Curable silicone-(meth)acrylate compositions, and methods of making and using the same

Abstract

A curable silicone-(meth)acrylate pressure-sensitive composition can be cured via a hydrosilylation reaction to form a silicone-(meth)acrylate pressure-sensitive adhesive with initial adhesion. When the silicone-(meth)acrylate pressure-sensitive adhesive is exposed to photochemical radiation, the resulting silicone-(meth)acrylate adhesive exhibits a higher subsequent adhesion than the initial adhesion.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 081367, filed September 22, 2020, pursuant to 35 U.S.SC §119(e). U.S. Provisional Patent Application Serial No. 63 / 081367 is incorporated herein by reference. Technical Field

[0003] This invention relates to curable silicone-(meth)acrylate compositions (compositions) suitable for forming silicone-(meth)acrylate pressure-sensitive adhesives (PSAs). More specifically, this invention relates to compositions suitable for forming PSAs that are sensitive to photochemical energy. These compositions and PSAs can be used in methods for manufacturing (opto)electronic devices. Background Technology

[0004] Silicone compositions suitable for forming pressure-sensitive adhesives have been previously reported. These silicone compositions typically contain at least two main components: a linear siloxane polymer and a compound substantially composed of the formula R3SiO2. 1 / 2 The three organosiloxane units and the formula SiO 4 / 2 The tackifying resin is composed of silicate (Q) units, where R represents a monovalent hydrocarbon group. In addition to the two components mentioned above, these silicone compositions typically have some crosslinking means to allow the silicone composition to cure and produce a pressure-sensitive adhesive.

[0005] Problems to be solved

[0006] The aforementioned conventional pressure-sensitive adhesives typically exhibit constant (or nearly constant) adhesive strength after curing. The adhesive strength of these conventional pressure-sensitive adhesives is generally lower than that of ordinary (permanent) adhesives, and it is difficult to further develop the adhesive strength of conventional pressure-sensitive adhesives after curing the aforementioned silicone compositions. This limits the use of conventional pressure-sensitive adhesives in various applications.

[0007] For example, in the manufacture of (opto)electronic devices, relatively low adhesive strength of the pressure-sensitive adhesive is desired for reworkability during the manufacturing process, and higher adhesive strength is desired thereafter (at the end of the process) for long-term practical use of the device. Furthermore, in protective film applications for edge-curved displays, higher retention strength of the adhesive layer in the protective film is required (compared to conventional pressure-sensitive adhesives) because conventional PSAs may suffer from delamination at curved edges due to the restoring force of the rigid substrate used in the protective film. Additionally, in some applications, sheet (or solid) adhesives are required when flowable liquid adhesives are difficult to use. Therefore, there is an industrial need for a curable composition that can form a pressure-sensitive adhesive with increased adhesion properties, wherein the increase in adhesion can be initiated upon exposure to a trigger such as photochemical ray (e.g., UV light) when needed. Summary of the Invention

[0008] A curable silicone-(meth)acrylate pressure-sensitive adhesive composition (the composition) is suitable for forming a silicone-(meth)acrylate pressure-sensitive adhesive (PSA). The composition and a method for its preparation are provided. Methods for preparing and using the PSA from the composition are also provided. Detailed Implementation

[0009] The above composition comprises:

[0010] (A) A linear or substantially linear polydiorganosiloxane polymer, wherein each molecule of the linear or substantially linear polydiorganosiloxane polymer has at least two aliphatic unsaturated hydrocarbon groups, and the linear or substantially linear polydiorganosiloxane polymer comprises 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

[0011] ) r (SiO 4 / 2 ) s , where each R 4is a monovalent hydrocarbon group independently selected and free of aliphatic unsaturation, and each R 3 is an aliphatic unsaturated monovalent hydrocarbon group independently selected; the subscripts m, n, o, p, q, r, and s represent the number of each unit in the formula and have values such that 0 ≤ m, 0 ≤ n, and the amount (m + n) ≥ 2; 0 < o < 10,000, p ≥ 0, and the amount (o + p) is from 100 to 10,000; 0 ≤ q ≤ 100, 0 ≤ r ≤ 100, and 0 ≤ s ≤ 100, provided that if any one or more of the subscripts q, r, or s is greater than 0, the ratio (o + p) / (q

[0012] + r + s) is from 50 / 1 to 10,000 / 1;

[0013] (B) A (meth)acryloyloxyalkyl-functional polyorganosiloxane resin, the (meth)acryloyloxyalkyl-functional polyorganosiloxane resin comprising units of the 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 , where each R 1 is a monovalent hydrocarbon group independently selected, each R 2 is a (meth)acryloyloxyalkyl group independently selected, each Z is independently selected from the group consisting of hydrogen and alkyl groups having 1 to 6 carbon atoms; the subscripts a, b, c, d, e, f, g, and h represent the relative molar amounts of each unit and have values such that subscript a ≥ 0, subscript b ≥ 0, subscript c ≥ 0, subscript d ≥ 0, subscript f ≥ 0, subscript g ≥ 0, subscript h ≥ 0, and the amount (a + b + c + d + e + f + g + h) = 100, provided that 10 ≥ (b + c + e) ≥ 0.5 and 99.5 > (f + g) ≥ 30; wherein the starting materials (A) and (B) are present in the composition in amounts sufficient to provide a weight ratio (resin / polymer ratio) of (B) resin / (A) polymer of 0.15 / 1 to <22 / 1;

[0014] (C) Polyorganohydrosiloxanes, which include units of the 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 , where each R 5 It is an independently chosen monovalent hydrocarbon group, and the subscripts t, u, v, w, x, y, and z indicate the quantity 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 amount (u+w+y)≥2 and 2,000≥(t+u+v+w+x+y+z)≥3; wherein the polyorganohydrosiloxane is present in an amount sufficient to provide 0.05 / 1 to 2 / 1 of the molar ratio (SiH / reactive group ratio) of silicon-bonded hydrogen atoms to reactive groups in the starting material (C), wherein these reactive groups are the aliphatic unsaturated monovalent hydrocarbon groups in the combined starting material (A) and the (meth)acryloyloxyalkyl groups in the starting material (B);

[0015] (D) Hydrosilylation catalyst, based on the combined weight of the starting materials (A), (B), (C), (D), (E) and (F) in the composition, the amount of the hydrosilylation catalyst is sufficient to provide 1 ppm to 1,000 ppm of platinum group metals;

[0016] (E) A photoradical initiator, provided that the amount of the photoradical initiator is sufficient to provide 0.01% to 10% based on the combined weight of the starting substances (A), (B), (C), (D), (E), and (F) in the composition; and

[0017] (F) Hydrosilylation inhibitor, the amount of which is sufficient to provide 5 ppm to 2% based on the combined weight of the starting materials (A), (B), (C), (D), (E) and (F) in the composition.

[0018] The composition may optionally further comprise 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).

[0019] (A) Polymer

[0020] The starting material (A) in the composition is a linear or substantially linear polydiorganosiloxane polymer (polymer) having at least two aliphatically unsaturated hydrocarbon groups per molecule. The polymer comprises units of the 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 , where each R 4 is a monovalent hydrocarbon group independently selected and free of aliphatic unsaturation, and each R 3 is a monovalent aliphatically unsaturated hydrocarbon group independently selected; the subscripts m, n, o, p, q, r, and s represent the number of each unit in the formula and have values such that 0 ≤ m, 0 ≤ n, the amount (m + n) ≥ 2; 0 < o < 10,000, p ≥ 0, the amount (o + p) is from 100 to 10,000; 0 ≤ q ≤ 100, 0 ≤ r ≤ 100, and 0 ≤ s ≤ 100, provided that if any one or more of the subscripts q, r, or s is greater than 0, the ratio (o + p) / (q + r + s) is from 50 / 1 to 10,000 / 1. Alternatively, for example when subscript q = 0, subscript r = 0, and subscript s = 0, the polydiorganosiloxane may be free of T and / or Q units. Alternatively, subscript m may be 0. Alternatively, subscript n may be 2. Alternatively, based on the weight of starting material (A), the amount of (n + o + p) may be sufficient to provide a polymer having an aliphatically unsaturated group content (e.g., vinyl content) of 0.01% to 0.5%.

[0021] For R 3Examples of suitable aliphatic unsaturated monovalent hydrocarbon groups include alkenyl 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 The alkenyl group can be chosen independently. Alternatively, each R 3 The group consisting of vinyl and hexenyl groups can be selected. Alternatively, each R... 3 It can be vinyl.

[0022] For R 4 The monovalent hydrocarbon group can be an alkyl group or an aryl group. Suitable alkyl groups are exemplified by, but not limited to, the following: 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 with 6 carbon atoms. Alternatively, the alkyl group can be methyl, ethyl, or propyl. Examples of suitable aryl groups are, but not limited to, phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl. Alternatively, each R 4 It can be a methyl group or a phenyl group. Alternatively, each R 4 It can be methyl.

[0023] Starting material (A) may contain alkenyl-functionalized polydiorganosiloxanes, such as

[0024] i) Bis(dimethyl)vinylsiloxy)-terminated polydimethylsiloxane

[0025] ii) Bis(dimethyl)vinylsiloxy)-terminated poly(dimethylsiloxane / methylvinylsiloxane),

[0026] iii) Bis(dimethyl)vinylsiloxy)-terminated polymethylvinylsiloxanes

[0027] iv) Bistrimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane),

[0028] v) Bistrimethylsiloxy-terminated polymethylvinylsiloxanes

[0029] vi) Bis(dimethyl)vinylsiloxy)-terminated poly(methylphenylsiloxane / methylvinylsiloxane),

[0030] vii) Bis(dimethylvinylsiloxy)-terminated poly(dimethylsiloxane / methylphenylsiloxane),

[0031] viii) Bis(dimethyl)vinylsiloxy)-terminated poly(dimethylsiloxane / diphenylsiloxane),

[0032] ix) Bisphenyl, methyl, vinyl-siloxy-terminated polydimethylsiloxane,

[0033] x) Bis(dimethylhexenyl)siloxy-terminated polydimethylsiloxane.

[0034] xi) Di(dimethylhexenylsiloxy)-terminated poly(dimethylsiloxane / methylhexenylsiloxane),

[0035] xii) Bis(dimethylhexenyl)siloxy-terminated polymethylhexenylsiloxane.

[0036] xiii) Bistrimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane),

[0037] xiv) Bistrimethylsiloxy-terminated polymethylhexenylsiloxane

[0038] xv) Bis(dimethylhexenyl)siloxy-terminated poly(methylphenylsiloxane / methylhexenylsiloxane),

[0039] xvi) Didimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane),

[0040] xvii) Bis(dimethylhexenylsiloxy)-terminated poly(dimethylsiloxane / methylphenylsiloxane),

[0041] xviii) Dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), and

[0042] Combinations of two or more of xix)i) to xviii).

[0043] Methods for preparing the linear alkenyl-functionalized polydiorganosiloxanes used as starting material (A), such as the hydrolysis and condensation of corresponding organohalosilanes and oligomers or the equilibrium of cyclic polydiorganosiloxanes, are known in the art, see, for example, U.S. Patents 3,284,406; 4,772,515; 5,169,920; 5,317,072; and 6,956,087, which disclose the preparation of linear polydiorganosiloxanes having alkenyl groups. Examples of linear polydiorganosiloxanes having alkenyl groups are commercially available, for example, from Gelest Inc. of 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, and DMS-V52.

[0044] (B) Resin

[0045] The starting material (B) in the composition described herein is a (meth)acryloyloxyalkyl-functionalized polysiloxane resin, which comprises 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 , where each R 1 It is an independently selected monovalent hydrocarbon group, each R 2Each Z is an independently chosen (meth)acryloyloxyalkyl group, each Z being independently chosen from the group consisting of hydrogen and alkyl groups with 1 to 6 carbon atoms; the subscripts a, b, c, d, e, f, g, and h represent the relative molar amount of each unit and have a value such that 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 amount (a + b + c + d + e + f + g) = 100, provided that 10 ≥ (b + c + e) ​​≥ 0.5 and 99.5 > (e + f + g) ≥ 30. Alternatively, the amount (c + d) can be 0 to 20. Alternatively, (e + f + g) can be 30 to 90. Alternatively, subscript a can be 35 to 55. Alternatively, subscript b can be 0. Alternatively, subscript c can be 1 to 10. Alternatively, the subscript d can be from 0 to 20. Alternatively, the subscript e can be from 0 to 5. Alternatively, the subscript f can be from 0 to 3. Alternatively, the subscript g can be from 35 to 50. The subscript h is not included in the relative molar ratio, and the subscript h can 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 can be from 0 to 5, alternatively from 0 to 1, and alternatively from 0 to 0.5.

[0046] Alternatively, the amount (b+c+e) can be from 0.5 to 8. It is not desirable to be bound by theory, but it is considered that units containing (meth)acryloyl functional groups exceeding 8 mol% may cause poor compatibility with polymer (A), which could lead to phase separation after the preparation of the PSA from the composition. Furthermore, it is not desirable to be bound by theory, but it is considered that units containing (meth)acryloyl functional groups less than 0.5 mol% may not be sufficient to effectively react by photochemical energies such as (UV) light to induce the desired increase in adhesion.

[0047] R in the above unit formula 1 Suitable monovalent hydrocarbon groups include aliphatic saturated monovalent hydrocarbon groups. Suitable aliphatic saturated monovalent hydrocarbon groups include alkyl groups and aryl groups. Alkyl groups can be straight-chain, branched, or cyclic. Examples of alkyl groups include methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (including isopentyl, 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 cycloalkyl groups, such as cyclopentyl or cyclohexyl. Alkyl groups may have at least one carbon atom. Alternatively, alkyl groups 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, for R 1 The monovalent hydrocarbon group can be as described above for R. 4As described. Alternatively, each R 1 It can be an alkyl group, and alternatively a methyl group.

[0048] For R 1 The aryl group includes, alternatively, a hydrocarbon group derived from an aromatic hydrocarbon by removing a hydrogen atom from a cyclic carbon atom. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, benzyl, tolyl, xylyl, phenethyl, phenylpropyl, and phenylbutyl. The aryl group has at least 5 carbon atoms. A monocyclic aryl group may have 5 to 12 carbon atoms, alternatively 6 to 9 carbon atoms, and alternatively 6 carbon atoms. A polycyclic aryl group may have 9 to 17 carbon atoms, alternatively 9 to 14 carbon atoms, and alternatively 9 to 12 carbon atoms.

[0049] Alternatively, for R 1 The alkyl group may be methyl, and the aryl group may be phenyl. Alternatively, each R 1 The resin can be independently selected from the group consisting of alkyl and aryl groups. Alternatively, (B) the resin may contain 70 mol% or more, or alternatively 90 mol% or more of total R. 1 ; and alternatively, each R 1 It can be methyl.

[0050] For R 2 Examples of suitable (meth)acryloyloxyalkyl groups are methacryloyloxypropyl and acryloyloxypropyl.

[0051] Alternatively, (B) the polyorganosilicon resin may include a unit formula selected from the group consisting of: (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 、 (R 1 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 SiO2 / 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 R2 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 (ZO 1 / 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 , where the subscripts a, b, c, d, e, f, g, and h are as described herein. Alternatively, the amount (b+d+e) is 1 to sufficient to provide the resin with up to 8 mol% of units containing (meth)acryloyl functional groups, i.e., formula (R 2 R 1 2SiO 1 / 2 The M' unit of ) and the formula (R) 1 R 2 SiO 2 / 2 The D' unit and / or formula (R) 2 SiO 3 / 2 The value of the T' unit. Alternatively, the amount (b+d+e) can be 2 to a value sufficient to provide up to 8 mol% of the combination of M', D', and T' units to the resin. Alternatively, when e = 0, the amount (b+d) can be 2 to a value sufficient to provide up to 8 mol% of the combination of M' and D'. Alternatively, when b = 0 and e = 0, the amount d can be 2 to a value sufficient to provide up to 8 mol% of the D' unit to the resin.

[0052] Not wanting to be bound by theory, the methyl group is considered to be non-reactive and may provide wettability to the surface of the adhesive and stability (e.g., no or minimal thermal shrinkage or degradation) after heat treatment of the composition during the (opto)electronic device manufacturing process and exposure of the PSA to heat (e.g., after exposure to temperatures up to 200°C).

[0053] The intermediates used to prepare resin (B) may have two, three, or four hydrolyzable substituents per molecule; for example, they may be diorganoalkoxysilanes, triorganoalkoxysilanes, and silanes or alkali metal silicates having four hydrolyzable substituents. The intermediates may have the formula R. M 2SiX 1 2. R M SiX 1 3. SiX 1 4, where R M Choose freely from the above R 1 and R 2 The group formed, and X 1 The substituents represent hydrolyzable groups. Silanes with four hydrolyzable substituents can have the formula SiX. 2 4, where each X 2 It can be halogenated, alkoxylated, or hydroxylated. Suitable alkali metal silicates include sodium silicate.

[0054] Methods for preparing (meth)acryloyloxyalkyl-functionalized polyorganosiloxane resins suitable as starting materials (B), such as equilibrium reactions of typical polyorganosiloxane resins with (meth)acryloyloxyalkyl-functionalized alkoxysilanes or halosilanes under acidic or alkaline conditions; hydrolysis / condensation reactions such as end-capping methods and hydrolysis following co-hydrolysis of typical organohalosilanes or organoalkoxysilanes with (meth)acryloyloxyalkyl-functionalized alkoxysilanes or halosilanes; and non-hydrolysis condensation reactions such as those of typical organohalosilanes or organoalkoxysilanes with (meth)acryloyloxyalkyl-functionalized alkoxysilanes or halosilanes, will be of interest to those skilled in the art. It is known that similar methods for preparing polyorganosiloxane resins are described in U.S. Patent No. 8,377,634 to Albaugh, U.S. Patent No. 5,516,858 to Morita et al., U.S. Patent No. 9,023,433 to Fu et al., U.S. Patent No. 6,281,285 to Becker et al., U.S. Patent No. 5,010,159 to Bank et al., U.S. Patent No. 2,676,182 to Daudt et al., U.S. Patent No. 4,611,042 to Rivers-Farrell et al., and U.S. Patent No. 4,774,310 to Butler et al.

[0055] The (meth)acryloyloxyalkyl functionalized alkoxysilane or halosilane used in the above method for preparing resin (B) can be selected from: 3-(chlorodimethylsilyl)propyl methacrylate (CAS#24636-31-5), 3-[dimethoxy(meth)silyl]propyl methacrylate (CAS#14513-34-9), methacryloyloxypropylmethyldichlorosilane (CAS#18301-56-9), (3-acryloyloxypropyl)methyldichlorosilane (CAS#71550-63-5), 3-[dimethoxy(meth)silyl]propyl acrylate (CAS#1 3732-00-8), 3-(trimethoxysilyl)propyl methacrylate (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), methacryloyloxypropyltrichlorosilane (CAS#7351-61-3), (3-acryloyloxypropyl)trichlorosilane (CAS#38595-89-0).

[0056] Another method for preparing resins containing M' units suitable as starting materials (B) is a hydrosilylation reaction between a hydrosilyl (-SiH)-functionalized polyorganosiloxane resin and a (meth)acryloyl-functionalized olefin or alkyne; or a hydrosilylation reaction between an alkenyl-functionalized polyorganosiloxane resin and a (meth)acryloyl-functionalized hydrosilane, as described in U.S. Patent No. 4,503,208 to Lin et al. and in Macromolecular Materials and Engineering, Vol. 292, No. 5, pp. 666-673 (2007) by Hung-Wen et al. The (meth)acryloyl-functionalized olefin or alkyne may be selected from allyl methacrylate (CAS#96-05-9) and propyl acrylate (CAS#10477-47-1). The (meth)acryloyl-functionalized hydrosilane used for hydrosilylation reactions may be selected from methacryloyloxypropyltris(dimethylsiloxy)silane (CAS#17096-08-1) and 2-acrylic acid, 2-methyl-3-(1,1,3,3-tetramethyldisiloxyl)propyl ester (CAS#96474-12-3).

[0057] The resin prepared as described above may contain silicon-bonded hydroxyl groups, i.e., of formula XSi. 3 / 2 XR M SiO 2 / 2 and / or XR M 2SiO 1 / 2The group, wherein X is a hydroxyl group or an alkoxy group. The resin may contain up to 5% silicon-bonded hydroxyl or alkoxy groups. The concentration of silicon-bonded hydroxyl or alkoxy groups present in the polyorganosiloxane resin can be determined by Fourier transform infrared (FTIR) spectroscopy according to ASTM standard E-168-16. For some applications, it may be desirable that the amount of silicon-bonded hydroxyl groups is 2% or less, alternatively less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, and alternatively from 0.3% to 0.8%. Silicon-bonded hydroxyl groups formed during resin preparation can be converted into triorgano (e.g., trialkyl)siloxane groups or different hydrolyzable groups by reacting the resin with a silane, disiloxane, or disilazane containing suitable terminal groups. The silane containing the hydrolyzable groups may be added in excess molar amounts required to react with the silicon-bonded hydroxyl groups on the polyorganosilicone resin.

[0058] (B) The Mn of the resin depends on various factors, including the presence of R. M The type of hydrocarbon group indicated. When the peak representing the new pentamer is excluded from the measurement, 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, Column 31 of U.S. Patent 9,593,209. The Mn of the resin can be from 500 g / mol to 5,000 g / mol. Alternatively, the Mn of the resin can be from 1,000 g / mol to 4,000 g / mol.

[0059] During preparation, the resin comprises the aforementioned units, and further comprises units having silanol or alkoxysilane (silicon-bonded hydroxyl or alkoxy) groups, and may contain low molecular weight molecules, such as Si(OSiR) M 3)4 new pentapolymers, of which R M As described above, when characterized by gel permeation chromatography (GPC), Mn has a low molecular weight molecule concentration of less than 500 g / mol and a fraction of less than 25%. As described in Reference Example 2, column 32 of U.S. Patent 9,593,209, by employing Si... 29 Nuclear magnetic resonance (NMR) spectroscopy can be used as a characterization method to measure the molar ratio of M units and Q units, wherein the ratio is expressed as {M(resin) + (M(new pentamer)} / {Q(resin) + Q(new pentamer)} and represents the molar ratio of the total number of triorganosylsiloxy groups in the resin portion and the new pentamer portion of the polyorganosilicon resin to the total number of silicate groups (Q units) in the resin portion and the new pentamer portion. The molar ratio of M, M', D, D', T, T' and Q of the starting material (B) is expressed based on the inclusion of organosylsiloxy groups in the resin and low molecular weight molecules.

[0060] The starting materials (A) and (B) are present in the composition in an amount sufficient to provide a (B) resin / (A) polymer weight ratio (resin / polymer ratio) of 0.15 / 1 to <22 / 1, alternatively 0.15 / 1 to 9 / 1, alternatively 0.2 / 1 to 9 / 1 and alternatively 0.2 / 1 to 4 / 1.

[0061] (C) Polyorganohydrosiloxane

[0062] The composition also contains starting materials (C), including units of (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 Polyorganohydrosiloxanes. In this unit formula, each R 5 For independently selected monovalent hydrocarbon groups. Alternatively, each R 5 The group consisting of alkyl and aryl groups can be selected. R 5 As mentioned above regarding R 1 The subscripts t, u, v, w, x, y, and z denote the quantity 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 quantity (u + w + y) ≥ 2, and 2,000 ≥ (t + u + v + w + x + y + z) ≥ 3. Alternatively, the quantity (t + u + v + w + x + y + z) is sufficient to give the viscosity of the polyorganohydrosiloxane at 25°C a range of 3 mPa·s to 1,000 mPa·s, or alternatively, a range of 5 mPa·s to 500 mPa·s at 25°C. Viscosity can be measured at 25°C from 0.1 RPM to 50 RPM on a Brookfield DV-III cone-plate viscometer with a #CP-52 rotor. Those skilled in the art will recognize that the rotational rate decreases as viscosity increases. Alternatively, the quantity (t+u+v+w+x+y+z) can be 3 to 2,000; 3 to 1,000; and 3 to 500.

[0063] Alternatively, when the subscripts x = y = z = 0, the polyorganohydrosiloxane may include the unit formula (R 5 3SiO1 / 2 ) t (R 5 2HSiO 1 / 2 ) u (R 5 2SiO 2 / 2 ) v (R 5 HSiO 2 / 2 ) w , where the subscript t is 0, 1 or 2; the subscript u is 0, 1 or 2; the quantity (t+u) = 2, the subscript v ≥ 0, the subscript w > 0; and the quantity (u+w) ≥ 3.

[0064] Examples of polyorganohydrosiloxanes used for starting material (C) are: Ci) dimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrosiloxane), Cii) dimethylsiloxy-terminated polymethylhydrosiloxane, Ciiii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrosiloxane), Ciiv) trimethylsiloxy-terminated polymethylhydrosiloxane, and combinations of two or more of Ci) to Ciiv).

[0065] Methods for preparing polyorganohydrosiloxanes suitable for use as starting materials (C), such as the hydrolysis and condensation of organohalosilanes, are well known in the art, as illustrated in U.S. Patent 5,310,843; U.S. Patent 4,370,358; U.S. Patent 4,707,531; and U.S. Patent 4,329,273. Furthermore, polyorganohydrosiloxanes are known in the art and are commercially available, for example from Dow Silicones Corporation of Midland, Michigan, USA, and from Gallustech of 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 silicone publication cited above. Linear and cyclic polydiorganosiloxanes can also be prepared as described, for example, in US2,823,218 and US4,329,273, granted to Speier et al.

[0066] The polyorganohydrosiloxane is present in an amount sufficient to provide 0.05 / 1 to 2 / 1 of the molar ratio (SiH / reactive group ratio) of silicon-bonded hydrogen atoms in the starting material (C) to the reactive groups in the composition. As used herein, the term 'reactive group' generally means the aliphatic unsaturated monovalent hydrocarbon group and (meth)acryloyloxyalkyl group present in the above-described starting material (i.e., represented by R in the above formula for the starting material (B)). 2(Indicated). Alternatively, the SiH / reactive group ratio may be at least 0.05 / 1, alternatively at least 0.1 / 1, and alternatively at least 0.2 / 1. Meanwhile, the SiH / reactive group ratio may be at most 2 / 1, alternatively at most 1 / 1, and alternatively at most 0.9 / 1. Alternatively, the SiH / reactive group ratio may be from 0.1 / 1 to 2 / 1, alternatively from 0.1 / 1 to 1 / 1, alternatively from 0.2 / 1 to 1 / 1, alternatively from 0.1 / 1 to 0.9 / 1, and alternatively from 0.2 / 1 to 0.9 / 1.

[0067] (D) Catalyst for hydrosilylation reaction

[0068] The starting material (D) in the composition is a hydrosilylation catalyst. Hydrosilylation catalysts include platinum group metal catalysts. For example, the hydrosilylation catalyst may be Di) a metal selected from platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the hydrosilylation catalyst may be Diii) a compound of such metals, such as tris(triphenylphosphine)rhodium(I) chloride (Wilkinson catalyst), rhodium diphosphine chelates such as [1,2-bis(diphenylphosphine)ethane]dichlorodirhodium or [1,2-bis(diethylphosphine)ethane]dichlorodirhodium, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride; or Diiii) a complex of such a compound with a low molecular weight organopolysiloxane. Alternatively, the hydrosilylation catalyst may be Div) a compound microencapsulated in a matrix or core / shell structure. For example, platinum complexes with low molecular weight organopolysiloxanes include complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with platinum (Karstedt catalyst). Alternatively, hydrosilylation catalysts may be Dv) microencapsulated complexes in a resin matrix. Exemplary hydrosilylation catalysts are described below: U.S. Patents 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 EP 0 347 895 B. Suitable hydrosilylation catalysts are known in the art and are commercially available. For example, SYL-OFF TM 4000 catalyst and SYL-OFF TM 2700 is available from Dow Silicones in Midland, Michigan, USA.

[0069] The amount of hydrosilylation catalyst used herein will depend on various factors, including the selection of the starting materials (A), (B), and (C) and the content of their respective aliphatic unsaturated monovalent hydrocarbon groups and silicon-bonded hydrogen atoms, as well as the presence of hydrosilylation inhibitors. However, the amount of catalyst is sufficient to catalyze the hydrosilylation reaction of SiH and aliphatic unsaturated monovalent hydrocarbon groups. Alternatively, the amount of catalyst is sufficient to provide 1 ppm to 1000 ppm of platinum group metals based on the combined weight of the starting materials (A), (B), (C), (D), (E), and (F) in the composition; alternatively, 2 ppm to 500 ppm and alternatively 10 ppm to 100 ppm of platinum group metals based on the same reference.

[0070] (E) Photoradical initiator

[0071] The starting material (E) in this composition is a photoradical initiator. Suitable photoradical initiators include UV initiators such as benzophenone derivatives, acetophenone derivatives (α-hydroxy ketones), benzoin and its alkyl esters, phosphine oxide derivatives, xanthone derivatives, oxime ester derivatives, and camphorquinone. Photoradical initiators are commercially available. For example, photoradical initiators suitable for this article include 2,6-bis(4-azidobenzyl)cyclohexanone, 2,6-bis(4-azidobenzyl)-4-methylcyclohexanone, and 1-hydroxy-cyclohexyl-phenyl-ketone (OMNIRAD). TM 184), 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (OMNIRAD) TM 907); 2-Hydroxy-2-methyl-1-phenyl-propane-1-one (OMNIRAD) TM 1173); 50% OMNIRAD TM A mixed initiator of 184C and 50% benzophenone (OMNIRAD) TM 500); 20% OMNIRAD TM 184C and 80% OMNIRAD TM 1173 mixed initiator (OMNIRAD) TM 1000); 2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (OMNIRAD) TM 2959); Methylbenzoylcarbamate (OMNIRAD) TM MBF); α,α-dimethoxy-α-phenylacetophenone (OMNIRAD) TM 651); 2-Benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (OMNIRAD) TM 369); 30% OMNIRADTM 369 and 70% of OMNIRAD TM 651 mixed initiator (OMNIRAD) TM 1300); Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (OMNIRAD) TM TPO), (2,4,6-trimethylbenzoyl)phenylphosphine ethyl ester (OMNIRAD) TM TPO-L), oxime esters (N-1919, NCI-831, NCI-930, NCI-730 and NCI-100 supplied by Adeka Corporation), thioxanthone; 10-methylphenthiazide; isopropyl-9H-thioxanthone; 2,4-diethyl-9H-thioxanthone; 2-chlorothioxanthone; 1-chloro-4-propoxy-9H-thioxanthone; or combinations of two or more of them. TM The branded photoradical initiator is commercially available from IGM Resins BV, Netherlands. Alternatively, the photoradical initiator may 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; Ex) substituted oxime ester compounds, and combinations of two or more of Exi) to Ex). Alternatively, the photoradical initiator may be a substituted acetophenone, such as 1-hydroxycyclohexylphenyl ketone. The type of photoradical initiator is not particularly limited; however, some photoradical initiators, especially those containing thioether, phosphonate, or phosphine oxide groups, can inhibit hydrosilylation catalysts. Therefore, when such photoradical initiators are included, it may be necessary to control the appropriate amount of (D) hydrosilylation catalyst and / or adjust the curing temperature / time.

[0072] The amount of photoradical initiator in the composition will depend on various factors, including the desired reaction rate, the photoradical initiator used, and the selection and amount of the starting material (B) and the content of its (meth)acryloyloxyalkyl groups. However, based on the combined weight of the starting materials (A), (B), (C), (D), (E), and (F) in the composition, this amount can be from 0.01% to 10%. Alternatively, based on the same reference, the amount of photoradical initiator can be at least 0.1%, alternatively at least 0.5%, and alternatively at least 1%. Meanwhile, based on the same reference, the amount of photoradical initiator can be up to 10%, alternatively up to 8%, alternatively up to 6%, alternatively up to 5%, alternatively up to 4%, and alternatively up to 3%.

[0073] (F) Inhibitors of hydrosilylation reaction

[0074] The starting material (F) in the composition is a hydrosilylation inhibitor. Examples of hydrosilylation inhibitors include alkynyl alcohols such as dimethylhexynyl alcohol 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-octyyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol and 1-ethynyl-1-cyclohexanol (ETCH) and combinations thereof; cycloalkenylsiloxanes such as methylvinylcyclosiloxanes, examples of which include 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, etc. Siloxanes and combinations thereof; alkenylene compounds, such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne and combinations thereof; triazoles, such as benzotriazoles; phosphines; thiols; hydrazides; amines, such as tetramethylethylenediamine, 3-dimethylamino-1-propyne, n-methylpropynylamine, propynylamine and 1-ethynylcyclohexylamine; fumarates, including dialkyl esters of fumarate such as diethyl fumarate and / or dialenyl esters of fumarate such as diallyl fumarate and / or dialkoxyalkyl fumarate; maleate 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.

[0075] Alternatively, the inhibitor of the hydrosilylation reaction can be a silylalkynyl compound. Without being bound by theory, it is believed that the addition of a silylalkynyl compound reduces the yellowing of the reaction product prepared by the hydrosilylation reaction compared to the product obtained from a starting material that does not contain a silylalkynyl compound or contains an organoalkynyl alcohol inhibitor (such as those mentioned above). Examples of silylated alkynes include (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3-methyl-1-butyn-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)trimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, and (3-methyl-1-butyn-3-oxy)trimethylsilane. Ethylsilane, 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, examples of silylated alkynyl compounds include methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or combinations thereof. Silyylated alkynyl compounds that can be used as inhibitors herein can be prepared by methods known in the art, for example, U.S. Patent 6,677,407 discloses the silylation of the aforementioned alkynyl alcohols by reacting them with chlorosilanes in the presence of an acid acceptor. Alternatively, hydrosilylation inhibitors can be selected from the group consisting of alkynyl alcohols, cycloalkenylsiloxanes, enyne compounds, triazoles, phosphines, thiols, hydrazides, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, alcohols, and silylated alkynyl alcohols. Alternatively, hydrosilylation inhibitors can be alkynyl alcohols, such as ETCH.

[0076] The amount of hydrosilylation inhibitor used in the composition will depend on various factors, including the desired reaction rate, the specific hydrosilylation inhibitor used, and the selection and amount of aliphatic unsaturated hydrocarbon groups and silicon-bonded hydrogen atoms in the other starting materials in the composition. However, when present, the amount of hydrosilylation inhibitor may be at least 5 ppm, alternatively at least 0.05%, and alternatively at least 0.1%, based on the combined weight of the starting materials (A), (B), (C), (D), (E), and (F) in the composition. Meanwhile, based on the same baseline, the amount of hydrosilylation inhibitor may be at most 2%, and alternatively at most 1%.

[0077] (G) Free radical scavengers

[0078] The starting material (G) is a free radical scavenger that may optionally be added to the composition. The starting material (G) is a free radical scavenger (scavenger) that can be used to control or inhibit the free radical reaction of the composition. Because the composition contains reactive (meth)acrylate functional groups, an effective free radical scavenger can be present to prevent premature reaction, for example, during storage and during use of the protective film prepared using the composition. Furthermore, when preparing the starting material (B) (a resin having (meth)acryloyl functional groups), a free radical scavenger can also be used to prevent premature reaction during reaction at high temperatures. Scavengers containing phenolic compounds are a class of substances that can be used in this invention, including, for example, 4-methoxyphenol (MEHQ, a methyl ether of hydroquinone), hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, tert-butylcatechol, butylated hydroxytoluene, and butylated hydroxyanisole, and combinations of two or more of these. Other scavengers that can be used include phenothiazines and anaerobic inhibitors, such as NPAL-type inhibitors (tris-(N-nitroso-N-phenylhydroxylamine) aluminum salt) from Albemarle Corporation (Baton Rouge, La.). Alternatively, free radical scavengers may be selected from the group consisting of free phenolic compounds, phenothiazines, and anaerobic inhibitors.

[0079] Free radical scavengers are known, for example, in U.S. Patent 9,475,968 and are commercially available. The amount of scavenger in the composition will depend on various factors, including the type and amount of (meth)acryloyloxyalkyl groups in the starting material (B); however, the scavenger may be present in amounts from 0.001 parts by weight to 0.1 parts by weight, or alternatively from 0.001 parts by weight to 0.05 parts by weight per 100 parts of the starting material (B).

[0080] (H) solvent

[0081] The starting material (H) is a solvent that may optionally be added to the composition. The solvent may be added during the preparation of the composition, for example to aid in the mixing and delivery of one or more starting materials, and / or may be added after the preparation of the composition, for example to facilitate coating on a substrate, as described below. When preparing the composition, certain starting materials such as (B) resins and / or (C) hydrosilylation catalysts may be delivered in a solvent. Suitable solvents include organic liquids, examples of which are, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, ketones, esters, ethers, glycols, and glycol ethers. Hydrocarbons include benzene, toluene, xylene, naphtha, hexane, cyclohexane, methylcyclohexane, heptane, octane, decane, hexadecane, isoparaffins (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, acetone-acetone, 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 containing both ester and ether moieties include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate; ethers and esters also include isodecanyl neopentanoate, neopentyl glycol heptanoate, distearate, dioctyl 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 (PGMEA), propylene glycol methyl ether (PGME), dipropylene glycol methyl ether, or ethylene glycol n-butyl ether, octyl dodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dioctyl ester / propylene glycol didecyl ester, octyl ether, and octyl palmitate. Alternatively, solvents may be selected from polyalkylsiloxanes, ketones, ethylene glycol ethers, tetrahydrofuran, solvent oils, naphtha, or combinations thereof. Polyalkylsiloxanes with suitable vapor pressures can be used as solvents, and these polyalkylsiloxanes include hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, tetra(trimethylsiloxy)silane, dodecylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecylpentasiloxane, tetradecylmethylhexasiloxane, hexadecylmethylheptasiloxane, 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 0.5 cSt to 1.5 cSt polydimethylsiloxane are known in the art and can be traded under the name DOWSIL.TM 200 fluid and DOWSIL TM OS fluids are commercially available and can be sourced from Dow Silicones. Alternatively, solvents may be selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters, and solvents having both ether and ester moieties. Alternatively, solvents may be selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons.

[0082] The amount of solvent will depend on various factors, including the type of solvent selected and the quantity and type of other starting materials chosen to adjust the coating viscosity. Alternatively, the amount of solvent may be from 0 to 300 parts by weight of all starting materials per 100 parts by weight of the composition. Alternatively, the amount of solvent may be from 0.5 to 200 parts by weight, or alternatively from 20 to 300 parts by weight, of all starting materials per 100 parts by weight of the composition.

[0083] (I) Nonfunctional polyorganosilicon resin

[0084] The composition may optionally further comprise a starting material (I) of a nonfunctional polyorganosilicon resin. It is not desired to be bound by theory, but it is considered that the nonfunctional polyorganosilicon resin can act as a tackifier to modify mechanical properties and / or help control the initial adhesive strength of the PSA (formed by curing the composition via hydrosilylation). The starting material (I) used in the composition may be sufficient to provide a weight ratio (nonfunctional resin / polymer ratio) of 0.1 / 1 to 4 / 1 of the nonfunctional resin to (A) polydiorganosilicon. The starting material (I) comprises formula (R) 1 3SiO 1 / 2 ) p (SiO 4 / 2 ) q (ZO) h The unit of the polyorganosilicate resin, 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 Daltons to 30,000 Daltons. Such nonfunctional resins are known in the art and are commercially available. Such nonfunctional resins can be prepared as described above with respect to starting material (B), but by replacing the (meth)acryloyl functional starting material with a starting material having alkyl groups and / or aryl groups, such as alkyl halosilanes like methylchlorosilane and / or alkylalkoxysilanes like methylmethoxysilane.

[0085] (J) Fixative Additives

[0086] Optionally, the composition may further comprise an adhesion promoter (J) which can be added to improve its adhesion to the basement membrane. Examples of starting materials (J) may include: silane coupling agents such as methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, bis(trimethoxysilyl)propane, and bis(trimethoxysilyl)hexane; mixtures or reaction mixtures of said silane coupling agents; and siloxane compounds having at least one silicon-bonded hydroxyl group and one silicon-bonded alkenyl group. The adhesion promoter is commercially available, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in DOWSIL TM Z-6043 silane is available from Dow Silicones. When present, the amount of the immobilizing additive may be from 0.05 parts by weight to 5 parts by weight of all starting materials per 100 parts by weight of the composition.

[0087] Methods for preparing compositions and PSA

[0088] The composition can be prepared by combining all starting materials in any convenient manner, such as mixing at RT or elevated temperatures. For example, when the composition will be prepared at elevated temperatures and / or when the composition will be prepared as a single-component composition, a hydrosilylation inhibitor can be added before the hydrosilylation catalyst.

[0089] The method may also include delivering one or more starting materials (e.g., a linear polydiorganosiloxane polymer (A), a (meth)acryloyloxyalkyl functionalized polyorganosiloxane resin (B), and / or a hydrosilylation catalyst (D) and / or, when present, a nonfunctional resin (I)) in a solvent, which are soluble in the solvent when mixed with one or more other starting materials in the composition. Optionally, all or substantially all of the solvent may subsequently be removed by conventional methods such as stripping and / or distillation (optionally under reduced pressure). Those skilled in the art will understand that the resulting composition is solvent-free or may contain trace amounts of residual solvent from the delivery of the starting materials; however, in some cases, solvents (e.g., organic solvents such as toluene or nonfunctional polydiorganosiloxanes) are not intentionally added to the composition. Alternatively, the composition may be solvent-based.

[0090] Alternatively, for example, when the composition will be stored for an extended period of time before use (e.g., up to 6 hours before coating the composition onto a substrate), the composition can be prepared as a multipart composition. In a multipart composition, the hydrosilylation catalyst is stored in a separate portion from any starting material having silicon-bonded hydrogen atoms (e.g., polyorganohydrosiloxanes), and the portions are combined just before the composition is used.

[0091] For example, a multipart composition can be prepared by any convenient method, such as mixing, by combining starting materials comprising at least some of the following to form a matrix portion: (A) a polymer, (C) a polyorganohydrosiloxane, and optionally one or more other additional starting materials as described above. A curing agent can be prepared by any convenient method, such as mixing, by combining starting materials comprising at least some of the following: (A) a polymer, (C) a hydrosilylation reaction catalyst, and optionally one or more other additional starting materials as described above. The starting materials can be mixed at ambient temperature or elevated temperature. A hydrosilylation reaction inhibitor can be included in one or more of the matrix portion, the curing agent portion, or a separate additional portion. When present, the starting material (I) a nonfunctional resin can be added to the matrix portion, the curing agent portion, or a separate additional portion. The starting material (B) a (meth)acryloyloxyalkyl functionalized polyorganosiloxane resin can be added to the matrix portion. A photoradical initiator and (G) a radical scavenger can be added to the matrix portion or a separate additional (third) portion. The starting material (J) and a fixing additive (when present) can be added to the matrix portion.

[0092] When using a two-part composition, the weight ratio of the matrix portion to the curing agent portion can range from 1:1 to 10:1. The composition will cure via a hydrosilylation reaction to form a PSA with initial adhesion. Curing is achieved by hydrosilylation at RT or by heating at a temperature sufficient for the composition to form a PSA at 60°C to 220°C, alternatively 70°C to 170°C, alternatively 80°C to 160°C for a duration sufficient to form a PSA.

[0093] Preparation of adhesive products

[0094] The above method may also include one or more additional steps. The composition prepared as described above can be used to form an adhesive article on a substrate, such as a pressure-sensitive adhesive (prepared by curing the above composition). Therefore, the method may also include applying the composition to the substrate.

[0095] The composition can be applied to the substrate in any convenient manner. For example, the pressure-sensitive adhesive curable composition can be applied to the substrate by a gravure coater, offset coater, photogravure coater, roller coater, reverse roller coater, air knife coater, or curtain (groove) coater.

[0096] The substrate can be any material capable of withstanding the curing conditions (described below) used to cure the composition to form a PSA on the substrate. For example, any substrate capable of withstanding heat treatment at a temperature equal to or greater than 120°C, or alternatively 150°C, is suitable. Examples of materials suitable for such substrates include plastic films such as polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), liquid crystal polyaramid, polyamide-imide (PAI), polyether sulfide (PES), polyethylene terephthalate (PET), polyethylene (PE), or polypropylene (PP). The thickness of the substrate is not critical; however, it can be from 5 micrometers to 300 micrometers, or alternatively from 25 micrometers to 300 micrometers. The substrate can be transparent; alternatively, opaque substrates can be used, provided that these substrates allow the PSA to be exposed to UV radiation.

[0097] To improve the adhesion between the PSA and the substrate, the method for forming the adhesive article may optionally include treating the substrate before applying the PSA composition. The substrate can be treated by any convenient means, such as applying a primer, or subjecting the substrate to corona discharge treatment, etching, or plasma treatment before applying the composition to the substrate.

[0098] Adhesive articles (such as protective films or tapes) can be prepared by applying the above-described composition to a substrate. The method may optionally include removing all or part of the solvent (if present) before and / or during curing. Solvent removal can be carried out by any convenient means, such as heating at a temperature that evaporates the solvent without completely curing the composition, for example, at 70°C to 120°C, alternatively 50°C to 100°C, and alternatively 70°C to 80°C for a time sufficient to remove all or part of the solvent (e.g., 30 seconds to 1 hour, alternatively 1 minute to 5 minutes). The method then further includes curing the composition by hydrosilylation at RT or by heating at 60°C to 220°C, alternatively 70°C to 170°C, and alternatively 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, alternatively 15 minutes to 45 minutes), which removes some or all of the solvent during the drying step. Drying to remove all or part of the solvent and / or hydrosilylation curing can be carried out by placing the substrate in an oven. The amount of composition to be applied to the substrate depends on the specific application; however, this amount may be sufficient to result in a PSA thickness of 50 micrometers to 1,000 micrometers, alternatively 100 micrometers to 700 micrometers, and alternatively 200 micrometers to 600 micrometers after curing via hydrosilylation.

[0099] Therefore, methods for forming an adhesive article (e.g., in the form of a protective film) comprising a PSA layer on a substrate surface include:

[0100] Optionally 1) the surface of the substrate is treated as described above;

[0101] 2) Apply the composition to the surface of the substrate, and

[0102] Optionally 3) If present, remove all or part of the solvent;

[0103] 4) The composition is cured via hydrosilylation reaction to form a PSA layer on the substrate surface.

[0104] If necessary, steps 2) through 4) of the above method can be repeated once or more to obtain an increased thickness of the PSA layer. (The required thickness is described herein). The above method may also optionally include applying a removable release liner to the PSA layer opposite the substrate, for example, to protect the PSA before use. The release liner can be removed before using the adhesive article. The obtained PSA layer contains free (meth)acryloyl functional groups, which can be analyzed by Fourier transform infrared (FT-IR) spectroscopy. The relative amount of these functional groups in the PSA film and their reaction upon exposure to UV irradiation can be monitored by the vibrational absorption intensity of unsaturated bonds in the FT-IR spectrum, as shown in the following reference: 'UV coatings: basics, recent developments and new applications', page 33 (Elsevier; December 21, 2006), Schwalm; Polymer Chemistry., 2013; Vol. 4, No. 8: pp. 2449-2456, Espeel. At approximately 1296 cm⁻¹ -1 and 938cm -1 Free (meth)acryloyl functional groups were detected in PSA obtained by using starting material (B).

[0105] How to use

[0106] The above method may also include the use of a protective film in the method for manufacturing (opto)electronic devices. This method may include exposing the PSA layer to photochemical radiation such as UV radiation. For example, improvements to the method for manufacturing (opto)electronic devices may include:

[0107] 5) Apply the protective film prepared as described above to the (opto)electronic device, so that the PSA layer contacts the surface of the (opto)electronic device;

[0108] 6) Use the protective film to protect the device; and thereafter

[0109] 7) Expose the PSA layer to photochemical radiation such as UV radiation. As a result of the radiation exposure in step 6), the adhesion will increase. A common (permanent) adhesive can be formed.

[0110] The irradiation in step 7) can be performed using general ultraviolet irradiation equipment, such as surface-mounted or conveyor-type ultraviolet irradiation equipment, in which low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electrodeless lamps, ultraviolet light-emitting diodes, etc., are used as the light source. The ultraviolet irradiation dose is typically 0.1 W / cm². 2 Up to 10W / cm2 The duration is from 0.1 seconds to 120 seconds (=0.1J / cm). 2 Up to 1200J / cm 2 ).

[0111] Example

[0112] These embodiments are provided to illustrate the invention to those skilled in the art and are not to be construed as limiting the scope of the invention as described in the claims. The starting materials used in these embodiments are shown in Table 1 below.

[0113] Table 1 - Starting Materials

[0114]

[0115]

[0116]

[0117] Comparative Reference Example 1: Preparation of Starting Material A'-5

[0118] In this A, a divinyldimethylsiloxy-terminated poly(dimethyl / methyl,methacryloyloxypropyl)siloxane copolymer, shown as comparative starting material A'-5 in Table 1 above, was synthesized as follows. 3-Methacryloxypropylmethyldimethoxysilane (108.92 g, DOWSIL) was added to a 1-liter round-bottom flask with four necks. TMZ-6033) and 0.1N HCl (128.87 g) were mixed at approximately 23°C using a magnetic stir bar. A simple distillation glassware apparatus was used to evacuate the solution to approximately 20 mmHg for 1.5 hours. After 1.5 hours, the vacuum was released, and 1179.75 g of dihydroxy-terminated polydimethylsiloxane (OH fluid in Table 1) along with 0.34 g of (G-1) MEHQ was added to the reaction solution. The magnetic stir bar was removed, and the solution was mixed using a Teflon paddle with a glass stir bar. The vacuum was evacuated to approximately 5 mmHg, and the reaction was heated at 80°C for 1.5 hours. The simple distillation glassware apparatus was removed, and a Dean Stark distillation apparatus was used for the final reaction step. (H-1) toluene (380 g, Sigma-Aldrich) and 2.87 g of dihydroxy-terminated polydimethylsiloxane (terminant in Table 1) were added to the reaction solution. The solution was then heated to 111-115°C, with 0.3 mL of phosphazene catalyst added when the temperature reached 90°C. The overhead distillate was collected in a Dean Stark trap, and another 0.3 mL of phosphazene catalyst was added. The solution was held under toluene reflux for 1 hour. The heat was removed, and the solution was cooled. Trihexylamine (0.3 g, Sigma-Aldrich) was added to the reaction solution at approximately 60°C and mixed for 2 hours. The solution was then heated to 120°C under nitrogen / 2% oxygen bubbling for 1 hour and cooled to RT. The solids content of the solution was adjusted to 75% by adding additional toluene. The resulting resin-containing solution (75% resin / 25% solvent) was then identified as having the unit formula M. Vi D MA 232 D Me 2488 M Vi .

[0119] Reference Implementation Examples 1 Starting material B-1 Preparation

[0120] In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, and Dean Stark trap, 375.31 g of a mixture containing 75% (I-1)MQ resin dissolved in 25% xylene, 1.5 g of 11N KOH aqueous solution, and toluene was refluxed to remove water for 2 hours. 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 with toluene. Toluene corresponding to the lost toluene was added to the mixture. The resulting mixture was refluxed again for 3 hours. After cooling to room temperature, acetic acid was added. The mixture was stirred for 1 hour and then filtered. The obtained resin-containing solution (75% resin / 25% solvent) was identified as having the unit formula M Me 49.6 D MA 3.9 Q 46.5 (OH) 0.45 (OCH3) 0.03 It has 2047 Mn and 1.425 Mw / Mn and 75% solids content by GPC (B-1 in Table 1 above).

[0121] Reference Implementation Examples 2 Starting material B-2 Preparation

[0122] In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, and condenser, a mixture of 92.94 g Z-6030, 375.31 g of a solution containing 75% (I-1) MQ resin dissolved in 25% xylene, 15 g water, and 0.11 g (G-1) MEHQ was placed in the flask, and 0.6 g trifluoromethanesulfonic acid (Aldrich) was added to the mixture at room temperature with stirring. The temperature was then raised to 47°C. After 1 hour, the mixture was cooled to room temperature, and 25.62 g methanol, 1.5 g 11N KOH aqueous solution, and toluene were added sequentially, followed by reflux for 2 hours. After replacing the Dean Stark trap with a condenser, the temperature was gradually raised to 125°C to remove methanol and water with toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to RT, acetic acid was added. The mixture was stirred for 1 hour and then filtered. The obtained resin-containing solution (75% resin / 25% solvent) was identified as having the unit formula M. Me 47.7 D MA 8.7 Q 43.6 (OH) 0.75It has a Mn content of 2095 and a Mw / Mn ratio of 1.327 and a solids content of 75% by GPC (B-2 in Table 1 above).

[0123] Reference Implementation Examples 3 Starting material B-3 Preparation

[0124] In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, and condenser, a mixture of 24.84 g Z-6030, 375.31 g of a solution containing 75% (I-1) MQ resin dissolved in 25% xylene, 7 g water, and 0.11 g (G-1) MEHQ was placed in the flask, and 0.5 g trifluoromethanesulfonic acid (Aldrich) was added to the mixture at room temperature with stirring. The temperature was then raised to 47°C. After 1 hour, the mixture was cooled to room temperature, and 25.62 g methanol, 1.44 g 11N KOH aqueous solution, and toluene were added sequentially, followed by reflux for 2 hours. After replacing the Dean Stark trap with a condenser, the temperature was gradually increased to 125°C to remove methanol and water with 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 obtained resin-containing solution (75% resin / 25% solvent) was identified as having the unit formula M. Me 52 T MA 2.1 Q 45.9 (OH) 0.92 It has 2131 Mn and 1.47 Mw / Mn and 75% solids content by GPC (B-3 in Table 1 above).

[0125] Reference Implementation Examples 4 Starting material B-4 Preparation

[0126] In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, and condenser, a mixture of 49.67 g Z-6030, 13 g water, and 0.1 g (G-1) MEHQ was placed in the flask, and 0.5 g trifluoromethanesulfonic acid was added to the mixture while stirring at RT. The temperature was then gradually increased to 47 °C. After cooling to RT, 375.31 g of a solution containing 75% (I-1) MQ resin dissolved in 25% xylene, 25.62 g methanol, 1.5 g of 11N KOH aqueous solution, and toluene were added sequentially, and the mixture was refluxed for 2 hours. After replacing the Dean Stark trap with a condenser, the temperature was gradually increased to 125 °C to remove methanol and water with toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 12 hours. After cooling to RT, acetic acid was added. The mixture was stirred for 1 hour and then filtered. The resulting resin-containing solution (75% resin / 25% solvent) was identified as having the unit formula M. Me 50.2 T MA 4.6 Q 45.2 (OH) 0.83 It has a Mn content of 2324 and a Mw / Mn ratio of 1.48 and a solids content of 75% by GPC (B-4 in Table 1 above).

[0127] Reference Implementation Examples 5 Starting material B-5 Preparation

[0128] In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, and condenser, a mixture of 116.18 g Z-6030, 81.70 g dihydroxy-terminated polydimethylsiloxane (DP=11), 18 g water, and 0.13 g (G-1) MEHQ was placed in the flask, and 0.6 g trifluoromethanesulfonic acid was added to the mixture while stirring at room temperature. The temperature was then gradually increased to 47 °C. After cooling to RT, 375.31 g of a solution containing 75% (I-1) MQ resin dissolved in 25% xylene, 32.02 g methanol, 1.73 g of 11N KOH aqueous solution, and toluene were added sequentially, and the mixture was refluxed for 2 hours. After replacing the Dean Stark trap with a condenser, the temperature was gradually increased to 125 °C to remove methanol and water with toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to RT, 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 was identified as having the unit formula M. Me 38.1 D MA 8.8 D Me 17.3 Q 35.8(OH) 0.97 It has a Mn content of 2079 and a Mw / Mn ratio of 1.45 and a solids content of 75% by GPC (B-5 in Table 1 above).

[0129] Reference Implementation Examples 6 Starting material B-6 Preparation

[0130] In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, and condenser, a mixture of 46.47 g Z-6030, 81.70 g dihydroxy-terminated polydimethylsiloxane (DP=11), 8.7 g water, and 0.13 g (G-1) MEHQ was placed in the flask, and 0.6 g trifluoromethanesulfonic acid was added to the mixture while stirring at RT. The temperature was then gradually increased to 47 °C. After cooling to RT, 375.31 g of a solution containing 75% (I-1) MQ resin dissolved in 25% xylene, 50 g methanol, 1.73 g 11N KOH aqueous solution, and toluene were added sequentially, and the mixture was refluxed for 2 hours. After replacing the Dean Stark trap with a condenser, the temperature was gradually increased to 125 °C to remove methanol and water with toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to RT, 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 was identified as having the unit formula M. Me 40.1 D MA 3.7 D Me 18.8 Q 37.4 (OH) 0.91 It has 2114 Mn and 1.504 Mw / Mn and 75% solids content by GPC (B-6 in Table 1 above).

[0131] Reference Implementation Examples 7 Starting material B-7 Preparation

[0132] In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, and condenser, a mixture of 23.24 g Z-6030, 4.3 g water, and 0.11 g (G-1) MEHQ was placed in the flask, and 0.5 g trifluoromethanesulfonic acid was added to the mixture while stirring at RT. The temperature was then gradually increased to 47 °C. After cooling to RT, 375.31 g of a solution containing 75% (I-1) MQ resin dissolved in 25% xylene, 50 g methanol, 1.44 g 11N KOH aqueous solution, and toluene were added sequentially, and the mixture was refluxed for 2 hours. After replacing the Dean Stark trap with a condenser, the temperature was gradually increased to 125 °C to remove methanol and water with toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to RT, acetic acid was added. The mixture was stirred for 1 hour and then filtered. The resulting resin-containing solution (75% resin / 25% solvent) was identified as having the unit formula M. Me 50.4 D MA 2.2 Q 47.4 (OH) 0.92 It has a Mn content of 2082 and a Mw / Mn ratio of 1.347 and a solids content of 75% by GPC (B-7 in Table 1 above).

[0133] Reference Implementation Examples 8 Starting material B-8 Preparation

[0134] In a 500 ml three-necked flask equipped with a mechanical stirrer, thermometer, and condenser, a mixture of 23.24 g Z-6030, 81.70 g dihydroxy-terminated polydimethylsiloxane (DP=11), 4.4 g water, and 0.13 g (G-1) MEHQ was placed in the flask, and 0.6 g trifluoromethanesulfonic acid was added to the mixture while stirring at RT. The temperature was then gradually increased to 47 °C. After cooling to RT, 375.31 g of a solution containing 75% (I-1) MQ resin dissolved in 25% xylene, 50 g methanol, 1.73 g of 11N KOH aqueous solution, and toluene were added sequentially, and the mixture was refluxed for 2 hours. After replacing the Dean Stark trap with a condenser, the temperature was gradually increased to 125 °C to remove methanol and water with toluene. After removing water and methanol, the resulting mixture was refluxed for an additional 9 hours. After cooling to RT, acetic acid was added. The mixture was stirred for 1 hour and then filtered. The obtained resin-containing solution (75% resin / 25% solvent) was identified as having the unit formula M. Me 41 D MA 1.8 D Me 18.4 Q 38.8 (OH)0.95 It has a Mn content of 2329 and a Mw / Mn ratio of 1.56 and a solids content of 75% by GPC (B-8 in Table 1 above).

[0135] In this reference example 9, a silicone-(meth)acrylate pressure-sensitive adhesive composition and a comparative composition were prepared. Starting materials (A) and (B) were soluble in a solvent. The general procedure was as follows: To prepare the sample labeled Inv.1, a solution was prepared by mixing the following starting materials in a mixer: First, starting material (A-1) was dissolved in toluene (H-1) to obtain a 30% solution by mixing. Then, 133.33 g of a solution containing 100 g of starting material (A-1) dissolved in toluene (H-1); 23.66 g of a solution containing 17.75 g of starting material (B-1) dissolved in a solvent; 0.59 g of polyorganohydrosiloxane (C-1); and 0.05 g of a hydrosilylation inhibitor (F-1) were mixed. After mixing the above starting materials, the resulting solution was further mixed with 1.18 g of a hydrosilylation catalyst (D-1) and 3.55 g of a photoradical initiator (E-1). The above starting materials were mixed with the above solution to produce a silicone-(meth)acrylate pressure-sensitive adhesive composition. This composition was used to manufacture adhesive tapes. The lamination properties and adhesive strength of the adhesive tapes were evaluated. Comparative Examples, Inv.2–29 and Inv.32–38 were prepared in the same manner using the starting materials and amounts listed in the table. To prepare the solvent-free sample labeled Inv.30, a solution was prepared by mixing the following starting materials in a mixer: 100 g of starting material (A-4) and 400 g of a solution containing 300 g of starting material (B-1), and the solvent was evaporated at 90°C under reduced pressure for 3 hours. Then, 2.01 g of polyorganohydrosiloxane (C-1) and 0.2 g of hydrosilylation inhibitor (F-1) were added. After mixing the above starting materials, the resulting fluid was further mixed with 4.02 g of hydrosilylation catalyst (D-1) and 12.06 g of photoradical initiator (E-1). Inv.31 uses the starting materials and amounts in the table to prepare the same way.

[0136] The composition has the formulations shown in the table below. Performance results of the PSA prepared from the composition are also shown in the table below. Values ​​in parentheses indicate the total amount of polysiloxane and solvent added when delivering the starting material in a solvent. Values ​​without parentheses indicate the amount of polysiloxane starting material other than the solvent. (Tables 2 through 7 show the starting materials used (described in detail in Table 1) and their amounts [based on grams of solids and (grams of solution)]. Values ​​(grams of solution) indicate that the starting material is first dissolved in the solvent and represent the weight of the solution in grams. Values ​​based on solids indicate the amount of starting material excluding the solvent.)

[0137] In this Reference Example 10, the adhesive strength (initial adhesion) before UV irradiation was measured as follows. For Comparative Examples 1 to 4 and Working Examples 1 to 33, a silicone (meth)acrylate pressure-sensitive adhesive composition was applied to a polyethylene terephthalate (PET, 75 μm) film to form a silicone mixed pressure-sensitive adhesive layer, which, after curing, had a thickness of 30 μm. A silicone mixed pressure-sensitive adhesive sheet was produced by heating the film at 150°C for 3 minutes. The obtained sheet was laminated onto a peelable polyethylene terephthalate film using a laminator, and the resulting laminate was aged at RT for 1 day. The obtained sheet was cut into 2.54 cm (1 inch) wide strips of adhesive tape, which were placed on a glass plate and bonded thereto by moving a 2 kg weighted roller with a rubber pad back and forth twice on the strips. The assembly was kept at room temperature for 1 hour. The required adhesion force (g / inch) is achieved by pulling the tape off the glass plate at a speed of 300 mm / min and an angle of 180°.

[0138] For working examples (Inv.) 34–38, a silicone (meth)acrylate pressure-sensitive adhesive composition was applied to a peelable polyethylene terephthalate (PET, 75 μm) film to form a double-sided silicone-mixed pressure-sensitive adhesive sheet, which, after curing, had a thickness of 50 μm. The silicone-mixed pressure-sensitive adhesive sheet was produced by heating the film at 150°C for 3 minutes. The obtained sheet was laminated onto the peelable PET film using a laminator, and the resulting laminate was aged at RT for 1 day. After removing 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 removing the peelable polyethylene terephthalate film from the opposite side, it was laminated onto another glass substrate with an overlap of 2.5 cm × 2 cm (= 5 cm). 2 The area of ​​the laminate was measured according to the overlap shear test method (ASTM D3163) after the laminate was subjected to a 2 kg weight for 30 minutes.

[0139] To measure the adhesive strength after UV irradiation, the components prepared as described above were held at RT for 1 day. Then, the components were irradiated with UV light under the following conditions: using a 365nm LED lamp (FireJet). TM FJ100 was used to irradiate the top surface of the substrate film at 0.7 W / cm². 2 UV light under UV illumination for 30 seconds.

[0140] Reference Example 11—Transmittance and Haze

[0141] The transmittance of the silicone-(meth)acrylate pressure-sensitive adhesive sheet cured as described above at 500 nm was measured using the method specified in ASTM D 1003 (UV-Vis spectrometer, reference = air). The haze was measured in the same manner as described above using ASTM D 1003-97 (spectrophotometer, CM-3600A, reference = 75 μm PET).

[0142] Reference Example 12—Si-NMR Analysis

[0143] The average molecular formulas of the above-mentioned polyorganosiloxane polymers and (meth)acryloyl-functionalized polyorganosiloxane resins were determined by combined Si-NMR and C-NMR analysis.

[0144] NMR equipment: Bruker 500MHz AVANCE 3NMR Fourier transform nuclear magnetic resonance spectrometer, equipped with a 10mm Si-free probe / 5mm BBFO probe.

[0145] Determination method: The integrated values ​​of the peaks were calculated based on the signals from the Si ' units derived from the various siloxane units shown below. D and DR' (where R' = (meth)acryloyl functional group or other organic functional group) were calculated using Si-Me number-normalized Si-NMR and C-NMR. The average molecular formula was identified by finding the ratio of the integrated signal values ​​obtained for each siloxane unit, and then determining the siloxane unit ratio based on the determined signal ratio.

[0146]

[0147] Reference Example 13 – Gel Permeation Chromatography

[0148] Samples were prepared in toluene at a concentration of 0.5% w / v, filtered through a 0.45 μm PTFE syringe filter, and analyzed relative to polystyrene standards. Relative calibration (third-order fit) for molecular weight determination was based on 16 polystyrene standards with molecular weights ranging from 580 Daltons to 2,610,000 Daltons. The chromatographic apparatus 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) pre-connected with Styragel guard columns (4.6 mm × 30 mm). Separation was performed using a toluene flow rate of 1.0 mL / min, with an injection volume of 100 μL and the column and detector heated to 45 °C. Data were collected over 60 min and processed using Empower software. As used in this article, Mn represents the molecular weight when the peak representing the new pentamer is excluded from the measurement.

[0149] Table 2

[0150]

[0151] Table 2 (continued)

[0152]

[0153]

[0154] Comparative Examples 1-3 are representative examples of conventional silicone pressure-sensitive adhesives, demonstrating the adhesive properties provided by using non-functional (e.g., trimethylated) polyorganosilicon resins based on the resin / polymer ratio. However, the adhesive strength of these conventional silicone pressure-sensitive adhesives is constant and does not provide an increase in adhesive strength after UV irradiation for silicone pressure-sensitive adhesives prepared from these compositions. In contrast, Working Examples 1-6 show that the silicone (meth)acrylate pressure-sensitive adhesive compositions described herein (comprising a polydiorganosiloxane polymer having aliphatic unsaturated groups and a (meth)acryloyloxyalkyl functionalized polyorganosilicon resin) exhibit a significantly increased adhesive strength after UV irradiation while maintaining good transmittance and haze properties suitable for (opto)electronic device applications. Working Examples 1-6 demonstrate 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 material. Furthermore, the subsequent adhesive strength after UV exposure is also significantly increased compared to the initial adhesive strength in each of the working examples 1-4.

[0155] Comparative Example 4 shows that the curable composition comprising a (meth)acryloyloxyalkyl-functionalized polydimethylsiloxane polymer and a (meth)acryloyloxyalkyl-functionalized polysilicate resin does not exhibit increased adhesion after UV irradiation. When comparing Comparative Example 4 and Example 4, it is believed that the combination of aliphatic unsaturated polydimethylsiloxane (a polymer without (meth)acryloyl functional groups) and (meth)acryloyloxyalkyl-functionalized polysilicate resin imparts the increased adhesion behavior after UV irradiation observed in Example 4, which was not exhibited in Comparative Example 4 under the test conditions. Without being bound by theory, it is believed that photoradical-induced intermolecular reactions between the (meth)acryloyloxyalkyl functional groups of the polysilicate resin in the linear polydimethylsiloxane chain matrix induce the increased adhesion after UV irradiation.

[0156] Table 3

[0157]

[0158] Working Examples 7-9 in Table 3 also demonstrate increased adhesion after UV irradiation using different types of polydiorganosiloxane polymers (A-2) as the resin / polymer ratio increases. Additionally, Working Examples 9-11 show increased adhesion using the same starting material when the SiH / reactive group ratios are 0.29, 0.44, and 0.59. In contrast, Comparative Example 4 shows no increase in adhesion strength after UV irradiation when the SiH / reactive group ratio is 2.36 under the test conditions. Not wanting to be bound by theory, it is considered that a SiH / reactive group ratio <2 helps to alter the adhesion after UV irradiation by ensuring sufficient reactive groups of the (meth)acryloyloxyalkyl functionalized polyorganosilicate resin present after hydrosilylation curing to allow further reaction when the silicone methyl (acrylate) pressure-sensitive adhesive is irradiated with UV light.

[0159] Table 4

[0160]

[0161] Working Examples 12-17 in Table 4 demonstrate that parameters such as resin / polymer ratio and SiH / reactive group ratio can also be demonstrated by using different types of polydiorganosiloxane polymers (A-2 and A-3) and polyorganohydrosiloxane (C-2).

[0162] Table 5

[0163]

[0164]

[0165] Table 6

[0166]

[0167]

[0168] Table 7

[0169]

[0170]

[0171] a Resin (B-1) / polymer ratio = 1.02, Resin (I-1) / polymer ratio = 0.51

[0172] b Resin (B-1) / polymer ratio = 1.05, Resin (I-1) / polymer ratio = 1.56

[0173] Examples 18-31 in Tables 5, 6, and 7 demonstrate that parameters such as the resin / polymer ratio and the SiH / reactive group ratio can also be demonstrated by using different types of (meth)acryloyloxyalkyl-functionalized polysilicate resins (B-2 to B-9). Examples 32 and 33 show that solvent-free silicone (meth)acrylate pressure-sensitive adhesive compositions can also be prepared, which cure to form pressure-sensitive adhesives with desired adhesive properties. Furthermore, Examples 34 and 35 show that silicone hybrid pressure-sensitive adhesive compositions may also contain (I) nonfunctionalized polysilicate resins.

[0174] Table 8

[0175]

[0176] Working Examples 36–40 in Table 8 demonstrate that silicone (meth)acrylate pressure-sensitive adhesive compositions can be used to prepare double-sided adhesive sheets. As shown in Working Examples 36–40 in Table 8, using different resin / polymer ratios (up to 21.1 1 / 1), the adhesive strength of the assembled samples increased significantly after UV irradiation. Although the upper limit of the resin / polymer ratio is not strictly limited, it is not desirable to be bound by theory, as excessively high resin / polymer ratios (e.g., >22) are thought to cause cracking of the adhesive sheet depending on the structure and amount of the polyorganosilicate resin. Therefore, it is not desirable to be bound by theory, as a resin / polymer ratio <22 / 1 is considered conducive to the proper formation of silicone mixed pressure-sensitive adhesives.

[0177] Definition and usage of terms

[0178] The invention summary and abstract are incorporated herein by reference. All quantities, ratios, and percentages are by weight unless otherwise specified in the context of this specification. Unless otherwise specified in the context of this specification, the articles “an,” “a,” and “described” each refer to one or more. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are used as described in Sections 2111.03I, II, and III of the Patent Examining Procedure Ninth Edition, revised January 2018, 08.2017. The abbreviations used herein have their definitions in Table 9.

[0179] Table 9 - Abbreviations used in this article

[0180]

[0181]

Claims

1. A method for manufacturing an electronic device, the improvement of which includes: A protective film, including a pressure-sensitive adhesive layer, is formed on the surface of a substrate using methods including the following: 1) Optionally process the surface of the substrate; 2) Applying the composition to the surface of the substrate, wherein the composition comprises: (A) A linear polydiorganosiloxane polymer, wherein each molecule of the linear polydiorganosiloxane polymer has at least two aliphatic unsaturated hydrocarbon groups, the linear polydiorganosiloxane polymer comprising the 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 , where each R 4 It is an independently selected monovalent hydrocarbon group that does not contain aliphatic unsaturation, and each R 3 It is an independently chosen aliphatic unsaturated monovalent hydrocarbon group; the subscripts m, n, o, p, q, r, and s indicate the quantity of each unit and have values ​​such that 0 ≤ m, 0 ≤ n, quantity (m + n) ≥ 2; 0 < o < 10,000, p ≥ 0, quantity (o + p) is 100 to 10,000; 0 ≤ q ≤ 100, 0 ≤ r ≤ 100 and 0 ≤ s ≤ 100, provided that if any one or more of the subscripts q, r, or s are greater than 0, then the ratio (o + p) / (q + r + s) is 50 / 1 to 10,000 / 1; (B) (Meth)acryloyloxyalkyl-functionalized polysiloxane resins, wherein the (meth)acryloyloxyalkyl-functionalized polysiloxane resins comprise 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 , where each R 1 It is an independently selected monovalent hydrocarbon group, each R 2 Z is an independently chosen (meth)acryloyloxyalkyl group, each Z being independently chosen from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms; the subscripts a, b, c, d, e, f, g, and h denote the relative molar amount of each unit and have a value such that 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 amount (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 (B) resin / (A) polymer weight ratio of 0.15 / 1 to < 22 / 1; (C) Polyorganohydrosiloxanes, said polyorganohydrosiloxanes comprising 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 , where each R 5 The units are independently chosen monovalent hydrocarbon groups, and the subscripts t, u, v, w, x, y, and z indicate the quantity 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 amount (u + w + y) ≥ 2, and 2,000 ≥ (t + u + v + w + x + y + z) ≥ 3; wherein the polyorganohydrosiloxane is present in an amount sufficient to provide a molar ratio of silicon-bonded hydrogen atoms to reactive groups in the starting material (C) of 0.05 / 1 to 2 / 1, wherein the reactive groups are collectively the aliphatic unsaturated monovalent hydrocarbon group and the (meth)acryloyloxyalkyl group; (D) A hydrosilylation catalyst, wherein the amount of the hydrosilylation catalyst is sufficient to provide 1 ppm to 1,000 ppm of platinum group metals based on the combined weight of the starting materials (A), (B), (C), (D), (E) and (F) in the composition; (E) Photoradical initiator, wherein the amount of photoradical initiator is sufficient to provide 0.01% by weight to 10% by weight, based on the combined weight of the starting substances (A), (B), (C), (D), (E) and (F) in the composition. (F) A hydrosilylation inhibitor, provided in an amount sufficient to provide 5 ppm to 2% by weight, based on the combined weight of the starting materials (A), (B), (C), (D), (E), and (F) in the composition. Optional (G) free radical scavengers; and Optional (H) solvent; 3) If present, optionally remove the solvent; 4) Curing the composition to form the pressure-sensitive adhesive layer on the surface of the substrate, thereby forming the protective film; 5) Apply the protective film to the electronic device such that the pressure-sensitive adhesive layer contacts the surface of the electronic device; 6) Use the protective film to protect the device; And thereafter 7) Expose the pressure-sensitive adhesive layer to photochemical radiation.

2. The method according to claim 1, wherein in the starting material (A), R is used 3 Each aliphatic unsaturated monovalent hydrocarbon group is an independently chosen alkenyl group; and for R 4 Each monovalent hydrocarbon group is independently selected from the group consisting of alkyl groups and aryl groups, with subscripts m = 0, q = 0, r = 0, s = 0, n = 2, and the amount (n + o + p) is sufficient to provide a starting material (A) with a vinyl content of 0.01 wt% to 0.5 wt% based on the weight of the starting material (A).

3. The method according to claim 1, wherein in the starting material (B), R 1 Each monovalent hydrocarbon group is independently selected from the group consisting of alkyl and aryl groups, used for R 2 Each (meth)acryloyloxyalkyl functional group is independently selected from the group consisting of acryloyloxypropyl and methacryloyloxypropyl, with subscripts a from 35 to 55, b = 0, c from 1 to 10, d from 0 to 20, e from 0 to 5, f from 0 to 3, g from 35 to 50, and h from 0 to 1.

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

5. The method according to claim 1, wherein the hydrosilylation catalyst (D) is selected from the group consisting of: i) platinum group metals, ii) compounds of the metals, iii) complexes of the metals or the compounds, and v) the complexes microencapsulated in a matrix or core-shell structure.

6. The method according to claim 1, wherein the photoradical initiator in (E) is selected from the group consisting of photoradical initiators, and is capable of being 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 combinations of two or more of Ei) to Ex).

7. The method of claim 1, wherein the composition further comprises (F) a hydrosilylation inhibitor, and the hydrosilylation inhibitor is selected from the group consisting of: cycloalkenylsiloxanes, enyne compounds, triazoles, phosphine, thiols, hydrazines, amines, fumarates, maleates, nitriles, ethers, carbon monoxide, and alcohols.

8. The method according to claim 7, wherein the hydrosilylation reaction inhibitor is selected from alkynols and silylated alkynols.

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

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

11. The method according to claim 1, wherein the composition further comprises (I) a nonfunctional polyorganosilicon resin.

12. The method of claim 1, wherein the resin / polymer ratio is from 0.2 / 1 to 9 / 1.

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

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