Release coatings, compositions for preparing release coating compositions, and related methods

Abstract

A base composition for forming a release coating composition is disclosed. The base composition comprises (A) a silicate resin that is liquid at 25°C in the absence of any solvent. The (A) silicate resin contains, on average, at least one silicon-bonded ethylenically unsaturated group per molecule. The composition further comprises (B) an organopolysiloxane that contains, on average, at least two silicon-bonded ethylenically unsaturated groups per molecule. The (A) silicate resin is miscible with the (B) organopolysiloxane in the absence of any solvent. Methods for preparing the base composition and the release coating composition are also disclosed.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the entire benefit of U.S. Provisional Patent Application No. 62 / 955,107, filed December 30, 2019, the contents of which are incorporated herein by reference.

[0002] FIELD OF THEINVENTION FIELD OF THE DISCLOSURE The present subject disclosure relates generally to compositions and, more specifically, to compositions and related methods for preparing release coatings. [Background technology]

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

[0004] Conventional release liners are typically formed by the addition reaction (or hydrosilylation) of an organopolysiloxane having an unsaturated hydrocarbon group with an organohydrogenpolysiloxane in the presence of a hydrosilylation reaction catalyst. In addition, various additives, such as release modifiers and antifog agents, are incorporated into the silicone release composition to improve the performance of the resulting release liner or its preparation method. Summary of the Invention

[0005] A base composition for forming a release coating composition is disclosed. The base composition comprises (A) a silicate resin that is liquid at 25° C. in the absence of any solvent. The (A) silicate resin comprises, on average, at least one silicon-bonded ethylenically unsaturated group per molecule. The base composition further comprises (B) an organopolysiloxane that comprises, on average, at least two silicon-bonded ethylenically unsaturated groups per molecule. The (A) silicate resin is miscible with the (B) organopolysiloxane in the absence of any solvent.

[0006] Methods of preparing the base composition and the release coating composition are also disclosed. Additionally, methods of preparing a coated substrate comprising a release coating disposed on a substrate, as well as a coated substrate formed according to the methods are disclosed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] A base composition for forming a release coating composition is disclosed. The base composition may be referred to herein simply as the composition.

[0008] The base composition comprises (A) a silicate resin that is liquid at 25° C. in the absence of any solvent. (A) silicate resin may alternatively be referred to as a silicone resin, but the Q siloxy, or SiO in (A) silicate resin is not particularly limited. 4 / 2In view of the presence of the unit, it is a silicate resin. In general, silicone resins, specifically silicate resins, are solid at 25°C due to their three-dimensional network structure. In view of the difficulty of processing solid silicone resins, silicone resins are typically dissolved in a solvent and utilized as silicone resin compositions that include or consist of solid silicone resins dissolved in a solvent, such as an aliphatic or aromatic hydrocarbon solvent. In this way, the silicone resin composition is liquid at 25°C or room temperature, making it possible to process the silicone resin composition more easily. For example, the silicone resin composition can be combined with other ingredients or compositions for various end-use applications in liquid form. Similarly, conventional silicone resins that are solid at 25°C in the absence of any solvent are not easily miscible with liquid silicones. This means that when preparing a silicone composition, conventional silicone resins that are solid at 25°C cannot be easily mixed or solubilized with liquid silicones, such as liquid organopolysiloxanes, in the absence of an organic solvent. Thus, when conventional silicone resins are utilized in silicone compositions, an organic solvent is typically required to form the silicone composition and then volatilizes, either in the form of the composition or upon curing.

[0009] However, one of the disadvantages of silicone composition is that the solvent is typically removed in the final use application.For example, when silicone composition is utilized to form a film or article, the solvent is typically removed when forming such a film or article.This requires additional processing steps to remove the solvent, for example, through volatilization, and energy and related costs.

[0010] In contrast, the (A) silicate resin is liquid at 25°C in the absence of any solvent. Thus, the fact that the (A) silicate resin is liquid at 25°C is not due to the presence of any solvent, such as an organic solvent, unlike conventional silicone resins. The (A) silicate resin consists of a silicate resin that does not contain any solvent or carrier vehicle. Furthermore, not only is the (A) silicate resin liquid at 25°C in the absence of any solvent, but the (A) silicate resin is miscible with a (B) organopolysiloxane containing on average at least two silicon-bonded ethylenically unsaturated groups per molecule in the base composition. This enables the easy formation of the base composition without the need for any solvent or the associated processing steps for removing the solvent from the base composition.

[0011] "Liquid" means that the (A) silicate resin is fluid at 25°C and / or has a measurable viscosity at 25°C in the absence of any solvent. Typically, the viscosity of the (A) silicate resin can be measured at 25°C via a Brookfield LV DV-E viscometer equipped with a spindle appropriately selected for the viscosity of the (A) silicate resin. The viscosity of the (A) silicate resin can vary, in particular, based on the content of M, D, T, and / or Q siloxy units present therein, as described below.

[0012] In a specific embodiment, the (A) silicate resin has the average formula [W] a [X] b [Y] c wherein 0 < a < 1, 0 < b < 1, and 0 < c < 1, provided that a + b + c = 1. The subscripts a, b, and c are the mole fractions of the W, X, and Y units in the (A) silicate resin. In the formula, 0 < a < 1, 0 < b < 1, and 0 < c < 1, provided that a + b + c = 1. The subscripts a, b, and c are the mole fractions of the W, X, and Y units in the (A) silicate resin.

[0013] In the above average formula for the (A) silicate resin, [W], [X], and [Y] are utilized in place of the more common nomenclature [M], [D], and [Q]. As understood in the art, an M siloxy unit contains one siloxane bond (i.e., -O-Si-), a D siloxy unit contains two siloxane bonds, and a Q siloxy unit contains four siloxane bonds.

[0014] However, for purposes of this disclosure, [W] represents a siloxy unit containing one -Si-O- bond, which may be a siloxane bond or a precursor thereof. A precursor of a siloxane bond is a -Si-OZ bond, where Z is independently H, an alkyl group, or K. + Or Na + Alternatively, it is a cation such as H or an alkyl group. Silanol and alkoxy groups can hydrolyze and / or condense to give siloxane bonds and are typically inherently present in most silicone resins. Such precursors of siloxane bonds can be minimized by thickening the silicone resin, which leads to further condensation with water and / or alcohol as by-products. Thus, for the purposes of this disclosure, [W] is defined as [R 3 SiO 1 / 2 wherein each R is an independently selected hydrocarbyl group.

[0015] Further, for purposes of this disclosure, [X] represents a siloxy unit containing two -Si-O- bonds, which may be independently a siloxane bond or a precursor thereof. Thus, for purposes of this disclosure, [X] represents a siloxy unit containing two -Si-O- bonds, which may be independently a siloxane bond or a precursor thereof. 2 SiO 1 / 2 (OZ)] b’ [R 2 SiO 2 / 2 ] b’’where each R is independently selected and defined above, 0≦b'≦b and 0≦b''≦b, with the proviso that b'+b''=b, and each Z is independently H, an alkyl group, or a cation. The subscripts b' and b'' indicate the relative mole fraction of the [X] siloxy units designated by subscript b' and those designated by subscript b'', respectively, and the sum of b' and b'' is b. In the [X] siloxy units designated by subscript b', there is one siloxane bond and one Si-OZ bond, and in the [X] siloxy units designated by subscript b'' there are two siloxane bonds.

[0016] Further, for purposes of this disclosure, [Y] represents a siloxy unit containing four -Si-O- bonds, which may be independently a siloxane bond or a precursor thereof. Thus, for purposes of this disclosure, [Y] represents [Si(OZ) c’ O 4-c’ / 2 [Y] is a siloxy unit represented by the subscript c, where each Z is independently selected and defined above, and the subscript c' is an integer from 0 to 3 and is independently selected for each siloxy unit represented by the subscript c in the (A) silicate resin. The (A) silicate resin can include a siloxy unit represented by the subscript c, where c' is 0, c' is 1, c' is 2, and c' is 3. The siloxy unit represented by [Y] can have 1, 2, 3, or 4 siloxane bonds, with the remainder being Si-OZ moieties.

[0017] In certain embodiments, subscript a is from greater than zero to 0.9, alternatively from 0 to 0.8, alternatively from greater than 0 to 0.7, alternatively from greater than 0 to 0.6, alternatively from greater than 0 to 0.5. In specific embodiments, subscript a is from 0.10 to 0.50, alternatively from 0.15 to 0.40, alternatively from 0.25 to 0.35.

[0018] In these or other embodiments, the subscript b is greater than zero to 0.9, alternatively greater than zero to 0.8, alternatively greater than zero to 0.7, alternatively greater than zero to 0.6, alternatively greater than zero to 0.5, alternatively greater than zero to 0.4. In a specific embodiment, the subscript b is 0.10 to 0.30, alternatively 0.15 to 0.30, alternatively 0.15 to 0.25. The subscripts b' and b'' define the relative amounts of the specific siloxy units represented by [X]. As described above, 0 ≦ b' ≦ b and 0 ≦ b'' ≦ b, provided that b' + b'' = b. While the subscript b' can be 0 and the subscript b'' can be b, or the subscript b' can be b and the subscript b'' can be 0. When both siloxy units represented by b' and b'' are present in the (A) silicate resin, 0 < b' < b and 0 < b'' < b, provided that b' + b'' = b.

[0019] In these or other embodiments, the subscript c is greater than zero to 0.9, alternatively greater than zero to 0.8, alternatively greater than zero to 0.7, alternatively greater than zero to 0.6. Alternatively, in these or other embodiments, c is 0.1 to 0.9, alternatively 0.2 to 0.9, alternatively 0.3 to 0.9, alternatively 0.4 to 0.9. In a specific embodiment, the subscript c is 0.35 to 0.60, alternatively 0.40 to 0.55.

[0020] R is an independently selected hydrocarbyl group, and on average at least one, alternatively at least two, R is an ethylenically unsaturated group per molecule of (A) silicate resin. In general, the hydrocarbyl groups suitable for R can be independently linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups, and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can be independently monocyclic or polycyclic. Linear and branched hydrocarbyl groups can be independently saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. Common examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, and the like, as well as derivatives, variants, and combinations thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the alkyl groups described above in which one or more hydrogen atoms have been replaced with a halogen atom, such as F or Cl.Specific examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and derivatives thereof. Examples of halogenated aryl groups include the above-mentioned aryl groups, in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0021] In specific embodiments, each R is independently selected from alkyl groups having 1 to 32, alternatively 1 to 28, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 8, alternatively 1 to 4, alternatively 1 carbon atom, and ethylenically unsaturated groups (i.e., alkenyl and / or alkynyl groups) having 2 to 32, alternatively 2 to 28, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 16, alternatively 2 to 12, alternatively 2 to 8, alternatively 2 to 4, alternatively 2 carbon atoms. "Alkenyl" refers to an acyclic, branched, or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples include vinyl, allyl, hexenyl, and octenyl. "Alkynyl" refers to an acyclic, branched, or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples include ethynyl, propynyl, and butynyl groups. Various examples of ethylenically unsaturated groups include CH 2 =CH-, CH 2 =CHCH 2 -, CH 2 =CH(CH 2 ) 4-, CH 2 =CH(CH 2 ) 6 -, CH 2 =C(CH 3 )CH 2 -, H 2 C=C(CH 3 )-, H 2 C=C(CH 3 )-, H 2 C=C(CH 3 )CH 2 -, H 2 C=CHCH 2 CH 2 -, H 2 C=CHCH 2 CH 2 CH 2 -, HC≡C-, HC≡CCH 2 -, HC≡CCH(CH 3 )-, HC≡CC(CH 3 ) 2 - and HC≡CC(CH 3 ) 2 CH 2 Typically, when R is an ethylenically unsaturated group, the ethylenic unsaturation is at the terminal end of R. As is understood in the art, the ethylenic unsaturation may be referred to as aliphatic unsaturation.

[0022] In specific embodiments, only the siloxy units designated by subscript b contain R groups with ethylenic unsaturation. In these embodiments, the R groups of the siloxy units designated by subscripts a and c do not contain ethylenic unsaturation, a specific example of which is methyl. In certain embodiments, the (A) silicate resin contains both dimethylsiloxy units and methylvinylsiloxy units as the siloxy units designated by subscript b. In other embodiments, the (A) silicate resin contains methylvinylsiloxy units but does not contain dimethylsiloxy units as the siloxy units designated by subscript b. The relative amount of such siloxy units can be selectively controlled when preparing the (A) silicate resin. As is understood in the art, the siloxy units described above are merely exemplary, and the methyl may be replaced with other hydrocarbyl groups and the vinyl may be replaced with other ethylenically unsaturated groups.

[0023] In certain embodiments, (A) the silicate resin has a SiOZ moiety content of 12 to 80, alternatively 15 to 70, alternatively 15 to 60, alternatively 15 to 50, alternatively 15 to 40, alternatively 15 to 30 percent based on the total moles of Si in each molecule. 29 It can be calculated via Si-NMR. Specifically, the molar content of the following siloxy units in (A) the silicate resin is determined: W=R 3 SiO 1 / 2 X1=R 2 (OZ)SiO 1 / 2 X2=R 2 SiO 2 / 2 T1=R(OZ) 2 SiO 1 / 2 T2 = R(OZ)SiO 2 / 2 T3=RSiO 3 / 2 Y1=(OZ) 3 SiO 1 / 2 Y2=(OZ) 2 SiO 1 / 2 Y3=(OZ)SiO 3 / 2 Y4=SiO 4 / 2 The OZ content relative to silicon atoms as mole % can be calculated by the following formula with the label of each peak in the formula corresponding to the integrated area under the peak corresponding to the label:

number

[0024] In these or other embodiments, the (A) silicate resin alternatively has more than 0 to 10 weight percent of silicon-bonded ethylenically unsaturated groups based on the total weight of the (A) silicate resin. The weight percent of silicon-bonded ethylenically unsaturated groups is independent of the viscosity of the (A) silicate resin, which is different from the weight percent of silicon-bonded ethylenically unsaturated groups of conventional solid silicone resins, which are a function of the viscosity of a particular siloxane polymer or vehicle when dispersed therein. Thus, for example, the weight percent of silicon-bonded ethylenically unsaturated groups can be increased without affecting the viscosity of the (A) silicate resin. The weight percent of silicon-bonded ethylenically unsaturated groups can be selectively controlled when preparing the (A) silicate resin, as described below.

[0025] In these or other embodiments, the weight percent of silicon-bonded ethylenically unsaturated groups in the (A) silicate resin can be selectively controlled independently of the viscosity of the (A) silicate resin. In contrast, in conventional silicone resins containing silicon-bonded ethylenically unsaturated groups, the content is a function of viscosity, limiting the ability to selectively control the content of silicon-bonded ethylenically unsaturated groups at a particular viscosity, essentially limiting the specific end-use application. In various embodiments, the (A) silicate resin has a weight average molecular weight of 1,000 to 100,000, alternatively 1,000 to 50,000, alternatively 1,000 to 10,000. The molecular weight can be measured via gel permeation chromatography (GPC) against polystyrene standards. In these or other embodiments, the (A) silicate resin has a viscosity of 10 to 500,000, alternatively 10 to 250,000, alternatively 10 to 100,000 cP at 25° C. The viscosity may be measured at 25° C. via a Brookfield LV DV-E viscometer with a spindle appropriately selected for the viscosity of the (A) silicate resin, as understood in the art. The viscosity and molecular weight of the (A) silicate resin may be controlled when preparing the (A) silicate resin.

[0026] In various embodiments, the silicate resin is prepared from an MQ resin, where M is (R 0 SiO 3 / 2 ) siloxy unit, Q is (SiO 4 / 2 ) siloxy units, where R 0 designates a silicon-bonded substituent. Such MQ resins are known in the art and are often in solid (e.g., powder or flake) form unless placed in a solvent. Typically, however, in the nomenclature utilized in the art, the M siloxy units are trimethylsiloxy units, although MQ resins may contain hydrocarbyl groups other than methyl groups. Typically, however, the M siloxy units of MQ resins are trimethylsiloxy units.

[0027] MQ resins have the formula M nThe formula may have a molar ratio of M siloxy units to Q siloxy units, where the subscript n refers to the mole ratio of M siloxy units to Q siloxy units when the moles of Q siloxy units are normalized to 1. The higher the value of n, the lower the crosslink density of the MQ resin. The converse is also true, as the value of n decreases, the number of M siloxy units decreases, and therefore more Q siloxy units are reticulated without terminating through M siloxy units. The fact that the formula of the MQ resin normalizes the content of Q siloxy units to 1 does not mean that the MQ resin contains only one Q unit. Typically, an MQ resin contains multiple Q siloxy units clustered or bonded together. The MQ resin may contain up to 4, alternatively up to 3, alternatively up to 2 weight percent hydroxyl groups in certain embodiments.

[0028] In specific embodiments, the subscript n is <1, for example, the subscript n is 0.05 to 0.99, alternatively 0.10 to 0.95, alternatively 0.15 to 0.90, alternatively 0.25 to 0.85, alternatively 0.40 to 0.80. In these embodiments, on a molar basis, there are more Q siloxy units in the MQ resin than M siloxy units. However, n can be >1, and in other embodiments, for example, >1 to 6, alternatively >1 to 5, alternatively >1 to 4, alternatively >1 to 3, alternatively >1 to 2.

[0029] In a specific embodiment, (A) silicate resin is prepared from the MQ resin by reacting the MQ resin with a silane compound in the presence of a base catalyst. The silane compound typically comprises a silicon-bonded ethylenically unsaturated group and two silicon-bonded alkoxy groups. The silicon-bonded alkoxy groups may be independently selected and typically have 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 or 2, alternatively 1 carbon atom. For example, the silicon-bonded alkoxy group may be methoxy, ethoxy, propoxy, butoxy, and the like. For example, the silane compound may be of the formula R 2 Si(OR) 2 wherein each R is independently selected and at least one R that is not part of an alkoxy group is an ethylenically unsaturated group.

[0030] In the method of preparing the (A) silicate resin, a base catalyst typically cleaves the siloxane bond of the MQ resin, typically between the M and Q siloxy units, to obtain a SiOZ group, where Z is defined above. The silane compound can hydrolyze and condense with the SiOZ group to be incorporated therein. By both the cleaved siloxy bond and the inclusion of linear siloxy units resulting from the silane compound, the (A) silicate resin becomes liquid at 25° C. in the absence of any solvent.

[0031] The silane compound is incorporated into the (A) silicate resin as a D siloxy unit, i.e., as indicated by [X] and subscript b, so the silane compound can be selected based on the desired D siloxy unit. For example, if the (A) silicate resin contains methylvinylsiloxy units, the silane compound is a methylvinyldialkoxysilane, such as methylvinyldimethoxysilane. If the (A) silicate resin contains dimethylsiloxy units and methylvinylsiloxy units, the silane compound can include methylvinyldimethoxysilane in combination with dimethyldimethoxysilane. Thus, the silane compound can include two or more different silane compounds simultaneously.

[0032] The relative amount of silane compound utilized compared to the MQ resin is a function of the desired subscript b in the (A) silicate resin. If more D siloxy units are desired, more silane compound is utilized, and vice versa. Those skilled in the art will understand how to selectively control such content in light of the description herein, including the examples following this detailed description.

[0033] The MQ resin and the silane compound react in the presence of a catalyst. Typically, the catalyst is an acid or a base, so that the reaction between the MQ resin and the silane compound is either an acid-catalyzed reaction or a base-catalyzed reaction. Typically, the reaction is base-catalyzed. Thus, in certain embodiments, the catalyst can be selected from the group of strong acid catalysts, strong base catalysts, and combinations thereof. The strong acid catalyst can be trifluoromethanesulfonic acid, etc. The catalyst is typically a strong base catalyst. Typically, the strong base catalyst is KOH, but other base catalysts, such as phosphazene base catalysts, may be utilized.

[0034] The phosphazene catalyst is generally an oligomer comprising at least one -(N=P<)- unit (i.e., a phosphazene unit), and usually having up to 10 such phosphazene units, for example having an average of 1.5 up to 5 phosphazene units. The phosphazene catalyst may be, for example, a halophosphazene such as a chlorophosphazene (phosphonitrile chloride), an oxygen-containing halophosphazene, an ionic derivative of a phosphazene such as a phosphazenium salt, in particular an ionic derivative of a phosphonitrile halide such as a perchlorooligophosphazenium salt, or a partially hydrolyzed form thereof.

[0035] In a specific embodiment, the catalyst comprises a phosphazene base catalyst. The phosphazene base catalyst can be any known in the art, but typically has the following chemical formula: ((R 3 2 N) 3 P=N) t (R 3 2 N) 3-t P=NR 3 In the formula, each R 3 is independently selected from the group consisting of a hydrogen atom, R, and combinations thereof, and t is an integer from 1 to 3. 3 If R, then R 3 is typically an alkyl group having 1 to 20, alternatively 1 to 10, alternatively 1 to 4 carbon atoms. 32 N) Two R 3 The groups are attached to the same nitrogen (N) atom and can be linked to complete a heterocyclic ring, preferably having 5 or 6 members.

[0036] Alternatively, the phosphazene base catalyst can be a salt and has the following alternative chemical formula: [((R 3 2 N) 3 P=N) t (R 3 2 N) 3-t P=N(H)R 3 ] + [A - ], or [((R 3 2 N) 3 P=N) s (R 3 2 N) 4-s P] + [A - ] In the formula, each R 3 are independently selected and defined above, subscript t is defined above, subscript s is an integer from 1 to 4, and [A] is an anion, typically selected from the group of fluorides, hydroxides, silanolates, alkoxides, carbonates, bicarbonates. In one embodiment, the phosphazene base is an aminophosphazenium hydroxide.

[0037] In certain embodiments, the MQ resin and the silane compound are reacted in the presence of a solvent at elevated temperatures, for example, 75-125°C. A suitable solvent may be a hydrocarbon. Suitable hydrocarbons include aromatic hydrocarbons, such as benzene, toluene, or xylene; and / or aliphatic hydrocarbons, such as heptane, hexane, or octane. Alternatively, the solvent may be a halogenated hydrocarbon, such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride. A neutralizing agent, such as acetic acid, may be utilized to neutralize the catalyst after the reaction. Those skilled in the art can readily determine the catalytic amount of catalyst utilized, which is a function of its selection and reaction conditions. The resulting (A) silicate resin may be isolated or recovered from the reaction product via conventional techniques, such as stripping or other volatilization techniques.

[0038] The base composition comprises the (A) silicate resin in an amount greater than 0 and less than 100 weight percent based on the total weight of the base composition. The relative amount of the (A) silicate resin is a function of the end use application of the base composition. When the base composition is utilized to prepare a release coating composition, the content of the (A) silicate resin in the base composition is selected based on the desired properties of the release coating composition and release coatings prepared therefrom. In certain embodiments, the (A) silicate resin serves as a release modifier in the release coating composition and release coatings prepared therefrom.

[0039] Typically, the remainder of the base composition comprises component (B), alternatively component (B), as described below. In certain embodiments, the base composition is substantially free of any solvent, particularly organic solvents. By substantially free, it is meant that the base composition comprises an organic solvent in an amount of less than 5, alternatively less than 1, alternatively less than 0.5, alternatively less than 0.25, alternatively less than 0.1, alternatively 0 weight percent, based on the total weight of the base composition. In addition, as described below, the base composition is typically formed in the absence of any solvent, including organic solvents, such that it is not necessary to strip the solvent from the mixture to obtain the base composition.

[0040] The composition further comprises (B) an organopolysiloxane having on average at least two silicon-bonded ethylenically unsaturated groups per molecule. In certain embodiments, (B) the organopolysiloxane has on average at least two silicon-bonded groups having terminal aliphatic unsaturation per molecule. This (B) organopolysiloxane can be linear, branched, partially branched, cyclic, resinous (i.e., having a three-dimensional network), or can include a combination of different structures. The polyorganosiloxane has an average formula R 4 a SiO (4-a) / 2 wherein each R 4 is independently selected from monovalent hydrocarbon groups or monovalent halogenated hydrocarbon groups, provided that in each molecule, at least two of the R 4 contain aliphatic unsaturation, and the subscript a is selected such that 0 < a ≤ 3.2. Suitable monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups for R 4 are those described above for R. The above average formula of the polyorganosiloxane can alternatively be written as (R 4 3 SiO 1 / 2 ) b (R 4 2 SiO 2 / 2 ) c (R 4 SiO 3 / 2 ) d (SiO 4 / 2 ) e wherein R 4is defined above, and the subscripts b, c, d, and e are each independently ≧0 to ≦1, provided that the quantity (b+c+d+e)=1. One of ordinary skill in the art will understand how such M, D, T, and Q units and their mole fractions affect the subscript a in the average formula above. T units (denoted by subscript d), Q units (denoted by subscript e), or both, are typically present in the polyorganosiloxane resin, while D units, denoted by subscript c, are typically present in the polyorganosiloxane polymer (and may also be present in the polyorganosiloxane resin or the branched polyorganosiloxane).

[0041] Alternatively, the (B) organopolysiloxane can be, and is, substantially linear. The substantially linear organopolysiloxane has the average formula R 4 a’ SiO (4-a’) / 2 wherein each R 4 is as defined above, and the subscript a' is selected such that 1.9≦a'≦2.2.

[0042] At 25° C., the substantially linear organopolysiloxane of component (B) may be a flowable liquid or may have the form of an uncured rubber. The substantially linear organopolysiloxane may have a viscosity of 10 mPa·s to 30,000,000 mPa·s, alternatively 10 mPa·s to 10,000 mPa·s, alternatively 100 mPa·s to 1,000,000 mPa·s, and alternatively 100 mPa·s to 100,000 mPa·s at 25° C. The viscosity may be measured at 25° C. via a Brookfield LV DV-E viscometer equipped with a spindle appropriately selected for the viscosity of the substantially linear polyorganopolysiloxane, i.e., RV-1 to RV-7. Typically, component (B) is a flowable liquid at 25° C. due to its miscibility with component (A).

[0043] Alternatively, when the (B) organopolysiloxane is substantially linear or linear, the (B) organopolysiloxane has an average unit formula (R6 R 5 2 SiO 1 / 2 ) aa (R 6 R 5 SiO 2 / 2 ) bb (R 6 2 SiO 2 / 2 ) cc (R 5 3 SiO 1 / 2 ) dd wherein each R 5 is an independently selected monovalent hydrocarbon radical free of aliphatic unsaturation, or a monovalent halogenated hydrocarbon radical free of aliphatic unsaturation, and each R 6 are independently selected from the group consisting of alkenyl and alkynyl, the subscript aa is 0, 1, or 2, the subscript bb is 0 or greater, the subscript cc is 1 or greater, and the subscript dd is 0, 1, or 2, provided that the quantity (aa+dd) is ≥ 2, the quantity (aa+dd) = 2, and provided that the quantity (aa+bb+cc+dd) is 3 to 2,000. Alternatively, the subscript cc is ≥ 0. Alternatively, the subscript bb is ≥ 2. Alternatively, the quantity (aa+dd) is 2 to 10, alternatively 2 to 8, and alternatively 2 to 6. Alternatively, the subscript cc is 0 to 1,000, alternatively 1 to 500, and alternatively 1 to 200. Alternatively, the subscript bb is from 2 to 500, alternatively from 2 to 200, and alternatively from 2 to 100.

[0044] R 5 The monovalent hydrocarbon radicals of are exemplified by alkyl groups of 1 to 6 carbon atoms, aryl groups of 6 to 10 carbon atoms, halogenated alkyl groups of 1 to 6 carbon atoms, halogenated aryl groups of 6 to 10 carbon atoms, aralkyl groups of 7 to 12 carbon atoms, or halogenated aralkyl groups of 7 to 12 carbon atoms, where the alkyl, aryl, and halogenated alkyl are as described herein. 5 is an alkyl group. Alternatively, each R 5 is independently methyl, ethyl, or propyl.5 Each instance of R may be the same or different. Alternatively, each R 5 is a methyl group.

[0045] R 6 The aliphatically unsaturated monovalent hydrocarbon group of R is capable of undergoing a hydrosilylation reaction. 6 Aliphatically unsaturated hydrocarbon groups suitable for are exemplified by alkenyl groups as defined herein and exemplified by vinyl, allyl, butenyl, and hexenyl, and alkynyl groups as defined herein and exemplified by ethynyl and propynyl. 6 may be vinyl or hexenyl. Alternatively, each R 6 is a vinyl group. The alkenyl or alkynyl content of (B) organopolysiloxane may be from 0.1% to 1% by weight, alternatively from 0.2% to 0.5% by weight, based on the weight of (B) organopolysiloxane.

[0046] (B) organopolysiloxane is substantially linear, alternatively when linear, the at least two aliphatically unsaturated groups may be bonded to silicon atoms at pendant positions, terminal positions, or both pendant and terminal positions. Specific examples of (B) organopolysiloxanes having pendant silicon-bonded aliphatically unsaturated groups include those having the average unit formula: [(CH 3 ) 3 SiO 1 / 2 ] 2 [(CH 3 ) 2 SiO 2 / 2 ] cc [(CH 3 )ViSiO 2 / 2 ] bbwhere the subscripts bb and cc are defined above and Vi represents a vinyl group. With respect to this average formula, any of the methyl groups may be replaced with a different monovalent hydrocarbon group, such as an alkyl or aryl, and any of the vinyl groups may be replaced with a different aliphatically unsaturated monovalent hydrocarbon group, such as an allyl or hexenyl. Alternatively, as a specific example of a polyorganosiloxane having an average of at least two silicon-bonded aliphatically unsaturated groups per molecule, the (B) organopolysiloxane may have the average formula Vi(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] cc Si(CH 3 ) 2 The (B) organopolysiloxane may have the average unit formula: ##STR1## where the subscripts cc and Vi are defined above. Dimethylpolysiloxanes terminated with silicon-bonded vinyl groups may be used alone or in combination with the dimethyl, methyl-vinylpolysiloxanes disclosed immediately above as (B) organopolysiloxane. With respect to this average formula, any of the methyl groups may be replaced with a different monovalent hydrocarbon group, and any of the vinyl groups may be replaced with any terminal aliphatically unsaturated monovalent hydrocarbon group. Since the at least two silicon-bonded aliphatically unsaturated groups may be both pendant and terminal, the (B) organopolysiloxane may alternatively have the average unit formula: [Vi(CH 3 ) 2 SiO 1 / 2 ] 2 [(CH 3 ) 2 SiO 2 / 2 ] cc [(CH 3 )ViSiO 2 / 2 ] bb where the subscripts bb and cc and Vi are defined above.

[0047] When the organopolysiloxane (B) is a substantially linear polyorganosiloxane, the organopolysiloxane (B) is selected from the group consisting of dimethylpolysiloxane capped at both molecular ends with dimethylvinylsiloxy groups, methylphenylpolysiloxane capped at both molecular ends with dimethylvinylsiloxy groups, copolymers of methylphenylsiloxane and dimethylsiloxane capped at both molecular ends with dimethylvinylsiloxy groups, copolymers of methylvinylsiloxane and methylphenylsiloxane capped at both molecular ends with dimethylvinylsiloxy groups, and methylphenylsiloxane capped at both molecular ends with dimethylvinylsiloxy groups. Examples of the copolymer include a copolymer of vinylsiloxane and diphenylsiloxane, a copolymer of methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane, both of which are end-capped with dimethylvinylsiloxy groups, a copolymer of methylvinylsiloxane and methylphenylsiloxane, both of which are end-capped with trimethylsiloxy groups, a copolymer of methylvinylsiloxane and diphenylsiloxane, both of which are end-capped with trimethylsiloxy groups, and a copolymer of methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane, both of which are end-capped with trimethylsiloxy groups.

[0048] Alternatively, the (B) organopolysiloxane is i) dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane); iii) 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 polydimethylsiloxanes; 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) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane) and xvii) substantially linear, alternatively linear polyorganosiloxanes selected from the group consisting of:

[0049] Alternatively, (B) the organopolysiloxane may comprise a resinous polyorganosiloxane having an average formula R 4 a” SiO (4-a”) / 2 wherein each R 4 are independently selected as defined above, and the subscript a″ is selected such that 0.5≦a″≦1.7.

[0050] Resinous polyorganosiloxanes have a branched or three-dimensional network molecular structure. At 25°C, resinous polyorganosiloxanes can be in liquid or solid form. Alternatively, resinous polyorganosiloxanes can be exemplified by polyorganosiloxanes that contain only T units, polyorganosiloxanes that contain T units in combination with other siloxy units (e.g., M, D, and / or Q siloxy units), or polyorganosiloxanes that contain Q units in combination with other siloxy units (i.e., M, D, and / or T siloxy units). Typically, resinous polyorganosiloxanes contain T units and / or Q units. Specific examples of resinous polyorganosiloxanes include vinyl-terminated silsesquioxanes (i.e., T resins) and vinyl-terminated MDQ resins.

[0051] Alternatively, (B) the organopolysiloxane may comprise a branched siloxane, a silsesquioxane, or both a branched siloxane and a silsesquioxane.

[0052] When the (B) organopolysiloxane comprises a blend of different organopolysiloxanes, the blend can be a physical blend or mixture. For example, when the (B) organopolysiloxane comprises a branched siloxane and a silsesquioxane, the branched siloxane and the silsesquioxane are present in amounts relative to each other such that the combined amount of the branched siloxane and the silsesquioxane totals 100 parts by weight, based on the total weight of all components present in the composition. The branched siloxane can be present in an amount of 50 to 100 parts by weight, and the silsesquioxane can be present in an amount of 0 to 50 parts by weight. Alternatively, the branched siloxane can be present in an amount of 50 to 90 parts by weight, and the silsesquioxane can be present in an amount of 10 to 50 parts by weight. Alternatively, the branched siloxane can be present in an amount of 50 to 80 parts by weight, and the silsesquioxane can be present in an amount of 20 to 50 parts by weight. Alternatively, the branched siloxane can be present in an amount of 50 to 76 parts by weight and the silsesquioxane can be present in an amount of 24 to 50 parts by weight. Alternatively, the branched siloxane can be present in an amount of 50 to 70 parts by weight and the silsesquioxane can be present in an amount of 30 to 50 parts by weight.

[0053] (B) The branched siloxane of the organopolysiloxane has the unit formula (R 7 3 SiO 1 / 2 ) p (R 8 R 7 2 SiO 1 / 2 ) q (R 7 2 SiO 2 / 2 ) r (SiO 4 / 2 ) s wherein each R 7 are independently a monovalent hydrocarbon group containing no aliphatic unsaturation, or a monovalent halogenated hydrocarbon group containing no aliphatic unsaturation, and each R 8 is an alkenyl or alkynyl group, both of which are as defined above, with subscript p≧0, subscript q>0, 15≧r≧995, and subscript s is >0.

[0054] In the immediately preceding unit formula, subscript p > 0. Subscript q > 0. Alternatively, subscript q > 3. Subscript r is 15 to 995. Subscript s > 0. Alternatively, subscript s > 1. Alternatively, for subscript p, 22 > p > 0, alternatively 20 > p > 0, alternatively 15 > p > 0, alternatively 10 > p > 0, and alternatively 5 > p > 0. Alternatively, for subscript q, 22 > q > 0, alternatively 22 > q > 4, alternatively 20 > q > 0, alternatively 15 > q > 1, alternatively 10 > q > 2, and alternatively 15 > q > 4. Alternatively, for subscript r, 800 > r > 15, and alternatively 400 > r > 15. Alternatively, for subscript s, 10≧s>0, alternatively, 10≧s≧1, alternatively, 5≧s>0, and alternatively, s=1. Alternatively, subscript s is 1 or 2. Alternatively, when subscript s=1, subscript p can be 0 and subscript q can be 4.

[0055] The branched siloxane is represented by the formula (R 72 SiO 2 / 2 ) m, where each subscript m is independently 2 to 100. Alternatively, the branched siloxane may contain at least two polydiorganosiloxane chains of the formula (R 7 2 SiO 2 / 2 ) o The four polydiorganosiloxane chains of the formula (SiO 4 / 2 ), where each subscript o is independently 1 to 100. Alternatively, the branched siloxane may have the formula: [ka] wherein subscript u is 0 or 1; each subscript t is independently 0 to 995, alternatively 15 to 995, and alternatively 0 to 100; and each R 9 are independently selected monovalent hydrocarbon radicals, and each R 7 are independently selected monovalent hydrocarbon radicals free of aliphatic unsaturation or monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, as described above, and each R 8 is independently selected from the group consisting of alkenyl and alkynyl, as described above. Suitable branched siloxanes are exemplified by those disclosed in U.S. Patent No. 6,806,339 and U.S. Patent Application Publication No. 2007 / 0289495.

[0056] In a specific embodiment, the branched siloxane has the formula (R 2 y R 1 3-y SiO 1 / 2 ) x (R 1 R 2 SiO 2 / 2 ) z (SiO 4 / 2 ), wherein each R 1 is an independently selected hydrocarbyl group free of ethylenic unsaturation, and each R 2 is R 1and an ethylenically unsaturated group, where subscript y is independently selected in each siloxy unit designated by subscript x and is 1 or 2, and where subscript x is 1.5 to 6 and subscript z is 3 to 1,000. Specific examples of hydrocarbyl groups and ethylenically unsaturated groups free of ethylenic unsaturation are described above for R.

[0057] Silsesquioxane has the unit formula (R 7 3 SiO 1 / 2 ) i (R 8 R 7 2 SiO 1 / 2 ) f (R 7 2 SiO 2 / 2 ) g (R 7 SiO 3 / 2 ) h wherein R 7 and R 8 is as above, with subscript i≧0, subscript f>0, subscript g is from 15 to 995, and subscript h>0. Subscript i can be from 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.

[0058] 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, and alternatively subscript h is 1 or 2. Alternatively, if subscript h = 1, subscript f can be 3 and subscript i can be 0. The value of subscript f may be sufficient for the silsesquioxane of formula (ii-II) to have an alkenyl content of from 0.1% to 1%, alternatively from 0.2% to 0.6%, by weight, based on the weight of the silsesquioxane. Suitable silsesquioxanes are exemplified by those disclosed in U.S. Pat. No. 4,374,967.

[0059] The (B) organopolysiloxane may comprise a combination or two or more different polyorganosiloxanes differing in at least one property, such as structure, molecular weight, monovalent groups bonded to silicon atoms, and content of aliphatic unsaturated groups, etc. The composition may comprise the (B) organopolysiloxane in an amount from 60 to 99.5, alternatively from 60 to 98, alternatively from 60 to 95, alternatively from 70 to 95, alternatively from 75 to 95 weight percent, based on the total weight of the composition.

[0060] In these or other embodiments, the base composition comprising, or alternatively consisting of, (A) silicate resin and (B) organopolysiloxane has a viscosity at 25° C. such that the base composition is flowable. For example, in certain embodiments, depending on the selection of components (A) and (B), a 40:60 blend by weight of (A):(B) has a viscosity of 500 to 100,000, alternatively 2,000 to 50,000, alternatively 4,000 to 30,000 centipoise (cP). The viscosity may be measured via a Brookfield LV DV-E viscometer with a spindle appropriately selected for the viscosity of the base composition. The above viscosity ranges are when the base composition does not contain any solvent, including organic solvents.

[0061] In these or other embodiments, the same base composition has a weight average molecular weight of from 500 to 500,000, alternatively from 1,000 to 250,000, alternatively from 10,000 to 150,000. Molecular weight may be measured via gel permeation chromatography (GPC) against polystyrene standards.

[0062] Also provided is a method for preparing a base composition. The method includes combining (A) a silicate resin and (B) an organopolysiloxane to obtain a base composition. Typically, (A) the silicate resin is disposed in (B) the organopolysiloxane. However, components (A) and (B) can be combined in any manner, in any order of addition, optionally with stirring or other mixing. Because (A) the silicate resin is miscible with or in (B) the organopolysiloxane, the method typically does not include any solvent.

[0063] Also provided is a release coating composition comprising the base composition. The release coating composition further comprises (C) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule. The (C) organosilicon compound can be linear, branched, partially branched, cyclic, resinous (i.e., having a three-dimensional network), or can comprise a combination of different structures. The (C) organosilicon compound is typically a crosslinker, which reacts with the ethylenically unsaturated groups of component (B) and, if present, those of component (A) when forming a coating, such as a release coating. Typically, the (C) organosilicon compound comprises an organohydrogensiloxane.

[0064] The (C) organosilicon compound may contain any combination of M, D, T, and / or Q siloxy units, so long as the (C) organosilicon compound contains at least two silicon-bonded hydrogen atoms per molecule. These siloxy units may be combined in various ways to form cyclic, linear, branched, and / or resinous (three-dimensional network) structures. The (C) organosilicon compound may be monomeric, polymeric, oligomeric, linear, branched, cyclic, and / or resinous, depending on the selection of M, D, T, and / or Q units.

[0065] Since the (C) organosilicon compound contains, on average, at least two silicon-bonded hydrogen atoms per molecule with respect to the siloxy units described above, the (C) organosilicon compound contains the following siloxy units (R 2 HSiO 1 / 2 ), (RH 2 SiO 1 / 2 ), (H 3 SiO 1 / 2 ), (RHSiO 2 / 2 ), (H 2 SiO 2 / 2 ), and / or (HSiO 3 / 2 ), optionally in combination with siloxy units that do not contain any silicon-bonded hydrogen atoms, where R is independently selected and defined above.

[0066] In a specific embodiment, the (C) organosilicon compound is a substantially linear, alternatively linear, polyorganohydrogensiloxane. The substantially linear or linear polyorganohydrogensiloxane is represented by the unit formula (HR 10 2 SiO 1 / 2 ) v’ (HR 10 SiO 2 / 2 ) w’ (R 10 2 SiO 2 / 2 ) x’ (R 10 3 SiO 1 / 2 ) y’ wherein each R 10 are independently selected monovalent hydrocarbon radicals, where subscript v' is 0, 1, or 2, subscript w' is 1 or greater, subscript x' is 0 or greater, and subscript y' is 0, 1, or 2, provided that the quantity (v'+y')=2 and the quantity (v'+w')≧3. 10 The monovalent hydrocarbon group of can be as described above for the monovalent hydrocarbon group of R. The quantity (v'+w'+x'+y') can be 2 to 1,000. The polyorganohydrogensiloxane is i) dimethylhydrogensiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymers; ii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane; iii) trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymers; iv) trimethylsiloxy-terminated polymethylhydrogensiloxane, and / or v) is exemplified by a combination of two or more of i), ii), iii), iv), and v).Suitable polyorganohydrogensiloxanes are commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

[0067] In one specific embodiment, the (C) organosilicon compound is linear and contains pendant silicon-bonded hydrogen atoms. In these embodiments, the (C) organosilicon compound has the average formula (CH 3 ) 3 SiO[(CH 3 ) 2 SiO] x’ [(CH 3 )HSiO] w’ Si(CH 3 ) 3 where x' and w' are defined above. Those skilled in the art will appreciate that in the above exemplary formula, the dimethylsiloxy and methylhydrogensiloxy units can be present in a random or block form, and any methyl group can be replaced with any other hydrocarbon group that does not contain aliphatic unsaturation.

[0068] In another specific embodiment, the (C) organosilicon compound is linear and contains terminal silicon-bonded hydrogen atoms. In these embodiments, the (C) organosilicon compound has the average formula H(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] x’ Si(CH 3 ) 2 H The organohydrogensiloxane may be a SiH-terminated dimethylpolysiloxane having the formula: ##STR1## where x' is as defined above. The SiH-terminated dimethylpolysiloxane may be utilized alone or in combination with the dimethyl, methylhydrogenpolysiloxane disclosed immediately above. When a mixture is utilized, the relative amount of each organohydrogensiloxane in the mixture may vary. One of ordinary skill in the art will appreciate that any methyl group in the above exemplary formula may be replaced with any other hydrocarbon group that does not contain aliphatic unsaturation.

[0069] Alternatively, the (C) organosilicon compound may also contain both pendant and terminal silicon-bonded hydrogen atoms.

[0070] In yet another specific embodiment, the (C) organosilicon compound is represented by the formula H y’ R 1 3-y’ Si-(OSiR 1 2 ) m -(OSiR 1 H) m’ -OSiR 1 3-y’ H y’ wherein each R 1 is an independently selected hydrocarbyl group free of ethylenic unsaturation, each y' is independently selected from 0 or 1, and the subscripts m and m' are each 0 to 1,000, provided that m and m' are not simultaneously 0, and m+m' is 1 to 1,000.

[0071] In certain embodiments, the (C) organosilicon compound may include an alkylhydrogencyclosiloxane or an alkylhydrogendialkylcyclosiloxane copolymer. Specific examples of suitable organohydrogensiloxanes of this type include (OSiMeH) 4 , (OSiMeH) 3 (OSiMeC 6 H 13 ), (OSiMeH) 2 (OSiMeC 6 H 13 ) 2 , and (OSiMeH)(OSiMeC 6 H 13 ) 3 In the formula, Me is methyl (-CH 3 )

[0072] Another example of the organohydrogensiloxane suitable for (C) organosilicon compound is one that has at least two SiH-containing cyclosiloxane rings in one molecule. Such organohydrogensiloxanes can be any organopolysiloxane that has at least two cyclosiloxane rings, with at least one silicon-bonded water (SiH) atom on each siloxane ring. The cyclosiloxane ring contains at least three siloxy units (i.e., the minimum number required to form a siloxane ring), and can be any combination of M, D, T, and / or Q siloxy units that form a cyclic structure, provided that on each siloxane ring, at least one of the cyclic siloxy units, which can be M siloxy units, D siloxy units, and / or T siloxy units, contains one SiH unit. These siloxy units can be represented as MH, DH, and TH siloxy units, respectively, when the other substituents are methyl.

[0073] The (C) organosilicon compound may comprise a combination or two or more different organohydrogensiloxanes differing in at least one property, such as structure, molecular weight, monovalent groups bonded to silicon atoms, and content of silicon-bonded hydrogen atoms. The release coating composition may comprise the (C) organosilicon compound in an amount that provides a molar ratio of silicon-bonded hydrogen atoms in component (C) to silicon-bonded ethylenically unsaturated groups in component (B) (and those of component (A), if present) in an amount of from 1:1 to 5:1, alternatively from 1.1:1 to 3.1.

[0074] In certain embodiments, the release coating composition further comprises (D) a hydrosilylation reaction catalyst. (D) The hydrosilylation reaction catalyst is not limited and can be any known hydrosilylation reaction catalyst for catalyzing a hydrosilylation reaction. A combination of different hydrosilylation reaction catalysts can be utilized.

[0075] In certain embodiments, the (D) hydrosilylation reaction catalyst comprises a transition metal from group VIII to group XI. For the group VIII to group XI transition metals, reference is made to the latest IUPAC nomenclature. The group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs), the group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir), the group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt), and the group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations thereof, their complexes (e.g., organometallic complexes), and other forms of such metals may be utilized as the (D) hydrosilylation reaction catalyst.

[0076] Additional examples of suitable catalysts for (D) hydrosilylation reaction catalysts 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 containing 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 (D) hydrosilylation reaction catalysts.

[0077] (D) Hydrosilylation catalyst can be in any suitable form.For example, (D) Hydrosilylation catalyst can be solid, examples of which include platinum-based catalysts, palladium-based catalysts, and similar precious metal-based catalysts, as well as nickel-based catalysts.Specific examples of which include nickel, palladium, platinum, rhodium, cobalt, and similar elements, as well as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts that include a combination of multiple metals.Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts.

[0078] (D) The hydrosilylation reaction catalyst may be in or on a solid carrier. Examples of carriers include activated carbon, silica, silica alumina, alumina, zeolite, and other inorganic powders / particles (e.g., sodium sulfate), and the like. (D) The hydrosilylation reaction catalyst may also be disposed in a vehicle, such as a solvent that solubilizes (D) the hydrosilylation reaction catalyst, or alternatively, a vehicle that simply carries but does not solubilize (D) the hydrosilylation reaction catalyst. Such vehicles are known in the art.

[0079] In specific embodiments, (D) hydrosilylation catalyst comprises platinum. In these embodiments, (D) hydrosilylation catalyst is exemplified by compounds such as platinum black, chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid and 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 matrix or core-shell type compounds. Microencapsulated hydrosilylation catalysts and their preparation methods are also known in the art, as exemplified in U.S. Pat. Nos. 4,766,176 and 5,017,654, which are incorporated herein by reference in their entirety.

[0080] (D) Platinum complexes with organopolysiloxanes suitable for use as hydrosilylation catalysts include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. These complexes may be microencapsulated in a resin matrix. Alternatively, (D) hydrosilylation catalysts may include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. (D) Hydrosilylation catalysts may be prepared by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane, or an alkene-platinum-silyl complex. The alkene-platinum-silyl complex may be prepared, for example, by reacting 0.015 moles of (COD)PtCl 20.045 moles of COD and 0.0612 moles of HMeSiCl 2 It can be prepared by mixing with

[0081] (D) The hydrosilylation reaction catalyst may also, or alternatively, be a photoactivatable hydrosilylation reaction catalyst, which may initiate curing via irradiation and / or heat. The photoactivatable hydrosilylation reaction catalyst may be any hydrosilylation reaction catalyst capable of catalyzing a hydrosilylation reaction, particularly upon exposure to radiation having a wavelength of 150 to 800 nanometers (nm).

[0082] Specific examples of photoactivatable hydrosilylation catalysts suitable for the (D) hydrosilylation catalyst include platinum(II) β-diketonate complexes, such as platinum(II) bis(2,4-pentanedioate), platinum(II) bis(2,4-hexanedioate), platinum(II) bis(2,4-heptanedioate), platinum(II) bis(1-phenyl-1,3-butanedioate, platinum(II) bis(1,3-diphenyl-1,3-propanedioate). platinum(II) bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedioate), (η-cyclopentadienyl)trialkylplatinum complexes such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsilyl-Cp)trimethylplatinum, where Cp is cyclopentadienyl; triazene oxide-transition metal complexes such as Pt[C 6 H 5 NNNOCH 3 ] 4 , Pt[p-CN-C 6 H 4 NNNOC 6 H 11 ] 4 , Pt[pH 3 COC 6 H 4 NNNOC 6 H 11 ] 4 , Pt[p-CH 3 (CH 2 ) x -C6 H 4 NNNOCH 3 ] 4 , 1,5-cyclooctadienePt[p-CN-C 6 H 4 NNNOC 6 H 11 ] 2 , 1,5-cyclooctadienePt[p-CH 3 O.C. 6 H 4 NNNOCH 3 ] 2 , [(C 6 H 5 ) 3 P] 3 Rh[p-CN-C 6 H 4 NNNOC 6 H 11 ], and Pd[p-CH 3 (CH 2 ) x -C 6 H 4 NNNOCH 3 ] 2 where x is 1, 3, 5, 11, or 17; (η-diolefin)(σ-aryl)platinum complexes, such as (η 4 -1,5-cyclooctadienyl)diphenylplatinum, η 4 -1,3,5,7-cyclooctatetraenyl)diphenylplatinum, (η 4 -2,5-norborazienyl)diphenylplatinum, (η 4 -1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (η 4 -1,5-cyclooctadienyl)bis-(4-acetylphenyl)platinum, and (η 4 Typically, the photoactivatable hydrosilylation reaction catalyst is a Pt(II) β-diketonate complex, and more typically, the catalyst is platinum(II) bis(2,4-pentanedioate).

[0083] (D) The hydrosilylation reaction catalyst is present in the release coating composition in a catalytic amount, i.e., an amount or quantity sufficient to promote its cure under desired conditions. (D) The hydrosilylation reaction catalyst can be a single hydrosilylation reaction catalyst or a mixture comprising two or more different hydrosilylation reaction catalysts.

[0084] The catalytic amount of the (D) hydrosilylation catalyst may be >0.01 ppm to 10,000 ppm, alternatively >1,000 ppm to 5,000 ppm. Alternatively, a typical catalytic amount of the (D) hydrosilylation catalyst is 0.1 ppm to 5000 ppm, alternatively 1 ppm to 2000 ppm, alternatively >0 to 1,000 ppm. Alternatively, the catalytic amount of the (D) hydrosilylation catalyst may be 0.01 ppm to 1,000 ppm, alternatively 0.01 ppm to 100 ppm, alternatively 20 ppm to 200 ppm, alternatively 0.01 ppm to 50 ppm of platinum group metal based on the total weight of the composition.

[0085] The release coating composition may further comprise one or more of (E) an inhibitor, (F) an anchor additive, (G) an antifog agent, (H) a release modifier, and (I) a vehicle.

[0086] In certain embodiments, the release coating composition further comprises an (E) inhibitor, which may be used to modify the reaction rate or cure rate of the release coating composition compared to a composition containing the same starting materials but omitting the (E) inhibitor. (E) Inhibitors include acetylenic alcohols such as methylbutynol, ethynylcyclohexanol, dimethylhexynol, 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 combinations thereof; cycloalkenylsiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl- ... Methylvinylcyclosiloxanes, as exemplified by hexenylcyclotetrasiloxane, and combinations 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 tetramethylethylenediamine; dialkylfumarates, dialkenylfumarates, dialkoxyalkylfumarates, maleates, such as diallylmaleate; nitriles; ethers; carbon monoxide; alkenes, such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols, such as benzyl alcohol; and combinations thereof. Alternatively, the (E) inhibitor may be selected from the group consisting of acetylene alcohols (e.g., 1-ethynyl-1-cyclohexanol) and maleates (e.g., diallylmaleate, bismaleate, or n-propylmaleate), and combinations of two or more thereof.

[0087] Alternatively, the (E) inhibitor can be a silylated acetylenic compound. Without being bound by theory, it is believed that the addition of the silylated acetylenic compound reduces the yellowing of the reaction product prepared from the hydrosilylation reaction of the release coating composition compared to the reaction product from the hydrosilylation of a composition that does not contain the silylated acetylenic compound or that contains an organic acetylenic alcohol inhibitor, such as those described above.

[0088] The silylated acetylene compounds are (3-methyl-1-butyne-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyne-3-oxy)dimethylsilane, bis(3-methyl-1-butyne-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyne-3-oxy))silane, (3-methyl-1-butyne-3-oxy)dimethylphenylsilane, (3-methyl-1-butyne-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyne-3-oxy)triethylsilane, bis(3-methyl-1- silane, (3,5-dimethyl-1-hexyne-3-oxy)trimethylsilane, (3-phenyl-1-butyne-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyne-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyne-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyne-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyne-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyne-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyne-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyne-1-oxy)trimethylsilane, and combinations thereof. Alternatively, the (E) inhibitors are exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or combinations thereof. Silylated acetylenic compounds useful as (E) inhibitors can be prepared by methods known in the art, such as silylation of the above-mentioned acetylenic alcohols by reaction with chlorosilanes in the presence of an acid acceptor.

[0089] The amount of (E) inhibitor present in the release coating composition will depend on a variety of factors, including the desired pot life of the release coating composition, whether the release coating composition is a one-part or multi-part composition, the particular inhibitor used, and the selection and amounts of components (A)-(D). However, if present, the amount of (E) inhibitor can be from 0% to 1%, alternatively from 0% to 5%, alternatively from 0.001% to 1%, alternatively from 0.01% to 0.5%, and alternatively from 0.0025% to 0.025%, based on the total weight of the release coating composition.

[0090] In certain embodiments, the release coating composition further comprises (F) an anchor additive. Suitable anchor additives are exemplified by the reaction product of vinyl alkoxysilane and epoxy functional alkoxysilane; the reaction product of vinyl acetoxysilane and epoxy functional alkoxysilane; and the combination (e.g., physical blend and / or reaction product) of polyorganosiloxane having at least one aliphatically unsaturated hydrocarbon group and at least one hydrolyzable group per molecule with epoxy functional alkoxysilane (e.g., the combination of hydroxy-terminated vinyl functional polydimethylsiloxane and glycidoxypropyltrimethoxysilane). Alternatively, the anchor additive may comprise a polyorganosilicate resin. Suitable anchor additives and their preparation methods are disclosed, for example, by U.S. Pat. No. 9,562,149, U.S. Patent Application Publication Nos. 2003 / 0088042, 2004 / 0254274, and 2005 / 0038188, and European Patent No. 0556023.

[0091] Further examples of suitable anchor additives include transition metal chelates, hydrocarbonoxysilanes such as alkoxysilanes, combinations of alkoxysilanes and hydroxy-functional polyorganosiloxanes, or combinations thereof. (F) anchor additive can be a silane having at least one substituent with an adhesion-promoting group such as an epoxy, acetoxy, or acrylate group. The adhesion-promoting group can additionally or alternatively be any hydrolyzable group that does not affect the (D) hydrosilylation reaction catalyst. Alternatively, (F) anchor additive can include a partial condensate of such a silane, such as an organopolysiloxane with an adhesion-promoting group. Alternatively, further, (F) anchor additive can include a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.

[0092] Alternatively, the (F) anchor additive may include an unsaturated or epoxy-functional compound. The (F) anchor additive may include an unsaturated or epoxy-functional alkoxysilane. For example, the functional alkoxysilane may include at least one unsaturated organic group or an epoxy-functional organic group. The epoxy-functional organic group is exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. The unsaturated organic group is exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, and undecylenyl. One specific example of an unsaturated compound is vinyltriacetoxysilane.

[0093] 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-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof.

[0094] The (F) anchor additive may also include a reaction product or partial reaction product of one or more of these compounds. For example, in a specific embodiment, the (F) anchor additive may include a reaction product or partial reaction product of vinyltriacetoxysilane and 3-glycidoxypropyltrimethoxysilane. Alternatively or additionally, the (F) anchor additive may include an alkoxy or alkenyl functional siloxane.

[0095] Alternatively, the (F) anchor additive may comprise an epoxy-functional siloxane, such as the reaction product of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane, or a physical blend of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane, as described above. The (F) anchor additive may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the (F) anchor additive is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and the reaction product of a hydroxy-terminated methylvinylsiloxane and 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.

[0096] Alternatively, the (F) anchor additive may include 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 (F) anchor additive may include a combination of a transition metal chelate and an alkoxysilane, such as a combination of glycidoxypropyltrimethoxysilane and an aluminum chelate or a zirconium chelate.

[0097] The particular amount of (F) anchor additive present in the release coating composition, if utilized, depends on a variety of factors, including the type of substrate and whether a primer is used. In a particular embodiment, the (F) anchor additive is present in the release coating composition in an amount of 0 to 2 parts by weight per 100 parts by weight of component (B). Alternatively, the (F) anchor additive is present in the release coating composition in an amount of 0.01 to 2 parts by weight per 100 parts by weight of component (B).

[0098] In certain embodiments, the composition further comprises (G) an anti-fog agent. (G) anti-fog agent can be utilized in the release coating composition to reduce or suppress silicone mist formation in the coating process, especially with high-speed coating equipment. (G) anti-fog agent can be a reaction product of an organohydrogensilicon compound, an oxyalkylene compound, or an organoalkenylsiloxane having at least three silicon-bonded alkenyl groups per molecule, and a suitable catalyst. Suitable anti-fog agents are disclosed, for example, in U.S. Patent Application Publication No. 2011 / 0287267, U.S. Patent No. 8,722,153, U.S. Patent No. 6,586,535, and U.S. Patent No. 5,625,023. Alternatively, (G) anti-fog agent can comprise an MDQ resin, which can optionally contain two or more silicon-bonded ethylenically unsaturated groups.

[0099] The amount of (G) antifog agent utilized in the release coating composition depends on various factors, including the amount and type of other starting materials selected for the release coating composition. However, (G) antifog agent is typically utilized in an amount of 0% to 10% by weight, alternatively 0.1% to 3% by weight, based on the total weight of the release coating composition. This amount excludes the amount associated with component (A) and only relates to the (G) antifog agent, which is separate and distinct from component (A).

[0100] In certain embodiments, the release coating composition further comprises (H) a release modifier, which may be used in the release coating composition to control (reduce) the level of release force (adhesion force between the release coating formed from the release coating composition and its adherend, such as a label containing a pressure sensitive adhesive). The (H) release modifier is distinct from component (A), which also serves as a release modifier when the base composition is utilized to prepare the release coating. By adjusting the level or concentration of the (H) release modifier, a release coating having the required or desired release force may be formulated from a composition that does not contain a modifier. Examples of release modifiers suitable for component (H) include trimethylsiloxy-terminated dimethyl, phenylmethyl siloxanes. Alternatively, the (H) release modifier may be a condensation reaction product of an organopolysiloxane resin having hydroxyl or alkoxy groups and a diorganopolysiloxane having at least one hydroxyl or hydrolyzable group. Examples of suitable release modifiers are disclosed, for example, in U.S. Patent No. 8,933,177 and U.S. Patent Application Publication No. 2016 / 0053056. If utilized, the (H) release modifier may be present in the release coating composition in an amount of 0 to 85 parts, alternatively 25 to 85 parts, per 100 parts of component (B).

[0101] In certain embodiments, the release coating composition further comprises (I) a vehicle. The (I) vehicle typically solubilizes the components of the release coating composition, and when the components are solubilized, the (I) vehicle can be referred to as a solvent. Suitable vehicles include both linear and cyclic silicones, organic oils, organic solvents, and mixtures thereof.

[0102] Typically, the (I) vehicle, when present in the release coating composition, is an organic liquid. Organic liquids include those considered to be oils or solvents. Organic liquids are exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having more than three carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, and aromatic halides. Hydrocarbons include isododecane, isohexadecane, Isopar L (C11-C13), Isopar H (C11-C12), hydrogenated polydecenes, aromatic hydrocarbons, and halogenated hydrocarbons. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, and octyl palmitate. Additional organic fluids suitable as independent compounds or as a source of the (I) vehicle include fats, oils, fatty acids, and fatty alcohols. The (I) vehicle may also be a 1 to 1,000 mm thick oil at 25°C. 2Low viscosity organopolysiloxanes or volatile methyl siloxanes or volatile ethyl siloxanes or volatile methylethyl siloxanes having a viscosity in the range of 1 / sec, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclopentasiloxane, tetradecamethylcyclo ... The siloxane may be methylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any mixtures thereof.

[0103] In specific embodiments, (I) the vehicle is selected from polyalkylsiloxanes, tetrahydrofuran; mineral spirits; naphtha; alcohols, such as methanol, ethanol, isopropanol, butanol, or n-propanol; ketones, such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; aromatic hydrocarbons, such as benzene, toluene, or xylene; aliphatic hydrocarbons, such as heptane, hexane, or octane; glycol ethers, such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether; or combinations thereof.

[0104] The amount of (I) vehicle depends on various factors, including the type of vehicle selected, as well as the amount and type of other components present in the release coating composition. However, the amount of (I) vehicle in the release coating composition can be 0% to 99% by weight, alternatively 0% to 50% by weight, based on the total weight of the release coating composition. The (I) vehicle can be added during preparation of the release coating composition, for example, to aid in mixing and delivery. All or a portion of the (I) vehicle can be optionally removed after the release coating composition is prepared, including before and / or simultaneously with preparing the release coating from the release coating composition. However, typically the release coating composition does not include the (I) vehicle, and thus the release coating composition is a solventless release coating composition.

[0105] Other optional ingredients may be present in the release coating composition including, for example, reactive diluents, fragrances, preservatives, colorants, dyes, and fillers, such as silica, quartz, or chalk.

[0106] Alternatively, the release coating composition and the release coating formed therefrom may be free of particulates or contain only limited amounts of particulates (e.g., fillers and / or pigments), such as 0-30% by weight of the release coating composition. Particulates may agglomerate or otherwise stick to the coating equipment used to form the release coating. In addition, if optical transparency is desired, particulates may interfere with the optical properties, e.g., transparency, of the release coating and the release liner formed therefrom. Particulates may be detrimental to adherend adhesion.

[0107] In certain embodiments, the release coating composition does not include fluoroorganosilicone compounds. It is believed that during curing, fluorocompounds can rapidly migrate to the interface between the release coating composition or the release coating formed therewith and the substrate on which the release coating composition is applied and the release coating is formed, such as the composition / PET film interface, due to their low surface tension. Such migration can prevent the release coating (prepared by curing the release coating composition) from adhering to the substrate by creating a fluorine-containing barrier. By creating a barrier, the fluoroorganosilicone compounds can prevent any of the components of the release coating composition from reacting at the interface, which can affect curing and related properties. In addition, fluoroorganosilicone compounds are usually expensive.

[0108] The release coating composition may be prepared by combining the above-mentioned components (A)-(D), as well as any optional components, in any order of addition, optionally in a masterbatch, and optionally under shear. In certain embodiments, the release coating composition is prepared by forming a base composition that includes or alternatively consists of components (A) and (B), and combining the base composition with components (C) and (D). As described in more detail below, the release coating composition may be a one-part composition, a two-part or 2K composition, or a multi-part composition. For example, components (A) and (B) may be a single part of the release coating composition. When the release coating composition is utilized to prepare a release coating or coated substrate as described below, components (A) and (B) are combined with components (C) and (D), as well as optional components, such that the release coating composition is a curable composition. When the release coating composition further includes components (C) and (D), the release coating composition may be referred to as a curable composition.

[0109] A method of preparing a coated substrate with a release coating composition includes applying, i.e., disposing, the release coating composition on a substrate. The method further includes curing the curable composition on the substrate to form a release coating on the substrate to obtain a coated substrate. Curing may be carried out by heating at an elevated temperature, for example, from 50°C to 180°C, alternatively from 50°C to 120°C, alternatively from 50°C to 90°C, to obtain a coated substrate. One skilled in the art will be able to select an appropriate temperature depending on various factors, including the selection of the components of the curable composition and the materials of the substrate composition or structure.

[0110] The curable composition may be disposed or distributed on the substrate in any suitable manner. Typically, the curable composition is applied in wet form via wet coating techniques. The curable composition may be applied by i) spin coating, ii) brush coating, iii) drop coating, iv) spray coating, v) dip coating, vi) roll coating, vii) flow coating, viii) slot coating, ix) gravure coating, x) Mayer bar coating, or xi) a combination of any two or more of i)-x). Typically, the curable composition is disposed on the substrate to produce a wet deposit on the substrate, which is then cured to obtain a cured film, i.e., a coated substrate, including a release coating formed from the curable composition on the substrate.

[0111] The substrate is not limited and can be any substrate. The cured film can be separable from the substrate or can be physically and / or chemically bonded to the substrate depending on the selection. The substrate can be subjected to an integrated hot plate or an integrated or stand-alone oven for curing the wet deposit. The substrate can optionally have continuous or non-continuous shapes, sizes, dimensions, surface roughness, and other properties. Alternatively, the substrate can have an elevated softening point temperature. However, the curable compositions and methods are not so limited.

[0112] Alternatively, the substrate may comprise a plastic, which may be thermoset and / or thermoplastic. However, the substrate may alternatively be or comprise glass, metal, cellulose (e.g., paper), wood, cardboard, paperboard, silicone, or polymeric materials, or combinations thereof.

[0113] Specific examples of suitable substrates include paper substrates such as kraft paper, polyethylene-coated kraft paper (PEK-coated paper), thermal paper, and plain paper; polymer substrates such as polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene; styrene resins; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); polyphenylene ether (polyphenylene ether, PPE); polyimide (polyimide, PI); polyamideimide (polyamideimide, PAI); polyetherimide (polyetherimide, PEI); polysulfone (polysulfone, PSU); polyethersulfone; polyketone (polyketone, PK); polyetherketone; polyvinyl alcohol (polyvinyl alcohol, PVA); polyetheretherketone (polyetheretherketone, PEEK); polyetherketoneketone (polyetherketoneketone, PEKK); polyarylate (polyarylate, PAR); polyethernitrile (polyethernitrile, PEN); phenolic resin; phenoxy resin; cellulose such as triacetyl cellulose, diacetyl cellulose, cellophane; fluorinated resin such as polytetrafluoroethylene;Thermoplastic elastomers such as polystyrene-type, polyolefin-type, polyurethane-type, polyester-type, polyamide-type, polybutadiene-type, polyisoprene-type, fluoro-type, and the like; and copolymers and combinations thereof.

[0114] The curable composition, or wet deposit, is typically cured at elevated temperature for a period of time. The period of time is typically sufficient to achieve curing, i.e., crosslinking, of the curable 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. The period of time depends on a variety of factors, including the elevated temperature utilized, the temperature selected, the desired film thickness, and the presence or absence of any water or vehicle in the curable composition.

[0115] Curing the curable composition typically has a residence time of 0.1 seconds to 50 seconds, alternatively 1 second to 10 seconds, alternatively 0.5 seconds to 30 seconds. The residence time selected may depend on the choice of substrate, the temperature selected, and the line speed. As used herein, residence time refers to the time that the curable composition or wet deposit is subjected to an elevated temperature. Residence time is distinct from cure time, since there may be ongoing curing even after the curable composition, wet deposit, or partially cured reaction intermediate thereof is no longer subjected to the elevated temperature that typically initiates curing. Alternatively, the coated article may be prepared on a conveyor belt in an oven, and the residence time may be calculated by dividing the length of the oven (e.g., in meters) by the line speed of the conveyor belt (e.g., meters / second).

[0116] The time can be subdivided into iterations of cure, e.g., a first cure and a post cure, e.g., 1 hour for the first cure and 3 hours for the post cure. The elevated temperature can be independently selected in such iterations from any temperature above room temperature and can be the same in each iteration.

[0117] Depending on the thickness and other dimensions of the film and coated substrate, the coated substrate can be formed through an iterative process. For example, a first deposit may be formed and subjected to a first elevated temperature for a first time to obtain a partially cured deposit. A second deposit may then be placed on the partially cured deposit and subjected to a second elevated temperature for a second time to obtain a second partially cured deposit. This partially cured deposit also further cures while being subjected to the second elevated temperature for a second time. A third deposit may be placed on the second partially cured deposit and subjected to a third elevated temperature for a third time to obtain a third partially cured deposit. The second partially cured deposit also further cures while being subjected to the second elevated temperature for a second time. This process may be repeated, for example, 1 to 50 times, to build up the coated article as desired. The composite of partially cured layers may be subjected to a final post-cure, for example, to the elevated temperatures and times described above. Each elevated temperature and time may be independently selected and may be the same or different from one another. When the article is formed via an iterative process, each deposit may be independently selected and may differ in the components selected in the curable composition, their amounts, or both. Alternatively or additionally, each repeating layer may be fully cured, rather than only partially cured, in such an iterative process.

[0118] Alternatively, the deposition may include a wet film. Alternatively, the iterative process may be wet-on-wet, depending on the cure state of the partially cured layer. Alternatively, the iterative process may be wet-on-dry.

[0119] The coated substrate comprising a film formed from the curable composition on the substrate can have a variety of dimensions, including the relative thickness of the film and the substrate. The film has a thickness that can vary depending on its end use application. The film can have a thickness of from greater than 0 to 4,000 μm, alternatively greater than 0 to 3,000 μm, alternatively greater than 0 to 2,000 μm, alternatively greater than 0 to 1,000 μm, alternatively greater than 0 to 500 μm, alternatively greater than 0 to 250 μm. However, other thicknesses are contemplated, for example, from 0.1 to 200 μm. For example, the thickness of the film can be from 0.2 to 175 μm, alternatively from 0.5 to 150 μm, alternatively from 0.75 to 100 μm, alternatively from 1 to 75 μm, alternatively from 2 to 60 μm, alternatively from 3 to 50 μm, and alternatively from 4 to 40 μm. Alternatively, when the substrate is plastic, the film may have a thickness of from greater than 0 to 200, alternatively from greater than 0 to 150 μm, and alternatively from greater than 0 to 100 μm.

[0120] If desired, the film may be subjected to further processing depending on its end use application. For example, the film may be subjected to oxide deposition (e.g., SiO 2 The film may be subjected to a variety of techniques, including chemical vapor deposition, resist deposition and patterning, etching, chemical stripping, corona or plasma stripping, metallization, or metal deposition. Such further processing techniques are generally known. Such deposition may be chemical vapor deposition (such as 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 high temperatures, particularly vacuum deposition, for which the film is well suited given its excellent thermal stability. However, depending on the end use of the film, the film may be utilized with such further processing.

[0121] The coated substrate may be utilized in a variety of 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, electronic applications, or electrical applications. However, the curable composition may be utilized in end use applications other than preparing the coated substrate, for example, preparing articles such as silicone rubber.

[0122] Alternatively, the coated substrate may be utilized as a release liner for a tape or adhesive, including any pressure sensitive adhesive, including, for example, acrylic, rubber, and silicone type pressure sensitive adhesives, as well as acrylic, synthetic rubber, silicone, epoxy, and polyurethane type adhesives. Each major surface of the substrate may have a double-sided tape or film disposed thereon for the adhesive.

[0123] Alternatively, when the curable composition is formulated as a release coating composition, for example to form a release coating or liner, the release coating composition can be prepared, for example, by mixing the components together to prepare a one-part composition. However, it may be desirable to prepare the release coating composition as a multi-part composition in which the component having SiH functionality (e.g., (C) organosilicon compound) and (D) hydrosilylation reaction catalyst are stored in separate parts until the parts are combined at the time of use (e.g., immediately prior to application to a substrate). When the curable composition is a release coating composition, the release coating composition can be utilized to form a coated substrate as described above, and the release coating is formed by applying and curing the release coating composition to a substrate, for example, the surface of the substrate.

[0124] For example, a multi-part curable composition may be a portion (A) referred to as a base portion comprising one or more of: (A) a silicate resin, (B) an organopolysiloxane containing an average of at least two silicon-bonded ethylenically unsaturated groups per molecule, and (D) a hydrosilylation reaction catalyst, and optionally, when present, (F) an anchor additive, and (I) a vehicle; and part (B) a curing agent part comprising (C) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule, and optionally, when present, (F) an anchor additive and / or (I) a vehicle. If utilized, (E) an inhibitor may be added to part (A), part (B), or both. Part (A) and part (B) may be combined in a weight ratio (A):(B) of 1:1 to 30:1, alternatively 1:1 to 10:1, alternatively 1:1 to 5:1, alternatively 1:1 to 2:1. Part (A) and part (B) may be provided in a kit, for example, with instructions on how to combine the parts to prepare the release coating composition, how to apply the release coating composition to a substrate, and how to cure the release coating composition.

[0125] Alternatively, (F) the anchor additive, if present, may be incorporated into either part (A) or part (B), or may be added to a separate (third) part.

[0126] The release coating composition can be applied to the substrate by any convenient means, such as, for example, spraying, doctor blading, dipping, screen printing, or by a roll coater, such as an offset web coater, kiss coater, or etched cylinder coater.

[0127] The release coating composition of the present invention can be applied to any substrate, such as those mentioned above. Alternatively, the release coating composition can be applied to a polymeric film substrate, such as a polyester film, particularly a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, or a polystyrene film. Alternatively, the release coating composition can be applied to a paper substrate, including a plastic-coated paper, such as a polyethylene-coated paper, a glassine, a supercalendered paper, or a clay-coated kraft paper. Alternatively, the release coating composition can be applied to a metal foil substrate, such as an aluminum foil.

[0128] In certain embodiments, the method of preparing a coated substrate may further include treating the substrate before applying or disposing the release coating composition on the substrate. The treatment of the substrate may be carried out by any convenient means, such as plasma treatment or corona discharge treatment. Alternatively, the substrate may be treated by applying a primer. In certain cases, the anchoring of the release coating may be improved if the substrate is treated before forming the release coating on the substrate from the release coating composition.

[0129] When the release coating composition includes (I) a vehicle, the method may further include removing the (I) vehicle, which may be carried out by any conventional means, such as by heating at 50°C to 100°C for a time sufficient to remove all or a portion of the (I) vehicle. The method may further include curing the release coating composition to form a release coating on the surface of the substrate. Curing may be carried out by any conventional means, such as by heating at 100°C to 200°C.

[0130] Under production coater conditions, curing may be accomplished with an air temperature of 120° C. to 150° C. and a residence time of 1 to 6 seconds, alternatively 1.5 to 3 seconds. Heating may be carried out in an oven, such as an air circulating oven or tunnel furnace, or by passing the coated film around a heated cylinder.

[0131] The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the invention in any way. The specific components utilized in the examples are set forth in Table 1 below, followed by the characterization and evaluation procedures utilized in the examples. [Table 1] Nuclear Magnetic Resonance (NMR) Spectroscopy

[0132] Nuclear magnetic resonance (NMR) spectra were obtained using silicon-free 10 mm tubes and CDCl 3 / Cr(AcAc) 3 Solvents were used and NMR was obtained on a BRUKER AVIII (400 MHz). 29 Chemical shifts for Si-NMR spectra are reported relative to tetramethylsilane, referenced to the internal solvent resonance. Gel Permeation Chromatography (GPC)

[0133] Gel permeation chromatography (GPC) analysis is performed on an Agilent 1260 Infinity II chromatograph equipped with a triple detector consisting of a differential refractometer, an online differential viscometer, low angle light scattering (LALS: detection angles of 15° and 90°), and a column (2 PL Gel Mixed C, Varian).Toluene (HPLC grade, Biosolve) is used as the mobile phase at a flow rate of 1 mL / min. Dynamic Viscosity (DV)

[0134] Dynamic viscosity (DV) is measured on a Brookfield DV-III Ultra Programmable Viscometer equipped with a CPA-52Z spindle using a sample volume of 0.5 mL at a temperature of 25°C. X-Ray Fluorescence (XRF)

[0135] X-ray fluorescence (XRF) is performed on an Oxford Instruments Lab-X3500 benchtop XRF analyzer. SiOZ content

[0136] The content of the SiOZ portion is 29 It can be calculated via Si-NMR. Specifically, the molar content of the following siloxy units in each (A) silicate resin is determined: W=R 3 SiO 1 / 2 X1=R 2 (OZ)SiO 1 / 2 X2=R 2 SiO 2 / 2 T1=R(OZ) 2 SiO 1 / 2 T2 = R(OZ)SiO 2 / 2 T3=RSiO 3 / 2 Y1=(OZ) 3 SiO 1 / 2 Y2=(OZ) 2 SiO 2 / 2 Y3=(OZ)SiO 3 / 2 Y4=SiO 4 / 2 The OZ content relative to silicon atoms as mole % can be calculated by the following formula with the label of each peak in the formula corresponding to the integrated area under the peak corresponding to the label:

number

[0137] The curing performance of the sample compositions is evaluated by determining the percent extractables (% Extractables). Specifically, the sample compositions are coated and cured on a substrate (glassine paper) to form a coated substrate, and immediately cut into three sample disks (die cutter, 1.375 inches (3.49 cm)), which are handled only with tweezers to minimize contamination and / or damage. Each sample disk is analyzed via XRF to determine the initial coating weight (W i s ) was determined and then placed into individual bottles (100 mL, covered with lids) containing solvent (methyl isobutyl ketone, 40 mL) and allowed to soak for 30 minutes on the lab bench. Each sample disk was then removed from the bottle, placed coated side up on a clean surface (tissue paper), allowed to evaporate the residual solvent (without blotting / wiping), and analyzed via XRF to determine the final coating weight (Wf s The % extractables for each sample are the percent change in coating weight from solvent immersion, i.e., calculated using the formula [(W i s -W f s ) / Wi×100%). The % Extractables indicates the amount of uncured components (e.g., uncrosslinked silicone) of the sample composition that can be extracted from the coating substrate, e.g., a lower % Extractables indicates higher / better cure performance. Hardening performance: Anchor (ROR%)

[0138] The anchorage of the sample composition is evaluated via the anchorage index, i.e., by determining the rub-off resistance (ROR%) value. Specifically, the sample composition is coated and cured on a substrate (glassine paper) to form a coated substrate. Immediately after curing, the coated substrate is cut into two sample disks (die cutter, 1.375 inches (3.49 cm)) and each sample disk is analyzed via XRF to determine the initial coating weight (W i a Each sample disk is then abraded with felt under a load (1.9 kg) using an automated abrasion device in a manner similar to Taber-type abrasion tests (e.g., ASTM D4060-19, "Standard Test Method for Abrasion Resistance of Organic Coatings by the Taber Abraser"), and then analyzed by XRF to determine the final coating weight (W f a The ROR% of each sample is calculated using the formula [W f s / W i s ]×100%). ROR% indicates how strongly the coating is anchored to the substrate, e.g., a higher ROR% indicates higher / better anchoring, e.g., a higher ROR% indicates better. Preparation Example 1: Silicate Resin (A1)

[0139] 300 g of Solvent 1 was placed in a 2 L flask equipped with a magnetic stir bar, followed by 300 g of MQ resin. 109.0 grams of Silane Compound 1 and 0.30 grams of Catalyst were placed in the flask. The contents of the flask were stirred under nitrogen at 100° C. and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23° C. and 0.5 grams of Neutralizing Agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear and viscous liquid. The silicate resin (A1) was isolated from the reaction product by removal of volatiles via roto-vap. The silicate resin (A1) was a colorless liquid having a DV of 39,000 cP at 25° C., a weight average molecular weight of 2,969, and a polydispersity of 1.46, each as measured via GPC. The (A1) silicate resin had a SiOZ content of 23.5 mol % and a vinyl content of 6.46 wt %. Preparation Example 2: Silicate Resin (A2)

[0140] 300 g of Solvent 1 was placed in a 2 L flask equipped with a magnetic stir bar, followed by 300 g of MQ resin. 165.0 grams of Silane Compound 1 and 0.30 grams of Catalyst were placed in the flask. The contents of the flask were stirred under nitrogen at 100° C. and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23° C. and 0.5 grams of Neutralizing Agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear and viscous liquid. The silicate resin (A2) was isolated from the reaction product by removal of volatiles via roto-vap. The silicate resin (A2) was a colorless liquid having a DV of 450 cP at 25° C., a weight average molecular weight of 3,160, and a polydispersity of 1.65, each as measured via GPC. (A2) The silicate resin had a SiOZ content of 30.9 mol % and a vinyl content of 7.58 wt %. Preparation Example 3: Silicate Resin (A3)

[0141] 300 g of Solvent 1 was placed in a 2 L flask equipped with a magnetic stir bar, followed by 300 g of MQ resin. 217.9 grams of Silane Compound 1 and 0.30 grams of Catalyst were placed in the flask. The contents of the flask were stirred under nitrogen at 100° C. and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23° C. and 0.5 grams of Neutralizing Agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1 micron filter to obtain a clear and viscous liquid. The silicate resin (A3) was isolated from the reaction product by removal of volatiles via roto-vap. The silicate resin (A3) was a colorless liquid having a DV of 200 cP at 25° C., a weight average molecular weight of 2,636, and a polydispersity of 1.50, each as measured via GPC. (A3) The silicate resin had a SiOZ content of 37.3 mol % and a vinyl content of 8.26 wt %. Preparation Example 4: Silicate Resin (A4)

[0142] 300g of solvent 1 was placed in a 2L flask equipped with a magnetic stir bar, followed by 300g of MQ resin. 20.16 grams of silane compound 1, 105.3 grams of silane compound 2, and 0.30 grams of catalyst were placed in the flask. The contents of the flask were stirred under nitrogen at 100°C, and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23°C, and 0.36 grams of neutralizing agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 0.45 micron filter to obtain a clear, viscous liquid. The silicate resin (A4) was isolated from the reaction product by removal of volatiles via roto-vap. The silicate resin (A4) was a colorless liquid having a DV of 75,000 cP, a weight average molecular weight of 5,450, and a polydispersity of 1.7149 at 25° C., each as measured via GPC. The (A4) silicate resin had a SiOZ content of 19.12 mol % and a vinyl content of 1.12 wt %. Preparation Example 5: Silicate Resin (A5)

[0143] 300 g of solvent 1 was placed in a 2 L flask equipped with a magnetic stir bar, followed by 300 g of MQ resin. 20.2 grams of silane compound 1, 131.1 grams of silane compound 2, and 0.30 grams of catalyst were placed in the flask. The contents of the flask were stirred under nitrogen at 100° C., and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23° C., and 0.5 grams of neutralizing agent was placed in the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 0.45 micron filter to obtain a clear, viscous liquid. The silicate resin (A5) was isolated from the reaction product by removal of volatiles via roto-vap. The silicate resin (A5) was a colorless liquid having a DV of 9,500 cP at 25° C., a weight average molecular weight of 7,380, and a polydispersity of 1.8996, each as measured via GPC. (A5) The silicate resin had a SiOZ content of 25.33 mol % and a vinyl content of 1.09 wt %. Preparation Example 6: Silicate Resin (A6)

[0144] The same method as in Preparation Example 5 was repeated. The silicate resin (A6) was a colorless liquid having a DV of 9,900 cP, a weight average molecular weight of 5,820, and a polydispersity of 1.7562 at 25° C., each measured via GPC. (A6) silicate resin had a SiOZ content of 25.35 mol% and a vinyl content of 0.24 wt%. Examples 1 to 11:

[0145] Examples 1-11 are release coating compositions containing the silicate resins prepared in Preparation Examples 1-6. In each of Examples 1-11, a particular silicate resin is combined with (B1) organopolysiloxane to obtain a base composition, and each particular base composition is combined with Inhibitor 1, an organosilicon compound (C1), and a catalyst (D1) to obtain a release coating composition. Each release coating composition of Examples 1-11 is prepared in the absence of any solvent, since it is solventless and the silicate resin is miscible with (B1) organopolysiloxane. In each of Examples 1-11, the SiH:SiVi molar ratio is 2:1 mole:mole, and the total Pt content of each of Examples 1-11 is 100 ppm. Table 2 below lists the relative amounts of each component in grams utilized to prepare the release coating compositions of Examples 1-11. [Table 2] Comparative Examples 1 to 9:

[0146] Comparative Examples 1-9 (designated CE1-9) are comparative release coating compositions. In each of Comparative Examples 1-9, the SiH:SiVi molar ratio is 2:1 mole:mole, and the total Pt content of each of Comparative Examples 1-9 is 100 ppm. Table 3 below shows the relative amounts of each component in grams utilized to prepare the comparative release coating compositions of Comparative Examples 1-9. [Table 3] Examples 12-22 and Comparative Examples 10-18: Coated Substrates

[0147] The release coating compositions of Examples 1-11 and Comparative Examples 1-9 are utilized to prepare coated substrates. Specifically, each composition is coated onto a substrate (glassine paper) and cured (exit web oven temperature: 165.56°C, residence time: 28.4 seconds) to form a coated substrate, and the samples are evaluated for instant extractables %, instant ROR%, 7-day RT aging ROR%, and 1-month RT aging ROR%. The 7-day and 1-month RT aging ROR% are performed after aging at RT for a set time at 50% RH under 40 lbs. The results are set forth in Tables 4 and 5 below. In Tables 4 and 5, n / a indicates that the value was not measured. Example 12 utilizes the composition of Example 1, Example 13 utilizes the composition of Example 2, Example 14 utilizes the composition of Example 3, and so on. The same applies to the correlation of Comparative Examples 10-18 to the compositions of Comparative Examples 1-9. [Table 4] [Table 5]

[0148] The peel force, 7-day aging peel force, and 1-month aging peel force were measured at various speeds, i.e., 0.3 m / min (MPM), 10 m / min (MPM), 100 m / min (MPM), and 300 m / min (MPM), with 180 degree peel. The peel force was measured via Imass SP-2100 and ZPE-1100W peel test system after lamination with Tesa 7475 standard tape under 40 lbs at RT and 50% RH. The aging peel force is measured by aging at RT and 50% RH under 40 lbs for the specified time. The results are listed in Tables 6-8 below. In Tables 6-8, TH indicates that the peel force was too high to measure, and n / a indicates that no measurement was performed. [Table 6] [Table 7] [Table 8] Examples 23 to 25

[0149] Examples 23-25 ​​are further release coating compositions comprising the silicate resins prepared in Preparation Examples 1-3. In each of Examples 23-25, a particular silicate resin is combined with (B1) organopolysiloxane to obtain a base composition, and each particular base composition is combined with Inhibitor 1, an organosilicon compound (C1), and a catalyst (D1) to obtain a release coating composition. Each release coating composition of Examples 23-25 ​​is prepared in the absence of any solvent, since it is solventless and the silicate resin is miscible with (B1) organopolysiloxane. Table 9 below lists the relative amount of each component in grams utilized to prepare the release coating compositions of Examples 23-25. [Table 9] Comparative Examples 19-20:

[0150] Comparative Examples 19-20 (designated CE19-20) are comparative release coating compositions. Table 10 below shows the relative amounts of each component in grams utilized to prepare the comparative release coating compositions of Comparative Examples 19-20. [Table 10]

[0151] Examples 26-28 and Comparative Examples 21-22:

[0152] The release coating compositions of Examples 23-25 ​​and Comparative Examples 19-20 are utilized to prepare coated substrates. Specifically, each composition is coated onto a substrate (glassine paper) and cured (exit web oven temperature: 165.56°C, residence time: 11 seconds) to form a coated substrate, and the samples are evaluated for instant extractables %, instant ROR %, and peel force at various speeds, i.e., 0.3 m / min (MPM), 10 m / min (MPM), 100 m / min (MPM), and 300 m / min (MPM) and 180 degree peel. The peel force is measured via an Imass SP-2100 and ZPE-1100W peel test system after lamination with Tesa 7475 standard tape under 40 lbs at RT and 50% RH after aging for 50 minutes. The results are listed in Table 11 below. Example 26 utilizes the composition of Example 23, Example 27 utilizes the composition of Example 24, and Example 28 utilizes the composition of Example 25. The same correlation applies to the compositions of Comparative Examples 21-22 and Comparative Examples 19-20. [Table 11] Definitions and Use of Terms

[0153] Definitions of the abbreviations used herein are provided in Table 12 below. [Table 12]

[0154] It is to be understood that the appended claims are not limited to reciting the specific compounds, compositions, or methods described in the detailed description, but may vary between specific embodiments falling within the scope of the appended claims.

Claims

1. 1. A base composition for forming a release coating composition, the base composition comprising: (A) a silicate resin that is liquid at 25° C. in the absence of any solvent and contains, on average, at least one silicon-bonded ethylenically unsaturated group per molecule; (B) an organopolysiloxane containing an average of at least two silicon-bonded ethylenically unsaturated groups per molecule; the (A) silicate resin is miscible with the (B) organopolysiloxane in the absence of any solvent; The (A) silicate resin has the following average formula: [W] a [X] b [Y] c, wherein subscript a is between 0.15 and 0.40, subscript b is between 0.10 and 0.40, and subscript c is between 0.35 and 0.60, provided that a+b+c=1; [W] is [R 3 SiO 1 / 2 ], where each R is an independently selected hydrocarbyl group; [X] is [R 2 SiO 1 / 2 (OZ)] b ' [R 2 SiO 2 / 2 ] b '' where each R is independently selected and defined above, with 0≦b'≦b and 0≦b''≦b, with the proviso that b'+b''=b, and each Z is independently H, an alkyl group, or a cation; [Y] is [Si(OZ) c' O 4-c' / 2 ], where each Z is independently selected and defined above, and subscript c' is an integer from 0 to 3 and is independently selected in each siloxy unit designated by subscript c in said (A) silicate resin; With the proviso that at least one of R is an ethylenically unsaturated group.

2. 10. The base composition of claim 1, which is substantially free of any organic solvent.

3. The (B) organopolysiloxane is (i) a linear or branched organopolysiloxane containing the silicon-bonded ethylenically unsaturated group in at least one M siloxy unit, or (ii) a linear or branched organopolysiloxane having the formula (R ２ ｙ R １ ３－ｙ SiO １／２ ) ｘ (R １ R ２ SiO ２／２ ) ｚ (SiO ４／２ ), wherein each R １ is an independently selected hydrocarbyl group free of ethylenic unsaturation, and each R ２ But independently, R １ and an ethylenically unsaturated group, subscript y is independently selected in each siloxy unit designated by subscript x and is 1 or 2, and subscript x is from 1.5 to 6 and subscript z is from 3 to 1,000, respectively.

4. 4. The base composition of any one of claims 1 to 3, wherein component (A) (i) has a mole percent of SiOZ moieties from 12 to 80 percent, based on the total moles of Si in each molecule, where Z is independently selected from H, an alkyl group, or a cation; (ii) has from greater than 0 to 10 weight percent silicon-bonded ethylenically unsaturated groups, based on the total weight of component (A); or (iii) includes both (i) and (ii).

5. 1. A release coating composition comprising: A base composition according to any one of claims 1 to 4, (C) an organosilicon compound having at least two silicon-bonded hydrogen atoms; (D) a hydrosilylation reaction catalyst; and and optionally, (E) an inhibitor.

6. 6. A method for preparing the release coating composition of claim 5, said method comprising: combining components (A) and (B) to obtain a base composition; combining said base composition with components (C) and (D) to obtain said release coating composition.

7. 1. A method of forming a coated substrate, the method comprising: applying the composition onto a substrate; and curing the composition to obtain a release coating on the substrate, thereby forming the coated substrate. The method of claim 5 , wherein the composition is a release coating composition.

8. A coated substrate formed according to the method of claim 7.

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