Antistatic silicone release coating and method for its preparation and use.

Abstract

The 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. Methods for the preparation of the silicone release coating dispersion and its use to form silicone release coatings are provided.

Description

[Technical Field]

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

[0002] Introduction Static charge generated during the delamination of the adhesive layer from the release liner must be dissipated to protect the adhesive film from discharge and dust adsorption. Current antistatic solutions in the silicone pressure-sensitive industry 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 release liners can be plagued by multiple process steps, potentially increasing costs and limiting productivity, and the antistatic primer may interfere with the curing reaction of the silicone release coating composition or impair the interfacial adhesion of the silicone release coating. [Overview of the project]

[0003] The silicone release coating dispersion comprises a continuous phase containing a hydrosilylated 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 peel-off coating dispersion can be formed by a method comprising: (1) dissolving (A) an ionic liquid in (B) water to form an aqueous solution; (2) dispersing the aqueous solution in a siloxane intermediate composition containing (C) a branched polyorganosiloxane polymer and (D) a silicone polyether to form a dispersion intermediate; and (3) combining the dispersion intermediate with additional starting materials, wherein the additional starting materials include (E) a polydiorganosiloxane having at least two aliphatic unsaturated groups per molecule, (F) a polyorganohydrogensiloxane having at least three silicon-bonded hydrogen atoms per molecule, and (G) a hydrosilylation reaction catalyst.

[0005] The release liner may be prepared using the above-mentioned dispersion by a method optionally comprising: (I) treating the surface of the backing substrate; (II) coating the surface of the backing substrate with the silicone release coating dispersion; (III) drying the silicone release coating dispersion to form a film; and (IV) curing the film to form a silicone release coating on the surface of the backing substrate. [Brief explanation of the drawing]

[0006] [Figure 1] A partial cross-sectional view of a laminated article (100) including a silicone release coating (102) having antistatic properties is shown.

[0007] Reference number 101 PET film substrate 102 Antistatic Silicone Release Coating 103 Adhesive 104 Second PET film substrate [Modes for carrying out the invention]

[0008] The silicone release coating dispersion (dispersion) described above is (I) A continuous phase comprising a hydrosilylated reaction curable silicone peelable coating composition (composition), (II) Surfactants and (III) A aqueous discontinuous phase dispersed in a continuous phase, (A) Ionic liquids and (B) Water and, It contains an aqueous discontinuous phase in which an ionic liquid is dissolved in water.

[0009] (A) Ionic liquid The starting material (A), an ionic liquid, is an antistatic additive that imparts antistatic properties to a silicone release coating prepared from a dispersion. Suitable ionic liquids for use herein are salts that may contain large cations and charge delocalized anions. Ionic liquids include water-soluble alkali metal salts such as lithium salts. 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 containing cations selected from lithium ions, sodium ions, and potassium ions, and anions 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. Examples of lithium salts include (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 individually or in any combination of two or more of (A1) to (A8). Alternatively, the ionic liquid may contain a mixture of (A1) lithium trifluoromethanesulfonate and (A2) lithium bis(trifluoromethylsulfonyl)imide. Lithium salts such as lithium trifluoromethanesulfonate and lithium bis(trifluoromethylsulfonyl)imide are commercially available, for example, from Monils Chemical Engineering Science & Technology (Shanghai) Co., Ltd.(A1) Lithium trifluoromethanesulfonate and (A2) Lithium bis(trifluoromethylsulfonyl)imide may be present in amounts such that (A) the ionic liquid contains 90% by weight of (A1) lithium trifluoromethylsulfonate and 10% by weight of (A1) and (A2) based on the total weight of (A1) and (A2). The starting material (A) is the ionic liquid and the starting material (B) is water may be present in the aqueous discontinuous phase in a weight ratio of 2:1 to 1:2 (A):(B).

[0010] (B)Water Water (B) is not generally limited, and neat (i.e., without carrier vehicle / solvent) and / or highly pure (i.e., free from or substantially free from minerals and / or other impurities) may be used. For example, water (B) may or may not be treated before dissolving the ionic liquid (A) in it. Examples of processes that may be used to purify water include distillation, filtration, deionization, and combinations of two or more of these, which may result in the water being deionized, distilled, and / or filtered. Alternatively, water (B) may be untreated (e.g., provided by tap water, i.e., from a city water system or well water used without further purification). Alternatively, water (B) may be purified before dissolving the ionic liquid (A) in it. Alternatively, water (B) may be used as a mixture (e.g., solution or suspension) containing a carrier vehicle / solvent such as any of the following that can be used in silicone release coating compositions.

[0011] Silicone release coating composition The hydrosilylation reaction-curable silicone release coating composition contains (C) a branched polyorganosiloxane polymer, (E) a polydiorganosiloxane having at least 2 aliphatic unsaturated groups per molecule, (F) a polyorganohydrogensiloxane having at least 3 silicon-bonded hydrogen atoms per molecule, and (G) a hydrosilylation reaction catalyst. The silicone release coating composition may optionally further contain one or more additional starting materials. The one or more additional starting materials may be selected from the group consisting of (H) a solvent, (I) a hydrosilylation reaction inhibitor, and (J) a fixing additive.

[0012] (C) Branched polyorganosiloxane polymer 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 )(where each R 1 is an independently selected monovalent hydrocarbon group that does not contain aliphatic unsaturation, and each R 2A is an independently selected aliphatic unsaturated monovalent hydrocarbon group, where subscripts a and b represent the average number of monofunctional units per molecule, subscripts c and represent the average number of difunctional units per molecule, and a, b, c, and d have mean values ​​such that 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 greater than 170 mPa·s to the branched polyorganosiloxane polymer as measured by rotational viscometric method at room temperature. Alternatively, the viscosity may be greater than 170 mPa·s to 1000 mPa·s, or greater than 170 mPa·s to 500 mPa·s, or 180 mPa·s to 450 mPa·s, or 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-plate viscometer equipped with a #CP-52 spindle. Those skilled in the art will recognize that the rotation speed decreases as viscosity increases. Suitable branched polyorganosiloxane polymers are known in the art and can be prepared by known methods, as exemplified by Cray et al.'s U.S. Patent No. 6,806,339 and U.S. Patent Application Publication No. 2007 / 0289495.

[0013] R 1 Suitable alkyl groups may be linear, branched, cyclic, or a combination of two or more of these. Examples of alkyl groups include 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, and octadecyl (and branched isomers having 5 to 18 carbon atoms), and examples of alkyl groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 1 The alkyl group can be selected from the group consisting of methyl, ethyl, propyl, and butyl, or methyl, ethyl, and propyl, or methyl or ethyl. Alternatively, R 1The aryl group can be methyl.

[0014] R 1 Suitable aryl groups can be monocyclic or polycyclic and may have a pendant hydrocarbyl group. For example, R 1 Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl, and further examples include aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. Alternatively, R 1 The aryl group may be a monocyclic group such as phenyl, tolyl, or benzyl, or R 1 The aryl group may be phenyl.

[0015] In the above and below formulas, R 2 R may be an alkenyl group. Preferred alkenyl groups may have terminal alkenyl functional groups to promote the hydrosilylation reaction, for example, R 2 is, formula

[0016] [ka] (In the formula, the subscript y is between 0 and 6, * It may have a bond point (i.e., a bond point to a silicon atom). Alternatively, each R 2 R may be independently selected from the group consisting of vinyl, allyl, and hexenyl. Alternatively, each R 2 These may be independently selected from the group consisting of vinyl and allyl. Alternatively, each R 2 It may be vinyl. Or, each R 2 It may also be an allele.

[0017] Alternatively, (C) branched polyorganosiloxane polymers are given by formula (C2):[R 2 R 1 Si-(O-SiR 1 2) x -O] (4-w) -Si-[O-(R 1 2SiO) v SiR1 3] w (In the formula, R 1 and R 2 As described above, the subscripts v, w, and x may have values ​​such that 200≧v≧1, 2≧w≧0, and 200≧x≧1. Alternatively, in formula (C2), each R 1 R may be independently selected from the group consisting of methyl and phenyl, and each R 2 The starting material (C2) may be independently selected from the group consisting of vinyl, allyl, and hexenyl. Branched polyorganosiloxanes suitable for the starting material (C2) can be prepared by known methods such as heating a mixture containing a polyorganosilicate resin and a cyclic polydiorganosiloxane or a linear polydiorganosiloxane in the presence of a catalyst such as an acid or phosphazene base, and then neutralizing the catalyst.

[0018] Alternatively, a branched polyorganosiloxane polymer for the starting material (C) is given by 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 (In the formula, R 1 and R 2As stated above, it may contain silsesquioxane (where subscript aa≧0, subscript bb>0, subscript cc is between 15 and 995, subscript dd>0, and subscript ee≧0). Subscript aa can be between 0 and 10. Alternatively, subscript aa may have a value such that 12≧aa≧0, or 10≧aa≧0, or 7≧aa≧0, or 5≧aa≧0, or 3≧aa≧0. Alternatively, subscript bb≧1. Alternatively, subscript bb≧3. Alternatively, subscript bb may have a value such that 12≧bb>0, or 12≧bb≧3, or 10≧bb>0, or 7≧bb>1, or 5≧bb≧2, or 7≧bb≧3. Alternatively, the subscript cc may have a value such that 800≧cc≧15 or 400≧cc≧15. Alternatively, the subscript ee may have a value such that 800≧ee≧0, or 800≧ee≧15, or 400≧ee≧15. Alternatively, the subscript ee may be 0. Alternatively, the quantity (cc+ee) may have a value such that 995≧(cc+ee)≧15. Alternatively, the subscript dd≧1. Alternatively, the subscript dd may be between 1 and 10. Alternatively, the subscript dd may have a value such that 10≧dd>0, or 5≧dd>0, or dd=1. Alternatively, the subscript dd may be between 1 and 10, or the subscript dd may be 1 or 2. Alternatively, if the subscript dd=1, the subscript bb may be 3 and the subscript cc may be 0. The subscript bb value may be sufficient to provide a silsesquioxane having an alkenyl content of 0.1% to 1%, or 0.2% to 0.6%, based on the weight of the silsesquioxane. Suitable silsesquioxanes for the starting material (C3) are exemplified by those disclosed in U.S. Patent No. 4,374,967 by Brown et al., U.S. Patent No. 6,001,943 by Enami et al., U.S. Patent No. 8,546,508 by Nabeta et al., and U.S. Patent No. 10,155,852 by Enami.

[0019] (E) Aliphatic unsaturated polydiorganosiloxane The starting material (E) in the silicone release coating composition is a polyorganosiloxane containing at least two aliphatic unsaturated groups per molecule. Polydiorganosiloxane has the unit formula (E1):(R 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) j (In the formula, R 1 and R 2 As stated above, the subscript j represents the average number of difunctional units per molecule, and may have 10,000 ≥ j ≥ 100.

[0020] The starting material (E) may include alkenyl-functionalized polydiorganosiloxanes, such as (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,vinylsiloxy-terminated polydimethylsiloxane, (E1-5) bis-dimethylhexenylsiloxy-terminated polydimethylsiloxane, (E1-6) bis-dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), (E1-7) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), and (E1-8) 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.

[0021] Methods for preparing the polydiorganosiloxanes described above with respect to the starting material (E), such as hydrolysis and condensation of the corresponding organohalosilanes and oligomers, or equilibration of cyclic polydiorganosiloxanes, are known in the art. See, for example, U.S. Patents 3,284,406, 4,772,515, 5,169,920, 5,317,072, and 6,956,087, which disclose the preparation of linear polydiorganosiloxanes having alkenyl groups. Examples of linear polydiorganosiloxanes containing alkenyl groups are commercially available from Gelest Inc. (Morrisville, Pennsylvania, USA) under 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 polydiorganosiloxanes containing alkenyl groups are commercially available from DSC.

[0022] The starting material (C) branched polyorganosiloxane polymer and the starting material (E) polydiorganosiloxane having at least two aliphatic unsaturated groups per molecule are present together in an amount totaling 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, or 3 to 9 parts by weight of the silicone release coating composition. Alternatively, the amount of starting material (E) may be 20 to 40 parts by weight of the silicone release coating composition.

[0023] (F) Polyorganohydrogensiloxane The starting material (F) in the silicone release coating composition is a polyorganohydrogensiloxane, which can function as a crosslinking agent for curing the silicone release coating composition. The polyorganohydrogensiloxane has at least 3 silicon-bonded hydrogen atoms per molecule. The unit formula for polyorganohydrogensiloxane is (F1):(R1 2HSiO 1 / 2 ) k (R 1 3SiO 1 / 2 ) m (R 1 HSiO 2 / 2 ) n (R 1 2SiO 2 / 2 ) o (In the formula, R 1 As stated above, the subscripts k and m represent the average number of monofunctional units per molecule, the subscripts n and o represent the average number of difunctional units per molecule, and the subscripts k, m, n, and o are such that 2≧k≧0. 2 It may have values ​​such that ≥m≧0, (k+m)=2, n>0, o≧0, (k+n)≧3, and 8≦(k+m+n+o)≦400.

[0024] Examples of polyorganohydrogensiloxanes suitable for use herein include: (i) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (ii) α,ω-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, (v) α-dimethylhydrogensiloxy, ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (vi) α-dimethylhydrogensiloxy, ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, (vii) any 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.

[0025] Polyorganohydrogensiloxanes are also commercially available, for example, from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as 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 hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified in U.S. Patent No. 2,823,218 by Speier, U.S. Patent No. 3,957,713 by Jeram et al., and U.S. Patent No. 4,329,273 by Hardman et al.

[0026] The silicon-bonded hydrogen (Si-H) content of polyorganohydrogensiloxanes can be determined using quantitative infrared analysis in accordance with ASTM E168. When dependent on the hydrosilylation curing process, the ratio of silicon-bonded hydrogen to aliphatic unsaturated groups (e.g., alkenyl and / or alkynyl groups such as vinyl) is important. Generally, this is determined by calculating the total weight % of aliphatic unsaturated groups (e.g., vinyl [V]) and the total weight % of silicon-bonded hydrogen [H] in the composition. If the molecular weight of hydrogen is 1 and the molecular weight of vinyl is 27, then the molar ratio of silicon-bonded hydrogen to vinyl is 27 [H] / [V]. Polyorganohydrogensiloxanes are present in sufficient quantities to provide a molar ratio of silicon-bonded hydrogen atoms to aliphatic unsaturated groups (SiH:Vi ratio) greater than 1:1 to 5:1 in silicone release coating compositions.

[0027] (G) Hydrosilylation reaction catalyst The starting material (G) in the silicone release coating composition is a hydrosilylation reaction catalyst. This catalyst will promote the reaction between the aliphatic unsaturated groups in the starting materials (C) and (E) and the silicon-bonded hydrogen atoms in the starting material (F). The catalyst contains 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.

[0028] For example, (G) the hydrosilylation reaction catalyst may be (G1) a platinum group metal as described above, (G2) a compound of such a metal, e.g., chloride tris(triphenylphosphane)rhodium(I) (Wilkinson catalyst), rhodium diphosphine chelate (e.g., [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium), chlorplatinic acid (Speier catalyst), chlorplatinic acid hexahydrate, platinum dichloride, (G3) a complex of compound (G2) with an aliphatic unsaturated organopolysiloxane, or (G4) a platinum group metal compound microencapsulated in a matrix or core-shell structure. Examples of complexes between platinum and aliphatic unsaturated organopolysiloxanes include a complex of platinum with 1,3-diethyl-1,1,3,3-tetramethyldisiloxane (Karstedt catalyst) and a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby complex). Alternatively, the hydrosilylation reaction catalyst may be one of the above compounds or complexes (G5) microencapsulated in a resin matrix. Specific examples of suitable platinum-containing catalysts include chloroplatinic acid in either hexahydrate or anhydrous form, or a platinum-containing catalyst obtained by a method involving the reaction of chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as vinyl-functionalized polydimethylsiloxane (e.g., divinyltetramethyldisiloxane), or the alkene-platinum-silyl complex described in Roy's U.S. Patent No. 6,605,734. Alkene-platinum-silyl complexes can be prepared, for example, by mixing 0.015 moles of (COD)PtCl2 with 0.045 moles of COD and 0.0612 moles of HMeSiCl2 (wherein COD represents cyclooctadienyl and Me represents methyl).Other exemplary hydrosilylation catalysts include Speier's U.S. Patent No. 2,823,218, Ashby's No. 3,159,601, Lamoreaux's No. 3,220,972, Chalk et al.'s No. 3,296,291, Willing's No. 3,419,593, Modic's No. 3,516,946, Karstedt's No. 3,715,334, Karstedt's No. 3,814, This is described in Patent No. 730, Chandra's Patent No. 3,928,629, Lee et al.'s Patent No. 3,989,668, Lee et al.'s Patent No. 4,766,176, Lee et al.'s Patent No. 4,784,879, Togashi's Patent No. 5,017,654, Chung et al.'s Patent No. 5,036,117, and Brown's Patent No. 5,175,325, as well as Togashi et al.'s European Patent Application Publication No. 0347895(A). Suitable hydrosilylation catalysts for the starting material (G) are commercially available, for example, SYL-OFF® 4000 catalyst and SYL-OFF® 2700, which are available from Dow Silicones Corporation (Midland, Michigan, USA).

[0029] The starting material (G) may be one hydrosilylation catalyst or a combination of two or more of the above hydrosilylation catalysts. The amount of (G) hydrosilylation catalyst in the composition depends on various factors, including the selection of starting materials (C), (E), and (F), their respective content of alkenyl groups and silicon-bonded hydrogen atoms, and the amount of (I) hydrosilylation inhibitor present in the silicone release coating composition, but the amount of catalyst is sufficient to catalyze the hydrosilylation reaction of SiH and alkenyl groups, or the amount of catalyst is sufficient to provide at least 0.01 ppm, or at least 0.05 ppm, or at least 0.1 ppm, or at least 0.5 ppm, or at least 1 ppm, or at least 170 ppm of platinum group metals, based on the weight of the silicone release coating dispersion. At the same time, the amount of catalyst is sufficient to provide up to 800 ppm by mass, or up to 500 ppm by mass, or up to 200 ppm by mass of platinum group metals, based on the same criteria.

[0030] (H) solvent The continuous phase of the silicone release coating dispersion may optionally further contain a solvent. A solvent may be added during the preparation of the silicone release coating composition to facilitate the fluidity of the composition and the introduction of specific starting materials, such as hydrosilylation reaction catalysts. The solvents used herein are those that assist in the fluidization of the starting materials in the silicone release coating composition but do not react with the starting materials in essence. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. Solubility refers to the solvent being sufficient to dissolve and / or disperse the starting materials. Volatility refers to the vapor pressure of the solvent. If the solvent is too volatile (too high vapor pressure), bubbles may form during the hydrosilylation reaction, which may rupture or otherwise weaken or adversely affect the properties of the reaction product. However, if the solvent is not sufficiently volatile (too low vapor pressure), it may remain as a plasticizer in the silicone release coating prepared by curing the silicone release coating composition.

[0031] Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as DOWSIL® 200 fluid and DOWSIL® OS fluid with a molecular weight of 0.5 to 1.5 cSt (these are commercially available from DSC).

[0032] Alternatively, the solvent may include an organic solvent. The organic solvent may be an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; or a halogenated hydrocarbon such as 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 two or more combinations thereof.

[0033] The amount of solvent will depend on various factors, including the type of solvent selected, as well as the amount and type of other starting materials selected for the silicone release coating composition. However, the amount of solvent may range from 1% to 99%, or 2% to 90%, based on the total weight of all starting materials in the silicone release coating composition. For example, the solvent may be added during the preparation of the composition to aid in mixing and delivery. Optionally, all or part of the solvent may be removed after the composition has been prepared. Alternatively, the continuous phase of the silicone release coating dispersion may contain up to 90% by weight of solvent, with the remainder up to 100% by weight of the continuous phase being the silicone release coating composition.

[0034] (I) Inhibitors Starting material (I) is a hydrosilylation inhibitor (inhibitor) that can be used to alter the hydrosilylation reaction compared to a composition containing the same starting material except that the inhibitor has been removed. Starting material (I) may be selected from the group consisting of (I1) acetylene alcohols, (I2) silylated acetylene alcohols, (I3) en-yne compounds, (I4) triazoles, (I5) phosphines, (I6) mercaptans, (I7) hydrazines, (I8) amines, (I9) fumarates, (I10) maleates, (I11) ethers, (I12) carbon monoxide, (I13) alkenyl-functionalized siloxane oligomers, and (I14) combinations of two or more of these. Alternatively, the hydrosilylation reaction inhibitor may be selected from the group consisting of (I1) acetylene alcohols, (I2) silylated acetylene alcohols, (I9) fumarate, (I10) maleate, (I13) carbon monoxide, or (I14) combinations of two or more of these. Alternatively, the inhibitor may include acetylene alcohols.

[0035] Acetylene alcohols are exemplified by methylbutynyl such as 3,5-dimethyl-1-hexyne-3-ol, 1-butyne-3-ol, 1-propyne-3-ol, 2-methyl-3-butyne-2-ol and 3-methyl-1-butyne-3-ol, ethynylcyclohexanol such as 3-methyl-1-pentin-3-ol, 3-phenyl-1-butyne-3-ol, 4-ethyl-1-octin-3-ol, 3,5-dimethyl-1-hexyne-3-ol, and 1-ethynyl-1-cyclohexanol, as well as combinations thereof. Acetylene alcohols are known in the art and are commercially available from various suppliers; see, for example, U.S. Patent No. 3,445,420 by Kookootsedes et al. Alternatively, the inhibitor may be a silylated acetylene compound. Although not bound by theory, it is thought that the addition of a silylated acetylene compound reduces the yellowing of the reaction product prepared from the hydrosilylation reaction compared to the reaction product obtained from the hydrosilylation reaction of a starting material that does not contain a silylated acetylene compound or contains an organic acetylene alcohol inhibitor such as the one mentioned above.Silylated acetylene compounds include (3-methyl-1-butyne-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyne-3-oxy)dimethylsilane, bis(3-methyl-1-butyne-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyne-3-oxy))silane, (3-methyl-1-butyne-3-oxy)dimethylphenylsilane, (3-methyl-1-butyne-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyne-3-oxy)triethylsilane, bis(3-methyl-1- These are exemplified by butyn-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-oxy)trimethylsilane, (3-phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, and combinations thereof. Silylated acetylene compounds useful as inhibitors in this specification can be prepared by methods known in the art. For example, U.S. Patent No. 6,677,407 by Bilgrien et al. discloses the silylation of the above-mentioned acetylene alcohol by reaction with chlorosilane in the presence of an acid acceptor.

[0036] Alternatively, the inhibitor may be an en-yne compound, such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, or a combination thereof. Alternatively, the inhibitor may contain a triazole, exemplified by benzotriazole. Alternatively, the inhibitor may contain a phosphine. Alternatively, the inhibitor may contain a mercaptan. Alternatively, the inhibitor may contain a hydrazine. Alternatively, the inhibitor may contain an amine. Examples of amines include tetramethylethylenediamine, 3-dimethylamino-1-propyne, n-methylpropargylamine, propargylamine, 1-ethynylcyclohexylamine, or a combination thereof. Alternatively, the inhibitor may contain a fumarate. Examples of fumarates include 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 contain a maleate. Examples of maleates include 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.

[0037] Alternatively, the inhibitor may contain carbon monoxide. Alternatively, the inhibitor may contain an alkenyl-functionalized siloxane oligomer, which may be cyclic or linear, such as methyl vinylcyclosiloxanes exemplified by 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 combinations of two or more thereof. Compounds useful as the above inhibitors are commercially available, for example, from Sigma-Aldrich Inc. or Gelest, Inc., and are known in the art; see, for example, U.S. Patent No. 3,989,667 by Lee et al. Suitable inhibitors for use in this specification are exemplified by those described as stabilizer E in paragraphs

[0148] to

[0165] of U.S. Patent Application Publication No. 2007 / 0099007.

[0038] The amount of inhibitor will depend on various factors, including the desired working time, the specific inhibitor used, and the selection and amount of catalyst. However, if present, the amount of inhibitor may be 0% to 1% by weight, or 0% to 5% by weight, or 0.001% to 1% by weight, or 0.01% to 0.5% by weight, or 0.0025% to 0.025% by weight, based on the weight of all starting materials in the silicone peel coating composition.

[0039] (J) Fixing additive The starting material (J) is an optional fixing additive. While not theoretically bound, it is believed that the fixing additive will facilitate the bonding of the silicone release coating, prepared from the silicone release coating dispersion described herein, to the backing substrate.

[0040] Suitable fixing additives include silane coupling agents (methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, bis(trimethoxysilyl)propane, and bis(trimethoxysilylhexane, etc.)); and mixtures or reaction mixtures of said silane coupling agents. Alternatively, the fixing additive may be tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, or 3-methacryloxypropyltrimethoxysilane.

[0041] Exemplary fixing additives are known in the art, such as in U.S. Patent Application Publication 2012 / 0328863 (paragraph

[0091] ) and U.S. Patent Application Publication 2017 / 0233612 (paragraph

[0041] ). Fixing additives are commercially available. For example, SYL-OFF® 297, SYL-OFF® SL 9176, and SYL-OFF® SL 9250 are available from DSC. Other exemplary fixing additives include (J-1) vinyltriacetoxysilane, (J-2) glycidoxypropyltrimethoxysilane, and (J-3) combinations of (J-1) and (J-2). This combination (J-3) may be a mixture and / or a reaction product.

[0042] The amount of fixing additive depends on various factors, including the type of substrate to which the composition is applied. However, the amount of fixing additive may be 1-5%, 1-3%, or 1.9-2.1%, based on the total weight of all starting materials in the composition.

[0043] (II) Surfactants The above silicone release coating dispersion further contains (II) a surfactant. The surfactant can form a dispersion of an aqueous discontinuous phase containing the above ionic liquid and water in a continuous phase containing the above silicone release coating composition. The surfactant contains (D) a silicone polyether.

[0044] The silicone polyether has a unit formula (D1): (R 1 3SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) e (R 1 R 3 SiO 2 / 2 ) f (wherein R 1 is as defined above, each R 3 is an independently selected polyether group, the subscript e is 1 to 500, or 1 to 200, or 1 to 50, or 40 to 50, or 10 to 45, and the subscript f is 1 to 1000, or 1 to 300, or 1 to 40, or 1 to 5, or 2 to 5). The R 3 that is a polyether group has the formula -(D 1 ) g O(D 2 O) h R 4 (wherein each D 1 is an independently selected divalent hydrocarbon group having 2 to 4 carbon atoms, each D 2 is an independently selected divalent hydrocarbon group having 2 to 4 carbon atoms, 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, or 1 to 3, and the subscript h is 1 to 50, or 4 to 50, or 8 to 40). Alternatively, D 1 has the formula C p H 2p (wherein the subscript p is 3 to 12, or 3 to 6). Alternatively, each D 2 may be selected from the group consisting of C2H4 and C3H6. Alternatively, R 4It 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 to Souda et al. Silicone polyethers suitable as starting materials (D) are commercially available; for example, DOWSIL (trademark) ES-5612 is commercially available from DSC.

[0045] The starting material (II) which is a surfactant may optionally further contain 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.

[0046] The second silicone polyether has a unit formula (D2): the formula (R 1 3SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) e’ (R 1 R 5 SiO 2 / 2 ) f’ (where R 1 and R 2 are as described above, and the subscript e’ and the subscript f’ represent the average number of bifunctional units per molecule, having values such that e is 0 to 500, or 0 to 200, or 0 to 50, or 0 to 45, provided that e’ < e, and the subscript f’ is 1 to 1000, or 1 to 300, or 1 to 40, or 1 to 5, or 1 to 2). R 5 is of the formula -(D 1 ) g O(D 3 O) i H (where each D 3 is an independently selected divalent hydrocarbon group having 2 to 4 carbon atoms, the subscript g is 1 to 20, or 1 to 3, and the subscript i is 1 to 50). Alternatively, each D 3The compound may be selected from the group consisting of C2H4 and C3H6. Alternatively, the subscript i may be 1 to 10 or 5 to 10. Alternatively, in the unit formula (D2), the subscript e' may be 0 and the subscript f' may be 1. Silicone polyethers of formula (D2) are commercially available; for example, XIAMETER® OFX-5211 is commercially available from DSC.

[0047] Alternatively, the silicone polyether cosurfactant may have a rake-shaped structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto a siloxane skeleton, or the silicone polyether may have an ABA block copolymer structure (wherein A in the ABA structure represents the polyether portion and B represents the siloxane portion). Alternatively, the SPE may have a resin structure such as a polyorganosilicate resin having polyether groups bonded to silicon atoms therein. A suitable SPE is DOWSIL® OFX-5329 Fluid manufactured by DSC. Other silicone polyether surfactants are known in the art and are commercially available; for example, DOWSIL® 502W and DOWSIL® 67 additives are commercially available from DSC.

[0048] Alternatively, the co-surfactant may include an organic polyether. Suitable organic polyethers are known and commercially available in the art. For example, suitable organic polyethers include DOWFAX® nonionic surfactants, such as linear EO / PO block copolymers like the DOWFAX® N series available from TDCC.

[0049] The amount of (II) surfactant in the silicone release coating dispersion depends on various factors, including the selection and amount of (C) branched polyorganosiloxane polymer and (E) polydiorganosiloxane having at least two aliphatic unsaturated groups per molecule, but the amount of (II) surfactant may be 0.1 to 5 parts by weight based on the total weight of the starting materials (C) and (E). Alternatively, the amount of (D1) silicone polyether may be 0.1 to 5 parts by weight based on the total weight of the starting materials (C) and (E). Alternatively, if a co-surfactant is present, the amount of (D1) silicone polyether may be 0.1 to less than 5 parts by weight based on the total weight of the starting materials (C) and (E).

[0050] 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 bulking and reinforcing fillers), surfactants, thixotropes, and pH buffers, may be present in the silicone release coating dispersion. The composition may be in any form or incorporated into further compositions. Alternatively, the silicone release coating dispersion may not contain particulate matter, or may contain only a limited amount of particulate matter (e.g., fillers and / or pigments), such as 0-30% by weight of the dispersion. While we do not wish to be bound by theory, it is conceivable that particulate matter may aggregate or adhere to coater equipment used to form the silicone release coating in other ways. In addition, if light transmittance is desired, particulate matter may interfere with the optical properties of the silicone release coating and the release liner formed using it, e.g., transmittance, and / or particulate matter may impair the adhesion of the substrate.

[0051] The silicone release coating dispersion does not necessarily have to contain a fluoroorganosilicon compound. During curing, due to its low surface tension, the fluoro compound is thought to rapidly migrate to the interface between the dispersion or the silicone release coating formed thereon and the substrate to which the dispersion is applied and the silicone release coating is formed, for example, the dispersion / PET film interface. Such migration may adversely affect the adhesion of the silicone release coating (prepared by curing) to the substrate by creating a fluorine-containing barrier. By creating a barrier, the fluoroorganosilicon compound may prevent any starting material of the silicone release coating dispersion from reacting at the interface, affecting the curing and / or antistatic properties. Furthermore, fluoroorganosilicon compounds are usually expensive.

[0052] Method for forming a silicone release coating dispersion The above-mentioned silicone peeling coating dispersion is (1) Dissolving (A) an ionic liquid in (B) water to form an aqueous solution, (2) The aqueous solution, (C) Branched polyorganosiloxane polymer and (D) Disperse in a siloxane intermediate composition containing a silicone polyether, thereby forming a dispersed intermediate. (3) Combining the dispersed intermediate with additional starting material, wherein the additional starting material is (E) Polydiorganosiloxane having at least two aliphatic unsaturated groups per molecule, (F) Polyorganohydrogensiloxane having at least 3 silicon-bonded hydrogen atoms per molecule, (G) Hydrosilylation reaction catalyst, Optionally, (H) solvent, Optionally, (I) a hydrosilylation reaction inhibitor, and Optionally, it may be prepared by a method that includes (J) a fixing additive, and a combination of these. Although not bound by theory, the above-described addition sequence in which the dispersion intermediate is prepared in step (2) facilitates the preparation of a stable dispersion, and when the antistatic additive is combined with the silicone release coating composition, it is thought that a composition is formed that does not harden and form a silicone release coating with the desired resistance, as shown in Comparative Example 4 below.

[0053] Step (1) can be carried out by any convenient means, such as mixing at room temperature or high temperature, in a batch, semi-batch, or continuous apparatus. Mixing in step (1) can be carried out using medium / low shear batch mixing equipment such as a change can mixer, double planetary mixer, conical screw mixer, ribbon blender, double arm, or sigma blade mixer. Alternatively, batch equipment with high shear and / or high-speed dispersers can be used in steps (1), (2), and / or (3), such as equipment manufactured by Charles Ross & Sons (NY), Hockmeyer Equipment Corp. (NJ), batch mixing equipment (e.g., those sold under the trade name Speedmixer®), and high-shear batch equipment including Banbury type (CW Brabender Instruments Inc., NJ) and Henschel type (Henschel mixers America, TX). Actual examples of continuous mixers / compounders include single-screw extruders, twin-screw extruders, and multi-screw extruders, co-rotating extruders, twin-screw counter-rotating extruders, two-stage extruders, twin-screw continuous mixers, dynamic or static mixers, or combinations thereof, such as those manufactured by Krupp Werner & Pfleiderer Corp (Ramsey, NJ) and Leistritz (NJ). Steps (2) and (3) may be carried out at room temperature.

[0054] Method for preparing release liners A release liner can be prepared using the silicone release coating dispersion prepared as described above. The release liner is Optionally, (I) treat the surface of the backing substrate, (II) Coating the above-mentioned silicone release coating dispersion onto the surface of the backing substrate, (III) Drying the silicone release coating dispersion to form a film, (IV) It can be prepared by a method comprising curing the film to form a silicone release coating on the surface of the backing substrate.

[0055] In step (I), the backing substrate (substrate) is not limited. The substrate may include plastics that are thermosetting and / or thermoplastic. However, the substrate may also be or may include glass, metal, cellulose (e.g., paper), cardboard, paperboard, polymer materials, or combinations thereof. Suitable substrates include paper substrates such as kraft paper, polyethylene-coated kraft paper (PEK coated paper), thermal paper, and plain paper; polymer substrates such as polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene; styrene resin; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); and polyphenylene ether (polyphenylene ether (PPE); polyimide (PI); polyamideimide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK);Examples include polyarylate (PAR); polyethernitrile (PEN); phenolic resins; phenoxy resins; celluloses such as triacetylcellulose, diacetylcellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene; thermoplastic elastomers of polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type, and fluoro type; and copolymers and combinations thereof.

[0056] In step (I), the surface of the substrate may be treated by any convenient means, such as plasma treatment or corona discharge treatment, before applying the stripping coating dispersion. Alternatively, the substrate can be treated by applying a primer. Step (I) is optional and may not be present.

[0057] The silicone release coating dispersion can be applied to the substrate by any convenient means, such as spraying, using a doctor blade, dipping, or screen printing, or by a roll coater, such as an offset web coater, kiss coater, or etched cylinder coater.

[0058] In step (II), the silicone release coating dispersion can be applied to any substrate, such as those described above. Alternatively, the silicone release coating composition may be applied to polymer film substrates, such as polyester, particularly polyethylene terephthalate (PET), polyethylene, polypropylene, polyester, or polystyrene films. Alternatively, the silicone release coating dispersion may be applied to plastic-coated paper, such as paper substrates including polyethylene-coated paper, glassine, supercalendered paper, or clay-coated kraft paper. The release coating composition can also be applied to metal foil substrates, such as aluminum foil.

[0059] Step (III) can be carried out 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, if present, (H) solvent. The method may further include curing the silicone release coating composition to form a silicone release coating on the surface of the substrate. Curing can be carried out by any conventional means, such as heating at 100°C to 200°C.

[0060] Under manufacturing coater conditions, curing can be carried out at an air temperature of 120°C to 150°C for 1 to 6 seconds, or with a residence time of 1.5 to 3 seconds. Heating can be performed in an oven, such as an air-circulating oven or tunnel furnace, or by passing the coated substrate around a heated cylinder.

[0061] Figure 1 shows a partial cross-sectional view of a laminated article (100) that can be manufactured as described above. The laminated article (100) has a release liner made of a backing substrate (101) having an antistatic silicone release coating (102) on the surface of a PET film backing substrate (101). The adhesive (103) on the surface of the second PET film substrate (104) is protected by the release liner, in which case the surface of the antistatic silicone release coating (102) is in contact with the surface of the adhesive (103). [Examples]

[0062] The following examples are provided to those skilled in the art to illustrate the present invention and should not be construed as limiting the scope of the invention as defined in the claims. The starting materials used in these examples are listed in Table 1.

[0063] [Table 1]

[0064] The starting materials for the DOWSIL (trademark), SYL-OFF (trademark), and XIAMETER (trademark) brands are commercially available from DSC. Lithium salts were purchased from Monils Chemical Engineering Science & Technology (Shanghai) Co., Ltd. Toluene was purchased from Sinopharm Chemical Reagent Co., Ltd. Antistatic additives 2 and 3 were also purchased from Monils Chemical Engineering Science & Technology (Shanghai) Co., Ltd.

[0065] In this Reference Example 1, the silicone release coating dispersion was prepared as follows: (1) An aqueous solution was prepared by dissolving the antistatic additive in water while vigorously stirring. (2) DOWSIL® 2-7757 and DOWSIL® ES-5612 were mixed using a SpeedMixer (3500 rpm, 60 seconds) to form a siloxane intermediate composition. (3) The aqueous solution was gradually blended into the siloxane intermediate composition using a SpeedMixer (3500 rpm, 60 seconds) (for example, in the order of 2 g, 2 g, 2 g, 3 g, 3 g, 3 g). The resulting dispersed intermediate was obtained in the form of a white cream with a maximum antistatic additive content of 40%. To produce dispersed intermediates with a lower antistatic additive content, the concentration of the antistatic additive in the discontinuous (internal) phase may be reduced accordingly. (4) The obtained dispersion intermediate was mixed with SYL-OFF® 7226 using a SpeedMixer (3500 rpm, 60 seconds). The mixture was diluted with toluene to obtain a composition containing 90% toluene. SYL-OFF® 297 fixing additive and SYL-OFF® 4000 catalyst were sequentially added and mixed (3500 rpm, 60 seconds) to form a silicone release coating dispersion. The amounts of each starting material used are shown in Tables 2 and 3 below.

[0066] In this Reference Example 2, the silicone release coating dispersion prepared according to Reference Example 1 was measured using a Meyer rod (#6) at a rate of 0.6-0.8 g / m². -2 10 cm² is equivalent to the coating weight. -1 The coating was applied to a PET film (210cm x 297cm, 50μm, corona-treated) at a speed of [speed not specified]. The resulting film was then dried and cured by heating at 140°C for 30 seconds, and then cooled to room temperature, thereby forming a release liner containing a silicone release coating on the surface of the PET film.

[0067] In this Reference Example 3, the surface resistance of each silicone release coating prepared as described in Reference Example 2 was measured using a digital surface resistance meter (TECMAN, TM385, measurement range: 10°). 3 ~10 12 Ωsq -1 Surface resistance was measured at room temperature (20-25°C) with an accuracy of ±10%. Surface resistance was measured triplicately at three different locations on each silicone release coating. Using a bare PET film as a reference, the coating weight (CW), i.e., the surface density of the silicone release coating, was determined by X-ray fluorescence spectroscopy (XRF, Oxford Lab-X Supreme8000). The silicone release coating was aged for 7 or 30 days before testing.

[0068] In this Reference Example 4, the release force at room temperature (RF-RT) was evaluated using a 180° peel test to measure the release force from the release liner. Tesa 7475 standard tape was laminated onto a (cured) silicone release coating, and 20 g / cm² was applied to the laminated sample. 2The sample was subjected to a load weight and left at room temperature (RT) of 25°C for 20 hours. After 20 hours, the load weight was removed and the sample was allowed to stand for 30 minutes. Then, the peeling force was tested using ChemInstruments' AR-1500 according to FINAT Test Method No. 10 (FINAT Technical Handbook 7th edition, 2005).

[0069] To measure the peel force from the release liner, a 180° peel test was used to evaluate the peel force after aging at 70°C (RF-70°C aging). Tesa7475 standard tape was laminated onto a (cured) silicone release coating, and 20 g / cm² of material was applied to the laminated sample. 2 The sample was subjected to a load and left at 70°C for 20 hours. After 20 hours, the load was removed and the sample was allowed to stand for 30 minutes. The peeling force was then tested using ChemInstruments' AR-1500 according to FINAT Test Method No. 10 (FINAT Technical Handbook 7th edition, 2005).

[0070] In Reference Example 3, the coat weight was evaluated as described above, and then each sample was rubbed for 30 cycles at a rate of 30 cycles / minute using an abrasion tester (Elcometer 1720). To measure the relative adhesion performance, the coat weight after friction wear was evaluated again as described above. Adhesion was calculated as (CW after friction wear) / (CW before friction wear) × 100%.

[0071] [Table 2]

[0072] [Table 3]

[0073] Comparative Examples 1 and 5 (CE1, CE5) showed that silicone release coatings prepared from silicone release coating compositions without antistatic additives exhibited surface resistance values ​​> 10 in Table 2.12 Ω sq -1 As shown, it was demonstrated that it is insulating under the tested conditions and therefore cannot dissipate static charge.

[0074] Comparative Examples 2 and 3 (CE2, CE3) showed that the conventional antistatic additives ([BMIM][TFSI]) and ([MeBu3N][TFSI]) did not provide sufficient antistatic effect to the silicone release coatings prepared from silicone release coating compositions containing these conventional antistatic additives. Under the tested conditions, the surface resistance values ​​of both CE1 and CE2 were 10, as shown in Table 2. 12 Ωsq -1 It was excessive. Although not bound by theory, the insufficient antistatic effect is thought to be due to the miscibility of conventional antistatic additives with the silicone release coating composition.

[0075] Comparative Example 4 (CE4) was prepared according to the method described in U.S. Patent Application Publication No. 2020 / 0048508(A1), which involves directly blending a lithium salt into a silicone release coating composition. The resulting silicone release coating had a low resistance value, indicating that the silicone release coating dispersion prepared as described herein (in the examples) performed well under the tested conditions.

[0076] Examples 1 and 2 (IE1 and IE2) contained 10% and 20% of antistatic additive 1, respectively, and showed that the surface resistance decreased by several orders of magnitude after the films were left at room temperature for several days.

[0077] Example 3 (IE3) contained 30% antistatic additive 1, and after 30 days, 10 8 Ωsq -1 The surface resistance was observed. A large amount of antistatic additive 1 may affect the appearance of the silicone release coating; therefore, this silicone release coating composition is more suitable for use in applications where a transparent silicone release coating is not required.

[0078] Example 4 (IE4) shows that even when the surfactant XIAMETER™ OFX-5211 is added to the silicone release coating composition of IE2, the surface resistance remains lower than all of the comparative examples in Table 2 (≤ 10). 11 Ωsq -1 It was shown that silicone release coatings having [specific properties] were still provided.

[0079] IE5, IE6, IE7: Compared to IE1-IE4, where antistatic agent 1 accounted for 40% of the aqueous phase, the proportion of antistatic agent 1 in the aqueous emulsion in silicone was reduced to 20% by decreasing the concentration of antistatic agent in the internal phase. When the same amount of aqueous phase was combined with other starting materials, the amount of antistatic agent 1 was halved. As a result, with 10% antistatic additive 1 (IE5, IE6), 10 9 Ωsq -1 The surface resistance was recorded. Under the tested conditions, the addition of a co-surfactant (XIAMETER® OFX-5211) did not change the initial resistance, but it affected the resistance after aging at room temperature. The surface resistance increased from 7 days to 10 days after the addition of 2% co-surfactant (IE6). 8 Ωsq -1 It decreased to [value]. Further reduction in the content of antistatic agent 1 resulted in a decrease in the initial conductivity (IE7) under the tested conditions.

[0080] Issues that need to be resolved Ionic liquids containing large ions with bulky substituents, particularly lithium salts, are useful as antistatic agents, but they have poor miscibility with nonpolar polyorganosiloxanes. Therefore, ionic liquids tend to separate from the polyorganosiloxane matrix, which can cause structural and cosmetic defects in silicone release coatings prepared from compositions containing a polyorganosiloxane matrix and ionic liquid, such as those disclosed in U.S. Patent Application Publication 2020 / 0048508(A1). In addition, the degree of dissociation and ion mobility of the ionic liquid are limited in the nonpolar matrix, resulting in limited ionic conductivity. While lithium salts have long been used as antistatic additives in silicone release coatings, for some applications they offer higher conductivity than desirable for providing antistatic properties to the silicone release coating. 12 Ωsq -1 It is possible to achieve extremely high surface resistance.

[0081] Industrial applicability This silicone release coating dispersion incorporates a water-soluble ionic liquid and a silicone release coating composition. As shown in the above examples, the film formed from the silicone release coating dispersion is dried and cured to a minimum of 10 after 7 to 30 days under test conditions. 11 Ωsq -1 A silicone release coating having a surface resistance can be formed. By using the silicone release coating dispersion described herein to prepare the silicone release coating, the surface resistance can be improved by an order of magnitude or more (i.e., reduced).

[0082] Definitions and Use of Terms All quantities, ratios, and percentages are based on weight unless otherwise specified. The total amount of all starting materials in a composition is 100% by weight. The summary and abstract of the invention are incorporated herein by reference. The articles “a,” “an,” and “the” each refer to one or more unless otherwise specified by the context of the specification. The singular form includes the plural form unless otherwise specified. The terms “comprising” and its derivatives, e.g., “comprise” and “comprises,” are used herein in their broadest sense to mean and encompass the view of “including,” “include,” “consisting essentially of,” and “consisting of.” The use of “for example,” “eg,” “such as,” and “including,” which list examples, is not limited to the examples listed. Therefore, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and includes other similar or equivalent examples.

[0083] It should be understood that the attached claims are intended to express “modes for carrying out the invention” and are not limited to the specific compounds, compositions, or methods described herein, and may vary between specific embodiments within the scope of the attached claims. With respect to any group of Markush elements on which this specification is used to describe specific features or aspects of various embodiments, different, special, and / or unexpected results may be obtained from each element of each group of Markush elements, independent of all other Markush elements. Each element of a group of Markush elements may be relied upon individually and / or in combination to provide sufficient support for specific embodiments within the scope of the attached claims.

[0084] The abbreviations used in this specification are defined in Table 4 below.

[0085] [Table 4]

[0086] Embodiments of the present invention In the first embodiment, the method for preparing a silicone peel-off coating dispersion is as follows: (1) Dissolving (A) an ionic liquid in (B) water to form an aqueous solution, wherein the ionic liquid contains a lithium salt, (A) an ionic liquid and (B) water are present in an aqueous solution in a weight ratio of 2:1 to 1:2 (A):(B), and the following is formed: (2) Dispersing an aqueous solution in a siloxane intermediate composition, wherein the siloxane intermediate 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 )(In the formula, each R 1 These are independently selected monovalent hydrocarbon groups that do not contain aliphatic unsaturated compounds, and each R 2 A is an independently selected aliphatic unsaturated monovalent hydrocarbon group, where subscripts a and b represent the average number of monofunctional units per molecule, subscripts c and d represent the average number of difunctional units per molecule, and a, b, c, and d have average values ​​such that 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 greater than 170 mPa·s as measured by rotational viscometric method at room temperature) in a branched polyorganosiloxane polymer, and (D) Unit formula (D1) (R 1 3SiO1 / 2 )2(R 1 2SiO 2 / 2 ) e (R 1 R 3 SiO 2 / 2 ) f (In the formula, the subscript e is 1 to 50, the subscript f is 1 to 5, and R 1 As stated above, R 4 R is selected from the group consisting of H and alkyl groups. 3 is, equation -(D 1 ) g O(D 2 O) h R 4 (In the formula, each D 1 It is a divalent hydrocarbon group consisting of 2 to 4 carbon atoms, and each D 2 (where g is a divalent hydrocarbon group of 2 to 4 independently selected carbon atoms, and h is a polyether group of 1 to 50, where g is 1 to 20 and h is 1 to 50) This includes distributing, (3) Combining the dispersed intermediate with additional starting material, wherein the additional starting material is (E) A polydiorganosiloxane having at least two aliphatic unsaturated groups per molecule, wherein the unit formula is (R 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) j (In the formula, R 1 and R 2 (E) Polydiorganosiloxane, as described above, where the subscript j represents the average number of difunctional units per molecule, and 10,000 ≥ j ≥ 100 (F) A polyorganohydrogensiloxane having at least 3 silicon-bonded hydrogen atoms per molecule, wherein formula (R 1 2HSiO 1 / 2 ) k (R 1 3SiO 1 / 2 ) m (R 1 HSiO 2 / 2 ) n (R 12SiO 2 / 2 ) o (In the formula, R 1 As stated above, the subscripts k and m represent the average number of monofunctional units per molecule, the subscripts n and o represent the average number of difunctional units per molecule, and the subscripts k, m, n, and o are such that 2≧k≧0. 2 (F) Polyorganohydrogensiloxane having values ​​such that ≥m≧0, (k+m)=2, n>0, o≧0, (k+n)≧3, and 8≦(k+m+n+o)≦400, and (G) Hydrosilylation reaction catalyst, including the combination of

[0087] In the second embodiment, the method of the first embodiment further comprises, in step (III), a starting material selected from the group consisting of (H) a solvent, (I) a hydrosilylation reaction inhibitor, (J) a fixing additive, or a combination of two or more of (H), (I), and (J).

[0088] In a third embodiment, the method of the first or second embodiment further includes adding a co-surfactant in step (II).

[0089] In the fourth embodiment, in any one of the methods of the first to third embodiments, (A) the ionic liquid is Based on the total weight of (A1) and (A2), 90% by weight of lithium trifluoromethylsulfonate (A1) and The present invention comprises 10% by weight of (A2) lithium bis(trifluoromethylsulfonyl)imide based on the total weight of (A1) and (A2), thereby forming an aqueous solution.

Claims

1. A silicone release coating dispersion, (I) A continuous phase comprising a hydrosilylated reaction curable silicone peelable coating composition, (II) Surfactants and (III) an aqueous discontinuous phase dispersed in the continuous phase, (A) Ionic liquids and (B) Water and, A silicone peeling coating dispersion comprising an aqueous discontinuous phase in which the ionic liquid is dissolved in the water.

2. The aforementioned silicone release coating composition (C) Unit type: (R ２ ３ SiO １／２ ) ａ (R １ ２ R ２ SiO １／２ ) ｂ (R １ R ２ SiO ２／２ ) ｃ (R １ ２ SiO ２／２ ) ｄ (SiO ４／２ ) (In the formula, each R １ is an independently selected monovalent hydrocarbon group that does not contain aliphatic unsaturation, each R ２ is an independently selected aliphatic unsaturated monovalent hydrocarbon group, the subscripts a and b represent the average number of monofunctional units per molecule, the subscripts c and represent the average number of bifunctional units per molecule, and a, b, c, and d have average values such that 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 more than 170 mPa·s measured by the rotational viscosity measurement method at room temperature) branched polyorganosiloxane polymer, (E) Polydiorganosiloxane having at least two aliphatic unsaturated groups per molecule, ((C) The amount of the branched polyorganosiloxane polymer and (E) the amount of the polydiorganosiloxane having at least two aliphatic unsaturated groups per molecule shall total 100 parts by weight.) (F) A polyorganohydrogensiloxane having at least three silicon-bonded hydrogen atoms per molecule in an amount sufficient to provide a molar ratio (SiH:Vi ratio) of silicon-bonded hydrogen atoms to aliphatic unsaturated groups in the peel-off coating composition greater than 1:1 to 5:

1. (G) A hydrosilylation reaction catalyst sufficient to provide 1 ppm to 500 ppm of platinum group metals based on the weight of the silicone peeling coating dispersion. Optionally, (I) a hydrosilylation reaction inhibitor, and A silicone peel-off coating dispersion according to claim 1, optionally comprising (J) a fixing additive.

3. The silicone release coating dispersion according to claim 1, wherein the continuous phase further comprises up to 90% by weight of a solvent, and the remainder of the continuous phase up to 100% by weight is the silicone release coating composition.

4. (C) The branched polyorganosiloxane polymer is of formula: [R ２ R １ ２ Si-(O-SiR １ ２ ) ｘ -O] （４－ｗ） -Si-[O-(R １ ２ SiO) ｖ SiR １ ３ ] ｗ (In the formula, R １ and R ２ The silicone peel-off coating dispersion according to claim 2, wherein the subscripts v, w, and x have values ​​such that 200 ≥ v ≥ 1, 2 ≥ w ≥ 0, and 200 ≥ x ≥ 1.

5. (E) The polydiorganosiloxane has the unit formula (R ２ R １ ２ SiO １／２ ) ２ (R １ ２ SiO ２／２ ) ｊ (In the formula, R １ and R ２ The silicone peel-off coating dispersion according to claim 2, wherein the above is true, and the subscript j represents the average number of bifunctional units per molecule, where 10,000 ≥ j ≥ 100.

6. (F) The polyorganohydrogensiloxane has the unit formula (R １ ２ HSiO １／２ ) ｋ (R １ ３ SiO １／２ ) ｍ (R １ HSiO ２／２ ) ｎ (R １ ２ SiO ２／２ ) ｏ (In the formula, R １ The silicone peel-off coating dispersion according to claim 2, wherein the subscripts k and m represent the average number of monofunctional units per molecule, the subscripts n and o represent the average number of difunctional units per molecule, and the 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.

7. Each R １ However, each R is independently selected from the group consisting of methyl and phenyl. ２ The silicone peeling coating dispersion according to claim 2, wherein the component is independently selected from the group consisting of vinyl, allyl, and hexenyl.

8. (II) The silicone peeling coating dispersion according to any one of claims 1 to 7, wherein the surfactant comprises (D) a silicone polyether.

9. (D) The silicone polyether has the unit formula (D1): (R １ ３ SiO １／２ ) ２ (R １ ２ SiO ２／２ ) ｅ (R １ R ３ SiO ２／２ ) ｆ (In the formula, the subscript e is 1 to 50, the subscript f is 1 to 5, R １ As stated above, each R ３ is equation - (D １ ) ｇ O(D) ２ O) ｈ R ４ (In the formula, R ４ is selected from the group consisting of H and alkyl groups, and each D １ This is a divalent hydrocarbon group consisting of 2 to 4 independently selected carbon atoms, and each D ２ The silicone peeling coating dispersion according to claim 8, wherein is a polyether group (where g is a divalent hydrocarbon group of 2 to 4 carbon atoms, g is 1 to 20, and h is 1 to 50).

10. Further comprising a co-surfactant, wherein the co-surfactant has a unit formula (D2): (R １ ３ SiO １／２ ) ２ (R １ ２ SiO ２／２ ) ｅ’ (R １ R ５ SiO ２／２ ) ｆ’ (wherein R １ is as described above, the subscript e' is 0 to 50, provided that e' < e, the subscript f' is 1 to 5, and R ５ has the formula -(D １ ) ｇ O(D ３ O) ｉ H (wherein D ３ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and the subscript i is 1 to 50)), the silicone release coating dispersion liquid according to claim 9.

11. (A) The ionic liquid is Based on the total weight of (A1) and (A2), 90% by weight of lithium trifluoromethylsulfonate (A1) and It comprises 10% by weight of (A2) lithium bis(trifluoromethylsulfonyl)imide based on the total weight of (A1) and (A2), thereby forming an aqueous solution. A silicone peeling coating dispersion according to any one of claims 1 to 7, wherein (A) the ionic liquid and (B) the water are present in the aqueous discontinuous phase in a weight ratio of 2:1 to 1:2 (A):(B).

12. A method for forming a silicone peel-off coating dispersion according to any one of claims 2 to 7, wherein the method is (1) (A) Dissolving the ionic liquid in (B) the water to form an aqueous solution, (2) The aqueous solution (C) Branched polyorganosiloxane polymer and (D) Disperse in a siloxane intermediate composition containing a silicone polyether, thereby forming a dispersed intermediate, (3) Combining the dispersed intermediate with additional starting material, wherein the additional starting material is (E) Polydiorganosiloxane having at least two aliphatic unsaturated groups per molecule, (F) Polyorganohydrogensiloxane having at least three silicon-bonded hydrogen atoms per molecule, (G) Hydrosilylation reaction catalyst, Optionally, (H) solvent, Optionally, (I) a hydrosilylation reaction inhibitor, and A method comprising, optionally, (J) a fixative additive, and a combination thereof.

13. A method for preparing a release liner, wherein the method is Optionally, (I) treat the surface of the substrate, (II) Coating the surface of the substrate with the silicone release coating dispersion according to any one of claims 1 to 7, (III) Drying the silicone release coating dispersion to form a film, (IV) A method comprising curing the film to form a silicone release coating on the surface of the substrate.

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