Antistatic silicone release coating and method of manufacturing and using the same

Abstract

A silicone release coating dispersion has a polyorganosiloxane continuous phase and an aqueous discontinuous phase. The aqueous discontinuous phase comprises water and an ionic liquid. The polyorganosiloxane continuous phase comprises a hydrosilylation reaction-curable silicone release coating composition. A method for preparing a silicone release coating dispersion and a method for using the same to form a silicone release coating are provided.

Description

Technology Field

[0001] A silicone release coating dispersion can be dried and cured to form a silicone release coating having antistatic properties. A method for manufacturing and using a silicone release coating dispersion is provided. Background Technology

[0002] The static electricity generated during the delamination of the adhesive from the release liner must be dissipated to protect the adhesive film from electrical discharge and dust adsorption. In the silicone pressure-sensitive industry, conventional antistatic solutions require the additional coating of an antistatic primer on one or both sides of a plastic substrate, such as polyethylene terephthalate (PET). This method for manufacturing such release liners can suffer from the disadvantages of multiple process steps, which can increase costs and limit productivity; furthermore, the antistatic primer may interfere with the curing reaction of the silicone release coating composition or impair the interfacial fixation of the silicone release coating.

[0003] A silicone release coating dispersion comprises a continuous phase comprising a hydrosilylation reaction-curable silicone release coating composition, a surfactant, and an aqueous discontinuous phase dispersed in the continuous phase. The aqueous phase comprises (A) an ionic liquid and (B) water.

[0004] A silicone release coating dispersion may be formed by a method comprising the following: (1) a step of forming an aqueous solution by dissolving (A) an ionic liquid in (B) water; (2) a step of forming a dispersion intermediate by dispersing the aqueous solution in a siloxane intermediate composition comprising (C) a branched polyorganosiloxane polymer, and (D) a silicone polyether; and (3) a step of combining the dispersion intermediate and an additional starting material, wherein the additional starting material comprises (E) a polydioganosiloxane having at least two aliphatic unsaturated groups per molecule, (F) a polyorganohydrogensiloxane having three or more silicon-bonded hydrogen atoms per molecule, and (G) a catalyst for a hydrosilylation reaction.

[0005] A release liner can be manufactured using the dispersion described above by a method comprising the following: optionally (I) a step of treating the surface of a substrate,

[0006] (II) a step of coating a silicone release coating dispersion of any one of claims 1 to 11 on the surface of the above substrate, (III) a step of drying the silicone release coating dispersion to form a film, and (IV) a step of curing the film to form a silicone release coating on the surface of the above substrate. Brief explanation of the drawing

[0007] FIG. 1 illustrates a partial cross-section of a laminate article (100) including a silicone release coating (102) having antistatic properties. [Explanation of the symbol] 101 PET film substrate 102 Antistatic Silicone Release Coating 103 Adhesive 104 Second PET film substrate Specific details for implementing the invention

[0008] The above-mentioned introduced silicone release coating dispersion (dispersion) is,

[0009] (I) A continuous phase comprising a hydrosilylated reaction-curable silicone release coating composition (composition),

[0010] (II) Surfactants, and

[0011] (III) comprises an aqueous discontinuous phase dispersed in a continuous phase, wherein the aqueous discontinuous phase is

[0012] (A) Ionic liquid, and

[0013] (B) Includes water,

[0014] The above ionic liquid is soluble in water.

[0015] (A) Ionic liquid

[0016] The starting material (A), which is an ionic liquid, is an antistatic additive that imparts antistatic properties to a silicone release coating prepared from a dispersion. An ionic liquid suitable for use in the present invention is a salt that may contain a large cation and a charge-delocalized anion. The ionic liquid includes a water-soluble alkali metal salt, e.g., a lithium salt. The ionic liquid may be a single alkali metal salt or a combination of two or more alkali metal salts. Examples of alkali metal salts include metal salts comprising: a cation selected from lithium ions, sodium ions, and potassium ions; and anion selected from chloride ions, bromide ions, iodide ions, tetrachloroaluminum ions, hexafluorophosphate ions, tetrafluoroborate ions, thiocyanate ions, perchlorate ions, p-toluenesulfonate ions, trifluoromethanesulfonate ions, pentafluoroethanesulfonate ions, bis(trifluoromethanesulfonyl)imide, dicyanamide ions, tris(trifluoromethylsulfonyl)methide ions, acetate ions, trifluoroacetate ions, and hexafluoroantimony ions. Alternatively, the alkali metal salt may be a lithium salt. The lithium salts may be, for example, (A1) lithium trifluoromethanesulfonate LiSO3CF3, (A2) lithium bis(trifluoromethylsulfonyl)imide LiN(SO2CF3)2, LiSO3C4F9, LiC(SO2CF3)3, (A3) LiBF4, (A4) LiClO4, (A5) LiPF6, (A6) LiAsF6, (A7) LiSbF6, and (A8) LiB(C6H5)4. These lithium salts may be used alone or in combination of two or more of (A1) to (A8). Alternatively, the ionic liquid may comprise a mixture of (A1) lithium trifluoromethanesulfonate and (A2) lithium bis(trifluoromethylsulfonyl)trifluoromethylsulfonylimide.Lithium salts such as lithium trifluoromethanesulfonate and lithium bis(trifluoromethylsulfonyl)trifluoromethylsulfonylmid, for example, (A1) lithium trifluoromethanesulfonate and (A2) lithium bis(trifluoromethanesulfonate)trifluoromethanesulfonatemid may be present in an amount such that (A) ionic liquid contains 90 weight% of (A1) lithium trifluoromethylsulfonate and 10 weight% of (A1) based on the total weight of (A1) and (A2). The ionic liquid, which is the starting material (A), and water, which is the starting material (B), may be present in an aqueous discontinuous phase in a weight ratio (A):(B) of 2:1 to 1:2.

[0017] (B) water

[0018] Water (B) is generally not limited and may be used without mixing anything and / or (neat) (i.e., without any carrier vehicle / solvent) and in a pure state (i.e., free from or substantially free of minerals and / or other impurities). For example, water (B) may be treated or untreated before dissolving (A) the ionic liquid inside it. Examples of processes that may be used to purify water include distillation, filtration, deionization, and combinations of two or more of these, so water (B) may be deionized, distilled, and / or filtered. Alternatively, water (B) may not be treated (e.g., tap water, i.e., provided by a municipal water system or well water and used without further purification). Alternatively, water (B) may be purified before dissolving (A) the ionic liquid inside it. Alternatively, water (B) may be used as a mixture (e.g., solution or suspension) comprising a carrier vehicle / solvent such as any of those described below that can be used in a silicone release coating composition.

[0019] Silicone release coating composition

[0020] The hydrosilylation reaction-curable silicone release coating composition comprises (C) a branched polyorganosiloxane polymer, (E) a polydioganosiloxane having two or more aliphatic unsaturated groups per molecule, (F) a polydioganosiloxane having at least three silicon-bonded hydrogen atoms per molecule, and (G) a hydrosilylation reaction catalyst. The silicone release coating composition may optionally further comprise one or more additional starting materials. One or more additional starting materials may be selected from the group consisting of: (H) a solvent; (I) a hydrosilylation reaction inhibitor; and (J) an anchorage additive.

[0021] (C) Branched polyorganosiloxane polymer

[0022] The starting material (C) is a branched polyorganosiloxane polymer. The branched polyorganosiloxane polymer has the unit formula (C1) (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 R 2 SiO 2 / 2 ) c (R 1 2SiO 2 / 2 ) d (SiO 4 / 2 It can have ). Here, each R 1 is an independently selected monovalent hydrocarbon group that is not aliphatic unsaturated, and each R 2is an independently selected aliphatic unsaturated monovalent hydrocarbon group; subscripts a and b indicate the average number of monofunctional units and subscript c indicates the average number of difunctional units per molecule, where a, b, c and d have values ​​sufficient to impart a viscosity of > 170 mPa·s to the branched polyorganosiloxane polymer when measured by a rotational viscometer at room temperature. Alternatively, the viscosity may be greater than 170 mPa·s to 1000 mPa·s, alternatively greater than 170 to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, and alternatively 190 mPa·s to 420 mPa·s. Viscosity can be measured at room temperature at 0.1 rpm to 50 rpm using a Brookfield DV-III cone-and-plate viscometer equipped with a #CP-52 spindle. Those skilled in the art will recognize that the rotation speed decreases as the viscosity increases. Suitable branched polyorganosiloxane polymers are known in the art and can be prepared by known methods as disclosed in U.S. Patent No. 6,806,339 of Cray et al. and U.S. Patent Application Publication No. 2007 / 0289495 of Cray et al.

[0023] R 1 The alkyl group suitable for may be linear, branched, cyclic, or a combination of two or more of these. The alkyl group is exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl); pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, octadecyl (and branched isomers having 5 to 18 carbon atoms), and the alkyl group is further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 1The alkyl group for can be selected from the group consisting of methyl, ethyl, propyl, and butyl; alternatively, methyl, ethyl, and propyl; alternatively, can be selected from the group consisting of methyl and ethyl. R 1 The alkyl group for can be methyl.

[0024] R 1 The aryl group suitable for can be monocyclic or polycyclic and can have a side-chain hydrocarbyl group. For example, R 1 The aryl groups for include phenyl, tolyl, xylyl, and naphthyl, and additionally include aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, R 1 The aryl group for can be monocyclic, such as phenyl, tolyl, or benzyl; alternatively, R 1 The aryl group for can be phenyl.

[0025] In the above and below chemical formulas, R 2 can be an alkenyl group. A suitable alkenyl group may have a terminal alkenyl functional group to promote the hydrosilylation reaction, for example, R 2 is a chemical formula where the subscript y is from 0 to 6 and * indicates the attachment point (i.e., to a silicon atom). It can have. Alternatively, each R 2 can be independently selected from the group consisting of vinyl, allyl, and hexenyl. Alternatively, each R 2 can be independently selected from the group consisting of vinyl and allyl. Alternatively, each R 2 can be vinyl. Alternatively, each R 2 It can be an alkyl.

[0026] Alternatively, (C) branched polyorganosiloxane polymers are given by the chemical formula (C2) [R 2 R 1 Si-(O-SiR 1 2) x -O](4-w) -Si-[O-(R 1 2SiO) v SiR 1 3] w It may include, where R 1 and R 2 is as described above; the subscripts v, w, and x have values ​​such that 200 ≥ v ≥ 1, 2 ≥ w ≥ 0, and 200 ≥ x ≥ 1. Alternatively, in this formula (C2), each R 1 can be independently selected from the group consisting of methyl and phenyl, and each R 2 The branched polyorganosiloxane suitable for the starting material (C2) can be independently selected from the group consisting of vinyl, allyl, and hexenyl. The branched polyorganosiloxane suitable for the starting material (C2) can be prepared by known methods such as heating a mixture comprising a polyorganosilicate resin and a cyclic polydiorganosiloxane or a linear polydiorganosiloxane in the presence of a catalyst such as an acid or a phosphazene base, and then neutralizing the catalyst.

[0027] Alternatively, a branched polyorganosiloxane polymer for the starting material (C) is of the unit formula (C3) (R 1 3SiO 1 / 2 ) aa (R 2 R 1 2SiO 1 / 2 ) bb (R 1 2SiO 2 / 2 ) cc (R 2 R 1 SiO 2 / 2 ) ee (R 1 SiO 3 / 2 ) dd It may include, where R 1 and R 2...is as described above, and subscript aa ≥ 0, subscript bb > 0, subscript cc is 15 to 995, subscript dd > 0, subscript ee ≥ 0. Subscript aa can be 0 to 10. Alternatively, subscript aa can have a value such as 12 ≥ aa ≥ 0. Alternatively, 10 ≥ aa > 0; alternatively, 7 ≥ aa > 0; alternatively, 5 ≥ aa ≥ 0; and alternatively, 3 ≥ aa ≥ 0. Alternatively, subscript bb is ≥ 1. Alternatively, subscript bb is ≥ 3. Alternatively, subscript bb can have a value such as 12 ≥ bb ≥ 0. Alternatively, 12 ≥ bb ≥ 3; Alternatively, 10 ≥ bb ≥ 0; alternatively, 7 ≥ bb ≥ 1; alternatively, 5 ≥ bb ≥ 2; and alternatively, 7 ≥ bb ≥ 3. Alternatively, the subscript cc can have a value such that 800 ≥ cc ≥ 15; and alternatively, 400 ≥ cc ≥ 15. Alternatively, the subscript ee can have a value such that 800 ≥ ee ≥ 0. Alternatively, 800 ≥ ee ≥ 15; and alternatively, 400 ≥ ee ≥ 15. Alternatively, the subscript ee can be 0. Alternatively, the quantity (cc + ee) can have a value such that 995 ≥ (cc + ee) ≥ 15. Alternatively, the subscript dd ≥ 1. Alternatively, the subscript dd can be 1 to 10. Alternatively, the subscript dd can have a value such as 10 ≥ dd ≥ 0. Alternatively, 5 ≥ dd > 0; and alternatively, dd = 1. Alternatively, the subscript dd can be 1 to 10, and alternatively, the subscript dd can be 1 or 2. Alternatively, when the subscript dd = 1, the subscript bb can be 3 and the subscript cc can be 0. The value of the subscript bb is 0.1% to 1% based on the weight of the silsesquioxane, alternatively 0.2% to 0.It may be sufficient to provide a silsesquioxane having an alkenyl content of 6%. Silsesquioxanes suitable for the starting material (C3) are exemplified by those disclosed below: U.S. Patent No. 4,374,967 of Brown et al.; U.S. Patent No. 6,001,943 of Enami et al.; U.S. Patent No. 8,546,508 of Nabeta et al.; and U.S. Patent No. 10,155,852 of Enami.

[0028] (E) Aliphatic unsaturated polydioganosiloxane

[0029] The starting material (E) in the silicone release coating composition is a polydioganosiloxane having two or more aliphatic unsaturated groups per molecule. The polydioganosiloxane is of the unit formula (E1) (R 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) j It can have, where R 1 and R 2 It is as described above, and the subscript j indicates the average number of difunctional units per molecule, and 10,000 ≥ j ≥ 100.

[0030] Starting material (E) is an alkenyl-functional polydiorganosiloxane, e.g., (E1-1) bis-dimethylvinylsiloxy-terminated polydimethylsiloxane, (E1-2) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), (E1-3) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane)), (E1-4) bis-phenyl,methyl,vinyl-siloxy-terminated polydimethylsiloxane, (E1-5) bis-dimethylhexenylsiloxy-terminated polydimethylsiloxane, (E1-6) bis-dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), (E1-7) dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), and (E1-8) It may include two or more combinations of (E1-1) to (E1-7). Alternatively, the starting material (E) may be selected from the group consisting of (E1-1) bis-dimethylvinylsiloxy-terminated polydimethylsiloxane, (E1-5) bis-dimethylhexenylsiloxy-terminated polydimethylsiloxane, or both.

[0031] With respect to the starting material (D), the method for producing the polyorganosiloxane described above, such as the hydrolysis and condensation of the corresponding organohalosilane and oligomer, or the equilibration of the cyclic polydioganosiloxane, is known in the art, and reference is made to U.S. Patents No. 3,284,406; 4,772,515; 5,169,920; 5,317,072; and 6,956,087, which disclose the production of a linear polydioganosiloxane having an alkenyl group. Examples of linear polydioganosiloxanes having alkenyl groups are commercially available, for example, from Gelest Inc., Morrisville, Pennsylvania, under the trade names DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V-31, DMS-V33, DMS-V34, DMS-V35, DMS-V41, DMS-V42, DMS-V43, DMS-V46, DMS-V51, and DMS-V52. Other linear polydioganosiloxanes having alkenyl groups are available for purchase from DSC.

[0032] Starting material (C), a branched polyorganosiloxane polymer and a polydioganosiloxane having two or more aliphatic unsaturated groups per molecule, is present in a combined amount of 100 parts by weight of the silicone release coating composition. Alternatively, the amount of starting material (C) may be 2 to 10 parts by weight of the silicone release coating composition, or alternatively 3 to 9 parts by weight. Alternatively, the amount of starting material (E) may be 20 to 40 parts by weight of the silicone release coating composition.

[0033] (F) Polyorganohydrogensiloxane

[0034] The starting material (F) in the silicone release coating composition is a polyorganohydrogensiloxane, which can function as a crosslinking agent to cure the silicone release coating composition. The polyorganohydrogensiloxane has at least three silicon-bonded hydrogen atoms per molecule. The polyorganohydrogensiloxane has the unit formula (F1) (R 1 2HSiO 1 / 2 ) k (R 1 3SiO 1 / 2 ) m (R 1 HSiO 2 / 2 ) n (R 1 2SiO 2 / 2 ) o It has, where R 1 ...is as described above, where subscripts k and m represent the average number of monofunctional units per molecule, subscripts n and o represent the average number of difunctional units per molecule, and subscripts k, m, n and o have values ​​such that 2 ≥ k ≥ 0, 2 ≥ m ≥ 0, (k + m) = 2, n > 0, o ≥ 0, (k + n) ≥ 3, and 8 ≤ (k + m + n + o) ≤ 400.

[0035] Polyorganohydrogensiloxanes suitable for use in this invention are exemplified as follows:

[0036] (i) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane),

[0037] (ii) α,ω-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane,

[0038] (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane),

[0039] (Iv) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane,

[0040] (v) α-dimethylhydrogensiloxy-ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane),

[0041] (vi) α-dimethylhydrogensiloxy-ω-trimethylsiloxy-terminated polymethylhydrogensiloxane,

[0042] (vii) a combination of two or more of these. Alternatively, (F) the polyorganohydrogensiloxane may be selected from the group consisting of (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, or both.

[0043] Polyorganohydrogensiloxanes are also available from Gelest, Inc., Morrisville, Pennsylvania, USA, for example, as follows: HMS-H271, HMS-071, HMS-993; HMS-301 and HMS-301 R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, HAM-301, HPM-502, and HMS-HM271. Methods for preparing linear and branched polyorganohydrogensiloxanes suitable for use herein, such as the hydrolysis and condensation of organohalosilanes, are well known in the art as exemplified in Speier’s U.S. Patent No. 2,823,218, Jeram et al.’s U.S. Patent No. 3,957,713, and Hardman et al.’s U.S. Patent No. 4,329,273.

[0044] The silicon-bonded hydrogen (Si-H) content of polyorganohydrogensiloxanes is determined using quantitative infrared analysis according to ASTM E168. The ratio of silicon-bonded hydrogen to aliphatic unsaturated groups (e.g., alkenyls such as vinyl and / or alkynyl) is important when relying on the hydrosilylation curing process. Generally, this is measured by calculating the total weight percentage of aliphatic unsaturated groups in the composition, e.g., vinyl [V], and the total weight percentage of silicon-bonded hydrogen [H] in the composition; considering that the molecular weight of hydrogen is 1 and that of vinyl is 27, the molar ratio of silicon-bonded hydrogen to vinyl is 27 [H] / [V]. Polyorganohydrogensiloxanes are present in sufficient amounts to provide a molar ratio of silicon-bonded hydrogen atoms to aliphatic unsaturated groups (SiH:Vi ratio) in silicone release coating compositions of >1:1 to 5:1.

[0045] (G) Hydrosilylation reaction catalyst

[0046] The starting material (G) in the silicon release coating composition is a hydrosilylation reaction catalyst. This catalyst will promote the reaction between the aliphatic unsaturated groups of starting materials (C) and (E) and the silicon-bonded hydrogen atoms in the starting material (F). The catalyst comprises a platinum group metal. The platinum group metal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum.

[0047] For example, (G) the hydrosilylation reaction catalyst is the (G1) platinum group metal described above; (G2) a compound of a metal such as, for example, chloridotris(triphenylphosphano)rhodium(I) (Wilkinson catalyst), rhodium diphosphine chelate, for example, [1,2-bis(diphenylphosphino)ethane]dichlorodirodium or [1,2-bis(diethylphosphino)ethane]dichlorodirodium, platinum chloride (Speier's Catalyst), platinum chloride hexahydrate, platinum dichloride; (G3) a complex of compound (G2) and an aliphatic unsaturated organopolysiloxane; or (G4) a platinum group metal compound microencapsulated in a matrix or core-shell structure. Complexes of platinum and aliphatic unsaturated organopolysiloxane include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes with platinum (Karstedt's catalyst) and Pt(0) complexes in tetramethyltetravinylcyclotetrasiloxane (Ashby's catalyst). Alternatively, the hydrosilylation reaction catalyst may be the compound or complex described above microencapsulated within a (G5) resin matrix. Specific examples of suitable platinum-containing catalysts include chloroplatinic acid in either the hexahydrate or anhydrous form, a platinum-containing catalyst obtained by a method comprising the step of reacting the chloroplatinic acid with an aliphatic unsaturated organosilicon compound, such as a vinyl functional polydimethylsiloxane (e.g., divinyltetramethyldisiloxane), or an alkene-platinum-silyl complex as described in Roy’s U.S. Patent No. 6,605,734. These alkene-platinum-silyl complexes 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, wherein COD represents cyclooctadienyl and Me represents methyl.Other exemplary hydrosilylation reaction catalysts are U.S. Patent No. 2,823,218 of Spire; U.S. Patent No. 3,159,601 of Ashby; U.S. Patent No. 3,220,972 of Lamoreaux; U.S. Patent No. 3,296,291 of Chalk et al.; U.S. Patent No. 3,419,593 of Willing; U.S. Patent No. 3,516,946 of Modic; U.S. Patent No. 3,715,334 of Karstedt; U.S. Patent No. 3,814,730 of Karstedt; U.S. Patent No. 3,928,629 of Chandra; U.S. Patent No. 3,989,668 of Lee et al.; U.S. Patent No. 4,766,176 of Lee et al.; U.S. Patent No. 4,784,879 of Lee et al.; U.S. Patent No. 5,017,654 of Togashi; As described in U.S. Patent No. 5,036,117 of Chung et al.; U.S. Patent No. 5,175,325 of Brown; and European Patent 0 347 895 A of Togashi et al. Suitable hydrosilylation reaction catalysts for starting material (g) are available for purchase, for example, SYL-OFF™ 4000 catalyst and SYL-OFF™ 2700 are available for purchase from Dow Silicones Corporation, Midland, Michigan, USA.

[0048] The starting material (G) may be one of the hydrosilylation reaction catalysts described above or a combination of two or more hydrosilylation reaction catalysts. The amount of (G) hydrosilylation reaction catalyst in the composition will depend on various factors including: the selection of starting materials (C), (E), and (F), the respective content of alkenyl groups and silicon-bonded hydrogen atoms, and the amount of (I) hydrosilylation reaction inhibitor present in the silicon release coating composition. However, the amount of catalyst is sufficient to catalyze the hydrosilylation reaction of SiH and alkenyl groups, or alternatively, the amount of catalyst is sufficient to provide at least 0.01 ppm, alternatively at least 0.05 ppm, alternatively at least 0.1 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, or alternatively at least 170 ppm (weight of platinum group metal based on the weight of the silicon release coating dispersion). At the same time, the amount of catalyst is sufficient to provide up to 800 ppm, alternatively up to 500 ppm, and alternatively up to 200 ppm of platinum group metal based on the same standard and mass of platinum group metal.

[0049] (H) solvent

[0050] The continuous phase of the silicone release coating dispersion may optionally further include a solvent. The solvent is added during the preparation of the silicone release coating composition to facilitate the composition and introduction of specific starting materials, such as a hydrosilylation reaction catalyst. The solvents that may be used herein are solvents that help fluidize the starting materials of the silicone release coating composition but do not inherently react with the starting materials. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. Solubility means that the solvent is sufficient to dissolve and / or disperse the starting materials. Volatility refers to the vapor pressure of the solvent. If the solvent is too volatile (having too high a vapor pressure), bubbles may form during the hydrosilylation reaction, and these bubbles may cause cracking of the reaction product, or otherwise weaken or adversely affect its properties. However, if the solvent is not sufficiently volatile (having too low a vapor pressure), the solvent may remain as a plasticizer in the silicone release coating prepared by curing the silicone release coating composition.

[0051] Suitable solvents include polyorganosiloxanes having a suitable vapor pressure, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as 0.5 to 1.5 cSt DOWSIL™ 200 Fluids and DOWSIL™ OS FLUIDS, which are commercially available from DSC.

[0052] Alternatively, the solvent may be an organic solvent. The organic solvent may be an aromatic hydrocarbon, e.g., benzene, toluene, ethylbenzene, or xylene; an aliphatic hydrocarbon, such as heptane, hexane, or octane; or a halogenated hydrocarbon, e.g., dichloromethane, 1,1,1-trichloroethane, or methylene chloride. Alternatively, the solvent may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, heptane, and combinations of two or more of these.

[0053] The amount of solvent will depend on various factors, including the type of solvent selected for the silicone release coating composition and the amount and type of other initiating materials selected for the release coating composition. However, the amount of solvent may be in the range of 1% to 99%, or alternatively 2% to 90%, based on the weight of all initiating materials of the silicone release coating composition. The solvent may be added during the preparation of the composition, for example, to aid in mixing and transport. After the composition is prepared, all or part of the solvent may optionally be removed. Alternatively, the continuous phase of the silicone release coating dispersion may contain up to 90% by weight of solvent, where the average is 100% by weight of the continuous phase, which is the silicone release coating composition.

[0054] (I) inhibitor

[0055] Starting material (I) is a hydrosilylation reaction inhibitor (inhibitor) that can be used to modify the hydrosilylation reaction compared to a composition containing the same starting material but with the inhibitor omitted. Starting material (I) may be selected from the group consisting of (I1) acetylene alcohol, (I2) silylated acetylene alcohol, (I3) n-phosphorus compound, (I4) triazole, (I5) phosphine, (I6) mercaptan, (I7) hydrazine, (I8) amine, (I9) fumarate, (I10) maleate, (I11) ether, (I12) carbon monoxide, (I13) alkenyl-functional siloxane oligomer, and (I14) a combination of two or more of these. Alternatively, the hydrosilylation reaction inhibitor may be selected from the group consisting of (I1) acetylene alcohol, (I2) silylated acetylene alcohol, (I9) fumarate, (I10) maleate, (I13) carbon monoxide, and (I14) a combination of two or more of these. Alternatively, the inhibitor may include acetylene alcohol.

[0056] Acetylene alcohols are exemplified by 3,5-dimethyl-1-hexin-3-ol, 1-butyn-3-ol, 1-propin-3-ol, methylbutynyl, e.g., 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, 3,5-dimethyl-1-hexin-3-ol, and ethinyl cyclohexanol, e.g., 1-ethynyl-1-cyclohexanol, and combinations thereof. Acetylene alcohols are known in the art and may be commercially available from various sources; see, for example, U.S. Patent No. 3,445,420 of Kookootsedes et al. Alternatively, the inhibitor may be a silylated acetylene compound. Without being bound by theory, the addition of a silylated acetylene compound is believed to reduce the yellowing of the reaction product prepared from the hydrosilylation reaction compared to the reaction product from the hydrosilylation of a starting material that does not contain a silylated acetylene compound or contains an organic acetylene alcohol inhibitor such as that described above.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, 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 are exemplified by. Silylated acetylene compounds useful as inhibitors in this invention can be prepared by methods known in the art, for example, U.S. Patent No. 6,677,407 by Bilgrien et al. discloses silylating the acetylene alcohol described above by reacting it with a chlorosilane in the presence of an acid acceptor.

[0057] Alternatively, the inhibitor may be an n-phosphorus compound, such as 3-methyl-3-pentene-1-phosphorus, 3,5-dimethyl-3-hexene-1-phosphorus; and combinations thereof. Alternatively, the inhibitor may comprise a triazole, exemplified by benzotriazole. Alternatively, the inhibitor may comprise phosphine. Alternatively, the inhibitor may comprise a mercaptan. Alternatively, the inhibitor may comprise hydrazine. Alternatively, the inhibitor may comprise an amine. The amine is exemplified by tetramethylethylenediamine, 3-dimethylamino-1-propine, n-methylpropagylamine, propagylamine, 1-ethynylcyclohexylamine, or a combination thereof. Alternatively, the inhibitor may comprise a fumarate. The fumarate includes dialkyl fumarates, such as diethyl fumarate, dialkenyl fumarates, such as diallyl fumarate, and dialkoxyalkyl fumarates, such as bis-(methoxymethyl)ethyl fumarate. Alternatively, the inhibitor may include a maleate. The maleate includes dialkyl maleates, such as diethyl maleate, dialkenyl maleates, such as diallyl maleate, and dialkoxyalkyl maleates, such as bis-(methoxymethyl)ethyl maleate. Alternatively, the inhibitor may include an ether.

[0058] Alternatively, the inhibitor may comprise carbon monoxide. Alternatively, the inhibitor may comprise an alkenyl-functional oligomer that may be cyclic or linear, such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane; 1,3-divinyl-1,1,3,3-tetramethyldisiloxane; and methylvinylcyclosiloxane exemplified by combinations of two or more of these. Compounds useful as the inhibitors described above are commercially available, for example, from Sigma-Aldrich Inc. or Gelest, Inc. and are known in the art (see, for example, U.S. Patent 3,989,667 of Lee et al.). Inhibitors suitable for use in this invention are exemplified by those described as stabilizer E in paragraphs

[0148] through

[0165] of U.S. Patent Application Publication 2007 / 0099007.

[0059] The amount of inhibitor depends on various factors including the desired availability time, the specific inhibitor used, the selection and amount of the catalyst. However, if present, the amount of inhibitor 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 weight of all initiating materials of the silicone release coating composition.

[0060] (J) Anchorage additive

[0061] The starting material (J) is a selective anchorage additive. Without being constrained by theory, the anchorage additive is thought to promote bonding to the backing substrate by a silicon release coating prepared from the silicon release coating dispersion described herein.

[0062] Suitable anchorage additives include silane coupling agents, such as methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, bis(trimethoxysilyl)propane and bis(trimethoxysilylhexane); and mixtures or reaction mixtures of said silane coupling agents. Alternatively, the anchorage additive may be tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, or 3-methacryloxypropyltrimethoxysilane.

[0063] Exemplary anchorage additives are known in the art, for example, in paragraph

[0091] of U.S. Patent Application Publication No. 2012 / 0328863 and paragraph

[0041] of U.S. Patent Application Publication No. 2017 / 0233612. Anchorage additives are commercially available. For example, SYL-OFF™ 297, SYL-OFF™ SL 9176, and SYL-OFF™ SL 9250 are available from DSC. Other exemplary anchorage additives include (J-1) vinyltriacetoxysilane, (J-2) glycidoxypropyltrimethoxysilane, and (J-3) a combination of (J-1) and (J-2). This combination (J-3) may be a mixture and / or reaction product.

[0064] The amount of anchorage additive varies depending on various factors, including the type of substrate to which the composition is applied. However, the amount of anchorage additive may be 1 to 5%, alternatively 1% to 3%, or alternatively 1.9% to 2.1% based on the total weight of all starting materials in the composition.

[0065] (II) Surfactants

[0066] The silicone release coating dispersion described above further comprises (II) a surfactant. The surfactant can form a dispersion of an aqueous discontinuous phase comprising the ionic liquid and water described above into a continuous phase comprising the silicone release coating composition, which is also described above. The surfactant comprises (D) a silicone polyether.

[0067] Silicon polyether is unit formula (D1) (R 1 3SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) e (R 1 R 3 SiO 2 / 2 ) f It has, where R 1 is as described above, and each R 3 is an independently selected polyether group, and the subscript e is 1 to 500, alternatively 1 to 200, alternatively 1 to 50, alternatively 40 to 50, and alternatively 10 to 45; the subscript f is 1 to 1000, alternatively 1 to 300, alternatively 1 to 40, alternatively 1 to 5, and alternatively 2 to 5. Polyether group R 3 is the formula -(D 1 ) g O(D 2 O) h R 4 It has, where each D 1 is an independently selected divalent hydrocarbon group of 2 to 4 carbon atoms, and each D 2 is an independently selected divalent hydrocarbon group of 2 to 4 carbon atoms, and R 4 is selected from the group consisting of H or an alkyl group having 1 to 10 carbon atoms, the subscript g is 1 to 20, alternatively 1 to 3, the subscript h is 1 to 50, alternatively 4 to 50, and alternatively 8 to 40. Alternatively, D1 Equation C p H 2p It may have, where the subscript p is 3 to 12, alternatively 3 to 6. Alternatively, each D 2 can be selected from the group consisting of C2H4 and C3H6. Alternatively, R 4 ... may be H. Suitable (D) silicone polyethers are known in the art and can be prepared by known methods such as those disclosed in U.S. Patent No. 8,877,886 of Souda et al. Silicone polyethers suitable for starting material (D) are commercially available, for example, DOWSIL™ ES-5612 is commercially available from DSC.

[0068] The starting material (II), which is a surfactant, may optionally additionally include a co-surfactant. The co-surfactant may be a second silicone polyether, an organic polyether, or a combination thereof that is different from (D1) in at least one aspect.

[0069] The second silicon polyether is unit formula (D2) (R 1 3SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) e' (R 1 R 5 SiO 2 / 2 ) f' It can have. Here, R 1 and R 2 ...is as described above, where subscripts e' and f' represent the average number of difunctional units per molecule, and e has a value such that e is 0 to 500, alternatively 0 to 200, alternatively 0 to 50, and alternatively 0 to 45, provided that e' < e, and subscript f" may have a value such that e is 1 to 1000, alternatively 1 to 300, alternatively 1 to 40, alternatively 1 to 5, and alternatively 1 to 2. R5 is the chemical formula -(D 1 )g O(D 3 O) i It has H, where each D 3 is a divalent hydrocarbon group of 2 to 4 independently selected carbon atoms, the subscript g is 1 to 20, alternatively 1 to 3, and the subscript i is 1 to 50. Alternatively, each D 3 can be selected from the group consisting of C2H4 and C3H6. Alternatively, the subscript i can be 1 to 10; alternatively, it can be 5 to 10. Alternatively, in unit formula (D2), the subscript e' can be 0 and the subscript f' can be 1. The silicon polyether of formula (D2) is commercially available, for example, XIAMETER™ OFX-5211 is commercially available from DSC.

[0070] Alternatively, the silicone polyether co-surfactant may have a rake-type structure, wherein polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto a siloxane backbone, or the silicone polyether may have an ABA block copolymer structure in which A represents the polyether portion of the ABA structure and B represents the siloxane portion of the ABA structure. Alternatively, the SPE may have a resinous structure, such as a polyorganosilicate resin having polyether groups bonded to silicone atoms. Suitable SPEs include DOWSIL™ OFX-5329 fluid from DSC. Other silicone polyether surfactants are known in the art and are also available for purchase; for example, DOWSIL™ 502W and DOWSIL™ 67 additives are available for purchase from DSC.

[0071] Alternatively, the co-surfactant may be an organic polyether. Suitable organic polyethers are known in the art and are commercially available. For example, suitable organic polyethers include linear EO / PO block copolymers such as DOWFAX™ nonionic surfactants, for example, the DOWFAX™ N series available from TDCC.

[0072] The amount of surfactant in the silicone release coating dispersion depends on various factors including the selection and amount of (C) a branched polyorganosiloxane polymer and (E) a polydioganosiloxane having two or more aliphatic unsaturated groups per molecule, but (II) the amount of surfactant may be 0.1 to 5 parts by weight based on the total weight of starting materials (C) and (E). Alternatively, (D1) the amount of silicone polyether may be 0.1 to 5 parts by weight based on the total weight of starting materials (C) and (E). Alternatively, when a co-surfactant is present, (D1) the amount of silicone polyether may be 0.1 to < 5 parts by weight based on the total weight of starting materials (C) and (E).

[0073] For example, other optional starting materials, including reactive diluents, fragrances, preservatives, colorants, dyes, pigments, antioxidants, heat stabilizers, flame retardants, flow control additives, biocides, fillers (including volume-enhancing fillers and reinforcing fillers), surfactants, thixotropic agents, and pH buffers, may be present in the silicone release coating dispersion. The composition may be of any form and may be incorporated into additional compositions. Alternatively, the silicone release coating dispersion 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 dispersion. Without being constrained by theory, it is thought that particulates may aggregate or otherwise adhere to the coating equipment used to form the silicone release coating. In addition, where optical transparency is required, microparticles may interfere with the optical properties, e.g., transparency, of the silicone release coating and the release liner formed using it, and / or microparticles may be detrimental to the adhesion of the substrate.

[0074] Fluoroorganosilicon compounds may be absent from silicone release coating dispersions. During curing, it is believed that fluorocompounds can rapidly migrate due to their low surface tension to the interface between the dispersion or the silicone release coating formed using it and the substrate where the dispersion is applied and the silicone release coating is formed, e.g., the dispersion / PET film interface. This migration can create a fluorine-containing barrier, which can have a detrimental effect on the fixation of the silicone release coating (produced by curing) to the substrate. By creating a barrier, the fluoroorganosilicon compound can prevent the starting material of the silicone release coating dispersion from reacting at the interface and affecting the curing and / or antistatic properties. Furthermore, fluoroorganosilicon compounds are generally expensive.

[0075] Method for forming a silicone release coating dispersion

[0076] The aforementioned silicone release coating dispersion can be prepared by a method comprising the following:

[0077] (1) (A) a step of dissolving an ionic liquid (B) in water to form an aqueous solution;

[0078] (2) Disperse an aqueous solution in a siloxane intermediate composition comprising the following (

[0079] (C) Branched polyorganosiloxane polymer, and

[0080] (D) a step of forming a silicon polyether), a dispersion intermediate; and

[0081] (3) A step of combining the above dispersion intermediate and additional starting material (the above additional starting material is

[0082] (E) Polydioganosiloxane having at least 2 aliphatic unsaturated groups per molecule,

[0083] (F) Polyorganohydrogensiloxane having three or more silicon-bonded hydrogen atoms per molecule,

[0084] (G) Catalyst for hydrosilylation reaction,

[0085] Optionally (H) solvent,

[0086] Selectively (I) a hydrosilylation reaction inhibitor, and

[0087] Optionally (J) contains an anchorage additive).

[0088] Without being constrained by theory, the order of addition in which the dispersion intermediate is prepared in step (2) facilitates the preparation of a stable dispersion, and it is believed that combining the antistatic additive with the silicone release coating composition will form a composition that does not cure, thereby forming a silicone release coating with a desired resistance as shown below in Comparative Example 4.

[0089] Step (1) may be performed by mixing at room temperature or elevated temperature in any convenient means, such as batch, semi-batch, or continuous equipment. In Step (1), mixing may take place using, for example, batch mixing equipment having medium / low shear, such as a change-can mixer, double-planetary mixer, conical-screw mixer, ribbon mixer, double-arm or sigma-blade mixer. Alternatively, batch equipment having high shear and / or high-speed dispersers may be used in Step (1), Step (2) and / or Step (3), including equipment manufactured by Charles Ross & Sons (New York, USA) and Hockmeyer Equipment Corp (New Jersey, USA); batch mixing equipment sold under the trade name Speedmixer™; Batch equipment with high shear action includes Banbury type (CW Brabender Instruments Inc., NJ, USA) and Henschel type (Henschel mixers America, Texas, USA). Exemplary examples of continuous mixers / compounders include single-screw extruders, twin-screw extruders, and multi-screw extruders, ball-rotating extruders, such as those manufactured by Krupp Werner & Pfleiderer Corp (Ramsey, NJ, USA) and Leistritz (NJ, USA); extruders, such as twin-screw counter-rotating extruders, two-stage extruders, dual-rotor continuous mixers, dynamic or static mixers, or combinations of these equipment. Steps (2) and (3) may also be performed at room temperature.

[0090] Method for manufacturing a release liner

[0091] A release liner can be manufactured using a silicone release coating dispersion prepared as described above. The release liner can be manufactured by a method comprising the following:

[0092] Optionally, (I) a step of treating the surface of the backing substrate,

[0093] (II) A step of coating a silicone release coating dispersion on the surface of the backing substrate as described above,

[0094] (III) A step of drying the above silicone release coating dispersion to form a film, and

[0095] (IV) A step of curing the above film to form a silicone release coating on the surface of the above backing substrate.

[0096] In step (I), the backing substrate (substrate) is not limited. The substrate may include plastics that may be thermosetting and / or thermoplastic. However, the substrate may alternatively be or include glass, metal, cellulose (e.g., paper), cardboard, carton, polymeric materials, or a combination thereof. Specific examples of suitable substrates include paper substrates, e.g., Kraft paper, polyethylene coated Kraft paper (PEK coated paper), thermal paper, and general 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 resins; 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 elastomer, e.g., polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type, and fluoro type; and copolymers and combinations thereof.

[0097] In step (I), the surface of the substrate before applying the release coating dispersion can be treated by any convenient means, such as plasma treatment or corona discharge treatment. Alternatively, the substrate can be treated by applying a primer. Step (I) is optional and may be omitted.

[0098] The silicone release coating dispersion can be applied to a substrate by any convenient means, such as spraying, doctor blade, dipping, or screen printing, or by a roll coating machine, such as an offset web coating machine, a kiss coating machine, or an etched cylinder coating machine.

[0099] In step (II), the silicone release coating dispersion may be applied to any substrate such as the one described above. Alternatively, the silicone release coating composition may be applied to a polymer film substrate, for example, a polyester, particularly polyethylene terephthalate (PET), polyethylene, polypropylene, polyester, or polystyrene film. Alternatively, the silicone release coating dispersion 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.

[0100] Step (III) 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 (B) water and (H) solvent if present. The method may further include the step of curing the silicone release coating composition to form a silicone release coating on the surface of the substrate. Curing may be performed by any conventional means, such as heating at 100°C to 200°C.

[0101] 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 substrate around a heated cylinder.

[0102] FIG. 1 illustrates a partial cross-section of a laminate article (100) that can be manufactured as described above. The laminate article (100) has a release liner composed of a PET film backing substrate (101) having an antistatic silicone release coating (102) on the surface of the backing substrate (101). An adhesive (103) on the surface of a second PET film substrate (104) is protected by the release liner, wherein the surface of the antistatic silicone release coating (102) is in contact with the surface of the adhesive (103).

[0103] Examples

[0104] The following examples are presented to explain the invention to those skilled in the art and should not be interpreted as limiting the scope of the invention as described in the claims. The starting materials used in these examples are described in Table 1.

[0105] [Table 1]

[0106]

[0107] Starting materials under the DOWSIL™, SYL-OFF™, and XIAMETER™ brands are available from DSC. Lithium salts were purchased from Monils Chemical Engineering Science & Technology (Shanghai) Co., Ltd. Toluene was obtained from Sinopharm Chemical Reagent Co. LTD. Antistatic additives 2 and 3 were also purchased from Monils Chemical Engineering Science & Technology (Shanghai) Co., Ltd.

[0108] In Reference Example 1, the silicone release coating dispersion was prepared as follows.

[0109] (1) An aqueous solution was prepared by dissolving an electric shock additive in water while vigorously stirring.

[0110] (2) DOWSIL™ 2-7757 and DOWSIL™ ES-5612 were mixed using a SpeedMixer (3500 rpm, 60 s) to form a siloxane intermediate composition.

[0111] (3) The aqueous solution was gradually mixed into the siloxane intermediate composition using a SpeedMixer (3500 rpm, 60 s) (e.g., in the order of 2 g, 2 g, 2 g, 3 g, 3 g, 3 g, 3 g). The resulting dispersion intermediate was obtained in the form of a white cream with an antistatic additive content of 40%. To produce a dispersion intermediate with a low antistatic additive, the concentration of the antistatic additive in the discontinuous (internal) phase can be reduced accordingly.

[0112] (4) The formed dispersion intermediate was mixed with SYL-OFF™ 7226 using a SpeedMixer (3500 rpm, 60 s). The mixture was diluted with toluene to obtain a composition containing 90% toluene. SYL-OFF™ 297 anchorage additive and SYL-OFF™ 4000 catalyst were added and mixed sequentially (3500 rpm, 60 s) to form a silicone release coating dispersion. The amounts of each starting material are shown in Tables 2 and 3 below.

[0113] In this Reference Example 2, the silicone release coating dispersion prepared according to Reference Example 1 was coated onto a PET film (210 cm × 297 cm, 50 μm, corona treated) using a Mayer rod (#6) with a coating weight of 0.6-0.8 gm -2 10 cm s corresponding to -1Coating was applied at a speed of [speed]. Subsequently, the resulting film was dried and cured by heating to 140°C for 30 seconds, and then cooled to room temperature to form a release liner containing a silicone release coating on the surface of the PET film.

[0114] In Reference Example 3, the surface resistance of each silicone release coating prepared as described in Reference Example 2 was measured at room temperature (20 to 25°C) using a digital surface resistance metric (TECMAN, TM385, measurement range: 10 3 -10 12 Ω sq- 1 , Accuracy: ± 10%). Surface resistance measurements were performed three times at three different locations on each silicon release coating. Coating weight (CW), i.e., the area density of the silicon release coating, was determined by an X-ray fluorescence spectrometer (XRF, Oxford Lab-X Supre 8000) with a bare PET film. The silicon release coatings were aged for 7 or 30 days prior to testing.

[0115] In Reference Example 4, the release force at room temperature (RF-RT) was evaluated to measure the release force from the release liner using a 180-degree peel test. Tesa 7475 standard tape was laminated onto a (cured) silicone release coating, and 20 g / cm² was applied to the laminated sample. 2 A loaded weight was placed and the sample was left at RT (room temperature of 25°C) for 20 hours. After 20 hours, the weight was removed, and the sample was allowed to stand for 30 minutes. Then, the release power was tested using a ChemInstruments AR-1500 according to FINAT test method No. 10 (FINAT Technical Handbook 7th edition, 2005).

[0116] Release force after aging at 70°C (RF-70°C aging) was evaluated using a 180-degree peel test to measure the peel force of the release liner. Tesa 7475 standard tape was laminated onto a (cured) silicone release coating, and 20 g / cm² on the laminated sample 2 A weight was placed on the sample and left at 70°C for 20 hours. After 20 hours, the weight was removed, and the sample was allowed to stand for 30 minutes. Subsequently, the release force was tested using a Chem Instruments AR-1500 according to FINAT Test Method No. 10 (FINAT Technical Handbook 7th edition, 2005).

[0117] The coating weight was evaluated as described above in Reference Example 3, and then each sample was frictionally rubbed for 30 cycles at a rate of 30 cycles / minute using an abrasion tester (Elcometer 1720). The coating weight after friction was evaluated again as described above to measure relative anchor performance. Anchorage was calculated as (CW after friction) / (CW before friction) × 100%.

[0118] [Table 2]

[0119]

[0120] [Table 3]

[0121]

[0122] Surface resistance values ​​in Table 2 > 1012 Ω sq -1 As shown in Comparative Examples 1 and 5 (CE1, CE5), a silicone release coating prepared from a silicone release coating composition without an antistatic additive was insulated under tested conditions and showed that it could not dissipate static charge.

[0123] Comparative Examples 2 and 3 (CE2, CE3) demonstrated that conventional antistatic additives ([BMIM][TFSI]) and ([MeBu3N][TFSI]) do not provide a sufficient antistatic effect on silicone release coatings prepared from silicone release coating compositions containing these conventional antistatic additives. Under the tested conditions, the surface resistance values ​​for both CE1 and CE2 were > 10 as shown in Table 2. 12 Ω sq- 1 Without being bound by theory, the poor antistatic effect is thought to be due to the incompatibility of conventional antistatic additives in silicone release coating compositions.

[0124] Comparative Example 4 (CE4) was prepared according to the method described in U.S. Patent Application Publication No. 2020 / 0048508 A1, wherein a lithium salt was directly blended into a silicon release coating composition. The resulting silicon release coating had poor resistance values, which demonstrates that the silicon release coating dispersion prepared as described herein had excellent performance under tested conditions.

[0125] Working Examples 1 and 2 (IE1, IE2) contained 10% and 20% of antistatic additive 1, respectively, and showed that the surface resistance decreased by several orders of magnitude after the film was left at room temperature for several days.

[0126] Example 3 (IE3) contained 30% of antistatic additive 1 and 10 after 30 d 8 Ω sq -1 The surface resistance of the product was shown. A large amount of antistatic additive (1) can affect the appearance of the silicone release coating, making this silicone release coating composition more suitable for use in applications that do not require a transparent silicone release coating.

[0127] Example 4 (IE4) still has a surface resistance ≤ 10, which is lower than all comparative examples in Table 2, even after adding the surfactant XIAMETER™ OFX-5211 to the silicone release coating composition of IE2. 11 Ω sq -1 It was shown that a silicon release coating is provided.

[0128] IE5, IE6, IE7: By reducing the concentration of the antistatic additive in the internal phase compared to IE1 to IE4, the fraction of antistatic additive 1, which accounts for 40% of the aqueous phase, was reduced to 20%. When the same amount of aqueous phase was combined with other starting materials, the amount of antistatic additive 1 was reduced by half. As a result, 10 9 Ω sq -1 The surface resistance of was recorded as 10% of antistatic additive 1 (IE5, IE6). Addition of co-surfactant (XIAMETER TM OFX-5211) did not alter the initial resistance, but did not affect the resistance after aging at room temperature under tested conditions. Surface resistance was 7 to 10 after the addition of 2% co-surfactant (IE6). 8 Ω sq- 1 It decreased. Further reducing the content of antistatic additive 1 reduced the initial conductivity (IE7) under tested conditions.

[0129] The problem to be solved

[0130] Ionic liquids containing large ions, particularly those with bulky substituents such as lithium salts, are useful as antistatic agents but are poorly miscible with non-polar polyorganosiloxanes. Consequently, ionic liquids are prone to separating from the polyorganosiloxane matrix, which can cause structural and appearance defects in silicone release coatings prepared from compositions containing a polyorganosiloxane matrix and an ionic liquid, such as disclosed in U.S. Patent Application Publication No. 2020 / 0048508 A1. Furthermore, the ionic mobility and degree of dissociation of the ionic liquid are limited to the non-polar matrix, resulting in limited ionic conductivity. Although lithium salts have previously been used as antistatic additives in silicone release coatings, they have surface resistances > 10 12 Ω sq -1 This can be achieved, which is higher than required to provide antistatic properties to silicon release coatings for some applications. Industrial applicability

[0131] The silicone release coating dispersion of the present invention comprises a water-soluble ionic liquid and a silicone release coating composition. As shown in the above examples, a film formed from the silicone release coating dispersion is dried and cured so that, under tested conditions, the surface resistance is ≤ 10 after 7 to 30 days. 11 Ω sq -1 A silicon release coating can be formed. By using the silicon release coating dispersion described herein to manufacture the silicon release coating, one or more improvements (i.e., reductions) in surface resistance can be achieved.

[0132] Definition and Use of Terms

[0133] All amounts, ratios, and percentages are by weight unless otherwise specified. The total amount of all starting materials in the composition is 100% by weight. Overviews and summaries are incorporated herein by reference. Expressions in the singular form each represent one or more, unless otherwise indicated by the context of the specification. The singular form includes the plural form, unless otherwise indicated. The terms "comprising" and their derivatives, e.g., "comprising" and "comprising," are used herein in the broadest sense to mean and encompass the concepts of "comprising," "comprising," "essentially made up," and "made up." "For example," "for example (" e The use of ”, “for example,” and “including” is not limited solely to the enumerated examples. Accordingly, “for example” or “for example” means “for example, but not limited thereto” or “for example, but not limited thereto,” and includes other similar or equivalent examples.

[0134] It should be understood that the appended claims are not limited to the specific compounds, compositions, or methods described in the detailed description and may vary among specific embodiments within the scope of the appended claims. With respect to any Markush group required herein in describing specific features or aspects of various embodiments, different, particular, and / or unexpected results may be obtained from each member of an individual Markush group, independently of all other Markush members. Each member of a Markush group may be required individually and / or in combination and provides appropriate support for specific embodiments within the scope of the appended claims.

[0135] The abbreviations used in this specification are defined in Table 4.

[0136] [Table 4]

[0137]

[0138] Embodiments of the present invention

[0139] In the first embodiment, the method for preparing a silicone release coating dispersion is,

[0140] (1) (A) a step of dissolving an ionic liquid (B) in water to form an aqueous solution (the ionic liquid contains a lithium salt,

[0141] (A) an ionic liquid and (B) water exist in an aqueous discontinuous phase in a weight ratio of (A)::(B) of 2:1 to 1:2;

[0142] (2) A step of dispersing the above aqueous solution in a siloxane intermediate composition (the above siloxane intermediate composition is

[0143] (C) Unit formula (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 R 2 SiO 2 / 2 ) c (R 1 2SiO 2 / 2 ) d (SiO 4 / 2 ) branched polyorganosiloxane polymer (wherein, each R 1 is an independently selected monovalent hydrocarbon group that is not aliphatic unsaturated, and each R 2 is an independently selected aliphatic unsaturated monovalent hydrocarbon group; subscripts a and b indicate the average number of monofunctional units and subscript c indicates the average number of difunctional units per molecule, where a, b, c, and d are 2 ≥ a ≥ 0, 4 ≥ b ≥ 0, (a + b) = 4, 4 ≥ c ≥ 0, 995 ≥ d ≥ 4, and (a + b + c + d) has a value sufficient to impart a viscosity > 170 mPa·s when measured by a rotational viscometer at room temperature);

[0144] (D) Unit formula (D1) (R 1 3SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) e (R 1 R 3 SiO 2 / 2 ) f Silicon polyether of (wherein the subscript e is 1 to 50, the subscript f is 1 to 5, and R 1 is as previously stated, and R 4 is selected from the group consisting of H and alkyl groups, and each R 3 is the chemical formula -(D 1 ) g O(D 2 O) h R 4 It is a polyether group of, where each D 1 is a divalent hydrocarbon group of 2 to 4 independently selected carbon atoms, and each D 2 is an independently selected divalent hydrocarbon group of 2 to 4 carbon atoms, where the subscript g is 1 to 20 and the subscript h is 1 to 50, thereby forming a dispersion intermediate); and

[0145] (3) A step of combining the above dispersion intermediate and additional starting material (the above additional starting material is

[0146] (E) Polydioganosiloxane having two or more aliphatic unsaturated groups per molecule (Polydioganosiloxane is of the following unit formula (R 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) j It has, where R 1 and R 2 is as described above, where subscript j indicates the average number of difunctional units per molecule, and 10,000 ≥ j ≥ 100);

[0147] (F) Polyorganohydrogensiloxane having at least 3 silicon-bonded hydrogen atoms per molecule (Polyorganohydrogensiloxane is of the unit formula (R 1 2HSiO 1 / 2 ) k (R 1 3SiO 1 / 2 ) m (R 1 HSiO 2 / 2 ) n (R 1 2SiO 2 / 2 ) o It has, where R 1 ...is as described above, where subscripts k and m represent the average number of monofunctional units per molecule, subscripts n and o represent the average number of difunctional units per molecule, and subscripts k, m, n and o have values ​​such that 2 ≥ k ≥ 0, 2 ≥ m ≥ 0, (k + m) = 2, n > 0, o ≥ 0, (k + n) ≥ 3, and 8 ≤ (k + m + n + o) ≤ 400); and

[0148] (G) Includes a catalyst for hydrosilylation reaction)

[0149] In the second embodiment, in the method of the first embodiment, the additional starting material in step (III) further comprises a starting material selected from the group consisting of (H) a solvent, (I) a hydrosilylation reaction inhibitor, (J) an anchorage additive, or a combination of two or more of (H), (I), and (J).

[0150] In the third embodiment, the method of the first or second embodiment further includes the step of recovering a low-boiling point oligomer (M).

[0151] In the fourth embodiment, in any one of the methods of the first to third embodiments, (A) the ionic liquid is,

[0152] Based on the total weight of (A1) and (A2), 90 weight% of (A1) lithium trifluoromethylsulfonate, and

[0153] An aqueous solution is formed containing 10% by weight of (A2) lithium bis(trifluoromethylsulfonyl)imide based on the total weight of (A1) and (A2).

Claims

Claim 1 A silicone release coating dispersion comprising (I) a continuous phase comprising a hydrosilylation reaction-curable silicone release coating composition, (II) a surfactant, and (III) an aqueous discontinuous phase dispersed in the continuous phase, wherein the aqueous discontinuous phase comprises (A) an ionic liquid and (B) water, and wherein the ionic liquid is soluble in the water. Claim 2 In claim 1, the silicone release coating composition is (C) unit formula (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 R 2 SiO 2 / 2 ) c (R 1 2SiO 2 / 2 ) d (SiO 4 / 2 ) branched polyorganosiloxane polymer (wherein, each R 1 is an independently selected monovalent hydrocarbon group that is not aliphatic unsaturated, and each R 2 is an independently selected aliphatic unsaturated monovalent hydrocarbon group; Subscripts a and b indicate the average number of monofunctional units and subscript c indicates the average number of difunctional units per molecule, where a, b, c, and d are 2 ≥ a ≥ 0, 4 ≥ b ≥ 0, (a + b) = 4, 4 ≥ c ≥ 0, 995 ≥ d ≥ 4, and (a + b + c + d) has a value sufficient to impart a viscosity of > 170 mPa·s when measured by a rotational viscometer at room temperature); (E) a polydioganosiloxane having at least two aliphatic unsaturated groups per molecule (wherein the amounts of (C) branched polyorganosiloxane polymer and (E) polydioganosiloxane having two or more aliphatic unsaturated groups per molecule are combined in a total of 100 parts by weight); (F) silicon bonds in the above release coating composition in a ratio of >1:1 to 5:1 A polyorganohydrogensiloxane having three or more silicon-bonded hydrogen atoms per molecule in an amount sufficient to provide a molar ratio of hydrogen atoms to aliphatic unsaturated groups (SiH:Vi ratio); (G) a hydrosilylation reaction catalyst sufficient to provide 1 ppm to 500 ppm of platinum group metal based on the weight of the silicone release coating dispersion; optionally (I) a hydrosilylation reaction inhibitor; and optionally (J) an anchorage additive, comprising a silicone release coating dispersion. Claim 3 ◈Claim 3 was abandoned upon payment of the registration fee.◈ The silicone release coating dispersion according to Claim 1, wherein the continuous phase further comprises 90 weight% or less of a solvent, and the remainder relative to 100 weight% of the continuous phase is the silicone release coating composition. Claim 4 ◈Claim 4 was abandoned upon payment of the registration fee.◈ In claim 2, the above (C) branched polyorganosiloxane polymer is of the formula [R 2 R 1 2Si-(O-SiR 1 2) x -O] (4-w) -Si-[O-(R 1 2SiO) v SiR 1 3] w It has, where R 1 and R 2 A silicone release coating dispersion as described above, wherein the subscripts v, w, and x have values ​​such that 200 ≥ v ≥ 1, 2 ≥ w ≥ 0, and 200 ≥ x ≥ 1. Claim 5 ◈Claim 5 was abandoned upon payment of the registration fee.◈ In Claim 2, the above (E) polydioganosiloxane is of the following unit formula (R 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) j A silicone release coating dispersion having, wherein R1 and R2 are as described above, the subscript j indicates the average number of difunctional units per molecule, and 10,000 ≥ j ≥ 100. Claim 6 ◈Claim 6 was abandoned upon payment of the registration fee.◈ In Claim 2, the above (F) polyorganohydrogensiloxane is of the following unit formula (R 1 2HSiO 1 / 2 ) k (R 1 3SiO 1 / 2 ) m (R 1 HSiO 2 / 2 ) n (R 1 2SiO 2 / 2 ) o It has, where R 1 A silicone release coating dispersion as described above, wherein subscripts k and m represent the average number of monofunctional units per molecule, subscripts n and o represent the average number of difunctional units per molecule, and subscripts k, m, n and o have values ​​such that 2 ≥ k ≥ 0, 2 ≥ m ≥ 0, (k + m) = 2, n > 0, o ≥ 0, (k + n) ≥ 3, and 8 ≤ (k + m + n + o) ≤ 400. Claim 7 ◈Claim 7 was abandoned upon payment of the establishment registration fee.◈ In Paragraph 2, each R 1 is independently selected from the group consisting of methyl and phenyl, and each R 2 A silicone release coating dispersion independently selected from the group consisting of vinyl, allyl, and hexenyl. Claim 8 ◈Claim 8 was abandoned upon payment of the registration fee.◈ In any one of Claims 1 to 7, the above (II) surfactant comprises (D) a silicone polyether, a silicone release coating dispersion. Claim 9 ◈Claim 9 was abandoned upon payment of the registration fee.◈ In Claim 8, the above (D) silicon polyether is unit formula (D1) (R 1 3SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) e (R 1 R 3 SiO 2 / 2 ) f It has, where subscript e is 1 to 50, subscript f is 1 to 5, and R 1 It is as described above, and each R 3 is sik ―(D 1 ) g O(D 2 O) h R 4 It is a polyether group of, where each D 1 is a divalent hydrocarbon group of 2 to 4 independently selected carbon atoms, and each D 2 is a divalent hydrocarbon group of 2 to 4 independently selected carbon atoms, and R 4 A silicone release coating dispersion selected from the group consisting of H and alkyl groups, wherein the subscript g is 1 to 20 and the subscript h is 1 to 50. Claim 10 ◈Claim 10 was abandoned upon payment of the registration fee.◈ In claim 9, further comprising a co-surfactant, said co-surfactant having unit formula (D2) (R 1 3SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) e' (R 1 R 5 SiO 2 / 2 ) f' It has, where R 1 ...is as described above, and the subscript e' is from 0 to 50, provided that e' < e, the subscript f' is from 1 to 5, and R 5 is the formula ―(D 1 ) g O(D 3 O) i It has H, where D 3 A silicon release coating dispersion in which is a divalent hydrocarbon group having 2 to 4 carbon atoms, and the subscript i is 1 to 50. Claim 11 ◈Claim 11 was abandoned upon payment of the registration fee.◈ In any one of claims 1 to 7, (A) the ionic liquid forms an aqueous solution comprising 90 wt% of (A1) lithium trifluoromethylsulfonate based on the total weight of (A1) and (A2), and 10 wt% of (A2) lithium bis(trifluoromethylsulfonyl)imide based on the total weight of (A1) and (A2), wherein the (A) ionic liquid and (B) water exist in the aqueous discontinuous phase in a weight ratio (A)::(B) of 2:1 to 1:

2. Claim 12 A method for preparing a silicone release coating dispersion according to any one of claims 2 to 7, comprising: (1) dissolving the (A) ionic liquid in the (B) water to form an aqueous solution; (2) dispersing the aqueous solution in a siloxane intermediate composition to form a dispersion intermediate, wherein the siloxane intermediate composition comprises the (C) branched polyorganosiloxane polymer and (D) silicone polyether; and (3) combining the dispersion intermediate with an additional starting material, wherein the additional starting material comprises the (E) polydioganosiloxane having at least two aliphatic unsaturated groups per molecule, the (F) polyorganohydrogensiloxane having three or more silicon-bonded hydrogen atoms per molecule, the (G) catalyst for a hydrosilylation reaction, optionally the (H) solvent, optionally the (I) hydrosilylation reaction inhibitor, and optionally the (J) anchorage additive. Claim 13 A method for forming a release liner, comprising optionally (I) a step of treating the surface of a substrate, (II) a step of coating a silicone release coating dispersion of any one of claims 1 to 7 on the surface of the substrate, (III) a step of drying the silicone release coating dispersion to form a film, and (IV) a step of curing the film to form a silicone release coating on the surface of the substrate. Claim 14 A release liner manufactured by the method of paragraph 13.

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