 1 to 130, alternatively from 1 to 120, alternatively from 1 to 110, alternatively from 1 to 100, alternatively from 1 to 90, alternatively from 1 to 80, alternatively from 1 to 70, alternatively from 1 to 60, alternatively from 1 to 50, alternatively from 1 to 40, alternatively from 1 to 30, alternatively from 1 to 20, alternatively from 1 to 10, alternatively from 1 to 9, alternatively from 1 to 8, alternatively from 1 to 7, alternatively from 1 to 6, alternatively from 1 to 5, alternatively from 1 to 4,. alternatively from 1 to 3, alternatively from 1 to 2, alternatively 1. When subscript d is 0, component (A) is linear and can be of formula (I). Subscript b is a function of subscript d, as the M units indicated by subscript b are present in a corresponding amount based in the presence of T units indicated by subscript d. When the T units of subscript d are not clustered together, then subscript b is 2d+1. However, the T units of subscript d may optionally be clustered together,thus reducing the number of M siloxy units indicated by subscript b. Subscript b can be from 2 to 401 , for example.

[0015] In yet embodiments, component (A) can include one or more organic segments separating siloxane segment(s) such that component (A) is not a pure siloxane or organopolysiloxane. In these embodiments, component (A) has formula (III):XSiRl2O[(SiRl2O)nDm]pSiRl 3 (III) wherein each X and each R1is independently selected and defined above, each D is an independently selected divalent hydrocarbon group having from 2 to 6 carbon atoms, subscript n is from 2 to 3,000, subscript m is independently 0 or 1 , subscript p is 1 to 100. As understood in the art, when component (A) has formula (I) and at least one subscript m is 1 , component (A) includes siloxane moieties indicated by subscript n and one or more hydrocarbon moieties represented by D and indicated by subscript m. In these embodiments, component (A) is typically made via hydrosilylation, and the presence of the divalent hydrocarbon group D is a result of the hydrosilylation reaction. For example, one of skill in the art understands how to prepare species of component (A) having formula (I) based on conventional hydrosilylation, optionally with chain extension. As one example, component (A) could be prepared by hydrosilylating an organopolysiloxane having dimethylvinyl terminals with an organohydrogensiloxane having one trimethylsiloxane terminal and one dimethylhydrogen terminal, resulting in component (A) of formula (I) where one D is present. One of skill in the art understands starting components suitable to prepare component (A) given that component (A) includes but one silicon-bonded functional group (A), including reaction conditions and catalysts for hydrosilylation.

[0016] Combinations of different organosilicon compounds may be utilized as component (A), which may differ from one another in terms of viscosity, degree of polymerization, structure, substitution, etc. However, when a combination of different organosilicon compounds are utilized together as component (A), each such organosilicon compound includes but one silicon-bonded functional group X.

[0017] In certain embodiments, component (A) has a molecular mass of from greater than 500 to 100,000, alternatively from 1 ,000 to 75,000, alternatively from 2,500 to 70,000. For example, in some specific embodiments, component (A) may have a molecular mass of from 4,000 to 8,000, alternatively from 5,000 to 7,000. In other specific embodiments, component (A) may have a molecular mass of from 40,000 to 88,000, alternatively from 50,000 to 70,000. Generally, component (A) is a flowable liquid at room temperature in the absence of any organic solvents.

[0018] As described in greater detail below, the composition can be solventless or solvent-borne. When the composition is solventless and free from organic solvent, component (A) is present in an amount of at least 30 weight percent (wt.%) based on the total weight of components (A)-(E). For example, when the composition is free from organic solvent, component (A) can be presenttin an amount of at least 30, alternatively at least 35, alternatively at least 40, alternatively at least45, alternatively at least 50, alternatively at least 55, alternatively at least 60, alternatively at least65, alternatively at least 70, alternatively at least 75, alternatively at least 80, alternatively at least81 , alternatively at least 82, alternatively at least 83, alternatively at least 84, alternatively at least85, alternatively at least 86, alternatively at least 87, alternatively at least 88, alternatively at least89, alternatively at least 89.5, wt.% based on the total weight of components (A)-(E). When the composition includes the organic solvent, component (A) is present in a wt / wt ratio of from 8:1 to 100:1 relative to component (B) in the composition, as described in greater detail below.

[0019] The composition also comprises (B) an organopolysiloxane including an average of at least two silicon-bonded functional groups X per molecule. The silicon-bonded functional groups X of component (B) are independently selected, but the same category as the silicon-bonded functional group X of component (A) (i.e., they are all silicon-bonded aliphatically unsaturated groups, or independently silicon-bonded hydrogen).

[0020] The organopolysiloxane (B) may have average formula: R2n’ iO(4-n’) / 2’ where each R2is independently selected from R1and X, with the proviso that in each molecule, at least two of R2are X, and where subscript m is selected such that 0 < m < 3.2. The average formula above for the organopolysiloxane (B) may be alternatively written as (R23SiO-| / 2)f(R22SiO2 / 2)g(R2SiO3 / 2) (SiO4 / 2)j, where R2is defined above, and subscripts f, g, h, and I are each independently from > 0 to < 1 , and that a quantity (f + g + h + i) = 1 . One of skill in the art understands how such M, D, T, and Q units and their molar fractions influence subscript m in the average formula above.

[0021] In one embodiment, the organopolysiloxane (B) may comprise a resinous polyorganosiloxane. The resinous polyorganosiloxane may have the average formula: R2m’SiO(4-m’) / 2, where each R2is independently selected as defined above, and where subscript m’ is selected such that 0.5 < m’ < 1 .7.

[0022] The resinous polyorganosiloxane has a branched or a three dimensional network molecular structure. At 25 °C, the resinous polyorganosiloxane may be in a liquid or in a solid form. Alternatively, the resinous polyorganosiloxane may be exemplified by a polyorganosiloxane that comprises only T units, a polyorganosiloxane that comprises T units in combination with other siloxy units (e.g., M, D, and / or Q siloxy units), or a polyorganosiloxane comprising Q units in combination with other siloxy units {i.e., M, D, and / or T siloxy units). Typically, the resinous polyorganosiloxane comprises T and / or Q units. Specific example of the resinous polyorganosiloxane include, when X is vinyl, for example, a vinyl-terminated silsesquioxane (i.e., T resin or silsesquioxane resin), a vinyl-terminated MDQ resin, and / or a vinyl-terminated MQ resin.

[0023] Alternatively, the organopolysiloxane (B) may comprise, alternatively consist of, a branched siloxane, a silsesquioxane, or both a branched siloxane and a silsesquioxane.

[0024] When the organopolysiloxane (B) comprises a blend of different organopolysiloxanes, the blend may be a physical blend or mixture. For example, when the organopolysiloxane (B) comprises the branched siloxane and the silsesquioxane, the branched siloxane and the silsesquioxane can be present in amounts relative to one another in any suitable amount. For example, the branched siloxane may be present in an amount of 50 to 100 parts by weight, and the silsesquioxane may be present in an amount of 0 to 50 parts by weight, based on 100 parts by weight of component (B). Alternatively, the branched siloxane may be present in an amount 50 to 90 parts by weight and the silsesquioxane may be present in an amount of 10 to 50 parts by weight, based on 100 parts by weight of component (B). Alternatively, the branched siloxane may be present in an amount of 50 to 80 parts by weight and the silsesquioxane may be present in an amount of 20 to 50 parts by weight, based on 100 parts by weight of component (B). Alternatively, the branched siloxane may be present in an amount of 50 to 76 parts by weight and the silsesquioxane may be present in an amount of 24 to 50 parts by weight, based on 100 parts by weight of component (B). Alternatively, the branched siloxane may be present in an amount of 50 to 70 parts by weight and the silsesquioxane may be present in an amount of 30 to 50 parts by weight, based on 100 parts by weight of component (B).

[0025] In certain embodiments, the branched siloxane of the organopolysiloxane (B) may have average unit formula:(R23SiO-| / 2)p(R22SiO2 / 2)q(SiO4 / 2)r’ wherein each R2is independently selected and defined above, 0 <p< 0.3, 0.4<q<0.97, and 0<r<0.3, with the proviso that p+q+r= 1 .

[0026] The branched siloxane of the organopolysiloxane (B) generally comprises M siloxy units (i.e., the (R23SiO-| / 2) siloxy units), D siloxy units (i.e., the (R22SiO2 / 2) siloxy units), and one or more Q siloxy units (i.e., the (SiO4 / 2) siloxy units), alternatively consists of M, D, and Q siloxy units. Although the branched siloxane of the organopolysiloxane (B) includes at least one Q siloxy unit, the branched siloxane of the organopolysiloxane (B) is considered a branched silicone polymer by one of skill in the art, rather than a silicone resin, due to the degree of polymerization (DP) in the branched siloxane of the organopolysiloxane (B) and the nominal molar fraction of Q siloxy units present therein.

[0027] The general formula of the branched siloxane of the organopolysiloxane (B) is representative of the average formula of the M, D and Q siloxy units. For example, the M siloxy units may be independently selected within the formula (R23SiO-| / 2), and the D siloxy units may be independently selected within the formula (R22SiO2 / 2)- The subscripts, or mole fractions ofthe M, D and Q siloxy units in the branched siloxane of the organopolysiloxane (B), are collectively based on all M siloxy units, all D siloxy units, and all Q siloxy units, respectively, present in the branched siloxane of the organopolysiloxane (B). By way of example, the branched siloxane of the organopolysiloxane (B) may include M units independently having zero, one, two, or three silicon-bonded functional groups X. Similarly, the branched siloxane of the organopolysiloxane (B) may include D units independently having zero, one, or two silicon- bonded functional groups X. Such silicon-bonded functional groups X present in M siloxy units are considered terminal, whereas those present in D siloxy units are considered pendent.

[0028] In specific embodiments, the branched siloxane of the organopolysiloxane (B) has one Q siloxy unit. In other embodiments, the branched siloxane of the organopolysiloxane (B) has two Q siloxy units, alternatively three Q siloxy units. The branched siloxane of the organopolysiloxane (B) may have a degree of polymerization (DP) of from 1 to 3000, alternatively from 2 to 2000, alternatively from 3 to 1000, alternatively from 4 to 750, alternatively from 5 to 400, alternatively from 10 to 200, alternatively from 14 to 180. The DP is generally the total number of D units present in the branched siloxane of the organopolysiloxane (B), i.e., the DP may be based on more than one linear chain within the branched siloxane of the organopolysiloxane (B).

[0029] In specific embodiments when the branched siloxane of the organopolysiloxane (B) includes one Q siloxy unit, the branched siloxane of the organopolysiloxane (B) may have average unit formula:(R23SiO-| / 2)s’(R22SiO2 / 2)t’(SiO4 / 2)’ where each R is independently a substituted or unsubstituted hydrocarbyl group, with the proviso that at least two of R are independently selected ethylen ically unsaturated groups, subscript s’ is from 0.05 to 4, and subscript t’ is from 1 to 3,000.

[0030] In specific embodiments, the silicon-bonded functional groups X are present in one or more M siloxy units (e.g. when each X is vinyl, as vinyldimethyl siloxy units, divinylmethyl siloxy units, and / or trivinyl siloxy units). Alternatively, in other embodiments, the silicon-bonded functional groups X are present in one or more D siloxy units (e.g. when each X is vinyl, as methylvinyl siloxy groups and / or as divinyl siloxy groups). Alternatively still, the silicon-bonded functional groups X may be present in one or more of each of the M and D siloxy units. One of skill in the art appreciates that these specific siloxy groups are exemplary only, and vinyl may be replaced with other ethylenically unsaturated groups, or may be H when X is H, and methyl may be replaced with other hydrocarbyl groups.

[0031] In specific embodiments in which the branched siloxane of the organopolysiloxane (B) includes a single Q siloxy unit, the branched siloxane of the organopolysiloxane (B) has the following general formula:Si-[[OSiR22]b.[OSiR23]]4wherein each R2is independently selected and defined above, with the proviso that at least two of R2are independently X, and each b’ independently is from 0 to 200, alternatively from 1 to 100.

[0032] However, because the branched siloxane of the organopolysiloxane (B) includes D siloxy units, all instances of b’ (i.e., all four instances) cannot simultaneously be 0. The DP of the branched siloxane of the organopolysiloxane (B) in these embodiments is based on the aggregate or collective amount of b’. The branched siloxane of the organopolysiloxane (B) includes at least one, alternatively at least two, alternatively at least three, alternatively four, substantially linear, alternatively linear, chains extending from the silicon atom of the Q unit. These substantially linear, alternatively linear, chains correspond to the repeating D siloxy units when any iteration of b’ is greater than 0.

[0033] In these specific embodiments, the branched siloxane of the organopolysiloxane (B) includes a single Q siloxy unit and no T siloxy units. T siloxy units, as understood in the art, may be represented by R2SiO3 / 2, and include one silicon-bonded substituent R2. The branched siloxane of the organopolysiloxane (B) includes D siloxy units, corresponding to each iteration of subscript b’. Because b’ is independently selected, each linear chain of D siloxy units indicated by subscript b’ may vary, i.e., each b’ may be the same as or different from one another. One or more instances of b’ may be 0 such that an M siloxy unit is bonded directly to the single Q siloxy unit, although typically each M siloxy unit is spaced from the Q siloxy unit by at least one D siloxy unit. The branched siloxane of the organopolysiloxane (B) may also be generally symmetrical, i.e., when all instances of b’ are the same. Each of the linear chains of D siloxy units in the branched siloxane of the organopolysiloxane (B) terminates with an M siloxy unit.

[0034] In specific embodiments, each X is vinyl and the branched siloxane of the organopolysiloxane (B) has the general formula:Si-[[OSiMe2]b’[OSiMe2Vi]]4where b’ is independently selected and defined above, Me designates methyl, and Vi designates vinyl.

[0035] In other specific embodiments, each X is vinyl the branched siloxane of the organopolysiloxane (B) has the general formula:Si-[[OSiViMe]b’[OSiMe3]]4where b’ is independently selected and defined above.

[0036] In yet other specific embodiments, each X is vinyl the branched siloxane of the organopolysiloxane (B) has the general formula:Si-[[OSiViMe]b’[OSiMe2Vi]]4where b’ is independently selected and defined above.

[0037] Further still, each D and M siloxy unit in the branched siloxane of the organopolysiloxane (B) is independently selected. As such, any of the specific examples above may be modified. For example, in one embodiment, the branched siloxane of the organopolysiloxane (B) may include three dimethylvinylsiloxy units, and one trimethylsiloxy unit.

[0038] Alternatively, the organopolysiloxane (B) may have formula:subscript u is 0 or 1 , each subscript t is independently from 0 to 995, alternatively from 15 to 995, alternatively from 0 to 100; each R2is independently selected and defined above with the proviso that at least two of R2are X.

[0039] The organopolysiloxane (B) may be a silsesquioxane having the average unit formula: (R13SiOi / 2)j(R2R12SiO-| / 2)f(R12SiO2 / 2)g(R1SiO3 / 2) , where each R1is independently selected and defined above, each R2is an independently selected and defined above, with the privos that at least two of R2are X, subscript i > 0, subscript f > 0, subscript g is 15 to 995, and subscript h > 0. Subscript i may be 0 to 10. Alternatively, for subscript i: 12 > i > 0; alternatively 10 > i > 0; alternatively 7 > i > 0; alternatively 5 > i > 0; and alternatively 3 > i > 0. Alternatively, subscript f > 1 . Alternatively, subscript f > 3. Alternatively, for subscript f: 12 > f > 0; alternatively 12 > f > 3; alternatively 10 > f > 0; alternatively 7 > f > 1 ; alternatively 5 > f > 2; and alternatively 7 > f > 3. Alternatively, for subscript g: 800 > g > 15; and alternatively 400 > g > 15. Alternatively, subscript h > 1. Alternatively, subscript h is 1 to 10. Alternatively, for subscript h: 10 > h > 0; alternatively 5 > h >0; and alternatively h = 1. Alternatively, subscript h is 1 to 10, alternatively subscript h is 1 or 2. Alternatively, when subscript h = 1 , then subscript f may be 3 and subscript i may be 0.

[0040] The organopolysiloxane (B) may have the formula (R23SiOi / 2)x’(R22SiO2 / 2)z’(SiO4 / 2)i .o(ZO-| / 2)w’ where each R2is independently selected and defined above, with the proviso that in each molecule, at least two of R are independently selected X, subscript x’ is from 1 .5 to 4; Z is independently selected from H and alkyl groups having from 1 to 4 carbon atoms; subscript w is from 0 to 3; and subscript z’ is from 3 to 1 ,000. Moieties represented by (ZO1 / 2)aretypically inherently present when the organopolysiloxane(B) is prepared via hydrolysis and condensation of silanes. Moieties represented by (ZO1 / 2) may be absent from the organopolysiloxane (B) depending on its method of preparation.

[0041] Regardless of the selection of the branched siloxane of the organopolysiloxane (B), the branched siloxane of the organopolysiloxane (B) has at least two, alternatively at least three silicon-bonded functional groups X. In certain embodiments, the branched siloxane of the organopolysiloxane (B) has a content of X of from 2.0 to 7.0, alternatively from 2.0 to 6.0, alternatively from 2.0 to 5.5, wt.% based on the total weight of the branched siloxane of the organopolysiloxane (B). This is typically the case when each R1group is methyl and each X is vinyl. However, as understood in the art, the same number of R1groups may constitute a lesser overall wt.% when R1 is something other than methyl (e.g. ethyl, aryl) and / or when X is something other than vinyl (e.g. allyl, hexenyl), which impact the molecular weight of the branched siloxane of the organopolysiloxane (B) . The content of R1can be interpreted and calculated using Silicon 29 Nuclear Magnetic Resonance Spectroscopy (2^Si NMR), as understood in the art. In certain embodiments, the branched siloxane of the organopolysiloxane (B) has a viscosity at 25 °C from greater than 0 to less than 400, alternatively from greater than 0 to less than 300, alternatively from greater than 0 to less than 200, mPa-s.

[0042] Alternatively, the organopolysiloxane (B) may be substantially linear, alternatively is linear. The substantially linear organopolysiloxane may have the average formula: R2a’^'O(4-a’) / 2’ where each R2and is as defined above, and where subscript a’ is selected such that 1 .9 < a’ < 2.2.

[0043] Alternatively, when the organopolysiloxane (B) is substantially linear, the substantially linear organopolysiloxane may have the average unit formula: (R2R12SiO1 / 2)aa(R2RlSiO2 / 2)bb(R22SiO2 / 2)cc(Rl3SiO1 / 2)dd> where each R1is independently selected and defined above; each R2is independently selected and defined above, with the proviso that component (B) includes at least two silicon-bonded functional groups X; subscript aa is 0, 1 , or 2, subscript bb is 0 or more, subscript cc is 1 or more, subscript dd is 0, 1 , or 2, with the provisos that a quantity (aa + dd) > 2, and (aa + dd) = 2, with the proviso that a quantity (aa + bb + cc + dd) is 3 to 2,000. Alternatively, subscript cc > 0. Alternatively, subscript bb > 2. Alternatively, the quantity (aa + dd) is 2 to 10, alternatively 2 to 8, and alternatively 2 to 6. Alternatively, subscript cc is 0 to 1 ,000, alternatively 1 to 500, and alternatively 1 to 200. Alternatively, subscript bb is 2 to 500, alternatively 2 to 200, and alternatively 2 to 100.

[0044] When the organopolysiloxane (B) is substantially linear, alternatively is linear, the silicon- bonded functional groups X may be bonded to silicon atoms in pendent positions, terminalpositions, or in both pendent and terminal locations in the organopolysiloxane that is substantially linear or linear. As a specific example, the organopolysiloxane (B) may comprise an organopolysiloxane that is substantially linear, alternatively is linear, having the average unit formula (when each X is vinyl):[(CH3)3SiO 2l2[(CH3)2SiO2 / 2]cc[(CH3)ViSiO2 / 2]bb’ where subscripts bb and cc are defined above, and Vi indicates a vinyl group. With regard to this average formula, any methyl group may be replaced with a different monovalent hydrocarbon group (such as alkyl or aryl), and any vinyl group may be replaced with a different aliphatically unsaturated monovalent hydrocarbon group (such as allyl or hexenyl), or X could be H. Alternatively, as a specific example of the polyorganosiloxane having an average, per molecule, of at least two silicon-bonded aliphatically unsaturated groups, the organopolysiloxane (B) may comprise an organopolysiloxane that is substantially linear, alternatively is linear, having the average formula: Vi(CH3)2SiO[(CH3)2SiO]ccSi(CH3)2Vi, where subscript cc and Vi are defined above. The dimethyl polysiloxane terminated with silicon-bonded vinyl groups may be used alone or in combination with the dimethyl, methyl-vinyl polysiloxane disclosed immediately above as a component of the organopolysiloxane (B). With regard to this average formula, any methyl group may be replaced with a different monovalent hydrocarbon group, and any vinyl group may be replaced with any terminally aliphatically unsaturated monovalent hydrocarbon group. Because the at least two silicon-bonded aliphatically unsaturated groups may be both pendent and terminal, the organopolysiloxane (B) may alternatively have the average unit formula:[Vi(CH3)2SiO 2l2[(CH3)2SiO2 / 2]cc[(CH3)ViSiO2 / 2]bb’ where subscripts bb and cc and Vi are defined above.

[0045] When the organopolysiloxane (B) comprises the substantially linear polyorganosiloxane, and when each X is an aliphatically unsaturated group, the substantially linear polyorganosiloxane can be exemplified by a dimethylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a methylphenylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylphenylsiloxane and dimethylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and a methylphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and diphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, a copolymer of a methylvinylsiloxane and a methylphenylsiloxane capped at both molecular terminals with trimethylsiloxy groups, a copolymer of a methylvinylsiloxane and diphenylsiloxane capped at both molecular terminals withtrimethylsiloxy groups, and a copolymer of a methylvinylsiloxane, methylphenylsiloxane, and a dimethylsiloxane capped at both molecular terminals with trimethylsiloxy groups.

[0046] Alternatively, the organopolysiloxane (B) may comprise a substantially linear, alternatively linear, polyorganosiloxane selected from the group consisting of (when each X is an aliphatically unsaturated group): i) dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), ill) dimethylvinylsiloxy-terminated polymethylvinylsiloxane, iv) trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), v) trimethylsiloxy-terminated polymethylvinylsiloxane, vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), ix) phenyl, methyl, vinyl-siloxy-terminated polydimethylsiloxane, x) dimethylhexenylsiloxy-terminated polydimethylsiloxane, xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane, xiii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xiv) trimethylsiloxy-terminated polymethylhexenylsiloxane xv) dimethylhexenyl-siloxy terminated poly(dimethylsiloxane / methylhexenylsiloxane), xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), and xvii) a combination thereof.

[0047] In certain embodiments, component (B) is a liquid at room temperature in the absence of any solvents. For example, at 25 °C, component (B) may be a flowable liquid or may have the form of an uncured rubber. The organopolysiloxane (B) may have a viscosity of from 2 mPa-s to 30,000,000 mPa-s, alternatively from 10 mPa-s to 10,000 mPa-s, alternatively from 100 mPa-s to 1 ,000,000 mPa-s, and alternatively from 100 mPa-s to 100,000 mPa-s at 25 °C. Viscosity may be measured at 25 °C via a Brookfield LV DV-E viscometer with a spindle selected as appropriate to the viscosity of the organopolysiloxane (B), i.e., RV-1 to RV-7. In specific embodiments, component (B) has a viscosity of from 2 to 1 ,000, alternatively from 2 to 800, alternatively from 2 to 600, alternatively from 2 to 400, mPa-s at 25 °C. In other embodiments, component (B) may be in the form of a gum at 25 °C without any measurable viscosity. For example, component (B) may be in the form of a gum when its viscosity exceeds 500,000 mPa-s at 25 °C.

[0048] Combinations of different organopolysiloxanes may be utilized together as component (B), which may differ from one another in terms of viscosity, degree of polymerization, structure, substitution, etc.

[0049] The amount of component (B) present in the composition is generally a function of whether the composition includes an optional organic solvent and the relative amount of component(A). As introduced above, the composition can be solventless or solvent-borne. When the composition is solventless and free from organic solvent, component (A) is present in an amount of at least 30 wt.% based on the total weight of components (A)-(E), and thus components (B)- (E) constitute 70 wt.% or less of the total composition weight. In such embodiments, component(B) is typically present in the composition in an amount of from 1 to 69, alternatively from 2 to 68, alternatively from 3 to 67, weight percent based on the total weight of components (A)-(E). In one embodiment, the composition is solventless and free from organic solvent, and component (A) is present in an amount of at least 30, alternatively at least 35, alternatively at least 40, alternatively at least 45, alternatively at least 50, alternatively at least 55, alternatively at least 60, alternatively at least 65, alternatively at least 70, alternatively at least 75, alternatively at least 80, weight percent based on the total weight of components (A)-(E). In other embodiments, component (B) is present in an amount of from greater than 1 , alternatively greater than 5, alternatively greater than 10, alternatively greater than 15, alternatively greater than 20, alternatively greater than 25, alternatively greater than 30, alternatively greater than 35, alternatively greater than 40, alternatively greater than 45, alternatively greater than 50, alternatively greater than 55, alternatively greater than 60, weight percent based on the total weight of components (A)-(E).

[0050] When the composition includes the organic solvent, component (A) is present in a wt / wt ratio of from 8:1 to 100:1 relative to component (B) in the composition. In certain embodiments when the composition includes the organic solvent, components (A) and (B) are present in a wt / wt ratio of from 15:1 to 100:1 , alternatively from 15:1 to 90:1 , alternatively from 15:1 to 80:1 , alternatively from 15:1 to 70:1 , alternatively from 15:1 to 60:1 , alternatively from 15:1 to 50:1 , alternatively from 15:1 to 40:1 , alternatively from 15:1 to 30:1 , alternatively from 15:1 to 20:1 , based on the wt / wt of (A) / (B). In other embodiments when the composition includes the organic solvent, components (A) and (B) are present in a wt / wt ratio of from 8:1 to 100:1 , alternatively from 9:1 to 100:1 , alternatively from 10:1 to 100:1 , alternatively from 11 :1 to 100:1 , alternatively from 12:1 to 100:1 , alternatively from 13:1 to 100:1 , alternatively from 14:1 to 100:1 , alternatively from 15:1 to 100:1 .

[0051] Further, the composition comprises (C) an organopolysiloxane including at least two silicon-bonded groups Y. The silicon-bonded groups Y are independently in terminal or pendant positions. For example, in one embodiment, each silicon-bonded group Y is terminal and present in an M siloxy unit. In another embodiment, each silicon-bonded group Y is present in D siloxy units independently of formula (YRl SiO2 / 2), where each R1 is an independently selected hydrocarbyl group free of ethylenic unsaturation, and each Y is an independently selected silicon- bonded group. As described below, each silicon-bonded group Y of component (C) can reactwith each silicon-bonded functional group X of components (A) and (B) in appropriate catalyzed conditions. The silicon-bonded functional group X is an independently selected silicon-bonded aliphatically unsaturated group or a silicon-bonded hydrogen atom, and when each X is the silicon-bonded aliphatically unsaturated group, each Y is H, and when each X is a silicon-bonded hydrogen atom, each Y is an independently selected silicon-bonded aliphatically unsaturated group. Component (C) is generally a cross-linker for component (B), and component (A) reduces crosslink density of the resultant release coating formed by the composition.

[0052] The organopolysiloxane (C) may be linear, branched, partly branched, cyclic, resinous ( / .e., have a three-dimensional network), or may comprise a combination of different structures. The organopolysiloxane (C) is typically a cross-linker, and reacts with the ethylenically unsaturated groups of component (A), when forming a coating, e.g. a release coating. Typically, the organopolysiloxane (C) comprises or is an organohydrogensiloxane such that Y is H.

[0053] Because the organopolysiloxane (C) includes an average of at least two silicon-bonded groups Y per molecule, with reference to the siloxy units set forth above, the organopolysiloxane (C) may comprise any of the following siloxy units including silicon-bonded groups Y, optionally in combination with siloxy units which do not include any silicon-bonded groups Y: (R^2HSiO-| / 2), (R10Y2SiO1 / 2), (Y3SiO1 / 2), (R1YSiO2 / 2), (Y2SiO2 / 2), and / or (YSiO3 / 2), where each R1is independently selected and defined above.

[0054] In specific embodiments, the organopolysiloxane (C) is a substantially linear, alternatively linear, organopolysiloxane. The substantially linear or linear polyorganohydrogensiloxane can have average unit formula: (YR12SiOi / 2)v’(YR1SiO2 / 2)w’(R12SiO2 / 2)z’(R13SiO-| / 2)y’> where each R1is independently selected and defined above, subscript v’ is 0, 1 , or 2, subscript w’ is 1 or more, subscript z’ is 0 or more, subscript y’ is 0, 1 , or 2, with the provisos that a quantity (v’ + y’) = 2, and a quantity (v’ + w’) > 3. A quantity (v’ + w’ + z’ + y’) may be 2 to 1 ,000. The polyorganohydrogensiloxane is exemplified, when each Y is H, by: i) dimethylhydrogensiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer, ii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, ill) trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer, iv) trimethylsiloxy-terminated polymethylhydrogensiloxane, and / or v) a combination of two or more of i), ii), iii), iv), and v). Suitable polyorganohydrogensiloxanes are commercially available from Dow Silicones Corporation of Midland, Michigan, USA.

[0055] The organopolysiloxane (C) may have the formula: Yy’R13_y’Si-(OSiR12)m'(OSiR1Y)m’- OSiR13_y’Yy’, where each R1is independently selected and defined above, each y’ is independently selected from 0 or 1 , subscripts m and m’ are each independently from 0 to 1 ,000with the proviso that m and m’ are not simultaneously 0 and m+m’ is from 1 to 1 ,000. In a specific embodiment, each of y’ is 0, and subscript m’ is > 2.

[0056] In one specific embodiment, the organopolysiloxane (C) is linear and includes pendent silicon-bonded groups Y. In these embodiments, the organopolysiloxane (C) may be a polysiloxane copolymer having the average formula;(CH3)3SiO[(CH3)2SiO]z>[(CH3)YSiO]w>Si(CH3)3Where Y, and subscripts z’ and w’ are defined above. One of skill in the art understands that in the exemplary formula above the siloxy may be present in randomized or block form, and that any methyl group may be replaced with any other hydrocarbon group free of aliphatic unsaturation.

[0057] In another specific embodiment, the organopolysiloxane (C) is linear and includes terminal silicon-bonded groups Y. In these embodiments, the organopolysiloxane (C) may be a polysiloxane having the average formula:Y(CH3)2SiO[(CH3)2SiO]z’Si(CH3)2YWhere Y and subscript z’ are as defined above. The polysiloxane may be utilized alone or in combination with the polysiloxane copolymer disclosed immediately above. When a mixture is utilized, the relative amount of each organopolysiloxane in the mixture may vary. One of skill in the art understands that any methyl group in the exemplary formula above may be replaced with any other hydrocarbon group free of aliphatic unsaturation.

[0058] Alternatively still, the organopolysiloxane (C) may include both pendent and terminal silicon-bonded groups Y.

[0059] In certain embodiments, when each Y is H, the organopolysiloxane (C) may comprise an alkylhydrogen cyclosiloxane or an alkylhydrogen dialkyl cyclosiloxane copolymer. Specific examples of suitable organohydrogensiloxanes of this type include (OSiMeH)4, (OSiMeH)3(OSiMeC6H1 3), (OSiMeH)2(OSiMeC6H1 3)2, and (OSiMeH)(OSiMeC6H1 3)3, where Me represents methyl ( — CH3).

[0060] Other examples of suitable organopolysiloxanes for component (C) are those having at least two SiY containing cyclosiloxane rings in one molecule. Such an organopolysiloxane may be any organopolysiloxane having at least two cyclosiloxane rings with at least one silicon- bonded group (SiY) on each siloxane ring. Cyclosiloxane rings contain at least three siloxy units (that is, the minimum needed in order to form a siloxane ring), and may be any combination of M, D, T, and / or Q siloxy units that forms a cyclic structure, provided that at least one of the cyclic siloxy units on each siloxane ring contains one SiY unit, which may be an M siloxy unit, a D siloxy unit, and / or a T siloxy unit. These siloxy units can be represented as MH, DH, and TH siloxy units respectively when other substituents are methyl and when Y is H.

[0061] In another specific embodiment, the organopolysiloxane (C) has the formula: [(YR1SiO2 / 2)a('R1iO3 / 2)b]c[(R12SiO2 / 2)wld, where each R1and each Y is independently selected and defined above, subscript a is from 0 to 10; subscript b is from 1 to 4, with the proviso that (a+b)=3 to 12; 0<c<100; 2<w<2,000; and 0<d<100, with the proviso that c>d. Such an organosilicon compound may be referred to as a branched cyclic polyorganosiloxane compound, which has cyclic SiY-functional branching groups interconnected by linear polydiorganosiloxane segments. An exemplary structure associated with such a branched cyclic polyorganohydrogensiloxane compound is as follows:where each R1is independently selected and defined above; subscript n is from 2 to 2,000, alternatively from 2 to 1 ,600, alternatively from 2 to 1 ,200, alternatively from 2 to 800, alternatively from 2 to 400, alternatively from 2 to 200, alternatively from 2 to 100, alternatively from 2 to 50; and each subscript o is independently from 0 to 9, alternatively from 0 to 8, alternatively from 0 to 6, alternatively from 0 to 4, alternatively from 2 to 4.

[0062] Such branched cyclic polyorganohydrogensiloxane compounds are known in the art and can be prepared by, for example, combining together (A) a hydroxyl terminated polydiorganosiloxane and (B) a cyclic polyorganosiloxane, in the presence of (C) a boron containing Lewis acid.

[0063] The organopolysiloxane (C) may comprise a combination or two or more different organosilicon compounds that differ in at least one property such as structure, molecular weight, monovalent groups bonded to silicon atoms and content of silicon-bonded groups Y. The composition may comprise the organopolysiloxane (C) in an amount to give a molar ratio of silicon-bonded groups Y in component (C) to silicon-bonded functional groups X in component (A) in an amount of from 1 :1 to 5:1 , alternatively from 1.1 :1 to 3.1. Typically, the composition comprises component (C) in an amount of from greater than 0 to 5, alternatively from 1 to 4, wt.% based on the total weight of components (A)-(E) in the composition.

[0064] Typically, component (C) comprises, alternatively is, a linear organopolysiloxane. In certain embodiments in which component (C) is the linear organopolysiloxane, component (C) has a degree of polymerization (DP) of from greater than 2 to 500, alternatively from 10 to 400.When component (C) has a DP of at least 234, the composition further includes an organic solvent, as described below as component (F).

[0065] In addition, the composition comprises (D) a hydrosilylation-reaction inhibitor (the “inhibitor”). The inhibitor (D) may be used for altering the reaction rate or curing rate of the composition, as compared to a composition containing the same starting materials but with the inhibitor (D) omitted. The inhibitor (D) is exemplified by acetylenic alcohols such as methyl butynol, ethynyl cyclohexanol, dimethyl hexynol, and 3,5-dimethyl-1 -hexyn-3-ol, 1 -butyn-3-ol, 1 - propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1 -butyn-3-ol, 3-methyl-1 -pentyn-3-ol, 3-phenyl-1 - butyn-3-ol, 4-ethyl-1 -octyn-3-ol, and 1 -ethynyl-1 -cyclohexanol, and a combination thereof; cycloalkenylsiloxanes such as methylvinylcyclosiloxanes exemplified by 1 ,3,5,7-tetramethyl- 1 ,3,5,7-tetravinylcyclotetrasiloxane, 1 ,3,5,7-tetramethyl-1 ,3,5,7-tetrahexenylcyclotetrasiloxane, and a combination thereof; ene-yne compounds such as 3-methyl-3-penten-1 -yne, 3,5-dimethyl- 3-hexen-1 -yne; triazoles such as benzotriazole; phosphines; mercaptans; hydrazines; amines, such as tetramethyl ethylenediamine, dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, maleates such as diallyl maleate; nitriles; ethers; carbon monoxide; alkenes such as cyclo-octadiene, divinyltetramethyldisiloxane; alcohols such as benzyl alcohol; and a combination thereof. Alternatively, the inhibitor (D) may be selected from the group consisting of acetylenic alcohols (e.g., 1 -ethynyl-1 -cyclohexanol) and maleates (e.g., diallyl maleate, bis maleate, or n-propyl maleate) and a combination of two or more thereof.

[0066] Alternatively, the inhibitor (D) may be a silylated acetylenic compound. Without wishing to be bound by theory, it is thought that adding a silylated acetylenic compound reduces yellowing of the reaction product prepared from hydrosilylation reaction of the composition as compared to a reaction product from hydrosilylation of a composition that does not contain a silylated acetylenic compound or that contains an organic acetylenic alcohol inhibitor, such as those described above.

[0067] The silylated acetylenic compound is exemplified by (3-methyl-1 -butyn-3- oxy)trimethylsilane, ((1 ,1 -dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1 -butyn-3- oxy)dimethylsilane, bis(3-methyl-1 -butyn-3-oxy)silanemethylvinylsilane, bis((1 ,1 -dimethyl-2- propynyl)oxy)dimethylsilane, methyl(tris(1 ,1 -dimethyl-2-propynyloxy))silane, methyl(tris(3- methyl-1 -butyn-3-oxy))silane, (3-methyl-1 -butyn-3-oxy)dimethylphenylsilane, (3-methyl-1 -butyn- 3-oxy)dimethylhexenylsilane, (3-methyl-1 -butyn-3-oxy)triethylsilane, bis(3-methyl-1 -butyn-3- oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1 -hexyn-3-oxy)trimethylsilane, (3-phenyl-1 -butyn- 3-oxy)diphenylmethylsilane, (3-phenyl-1 -butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1 -butyn-3- oxy)dimethylvinylsilane, (3-phenyl-1 -butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1 -ethyn-1 - oxy)dimethylhexenylsilane, (cyclohexyl-1 -ethyn-1 -oxy)dimethylvinylsilane, (cyclohexyl-1 -ethyn- 1 -oxy)diphenylmethylsilane, (cyclohexyl-1 -ethyn-1 -oxy)trimethylsilane, and combinationsthereof. Alternatively, the inhibitor (D) is exemplified by methyl(tris(1 ,1 -dimethyl-2- propynyloxy))silane, ((1 ,1 -dimethyl-2-propynyl)oxy)trimethylsilane, or a combination thereof. The silylated acetylenic compound useful as the inhibitor (D) may be prepared by methods known in the art, such as silylating an acetylenic alcohol described above by reacting it with a chlorosilane in the presence of an acid receptor.

[0068] The amount of the inhibitor (D) present in the composition will depend on various factors including the desired bathlife of the composition, whether the composition will be a one part composition or a multiple part composition, the particular inhibitor used, and the selection and amount of components (A)-(C). However, when present, the amount of the inhibitor (D) may be 0% to 1%, alternatively 0% to 5%, alternatively 0.001% to 1%, alternatively 0.01% to 0.5%, and alternatively 0.0025% to 0.025%, based on the total weight of components (A)-(E) of the composition.

[0069] The composition further comprises (E) a hydrosilylation-reaction catalyst. The hydrosilylation-reaction catalyst (E) is not limited and may be any known hydrosilylation-reaction catalyst for catalyzing hydrosilylation reactions. Combinations of different hydrosilylation-reaction catalysts may be utilized.

[0070] In certain embodiments, the hydrosilylation-reaction catalyst (E) comprises a Group VIII to Group XI transition metal. Group VIII to Group XI transition metals refer to the modern IUPAC nomenclature. Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs); Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations thereof, complexes thereof (e.g. organometallic complexes), and other forms of such metals may be utilized as the hydrosilylationreaction catalyst (E).

[0071] Additional examples of catalysts suitable for the hydrosilylation-reaction catalyst (E) include rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr), and / or hafnium (Hf)), lanthanides, actinides, and Group I and II metal complexes (e.g. those comprising calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations thereof, complexes thereof (e.g. organometallic complexes), and other forms of such metals may be utilized as the (D) hydrosilylation-reaction catalyst.

[0072] The hydrosilylation-reaction catalyst (E) may be in any suitable form. For example, the hydrosilylation-reaction catalyst (E) may be a solid, examples of which include platinumbased catalysts, palladium-based catalysts, and similar noble metal-based catalysts, and also nickel-based catalysts. Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt, and similar elements, and also platinum-palladium, nickel-copper-chromium, nickel- copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts comprising combinationsof a plurality of metals. Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu- Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts, and the like.

[0073] The hydrosilylation-reaction catalyst (E) may be in or on a solid carrier. Examples of carriers include activated carbons, silicas, silica aluminas, aluminas, zeolites and other inorganic powders / particles (e.g. sodium sulphate), and the like. The hydrosilylation-reaction catalyst (E) may also be disposed in a vehicle, e.g. a solvent which solubilizes the hydrosilylation-reaction catalyst (E), alternatively a vehicle which merely carries, but does not solubilize, the hydrosilylation-reaction catalyst (E). Such vehicles are known in the art.

[0074] In specific embodiments, the hydrosilylation-reaction catalyst (E) comprises platinum. In these embodiments, the hydrosilylation-reaction catalyst (E) is exemplified by, for example, platinum black, compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, a reaction product of chloroplatinic acid and a monohydric alcohol, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, as well as platinum compounds microencapsulated in a matrix or coreshell type compounds. Microencapsulated hydrosilylation catalysts and methods of their preparation are also known in the art, as exemplified in U.S. Patent Nos. 4,766,176 and 5,017,654, which are incorporated by reference herein in their entireties.

[0075] Complexes of platinum with organopolysiloxanes suitable for use as the hydrosilylationreaction catalyst (E) include 1 ,3-diethenyl-1 ,1 ,3,3-tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix. Alternatively, the hydrosilylation-reaction catalyst (E) may comprise 1 ,3-diethenyl-1 ,1 ,3,3- tetramethyldisiloxane complex with platinum. The hydrosilylation-reaction catalyst (E) may be prepared by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or alkene-platinum-silyl complexes. Alkene-platinum-silyl complexes may be prepared, for example by mixing 0.015 mole (COD)PtCl2 with 0.045 mole COD and 0.0612 moles HMeSiC^-

[0076] The hydrosilylation-reaction catalyst (E) may also, or alternatively, be a photoactivatable hydrosilylation-reaction catalyst, which may initiate curing via irradiation and / or heat. The photoactivatable hydrosilylation-reaction catalyst can be any hydrosilylation-reaction catalyst capable of catalyzing the hydrosilylation reaction, particularly upon exposure to radiation having a wavelength of from 150 to 800 nanometers (nm).

[0077] Specific examples of photoactivatable hydrosilylation-reaction catalysts suitable for the hydrosilylation-reaction catalyst (E) include, but are not limited to, platinum(ll) p-diketonate complexes such as platinum(ll) bis(2,4-pentanedioate), platinum(ll) bis(2,4-hexanedioate), platinum(ll) bis(2,4-heptanedioate), platinum(ll) bis(1 -phenyl-1 ,3-butanedioate, platinum(ll) bis( 1 ,3-diphenyl-1 ,3-propanedioate), platinum(ll) bis( 1 ,1 ,1 ,5,5,5-hexafluoro-2,4-pentanedioate);(ri-cyclopentadienyl)trialkylplatinum complexes, such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsilyl- Cp)trimethylplatinum, where Cp represents cyclopentadienyl; triazene oxide-transition metal complexes, such as PttCgHgNNNOCH^, Pt[p-CN-CgH4NNNOCgH-| -| ]4, Pt[p- H3COC6H4NNNOC6H-| ! ]4, Pt[p-CH3(CH2)X-C6H4NNNOCH3]4,1,5-cyclooctadiene.Pt[p-CN- C6H4NNNOC6H-| i]2, 1 ,5-cyclooctadiene.Pt[p-CH30-C6H4NNNOCH3]2, [(C6H5)3P]3Rh[p- CN-C6H4NNNOC6H-| -| ], and Pd[p-CH3(CH2)X— C6H4NNNOCH3]2, where x is 1 , 3, 5, 1 1 , or 17; (r|-diolefin)(o-aryl)platinum complexes, such as (r|4-1 ,5-cyclooctadienyl)diphenylplatinum, 1 ,3,5,7-cyclooctatetraenyl)diphenylplatinum, (r|4-2,5-norboradienyl)diphenylplatinum, (r|4- 1 ,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (r|4- 1 ,5-cyclooctadienyl)bis-(4- acetylphenyl)platinum, and (r|4-1 ,5-cyclooctadienyl)bis-(4-trifluormethylphenyl)platinum. Typically, the photoactivatable hydrosilylation-reaction catalyst is a Pt(ll) p-diketonate complex and more typically the catalyst is platinum(ll) bis(2,4-pentanedioate).

[0078] The hydrosilylation-reaction catalyst (E) is present in the composition in a catalytic amount, i.e., an amount or quantity sufficient to promote curing thereof at desired conditions. The hydrosilylation-reaction catalyst can be a single hydrosilylation-reaction catalyst or a mixture comprising two or more different hydrosilylation-reaction catalysts.

[0079] The catalytic amount of the hydrosilylation-reaction catalyst (E) may be > 0.01 ppm to 10,000 ppm; alternatively > 1 ,000 ppm to 5,000 ppm. Alternatively, the typical catalytic amount of the hydrosilylation-reaction catalyst (E) is 0.1 ppm to 5,000 ppm, alternatively 1 ppm to 2,000 ppm, alternatively > 0 to 1 ,000 ppm. Alternatively, the catalytic amount of hydrosilylation-reaction catalyst (E) may be 0.01 ppm to 1 ,000 ppm, alternatively 0.01 ppm to 100 ppm, alternatively 20 ppm to 200 ppm, and alternatively 0.01 ppm to 50 ppm of platinum group metal; based on the total weight of composition.

[0080] In certain embodiments, the composition additionally comprises component (F), an organic solvent.

[0081] Typically, the organic solvent (F), if present in the composition, is an organic liquid. Organic liquids includes those considered oils or solvents. The organic liquids are exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having more than 3 carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides and aromatic halides. Hydrocarbons include isododecane, isohexadecane, Isopar L (C1 1 -C13), Isopar H(C1 1 -C12), hydrogentated polydecene, and aromatic hydrocarbons. Ethers and esters include isodecyl neopentanoate, neopentylglycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyletheracetate (PGMEA), propylene glycol methylether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, and octyl palmitate. Additional organic fluids suitable as a stand-alone compound or as an ingredient to the (H) vehicle include fats, oils, fatty acids, and fatty alcohols.

[0082] When utilized, the organic solvent (F) is typically utilized to carry or solubilize component (B), particularly when component (B) is a gum at 25 °C. When utilized, the organic solvent (F) may be combined with component (B), e.g. to give a homogenous mixture, prior to incorporation into the composition.

[0083] In certain embodiments, the composition is free from organic solvent (F), and the composition is solventless. In other embodiments, the composition includes the organic solvent (F). The content of organic solvent (F), if utilized, is typically desirably minimized simply to solubilize component (B). for example, when utilized, the organic solvent (F) may be present in an amount to give a non-volatile content (NVC), when mixed with component (B), of from 10 to 90, alternatively from 10 to 80, alternatively from 10 to 70, alternatively from 10 to 60, alternatively from 15 to 50, alternatively from 20 to 40, wt.% of the combined amount of components (B) and (F). The organic solvent (F) may be added during preparation of the composition, for example, to aid mixing and delivery. All or a portion of the organic solvent (F) may optionally be removed after the composition is prepared, including prior to and / or contemporaneous with preparing the release coating from the composition. In certain embodiments, the composition is free from the organic solvent (F), and the composition is solventless and free from solvents and vehicles, including organic solvents.

[0084] In certain embodiments, the composition further comprises at least one of (G) an anchorage additive, (H) an anti-mist additive, (I) a release modifier, and / or (J) an alphaunsaturated olefin. If utilized, these components can be present in the composition in an amount of up to 10 wt.% based on the combined weights of components (A)-(E).

[0085] In certain embodiments, the composition further comprises the anchorage additive (G). Suitable anchorage additives are exemplified by a reaction product of a vinyl alkoxysilane and an epoxy-functional alkoxysilane; a reaction product of a vinyl acetoxysilane and epoxy-functional alkoxysilane; and a combination {e.g., physical blend and / or a reaction product) of a polyorganosiloxane having at least one aliphatically unsaturated hydrocarbon group and at least one hydrolyzable group per molecule and an epoxy-functional alkoxysilane e.g., a combination of a hydroxy-terminated, vinyl functional polydimethylsiloxane with glycidoxypropyltrimethoxysilane). Alternatively, the anchorage additive may comprise a polyorganosilicate resin. Suitable anchorage additives and methods for their preparation are commercially available and known in the art.

[0086] Further examples of suitable anchorage additives include a transition metal chelate, a hydrocarbonoxysilane such as an alkoxysilane, a combination of an alkoxysilane and a hydroxyfunctional polyorganosiloxane, or a combination thereof. The anchorage additive (G) may be a silane having at least one substituent having an adhesion-promoting group, such as an epoxy, acetoxy or acrylate group. The adhesion-promoting group may additionally or alternatively be any hydrolysable group which does not impact the (C) hydrosilylation-reaction catalyst. Alternatively, the anchorage additive (G) may comprise a partial condensate of such a silane, e.g. an organopolysiloxane having an adhesion-promoting group. Alternatively still, the anchorage additive (G) may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.

[0087] Alternatively, the anchorage additive (G) may comprise an unsaturated or epoxyfunctional compound. The anchorage additive (G) may comprise an unsaturated or epoxyfunctional alkoxysilane. For example, the functional alkoxysilane can include at least one unsaturated organic group or an epoxy-functional organic group. Epoxy-functional organic groups are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. Unsaturated organic groups are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl. One specific example of an unsaturated compound is vinyltriacetoxysilane.

[0088] Specific examples of suitable epoxy-functional alkoxysilanes include 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,(epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3-methacryloyloxypropyl triethoxysilane, 3- acryloyloxypropyl trimethoxysilane, 3-acryloyloxypropyl triethoxysilane, and combinations thereof.

[0089] The anchorage additive (G) may also comprise the reaction product or partial reaction product of one or more of these compounds. For example, in a specific embodiment, the anchorage additive (G) may comprise the reaction product or partial reaction product of vinyltriacetoxysilane and 3-glycidoxypropyltrimethoxysilane. Alternatively or in addition, the anchorage additive (G) may comprise alkoxy or alkenyl functional siloxanes.

[0090] Alternatively, the anchorage additive (G) may comprise an epoxy-functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane, as described above, or a physical blend of the hydroxy-terminated polyorganosiloxane with the epoxy-functional alkoxysilane. The anchorage additive (G) may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane.For example, the anchorage additive (G) is exemplified by a mixture of 3- glycidoxypropyltrimethoxysilane and a reaction product of hydroxy-terminated methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane, or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

[0091] Alternatively, the anchorage additive (G) may comprise a transition metal chelate. Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof. Alternatively, the anchorage additive (G) may comprise a combination of a transition metal chelate with an alkoxysilane, such as a combination of glycidoxypropyltrimethoxysilane with an aluminum chelate or a zirconium chelate.

[0092] The particular amount of the anchorage additive (G) present in the composition, if utilized, depends on various factors including the type of substrate and whether a primer is used. In certain embodiments, the anchorage additive (G) is present in the composition in an amount of from 0 to 2 parts by weight, per 100 parts by weight of components (A)-(E). Alternatively, the anchorage additive (G) is present in the composition in an amount of from 0.01 to 2 parts by weight, per 100 parts by weight of components (A)-(E).

[0093] In certain embodiments, the composition further comprises the anti-mist additive (H). The anti-mist additive (H) may be utilized in the composition to reduce or suppress silicone mist formation in coating processes, particularly with high speed coating equipment. The anti-mist additive (H) may be a reaction product of an organohydrogensilicon compound, an oxyalkylene compound or an organoalkenylsiloxane with at least three silicon bonded alkenyl groups per molecule, and a suitable catalyst. Suitable anti-mist additives are disclosed, for example, in U.S. Patent Application 201 1 / 0287267; U.S. Patent 8,722,153; U.S. Patent 6,586,535; and U.S. Patent 5,625,023.

[0094] The amount of the anti-mist additive (H) utilized in the composition will depend on various factors including the amount and type of other starting materials selected for the composition. However, the anti-mist additive (H) is typically utilized in an amount of from 0% to 10%, alternatively 0.1% to 3%, based on the total weight of the composition.

[0095] In certain embodiments, the composition further comprises (I) a release modifier, which may be utilized in the composition to control (decrease) the level of release force (the adhesive force between the release coating formed from the composition and an adherend thereto, such as a label including a pressure sensitive adhesive). Release coatings having the required or desired release force can be formulated from a modifier-free composition by adjusting the level or concentration of the release modifier. Examples of suitable release modifiers includetrimethylsiloxy-terminated dimethyl, phenylmethylsiloxanes. Alternatively, the release modifier may be a condensation reaction product of an organopolysiloxane resin having hydroxyl or alkoxy groups and a diorganopolysiloxane with at least one hydroxyl or hydrolyzable group. Examples of suitable release modifiers are disclosed, for example, in U.S. Patent 8,933,177 and U.S. Patent Application Publication 2016 / 0053056. When utilized, the release modifier can be present in the composition in an amount of from 0 to 85 parts by weight, alternatively 25 to 85 parts, per 100 parts of components (A)-(E).

[0096] In certain embodiments, the composition further comprises (J) an alpha-unsaturated olefin. The alpha-unsaturated olefin (J), if utilized, is typically utilized in combination with component (A), and includes but one unsaturated moiety, which is typically terminal in the alphaunsaturated olefin (J). The alpha-unsaturated olefin generally includes from 8 to 32, alternatively from 8 to 30, alternatively from 8 to 28, alternatively from 8 to 26, alternatively from 8 to 24, alternatively from 8 to 22, alternatively from 8 to 20, carbon atoms. Example include 1 -dodecene and 1 -octadecene.

[0097] Other optional components may be present in the composition, including, for example, reactive diluents, fragrances, preservatives, colorants, dyes, pigments, anti-oxidants, heat stabilizers, flame retardants, flow control additives, biocides, fillers (including extending and reinforcing fillers), surfactants, thixotroping agents, pH buffers, etc. The composition may be in any form and may be incorporated into further compositions.

[0098] Alternatively, the composition and release coating formed therefrom may be free of particulates or contains only a limited amount of particulate (e.g., filler and / or pigment), such as 0 to 30% by weight of the composition. Particulates can agglomerate or otherwise stick to the coater equipment used to form the release coating. In addition, particulates can hinder optical properties, for example transparency, of the release coating and of the release liner formed therewith, if optical transparency is desired. The particulates may be prejudicial to the adherence of an adherend.

[0099] In certain embodiments, the composition is free from fluoroorganosilicone compounds. It is believed that, during the cure, a fluorocompound, because of its low surface tension, may rapidly migrate to the interface of the composition or the release coating formed therewith and a substrate on which the composition is applied and the release coating is formed, for example a composition / PET film interface. Such migration may prevent adherence of the release coating (prepared by curing the composition) to the substrate by making a fluorine containing barrier. By making a barrier, the fluoroorganosilicone compounds may prevent any component of the composition from reacting at the interface, impacting curing and related properties. Moreover, fluoroorganosilicone compounds are usually expensive. In more specific embodiments, the composition is free from fluorine atoms altogether.

[0100] The composition in its curable form may be prepared by combining components (A)-(E), as well as any optional components, described above, in any order of addition, optionally with a master batch, and optionally under shear. As described in greater detail below, the composition may be a one part composition, a two component or 2K composition, or a multi-part composition. For example, components (A)-(E) may be present in the same or different parts until formation of a bath to prepare release coatings.

[0101] In certain embodiments, the composition has a bathlife of 10, alternatively 20, alternatively 30, alternatively 40 minutes at 40 °C. Bathlife is the time it takes for the viscosity of the composition to double at 40 °C, and is thus indicative of stability. Longer bathlife is indicative of better coating performance. As understood in the art, viscosity can be measured via a suitable viscometer, e.g. a Brookfield DV2TLV viscometer, continuously at 40 °C. Conventional compositions for preparing release coatings can generally only achieve such a bathlife with significant concentrations of inhibitor(s).

[0102] A method of preparing a coated substrate with the composition comprises applying, i.e., disposing, the composition on the substrate. The method further comprises curing the composition on the substrate, which results in the formation of the release coating on the substrate to give the coated substrate. Curing may be performed by heating at an elevated temperature, e.g., 50 °C to 200 °C, alternatively 50 °C to 180 °C, and alternatively 50 °C to 160 °C, to give the coated substrate. One skilled in the art would be able to select an appropriate temperature depending on various factors including the selection of the components in the composition and the substrate composition or material of construction.

[0103] The composition may be disposed or dispensed on the substrate in any suitable manner. Typically, the composition is applied in wet form via a wet coating technique. The composition may be applied by i) spin coating; ii) brush coating; ill) drop coating; iv) spray coating; v) dip coating; vi) roll coating; vii) flow coating; viii) slot coating; ix) gravure coating; x) Meyer bar coating; or xi) a combination of any two or more of i) to x). Typically, disposing the composition on the substrate results in a wet deposit on the substrate, which is subsequently cured to give the coated substrate, which comprises a cured film, i.e., the release coating, formed from the composition on the substrate.

[0104] The substrate is not limited and may be any substrate. The release coating may be separable from the substrate or may be physically and / or chemically bonded to the substrate depending on its selection. The substrate may have an integrated hot plate or an integrated or stand-alone furnace for curing the wet deposit. The substrate may optionally have a continuous or non-continuous shape, size, dimension, surface roughness, and other characteristics. Alternatively, the substrate may have a softening point temperature at the elevated temperature. However, the composition and method are not so limited.

[0105] Alternatively, the substrate may comprise a plastic, which maybe a thermosetting and / or thermoplastic. However, the substrate may alternatively be or comprise glass, metal, cellulose (e.g. paper), wood, cardboard, paperboard, a silicone, or polymeric materials, or a combination thereof.

[0106] Specific examples of suitable substrates include paper substrates such as Kraft paper, polyethylene coated Kraft paper (PEK coated paper), thermal paper, and regular papers; polymeric substrates such polyamides (PA); polyesters such as polyethylene terephthalates (PET), polybutylene terephthalates (PET), polytrimethylene terephthalates (PTT), polyethylene naphthalates (PEN), and liquid crystalline polyesters; polyolefins such as polyethylenes (PE), polypropylenes (PP), and polybutylenes; styrenic resins; polyoxymethylenes (POM); polycarbonates (PC); polymethylenemethacrylates (PMMA); polyvinyl chlorides (PVC); polyphenylene sulfides (PPS); polyphenylene ethers (PPE); polyimides (PI); polyamideimides (PAI); polyetherimides (PEI); polysulfones (PSU); polyethersulfones; polyketones (PK); polyetherketones; polyvinyl alcohols (PVA); polyetheretherketones (PEEK); polyetherketoneketones (PEKK); polyarylates (PAR); polyethernitriles (PEN); phenolic resins; phenoxy resins; celluloses such as triacetylcellulose, diacetylcellulose, and cellophane; fluorinated resins, such as polytetrafluoroethylenes; thermoplastic elastomers, such as polystyrene types, polyolefin types, polyurethane types, polyester types, polyamide types, polybutadiene types, polyisoprene types, and fluoro types; and copolymers, and combinations thereof.

[0107] The composition, or wet deposit, is typically cured at the elevated temperature for a period of time. The period of time is typically sufficient to effect curing, i.e., cross-linking, of the composition. The period of time may be from greater than 0 to 8 hours, alternatively from greater than 0 to 2 hours, alternatively from greater than 0 to 1 hour, alternatively from greater than 0 to 30 minutes, alternatively from greater than 0 to 15 minutes, alternatively from greater than 0 to 10 minutes, alternatively from greater than 0 to 5 minutes, alternatively from greater than 0 to 2 minutes, alternatively from greater than 0 to 1 minute, alternatively from greater than 0 to 50 seconds, alternatively from greater than 0 to 40 seconds, alternatively from greater than 0 to 30 seconds, alternatively from greater than 0 to 20 seconds, alternatively from greater than 0 to 10 seconds, alternatively from greater than 0 to 5 seconds. The period of time depends on various factors including on the elevated temperature is utilized, the temperature selected, desired release coating thickness, and the presence of absence of any vehicle in the composition.

[0108] Curing the composition typically has a dwell time of from 0.1 second to 50 seconds, alternatively from 0.5 second to 30 seconds, alternatively from 1 second to 10 seconds. Dwell time selected may depend on the substrate selection, temperature selected, and line speed. Dwell time, as used herein, refers to the time during which the composition, or wet deposit, issubjected to the elevated temperature. Dwell time is distinguished from cure time, as there may be ongoing curing even after the composition, wet deposit, or partially cured reaction intermediary thereof is no longer subjected to the elevated temperature, which typically initiates curing. Alternatively, the coated substrate may be prepared on a conveyor belt in an oven, and the dwell time may be calculated by dividing a length of the oven e.g. in meters) by a line speed of the conveyor belt e.g. in meters / sec). In some embodiments, the dwell time may be equivalent to the period of time in which the composition, or wet deposit, is cured.

[0109] The period of time may be broken down into cure iterations, e.g. a first-cure and a postcure, with the first-cure being, for example, one hour and the post cure being, for example, three hours. The elevated temperature may be independently selected from any temperature above room temperature in such iterations, and may be the same in each iteration.

[0110] Depending on the optional presence and selection of the organic solvent (F), curing the composition may also include the step of drying. For example, when the composition comprises the organic solvent (F), the step of curing typically also removes drying, volatilizing, or removing the organic solvent (F) from the composition. Drying may be contemporaneous with curing or may be separate from curing.

[0111] Depending on a thickness and other dimensions of the release coating and coated substrate, the coated substrate can be formed via an iterative process. For example, a first deposit may be formed and subjected to a first elevated temperature for a first period of time to give a partially cured deposit. Then, a second deposit may be disposed on the partially cured deposit and subjected to a second elevated temperature for a second period of time to give a second partially cured deposit. The partially cured deposit will also further cure during exposure to the second elevated temperature for the second period of time. A third deposit may be disposed on the second partially cured deposit and subjected to a third elevated temperature for a third period of time to give a third partially cured deposit. The second partially cured deposit will also further cure during exposure to the second elevated temperature for the second period of time. This process may be repeated, for example, from 1 to 50 times, to build the coated substrate as desired. A composite is of partially cured layers may be subjected to a final post-cure, e.g. at the elevated temperature and period of time above. Each elevated temperature and period of time may be independently selected and may be the same as or different from one another. When the coated substrate is formed via the iterative process, each deposit may also be independently selected and may differ in terms of components selected in the composition, their amounts, or both. Alternatively still, each iterative layer may be fully cured, rather than only being partially cured, in such an iterative process.

[0112] Alternatively, each deposit may comprise or be a wet film. Alternatively, the iterative process may be wet-on-wet, depending on a cure state of the partially cured layer. Alternatively, the iterative process may be wet-on-dry.

[0113] The coated substrate, which comprises the release coating formed from the composition on the substrate, may have varying dimensions, including relative thicknesses of the release coating and the substrate. The release coating has a thickness that may vary depending upon its end use application. The release coating may have a thickness of greater than 0 to 4,000 pm, alternatively greater than 0 to 3,000 pm, alternatively greater than 0 to 2,000 pm, alternatively greater than 0 to 1 ,000 pm, alternatively greater than 0 to 500 pm, alternatively greater than 0 to 250 pm. However, other thicknesses are contemplated, e.g. 0.1 to 200 pm. For example, the thickness of the release coating may be 0.2 to 175 pm; alternatively 0.5 to 150 pm; alternatively 0.75 to 100 pm; alternatively 1 to 75 pm; alternatively 2 to 60 pm; alternatively 3 to 50 pm; and alternatively 4 to 40 pm. Alternatively, when the substrate is plastic, the release coating may have a thickness of greater than 0 to 200, alternatively greater than 0 to 150 pm, and alternatively greater than 0 to 100 pm.

[0114] If desired, the release coating may be subjected to further processing depending upon its end use application. For example, the release coating may be subjected to oxide deposition e.g. SiC>2 deposition), resist deposition and patterning, etching, chemical, corona, or plasma stripping, metallization, or metal deposition. Such further processing techniques are generally known. Such deposition may be chemical vapor deposition (including low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and plasma-assisted chemical vapor deposition), physical vapor deposition, or other vacuum deposition techniques. Many such further processing techniques involve elevated temperatures, particularly vacuum deposition, for which the release coating is well suited in view of its excellent thermal stability. Depending on an end use of the release coating, however, the release coating may be utilized with such further processing.

[0115] The coated substrate may be utilized in diverse end use applications. For example, the coated substrate may be utilized in coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, construction applications, transportation applications, electronics applications, or electrical applications. However, the composition may be utilized in end use applications other than preparing the coated substrate, e.g. in the preparation of articles, such as silicone rubbers.

[0116] Alternatively, the coated substrate may be utilized as a release liner, e.g. for a tape or adhesive, including any pressure-sensitive adhesives, including acrylic resin-type pressuresensitive adhesives, rubber-type pressure-sensitive adhesives, and silicone-type pressuresensitive adhesives, as well as acrylic resin-type adhesives, synthetic rubber-type adhesives, silicone-type adhesives, epoxy resin-type adhesives, and polyurethane-type adhesives. Eachmajor surface of the substrate may having a release coating disposed thereon for double sided tapes or adhesives.

[0117] Alternatively, when the composition will be formulated to prepare a release coating, the composition may be prepared by mixing the components together, for example, to prepare a one part composition. However, it may be desirable to prepare the composition as a multiple part composition, in which components having SiH functionality and the hydrosilylation-reaction catalyst (E) are stored in separate parts, until the parts are combined at the time of use (e.g., shortly before application to a substrate).

[0118] As described above, the composition can for example be applied to the substrate by any convenient means such as spraying, doctor blade, dipping, screen printing or by a roll coater, e.g. an offset web coater, kiss coater or etched cylinder coater.

[0119] The composition of the invention can be applied to any substrate, such as those described above. Alternatively, the composition may be applied to polymer film substrates, for example polyester, particularly polyethylene terephthalate (PET), polyethylene, polypropylene, or polystyrene films. The composition can alternatively be applied to a paper substrate, including plastic coated paper, for example paper coated with polyethylene, glassine, super calender paper, or clay coated kraft. The composition can alternatively be applied to a metal foil substrate, for example aluminum foil.

[0120] The composition is particularly well suited to prepare release coatings for use with silicone- based pressure sensitive adhesives, with excellent compatibility and desirable release force.

[0121] In certain embodiments, the method of preparing the coated substrate may further comprise treating the substrate before applying or disposing the composition on the substrate. Treating the substrate may be performed by any convenient means such as a plasma treatment or a corona discharge treatment. Alternatively, the substrate may be treated by applying a primer. In certain instances, anchorage of the release coating may be improved if the substrate is treated before forming the release coating thereon from the composition.

[0122] When the composition includes the organic solvent (F), the method may further comprise removing the organic solvent (F), which may be performed by any conventional means, such as heating at 50 °C to 100 °C for a time sufficient to remove all or a portion of the organic solvent (F). The method may further comprise curing the composition to form the release coating on a surface of the substrate. Curing may be performed by any conventional means such as heating at 100 °C to 200 °C.

[0123] Under production coater conditions, cure can be effected in a residence time of 1 second to 6 seconds, alternatively 1 .5 seconds to 3 seconds, at an air temperature of 120°C to 150°C. Heating can be performed in an oven, e.g., an air circulation oven or tunnel furnace or by passing the substrate including the wet deposit disposed thereon around heated cylinders.

[0124] The following examples are intended to illustrate the invention and are not to be viewed in any way as limiting to the scope of the invention.

[0125] Certain components utilized in the Examples are set forth in Table 1 below. The components utilized in the Examples and set forth in Table 1 below are commercially available from various suppliers or synthesized through methods known in the art. For example, components (A-1)-(A-3), (B-7) and (C-3) were obtained from Gelest, Inc. of Morrisville, PA. Components (B-1) to (B-4) were synthesized as described in US 4,898,961 and US 5,756,796. Components (B-5) and (B-6) were synthesized by solubilizing each commercially available copolymer gum from Dow Silicones Corporation of Midland, Ml in toluene to give 30 wt% nonvolatile content. Components (C-1), (C-2), (E), and (G) are commercially available from Dow Silicones Corporation of Midland, Ml. Component (D) was obtained from Sigma-Aldrich of St. Louis, MO.

[0126] Table 1 : Components / Compounds UtilizedAged Release Force (RF-70 °C or RT)

[0127] To measure aged release force at 70 °C or room temperature (RT), a 180speeling test was utilized. In particular, a MY2G standard tape including a silicone pressure sensitive adhesive (PSA) was laminated on each release coating to give a laminated sample. The laminated sample was prepared by using four passes of a two-kilogram rolling weight during lamination. Each laminated sample was trimmed to have a width of approximately one inch. A loaded weight of 40 lbs over a surface area of 12x12 inches was disposed on each laminated sample for 1 day at 70 °C or room temperature (RT). After 1 day, the loaded weight was removed. The aged release force was measured using an l-Mass SP-2100 peel tester at a peel speed of 0.3 meters per minute at 180s. Aged release force is reported as an average of three measured values. Subsequent Adhesive Strength (SAS)

[0128] SAS is an indicator of silicone migration. After release testing of each laminated sample at 0.3 meters per minute, the MY2G standard tape including the silicone PSA (the “tape strips”) were retained and laminated and thus re-used. The tape strips were laminated using four passes of a two-kilogram rolling weight onto clean two-inch by five-inch stainless steel panels. Three strips of unused MY2G standard tape including the silicone PSA (i.e., without being used in the laminate samples prepared for aged release force testing) were also laminated with the stainless steel panels as a control. The laminated panels were left to dwell for 1 hour after lamination. After 1 hour, the laminated panels were tested using a Lab Master Release and Adhesion Tester by Testing Machines Inc. Samples were tested at an 180° angle and a speed of 0.3 meters per minute. Adhesion force, in grams per inch, was calculated by taking the average of the adhesion force of three separate strips. A standard deviation of the adhesion force was also recorded. The peel force of an unused PSA strip is tabulated below. SAS% is calculated based on adhesion of used tape after delamination / adhesion of control tape x 100%.

[0129] General Procedure 1 : Examples 1 -31 and Comparative Examples 1 -25

[0130] Examples 1-31 and Comparative Examples 1 -25 followed General Procedure 1 to prepare compositions for preparing release coatings. The particular amounts of each component utilized in the compositions of Examples 1-31 and Comparative Examples 1-22 are detailed below in Tables 2-11.

[0131] In General Procedure 1 , all of the components for each of Examples 1-31 and Comparative Examples 1-25 except for Component (E), were combined in a vessel and mixed via a dental mixer for 1 minute at 3500 revolutions per minute (rpm) to give a mixture. In each mixture, the molar ratio of silicon-bonded hydrogen atoms to silicon-bonded aliphatically unsaturated groups (vinyl and hexenyl) was 1.5:1 unless the particular Example or Comparative Example utilized Component (F), toluene. Component (F) is not discretely added to any composition, but is present along in components (B-5) and (B-6), and thus any Example or Comparative Example including Component (B-5) or (B-6) includes toluene. For any such example, the molar ratio of silicon-bonded hydrogen atoms to silicon-bonded aliphatically unsaturated groups (vinyl and hexenyl) was 1.4:1 or 1.5:1.

[0132] Then, Component (E) was disposed in each mixture to give a composition, and each composition was mixed via the dental mixture for 1 minute at 3500 rpm. In these Examples, reference to platinum or metal content is with regard to the platinum or metal itself, and not any ligands present in a complex.

[0133] Tables 2, 4-7, and 9-10 are based in grams of each component utilized in each Example or Comparative Example. However, Tables 3 and 8 are based on the relative amount of each component utilized in each composition based on parts by weight and not grams.

[0134] Table 2: Examples 1-8

[0135] Table 3: Examples 10-13

[0136] Table 4: Examples 14-21

[0137] Table 5: Examples 22-29

[0138] Table 6: Examples 30-31

[0139] Table 7: Comparative Examples 1 -9

[0140] Table 8: Comparative Examples 10-14

[0141] Table 9: Comparative Examples 15-19

[0143] Table 11 : Comparative Examples 23-25

[0144] Release coatings were formed with the compositions of Examples 1 -31 and Comparative Examples 1 -25. After mixing the components to give each composition, each composition was coated onto a substrate (50 pm polyethylene terephthalate (PET)) with a controlled thickness of ~ 1 pm or ~10pm with the aid of a coater at room temperature to give a wet deposit on the substrate. The compositions of Examples 5-6 and 29-31 and Comparative Examples 4, 9-14, and 20-22 utilized Mayer bar (OSP A-bar) #14, the compositions of Examples 1 -4 and 7-13 and Comparative Examples 1 -3, 5-8, and 18-19 utilized Mayer bar (OSP A-bar) #4, and the compositions of Examples 14-28 and Comparative Examples 15-17 utilized a single roll coater(38 psi). Tables 12-21 all include supplemental information regarding the release coatings and their associated compositions for the various Examples and Comparative Examples.

[0145] Table 12: Examples 1 -8 Supplemental Information

[0146] Table 13: Examples 9-13 Supplemental Information

[0147] Table 14: Examples 14-21 Supplemental Information

[0148] Table 15: Examples 22-29 Supplemental Information

[0149] Table 16: Examples 5-6 and 29-31 Supplemental Information

[0150] Table 17: Comparative Examples 1-9 Supplemental Information

[0151] Table 18: Comparative Examples 10-14 Supplemental Information

[0152] Table 19: Comparative Examples 15-19 Supplemental Information

[0153] Table 20: Comparative Examples 20-22 Supplemental Information

[0154] Table 21 : Comparative Examples 23-25 Supplemental Information

[0155] Then, each wet deposit on the substrate was put into a hot wind circulation chamber at an elevated temperature (110 °C) to cure each wet deposit into a corresponding release coating. Aged release force (RF) and subsequent adhesive strength (SAS) were measured as described above, and results are below in Tables 22-29. In the Tables 22-29, n / a means that release forcecould not be measured because of the strong adhesion or bond between the release coating and substrate. All of the Examples 1 -31 and Comparative Examples 1 -25 had their RF measured at 70 °C (designated below as RF (70)). All of Examples 23-28 and Comparative Examples 15-17 also had their RF measured at room temperature.

[0156] Table 22: Release Coating Properties of Examples 1 -13:

[0157] Table 23: Release Coating Properties of Examples 14-22

[0158] Tab e 24: Release Coating Properties of Examples 23-28

[0159] Table 25: Release Coating Properties of Examples 29-31

[0160] Table 26: Release Coating Properties of Comparative Examples 1 -14:

[0161] Table 27: Release Coating Properties of Comparative Examples 15-19

[0162] RF and SAS% were also attempted to be measured for Comparative Examples 18 and 19 based on a wet coating method where the composition was applied via a wet-cast method with a Mayer bar on a silicone pressure sensitive adhesive. However, the compositions of Comparative Examples 18 and 19 exhibited lock-up, and RF and SAS% could not be measured.

[0163] Table 28: Release Coating Properties of Comparative Examples 20-22

[0164] Table 29: Release Coating Properties of Comparative Examples 23-25

[0165] The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described.

Claims

THE CLAIMSWhat is claimed is:1 . A composition for forming a release coating, said composition comprising:(A) an organosilicon compound having only one silicon-bonded functional group X, the silicon-bonded functional group X being present in an M siloxy unit of formula (XR12SiO-| / 2), where X is the silicon-bonded functional group, and each R1is an independently selected hydrocarbyl group free of ethylenic unsaturation;(B) an organopolysiloxane including an average of at least two silicon-bonded functional groups X per molecule;(C) an organopolysiloxane including at least two silicon-bonded groups Y, optionally present in D siloxy units independently of formula (YRl SiO2 / 2), where each R1 is an independently selected hydrocarbyl group free of ethylenic unsaturation, and each Y is an independently selected silicon-bonded group;(D) a hydrosilylation-reaction inhibitor;(E) a catalyst; and optionally (F), an organic solvent; subject to the following provisos:(i) when the composition is solventless and free from the organic solvent (F), component (A) is present in an amount of at least 30 wt.% based on the total weight of components (A)-(E); and(ii) when the composition includes the organic solvent (F), component (A) is present in a wt / wt ratio of from 8:1 to 100:1 relative to component (B) in the composition; wherein X is an independently selected silicon-bonded aliphatically unsaturated group or a silicon-bonded hydrogen atom, and when each X is the silicon-bonded aliphatically unsaturated group, each Y is H, and when each X is a silicon-bonded hydrogen atom, each Y is an independently selected silicon-bonded aliphatically unsaturated group; and wherein if component (C) has a degree of polymerization (DP) of 234 or more, then component (F) is present in the composition.

2. The composition of claim 1 , wherein each X is an independently selected silicon-bonded aliphatically unsaturated group, and each Y is a silicon-bonded hydrogen atom.

3. The composition of claim 1 or 2, wherein component (A) has the formula (I), or the formula (II), or the formula (III):XSiR12O(SiR12O)eSiR13(I) (XR’l2SiO1 / 2)(R^3SiO1 / 2)b(R^2SiO2 / 2)c(R^ SiO3 / 2)c| (II) XSiR12O[(SiR12O)nDm]pSiR13 (III), wherein each X and each R1is independently selected and defined above, each D is an independently selected divalent hydrocarbon group having from 2 to 6 carbon atoms, subscript n is from 2 to 3,000, subscript m is independently 0 or 1 , subscript p is 1 to 100, subscript b is 2 to 401 , subscript c is from 2 to 3000, subscript d is 0 to 200, and subscript e is 2 to 3000.

4. The composition of any one preceding claim, wherein the composition is free from the organic solvent (F), and wherein component (A) is present in an amount of at least 30 wt.% based on the total weight of components (A)-(E).

5. The composition of any one of claims 1 -3, wherein the composition includes the organic solvent (F), component (A) is present in a wt / wt ratio of from 8:1 to 100:1 relative to component (B) in the composition.

6. The composition of any one preceding claim, wherein the organopolysiloxane (B): (i) is a linear or branched organopolysiloxane including the silicon-bonded functional groups X in at least one M siloxy unit; or (ii) has the formula (R2yR13-ySiO-| / 2)x(R1R2SiO2 / 2)z(SiO4 / 2), where each R1is an independently selected and defined above; each R2is independently selected from R1and X, subscript y is independently selected in each siloxy unit indicated by subscript x and is 1 or 2; each; subscript x is from 1.5 to 6; and subscript z is from 3 to 1 ,000; or (iii) is a gum at room temperature in the absence of any organic solvents.

7. The composition of any one preceding claim, wherein the organopolysiloxane (C) has the formula: Yy’R13ySi-(OSiR12)m-(OSiR1Y)m’-OSiR13-y’Yy’, where each R1is independently selected and defined above, each Y is independently selected and defined above, each y’ is independently selected from 0 or 1 , subscripts m is 0 to 1 ,000, and subscript m’ is 2 to 1 ,000; or wherein the (B) organosilicon compound has the formula: [(YR1SiO2 / 2)a(- R1SiO3 / 2)b]c[(R12SiO2 / 2)w]c|jwhere each R1is independently selected and defined above, subscript a is from 0 to 10; subscript b is from 1 to 4, with the proviso that (a+b)=3 to 12;0<c<100; 2<w<2,000; and 0<d<100, with the proviso that c>d.

8. The composition of any one preceding claim, further comprising at least one of (G) an anchorage additive, (H) an anti-mist additive, (I) a release modifier, and / or an alphaunsaturated olefin having from 8 to 30 carbon atoms.

9. The composition of any one preceding claim free from any fluorine atoms.

10. A method of preparing the composition of any one preceding claim, said method comprising combining and mixing component (A)-(E), and optionally component (F), to give the composition.11 . A coating formed by curing the composition of any one of claims 1-9.

12. A laminate comprising the coating of claim 11 adjacent a silicone-based pressure sensitive adhesive.

13. A method of forming a coated substrate, said method comprising: applying a composition on a substrate; and curing the composition to give a release coating on the substrate, thereby forming the coated substrate; wherein the composition is the composition of any one of claims 1 -9.

14. The method of claim 13, wherein the substrate comprises cellulose and / or a polymer.

15. A coated substrate comprising a release coating disposed on a substrate formed in accordance with the method of claim 13 or 14.