Printable silicone composition and method of preparation and use thereof

Abstract

The curable silicone composition has a viscosity of 100 mPa·s or less at 25° C. The composition is suitable for use in printing processes. The composition can be cured by a hydrosilylation reaction to form a silicone adhesive suitable for use in the field of (opto)electronic device manufacturing.

Description

[Technical Field]

[0001] Cross-reference of related applications This application asserts the interests of U.S. Provisional Patent Application No. 63 / 144504, filed on 2 February 2021, pursuant to Section 119(e) of the U.S. Patent Act. U.S. Provisional Patent Application No. 63 / 144504 ​​is incorporated herein by reference.

[0002] The present invention relates to a curable silicone composition having a viscosity of 100 mPa·s or less. The composition is useful in an inkjet printing method for producing an adhesive layer suitable for use in the field of (opto)electronic device manufacturing.

[0003] Introduction Conventional curable silicone compositions for forming silicone pressure-sensitive adhesives typically consist of linear silicone gum (e.g., having a viscosity higher than 1,000,000 mPa·s) and triorganosiloxane units (formula R3SiO2). 1 / 2 (In the formula, R represents a monovalent hydrocarbon group) and silicate (Q) units (Formula SiO 4 / 2 The composition contains a solid tackifying resin which is essentially made from (the above). In addition to the two components mentioned above, such a silicone composition may contain a solvent to reduce viscosity when the curable silicone composition is coated onto the surface of a substrate to form a silicone pressure-sensitive adhesive layer. However, the use of volatile solvents has several drawbacks. Firstly, a solvent drying process is required when using the composition, which is undesirable. Also, solvent drying can cause non-uniformity of the inkjet-printed layer or other features (e.g., layers with uneven dot size and / or roughness), and / or shrinkage of the dot size during solvent evaporation. Furthermore, the use of volatile solvents is undesirable from an environmental standpoint.

[0004] Solvent-free silicone pressure-sensitive adhesive compositions are disclosed that can be used to form a silicone pressure-sensitive layer by typical coating and curing methods. However, the viscosity of such solvent-free silicone adhesive compositions at 25°C is typically several thousand mPa·s or more. For example, the compositions disclosed in U.S. Patent No. 7,687,591 by Bhagwagar et al. and U.S. Patent No. 8,754,174 by Aoki have high viscosity and are not suitable for use in inkjet printing processes.

[0005] In the field of (optical)electronic device manufacturing, various pressure-sensitive adhesives have been proposed for attaching two different layers or display components to a device. Dry lamination using pressure-sensitive adhesive sheets is widely applied in this field. In addition, dispensing methods, which form layers on a substrate using liquid-curable adhesives, have also been proposed. However, these methods have limitations in manufacturing thinner (optical)electronic devices because it is difficult to achieve layers with a thickness of 50 μm or less. [Overview of the Initiative]

[0006] A curable silicone composition, (A) An aromatic compound having two alkenyl groups per molecule and a molecular weight of less than 1,000 g / mol, in an amount of 10 to 90 parts by mass, (B) An aromatic compound having two silicon-bonded hydrogen atoms per molecule and a molecular weight of less than 1,000 g / mol, in an amount of 90 to 10 parts by mass, Aromatic compounds are defined as having a total amount of starting material (A) and starting material (B) of 100 parts by mass, (C) Alkenyl-functionalized polyorganosilicate resin in an amount of 10 to 130 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), (D) an alkenyl-functionalized polydiorganosiloxane in an amount of 0 to 52.5 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), Optionally, (E) a reactive diluent in an amount of 0 to 25 parts by mass of the total of starting materials (A) and (B), comprising an 8 to 18 carbon-carbon hydrocarbon compound having at least one aliphatic group per molecule, (F) A polyorganohydrogensiloxane in an amount of 0 to 8 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), A polyorganohydrogensiloxane is provided, provided that the starting materials (A), (B), (C), (D), (E), and (F) are present in sufficient quantities to provide a silicon-bonded hydrogen atom / alkenyl group molar ratio (SiH / Vi ratio) of 0.5 / 1 to 2 / 1 and an aryl content of 246 mmol / 100 g to 450 mmol / 100 g. (G) Based on the total amount of the starting materials (A), (B), (C), (D), (E), (F), (G), and (H), a sufficient amount of hydrosilylation catalyst to provide 0.1 mass ppm to 5,000 mass ppm of platinum group metals, The solution optionally comprises (H) a hydrosilylation reaction inhibitor in an amount of 0 to 10,000 ppm by mass, based on the total amount of the starting materials (A), (B), (C), (D), (E), (F), (G), and (H). [Brief explanation of the drawing]

[0007] [Figure 1] [Modes for carrying out the invention]

[0008] The above curable silicone composition (composition) may have a maximum viscosity of 100 mPa·s, as measured by using a Brookfield DV1 viscometer with a CPA-40Z spindle at 25°C. The starting materials used in the curable silicone composition are described in detail below.

[0009] Starting material (A) The starting material (A) in the curable silicone composition has two alkenyl groups per molecule and is an aromatic compound having a molecular weight of less than 1,000 g / mol, or less than 900 g / mol, or less than 800 g / mol, or less than 700 g / mol, or less than 600 g / mol, or less than 500 g / mol, or less than 400 g / mol. At the same time, the molecular weight of the starting material (A) can be at least 130 g / mol, or at least 150 g / mol, or at least 200 g / mol, or at least 300 g / mol. Alternatively, the starting material (A) can have a molecular weight of 130 g / mol to 1,000 g / mol, or 130 g / mol to 900 g / mol, or 154 g / mol to 900 g / mol, or 130 g / mol to 400 g / mol, or 130 g / mol to 320 g / mol, or 130 g / mol to 250 g / mol. The starting material (A) is Formula (A-I): R 1 -R 2 -R 1 organic compound of Formula (A-II):

[0010] [Chemical formula] siloxane oligomer of and may be selected from the group consisting of both a combination of an organic compound of formula (A-I) and a siloxane oligomer of formula (A-II). In formulas (A-I) and (A-II), each R 1 is an alkenyl group having 2 to 12 carbon atoms independently selected, each R 2 is an arylene group having 6 to 20 carbon atoms, each R 3 is independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 20 carbon atoms, provided that 15 mol% to 50 mol% in all cases of R 3 is an aryl group, and 50 mol% to 85 mol% in all cases of R 3 is an alkyl group, and the subscript a is an integer having a value of 2 to 3. R 1Suitable alkenyl groups include vinyl, allyl, and hexenyl, or vinyl and hexenyl, or vinyl. 2 Suitable alkyl groups include phenylene, naphthalene, and biphenylene, or phenylene. Alternatively, each R 2 Independently,

[0011] [ka] It may be phenylene selected from the group consisting of R. 3 Suitable alkyl groups include methyl, ethyl, propyl (including isopropyl and n-propyl), butyl (including isobutyl, n-butyl, sec-butyl, and tert-butyl), pentyl (including cyclopentyl and linear and branched alkyl groups having 5 carbon atoms), and hexyl (including cyclohexyl and linear and branched alkyl groups having 6 carbon atoms). Alternatively, R 3 The alkyl group can be selected from the group consisting of methyl and ethyl, or methyl. 3 Suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and 2-phenylethyl. Alternatively, R 3 The aryl group can be phenyl. Alternatively, each R 3 This can be selected from the group consisting of methyl and phenyl.

[0012] Compounds of formula (AI) are known in the art and are commercially available. For example, formula

[0013] [ka] Divinylbenzene (AI-1) (including m-divinylbenzene, o-divinylbenzene, and p-divinylbenzene, and combinations thereof), and formula

[0014] [ka] Diallylbenzene (AI-2) (including m-diallylbenzene, o-diallylbenzene, and p-diallylbenzene, and combinations thereof) is commercially available from Gelest, Inc. (Morrisville, Pennsylvania, USA) and Sigma-Aldrich, Inc. (St. Louis, Missouri, USA). Compounds of (A-II) are also known in the art and commercially available. For example, formula

[0015] [ka] 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (A-II-1) (384 g / mol), and formula

[0016] [ka] 1,5-divinyl-3-phenylpentamethyltrisiloxane (A-II-2) (323 g / mol) is also known in the art and is commercially available from various suppliers such as Gelest, Inc. and Sigma-Aldrich, Inc.

[0017] The starting material (A) may be one of the above compounds or a combination of two or more. For example, the starting material (A) may be a combination of divinylbenzene (AI-1) and diallylbenzene (AI-2). Alternatively, the starting material (A) may be a combination of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (A-II-1) and 1,5-divinyl-3-phenylpentamethyltrisiloxane (A-II-2). Alternatively, the starting material (A) may be a combination of divinylbenzene (AI-1) and 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (A-II-1). Alternatively, the starting material (A) may be a combination of divinylbenzene (AI-1) and 1,5-divinyl-3-phenylpentamethyltrisiloxane (A-II-2). Alternatively, the starting material (A) may be a combination of diallylbenzene and (AI-2)1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (A-II-1). Alternatively, the starting material (A) may be a combination of diallylbenzene (AI-2) and 1,5-divinyl-3-phenylpentamethyltrisiloxane (A-II-2).

[0018] Starting material (B) The starting material (B) in the curable silicone composition is an aromatic compound having two silicon-bonded hydrogen atoms per molecule and a molecular weight of less than 1,000 g / mol or less than 900 g / mol. At the same time, the molecular weight of the starting material (B) may be at least 194 g / mol. Alternatively, the starting material (B) may have a molecular weight of 194 g / mol ~ < 1,000 g / mol, or 194 g / mol ~ < 900 g / mol, or 194 g / mol ~ 800 g / mol, or 194 g / mol ~ 700 g / mol, or 194 g / mol ~ 600 g / mol, or 194 g / mol ~ 550 g / mol, or 194 g / mol ~ 350 g / mol. The starting material (B) is given by formula (BI):

[0019] [ka] Siloxane oligomer, formula (B-II):

[0020] [ka] The group can be selected from organosilicon oligomers, as well as combinations of both siloxane oligomers and organosilicon oligomers. In formulas (BI) and (B-II), R 2 and R 3 The starting material (A) is as described above. Each R 4 R is an independently selected alkyl group consisting of 1 to 12 carbon atoms, and the subscript b is an integer having a value of 1 to 3. 4 Suitable alkyl groups include methyl, ethyl, propyl (including isopropyl and n-propyl), butyl (including isobutyl, n-butyl, sec-butyl, and tert-butyl), pentyl (including cyclopentyl and linear and branched alkyl groups having 5 carbon atoms), and hexyl (including cyclohexyl and linear and branched alkyl groups having 6 carbon atoms). Alternatively, R 4 The alkyl group can be selected from the group consisting of methyl and ethyl, or methyl.

[0021] Compounds of formula (BI) are known in the art and are commercially available. For example, formula (I)

[0022] [ka] 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (BI-1) (332 g / mol), and formula

[0023] [ka] 1,1,7,7,-tetramethyl-3,3,5,5,-tetraphenyltetrasiloxane (BI-2) (530 g / mol) is commercially available from various suppliers, including Gelest, Inc. and Sigma-Aldrich, Inc. Compounds of formula (B-II) are also known and commercially available in the art. For example, formula

[0024] [ka] 1,4-bis(dimethylsilyl)benzene (B-II-1) (194 g / mol) is also commercially available from various suppliers, including Gelest, Inc. and Sigma-Aldrich, Inc.

[0025] The starting material (B) may be a combination of one or more of the above compounds. For example, the starting material (B) may be a combination of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (BI-1) and 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyltetrasiloxane (BI-2). Alternatively, the starting material (B) may be a combination of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (BI-1) and 1,4-bis(dimethylsilyl)benzene (B-II-1). Alternatively, the starting material (B) may be a combination of 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyltetrasiloxane (BI-2) and 1,4-bis(dimethylsilyl)benzene (B-II-1).

[0026] Starting material (A) is used in the composition in an amount of 10 to 90 parts by mass. Starting material (B) is used in the composition in an amount of 90 to 10 parts by mass. The sum of the amounts of starting material (A) and starting material (B) is 100 parts by mass.

[0027] Starting material (C) The starting material (C) is an alkenyl-functionalized polyorganosilicate resin. The average unit formula for alkenyl-functionalized polyorganosilicate resin is (R): 4 3SiO 1 / 2 ) c (R 1 R 4 2SiO 1 / 2 ) d (SiO 4 / 2 ) e (HO 1 / 2 ) f It may have, in the formula, R 1 and R 4 As described above, the subscripts c, d, e, and f represent mole fractions. In formula (CI), the subscript c ≥ 0, subscript d > 0, 0.3 ≤ (c + d) ≤ 0.7, 0.3 ≤ e ≤ 0.7, and 0 ≤ f ≤ 0.05, provided that the amount (c + d + e + f) = 1, the alkenyl-functionalized polyorganosilicate resin of average formula (CI) has a number-average molecular weight of 1,500 g / mol to 5,000 g / mol as measured by GPC. Alkenyl-functionalized polyorganosilicate resins have trifunctional units (e.g., formula (R 1 SiO 3 / 2 ) and / or (R 4 SiO 3 / 2 The unit of ) does not need to be included.

[0028] Alternatively, alkenyl-functionalized polyorganosilicate resins have an average unit formula (C-II):(R 4 3SiO 1 / 2 ) m (R 1 R 4 2SiO 1 / 2 ) n (R 6 SiO 3 / 2 ) o (SiO 4 / 2 ) p (HO 1 / 2 ) q It may have, in the formula, R 1 and R 4 As stated above, R 6A is an aryl group with 6 to 20 carbon atoms, and the subscripts m, n, o, p, and q represent mole fractions. In formula (C-II), under the conditions that subscript m≧0, subscript n>0, 0.3≦(m+n)≦0.7, 0≦o≦0.3, 0.3≦p≦0.7, and 0≦q≦0.05, provided that the amount (m+n+o+p+q)=1, the alkenyl-functionalized polyorganosilicate resin of formula (C-II) has a number-average molecular weight of 1,500 g / mol to 5,000 g / mol as measured by GPC. 6 Suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and 2-phenylethyl. Alternatively, R 6 The aryl group can be phenyl.

[0029] Polyorganosilicate resins can be prepared by silica hydrosol capping processes, such as those disclosed in U.S. Patent No. 2,676,182 by Daudt et al., U.S. Patent No. 4,611,042 by Rivers-Farrell et al., and U.S. Patent No. 4,774,310 by Butler et al. The method of Daudt et al. involves reacting a silica hydrosol with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a mixture thereof under acidic conditions, and recovering a copolymer having triorganosiloxy (M) units and silicate (Q) units. The resulting copolymer generally contains 2 to 5 weight percent of hydroxyl groups. The concentration of silicon-bonded hydroxyl groups present in the polyorganosilicate resin can be determined using FTIR spectroscopy according to ASTM standard E-168-16.

[0030] When prepared, the polyorganosilicate resin contains the above-mentioned M and Q units, and further contains units having a silanol (silicon-bonded hydroxyl) group, with the formula Si(OSiR M 3) May contain a neopentamer of 4, where R M This is a monovalent hydrocarbyl group. As described in Reference Example 2, column 32 of U.S. Patent No. 9,593,209, Si29 Nuclear magnetic resonance (NMR) spectroscopy can be used to measure the molar ratio of M units to Q units, which is expressed as {M(resin) + (M(neopentamer))} / {Q(resin) + Q(neopentamer)} and represents the molar ratio of the total number of triorganosiloxy groups (M units) in the resin and neopentamer portions of a polyorganosilicate resin to the total number of silicate groups (Q units) in the resin and neopentamer portions.

[0031] The number-average molecular weight (Mn) of polyorganosilicate resins is determined by the presence of R M It depends on various factors, including the type of hydrocarbyl group represented by . Mn of polyorganosilicate resin means the number-average molecular weight measured using gel permeation chromatography (GPC) according to the procedure in Reference Example 1 of U.S. Patent No. 9,593,209, column 31. Alternatively, peaks representing neopentamers may be excluded from the measurement. Alternatively, the Mn of polyorganosilicate resin may be at least 1,500 g / mol, or at least 2,000 g / mol, while at the same time, the Mn of polyorganosilicate may be up to 5,000 g / mol, or up to 4,500 g / mol. Alternatively, the Mn of polyorganosilicate resin may be 1,500 g / mol to 5,000 g / mol, or 2,000 g / mol to 4,500 g / mol, or 2,500 g / mol to 4,000 g / mol.

[0032] Silicon-bonded hydroxyl groups formed during the preparation of polyorganosilicate resins can be converted to trihydrocarbylsiloxane groups by reacting the silicone resin with an end-blocking agent containing suitable end groups, such as silane, disiloxane, or disilazane. Silanes containing hydrolyzable groups may be added in molar excess beyond the amount required to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin. The above alkenyl-functionalized polyorganosilicate resins can be prepared by reacting the product of Daudt et al. with an alkenyl-containing end-blocking agent and an unsaturated aliphatic-free end-blocking agent in an amount sufficient to provide the resin with, for example, 3 to 30 molar percent of alkenyl groups. Suitable end-blocking agents are known in the art and are exemplified in U.S. Patents 4,584,355, 4,591,622, and 4,585,836. Such alkenyl-functionalized polyorganosilicate resins can be prepared using a single end-capping agent or a mixture of such agents.

[0033] The starting material (C) may be a combination of one or more of the resins described above. The starting material (C) is used in an amount sufficient to provide 10 to 130 parts by mass per 100 parts by mass of the total of starting materials (A) and (B) in the composition. Alternatively, the amount of starting material (C) may be at least 10 parts by mass, or at least 30 parts by mass, or at least 40 parts by mass, or at least 50 parts by mass, or at least 60 parts by mass per 100 parts by mass of the total of starting materials (A) and (B). At the same time, the amount of starting material (C) may be up to 130 parts by mass, or up to 120 parts by mass, or up to 100 parts by mass, or up to 90 parts by mass, or up to 80 parts by mass per 100 parts by mass of the total of starting materials (A) and (B). Alternatively, the amount of starting material (C) may be 30 to 130 parts by mass, 40 to 120, 50 to 100, or 60 to 90 parts by mass per 100 parts by mass of the total of starting materials (A) and (B), according to the same criteria.

[0034] Starting material (D) The starting material (D) is a polyorganosiloxane having a silicon-bonded unsaturated aliphatic monovalent hydrocarbyl group, which may optionally be added to the composition described herein, for example, for the purpose of improving the fluidity of the composition and / or for the purpose of improving the mechanical strength of the cured silicone pressure-sensitive adhesive. The starting material (D) has the unit formula (D-I): (R 5 3SiO 1 / 2 ) g (R 5 2SiO 2 / 2 ) h (R 5 SiO 3 / 2 ) i (SiO 4 / 2 ) j and may contain, wherein each R 5 is independently a monovalent hydrocarbyl group selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms, provided that 0.01 mol% to 1 mol% of all cases of R 5 is an alkenyl group, and the subscripts g, h, i, and j represent mole fractions having values such that 0 < g ≦ 0.4, 0.6 ≦ h ≦ 1, 0 ≦ i ≦ 0.03, 0 ≦ j ≦ 0.03, and the amount (g + h + i + j) = 1. The starting material (D) may have a viscosity of 1 mPa·s to 100,000 mPa·s at 25°C, or 3 mPa·s to 50,000 mPa·s at 25°C, or 5 mPa·s to 1,000 mPa·s at 25°C. Suitable alkyl and aryl groups for R 5 are as described above for R 3 , and suitable alkenyl groups for R 5 are as described above for R 1 . Alternatively, when the polyorganosiloxane is linear, the subscripts i and j may each be 0. Examples of the polyorganosiloxane of the starting material (D) include the following: i) α,ω-dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), iii) α,ω-dimethylvinylsiloxy-terminated polymethylvinylsiloxane, iv) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), v) α,ω-trimethylsiloxy-terminated polymethylvinylsiloxane, vi) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane / methylvinylsiloxane), vii) α, ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), ix) α,ω-phenyl,methyl,vinyl-siloxyterminated polydimethylsiloxane, x)α,ω-dimethylhexenylsiloxy-terminated polydimethylsiloxane, xi)α,ω-dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xii)α,ω-dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane, xiii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xiv) α,ω-trimethylsiloxy-terminated polymethylhexenylsiloxane, xv)α,ω-dimethylhexenyl-siloxy-terminated poly(methylphenylsiloxane / methylhexenylsiloxane), xvi)α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), xvii)α,ω-dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), xviii) Dimethylhexenyl-siloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), xix)1,3-dihexyl-1,1,3,3-tetramethyldisiloxane, and A combination of two or more of the following: xx)i)~xix).

[0035] Methods for preparing the above polyorganosiloxanes from the starting material (D), such as hydrolysis and condensation of the corresponding organohalosilanes and oligomers, or equilibration of cyclic polydiorganosiloxanes, are known in the art. See, for example, U.S. Patents 3,284,406, 4,772,515, 5,169,920, 5,317,072, and 6,956,087, which disclose the preparation of linear polydiorganosiloxanes having alkenyl groups. Examples of such polyorganosiloxanes are commercially available from Gelest Inc. (Morrisville, Pennsylvania, USA) under trade names DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V-31, DMS-V33, DMS-V34, DMS-V35, DMS-V41, DMS-V42, DMS-V43, DMS-V46, DMS-V51, and DMS-V52.

[0036] The starting material (D) may be one polyorganosiloxane or a combination of two or more of the above polyorganosiloxanes. For example, the starting material (D) may be selected from the group consisting of i) α,ω-dimethylvinylsiloxy-terminated polydimethylsiloxane, vii) α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), and combinations of both i) and vii).

[0037] The starting material (D) is optional. However, if present, its amount depends on various factors, including the type and amount of starting material (A) and whether starting material (E) is present. The amount of starting material (D) may be selected so that the viscosity of the composition does not exceed 100 mPa·s. If present, starting material (D) may be used in the composition in an amount of >0 parts by mass, or at least 0.1 parts by mass, or at least 10 parts by mass, per 100 parts by mass of the total of starting materials (A) and (B). At the same time, the amount of starting material (D) may be a maximum of 52.5 parts by mass, a maximum of 50 parts by mass, a maximum of 40 parts by mass, or a maximum of 39 parts by mass, per 100 parts by mass of the total of starting materials (A) and (B). Alternatively, the starting material (D) may be present in the composition in an amount of 0 to 52.5 parts by mass, or 0 to 50 parts by mass, or 0 to 45 parts by mass, or 0 to 40 parts by mass, or 1 to 39 parts by mass, or 2 to 38 parts by mass, or 1 to 15 parts by mass, per 100 parts by mass of the total of the starting materials (A) and (B).

[0038] Starting material (E) The starting material (E) is a reactive diluent that can be optionally added to the composition. The reactive diluent comprises a hydrocarbon compound containing 8 to 18 carbon atoms and at least one unsaturated aliphatic atom per molecule. The reactive diluent may be linear or branched, and the unsaturated aliphatic atom may be a side chain (pendant) or terminal. Examples of reactive diluents include dodecene, tetradecene, hexadecene, octadecene, and combinations thereof. Alternatively, the reactive diluent may comprise an alkene containing 8 to 18 carbon atoms with a terminal double bond. Alternatively, the reactive diluent may comprise an alkene containing 12 to 14 carbon atoms and at least one terminal double bond. Alternatively, the reactive diluent may be tetradecene. Reactive diluents are known in the art, for example, in U.S. Patent No. 7,687,591 by Bhagwagar et al. (column 5, lines 16-26), European Patent No. 3,757186(A1) by Hino (paragraph

[0025] ), and PCT Publication No. WO2020 / 000389 by Cao et al. (paragraph

[0027] ).

[0039] The starting material (E) is optional. However, if present, its amount depends on various factors including the type and amount of the starting material (A) and whether the starting material (D) is present. The amount of the starting material (E) can be selected such that the viscosity of the composition does not exceed 100 mPa·s. When present, the starting material (E) can be used in an amount of >0 parts by mass, or at least 0.1 parts by mass, or at least 10 parts by mass per 100 parts by mass in total of the starting materials (A) and (B) in the composition. At the same time, the amount of the starting material (D) can be at most 25 parts by mass, or at most 20 parts by mass, or at most 15 parts by mass per 100 parts by mass in total of the starting materials (A) and (B). Alternatively, the starting material (D) can be present in the composition in an amount of 0 to 25 parts by mass, or 3 to 23 parts by mass, or 3 to 10 parts by mass, or 10 to 23 parts by mass per 100 parts by mass in total of the starting materials (A) and (B).

[0040] Starting material (F) The starting material (F) is an optional polyorganohydrogensiloxane that can be added to the composition to improve crosslinking. The starting material (F) has the unit formula (F-I): (R 4 3SiO 1 / 2 ) t (HR 4 2SiO 1 / 2 ) u (R 4 2SiO 2 / 2 ) v (HR 4 SiO 2 / 2 ) w (R 4 SiO 3 / 2 ) x (HSiO 3 / 2 ) y (SiO 4 / 2 ) z and may have the formula, where R 4As stated above, the subscripts t, u, v, w, x, y, and z represent the average number of each unit in the formula, and have values ​​such that t≧0, u≧0, v≧0, w≧0, x≧0, y≧0, z≧0, and quantity (u+w+y)≧2, where quantity (t+u+v+w+x+y+z) is sufficient to give polyorganohydrogensiloxane a viscosity of 2mPa·s to 1,000mPa·s at 25°C, or 5mPa·s to 500mPa·s at 25°C. Alternatively, the subscript y may be 0, and the subscript z may be 0.

[0041] Examples of polyorganohydrogensiloxanes suitable for use herein include: (i) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (ii) α,ω-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, and (v) α-dimethylhydrogensiloxy, ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (vi) α-dimethylhydrogensiloxy, ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, (vii) any combination of two or more of these. Alternatively, the polyorganohydrogensiloxane of the starting material (F) may be selected from the group consisting of (iii) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, and combinations of both (iii) and (iv).

[0042] Methods for preparing polyorganohydrogensiloxanes suitable for use herein, such as hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified in U.S. Patent No. 2,823,218 by Speier et al., U.S. Patent No. 3,957,713 by Jeram et al., and U.S. Patent No. 4,329,273 by Hardman et al. Polyorganohydrogensiloxanes are also commercially available (for example, those available from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as HMS-H271, HMS-071, HMS-993, HMS-301 and HMS-301 R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, HPM-502, and HMS-HM271). The amount of starting material (F) may be 0 to 8 parts by mass per 100 parts by mass of the total of starting materials (A) and (B). Alternatively, starting material (F) may be present in an amount of >0 to 8 parts by mass, >0 to 2 parts by mass, or 1 to 2 parts by mass per 100 parts by mass of the total of starting materials (A) and (B).

[0043] The starting materials (A), (B), (C), (D), (E), and (F) are used in the composition in amounts sufficient to provide a silicon-bonded hydrogen atom to alkenyl group molar ratio (SiH / Vi ratio) of at least 0.5 / 1, or at least 0.6 / 1. At the same time, the amounts of the starting materials (A), (B), (C), (D), (E), and (F) are sufficient to provide a silicon-bonded hydrogen atom to alkenyl group molar ratio of up to 2.0 / 1, or up to 1.5 / 1, or up to 1.0 / 1. This molar ratio is calculated by summing the silicon-bonded hydrogen content of starting material (B) and, if present, starting material (F), and dividing by the total amount of alkenyl groups in starting materials (A) and (C), and, if present, starting materials (D) and (E).

[0044] Starting material (G) The starting material (G) in the composition is a hydrosilylation catalyst. This catalyst facilitates the reaction between the alkenyl groups in starting materials (A) and (C), and if present, starting materials (D) and (E), and the silicon-bonded hydrogen atoms in starting material (B) and, if present, starting material (F). The catalyst contains a platinum group metal. The platinum group metal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum. The hydrosilylation catalyst may be a radiation-activated catalyst (GI) (i.e., a catalyst that can catalyze the hydrosilylation reaction after irradiation (exposure to chemical radiation, e.g., exposure to visible light or UV light)), a hydrosilylation catalyst that can be activated by means other than irradiation (G-II) (e.g., by heating, which can catalyze the hydrosilylation reaction without irradiation), or a combination of both (GI) and (G-II) (G-III).

[0045] Suitable radiation-activated catalysts for use as starting materials (GI) can be activated by exposure to radiation having wavelengths of 200 nm to 500 nm. Suitable radiation-activated hydrosilylation catalysts include cyclopentadienyl platinum complexes (e.g., η5-cyclopentadienyl)tri(α-alkyl)platinum(IV)), cyclopentadienyltrimethylplatinum and trimethyl(methylcyclopentadienyl)platinum(IV), cyclooctadienyl platinum complexes (e.g., η4-1,5-cyclooctadienediarylplatinum complexes), and Pt(II)-β-diketonate complexes (e.g., bis(acetylacetonate)platinum(II)). Examples of cyclopentadienyl platinum complexes are known in the art and are disclosed, for example, in U.S. Patent Nos. 4,510,094 and 4,600,484 by Drhnak, U.S. Patent Nos. 4,916,169 by Boardman et al., U.S. Patent Nos. 6,127,446 and 6,451,869 by Butts, U.S. Patent Nos. 6,376,569 by Oxman et al., U.S. Patent No. 8,088,878 by Koellnberger, and Chinese Patent No. 101925608(B). Cycloctadienyl platinum complexes are disclosed, for example, in U.S. Patent No. 6,046,250 by Boardman et al. Platinum(II)β-diketonate catalysts are disclosed, for example, in European Patent No. 0398701(B1) by Oxman et al., U.S. Patent No. 8,642,674 by Ikeno, and Chinese Patent No. 10403160(2A). U.S. Patent Publication No. 2005 / 0154079 by Walker et al., U.S. Patent Publication No. 2011 / 0171400(A1) by Thompson et al., and U.S. Patent Publication No. 03865638(B2) by Ikeno similarly disclose various radioactive hydrosilylation catalysts, respectively. Alternatively, the hydrosilylation catalyst may be one described in U.S. Patent Publication No. 03865638(B2).

[0046] Alternatively, the hydrosilylation catalyst may be a hydrosilylation catalyst (G-II) that can be activated by means other than irradiation. For example, (G-II) may be the platinum group metal (G-II-1) mentioned above, a compound of such a metal (G-II-2), such as chloride tris(triphenylphosphane)rhodium(I) (Wilkinson catalyst), rhodium diphosphine chelate (e.g., [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium), chlorplatinic acid (Speier catalyst), chlorplatinic acid hexahydrate, platinum dichloride, and a complex of compound (G-II-2) with an alkenyl-functional organopolysiloxane (G-II-3), or a platinum group metal compound (G-II-4) microencapsulated in a matrix or core-shell structure. Examples of platinum-low molecular weight organopolysiloxane complexes include the complex of 1,3-diethyl-1,1,3,3-tetramethyldisiloxane with platinum (Karstedt catalyst) and the Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby complex). Alternatively, the hydrosilylation reaction catalyst may be the above-mentioned compound or complex (G-II-5) microencapsulated in a resin matrix. Specific examples of platinum-containing catalysts suitable for (G-II) include chloroplatinic acid in either hexahydrate or anhydrous form, or platinum-containing catalysts obtained by a method involving the reaction of chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or the alkene-platinum-silyl complex described in Roy's U.S. Patent No. 6,605,734. Alkene-platinum-silyl complexes can be prepared, for example, by mixing 0.015 moles of (COD)PtCl2 with 0.045 moles of COD and 0.0612 moles of HMeSiCl2 (wherein COD represents cyclooctadienyl and Me represents methyl).Other exemplary hydrosilylation catalysts include Speier's U.S. Patent No. 2,823,218, Ashby's No. 3,159,601, Lamoreaux's No. 3,220,972, Chalk et al.'s No. 3,296,291, Willing's No. 3,419,593, Modic's No. 3,516,946, Karstedt's No. 3,814,730, Chandra's No. 3,928,629, Lee et al.'s No. 3,989,668, and Lee et al.'s No. 4,76 This is described in Patent No. 6,176, No. 4,784,879 by Lee et al., No. 5,017,654 by Togashi, No. 5,036,117 by Chung et al., and No. 5,175,325 by Brown, as well as in European Patent No. 0347895(A) by Togashi and U.S. Patent Application Publication 2019 / 0367744 by Chevalier et al. (disclosing both radiation-activated catalysts (GI) and catalysts activatable by means other than radiation (G-II) (e.g., thermally activated catalysts)). Suitable hydrosilylation catalysts for the starting material (F-II) are commercially available, for example, SYL-OFF® 4000 catalyst and SYL-OFF® 2700, available from Dow Silicones Corporation (Midland, Michigan, USA).

[0047] The starting material (G) may be one hydrosilylation catalyst or a combination of two or more of the above hydrosilylation catalysts. For example, if both exposure to radiation and heating are used to cure the composition, the starting material (G) may be a combination of (GI) and (G-II). Alternatively, the starting material (G) may be a combination of two or more radiation-activated catalysts, such as a combination of a cyclopentadienyl platinum complex and a Pt(II)-β-diketonate complex. Those skilled in the art will recognize that certain catalyst species may be activated by either irradiation or heating, as described herein, and that when a combination of two or more catalysts is used, the selected catalyst species will differ from one another.

[0048] The amount of hydrosilylation catalyst (G) in the composition depends on various factors, including the selection of starting materials (A), (B), and (C), and (D), (E), and (F) if present. The amount of catalyst is sufficient to catalyze the hydrosilylation reaction between SiH and the alkenyl group, or sufficient to provide at least 0.01 ppm by mass, or at least 0.05 ppm by mass, or at least 0.1 ppm by mass, or at least 0.5 ppm by mass, or at least 1 ppm by mass of platinum group metal, based on the total amount of starting materials (A), (B), (C), (D), (E), (F), (G), and (H) in the composition. Simultaneously, the amount of catalyst is sufficient to provide up to 5,000 ppm by mass, or up to 800 ppm by mass, or up to 500 ppm by mass, or up to 100 ppm by mass, based on the total amount of starting materials (A), (B), (C), (D), (E), (F), (G), and (H) in the composition. Alternatively, the amount of hydrosilylation reaction catalyst may be sufficient to provide 0.01 ppm to 5,000 ppm by mass, or 0.1 ppm to 800 ppm by mass, or 0.5 ppm to 500 ppm by mass, or 1 ppm to 100 ppm by mass, based on the total amount of starting materials (A), (B), (C), (D), (E), (F), (G), and (H) in the composition.

[0049] Starting material (H) The starting material (H) is an optional hydrosilylation reaction catalyst inhibitor. The hydrosilylation reaction inhibitor can be added, for example, when preparing a composition as a one-component composition, or to extend the pot life of the composition. The starting material (H) may be, for example, an acetylene alcohol (H-1), a silylated acetylene alcohol (H-II), an en-yne compound (H-III), a triazole (H-IV), a phosphine (HV), a mercaptan (H-VI), a hydrazine (H-VII), an amine (H-VIII), a fumarate (H-IX), a maleate (HX), an ether (H-XI), carbon monoxide (H-XII), an alkenyl-functionalized organosiloxane oligomer (H-XIII) (different from starting material A-II), or a combination of two or more of these (H-XIV). Alternatively, the hydrosilylation reaction inhibitor may be an acetylene alcohol (e.g., ETCH), a fumarate (e.g., diethyl fumarate), a maleate (e.g., bis-(methoxymethyl)ethyl maleate), or a combination of two or more of these.

[0050] Examples of acetylene alcohols include 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyne-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-octin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and ETCH, as well as combinations thereof. Alternatively, the inhibitor may be a silylated acetylene compound. Although not bound by theory, it is thought that the addition of a silylated acetylene compound reduces the yellowing of the reaction product prepared from the hydrosilylation reaction compared to the reaction product from hydrosilylation of starting materials that do not contain a silylated acetylene compound or that contain an organic acetylene alcohol inhibitor such as those mentioned above.Silylated acetylene compounds include (3-methyl-1-butyne-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyne-3-oxy)dimethylsilane, bis(3-methyl-1-butyne-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyne-3-oxy))silane, (3-methyl-1-butyne-3-oxy)dimethylphenylsilane, (3-methyl-1-butyne-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyne-3-oxy)triethylsilane, bis(3-methyl-1- These are exemplified by butyn-3-oxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-oxy)trimethylsilane, (3-phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, and combinations thereof. Silylated acetylene compounds useful as inhibitors in this specification can be prepared by methods known in the art. For example, U.S. Patent No. 6,677,407 by Bilgrien et al. discloses the silylation of the above-mentioned acetylene alcohol by reaction with chlorosilane in the presence of an acid acceptor.

[0051] En-yne compounds are exemplified by 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and combinations thereof. Triazoles are exemplified by benzotriazole. Amines are exemplified by tetramethylethylenediamine, 3-dimethylamino-1-propyne, n-methylpropargylamine, propargylamine, and 1-ethynylcyclohexylamine. Fumarates include dialkyl fumarates such as diethyl fumarate, dialkenyl fumarates such as diallyl fumarate, and dialkoxyalkyl fumarates such as bis-(methoxymethyl)ethyl fumarate. Maleates include dialkyl maleates such as diethyl maleate, dialkenyl maleates such as diallyl maleate, and dialkoxyalkyl maleates such as bis-(methoxymethyl)ethyl maleate. Alkenyl-functional organosiloxane oligomers suitable for use as inhibitors are given by formula

[0052] [ka] Examples include 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and combinations of two or more of these. Compounds useful as the above inhibitors are commercially available, for example, from Sigma-Aldrich Inc. or Gelest, Inc.

[0053] The starting material (H) may be one hydrosilylation inhibitor or a combination of two or more of the above hydrosilylation inhibitors. The amount of inhibitor used in the composition will depend on various factors, including the desired reaction rate, the specific inhibitor used, and the selection and amount of each of the starting materials (A) to (G). However, if present, the amount of inhibitor may be >0 parts by mass or at least 1 ppm by mass, based on the total amount of starting materials (A), (B), (C), (D), (E), (F), (G), and (H) in the composition. At the same time, the amount of inhibitor may be up to 10,000 ppm by mass, or up to 1,000 ppm by mass, or up to 500 ppm by mass, based on the total amount of starting materials (A), (B), (C), (D), (E), (F), (G), and (H) in the composition. Alternatively, the amount of the inhibitor may be 0 to 10,000 ppm by mass, or >0 to 1,000 ppm by mass, or 1 to 500 ppm by mass, based on the total amount of the starting materials (A), (B), (C), (D), (E), (F), (G), and (H) in the composition.

[0054] Other optional starting materials The composition may optionally contain additional starting materials such as silicone tackifiers, fumed silica, leveling agents, surfactants (such as hydroxyalkyl or hydroxysiloxy group-containing silicone polymers or resins), wetting agents (moisturizers), thickeners, rheology modifiers, plasticizers, and other non-reactive diluents (not intentionally removed during and / or after curing of the composition), silicone oils, hydrocarbon oils (such as isoparaffins), or combinations of two or more of these. The starting materials are optional, and the type and amount of additional starting materials may be selected by those skilled in the art depending on various considerations, including the final use of the composition and its cured product.

[0055] Method for preparing a curable silicone composition The composition may be prepared by a method comprising mixing the starting materials at room temperature or high temperature. Alternatively, certain starting materials may be dissolved in a solvent to facilitate mixing; for example, commercially available starting materials (C) alkenyl-functionalized polyorganosilicate resins and / or starting material (F) may be provided in the solvent. The solvent, if present, may be removed from the starting materials and replaced with (E) a reactive diluent before combining with one or more other starting materials of the composition. Solvent removal may be carried out by any convenient means, such as optionally under reduced pressure and optionally by heating with a purge gas such as nitrogen. The solvent may also be removed by stripping and / or distillation.

[0056] The starting materials may be added in any order, but the hydrosilylation reaction inhibitor may be added before the hydrosilylation reaction catalyst, for example, when preparing the composition at high temperature and / or when preparing the composition as a partial composition.

[0057] Alternatively, the composition may be prepared as a multi-component composition if it is to be stored for a long period of time before use, for example, up to 6 hours before coating the composition onto a substrate. In a multi-component composition, the hydrosilylation reaction catalyst is stored in a separate portion from any starting material having silicon-bonded hydrogen atoms, for example, an aromatic compound (B) having two silicon-bonded hydrogen atoms per molecule and / or a polyorganohydrogensiloxane (F) if present, and these portions are mixed immediately before use of the composition.

[0058] For example, a multi-component composition can be prepared by combining a starting material, which includes at least a portion of an aromatic compound (A) having two alkenyl groups per molecule, an alkenyl-functionalized polyorganosiloxane (D) and / or a reactive diluent (E), if used, an aromatic compound (B) having two silicon-bonded hydrogen atoms per molecule, a polyorganohydrogensiloxane (F), if used, and optionally one or more other additional starting materials to form the base portion, by any convenient means such as mixing. A curing agent can be prepared by combining a starting material, which includes at least a portion of an aromatic compound (A) having two alkenyl groups per molecule, an alkenyl-functionalized polydiorganosiloxane (D) and / or a reactive diluent (E), if used, a hydrosilylation reaction catalyst (G), and optionally one or more other additional starting materials, by any convenient means such as mixing. The starting materials may be mixed at ambient temperature or at high temperatures. The starting material (H), a hydrosilylation reaction inhibitor, may be included in one or more of the base portion, the curing agent portion, or a separate additional portion. The starting material (C), an alkenyl-functionalized polyorganosilicate resin, may be added to the base portion, the curing agent portion, or a separate additional portion. When a two-part composition is used, the weight ratio of the amount of the base to the amount of the curing agent portion can be in the range of 1:1 to 10:1. The composition will cure by a hydrosilylation reaction to form a silicone pressure-sensitive adhesive.

[0059] How to use An adhesive article can be formed using the composition prepared as described above, and this adhesive article includes a silicone pressure-sensitive adhesive layer on the surface of a substrate. A method for forming an adhesive article is: Optionally, 1) treat the surface of the substrate, 2) Applying the above composition to the surface of a substrate to form a film on the surface, Optionally, 3) heating the film, 4) Irradiating the film to form a silicone pressure-sensitive adhesive layer on the surface of the substrate, Optionally, this includes 5) heating the silicone pressure-sensitive adhesive layer.

[0060] The substrate can be any material capable of withstanding the conditions (described below) used to cure the composition and form a silicone pressure-sensitive adhesive on the substrate. For example, any substrate capable of withstanding heat treatment at temperatures of 120°C or above, or 150°C, is preferred. Examples of suitable materials for such a substrate include glass, or plastic films such as polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide (PAI), polyether sulfide (PES), and polyethylene terephthalate (PET). The thickness of the substrate is not critical, but may be between 5 micrometers and 300 micrometers, or between 25 micrometers and 300 micrometers. The substrate may be transparent, or a non-transparent substrate may be used, as long as it allows the PSA to be exposed to UV irradiation. Alternatively, the substrate may be a component or layer of an (optical)electronic device, such as glass, a polarizer film, a thin-film transistor (TFT), or a support (e.g., a steel support on which a TFT is mounted).

[0061] Process 1) To improve the bonding of a silicone pressure-sensitive adhesive layer to a substrate, a method for forming an adhesive article may optionally include treating the surface of the substrate before applying the composition. The substrate treatment can be carried out by any convenient means, such as applying a primer before applying the composition to the treated surface, or subjecting the substrate to corona discharge treatment, etching, or plasma treatment.

[0062] Process 2) The composition can be applied to the substrate by any convenient means. For example, the composition can be applied to the substrate by a gravure coater, offset coater, offset-gravure coater, roller coater, and reverse roller coater. Alternatively, the application of the composition to the surface of the substrate can be carried out by a printing process such as screen printing, pin transfer, stencil printing, or inkjet printing. For example, the use of the above-mentioned composition as an ink in an inkjet printing process is intended herein. The film applied to the surface of the substrate in step 2) by any means described herein may be continuous (i.e., uniformly covering all or part of the substrate) and may cure to form a continuous layer on the surface of the substrate. Alternatively, the film may be discontinuous, and for example, a printing process such as inkjet printing may be used to apply the composition in a discontinuous layer on the surface of the substrate. A discontinuous film can be applied, for example, when it is desirable to form a pattern on the surface of the substrate. Suitable inkjet printing apparatuses are known and commercially available in the art (see, for example, the apparatus described in Linton et al., U.S. Patent Application Publication No. 2019 / 0292394 (paragraphs

[0052] to

[0055] )).

[0063] The amount of composition applied to the surface substrate depends on various factors, including whether a continuous or discontinuous silicone pressure-sensitive adhesive layer is desired on the surface, the desired thickness of the silicone pressure-sensitive adhesive layer to be formed, and the specific end use of the adhesive article. However, the amount may be sufficient so that, after curing by the hydrosilylation reaction, the thickness of the silicone pressure-sensitive adhesive can be greater than 0 to a maximum of 100 micrometers, or a maximum of 50 micrometers. For example, if a thicker silicone pressure-sensitive adhesive is desired, steps 2) to 5) can be optionally repeated to deposit additional composition.

[0064] Step 4) In step 4), the film is irradiated using a commercially available ultraviolet irradiation device (e.g., a face-type or conveyor belt-type ultraviolet irradiation device) by any convenient means, and a lamp (e.g., low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, ultraviolet light-emitting diode, etc.) is used as the radiation source. The ultraviolet irradiation dose is 0.1 W / cm². 2 ~10W / cm 2 for 0.1 seconds to 120 seconds (= 0.1 to 1200 J / cm²) 2 )

[0065] Optional steps 3) and 5) Steps 3) and 5) are optional in the above method, but if either or both of steps 3) and 5) are omitted, the curing rate of the composition may be slower than desired in some end uses. Therefore, optional steps 3) and / or optional step 5) may be included to increase the curing rate. In steps 3) and 5), heating is carried out at a temperature of at least 30°C, or at least 40°C, or at least 50°C. At the same time, the temperature may be up to 200°C, or up to 150°C, or up to 100°C. Alternatively, heating may be carried out between 30°C and 200°C, or 40°C and 150°C, or 50°C and 100°C. Heating is carried out for a sufficient time to conduct heat to the film or layer, and the exact time will depend on various factors such as the selected temperature, the thickness of the layer, and whether a hydrosilylation reaction inhibitor is used. Conventional heating devices such as box ovens, reflow ovens, (near) infrared lamps, or (near) infrared light-emitting diodes (NIR-LEDs) can be used.

[0066] After step 4), or if step 5) is present, a silicone pressure-sensitive adhesive layer is formed by curing the composition. The method may further include bringing the surface of the adherend into contact with the cured silicone pressure-sensitive adhesive on the opposite side of the substrate to form a bond. The surface of the adherend may optionally be treated before contact using the treatment method described above for step 1). [Examples]

[0067] These examples are intended to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the invention as defined in the claims. The starting materials used in these examples are summarized in Table 1.

[0068] [Table 1]

[0069] Reference Example 1 - Preparation of a curable silicone composition In this Reference Example 1, samples of curable silicone compositions containing the starting materials in Table 1 in the amounts shown in Tables 2-4 were prepared as follows: Starting material (C) may be dissolved in a solvent such as toluene or xylene due to its high viscosity. To prepare a solvent-free composition, for any starting material delivered in a solvent, the solvent may be evaporated and replaced with a reactive diluent to facilitate mixing. For example, to prepare Inv. 1, 21.51 g of starting material (A-1) and 78.49 g of starting material (B-1) were first added to a 103.22 g solution containing 77.42 g of starting material (C-1) dissolved in xylene (75 wt%). The solvent was then removed under reduced pressure at 80°C for 5 hours while bubbling with nitrogen, and the residual solvent was controlled to be less than 10 ppm. After cooling to room temperature, 39.06 g of starting material (D-1) was added to the above mixture and mixed with a stirrer at room temperature for 10 minutes. In addition, 0.04 g of the starting material (F-1) was added and mixed with a stirrer at room temperature for 10 minutes. Comps 7-12 and Inv. 2-18 were prepared similarly using the starting materials and amounts shown in the table. Comps 1-6 were prepared similarly, except for the solvent evaporation process, as no solvents containing intermediates such as (C-1) and (C-2) were used.

[0070] Reference example 2 - Viscosity In this Reference Example 2, the viscosity of each sample of the curable silicone composition prepared according to Reference Example 1 was measured as follows: Viscosity was measured at 25°C using a Brookfield DV1 viscometer with a CPA-40Z spindle. Viscosity was measured for 2 minutes, with the torque controlled in the range of 20-80%. The latest data was collected after the measurement was completed. The results are shown in Tables 2-4 below.

[0071] Reference example 3-Adhesive strength In this Reference Example 3, samples of the curable silicone composition prepared as described above were cured, and the adhesive strength of the resulting pressure-sensitive adhesive layer was evaluated as follows: Each sample prepared as described above was applied as a film on a glass plate. The adhesive layer was formed by UV irradiation followed by heating at 80°C for 30 minutes, thereby forming a layer with a thickness of 40 μm. The UV irradiation conditions were a UV irradiance of 10 J / cm using a 365 nm LED lamp (FireJet® FJ100) from the top surface of the film. 2 Ultraviolet light was then applied.

[0072] A strip of corona-treated polyethylene terephthalate (PET) film was placed on the resulting layer and bonded to it by moving a 2 kg rubber-coated pressure roller back and forth twice over the strip. The resulting laminate was aged at room temperature for one day. The PET film layer was cut into 2.54 cm (1 inch) wide tape strips, and the adhesive force (g / inch) required to peel the tape from a glass plate was measured by pulling it at a speed of 2400 mm / min and at a 180-degree angle. Data were collected using a multi-speed peel tester (CKTS-770, CKSI Co., Ltd). The results are shown in Tables 2-4 below.

[0073] Reference Example 4 - Elastic Modulus In this Reference Example 4, samples of the curable silicone composition prepared as described above were cured, and the adhesive strength of the resulting pressure-sensitive adhesive layer was evaluated as follows: Each sample prepared as described above was poured into a mold (thickness = 1 mm) and sandwiched between release films. The assembled sample was cured in the same manner as described above in Reference Example 3. After removing the release films, the sample was mounted on a parallel plate shape (25 mm) of a rheometer (AtonParr® MCR-502). The dynamic storage modulus (G') was then collected at a fixed frequency of 1 Hz at 25°C, with a strain of 1.0% and a normal force of 0 N.

[0074] Reference example 5-Transmittance Each sample prepared as described above was poured into a mold (thickness = 50 μm) and sandwiched between micro-slide glass (Matsunami Glass Co., Ltd, product number 9213). The assembled sample was cured in the same manner as described above in Reference Example 3. The transmittance and CIE (L, a, b) at 500 nm were measured according to the method specified in ASTM D 1003 (UV-Vis spectrophotometer, Konica Minolta CM-3600A, reference = Matsunami Glass Co., Ltd, product #9213). The results are shown in Tables 2 to 4 below.

[0075] Reference Example 6 - Inkjet Performance A sample of the curable silicone composition prepared according to Reference Example 1 was injected into an inkjet head (KM1024i 30pl, supplied by KONICA MINOLTA, INC). The inkjet process operation was performed using an OmniJet series supplied by Unijet. The operating temperature of the inkjet head was 25°C, and the distance between the inkjet head and the substrate was 400 μm. The substrate was 100 mm × 100 mm glass supplied by Corning® Eagle. Figure 1 shows an image of a droplet of the curable silicone composition by INV1. This demonstrates that the droplet is properly formed without trailing when ejected from the inkjet head. The dropping rate and volume were 2.56 m / sec and 24 pl, respectively.

[0076] [Table 2]

[0077] [Table 3]

[0078] [Table 4]

[0079] [Table 5]

[0080] Comparative Examples 1-6 demonstrate that omitting the alkenyl-functionalized polyorganosilicate resin (C) results in insufficient adhesion under the tested conditions. However, Comparative Example 12 shows that when the amount of resin (C) is too high, the viscosity of the composition is also higher than desirable for inkjet printing applications. Comparative Examples 7 and 8 demonstrate that when the starting material (A) is omitted and the amount of starting material (D) is too high, the total phenyl content is too low, resulting in lower adhesion under the tested conditions than desirable. Comparative Examples 9-11 demonstrate that when the phenyl content in the composition is too low (≤245 mmol / 100g), the resulting film has undesirable low adhesion under the tested conditions. While we do not wish to be bound by theory, it is considered that in order to increase the phenyl content in the composition, the amount of starting material (D) should be between 0 and 52.5 parts by mass per 100 parts by mass of the total of starting materials (A) and (B). While we do not wish to be bound by theory, it is considered that the aryl (phenyl) content should be >245~430 mmol / 100g based on the total amount of starting materials (A), (B), (C), (D), (E), and (F). Therefore, Examples 1~22 (INV1~INV22) demonstrate an appropriate range for phenyl content and the amount of starting material (C) to have higher adhesion (at least greater than 100 gf / in), which shows that the combined effect of both aromatic compounds (starting materials (A) and (B)) and alkenyl-functionalized polyorganosilicate resin (starting material (C)) is important for achieving higher adhesion while maintaining the composition at low viscosity.

[0081] Industrial applicability The examples demonstrate that a curable silicone composition having a viscosity of <100 mPa·s at 25°C can be prepared as described herein. Furthermore, when coated onto a substrate and cured to form a silicone pressure-sensitive adhesive layer by a dry bonding method, the silicone pressure-sensitive adhesive has a viscosity of 10 at 25°C.3 <G<10 6 It has an elastic modulus (G) of a certain value and an average adhesive strength of over 100 gf / in. Furthermore, Examples 1-8 in Table 3 showed that different types of starting materials (A) and (B) were effective under the tested conditions. In addition, Examples 23-26 showed high light transmittance and photostability under high-temperature aging conditions. Figure 1 shows appropriate inkjet performance.

[0082] Issues that need to be resolved Inkjet printing of polymer materials has been used in the manufacture of OLEDs to directly deposit organic thin film layers. Conventional solvents such as toluene or xylene do not work well for this deposition. The inkjet printing process can be used to form layers or fine patterns on either planar or curved surfaces. In particular, inkjet printing is advantageous in that it can reduce the thickness of the printed layer to less than 50 μm and prevent non-uniformity of the printed layer or pattern. However, known solvent-free silicone pressure-sensitive adhesive compositions, such as those disclosed in U.S. Patents 7,687,591 and 8,754,174, have viscosities that are too high for use in inkjet printing processes to form very thin adhesive layers (e.g., less than 50 μm) when the composition has cured.

[0083] solution This silicone pressure-sensitive adhesive composition has a viscosity of less than 100 mPa·s, less than 50 mPa·s, or less than 30 mPa·s, as measured at 25°C using a Brookfield DV1 viscometer with a CPA-40Z spindle. This low viscosity makes the silicone pressure-sensitive adhesive composition of the present invention suitable for use in inkjet printing processes. This silicone pressure-sensitive adhesive composition can be printed onto a substrate and cured to form a silicone pressure-sensitive adhesive (layer or pattern) with a thickness of 50 μm or less. This silicone pressure-sensitive adhesive composition can be used in any optical bonding application, such as injection bonding, that requires a low viscosity of less than 100 mPa·s.

[0084] Definitions and Use of Terms All quantities, ratios, and percentages are based on weight unless otherwise specified. The "Summary of the Invention" and "Abstract" are incorporated herein by reference. The terms "comprising" or "comprise" are used herein in their broadest sense to mean and encompass the concepts of "including," "include," "consisting essentially of," and "consisting of." The use of "for example," "eg," "such as," and "including" to list examples is not limited to the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," encompassing other similar or equivalent examples. Abbreviations used herein have their definitions in Table 6.

[0085] [Table 6]

[0086] Test method In this specification, the following test methods were used.

[0087] Viscosity was measured at 25°C using a Brookfield DV1 viscometer with a CPA-40Z spindle. Viscosity was measured for 2 minutes, with the torque controlled within the range of 20–80%. The latest data was collected after the measurement was completed.

[0088] Molecular weight was measured by gel permeation chromatography according to the following method. Samples were prepared in toluene at a concentration of 0.5% w / v, filtered through a 0.45 μm PTFE syringe filter, and analyzed against polystyrene standards. The relative calibration curve (tertiary fit) used to determine molecular weight was based on 16 polystyrene standards with molecular weight ranges of 580 to 2,610,000 daltons. The chromatography equipment consisted of a Waters 2695 separation module with a vacuum degasser, a Waters 2414 differential refractometer, and two styragel HR columns (7.8 mm × 300 mm) with styragel guard columns (4.6 × 30 mm) in front (molecular weight separation range of 100 to 4,000,000). Separation was performed using toluene programmed to flow at 1.0 mL / min, with the injection volume set to 100 μL, and the column and detector heated to 45°C. Data acquisition was performed for 60 minutes, and processing was carried out using Empower software. Where used herein for resins, Mw (Weight Average Molecular Weight) and Mn (Number Average Molecular Weight) represent the molecular weight when peaks representing neopentamers are excluded from the measurement.

[0089] The amount of unsaturated aliphatic hydrocarbon groups and silicon-bonded hydrogen in the total monovalent hydrocarbon groups of each starting material was measured by analytical methods exemplified by nuclear magnetic resonance (NMR). The average molecular formula of the starting materials is: 29 Si-NMR and 13 Determined by 13C-NMR analysis. NMR spectrometer: Bruker 500MHz AVANCE 3 NMR, equipped with a 10mm Si-free probe and a 5mm BBFO probe.

[0090] The SiH / Vi ratio was calculated using the following formula.

[0091]

number

[0092] The phenyl content in the starting materials was calculated using the following formula. The total phenyl content (mmol / g100g) was calculated based on the phenyl content of the phenyl portion of starting materials (A), (B), (C), (D), (E), and (F) per 100g of the total weight of starting materials (A), (B), (C), (D), (E), and (F).

[0093]

number

[0094] The present invention is described in an exemplary manner, and it should be understood that the terminology used is intended to be descriptive rather than restrictive. With respect to any group of Markush on which the description of individual features or embodiments herein relies, different, specific, and / or unforeseen results may be obtained from each element of that Markush group independently of all other elements of the Markush groups. Each element of a Markush group may be relied upon individually and / or in combination in particular embodiments within the scope of the appended claims, providing sufficient support.

[0095] Furthermore, any ranges and subranges on which the present invention is relied upon, independently and comprehensively, fall within the scope of the appended claims, and even if all and / or partial values ​​within them are not explicitly stated herein, it is understood that the entire range encompassing all and / or partial values ​​within them is described and conceived. Those skilled in the art will readily recognize that the listed ranges and subranges adequately describe and enable various embodiments of the present invention, and that such ranges and subranges may be further divided into related bisections, trisections, quadrisections, quintes, and so on. As merely one example, the range "1-18" can be further divided into a lower third (i.e., 1-6), a middle third (i.e., 7-12), and an upper third (i.e., 13-18), which individually and collectively fall within the scope of the appended claims and may individually and / or collectively rely on and provide appropriate grounds for specific embodiments within the scope of the appended claims. In addition, with respect to words that define or modify a range, such as "at least," "greater than," "less than," and "less than or equal to," such words should be understood to include subranges and / or upper or lower limits.

[0096] Embodiments of the present invention In the first embodiment, a curable silicone composition, (A) An aromatic compound having two alkenyl groups per molecule and a molecular weight of less than 1,000 g / mol, in an amount of 10 to 90 parts by mass, Formula (AI):R 1 -R 2 -R 1 Organic compounds, Equation (A-II):

[0097] [ka] Siloxane oligomers, and (A-III) Selected from the group consisting of combinations of both the organic compound of formula (AI) and the siloxane oligomer of formula (A-II), where each R 1R is an independently selected alkenyl group of 2 to 12 carbon atoms, and each R 2 This is the arylene moiety of 6-20 carbon atoms, and each R 3 R is independently selected from the group consisting of alkyl groups with 1 to 12 carbon atoms and aryl groups with 6 to 20 carbon atoms, however, 3 In all cases, 15 mol% to 50 mol% are aryl groups, and R 3 The condition is that in all cases 50 mol% to 85 mol% is alkyl, and the subscript a is an integer with a value of 2 to 3, for aromatic compounds, (B) An aromatic compound having two silicon-bonded hydrogen atoms per molecule and a molecular weight of less than 1,000 g / mol, in an amount of 90 to 10 parts by mass, Aromatic compounds are defined as having a total amount of starting material (A) and starting material (B) of 100 parts by mass, (C) Alkenyl-functionalized polyorganosilicate resin in an amount of 10 to 130 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), (D) an alkenyl-functionalized polydiorganosiloxane in an amount of 0 to 52.5 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), Optionally, (E) a reactive diluent in an amount of 0 to 25 parts by mass of the total of starting materials (A) and (B), comprising an 8 to 18 carbon-carbon hydrocarbon compound having at least one aliphatic group per molecule, (F) A polyorganohydrogensiloxane in an amount of 0 to 8 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), A polyorganohydrogensiloxane is provided, provided that the starting materials (A), (B), (C), (D), (E), and (F) are present in sufficient quantities to provide a silicon-bonded hydrogen atom / alkenyl group molar ratio (SiH / Vi ratio) of 0.5 / 1 to 2 / 1 and an aryl content of 246 mmol / 100 g to 450 mmol / 100 g. (G) Based on the total amount of the starting materials (A), (B), (C), (D), (E), (F), (G), and (H), a sufficient amount of hydrosilylation catalyst to provide 0.1 mass ppm to 5,000 mass ppm of platinum group metals, The solution optionally comprises (H) a hydrosilylation reaction inhibitor in an amount of 0 to 10,000 ppm by mass, based on the total amount of the starting materials (A), (B), (C), (D), (E), (F), (G), and (H).

[0098] In the second embodiment, in the composition described in the first embodiment, the compound of formula (AI) is selected from the group consisting of divinylbenzene, diallylbenzene, and combinations thereof.

[0099] In the third embodiment, in the composition described in the first embodiment, the compound of formula (A-II) is selected from the group consisting of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, 1,5-divinyl-3-phenylpentamethyltrisiloxane, and combinations thereof.

[0100] In the fourth embodiment, in the composition described in any one of the first to third embodiments, the starting material (B) has formula (BI).

[0101] In the fifth embodiment, in the composition described in the fourth embodiment, the siloxane oligomer of formula (BI) is selected from the group consisting of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyltetrasiloxane, and combinations thereof.

[0102] In the sixth embodiment, in the composition described in any one of the first to third embodiments, the organosilicon oligomer has formula (B-II).

[0103] In the seventh embodiment, the composition described in the sixth embodiment comprises the siloxane organic hybrid oligomer of formula (B-II) with respect to 1,4-bis(dimethylsilyl)benzene.

[0104] In the eighth embodiment, in the composition described in any one of the first to seventh embodiments, the alkenyl-functionalized polyorganosilicate resin is the average formula (CI):(R 4 3SiO 1 / 2 ) c (R 1 R 4 2SiO 1 / 2 ) d (SiO 4 / 2 ) e (HO 1 / 2 ) f It has, in the formula, each R 1 R is an independently selected alkenyl group of 2 to 12 carbon atoms, and each R 4 A is an independently selected alkyl group of 1 to 12 carbon atoms, where subscripts c, d, e, and f represent mole fractions, with c≧0, subscript d>0, 0.3≦(c+d)≦0.7, 0.3≦e≦0.7, and 0≦f≦0.05, provided that the amount (c+d+e+f)=1, and the alkenyl-functionalized polyorganosilicate resin has an average formula and a number-average molecular weight of 1,500 g / mol to 5,000 g / mol as measured by GPC.

[0105] In the ninth embodiment, in the composition described in any one of the first to seventh embodiments, the alkenyl-functionalized organosilicate resin is equal to the average formula (C-II):(R 4 3SiO 1 / 2 ) m (R 1 R 4 2SiO 1 / 2 ) n (R 6 SiO 3 / 2 ) o (SiO 4 / 2 ) p (HO 1 / 2 ) q It has, in the formula, each R 1 R is an independently selected alkenyl group of 2 to 12 carbon atoms, and each R4 R is an independently selected alkyl group of 1 to 12 carbon atoms, 6 is an aryl group with 6 to 20 carbon atoms, and the subscripts m, n, o, p, and q represent mole fractions having values ​​such that m≧0, n>0, 0.3≦(m+n)≦0.7, 0≦o≦0.3, 0.3≦p≦0.7, and 0≦q≦0.05, provided that the amount (m+n+o+p+q)=1. The alkenyl-functionalized polyorganosilicate resin has a number-average molecular weight of 1,500 g / mol to 5,000 g / mol as measured by GPC.

[0106] In the tenth embodiment, in the composition described in the eighth or ninth embodiment, each R 1 However, it is vinyl, and each R 4 However, it is methyl, and R 6 But it is phenyl.

[0107] In the eleventh embodiment, the composition described in any one of the first to tenth embodiments contains the starting material (D) in an amount of >0 to 40 parts by mass.

[0108] In the twelfth embodiment, a starting material (D) is present in the composition described in any one of the first to eleventh embodiments, and the starting material (D) is selected from the group consisting of α,ω-dimethylvinylsiloxy-terminated polydimethylsiloxane, α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), and combinations of both α,ω-dimethylvinylsiloxy-terminated polydimethylsiloxane and α,ω-dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane).

[0109] In the twelfth embodiment, the composition according to any one of the first to eleventh embodiments is present and contains a starting material (E) and 1-tetradecene.

[0110] In the 13th embodiment, in any one of the first to 12th embodiments, the starting material (F) is present in an amount of >0 to 2 parts by mass.

[0111] In the 14th embodiment, in the composition described in any one of the 1st to 13th embodiments, a starting material (F) is present, and the starting material (F) is selected from the group consisting of α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, and combinations of both α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane) and α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane.

[0112] In the 15th embodiment, in the composition described in any one of the 1st to 14th embodiments, the starting material (G) is selected from the group consisting of trimethyl(methylcyclopentadienyl)platinum(IV), platinum, 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex, and combinations of both trimethyl(methylcyclopentadienyl)platinum(IV) and platinum, 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex.

[0113] In the sixteenth embodiment, the composition described in any one of the first to fifteenth embodiments contains a starting material (H), which is selected from the group consisting of diethyl fumarate, bis-(methoxymethyl)ethyl maleate, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and two or more combinations thereof.

[0114] In the 17th embodiment, the composition described in any one of the 1st to 16th embodiments is used in an inkjet printing process to form a silicone pressure-sensitive adhesive.

[0115] In the 18th embodiment, a silicone pressure-sensitive adhesive prepared by the inkjet printing process described in the 17th embodiment is used to bond a thin-film transistor to a support.

Claims

1. A curable silicone composition, (A) An aromatic compound having two alkenyl groups per molecule and a molecular weight of less than 1,000 g / mol, in an amount of 10 to 90 parts by mass, Equation (A-I): R １ -R ２ -R １ Organic compounds, Equation (A-II): 【Chemistry 1】 Siloxane oligomers, and (A-III) Selected from the group consisting of combinations of both the organic compound of formula (A-I) and the siloxane oligomer of formula (A-II), where each R １ R is an independently selected alkenyl group of 2 to 12 carbon atoms, ２ This is the arylene moiety of 6 to 20 carbon atoms, and each R ３ R is independently selected from the group consisting of alkyl groups with 1 to 12 carbon atoms and aryl groups with 6 to 20 carbon atoms, however, R ３ In all cases, 15 mol% to 50 mol% are aryl groups, ３ The condition is that in all cases 50 mol% to 85 mol% is alkyl, and the subscript a is an integer with a value of 2 to 3, for aromatic compounds, (B) An aromatic compound having two silicon-bonded hydrogen atoms per molecule and a molecular weight of less than 1,000 g / mol, in an amount of 90 to 10 parts by mass, Aromatic compounds are provided, provided that the total amount of starting material (A) and starting material (B) is 100 parts by mass, (C) An alkenyl-functional polyorganosilicate resin in an amount of 10 to 130 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), The alkenyl-functionalized polyorganosilicate resin has the average formula (C-I): (R 4 3 SiO 1 / 2) c (R 1 R 4 2 SiO 1 / 2) d (SiO 4 / 2) e (HO 1 / 2) f, where each R 4 A is an independently selected alkyl group of 1 to 12 carbon atoms, where subscripts c, d, e, and f represent mole fractions, with c ≥ 0, subscript d > 0, 0.3 ≤ (c + d) ≤ 0.7, 0.3 ≤ e ≤ 0.7, and 0 ≤ f ≤ 0.05, provided that the amount (c + d + e + f) = 1, and the alkenyl-functionalized polyorganosilicate resin has an average formula and a number-average molecular weight of 1,500 g / mol to 5,000 g / mol, (D) an alkenyl-functionalized polydiorganosiloxane in an amount of 0 to 52.5 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), Optionally, a reactive diluent in an amount of 0 to 25 parts by mass of the total of starting materials (A) and (B), comprising (E) an 8 to 18 carbon-carbon hydrocarbon compound having at least one aliphatic group per molecule, (F) A polyorganohydrogensiloxane in an amount of 0 to 8 parts by mass per 100 parts by mass of the total of starting material (A) and starting material (B), A polyorganohydrogensiloxane is provided, provided that the starting materials (A), (B), (C), (D), (E), and (F) are present in sufficient quantities to provide a silicon-bonded hydrogen atom / alkenyl group molar ratio (SiH / Vi ratio) of 0.5 / 1 to 2 / 1 and an aryl content of 246 mmol / 100 g to 450 mmol / 100 g. (G) A hydrosilylation catalyst in an amount sufficient to provide 0.1 ppm to 5,000 ppm of platinum group metals based on the total amount of the starting materials (A), (B), (C), (D), (E), (F), (G), and (H), A curable silicone composition comprising, optionally, (H) a hydrosilylation reaction inhibitor in an amount of 0 to 10,000 ppm by mass, based on the total amount of the starting materials (A), (B), (C), (D), (E), (F), (G), and (H).

2. In Formula (A-I) and Formula (A-II), each R １ is independently selected from the group consisting of vinyl, allyl, and hexenyl, and R ２ is independently 【Chemistry 2】 Selected from the group consisting of each R ３ The composition according to claim 1, wherein the group is independently selected from the group consisting of methyl groups and phenyl groups.

3. The composition according to claim 1, wherein the compound of formula (A-I) is selected from the group consisting of divinylbenzene, diallylbenzene, and combinations thereof, and the compound of formula (A-II) is selected from the group consisting of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, 1,5-divinyl-3-phenylpentamethyltrisiloxane, and combinations thereof.

4. The starting material (B) is given by formula (B-I): 【Transformation 3】 Siloxane oligomer, formula (B-II): 【Chemistry 4】 Selected from the group consisting of organosilicon oligomers and combinations of both the siloxane oligomer and the organosilicon oligomer, in the formula R ２ However, the arylene portion consists of 6 to 20 carbon atoms, and each R ３ However, independently selected from the group consisting of alkyl groups with 1 to 12 carbon atoms and aryl groups with 6 to 20 carbon atoms, provided that R ３ In all cases, 15 mol% to 50 mol% are aryl groups, ３ The condition is that in all cases 50 mol% to 85 mol% is an alkyl group, and each R ４ The composition according to claim 1, wherein the alkyl group is independently selected from 1 to 12 carbon atoms, and the subscript b is 1 to 3.

5. In equations (B-I) and (B-II), R ２ but, 【Transformation 5】 Selected from the group consisting of each R ３ However, each R is either a methyl group or a phenyl group. ４ The composition according to claim 4, wherein the group is a methyl group.

6. The starting material (B) A siloxane oligomer of the above formula (B-I), selected from the group consisting of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1,1,7,7-tetramethyl-3,3,5,5,-tetraphenyltetrasiloxane, and combinations thereof, or The organosilicon oligomer of formula (B-II), wherein the siloxane organic hybrid oligomer of formula (B-II) contains 1,4-bis(dimethylsilyl)benzene, The composition according to claim 1, comprising a combination of both the siloxane oligomer of formula (B-I) and the siloxane organic hybrid oligomer of formula (B-II).

7. Starting material (D) exists, and the unit formula is (R ５ ３ SiO １／２ ) ｇ (R ５ ２ SiO ２／２ ) ｈ (R ５ SiO ３／２ ) ｉ (SiO ４／２ ) ｊ It has, in the formula, each R ５ R is independently a monovalent hydrocarbon group selected from the group consisting of alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, and aryl groups with 6 to 20 carbon atoms, provided that R ５ The composition according to claim 1, provided that in all cases 0.01 mol% to 1 mol% is an alkenyl group, the subscripts g, h, i, and j represent mole fractions having values ​​such that 0 < g ≤ 0.4, 0.6 < h < 1, 0 ≤ i ≤ 0.03, 0 ≤ j ≤ 0.03, and the amount (g + h + i + j) = 1, and the starting material (D) has a viscosity of 1 mPa·s to 100,000 mPa·s at 25°C.

8. The composition according to claim 1, wherein the starting material (E) comprises a 1-alkene with 8 to 12 carbon atoms.

9. The starting material (F) is present, and the unit formula is (R ４ ３ SiO １／２ ) ｔ (HR ４ ２ SiO １／２ ) ｕ (R ４ ２ SiO ２／２ ) ｖ (HR ４ SiO ２／２ ) ｗ (R ４ SiO ３／２ ) ｘ (HSiO ３／２ ) ｙ (SiO ４／２ ) ｚ It has, in the formula, each R ４ The composition according to claim 1, wherein is an independently selected alkyl group of 1 to 12 carbon atoms, and the subscripts t, u, v, w, x, y, and z represent the average number of each unit in the formula, with t≧0, u≧0, v≧0, w≧0, x≧0, y≧0, z≧0, amount(u+w+y)≧2, and amount(t+u+v+w+x+y+z) having a value sufficient to give the polyorganohydrogensiloxane a viscosity of 2 mPa·s to 1,000 mPa·s at 25°C.

10. The composition according to claim 1, wherein the starting material (G) is selected from the group consisting of (G-I) a radiation-activated hydrosilylation catalyst, (G-II) a hydrosilylation catalyst that can be activated by means other than irradiation, or (G-III) a combination thereof.

11. The composition according to claim 1, wherein a starting material (H) is present and selected from the group consisting of acetylene alcohols, silylated acetylene alcohols, en-yne compounds, triazoles, phosphines, mercaptans, hydrazines, amines, fumarates, maleates, ethers, carbon monoxide, and two or more combinations thereof.

12. Use of the composition according to any one of claims 1 to 11 as an ink in an inkjet printing process.

13. It is a method, Optionally, 1) treat the surface of the substrate, 2) Applying the composition described in any one of claims 1 to 11 onto the surface of the substrate, 3) A method comprising curing the composition to form a silicone pressure-sensitive adhesive on the surface.

14. Optionally, 4) treat the surface of the adherend, The method according to claim 13, further comprising optionally, 5) bringing the surface of the adherend into contact with the silicone pressure-sensitive adhesive on the opposite side of the substrate.

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