Compositions for preparing release coatings, 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. (A) The silicate resin contains an average of at least one silicon-bonded ethylenically unsaturated group per molecule. The composition further comprises (B) an organopolysiloxane containing an average of at least two silicon-bonded ethylenically unsaturated groups per molecule. 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 all benefits of U.S. Provisional Patent Application No. 62 / 955,114, filed December 30, 2019, the contents of which are incorporated herein by reference.

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

[0003] Silicone compositions are known in the art and are utilized in numerous industries and end uses.One such end use is to form a release coating or release liner that can remove adhesives.For example, silicone release compositions can be used 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 unsaturated hydrocarbon groups with an organohydrogenpolysiloxane in the presence of a hydrosilylation catalyst. In addition, various additives, such as release modifiers and antifog agents, are incorporated into the silicone release compositions or the methods for preparing them to improve the performance of the resulting release liner. 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. (A) The silicate resin contains an average of at least one silicon-bonded ethylenically unsaturated group per molecule. The composition further comprises (B) an organopolysiloxane containing an average of at least two silicon-bonded ethylenically unsaturated groups per molecule.

[0006] Also disclosed are methods for preparing the base composition and the release coating composition. Additionally, methods for preparing a coated substrate comprising a release coating disposed on a substrate, as well as the coated substrate formed according to the methods, are disclosed. DETAILED DESCRIPTION OF THE INVENTION

[0007] A base composition for forming a release coating composition is disclosed, which 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) The silicate resin may alternatively be referred to as a silicone resin, and the Q siloxy units or SiO in the (A) silicate resin are 4 / 2Considering the presence of units, it is a silicate resin. Generally, silicone resins, especially silicate resins, are solid at 25°C due to their three-dimensional network structure. Considering the difficulty of processing solid silicone resins, silicone resins are typically dissolved in a solvent and used as a silicone resin composition comprising or consisting of a solid silicone resin 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, which allows for easier processing of the silicone resin composition. For example, the silicone resin composition can be combined with other components or compositions for various end uses in liquid form. Similarly, in the absence of any solvent, conventional silicone resins that are solid at 25°C 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 presence of an organic solvent. Thus, when conventional silicone resins are utilized in silicone compositions, an organic solvent is typically required for the purposes of forming the silicone composition, and then either volatilizes in the composition form or volatilizes upon curing.

[0009] In contrast, the (A) silicate resin is liquid at 25°C in the absence of a solvent. Therefore, unlike conventional silicone resins, the (A) silicate resin is liquid at 25°C without the presence of any solvent, such as an organic solvent. The (A) silicate resin is composed of a silicate resin that does not contain any solvent or carrier vehicle. In certain embodiments, depending on the selection of the (A) silicate resin and its properties, not only is the (A) silicate resin liquid at 25°C in the absence of any solvent, but the (A) silicate resin is also miscible with the organopolysiloxane containing an average of at least two silicon-bonded ethylenically unsaturated groups per molecule in the base composition. This allows the base composition to be easily formed without the need for any solvent or associated processing steps to remove the solvent from the base composition.

[0010] "Liquid" means that in the absence of any solvent, (A) the silicate resin is flowable at 25 °C and / or has a measurable viscosity at 25 °C. Typically, the viscosity of (A) the silicate resin is measurable at 25 °C by a Brookfield LV DV-E viscometer equipped with a spindle appropriately selected for the viscosity of (A) the silicate resin. The viscosity of (A) the silicate resin can vary, inter alia, based on the content of M, D, T, and / or Q siloxy units present therein, as described below.

[0011] In certain embodiments, (A) the silicate resin has the following average formula: [W] a [X] b [Y] c [Z] d where 0 < a < 1, 0 ≤ b < 1, 0 < c < 1, 0 < d < 1, provided that a + b + c + d = 1. The subscript letters a, b, c, and d are the mole fractions of the W, X, Y, and Z units in (A) the silicate resin.

[0012] In the above average formula of (A) the silicate resin, [W], [X], [Y], and [Z] are used in place of the more common designations [M], [D], [T], and [Q]. As understood in the art, the M siloxy unit contains one siloxane bond (i.e., -O-Si-), the D siloxy unit contains two siloxane bonds, the T siloxy unit contains three siloxane bonds, and the Q siloxy unit contains four siloxane bonds.

[0013] However, for the purposes of the present disclosure, [W] represents a siloxy unit containing one -Si-O- bond that can 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 a cation, such as K + or Na +Alternatively, [W] is H or an alkyl group. Silanol groups and alkoxy groups hydrolyze and / or condense to provide siloxane bonds, which are typically inherently present in most silicone resins. Such precursors of siloxane bonds can be minimized by forming silicone resins that undergo further condensation with water and / or alcohol as by-products. Therefore, for purposes of this disclosure, [W] is defined as [RSiO 1 / 2 wherein each R is an independently selected hydrocarbyl group.

[0014] Furthermore, for purposes of this disclosure, [X] represents a siloxy unit containing two -Si-O- bonds, which may independently be siloxane bonds or precursors thereof. Thus, for purposes of this disclosure, [X] represents a siloxy unit containing two -Si-O- bonds, which may independently be siloxane bonds or precursors thereof. 1 / 2 (OZ)] b’ [R2SiO 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″ represent the relative mole fractions of the [X] siloxy units designated by subscript b′ and the [X] siloxy units designated by subscript b″, respectively, in (A) the silicate resin, and the sum of b′ and b″ is b. The [X] siloxy units designated by subscript b′ contain one siloxane bond and one Si-OZ bond, and the [X] siloxy units designated by subscript b″ contain two siloxane bonds.

[0015] Furthermore, for purposes of this disclosure, [Y] represents a siloxy unit containing three -Si-O- bonds, which may independently be siloxane bonds or precursors thereof. Thus, for purposes of this disclosure, [Y] represents [RSi(OZ) c’ O 3-c’ / 2[wherein each R is independently selected and defined above, and c' is an integer from 0 to 2, and each Y siloxy unit designated by the subscript c is independently selected]. Thus, [Y] is a siloxy unit of the following: [RSiO 3 / 2 ], [RSi(OZ)1O 2 / 2 ], and / or [RSi(OZ)2O 1 / 2 ] can represent any combination of

[0016] Furthermore, for purposes of this disclosure, [Z] represents a siloxy unit containing four -Si-O- bonds, which may independently be siloxane bonds or precursors thereof. Thus, for purposes of this disclosure, [Z] represents [Si(OZ) d’ O 4-d’ / 2 [wherein each Z is independently selected and defined above, and subscript d' is an integer from 0 to 3, and is independently selected for each siloxy unit designated by subscript d in the (A) silicate resin]. The (A) silicate resin can include siloxy units designated by subscript d, where d' is 0, d' is 1, d' is 2, and d' is 3. The siloxy unit designated by [Z] can have 1, 2, 3, or 4 siloxane bonds, with the remainder being Si-OZ moieties. Thus, [Z] can be any of the following siloxy units: [SiO 4 / 2 ], [Si(OZ)O 3 / 2 ], [Si(OZ)2O 2 / 2 ], and / or [Si(OZ)O 1 / 2 ] can represent any combination of

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

[0018] In these or other embodiments, subscript b is zero to 0.9, or 0 to 0.8, or 0 to 0.7, or 0 to 0.6, or 0 to 0.5, or 0 to 0.4. In certain embodiments, subscript b is greater than 0 to 0.30, or greater than 0 to 0.25, or greater than 0 to 0.20, or 0.10 to 0.20. In other embodiments, subscript b is 0. Subscripts b' and b'' define the relative amounts of specific siloxy units represented by [X]. As described above, 0 ≤ b' ≤ b and 0 ≤ b'' ≤ b, provided that b' + b'' = b. While subscript b' can be 0, subscript b'' is b, or while subscript b' can be b, subscript b'' is 0, or both subscripts b' and b'' are 0. When both siloxy units represented by b' and b'' are present in the (A) silicate resin, 0 < b' < 1 and 0 < b'' < 1, provided that b' + b'' = b.

[0019] In these or other embodiments, subscript c is greater than zero to 0.9, or greater than zero to 0.8, or 0 to 0.7, or greater than zero to 0.6, or greater than zero to 0.5, or greater than zero to 0.4. In certain embodiments, subscript c is greater than 0 to 0.30, or greater than 0 to 0.25, or greater than 0 to 0.20.

[0020] In these or other embodiments, subscript d is greater than zero to 0.9, or greater than zero to 0.8, or greater than zero to 0.7, or greater than zero to 0.6. Alternatively, in these or other embodiments, d is 0.1 to 0.9, or 0.2 to 0.9, or 0.3 to 0.9, or 0.4 to 0.9. In certain embodiments, subscript d is 0.35 to 0.60, or 0.40 to 0.60, or 0.40 to 0.55, or 0.45 to 0.55.

[0021] R is an independently selected hydrocarbyl group, and an average of at least one or at least two R per molecule of (A) silicate resin is an ethylenically unsaturated group. Generally, hydrocarbyl groups suitable for R can be independently linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups can independently be 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, etc., as well as derivatives, modifications, 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. 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. 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.

[0022] In certain 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, or 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, or 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, and hexenyl groups. "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 CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, HC=C(CH3)-, HC=C(CH3)-, HC=C(CH3)CH2-, HC=CHCH2CH2-, HC=CHCH2CH2-, HC≡C-, HC≡CCH2-, HC≡CCH(CH3)-, HC≡CC(CH3)2-, and HC≡CC(CH3)2CH2-.Typically, when R is an ethylenically unsaturated group, the ethylenic unsaturation is at the terminal of R.As understood in the art, ethylenic unsaturation can be referred to as aliphatic unsaturation.

[0023] In certain embodiments, only the siloxy units designated by subscript b or c contain R groups with ethylenic unsaturation. In these embodiments, the R groups of the siloxy units designated by subscript a 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 as the siloxy units designated by subscript b, but does not contain dimethylsiloxy units. In other embodiments, the ethylenic unsaturation is present only in the units designated by subscript c but not subscript b, or in the units designated by both subscript b and subscript c. The relative amount of such siloxy units can be selectively controlled when preparing the (A) silicate resin. As is understood in the art, the above siloxy units are merely exemplary and the methyl may be replaced with other hydrocarbyl groups and the vinyl may be replaced with other ethylenically unsaturated groups.

[0024] In certain embodiments, (A) the silicate resin has an 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. Typically, the SiOZ moiety content is higher, e.g., 40 to 60, alternatively 45 to 55, when the subscript b is 0. The SiOZ moiety content is: 29 This can be calculated by Si-NMR. Specifically, the molar content of the following siloxy units in (A) the silicate resin is determined. W=R3SiO 1 / 2 X1=R2(OZ)SiO 1 / 2 X2=R2SiO 2 / 2 Y1=R(OZ)2SiO 1 / 2 Y2 = R(OZ)SiO 2 / 2 Y3=RSiO 3 / 2 Z1=(OZ)3SiO 1 / 2 Z2=(OZ)2SiO 1 / 2 Z3=(OZ)SiO 3 / 2 Z4=SiO 4 / 2 The OZ content relative to silicon atoms as mole % can be calculated using the following formula, where the label of each peak in the formula corresponds to the integrated area under the peak corresponding to that label:

number

[0025] In these or other embodiments, the (A) silicate resin has greater than 0 to 10, or alternatively, 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 differs from the weight percent of silicon-bonded ethylenically unsaturated groups in conventional solid silicone resins, which is a function of viscosity after dispersion in a particular siloxane polymer or vehicle. 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.

[0026] 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, which limits the ability to selectively control the content of silicon-bonded ethylenically unsaturated groups at a particular viscosity, essentially limiting certain end uses. 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, or alternatively 1,000 to 10,000. The molecular weight can be measured via gel permeation chromatography (GPC) against a polystyrene standard. In these or other embodiments, the (A) silicate resin has a viscosity at 25° C. of 10 to 500,000 cP, alternatively 10 to 250,000 cP, alternatively 10 to 100,000 cP. Viscosity may be measured at 25° C. with a Brookfield LV DV-E viscometer equipped 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 can be controlled when preparing the (A) silicate resin.

[0027] In various embodiments, the (A) silicate resin is prepared from an MQ resin, where M is (R 0 3SiO 1 / 2 ) siloxy unit, and Q is (SiO 4 / 2 ) siloxy unit, R 0 refers to 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, the nomenclature utilized in the art refers to the M siloxy units as trimethylsiloxy units, although MQ resins may contain hydrocarbyl groups other than methyl groups. Typically, however, the M siloxy groups of MQ resins are trimethylsiloxy groups.

[0028] MQ resins have the formula M nThe MQ resin may have a formula of Q (where the subscript n refers to the molar 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, as the number of M siloxy units decreases and, therefore, more Q siloxy units are networked without terminating M siloxy units. The fact that the formula for an MQ resin normalizes the Q siloxy unit content 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. MQ resins may contain up to 4, alternatively up to 3, or alternatively up to 2 weight percent hydroxyl groups in certain embodiments.

[0029] In certain embodiments, the subscript n is less than 1, e.g., the subscript n is from 0.05 to 0.99, alternatively from 0.10 to 0.95, alternatively from 0.15 to 0.90, alternatively from 0.25 to 0.85, or alternatively from 0.40 to 0.80. In these embodiments, on a molar basis, there are more Q siloxy units than M siloxy units in the MQ resin. However, in other embodiments, n can be greater than 1, e.g., from greater than 1 to 6, alternatively from greater than 1 to 5, alternatively from greater than 1 to 4, alternatively from greater than 1 to 3, or alternatively from greater than 1 to 2.

[0030] In certain embodiments, to prepare (A) silicate resin from an MQ resin, the MQ resin is reacted with a silane compound in the presence of a base catalyst. The silane compound typically contains a silicon-bonded ethylenically unsaturated group and at least two, or alternatively, three, silicon-bonded alkoxy groups. The silicon-bonded alkoxy groups can be independently selected and typically have 1 to 10, alternatively, 1 to 8, alternatively, 1 to 6, alternatively, 1 to 4, alternatively, 1 to 2, or alternatively, 1 carbon atom. For example, the silicon-bonded alkoxy group can be methoxy, ethoxy, propoxy, butoxy, or the like. For example, the silane compound can have the formula RSi(OR)3 or R2Si(OR)2, where each R is independently selected and at least one R that is not part of an alkoxy group is an ethylenically unsaturated group. When the silane compound has three silicon-bonded alkoxy groups, the silane compound is incorporated into the (A) silicate resin as T siloxy units, represented by [Y] in the (A) silicate resin. When the silane compound has only two silicon-bonded alkoxy groups, the silane compound is incorporated into the (A) silicate resin as D siloxy units, represented by [X] in the (A) silicate resin.

[0031] In certain embodiments where the subscript b is greater than 0, the (A) silicate resin is further prepared with a second silane compound different from the first silane compound. When the subscript b is greater than 0, the second silane compound has two silicon-bonded alkoxy groups and can have the formula R2Si(OR)2, where each R is independently selected and defined above. When the siloxy unit represented by the subscript b contains ethylenic unsaturation, at least one R in the second silane compound is an ethylenically unsaturated group. When a second silane compound is utilized, it is incorporated into the (A) silicate resin as a D siloxy unit, i.e., represented by [X] and the subscript b, and therefore the second silane compound can be selected based on the desired D siloxy unit. For example, when the (A) silicate resin contains methylvinylsiloxy units, the second silane compound is a methylvinyldialkoxysilane, such as methylvinyldimethoxysilane. When the (A) silicate resin contains dimethylsiloxy units and methylvinylsiloxy units, the second silane compound can include methylvinyldimethoxysilane in combination with dimethyldimethoxysilane. When the (A) silicate resin contains dimethylsiloxy units, the second silane compound can be a dimethyldialkoxysilane, for example, dimethyldimethoxysilane. Thus, the second silane compound can include two or more different silane compounds in concert.

[0032] In the process for 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 provide an SiOZ group, where Z is defined above. The silane compound and a second silane compound (if utilized) can hydrolyze and condense with the SiOZ group to be incorporated therein. The inclusion of both cleaved siloxy bonds and linear siloxy units resulting from the silane compound results in an (A) silicate resin that is liquid at 25°C in the absence of a solvent.

[0033] The relative amount of silane compound utilized compared to the MQ resin is a function of the desired subscript c in the (A) silicate resin. If more T siloxy units, represented by [Y], are desired in the (A) silicate resin, more silane compound is utilized, and vice versa. Additionally, the second silane compound introduced above is utilized in an amount based on the desired subscript b in the silicate resin, which can be 0. Those skilled in the art will understand how to selectively control such content in light of the description herein, including the examples according to the preferred embodiment of the present invention.

[0034] The MQ resin and the silane compound (and, if utilized, the second silane compound) are reacted in the presence of a catalyst. Typically, the catalyst is an acid or a base, such 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 may be selected from the group consisting of a strong acid catalyst, a strong base catalyst, and combinations thereof. A strong acid catalyst may be trifluoromethanesulfonic acid, or the like. The catalyst is typically a strong base catalyst. Typically, the strong base catalyst is KOH, although other base catalysts, such as phosphazene base catalysts, may be utilized.

[0035] Phosphazene catalysts generally contain at least one -(N=P<)- unit (i.e., a phosphazene unit) and are usually oligomers having up to 10 such phosphazene units, e.g., an average of from 1.5 to a maximum of 5 phosphazene units. Phosphazene catalysts are, for example, halophosphazenes such as chlorophosphazenes (phosphonitrile chlorides), oxygen-containing halophosphazenes, ionic derivatives of phosphazenes such as phosphazenium salts, particularly ionic derivatives of phosphonitrile halides such as perchlorooligophosphazenium salts, or partially hydrolyzed forms thereof.

[0036] In certain embodiments, the catalyst comprises a phosphazene base catalyst. The phosphazene base catalyst may be any known in the art, but typically has the following chemical formula: ((R 3 2N)3P=N) t (R 3 2N) 3-t P=NR 3 [In the formula, each R 3 are 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 is R, then R 3 is typically an alkyl group having 1 to 20, alternatively 1 to 10, alternatively 1 to 4 carbon atoms. 3 2N) two R 3 The groups can be attached to the same nitrogen (N) atom and linked to complete a heterocyclic ring, preferably having 5 or 6 members.

[0037] Alternatively, the phosphazene base catalyst can be a salt, and can be represented by the following alternative chemical formula: [((R 3 2N)3P=N) t (R 3 2N) 3-t P=N(H)R 3 ] + [A - ], or [((R 3 2N)3P=N) s (R 3 2N) 4-s P] + [A - ] [In the formula, each R 3 are independently selected and defined above, the subscript t is defined above, the subscript s is an integer from 1 to 4, and [A] is an anion, typically selected from the group of fluoride, hydroxide, silanolate, alkoxide, carbonate, bicarbonate. In one embodiment, the phosphazene base is an aminophosphazenium hydroxide.

[0038] In certain embodiments, the MQ resin and silane compound (and, if utilized, the second silane compound) are reacted in the presence of a solvent at elevated temperatures, e.g., 75-125°C. Suitable solvents may be hydrocarbons. 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 the 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 by conventional techniques, such as stripping or other volatilization techniques.

[0039] The base composition comprises (A) silicate resin in an amount greater than 0 to 100 weight percent, based on the total weight of the base composition. The relative amount of (A) silicate resin is a function of the end use of the base composition. When the base composition is utilized to prepare a release coating composition, the content of (A) silicate resin in the base composition is selected based on the desired properties of the release coating composition and the release coatings prepared therefrom. In certain embodiments, the (A) silicate resin functions as a release modifier in the release coating composition and the release coatings prepared therefrom.

[0040] Typically, the remainder of the base composition either comprises component (B) or is component (B), as described below. In certain embodiments, the base composition is substantially free of any solvent, specifically, organic solvents. Substantially free means that the base composition contains less than 5 weight percent, or less than 1 weight percent, or less than 0.5 weight percent, or less than 0.25 weight percent, or less than 0.1 weight percent, or 0 weight percent of an organic solvent, based on the total weight of the base composition. Depending on the selection of the (A) silicate resin, the base composition can be formed in the absence of, or using, a solvent, such as an organic solvent. In certain embodiments, the (A) silicate resin is miscible with component (B), as described below, in which case a solvent is not required to form the base composition. In other embodiments, a solvent is utilized to aid in the miscibility of component (A) and component (B) and is then removed.

[0041] This composition further comprises an organopolysiloxane having on average at least two silicon-bonded ethylenically unsaturated groups per molecule of (B). In certain embodiments, the (B) 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 comprise a combination of different structures. The polyorganosiloxane has the 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 at least two of the R 4 in each molecule 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 as described above for R. The above average formula for the polyorganosiloxane can alternatively be (R 4 3SiO 1 / 2 ) b (R4 2SiO 2 / 2 ) c (R 4 SiO 3 / 2 ) d (SiO 4 / 2 ) e [In the formula, R 4 are defined above, and the subscripts b, c, d, and e each independently range from 0 to 1, inclusive, 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 above average formula. 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 branched polyorganosiloxane).

[0042] Alternatively, the (B) organopolysiloxane may be substantially linear or linear. A substantially linear organopolysiloxane has the average formula R 4 a’ SiO (4-a’) / 2 [In the formula, each R 4 is as defined above, and the subscript a' is selected so that 1.9≦a'≦2.2.

[0043] The substantially linear organopolysiloxane of component (B) can be a flowable liquid or can be in the form of an uncured rubber at 25°C. The substantially linear organopolysiloxane may have a viscosity at 25°C 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, alternatively 100 mPa·s to 100,000 mPa·s. Viscosity can 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).

[0044] Alternatively, when the (B) organopolysiloxane is substantially linear or linear, the (B) organopolysiloxane has the average unit formula (R 6 R 5 2SiO 1 / 2 ) aa (R 6 R 5 SiO 2 / 2 ) bb (R 6 2SiO 2 / 2 ) cc (R 5 3SiO 1 / 2 ) dd [In the formula, each R 5 are independently selected monovalent hydrocarbon radicals free of aliphatic unsaturation or monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, and each R 6are independently selected from the group consisting of alkenyl and alkynyl, and the subscript aa is 0, 1, or 2, the subscript bb is 0 or more, the subscript cc is 1 or more, and the subscript dd is 0, 1, or 2, with the proviso that the quantity (aa+dd) is 2 or more and the quantity (aa+dd)=2, and with the proviso that the quantity (aa+bb+cc+dd) is 3 to 2,000. Alternatively, the subscript cc is 0 or more. Alternatively, the subscript bb is 2 or more. Alternatively, the quantity (aa+dd) is 2 to 10, alternatively 2 to 8, alternatively 2 to 6. Alternatively, the subscript cc is 0 to 1,000, alternatively 1 to 500, alternatively 1 to 200. Alternatively, the subscript bb is 2 to 500, alternatively 2 to 200, alternatively 2 to 100.

[0045] R 5 The monovalent hydrocarbon group is exemplified by an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a halogenated aralkyl group having 7 to 12 carbon atoms, where the alkyl, aryl, and halogenated alkyl are as described herein. Alternatively, each R 5 is an alkyl group. Alternatively, each R 5 are independently methyl, ethyl, or propyl. 5 Each instance of R may be the same or different. 5 is a methyl group.

[0046] R 6 The monovalent hydrocarbon group having aliphatic unsaturation of R is capable of undergoing a hydrosilylation reaction. 6 Suitable aliphatic unsaturated hydrocarbon groups 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 6is a vinyl group. The alkenyl or alkynyl content of (B) organopolysiloxane can be 0.1 wt % to 1 wt %, alternatively 0.2 wt % to 0.5 wt %, based on the weight of (B) organopolysiloxane.

[0047] The (B) organopolysiloxane may be substantially linear, or if linear, the at least two aliphatically unsaturated groups may be bonded to the silicon atom at pendant positions, terminal positions, or both pendant and terminal positions. Specific examples of (B) organopolysiloxanes having pendant silicon-bonded aliphatic unsaturated groups include those having the average unit formula: [(CH3)3SiO 1 / 2 ]2[(CH3)2SiO 2 / 2 ] cc [(CH3)ViSiO 2 / 2 ] bb where the subscripts bb and cc are as defined above, and Vi represents a vinyl group. With respect to this average formula, any methyl group may be replaced with a different monovalent hydrocarbon group (such as an alkyl or aryl), and any vinyl group 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, (B) organopolysiloxane may have the average formula Vi(CH3)2SiO[(CH3)2SiO] cc Si(CH3)2Vi, where the subscripts cc and Vi are defined above. Dimethylpolysiloxanes terminated with silicon-bonded vinyl groups can be used alone or in combination with the dimethyl, methyl-vinylpolysiloxanes immediately disclosed as (B) organopolysiloxane. With respect to this average formula, any methyl group can be replaced with a different monovalent hydrocarbon group, and any vinyl group can be replaced with any terminal aliphatically unsaturated monovalent hydrocarbon group. Because the at least two silicon-bonded aliphatically unsaturated groups can be both pendant and terminal, the (B) organopolysiloxane can instead have the average unit formula [Vi(CH3)2SiO 1 / 2]2[(CH3)2SiO 2 / 2 ] cc [(CH3)ViSiO 2 / 2 ] bb where the subscripts bb and cc and Vi are defined above.

[0048] When the organopolysiloxane (B) is a substantially linear polyorganosiloxane, the organopolysiloxane (B) may be selected from the group consisting of dimethylpolysiloxanes capped at both molecular ends with dimethylvinylsiloxy groups, methylphenylpolysiloxanes capped at both molecular ends with dimethylvinylsiloxy groups, copolymers of methylphenylsiloxanes and dimethylsiloxanes capped at both molecular ends with dimethylvinylsiloxy groups, copolymers of methylvinylsiloxanes and methylphenylsiloxanes capped at both molecular ends with dimethylvinylsiloxy groups, and methylvinylsiloxanes capped at both molecular ends with dimethylvinylsiloxy groups. copolymers of methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane, both of which are end-capped with dimethylvinylsiloxy groups; copolymers of methylvinylsiloxane and methylphenylsiloxane, both of which are end-capped with trimethylsiloxy groups; copolymers of methylvinylsiloxane and diphenylsiloxane, both of which are end-capped with trimethylsiloxy groups; and copolymers of methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane, both of which are end-capped with trimethylsiloxy groups.

[0049] Alternatively, the organopolysiloxane (B) 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 polydimethylsiloxane; x) dimethylhexenylsiloxy-terminated polydimethylsiloxane, xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane; xiii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xiv) Trimethylsiloxy-terminated polymethylhexenylsiloxane xv) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane) and xvii) It may include a substantially linear or linear polyorganosiloxane selected from the group consisting of combinations thereof.

[0050] Alternatively, (B) the organopolysiloxane may comprise a resinous polyorganosiloxane having an average formula R 4 a’’ SiO (4-a’’) / 2 [In the formula, each R 4 are independently selected as defined above, and the subscript a'' is selected such that 0.5≦a''≦1.7.

[0051] Resinous polyorganosiloxanes have a branched or three-dimensional network molecular structure. At 25°C, resinous polyorganosiloxanes may be in liquid or solid form. Alternatively, resinous polyorganosiloxanes can be exemplified by polyorganosiloxanes containing only T units, polyorganosiloxanes containing T units in combination with other siloxy units (e.g., M, D, and / or Q siloxy units), or polyorganosiloxanes containing 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.

[0052] Alternatively, (B) the organopolysiloxane may comprise a branched siloxane, a silsesquioxane, or both a branched siloxane and a silsesquioxane.

[0053] 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 amounts of the branched siloxane and the silsesquioxane total 100 parts by weight, based on the total weight of all components present in the composition. The branched siloxane may be present in an amount of 50 to 100 parts by weight, and the silsesquioxane may be present in an amount of 0 to 50 parts by weight. Alternatively, the branched siloxane may be present in an amount of 50 to 90 parts by weight, and the silsesquioxane may be present in an amount of 10 to 50 parts by weight. Alternatively, the branched siloxane may be present in an amount of 50 to 80 parts by weight, and the silsesquioxane may be present in an amount of 20 to 50 parts by weight. Alternatively, the branched siloxane may be present in an amount of 50 to 76 parts by weight and the silsesquioxane may be present in an amount of 24 to 50 parts by weight, or alternatively, the branched siloxane may be present in an amount of 50 to 70 parts by weight and the silsesquioxane may be present in an amount of 30 to 50 parts by weight.

[0054] (B) The branched siloxane of the organopolysiloxane has the unit formula (R 7 3SiO 1 / 2 ) p (R 8 R 7 2SiO 1 / 2 ) q (R 7 2SiO 2 / 2 ) r (SiO 4 / 2 ) s [In the formula, each R 7 are independently a monovalent hydrocarbon group free of aliphatic unsaturation or a monovalent halogenated hydrocarbon group free of aliphatic unsaturation, and each R 8 is an alkenyl or alkynyl group, both as defined above, and may have the subscript p≧0, the subscript q>0, 15≧r≧995, and the subscript s is >0.

[0055] In the above unit formula, subscript p is ≧0. Subscript q is >0. Alternatively, subscript q is ≧3. Subscript r is 15 to 995. Subscript s is >0. Alternatively, subscript s is ≧1. Alternatively, for subscript p, 22≧p≧0, or 20≧p≧0, or 15≧p≧0, or 10≧p≧0, or 5≧p≧0. Alternatively, for subscript q, 22≧q>0, or 22≧q≧4, or 20≧q>0, or 15≧q>1, or 10≧q≧2, or 15≧q≧4. Alternatively, for subscript r, 800≧r≧15, or 400≧r≧15. Alternatively, for subscript s, 10≧s>0, alternatively, 10≧s≧1, alternatively, 5≧s>0, alternatively, s=1. Alternatively, subscript s is 1 or 2. Alternatively, when subscript s=1, subscript p may be 0 and subscript q may be 4.

[0056] The branched siloxane is represented by the formula (R 7 2SiO 2 / 2 ) m wherein each subscript m is independently 2 to 100. Alternatively, the branched siloxane may comprise at least two polydiorganosiloxane chains of the formula (R 7 2SiO 2 / 2 ) o wherein each subscript o is independently 1 to 100; 4 / 2 Alternatively, the branched siloxane may comprise at least one unit of the formula [ka] wherein the subscript u is 0 or 1; each subscript t is independently 0 to 995, alternatively 15 to 995, alternatively 0 to 100; and each R 9 are independently selected monovalent hydrocarbon groups, as described above, and each R 7are independently selected monovalent hydrocarbon radicals free of aliphatic unsaturation or monovalent halogenated hydrocarbon radicals free of aliphatic unsaturation, and each R 8 and may each have the same meaning as defined above and be independently selected from the group consisting of alkenyl and alkynyl. Suitable branched siloxanes are exemplified by those disclosed in U.S. Pat. No. 6,806,339 and U.S. Patent Application Publication No. 2007 / 0289495.

[0057] In certain embodiments, 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 )[where each R 1 are independently selected hydrocarbyl groups free of ethylenic unsaturation, and each R 2 are independent, R 1 and an ethylenically unsaturated group, wherein subscript y is independently selected for each siloxy unit designated by subscript x and is 1 or 2, and wherein subscript x is 1.5 to 6 and subscript z is 3 to 1,000, respectively. Specific examples of hydrocarbyl groups that are free of ethylenic unsaturation and ethylenically unsaturated groups are described above for R.

[0058] Silsesquioxane has the unit formula (R 7 3SiO 1 / 2 ) i (R 8 R 7 2SiO 1 / 2 ) f (R 7 2SiO 2 / 2 ) g (R 7 SiO 3 / 2 ) h [In the formula, R 7 and R 8is as above, and may have subscript i≧0, subscript f>0, subscript g is 15-995, and subscript h>0. Subscript i may be 0-10. Alternatively, for subscript i, 12≧i≧0, or 10≧i≧0, or 7≧i≧0, or 5≧i≧0, or 3≧i≧0.

[0059] Alternatively, the subscript f is ≧1. Alternatively, the subscript f is ≧3. Alternatively, for subscript f, 12≧f>0, or 12≧f≧3, or 10≧f>0, or 7≧f>1, or 5≧f≧2, or 7≧f≧3. Alternatively, for subscript g, 800≧g≧15, or 400≧g≧15. Alternatively, the subscript h is ≧1. Alternatively, the subscript h is 1 to 10. Alternatively, for subscript h, 10≧h>0, or 5≧h>0, or h=1. Alternatively, the subscript h is 1 to 10, or the subscript h is 1 or 2. Alternatively, if subscript h=1, the subscript f may be 3 and the subscript i may be 0. The value of subscript f may be sufficient to provide the silsesquioxane of unit formula (ii-II) with an alkenyl content of from 0.1 wt. % to 1 wt. %, alternatively from 0.2 wt. % to 0.6 wt. %, based on the weight of the silsesquioxane. Suitable silsesquioxanes are exemplified by those disclosed in U.S. Pat. No. 4,374,967.

[0060] The (B) organopolysiloxane may comprise a combination or two or more different polyorganosiloxanes differing in at least one property, such as structure, molecular weight, content of monovalent groups bonded to silicon atoms, and aliphatic unsaturated groups. The composition may comprise the (B) organopolysiloxane in an amount of 60 to 99.5 weight percent, alternatively 60 to 98 weight percent, alternatively 60 to 95 weight percent, alternatively 70 to 95 weight percent, or alternatively 75 to 95 weight percent, based on the total weight of the composition.

[0061] In these or other embodiments, the base composition comprising or 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). Viscosity can be measured using a Brookfield LV DV-E viscometer with a spindle appropriately selected for the viscosity of the base composition. The above viscosity ranges are for the base composition without any solvent, such as an organic solvent.

[0062] In these or other embodiments, the same base composition has a weight average molecular weight of 500 to 500,000, alternatively 1,000 to 250,000, alternatively 10,000 to 150,000. Molecular weight may be measured via gel permeation chromatography (GPC) against polystyrene standards.

[0063] A method for preparing a base composition is also provided. The method includes combining (A) a silicate resin and (B) an organopolysiloxane to obtain the base composition. Typically, the (A) silicate resin is disposed in the (B) organopolysiloxane. However, components (A) and (B) can be combined in any manner and in any order of addition, optionally with stirring or other mixing. Because the (A) silicate resin is miscible with or miscible in the (B) organopolysiloxane, the method typically does not include any solvent.

[0064] 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, reacting with the ethylenically unsaturated groups of component (B), if present, of component (A), to form a coating, e.g., a release coating. Typically, the (C) organosilicon compound comprises an organohydrogensiloxane.

[0065] 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 can 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.

[0066] Since the (C) organosilicon compound contains an average of at least two silicon-bonded hydrogen atoms per molecule for the siloxy units described above, the (C) organosilicon compound contains the following siloxy units containing silicon-bonded hydrogen atoms: (R2H2SiO 1 / 2 ), (RH2SiO 1 / 2 ), (HSiO 1 / 2 ), (RHSiO 2 / 2 ), (H2SiO 2 / 2 ), and / or (HSiO 3 / 2 ) where R is independently selected and defined above, optionally in combination with siloxy units that do not contain any silicon-bonded hydrogen atoms.

[0067] In certain embodiments, the (C) organosilicon compound is a substantially linear or linear polyorganohydrogensiloxane. The substantially linear or linear polyorganohydrogensiloxane has the unit formula: (HR 10 2SiO 1 / 2 ) v’ (HR 10 SiO 2 / 2 ) w’ (R 10 2SiO 2 / 2 ) x’ (R 10 3SiO 1 / 2 ) y’ [In the formula, each R 10 are independently selected monovalent hydrocarbon radicals, wherein the subscript v' is 0, 1, or 2, the subscript w' is 1 or greater, the subscript x' is 0 or greater, and the subscript y' is 0, 1, or 2, provided that the quantity (v'+y')=2 and the quantity (v'+w')≧3. 10 The monovalent hydrocarbon groups of can be as described above for the monovalent hydrocarbon groups of R. The quantity (v'+w'+x'+y') can be from 2 to 1,000. The polyorganohydrogensiloxane can be i) dimethylhydrogensiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer; ii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane; iii) trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer; 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).

[0068] In one particular 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 (CH3)3SiO[(CH3)2SiO] x’ [(CH3)HSiO] w’ Si(CH3)3

[0023] The polysiloxane may be a dimethyl,methyl-hydrogenpolysiloxane having the formula:

[0024] 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 may be present in random or block form, and any methyl group may be replaced with any other hydrocarbon group that does not contain aliphatic unsaturation.

[0069] 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(CH3)2SiO[(CH3)2SiO] x’ Si(CH3)2H The organohydrogensiloxane may be a SiH-terminated dimethylpolysiloxane having the formula: [wherein x' is as defined above]. The SiH-terminated dimethylpolysiloxane may be used alone or in combination with the dimethyl, methylhydrogenpolysiloxane disclosed above. When a mixture is used, the relative amount of each organohydrogensiloxane in the mixture may vary. Those skilled in the art will understand that any methyl group in the above exemplary formula may be replaced with any other hydrocarbon group that does not contain aliphatic unsaturation.

[0070] Alternatively, the (C) organosilicon compound may contain both pendant and terminal silicon-bonded hydrogen atoms.

[0071] In yet another particular embodiment, the (C) organosilicon compound is of formula H y’ R 1 3-y’ Si-(OSiR 1 2) m -(OSiR 1 H)m’ -OSiR 1 3-y’ H y’ [In the formula, each R 1 are independently selected hydrocarbyl groups 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.

[0072] In certain embodiments, the (C) organosilicon compound can include an alkylhydrogencyclosiloxane or an alkylhydrogendialkylcyclosiloxane copolymer. Specific examples of suitable organohydrogensiloxanes of this type include (OSiMeH), (OSiMeH), (OSiMeCH), and the like. 13 ), (OSiMeH)2(OSiMeC6H 13 )2, and (OSiMeH)(OSiMeCH 13 )3 [wherein Me represents methyl (—CH3)].

[0073] Other examples of organohydrogensiloxanes suitable for (C) organosilicon compounds are those having at least two SiH-containing cyclosiloxane rings in one molecule. Such organohydrogensiloxanes may be any organopolysiloxane having at least two cyclosiloxane rings, each with at least one silicon-bonded hydrogen (SiH) atom on the ring. The cyclosiloxane rings contain at least three siloxy units (i.e., the minimum number required to form a siloxane ring) and may be any combination of M, D, T, and / or Q siloxy units forming a cyclic structure, provided that at least one of the cyclic siloxy units in each siloxane ring, which may be M, D, 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 substituent is methyl.

[0074] The (C) organosilicon compound may comprise a combination or two or more different organohydrogensiloxanes that differ 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 such that the molar ratio of silicon-bonded hydrogen atoms in component (C) to silicon-bonded ethylenically unsaturated groups in component (B) (and those in component (A), if present) is 1:1 to 5:1, or 1.1:1 to 3.1.

[0075] In certain embodiments, the release coating composition further comprises (D) a hydrosilylation catalyst. The (D) hydrosilylation catalyst is not limited and can be any known hydrosilylation catalyst for catalyzing a hydrosilylation reaction. Combinations of different hydrosilylation catalysts may also be utilized.

[0076] In certain embodiments, the (D) hydrosilylation reaction catalyst comprises a transition metal from Group VIII to Group XI. For Group VIII-Group XI transition metals, reference is made to the latest IUPAC nomenclature. Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs); Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals can be utilized as the (D) hydrosilylation reaction catalyst.

[0077] 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 can be utilized as (D) hydrosilylation reaction catalysts.

[0078] The (D) hydrosilylation catalyst may be in any suitable form. For example, the (D) hydrosilylation catalyst may be solid, and examples thereof include platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, as well as nickel-based catalysts. Specific examples thereof 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 containing combinations of multiple metals. Further examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts.

[0079] The (D) hydrosilylation catalyst may be in or on a solid support. Examples of supports include activated carbon, silica, silica alumina, alumina, zeolites, and other inorganic powders / particles (e.g., sodium sulfate). The (D) hydrosilylation catalyst may also be placed in a vehicle, such as a solvent that solubilizes the (D) hydrosilylation catalyst, or a vehicle that simply carries but does not solubilize the (D) hydrosilylation catalyst. Such vehicles are known in the art.

[0080] In certain embodiments, (D) the hydrosilylation catalyst comprises platinum. In these embodiments, (D) the hydrosilylation catalyst is exemplified by compounds such as platinum black, chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid with monohydric alcohols, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, as well as platinum compounds microencapsulated in matrices or core-shell compounds. Microencapsulated hydrosilylation catalysts and methods for their preparation are also known in the art, as exemplified by U.S. Pat. Nos. 4,766,176 and 5,017,654, which are incorporated herein by reference in their entireties.

[0081] Platinum complexes with organopolysiloxanes suitable for use as (D) hydrosilylation catalysts include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. These complexes may be microencapsulated in a resin matrix. Alternatively, the (D) hydrosilylation catalyst may include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. The (D) hydrosilylation catalyst 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 mixing 0.015 moles of (COD)PtCl with 0.045 moles of COD and 0.0612 moles of HMeSiCl.

[0082] (D) The hydrosilylation catalyst may also, or instead, be a photoactivatable hydrosilylation catalyst, which may initiate curing via irradiation and / or heat. The photoactivatable hydrosilylation catalyst may be any hydrosilylation catalyst capable of catalyzing a hydrosilylation reaction, particularly when exposed to radiation having a wavelength of 150 to 800 nanometers (nm).

[0083] Specific examples of photoactivatable hydrosilylation catalysts suitable for (D) hydrosilylation catalyst include 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- Platinum(II) β-diketonate complexes such as platinum(II) 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 represents cyclopentadienyl; [Pt[CHNNNOCH], Pt[p-CN-CHNNNOCH 11 ]4, Pt[p-H3COC6H4NNNOC6H 11 ]4, Pt[p-CH3(CH2) x -C6H4NNNOCH3]4, 1,5-cyclooctadienePt[p-CN-C6H4NNNOC6H 11 ]2, 1,5-cyclooctadiene Pt[p-CH3O-C6H4NNNOCH3]2, [(C6H5)3P]3Rh[p-CN-C6H4NNNOC6H 11 ], and Pd[p-CH3(CH2) x triazene oxide-transition metal 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 4Typically, the photoactivatable hydrosilylation catalyst is a Pt(II) β-diketonate complex, and more typically, the catalyst is platinum(II) bis(2,4-pentanedioate).

[0084] (D) The hydrosilylation catalyst is present in the release coating composition in a catalytic amount, i.e., an amount or quantity sufficient to promote its cure under the desired conditions. The hydrosilylation catalyst can be a single hydrosilylation catalyst or a mixture comprising two or more different hydrosilylation catalysts.

[0085] The catalytic amount of (D) hydrosilylation catalyst can be >0.01 ppm to 10,000 ppm, alternatively >1,000 ppm to 5,000 ppm. Alternatively, typical catalytic amounts of (D) hydrosilylation catalyst are 0.1 ppm to 5,000 ppm, alternatively 1 ppm to 2,000 ppm, alternatively >0 to 1,000 ppm. Alternatively, the catalytic amount of (D) hydrosilylation catalyst can 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.

[0086] The release coating composition may further comprise one or more of (E) an inhibitor, (F) an anchor additive, (G) an anti-fog agent, (H) a release modifier, and (I) a vehicle.

[0087] In certain embodiments, the release coating composition further comprises an (E) inhibitor, which can 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- ... Examples include methylvinylcyclosiloxanes, such as hexenylcyclotetrasiloxane, and combinations thereof; ene-yne ​​compounds, such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; triazoles such as benzotriazole; phosphines; mercaptans; hydrazines; amines, such as tetramethylethylenediamine; dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, maleates, such as diallyl maleate; nitriles; ethers; carbon monoxide; alkenes, such as cyclooctadiene and divinyltetramethyldisiloxane; alcohols, such as benzyl alcohol; and combinations thereof. Alternatively, the (E) inhibitor can be selected from the group consisting of acetylene alcohols (e.g., 1-ethynyl-1-cyclohexanol) and maleates (e.g., diallyl maleate, bismaleate, or n-propyl maleate), and combinations of two or more thereof.

[0088] 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 yellowing of the reaction product prepared from the hydrosilylation reaction of the release coating composition when compared to the reaction product from the hydrosilylation of a composition that does not contain the silylated acetylenic compound or that contains the organic acetylenic alcohol inhibitor described above.

[0089] The silylated acetylene compounds are (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3-methyl-1-butyn-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane, bis(3-methyl-1- cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, (cyclohexyl-1-ethyn-1-oxy)trifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-oxy)trimethylsilane, (3-phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, and combinations thereof. Alternatively, the (E) inhibitor is exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or a combination 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 a chlorosilane in the presence of an acid acceptor.

[0090] The amount of (E) inhibitor present in the release coating composition will depend on various 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) through (D). However, if present, the amount of (E) inhibitor can be from 0 to 1 weight percent, alternatively from 0 to 5 weight percent, alternatively from 0.001 to 1 weight percent, alternatively from 0.01 to 0.5 weight percent, alternatively from 0.0025 to 0.025 weight percent, based on the total weight of the release coating composition.

[0091] In certain embodiments, the release coating composition further comprises (F) an anchor additive. Suitable anchor additives are exemplified by the reaction product of a vinylalkoxysilane with an epoxy-functional alkoxysilane; the reaction product of a vinylalkoxysilane with an epoxy-functional alkoxysilane; and a combination (e.g., a physical blend and / or reaction product) of a polyorganosiloxane having at least one aliphatic unsaturated hydrocarbon group and at least one hydrolyzable group per molecule with an epoxy-functional alkoxysilane (e.g., a combination of a hydroxy-terminated vinyl-functional polydimethylsiloxane with glycidoxypropyltrimethoxysilane). Alternatively, the anchor additive may comprise a polyorganosilicate resin. Suitable anchor additives and methods for their preparation are disclosed, for example, in U.S. Pat. No. 9,562,149, U.S. Patent Application Publication Nos. 2003 / 0088042, 2004 / 0254274, and 2005 / 0038188, and European Patent No. 0 556 023.

[0092] Further examples of suitable anchor additives include transition metal chelates, hydrocarbonoxysilanes such as alkoxysilanes, combinations of alkoxysilanes with hydroxy-functional polyorganosiloxanes, or combinations thereof. (F) The 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) the anchor additive can include a partial condensate of such a silane, such as an organopolysiloxane with an adhesion-promoting group. Alternatively, (F) the anchor additive can include a combination of an alkoxysilane with a hydroxy-functional polyorganosiloxane.

[0093] 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. Epoxy-functional organic groups are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. Unsaturated organic groups are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, and undecylenyl. One specific example of an unsaturated compound is vinyltriacetoxysilane.

[0094] 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.

[0095] The (F) anchor additive may also include a reaction product or partial reaction product of one or more of these compounds. For example, in certain embodiments, the (F) anchor additive may include a reaction product or partial reaction product of vinyltriacetoxysilane and 3-glycidoxypropyltrimethoxysilane. Alternatively, or in addition, the (F) anchor additive may include an alkoxy- or alkenyl-functional siloxane.

[0096] Alternatively, the (F) anchor additive may comprise an epoxy-functional siloxane, such as the reaction product of a hydroxy-terminated polyorganosiloxane with the above-described epoxy-functional alkoxysilane, or a physical blend of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane. The (F) anchor additive may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the (F) anchor additive may be exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane with the reaction product of a hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinylsiloxane / dimethylsiloxane copolymer.

[0097] 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.

[0098] The specific amount of (F) anchor additive present in the release coating composition will depend on various factors, including the type of substrate and whether a primer, if any, is used. In certain embodiments, 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).

[0099] In certain embodiments, the composition further comprises (G) an anti-fog agent. The (G) anti-fog agent can be utilized in the release coating composition to reduce or inhibit silicone mist formation during the coating process, particularly when using high-speed coating equipment. The (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, the (G) anti-fog agent can comprise an MDQ resin, which may optionally contain two or more silicon-bonded ethylenically unsaturated groups.

[0100] The amount of (G) antifog agent utilized in the release coating composition will depend on various factors, including the amount and type of other starting materials selected for the release coating composition. However, the (G) antifog agent is typically utilized in an amount of 0 to 10 weight percent, alternatively 0.1 to 3 weight percent, based on the total weight of the release coating composition. This amount excludes the amount associated with component (A) and relates only to the (G) antifog agent, which is separate and distinct from component (A).

[0101] In certain embodiments, the release coating composition further comprises (H) a release modifier, which can be utilized in the release coating composition to control (reduce) the level of release force (adhesion between a 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 functions as a release modifier when the base composition is utilized to prepare a release coating. By adjusting the level or concentration of the (H) release modifier, a release coating having the necessary or desired release force can be formulated from a modifier-free composition. Examples of release modifiers suitable for component (H) include trimethylsiloxy-terminated dimethyl, phenylmethyl siloxanes. Alternatively, the (H) release modifier can 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 can 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).

[0102] 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.

[0103] Typically, (I) the vehicle, when present in the release coating composition, is an organic liquid. Organic liquids include those considered to be oils or solvents. Organic liquids include, but are 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 halogenated aromatics. Hydrocarbons include isododecane, isohexadecane, Isopar L (C11-C13), Isopar H (C11-C12), hydrogenated polydecene, 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 components of the (I) vehicle include fats, oils, fatty acids, and fatty alcohols.(I) The vehicle may also be a 1 to 1,000 mm at 25°C vehicle such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxanepentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any mixture thereof. 2 The organopolysiloxane may be a low viscosity organopolysiloxane or a volatile methyl siloxane or a volatile ethyl siloxane or a volatile methylethyl siloxane having a viscosity in the range of 1 / 2 s. / sec.

[0104] In certain embodiments, (I) the vehicle can be a polyalkylsiloxane, tetrahydrofuran, mineral spirits, naphtha, an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol, a ketone such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, an aromatic hydrocarbon such as benzene, toluene, or xylene, an aliphatic hydrocarbon such as heptane, hexane, or octane, a glycol ether 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 a combination thereof.

[0105] The amount of (I) vehicle depends on various factors, including the type of vehicle selected and 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. After the release coating composition is prepared, all or a portion of the (I) vehicle can be optionally removed, for example, before and / or simultaneously with preparing the release coating from the release coating composition. However, typically, the release coating composition does not include an (I) vehicle, and therefore, the release coating composition is a solvent-free release coating composition.

[0106] 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.

[0107] Alternatively, the release coating composition and the release coating formed therefrom may be free of particulates or may 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 anchor to the coating equipment used to form the release coating. Furthermore, if optical clarity 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.

[0108] In certain embodiments, the release coating composition does not contain a fluoroorganosilicone compound. It is believed that during curing, due to its low surface tension, the fluorocompound may rapidly migrate to the interface of the release coating composition or the release coating formed therewith, and to the substrate to which the release coating composition is applied and the release coating is formed, such as the composition / PET film interface. Such migration may prevent adhesion of the release coating (prepared by curing the release coating composition) to the substrate by creating a fluorine-containing barrier. By creating a barrier, the fluoroorganosilicone compound may prevent any of the components of the release coating composition from reacting at the interface, which may affect the cure and related properties. Furthermore, fluoroorganosilicone compounds are typically expensive.

[0109] The release coating composition can be prepared by combining components (A) through (D), and any optional components described above, in any order of addition, optionally using a masterbatch, and optionally under shear. In certain embodiments, the release coating composition is prepared by forming a base composition comprising or consisting 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 can be a one-part composition, a two-component or 2K composition, or a multi-part composition. For example, components (A) and (B) can be a single part of the release coating composition. As described below, when the release coating composition is utilized to prepare a release coating or coated substrate, components (A) and (B) are combined with components (C) and (D), and any optional components, such that the release coating composition is a curable composition. When the release coating composition further comprises components (C) and (D), the release coating composition can be referred to as a curable composition.

[0110] A method for preparing a coated substrate using 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, thereby forming a release coating on the substrate to obtain a coated substrate. Curing is carried out by heating at an elevated temperature, e.g., from 50°C to 180°C, alternatively from 50°C to 120°C, or alternatively from 50°C to 90°C, to obtain a coated substrate. One skilled in the art can select an appropriate temperature depending on various factors, including the components of the curable composition and the selection of materials for the substrate composition or structure.

[0111] The curable composition can be disposed or dispensed onto a substrate in any suitable manner. Typically, the curable composition is applied in wet form by a wet coating technique. The curable composition can 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, disposing the curable composition on a substrate results in 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.

[0112] The substrate is not limited and may be any substrate. The cured film may be separable from the substrate or may be physically and / or chemically bonded to the substrate, depending on the choice. The substrate may have an integrated hotplate or an integrated or stand-alone oven for curing the wet deposit. The substrate may optionally have continuous or discontinuous shapes, sizes, dimensions, surface roughness, and other properties. Alternatively, the substrate may have an elevated softening point temperature. However, the curable compositions and methods are not so limited.

[0113] Alternatively, the substrate may comprise a plastic, which may be thermoset and / or thermoplastic, although the substrate may alternatively be or comprise glass, metal, cellulose (e.g., paper), wood, cardboard, paperboard, silicone, or a polymeric material, or a combination thereof.

[0114] 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); and polyphenylene ether (polyphenylene ether (PPE); polyimide (PI); polyamideimide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyethernitrile (PEN); phenolic resin; phenoxy resin; cellulose such as triacetyl cellulose, diacetyl cellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene;Thermoplastic elastomers such as polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluoro-type elastomers; and copolymers and combinations thereof.

[0115] The curable composition, or wet deposit, is typically cured at elevated temperature for a period of time that is typically sufficient to effect cure, 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, or alternatively from greater than 0 to 2 minutes. The period of time will depend 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.

[0116] 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 can vary depending on the substrate selection, the selected temperature, and the line speed. As used herein, residence time refers to the time the curable composition or wet deposit is exposed to an elevated temperature. Residence time is distinct from cure time because there may be ongoing curing even after the curable composition, wet deposit, or partially cured reaction intermediate thereof is no longer exposed to the elevated temperature that typically initiates curing. Alternatively, the coated article can be prepared on a conveyor belt in an oven, and residence time can 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).

[0117] The time can be subdivided into cure iterations, 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.

[0118] 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 can be formed and exposed to a first elevated temperature for a first period of time to obtain a partially cured deposit. A second deposit can then be placed on the partially cured deposit and exposed to a second elevated temperature for a second period of time to obtain a second partially cured deposit. This partially cured deposit can also be further cured while exposed to the second elevated temperature for a second period of time. A third deposit can be placed on the second partially cured deposit and exposed to a third elevated temperature for a third period of time to obtain a third partially cured deposit. The second partially cured deposit can also be further cured while exposed to the second elevated temperature for a second period of time. This process can be repeated, for example, 1 to 50 times, to obtain the desired structure of the coated article. The composite of partially cured layers can then be subjected to a final post-cure, for example, at the elevated temperature and time described above. Each elevated temperature and time can be independently selected and can be the same or different from each other. When an article is formed via an iterative process, each deposit may be independently selected, and the components selected in the curable composition, their amounts, or both may vary. Alternatively, or even further, each repeating layer may be fully cured rather than only partially cured in such an iterative process.

[0119] Alternatively, the deposition may comprise a wet film. Alternatively, the iterative process may be wet-on-wet, depending on the state of cure of the partially cured layer. Alternatively, the iterative process may be wet-on-dry.

[0120] Coated substrates comprising a film formed from a curable composition on a substrate can have a variety of dimensions, including the relative thicknesses of the film and the substrate. The film has a thickness that can vary depending on the end use. The film may have a thickness of 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, or alternatively greater than 0 to 250 μm. However, other thicknesses, e.g., 0.1 to 200 μm, are also contemplated. For example, the film thickness may be 0.2 to 175 μm, alternatively 0.5 to 150 μm, alternatively 0.75 to 100 μm, alternatively 1 to 75 μm, alternatively 2 to 60 μm, alternatively 3 to 50 μm, or alternatively 4 to 40 μm. Alternatively, when the substrate is plastic, the film may have a thickness of from greater than 0 to 200 μm, alternatively from greater than 0 to 150 μm, alternatively from greater than 0 to 100 μm.

[0121] If desired, the film can undergo further processing depending on its end use. For example, the film can undergo oxide deposition (e.g., SiO 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 can 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 can be utilized after such further processing.

[0122] The coated substrates can be utilized in a variety of end uses. For example, the coated substrates can be utilized in coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, construction applications, transportation applications, electronics applications, or electrical applications. However, the curable compositions can be utilized for end uses other than preparing coated substrates, such as preparing articles such as silicone rubber.

[0123] Alternatively, the coated substrate can be utilized as a release liner for a tape or adhesive, including any pressure-sensitive adhesive, such as, for example, acrylic resin-type pressure-sensitive adhesives, rubber-type pressure-sensitive adhesives, and silicone-type pressure-sensitive adhesives, as well as acrylic resin-type adhesives, synthetic rubber-type adhesives, silicone-type adhesives, epoxy resin-type adhesives, and polyurethane-type adhesives. Each major surface of the substrate can have a film disposed thereon for a double-sided tape or adhesive.

[0124] 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 form 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 before 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 the release coating composition to a substrate, e.g., the surface of the substrate, and curing it.

[0125] For example, the multi-part curable composition may be (A) part, referred to as a base part, 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; The release coating composition includes (C) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule, and, optionally, (F) an anchor additive and / or (I) a curing agent part comprising a vehicle. If utilized, (E) an inhibitor may be added to part (A), part (B), or both. Parts (A) and (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. Parts (A) and (B) can be provided in a kit, along with instructions, for example, 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.

[0126] Alternatively, (F) anchor additive, if present, can be incorporated into either part (A) or part (B), or added to a separate (third) part.

[0127] The release coating composition can be applied to the substrate by any convenient means such as spraying, doctor blading, dipping, screen printing, or by a roll coater, for example, an offset web coater, kiss coater, or etched cylinder coater.

[0128] The release coating composition of the present invention can be applied to any substrate, such as those described 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 polyethylene-coated paper, glassine, supercalendered paper, or clay-coated kraft paper. Alternatively, the release coating composition can be applied to a metal foil substrate, such as aluminum foil.

[0129] In certain embodiments, the method for 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 can be carried out by any convenient means, such as plasma treatment or corona discharge treatment. Alternatively, the substrate can be treated by applying a primer. In certain examples, the anchorage of the release coating can be improved if the substrate is treated before forming the release coating on the substrate from the release coating composition.

[0130] If the release coating composition includes (I) a vehicle, the method can further include removing (I) the vehicle, which can be done by any conventional means, such as heating at 50°C to 100°C for a time sufficient to remove all or a portion of the (I) vehicle. The method can further include curing the release coating composition to form a release coating on the surface of the substrate. Curing can be done by any conventional means, such as heating at 100°C to 200°C.

[0131] Under production coater conditions, curing can be accomplished at air temperatures of 120° C. to 150° C. with dwell times of 1 to 6 seconds, or alternatively 1.5 to 3 seconds. Heating can be accomplished in an oven, such as an air circulating oven or tunnel furnace, or by passing the coated film around a heated cylinder.

[0132] 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 a description of the characterization and evaluation procedures also used in the examples. [Table 1] Nuclear Magnetic Resonance (NMR) spectroscopy

[0133] Nuclear magnetic resonance (NMR) spectra are obtained on an NMR BRUKER AVIII (400 MHz) using silicon-free 10 mm tubes and CDCl3 / Cr(AcAc)3 solvent. 29 Chemical shifts for Si-NMR spectra are referenced to internal solvent resonances and reported relative to tetramethylsilane. Gel Permeation Chromatography (GPC)

[0134] 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)

[0135] 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)

[0136] X-ray fluorescence (XRF) is performed on an Oxford Instruments Lab-X3500 benchtop XRF analyzer. SiOZ content

[0137] The SiOZ fraction content is 29 This can be calculated by Si-NMR. Specifically, the molar content of the following siloxy units in each (A) silicate resin is determined. W=R3SiO 1 / 2 X1=R2(OZ)SiO 1 / 2 X2=R2SiO 2 / 2 Y1=R(OZ)2SiO 1 / 2 Y2 = R(OZ)SiO 2 / 2 Y3=RSiO 3 / 2 Z1=(OZ)3SiO 1 / 2 Z2=(OZ)2SiO 1 / 2 Z3=(OZ)SiO 3 / 2 Z4=SiO 4 / 2 The OZ content relative to silicon atoms as mole % can be calculated using the following formula, where the label of each peak in the formula corresponds to the integrated area under the peak corresponding to that label:

number

[0138] The curing performance of the sample compositions is evaluated by determining the percent extractables value (% Extractables). Specifically, the sample compositions are coated and cured on a substrate (glassine paper) to form a coated substrate, which is then cut into three sample discs (die cutter, 1.375 inches (3.49 cm)) that are handled only with tweezers to minimize contamination and / or damage. Each sample disc is analyzed by XRF to determine the initial coating weight (W i s ) was determined and placed in individual bottles (100 mL, covered with lids) containing solvent (methyl isobutyl ketone, 40 mL) and allowed to soak on the lab bench for 30 minutes. Each sample disk was then removed from the bottle, placed coated side up on a clean surface (tissue paper), allowed to evaporate (without blotting / wiping) any residual solvent, and analyzed by XRF to determine the final coating weight (W f s The % extractables for each sample is the percentage change in coating weight from solvent immersion, i.e., calculated using the formula [(W i s -W f s ) / Wi x 100%). The % Extractables indicates the amount of uncured components (e.g., uncrosslinked silicone) of the sample composition that can be extracted from the coated substrate, e.g., a lower % Extractables indicates higher / better cure performance. Hardening performance: Anchor (ROR%)

[0139] The anchorage of the sample composition is evaluated via the anchorage index, i.e., by determining the percent 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 discs (die cutter, 1.375 inches (3.49 cm)), and each sample disc is analyzed by XRF to determine the initial coating weight (W i aEach sample disc is then abraded with a felt (1.9 kg) under load using an automated abrasion device in a manner similar to a Taber-type abrasion test (e.g., ASTM D4060-19, "Standard Test Method for Abrasion Resistance"), and subsequently analyzed by XRF to determine the final coating weight (W f a ) is determined. The ROR% of each sample is calculated using the formula [W f s / W i s ]×100%). ROR% indicates the strength of the coating's anchoring to the substrate, e.g., a higher ROR% indicates a stronger / better anchor, e.g., a higher ROR% indicates a better coating. Preparation Example 1: Silicate Resin (A1)

[0140] 800 g of solvent 1, followed by 600 g of MQ resin, were placed in a 2 L flask equipped with a magnetic stir bar. 367 grams of silane compound 1 and 0.80 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 by GC. After 6 hours, the contents of the flask were cooled to 23°C, and 1.2 grams of neutralizing agent were 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, viscous liquid. Silicate resin (A1) was isolated from the reaction product by removing volatiles using a rotary evaporator. Silicate resin (A1) was a colorless liquid with a DV of 834 cP at 25°C, a weight average molecular weight of 4,800, and a polydispersity of 1.75, each measured by GPC. The (A1) silicate resin had a SiOZ content of 50.8 mol % and a vinyl content of 8.80 wt %. Preparation Example 2: Silicate Resin (A2)

[0141] 200 g of solvent 1, followed by 300 g of MQ resin, were placed in a 2 L flask equipped with a magnetic stir bar. 12.2 grams of silane compound 1, 138.7 grams of silane compound 3, 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 by 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. Silicate resin (A2) was isolated from the reaction product by removing volatiles using a rotary evaporator. Silicate resin (A2) was a colorless liquid with a DV of 21,000 cP, a weight average molecular weight of 3,130, and a polydispersity of 1.39 at 25°C, each measured by GPC. (A2) The silicate resin had a SiOZ content of 25.0 mol % and a vinyl content of 1.00 wt %. Preparation Example 3: Silicate Resin (A3)

[0142] 200 g of solvent 1, followed by 300 g of MQ resin, were placed in a 2 L flask equipped with a magnetic stir bar. 31.1 grams of silane compound 1, 109.0 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 by 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. Silicate resin (A3) was isolated from the reaction product by removing volatiles using a rotary evaporator. Silicate resin (A3) was a colorless liquid with a DV of 459,600 cP, a weight average molecular weight of 5,148, and a polydispersity of 1.92 at 25°C, each measured by GPC. The (A3) silicate resin had a SiOZ content of 21.44 mol % and a vinyl content of 8.66 wt %. Preparation Example 4: Silicate Resin (A4)

[0143] 200 g of solvent 1, followed by 300 g of MQ resin, were placed in a 2 L flask equipped with a magnetic stir bar. 28.1 grams of silane compound 4, 109.0 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 by 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. Silicate resin (A4) was isolated from the reaction product by removing volatiles using a rotary evaporator. Silicate resin (A4) was a colorless liquid with a DV of 4,260 cP, a weight average molecular weight of 5,240, and a polydispersity of 1.92 at 25°C, each measured by GPC. (A4) The silicate resin had a SiOZ content of 20.80 mol % and a vinyl content of 6.82 wt %. Preparation Example 5: Silicate Resin Blend (A5)

[0144] 47.88 grams of silicate resin (A1) was dissolved in 26.67 grams of solvent 1 in a flask to obtain a solution. 21.29 grams of organopolysiloxane (B1) was then mixed with the solution using a rotary mixer to obtain a mixture. Solvent 1 was stripped from the mixture using a rotary evaporator at 150°C for 3 hours at 0-1 Torr to obtain the (A5) silicate resin blend. Thus, the (A5) silicate resin blend is solvent-free but is formed in the presence of a solvent. Examples 1 to 5:

[0145] Examples 1-5 are release coating compositions containing the silicate resins prepared in Preparative Examples 2-5. In Examples 3-5, a specific silicate resin is combined with an organopolysiloxane (B1) to obtain a base composition, and each specific base composition is combined with an inhibitor 1, an organosilicon compound (C1), and a catalyst (D1) to obtain a release coating composition. Each release coating composition in Examples 3-5 is solventless and prepared in the absence of any solvent because the silicate resin is miscible with the organopolysiloxane (B1). However, as described in Preparative Example 5 above, because the silicate resin (A1) was not completely miscible in the organopolysiloxane (B1), an (A5) silicate resin blend was formed in the presence of a solvent that was subsequently removed, and the (A5) silicate resin blend was combined with the other components of the release coating compositions of Examples 1 and 2. The SiH:SiVi molar ratio in each of Examples 1-5 was 2:1 mol:mol, and the total Pt content in each of Examples 1-5 was 100 ppm. Table 2 below shows the relative amounts of each component in grams utilized to prepare the release coating compositions of Examples 1-5. [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 mol:mol, and the total Pt content in 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 6 to 10 and Comparative Examples 10 to 18: Coated substrate

[0147] Coated substrates were prepared using the release coating compositions of Examples 1-5 and Comparative Examples 1-9. Specifically, each composition was 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. The samples were then evaluated for immediate extractables, immediate ROR, 7-day room temperature aged ROR, and 1-month room temperature aged ROR. The 7-day room temperature aged ROR and 1-month room temperature aged ROR were measured after aging at room temperature for the designated time period at 40 pounds and 50% relative humidity. The results are listed in Tables 4 and 5 below. In Tables 4 and 5, "n / a" indicates that the value was not measured. Example 6 utilized the composition of Example 1, Example 7 utilized the composition of Example 2, Example 8 utilized the composition of Example 3, and so on. The same applies to the correlation between Comparative Examples 10-18 and the compositions of Comparative Examples 1-9. [Table 4] [Table 5]

[0148] Peel force, 7-day aged peel force, and 1-month aged 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), using a 180-degree peel. Peel force was measured using an SP-2100 and ZPE-1100W peel test system after laminating Tesa 7475 standard tape at 40 lbs, room temperature, and 50% relative humidity. Aged peel force was measured by aging at 40 lbs, room temperature, and 50% relative humidity for the specified time. The values ​​are listed in Tables 6-8 below. In Tables 6-8, TH indicates the peel force was too high to measure, and n / a indicates that a measurement was not performed. [Table 6] [Table 7] [Table 8] Definitions and Use of Terms

[0149] The abbreviations used herein have the definitions in Table 9 below. [Table 9]

[0150] It is to be understood that the appended claims are not limited to the specific compounds, compositions, or methods described therein for purposes of describing the Detailed Description of the Invention, and that variations may occur among specific embodiments within the scope of the appended claims.

Claims

1. 1. A base composition for forming a release coating composition, comprising: (A) a silicate resin that is liquid at 25°C in the absence of any solvent and that contains an average of 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 silicate resin (A) has the following average formula: [W] ａ [X] ｂ [Y] ｃ [Z] ｄ wherein 0<a≦0.5, 0≦b<0.4, 0<c≦0.5, and 0.35≦d≦0.6, with the proviso that a+b+c+d=1; [W] is [R ３ SiO1 / 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’’ wherein 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; [Y] is [RSi(OZ) ｃ’ O ３－ｃ’／２ wherein each R is independently selected and defined above, each Z is independently selected and defined above, and c′ is an integer from 0 to 2, and each siloxy unit designated by subscript c in said (A) silicate resin is independently selected; [Z] is [Si(OZ) ｄ’ O ４－ｄ’／２ wherein each Z is independently selected and defined above, and subscript d' is an integer from 0 to 3, and each siloxy unit designated by subscript d in said (A) silicate resin is independently selected; provided that at least one of R is an ethylenically unsaturated group, A base composition wherein component (A) has 12 to 80 mole percent SiOZ moieties, where Z is independently selected from H, an alkyl group, or a cation, based on the total number of moles of Si in each molecule.

2. 2. The base composition of claim 1, wherein subscript a is from 0.15 to 0.40, subscript b is from 0 to 0.40, subscript c is from greater than 0 to 0.40, and subscript d is from 0.40 to 0.

60.

3. 3. The base composition of claim 1 or 2, wherein component (A) has from greater than 0 to 10 weight percent silicon-bonded ethylenically unsaturated groups, based on the total weight of component (A).

4. A release coating composition comprising: A base composition according to any one of claims 1 to 3; (C) an organosilicon compound having at least two silicon-bonded hydrogen atoms; and (D) a hydrosilylation catalyst; and and optionally, (E) an inhibitor.

5. the (C) organosilicon compound has 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 is an independently selected monovalent hydrocarbon radical, 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, with the proviso that the quantity (v'+y')=2 and the quantity (v'+w')≧3; The monovalent hydrocarbon group of R 10 can be a hydrocarbyl group; The release coating composition of claim 4, wherein the quantity (v'+w'+x'+y') can be from 2 to 1,000.

6. 6. A method for preparing the release coating composition of claim 4 or 5, comprising: combining component (A) and component (B) to obtain a base composition; combining said base composition with components (C) and (D) to obtain said release coating composition.

7. combining component (A) and a vehicle to obtain a first mixture; combining the first mixture with component (B) to obtain a second mixture; removing the vehicle from the second mixture to obtain a siloxane mixture; 7. The method of claim 6, further comprising combining the siloxane mixture with component (C) and component (D) to provide the release coating composition.

8. 8. The method of claim 7, further comprising forming the (A) silicate resin from a solid silicate resin, wherein the (A) silicate resin is formed by reacting an MQ resin with a silane compound having at least two independently selected silicon-bonded alkoxy groups and at least one silicon-bonded ethylenically unsaturated group in the presence of a catalyst, and optionally in the presence of a solvent.

9. 1. A method of forming a coated substrate, comprising: applying the composition onto a substrate; and curing the composition to provide a release coating on the substrate, thereby forming the coated substrate; The method of claim 4 or 5, wherein the composition is a composition according to claim 4 or 5.

10. A coated substrate comprising a release coating disposed on a substrate formed according to the method of claim 9.

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