Hardened silicone-(meth)acrylate composition and method for its preparation and use

Abstract

The curable silicone-(meth)acrylate pressure-sensitive composition is curable via a hydrosilylation reaction to form a silicone-(meth)acrylate pressure-sensitive adhesive having initial adhesion. When the silicone-(meth)acrylate pressure-sensitive adhesive is exposed to actinic radiation, the resulting silicone-(meth)acrylate adhesive has subsequent adhesion that is greater than the initial adhesion.

Description

Technical Field

[0001] Cross - reference to related applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 813,67 filed on September 22, 2020, under 35 U.S.C. § 119(e). U.S. Provisional Patent Application No. 63 / 081,367 is hereby incorporated by reference herein.

[0002] The present invention relates to a curable silicone - (meth) acrylate composition (composition) suitable for the formation of silicone - (meth) acrylate pressure - sensitive adhesives (PSAs). More particularly, the present invention relates to a composition suitable for the formation of active - energy - ray - sensitive PSAs. The composition and the PSA are useful in methods for manufacturing (opto) electronic devices.

Background Art

[0003] Silicone compositions suitable for the formation of pressure - sensitive adhesives have been reported heretofore. These silicone compositions typically contain at least two main components, namely, a linear siloxane polymer and a tackifying resin consisting essentially of triorganosiloxane units of the formula R3SiO 1 / 2 (wherein R represents a monovalent hydrocarbon group), and silicate (Q) units of the formula SiO 4 / 2 . In addition to the above two components, these silicone compositions generally have some cross - linking means for curing the silicone composition to produce a pressure - sensitive adhesive.

[0004] Problems to be Solved by the Invention The above - mentioned conventional pressure - sensitive adhesives generally have a constant (or nearly constant) adhesive strength after curing. The adhesive strength is typically lower than that of ordinary (permanent) adhesives, and it is difficult to further increase the adhesive strength of the conventional pressure - sensitive adhesives after curing the above - mentioned silicone composition. This poses limitations on the use of conventional pressure - sensitive adhesives in various applications.

[0005] For example, when manufacturing (opto)electronic devices, the relatively low adhesion strength of pressure-sensitive adhesives is desirable for reworkability during the manufacturing process, and then (at the end of the process), a higher adhesion strength is desired for the long-term actual use of the device. Also, in the application of a protective film for the long-term use of a display with a curved edge, conventional pressure-sensitive adhesives may have the drawback of peeling at the curved edge due to the restoring force of the rigid substrate used for the protective film. Therefore, for a display with a curved edge, a higher holding strength in the adhesive layer in the protective film (compared to conventional PSAs) is required. Further, in some applications, when it is difficult to use a liquid flowable adhesive, an adhesive in the form of a sheet (or in a solid state) is desirable. Accordingly, there is a need in the industry for a curable composition capable of forming a pressure-sensitive adhesive having increased adhesion properties, which can initiate an increase in adhesion upon exposure to a trigger such as active energy rays (e.g., UV light) when desired. SUMMARY OF THE INVENTION

[0006] The curable silicone-(meth)acrylate pressure-sensitive adhesive composition (the composition) is suitable for the formation of a silicone-(meth)acrylate pressure-sensitive adhesive (PSA). The composition and a method for preparing the same are provided. A method for preparing and using the PSA from the composition is also provided. DETAILED DESCRIPTION OF THE INVENTION

[0007] The above composition comprises (A) a linear or substantially linear polydiorganosiloxane polymer having at least two aliphatic unsaturated hydrocarbon groups per molecule, having a unit formula (R 4 3SiO 1 / 2 ) m (R 4 2R 3 SiO 1 / 2 ) n (R 4 2SiO 2 / 2 ) o (R 4 R 3 SiO 2 / 2 ) p (R4 SiO 3 / 2 ) q (R 3 SiO 3 / 2 ) r (SiO 4 / 2 ) s containing, wherein each R 4 is an independently selected monovalent hydrocarbon group containing no aliphatic unsaturation, each R 3 is an independently selected aliphatic unsaturated monovalent hydrocarbon group, and the subscripts m, n, o, p, q, r, and s represent the number of each unit in the formula, having values of 0 ≦ m, 0 ≦ n, and number (m + n) ≧ 2, 0 < o < 10,000, p ≧ 0, number (o + p) is 100 to 10,000, 0 ≦ q ≦ 100, 0 ≦ r ≦ 100, and 0 ≦ s ≦ 100, provided that when any one or more of the subscripts q, r, or s is greater than 0, the ratio (o + p) / (q + r + s) is 50 / 1 to 10,000 / 1, a polydiorganosiloxane polymer, and (B) A (meth)acryloxyalkyl-functional polydiorganosiloxane resin having a unit formula (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 R 2 SiO 2 / 2 ) c (R 1 2SiO 2 / 2 ) d (R 2 SiO 3 / 2 ) e (R 1 SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h containing, wherein each R 1 is an independently selected monovalent hydrocarbon group, each R 2is an independently selected (meth)acryloyloxyalkyl group, each Z is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 6 carbon atoms, and the subscripts a, b, c, d, e, f, g, and h represent the relative molar amounts of each unit, with subscript a≥0, subscript b≥0, subscript c≥0, subscript d≥0, subscript f≥0, subscript g≥0, subscript h≥0, and the number (a + b + c + d + e + f + g + h)=100, provided that 10≥(b + c + e)≥0.5 and 99.5>(f + g)≥30. The starting materials (A) and (B) are present in the composition in an amount sufficient to provide a weight ratio of (B) resin / (A) polymer of 0.15 / 1 to <22 / 1 (resin / polymer ratio), a (meth)acryloyloxyalkyl-functional polyorganosiloxane resin, (C) is a polyorganohydrogensiloxane having the unit formula (R 5 3SiO 1 / 2 ) t (R 5 2HSiO 1 / 2 ) u (R 5 2SiO 2 / 2 ) v (R 5 HSiO 2 / 2 ) w (R 5 SiO 3 / 2 ) x (HSiO 3 / 2 ) y (SiO 4 / 2 ) z and in the formula, each R 5is a monovalent hydrocarbon group selected independently, and the subscripts t, u, v, w, x, y, and z represent the number of each unit in the formula, where t≧0, u≧0, v≧0, w≧0, x≧0, y≧0, z≧0, the number (u + w + y)≧2, and 2,000≧(t + u + v + w + x + y + z)≧3. The polyorganohydrogensiloxane is present in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms to reactive groups (SiH / reactive group ratio) in the starting material (C) of 0.05 / 1 to 2 / 1. The reactive groups are the combined aliphatic unsaturated monovalent hydrocarbon groups in the starting material (A) and the (meth)acryloxyalkyl groups in the starting material (B). The polyorganohydrogensiloxane and, a hydrosilylation reaction catalyst in an amount sufficient to provide 1 ppm to 1,000 ppm of a platinum group metal based on the total weight of the starting materials (A), (B), (C), (D), (E), and (F) in the composition (D); a photoinitiator in an amount sufficient to provide 0.01% to 10% based on the total weight of the starting materials (A), (B), (C), (D), (E), and (F) in the composition (E); a hydrosilylation reaction inhibitor in an amount sufficient to provide 5 ppm to 2% based on the total weight of the starting materials (A), (B), (C), (D), (E), and (F) in the composition (F).

[0008] The composition may optionally further include one or more additional starting materials selected from the group consisting of (G) a radical scavenger, (H) a solvent, (I) a non-functional polyorganosilicate resin, and combinations of two or more of (G), (H), and (I).

[0009] (A) Polymer The starting material (A) in the composition is a linear or substantially linear polydiorganosiloxane polymer (polymer) having at least two aliphatic unsaturated hydrocarbon groups per molecule. Such a polymer has a unit formula (R 4 3SiO 1 / 2 ) m (R 4 2R 3 SiO 1 / 2 )n (R 4 2SiO 2 / 2 ) o (R 4 R 3 SiO 2 / 2 ) p (R 4 SiO 3 / 2 ) q (R 3 SiO 3 / 2 ) r (SiO 4 / 2 ) s containing, wherein each R 4 is an independently selected monovalent hydrocarbon group containing no aliphatic unsaturation, each R 3 is an independently selected aliphatic unsaturated monovalent hydrocarbon group, the subscripts m, n, o, p, q, r, and s represent the number of each unit in the formula, having values of 0 ≦ m, 0 ≦ n, and number (m + n) ≧ 2, 0 < o < 10,000, p ≧ 0, number (o + p) is 100 to 10,000, 0 ≦ q ≦ 100, 0 ≦ r ≦ 100, and 0 ≦ s ≦ 100, provided that when any one or more of the subscripts q, r, or s is greater than 0, the ratio (o + p) / (q + r + s) is 50 / 1 to 10,000 / 1. Alternatively, the polydiorganosiloxane may not contain T and / or Q units, for example, when subscript q = 0, subscript r = 0, and subscript s = 0. Alternatively, subscript m may be 0. Alternatively, subscript n may be 2. Alternatively, the number (n + o + p) may be sufficient to provide a polymer having an aliphatic unsaturated group content (e.g., vinyl content) of 0.01% to 0.5% based on the weight of the starting material (A).

[0010] R 3 Examples of suitable aliphatic unsaturated monovalent hydrocarbon groups for R 3 include alkenyl groups and alkynyl groups. Examples of suitable alkenyl groups include vinyl, allyl, and hexenyl. Examples of suitable alkynyl groups include ethynyl and propynyl. Alternatively, each R 3 may be an independently selected alkenyl group. Alternatively, each R3 may be vinyl.

[0011] R 4 The monovalent hydrocarbon group of may be an alkyl group or an aryl group. Suitable alkyl groups are exemplified by, but not limited to, methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl and / or tert-pentyl), hexyl, and branched saturated hydrocarbon groups having 6 carbon atoms. Alternatively, the alkyl group may be methyl, ethyl, or propyl. Suitable aryl groups are exemplified by, but not limited to, phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl. Alternatively, each R 4 may be a methyl group or a phenyl group. Alternatively, each R 4 may be methyl.

[0012] The starting material (A) is an alkenyl-functional polydiorganosiloxane, for example, i) bis-dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), iii) bis-dimethylvinylsiloxy-terminated polymethylvinylsiloxane, iv) bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), v) bis-trimethylsiloxy-terminated polymethylvinylsiloxane, vi) bis-dimethylvinylsiloxy-terminated poly(methylphenylsiloxane / methylvinylsiloxane), vii) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenylmethylvinyl-siloxy-terminated polydimethylsiloxane, x) Bis-dimethylhexenylsiloxy-terminated polydimethylsiloxane, xi) Bis-dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xii) Bis-dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane, xiii) Bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xiv) Bis-trimethylsiloxy-terminated polymethylhexenylsiloxane, xv) Bis-dimethylhexenyl-siloxy-terminated poly(methylphenylsiloxane / methylhexenylsiloxane), xvi) Bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xvii) Bis-dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), xviii) Dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), and xix) may include a combination of two or more of i) to xviii).

[0013] The method for preparing the above-mentioned linear alkenyl-functional polydiorganosiloxane for the starting material (A), for example, hydrolysis and condensation of the corresponding organohalosilane and oligomer, or equilibration of cyclic polydiorganosiloxane, are known in the art. For example, reference is made to U.S. Patent Nos. 3,284,406, 4,772,515, 5,169,920, 5,317,072, and 6,956,087, which disclose the preparation of linear polydiorganosiloxanes having alkenyl groups. Examples of linear polydiorganosiloxanes having alkenyl groups are, for example, commercially available from Gelest Inc. (Morrisville, Pennsylvania, USA) under the trade names DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V-31, DMS-V33, DMS-V34, DMS-V35, DMS-V41, DMS-V42, DMS-V43, DMS-V46, DMS-V51, DMS-V52.

[0014] (B) Resin The starting material (B) in the composition described herein is a (meth)acryloxyalkyl-functional polyorganosiloxane resin having the unit formula (R 1 3SiO 1 / 2 ) a (R 1 2R 2 SiO 1 / 2 ) b (R 1 R 2 SiO 2 / 2 ) c (R 1 2SiO 2 / 2 ) d (R 2 SiO 3 / 2 ) e (R 1 SiO 3 / 2 ) f (SiO 4 / 2 ) g (ZO 1 / 2 ) h and in the formula, each R 1 is an independently selected monovalent hydrocarbon group, and each R 2is an independently selected (meth)acryloxyalkyl group, each Z is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 6 carbon atoms, and the subscripts a, b, c, d, e, f, g, and h represent the relative molar amounts of each unit. The subscript a ≥ 0, the subscript b ≥ 0, the subscript c ≥ 0, the subscript d ≥ 0, the subscript e ≥ 0, the subscript f ≥ 0, the subscript g ≥ 0, the subscript h ≥ 0, and the number (a + b + c + d + e + f + g) = 100. However, 10 ≥ (b + c + e) ≥ 0.5 and 99.5 > (e + f + g) ≥ 30. Alternatively, the number (c + d) may be from 0 to 20. Alternatively, (e + f + g) may be from 30 to 90. Alternatively, the subscript a may be from 35 to 55. Alternatively, the subscript b may be 0. Alternatively, the subscript c may be from 1 to 10. Alternatively, the subscript d may be from 0 to 20. Alternatively, the subscript e may be from 0 to 5. Alternatively, the subscript f may be from 0 to 3. Alternatively, the subscript g may be from 35 to 50. The subscript h is not included in the relative molar ratio, and the subscript h may be from 0 to a value sufficient to provide up to 5 mol% of hydroxyl and / or alkoxy groups to the resin. Alternatively, the subscript h may be from 0 to 5, or from 0 to 1, or from 0 to 0.5.

[0015] Alternatively, the number (b + c + e) may be from 0.5 to 8. Without being bound by theory, if the units containing (meth)acrylic functional groups exceed 8 mol%, the compatibility with (A) polymer may deteriorate, and phase separation may occur after preparing PSA from the composition. Also, without being bound by theory, if the units containing (meth)acrylic functional groups are less than 0.5 mol%, it may not be sufficient to efficiently react with active energy rays such as (UV) light and cause the desired enhancement of adhesion.

[0016] R in the above unit formula 1Suitable monovalent hydrocarbon groups include aliphatic saturated monovalent hydrocarbon groups. Suitable aliphatic monovalent hydrocarbon groups include alkyl groups and aryl groups. The alkyl group may be branched, unbranched, or cyclic. Examples of alkyl groups include methyl, ethyl, propyl (including n-propyl and / or iso-propyl), butyl (including iso-butyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (including iso-pentyl, neopentyl, and / or tert-pentyl); and hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbon groups having 6 or more carbon atoms; and cyclic alkyl groups such as cyclopentyl or cyclohexyl. The alkyl group has at least 1 carbon atom. Alternatively, the alkyl group may have 1 to 12 carbon atoms, alternatively 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms, and alternatively 1 carbon atom. Alternatively, R 1 's monovalent hydrocarbon group may be as described above for R 4 . Alternatively, each R 1 may be alkyl, or methyl.

[0017] R 1 's aryl group includes hydrocarbon groups derived from arenes by removing hydrogen atoms from ring carbon atoms, or is such. Aryl is exemplified by, but not limited to, phenyl, naphthyl, benzyl, tolyl, xylyl, phenylethyl, phenylpropyl, and phenylbutyl. The aryl group has at least 5 carbon atoms. Monocyclic aryl groups may have 5 to 12 carbon atoms, or 6 to 9 carbon atoms, or 6 carbon atoms. Polycyclic aryl groups may have 9 to 17 carbon atoms, or 9 to 14 carbon atoms, or 9 to 12 carbon atoms.

[0018] Alternatively, for R 1 , the alkyl group may be methyl and the aryl group may be phenyl. Alternatively, each R 1may be independently selected from the group consisting of alkyl and aryl. Alternatively, the (B) resin may contain 70 mol% or more, or 90 mol% or more of all R 1 , or each R 1 may be methyl.

[0019] R 2 Suitable (meth)acryloxyalkyl groups are exemplified by methacryloxypropyl and acryloxypropyl.

[0020] Alternatively, the (B) polyorganosilicate resin is (R 1 3SiO 1 / 2 ) a (R 2 R 1 2SiO 1 / 2 ) b (SiO 4 / 2 ) g (ZO 1 / 2 ) h , (R 1 3SiO 1 / 2 ) a (R 1 R 2 SiO 2 / 2 ) d (SiO 4 / 2 ) g (ZO 1 / 2 ) h , (R 1 3SiO 1 / 2 ) a (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) g (ZO 1 / 2 ) h , (R 1 3SiO 1 / 2 ) a (R 2 R 1 2SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (SiO 4 / 2 ) g (ZO 1 / 2 ) h , (R1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d (SiO 4 / 2 ) g (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) g (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) c (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) g (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 2 R 1 2SiO 1 / 2 ) b (R 1 R 2 SiO 2 / 2 ) d (SiO 4 / 2 ) g (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 2 R 1 2SiO 1 / 2 ) b (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) g (ZO 1 / 2 ) h、(R 1 3SiO 1 / 2 ) a (R 1 R 2 SiO 2 / 2 ) d (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) g (ZO 1 / 2 ) h、 (R 1 3SiO 1 / 2 ) a (R 2 R 1 2SiO 1 / 2 ) b (R 2 SiO 3 / 2 ) f (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 1 R 2 SiO 2 / 2 ) d (SiO 4 / 2 ) g (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 2 SiO 3 / 2 ) f (R 1 SiO 3 / 2 ) e (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 2 R 1 2SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 2 SiO 3 / 2 ) f (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a(R 1 2SiO 2 / 2 ) c (R 1 R 2 SiO 2 / 2 ) d (R 2 SiO 3 / 2 ) f (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 2 SiO 3 / 2 ) f (R 1 SiO 3 / 2 ) e (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) c (R 2 SiO 3 / 2 ) f (R 1 SiO 3 / 2 ) e (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 2 R 1 2SiO 1 / 2 ) b (R 1 R 2 SiO 2 / 2 ) d (R 2 SiO 3 / 2 ) f (ZO 1 / 2 ) h 、(R 1 3SiO 1 / 2 ) a (R 2 R 1 2SiO 1 / 2 ) b (R 2 SiO 3 / 2 ) f (R 1 SiO 3 / 2 ) e (ZO1 / 2 ) h、 and (R 1 3SiO 1 / 2 ) a (R 1 R 2 SiO 2 / 2 ) d (R 2 SiO 3 / 2 ) f (R 1 SiO 3 / 2 ) e (ZO 1 / 2 ) h and may contain a unit formula selected from the group consisting of, wherein the subscripts a, b, c, d, e, f, g, and h are as described above. Alternatively, the number (b + d + e) is from 1 to a number sufficient to provide to the resin units containing up to 8 mol% of (meth)acrylic functional groups, i.e., the M' units of the formula (R 2 R 1 2SiO 1 / 2 ), the D' units of the formula (R 1 R 2 SiO 2 / 2 ), and / or the T' units of the formula (R 2 SiO 3 / 2 ). Alternatively, the number (b + d + e) may be from 2 to a number sufficient to provide up to a combined 8 mol% of M', D', and T' units to the resin. Alternatively, the number (b + d) may be from 2 to a number sufficient to provide up to a combined 8 mol% of M' and D' when e = 0. Alternatively, the number d may be from 2 to a number sufficient to provide up to 8 mol% of D' units to the resin when b = 0 and e = 0.

[0021] While not wishing to be bound by theory, the methyl group is believed to be non-reactive and is likely to provide wettability on the surface of the adherend and stability (e.g., no or minimal thermal shrinkage or decomposition) after heat treatment of the composition and exposure of the PSA to heat (e.g., after exposure to a temperature of up to 200 °C during the manufacturing process of an (opto)electronic device).

[0022] (B) The intermediates used to prepare the resin may have two, three, or four hydrolyzable substituents per molecule and can be, for example, diorganoalkoxysilanes, triorganoalkoxysilanes, and silanes having four hydrolyzable substituents, or alkali metal silicates. The intermediates may each have the formula R M 2SiX 1 2, R M SiX 1 3, SiX 1 4, where R M is selected from the group consisting of R 1 and R 2 above, and X 1 represents a hydrolyzable substituent. The silane having four hydrolyzable substituents may have the formula SiX 2 4, where each X 2 is halogen, alkoxy, or hydroxyl. A preferred alkali metal silicate is sodium silicate.

[0023] A method for preparing a (meth)acryloxyalkyl-functional polyorganosiloxane resin containing the above M', D', and T' units suitable for use as the starting material (B), for example, an equilibration reaction of a typical polyorganosiloxane resin that reacts with a (meth)acryloxyalkyl-functional alkoxysilane or halosilane under acidic or basic conditions, for example, a capping reaction, for example, a hydrolytic hydrolysis / condensation reaction after co-hydrolysis of a typical organohalosilane or organoalkoxysilane with a (meth)acryloxyalkyl-functional alkoxysilane or halosilane, and also, for example, a non-hydrolytic condensation reaction of a typical organohalosilane or organoalkoxysilane with a (meth)acryloxyalkyl-functional alkoxysilane or halosilane are known to those skilled in the art, and similar methods for preparing polyorganosiloxane resins are described in U.S. Patent Nos. 8,377,634 (Albaugh), 5,516,858 (Morita et al), 9,023,433 (Fu et al), 6,281,285 (Becker et al), 5,010,159 (Bank et al), 2,676,182 (Daudt, et al), 4,611,042 (Rivers-Farrell et al), and 4,774,310 (Butler, et al).

[0024] The (meth)acryloxyalkyl-functional alkoxysilane or halosilane used in the above method for preparing the (B) resin can be selected from 3-(chlorodimethylsilyl)propyl methacrylate (CAS#24636-31-5), 3-[dimethoxy(methyl)silyl]propyl methacrylate (CAS#14513-34-9), methacryloxypropylmethyldichlorosilane (CAS#18301-56-9), (3-acryloxypropyl)methyldichlorosilane (CAS#71550-63-5), 3-[dimethoxy(methyl)silyl]propyl acrylate (CAS#13732-00-8), 3-(trimethoxysilyl)propyl acrylate (CAS#4369-14-6), 3-[diethoxy(methyl)silyl]propyl methacrylate (CAS#65100-04-1), 3-(trimethoxysilyl)propyl methacrylate (CAS#2530-85-0), 3-(triethoxysilyl)propyl methacrylate (CAS#21142-29-0), methacryloxypropyltrichlorosilane (CAS#7351-61-3), (3-acryloxypropyl)trichlorosilane (CAS#38595-89-0).

[0025] Another method for preparing a resin containing M' units suitable for use as starting material (B) is a hydrosilylation reaction between a hydrosilyl (-SiH) functional polyorganosiloxane resin and a (meth)acrylic functional alkene or alkyne, or between an alkenyl functional polyorganosiloxane resin and a (meth)acrylic functional hydrosilane, as described in U.S. Patent No. 4,503,208 (Lin et al), "Macromolecular Materials and Engineering" by Hung-Wen et al, Vol. 292, Issue 5, pages 666-673 (2007). The (meth)acrylic functional alkene or alkyne can be selected from allyl methacrylate (CAS# 96-05-9) and propargyl acrylate (CAS# 10477-47-1). The (meth)acrylic functional hydrosilane for use in the hydrosilylation reaction can be selected from methacryloxypropyltris(dimethylsiloxy)silane (CAS# 17096-08-1) and 2-propenoic acid, 2-methyl-3-(1,1,3,3-tetramethyldisiloxanyl)propyl ester (CAS# 96474-12-3).

[0026] The resin prepared as described above has silicon-bonded hydroxyl groups, i.e., of the formula XSi 3 / 2 、XR M SiO 2 / 2 、and / or XR M 2SiO 1 / 2(wherein X is a hydroxyl group or an alkoxy group) may be contained. The resin may contain up to 5% of silicon-bonded hydroxyl groups or alkoxy groups. The concentration of silicon-bonded hydroxyl groups or alkoxy groups present in the polyorganosiloxane resin can be determined using Fourier Transform-Infra Red (FTIR) spectroscopy according to ASTM Standard E-168-16. For certain applications, the amount of silicon-bonded hydroxyl groups may desirably be 2% or less, or less than 0.7%, or less than 0.3%, or less than 1%, or 0.3% to 0.8%. By reacting the resin with a silane, disiloxane, or disilazane containing appropriate end groups, the silicon-bonded hydroxyl groups formed during the preparation of the resin can be converted to triorgano (e.g., trihydrocarbyl) siloxane groups or different hydrolyzable groups. The silane containing hydrolyzable groups may be added in a molar excess over the amount required to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin.

[0027] (B) The Mn of the resin depends on various factors including the type of hydrocarbon group represented by R M The Mn of the resin refers to the number average molecular weight measured using gel permeation chromatography (GPC) according to the procedure in Reference Example 1 in Column 31 of U.S. Patent No. 9,593,209 when the peak representing the neopentamer is excluded from the measurement. The Mn of the resin may be 500 g / mol to 5,000 g / mol. Alternatively, the Mn of the resin may be 1,000 g / mol to 4,000 g / mol.

[0028] When prepared, the resin contains the above units and the resin further contains units having silanol or alkoxysilane (silicon-bonded hydroxyl or alkoxy) groups and may contain low molecular weight molecules such as the neopentamer of the formula Si(OSiR M 3)4, wherein R MAs described above, when the low molecular weight molecules are characterized by gel permeation chromatography (GPC) method, they have an Mn of less than 500 g / mol and a fraction of less than 25%. Si as described in Reference Example 2 of Column 32 of U.S. Patent No. 9,593,209 29 The molar ratio of M and Q units can be measured using nuclear magnetic resonance (NMR) spectroscopy. In this case, the ratio is expressed as {M(resin) + (M(neopentamer)} / {Q(resin) + Q(neopentamer)}, and by adopting a characterization method that represents the molar ratio (M:Q ratio) of the total number of triorganosiloxy groups in the resin and neopentamer portions of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resin and neopentamer portions, based on the inclusion of organosiloxy groups in resinous and low molecular weight molecules, the molar ratios of M, M’, D, D’, T, T’, and Q of starting material (B) are represented.

[0029] Starting materials (A) and (B) are present in the composition in an amount sufficient to provide a weight ratio of (B) resin / (A) polymer (resin / polymer ratio) of 0.15 / 1 to <22 / 1, or 0.15 / 1 to 9 / 1, or 0.2 / 1 to 9 / 1, and or 0.2 / 1 to 4 / 1.

[0030] (C) Polyorganohydrogensiloxane The composition has the unit formula (R 5 3SiO 1 / 2 ) t (R 5 2HSiO 1 / 2 ) u (R 5 2SiO 2 / 2 ) v (R 5 HSiO 2 / 2 ) w (R 5 SiO 3 / 2 ) x (HSiO 3 / 2 ) y (SiO 4 / 2 ) z and further contains starting material (C) which is a polyorganohydrogensiloxane. In this unit formula, each R 5is a monovalent hydrocarbon group selected independently. Alternatively, each R 5 may be selected from the group consisting of an alkyl group and an aryl group. R 5 may be as described above for R 1 . The subscripts t, u, v, w, x, y, and z represent the number of each unit in the formula, and have values such that t≧0, u≧0, v≧0, w≧0, x≧0, y≧0, z≧0, the number (u + w + y)≧2, and 2,000≧(t + u + v + w + x + y + z)≧3. Alternatively, the number (t + u + v + w + x + y + z) is sufficient to give the polyorganohydrogensiloxane a viscosity of 3 MPa·s to 1,000 MPa·s at 25°C, or 5 MPa·s to 500 MPa·s at 25°C. The viscosity can be measured at 0.1 to 50 RPM at 25°C with a Brookfield DV-III cone and plate viscometer equipped with a #CP-52 spindle. Those skilled in the art will recognize that the rotational speed decreases as the viscosity increases. Alternatively, the number (t + u + v + w + x + y + z) may be 3 to 2,000, or 3 to 1,000, or 3 to 500.

[0031] Alternatively, when the subscripts x = y = z = 0, the polyorganohydrogensiloxane has the unit formula (R 5 3SiO 1 / 2 ) t (R 5 2HSiO 1 / 2 ) u (R 5 2SiO 2 / 2 ) v (R 5 HSiO 2 / 2 ) w and may contain, where the subscript t is 0, 1, or 2, the subscript u is 0, 1, or 2, the number (t + u)=2, the subscript v≧0, the subscript w>0, and the number (u + w)≧3.

[0032] The polyorganohydrogensiloxanes for the starting material (C) are exemplified by (i) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (ii) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, (iii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) trimethylsiloxy-terminated polymethylhydrogensiloxane, and (v) combinations of two or more of (i) to (iv).

[0033] Methods for preparing polyorganohydrogensiloxanes suitable for use as the starting material (C), such as hydrolysis and condensation of organohalosilanes, are well known in the art and are exemplified in U.S. Patent Nos. 5,310,843, 4,370,358, 4,707,531, and 4,329,273. Further, polyorganohydrogensiloxanes are known in the art and are commercially available, for example, from Dow Silicones Corporation (Midland, Michigan, USA), and similarly, from Gelest, Inc. (Morrisville, Pennsylvania, USA) under the trade names HMS-301, DMS-HM15, DMS-H03, DMS-H25, DMS-H31, and DMS-H41. See also pages 18-21 of the same Reactive Silicones publication referenced above. Linear and cyclic polydiorganohydrogensiloxanes can also be prepared as described, for example, in U.S. Patent Nos. 2,823,218 (Speier, et al.) and 4,329,273.

[0034] The polyorganohydrogensiloxane is present in an amount sufficient to provide a molar ratio (SiH / reactive group ratio) of silicon-bonded hydrogen atoms in the starting material (C) to the reactive groups in the composition of from 0.05 / 1 to 2 / 1. As used herein, the term "reactive group" collectively means the aliphatic unsaturated monovalent hydrocarbon groups and (meth)acryloxyalkyl groups (i.e., R in the formula described above for the starting material (B)) present in the above starting materials. Alternatively, the SiH / reactive group ratio may be at least 0.05 / 1, or at least 0.1 / 1, and / or at least 0.2 / 1. At the same time, the SiH / reactive group ratio may be at most 2 / 1, or at most 1 / 1, and / or at most 0.9 / 1. Alternatively, the SiH / reactive group ratio may be from 0.1 / 1 to 2 / 1, or from 0.1 / 1 to 1 / 1, or from 0.2 / 1 to 1 / 1, or from 0.1 / 1 to 0.9 / 1, and / or from 0.2 / 1 to 0.9 / 1. 2 represented by).

[0035] (D) Hydrosilylation reaction catalyst The starting material (D) in the composition is a hydrosilylation reaction catalyst. Examples of the hydrosilylation reaction catalyst include platinum group metal catalysts. For example, the hydrosilylation reaction catalyst may be a metal selected from (Di) platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the hydrosilylation reaction catalyst may be (Dii) a compound of such a metal, such as chlorotris(triphenylphosphine)rhodium(I) (Wilkinson's catalyst), [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphospino)ethane]dichlorodirhodium, etc. rhodium diphosphine chelates, chloroplatinic acid (Speier's catalyst), chloroplatinic acid hexahydrate, platinum dichloride; or (Diii) a complex of such a compound and a low molecular weight organopolysiloxane. Alternatively, the hydrosilylation reaction catalyst may be (Div) a compound microencapsulated in a matrix or core / shell type structure. For example, examples of the complex of platinum and a low molecular weight organopolysiloxane include the platinum complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst). Alternatively, the hydrosilylation reaction catalyst may be (Dv) a complex microencapsulated in a resin matrix. Exemplary hydrosilylation reaction catalysts are described in U.S. Patent Nos. 3,159,601, 3,220,972, 3,296,291, 3,419,593, 3,516,946, 3,814,730, 3,989,668, 4,766,176, 4,784,879, 5,017,654, 5,036,117, and 5,175,325, and European Patent No. 0 347 895 (B). Suitable hydrosilylation reaction catalysts are known in the art and are commercially available. For example, SYS-OFF (trademark) 4000 catalyst and SYL-OFF (trademark) 2700 are available from Dow Silicones Corporation (Midland, Michigan, USA).

[0036] The amount of the hydrosilylation reaction catalyst used in the present specification depends on various factors including the selection of starting materials (A), (B), and (C), the respective contents of the aliphatic unsaturated monovalent hydrocarbon group and the silicon-bonded hydrogen atom, and the presence or absence of a hydrosilylation reaction inhibitor. However, the amount of the catalyst is sufficient to catalyze the hydrosilylation reaction of SiH and the aliphatic unsaturated monovalent hydrocarbon group, or the amount of the catalyst provides from 1 ppm to 1000 ppm, or based on the same criterion, from 2 ppm to 500 ppm, or from 10 ppm to 100 ppm of a platinum group metal based on the total weight of starting materials (A), (B), (C), (D), (E), and (F) in the composition.

[0037] (E) Photo radical initiator The starting material (E) in the composition is a photoinitiator. Suitable photoinitiators include benzophenone derivatives, acetophenone derivatives (α-hydroxy ketones), benzoin and its alkyl esters, phosphine oxide derivatives, xanthone derivatives, oxime ester derivatives, and UV initiators such as camphorquinone. The photoinitiator is commercially available.For example, suitable photoinitiators for use in this specification include 2,6-bis(4-azidobenzylidene)cyclohexanone, 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone, 1-hydroxy-cyclohexyl-phenyl-ketone (OMNIRAD™ 184), 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one (OMNIRAD™ 907); 2-hydroxy-2-methyl-1-phenyl-propan-1-one (OMNIRAD™ 1173); a mixed initiator of 50% OMNIRAD™ 184C and 50% benzophenone (OMNIRAD™ 500); a mixed initiator of 20% OMNIRAD™ 184C and 80% OMNIRAD™ 1173 (OMNIRAD™ 1000); 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (OMNIRAD™ 2959); methyl benzoylformate (OMNIRAD™ MBF); alpha,alpha-dimethoxy-alpha-phenylacetophenone (OMNIRAD™ 651); 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (OMNIRAD™ 369); a mixed initiator of 30% OMNIRAD™ 369 and 70% OMNIRAD™ 651 (OMNIRAD™ 1300); diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (OMNIRAD™ TPO), ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (OMNIRAD™ TPO-L), oxime ester compounds (N-1919, NCI-831, NCI-930, NCI-730, and NCI-100 supplied by Adeka Corporation), thioxanthen-9-one; 10-methylphenothiazine; isopropyl-9H-thioxanthen-9-one; 2,4-diethyl-9H-thioxanthen-9-one; 2-chlorothioxanthen-9-one; 1-chloro-4-propoxy-9H-thioxanthen-9-one; or a combination of two or more of these may be mentioned.The photoinitiator of the OMNIRAD (trademark) brand is commercially available from IGM Resins B.V. (Netherland). Alternatively, the photoinitiator may be selected from the group consisting of (Ei) benzophenone, (Eii) a substituted benzophenone compound, (Eiii) acetophenone, (Eiv) a substituted acetophenone compound, (Ev) benzoin, (Evi) an alkyl ester of benzoin, (Evii) a substituted phosphine oxide compound, (Eviii) xanthone, and (Eix) a substituted xanthone, (Ex) a substituted oxime ester compound, and (Exi) a combination of two or more of (Ei) to (Ex). Alternatively, the photoinitiator may be a substituted acetophenone such as 1-hydroxycyclohexyl phenyl ketone. The type of the photoinitiator is not particularly limited, but some photoinitiators, particularly those containing a thioether, phosphinate, or phosphine oxide group, may inhibit the hydrosilylation reaction catalyst. When such a photoinitiator is included, it may be necessary to control an appropriate amount of the (D) hydrosilylation reaction catalyst, and / or the curing temperature / time may be adjusted.

[0038] The amount of the photoinitiator in the composition depends on various factors including the desired reaction rate, the photoinitiator used, and the selection and amount of the starting material (B) and the content of its (meth)acryloxyalkyl group. However, the amount may be from 0.01% to 10% based on the total weight of the starting materials (A), (B), (C), (D), (E), and (F) in the composition. Alternatively, the amount of the photoinitiator may be at least 0.1%, or at least 0.5%, and / or at least 1% on the same basis. At the same time, the amount of the photoinitiator may be at most 10%, or at most 8%, or at most 6%, or at most 5%, or at most 4%, and / or at most 3% on the same basis.

[0039] (F) Hydrosilylation reaction inhibitor The starting material (F) in the composition is a hydrosilylation reaction inhibitor. Hydrosilylation reaction inhibitors include acetylenic alcohols such as dimethylhexynol, and 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol (ETCH), and combinations thereof; cycloalkenyl siloxanes such as methylvinylcyclosiloxanes exemplified by 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and combinations thereof; en-yne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and combinations thereof; triazoles such as benzotriazole; phosphine; mercaptan; hydrazine; amines such as tetramethylethylenediamine, 3-dimethylamino-1-propene, n-methylpropargylamine, propargylamine, and 1-ethynylcyclohexylamine; dialkyl fumarates such as diethyl fumarate, and / or diallyl fumarate, and / or dialkoxyalkyl fumarates, maleic acid esters such as diallyl maleate and diethyl maleate; nitriles; ethers; carbon monoxide; alkenes such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols such as benzyl alcohol; and combinations thereof.

[0040] Alternatively, the hydrosilylation reaction inhibitor may be a silylated acetylene compound. Without being bound by theory, when a silylated acetylene compound is added, the yellowing of the reaction product prepared from the hydrosilylation reaction is considered to be reduced as compared to the reaction product by hydrosilylation of a starting material that does not contain a silylated acetylene compound or contains an organic acetylene alcohol inhibitor such as those described above. The silylated acetylene compounds are exemplified by (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)silane methylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane, bis(3-methyl-1-butyn-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-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. Alternatively, the silylated acetylene compounds are exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or combinations thereof.The silylated acetylene compounds useful as inhibitors in this specification can be prepared by methods known in the art. For example, U.S. Patent No. 6,677,407 discloses silylating the above acetylene alcohols by reacting chlorosilane with the above acetylene alcohols in the presence of an acid acceptor. Alternatively, the hydrosilylation reaction inhibitor may be selected from the group consisting of acetylene alcohols, cycloalkenyl siloxanes, enyne compounds, triazoles, phosphines, mercaptans, hydrazines, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, alcohols, and silylated acetylene alcohols. Alternatively, the hydrosilylation reaction inhibitor may be an acetylene alcohol such as ETCH.

[0041] The amount of the hydrosilylation reaction inhibitor used in the composition depends on various factors including the desired reaction rate, the specific hydrosilylation reaction inhibitor used, and the selection and amount of aliphatic unsaturated hydrocarbon groups and silicon-bonded hydrogen atoms in other starting materials in the composition. However, when present, the amount of the hydrosilylation reaction inhibitor may be at least 5 ppm, or at least 0.05%, or at least 0.1% based on the total weight of starting materials (A), (B), (C), (D), (E), and (F) in the composition. At the same time, the amount of the hydrosilylation reaction inhibitor may be at most 2%, or at most 1% on the same basis.

[0042] (G) Radical scavenger The starting material (G) is a radical scavenger that can be optionally added to the composition. The starting material (G) is a radical scavenger (scavenger) that can be used to control or inhibit the radical reaction of the composition. Since the composition contains reactive (meth)acrylate functional groups, a sustainable radical scavenger may be present, for example, to prevent premature reactions during storage and use of the protective film prepared using the composition. Further, the radical scavenger can also be used to prevent premature reactions during the reaction at high temperature during the production of the resin having (meth)acrylic functional groups which is the starting material (B). Scavengers containing phenolic compounds are, for example, 4-methoxyphenol (MEHQ, methyl ether of hydroquinone), hydroquinone, 2-methylhydroquinone, 2-t-butylhydroquinone, t-butylcatechol, butylated hydroxytoluene, and butylated hydroxyanisole, and combinations of two or more of them, and are one class of such materials that can be used in the present invention. Other scavengers that can be used include phenothiazines and oxygen-free inhibitors such as the NPAL type inhibitor (tris-(N-nitroso-N-phenylhydroxylamine) aluminum salt) manufactured by Albemarle Corporation (Baton Rouge, La). Alternatively, the radical scavenger may be selected from the group consisting of phenolic compounds, phenothiazines, and oxygen-free inhibitors. Alternatively, the radical scavenger may be selected from the group consisting of phenolic compounds, phenothiazines, and oxygen-free inhibitors.

[0043] Radical scavengers are known, for example, from U.S. Patent No. 9,475,968 and are commercially available. The amount of the scavenger in the composition depends on various factors including the type and amount of the (meth)acryloxyalkyl group in the starting material (B), but the scavenger may be present in an amount of 0.001 parts by weight to 0.1 parts by weight, or 0.001 parts by weight to 0.05 parts by weight per 100 parts by weight of the starting material (B).

[0044] (H) Solvent The starting material (H) is a solvent that can be optionally added to the composition. The solvent may be added during the preparation of the composition, for example, to assist in the mixing and delivery of one or more starting materials, and / or the solvent may be added after the preparation of the composition, for example, to facilitate coating onto a substrate, as described below. When preparing the composition, certain starting materials such as (B) resin and / or (C) hydrosilylation reaction catalyst can be delivered in a solvent. Suitable solvents include, but are not limited to, organic liquids exemplified by aromatic hydrocarbons, aliphatic hydrocarbons, ketones, esters, ethers, glycols, and glycol ethers. Hydrocarbons include benzene, toluene, xylene, naphtha, hexane, cyclohexane, methylcyclohexane, heptane, octane, decane, hexadecane, isoparaffin, such as Isopar L (C11 - C13), Isopar H (C11 - C12), and hydrogenated polydecene. Suitable ketones include, but are not limited to, acetone, methyl ethyl ketone, 2 - pentanone, 3 - pentanone, 2 - hexanone, 2 - heptanone, 4 - heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonylacetone, and cyclohexanone. Esters include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate. Ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2 - dimethoxyethane, and 1,4 - dioxane.Solvents having both an ester moiety and an ether moiety include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate. Ethers and esters further include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-propyl ether, propylene glycol-n-butyl ether, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (propylene glycol methylether acetate, PGMEA), propylene glycol methyl ether (propylene glycol methylether, PGME), dipropylene glycol methyl ether, or ethylene glycol n-butyl ether, octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, and octyl palmitate. Alternatively, the solvent may be selected from polyalkylsiloxanes, ketones, glycol ethers, tetrahydrofuran, mineral spirits, naphtha, or combinations thereof.A polyalkylsiloxane having a suitable vapor pressure may be used as a solvent, and examples thereof include hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, tetrakis(trimethylsiloxy)silane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{ (trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, and combinations thereof. Low molecular weight polyalkylsiloxanes such as polydimethylsiloxane having a viscosity of 0.5 to 1.5 cSt are known in the art and are commercially available as DOWSIL (trademark) 200 Fluids and DOWSIL (trademark) OS FLUIDS from Dow Silicones Corporation. Alternatively, the solvent may be selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters, and solvents having both ether and ester moieties. Alternatively, the solvent may be selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons.

[0045] The amount of the solvent varies depending on various factors including the type of the selected solvent and the amounts and types of other starting materials selected to adjust the viscosity of the coating. Alternatively, the amount of the solvent may be 0 to 300 parts by weight per 100 parts by weight of the total starting materials in the composition. Alternatively, the amount of the solvent may be 0.5 parts by weight to 200 parts by weight, or 20 parts by weight to 300 parts by weight per 100 parts by weight of the total starting materials in the composition.

[0046] (I) Non-functional polyorganosilicate resin The composition may optionally further comprise a non-functional polyorganosilicate resin which is the starting material (I). Without being bound by theory, it is believed that the non-functional polyorganosilicate resin may act as a tackifier that modifies the mechanical properties of the PSA (formed by curing the composition via a hydrosilylation reaction) and / or controls the initial adhesion strength. The starting material (I) is used in the composition in an amount sufficient to provide a weight ratio of (I) non-functional resin to (A) polydiorganosiloxane of 0.1 / 1 to 4 / 1 (non-functional resin / polymer ratio). The starting material (I) is a polyorganosilicate resin containing units of the formula (R 1 3SiO 1 / 2 ) p (SiO 4 / 2 ) q (ZO) h wherein R 1 , Z, and the subscript h are as described above, and the subscripts p and q have values such that the molar ratio (p / q) is 0.6 to <1.9 and Mw = 1,000 to 30,000 daltons. Such non-functional resins are known in the art and are commercially available. Such non-functional resins can be prepared as described above for the starting material (B), but by substituting the (meth)acrylic functional starting material with a starting material having an alkyl and / or aryl group, such as an alkyl halosilane such as methylchlorosilane and / or an alkyl alkoxysilane such as methylmethoxysilane.

[0047] (J) Anchor additive Optionally, the composition may further comprise an anchor additive (J) that can be added to improve adhesion to the substrate film. The starting material (J) is exemplified by a silane coupling agent such as methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, bis(trimethoxysilyl)propane, and bis(trimethoxysilyl)hexane, a mixture or reaction mixture of such a silane coupling agent and a siloxane compound having at least one silicon-bonded hydroxy group and a silicon-bonded alkenyl group. The anchor additive is commercially available. For example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is available from Dow Silicones as DOWSIL™ Z-6043 silane. The amount of the anchor additive, when present, may be from 0.05 to 5 parts by weight per 100 parts by weight of the total starting materials in the composition.

[0048] Method for producing the composition and PSA The composition can be prepared by a method that includes combining all the starting materials by any convenient means, such as mixing at RT or at elevated temperature. The hydrosilylation reaction inhibitor may be added before the hydrosilylation reaction catalyst, for example, when the composition is prepared at an elevated temperature and / or when the composition is prepared as a partial composition.

[0049] This method may further include delivering one or more starting materials (e.g., linear polydiorganosiloxane polymer (A), (meth)acryloxyalkyl-functional polydiorganosiloxane resin (B) and / or hydrosilylation reaction catalyst (D), and / or, if present, non-functional resin (I)) in a solvent, and these starting materials may be dissolved in the solvent when combined with one or more other starting materials in the composition. Optionally, then, all or substantially all of the solvent can be removed by conventional means such as stripping and / or distillation, optionally under reduced pressure). One skilled in the art will understand that the resulting composition may be solvent-free or may contain trace amounts of residual solvent from the delivery of the starting materials, but in certain cases, the solvent (e.g., an organic solvent such as toluene or non-functional polydiorganosiloxane) is not intentionally added to the composition. Alternatively, the composition may be a solvent-based system.

[0050] Alternatively, the composition may be prepared as a multi-liquid composition, for example, if the composition is stored for a long period before use, for example, up to 6 hours before coating the composition on a substrate. In a multi-liquid composition, the hydrosilylation reaction catalyst is stored in a separate part from any starting material having silicon-bonded hydrogen atoms, such as a polyorganohydrogensiloxane, and these parts are combined immediately before use of the composition.

[0051] For example, the multi-liquid composition may be prepared by combining starting materials including (A) a polymer, (C) a polyorganohydrogensiloxane, and optionally at least some of one or more other additional starting materials among the above, by any convenient method such as mixing, to form a base. The curing agent may be prepared by combining starting materials including (A) a polymer, (D) a hydrosilylation reaction catalyst, and optionally at least some of one or more other additional starting materials among the above, by any convenient method such as mixing. The starting materials may be mixed at ambient temperature or elevated temperature. The hydrosilylation reaction inhibitor may be included in one or more of the base, the curing agent part, or a separate additional part. The non-functional resin of the starting material (I), if present, may be added to the base, the curing agent part, or a separate additional part. The (meth)acryloxyalkyl-functional polyorganosiloxane resin of the starting material (B) may be added to the base. The photo radical initiator and (G) free radical scavenger may be added to the base or a separate additional (e.g., third) part. The anchor additive of the starting material (J), if present, may be added to the base.

[0052] When a two-part composition is used, the weight ratio of the amount of the base to the curing agent part can be in the range of 1:1 to 10:1. The composition cures by a hydrosilylation reaction to form a pressure-sensitive adhesive having initial adhesiveness. Curing is by heating the composition for a time sufficient to form a PSA via a hydrosilylation reaction at RT or at a temperature of 60°C to 220°C, or 70°C to 170°C, or 80°C to 160°C.

[0053] Preparation of an Adhered Article The above method may further include one or more additional steps. Using the composition prepared as described above, an adhesive article, for example, a pressure-sensitive adhesive (prepared by thermally curing the above composition), may be formed on a substrate. Thus, the method may further include applying the composition to the substrate.

[0054] Coating the composition on the substrate can be carried out by any convenient means. For example, the pressure-sensitive adhesive curable composition can be coated on the substrate by a gravure coater, an offset coater, an offset gravure coater, a roller coater, a reverse roller coater, an air knife coater or a curtain (slot die) coater.

[0055] The substrate can be any material that can withstand the curing conditions (described below) used to cure the composition to form PSA on the substrate. For example, any substrate that can withstand heat treatment at a temperature of 120 °C or higher, or 150 °C or higher, is suitable. Examples of suitable materials for such substrates include plastic films such as polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide (PAI), polyethersulfide (PES), polyethylene terephthalate (PET), polyethylene (PE), or polypropylene (PP). The thickness of the substrate is not critical, but the thickness may be 5 micrometers to 300 micrometers, or 25 micrometers to 300 micrometers. The substrate may be transparent, or a non-transparent substrate may be used as long as it allows the PSA to be exposed to UV irradiation.

[0056] To improve the bonding of the PSA to the substrate, the method for forming the adhesive article may optionally further include treating the substrate before applying the composition. The treatment of the substrate may be carried out by any convenient method such as applying a primer before applying the composition to the substrate, or subjecting the substrate to corona discharge treatment, etching, or plasma treatment.

[0057] An adhesive article such as a protective film or tape can be prepared by applying the above composition onto the above substrate. The method may optionally further include removing all or part of the solvent before and / or during curing (if a solvent is present). Removal of the solvent can be carried out by heating the composition at a temperature that vaporizes the solvent without completely curing the composition, for example, heating at a temperature of 70°C to 120°C, or 50°C to 100°C, or 70°C to 80°C for a time sufficient to remove all or part of the solvent (e.g., 30 seconds to 1 hour, or 1 minute to 5 minutes), or any convenient method. Then, the method further includes curing the composition (which may have a part or all of the solvent removed during the drying process) via a hydrosilylation reaction at RT or at a temperature of 60°C to 220°C, or 70°C to 170°C, or 80°C to 160°C for a time sufficient to form a PSA on the surface of the substrate (e.g., 30 seconds to 1 hour, or 15 minutes to 45 minutes). Drying and / or hydrosilylation reaction curing to remove all or part of the solvent may be carried out by placing the substrate in an oven. The amount of the composition applied to the substrate depends on the specific application, but the amount is sufficient such that after curing via the hydrosilylation reaction, the thickness of the PSA after curing can be 50 micrometers to 1,000 micrometers, or 100 micrometers to 700 micrometers, or 200 micrometers to 600 micrometers.

[0058] Accordingly, a method of forming an adhesive article (e.g., in the form of a protective film) comprising a PSA layer on the surface of a substrate is optionally, 1) treating the surface of the above substrate; 2) applying the above composition to the surface of the substrate; optionally, 3) removing all or part of the solvent, if present; 4) curing the composition via a hydrosilylation reaction to form a PSA layer on the surface of the substrate, and includes.

[0059] If desired, steps 2) to 4) of the above method may be repeated one or more times to increase the thickness of the PSA layer (the desired thickness is described in this specification). The above method may optionally further include, for example, applying a removable release liner to the PSA layer on the opposite side of the substrate to protect the PSA before use. The release liner may be removed before use of the adhesive article. The resulting PSA layer contains free (meth)acrylic functional groups that can be analyzed by Fourier transform infrared (FT-IR) spectroscopy, and the relative amount of the PSA film and its reaction when exposed to UV irradiation can be monitored by the absorption intensity of the vibration of the unsaturated bond in the FT-IR spectrum as shown below: "UV coatings: basics, recent developments and new applications", page 33 (Elsevier; December 21, 2006) to Schwalm; Polymer Chemistry. 2013; 4(8): 2449-56 to Espeel. The free (meth)acrylic functional groups in the PSA by using the starting material (B) are at about 1296 cm -1 and 938 cm -1 were detected.

[0060] Method of use The above method may further include using the protective film in a method of manufacturing an (opto)electronic device. This method may include exposing the PSA layer to active energy rays such as UV rays. For example, in a method of fabricating an (opto)electronic device, the improvement is 5) applying the protective film prepared as described above to the (opto)electronic device such that the PSA layer is in contact with the surface of the (opto)electronic device, 6) using the protective film to protect the device, and then 7) exposing the PSA layer to active energy rays such as UV rays. The adhesiveness increases as a result of the radiation exposure in step 6). A normal (permanent) adhesive may be formed.

[0061] The irradiation in step 7) may be carried out using a general ultraviolet irradiation device, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, an ultraviolet light-emitting diode, etc. as a light source, using a counter-type or conveyor belt-type ultraviolet irradiation device. The ultraviolet irradiation dose is generally 0.1 to 10 W / cm 2 for 0.1 second to 120 seconds (=0.1 to 1200 J / cm 2 ).

Examples

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

[0063]

Table 1-1

[0064]

Table 1-2

[0065] Comparative Reference Example 1: Preparation of Starting Material A'-5 In this Example A, the bis-vinyldimethylsiloxy-terminated poly(dimethyl / methyl, methacryloxypropyl) siloxane copolymer shown as Comparative Starting Material A'-5 in Table 1 above was synthesized as follows. Into a four-necked 1-liter round-bottom flask, 3-methacryloxypropylmethyldimethoxysilane (108.92 g, DOWSIL™ Z-6033) and 0.1 N HCl (128.87 g) were added and mixed using a magnetic stir bar at about 23 °C. Using a simple distillation glassware setup, the vacuum was drawn down to about 20 mmHg over 1.5 hours. After 1.5 hours, the vacuum was released and bis-hydroxyl-terminated polydimethylsiloxane (1179.75 g, OH fluid in Table 1) was added to the reaction solution along with 0.34 g of (G-1) MEHQ. The magnetic stir bar was removed and the solution was mixed using a Teflon paddle with a glass stirring rod. The vacuum was drawn down to about 5 mmHg and the reaction was heated at 80 °C over 1.5 hours. The simple distillation glassware setup was disassembled and a Dean-Stark distillation setup was used for the final reaction step. To the reaction solution, (H-1) toluene (380 g, Sigma-Aldrich) and bis-dimethylvinylsiloxy-terminated polydimethylsiloxane (2.87 g, endblock in Table 1) were added. The solution was then heated to 111 - 115 °C and when the temperature reached 90 °C, 0.3 mL of phosphazen catalyst was added. The overhead was collected in the Dean-Stark trap and an additional 0.3 mL of phosphazen catalyst was added. The solution was held under toluene reflux for 1 hour. The heat was removed and the solution was cooled. At about 60 °C, trihexylamine (0.3 g, Sigma-Aldrich) was added to the reaction solution and mixed for 2 hours. Then, the solution was heated to 120 °C over 1 hour while blowing in nitrogen / 2% oxygen gas and cooled to room temperature. The solid content of the solution was adjusted to 75% by adding additional toluene. Then, the resulting resin solution (resin 75% / solvent 25%) was identified as having a unit formula M Vi D MA 232 D Me 2488 M Vi and was identified as such.

[0066] Reference Example 1: Preparation of Starting Material B-1 In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a Dean-Stark trap, 375.31 g of a solution containing 75% (I-1) MQ resin dissolved in 25% xylene, 1.5 g of 11N KOH aqueous solution, and a mixture with toluene were refluxed for 2 hours to remove water. 46.47 g of Z-6033 and 0.11 g of (G-1) MEHQ were added to the mixture, and the resulting mixture was refluxed for 5 hours. After cooling to below 50 °C, toluene, methanol, and water were added, and the mixture was refluxed at 73 °C for 1 hour. Methanol and water were removed together with toluene. Toluene corresponding to the lost toluene was added to the mixture together with methanol and water. The resulting mixture was refluxed for an additional 3 hours. After cooling to room temperature, acetic acid was added. The mixture was stirred for 1 hour and then filtered. The resulting resin solution (resin 75% / solvent 25%) has a unit formula M Me 49.6 D MA 3.9 Q 46.5 (OH) 0.45 (OCH3) 0.03 and was identified by GPC to have a Mn of 2047, a Mw / Mn of 1.425, and a solid content of 75% (B-1 in Table 1 above).

[0067] Reference Example 2: Preparation of Starting Material B-2 In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, a mixture of 92.94 g of Z-6030, a solution containing 75% (I-1) MQ resin dissolved in 375.31 g of 25% xylene, 15 g of water, and 0.11 g of (G-1) MEHQ was placed in the flask, and 0.6 g of trifluoromethanesulfonic acid (Aldrich) was added to the mixture while stirring at room temperature. Next, the temperature was raised to 47 °C. After 1 hour, the mixture was cooled to room temperature, 25.62 g of methanol, 1.5 g of 11N aqueous KOH solution, and toluene were sequentially added, and the mixture was refluxed for 2 hours. After replacing the Dean-Stark trap with the condenser, the temperature was gradually raised to 125 °C to remove water containing methanol and toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to room temperature, acetic acid was added. After stirring the mixture for 1 hour, it was filtered. The resulting resin solution (resin 75% / solvent 25%) has a unit formula M Me 47.7 D MA 8.7 Q 43.6 (OH) 0.75 and was identified by GPC to have a Mn of 2095, a Mw / Mn of 1.327, and a solid content of 75% (B-2 in Table 1 above).

[0068] Reference Example 3: Preparation of Starting Material B-3 In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, a mixture of 24.84 g of Z-6030, a solution containing 75% (I-1) MQ resin dissolved in 375.31 g of 25% xylene, 7 g of water, and 0.11 g of (G-1) MEHQ was placed in the flask, and 0.5 g of trifluoromethanesulfonic acid (Aldrich) was added to the mixture while stirring at room temperature. Next, the temperature was raised to 47 °C. After cooling the mixture to room temperature for 1 h, 25.62 g of methanol, 1.44 g of 11N aqueous KOH solution, and toluene were sequentially added, and the mixture was refluxed for 2 h. After replacing the Dean-Stark trap with the condenser, the temperature was gradually raised to 125 °C to remove water containing methanol and toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 h. After cooling to room temperature, acetic acid was added. After stirring the mixture for 1 h, it was filtered. The resulting resin solution (resin 75% / solvent 25%) has the unit formula M Me 52 T MA 2.1 Q 45.9 (OH) 0.92 and was identified by GPC to have a Mn of 2131, a Mw / Mn of 1.47, and a solids content of 75% (B-3 in Table 1 above).

[0069] Reference Example 4: Preparation of Starting Material B-4 In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, a mixture of 49.67 g of Z-6030, 13 g of water, and 0.1 g of (G-1) MEHQ was placed in the flask, and 0.5 g of trifluoromethanesulfonic acid was added to the mixture while stirring at RT. Next, the temperature was gradually raised to 47 °C. After cooling to RT, a solution containing 75% (I-1) MQ resin dissolved in 375.31 g of 25% xylene, 25.62 g of methanol, 1.5 g of 11N aqueous KOH solution, and toluene were added in sequence, and the mixture was refluxed for 2 hours. After replacing the Dean-Stark trap with a condenser, the temperature was gradually raised to 125 °C to remove water containing methanol and toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 12 hours. After cooling to room temperature, acetic acid was added. After stirring the mixture for 1 hour, it was filtered. The resulting resin solution (resin 75% / solvent 25%) has the unit formula M Me 50.2 T MA 4.6 Q 45.2 (OH) 0.83 and was identified by GPC to have a Mn of 2324, a Mw / Mn of 1.48, and a solids content of 75% (B-4 in Table 1 above).

[0070] Reference Example 5: Preparation of Starting Material B-5 In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, a mixture of 116.18 g of Z-6030, 81.70 g of bis-hydroxyl-terminated polydimethylsiloxane (DP = 11), 18 g of water, and 0.13 g of (G-1) MEHQ was placed in the flask, and 0.6 g of trifluoromethanesulfonic acid was added to the mixture while stirring at room temperature. Next, the temperature was gradually raised to 47 °C. After cooling to RT, a solution containing 75% (I-1) MQ resin dissolved in 375.31 g of 25% xylene, 32.02 g of methanol, 1.73 g of 11N KOH aqueous solution, and toluene were added in order, and refluxed for 2 hours. After replacing the Dean-Stark trap with a condenser, the temperature was gradually raised to 125 °C to remove water containing methanol and toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to room temperature, acetic acid was added. After stirring the mixture for 1 hour, it was filtered. Toluene and xylene were evaporated at 100 °C under reduced pressure for 2 hours. The resulting viscous resin had the unit formula M Me 38.1 D MA 8.8 D Me 17.3 Q 35.8 (OH) 0.97 and was identified by GPC to have a Mn of 2079, a Mw / Mn of 1.45, and a solids content of 75% (B-5 in Table 1 above).

[0071] Reference Example 6: Preparation of Starting Material B-6 In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, a mixture of 46.47 g of Z-6030, 81.70 g of bis-hydroxyl-terminated polydimethylsiloxane (DP = 11), 8.7 g of water, and 0.13 g of (G-1) MEHQ was placed in the flask, and 0.6 g of trifluoromethanesulfonic acid was added to the mixture while stirring at RT. Next, the temperature was gradually raised to 47 °C. After cooling to RT, a solution containing 75% (I-1) MQ resin dissolved in 375.31 g of 25% xylene, 50 g of methanol, 1.73 g of 11N aqueous KOH solution, and toluene were added in sequence, and the mixture was refluxed for 2 hours. After replacing the Dean-Stark trap with a condenser, the temperature was gradually raised to 125 °C to remove water containing methanol and toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to room temperature, acetic acid was added. The mixture was stirred for 1 hour and then filtered. Toluene and xylene were evaporated at 100 °C under reduced pressure for 2 hours. The resulting viscous resin has the unit formula M Me 40.1 D MA 3.7 D Me 18.8 Q 37.4 (OH) 0.91 and was identified by GPC to have a Mn of 2114, a Mw / Mn of 1.504, and a solid content of 75% (B-6 in Table 1 above).

[0072] Reference Example 7: Preparation of Starting Material B-7 In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, a mixture of 23.24 g of Z-6030, 4.3 g of water, and 0.11 g of (G-1) MEHQ was placed in the flask, and 0.5 g of trifluoromethanesulfonic acid was added to the mixture while stirring at RT. Next, the temperature was gradually raised to 47 °C. After cooling to RT, a solution containing 75% (I-1) MQ resin dissolved in 375.31 g of 25% xylene, 50 g of methanol, 1.44 g of 11N aqueous KOH solution, and toluene were added in sequence, and the mixture was refluxed for 2 hours. After replacing the Dean-Stark trap with a condenser, the temperature was gradually raised to 125 °C to remove water containing methanol and toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to room temperature, acetic acid was added. The mixture was stirred for 1 hour and then filtered. The resulting resin solution (resin 75% / solvent 25%) has the unit formula M Me 50.4 D MA 2.2 Q 47.4 (OH) 0.92 and was identified by GPC to have a Mn of 2082, a Mw / Mn of 1.347, and a solid content of 75% (B-7 in Table 1 above).

[0073] Reference Example 8: Preparation of Starting Material B-8 In a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, a mixture of 23.24 g of Z-6030, 81.70 g of bis-hydroxyl-terminated polydimethylsiloxane (DP = 11), 4.4 g of water, and 0.13 g of (G-1) MEHQ was placed in the flask, and 0.6 g of trifluoromethanesulfonic acid was added to the mixture while stirring at RT. Next, the temperature was gradually raised to 47 °C. After cooling to RT, a solution containing 75% (I-1) MQ resin dissolved in 375.31 g of 25% xylene, 50 g of methanol, 1.73 g of 11N KOH aqueous solution, and toluene were added in order, and refluxed for 2 hours. After replacing the Dean-Stark trap with a condenser, the temperature was gradually raised to 125 °C to remove water containing methanol and toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to room temperature, acetic acid was added. After stirring the mixture for 1 hour, it was filtered. The resulting resin solution (resin 75% / solvent 25%) has the unit formula M Me 41 D MA 1.8 D Me 18.4 Q 38.8 (OH) 0.95 and was identified by GPC to have a Mn of 2329, a Mw / Mn of 1.56, and a solids content of 75% (B-8 in Table 1 above).

[0074] In this Reference Example 9, a silicone-(meth)acrylate pressure-sensitive adhesive composition and a comparative composition were prepared. The starting materials (A) and (B) may be dissolved in a solvent. The general procedure is as follows. For the preparation of the sample labeled as Example 1, a solution was prepared by mixing the following starting materials in a mixer. First, the starting material (A-1) was dissolved in toluene (H-1) and mixed to obtain a 30% solution. Next, 133.33 g of a solution in which 100 g of the starting material (A-1) was dissolved in toluene (H-1), 23.66 g of a solution containing 17.75 g of the starting material (B-1) dissolved in a solvent, 0.59 g of polyorganohydrogensiloxane (C-1), and 0.05 g of a hydrosilylation reaction inhibitor (F-1) were mixed. After mixing the above starting materials, the resulting solution was further mixed with 1.18 g of a hydrosilylation reaction catalyst (D-1) and 3.55 g of a photoinitiator (E-1). By mixing the above starting materials with the aforementioned solution, a silicone-(meth)acrylate pressure-sensitive adhesive composition was prepared. This composition was used for the production of an adhesive tape. The adhesive tape was evaluated for its lamination properties and adhesive strength. The comparative examples, Examples 2 to 29, and Examples 32 to 38 were prepared in the same manner using the starting materials and amounts shown in the table. For the preparation of the solvent-free sample labeled as Example 30, a solution was prepared by mixing the following starting materials, namely, 400 g of a solution containing 100 g of the starting material (A-4) and 300 g of the starting material (B-1) in a mixer, and the solvent was evaporated under reduced pressure at 90°C for 3 hours. Then, 2.01 g of polyorganohydrogensiloxane (C-1) and 0.2 g of a hydrosilylation reaction inhibitor (F-1) were added. After mixing the above components, the resulting fluid was further mixed with 4.02 g of a hydrosilylation reaction catalyst (D-1) and 12.06 g of a photoinitiator (E-1). Example 31 was prepared in the same manner using the starting materials and amounts shown in the table.

[0075] The composition had the formulation shown in the following table. The PSA prepared from the composition had the performance results also shown in the following table. The values in parentheses indicate the total amount added, including the polyorganosiloxane and the solvent, when the starting material was delivered in the solvent. The numerical values without parentheses represent the amount of the polyorganosiloxane starting material excluding the solvent. (Tables 2 to 7 show the starting materials used (described in detail in Table 1) and their amounts [based on solids (grams) and (solution (grams))]. The value (solution (grams)) indicates that the starting material was initially dissolved in the solvent and represents the weight of the solution in grams. The value based on solids indicates the amount of the starting material excluding the solvent.)

[0076] In this Reference Example 10, the adhesive strength before UV irradiation (initial adhesiveness) was measured as follows. In Comparative Examples (Comp.) 1 to 4 and Examples (Inv.) 1 to 33, a silicone (meth)acrylate pressure-sensitive adhesive composition was applied onto a polyethylene terephthalate (PET, 75 μm) film in order to form a silicone hybrid pressure-sensitive adhesive layer having a thickness of 30 μm after curing. The film was heated at 150° C. for 3 minutes to prepare a silicone hybrid pressure-sensitive adhesive sheet. The obtained sheet was attached onto a peelable polyethylene terephthalate film using a laminator, and the obtained laminate was aged at room temperature for 1 day. The obtained sheet was cut into tape strips having a width of 2.54 cm (1 inch), and this was placed on a glass plate and adhered thereto by moving a rubber-covered pressure roller with a weight of 2 kg back and forth twice on the strip. This assembly was held at room temperature for 1 hour. The adhesive strength (g / inch) was required to peel the tape from the glass plate by pulling at a speed of 300 mm / min and an angle of 180°.

[0077] In Examples (Inv.) 34 to 38, in order to form a double-sided silicone hybrid pressure-sensitive adhesive sheet having a thickness of 50 μm after curing, a silicone-(meth)acrylate pressure-sensitive adhesive composition was applied onto a peelable polyethylene terephthalate (PET, 75 μm) film. By heating the film at 150 °C for 3 minutes, a silicone hybrid pressure-sensitive adhesive sheet was produced. The obtained sheet was pasted onto a peelable PET film using a laminator, and the obtained laminate was aged at room temperature for 1 day. After peeling one side of the peelable polyethylene terephthalate film from the adhesive layer, the adhesive sheet was laminated onto a glass substrate (width = 25 mm, height = 76 mm, thickness = 5 mm). After peeling the peelable polyethylene terephthalate film on the opposite side, it was laminated onto the other glass so that the areas of 2.5 cm × 2 cm (= 5 cm 2 ) overlapped. After pressing the laminated article with a weight of 2 kg for 30 minutes, the adhesive strength was measured according to the double lap shear test method (ASTM D3163).

[0078] To measure the adhesive force after UV irradiation, the assembly prepared as described above was held at RT for 1 day. Then, the assembly was irradiated with UV light under the following conditions: UV light with a UV illuminance of 0.7 W / cm 2 was irradiated from the upper surface of the base film for 30 seconds using a 365 nm LED lamp (FireJet (trademark) FJ100).

[0079] Reference Example 11 - Transmittance and haze The transmittance at 500 nm of the silicone-(meth)acrylate pressure-sensitive adhesive sheet cured as described above was measured by the method specified in ASTM D 1003 (UV-visible spectrometer, reference = air). The haze was measured in the same manner as above by ASTM D 1003-97 (spectrophotometer, CM-3600A, reference = 75 μm PET).

[0080] Reference Example 12 - Si-NMR analysis The average molecular formulas of the above polyorganosiloxane polymer and (meth)acrylic-functional polyorganosiloxane resin were determined by combining Si-NMR and C-NMR analyses.

[0081] NMR apparatus: Fourier transform nuclear magnetic resonance spectrometer Bruker 500 MHz AVANCE 3 NMR equipped with a 10 mm Si-free probe / 5 mm BBFO probe.

[0082] Determination method: Based on the signals derived from 29Si of various siloxane units shown in the following table, the integral values of the peaks were calculated. D and DR' (R' = (meth)acrylic-functional or other organic functional groups) were calculated by normalizing Si-NMR and C-NMR using the number of Si-Me. The average molecular formula was identified by finding the ratio of the integral signal values obtained for various siloxane units and then finding the siloxane unit ratio based on the obtained signal ratio.

[0083]

Table 2

[0084] Reference Example 13 - Gel Permeation Chromatography The sample was prepared in toluene at a concentration of 0.5% w / v, filtered through a 0.45 μm PTFE syringe filter, and analyzed against polystyrene standards. The relative calibration curve (cubic fit) used to determine the molecular weight was based on 16 polystyrene standards in the molecular weight range of 580 to 2,610,000 daltons. The chromatography equipment consisted of a Waters 2695 Separation Module equipped with a vacuum degasser, a Waters 2414 differential refractometer, and two (7.8 mm × 300 mm) styragel HR columns (molecular weight separation range: 100 to 4,000,000) with a styrager guard column (4.6 × 30 mm) installed in front. Separation was carried out using toluene programmed to flow at 1.0 mL / min, the injection volume was set to 100 μL, and the column and detector were heated to 45 °C. Data collection was performed for 60 minutes and processing was carried out using Empower software. As used herein, Mn represents the molecular weight when the peak indicating the neopentamer is excluded from the measurement.

[0085]

Table 3

[0086]

Table 4

[0087] Comparative Examples 1-3 are representative of conventional silicone pressure sensitive adhesives and show that the use of non-functional (e.g., trimethylated) polyorganosilicate resins imparts adhesive properties depending on the resin / polymer ratio. However, their adhesive strengths are constant and do not result in increased adhesion after UV irradiation for silicone pressure sensitive adhesives prepared from this composition. In contrast, Examples 1-6 show that the silicone (meth)acrylate pressure sensitive adhesive compositions described herein (containing both polydiorganosiloxane polymers with aliphatic unsaturated groups and (meth)acryloxyalkyl-functional polyorganosilicate resins) have significantly increased adhesion after UV irradiation while maintaining good transmittance and haze properties suitable for use in (opto)electronic device applications. Examples 1-6 show that the initial adhesive strength increases as the resin / polymer ratio increases from 0.18 to 3.06 using different amounts of the same starting materials. The adhesive strength after UV exposure also increases dramatically in each of Examples 1-4 compared to the initial adhesive strength.

[0088] Comparative Example 4 shows that the curable composition containing (meth)acryloxyalkyl functional polydimethylsiloxane polymer and (meth)acryloxyalkyl functional polyorganosilicate resin does not increase adhesion after UV irradiation. Comparing Comparative Example 4 with Example 4, it is believed that the combination of aliphatically unsaturated polydiorganosiloxane (polymer without (meth)acryl functional group) and (meth)acryloxyalkyl functional polyorganosilicate resin gives the adhesion increase behavior of Example 4 after UV irradiation, which is not shown by Comparative Example 4 under the tested conditions. Without being bound by theory, it is believed that the intermolecular reaction between (meth)acryloxyalkyl functional groups of polyorganosilicate resin in linear polydiorganosiloxane chain matrix by photoradical initiator induces the increase in adhesion after UV irradiation.

[0089] [Table 5]

[0090] Examples 7 - 9 in Table 3 also show the adhesion - increasing performance after UV irradiation using different types of polydiorganosiloxane polymers (A - 2) as the resin / polymer ratio increases. In addition, Examples 9 - 11 show the adhesion - increasing characteristics with the same starting materials when the SiH / reactive group ratios are 0.29, 0.44, and 0.59. In contrast, Comparative Example 4 shows that the adhesive strength does not increase after UV irradiation when the SiH / reactive group ratio is 2.36 under the tested conditions. Without wishing to be bound by theory, an SiH / reactive group ratio < 2 is thought to contribute to the effect on the change in adhesion after UV irradiation by ensuring the presence of sufficient reactive groups of the (meth)acryloxyalkyl - functionalized polyorganosilicate resin after hydrosilylation curing, in order to enable further reaction when the silicone meth(acrylate) pressure - sensitive adhesive is irradiated with ultraviolet light.

[0091] [Table 6]

[0092] Examples 12 - 17 in Table 4 show that parameters such as the resin / polymer ratio and the SiH / reactive group ratio can also be demonstrated by using different types of polydiorganosiloxane polymers (A - 2 and A - 3) and polyorganohydrogensiloxane (C - 2).

[0093] [Table 7]

[0094] [Table 8]

[0095] [Table 9] a: Resin (B-1) / polymer ratio = 1.02, Resin (I-1) / polymer ratio = 0.51 b : Resin (B-1) / polymer ratio = 1.05, Resin (I-1) / polymer ratio = 1.56

[0096] Examples 18 - 31 in Tables 5, 6, and 7 show that by using different types of (meth)acryloxyalkyl-functional polyorganosilicate resins (B-2 - B-9), parameters such as resin / polymer ratio and SiH / reactive group ratio can also be demonstrated. Examples 32 and 33 demonstrate that it is also possible to prepare a solvent-free silicone (meth)acrylate pressure-sensitive adhesive composition that cures to form a pressure-sensitive adhesive with desired adhesive properties. Additionally, Examples 34 and 35 demonstrate that a silicone hybrid pressure-sensitive adhesive composition may further include (I) a non-functional polyorganosilicate resin.

[0097]

Table 10

[0098] Examples 36 - 40 in Table 8 show that a double-sided adhesive sheet can be prepared using a silicone (meth)acrylate pressure-sensitive adhesive composition. As shown in Examples 36 - 40 of Table 8, the adhesive strength of the assembled samples increases significantly after UV irradiation at different resin / polymer ratios up to 21.11 / 1. The upper limit of the resin / polymer ratio may not be strictly limited, and while not wishing to be bound by theory, if the resin / polymer ratio is too high (e.g., >22), it is considered that cracks in the adhesive sheet may be caused depending on the structure and amount of the polyorganosilicate resin. Therefore, while not being bound by theory, a resin / polymer ratio <22 / 1 is considered to contribute to the benefits in appropriately forming a silicone hybrid pressure-sensitive adhesive.

[0099] Definition and Use of Terms "Summary of the Invention" and "Abstract" are incorporated herein by reference. All amounts, ratios, and percentages are by weight unless otherwise indicated in the context of the specification. Unless otherwise specified in the context of the specification, the articles "a", "an", and "the" each refer to one or more. The transitional phrases "comprising", "consisting essentially of", and "consisting of" are used as described in sections §2111.03 I., II., and III. of the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018. The abbreviations used in this specification have the definitions in Table 9.

[0100] [Table 11]

Claims

1. In a method of fabricating an (opto)electronic device, the improvement comprises forming a protective film comprising a pressure-sensitive adhesive layer on a surface of a substrate, 1) optionally, treating the surface of the substrate; 2) applying a composition to the surface of the substrate, the composition comprising A linear or substantially linear polydiorganosiloxane polymer having at least two aliphatic unsaturated hydrocarbon groups per molecule, having the unit formula (R ４ ３ SiO １／２ ), ｍ wherein each R ４ ２ R ３ SiO １／２ ), ｎ wherein each R ４ ２ SiO ２／２ ), ｏ wherein each R ４ R ３ SiO ２／２ ), ｐ wherein each R ４ SiO ３／２ ), ｑ wherein each R ３ SiO ３／２ ), ｒ wherein (SiO ４／２ ), ｓ and in the formula, each R ４ is an independently selected monovalent hydrocarbon group not containing aliphatic unsaturation, each R ３ is an independently selected aliphatic unsaturated monovalent hydrocarbon group, the subscripts m, n, o, p, q, r and s represent the number of each unit, 0 ≦ m, 0 ≦ n, the value of the number (m + n) ≧ 2, 0 < o < 10,000, p ≧ 0, the number (o + p) is 100 to 10,000, 0 ≦ q ≦ 100, 0 ≦ r ≦ 100, and 0 ≦ s ≦ 100, provided that when any one or more of the subscripts q, r, or s is greater than 0, the ratio (o + p) / (q + r + s) is 50 / 1 to 10,000 / 1, a polydiorganosiloxane polymer, and (B) A (meth)acryloxyalkyl-functional polyorganosiloxane resin having a unit formula (R １ ３ SiO １／２ ) ａ (R １ ２ R ２ SiO １／２ ) ｂ (R １ R ２ SiO ２／２ ) ｃ (R １ ２ SiO ２／２ ) ｄ (R ２ SiO ３／２ ) ｅ (R １ SiO ３／２ ) ｆ (SiO ４／２ ) ｇ (ZO １／２ ) ｈ wherein each R １ is an independently selected monovalent hydrocarbon group, each R ２ is an independently selected (meth)acryloxyalkyl group, each Z is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 6 carbon atoms, and the subscripts a, b, c, d, e, f, g, and h represent the relative molar amounts of each unit, with subscript a ≥ 0, subscript b ≥ 0, subscript c ≥ 0, subscript d ≥ 0, subscript e ≥ 0, subscript f ≥ 0, subscript g ≥ 0, subscript h ≥ 0, and the number (a + b + c + d + e + f + g + h) = 100, provided that 10 ≥ (b + c + e) ≥ 0.5 and 99.5 > (f + g) ≥ 30, starting materials (A) and (B) present in the composition in an amount sufficient to provide a weight ratio of (B) resin / (A) polymer of 0.15 / 1 to <22 / 1 (resin / polymer ratio), a (meth)acryloxyalkyl-functional polyorganosiloxane resin; (C) A polyorganohydrogensiloxane having the unit formula (R ５ ３ SiO １／２ ) ｔ (R ５ ２ HSiO １／２ ) ｕ (R ５ ２ SiO ２／２ ) ｖ (R ５ HSiO ２／２ ) ｗ (R ５ SiO ３／２ ) ｘ (HSiO ３／２ ) ｙ (SiO ４／２ ) ｚ wherein each R ５ is an independently selected monovalent hydrocarbon group, the subscripts t, u, v, w, x, y, and z represent the number of each unit in the above formula, t≥0, u≥0, v≥0, w≥0, x≥0, y≥0, z≥0, the number (u + w + y)≥2, and 2,000≥(t + u + v + w + x + y + z)≥3, and the polyorganohydrogensiloxane is present in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms to reactive groups (SiH / reactive group ratio) in the starting material (C) of 0.05 / 1 to 2 / 1, and the reactive groups are collectively the aliphatic unsaturated monovalent hydrocarbon group and the (meth)acryloxyalkyl group, a polyorganohydrogensiloxane, and (D) a hydrosilylation reaction catalyst in an amount sufficient to provide from 1 ppm to 1,000 ppm of a platinum group metal based on the total weight of starting materials (A), (B), (C), (D), (E), and (F) in the composition; (E) a photo radical initiator in an amount sufficient to provide from 0.01 wt% to 10 wt% based on the total weight of starting materials (A), (B), (C), (D), (E), and (F) in the composition; (F) a hydrosilylation reaction inhibitor in an amount sufficient to provide from 5 ppm to 2 wt% based on the total weight of starting materials (A), (B), (C), (D), (E), and (F) in the composition; optionally, (G) a radical scavenger; optionally, (H) a solvent, 3) optionally, removing the solvent, if present; 4) curing the composition to form the pressure-sensitive adhesive layer on the surface of the substrate, thereby forming the protective film; 5) applying the protective film to the (opto)electronic device such that the pressure-sensitive adhesive layer contacts the surface of the (opto)electronic device; 6) using the protective film to protect the device, and then 7) exposing the pressure-sensitive adhesive layer to actinic radiation.

2. In the starting material (A), R ３ each of the aliphatic unsaturated monovalent hydrocarbon groups is an alkenyl group independently selected, and R ４ each of the monovalent hydrocarbon groups is independently selected from the group consisting of an alkyl group and an aryl group, subscript m = 0, subscript q = 0, subscript r = 0, subscript s = 0, subscript n = 2, and the number (n + o + p) is sufficient to provide a starting material (A) having a vinyl content of 0.01% to 0.5% by weight based on the weight of the starting material (A), the method according to claim 1.

3. In the starting material (B), R １ each monovalent hydrocarbon group is independently selected from the group consisting of an alkyl group and an aryl group, and each (meth)acryloxyalkyl functional group of R ２ is independently selected from the group consisting of acryloxypropyl and methacryloxypropyl, subscript a is 35 to 55, subscript b = 0, subscript c is 1 to 10, subscript d is 0 to 20, subscript e is 0 to 5, subscript f is 0 to 3, subscript g is 35 to 50, and subscript h is 0 to 1, The method according to claim 1.

4. In the starting material (C), each R ５ is independently selected from the group consisting of an alkyl group and an aryl group, the subscript t is 0, 1, or 2, the subscript u is 0, 1, or 2, the number (t + u) = 2, the subscript v ≥ 0, the subscript w > 0, the subscript x = 0, the subscript y = 0, the subscript z = 0, and the number (t + u + v + w) is sufficient to provide a viscosity of the starting material (C) of 3 MPa·s to 1,000 MPa·s at 25°C. The method according to claim 1.

5. (D) The method of claim 1, wherein the hydrosilylation reaction catalyst is selected from the group consisting of i) a platinum group metal, ii) a compound of the metal, iii) a complex of the metal or the compound, and v) the complex microencapsulated in a matrix or core-shell type structure.

6. The method according to claim 1, wherein the photoinitiator is selected from the group consisting of photoinitiators that can be selected from the group consisting of (Ei) benzophenone, (Eii) substituted benzophenone compounds, (Eiii) acetophenone, (Eiv) substituted acetophenone compounds, (Ev) benzoin, (Evi) alkyl esters of benzoin, (Evii) substituted phosphine oxide compounds, (Eviii) xanthone, and (Eix) substituted xanthone, and (Ex) substituted oxime ester compounds, and (Exi) combinations of two or more of (Ei) to (Ex).

7. The method according to claim 1, wherein the composition further comprises (F) a hydrosilylation reaction inhibitor, and the hydrosilylation reaction inhibitor is selected from the group consisting of acetylenic alcohols, cycloalkenylsiloxanes, enyne compounds, triazoles, phosphines, mercaptans, hydrazines, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, alcohols, and silylated acetylenic alcohols.

8. The method according to claim 1, wherein the composition further comprises (G) a radical scavenger, and the radical scavenger is selected from the group consisting of phenolic compounds, phenothiazines, and oxygen-free inhibitors.

9. The method according to claim 1, wherein the composition further comprises (H) a solvent, and the solvent is present and is selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons.

10. The method according to claim 1, wherein the composition further comprises (I) a non-functional polyorganosilicate resin.

11. The method according to claim 1, wherein the resin / polymer ratio is 0.2 / 1 to 9 / 1.

12. The method according to claim 1, wherein the SiH / reactive group ratio is 0.1 / 1 to 0.9 / 1.

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