Silicone emulsions and their preparation and application methods

Abstract

Silicone release coating emulsions can be dried and cured to form a silicone release coating on both paper and plastic substrates. The coated substrates can be used in a variety of end-use applications, including (opto)electronic device fabrication and food contact applications.

Description

[0001] Cross-citation of related applications and statements regarding federally funded research

[0002] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 152,354, filed February 23, 2021, pursuant to 35 USC §119(e). U.S. Provisional Patent Application Serial No. 63 / 152,354 is hereby incorporated by reference. Technical Field

[0003] This invention relates to silicone emulsions and methods for their preparation and use. More specifically, this invention relates to aqueous silicone emulsions that can be cured to form silicone release coatings suitable for various substrates, including paper and plastics. Background Technology

[0004] Curable silicone compositions can be applied to a substrate and cured to form a coating, thereby improving or altering various properties of the substrate. The substrate to which the composition is applied can contain one or more materials. Such materials can be fibrous, cellulose-based, for example, paper-based materials such as paper or paperboard. The paper can be glazed or unglazed, calendered or uncalendered. Alternatively, the substrate can be plastic-based rather than paper-based, including, for example, acrylic, polycarbonate, or polyethylene terephthalate materials, or the substrate can be a laminated paper / plastic.

[0005] Curable silicone compositions can be water-based, solvent-based, or solvent-free. Solvent-free compositions include, for example, SYL-OFF from Dow Silicones Corporation of Midland, Michigan, USA. TM The 7000 coating can be applied at a relatively high thickness (≥1 μm), but it has the disadvantage that existing coating machines cannot be used to reduce the thickness of the coating. In addition, due to the relatively high viscosity of the solvent-free composition, especially at high production speeds, undesirable fogging and surface defects in the resulting coating may occur during processing.

[0006] Aqueous compositions may be desirable in several applications, such as those requiring well-controlled, low-thickness deposition and those regulated by food regulations (e.g., food contact applications). Coated paper suitable for food contact applications can be obtained by treating the paper substrate with a compound or composition to form a layer on the paper. Known treatments are based on fluorinated compounds that provide non-stick properties by forming a film with low surface energy, which is resistant to chemical reagents, thus providing the treated paper with oil, grease, and water resistance. However, environmental and health concerns regarding fluorinated compounds are increasing, and the industry trend is towards restricting or banning their use through various regulations, particularly in the food packaging industry.

[0007] Another approach is to treat the paper substrate with a mixture of polyvinyl alcohol and chromate-fatty acid complexes. However, the use of heavy metals such as chromium also raises environmental and health concerns in food packaging applications. Other treatments can impart some oleophobicity to the paper, but they typically require relatively large amounts of material to be effective and form a thicker coating on the paper, which can impair mechanical properties and durability when the paper is crumpled or folded. Furthermore, using large amounts of material may not be cost-effective. Summary of the Invention

[0008] The silicone release coating emulsion comprises: (A) an aliphatic unsaturated polyorganosiloxane composition comprising a hexenyl functionalized polyorganosiloxane, (B) a polyorganohydrosiloxane, (C) a hydrosilylation catalyst, (D) a hydrosilylation inhibitor, (E) water, (F) a buffer, and one or both of a surfactant and (H) polyvinyl alcohol. Detailed Implementation

[0009] The aforementioned silicone release coating emulsion (emulsion) may optionally contain additional starting materials selected from the group consisting of: (I) a biocide, (J) an antifoaming agent, and (K) a combination of both (I) and (J). Alternatively, the emulsion may consist substantially of: (A) the aliphatic unsaturated polyorganosiloxane composition comprising the hexenyl-functionalized polyorganosiloxane, (B) the polyorganohydrosiloxane, (C) the hydrosilylation catalyst, (D) the hydrosilylation inhibitor, (E) water, (F) the buffer, and (G) one or both of the surfactant and (H) the polyvinyl alcohol; and additional starting materials optionally selected from the group consisting of: (I) the biocide, (J) the antifoaming agent, and (K) a combination of both (I) and (J). Alternatively, the emulsion may consist of: (A) the aliphatic unsaturated polyorganosiloxane composition comprising the hexenyl functionalized polyorganosiloxane, (B) the polyorganohydrosiloxane, (C) the hydrosilylation catalyst, (D) the hydrosilylation inhibitor, (E) water, (F) the buffer, and (G) the surfactant and (H) one or both of the polyvinyl alcohol; and optionally the additional starting material selected from the group consisting of: (I) the biocide, (J) the defoamer, and (K) a combination of (I) and (J).

[0010] (A) Aliphatic unsaturated polyorganosiloxane composition

[0011] The starting material (A) in the above emulsion is an aliphatic unsaturated polyorganosiloxane composition. The amount of the starting material (A) in the emulsion is 100 parts by weight. The aliphatic unsaturated polyorganosiloxane composition of the starting material (A) comprises (A1) a hexenyl functionalized polyorganosiloxane and optionally (A2) a vinyl functionalized polyorganosiloxane.

[0012] The starting material (A1) is a hexenyl-functionalized polyorganosiloxane. Hexenyl-functionalized polyorganosiloxanes can have the unit formula (A1-I): (R 1 3SiO1 / 2) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d (SiO 4 / 2 ) e , where each R 1 It is an independently chosen alkyl or aryl group, R2 It is a hexenyl group, with subscripts a from 0 to 4, b from 0 to 4, c from 0 to 400, d from 0 to 50, and e from 0 or 1, provided that (a+b) = 2 to 4, (b+d) ≥ 2, and (a+b+c+d) = 15 to 400. Applicable to R 1 The alkyl group can have 1 to 6 carbon atoms, such as methyl, ethyl, propyl (including isopropyl and n-propyl), butyl (including n-butyl, tert-butyl, sec-butyl, and isobutyl), pentyl (including straight-chain, branched, and cyclic 5-carbon groups), and hexyl (including straight-chain, branched, and cyclic hexyl groups). Applicable to R 1 The aryl group includes those having 6 to 20 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, and styryl. Alternatively, the aryl group can be phenyl. Alternatively, each R 1 It can be methyl or ethyl. Alternatively, each R 1 It can be methyl or phenyl. Alternatively, each R 1 It can be methyl. Hexenyl-functionalized polyorganosiloxanes can be linear or branched.

[0013] Alternatively, when the subscript e = 0, hexenyl-functionalized polysiloxanes can be linear. Linear hexenyl-functionalized polysiloxanes can include the unit formula (A1-II): (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d , where R 1 and R 2 As mentioned above, the subscript a is 0, 1, or 2, the subscript b is 0, 1, or 2, the subscript c is 0 to 400, and the subscript d is 0 to 50, provided that (a+b) = 2, (b+d) ≥ 2, and (a+b+c+d) is 15 to 400.

[0014] Alternatively, hexenyl-functionalized polyorganosiloxanes may include those having the unit formula (A1-III): (R 1 2R 2 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c Hexenyl-terminated polydialkylsiloxanes, wherein each R 1It is an alkyl group as described above, R 2 As mentioned above, and the subscript c ranges from 15 to 400.

[0015] Alternatively, hexenyl-functionalized polyorganosiloxanes may include those having the unit formula (A1-IV): (R 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d Poly(dialkyl / alkylhexenyl)siloxanes, wherein each R 1 It is an alkyl group, R 2 As mentioned above, the subscript c ranges from 0 to 400, and the subscript d ranges from 2 to 50.

[0016] Starting materials (A1) may include linear hexenyl-functionalized polyorganosiloxanes, such as

[0017] A1-1)α,ω-dimethylhexenylsiloxy-terminated polydimethylsiloxane

[0018] A1-2)α,ω-dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane),

[0019] A1-3)α,ω-dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane

[0020] A 1-4) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane),

[0021] A1-5)α,ω-trimethylsiloxy-terminated polymethylhexenylsiloxane

[0022] A 1-6) α,ω-dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane / methylhexenylsiloxane),

[0023] A 1-7)α,ω-dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane),

[0024] A 1-8)α,ω-dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), and

[0025] A combination of two or more of A1-9), A1-1), to A1-8).

[0026] Methods for preparing the linear hexenyl-functionalized polydiorganosiloxanes described above for use as starting materials (A1), such as the hydrolysis and condensation of corresponding organohalosilanes and oligomers or the equilibrium of cyclic polydiorganosiloxanes, are known in the art, see, for example, U.S. Patent 3,284,406 to Nelson; U.S. Patent 4,772,515 to Hara et al.; U.S. Patent 5,169,920 to Okawa; U.S. Patent 5,317,072 to Bokerman et al.; and U.S. Patent 6,956,087 to Lai et al., which disclose the preparation of linear polydiorganosiloxanes having alkenyl groups. Hexenyl-functionalized polydiorganosiloxanes can be prepared by changing the appropriate starting materials used in such methods.

[0027] In addition to (or instead of) the aforementioned linear hexenyl-functionalized polydiorganosiloxanes, the starting material (A1) may also include branched hexenyl-functionalized polyorganosiloxanes. When the subscript e in formula (A1-I) has a value sufficient to provide >0 mol% to 5 mol% of tetrafunctional units, the branched hexenyl-functionalized polyorganosiloxane may have >0 mol% to 5 mol% of tetrafunctional units.

[0028] For example, branched hexenyl-functionalized polyorganosiloxanes may include those having the unit formula (A1-V): (R 1 3SiO 1 / 2 ) q (R 1 2R 2 SiO 1 / 2 ) r (R 1 2SiO 2 / 2 ) s (SiO 4 / 2 ) t Q-branched polyorganosiloxanes, wherein R 1 and R 2As described above, and with subscripts q, r, s, and t having average values ​​such that 2 ≥ q ≥ 0, 4 ≥ r ≥ 0, 995 ≥ s ≥ 4, t = 1, (q + r) = 4, and (q + r + s + t) > 50. Alternatively, the amount (q + r + s + t) can have a value sufficient to impart a viscosity > 170 mPa·s as measured by rotational viscometry (as described below with respect to the test method). Alternatively, the viscosity can be > 170 mPa·s to 1000 mPa·s, alternatively > 170 mPa·s to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, and alternatively 190 mPa·s to 420 mPa·s. Suitable branched hexenyl functionalized polyorganosiloxanes for the starting material (A1) can be prepared by known methods. For example, examples of branched hexenyl functionalized polysiloxanes (wherein the subscript e > 0 in the above unit formula) used as starting materials (A1) include branched hexenyl functionalized polysiloxanes disclosed in U.S. Patent 6,806,339 to Cray et al. and U.S. Patent Publication 2007 / 0289495 to Cray et al. by changing appropriate starting materials.

[0029] The starting material (A2) is a vinyl-functionalized polyorganosiloxane. Vinyl-functionalized polyorganosiloxanes can have the unit formula (A2-I): (R 1 3SiO 1 / 2 ) i (R 1 2R 3 SiO 1 / 2 ) f (R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h (SiO 4 / 2 ) j , where each R 1 It is an independently chosen alkyl group or aryl group as described above, R 3 The subscripts are vinyl groups, with subscripts i from 0 to 4, f from 0 to 4, g from 0 to 1400, h from 0 to 200, and j from 0 or 1, provided that (i+f) = 2 to 4, (f+h) ≥ 2, and (i+f+g+h) = 15 to 1400. Alternatively, subscript g can be from 0 to 1200. Vinyl-functionalized polysiloxanes can be linear or branched. For example, when subscript j = 0, vinyl-functionalized polysiloxanes can be linear.

[0030] Alternatively, linear vinyl-functionalized polysiloxanes may include the unit formula (A2-II): (R1 3SiO 1 / 2 ) i (R 1 2R 3 SiO 1 / 2 ) f (R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h , where R 1 R3 is an alkyl or aryl group selected independently as described above, R4 is a vinyl group, subscript i is 0, 1 or 2, subscript f is 0, 1 or 2, subscript g is 0 to 1200, and subscript h is 0 to 200, provided that (i+f) = 2, (f+h) ≥ 2, and (i+f+g+h) is 15 to 1200.

[0031] Alternatively, linear vinyl-functionalized polyorganosiloxanes may include those having the unit formula (A2-III)(R 1 2R 3 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g Vinyl-terminated polydialkylsiloxanes, wherein each R 1 It is an alkyl group as described above, R 3 It is a vinyl group, and the subscript g is from 15 to 1200.

[0032] Alternatively, linear vinyl-functionalized polyorganosiloxanes may include those having the unit formula (A2-IV): (R 3 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h Poly(dialkyl / alkylvinyl)siloxanes, wherein each R 1 It is an alkyl group as described above, R 3 It is a vinyl group, with subscript g ranging from 0 to 1200 and subscript h ranging from 2 to 200.

[0033] Starting materials (A2) may include linear vinyl-functionalized polysiloxanes, such as

[0034] i) α,ω-Dimethylvinylsiloxy-terminated polydimethylsiloxanes

[0035] ii) α,ω-Dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane),

[0036] iii) α,ω-Dimethylvinylsiloxy-terminated polymethylvinylsiloxanes

[0037] iv) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane),

[0038] v)α,ω-trimethylsiloxy-terminated polymethylvinylsiloxane

[0039] vi) α,ω-Dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane / methylvinylsiloxane),

[0040] vii)α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane),

[0041] viii)α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane),

[0042] ix)α,ω-phenyl,methyl,vinyl-siloxy-terminated polydimethylsiloxane,

[0043] Combinations of two or more of the following from x)i) to ix).

[0044] Methods for preparing the linear vinyl-functional polydiorganosiloxanes described above for use as starting materials (A2), such as the hydrolysis and condensation of corresponding organohalosilanes and oligomers or the equilibrium 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.

[0045] In addition to (or instead of) the linear vinyl-functionalized polydiorganosiloxanes described above, the starting material (A2) may also include branched vinyl-functionalized polyorganosiloxanes. The branched vinyl-functionalized polyorganosiloxanes may have tetrafunctional units with a content >0 mol% to 5 mol% relative to the branched vinyl-functionalized polyorganosiloxane. For example, the branched vinyl-functionalized polyorganosiloxane may have the unit formula (A2-V): (R 1 3SiO 1 / 2 ) q (R 1 2R 3 SiO 1 / 2 ) r (R 1 2SiO 2 / 2 ) s (SiO4 / 2 ) t , where R 1 and R 3 As described above, and with subscripts q, r, s, and t having average values ​​such that 2 ≥ q ≥ 0, 4 ≥ r ≥ 0, 995 ≥ s ≥ 4, t = 1, (q + r) = 4, and (q + r + s + t) > 50. Alternatively, the quantity (q + r + s + t) can have a value sufficient to impart a viscosity > 170 mPa·s as measured by rotational viscometry (as described below with respect to the test method). Alternatively, the viscosity can be > 170 mPa·s to 1000 mPa·s, alternatively > 170 mPa·s to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, and alternatively 190 mPa·s to 420 mPa·s. Branched vinyl-functionalized polyorganosiloxanes suitable for starting materials (A2) are known in the art and can be prepared by known methods, exemplified by methods disclosed in U.S. Patent 6,806,339 and U.S. Patent Publication 2007 / 0289495.

[0046] The starting material (A), an aliphatic unsaturated polyorganosiloxane composition, is present in the emulsion in an amount of 100 parts by weight (e.g., the sum of the amounts of starting material (A1) and starting material (A2) = 100 parts by weight). The amount of the starting material (A1), a hexenyl functionalized polyorganosiloxane, in (A) is from 25 parts by weight to 100 parts by weight, and the amount of the starting material (A2) in (A) is from 0 parts by weight to 75 parts by weight. Alternatively, the starting material (A1) may be present in an amount of 25 parts by weight to <100 parts by weight, alternatively >25 parts by weight to <100 parts by weight, alternatively 50 parts by weight to <100 parts by weight, and alternatively >50 parts by weight to <100 parts by weight. The starting material (A2) may be present in amounts ranging from 0 to 75 parts by weight, or alternatively >0 to 75 parts by weight, or alternatively >0 to <75 parts by weight, or alternatively >0 to 50 parts by weight, and alternatively >0 to <50 parts by weight.

[0047] The selection of starting materials (A1), starting materials (A2), and their respective amounts will depend on various factors, including the substrate on which the emulsion will be coated and the desired properties of the release coating prepared from the emulsion. For example, starting material (A1) may be a hexenyl-terminated polydialkylsiloxane, and starting material (A2) may be a vinyl-terminated polydialkylsiloxane. Alternatively, starting material (A1) may be a poly(dialkyl / alkylhexenyl)siloxane, and starting material (A2) may be a vinyldialkylsiloxy-terminated polydialkylsiloxane having a monomeric formula. Alternatively, starting material (A1) may be a poly(dialkyl / alkylhexenyl)siloxane, and starting material (A2) may be a poly(dialkyl / alkylvinyl)siloxane.

[0048] Alternatively, when the starting material (A1) is a hexenyl-terminated polydialkylsiloxane and the starting material (A2) is a vinyl-terminated polydialkylsiloxane, the amount of (A1) may be at least 50 parts by weight, alternatively at least 75 parts by weight, and simultaneously at most <100 parts by weight, or alternatively at most 90 parts by weight; and the amount of (A2) may be >0, alternatively at least 10 parts by weight, and simultaneously at most 50 parts by weight, or alternatively at most 25 parts by weight; each condition being that the total amount of (A1) and (A2) is 100 parts by weight. Alternatively, when the starting material (A1) is a poly(dialkyl / alkylhexenyl)siloxane and the starting material (A2) is a poly(dialkyl / alkylvinyl)siloxane, the amount of (A1) can be at least >50 parts by weight, alternatively at least 75 parts by weight, and alternatively at least 90 parts by weight, while the amount of (A1) can be at most <100 parts by weight, and alternatively at most 90 parts by weight. Furthermore, the amount of (A2) can be at least >0, alternatively at least 10 parts by weight, while the amount of (A2) can be at most <50 parts by weight, and alternatively at most 25 parts by weight. The above combination of (A1) and (A2) can be particularly used to prepare emulsions for preparing release coatings on paper substrates.

[0049] Alternatively, when the starting material (A1) is a poly(dialkyl / alkylhexenyl)siloxane and the starting material (A2) is a poly(dialkyl / alkylvinyl)siloxane, the amount of (A1) can be at least >25 parts by weight, alternatively at least 33 parts by weight, alternatively at least 50 parts by weight, while the amount of (A1) can be at most <100 parts by weight, alternatively at most 90 parts by weight, alternatively at most 75 parts by weight, and alternatively at most 67 parts by weight. Furthermore, the amount of (A2) can be at least 10 parts by weight, alternatively at least 33 parts by weight, alternatively at least 50 parts by weight, while the amount of (A2) can be at most 67 parts by weight, alternatively at most 50 parts by weight. The above combination of (A1) and (A2) can be particularly used to prepare emulsions for preparing release coatings on plastic substrates.

[0050] (B) Polyorganohydrosiloxane

[0051] The starting material (B) in the emulsion is a polyorganohydrosiloxane. This polyorganohydrosiloxane can have a unit formula (R... 1 3SiO 1 / 2 ) w (R 1 2HSiO 1 / 2 ) x (R 1 2SiO 2 / 2 ) y (R 1 HSiO 2 / 2 ) z , where R 1 As described above, the subscript w is 0, 1, or 2; the subscript x is 0, 1, or 2; the subscript y is 0 to 250; and the subscript z is 1 to 250, provided that (w+x) = 2, (x+z) ≥ 3, and the quantity (w+x+y+z) is 10 to 300. Alternatively, the subscript w can be 2, and the subscript x can be 0. Alternatively, the subscript y can be > 0 to 250.

[0052] Examples of polyorganohydrosiloxanes suitable for this article include:

[0053] (i) α,ω-dimethylsiloxane-terminated poly(dimethylsiloxane / methylsiloxane),

[0054] (ii) α,ω-dimethylhydrosiloxanes terminalized with polymethylhydrosiloxanes

[0055] (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrosiloxane),

[0056] (iv) α,ω-trimethylsiloxy-terminated polymethylhydrosiloxanes, and

[0057] (v) α-Dimethylhydrosiloxy-ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrosiloxane),

[0058] (vi) α-Dimethylhydrosiloxy-ω-trimethylsiloxy-terminated polymethylhydrosiloxanes, and

[0059] (vii) A combination of two or more of them.

[0060] Polyorganohydrosiloxanes are also commercially available, such as those from Gelest, Inc. of Morrisville, Pennsylvania, USA, including HMS-H271, HMS-071, HMS-993, HMS-301, HMS-301R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, and HMS-HM271. Methods for preparing linear and branched polyorganosiloxanes suitable for this purpose, such as the hydrolysis and condensation of organohalosilanes, are well known in the art, as illustrated in U.S. Patent 2,823,218 to Speier, U.S. Patent 3,957,713 to Jeram et al., and U.S. Patent 4,329,273 to Hardman et al.

[0061] The starting material (B) polyorganohydrosiloxane is used in the emulsion in an amount sufficient to provide a molar ratio (i.e., SiH / Vi ratio) of silicon-bonded hydrogen atoms in the starting material (B) to the combined amount of vinyl groups and hexenyl groups in the starting material (A) of 1.2 / 1 to 3.0 / 1, or alternatively 1.4 / 1 to 2.5 / 1.

[0062] (C) Catalyst for hydrosilylation reaction

[0063] The starting material (C) in the emulsion is a hydrosilylation catalyst. This catalyst promotes the reaction between the alkenyl group in the starting material (A) and the hydrogen atom bonded to silicon in the starting material (B). The catalyst may include a metal selected from Fe, Ni, Co, Zr, Ti, or platinum group metals. Alternatively, the metal may include platinum group metals. Platinum group metals may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum. The hydrosilylation catalyst may be: (C1) a radiation-activated catalyst, i.e., capable of catalyzing the hydrosilylation reaction after irradiation (exposure to photochemical radiation, e.g., exposure to visible or UV light); (C-II) a hydrosilylation catalyst that can be activated by means other than irradiation, e.g., capable of catalyzing the hydrosilylation reaction without irradiation, such as by heating; or (C-III) a combination of both (C1) and (C-II).

[0064] Suitable radiation-activated catalysts for use as starting materials (CI) can be activated by exposure to radiation with wavelengths from 200 nm to 500 nm. Suitable radiation-activated hydrosilylation catalysts include: cyclopentadienylplatinum complexes, such as n5-cyclopentadienyl)tri(α-alkyl)platinum(IV); cyclopentadienyltrimethylplatinum and trimethyl(methylcyclopentadienyl)platinum(IV); cyclooctadienylplatinum complexes, such as n4-1,5-cyclooctadienyl diarylplatinum complexes; and Pt(II)-β-diketone complexes, such as bis(acetylacetone)platinum(II). Examples of cyclopentadienylplatinum complexes are known in the art and are disclosed, for example, in U.S. Patent 4,510,094 to Drahnak; U.S. Patent 4,600,484 to Drahnak; U.S. Patent 4,916,169 to Boardman et al.; U.S. Patent 6,127,446 to Butts; U.S. Patent 6,451,869 to Butts; U.S. Patent 6,376,569 to Oxman et al.; U.S. Patent 8,088,878 to Koellnberger; and CN101925608B. Cyclooctadienylplatinum complexes are disclosed, for example, in U.S. Patent 6,046,250 to Boardman et al. β-diketoplasmic(II) catalysts are disclosed, for example, in EP0398701B1 to Oxman et al.; U.S. Patent 8,642,674 to Ikeno; and CN104031602A. U.S. Patent Application Publication 2005 / 0154079 granted to Walker et al.; U.S. Patent Application Publication 2011 / 0171400A1 granted to Thompson et al.; and JP03865638 B2 granted to Ikeno also disclose various radiation-activated hydrosilylation reaction catalysts.

[0065] Alternatively, the hydrosilylation catalyst can be (C-II) a hydrosilylation catalyst that can be activated by means other than irradiation. For example, (C-II) can be: (C-II-1) the platinum group metals mentioned above; (C-II-2) compounds of such metals, such as triphenylphosphine chloride (I) (Wilkinson's Catalyst), rhodium diphosphide chelates such as [1,2-bis(diphenylphosphine)ethane]dichlorodirhodium or [1,2-bis(diethylphosphine)ethane]dichlorodirhodium, chloroplatinic acid (Speier's Catalyst), chloroplatinic acid hexahydrate, platinum dichloride; and (C-II-3) a complex of compound (C-II-2) with an alkenyl-functionalized organopolysiloxane oligomer; or (C-II-4) a platinum group metal compound microencapsulated in a matrix or core-shell structure. Complexes of platinum with alkenyl-functionalized organopolysiloxane oligomers include complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with platinum (Karstedt's Catalyst) and complexes of Pt(0) with tetramethyltetravinylcyclotetrasiloxane (Ashby's Catalyst). Alternatively, the hydrosilylation catalyst can be a compound or complex of (C-II-5) micro-encapsulated in a resin matrix as described above. Specific examples of platinum-containing catalysts suitable for (C-II) include chloroplatinic acid in hexahydrate or anhydrous form, or platinum-containing catalysts obtained by methods comprising reacting chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or olefin-platinum-silicon complexes as described in U.S. Patent 6,605,734 to Roy. These olefin-platinum-silicon complexes can be prepared, for example, by mixing 0.015 moles (COD)PtCl2 with 0.045 moles COD and 0.0612 moles HMeSiCl2, where COD represents cyclooctadienyl and Me represents methyl.Other exemplary hydrosilylation reaction catalysts are described in U.S. Patents 2,823,218 to Speier, 3,159,601 to Ashby, 3,220,972 to Lamoreaux, 3,296,291 to Chalk et al., 3,419,593 to Willing, 3,516,946 to Modic, 3,814,730 to Karstedt, 3,928,629 to Chandra, 3,989,668 to Lee et al., 4,766,176 to Lee et al., 4,784,879 to Lee et al., 5,017,654 to Togashi, 5,036,117 to Chung et al., 5,175,325 to Brow, and EP 0 347 to Togashi et al. Those described in 895 A. U.S. Patent Application Publication 2019 / 0367744, granted to Chevalier et al., discloses (C-II) radiation-activated catalysts and (C-II) catalysts that can be activated by means other than radiation (e.g., thermally activated catalysts). Other hydrosilylation catalysts that can be used in this paper are disclosed in the following literature: Y. Nakajima and S. Shimada, "Hydrosilylation reaction of olefins: recent advances and perspectives", RSC Adv., 2015, 5, 20603-20616 and "Hydrosilylation, Advances in Silicon Science", Chapter 1, Hydrosilylation of Alkenes and Their Derivatives, B. Marciniec (ed.) DOI 10.1007 / 978-1-4020-8172-91. Springer Science + Business Media BV 2009 (pp. 2-49). Hydrosilylation catalysts suitable for starting materials (C-II) are commercially available, for example, SYL-OFF. TM 4000 catalyst and SYL-OFF TM 2700 is available from Dow Silicones in Midland, Michigan, USA.

[0066] The starting material (C) can be a hydrosilylation catalyst or a combination of two or more of the above-described hydrosilylation catalysts. For example, the starting material (C) can be a combination of (CI) and (C-II), for instance, when exposure to both radiation and heating would be used for the hydrosilylation reaction. Alternatively, the starting material (C) can be a combination of two or more radiation-activated catalysts, such as a combination of cyclopentadienylplatinum complexes and Pt(II)-β-diketone complexes. Those skilled in the art will recognize that certain catalyst species can be activated by irradiation or heating, as described herein, and that when using a combination of two or more catalysts, the selected catalyst species will differ from one another.

[0067] The amount of (C) hydrosilylation catalyst in the emulsion will depend on various factors, including the selection of starting materials (A) and (B); the content of hydrogen atoms in their respective alkenyl groups and silicon bonds; and the amount of (D) hydrosilylation inhibitor present in the composition. However, the amount of catalyst is sufficient to catalyze the hydrosilylation reaction of SiH and alkenyl groups. Alternatively, based on the combined amount of starting materials (A), (B), (C), (D), (E), (F), and (G) in the composition, the amount of catalyst is sufficient to provide at least 10 ppm by mass, alternatively at least 15 ppm, alternatively at least 20 ppm, alternatively at least 50 ppm, and alternatively at least 100 ppm of platinum group metals. Meanwhile, based on the combined weight of the starting materials (A) and (B) in the emulsion, the amount of catalyst is sufficient to provide up to 1,000 ppm by mass, alternatively up to 800 ppm, alternatively up to 500 ppm, and alternatively up to 100 ppm of platinum group metals.

[0068] (D) Inhibitor of hydrosilylation reaction

[0069] The starting material (D) in the emulsion is a hydrosilylation inhibitor. Compared to compositions containing the same starting material but omitting the inhibitor, the starting material (D) is a hydrosilylation inhibitor (inhibitor) that can be used to modify the hydrosilylation reaction. The starting material (D) can be, for example, (D1) alkynyl alcohol, (D2) silylated alkynyl alcohol, (D3) en-alkynyl compound, (D4) triazole, (D5) phosphine, (D6) thiol, (D7) hydrazine, (D8) amine, (D9) fumarate, (D10) maleate, (D11) ether, (D12) carbon monoxide, (D13) alkenyl functional siloxane oligomer, and (D14) a combination of two or more of them. Alternatively, the hydrosilylation inhibitor can be selected from the group consisting of: (D1) alkynyl alcohol, (D2) silylated alkynyl alcohol, (D9) fumarate, (D10) maleate, and (D13) a combination of two or more of them. Alternatively, the inhibitor of hydrosilylation reaction may be selected from the group consisting of: (D1) alkynols, (D2) silyl alkynyl compounds, (D9) fumarates, (D10) maleates, (D13) carbon monoxide and (D14) combinations of two or more of them.

[0070] Examples of alkynols include: 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol, as well as combinations thereof. Alternatively, the inhibitor may be a silylated alkynyl compound. Without being bound by theory, it is believed that the addition of a silylated alkynyl compound reduces the yellowing of the reaction product prepared by the hydrosilylation reaction compared to the product obtained by the hydrosilylation reaction from a starting material that does not contain a silylated alkynyl compound or contains an organic alkynol inhibitor (such as those mentioned above). Examples of silyl-based alkynes 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, and (3-methyl-1-butyn-3-oxy)triethyl Cyclohexylsilane, bis(3-methyl-1-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. The silylated alkyne compounds that can be used as inhibitors in this article can be prepared by methods known in the art, such as U.S. Patent 6,677,407 to Bilgrien et al., which discloses silylating alkynes by reacting the alkynes described above with chlorosilanes in the presence of an acid acceptor.

[0071] Alternatively, the inhibitor may be an enynyne compound, such as 3-methyl-3-penten-1-yne; 3,5-dimethyl-3-hexen-1-yne; and combinations thereof. Alternatively, the inhibitor may include triazoles, examples of which are benzotriazoles. Alternatively, the inhibitor may include phosphine. Alternatively, the inhibitor may include thiols. Alternatively, the inhibitor may include hydrazine. Alternatively, the inhibitor may include amines. Examples of amines include tetramethylethylenediamine, 3-dimethylamino-1-propyne, N-methylpropyne, propyne, 1-ethynylcyclohexylamine, or combinations thereof. Alternatively, the inhibitor may include fumarate esters. Fumarate esters include dialkyl fumarate esters such as diethyl fumarate, diallyl fumarate esters such as diallyl fumarate, and dialkoxyalkyl fumarate esters such as bis(methoxymethyl)ethyl fumarate. Alternatively, the inhibitor may include maleate esters. Maleate esters include dialkyl maleates such as diethyl maleate, diallyl maleates such as diallyl maleate, and dialkoxyalkyl maleates such as bis(methoxymethyl)ethyl maleate. Alternatively, inhibitors may include ethers.

[0072] Alternatively, the inhibitor may include carbon monoxide. Alternatively, the inhibitor may include alkenyl-functionalized siloxane oligomers, which may be cyclic or linear, such as methyl vinylcyclosiloxanes, examples of which are 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 of these. Compounds that can be used as the above-mentioned inhibitors are commercially available, for example from Sigma-Aldrich Inc. or Gell-Hill Corporation, and examples of inhibitors applicable herein include the inhibitor described as stabilizer E in paragraphs

[0148] to

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

[0073] The starting material (D) can be a hydrosilylation inhibitor or a combination of two or more of the aforementioned hydrosilylation inhibitors. The amount of inhibitor used will depend on various factors, including the desired reaction rate, the specific inhibitor used, and the selection and amount of each of the starting materials (A) to (C). However, when present, the amount of inhibitor can be >0 parts by weight per 100 parts by weight of starting material (A), or alternatively 0.02 parts by weight to 0.8 parts by weight.

[0074] (E) Water

[0075] The starting material (E) is water, which is generally unrestricted and can be used in net form (i.e., without any carrier medium / solvent) and / or pure form (i.e., free of minerals and / or other impurities). For example, water may be treated or untreated before it combines with other starting materials in the emulsion. Examples of methods that can be used to purify water include distillation, filtration, deionization, and combinations of two or more of these, such that water can be deionized, distilled, and / or filtered. Alternatively, water may be untreated (e.g., it may be tap water, i.e., supplied by a municipal water supply or well water, used without further purification). Water can be used in any amount, which will be selected by those skilled in the art based on various factors, including the desired dilution of the emulsion. However, based on the combined weight of all starting materials in the emulsion, the amount of water may be 30% to 99%, alternatively 50% to 99%, or alternatively 50% to 95%.

[0076] (F) Buffer System

[0077] The buffering system (buffer) used to maintain the desired pH of the emulsion can be any suitable buffer, which may include a monoprotic acid or a polyprotic acid and its conjugate base. For example, it may include HCO3-. - / CO3 2- and H2PO4 - / HPO4 2- The buffer described as reagent F in paragraphs

[00145] to

[00147] of U.S. Patent Application Publication 2007 / 0099007 may be used herein. The buffer may include NaCO3 and NaHCO3; and / or citric acid and citrates, such as potassium citrate or sodium citrate. The amount of buffer may be >0 per 100 parts by weight of starting material (A), alternatively at least 0.2 parts by weight, and alternatively at least 0.4 parts by weight. Simultaneously, the amount of buffer may be up to 1.6 parts by weight per 100 parts by weight of starting material (A), alternatively up to 1.5 parts by weight, and alternatively up to 1.25 parts by weight.

[0078] (G) Surfactant

[0079] The surfactant used for emulsification can be nonionic or ionic. Alternatively, the surfactant can be nonionic. Suitable surfactants can be selected from surfactants known in the art and commercially available. Suitable nonionic surfactants include alkylphenols, fatty alcohols, or fatty acids having olefinic groups such as vinyl oxide groups or propylene oxide groups. Suitable ionic surfactants include anionic surfactants such as sulfates, sulfonates, phosphates, and sulfosuccinates. Examples of surfactants suitable for use herein are surfactants described as surfactant (G) in paragraphs

[0167] to

[0176] of U.S. Patent Application Publication 2007 / 0099007. The amount of surfactant depends on various factors, including the presence of a polyvinyl alcohol compound in the starting material (H); however, the amount of surfactant can be 0 to 3 parts by weight, alternatively 0 to 2 parts by weight, alternatively 0 to 1 part by weight, or alternatively 0 to 0.3 parts by weight per 100 parts by weight of the starting material (A).

[0080] (H) Polyvinyl alcohol

[0081] The starting material (H) in the emulsion is a polyvinyl alcohol compound. Polyvinyl alcohol compounds are known in the art and disclosed, for example, in U.S. Patent Application Publication 2007 / 0099007, paragraphs

[0172] and

[0173] . The polyvinyl alcohol compound can be prepared by saponification of polyvinyl acetate, so that up to 15% of polyvinyl acetate can be retained in the polyvinyl alcohol compound used herein. Alternatively, the polyvinyl alcohol compound can be 80% to 98% polyvinyl alcohol (the balance being 20% ​​to 2% polyvinyl acetate). At 20°C, the polyvinyl alcohol compound can have a minimum viscosity of 5 cP in a 4% aqueous solution. The amount of the polyvinyl alcohol compound depends on various factors, including the presence of a surfactant in the starting material (G); however, the amount of polyvinyl alcohol can be 0 to 10 parts by weight per 100 parts by weight of the starting material (A), alternatively 0 to 5 parts by weight, and alternatively 0 to 3.0 parts by weight. However, at least one of (G) surfactant and (H) polyvinyl alcohol is present in the emulsion. The amount of (G), (H), or a combination of both (G) and (H) may be at least 5.0 parts by weight per 100 parts by weight of starting material (A).

[0082] (I) Biocides

[0083] The starting material (I) is an optional biocide that can be added to the emulsion. Biocides are known in the art, and examples of biocides include (I1) fungicides, (I2) herbicides, (I3) insecticides, (I4) antimicrobial agents, and combinations of two or more of these. Exemplary biocides are disclosed, for example, in U.S. Patent 9,221,041 to Brandstadt et al. Biocides are optional. However, when used, the biocide may be present in an amount of up to 1.0 part by weight per 100 parts by weight of the starting material (A).

[0084] (J) Defoamer

[0085] The emulsion may optionally contain a starting material (J) and an anti-foaming agent / anti-foam. The amount of the starting material (J) may be no more than 0.2 parts by weight per 100 parts by weight of the starting material (A). Examples of suitable defoamers include emulsions containing silica and polydimethylsiloxane. Such defoamers are commercially available from Dow Silicones, Inc., Midland, Michigan, USA.

[0086] Other starting materials

[0087] One or more additional starting materials may be added to the emulsion described herein. These additional starting materials may be selected from the group consisting of: bactericides (e.g., sorbic acid), colorants (e.g., dyes or pigments), fillers (e.g., silica), and wetting agents (e.g., glycols, such as propylene glycol or ethylene glycol). Examples of additional starting materials suitable for use herein include additives described in paragraphs

[0177] to

[0190] of U.S. Patent Application Publication 2007 / 0099007 and paragraphs

[0055] to

[0056] of U.S. Patent Application Publication 2002 / 0061365.

[0088] Despite the foregoing description, the emulsions described herein are free of stabilizers selected from aliphatic polyethers, (co)polyacrylamide, polysaccharides, and polyacrylates. These stabilizers are long, flexible, high-molecular-weight hydrophilic macromolecules. As used herein, "free of stabilizers selected from aliphatic polyethers, (co)polyacrylamide, polysaccharides, and polyacrylates" means that such macromolecules are not intentionally added to the emulsion. The emulsion may contain no such macromolecules or contain undetectable amounts of such macromolecules. If any such macromolecules are present in one or more of the starting materials used in the emulsion, any amount is insufficient to alter the properties of any release coating prepared from the emulsion.

[0089] The emulsions described herein also do not contain non-reactive organopolysiloxanes. As used herein, "non-reactive organopolysiloxane" refers to a polysiloxane that does not undergo a hydrosilylation reaction with starting materials (A) and (B). Such non-reactive organopolysiloxanes may have the formula (R) 1 ) e SiO (4-e) / 2 , where R 1 = A monovalent, optionally substituted hydrocarbon radical having 1 to 10 carbon atoms, derived from the group consisting of substituted and unsubstituted alkyl radicals, phenyl radicals, and phenylalkyl radicals that may be the same or different within the molecule, and e can be an integer between 1 and 3. Examples of nonreactive organopolysiloxanes are α,ω-trialkylsiloxy-terminated polydialkylsiloxanes, such as α,ω-trimethylsiloxy-terminated polydimethylsiloxanes. As used herein, "free from nonreactive organopolysiloxanes" means that such nonreactive organopolysiloxanes are not intentionally added to the emulsion. The emulsion may contain no such nonreactive organopolysiloxanes or contain undetectable amounts of such nonreactive organopolysiloxanes. If any such nonreactive organopolysiloxane is present as an impurity in one or more of the starting materials used in the emulsion, any amount thereof is insufficient to alter the properties of any release coating prepared from the emulsion. Without being bound by theory, it is believed that the presence of non-reactive organopolysiloxanes in release coatings prepared from the emulsions described herein may be detrimental to the performance of the release coating by, for example, increasing extractability and / or reducing anchoring on certain substrates, compared to release coatings prepared from emulsions that do not contain non-reactive organopolysiloxanes.

[0090] The emulsion can be prepared by combining the above-described starting materials in the described amounts, in any order of addition, optionally with the masterbatch, and optionally under shear. Alternatively, the emulsion can be formed by subjecting the starting materials to high shear, for example in a rotor and stator type mixer or in a device that applies increased shear, such as a high-pressure homogenizer, microfluidizer, colloid mill, or ultrasonic spectrometer (ultrasonic mixer). To avoid premature reactions during emulsion formation, some of the starting materials can be emulsified separately. For example, all or part of the starting material (A) can be emulsified in the absence of starting material (B), followed by the addition of starting material (B). Alternatively, starting materials (A) and (B) can be emulsified in the absence of a catalyst, wherein the catalyst is emulsified and added separately.

[0091] The present invention also provides a method for preparing a coated substrate using an emulsion. The method includes applying an emulsion to the surface of a substrate. The method further includes curing at an elevated temperature (such as 50°C to 120°C) to remove water and cure starting materials (A) and (B), thereby obtaining the coated substrate.

[0092] The emulsion can be applied or dispensed onto the surface of a substrate in any suitable manner. Typically, the emulsion is applied in a wet form using a wet coating technique. In some embodiments, the emulsion is applied by: i) spin coating; ii) brush coating; iii) drop coating; iv) spray coating; v) dip coating; vi) roll coating; vii) flow coating; viii) trench coating; ix) concave coating; or any combination of x)i) to ix). Typically, the emulsion is applied to the substrate to create a wet deposit on the substrate, which is then dried and cured to obtain a coated substrate comprising a cured silicone release coating on the substrate.

[0093] The substrate is unrestricted and can be any substrate. The substrate may have an integrated hot plate or integrated furnace or a separate furnace for drying and curing the deposit. The substrate may optionally have continuous or discontinuous shapes, dimensions, dimensions, surface roughness, and other properties. In some embodiments, the substrate has a softening point temperature at elevated temperatures.

[0094] The substrate may include plastics, which may be thermosetting and / or thermoplastic. Alternatively, the substrate may include paper suitable for food contact applications. Specific examples of suitable substrates include polyamides (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polypropylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyesters; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutene; styrene-based resins; polyoxymethylene (POM); polycarbonate (PC); polymethyl methacrylate (PMMA); and polyvinyl chloride (PVC). C); polyphenylene sulfide (PPS); polyphenylene ether (PPE); polyimide (PI); polyamide-imide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone (PEK); polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); or polyether nitrile (PEN); cellulose, such as triacetyl cellulose, diacetyl cellulose, or cellophane; and paper, such as kraft paper.

[0095] The emulsion or wet deposit is typically dried and cured at an elevated temperature for a period of time. This period is usually sufficient to achieve curing, i.e., crosslinking, of the starting materials, including (A) and (B). In some embodiments, this period is greater than 0 to 8 hours, alternatively greater than 0 to 2 hours, alternatively greater than 0 to 1 hour, alternatively greater than 0 to 30 minutes, alternatively greater than 0 to 15 minutes, alternatively greater than 0 to 10 minutes, alternatively greater than 0 to 5 minutes, or alternatively greater than 0 to 2 minutes. This period depends on various factors, including the selected elevated temperature, the desired film thickness, and the amount of water.

[0096] Curing typically has a holding time of 1 to 50 seconds; alternatively, a holding time of 2 to 10 seconds. As used herein, holding time refers to the time during which the starting materials, including (A) and (B), are subjected to elevated temperatures. Holding time differs from curing time because curing may continue even after the wet deposit or its partially cured reaction intermediates are no longer subjected to elevated temperatures (which typically trigger curing). Alternatively, coated articles can be prepared on a conveyor belt in an oven, and the holding time can be calculated by dividing the length of the oven (e.g., in meters) by the linear speed of the conveyor belt (e.g., in meters per second).

[0097] This time period can be broken down into curing iterations, for example, a first curing and a post-curing, where the first curing is, for example, one hour and the post-curing is, for example, three hours. The elevated temperature can be independently selected from any temperature above room temperature in such iterations, and can be the same in each iteration.

[0098] Depending on the thickness and other dimensions of the film and the coated substrate, the coated substrate can be formed through an iterative process. For example, a first deposit can be formed and subjected to a first elevated temperature for a first period of time to obtain a partially cured deposit. A second deposit can then be applied to the partially cured deposit and subjected to a second elevated temperature for a second period of time to obtain a second partially cured deposit. The partially cured deposit will also be further cured for a second period of time during exposure to the second elevated temperature. A third deposit can be applied to the second partially cured deposit and subjected to a third elevated temperature for a third period of time to obtain a third partially cured deposit. The second partially cured deposit will also be further cured for a second period of time during exposure to the second elevated temperature. This process can be repeated, for example, 1 to 50 times, to construct a coated article as needed. The composite having a partially cured layer is typically subjected to a final post-curing, for example, at the elevated temperatures and time periods described above. Each elevated temperature and time period can be independently selected and can be the same as or different from each other. When articles are formed through an iterative process, each deposit can be independently selected and can vary in terms of the components selected in the composition and / or their amounts. Alternatively, in such an iterative process, each iterative layer can be fully cured rather than only partially cured.

[0099] The deposit may include a wet film, and the iterative process may be wet-on-wet, depending on the curing state of the partially cured layer. Alternatively, the iterative process may be wet-on-dry. The coated substrate (which includes a film formed from an emulsion on the substrate) may have different dimensions, including the relative thickness of the film and the substrate. Upon curing, the resulting silicone release coating has a thickness that varies depending on its end-use application. Typically, silicone release coatings have thicknesses greater than 0 μm to < 1 μm, alternatively greater than 0 μm to 0.9 μm, alternatively greater than 0 μm to 0.75 μm, alternatively greater than 0 μm to 0.5 μm, alternatively greater than 0 μm to 0.25 μm, and alternatively greater than 0 μm to 0.2 μm. However, other thicknesses are conceivable, for example, 0.05 μm to 0.2 μm. For example, the film thickness can be from 0.1 μm to 10 μm; alternatively, from 0.15 μm to 5 μm; alternatively, from 0.2 μm to 2 μm; and alternatively, from 0.2 μm and 0.6 μm. Alternatively, when the substrate is plastic, the film can have a thickness of 0.05 μm to <1 μm, alternatively from 0.05 μm to 0.9 μm, or alternatively from 0.05 μm to 0.8 μm. Alternatively, when the substrate is paper, the film can have a thickness of 0.2 μm to <1 μm, alternatively from 0.2 μm to 0.9 μm, alternatively from 0.2 μm to 0.8 μm, alternatively from 0.2 μm to 0.7 μm, or alternatively from 0.2 μm to 0.6 μm; alternatively from 0.2 μm to 0.5 μm; and alternatively from 0.2 μm to 0.3 μm.

[0100] Coated substrates can be used in a variety of end-use applications. For example, they can be used in coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, construction applications, transportation applications, (opto)electronic applications (such as device fabrication), electrical applications, photonic applications, and food contact applications (such as oven-peeling). Alternatively, when the substrate is paper, the coated substrate can be used for food contact applications, such as oven-peeling. Alternatively, when the substrate is plastic, the coated substrate can be used for (opto)electronic applications, such as device fabrication.

[0101] Example

[0102] These examples are intended to illustrate the invention to those skilled in the art and are not to be construed as limiting the invention as set forth in the claims. The starting materials used in these examples are described in Table 1 below.

[0103] Table 1 - Starting Materials

[0104]

[0105]

[0106] With DOWSIL TM The starting materials for the SYL-OFF trademark are available from DSC, which refers to Dow Silicones, Inc. of Midland, Michigan, USA.

[0107] Reference Example A - Vi / hexenyl content and SiH content measured by NMR

[0108] The vinyl, hexenyl, and SiH contents of the starting materials in Table 1 were determined using NMR spectroscopy as follows. Nuclear magnetic resonance (NMR) spectra were obtained on an NMR BRUKERAVIII (400 MHz) using a silicon-free 10 mm tube and CDCl3 / Cr(AcAc)3 solvent. 29 The chemical shift of the Si-NMR spectrum references the internal solvent resonance and is reported relative to tetramethylsilane.

[0109] Reference Example B - Dynamic Viscosity (cSt)

[0110] The dynamic viscosity of the starting materials in Table 1 was measured as follows. The dynamic viscosity (DV) was measured using a Brookfield viscometer (DV-IPrime) equipped with spindles 2 to 4 at speeds from 20 rpm to 100 rpm and at a temperature of 25°C.

[0111] In this example, a sample of the base emulsion was prepared by combining the starting materials and their amounts as shown in the table below. The amount of each starting material is expressed as a percentage by weight (%). The preparation of the base emulsion was carried out in the laboratory. First, a pH buffer containing water, citric acid monohydrate, and sodium hydroxide was weighed and blended. The polymer was weighed and blended separately, with a surfactant added during the blending process. Then, the buffer water was poured in and the mixture was stirred for 5 minutes. The premix was then emulsified at 100 bar using a high-pressure acoustic spectrometer until the target particle size was achieved. The recovered amount was blended with packages of hydrosilylation inhibitors and biocides.

[0112] Table 2 - Comparison of basic emulsions (amount in weight %)

[0113]

[0114] Table 3 - Other Base Emulsions

[0115]

[0116] Table 4 - Other Base Emulsions

[0117]

[0118]

[0119] In Reference Example 2, a sample of emulsion (bath / emulsion) was prepared as follows: a base emulsion prepared as described in Reference Example 1 was combined with a catalyst emulsion (C-1) or (C-2) as described in Table 1, water, and an antifoaming agent. The amounts by weight are shown in Table 5.

[0120] Table 5 - Emulsions

[0121] Starting materials Bath / Lotion1 Bath / Lotion 2 base emulsion 95 90 Catalyst emulsion (C-1) 0 10 Catalyst emulsion (C-2) 5 0 Water (E-1) 430 430 Defoamer (J-1) 0.3 0.3 total 530.3 530.3

[0122] In this Reference Example 3, the sample prepared as described in Reference Example 2 has a concentration of 0.32 g / m³. 2 The average weight of the silicone coating on the emulsion-treated baking paper substrate. The silicone coating weight, post-cured extractables, absorbency, and anchoring properties were evaluated as follows:

[0123] After silicon elemental calibration using standard samples, the weight of the silicon coating was measured by X-ray fluorescence using an Oxford Lab-X3500 XRF analyzer. XRF measurements were performed on a blank substrate before three measurements were performed on the coated paper sample, thus obtaining the weight in g / m³. 2 The average weight or thickness of the silicon coating.

[0124] The water resistance of paper substrates is tested using a standard absorption test (referred to as the Cobb test, for example, as described in the TAPPI 441om-04 test method). The sample is exposed to water for 45 seconds, and the amount of water absorbed after a total of 60 seconds is measured by weight. The "Cobb value" is expressed in g / m³. 2 This indicates the mass of water absorbed. A lower Cobb value indicates higher water resistance of the substrate. Some consumers expect less than 20 g / m³. 2 The Cobb value is less than 15g / m³, while other consumers expect less than 15g / m³. 2 The Cobb value.

[0125] Anchorage testing provides a quantitative determination of the abrasion resistance of a silicone release coating anchored to a substrate after abrasion testing. The silicon content of the coated substrate is determined by XRF before and after abrasion testing with an abrasion tester and expressed as the percentage of Si remaining after abrasion compared to 100% of the initial coating. A higher percentage of Si remaining after abrasion indicates greater anchorage or abrasion resistance.

[0126] The percentage of silicone extractable on the coated paper was measured by its silicone CW before and after immersion in MIBK (20 minutes). Uncured silicone was dissolved in solvent, and the percentage loss was determined. This test was performed immediately after coating and after aging at RT for 24 hours, termed Immediate Extractable ("IM Ext") and Post-Cure Extractable ("PC Ext"). The results are reported in Table 6.

[0127] Table 6 - Regarding 0.32 g / m 2 Results of average silicone coating weight of baking paper

[0128]

[0129] The results in Table 6 indicate that the release coatings produced by the comparative samples (i.e., 1 and 3) without hexenyl functionalized polysiloxanes have insufficient anchoring or water absorption, which is higher than the anchoring and water absorption expected for baking paper applications.

[0130] Release coatings made from emulsions containing the sample 8 from Table 3 showed significantly higher anchoring (92.2% vs. 82.7%), and therefore better abrasion resistance than sample 1 from Table 2. Not wishing to be bound by theory, it is believed that the higher anchoring (higher abrasion resistance) reduces dust formation when hexenyldimethylsiloxy-terminated polydimethylsiloxane (in sample 8) is used instead of vinyldimethylsiloxy-terminated polydimethylsiloxane (in sample 1). Water absorption or Cobb value was also significantly lower (13.1 g / m³) when hexenyldimethylsiloxy-terminated polydimethylsiloxane was used instead of vinyldimethylsiloxy-terminated polydimethylsiloxane. 2 For 16.7g / m 2 Furthermore, higher water resistance is beneficial for food contact applications; for example, for releasing vapors from food and for water resistance in frozen foods.

[0131] Samples 10 and 12 from Table 3 contained 1% and 2% of non-reactive trimethylsiloxy-terminated PDMS, respectively, and the resulting release coatings exhibited excellent anchoring properties, similar to those of the release coating produced by Sample 3 (90.6% and 92.9% vs. 91.3%), while water absorption was again significantly reduced (13.8 g / m³). 2 and 12.5g / m 2 For 15.9g / m 2 ).

[0132] In this Reference Example 4, the sample prepared as described in Reference Example 2 has a concentration of 0.44 g / m³. 2 The average weight of the silicone coating on the emulsion-treated baking paper. The samples obtained were evaluated as described in Reference Example 3 above. Additionally, air barrier properties and baking residue were evaluated as follows.

[0133] The air permeability of different paper substrates is measured using an L&W air permeability tester by sensing the airflow passing through the sample and the pressure difference across it. The standard test method SCAN-P 26:78 or TAPPI 536om-12, "Resistance of paper too passage of air (high-pressure Gurley method)," is applied. Air permeability is expressed in Gurley seconds or Gurley units. The longer the Gurley time, the lower the air permeability of the paper sample and the better its air barrier properties.

[0134] The oven-peel or baking test measures the amount of food remaining on the substrate after oven baking and peeling. A coated paper sample is folded into a mold and weighed. Cake dough containing 4 eggs, 80g of sugar, 80g and 85g of potato and wheat flour, and 5.5g of baking powder is processed at room temperature using a general kitchen machine and placed in the mold before oven baking. The baked product is allowed to cool. The coated paper to be tested is then removed from the baked product, and the amount of baked product still adhering to the paper is weighed and converted to g / m³. 2 The lower the calcination exfoliation value, the better. The results are reported in Table 7.

[0135] Table 7 - Polydimethylsiloxanes and hexenyldimethylsiloxanes with vinyl dimethylsiloxy end-capping Release coatings prepared from base emulsions of both end-capped polydimethylsiloxane and those using vinyl dimethylsiloxane end-capping agents Ionized polydimethylsiloxane or hexenyldimethylsiloxy-terminated polydimethylsiloxane base emulsions prepared ionized polydimethylsiloxane In comparison of different coating types, the average weight of the silicon coating is 0.44 g / m². 2

[0136]

[0137]

[0138] The results in Table 7 show that the release coating prepared with Sample 1 in Table 2 has the disadvantage of low abrasion resistance, as demonstrated by its low anchoring strength of 81.9% and low air barrier properties of 833%. Abrasion resistance (anchoring strength) was increased by increasing the content of hexenyldimethylsiloxy-terminated polydimethylsiloxane relative to vinyldimethylsiloxy-terminated polydimethylsiloxane in the base emulsion, as shown in the release coatings prepared with Samples 15 to 18 in Table 3. Unwilling to be bound by theory, it is believed that, under the test conditions, when the ratio of hexenyldimethylsiloxy-terminated polydimethylsiloxane to vinyldimethylsiloxy-terminated polydimethylsiloxane was achieved in sample 18, the anchoring property was maximized because increasing the amount of hexenyldimethylsiloxy-terminated polydimethylsiloxane to 90% or 100% (and correspondingly decreasing the amount of vinyldimethylsiloxy-terminated polydimethylsiloxane to 10% or 0%) in samples 19 and 20 did not significantly alter the anchoring property. The data in Table 7 also show that as the amount of hexenyldimethylsiloxy-terminated polydimethylsiloxane increased from 75% to 100%, the air barrier properties improved (increased), but the baking residue properties were adversely affected (increased). However, samples 15 to 20 produced coated papers suitable for preparing baking paper.

[0139] In this Reference Example 5, the sample prepared as described in Reference Example 2 has a concentration of 0.45 g / m³. 2 The average weight of the silicone coating on the emulsion-treated baking paper. The samples were evaluated as described above in Reference Example 3. The results are shown in Table 8 below.

[0140] Table 8 - Preparation of emulsions using Vi-functionalized polysiloxanes, Hex-functionalized polysiloxanes, or both. Release coating

[0141]

[0142]

[0143] The relative amounts of vinyldimethylsiloxy-terminated poly(dimethyl / methylvinyl)siloxane and hexenyldimethylsiloxy-terminated poly(dimethyl / methylhexenyl)siloxane were evaluated, and the results are shown in Table 8 above. The combination of the two polyorganosiloxanes significantly improved curing (e.g., when using a 90:10 ratio of hexenyldimethylsiloxy-terminated poly(dimethyl / methylhexenyl)siloxane and vinyldimethylsiloxy-terminated poly(dimethyl / methylvinyl)siloxane in the base emulsion alone, the post-curing extractable percentage decreased from 18.9 to 9.5), improved anchoring (from 85.9 to 90.4), and positively reduced water absorption (from 13.2 to 12.4). These examples demonstrate that when only 10% of hexenyldimethylsiloxy-terminated poly(dimethyl / methylhexenyl)siloxane is used in the base emulsion of the release coating composition formulated on a paper substrate, the resulting release coating does not exhibit the absorbency expected for food contact applications. Surprisingly, the best performance was obtained under the test conditions described herein when a combination of 90% hexenyldimethylsiloxy-terminated poly(dimethyl / methylhexenyl)siloxane and 10% vinyldimethylsiloxy-terminated poly(dimethyl / methylvinyl)siloxane was used, as this sample (13) produced a release coating with the lowest absorbency and highest anchoring properties among the tested samples (including Sample 2 using 100% vinyldimethylsiloxy-terminated poly(dimethyl / methylvinyl)siloxane (without hexenyl) and Sample 14 using 100% hexenyldimethylsiloxy-terminated poly(dimethyl / methylhexenyl)siloxane (without vinyl)).

[0144] In this Reference Example 6, the sample prepared as described in Reference Example 2 has a concentration of 0.2 g / m³. 2 The average weight of the silicone coating on the emulsion-treated PET film substrate was measured. A combination of vinyl-functionalized and hexenyl-functionalized polysiloxanes was used in the base emulsion. The samples obtained were evaluated as described above in Reference Example 3. The results are shown in Table 9 below.

[0145] Table 9 - Preparation of base emulsions using various Vi-functional and Hex-functional polysiloxanes Comparison of release coatings

[0146]

[0147] Release coatings prepared from emulsions containing vinyldimethylsiloxanes (5 and 6) with end-capped polydimethylsiloxanes exhibited high extractability (over 10%) and poor (low) anchoring to PET films (and therefore poor abrasion resistance on PET films). Sample 6, containing 1% trimethylsiloxane with end-capped polydimethylsiloxanes, had even worse anchoring and extractability than Sample 5, which did not contain trimethylsiloxane with end-capped polydimethylsiloxanes. Although Sample 7 had reduced extractability compared to Samples 5 and 6, its extractability was still higher than expected (>5%), and its anchoring value of 41.9% was still quite low. To avoid being bound by theory, it is believed that the presence of non-reactive organopolysiloxanes (such as 1% trimethylsiloxy-terminated polydimethylsiloxane in Sample 6) would adversely affect (increase) the extractability in release coatings prepared from emulsions containing even small amounts of non-reactive organopolysiloxanes (e.g., 1% to 2%). Therefore, the emulsions described herein do not contain non-reactive organopolysiloxanes (such as trimethylsiloxy-terminated polydimethylsiloxanes as described in Table 1).

[0148] The release coatings prepared from Samples 21 and 22 (which comprise combinations of hexenyldimethylsiloxy-terminated poly(dimethyl / methylhexenyl)siloxanes and vinyldimethylsiloxy-terminated polydimethylsiloxanes) exhibited minimal extractables, and therefore the tested samples in Table 9 showed the highest abrasion resistance. Without being bound by theory, it is believed that the reduction in extractables is due to the addition of polyorganosiloxanes with hexenyl groups.

[0149] In this example 7, we focus on using poly(dimethyl / methylhexenyl)siloxane blended with poly(dimethyl / methylvinyl)siloxane in different ratios under different coating conditions (average coating weight 0.2 g / m²). 2 Under the same conditions, repeat the study in Example 6.

[0150] Table 10 below again shows that the release coating made from Sample 7 (which contains vinyl dimethylsiloxy-terminated poly(dimethyl / methyl vinyl)siloxane and no hexenyl-functionalized polyorganosiloxane) exhibited the lowest anchoring (lowest abrasion resistance) under the test conditions. Anchoring increased with increasing amounts of hexenyl dimethylsiloxy-terminated poly(dimethyl / methyl hexenyl)siloxane in the base emulsion. At a poly(dimethyl / methyl vinyl)siloxane:poly(dimethyl / methyl hexenyl)siloxane ratio of 50:50, anchoring more than doubled, and then stabilized above this ratio.

[0151] Table 10 - Compositions of poly(dimethyl / methylhexenyl)siloxane and poly(dimethyl / methylethylene) with different contents Release coating prepared from emulsion of siloxane

[0152]

[0153] In Table 10, optimal performance was found at a poly(dimethyl / methylhexenyl)siloxane:poly(dimethyl / methylvinyl)siloxane ratio of 50:50 in the base emulsion. Not wishing to be bound by theory, this further demonstrates that the inclusion of both hexenyl-functionalized and vinyl-functionalized polysiloxanes in the base emulsion results in the formation of a release coating on the PET film substrate, which offers the benefit of one or more of prolonged curing (reduced extractability) and increased anchoring (increased abrasion resistance).

[0154] Not wanting to be bound by theory, it is also believed that combining hexenyl-functionalized polysiloxanes, particularly poly(dimethyl / methylhexenyl)siloxanes and vinyl-functionalized polysiloxanes, in emulsions as described herein can provide one or more benefits (compared to comparable release coating emulsions containing vinyl-functionalized polysiloxanes but not hexenyl-functionalized polysiloxanes), especially on plastic film substrates such as PET. For example, it is believed that curing speed is increased, extractables are reduced by up to 5 times, and anchoring properties are increased by up to 2 times.

[0155] Industrial applicability

[0156] The problem to be solved: The desire is to use silicone emulsions to coat paper substrates for food contact applications, thereby providing peel strength and water resistance, as an attractive alternative to the health concerns associated with fluorinated and chromium-containing materials used in the same applications. However, online operating issues of paper machines, such as dust formation, have been a major challenge in using silicone emulsions.

[0157] Furthermore, for many applications, it is desirable to use silicone emulsions to coat other substrates, such as plastic films, including but not limited to labels, general-purpose tapes, and liner for sunscreen films and waterproof tapes. Additionally, release liners with release coatings on plastic film substrates can be used in the (opto)electronics industry, where a smooth surface and minimal or no dust are desired in the release coating. Industrially, there is a need for silicone emulsions that are stable and can be cured to form release coatings with high SAS (subsequent adhesion strength) and low and stable peel strength.

[0158] Solution: The silicone emulsion described herein is general-purpose as it can be used to prepare release coatings on a variety of substrates, including both paper and plastic film substrates. The silicone emulsion described herein can be used to prepare release coatings on paper substrates suitable for food contact applications. The silicone emulsion can be applied to and cured onto the paper substrate to form a release coating on the paper substrate with little or no dust formation (as shown in the examples above), wherein the anchoring test method described above shows a high percentage of the silicone release coating remaining on the substrate after testing.

[0159] Furthermore, the silicone release coating emulsions described herein have a lower viscosity than previously disclosed solvent-free curing silicone compositions. Without being bound by theory, it is believed that, at the same coating speed used in solvent-free methods and without observed fogging during application of the emulsion to the substrate, the emulsions described herein offer better control over the thickness of the prepared silicone release coating, and a lower thickness range. This can provide environmental, health, and safety benefits, economic benefits in terms of lower production costs, and coating quality benefits (because fog elimination reduces or eliminates surface defects). Moreover, the thinner silicone release coating obtained on paper substrates can make the coated paper more conducive to composting / recycling because less silicone release coating is deposited on the substrate surface. Furthermore, compared to solvent-free curing silicone compositions, the emulsions described herein can produce silicone release coatings with additional technical advantages because the coating is thinner, cures faster, and has a deeper curing cross-section, which is not achievable with thicker solvent-free coatings. Furthermore, the emulsions described herein can produce silicone release coatings with other benefits (compared to coatings produced with solvent-free curable silicone compositions), such as: less extractable material, thereby minimizing migration to potentially contaminated food or sensitive (opto)electronic components; anchoring / abrasion resistance greater than 90%; low / no fogging; less dust formation; and / or lower cost. Additionally, the emulsions described herein produce smooth silicone release coating surfaces with lower coating weight, which can minimize the risk of clogging problems. This is important for, for example, baking paper with a thin / breathable substrate during oven baking or microwave cooking to allow steam to escape for proper cooking; and high-quality coatings for multilayer ceramic capacitors (MLCCs) and polarizing film applications. The emulsions described herein can also allow the addition of hydrophilic additives, such as antistatic additives, or anchoring additives, such as alkoxysilanes, which are not readily soluble or dispersed in solvent-free tack-curable silicone compositions.

[0160] Definition and usage of terms

[0161] In this application, unless otherwise specified, all amounts, ratios, and percentages are by weight. The total amount of all starting materials in an emulsion or other composition is 100% by weight. The summary of the invention and the abstract of the specification are incorporated herein by reference. Unless the context of this specification indicates otherwise, the articles “a,” “an,” and “the” each refer to one (an) or more (a plurality of). Unless otherwise specified, the singular includes the plural meaning. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are used as described in Chapters §2111.03I, II, and III of the Patent Examining Procedure Ninth Edition, last revised January 2018, Amendment 08.2017. Abbreviations used herein have their definitions in Table 11. The disclosure of the scope includes the scope itself and any values ​​and endpoints contained therein. For example, disclosures with a range of, for example, 15 to 400 include, for example, subsets of 15 to 137, 138 to 265, and 266 to 400, as well as any other subsets contained within that range. Similarly, disclosures of the Markush group include the entire group and also any individual members and subgroups contained therein. For example, the Markush group includes (i) α,ω-dimethylsiloxy-terminated poly(dimethylsiloxane / methylsiloxane), (ii) α,ω-dimethylsiloxy-terminated polymethylsiloxane, (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylsiloxane), (iv) α,ω-trimethylsiloxy-terminated polymethylsiloxane, (v) α-dimethylsiloxy-ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylsiloxane), (vi) α The disclosure of dimethylsiloxy-ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylsiloxane), (vii) combinations of two or more thereof, individually includes member (iii) α, ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylsiloxane); subgroups (iii) α, ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylsiloxane) and (iv) α, ω-trimethylsiloxy-terminated poly(methylsiloxane / methylsiloxane), and any other individual member and subgroup contained therein.

[0162] The following abbreviations used in this application have the definitions described in Table 11 below.

[0163] Table 11 - Abbreviations

[0164] abbreviation definition AcAc Acetylacetone ℃ Celsius cP centipo cSt Litchi CW Coating weight EB End g gram h Hour Hex Hexenyl <![CDATA[m 2 ]]> square meters Me methyl MF Multifunctionality refers to polyorganosiloxanes having side functional groups (e.g., alkenyl groups). MIBK Methyl isobutyl ketone mPa·s millipascal second PDMS polydimethylsiloxane Ppm One million portions Rpm Revolutions per minute RT Room temperature of 25±2℃ Q <![CDATA[The tetrafunctional siloxane unit (silicate unit) of the formula (SiO 4 / 2 )]]> μm micrometer Vi vinyl XRF X-ray fluorescence method

[0165] Embodiments of the present invention

[0166] In a first embodiment, a silicone release coating emulsion comprises:

[0167] (A) 100 parts by weight of an aliphatic unsaturated polyorganosiloxane composition, wherein the aliphatic unsaturated polyorganosiloxane composition...

[0168] The saturated polyorganosiloxane composition contains

[0169] (A1) 25 to 100 parts by weight of a single-component (R) 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d (SiO 4 / 2 ) e Hexenyl-functionalized polyorganosiloxanes, wherein R 1 It is an alkyl group, R 2 It is a hexenyl group, with subscripts a from 0 to 4, b from 0 to 4, c from 0 to 400, d from 0 to 50, and e either 0 or 1, provided that (a+b) = 2 to 4, (b+d) ≥ 2, and (a+b+c+d) is 15 to 400.

[0170] (A2) 0 to 75 parts by weight of products with a single-component (R) 1 3SiO 1 / 2 ) i (R 1 2R 3 SiO 1 / 2 ) f (R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h (SiO 4 / 2 ) j Vinyl-functionalized polyorganosiloxanes, wherein R 1 It is an alkyl group, R 3It is a vinyl group, with subscript i from 0 to 4, subscript f from 0 to 4, subscript g from 0 to 1400, subscript h from 0 to 200, and subscript j from 0 or 1, provided that (i+f) = 2 to 4, (f+h) ≥ 2, and (i+f+g+h) is 15 to 1400;

[0171] (B) A polyorganohydrosiloxane, wherein the amount of the polyorganohydrosiloxane is sufficient to provide a molar ratio (i.e., SiH / Vi ratio) of 1.2 / 1 to 3.0 / 1 of the combined amount of silicon-bonded hydrogen atoms in the starting material (B) to the amount of vinyl groups and hexenyl groups in the starting material (A).

[0172] (C) A hydrosilylation catalyst, wherein the amount of the hydrosilylation catalyst is sufficient to provide 10 ppm to 1000 ppm of platinum group metals based on the combined weight of the starting materials (A) and (B);

[0173] (D) 0.02 to 0.8 parts by weight of hydrosilylation inhibitor per 100 parts by weight of starting material (A);

[0174] (E) Water;

[0175] (F) 0.4 to 1.6 parts by weight of buffer per 100 parts by weight of starting material (A);

[0176] (G) Per 100 parts by weight of starting material (A) 0 to 3.0 parts by weight of surfactant; and

[0177] (H) Per 100 parts by weight of starting material (A) 0 to 10 parts by weight of polyvinyl alcohol,

[0178] The condition is that the combined amount of starting material (G) and starting material (H) is 100 parts by weight of starting material.

[0179] (A) ≥ 0.1 parts by weight; and

[0180] The condition is that the emulsion does not contain stabilizers selected from aliphatic polyethers, (co)polyacrylamide, polysaccharides and polyacrylates, and does not contain non-reactive organopolysiloxanes.

[0181] In the second embodiment, the starting material (A1) is present in the emulsion according to the first embodiment in an amount of 25 parts by weight to <100 parts by weight, and the starting material (A2) is present in an amount of >0 parts by weight to 75 parts by weight.

[0182] In the third embodiment, in the emulsion according to the first or second embodiment, the polyorganohydrosiloxane (B) has the unit formula (R 1 3SiO 1 / 2 )w (R 1 2HSiO 1 / 2 ) x (R 1 2SiO 2 / 2 ) y (R 1 HSiO 2 / 2 ) z The subscript w is 0, 1 or 2, the subscript x is 0, 1 or 2, the subscript y is 0 to 250, and the subscript z is 1 to 250. The conditions are (w+x) = 2, (x+z) ≥ 3, and the quantity (w+x+y+z) is 10 to 300.

[0183] In the fourth embodiment, in the emulsion according to any one of the first to third embodiments, (B) the polyorganohydrosiloxane is selected from the group consisting of: (i) α,ω-dimethylhydrosiloxy-terminated poly(dimethylsiloxane / methylhydrosiloxane),

[0184] (ii) α,ω-dimethylsiloxy-terminated polymethylsiloxanes

[0185] (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrosiloxane),

[0186] (iv) α,ω-trimethylsiloxy-terminated polymethylhydrosiloxanes, and

[0187] (v) α-Dimethylhydrosiloxy-ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrosiloxane),

[0188] (vi) α-Dimethylhydrosiloxy-ω-trimethylsiloxy-terminated polymethylhydrosiloxanes, and

[0189] (vii) A combination of two or more of them.

[0190] In the fifth embodiment, in the emulsion according to any one of the first to fourth embodiments, the polyorganohydrosiloxane (B) is present in an amount sufficient to provide a SiH / Vi ratio of 1.4 / 1 to 2.5 / 1.

[0191] In the sixth embodiment, in the emulsion according to any one of the first to fifth embodiments, the hydrosilylation catalyst is selected from the group consisting of: (CI) radiation-activated catalysts, (C-II) hydrosilylation catalysts that can be activated by means other than irradiation, and (C-III) combinations of (CI) and (C-II).

[0192] In the seventh embodiment, in the emulsion according to any one of the first to sixth embodiments, (C) the hydrosilylation catalyst is selected from the group consisting of: (C1) a metal selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium and iridium; (C2) a compound of the metal; (C3) a complex of the metal or the compound; (C4) the compound or the complex microencapsulated in a resin matrix or a core-shell structure.

[0193] In the eighth embodiment, in the emulsion according to any one of the first to seventh embodiments, the hydrosilylation inhibitor (D) is selected from the group consisting of: (D1) alkynols, (D2) silyl alkynols, (D3) ene-alkynyl compounds, (D4) triazoles, (D5) phosphines, (D6) thiols, (D7) hydrazines, (D8) amines, (D9) fumarates, (D10) maleate esters, (D11) ethers, (D12) carbon monoxide, and (D13) combinations of two or more of them.

[0194] In the ninth embodiment, in the emulsion according to any one of the first to eighth embodiments, the hydrosilylation inhibitor (D) is selected from the group consisting of: (D1) alkynols, (D2) silyl alkynols, (D9) fumarate, (D10) maleate, (D13) a combination of two or more of them.

[0195] In the tenth embodiment, in the emulsion according to any one of the first and ninth embodiments, the (F) buffer system comprises a monoprotic acid or a polyprotic acid and the conjugate base of the monoprotic acid or polyprotic acid.

[0196] In the eleventh embodiment, the surfactant (G) is present in the emulsion according to any one of the first to tenth embodiments and includes a nonionic surfactant.

[0197] In the twelfth embodiment, the polyvinyl alcohol (H) is present in the emulsion according to any one of the first to eleventh embodiments.

[0198] In the thirteenth embodiment, the emulsion according to any one of the first to twelfth embodiments further comprises a starting material (I) of up to 1.0 part by weight of a biocide per 100 parts by weight of starting material (A).

[0199] In the fourteenth embodiment, the emulsion according to any one of the first to thirteenth embodiments further comprises at most 0.2 parts by weight of defoamer per 100 parts by weight of starting material (J) of starting material (A).

[0200] In the fifteenth embodiment, in the emulsion according to any one of the foregoing embodiments,

[0201] The hexenyl-functionalized polyorganosiloxane of the starting material (A1) includes the unit formula (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d Where subscript a is 0, 1, or 2, subscript b is 0, 1, or 2, subscript c is 0 to 400, and subscript d is 0 to 50, provided that (a+b) = 2 to 4, (b+d) ≥ 2, and (a+b+c+d) is 15 to 400; and

[0202] The vinyl-functionalized polysiloxanes described in starting material (A2) include those with the unit formula (R 1 3SiO 1 / 2 ) i (R 1 2R 3 SiO 1 / 2 ) f (R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h The subscript i is 0, 1 or 2, the subscript f is 0, 1 or 2, the subscript g is 0 to 1200, and the subscript h is 0 to 200. The conditions are (i+f) = 2, (f+h) ≥ 2, and (i+f+g+h) is 15 to 1200.

[0203] In the sixteenth embodiment, in the emulsion according to the fifteenth embodiment,

[0204] The starting material (A1) is 50 parts by weight to <100 parts by weight of a unitary material (R... 1 2R 2 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c Hexenyl-terminated polydialkylsiloxanes, wherein the subscript c is from 15 to 400; and

[0205] The starting material (A2) is >0 parts by weight to 50 parts by weight of a unitary material (R... 1 2R 3 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g Vinyl-terminated polydialkylsiloxanes, wherein the subscript g is from 15 to 1200.

[0206] In the seventeenth embodiment, in the emulsion according to the fifteenth embodiment,

[0207] The starting material (A1) is >50 parts by weight to <100 parts by weight of a unitary material (R... 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d Poly(dialkyl / alkylhexenyl)siloxanes, wherein the subscript c is from 0 to 400 and the subscript d is from 2 to 50, and

[0208] The starting material (A2) is >0 parts by weight to <50 parts by weight of a unitary material (R... 3 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h Poly(dialkyl / alkylvinyl)siloxanes, wherein the subscript g is from 0 to 1200 and the subscript h is from 2 to 200.

[0209] In the eighteenth embodiment, one method includes:

[0210] The emulsion described in the sixteenth or seventeenth embodiment is applied to the surface of the substrate, and

[0211] The material is dried and cured, thus forming a coated substrate.

[0212] In the nineteenth embodiment, in the method according to the eighteenth embodiment, the substrate is paper.

[0213] In the twentieth embodiment, in the emulsion according to the fifteenth embodiment,

[0214] The starting material (A1) is >25 parts by weight to <100 parts by weight of a unitary material (R... 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d Poly(dialkyl / alkylhexenyl)siloxanes, wherein the subscript c is from 0 to 400 and the subscript d is from 2 to 50, and

[0215] The starting material (A2) is >0 parts by weight to <75 parts by weight of a unitary material (R... 3 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h Poly(dialkyl / alkylvinyl)siloxanes, wherein the subscript g is from 0 to 1200 and the subscript h is from 2 to 200.

[0216] In the twenty-first embodiment, in the emulsion according to the fifteenth embodiment,

[0217] The starting material (A1) is a unitary material (R) 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d Poly(dialkyl / alkylhexenyl)siloxanes, wherein the subscript c is from 0 to 400 and the subscript d is from 2 to 50; and

[0218] The starting material (A2) is a unitary material (R) 1 2R 3 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g Vinyl dialkylsiloxy-terminated polydialkylsiloxanes, wherein R 1 It is an alkyl group, R 3 It is a vinyl group, and the subscript g is from 15 to 1200.

[0219] In the twenty-second embodiment, one method includes:

[0220] The emulsion described in the twentieth embodiment or the twentieth or seventeenth embodiment is applied to the surface of the substrate, and

[0221] The material is dried and cured, thus forming a coated substrate.

[0222] In the twenty-third embodiment, in the method according to the twenty-second embodiment, the substrate is plastic.

[0223] In the twenty-fourth embodiment, in the emulsion or method according to any one of the foregoing embodiments, each R 1 It is a methyl group.

[0224] In the twenty-fifth embodiment, a silicone release coating emulsion comprises:

[0225] (A) 100 parts by weight of an aliphatic unsaturated polyorganosiloxane composition, said aliphatic unsaturated polyorganosiloxane composition comprising

[0226] (A1) >25 parts by weight to <100 parts by weight of products with a single-component formula (R) 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d (SiO 4 / 2 ) e Hexenyl-functionalized polyorganosiloxanes, wherein R 1 It is an alkyl group, R 2 It is a hexenyl group, with subscripts a from 0 to 4, b from 0 to 4, c from 0 to 400, d from 0 to 50, and e either 0 or 1, provided that (a+b) = 2 to 4, (b+d) ≥ 2, and (a+b+c+d) is 15 to 400.

[0227] (A2) > 0 parts by weight to 50 parts by weight of products with a single-component formula (R) 1 3SiO 1 / 2 ) i (R 1 2R 3 SiO 1 / 2 ) f (R 1 2SiO2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h (SiO 4 / 2 ) j Vinyl-functionalized polyorganosiloxanes, wherein R 1 It is an alkyl group, R 3 It is a vinyl group, with subscript i from 0 to 4, subscript f from 0 to 4, subscript g from 0 to 1400, subscript h from 0 to 200, and subscript j from 0 or 1, provided that (i+f) = 2 to 4, (f+h) ≥ 2, and (i+f+g+h) is 15 to 1400;

[0228] (B) A polyorganohydrosiloxane, wherein the amount of the polyorganohydrosiloxane is sufficient to provide a molar ratio (i.e., SiH / Vi ratio) of 1.2 / 1 to 3.0 / 1 of the combined amount of silicon-bonded hydrogen atoms in the starting material (B) to the amount of vinyl groups and hexenyl groups in the starting material (A).

[0229] (C) A hydrosilylation catalyst, wherein the amount of the hydrosilylation catalyst is sufficient to provide 10 ppm to 1000 ppm of platinum group metals based on the combined weight of the starting materials (A) and (B);

[0230] (D) 0.02 to 0.8 parts by weight of hydrosilylation inhibitor per 100 parts by weight of starting material (A);

[0231] (E) Water;

[0232] (F) 0.4 to 1.6 parts by weight of buffer per 100 parts by weight of starting material (A);

[0233] (G) Per 100 parts by weight of starting material (A) 0 to 3.0 parts by weight of surfactant; and

[0234] (H) Per 100 parts by weight of starting material (A) 0 to 10 parts by weight of polyvinyl alcohol,

[0235] The condition is that the combined amount of starting material (G) and starting material (H) is ≥ 0.1 parts by weight per 100 parts by weight of starting material (A); and

[0236] The condition is that the emulsion does not contain stabilizers selected from aliphatic polyethers, (co)polyacrylamide, polysaccharides and polyacrylates, and does not contain non-reactive organopolysiloxanes.

[0237] In the twenty-sixth embodiment, in the emulsion according to the twenty-fifth embodiment, the starting material (A1) is present in an amount of 75 to 90 parts by weight, and the starting material (A2) is present in an amount of 10 to 25 parts by weight.

[0238] In the twenty-seventh embodiment, in the emulsion according to the twenty-fifth embodiment, the starting material (A1) is present in an amount of >50 parts by weight to <100 parts by weight, and the starting material (A2) is present in an amount of >0 to <50 parts by weight.

[0239] In the twenty-eighth embodiment, in the emulsion according to the twenty-fifth embodiment, the starting material (A1) is present in an amount of 33 to 90 parts by weight, and the starting material (A2) is present in an amount of 10 to 67 parts by weight.

[0240] In the twenty-ninth embodiment, in the method according to the nineteenth embodiment, the method produces a silicone release coating having a thickness of 0.2 μm to <1 μm on the substrate.

[0241] In the thirtieth embodiment, in the method according to the twenty-ninth embodiment, the method produces a silicone release coating having a thickness of 0.2 μm to 0.6 μm on the substrate.

[0242] In the thirty-first embodiment, in the method according to the twenty-third embodiment, the method produces a silicone release coating having a thickness of 0.05 μm to <1 μm on the substrate.

[0243] A release coating with a thickness of 0.2 μm to 0.6 μm is applied to the substrate.

[0244] In the thirty-second embodiment, in the method according to the thirty-first embodiment, the method produces a silicone release coating having a thickness of 0.05 μm to 0.6 μm on the substrate.

Claims

1. A silicone release coating emulsion comprising: (A) 100 parts by weight of an aliphatically unsaturated polyorganosiloxane composition comprising (A1) 25 to 100 parts by weight of a hexenyl-functional polyorganosiloxane having the unit formula (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d (SiO 4 / 2 ) e wherein R 1 is an alkyl group, R 2 is a hexenyl group, subscript a is 0 to 4, subscript b is 0 to 4, subscript c is 0 to 400, subscript d is 0 to 50, and subscript e is 0 or 1, provided that (a+b) = 2 to 4, (b+d) > 2, (a+b+c+d) is 15 to 400, and (A2) 0 to 75 parts by weight of a vinyl-functional polyorganosiloxane having the unit formula (R 1 3SiO 1 / 2 ) i (R 1 2R 3 SiO 1 / 2 ) f (R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h (SiO 4 / 2 ) j wherein R 1 is an alkyl group, R 3 is a vinyl group, subscript i is 0 to 4, subscript f is 0 to 4, subscript g is 0 to 1400, subscript h is 0 to 200, and subscript j is 0 or 1, provided that (i+f) = 2 to 4, (f+h) > 2, and (i+f+g+h) is 15 to 1400; (B) a polyorganohydrogensiloxane having a unit formula (R 1 3SiO 1 / 2 ) w (R 1 2HSiO 1 / 2 ) x (R 1 2SiO 2 / 2 ) y (R 1 HSiO 2 / 2 ) z wherein subscript w is 0, 1 or 2, subscript x is 0, 1 or 2, subscript y is 0 to 250, and subscript z is 1 to 250, provided that (w+x) = 2, (x+z) > 3, and the amount (w+x+y+z) is 10 to 300, the amount of the polyorganohydrogensiloxane being sufficient to provide a molar ratio of silicon-bonded hydrogen atoms in the polyorganohydrogensiloxane (B) to the combined amount of vinyl groups and hexenyl groups in the aliphatically unsaturated organopolysiloxane composition (A) of 1.2 / 1 to 3.0 / 1 (i.e., SiH / Vi ratio); (C) a hydrosilylation reaction catalyst in an amount sufficient to provide 10 ppm to 1000 ppm of platinum group metals, based on the combined weight of aliphatically unsaturated polyorganosiloxane composition (A) and polyorganohydrogensiloxane (B); (D) 0.02 parts by weight to 0.8 parts by weight of a hydrosilylation reaction inhibitor per 100 parts by weight of aliphatically unsaturated polyorganosiloxane composition (A); (E) water; (F) 0.4 parts by weight to 1.6 parts by weight of a buffer per 100 parts by weight of aliphatically unsaturated polyorganosiloxane composition (A); (G) 0 parts by weight to 3.0 parts by weight of a surfactant per 100 parts by weight of aliphatically unsaturated polyorganosiloxane composition (A); and (H) 0 parts by weight to 10.0 parts by weight of a polyvinyl alcohol per 100 parts by weight of aliphatically unsaturated polyorganosiloxane composition (A), provided that the combined amount of surfactant (G) and polyvinyl alcohol (H) is > 0.1 parts by weight per 100 parts by weight of aliphatically unsaturated polyorganosiloxane composition (A); and provided that the emulsion is free of stabilizers selected from aliphatic polyethers, (co)polyacrylamides, polysaccharides, and polyacrylates, and free of non-reactive organopolysiloxanes.

2. The emulsion of claim 1, wherein (C) the hydrosilylation reaction catalyst is selected from the group consisting of (C1) a metal selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium; (C2) a compound of the metal; (C3) a complex of the metal or the compound; and (C4) the compound or the complex microencapsulated in a resin matrix or a core-shell structure.

3. The emulsion of claim 1, wherein (D) the hydrosilylation reaction inhibitor is selected from the group consisting of (D1) an alkyne alcohol, (D2) a silylated alkyne alcohol, (D3) an ene-yne compound, (D4) a triazole, (D5) a phosphine, (D6) a thiol, (D7) a hydrazine, (D8) an amine, (D9) a fumarate, (D10) a maleate, (D11) an ether, (D12) carbon monoxide, and (D13) a combination of two or more thereof.

4. The emulsion of claim 1, wherein buffer (F) comprises a monoprotic acid or a polyprotic acid and a conjugate base of the monoprotic acid or polyprotic acid.

5. The emulsion of claim 1, wherein surfactant (G) is present and comprises a non-ionic surfactant.

6. The emulsion of claim 1, wherein polyvinyl alcohol (H) is present.

7. The emulsion according to claim 1, further comprising a starting material selected from the group consisting of (I) up to 1.0 parts by weight of a biocide per 100 parts by weight of the fatty group unsaturated polyorganosiloxane composition (A), (J) up to 0.2 parts by weight of an antifoam agent per 100 parts by weight of the fatty group unsaturated polyorganosiloxane composition (A), or both (I) and (J).

8. The emulsion according to any one of the preceding claims, wherein: said hexenyl-functional polyorganosiloxane (A1) comprises the unit formula (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d wherein subscript a is 0, 1 or 2, subscript b is 0, 1 or 2, subscript c is 0 to 400, and subscript d is 0 to 50, with the proviso that (a+b) = 2 to 4, (b+d) > 2, and (a+b+c+d) is 15 to 400; and said vinyl-functional polyorganosiloxane (A2) comprises the unit formula (R 1 3SiO 1 / 2 ) i (R 1 2R 3 SiO 1 / 2 ) f (R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h wherein subscript i is 0, 1, or 2, subscript f is 0, 1, or 2, subscript g is 0 to 1200, and subscript h is 0 to 200, with the provisos that (i+f)=2, (f+h)≥2, (i+f+g+h) is 15 to 1200.

9. The emulsion according to claim 8, wherein: Hexenyl-functional polyorganosiloxane (A1) is 50 to < 100 parts by weight of a hexenyl-terminated polydialkylsiloxane having the unit formula (R 1 2R 2 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c wherein subscript c is 15 to 400; and Vinyl functional polyorganosiloxane (A2) is > 0 to 50 parts by weight of a vinyl terminated polydialkylsiloxane having the unit formula (R 1 2R 3 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g wherein subscript g is 15 to 1200.

10. The emulsion according to claim 8, wherein: The hexenyl-functional polyorganosiloxane (A1) is > 50 to < 100 parts by weight of a poly(di-alkyl / alkyl hexenyl) siloxane having the unit formula 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d wherein subscript c is 0 to 400, subscript d is 2 to 50, and The vinyl-functional polyorganosiloxane (A2) is > 0 to < 50 parts by weight of a poly(di-alkyl / alkyl vinyl) siloxane having the unit formula (R 3 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h wherein subscript g is 0 to 1200 and subscript h is 2 to 200.

11. Use of the emulsion according to claim 9 or claim 10 on a paper substrate.

12. The emulsion according to claim 8, wherein: The hexenyl-functional polyorganosiloxane (A1) is > 25 to < 100 parts by weight of a poly(di-alkyl / alkyl hexenyl) siloxane having the unit formula 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d wherein subscript c is 0 to 400, subscript d is 2 to 50, and The vinyl-functional polyorganosiloxane (A2) is > 0 to < 75 parts by weight of a poly(di-alkyl / alkyl vinyl) siloxane having the unit formula (R 3 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g (R 1 R 3 SiO 2 / 2 ) h wherein subscript g is 0 to 1200 and subscript h is 2 to 200.

13. The emulsion according to claim 8, wherein: Hexenyl-functional polyorganosiloxane (A1) is a poly(di-alkyl / alkyl hexenyl) siloxane having the unit formula 2 R 1 2SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d wherein subscript c is 0 to 400 and subscript d is 2 to 50; and The vinyl-functional polyorganosiloxane (A2) is a vinyl-dialkylsiloxy-terminated polydialkylsiloxane having the unit formula 1 2R 3 SiO 1 / 2 )2(R 1 2SiO 2 / 2 ) g where R 1 is an alkyl group, R 3 is a vinyl group, and the subscript g is from 15 to 1200.

14. Use of the emulsion according to claim 12 or claim 13 on a plastic substrate.

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