Composition for preparing a release coating

Abstract

A composition for forming a release coating is disclosed. The composition includes (A) an organopolysiloxane comprising the reaction product of (i) a silicone resin having a specific formula, (ii) a cyclic siloxane, and (iii) at least one of (A)(iii)(a) a branched organopolysiloxane having a specific formula or (A)(iii)(b) a terminator, in the presence of a polymerization catalyst. The composition further includes (B) an organopolysiloxane containing an average of at least two silicon-bonded ethylenically unsaturated groups per molecule.

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 / 942,681, filed December 2, 2019, the contents of which are incorporated herein by reference.

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

[0003] Silicone compositions are known in the art and are used in a great many industries and end uses.One such end use application is to form a release coating or release liner that can remove adhesive.For example, silicone 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 compositions are typically addition curable.

[0004] Conventional release liners are typically formed by addition reaction (or hydrosilylation) of organopolysiloxanes having unsaturated hydrocarbon groups with organohydrogenpolysiloxanes in the presence of a hydrosilylation reaction catalyst. In certain applications, release liners are formed at high speeds through a coating process. However, during such processes of preparing release liners, mist is often generated. It is desirable to minimize the formation of such mist without affecting the performance properties of the release liner. Summary of the Invention

[0005] A composition for forming a release coating is disclosed, the composition comprising: (i) Formula (R 1 y R 2 3-y SiO1 / 2 ) x (SiO 4 / 2 ) 1.0 (ZO 1 / 2 ) w [In the formula, each R 1 is independently selected from hydrocarbyl groups having 1 to 32 carbon atoms, and each R 2 is R 1 , an alkoxy group, and a hydroxyl group, Z is independently H or an alkyl group, y is an integer from 0 to 3, and in each siloxy unit denoted by subscript x, subscript z is 0.05 to 0.99, and subscript w is 0 to 3; (ii) Formula (R 1 2 SiO 2 / 2 ) n [In the formula, each R 1 is defined above, and n is an integer from 3 to 15; (iii)(A)(iii)(a) Formula (R 3 y’ R 1 3-y’ SiO 1 / 2 ) x’ (SiO 4 / 2 ) 1.0 (ZO 1 / 2 ) w’ [Each R 3 are independently an ethylenically unsaturated group, the subscript y′ is 1 or 2, and each R 1 is independently selected and defined above, each Z is independently selected and defined above, subscript x' is 1 to 4, and subscript w' is 0 to 3; or (A)(iii)(b) an organopolysiloxane comprising the reaction product, in the presence of a polymerization catalyst, with at least one of a terminating agent. The composition further comprises (B) an organopolysiloxane containing an average of at least two silicon-bonded ethylenically unsaturated groups per molecule.

[0006] Methods for preparing the compositions are also disclosed. Further disclosed are methods for preparing a coated substrate comprising a release coating disposed on a substrate, and coated substrates formed according to such methods.

DETAILED DESCRIPTION OF THE INVENTION

[0007] Compositions for forming a release coating are disclosed. The composition comprises (i) a silicone resin having the formula (R 1 y R 2 3-y SiO 1 / 2 ) x (SiO 4 / 2 ) 1.0 (ZO 1 / 2 ) w [wherein each R 1 is independently selected from hydrocarbyl groups having 1 to 32 carbon atoms, each R 2 is independently selected from R 1 , alkoxy groups, and hydroxyl groups, Z is independently H or an alkyl group, y is an integer from 0 to 3, is independently selected in each siloxy unit indicated by the subscript x, the subscript z is from 0.05 to 0.99, and the subscript w is from 0 to 3], and (ii) a cyclic siloxane having the formula (R 1 2 SiO 2 / 2 ) n [wherein each R 1 is as defined above and n is an integer from 3 to 15], and (iii)(A)(iii)(a) a compound having the formula (R 3 y’ R 1 3-y’ SiO 1 / 2 ) x’ (SiO 4 / 2 ) 1.0 (ZO 1 / 2 ) w’ [each R 3 is independently an ethylenically unsaturated group, the subscript y’ is 1 or 2, each R 1is independently selected and defined above, each Z is independently selected and defined above, subscript x' is 1 to 4, and subscript w' is 0 to 3; or (A)(iii)(b) an organopolysiloxane comprising the reaction product, in the presence of a polymerization catalyst, with at least one of a terminating agent.

[0008] (i) Silicone resins are sometimes called MQ resins, where M is (R 0 3 SiO 1 / 2 ) siloxy units, where Q is (SiO 4 / 2 ) siloxy unit, R 0 indicates 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. As is understood in the art, at least some of the silicon atoms in the Q siloxy units may contain SiOZ moieties (i.e., silicon-bonded hydroxyl or alkoxy groups). Such SiOZ moieties present in the Q siloxy units are designated ZOZ moieties, indicated by the subscript w. 1 / 2 It is recognized through the moiety that: (i) the silicone resin does not contain any D or T siloxy units which contain silicon-bonded organic groups.

[0009] (i) The average formula of silicone resin is (R 1 y R 2 3-y SiO 1 / 2 ) x (SiO 4 / 2 ) 1.0 (ZO 1 / 2 ) w and [M] x Typically, however, in the nomenclature used in the art, M siloxy units are trimethylsiloxy units, whereas (i) R siloxy units in silicone resins can be represented as 1 and R 2does not have to be a methyl group. In the (i) silicone resin, the subscript x indicates 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 x, the lower the crosslink density of the (i) silicone resin. The converse is also true, as the value of x decreases, the number of M siloxy units decreases, and therefore more Q siloxy units are reticulated without terminating M siloxy units. The fact that the formula for the (i) silicone resin normalizes the content of Q siloxy units to 1 does not mean that the (i) silicone resin contains only one Q unit. The (i) silicone resin contains multiple Q siloxy units clustered or bonded together. Furthermore, for purposes of this disclosure and the above average formula, siloxy units containing silicon-bonded hydroxyl groups that are not fully condensed or capped may be considered Q siloxy units (as long as the silicon atom containing the silicon-bonded hydroxyl group does not contain a silicon-carbon bond). Such silicon-bonded hydroxyl groups may condense to give Q siloxy units. Thus, as explained below, even after the (i) silicone resin has been bulked, the value of subscript x and the ratio of M to Q siloxy units remain the same after further condensation of any residual silicon-bonded hydroxyl groups present in the Q siloxy units. For example, the (i) silicone resin may, in certain embodiments, contain up to 10 weight percent, alternatively up to 8 weight percent, alternatively up to 6 weight percent, alternatively up to 5 weight percent, alternatively up to 4 weight percent, alternatively up to 3 weight percent, or alternatively up to 2 weight percent hydroxyl groups. Without considering any SiOZ content in the Q siloxy units, the (i) silicone resin may have an average formula of (R 1 y R 2 3-y SiO 1 / 2 ) x (SiO 4 / 2 ) 1.0 has.

[0010] In the (i) silicone resin, the subscript x is from 0.05 to 0.99, alternatively from 0.10 to 0.95, alternatively from 0.15 to 0.90, alternatively from 0.20 to 0.85, alternatively from 0.25 to 0.80, alternatively from 0.30 to 0.75. In certain embodiments, the subscript x is from 0.50 to 0.80, alternatively from 0.55 to 0.75, alternatively from 0.60 to 0.75, alternatively from 0.65 to 0.75, alternatively from 0.70 to 0.75. In other particular embodiments, the subscript x is from 0.05 to 0.85. In yet other particular embodiments, the subscript x is from 0.4 to 0.90, alternatively from 0.70 to 0.85. Thus, on a molar basis, there are more Q siloxy units than M siloxy units in the (i) silicone resin.

[0011] The subscript w is 0 to 3, alternatively 0 to 2, alternatively 0 to 1, alternatively 0 to 0.9, alternatively 0 to 0.8, alternatively 0 to 0.7, alternatively 0 to 0.6, alternatively 0 to 0.5, alternatively 0 to 0.4, alternatively 0 to 0.3, alternatively 0 to 0.2, alternatively 0 to 0.1, and (i) represents the SiOZ content of the silicone resin. The SiOZ content is SiOH (wherein Z is H or a silanol group) or silicon-bonded alkoxy (wherein Z is an alkyl group). For example, "(SiO 4 / 2 )(ZO 1 / 2 )" refers to a Q-type group with a silicon atom bonded to a "Z" group through a single oxygen. In NMR nomenclature, such "(SiO 4 / 2 )(ZO 1 / 2 )" moiety is still considered a Q siloxy unit. When Z is an alkyl group, the alkyl group is typically a C1-C8, alternatively a C1-C6, alternatively a C1-C4, alternatively a C1-C2, alternatively a C1 (i.e., methyl) alkyl group.

[0012] In general, R 1Suitable hydrocarbyl groups may be independently linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups, and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be independently monocyclic or polycyclic. Linear and branched hydrocarbyl groups may be independently saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, and the like, as well as derivatives, variants, and combinations thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, octenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the above-mentioned alkyl groups in which one or more hydrogen atoms are replaced with halogen atoms 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.

[0013] In certain embodiments, each R 1 are independently selected from alkyl groups having 1 to 32, alternatively 1 to 28, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 8, alternatively 1 to 4, alternatively 1 carbon atom, and ethylenically unsaturated groups (i.e., alkenyl and / or alkynyl groups) having 2 to 32, alternatively 2 to 28, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 16, alternatively 2 to 12, alternatively 2 to 8, alternatively 2 to 4, alternatively 2 carbon atoms. "Alkenyl" refers to a non-cyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples include vinyl, allyl, hexenyl, and octenyl groups. "Alkynyl" refers to a non-cyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples include ethynyl, propynyl, and butynyl groups. Various examples of ethylenically unsaturated groups include CH 2 =CH-, CH 2 =CHCH 2 -, CH 2 =CH(CH2 ) 4 -, CH 2 =CH(CH 2 ) 6 -, CH 2 =C(CH 3 )CH 2 -, H 2 C=C(CH 3 )-, H 2 C=C(CH 3 )-, H 2 C=C(CH 3 )CH 2 -, H 2 C=CHCH 2 CH 2 -, H 2 C=CHCH 2 CH 2 CH 2 -, HC≡C-, HC≡CCH 2 -, HC≡CCH(CH 3 )-, HC≡CC(CH 3 ) 2 - and HC≡CC(CH 3 ) 2 CH 2 Typically, R 1 is an ethylenically unsaturated group, the ethylenic unsaturation is 1 As is understood in the art, ethylenic unsaturation is sometimes referred to as aliphatic unsaturation.

[0014] At least one R 1 When R is an ethylenically unsaturated group, i.e., an alkenyl or alkynyl group, the (A) organopolysiloxane formed from the (i) silicone resin can participate in an addition reaction or a hydrosilylation reaction to provide a coating, such as a release coating, as described above. However, the (A) organopolysiloxane can also include each R 1 Even when is an alkyl group, (A) the organopolysiloxane offers the surprising advantage of not being functionalized or reactive, particularly with respect to anti-mist properties when forming release coatings.

[0015] In certain embodiments, (i) each R 1 are independently selected alkyl groups. In these embodiments, each R 1 is methyl and y is 3, (i) the silicone resin has the formula ((CH 3 ) 3 SiO 1 / 2 ) x (SiO 4 / 2 ) 1.0 (ZO 1 / 2 ) w In another embodiment, (i) at least one R 1 is an ethylenically unsaturated group. (i) At least one R 1 is a vinyl group (as an ethylenically unsaturated group), the remaining R 1 is a methyl group, and when subscript y is 0, (i) the silicone resin can include any combination of the following M siloxy units, so long as there is at least one M siloxy unit that includes a silicon-bonded vinyl group: ((CH 3 ) 3 SiO 1 / 2 ), ((CH 3 ) 2 (CH=CH 2 )SiO 1 / 2 ), ((CH 3 )(CH=CH 2 ) 2 SiO 1 / 2 ), and ((CH=CH 2 ) 3 SiO 1 / 2 Typically, (i) the silicone resin is R 1 at least one silicon-bonded alkenyl group, such as vinyl, as R 1 where the remainder is an alkyl group, e.g., a methyl group, (i) the silicone resin is ((CH 3 ) 3 SiO 1 / 2 ) and ((CH 3 ) 2 (CH=CH 2 )SiO 1 / 2It is understood that the above examples are merely illustrative and that any methyl group can be replaced with any other alkyl or even hydrocarbyl group, and any vinyl group can be replaced with any other alkenyl or ethylenically unsaturated group.

[0016] R 2 is R 1 , an alkoxy group, and a hydroxyl group. Typically, each R 2 is R 1 However, as is understood in the art, (i) the silicone resin may inherently contain some silicon-bonded hydroxyl and / or alkoxy groups resulting from the formation of the (i) silicone resin, which is typically obtained by cohydrolysis / condensation. Thus, R 2 One or more of may be an alkoxy group or a hydroxyl group, even though such alkoxy groups or hydroxyl groups are typically not (i) intentionally included in the silicone resin.

[0017] The subscript y is an integer from 0 to 3, alternatively from 1 to 3, alternatively from 2 to 3, alternatively from 3. Further, the subscript y is independently selected for each M siloxy unit represented by the subscript x. Thus, (i) a silicone resin can be, for example, (R 1 3 SiO 1 / 2 ), if y is 2, then (R 1 2 R 2 SiO 1 / 2 Typically, (i) a majority of all M siloxy units in the silicone resin, i.e., at least 50 mol%, alternatively at least 60 mol%, alternatively at least 70 mol%, alternatively at least 80 mol%, alternatively at least 90 mol%, alternatively at least 95 mol%, are represented by the formula (R 1 3 SiO 1 / 2(i) All of the M siloxy units in the silicone resin are grouped together by means of the subscript x defined above.

[0018] By way of example only, (i) exemplary species of silicone resin include [(CH 3 ) 3 SiO 1 / 2 ] 0.7 [SiO 4 / 2 ] and [(CH 3 ) 2 (CH=CH 2 )SiO 1 / 2 ] 0.7 [SiO 4 / 2 Another exemplary species is [(CH 3 ) 3 SiO 1 / 2 ] and [(CH 3 ) 2 (CH=CH 2 )SiO 1 / 2 ] units, and the total number of moles of M siloxy units is less than the number of moles of Q siloxy units.

[0019] (i) a silicone resin, (ii) a compound represented by the formula (R 1 2 SiO 2 / 2 ) n [In the formula, R 1 is defined above, and n is an integer from 3 to 15, to produce (A) an organopolysiloxane. In the cyclic siloxane, each R 1 are typically independently selected alkyl groups, and most typically, each R 1 is a methyl group. 1 is a methyl group, the (ii) cyclic siloxane may be referred to based on n. For example, if n is 3, the (ii) cyclic siloxane is referred to as D3, if n is 4, the (ii) cyclic siloxane is referred to as D4, etc. If n is 5, the (ii) cyclic siloxane is referred to as D5, etc. However, in other embodiments, at least one R of the (ii) cyclic siloxane may be referred to as D6. 1is a silicon-bonded ethylenically unsaturated group, i.e., a silicon-bonded alkenyl or alkynyl group. For example, (ii) at least one R of the cyclic siloxane is 1 When is a silicon-bonded ethylenically unsaturated group, (ii) the cyclic siloxane can include, for example, methylvinylsiloxy units, or divinylsiloxy units. (ii) Each D siloxy unit of the cyclic siloxane is independently selected such that methylvinylsiloxy units can be present in combination with dimethylsiloxy units.

[0020] The subscript n is 3 to 15, alternatively 3 to 12, alternatively 3 to 10, alternatively 3 to 8, alternatively 3 to 6, alternatively 4 to 5. Additionally, the (ii) cyclic siloxane may include a blend of different cyclic siloxanes, such as a blend of n=4 and n=5. In certain embodiments, the (ii) cyclic siloxane is selected from the group of cyclotrisiloxane, cyclotetrasiloxanes such as octamethylcyclotetrasiloxane, cyclopentasiloxanes such as decamethylcyclopentasiloxane, cyclohexasiloxane, and combinations thereof. For illustrative purposes only, the chemical structures of decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane are shown below. [ka] (ii) The cyclic siloxane typically has a molecular weight from 100 to 750 g / mol, alternatively from 150 to 500 g / mol, alternatively from 275 to 375 g / mol.

[0021] In certain embodiments, (A) the organopolysiloxane is the reaction product of (i) a silicone resin, (ii) a cyclic siloxane, and (A)(iii)(a) a branched organopolysiloxane. The (A)(iii)(a) branched organopolysiloxane has the formula (R 3 y’ R 1 3-y’ SiO 1 / 2 ) x’ (SiO 4 / 2 ) 1.0 (ZO 1 / 2) w’ [Each R 3 are independently an ethylenically unsaturated group, the subscript y′ is 1 or 2, and each R 1 is independently selected and defined above, each Z is independently selected and defined above, subscript x' is 1 to 4, and subscript w' is 0 to 3. Suitable ethylenically unsaturated groups include R 1 Regarding R 3 It is.

[0022] Similar to the (i) silicone resins, the (A)(iii)(a) branched organopolysiloxanes can be referred to as MQ resins. However, unlike the (i) silicone resins, x', which represents the ratio of M siloxy units to Q siloxy units, is greater than 1. In the (A)(iii)(a) branched organopolysiloxanes, x' is 1 to 4, alternatively 1 to 3.5, alternatively 1 to 3, alternatively 1 to 2.5, alternatively 1 to 2. In other embodiments, x' is 1 to 4, alternatively 1.5 to 3, alternatively 1.5 to 2.5, alternatively 1.75 to 2.25. The subscript w' is 0 to 3, alternatively 0 to 2, alternatively 0 to 1, alternatively 0 to 0.9, alternatively 0 to 0.8, alternatively 0 to 0.7, alternatively 0 to 0.6, alternatively 0 to 0.5, alternatively 0 to 0.4, alternatively 0 to 0.3, alternatively 0 to 0.2, alternatively 0 to 0.1.

[0023] In certain embodiments, y' is 1. Subscript y' is independently selected in each M siloxy unit denoted by subscript x'. Thus, (A)(iii)(a) branched organopolysiloxane comprises R 3 is vinyl and R 1is methyl, it can contain, for example, vinyldimethylsiloxy units and methyldivinylsiloxy units (M siloxy units where y' is 1 and the other corresponding M siloxy units where y' is 2). As is understood in the art, the (A)(iii)(a) branched organopolysiloxane can contain some minor amounts of silicon-bonded hydroxyl and / or silicon-bonded alkoxy groups, even if the average unit formula of the (A)(iii)(a) branched organopolysiloxane is not explicitly recited on the basis of any minor amounts.

[0024] In certain embodiments, (A) the organopolysiloxane is the reaction product of (i) a silicone resin, (ii) a cyclic siloxane, and (A)(iii)(b) a terminating agent. The (A)(iii)(b) terminating agent can be any terminating agent for capping any residual silicon-bonded hydroxyl groups in the (i) silicone resin. The (A)(iii)(b) terminating agent can be, for example, a silane, a siloxane, or a silazane.

[0025] For example, in certain embodiments, the terminator has the general formula R 1 3 SiX[Each R 1 are independently selected and defined above, and X is a hydrolyzable group, such as OH, a carboxy group, a halogen atom, etc. When X is a halogen atom, X can be selected from F, Cl, Br, I, and At, or from F, Cl, and Br, or from F and Cl. In various embodiments, X is Cl. In certain embodiments, each R 1 are independently selected and are defined above.

[0026] R 1 Depending on the selection of and X, the terminating agent may be exemplified by trimethylchlorosilane, dimethylethylchlorosilane, trimethylfluorosilane, methyldipropylchlorosilane, dimethylphenylchlorosilane, etc. Combinations of different triorganohalosilanes may be utilized together as terminating agents.

[0027] Other specific examples of silane or silazane terminating agents are trimethylmethoxysilane, hexamethyldisiloxane, diphenylmethylmethoxysilane, dimethylphenylmethoxysilane, diphenylmethylcorosilane, dimethylphenylchlorosilane, hexamethyldisilazane, tetramethyldivinyldisiloxane, and hydrolyzates thereof. One specific example of a siloxane suitable for the (A)(iii)(b) terminating agent is trimethyl endblocked polydimethylsiloxane.

[0028] In certain embodiments, the (A)(iii)(b) terminating agent has the formula R 3 y’ R 1 3-y’ Si-O-(SiR 1 2 O) m -SiR 3 y’ R 1 3-y’ [In the formula, R 3 and R 1 are independently selected and defined above, y' is defined above, and m is an integer from 0 to 250. In certain embodiments, m is 0 to 250, alternatively 0 to 225, alternatively 0 to 200, alternatively 0 to 175, alternatively 0 to 150, alternatively 0 to 125, alternatively 0 to 100, alternatively 0 to 75, alternatively 0 to 50, alternatively 0 to 25, alternatively 0 to 20, alternatively 0 to 15, alternatively 0 to 10, alternatively 0 to 5, alternatively 0 or 1, or alternatively 0. For example, when m is 0 and each y' is 1, R 1 is methyl and R 3 When is vinyl, the (A)(iii)(b) terminating agent is divinyltetramethyldisiloxane. In other embodiments, m is from 0 to 250, alternatively from 25 to 225, alternatively from 50 to 200, alternatively from 100 to 200.

[0029] In another embodiment, (A) the organopolysiloxane is the reaction product of (i) a silicone resin, (ii) a cyclic siloxane, (A)(iii)(a) a branched organopolysiloxane, and (A)(iii)(b) a terminating agent.

[0030] (i) silicone resin, (ii) cyclic siloxane, (A)(iii) branched organopolysiloxane and / or (A)(iii)(b) at least one of the terminators are reacted in the presence of a polymerization catalyst. Typically, the polymerization catalyst is an acid or a base, so that the reaction is either an acid-catalyzed reaction or a base-catalyzed reaction. Thus, in certain embodiments, the polymerization catalyst can be selected from the group of strong acid catalysts, strong base catalysts, and combinations thereof. The strong acid catalyst can be trifluoromethanesulfonic acid, etc. The polymerization catalyst is typically a strong base catalyst. Typically, the strong base catalyst is a phosphazene catalyst, but other strong base catalysts, such as KOH, can be used instead of the phosphazene base catalyst.

[0031] Phosphazene catalysts generally contain at least one -(N=P<)- unit (i.e., phosphazene unit) and are usually oligomers having up to 10 such phosphazene units, e.g., an average of 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, especially ionic derivatives of phosphonitrile halides such as perchlorooligophosphazenium salts, or partially hydrolyzed forms thereof.

[0032] In certain embodiments, the polymerization 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 4 2 N) 3 P=N) t (R 4 2 N) 3-t P=NR 4 [In the formula, each R 4 is a hydrogen atom, R 1 and combinations thereof, and t is an integer from 1 to 3. 4 R1 If R 4 is typically an alkyl group having 1 to 20, alternatively 1 to 10, alternatively 1 to 4 carbon atoms. 4 2 N) Two R 4 The groups can be attached to the same nitrogen (N) atom and linked to complete a heterocyclic ring, preferably having 5 or 6 members.

[0033] Alternatively, the phosphazene base catalyst can be a salt and has the following alternative chemical formula: [((R 4 2 N) 3 P=N) t (R 4 2 N) 3-t P=N(H)R 4 ] + [A - ], or [((R 4 2 N) 3 P=N) s (R 4 2 N) 4-s P] + [A - ] [In the formula, each R 4 are independently selected and defined above, subscript t is defined above, subscript s is an integer from 1 to 4, and [A] is an anion, typically selected from the group of fluoride, hydroxide, silanolate, alkoxide, carbonate, bicarbonate. In one embodiment, the phosphazene base is an aminophosphazenium hydroxide.

[0034] Reaction in the presence of a polymerization catalyst results in the ring-opening of the (ii) cyclic siloxanes and the incorporation of D siloxy units into the (A) branched organopolysiloxane. The relative amounts of (i) silicone resin, (ii) cyclic siloxane, (A)(iii)(a) branched organopolysiloxane, and / or (A)(iii)(b) terminating agent utilized are a function of the desired content of D siloxy units in the (A) organopolysiloxane, as well as the relative number of Q siloxy units, as described below. Although the (A) organopolysiloxane contains branches attributable to Q siloxy units and is not linear, the number of D siloxy units in the (A) organopolysiloxane may be referred to as the degree of polymerization (DP) of the (A) organopolysiloxane. Similarly, the selection of the (A)(iii)(a) branched organopolysiloxane and / or (A)(iii)(b) terminating agent utilized is a function of the desired structure of the (A) organopolysiloxane.

[0035] In certain embodiments, (i) silicone resin, (ii) cyclic siloxane, (A)(iii) branched organopolysiloxane and / or (A)(iii)(b) terminator are reacted in the presence of a solvent at elevated temperatures, for example, 125-175°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. Complexing agents, such as bis(trimethylsilyl) hydrogen phosphate, may be used after the reaction to inhibit the activity of the polymerization catalyst. Those skilled in the art may readily determine the catalytic amount of polymerization catalyst used, which is a function of its selection and reaction conditions. The solvent may be removed after the reaction via conventional methods.

[0036] (i) The silicone resin may be optionally body-modified before reacting (i) the silicone resin, (ii) the cyclic siloxane, (A)(iii)(a) the branched organopolysiloxane and / or (A)(iii)(b) the terminator. As understood in the art, bodying the silicone resin typically results in an increase in molecular weight through further condensation of residual silicon-bonded hydroxy groups that may be present in the silicone resin from its formation. Bodying the (i) silicone resin typically involves heating the (i) silicone resin at an elevated temperature while the (i) silicone resin is generally placed in a solvent. Suitable solvents are disclosed above. Bodying the (i) silicone resin results in water as a by-product from the condensation of silanol groups.

[0037] (A) Organopolysiloxane is represented by the formula (R 1 y R 2 3-y SiO 1 / 2 ) x (R 1 2 SiO 2 / 2 ) m (SiO 4 / 2 )(ZO 1 / 2 ) w [In the formula, each R 1 and R 2 are independently selected and defined as above, each Z is independently selected and defined as above, the subscripts y, x, and w are defined above, and the subscript m is 3 to 3,000. 1 2 SiO 2 / 2) units are formed from (ii) ring-opening and polymerization of cyclic siloxanes. Furthermore, when (A)(iii)(b) terminating agents are utilized and subscript m is 1 or greater, additional D units can be imparted to (A) organopolysiloxane from (A)(iii)(b) terminating agents. (A) organopolysiloxanes typically have the above formula, regardless of whether (A)(iii)(a) branched organopolysiloxanes and / or (A)(iii)(b) terminating agents are utilized in the reaction. The difference is related to the molar ratio of siloxy units in (A) organopolysiloxane. D siloxy units are inserted between a given M siloxy unit and a Q siloxy unit. The number of D siloxy units present between each particular Q and M siloxy unit of any given linear siloxane moiety can be different in each case. The above formula represents all the D units present in the (A) organopolysiloxane, regardless of their position in the (A) organopolysiloxane. Not all the Q siloxy units in the (A) organopolysiloxane can be bonded to D siloxy units. Instead, a significant number of Q siloxy units are typically clustered in the (A) organopolysiloxane. In certain embodiments, D siloxy units are not present between the Q siloxy units in the (A) organopolysiloxane, and D siloxy units are only present between the M siloxy units and the Q siloxy units. Thus, the (A) organopolysiloxane comprises a highly branched portion of Q siloxy units bonded together.

[0038] In certain embodiments, m is between 3 and 3,000, alternatively between 3 and 2,000, alternatively between 3 and 1,000, alternatively between 3 and 750, alternatively between 3 and 500, alternatively between 50 and 500, alternatively between 100 and 500, alternatively between 110 and 475, alternatively between 120 and 450, alternatively between 130 and 425, alternatively between 140 and 400, alternatively between 150 and 375, alternatively between 160 and 350, alternatively between 170 and 325, alternatively between 180 and 300, alternatively between 190 and 275, alternatively between 200 and 250.

[0039] (A) One exemplary species of organopolysiloxane is [(CH 3 ) 3 SiO1 / 2 ] 0.38 [(CH 3 ) 2 (CH=CH 2 )SiO 1 / 2 ] 1.22 [(CH 3 ) 2 SiO 2 / 2 ] 181.93 [SiO 4 / 2 Another exemplary species of organopolysiloxane (A) is [(CH 3 ) 3 SiO 1 / 2 ] 0.69 [(CH 3 ) 2 (CH=CH 2 )SiO 1 / 2 ] 0.44 [(CH 3 ) 2 SiO 2 / 2 ] 228.83 [SiO 4 / 2 As understood in the art, each subscript in the above formula is not a mole fraction, but a molar ratio based on that particular siloxy unit versus the Q siloxy units. These species are merely exemplary, and the methyl groups of the M siloxy units can be replaced with other hydrocarbyl groups containing ethylenically unsaturated groups, the vinyl groups can be replaced with other ethylenically unsaturated groups, and the molar ratio of each particular siloxy unit can be modified or deviated from this exemplary species.

[0040] The composition comprises (A) organopolysiloxane in an amount from greater than 0 to 15 weight percent, alternatively from 0.5 to 10 weight percent, alternatively from 0.75 to 7 weight percent, alternatively from 1 to 4 weight percent, based on the total weight of the composition.

[0041] This composition further comprises (B) an organopolysiloxane having on average at least two silicon-bonded ethylenically unsaturated groups per molecule. In certain embodiments, (B) the organopolysiloxane has on average at least two silicon-bonded groups having terminal aliphatic unsaturation per molecule. This (B) organopolysiloxane can be linear, branched, partially branched, cyclic, resinous (i.e., having a three-dimensional network), or can include a combination of different structures. The polyorganosiloxane has the average formula R 1 a SiO (4-a) / 2 [wherein each R 1 is independently selected and defined as above, provided that in each molecule, at least two of the R 1 contain aliphatic unsaturation and the subscript a is selected such that 0 < a ≦ 3.2]. The above average formula for (B) the organopolysiloxane can alternatively be (R 1 3 SiO 1 / 2 ) b (R 1 2 SiO 2 / 2 ) c (R 1 SiO 3 / 2 ) d (SiO 4 / 2 ) e [wherein R 1 is defined as above and the subscripts b, c, d, and e are each independently ≧ 0 to ≦ 1, provided that the quantity (b + c + d + e) = 1]. One of ordinary skill in the art will understand how such M, D, T, and Q units, and their mole fractions, affect the subscript a in the above average formula. T units (represented by the subscript d), Q units (represented by the subscript e), or both are typically present in the organopolysiloxane resin, while the D units represented by the subscript c are typically present in the organopolysiloxane polymer (and can also be present in the organopolysiloxane resin or branched organopolysiloxane).

[0042] Alternatively, the (B) organopolysiloxane may be substantially linear or may be linear. The substantially linear organopolysiloxane has the average formula R 1 a’ SiO (4-a’) / 2 [In the formula, each R 1 is as defined above, and subscript a' is selected such that 1.9≦a'≦2.2.

[0043] The substantially linear organopolysiloxane of component (B) may be a flowable liquid or may have the form of an uncured rubber at 25° C. The substantially linear organopolysiloxane may have a viscosity of from 10 mPa·s to 30,000,000 mPa·s, alternatively from 10 mPa·s to 10,000 mPa·s, alternatively from 100 mPa·s to 1,000,000 mPa·s, alternatively from 100 mPa·s to 100,000 mPa·s, at 25° C. Viscosity may be measured at 25° C. via a Brookfield LV DV-E viscometer equipped with a spindle appropriately selected for the viscosity of the substantially linear polyorganopolysiloxane, i.e., RV-1 to RV-7.

[0044] Alternatively, when the (B) organopolysiloxane is substantially linear or linear, the (B) organopolysiloxane has the average unit formula (R 6 R 5 2 SiO 1 / 2 ) aa (R 6 R 5 SiO 2 / 2 ) bb (R 6 2 SiO 2 / 2 ) cc (R 5 3 SiO 1 / 2 ) dd [In the formula, each R 5 is an independently selected monovalent hydrocarbon radical free of aliphatic unsaturation, or a monovalent halogenated hydrocarbon radical free of aliphatic unsaturation, and each R 6are independently selected from the group consisting of alkenyl and alkynyl, 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, 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. Alternatively, the subscript bb is ≥ 2. 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 of 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. 5 is an alkyl group. Alternatively, each R 5 is independently methyl, ethyl, or propyl. 5 Each instance of R may be the same or different. 5 is a methyl group.

[0046] R 6 The aliphatically unsaturated monovalent hydrocarbon group of R is capable of undergoing a hydrosilylation reaction. 6 Suitable aliphatically unsaturated hydrocarbon groups for are as defined herein and 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 may be from 0.1 weight percent to 1 weight percent, alternatively from 0.2 weight percent to 0.5 weight percent, based on the weight of (B) organopolysiloxane.

[0047] The (B) organopolysiloxane is substantially linear, or if linear, the at least two aliphatically unsaturated groups may be bonded to the silicon atoms at pendant positions, terminal positions, or both pendant and terminal positions. As a specific example of the (B) organopolysiloxane having pendant silicon-bonded aliphatically unsaturated groups, the (B) organopolysiloxane may be of the average unit formula [(CH 3 ) 3 SiO 1 / 2 ] 2 [(CH 3 ) 2 SiO 2 / 2 ] cc [(CH 3 )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 of the methyl groups may be replaced with a different monovalent hydrocarbon group, such as an alkyl or aryl, and any of the vinyl groups may be replaced with a different aliphatically unsaturated monovalent hydrocarbon group, such as an allyl or hexenyl. Alternatively, as a specific example of a polyorganosiloxane having an average of at least two silicon-bonded aliphatically unsaturated groups per molecule, the (B) organopolysiloxane may have the average formula Vi(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] cc Si(CH 3 ) 2Vi, where the subscripts cc and Vi are defined above. Dimethylpolysiloxanes terminated with silicon-bonded vinyl groups may be used alone or in combination with the dimethyl,methyl-vinylpolysiloxanes disclosed immediately above as (B) organopolysiloxane. With respect to this average formula, any of the methyl groups may be replaced with a different monovalent hydrocarbon group, and any of the vinyl groups may be replaced with any terminal aliphatically unsaturated monovalent hydrocarbon group. Since the at least two silicon-bonded aliphatically unsaturated groups may be both pendant and terminal, the (B) organopolysiloxane may alternatively have the average unit formula [Vi(CH 3 ) 2 SiO 1 / 2 ] 2 [(CH 3 ) 2 SiO 2 / 2 ] cc [(CH 3 )ViSiO 2 / 2 ] bb where the subscripts bb and cc and Vi are defined above.

[0048] When the organopolysiloxane (B) is a substantially linear polyorganosiloxane, the organopolysiloxane (B) is, for example, a dimethylpolysiloxane capped at both molecular ends with dimethylvinylsiloxy groups, a methylphenylpolysiloxane capped at both molecular ends with dimethylvinylsiloxy groups, a copolymer of methylphenylsiloxane and dimethylsiloxane capped at both molecular ends with dimethylvinylsiloxy groups, a copolymer of methylvinylsiloxane and methylphenylsiloxane capped at both molecular ends with dimethylvinylsiloxy groups, a methylvinyl ... or a methylvinylsiloxane capped at both molecular ends with dimethylvinylsiloxy groups. Examples of the copolymers include copolymers of methylvinylsiloxane and diphenylsiloxane, 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 polydimethylsiloxanes; x) dimethylhexenylsiloxy-terminated polydimethylsiloxane, xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane, xiii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xiv) Trimethylsiloxy-terminated polymethylhexenylsiloxane xv) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane); xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane) and xvii) may include substantially linear, or linear polyorganosiloxanes 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 may 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 amount of the branched siloxane and the amount of the silsesquioxane combined totals 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. 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 3 SiO 1 / 2 ) p (R 8 R 7 2 SiO 1 / 2 ) q (R 7 2 SiO 2 / 2 ) r (SiO 4 / 2 ) s [In the formula, each R 7 are independently a monovalent hydrocarbon group containing no aliphatic unsaturation, or a monovalent halogenated hydrocarbon group containing no aliphatic unsaturation, and each R 8 is an alkenyl or alkynyl group, both 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 immediately preceding formula, subscript p>0. Subscript q>0. Or, subscript q>3. Subscript r is 15-995. Subscript s>0. Or, subscript s>1. Or, for subscript p, 22>p>0, or 20>p>0, or 15>p>0, or 10>p>0, or 5>p>0. Or, 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. Or, 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 has at least two groups of the formula (R 7 2 SiO 2 / 2 ) m wherein each subscript m is independently 2 to 100. Alternatively, the branched siloxane may comprise a polydiorganosiloxane chain of the formula (R 7 2 SiO 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 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 radicals, 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 each may have an independently selected group consisting of alkenyl and alkynyl, as described above. Suitable branched siloxanes are exemplified by those disclosed in U.S. Patent No. 6,806,339 and U.S. Patent Application Publication No. 2007 / 0289495.

[0057] Silsesquioxanes have the unit formula (R 7 3 SiO 1 / 2 ) i (R 8 R 7 2 SiO 1 / 2 ) f (R 7 2 SiO 2 / 2 ) g (R 7 SiO 3 / 2 ) h [In the formula, R 7 and R 8 is as above, with subscript i≧0, subscript f>0, subscript g is 15 to 995, and subscript h>0. Subscript i may be 0 to 10. Alternatively, for subscript i, 12≧i≧0, alternatively 10≧i≧0, alternatively 7≧i≧0, alternatively 5≧i≧0, or alternatively 3≧i≧0.

[0058] Alternatively, the subscript f is ≧1. Alternatively, the subscript f is ≧3. Alternatively, for the subscript f, 12≧f>0, alternatively 12≧f≧3, alternatively 10≧f>0, alternatively 7≧p>1, alternatively 5≧f≧2, alternatively 7≧f≧3. Alternatively, for the subscript g, 800≧g≧15, alternatively 400≧g≧15. Alternatively, the subscript h is ≧1. Alternatively, the subscript h is 1 to 10. Alternatively, for the subscript h, 10≧h>0, alternatively 5≧h>0, alternatively h=1. Alternatively, the subscript h is 1 to 10, alternatively the subscript h is 1 or 2. Alternatively, when the subscript h=1, the subscript f may be 3 and the subscript i may be 0. The value of subscript f may be sufficient for the silsesquioxane of formula (ii-II) to have an alkenyl content of from 0.1% to 1%, alternatively from 0.2% to 0.6%, by weight, based on the weight of the silsesquioxane. Suitable silsesquioxanes are exemplified by those disclosed in U.S. Pat. No. 4,374,967.

[0059] (B) The organopolysiloxane has the formula (R 3 y R 1 3-y SiO 1 / 2 ) x’ (R 1 2 SiO 2 / 2 ) z’ (SiO 4 / 2 ) 1.0 (ZO 1 / 2 ) w [In the formula, each R 3 is an independently selected ethylenically unsaturated group, the subscript y is independently selected in each siloxy unit denoted by the subscript x, and each R 1 is independently selected and defined above, subscript x' is 1.5 to 4, Z is independently selected and defined above, subscript w is 0 to 3, and subscript z' is 3 to 1,000.

[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, monovalent groups bonded to silicon atoms, and content of aliphatically unsaturated groups, etc. 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, alternatively 75 to 95 weight percent, based on the total weight of the composition.

[0061] When the composition consists essentially of or consists of components (A) and (B), i.e., no catalyst or crosslinker is present, the composition may be referred to as a base composition. The base composition is typically combined with other components to obtain a composition that is curable, generally via hydrosilylation, and the composition may be cured to obtain a release coating. In other words, the base composition is typically combined with other components to provide a curable composition that may be used to form a release coating or liner. The curable composition may be referred to as a release composition or release coating composition.

[0062] In these or other embodiments, the base composition comprising the (A) organopolysiloxane and the (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 of (A):(B) by weight 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 via a Brookfield LV DV-E viscometer with a spindle appropriately selected for the viscosity of the base composition.

[0063] In these or other embodiments, the same base composition has a weight average molecular weight of 500 to 500,000, or 1,000 to 250,000, or 10,000 to 150,000. The molecular weight can be measured by gel permeation chromatography (GPC) against polystyrene standards.

[0064] In certain embodiments, the composition further comprises an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule of (C). The organosilicon compound of (C) can be linear, branched, partially branched, cyclic, resinous (i.e., having a three-dimensional network), or can comprise a combination of different structures. The organosilicon compound of (C) is typically a crosslinking agent that reacts with the ethylenically unsaturated groups of component (B) and, if present, the ethylenically unsaturated groups of component (A) to form a coating, for example, a release coating. Typically, the organosilicon compound of (C) comprises an organohydrogensiloxane.

[0065] The organosilicon compound of (C) can comprise any combination of M, D, T, and / or Q siloxy units as long as the organosilicon compound of (C) 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 organosilicon compound of (C) can be monomeric, polymeric, oligomeric, linear, branched, cyclic, and / or resinous depending on the choice of M, D, T, and / or Q units.

[0066] Since the organosilicon compound of (C) contains an average of at least two silicon-bonded hydrogen atoms per molecule with respect to the siloxy units described above, the organosilicon compound of (C) can optionally be combined with siloxy units that contain no silicon-bonded hydrogen atoms at all, with the following siloxy units containing silicon-bonded hydrogen atoms (R 1 2 HSiO 1 / 2 )、(R 1 H 2 SiO 1 / 2 )、(H 3 SiO1 / 2 ), (R 1 HSiO 2 / 2 ), (H 2 SiO 2 / 2 ), and / or (HSiO 3 / 2 )[where each R 1 are independently selected and defined above.

[0067] In certain embodiments, the (C) organosilicon compound is a substantially linear or linear polyorganohydrogensiloxane. The substantially linear or linear polyorganohydrogensiloxane is represented by the unit formula (HR 10 2 SiO 1 / 2 ) v’ (HR 10 SiO 2 / 2 ) w’ (R 10 2 SiO 2 / 2 ) z’ (R 10 3 SiO 1 / 2 ) y’ [In the formula, each R 10 are independently selected monovalent hydrocarbon radicals, subscript v' is 0, 1, or 2, subscript w' is 1 or greater, subscript z' 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. 10 The monovalent hydrocarbon group of R 1 The monovalent hydrocarbon group may be as described above. The quantity (v'+w'+z'+y') may be from 2 to 1,000. The polyorganohydrogensiloxane may be i) dimethylhydrogensiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymers; ii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane; iii) trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymers; iv) trimethylsiloxy-terminated polymethylhydrogensiloxane, and / or v) is exemplified by a combination of two or more of i), ii), iii), iv), and v).Suitable polyorganohydrogensiloxanes are commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

[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 (CH 3 ) 3 SiO[(CH 3 ) 2 SiO] z’ [(CH 3 )HSiO] w’ Si(CH 3 ) 3

[0033] The polysiloxane may be a dimethyl, methyl-hydrogenpolysiloxane having the formula: where z' and w' are defined above. One of ordinary skill in the art will appreciate that in the above exemplary formula, the dimethylsiloxy and methylhydrogensiloxy units may be present in a 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 particular embodiment, the (C) organosilicon compound is linear and contains terminal silicon-bonded hydrogen atoms. In these embodiments, the (C) organosilicon compound has the average formula H(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] z’ Si(CH 3 ) 2 H The organohydrogensiloxane may be a SiH-terminated dimethylpolysiloxane having the formula: where z' is as defined above. The SiH-terminated dimethylpolysiloxane may be used alone or in combination with the dimethyl, methylhydrogenpolysiloxane disclosed immediately above. When mixtures are used, the relative amounts of each organohydrogensiloxane in the mixture may vary. Those skilled in the art will appreciate that any methyl group in the above exemplary formula may be replaced with any other hydrocarbon group that does not contain aliphatic unsaturation.

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

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

[0072] Other examples of organohydrogensiloxanes suitable for (C) organosilicon compounds are those that have at least two SiH-containing cyclosiloxane rings in one molecule. Such organohydrogensiloxanes may be any organopolysiloxanes that have at least two cyclosiloxane rings with at least one silicon-bonded hydrogen (SiH) atom on each siloxane 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 siloxy units, D siloxy units, T siloxy units, and / or Q siloxy units that form a cyclic structure, provided that at least one of the cyclic siloxy units in each siloxane ring, which may be M siloxy units, D siloxy units, and / or T siloxy units, contains one SiH unit. These siloxy units may be represented as MH, DH, and TH siloxy units, respectively, when the other substituents are methyl.

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

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

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

[0076] Additional examples of suitable catalysts for (D) hydrosilylation reaction catalysts include rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr), and / or hafnium (Hf)), lanthanides, actinides, and Group I and II metal complexes (e.g., those containing calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals may be used as (D) hydrosilylation reaction catalysts.

[0077] (D) Hydrosilylation catalyst can be in any suitable form.For example, (D) Hydrosilylation catalyst can be solid, and examples thereof include platinum-based catalysts, palladium-based catalysts, and similar precious metal-based catalysts, and nickel-based catalysts.Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt, and similar elements, and also platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts that include a combination 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.

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

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

[0080] (D) Platinum complexes with organopolysiloxanes suitable for use as hydrosilylation catalysts include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. These complexes may be microencapsulated in a resin matrix. Alternatively, (D) hydrosilylation catalysts may include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. (D) Hydrosilylation catalysts may be prepared by a process comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane, or an alkene-platinum-silyl complex.

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

[0082] Specific examples of photoactivatable hydrosilylation catalysts suitable for the (D) hydrosilylation catalyst include platinum(II) 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 platinum(II) β-diketonate complexes such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsilyl-Cp)trimethylplatinum, where Cp represents cyclopentadienyl; (η-cyclopentadienyl)trialkylplatinum complexes such as [Pt[C 6 H 5 NNNOCH 3 ] 4 , Pt[p-CN-C 6 H 4 NNNOC 6 H 11 ] 4 , Pt[pH 3 COC 6 H 4 NNNOC 6 H 11 ] 4 , Pt[p-CH 3 (CH 2 ) x -C 6 H 4 NNNOCH 3 ] 4 , 1,5-cyclooctadienePt[p-CN-C 6 H 4 NNNOC6 H 11 ] 2 , 1,5-cyclooctadienePt[p-CH 3 O.C. 6 H 4 NNNOCH 3 ] 2 , [(C 6 H 5 ) 3 P] 3 Rh[p-CN-C 6 H 4 NNNOC 6 H 11 ], and Pd[p-CH 3 (CH 2 ) x -C 6 H 4 NNNOCH 3 ] 2 wherein x is 1, 3, 5, 11, or 17; 4 -1,5-cyclooctadienyl)diphenylplatinum, (η 4 -1,3,5,7-cyclooctatetraenyl)diphenylplatinum, (η 4 -2,5-norborazienyl)diphenylplatinum, (η 4 -1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (η 4 -1,5-cyclooctadienyl)bis-(4-acetylphenyl)platinum, and (η 4 Typically, the photoactivatable hydrosilylation reaction catalyst is a Pt(II) β-diketonate complex, and more typically, the catalyst is platinum(II) bis(2,4-pentanedioate).

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

[0084] The catalytic amount of the (D) hydrosilylation catalyst can be >0.01 ppm to 10,000 ppm, alternatively >1,000 ppm to 5,000 ppm. Alternatively, typical catalytic amounts of the (D) hydrosilylation catalyst are 0.1 ppm to 5000 ppm, alternatively 1 ppm to 2000 ppm, alternatively >0 to 1,000 ppm. Alternatively, the catalytic amount of the (D) hydrosilylation catalyst 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.

[0085] The composition may further comprise one or more of: (E) an inhibitor; (F) an anchor additive; (G) an anti-mist additive; (H) a release modifier; and (I) a vehicle.

[0086] In certain embodiments, the composition further comprises an (E) inhibitor, which may be used to modify the reaction rate or cure rate of the composition compared to a composition comprising the same starting materials but omitting the (E) inhibitor. (E) Inhibitors include acetylenic alcohols such as methylbutynol, ethynylcyclohexanol, dimethylhexynol, and 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyn-3-ol, and 1-ethynyl-1-cyclohexanol, and combinations thereof; cycloalkenylsiloxanes, such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl- ... Methylvinylcyclosiloxanes, as exemplified by hexenylcyclotetrasiloxane, and combinations thereof; ene-yne ​​compounds, such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; triazoles, such as benzotriazole; phosphines; mercaptans; hydrazines; amines, such as tetramethylethylenediamine; dialkylfumarates, dialkenylfumarates, dialkoxyalkylfumarates, maleates, such as diallylmaleate; nitriles; ethers; carbon monoxide; alkenes, such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols, such as benzyl alcohol; and combinations thereof. Alternatively, the (E) inhibitor can be selected from the group consisting of acetylene alcohols (e.g., 1-ethynyl-1-cyclohexanol) and maleates (e.g., diallylmaleate, bismaleate, or n-propylmaleate), and combinations of two or more thereof.

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

[0088] The silylated acetylene compounds are (3-methyl-1-butyne-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyne-3-oxy)dimethylsilane, bis(3-methyl-1-butyne-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyne-3-oxy))silane, (3-methyl-1-butyne-3-oxy)dimethylphenylsilane, (3-methyl-1-butyne-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyne-3-oxy)triethylsilane, bis(3-methyl-1- silane, (3,5-dimethyl-1-hexyne-3-oxy)trimethylsilane, (3-phenyl-1-butyne-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyne-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyne-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyne-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyne-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyne-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyne-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyne-1-oxy)trimethylsilane, and combinations thereof. Alternatively, the (E) 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 chlorosilanes in the presence of an acid acceptor.

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

[0090] In certain embodiments, the composition further comprises (F) an anchor additive. Suitable anchor additives are exemplified by the reaction product of vinylalkoxysilane and epoxy-functional alkoxysilane; the reaction product of vinylalkoxysilane and epoxy-functional alkoxysilane; and the combination (e.g., physical blend and / or reaction product) of polyorganosiloxane having at least one aliphatically unsaturated hydrocarbon group and at least one hydrolyzable group per molecule with epoxy-functional alkoxysilane (e.g., the combination of hydroxy-terminated vinyl-functional polydimethylsiloxane and glycidoxypropyltrimethoxysilane). Alternatively, the anchor additive may comprise a polyorganosilicate resin. Suitable anchor additives and their preparation methods are disclosed, for example, 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. 0556023.

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

[0092] Alternatively, the (F) anchor additive may include an unsaturated or epoxy-functional compound. The (F) anchor additive may include an unsaturated or epoxy-functional alkoxysilane. For example, the functional alkoxysilane may include at least one unsaturated organic group or an epoxy-functional organic group. 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.

[0093] Specific examples of suitable epoxy-functional alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof.

[0094] The (F) anchor additive may also include a reaction product or partial reaction product of one or more of these compounds. For example, in 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.

[0095] Alternatively, the (F) anchor additive may comprise an epoxy-functional siloxane, such as the reaction product of a hydroxy-terminated polyorganosiloxane with the above-mentioned 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 is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and a reaction product of a hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

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

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

[0098] In certain embodiments, the composition further comprises (G) a mist suppressant. (G) mist suppressant is distinct from component (A), which also functions as a mist suppressant when the composition is used to prepare a release coating. (G) mist suppressant can be used in the composition to reduce or inhibit silicone mist formation in the coating process, especially with high speed coating equipment. (G) mist suppressant 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 mist suppressant additives 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.

[0099] The amount of (G) mist suppressant used in the composition will depend on a variety of factors, including the amount and type of other starting materials selected for the composition. However, (G) mist suppressant is typically used in an amount of 0% to 10%, alternatively 0.1% to 3% by weight, based on the total weight of the composition. This amount excludes the amount associated with component (A) and only relates to the (G) mist suppressant which is separate and distinct from component (A).

[0100] In certain embodiments, the composition further comprises (H) a release modifier that can be used in the composition to control (reduce) the level of release force (adhesion between a release coating formed from the composition and its adherend, such as a label containing a pressure-sensitive adhesive). By adjusting the level or concentration of the (H) release modifier, a release coating having the required or desired release force can be formulated from a composition that does not contain a modifier. Examples of suitable release modifiers 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. Pat. No. 8,933,177 and U.S. Patent Application Publication No. 2016 / 0053056. If used, (H) the release modifier may be present in the composition in an amount of from 0 to 85 parts, alternatively 25-85 parts, per 100 parts of component (B).

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

[0102] Typically, the (I) vehicle, when present in the composition, is an organic liquid. Organic liquids include those considered to be oils or solvents. Organic liquids are exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols with more than three carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, and aromatic halides. Hydrocarbons include isododecane, isohexadecane, Isopar L (C11-C13), Isopar (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 siloxane having a viscosity of 1 to 1,000 mm at 25° C., such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any 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 1000 rpm / sec.

[0103] In certain embodiments, the (I) vehicle may 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. In one embodiment, when the composition is in the form of an emulsion, the (I) vehicle may instead comprise an aqueous medium, or water.

[0104] The amount of (I) vehicle depends on various factors, including the type of vehicle selected and the amount and type of other ingredients present in the composition. However, the amount of (I) vehicle in the composition can be 0% to 99% by weight, alternatively 2% to 50% by weight, based on the total weight of the composition. (I) vehicle can be added during preparation of the composition, for example, to aid in mixing and delivery. All or a portion of (I) vehicle can be optionally removed after the composition is prepared, before and / or simultaneously with preparing a release coating from the composition.

[0105] Other optional components may be present in the composition, including, for example, reactive diluents, fragrances, preservatives, colorants, dyes, pigments, antioxidants, heat stabilizers, flame retardants, flow control additives, biocides, fillers (including extending and reinforcing fillers), surfactants, thixotropic agents, pH buffers, and the like. The composition may be in any form and may be further incorporated into the composition. For example, the composition may be in the form of an emulsion or may be incorporated into an emulsion. The emulsion may be an oil-in-water emulsion, a water-in-oil emulsion, a silicone-in-oil emulsion, and the like. The composition itself may be the continuous or discontinuous phase of such an emulsion.

[0106] Alternatively, the composition and 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 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 release liner formed therewith. Particulates may be detrimental to adherend adhesion.

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

[0108] The composition in its curable form can be prepared by combining components (A)-(D) and any optional components described above, in any order of addition, optionally in a masterbatch, and optionally under shear. As described in more detail below, the composition can be a one part composition, a two part or 2K composition, or a multi-part composition. For example, components (A) and (B) can be a single part of the composition. When the composition is used to prepare a release coating or coating substrate, as described below, components (A) and (B) are combined with components (C) and (D), and any optional components, such that the composition is a curable composition. When the composition further comprises components (C) and (D), the composition can be referred to as a curable composition. Any description herein of optional components, certain embodiments, or certain method steps below applies equally to the composition and the curable composition.

[0109] In various embodiments, the composition may be prepared as an emulsion, for example, an oil-in-water or water-in-oil emulsion, depending on the selection of its continuous and discontinuous phases. In these embodiments, the (I) vehicle is present in the composition as an aqueous medium or water. The oil phase of the emulsion comprises the silicone components of the composition, i.e., at least components (A) and (B), and, if present, component (C). In certain embodiments, the oil phase may further comprise an organic oil or silicone oil to carry at least components (A) and (B), and, if present, component (C). However, the organic oil or silicone oil is not essential to prepare the emulsion. Furthermore, the emulsion may be a multi-part emulsion with different emulsions of different components, and the multiple parts of the emulsion are combined and mixed in connection with curing. The emulsion may comprise any of the optional components described above in any part.

[0110] When used, the organic oil is typically non-reactive or inert, i.e., the organic oil does not participate in any reactions related to the curing of the reactive components of the composition.Typically, the silicone components (e.g., components (A), (B), and, if present, (C)) are dispersed in the oil phase of the emulsion rather than in the water phase.

[0111] In certain embodiments, suitable organic oils include those that dissolve at least components (A) and (B), typically forming a clear solution, and those that can be combined with at least components (A) and (B) to form a homogeneous dispersion without phase separation before, during, and / or after formation of the emulsion. The organic oil may be any one or combination of the following, for example: hydrocarbon oils in which the hydrocarbons in the oil fraction contain from 5 to 25 carbon atoms per molecule, such as oil fractions containing linear (e.g., n-paraffinic), branched (isoparaffinic), and / or cyclic (sometimes referred to as naphthenic) mineral oils, and are liquid linear or branched paraffins containing from 12 to 40 carbon atoms; linear or branched monounsaturated hydrocarbons, such as polyisobutylene (PIB), phosphate esters such as trioctyl phosphate, polyalkylbenzenes, heavy alkylates, linear and / or branched alkylbenzenes such as dodecylbenzene and other alkylarenes, aliphatic monocarboxylic acid esters, linear or branched alkenes containing from 8 to 25 carbon atoms or mixtures thereof; and natural oils and their derivatives.

[0112] In one embodiment, the organic oil may include mineral oil fractions, natural oils, alkylcycloaliphatic compounds, alkylbenzenes including polyalkylbenzenes, or combinations thereof.

[0113] Alkylbenzene compounds suitable for use as organic oils include, for example, heavy alkylated alkylbenzenes and alkylcycloaliphatic compounds. Heavy alkylated alkylbenzenes include, for example, alkyl-substituted aryl compounds having aryl groups, such as benzene substituted with alkyl and / or other substituents. Further examples include the extenders described in U.S. Pat. No. 4,312,801, which is incorporated by reference in its entirety.

[0114] Mineral oil fractions or any suitable mixture of mineral oil fractions in combination with any other organic oils may be used as organic oil. Further examples of organic oils include alkylcyclohexanes and paraffinic hydrocarbons (which may be linear, branched or cyclic). Cycloparaffinic hydrocarbons may be monocyclic and / or polycyclic hydrocarbons (naphthenic).

[0115] In another embodiment, the organic oil may include natural oil. Natural oil is oil that is not derived from petroleum. More specifically, natural oil is derived from animal and / or vegetable matter (including seeds and nuts). Common natural oils include triglycerides of mixtures of fatty acids, especially mixtures that contain some unsaturated fatty acids. Alternatively, the organic oil may be a derivative of natural oil, such as transesterified vegetable oil, boiled natural oil, blown natural oil, or thickened oil (e.g., heat-polymerized oil). Natural oil may be derived from various sources, and may include, for example, wheat germ, sunflower, grape seed, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, black currant, evening primrose, and combinations thereof.

[0116] Instead of the liquids exemplified above, the organic oil may be a solid, such as a wax. When the organic oil comprises a wax, the wax typically has a melting point of 30-100°C. The wax may be, for example, a hydrocarbon wax, such as wax derived from petroleum, a wax containing carboxyl esters, such as beeswax, lanolin, tallow, carnauba, candelilla, tribehenin, or a wax derived from plant seeds, fruits, nuts, or grains, including softer waxes called "butter", such as mango butter, shea butter, or cocoa butter. Alternatively, the wax may be a polyether wax or a silicone wax.

[0117] In particular, when the organic oil comprises a mineral oil, the organic oil and at least components (A) and (B) are typically miscible, i.e., form a homogeneous mixture. In contrast, when the organic oil comprises a natural oil, the organic oil and at least components (A) and (B) are generally immiscible, i.e., form a heterogeneous mixture.

[0118] The mixture formed by combining components (A), (B), and optionally components (C) and / or (D), if used, with organic oil and / or silicone oil, can be heterogeneous or homogeneous. The organic oil can solubilize or partially solubilize at least components (A) and (B), and optionally also components (C) and (D), if present. The organic oil may be referred to as a carrier or a solvent, depending on whether components (A) and (B) are solubilized or dissolved in the organic oil. The mixture can be formed in any manner, including any order of addition, with optional mixing or stirring.

[0119] The method further includes combining the mixture, the aqueous medium, and the surfactant to form an emulsion. The mixture is typically a discontinuous phase in the aqueous medium of the emulsion. The emulsion may be formed by application of shear, for example, by mixing, shaking, stirring, etc. The discontinuous phase of the emulsion is generally present as particles in the aqueous medium. The particles are liquid and may generally have spherical or other shapes and may have a variety of sizes based on the ingredients selected and their relative amounts.

[0120] Typically, the discontinuous phase of an emulsion exists as particles in an aqueous medium. The particles are liquid and may generally have a spherical or other shape and may have various sizes based on the selected components and their relative amounts. For example, using a Mastersizer 3000 particle size analyzer available from Malvern Panalytical Ltd (Malvern, UK), the particle size and the distribution curve of the emulsion particles can be determined by laser diffraction particle size analysis (i.e., laser light scattering). As will be understood by those skilled in the art, the reported volume median diameter (VMD or "Dv(0.5)") represents the median diameter (μm), i.e., 50% of the particles have a diameter greater than the median and 50% of the particles have a diameter smaller than the median. Similarly, the reported Dv(0.9) represents the diameter below which 90% of the volume distribution of the particles lies, and the reported Dv(0.1) represents the diameter below which 10% of the volume distribution of the particles lies. In some embodiments, the release coating composition is prepared as an emulsion having a Dv(0.5) of less than 1.5 μm, such as 0.3 to 1.0 μm, or 0.4 to 0.9 μm. In these or other embodiments, the emulsion has a DV(0.9) of less than 3.0 μm, such as 0.5 to 2.5 μm, or 1.2 to 2.0 μm. In these or other embodiments, the emulsion has a DV(0.1) of less than 0.9 μm, such as 0.1 to 0.7 μm, or 0.2 to 0.5 μm. Particle sizes and distributions outside the above ranges may be used and these will typically be selected by those skilled in the art in view of the desired properties of the release coating composition (e.g., viscosity, transparency, light transmittance, etc.).

[0121] The aqueous medium contains water. The water may be from any source and may optionally be purified, for example, by distillation, reverse osmosis, etc. The aqueous medium may further contain one or more additional components other than water as described below.

[0122] The surfactant can be any surfactant capable of emulsifying the various ingredients or improving the stability of an emulsion. For example, the surfactant may include one or more of anionic, cationic, nonionic, and / or amphoteric surfactants, organically modified silicones such as dimethicone copolyols; oxyethylenated and / or oxypropylenated ethers of glycerol; oxyethylenated and / or oxypropylenated ethers of fatty alcohols such as ceteareth-30, C12-15 pareth-7; fatty acid esters of polyethylene glycols such as PEG-50 stearate, PEG-40 monostearate; sugar esters and ethers such as sucrose stearate, sucrose cocoate, and sorbitan stearate, and mixtures thereof; phosphate esters and salts thereof such as DEA oleth-10 phosphate; sulfosuccinates such as disodium PEG-5 citrate lauryl sulfosuccinate and disodium ricinoleamide MEA sulfosuccinate; alkyl ether sulfates such as sodium lauryl ether sulfate; isethionates; betaine derivatives, and mixtures thereof.

[0123] In certain embodiments, the surfactant includes an anionic surfactant, such as carboxylates (sodium 2-(2-hydroxyalkyloxy)acetate), amino acid derivatives (N-acyl glutamate, N-acyl glycinate, or acylsarcosinate), alkyl sulfates, alkyl ether sulfates and their oxyethylenated derivatives, sulfonates, isethionates and N-acyl isethionates, taurates and N-acyl N-methyl taurates, sulfosuccinates, alkyl sulfoacetates, phosphates and alkyl phosphates, polypeptides, anionic derivatives of alkyl polyglucosides (acyl-D-galactosiduronates), and fatty acid soaps, alkali metal sulforicinates; sulfonated glyceryl esters of fatty acids, such as sulfonated monoglycerides of coconut oil acid; sodium oleylacetate ... Salts of sulfonated monohydric alcohol esters such as oleylisethianate; Amides of aminosulfonic acids such as the sodium salt of oleyl methyl tauride; Sulfonated fatty acid nitriles such as palmitonitrile sulfonate; Sulfonated aromatic hydrocarbons such as sodium α-naphthalene monosulfonate; Condensation products of naphthalenesulfonic acid and formaldehyde; Sodium octahydroanthracenesulfonate; Alkali metal alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate and triethanolamine lauryl sulfate; Sodium lauryl ether sulfate, ammonium lauryl ether sulfate ether sulfates having an alkyl group having 8 or more carbon atoms, such as ammonium, sodium alkylaryl ether sulfate, and ammonium alkylaryl ether sulfate; alkylaryl ether sulfates having one or more alkyl groups having 8 or more carbon atoms; alkali metal salts of alkylbenzenesulfonates, exemplified by sodium hexylbenzenesulfonate, sodium octylbenzenesulfonate, sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium cetylbenzenesulfonate, and sodium myristylbenzenesulfonate; 3 (CH 2 )6 CH 2 O(C 2 H 4 O) 2 SO 3 H, C.H. 3 (CH 2 ) 7 CH 2 O(C 2 H 4 O) 3.5 SO 3 H, C.H. 3 (CH 2 ) 8 CH 2 O(C 2 H 4 O) 8 SO 3 H, C.H. 3 (CH 2 ) 19 CH 2 O(C 2 H 4 O) 4 SO 3 H, and CH 3 (CH 2 ) 10 CH 2 O(C 2 H 4 O) 6 SO 3 H; the sodium, potassium, and amine salts of alkyl naphthylsulfonic acids, and mixtures thereof.

[0124] In these or other embodiments, the surfactant includes a cationic surfactant. The cationic surfactant includes, for example, various fatty acid amines and amides and their derivatives, as well as salts of fatty acid amines and amides. Examples of fatty acid amines include dodecylamine acetate, octadecylamine acetate, and acetate salts of amines of tallow fatty acid, homologues of aromatic amines with fatty acids such as dodecylanalin, fatty amides derived from fatty diamines such as undecyl imidazoline, fatty amides derived from fatty diamines such as undecyl imidazoline, fatty amides derived from disubstituted amines such as oleylaminodiethylamine, derivatives of ethylenediamine, quaternary ammonium compounds and their derivatives such as tallow trimethylammonium chloride, dioctadecyl dimethylammonium chloride, didodecyl dimethylammonium chloride, dihexadecyl ammonium chloride, octyl trimethylammonium hydroxide, dodecyl trimethylammonium hydroxide, dodecyl trimethylammonium chloride ... methyl ammonium hydroxide, and alkyl trimethyl ammonium hydroxides such as hexadecyl trimethyl ammonium hydroxide, dialkyl dimethyl ammonium hydroxides such as octyl dimethyl ammonium hydroxide, decyl dimethyl ammonium hydroxide, didodecyl dimethyl ammonium hydroxide, dioctadecyl dimethyl ammonium hydroxide, tallow trimethyl ammonium hydroxide, exemplified by coconut oil, trimethyl ammonium hydroxide, methyl polyoxyethylene coco ammonium chloride, and dipalmityl hydroxyethyl ammonium methosulfate, amide derivatives of amino alcohols such as β-hydroxyethyl stearylamide, amine salts of long chain fatty acids, and mixtures thereof.

[0125] In these or other embodiments, the surfactant includes a non-ionic surfactant. Nonionic surfactants include, for example, polyoxyethylene alkyl ethers (such as lauryl, iso-tridecyl, branched decyl, cetyl, stearyl, or octyl), polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanol, polyoxyalkylene glycol modified polysiloxane surfactants, polyoxyalkylene substituted silicones (lake or ABn type), silicone alkanolamides, silicone esters, silicone glycosides, dimethicone copolyols, fatty acid esters of polyols such as sorbitol and glyceryl mono-, di-, tri-, and sesqui-oleates and stearates, glyceryl, and polyethylene glycol laurate; fatty acid esters of polyethylene glycol (such as polyethylene glycol monostearate and monolaurate), polyoxyethylenated fatty acid esters of sorbitol (such as stearates and oleates), and mixtures thereof.

[0126] In these or other embodiments, the surfactant comprises an amphoteric surfactant, such as, for example, amino acid surfactants, betaine acid surfactants, trimethylnonyl polyethylene glycol ethers, and polyethylene glycol ether alcohols containing linear alkyl groups having 11 to 15 carbon atoms, such as 2,6,8-trimethyl-4-nonyloxypolyethyleneoxyethanol (6EO) (sold as Tergitol® TMN-6 by OSi Specialties, Witco Company, Endicott, NY), 2,6,8-trimethyl-4-nonyloxypolyethyleneoxyethanol (10EO) (sold as Tergitol® TMN-10 by OSi Specialties, Witco Company, Endicott, NY), alkylene-oxypolyethyleneoxyethanol (C 11~15 secondary alkyl, 9EO) (sold as Tergitol® 15-S-9 by OSi Specialties, a Witco Company of Endicott, NY), alkyleneoxypolyethyleneoxyethanol (C 11~15octylphenoxypolyethoxyethanols having various amounts of ethylene oxide units, such as secondary alkyl, 15 EO) (sold as Tergitol® 15-S-15 by OSi Specialties, a Witco Company of Endicott, NY), octylphenoxypolyethoxyethanols (40 EO) (sold as Triton® X405 by Rohm and Haas Company of Philadelphia, Pa), nonionic ethoxylated tridecyl ethers (available under the generic trade name Trycol by Emery Industries of Mauldin, SC), alkali metal salts of dialkyl sulfosuccinates (available under the generic trade name Aersol by American Cyanamid Company of Wayne, NJ), polyethoxylated quaternary ammonium salts and ethylene oxide condensation products of primary aliphatic amines (Armak Available from Sigma Chemical Company, Chicago, Illinois under the trade names Ethoquad, Ethomeen, or Arquad, polyoxyalkylene glycol modified polysiloxanes, N-alkylamidobetaines and their derivatives, proteins and their derivatives, glycine derivatives, sultaines, alkyl polyaminocarboxylates and alkyl amphoacetates, and mixtures thereof. These surfactants are also available under various trade names from other sources.

[0127] Those skilled in the art can easily optimize the relative amounts of components in the emulsion and the method of preparation thereof. For example, if the release coating composition (e.g., curable composition) is in the form of an emulsion, the emulsion can be a two-part emulsion with the reactive components and / or catalyst separated therefrom. In some embodiments, the emulsion is prepared to contain a specific non-volatile content (NVC). For example, a sample of the emulsion can be evaluated with microwave-mediated drying by continuous mass balance (i.e., a microprocessor-controlled system including an integrated microwave drying chamber, an electronic balance, and an infrared temperature controller) to determine the NVC using a Smart System5 Moisture and Solids Analyzer available from CEM Corporation (Matthews, North Carolina, USA). As will be appreciated by those skilled in the art, the NVC is calculated and reported (in weight percent) based on the weight of solids remaining after sample drying. In some embodiments, the release coating composition is prepared as an emulsion containing 25-60 wt. % NVC, such as 30-50, alternatively 35-45, alternatively 39-43 wt. % NVC.

[0128] A method of preparing a coated substrate with the composition includes applying, i.e., disposing, the 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 may be carried out by heating at an elevated temperature, for example, from 50° C. to 180° C., alternatively from 50° C. to 120° C., alternatively from 50° C. to 90° C., to obtain a coated substrate. One skilled in the art can select an appropriate temperature depending on a variety of factors, including the selection of the components of the curable composition and the materials of the substrate composition or structure.

[0129] The curable composition can be disposed or distributed on the substrate in any suitable manner. Typically, the curable composition is applied in wet form by wet coating techniques. 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, the curable composition is disposed on the substrate to produce a wet deposit on the substrate, which is then cured to obtain a cured film, i.e., a coated substrate, including a release coating formed from the curable composition on the substrate.

[0130] 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 be subjected to an integrated hotplate or an integrated or stand-alone oven for curing the wet deposit. The substrate may optionally have a continuous or non-continuous shape, size, dimension, surface roughness, and other characteristics. Alternatively, the substrate may have an elevated softening point temperature. However, the curable compositions and methods are not so limited.

[0131] Alternatively, the substrate may comprise a plastic, which may be thermoset and / or thermoplastic, but the substrate may also be or comprise glass, metal, cellulose (e.g., paper), wood, cardboard, paperboard, silicone, or polymeric materials, or combinations thereof.

[0132] Specific examples of suitable substrates include paper substrates such as kraft paper, polyethylene-coated kraft paper (PEK-coated paper), thermal paper, and plain paper; polymer substrates such as polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene; styrene resins; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); polyphenylene ether (PPE); polyimide (PI); Examples of suitable thermoplastic elastomers include polyamide-imide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyethernitrile (PEN); phenolic resins; phenoxy resins; cellulose such as triacetyl cellulose, diacetyl cellulose, cellophane, etc.; fluorinated resins such as polytetrafluoroethylene; thermoplastic elastomers such as polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type, fluoro type, etc.; and copolymers and combinations thereof.

[0133] 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, alternatively from greater than 0 to 2 minutes. The period of time depends on a variety of factors, including the elevated temperature used, the temperature selected, the desired film thickness, and the presence or absence of any water or vehicle in the curable composition.

[0134] The step of curing the curable composition typically has a residence time of 0.1 seconds to 50 seconds, alternatively 1 second to 10 seconds, alternatively 0.5 seconds to 30 seconds. The residence time selected may vary depending on the choice of substrate, the temperature selected, and the line speed. As used herein, residence time refers to the time that the curable composition or wet deposit is exposed to an elevated temperature. Residence time is distinct from cure time, since there may be ongoing curing even after the curable composition, wet deposit, or partially cured reaction intermediate thereof is no longer exposed to the elevated temperatures that typically initiate curing. Alternatively, the coated article may be prepared on a conveyor belt in an oven, and the residence time may be calculated by dividing the length of the oven (e.g., in meters) by the line speed of the conveyor belt (e.g., meters / second).

[0135] The time can be subdivided into iterations of cure, e.g., a first cure and a post cure, e.g., 1 hour for the first cure and 3 hours for the post cure. The elevated temperature can be independently selected in such iterations from any temperature above room temperature and can be the same in each iteration.

[0136] Depending on the optional presence and choice of (I) vehicle, the curing of the composition may also include a drying step. For example, if the composition is in the form of an emulsion in which (I) vehicle is present and includes water, the curing step also typically involves drying or removing the water from the emulsion. Drying may be performed simultaneously with curing or may be separate from curing.

[0137] 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 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 time to obtain a second partially cured deposit. This partially cured deposit also further cures while exposed to the second elevated temperature for a second time. A third deposit can be placed on the second partially cured deposit and exposed to a third elevated temperature for a third time to obtain a third partially cured deposit. The second partially cured deposit also further cures while exposed to the second elevated temperature for a second time. This process can be repeated, for example, 1 to 50 times, to build up the coated article as desired. The composite of partially cured layers is subjected to a final post-cure, for example, exposed to an elevated temperature and time as described above. Each elevated temperature and time may be selected independently and may be the same or different from each other. When the article is formed via an iterative process, each deposit may be independently selected and may differ in the components selected in the curable composition, their amounts, or both, or, alternatively, each repeating layer may be fully cured, rather than only partially cured, in such an iterative process.

[0138] Alternatively, the deposition may include a wet film. Alternatively, the iterative process may be wet-on-wet, depending on the cure state of the partially cured layer. Alternatively, the iterative process may be wet-on-dry.

[0139] The coated substrate comprising a film formed from the curable composition on a substrate may have a variety of dimensions, such as the relative thickness of the film and substrate. The film has a thickness that may vary depending on the end use application. The film may have a thickness of from greater than 0 to 4,000 μm, alternatively greater than 0 to 3,000 μm, alternatively greater than 0 to 2,000 μm, alternatively greater than 0 to 1,000 μm, alternatively greater than 0 to 500 μm, alternatively greater than 0 to 250 μm. However, other thicknesses are contemplated, for example, from 0.1 to 200 μm. For example, the thickness of the film may be from 0.2 to 175 μm; alternatively, from 0.5 to 150 μm; alternatively, from 0.75 to 100 μm; alternatively, from 1 to 75 μm; alternatively, from 2 to 60 μm; alternatively, from 3 to 50 μm, alternatively, from 4 to 40 μm. Alternatively, when the substrate is plastic, the film may have a thickness of from greater than 0 to 200 μm, alternatively from greater than 0 to 150 μm, alternatively from greater than 0 to 100 μm.

[0140] If desired, the film can undergo further processing depending on its end use application. For example, the film can be treated with an oxide deposition (e.g., SiO 2 The film may be subjected to a variety of processes, including photochemical deposition, resist deposition and patterning, etching, chemical stripping, corona or plasma stripping, metallization, or metal deposition. Such further processing techniques are generally known. Such deposition may be chemical vapor deposition (such as low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, and plasma assisted chemical vapor deposition), physical vapor deposition, or other vacuum deposition techniques. Many such further processing techniques involve high temperatures, particularly vacuum deposition, for which the film is well suited in view of its excellent thermal stability. However, depending on the end use of the film, the film may be used with such further processing.

[0141] The coated substrate can be used in a variety of end-use applications. For example, the coated substrate can be used in coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, construction applications, transportation applications, electronic applications, or electrical applications. However, the curable composition can be used in end-use applications other than preparing the coated substrate, such as preparing articles such as silicone rubber.

[0142] Alternatively, the coated substrate can be used as a release liner for a tape or adhesive, including any pressure sensitive adhesive, such as, for example, acrylic, rubber, and silicone type pressure sensitive adhesives, as well as acrylic, synthetic rubber, silicone, epoxy, and polyurethane type adhesives. Each major surface of the substrate can have a double-sided tape or film disposed thereon for the adhesive.

[0143] Alternatively, when the curable composition is formulated as a release coating composition, for example to form a release coating or liner, the release coating composition can be prepared, for example, by mixing the components together to prepare a one-part composition. However, it may be desirable to prepare the release coating composition as a multi-part composition in which the component having SiH functionality (e.g., (C) the organosilicon compound) and (D) the hydrosilylation reaction catalyst are stored in separate parts until the parts are combined at the time of use (e.g., immediately prior to application to a substrate). When the curable composition is a release coating composition, the release coating composition can be used to form a coated substrate as described above, and the release coating is formed by applying and curing the release coating composition to a substrate, for example, the surface of the substrate.

[0144] For example, the multi-part curable composition may include (A) part, a base part comprising one or more of: (A) an organopolysiloxane, (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; (C) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule, and optionally, when present, (F) an anchor additive and / or (I) a hardener portion comprising a vehicle (B). If used, (E) an inhibitor may be added to part (A), part (B), or both. Parts (A) and (B) may be combined in a weight ratio of (A):(B) of 1:1 to 30:1, 1:1 to 10:1, alternatively 1:1 to 5:1, alternatively 1:1 to 2:1. Parts (A) and (B) may 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.

[0145] Alternatively, (F) anchor additive, if present, can be incorporated into either part (A) or part (B) or added to a separate (third) part.

[0146] 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.

[0147] The release coating composition of the present invention can be applied to any substrate, such as those mentioned above. Alternatively, the release coating composition can be applied to a polymeric film substrate, such as a polyester film, particularly a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, or a polystyrene film. Alternatively, the release coating composition can be applied to a paper substrate, including a plastic-coated paper, such as a polyethylene-coated paper, a glassine, a supercalendered paper, or a clay-coated kraft paper. Alternatively, the release coating composition can be applied to a metal foil substrate, such as an aluminum foil.

[0148] In certain embodiments, the method of preparing a coated substrate may further include treating the substrate before applying or disposing the release coating composition on the substrate. The treatment of the substrate may be carried out by any convenient means, such as plasma treatment or corona discharge treatment. Alternatively, the substrate may be treated by applying a primer. In certain examples, the anchorage of the release coating may be improved if the substrate is treated before forming the release coating on the substrate from the release coating composition.

[0149] When the release coating composition includes (I) a vehicle, the method may further include removing the (I) vehicle, which may be carried out by any conventional means, such as by heating at 50°C to 100°C for a time sufficient to remove all or a portion of the (I) vehicle. The method may further include curing the release coating composition to form a release coating on the surface of the substrate. Curing may be carried out by any conventional means, such as by heating at 100°C to 200°C.

[0150] Under production coater conditions, curing can be accomplished at air temperatures of 120° C. to 150° C. with residence times of 1 to 6 seconds, 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.

[0151] 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.

[0152] The specific components used in the examples are set forth in Table 1 below, followed by the characterization and evaluation procedures also used in the examples. [Table 1]

[0153] Nuclear Magnetic Resonance (NMR) Spectroscopy Nuclear magnetic resonance (NMR) spectra were obtained using silicon-free 10 mm tubes and CDCl 3 / Cr(AcAc) 3 Solvents were used and NMR was obtained on a BRUKER AVIII (400 MHz). 29 Chemical shifts for Si-NMR spectra are referenced to internal solvent resonances and reported relative to tetramethylsilane.

[0154] Dynamic Viscosity (DV) Dynamic viscosity (DV) is measured at room temperature (~21.3°C) using a Brookfield DV-2T viscometer equipped with an LV-4 spindle.

[0155] X-ray fluorescence (XRF) X-ray fluorescence (XRF) is performed on an Oxford Instruments Lab-X3500 benchtop XRF analyzer.

[0156] Mist Level Rating (MLE) Mist evaluation is performed using a mist evaluation system that includes a custom-built two-roll coater placed in an enclosed chamber with a ventilation system. The coater includes a top roll (chrome) arranged in a stacked configuration on top of a rubber bottom roll (neoprene), which is placed over a sample pan and driven by a motor (1000 meters per minute rotations during operation). Each roll is 6 inches in diameter and 12 inches wide. The ventilation system is configured to draw air into the back wall of the enclosure and includes a magnetic gauge positioned in the ceiling of the enclosure to measure / monitor the airflow (velocity of 0.20-0.25 inches of water (i.e., 0.05-0.062 kPa) at the magnetic gauge), two mist collection tubes positioned above the center of the top roll (6 inches) of the coater to collect the mist, and an aerosol monitor (DustTrak 8530, records mist levels every 5 seconds) connected to each mist collection tube.

[0157] The sample (600 g) is placed in a sample pan, which is inserted under the bottom roll to collect and transfer to the top roll as a film. The coater is operated for 6 minutes and the mist generated from the coater is collected by a mist collection tube and measured by an aerosol monitor. The mist levels obtained between 120 s and 360 s are averaged and reported as the mist value of the sample.

[0158] Mist Level Industrial Evaluation (MLIE) The industrial evaluation of mist value (MLIE) is carried out on an industrial pilot line based on a six-roll coating head with five rollers in an alternating configuration of chrome steel and rubber sleeved rolls. Specifically, the two bottom rolls are aligned horizontally together to form a nip (i.e., the "first nip") where the coating bath is held, and the remaining rolls are aligned vertically to facilitate the transfer of the sample from one roll to the next between the coating bath and the paper surface to be coated in the nip (i.e., the "second nip") formed between the top two rolls. Each roll is independently driven by a separate motor. The mist collection stationary pipe is located less than 20 cm from the second nip and is connected to an aerosol monitor (DustTrak 8530).

[0159] The sample is placed in the coating bath and each roll is driven independently at separate speeds and pressed together using independent pressure settings to promote a gradual reduction in coating thickness along the roll line from the coating bath to the paper surface. The top two rolls are driven at a speed close to the final desired speed (e.g., 1000 m / min rotation) for the mist evaluation period, during which the mist values ​​are recorded and averaged to obtain the mist value (mg / m) of the sample. 3 Report as (in

[0160] Curing performance: extractable percentage The cure performance of the sample compositions is evaluated by determining the percent extractables (% Extractables). Specifically, the sample compositions are coated and cured on a substrate (glassine paper) to form a coated substrate and immediately cut into three sample disks (die cutter, 1.375 inches (3.49 cm)). The sample disks are handled only with tweezers to minimize contamination and / or damage. Each sample disk is analyzed by XRF to determine the initial coating weight (W i s) was determined and placed into individual bottles (100 mL, covered with lid) of solvent (methyl isobutyl ketone, 40 mL) and allowed to soak for 30 minutes on the lab bench. Each sample disk was then removed from the bottle, placed coated side up on a clean surface (tissue paper), allowed to evaporate (without blotting / wiping) any residual solvent, and analyzed by XRF to determine the final coating weight (W f s The % extractables for each sample are the percent change in coating weight from solvent immersion, i.e., calculated using the formula [(W i s -W f s ) / Wi×100%). The % Extractables indicates the amount of uncured components (e.g., uncrosslinked silicone) of the sample composition that can be extracted from the coating substrate, e.g., a lower % Extractables indicates higher / better cure performance.

[0161] Comparative example CC1 Organopolysiloxane (A-C1) was tested and / or analyzed as a blank / control along with certain specific examples below and is referred to as composition (CC1).

[0162] Comparative example CC2 A blend of 50 parts by weight of organopolysiloxane (A-C2) (63% solids in solvent 1) and 49 parts of organopolysiloxane (B1) is prepared and the solvent 1 is stripped to obtain a polymer blend. Inhibitor 2 (0.2% by weight) is added to the polymer blend to obtain a composition that was tested and / or analyzed with certain examples below and is referred to as composition (CC2).

[0163] Preparation Example 1 Branched organopolysiloxane (iii-a) (17.15 g), silicone resin (i) (10.00 g) and cyclic siloxane (ii) (2000.00 g) are mixed together at room temperature under N2 protection in a 3 L three-necked round bottle flask equipped with a condenser, thermocouple, and mechanical stirrer to form a mixture. The mixture is heated and held at 150°C and polymerization catalyst 1 (0.012 g) is added to initiate polymerization. After 3.25 hours, the reaction mixture is cooled to 80°C, charged with inhibitor 1 (0.044 g), cooled to room temperature, and concentrated in vacuum on a wiped film evaporator (240°C, 0-1 torr) to give 1,2-dichlorophenylsiloxane (III) of general formula M 0.38 M Vi 1.22 D 181.93 A colorless, viscous liquid of organopolysiloxane A1 is obtained. Organopolysiloxane A1 is then mixed with 29 It was analyzed by Si-NMR, GPC, and DV, the results of which are further shown in Table 2 below, along with similar results obtained from organopolysiloxane (A-C1).

[0164] Preparation Example 2 Silicone resin (i) (7.88 g), siloxane (iii-b) (0.65 g), and cyclic siloxane (ii) are mixed together at room temperature under N2 protection in a 3 L three-necked round bottle flask equipped with a condenser, thermocouple, and mechanical stirrer to form a mixture. The mixture is heated and held at 150°C, and polymerization catalyst 1 (0.0036 g) is added to initiate polymerization. After 3.25 hours, the reaction mixture is cooled to 80°C, and inhibitor 1 (0.044 g) is added. The general formula M 0.69 M Vi 0.44 D 228.83 The gum-like product of Q is obtained as the final product ("Organopolysiloxane A2") after cooling to room temperature. Organopolysiloxane A2 is then 29 It was analyzed by Si-NMR, GPC, and DV, and the results are shown in Table 2 below, along with similar results obtained from organopolysiloxane (A-C1). [Table 2]

[0165] Examples 1 to 2 and Comparative Examples 1 to 4 Various compositions for forming release coatings are prepared using organopolysiloxane (B1) and certain specific components and compositions described above to obtain Examples 1-2 and Comparative Examples 1-4. The compositions are then analyzed by DV and evaluated by MLE. The specific components, parameters, and evaluation results of Examples 1-2 and Comparative Examples 1-4 are shown in Table 3 below. [Table 3]

[0166] As shown, the compositions of the present invention provide mist suppression to release coatings prepared therewith. Furthermore, there is less misting when utilizing the compositions of the present invention (i.e., compared to conventional / comparative aerosol / mist suppressants).

[0167] Examples 3 to 4 and Comparative Example 5 Various compositions for forming release coatings are prepared to give Examples 3-4 and Comparative Example 5. The compositions are then evaluated by MLIE as described above at a line speed of 1000 m / min. The specific components, parameters, and evaluation results of Examples 3-4 and Comparative Example 5 are shown in Table 4 below. Example 3 includes organopolysiloxane A1 prepared in Preparative Example 1, and Example 4 includes organopolysiloxane A2 prepared in Preparative Example 2 above. The average mist level measured according to MLIE, and the cure performance (% extractables) were measured and are included in Table 4 below. [Table 4]

[0168] As shown, the compositions of the present invention provide mist suppression to release coatings prepared therewith. Furthermore, there is less misting when utilizing the compositions of the present invention (i.e., compared to conventional / comparative aerosol / mist suppressants).

[0169] Definitions and Use of Terms The definitions of abbreviations used in the specification are given in Table 5 below. [Table 5]

[0170] All amounts, ratios and percentages are by weight unless otherwise indicated. The amounts of all starting materials in the composition total 100% by weight. The Summary and Abstract of the Invention are incorporated herein by reference. The articles "a," "an," and "the" each refer to one or more, unless otherwise indicated by the context of the specification. The singular includes the plural unless otherwise indicated. The disclosure of a range includes the range itself and any subsumed within the range, as well as the endpoints. For example, the disclosure of a range of 2.0 to 4.0 includes not only the range 2.0 to 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0 individually, as well as any other numbers subsumed within the range. Further, for example, the disclosure of a range of 2.0 to 4.0 also includes subsets, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subsets subsumed within that range. Similarly, a disclosure of a Markush group includes the group as a whole, as well as any individual members and subgroups subsumed therein. For example, disclosure of the Markush group "a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group" includes the individual members alkyl, the subgroups alkyl and aryl, and any other individual members and subgroups subgrouped therein.

Claims

1. 1. A composition for forming a release coating comprising: (i) Formula (R １ ｙ R ２ ３－ｙ SiO １／２ ) ｘ (SiO ４／２ ) [wherein, each R １ is an independently selected hydrocarbyl group having 1 to 32 carbon atoms, and each R ２ is R １ , an alkoxy group, and a hydroxyl group, y being an integer from 0 to 3, and independently selected in each siloxy unit denoted by the subscript x, where the subscript x is from 0.05 to 0.99; (ii) Formula (R １ ２ SiO ２／２ ) ｎ [In the formula, each R １ is defined above, and n is an integer from 3 to 15; (iii) (A) (iii) (a) Formula (R ３ ｙ’ R １ ３－ｙ’ SiO １／２ ) ｘ’ (SiO ４／２ ) [Each R ３ is independently an ethylenically unsaturated group, the subscript y′ is 1 or 2, and each R １ are independently selected and defined above, and x′ is 1 to 4; or (A)(iii)(b) a reaction product in the presence of a polymerization catalyst with at least one of a branched organopolysiloxane having the formula: (B) an organopolysiloxane containing an average of at least two silicon-bonded ethylenically unsaturated groups per molecule; A composition comprising:

2. 2. The composition of claim 1, wherein component (A)(iii) is said (A)(iii)(a) branched organopolysiloxane.

3. 2. The composition of claim 1, wherein component (A)(iii) is said (A)(iii)(b) terminator.

4. (i) Each R １ is an independently selected alkyl or alkenyl group, provided that at least one R １ is an alkenyl group; (ii) subscript y is 3; (iii) subscript x is 0.05 to 0.9; (iv) subscript n is 4 or 5; or (v) any combination of (i) to (iv).

5. (C) an organosilicon compound containing an average of at least two silicon-bonded hydrogen atoms per molecule; (D) a hydrosilylation catalyst; and The composition according to any one of claims 1 to 4, further comprising:

6. 6. The composition of claim 5, wherein (i) said (C) organosilicon compound comprises an organohydrogensiloxane containing an average of at least two pendant silicon-bonded hydrogen atoms per molecule, (ii) the molar ratio of SiH to silicon-bonded ethylenically unsaturated groups in said (C) organosilicon compound is from 1:1 to 5:1, or (iii) both (i) and (ii).

7. The composition according to any one of claims 1 to 6, comprising the (A) organopolysiloxane in an amount of 0.5 to 10 weight percent, based on the total weight of the composition, and the (B) organopolysiloxane in an amount of 80 to 99.5 weight percent, based on the total weight of the composition.

8. A method for preparing the composition according to any one of claims 1 to 4, comprising reacting the (i) silicone resin, the (ii) cyclic siloxane, and (iii) at least one of the (A)(iii)(a) branched organopolysiloxane or the (A)(iii)(b) terminator in the presence of a polymerization catalyst to obtain the (A) organopolysiloxane; combining the (A) organopolysiloxane with the (B) organopolysiloxane to obtain the composition; A method comprising:

9. 1. A method of forming a coated substrate, comprising: applying a composition onto a substrate; coating the composition to provide a release coating on the substrate, thereby forming the coated substrate; wherein the composition is the composition of claim 5 or 6.

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

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