Composition for manufacturing release coatings, release coating composition, and related methods

Abstract

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

Description

Technology Field

[0001] Cross-reference of related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 955,107 filed December 30, 2019, and all the advantages of this application, the contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present disclosure generally relates to compositions, more specifically to compositions for manufacturing release coatings and related methods. Background Technology

[0005] Silicone compositions are known in the art and are used in numerous industrial and end-use applications. One of these end-use applications is to form release coatings or liners from which adhesives can be removed. For example, silicone release compositions can be used to coat various substrates, such as paper, to provide release liners for laminating pressure-sensitive adhesives (e.g., tapes). These silicone release compositions are typically addition-curable.

[0006] Conventional release liners are typically formed by adding (or hydrosilylating) an organopolysiloxane having unsaturated hydrocarbon groups with an organohydrogenpolysiloxane in the presence of a hydrosilylation reaction catalyst. Additionally, various additives, such as release modifiers and anti-mist additives, are incorporated into the silicone release composition to improve the performance of the resulting release liner or the method of manufacturing them.

[0007] A base composition for forming a release coating composition is disclosed. The base composition comprises (A) a silicate resin that is liquid at 25°C in the absence of a solvent. (A) the silicate resin comprises an average of at least one silicon-bonded ethylene-based unsaturated group per molecule. The base composition further comprises (B) an organopolysiloxane comprising an average of at least two silicon-bonded ethylene-based unsaturated groups per molecule. (A) the silicate resin is miscible with (B) the organopolysiloxane in the absence of any solvent.

[0008] A method for preparing a base composition and a method for preparing a release coating composition are also disclosed. Additionally, a method for preparing a coated substrate comprising a release coating disposed on a substrate, as well as a coated substrate formed according to said method, are disclosed. Specific details for implementing the invention

[0009] A base composition for forming a release coating composition is disclosed. The base composition may be referred to herein simply as a composition.

[0010] The base composition comprises a (A) silicate resin that is liquid at 25°C in the absence of a solvent. The (A) silicate resin may alternatively be referred to as a silicone resin, but Q siloxy or SiO₂ in the (A) silicate resin 4 / 2Considering the presence of units, it is a silicate resin. Generally, silicone resins, particularly silicate resins, are solid at 25°C due to their three-dimensional network structure. Given the difficulty of processing solid silicone resins, silicone resins are typically dissolved in a solvent and utilized as silicone resin compositions; such silicone resin compositions include or consist of solid silicone resins dissolved in a solvent, for example, an aliphatic or aromatic hydrocarbon solvent. As such, silicone resin compositions are liquid at 25°C or room temperature, which facilitates the processing of silicone resin compositions. For example, silicone resin compositions can be combined with other components or compositions for various end-use applications in liquid form. Similarly, conventional silicone resins that are solid at 25°C in the absence of any solvent do not easily miscible with liquid silicone. This means that when preparing silicone compositions, conventional silicone resins that are solid at 25°C cannot be easily mixed with or solubilized by liquid silicone, for example, liquid organopolysiloxane, in the absence of a retaining solvent. Therefore, when conventional silicone resins are used in silicone compositions, organic solvents are typically required to form the silicone composition and subsequently vaporize either in the form of the composition or during curing.

[0011] However, one drawback of silicone compositions is that the solvent is typically removed at the end-use stage. For example, when a film or article is formed using a silicone composition, the solvent is typically removed during the formation of such film or article. This requires additional processing steps, energy, and associated costs to remove the solvent, such as through a vaporization process.

[0012] In contrast, (A) silicate resin is liquid at 25°C in the absence of any solvent. Therefore, unlike conventional silicone resins, (A) silicate resin being liquid at 25°C is not due to the presence of any solvent, such as an organic solvent. (A) silicate resin consists of a silicate resin without any solvent or carrier vehicle. Furthermore, (A) silicate resin is not only liquid at 25°C in the absence of any solvent, but (A) silicate resin is miscible with (B) organopolysiloxane containing at least two silicon-bonded ethylene-based unsaturated groups per molecule in the base composition. This allows the base composition to be easily formed without requiring any solvent or related process steps for removing the solvent from the base composition.

[0013] "Liquid" means that (A) silicate resin is fluid at 25°C and / or has a measurable viscosity at 25°C in the absence of any solvent. Typically, the viscosity of (A) silicate resin can be measured at 25°C using a Brookfield LV DV-E viscometer equipped with a spindle appropriately selected for the viscosity of (A) silicate resin. The viscosity of (A) silicate resin may vary depending on the content of M, D, T, and / or Q siloxy units present therein, particularly as described below.

[0014] In a specific embodiment, (A) the silicate resin has the following average chemical formula:

[0015] [W] a [X] b [Y] c ,

[0016] In the above equation, 0 <a<1; 0<b<1; 및 0<c<1이나; 단, a+b+c=1이다. 아래첨자 a, b 및 c는 (A) 실리케이트 수지에서 W, X 및 Y 단위의 몰 분율이다.

[0017] (A) In the above average chemical formula for silicate resins, [W], [X], and [Y] are used instead of [M], [D], and [Q]. As is understood in the art, the M siloxy unit contains one siloxane bond (i.e., -O-Si-); the D siloxy unit contains two siloxane bonds; and the Q siloxy unit contains four siloxane bonds.

[0018] However, for the purposes of this disclosure, [W] represents a siloxy unit comprising one -Si-O- bond that may be a siloxane bond or a precursor thereof. A precursor of a siloxane bond is a -Si-OZ bond, where Z is independently H, an alkyl group, or a cation, e.g., K + or Na + , alternatively, H or alkyl groups. Silanol and alkoxy groups can hydrolyze and / or condense to provide siloxane bonds, which are typically inherently present in most silicone resins. These precursors of siloxane bonds can be minimized by bodying the silicone resin, which results in further condensation with water and / or alcohol as byproducts. Therefore, for the purposes of this disclosure, [W] is [R3SiO 1 / 2 ] represents, where each R is an independently selected hydrocarbyl group.

[0019] Additionally, for the purposes of this disclosure, [X] represents a siloxy unit comprising two -Si-O- bonds that may independently be a siloxane bond or a precursor thereof. Thus, for the purposes of this disclosure, [X] represents [R2SiO 1 / 2 (OZ)] b' [R2SiO 2 / 2 ] b'', where each R is independently selected and as defined above; 0 ≤ b' ≤ b; 0 ≤ b" ≤ b; provided that b' + b" = b; and where each Z is independently H, an alkyl group, or a cation. Subscripts b' and b" represent the relative mole fractions of the [X] siloxy unit denoted by subscript b' and the [X] siloxy unit denoted by subscript b", respectively, and the sum of b' and b" is b. The [X] siloxy unit denoted by b' has one siloxane bond and one Si-OZ bond, and the [X] siloxy unit denoted by subscript b" has two siloxane bonds.

[0020] Additionally, for the purposes of this disclosure, [Y] represents a siloxy unit comprising four -Si-O- bonds that may independently be a siloxane bond or a precursor thereof. Thus, for the purposes of this disclosure, [Y] represents [Si(OZ) c' O 4-c' / 2 ], where each Z is independently selected and as defined above, and the subscript c' is an integer from 0 to 3 and is independently selected from each siloxy unit denoted by subscript c in (A) silicate resin. (A) silicate resin may contain a siloxy unit denoted by subscript c, where c' is 0, c' is 1, c' is 2, and c' is 3. The siloxy unit denoted by [Y] may have 1, 2, 3, or 4 siloxane bonds, and the remainder is a Si-OZ moiety.

[0021] In certain embodiments, the subscript a is greater than 0 to 0.9, alternatively greater than 0 to 0.8, alternatively greater than 0 to 0.7, alternatively greater than 0 to 0.6, and alternatively greater than 0 to 0.5. In certain embodiments, the subscript a is 0.10 to 0.50, alternatively 0.15 to 0.40, and alternatively 0.25 to 0.35.

[0022] In these or other embodiments, the subscript b is greater than 0 to 0.9, alternatively greater than 0 to 0.8, alternatively greater than 0 to 0.7, alternatively greater than 0 to 0.6, alternatively greater than 0 to 0.5, alternatively greater than 0 to 0.4. In certain embodiments, the subscript b is 0.10 to 0.30, alternatively 0.15 to 0.30, alternatively 0.15 to 0.25. The subscripts b' and b" define relative amounts of a specific siloxy unit denoted by [X]. As previously stated, 0 ≤ b' ≤ b; and 0 ≤ b" ≤ b; Provided that b'+b"=b. The subscript b' may be 0 while the subscript b" is b, or the subscript b' may be b while the subscript b" is 0. If both siloxy units denoted by b' and b" are present in (A) silicate resin, 0 <b'<b이고; 0<b"<b이나; 단, b'+b"=b이다.

[0023] In these or other embodiments, the subscript c is greater than 0 to 0.9, alternatively greater than 0 to 0.8, alternatively greater than 0 to 0.7, alternatively greater than 0 to 0.6. Alternatively, in these or other embodiments, c is 0.1 to 0.9, alternatively 0.2 to 0.9, alternatively 0.3 to 0.9, alternatively 0.4 to 0.9. In certain embodiments, the subscript c is 0.35 to 0.60, alternatively 0.40 to 0.55.

[0024] R is an independently selected hydrocarbyl group, and (A) at least one, or alternatively at least two, of R per molecule of the silicate resin is an ethylene-based unsaturated group. Generally, the hydrocarbyl group suitable for R may be independently linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups as well as 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. Common examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as derivatives, modifications, and combinations thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., iso-propyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, as well as branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups) include alkyl halides, aryl groups, and combinations thereof. Examples of alkyl halides include the aforementioned alkyl groups in which one or more hydrogen atoms are replaced by halogen atoms, for example, F or Cl.Specific examples of alkyl halide 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, as well as derivatives thereof. Examples of aryl halide groups include the aforementioned aryl groups in which one or more hydrogen atoms are replaced by halogen atoms, e.g., F or Cl. Specific examples of aryl halide groups include chlorobenzyl groups and fluorobenzyl groups.

[0025] In specific embodiments, each R is independently selected from an alkyl group 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 an ethylene-based unsaturated group 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 (i.e., alkenyl and / or alkynyl groups). "Alkenyl" means an acyclic, branched, or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples include vinyl, allyl, hexenyl, and octenyl groups. "Alkynyl" means an acyclic, branched, or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples include ethinyl, propynyl, and butynyl groups. Various examples of ethylene unsaturated groups include CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, H2C=C(CH3)-, H2C=C(CH3)-, H2C=C(CH3)CH2-, H2C=CHCH2CH2-, H2C=CHCH2CH2CH2-, HC≡C-, HC≡CCH2-, HC≡CCH(CH3)-, HC≡CC(CH3)2-, and HC≡CC(CH3)2CH2-. Typically, when R is an ethylene unsaturated group, the ethylene unsaturation is terminal at R. As understood in the art, ethylene unsaturation may be referred to as aliphatic unsaturation.

[0026] In certain embodiments, only the siloxy unit indicated by subscript b contains an R group having ethylenically unsaturated. In these embodiments, the R groups of the siloxy units indicated by subscripts a and c do not have ethylenically unsaturated, and a specific example thereof is methyl. In certain embodiments, the (A) silicate resin contains both a dimethylsiloxy unit and a methylvinylsiloxy unit as the siloxy unit indicated by subscript b. In other embodiments, the (A) silicate resin contains a methylvinylsiloxy unit but not a dimethylsiloxy unit as the siloxy unit indicated by subscript b. The relative amounts of these siloxy units may be optionally controlled when manufacturing the (A) silicate resin. As is understood in the art, the siloxy units described above are merely examples, and methyl may be replaced with other hydrocarbyl groups, and vinyl may be replaced with other ethylenically unsaturated groups.

[0027] In a specific embodiment, (A) the silicate resin has a content of SiOZ moiety of 12 to 80 percent, alternatively 15 to 70 percent, alternatively 15 to 60 percent, alternatively 15 to 50 percent, alternatively 15 to 40 percent, and alternatively 15 to 30 percent, based on the total moles of Si in each molecule. The content of SiOZ moiety is 29 It can be calculated via Si-NMR. In particular, (A) the molar content of the following siloxy units is measured in the silicate resin:

[0028] W = R3SiO 1 / 2

[0029] X1 = R2(OZ)SiO 1 / 2

[0030] X2 = R2SiO 2 / 2

[0031] T1= R(OZ)2SiO 1 / 2

[0032] T2= R(OZ)SiO 2 / 2

[0033] T3= RSiO 3 / 2

[0034] Y1= (OZ)3SiO 1 / 2

[0035] Y2= (OZ)2SiO 1 / 2

[0036] Y3= (OZ)SiO 3 / 2

[0037] Y4= SiO 4 / 2

[0038] The OZ content of silicon atoms as mol% can be calculated using the following formula, using the label for each peak in the formula corresponding to the integration region under the peak corresponding to the label:

[0039] OZ content (mol%) = 100 x

[0040] In the aforementioned embodiments, (A) the silicate resin does not contain T siloxy units, but they are included in the calculation for other embodiments.

[0041] In these or other embodiments, (A) silicate resin has a weight percentage of silicon-bonded ethylene-based unsaturated groups of greater than 0 to 10, based on the total weight of (A) silicate resin. The weight percentage of silicon-bonded ethylene-based unsaturated groups is independent of the viscosity of (A) silicate resin, which is different from the weight percentage of silicon-bonded ethylene-based unsaturated groups of conventional solid silicone resins, which is a function of the viscosity of a specific siloxane polymer or vehicle when dispersed therein. Thus, for example, the weight percentage of silicon-bonded ethylene-based unsaturated groups can be increased without affecting the viscosity of (A) silicate resin. The weight percentage of silicon-bonded ethylene-based unsaturated groups can be optionally controlled when manufacturing (A) silicate resin, as described below.

[0042] In these or other embodiments, the weight percentage of silicon-bonded ethylene-based unsaturated groups in the (A) silicate resin can be selectively controlled independently of the viscosity of the (A) silicate resin. In contrast, in conventional silicone resins containing silicon-bonded ethylene-based unsaturated groups, their content is a function of viscosity, which essentially limits the specific end-use application by limiting the ability to selectively control the content of silicon-bonded ethylene-based unsaturated groups at a specific viscosity. In various embodiments, the (A) silicate resin has a weight-average molecular weight of 1,000 to 100,000, alternatively 1,000 to 50,000, or alternatively 1,000 to 10,000. The molecular weight can be measured via gel permeation chromatography (GPC) on a polystyrene standard. In these or other embodiments, (A) silicate resin has a viscosity at 25°C of 10 to 500,000 cP, alternatively 10 to 250,000 cP, or alternatively 10 to 100,000 cP. Viscosity can be measured at 25°C using a Brookfield LV DV-E viscometer with a spindle appropriately selected for the viscosity of (A) silicate resin as understood in the art. The viscosity and molecular weight of (A) silicate resin can be controlled when manufacturing (A) silicate resin.

[0043] In various embodiments, the silicate resin is prepared from the MQ resin, where M is (R 0 SiO 3 / 2 ) represents the unit of Siloksi, and Q is (SiO 4 / 2 ) Represents the unit of the Silloksi, and R 0represents a silicon-bonded substituent. Such MQ resins are known in the art and are often in solid form (e.g., powder or flake) unless placed in a solvent. However, in nomenclature typically used in the art, the M siloxy unit is a trimethylsiloxy unit, whereas the MQ resin may contain a methyl group and other hydrocarbyl groups. However, typically, the M siloxy unit of the MQ resin is a trimethylsiloxy unit.

[0044] MQ resin is the chemical formula M n Q may have a mole ratio of M siloxy units to Q siloxy units when the number of moles of Q siloxy units is normalized to 1. As the value of n increases, the crosslinking density of the MQ resin decreases. The converse is also true, as as the value of n decreases, the number of M siloxy units decreases, and thus more Q siloxy units are networked without terminalization through M siloxy units. The fact that the chemical formula for the MQ resin normalizes the content of Q siloxy units to 1 does not mean that the MQ resin contains only one Q unit. Typically, the MQ resin contains multiple Q siloxy units clustered or bonded together. The MQ resin may contain 4 weight percent or less, alternatively 3 weight percent or less, or alternatively 2 weight percent or less of hydroxyl groups in certain embodiments.

[0045] In certain embodiments, the subscript n is < 1, for example, the subscript n is 0.05 to 0.99, alternatively 0.10 to 0.95, alternatively 0.15 to 0.90, alternatively 0.25 to 0.85, alternatively 0.40 to 0.80. In these embodiments, based on moles, the MQ resin contains more Q siloxy units than M siloxy units. However, in other embodiments, n may be >1, for example >1 to 6, alternatively >1 to 5, alternatively >1 to 4, alternatively >1 to 3, or alternatively >1 to 2.

[0046] In a specific embodiment, to produce (A) a silicate resin from the MQ resin, the MQ resin is reacted with a silane compound in the presence of a base catalyst. The silane compound typically comprises one silicon-bonded ethylene-based unsaturated group and two silicon-bonded alkoxy groups. The silicon-bonded alkoxy groups may be independently selected and may typically have 1 to 10 carbon atoms, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 or 2, or alternatively 1 carbon atom. For example, the silicon-bonded alkoxy groups may be methoxy, ethoxy, propoxy, butoxy, etc. For example, the silane compound may have the chemical formula R2Si(OR)2, where each R is independently selected and at least one R that is not part of the alkoxy group is an ethylene-based unsaturated group.

[0047] (A) In a method for preparing a silicate resin, a base catalyst typically cleaves the siloxane bonds of the MQ resin, typically between the M siloxy unit and the Q siloxy unit, to provide SiOZ groups, where Z is defined above. A silane compound may be hydrolyzed and condensed with the SiOZ groups to be incorporated therein. Both the cleaved siloxy bonds and the inclusion of linear siloxy units attributable to the silane compound cause the (A) silicate resin to become liquid at 25°C in the absence of a solvent.

[0048] Since the silane compound is incorporated into the (A) silicate resin as a D siloxy unit, i.e., a siloxy unit indicated by [X] and subscript b, the silane compound can be selected based on the desired D siloxy unit. For example, the (A) silicate resin contains a methylvinyl siloxy unit, and the silane compound is a methylvinyldialkoxysilane, e.g., methylvinyldimethoxysilane. If the (A) silicate resin contains a dimethylsiloxy unit and a methylvinylsiloxy unit, the silane compound may contain methylvinyldimethoxysilane in combination with dimethyldimethoxysilane. Thus, the silane compound may contain two or more different silane compounds together.

[0049] The relative amount of silane compound used in comparison to the MQ resin is a function of the desired subscript b in the (A) silicate resin. If more D siloxy units are required, more silane compound is used, and vice versa. Those skilled in the art will understand how to selectively control these contents by considering the description herein, including the examples following this detailed description.

[0050] The MQ resin and the silane compound react in the presence of a catalyst. Typically, the catalyst is an acid or a base that causes the reaction between the MQ resin and the silane compound to be an acid-catalyzed or base-catalyzed reaction. Typically, the reaction is base-catalyzed. As such, in certain embodiments, the catalyst may be selected from the group consisting of strong acid catalysts, strong base catalysts, and combinations thereof. The strong acid catalyst may be trifluoromethanesulfonic acid, etc. The catalyst is typically a strong base catalyst. Typically, the strong base catalyst is KOH, but other base catalysts such as phosphazene base catalysts may be used.

[0051] The phosphazene catalyst is generally an oligomer having at least one -(N=P<)- unit (i.e., a phosphazene unit) and generally having 10 or fewer such phosphazene units, for example, an average of 1.5 to 5 or fewer phosphazene units. The phosphazene catalyst may be, for example, a halophosphazene, for example, chlorophosphazene (phosphonitrile chloride), an oxygen-containing halophosphazene, an ionic derivative of phosphazene, for example, a phosphazene salt, in particular an ionic derivative of a phosphonitrile halide, for example, a perchlorooligophosphazene salt, or a partially hydrolyzed form thereof.

[0052] In certain embodiments, the catalyst comprises a phosphazene base catalyst. The phosphazene base catalyst may be any known in the art, but typically has the following chemical formula:

[0053] ((R 3 2N)3P=N) t (R 3 2N) 3-t P=NR 3

[0054] In the above equation, each R 3 is independently selected from the group consisting of a hydrogen atom, R, and combinations thereof, where t is an integer from 1 to 3. R 3 If this is R, R 3is typically an alkyl group having 1 to 20, alternatively 1 to 10, or alternatively 1 to 4 carbon atoms. Any (R 3 2N) Two Rs within the moiety 3 The group can be bonded to the same nitrogen (N) atom and preferably connected to complete a heterocyclic ring having 5 or 6 members.

[0055] Alternatively, the phosphazene base catalyst can be a salt and may have one of the following alternative chemical formulas:

[0056] [((R 3 2N)3P=N) t (R 3 2N) 3-t P=N(H)R 3 ] + [A - ]; or

[0057] [((R 3 2N)3P=N) s (R 3 2N) 4-s P] + [A - ]

[0058] In the above equation, each R 3 is independently selected and as defined above, the subscript t is as defined above, the subscript s is an integer from 1 to 4, and [A] is an anion and is typically selected from the group consisting of fluorides, hydroxides, silanolates, alkoxides, carbonates, and bicarbonates. In one embodiment, the phosphazene base is aminophosphazeneum hydroxide.

[0059] In certain embodiments, the MQ resin and the silane compound are reacted at an elevated temperature, e.g., 75 to 125°C, in the presence of a solvent. A suitable solvent may be a hydrocarbon. Suitable hydrocarbons include aromatic hydrocarbons, e.g., benzene, toluene, or xylene; and / or aliphatic hydrocarbons, e.g., heptane, hexane, or octane. Alternatively, the solvent may be a halogenated hydrocarbon, e.g., dichloromethane, 1,1,1-trichloroethane, or methylene chloride. A neutralizing agent, such as acetic acid, may be used to neutralize the catalyst after the reaction. A person skilled in the art can easily determine the amount of catalyst to be used, which is a function of his choice and reaction conditions. The resulting (A) silicate resin may be isolated or recovered from the reaction product through conventional techniques, e.g., stripping or other vaporization techniques.

[0060] The base composition comprises (A) silicate resin in an amount greater than 0 and less than 100 weight percent based on the total weight of the base composition. The relative amount of (A) silicate resin is a function of the end use of the base composition. When a release coating composition is prepared using the base composition, the content of (A) silicate resin in the base composition is selected based on the desired properties of the release coating composition and the release coating prepared therefrom. In certain embodiments, (A) silicate resin acts as a release modifier in the release coating composition and the release coating prepared therefrom.

[0061] Typically, the remainder of the base composition comprises component (B) as described below, or alternatively comprises it. In certain embodiments, the base composition is substantially free of any solvent, particularly an organic solvent. "Substantially free" means that the base composition contains an organic solvent in an amount of less than 5 wt%, alternatively less than 1 wt%, alternatively less than 0.5 wt%, alternatively less than 0.25 wt%, alternatively less than 0.1 wt%, or alternatively 0 wt%, based on the total weight of the base composition. Additionally, as described below, the base composition is typically formed in the absence of any solvent, including organic solvents, so there is no need to remove the solvent from the mixture to provide the base composition.

[0062] The composition further comprises (B) an organopolysiloxane having an average of at least two silicon-bonded ethylene-based unsaturated groups per molecule. In certain embodiments, the (B) organopolysiloxane has at least two silicon-bonded groups having an average of terminal aliphatic unsaturation per molecule. Such (B) organopolysiloxane may be linear, branched, partially branched, cyclic, resinous (i.e., having a three-dimensional network), or may comprise a combination of different structures. The polyorganosiloxane has an average chemical formula R 4 a SiO (4-a) / 2 It can have, where each R 4 is independently selected from a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, provided that in each molecule, at least two Rs 4 contains aliphatic unsaturation, and the subscript a is selected such that 0 < a ≤ 3.2. R 4 The suitable monovalent hydrocarbon group and monovalent halogenated hydrocarbon group for are as described above for R. The above average chemical formula for polyorganosiloxane is alternatively (R 4 3SiO1 / 2 ) b (R 4 2SiO 2 / 2 ) c (R 4 SiO 3 / 2 ) d (SiO 4 / 2 ) e It can be denoted as, where R 4 is as defined above, and the subscripts b, c, d, and e are each independently ≥ 0 to ≤ 1, provided that the amount (b + c + d + e) ​​= 1. Those skilled in the art understand how these M, D, T, and Q units and their mole fractions affect the subscript a of the above average formula. The T unit (indicated by subscript d), the Q unit (indicated by subscript e), or both are typically present in the polyorganosiloxane resin, whereas the D unit (indicated by subscript c) is typically present in the polyorganosiloxane polymer (and may also be present in the polyorganosiloxane resin or branched polyorganosiloxane).

[0063] Alternatively, (B) organopolysiloxanes can be substantially linear, or alternatively, linear. A substantially linear organopolysiloxane has an average chemical formula R 4 a' SiO (4-a') / 2 It can have, where each R 4 is as defined above, and the subscript a' is selected such that 1.9 ≤ a' ≤ 2.2.

[0064] At 25°C, the substantially linear organopolysiloxane of component (B) may be a fluid liquid or may have the form of uncured rubber. The substantially linear organopolysiloxane may have a viscosity of 10 mPa·s to 30,000,000 mPa·s at 25°C, alternatively 10 mPa·s to 10,000 mPa·s, alternatively 100 mPa·s to 1,000,000 mPa·s, and alternatively 100 mPa·s to 100,000 mPa·s. Viscosity can be measured at 25°C using a Brookfield LV DV-E viscometer equipped with spindles appropriately selected for the viscosity of the substantially linear polyorganosiloxane, namely RV-1 to RV-7. Typically, component (B) is a fluid liquid at 25°C for miscibility with component (A).

[0065] Alternatively, if (B) the organopolysiloxane is substantially linear or linear, (B) the organopolysiloxane may have the following average unit chemical formula: (R 6 R 5 2SiO 1 / 2 ) aa (R 6 R 5 SiO 2 / 2 ) bb (R 6 2SiO 2 / 2 ) cc (R 5 3SiO 1 / 2 ) dd ; In the above equation, each R 5 is an independently selected monovalent hydrocarbon group without aliphatic unsaturation or a monovalent halogenated hydrocarbon group without aliphatic unsaturation; and each R 6is independently selected from the group consisting of alkenyl and alkynyl; subscript aa is 0, 1, or 2, subscript bb is 0 or more, subscript cc is 1 or more, and subscript dd is 0, 1, or 2, provided that the amount (aa + dd) ≥ 2 and (aa + dd) = 2, provided that the amount (aa + bb + cc + dd) is 3 to 2,000. Alternatively, subscript cc is ≥ 0. Alternatively, subscript bb is ≥ 2. Alternatively, the amount (aa + dd) is 2 to 10, alternatively 2 to 8, alternatively 2 to 6. Alternatively, 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.

[0066] R 5 The monovalent hydrocarbon group for is exemplified as an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl halide group having 1 to 6 carbon atoms, an aryl halide group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyl halide group having 7 to 12 carbon atoms, wherein alkyl, aryl, and alkyl halides are as described herein. Alternatively, each R 5 is an alkyl group. Alternatively, each R 5 is independently methyl, ethyl, or propyl. In each case, R 5 may be the same or different. Alternatively, each R 5 is a methyl group.

[0067] R 6 The aliphatic unsaturated monovalent hydrocarbon group of can undergo a hydrosilylation reaction. R 6Suitable aliphatic unsaturated hydrocarbon groups for are alkenyl groups defined herein and exemplified by vinyl, allyl, butenyl, and hexenyl; and alkynyl groups defined herein and exemplified by ethinyl and propynyl. Alternatively, each R 6 It can be vinyl or hexenyl. Alternatively, each R 6 (B) The alkenyl or alkynyl content of the organopolysiloxane may be 0.1% to 1% by weight, or alternatively 0.2% to 0.5% by weight, based on the weight of the organopolysiloxane.

[0068] (B) If the organopolysiloxane is substantially linear, alternatively linear, at least two aliphatic unsaturated groups may be bonded to silicon atoms at a pendant position, a terminal position, or both a pendant position and a terminal position. As a specific example of (B) organopolysiloxane having a pendant silicon-bonded aliphatic unsaturated group, (B) organopolysiloxane may have the following average unit chemical formula:

[0069] [(CH3)3SiO 1 / 2 ]2[(CH3)2SiO 2 / 2 ] cc [(CH3)ViSiO 2 / 2 ] bb ; In the above formula, the subscripts bb and cc are as defined above, and Vi represents a vinyl group. With respect to this average formula, any methyl group may be replaced with another monovalent hydrocarbon group (e.g., alkyl or aryl), and any vinyl group may be replaced with another aliphatic unsaturated monovalent hydrocarbon group (e.g., allyl or hexenyl). Alternatively, as a specific example of a polyorganosiloxane having an average of at least two silicon-bonded aliphatic unsaturated groups per molecule, (B) the organopolysiloxane may have the following average unit formula: Vi(CH3)2SiO[(CH3)2SiO] ccSi(CH3)2Vi; in the above formula, the subscripts cc and Vi are as defined above. Dimethyl polysiloxanes terminated by silicon-bonded vinyl groups may be used alone or in combination with the dimethyl, methyl-vinyl polysiloxane disclosed immediately prior as (B) organopolysiloxane. With respect to this average formula, any methyl group may be replaced with another monovalent hydrocarbon group, and any vinyl group may be replaced with any terminal aliphatic unsaturated monovalent hydrocarbon group. Since at least two silicon-bonded aliphatic unsaturated groups may be present at both the pendant and terminal positions, (B) organopolysiloxane may alternatively have the following average unit formula:

[0070] [Vi(CH3)2SiO 1 / 2 ]2[(CH3)2SiO 2 / 2 ] cc [(CH3)ViSiO 2 / 2 ] bb ; In the above formula, the subscripts bb, cc, and Vi are as defined above.

[0071] (B) Where the organopolysiloxane is a substantially linear polyorganosiloxane, (B) the organopolysiloxane comprises: dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecule; methylphenylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecule; a copolymer of methylphenylsiloxane and dimethylsiloxane capped with dimethylvinylsiloxy groups at both ends of the molecule; a copolymer of methylvinylsiloxane and methylphenylsiloxane capped with dimethylvinylsiloxy groups at both ends of the molecule; a copolymer of methylvinylsiloxane and diphenylsiloxane capped with dimethylvinylsiloxy groups at both ends of the molecule; a copolymer of methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane capped with dimethylvinylsiloxy groups at both ends of the molecule; and a copolymer of trimethylsiloxy groups capped with It can be exemplified by a copolymer of methylvinylsiloxane and methylphenylsiloxane, a copolymer of methylvinylsiloxane and diphenylsiloxane capped with trimethylsiloxy groups at both ends of the molecule, and a copolymer of methylvinylsiloxane, methylphenylsiloxane, and dimethylsiloxane capped with trimethylsiloxy groups at both ends of the molecule.

[0072] Alternatively, (B) the organopolysiloxane may comprise a substantially linear, alternatively linear polyorganosiloxane selected from the group consisting of:

[0073] i) Dimethylvinylsiloxy-terminated polydimethylsiloxane,

[0074] ii) Dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane),

[0075] iii) Dimethylvinylsiloxy-terminated polymethylvinylsiloxane,

[0076] iv) Trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane),

[0077] v) Trimethylsiloxy-terminated polymethylvinylsiloxane,

[0078] vi) Dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane),

[0079] vii) Dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane),

[0080] viii) Dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane),

[0081] ix) Phenyl,methyl,vinyl-siloxy-terminated polydimethylsiloxane,

[0082] x) Dimethylhexenylsiloxy-terminated polydimethylsiloxane,

[0083] xi) Dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane),

[0084] xii) Dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane,

[0085] xiii) Trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane),

[0086] xiv) Trimethylsiloxy-terminated polymethylhexenylsiloxane,

[0087] xv) Dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane),

[0088] xvi) Dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), and

[0089] xvii) Combinations of these.

[0090] Alternatively, (B) the organopolysiloxane may include a dendritic polyorganosiloxane. The dendritic polyorganosiloxane has the average chemical formula: R 4 a'' SiO (4-a'') / 2 It can have, where each R 4 is selected independently as defined above, and the subscript a" is selected such that 0.5 ≤ a" ≤ 1.7.

[0091] Dendritic polyorganosiloxanes have a branched or three-dimensional network molecular structure. At 25°C, dendritic polyorganosiloxanes may be in liquid or solid form. Alternatively, dendritic polyorganosiloxanes may be exemplified as 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, dendritic polyorganosiloxanes contain T units and / or Q units. Specific examples of dendritic polyorganosiloxanes include vinyl-terminated silsesquioxanes (i.e., T resins) and vinyl-terminated MDQ resins.

[0092] Alternatively, (B) the organopolysiloxane may include branched siloxane, silsesquioxane, or both branched siloxane and silsesquioxane.

[0093] (B) Where the organopolysiloxane comprises a blend of different organopolysiloxanes, the blend may be a physical blend or a mixture. For example, where (B) the organopolysiloxane comprises a branched siloxane and a silsesquioxane, the branched siloxane and the silsesquioxane are present in relative amounts such that the amount of the branched siloxane and the amount of the silsesquioxane are blended to a total of 100 parts by weight, based on the total weight of all components present in the composition. Alternatively, 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, branched siloxane may be present in an amount of 50 to 80 parts by weight and silsesquioxane may be present in an amount of 20 to 50 parts by weight. Alternatively, branched siloxane may be present in an amount of 50 to 76 parts by weight and silsesquioxane may be present in an amount of 24 to 50 parts by weight. Alternatively, branched siloxane may be present in an amount of 50 to 70 parts by weight and silsesquioxane may be present in an amount of 30 to 50 parts by weight.

[0094] (B) The unit chemical formula of the branched siloxane of organopolysiloxane is: (R 7 3SiO 1 / 2 ) p (R 8 R 7 2SiO 1 / 2 ) q (R 7 2SiO 2 / 2 ) r (SiO 4 / 2 ) s It can have, where each R 7 is independently an aliphatic unsaturated monovalent hydrocarbon group or an aliphatic unsaturated monovalent halogenated hydrocarbon group, and each R 8is an alkenyl group or an alkynyl group (both as described above), subscript p is ≥ 0, subscript q is > 0, 15 ≥ r ≥ 995, and subscript s is > 0.

[0095] In the unit formula immediately above, the subscript p is ≥ 0. The subscript q is > 0. Alternatively, the subscript q is ≥ 3. The subscript r is 15 to 995. The subscript s is > 0. Alternatively, the subscript s is ≥ 1. Alternatively, for the subscript p: 22 ≥ p ≥ 0; alternatively, 20 ≥ p ≥ 0; alternatively, 15 ≥ p ≥ 0; alternatively, 10 ≥ p ≥ 0; alternatively, 5 ≥ p ≥ 0. Alternatively, for the subscript q: 22 ≥ q > 0; alternatively, 22 ≥ q ≥ 4; alternatively, 20 ≥ q > 0; alternatively, 15 ≥ q > 1; alternatively, 10 ≥ q ≥ 2; Alternatively, 15 ≥ q ≥ 4. Alternatively, for subscript r: 800 ≥ r ≥ 15; alternatively, 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 is 1, subscript p can be 0 and subscript q can be 4.

[0096] Branched siloxane has the chemical formula (R 7 2SiO 2 / 2 ) m It may contain at least two polydiorganosiloxane chains, wherein each subscript m is independently 2 to 100. Alternatively, the branched siloxane may have the formula (R 7 2SiO 2 / 2 ) o Chemical formula (SiO₂) bonded to 4 polydiorganosiloxane chains 4 / 2It may include at least one unit of ), wherein, in the above formula, each subscript o is independently 1 to 100. Alternatively, the branched siloxane may have the following chemical formula:

[0097] , in the above formula, the subscript u is 0 or 1, and each subscript t is independently 0 to 995, alternatively 15 to 995, alternatively 0 to 100; and each R 9 is an independently selected monovalent hydrocarbon group, and each R 7 is an independently selected monovalent hydrocarbon group without aliphatic unsaturation as described above or a monovalent halogenated hydrocarbon group without aliphatic unsaturation, and each R 8 It is independently selected from the group consisting of alkenyl and alkynyl as described above. Suitable branched siloxanes are exemplified by those disclosed in U.S. Patent No. 6,806,339 and U.S. Patent Application Publication No. 2007 / 0289495.

[0098] In certain embodiments, branched siloxane has the chemical formula (R 2 y R 1 3-y SiO 1 / 2 ) x (R 1 R 2 SiO 2 / 2 ) z (SiO 4 / 2 Having ), and in the above formula, each R 1 is an independently selected hydrocarbyl group without ethylenically unsaturated; and each R 2 is R 1and independently selected from ethylene-based unsaturated groups, and the subscript y is independently selected from each siloxy unit denoted by the subscript x, and is 1 or 2; each subscript x is 1.5 to 6; and the subscript z is 3 to 1,000. Specific examples of hydrocarbyl groups without ethylene-based unsaturated and ethylene-based unsaturated groups are described above for R.

[0099] Silsesquioxane is the unit chemical formula:

[0100] (R 7 3SiO 1 / 2 ) i (R 8 R 7 2SiO 1 / 2 ) f (R 7 2SiO 2 / 2 ) g (R 7 SiO 3 / 2 ) h It can have, and in the above equation R 7 and R 8 ...is as described above, and subscript i is ≥ 0, subscript f is > 0, subscript g is 15 to 995, and subscript h is > 0. Subscript i can be 0 to 10. Alternatively, for subscript i: 12 ≥ i ≥ 0; alternatively 10 ≥ i ≥ 0; alternatively 7 ≥ i ≥ 0; alternatively 5 ≥ i ≥ 0; alternatively 3 ≥ i ≥ 0.

[0101] 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 ≥ f > 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, and alternatively, the subscript h is 1 or 2. Alternatively, when the subscript h is 1, the subscript f may be 3 and the subscript i may be 0. The value for the subscript f may be sufficient to provide a silsesquioxane of unit formula (ii-II) having an alkenyl content of 0.1% to 1%, alternatively 0.2% to 0.6%, based on the weight of the silsesquioxane. Suitable silsesquioxanes are exemplified by those disclosed in U.S. Patent No. 4,374,967.

[0102] (B) The organopolysiloxane may comprise a combination of two or more different polyorganosiloxanes having one or more different characteristics, such as structure, molecular weight, and the content of monovalent and aliphatic unsaturated groups bonded to silicon atoms. The composition may comprise (B) the organopolysiloxane in an amount of 60 to 99.5 weight percent, alternatively 60 to 98 weight percent, alternatively 60 to 95 weight percent, alternatively 70 to 95 weight percent, or alternatively 75 to 95 weight percent, based on the total weight of the composition.

[0103] In these or other embodiments, a base composition comprising (A) a silicate resin and (B) an organopolysiloxane, or alternatively composed thereof, has a viscosity such that the base composition is flowable at 25°C. For example, in a specific embodiment, 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 centipoise (cP), alternatively 2,000 to 50,000 cP, or alternatively 4,000 to 30,000 cP. Viscosity can be measured using a Brookfield LV DV-E viscometer with a spindle appropriately selected for the viscosity of the base composition. The viscosity range is for cases where the base composition does not contain a solvent including an organic solvent.

[0104] In these or other embodiments, the base composition has a weight average molecular weight of 500 to 500,000, alternatively 1,000 to 250,000, or alternatively 10,000 to 150,000. The molecular weight can be measured by gel permeation chromatography (GPC) on a polystyrene standard.

[0105] A method for preparing a base composition is also provided. The method comprises the step of providing a base composition by combining (A) a silicate resin and (B) an organopolysiloxane. Typically, (A) the silicate resin is disposed within (B) the organopolysiloxane. However, components (A) and (B) may be combined in any manner and in any order of addition, optionally by stirring or mixing in other ways. Since (A) the silicate resin is miscible with or miscible within (B) the organopolysiloxane, this method is typically solvent-free.

[0106] A release coating composition comprising a base composition is also provided. The release coating composition further comprises (C) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule. (C) The organosilicon compound may be linear, branched, partially branched, cyclic, dendritic (i.e., having a three-dimensional network), or may comprise a combination of different structures. (C) The organosilicon compound is typically a crosslinking agent and reacts with the ethylene-based unsaturated groups of component (B) and, if present, the ethylene-based unsaturated groups of component (A) when forming a coating, e.g., a release coating. Typically, (C) the organosilicon compound comprises an organohydrogensiloxane.

[0107] (C) As long as the organosilicon compound comprises at least two silicon-bonded hydrogen atoms per molecule, the (C) organosilicon compound may comprise any combination of M, D, T and / or Q siloxy units. These siloxy units may be combined in various ways to form cyclic, linear, branched and / or dendritic (three-dimensional network) structures. Depending on the selection of the M, D, T, and / or Q units, the (C) organosilicon compound may be monomeric, polymeric, oligomeric, linear, branched, cyclic, and / or dendritic.

[0108] (C) Since the organosilicon compound contains an average of at least two silicon-bonded hydrogen atoms per molecule, with respect to the aforementioned siloxy unit, (C) the organosilicon compound may contain any of the following siloxy units containing silicon-bonded hydrogen atoms, optionally in combination with any siloxy unit not containing silicon-bonded hydrogen atoms: (R2HSiO 1 / 2 ), (RH2SiO 1 / 2 ), (H3SiO 1 / 2 ), (RHSiO 2 / 2 ), (H2SiO 2 / 2 ), and / or (HSiO 3 / 2)(Here, R is independently selected and as defined above).

[0109] In certain embodiments, (C) the organosilicon compound is a substantially linear, alternatively linear polyorganohydrogensiloxane. The substantially linear or linear polyorganohydrogensiloxane has the unit chemical formula:

[0110] (HR 10 2SiO 1 / 2 ) v' (HR 10 SiO 2 / 2 ) w' (R 10 2SiO 2 / 2 ) x' (R 10 3SiO 1 / 2 ) y' having, and in the above formula, each R 10 R is an independently selected monovalent hydrocarbon group, where subscript v' is 0, 1, or 2, subscript w' is 1 or greater, subscript x' is 0 or greater, and subscript y' is 0, 1, or 2, provided that positive(v' + y') is 2 and positive(v' + w') is ≥ 3. 10 The monovalent hydrocarbon group for may be as described above for the monovalent hydrocarbon group for R. The amount (v' + w' + x' + y') may be 2 to 1,000. The polyorganohydrogensiloxane is as follows:

[0111] i) Dimethylhydrogensiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer,

[0112] ii) Dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane,

[0113] iii) Trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer,

[0114] iv) trimethylsiloxy-terminated polymethylhydrogensiloxane, and / or

[0115] 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.

[0116] In one specific embodiment, (C) the organosilicon compound is linear and comprises a pendant silicon-bonded hydrogen atom. In this embodiment, (C) the organosilicon compound may be a dimethyl, methyl-hydrogen polysiloxane having the following average chemical formula:

[0117] (CH3)3SiO[(CH3)2SiO] x' [(CH3)HSiO] w' Si(CH3)3

[0118] In the above formula, x' and w' are as defined above. Those skilled in the art understand that in the above exemplary formula, the dimethylsiloxy unit and the methylhydrogensiloxy unit may be present in a random or block form, and any methyl group may be replaced by any other hydrocarbon group that is not aliphatic unsaturated.

[0119] In another specific embodiment, (C) the organosilicon compound is linear and comprises a terminal silicon-bonded hydrogen atom. In this embodiment, (C) the organosilicon compound may be a SiH-terminated dimethylpolysiloxane having the following average chemical formula:

[0120] H(CH3)2SiO[(CH3)2SiO] x' Si(CH3)2H

[0121] In the above formula, x' is as defined above. SiH-terminated dimethyl polysiloxane may be used alone or in combination with the dimethyl, methyl-hydrogen polysiloxane disclosed immediately prior. When a mixture is used, the relative amounts of each organohydrogen siloxane in the mixture may vary. Those skilled in the art understand that any methyl group in the above exemplary formula may be replaced with any other hydrocarbon group that is not aliphatic unsaturated.

[0122] Alternatively, (C) the organosilicon compound may contain both the pendant and the terminal silicon-bonded hydrogen atom.

[0123] In another specific embodiment, (C) the organosilicon compound is of the formula H y' R 1 3-y' Si-(OSiR 1 2) m -(OSiR 1 H) m' -OSiR 1 3-y' H y' having, and in the above formula, each R 1 is an independently selected hydrocarbyl group that is not ethylenically unsaturated, each y' is independently selected from 0 or 1, and subscripts m and m' are each from 0 to 1,000, provided that m and m' are not simultaneously 0, and m+m' is from 1 to 1,000.

[0124] In certain embodiments, (C) the organosilicon compound may comprise an alkylhydrogen cyclosiloxane or an alkylhydrogen dialkyl cyclosiloxane copolymer. Specific examples of suitable organosilicon of this type are (OSiMeH)4, (OSiMeH)3(OSiMeC6H 13 ), (OSiMeH)2(OSiMeC6H 13 )2, and (OSiMeH)(OSiMeC6H 13It includes )3, where Me represents methyl (-CH3).

[0125] (C) Other examples of organohydrogensiloxanes suitable for organosilicon compounds are those having at least two SiH-containing cyclosiloxane rings within a single molecule. These organohydrogensiloxanes may be any organopolysiloxane having at least two cyclosiloxane rings having 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 unit required to form a siloxane ring) and may be any combination of M, D, T, and / or Q siloxy units forming a cyclic structure, provided that at least one of the cyclic siloxy units on each siloxane ring contains one SiH unit, which may be an M siloxy unit, a D siloxy unit, and / or a T siloxy unit. These siloxy units may be represented as MH, DH, and TH siloxy units, respectively, when the other substituent is methyl.

[0126] (C) The organosilicon compound may comprise a combination of two or more different organohydrogensiloxanes that differ in one or more characteristics, such as structure, molecular weight, the content of monovalent groups bonded to silicon atoms and silicon-bonded hydrogen atoms. The release coating composition may comprise the organosilicon compound (C) in an amount that provides a molar ratio of silicon-bonded hydrogen atoms in component (C) to silicon-bonded ethylene-unsaturated groups in component (B) (and, if present, silicon-bonded ethylene-unsaturated groups in component (A)) of 1:1 to 5:1, alternatively 1.1:1 to 3.1.

[0127] In certain embodiments, the release coating 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 the hydrosilylation reaction. Combinations of different hydrosilylation reaction catalysts may be used.

[0128] In certain embodiments, (D) the hydrosilylation reaction catalyst comprises group VIII to XI transition metals. Group VIII to XI transition metals refer to modern IUPAC nomenclature. Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs); Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations of these, complexes of these (e.g., organometallic complexes), and other forms of such metals may be used as (D) the hydrosilylation reaction catalyst.

[0129] (D) Additional examples of catalysts suitable for a hydrosilylation reaction 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 including calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations of these, complexes of these (e.g., organometallic complexes), and other forms of such metals may be used as catalysts for (D) a hydrosilylation reaction.

[0130] (D) The hydrosilylation reaction catalyst may be of any suitable form. For example, (D) the hydrosilylation reaction catalyst may be a solid, examples of which include platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, and also nickel-based catalysts. Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt, and similar elements, and also similar catalysts including platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and combinations of multiple metals. Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts, etc.

[0131] (D) The hydrosilylation reaction catalyst may be present in or on a solid support. Examples of supports include activated carbon, silica, silica alumina, alumina, zeolite, and other inorganic powders / particles (e.g., sodium sulfate). (D) The hydrosilylation reaction catalyst may also be placed in a vehicle, for example, a solvent that solubilizes the (D) hydrosilylation reaction catalyst, or alternatively, a vehicle that merely supports the (D) hydrosilylation reaction catalyst but does not solubilize it. Such vehicles are known in the art.

[0132] In certain embodiments, (D) the hydrosilylation reaction catalyst comprises platinum. In such embodiments, (D) the hydrosilylation reaction catalyst is exemplified, for example, platinum black; compounds, for example, 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 within a matrix or core-shell type compound. Microencapsulated hydrosilylation catalysts and methods for preparing the same are also known in the art, as exemplified in U.S. Patents No. 4,766,176 and No. 5,017,654, the full text of which is incorporated herein by reference.

[0133] (D) Complexes of organopolysiloxane and platinum suitable for use as a hydrosilylation reaction catalyst include complexes of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane and platinum. Such complexes may be microencapsulated within a resin matrix. Alternatively, (D) the hydrosilylation reaction catalyst may include a complex of platinum and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane. (D) The hydrosilylation reaction catalyst may be prepared by a method comprising the step of reacting a platinum-chloroacetic acid with an aliphatic unsaturated organosilicon compound such as an alkene-platinum-silyl complex or divinyltetramethyldisiloxane. The alkene-platinum-silyl complex can be prepared, for example, by mixing 0.015 mol of (COD)PtCl2 with 0.045 mol of COD and 0.0612 mol of HMeSiCl2.

[0134] Also or alternatively, (D) the hydrosilylation reaction catalyst may be a photoactivable hydrosilylation reaction catalyst, which may initiate curing through irradiation and / or heating. The photoactivable hydrosilylation reaction catalyst may be any hydrosilylation reaction catalyst capable of catalyzing the hydrosilylation reaction, particularly when exposed to radiation having a wavelength of 150 to 800 nanometers (nm).

[0135] (D) Specific examples of photoactivable hydrosilylation reaction catalysts suitable for hydrosilylation reaction catalysts include platinum(II) β-diketonate complexes, e.g. platinum(II)bis(2,4-pentanedioate), platinum(II)bis(2,4-hexanedioate), platinum(II)bis(2,4-heptanedioate), platinum(II)bis(1-phenyl-1,3-butanedioate, platinum(II)bis(1,3-diphenyl-1,3-propanedioate), platinum(II)bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedioate); (η-cyclopentadienyl)trialkylplatinum complexes, e.g. (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsilyl-Cp)trimethylplatinum (where Cp represents cyclopentadienyl); triazene oxide-transition metal complexes, e.g., Pt[C6H5NNNOCH3]4, Pt[p-CN-C6H4NNNOC6H 11 ]4, Pt[p-H3COC6H4NNNOC6H 11 ]4, Pt[p-CH3(CH2) x -C6H4NNNOCH3]4, 1,5-Cyclooctadiene.Pt[p-CN-C6H4NNNOC6H 11 ]2, 1,5-cyclooctadiene.Pt[p-CH3O-C6H4NNNOCH3]2, [(C6H5)3P]3Rh[p-CN-C6H4NNNOC6H 11 ], and Pd[p-CH3(CH2) x-C6H4NNNOCH3]2(where x is 1, 3, 5, 11, or 17); (η-diolefin)(σ-aryl)platinum complex, e.g. (η 4 -1,5-cyclooctadienyl)diphenylplatinum, η 4 -1,3,5,7-cyclooctatetraenyl)diphenylplatinum, (η 4 -2,5-norboradienyl)diphenylplatinum, (η 4 -1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (η 4 -1,5-cyclooctadienyl)bis-(4-acetylphenyl)platinum, and (η 4 -1,5-cyclooctadienyl)bis-(4-trifluoromethylphenyl)platinum, but is not limited thereto. Typically, a photoactivable hydrosilylation reaction catalyst is a Pt(II) β-diketonate complex, and more typically, the catalyst is platinum(II) bis(2,4-pentanedioate).

[0136] (D) The hydrosilylation reaction catalyst is present in the release coating composition in a catalytic amount, that is, in an amount or quantity sufficient to promote the curing of the composition under desired conditions. (D) The hydrosilylation reaction catalyst may be a single hydrosilylation reaction catalyst or a mixture comprising two or more different hydrosilylation reaction catalysts.

[0137] (D) The catalyst amount of the hydrosilylation reaction catalyst may be > 0.01 ppm to 10,000 ppm; alternatively, > 1,000 ppm to 5,000 ppm. Alternatively, a typical catalyst amount of (D) the hydrosilylation reaction catalyst is 0.1 ppm to 5,000 ppm, alternatively 1 ppm to 2,000 ppm, alternatively > 0 ppm to 1,000 ppm. Alternatively, the catalyst amount of (D) the hydrosilylation reaction catalyst may be a platinum group metal of 0.01 ppm to 1,000 ppm, alternatively 0.01 ppm to 100 ppm, alternatively 20 ppm to 200 ppm, or alternatively 0.01 ppm to 50 ppm, based on the total weight of the composition.

[0138] The release coating composition may further include one or more of (E) an inhibitor, (F) an anchorage additive, (G) a mist-preventing additive, (H) a release modifier, and (I) a vehicle.

[0139] In certain embodiments, the release coating composition further comprises (E) an inhibitor. (E) the inhibitor may be used to alter the reaction rate or curing rate of the release coating composition compared to a composition containing the same starting material but in which the (E) inhibitor is omitted. (E) the inhibitor is an acetylene alcohol, e.g., methyl butynol, ethinylcyclohexanol, dimethylhexinol, and 3,5-dimethyl-1-hexin-3-ol, 1-butyn-3-ol, 1-propin-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-octin-3-ol, and 1-ethynyl-1-cyclohexanol, and combinations thereof; Cycloalkenylsiloxanes such as methylvinylcyclosiloxane exemplified by 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and combinations thereof; ene-yne ​​compounds, e.g., 3-methyl-3-pentene-1-phosphorus, 3,5-dimethyl-3-hexene-1-phosphorus; triazoles, e.g., benzotriazole; phosphine; mercaptan; hydrazine; amines, e.g., tetramethylethylenediamine, maleates such as dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, diallyl maleate; nitriles; ethers; carbon monoxide; alkenes, e.g., cyclooctadiene, divinyltetramethyldisiloxane; Alcohols, e.g., benzyl alcohol; and combinations thereof are exemplified. Alternatively, (E) inhibitors may be selected from the group consisting of acetylene alcohols (e.g., 1-ethynyl-1-cyclohexanol) and maleates (e.g., diallyl maleate, bis-maleate, or n-propyl maleate) and combinations of two or more of these.

[0140] Alternatively, (E) the inhibitor may be a silylated acetylene-based compound. Although not intended to be theoretical, it is thought that the addition of a silylated acetylene-based compound reduces the yellowing of the reaction product produced from the hydrosilylation reaction of the release coating composition compared to the reaction product produced from the hydrosilylation of a composition that does not contain a silylated acetylene-based compound or contains an organic acetylene-based alcohol stabilizer as described above.

[0141] Silylated acetylene compounds include (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3-methyl-1-butyn-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane, Examples include bis(3-methyl-1-butyn-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexine-3-oxy)trimethylsilane, (3-phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-etyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-etyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-etyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-etyn-1-oxy)trimethylsilane and combinations thereof. Alternatively, (E) inhibitors are exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or combinations thereof. Silylated acetylene compounds useful as (E) inhibitors may be prepared by methods known in the art, such as silylating the aforementioned acetylene alcohols by reacting them with chlorosilane in the presence of an acid acceptor.

[0142] The amount of inhibitor (E) present in the release coating composition will depend on various factors including the desired pot life of the release coating composition, whether the release coating composition is a one-part composition or a multi-part composition, the specific inhibitor used, and the selection and amount of components (A) to (D). However, where present, the amount of inhibitor (E) may be 0% to 1%, alternatively 0% to 5%, alternatively 0.001% to 1%, alternatively 0.01% to 0.5%, or alternatively 0.0025% to 0.025% based on the total weight of the release coating composition.

[0143] In certain embodiments, the composition further comprises (F) a fixing additive. Suitable fixing additives are exemplified by the reaction product of a vinyl alkoxysilane and an epoxy-functional alkoxysilane; the reaction product of a vinyl acetoxysilane and an epoxy-functional alkoxysilane; and a combination of a polyorganosiloxane having at least one aliphatic unsaturated hydrocarbon group and at least one hydrolyzable group per molecule and an epoxy-functional alkoxysilane (e.g., a combination of a hydroxy-terminated vinyl functional polydimethylsiloxane and a glycidoxypropyltrimethoxysilane) (e.g., physical blends and / or reaction products). Alternatively, the fixing additive may comprise a polyorganosilicate resin. Suitable fixing additives and methods for their preparation are, for example, U.S. Patent No. 9,562,149; It is disclosed in U.S. Patent Application Publications No. 2003 / 0088042, No. 2004 / 0254274, and No. 2005 / 0038188; and European Patent No. 0 556 023.

[0144] Further examples of suitable fixing additives include transition metal chelates, hydrocarbon oxysilanes, e.g., alkoxysilanes, combinations of alkoxysilanes and hydroxy-functional polyorganosiloxanes, or combinations thereof. (F) The fixing additive may be a silane having at least one substituent having an adhesion-promoting group such as an epoxy, acetoxy, or acrylate group. The adhesion-promoting group may additionally or alternatively be any hydrolyzable group that does not affect the (D) hydrosilylation reaction catalyst. Alternatively, (F) the fixing additive may comprise a partial condensate of such silane, e.g., an organopolysiloxane having an adhesion-promoting group. Also alternatively, (F) the fixing additive may comprise a combination of alkoxysilanes and hydroxy-functional polyorganosiloxanes.

[0145] Alternatively, (F) the fixing additive may comprise an unsaturated or epoxy-functional compound. (F) The fixing additive may comprise an unsaturated or epoxy-functional alkoxysilane. For example, the functional alkoxysilane may comprise 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, e.g., vinyl, allyl, hexenyl, undecylenyl. One specific example of an unsaturated compound is vinyltriacetoxysilane.

[0146] 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-acryloyloxypropyltrimethoxysilane, and combinations thereof.

[0147] (F) The fixing additive may also include one or more reaction products or partial reaction products of these compounds. For example, in certain embodiments, (F) the fixing additive may include a reaction product or partial reaction product of vinyltriacetoxysilane and 3-glycidoxypropyltrimethoxysilane. Alternatively or additionally, (F) the fixing additive may include an alkoxy or alkenyl functional siloxane.

[0148] Alternatively, (F) the fixing additive may comprise an epoxy-functional siloxane, for example, a reaction product of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane as described above, or a physical blend of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane. (F) The fixing additive may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, (F) the fixing additive is exemplified by a mixture of the reaction product of hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

[0149] Alternatively, (F) the fixing additive may include a transition metal chelate. Suitable transition metal chelates include titanates, zirconates, e.g., zirconium acetylacetonate, aluminum chelates, e.g., aluminum acetylacetonate, and combinations thereof. Alternatively, (F) the fixing additive may include a combination of a transition metal chelate and an alkoxysilane, e.g., a combination of glycidoxypropyltrimethoxysilane and an aluminum chelate or a zirconium chelate.

[0150] When used, the specific amount of (F) fixing additive present in the release coating composition depends on various factors including the type of substrate and whether a primer is used. In certain embodiments, (F) fixing additive is present in the release coating composition in an amount of 0 to 2 parts by weight per 100 parts by weight of component (B). Alternatively, (F) fixing additive is present in the release coating composition in an amount of 0.01 to 2 parts by weight per 100 parts by weight of component (B).

[0151] In certain embodiments, the composition further comprises (G) a mist-preventing additive. (G) The mist-preventing additive may be used in the release coating composition to reduce or suppress silicon mist formation, particularly in coating processes using high-speed coating equipment. (G) The mist-preventing additive may be the 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-preventing 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. Alternatively, (G) the mist-preventing additive may comprise an MDQ resin that may optionally comprise two or more silicon-bonded ethylene-based unsaturated groups.

[0152] The amount of (G) anti-mist additive used in the release coating composition will depend on various factors, including the amount and type of other starting materials selected for the release coating composition. However, (G) anti-mist additive is typically used in an amount of 0% to 10%, or alternatively 0.1% to 3%, based on the total weight of the release coating composition. These amounts exclude those related to component (A) and relate only to the (G) anti-mist additive, which is separate from and distinct from component (A).

[0153] In certain embodiments, the release coating composition further comprises (H) a release modifier, which may be used in the release coating composition to control (reduce) the level of release force (adhesion force between the release coating formed from the release coating composition and the substrate thereon, e.g., a label including a pressure-sensitive adhesive). (H) the release modifier is distinct from component (A), which also acts as a release modifier when the base composition is used to manufacture the release coating. A release coating having the required or desired release force may be formulated from a modifier-free composition by adjusting the level or concentration of (H) the release modifier. Examples of release modifiers suitable for component (H) include trimethylsiloxy-terminated dimethyl, phenylmethylsiloxane. Alternatively, (H) the release modifier may be a condensation reaction product of an organopolysiloxane resin having hydroxyl or alkoxy groups and a diorganopolysiloxane having one or more hydroxyl or hydrolyzable groups. Examples of suitable release modifiers are disclosed, for example, in U.S. Patent No. 8,933,177 and U.S. Patent Application Publication No. 2016 / 0053056. When used, (H) the release modifier may be present in the release coating composition in an amount of 0 to 85 parts by weight, alternatively 25 to 85 parts by weight, per 100 parts by weight of component (B).

[0154] In certain embodiments, the release coating composition further comprises (I) a vehicle. (I) vehicle typically solubilizes the components of the release coating composition, and if the components are solubilized, (I) vehicle may be referred to as a solvent. Suitable vehicles include silicone, linear and cyclic organic oils, organic solvents, and mixtures thereof.

[0155] Typically, (I) the vehicle is an organic liquid when present in the release coating composition. The organic liquid includes an oil or a liquid considered as a solvent. The organic liquid is exemplified, but is not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having more than three carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, and aromatic halides. The hydrocarbons include isododecane, isohexadecane, Isopar L (C11-C13), Isopar H (C11-C12), hydrogenated polydecene, aromatic hydrocarbons, and halogenated hydrocarbons. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, and octyl palmitate. Additional organic fluids suitable as a single compound or as a component for (I) vehicle include fats, oils, fatty acids, and fatty alcohols.(I) The vehicle also comprises a low-viscosity organopolysiloxane or volatile methylsiloxane or volatile ethylsiloxane or volatile methylethylsiloxane having a viscosity at 25°C in the range of 1 to 1,000 mm² / sec, e.g., 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 and polyethylsiloxane. It may be polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any mixture thereof.

[0156] In certain embodiments, (I) the vehicle is selected from polyalkylsiloxane; tetrahydrofuran; mineral spirit; naphtha; alcohol, e.g., methanol, ethanol, isopropanol, butanol, or n-propanol; ketone, e.g., acetone, methyl ethyl ketone, or methyl isobutyl ketone; aromatic hydrocarbon, e.g., benzene, toluene, or xylene; aliphatic hydrocarbon, e.g., heptane, hexane, or octane; glycol ether, e.g., 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.

[0157] (I) The amount of vehicle will depend on various factors including the type of vehicle selected and the amount and type of other components present in the release coating composition. However, the amount of vehicle (I) in the release coating composition may be 0% to 99%, or alternatively 0% to 50%, based on the total weight of the release coating composition. Vehicle (I) may be added during the preparation of the release coating composition, for example, to aid in mixing and delivery. All or part of vehicle (I) may be optionally removed after the release coating composition is prepared, including before and / or simultaneously with the preparation of the release coating from the release coating composition. However, typically, the release coating composition is free of vehicle (I) and is therefore a solvent-free release coating composition.

[0158] For example, reactive diluents, fragrances, preservatives, colorants, dyes, and other optional components including fillers, such as silica, quartz, or chalk, may be present in the release coating composition.

[0159] Alternatively, the release coating composition and the release coating formed therefrom may be free of particulates, or may contain only a limited amount of particulates (e.g., fillers and / or pigments), for example, 0 to 30 weight percent of the release coating composition. The particulates may aggregate or otherwise adhere to the coating equipment used to form the release coating. Additionally, where optical transparency is required, the particulates may interfere with the optical properties, for example, transparency, of the release coating and the release liner formed using it. The particulates may be detrimental to the adhesion of the substrate.

[0160] In certain embodiments, the release coating composition does not contain a fluoroorganosilicon compound. During curing, it is believed that the fluorocompound can rapidly migrate due to its low surface tension to the interface between the release coating composition or the release coating formed using it and the substrate on which the release coating composition is applied and the release coating is formed, e.g., the composition / PET film interface. This migration can prevent the attachment of the release coating (prepared by curing the release coating composition) to the substrate by creating a fluorine-containing barrier. By creating a barrier, the fluoroorganosilicon compound can prevent any component of the release coating composition from reacting at the interface, which may affect curing and related properties. Furthermore, fluoroorganosilicon compounds are generally expensive.

[0161] A release coating composition can be prepared by combining components (A) through (D), as well as any of the aforementioned optional components, in any order of addition, optionally using a master batch, and optionally under shear. In certain embodiments, the release coating composition is prepared by comprising components (A) and (B), or alternatively forming a base composition made thereof, and combining the base composition with components (C) and (D). As described in more detail below, the composition may be a one-part composition, a two-component or two-k composition, or a multi-part composition. For example, components (A) and (B) may be a single part of the release coating composition. When the release coating composition is used to produce a release coating or a coated substrate, components (A) and (B) are combined with components (C) and (D), as well as any optional components, so that the release coating composition becomes a curable composition, as described below. If the release coating composition further comprises component (C) and component (D), such release coating composition may be referred to as a curable composition.

[0162] A method for manufacturing a coated substrate using a release coating composition comprises the step of applying, i.e., placing, the release coating composition onto a substrate. The method further comprises the step of curing a curable composition onto the substrate, thereby forming a release coating on the substrate and providing a coated substrate. Curing may be performed by heating to an elevated temperature, for example, 50°C to 180°C, alternatively 50°C to 120°C, or alternatively 50°C to 90°C, thereby providing the coated substrate. A person skilled in the art may select an appropriate temperature based on various factors, including the selection of components in the curable composition and the substrate composition or constituent material.

[0163] The curable composition may be placed or distributed onto a substrate in any suitable manner. Typically, the curable composition is applied in a wet form via a wet coating technique. The curable composition may be applied by i) spin coating; ii) brush coating; iii) drop coating; iv) spray coating; v) dip coating; vi) roll coating; vii) flow coating; viii) slot coating; ix) gravure coating; x) Meyer bar coating; or xi) any two or more combinations of i) to x). Typically, the step of placing the curable composition onto a substrate creates a wet deposit on the substrate and then cures the wet deposit to provide a coated substrate, the coated substrate comprising a cured film formed from the curable composition on the substrate, i.e., a release coating.

[0164] 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 of substrate. The substrate may have an integral hot plate or an integral or standalone furnace for curing the wet deposit. The substrate may optionally have continuous or discontinuous shapes, sizes, dimensions, surface roughness, and other features. Alternatively, the substrate may have a softening point temperature at elevated temperatures. However, the curable composition and method are not so limited.

[0165] Alternatively, the substrate may comprise plastic, which may be thermosetting and / or thermoplastic. However, the substrate may alternatively be or comprise glass, metal, cellulose (e.g., paper), wood, cardboard, paperboard, silicone, or polymeric materials, or a combination thereof.

[0166] Specific examples of suitable substrates include paper substrates, e.g., kraft paper, polyethylene-coated kraft paper (PEK coated paper), thermal paper, and ordinary paper; polymeric substrates, e.g., polyamide (PA); polyesters, e.g., polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins, e.g., polyethylene (PE), polypropylene (PP), and polybutylene; styrene resin; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); polyphenylene ether (PPE); polyimide (PI); polyamideimide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; Polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyethernitrile (PEN); phenolic resin; phenoxy resin; cellulose, e.g., triacetylcellulose, diacetylcellulose, and cellophane; fluorinated resin, e.g., polytetrafluoroethylene; thermoplastic elastomers, e.g., polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type, and fluoro type; and copolymers and combinations thereof.

[0167] The curable composition or wet deposit is typically cured at an elevated temperature for a specified period. This period is typically sufficient to perform the curing of the curable composition, i.e., crosslinking. This period may be greater than 0 to 8 hours, alternatively greater than 0 to 2 hours, alternatively greater than 0 to 1 hour, alternatively greater than 0 to 30 minutes, alternatively greater than 0 to 15 minutes, alternatively greater than 0 to 10 minutes, alternatively greater than 0 to 5 minutes, or alternatively greater than 0 to 2 minutes. This period depends on various factors including the elevated temperature used, the selected temperature, the desired film thickness, and the presence or absence of any water or vehicle in the curable composition.

[0168] The curing step of the curable composition typically has a residence time of 0.1 to 50 seconds; alternatively, 1 to 10 seconds; or alternatively, 0.5 to 30 seconds. The selected residence time may depend on the choice of substrate, the selected temperature, and the line speed. As used herein, the residence time refers to the time during which the curable composition or the wet deposit is processed at the elevated temperature. Since curing may continue even after the curable composition, the wet deposit, or its partially cured reaction intermediate is no longer processed at the elevated temperature that typically initiates curing, the residence time is distinguished from the curing time. Alternatively, the coated article may be manufactured on a conveyor belt inside 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., in meters / second).

[0169] The duration may be divided into curing repetition steps, for example, a first curing step and a post-curing step, where the first curing step is for example 1 hour and the post-curing step is for example 3 hours. The temperature increase may be independently selected from any temperature exceeding room temperature in these repetition steps and may be the same in each repetition step.

[0170] Depending on the thickness and other dimensions of the film and the coated substrate, the coated substrate may be formed through a repetitive process. For example, a first deposition may be formed and treated with a first temperature for a first period to provide a partially cured deposition. Subsequently, a second deposition may be placed on the partially cured deposition and treated with a second temperature for a second period to provide a second partially cured deposition. The partially cured deposition will also be further cured while treated with a second temperature for a second period. A third deposition may be placed on the second partially cured deposition and treated with a third temperature for a third period to provide a third partially cured deposition. The second partially cured deposition will also be further cured while treated with a second temperature for a second period. By repeating this process, for example, 1 to 50 times, the coated article may be made as desired. The composite of the partially cured layers may be treated, for example, with the aforementioned temperature and period as a final post-curing step. Each heating and duration may be selected independently and may be the same or different from one another. If the article is formed through a repeating process, each deposition may also be selected independently and may differ in terms of the selected components in the curable composition, their amounts, or both. Alternatively, each repeating layer may be fully cured rather than only partially cured in such a repeating process.

[0171] Alternatively, the deposit may include a wet film. Alternatively, the iterative process may be wet-on-wet depending on the curing state of the partially cured layer. Alternatively, the iterative process may be wet-on-dry.

[0172] A coated substrate comprising a film formed from a curable composition on a substrate may have various dimensions, including the relative thickness of the film and the substrate. Such a film may have a thickness that varies depending on its end use. The film may have a thickness greater than 0 to 4,000 μm, alternatively greater than 0 to 3,000 μm, alternatively greater than 0 to 2,000 μm, alternatively greater than 0 to 1,000 μm, alternatively greater than 0 to 500 μm, or alternatively greater than 0 to 250 μm. However, other thicknesses, for example, 0.1 to 200 μm, are considered. For example, the thickness of the film may be 0.2 to 175 μm; alternatively 0.5 to 150 μm; alternatively 0.75 to 100 μm; alternatively 1 to 75 μm; alternatively 2 to 60 μm; or alternatively 3 to 50 μm. Alternatively, it may be 4 to 40 μm. Alternatively, if the substrate is plastic, the film may have a thickness of greater than 0 to 200 μm, alternatively greater than 0 to 150 μm, or alternatively greater than 0 to 100 μm.

[0173] In some cases, the film may be treated with additional processes depending on its end use. For example, the film may be treated by oxide deposition (e.g., SiO2 deposition), resist deposition and patterning, etching, chemical treatment, corona treatment, or plasma stripping, metallization, or metal deposition. These additional treatment techniques are generally known. Such deposition may be chemical vapor deposition (including low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and plasma-assisted chemical vapor deposition), physical vapor deposition, or other vacuum deposition techniques. Many of these additional treatment techniques involve elevated temperatures, particularly vacuum deposition, in which case the film is highly suitable due to its excellent thermal stability. However, depending on the end use of the film, the film may be used with these additional treatments.

[0174] Coated substrates can be used for various end-use applications. For example, coated substrates can be used for coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, construction applications, transportation applications, electronic device applications, or electrical applications. However, such curable compositions can be used for other end-use applications other than manufacturing coated substrates, for example, in the manufacture of articles such as silicone rubber.

[0175] Alternatively, the coated substrate may be used as a release liner for tape or adhesive, including any pressure-sensitive adhesive, such as, for example, acrylic resin-type pressure-sensitive adhesive, rubber-type pressure-sensitive adhesive, and silicone-type pressure-sensitive adhesive, as well as acrylic resin-type adhesive, synthetic rubber-type adhesive, silicone-type adhesive, epoxy resin-type adhesive, and polyurethane-type adhesive. Each major surface of the substrate may have a film disposed thereon for double-sided tape or adhesive.

[0176] Alternatively, if the curable composition is formulated as a release coating composition for forming, for example, a release coating or liner, the release coating composition may be prepared by mixing the components together, for example, to prepare a one-part composition. However, it may be preferable to prepare the release coating composition as a multi-part composition in which the component having a SiH functional group (e.g., (C) an organosilicon compound) and (D) a hydrosilylation reaction catalyst are stored as separate parts until these parts are combined at the time of use (e.g., immediately before being applied to a substrate). If the curable composition is a release coating composition, the release coating composition may be used to form a coated substrate as described above, and the release coating is formed by applying and curing the release coating composition on the substrate, for example, on the surface of the substrate.

[0177] For example, a multi-part curable composition may include the following:

[0178] A base part comprising one or more of (A), (A) a silicate resin, (B) an organopolysiloxane comprising an average of at least two silicon-bonded ethylene-based unsaturated groups per molecule, and (D) a hydrosilylation reaction catalyst, and optionally, if present, (F) a fixing additive, and (I) a vehicle, and

[0179] Part (B), (C) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule, and optionally, if present, (F) a fixing additive and / or (I) a curing agent part comprising a vehicle. If used, (E) an inhibitor may be added to Part (A), Part (B), or both. Part (A) and Part (B) may be combined in a weight ratio of (A):(B) of 1:1 to 30:1, alternatively 1:1 to 10:1, alternatively 1:1 to 5:1, or alternatively 1:1 to 2:1. Part (A) and Part (B) may be provided in a kit, for example, with instructions on how to combine the parts to prepare a release coating composition, how to apply the release coating composition to a substrate, and how to cure the release coating composition.

[0180] Alternatively, if (F) a fixing additive is present, it may be incorporated into either part (A) or part (B) or added to a separate (third) part.

[0181] The release coating composition can be applied to a substrate by any convenient means, such as spraying, doctor blade, dipping, or screen printing, or by a roll coater, such as an offset web coater, a kiss coater, or an etched cylinder coater.

[0182] The release coating composition of the present invention may be applied to any substrate such as those described above. Alternatively, the release coating composition may be applied to a polymer film substrate, for example, a polyester, particularly polyethylene terephthalate (PET), polyethylene, polypropylene, or polystyrene film. Alternatively, the release coating composition may be applied to a paper substrate including plastic-coated paper, for example, polyethylene-coated paper, glassine, super calender paper, or clay-coated kraft paper. Alternatively, the release coating composition may be applied to a metal foil substrate, for example, aluminum foil.

[0183] In certain embodiments, the method for manufacturing a coated substrate may further include a step of treating the substrate before applying or placing a release coating composition on the substrate. The treatment of the substrate may be performed by any convenient means, such as plasma treatment or corona discharge treatment. Alternatively, the substrate may be treated by applying a primer. In certain cases, the fixation of the release coating may be improved when the substrate is treated before forming the release coating thereon from the release coating composition.

[0184] If the release coating composition comprises (I) a vehicle, the method may further include a step of removing (I) the vehicle, which may be performed by any conventional means, such as heating at 50°C to 100°C for a time sufficient to remove all or part of (I) the vehicle. The method may further include a step of curing the release coating composition to form a release coating on the surface of a substrate. Curing may be performed by any conventional means, such as heating at 100°C to 200°C.

[0185] Under production coating machine conditions, curing can be achieved at an air temperature of 120°C to 150°C for 1 to 6 seconds, or alternatively, for a residence time of 1.5 to 3 seconds. Heating can be performed in an oven, for example, an air circulation oven or a tunnel furnace, or by passing the coated film around a heated cylinder.

[0186] The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention in any way. Specific components used in the examples are listed in Table 1 below, followed by the characterization and evaluation procedures also used in the examples.

[0187] [Table 1]

[0188]

[0189] Nuclear Magnetic Resonance Spectroscopy (NMR)

[0190] Nuclear magnetic resonance (NMR) spectra are obtained on an NMR Bruker AVIII (400 MHz) using a silicon-free 10 mm tube and CDCl3 / Cr(AcAc)3 solvent. 29 Chemical variations in the Si-NMR spectrum are shown based on internal solvent resonance and recorded in contrast to tetramethylsilane.

[0191] Gel Permeation Chromatography (GPC)

[0192] Gel permeation chromatography (GPC) analysis is performed on an Agilent 1260 Infinity II chromatograph equipped with a triple detector consisting of a differential refractometer, an online differential viscometer, low-angle light scattering (LALS: 15° and 90° detection angles), and a column (2 PL gel mixture C, Varian). Toluene (HPLC grade, Biosolve) is used as the mobile phase at a flow rate of 1 mL / min.

[0193] Absolute viscosity (DV: Dynamic Viscosity)

[0194] Absolute viscosity (DV) is measured using a Brookfield DV-III Ultra programmable rheometer with a CPA-52Z spindle using a sample volume of 0.5 mL at a temperature of 25°C.

[0195] X-ray fluorescence (XRF)

[0196] X-ray fluorescence (XRF) is performed on an Oxford Instruments Lab-X 3500 benchtop XRF analyzer.

[0197] SiOZ content

[0198] The content of SiOZ moiety is 29 It can be calculated via Si-NMR. In particular, the molar content of the following siloxy units is measured in each (A) silicate resin:

[0199] W = R3SiO 1 / 2

[0200] X1 = R2(OZ)SiO 1 / 2

[0201] X2 = R2SiO 2 / 2

[0202] T1= R(OZ)2SiO 1 / 2

[0203] T2= R(OZ)SiO 2 / 2

[0204] T3= RSiO 3 / 2

[0205] Y1= (OZ)3SiO 1 / 2

[0206] Y2= (OZ)2SiO 2 / 2

[0207] Y3= (OZ)SiO 3 / 2

[0208] Y4= SiO 4 / 2

[0209] The OZ content of silicon atoms as mol% can be calculated using the following formula, using the label for each peak in the formula corresponding to the integration region under the peak corresponding to the label:

[0210] OZ content (mol%) = 100 x

[0211] In the examples, R may be methyl or vinyl.

[0212] Curing performance: Extractable percentage

[0213] The curing performance of the sample composition is evaluated by measuring the extractable percentage value (extractable %). Specifically, the sample composition is coated and cured on a substrate (glassine paper) to form a coated substrate, which is then immediately cut into three sample discs (die cutter, 1.375 inches (3.49 cm)) handled exclusively by tweezers to minimize contamination and / or damage. Each sample disc is analyzed via XRF to determine the initial coat weight (W i s After measuring ), place the discs in individual bottles (100 mL, lidded) containing solvent (methyl isobutyl ketone, 40 mL) and immerse them on a bench for 30 minutes. Subsequently, remove each sample disc from the bottle, place it on a clean surface (tissue paper) with the coated side facing up to evaporate the residual solvent (without blotting / wiping), and then analyze via XRF to determine the final coat weight (W f s Measure ). The extractable % of each sample is the percentage change in coat weight from solvent immersion, i.e., calculated using the following mathematical formula: [(W i s - W f s) / Wi] x 100%). Extractable % represents the amount of uncured component (e.g., non-crosslinked silicone) of the sample composition extractable from the coated substrate, and, for example, a lower extractable % indicates higher / better curing performance.

[0214] Curing Performance: Fixation (ROR%)

[0215] The fixation of the sample composition is evaluated through the fixation index, that is, by measuring the rub-off resistance percentage (ROR%) value. Specifically, the sample composition is coated onto a substrate (glassine paper) and cured to form a coated substrate. Immediately after curing, the coated substrate is cut into two sample discs (die cutter, 1.375 inches (3.49 cm)), and each is analyzed via XRF to determine the initial coat weight (W i a ) is measured. Subsequently, each sample disc is felted under a load (1.9 kg) using an automated abrasive machine in a manner similar to the Taber-type abrasion test (e.g., the method of ASTM D4060-19, i.e., "Standard Test Method for Abrasion Resistance of Organic Coatings by the Taber Abraser"), and then analyzed via XRF to determine the final coat weight (W f a ) was measured. The ROR% of each sample is calculated using the following mathematical formula: [W f s / W i s ] x 100%). Since ROR% indicates how strongly a coating adheres to a substrate, a higher ROR% indicates higher / better adhesion, and the higher the ROR% value, the better.

[0216] Preparation Example 1: Silicate resin (A1)

[0217] 300 g of solvent 1 was followed by 300 g of MQ resin in a 2 L flask equipped with a magnetic stirring rod. 109.0 g of silane compound 1 and 0.30 g of catalyst were added to the flask. The contents of the flask were stirred at 100°C under nitrogen, and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23°C, and then 0.5 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1-micron filter to obtain a clear viscous liquid. The silicate resin (A1) was isolated from the reaction product by removing volatile substances using a rotary evaporator (roto-vap). The silicate resin (A1) was a colorless liquid with a DV of 39,000 cP, a weight average molecular weight of 2,969, and a polydispersity of 1.46 at 25°C, as measured by GPC. (A1) The silicate resin had a SiOZ content of 23.5 mol% and a vinyl content of 6.46 wt%.

[0218] Preparation Example 2: Silicate resin (A2)

[0219] 300 g of solvent 1 was followed by 300 g of MQ resin into a 2 L flask equipped with a magnetic stirring rod. 165.0 g of silane compound 1 and 0.30 g of catalyst were added to the flask. The contents of the flask were stirred at 100°C under nitrogen, and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23°C, and then 0.5 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1-micron filter to obtain a clear viscous liquid. Volatile substances were removed using a rotary evaporator to isolate the silicate resin (A2) from the reaction product. The silicate resin (A2) was a colorless liquid with a DV of 450 cP, a weight-average molecular weight of 3,160, and a polydispersity of 1.65 at 25°C, as measured by GPC. (A2) The silicate resin had a SiOZ content of 30.9 mol% and a vinyl content of 7.58 wt%.

[0220] Preparation Example 3: Silicate resin (A3)

[0221] 300 g of solvent 1 was followed by 300 g of MQ resin into a 2 L flask equipped with a magnetic stirring rod. 217.9 g of silane compound 1 and 0.30 g of catalyst were added to the flask. The contents of the flask were stirred at 100°C under nitrogen, and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23°C, and then 0.5 g of neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 1-micron filter to obtain a clear viscous liquid. Volatile substances were removed using a rotary evaporator to isolate the silicate resin (A3) from the reaction product. The silicate resin (A3) was a colorless liquid with a DV of 200 cP, a weight-average molecular weight of 2,636, and a polydispersity of 1.50 at 25°C, as measured by GPC. (A3) The silicate resin had a SiOZ content of 37.3 mol% and a vinyl content of 8.26 wt%.

[0222] Preparation Example 4: Silicate resin (A4)

[0223] 300 g of solvent 1 was followed by 300 g of MQ resin in a 2 L flask equipped with a magnetic stirring rod. 20.16 g of silane compound 1, 105.3 g of silane compound 2, and 0.30 g of catalyst were added to the flask. The contents of the flask were stirred at 100°C under nitrogen, and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23°C, and then 0.36 g of a neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 0.45 micron filter to obtain a clear viscous liquid. Volatile substances were removed using a rotary evaporator to isolate the silicate resin (A4) from the reaction product. The silicate resin (A4) was a colorless liquid with a DV of 75,000 cP, a weight average molecular weight of 5,450, and a polydispersity of 1.7149 at 25°C, as measured by GPC. (A4) The silicate resin had a SiOZ content of 19.12 mol% and a vinyl content of 1.12 wt%.

[0224] Preparation Example 5: Silicate resin (A5)

[0225] 300 g of solvent 1 was followed by 300 g of MQ resin in a 2 L flask equipped with a magnetic stirring rod. 20.2 g of silane compound 1, 131.1 g of silane compound 2, and 0.30 g of catalyst were added to the flask. The contents of the flask were stirred at 100°C under nitrogen, and the progress of the reaction in the flask was monitored via GC. After 10 hours, the contents of the flask were cooled to 23°C, and then 0.5 g of a neutralizing agent was added to the flask to neutralize the catalyst. The reaction product in the flask was filtered through a 0.45 micron filter to obtain a clear viscous liquid. Volatile substances were removed using a rotary evaporator to isolate the silicate resin (A5) from the reaction product. The silicate resin (A5) was a colorless liquid with a DV of 9,500 cP, a weight average molecular weight of 7,380, and a polydispersity of 1.8996 at 25°C, as measured by GPC. (A5) The silicate resin had a SiOZ content of 25.33 mol% and a vinyl content of 1.09 wt%.

[0226] Preparation Example 6: Silicate resin (A6)

[0227] The same method as in Preparation Example 5 was repeated. The silicate resin (A6) was a colorless liquid having a DV of 9,900 cP, a weight-average molecular weight of 5,820, and a polydispersity of 1.7562 at 25°C, as measured by GPC. (A6) The silicate resin had a SiOZ content of 25.35 mol% and a vinyl content of 0.24 wt%.

[0228] Examples 1 to 11:

[0229] Examples 1 to 11 are release coating compositions comprising silicate resins prepared in Preparation Examples 1 to 6. In each of Examples 1 to 11, a specific silicate resin is combined with (B1) organopolysiloxane to provide a base composition, and each specific base composition is combined with inhibitor 1, an organosilicon compound (C1), and a catalyst (D1) to provide a release coating composition. Each release coating composition of Examples 1 to 11 is solvent-free and is prepared in the absence of any solvent because the silicate resin is miscible with (B1) organopolysiloxane. In each of Examples 1 to 11, the SiH:SiVi molar ratio is 2:1 mol:mol, and in each of Examples 1 to 11, the total Pt content is 100 ppm. Table 2 below shows the relative amounts (g) of each component used to prepare the release coating compositions of Examples 1 to 11.

[0230] [Table 2]

[0231]

[0232] Comparative Examples 1 to 9:

[0233] Comparative Examples 1 to 9 (indicated by CE 1 to 9) are comparative release coating compositions. In each of Comparative Examples 1 to 9, the SiH:SiVi molar ratio is 2:1 mol:mol, and in each of Comparative Examples 1 to 9, the total Pt content is 100 ppm. Table 3 below shows the relative amounts (g) of each component used to prepare the comparative release coating compositions of Comparative Examples 1 to 9.

[0234] [Table 3]

[0235]

[0236] Examples 12 to 22 and Comparative Examples 10 to 18: Coated substrates

[0237] Coated substrates were prepared using the release coating compositions of Examples 1 to 11 and Comparative Examples 1 to 9. Specifically, each composition was coated onto a substrate (glassine paper) and cured (exit web oven temperature: 165.56°C; residence time: 28.4 seconds) to form a coated substrate, and the samples were evaluated for immediate extractability %, immediate ROR%, 7-day RT aging ROR%, and 1-month RT aging ROR%. The 7-day and 1-month RT aging ROR% were performed after aging at RT for a designed time at 50% RH under 40 lb. The results are presented in Tables 4 and 5 below. In Tables 4 and 5, n / a indicates that the value was not measured. Example 12 uses the composition of Example 1; Example 13 uses the composition of Example 2; Example 14 uses the composition of Example 3; and the same applies below. The same applies to the correlation between the compositions of Comparative Examples 10 to 18 and Comparative Examples 1 to 9.

[0238] [Table 4]

[0239]

[0240] [Table 5]

[0241]

[0242] At a 180-degree peel angle, release force, 7-day aging release force, and 1-month aging release force were measured at various speeds, namely 0.3 m / min (MPM), 10 m / min (MPM), 100 m / min (MPM), and 300 m / min (MPM). Release force was measured using the Imass SP-2100 and ZPE-1100W release test systems after lamination with Tesa 7475 standard tape at RT and 50% RH under 40 lb. Aging release force is measured by aging at RT and 50% RH under 40 lb for a specified time. The values ​​are shown in Tables 6 through 8 below. In Tables 6 through 8, TH indicates that the release force is too high to measure, and n / a indicates that no measurement was performed.

[0243] [Table 6]

[0244]

[0245] [Table 7]

[0246]

[0247] [Table 8]

[0248]

[0249] Examples 23 to 25

[0250] Examples 23 to 25 are additional release coating compositions comprising silicate resins prepared in Preparation Examples 1 to 3. In each of Examples 23 to 25, a specific silicate resin is combined with (B1) organopolysiloxane to provide a base composition, and each specific base composition is combined with inhibitor 1, an organosilicon compound (C1), and a catalyst (D1) to provide a release coating composition. Each release coating composition of Examples 23 to 25 is solvent-free and is prepared in the absence of any solvent because the silicate resin is miscible with (B1) organopolysiloxane. Table 9 below shows the relative amounts (g) of each component used to prepare the release coating compositions of Examples 23 to 25.

[0251] [Table 9]

[0252]

[0253] Comparative Examples 19 and 20:

[0254] Comparative Examples 19 and 20 (indicated as CE 19 and 20) are comparative release coating compositions. Table 10 below shows the relative amounts (g) of each component used to prepare the comparative release coating compositions of Comparative Examples 19 and 20.

[0255] [Table 10]

[0256]

[0257] Examples 26 to 28 and Comparative Examples 21 and 22:

[0258] Coated substrates were prepared using the release coating compositions of Examples 23 to 25 and Comparative Examples 19 and 20. In particular, each composition was coated onto a substrate (glassine paper) and cured (exit web oven temperature: 165.56°C; residence time: 11 seconds) to form a coated substrate, and samples thereof were evaluated for immediate extractability %, immediate ROR%, and release force at various speeds, namely 0.3 m / min (MPM), 10 m / min (MPM), 100 m / min (MPM), and 300 m / min (MPM), at a 180-degree peel angle. After aging for 50 minutes, the substrates were laminated with Tesa 7475 standard tape at RT and 50% RH under 40 lb, and the release force was measured using an Imass SP-2100 and ZPE-1100W release test system. The results are shown in Table 11 below. Example 26 uses the composition of Example 23; Example 27 uses the composition of Example 24; and Example 28 uses the composition of Example 25. The same correlation is applied to the compositions of Comparative Examples 21 and 22 and Comparative Examples 19 and 20.

[0259] [Table 11]

[0260]

[0261] Definition and Use of Terms

[0262] The abbreviations used in this specification have the definitions in Table 12 below.

[0263] [Table 12]

[0264]

[0265] The appended claims are not limited to the specific compounds, compositions, or methods described in the detailed description, and should be understood that they may be modified among specific embodiments falling within the scope of the appended claims.

Claims

Claim 1 A base composition for forming a release coating composition comprises: (A) a silicate resin that is liquid at 25°C in the absence of any solvent - said (A) silicate resin comprises an average of at least one silicon-bonded ethylene-based unsaturated group per molecule -; (B) an organopolysiloxane comprising an average of at least two silicon-bonded ethylene-based unsaturated groups per molecule; wherein said (A) silicate resin is miscible with said (B) organopolysiloxane in the absence of any solvent; and said (A) silicate resin has the following average chemical formula: [W] a [X] b [Y] c ,in the above formula, subscript a is 0.15 to 0.40; subscript b is 0.10 to 0.40; subscript c is 0.35 to 0.60, provided that a+b+c=1; and [W] is [R3SiO 1 / 2 ] and, where each R is an independently selected hydrocarbyl group; [X] is [R2SiO 1 / 2 (OZ)] b' [R2SiO 2 / 2 ] b'' and, where each R is independently selected and as defined above; 0 ≤ b' ≤ b; 0 ≤ b" ≤ b; provided that b' + b" = b; each Z is independently H, an alkyl group, or a cation; and [Y] is [Si(OZ) c' O 4-c' / 2 ] and, wherein each Z is independently selected and as defined above, and the subscript c' is an integer from 0 to 3 and is independently selected from each siloxy unit indicated by subscript c in (A) silicate resin; provided that at least one of R is an ethylene-based unsaturated group; and the (A) silicate resin has a mole percentage of SiOZ moiety of 12 to 80 percent based on the total moles of Si in each molecule, wherein Z is independently selected from H, an alkyl group, or a cation, a base composition. Claim 2 delete Claim 3 A base composition according to claim 1, substantially free of any organic solvent. Claim 4 delete Claim 5 In claim 1, the (B) organopolysiloxane is: (i) a linear or branched organopolysiloxane comprising a silicon-bonded ethylene-based unsaturated group to at least one M siloxy unit; or (ii) formula (R 2 y R 1 3-y SiO 1 / 2 ) x (R 1 R 2 SiO 2 / 2 ) z (SiO 4 / 2 It has ), where, each R 1 is an independently selected hydrocarbyl group without ethylenically unsaturated; and each R 2 is R 1 A base composition independently selected from ethylene-based unsaturated groups, wherein the subscript y is independently selected from each siloxy unit denoted by the subscript x, and is 1 or 2; each subscript x is 1.5 to 6; and the subscript z is 3 to 1,000. Claim 6 A base composition according to claim 1, wherein the component (A) has a weight percentage of silicon-bonded ethylene-based unsaturated groups of greater than 0 to 10 based on the total weight of the component (A). Claim 7 A release coating composition comprising: a base composition according to claim 1; (C) an organosilicon compound having at least two silicon-bonded hydrogen atoms; (D) a hydrosilylation catalyst; and optionally, (E) an inhibitor. Claim 8 A method for preparing a release coating composition of claim 7, comprising: a step of providing a base composition by combining components (A) and (B); and a step of providing a release coating composition by combining the base composition with components (C) and (D). Claim 9 A method for forming a coated substrate comprising: a step of applying a composition onto a substrate; and a step of curing the composition to provide a release coating on the substrate to form the coated substrate; wherein the composition is the release coating composition of claim 7. Claim 10 A coated substrate formed according to the method of claim 9. Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete

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