Curable silicone composition, encapsulation material, and opto-semiconductor device

Abstract

A curable silicone composition is provided that can be used to form a cured product having a practically effective pot life, curable at low temperatures, excellent surface smoothness, transparency, and high hardness. This curable silicone composition comprises (A) a dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule; (B) a dendritic organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule; (C) an additive selected from combinations of molecular chain side-chain polyether-modified organopolysiloxane, phenyl-modified organopolysiloxane, non-terminal hydroxyl group-containing dimethylpolysiloxane not containing aryl groups, and phenolic antioxidants, having a wettability-improving effect; and (D) a curing reaction inhibitor.

Description

Technology Field

[0001] The present invention relates to a curable silicon composition, and more specifically, to a curable silicon composition advantageously used as an opto-semiconductor encapsulator. Furthermore, the present invention relates to an encapsulator comprising such a curable silicon composition, and an opto-semiconductor device encapsulated by said encapsulator. Background Technology

[0002] Curable silicone compositions are used in a wide range of industrial fields because they form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency after curing. In particular, since these cured products have a lower potential for discoloration and exhibit less degradation of physical properties such as durability compared to other organic materials, they are widely used as silicone sealants for optical components, and are especially used in opto-semiconductor devices such as light-emitting diodes (LEDs).

[0003] In particular, curable organopolysiloxane compositions that are cured through a hydrosilylation reaction are used as protective coatings and encapsulating materials for opto-semiconductor devices in opto-semiconductor devices, such as photocouplers, light-emitting diodes, and solid-state imaging devices. Since opto-semiconductor devices emit light and receive light, it is required that the protective coatings and encapsulating materials for such opto-semiconductor devices do not absorb or scatter light.

[0004] For this reason, a hydrosilylation reaction-curable organopolysiloxane composition that forms a cured product with high refractive index and light transmittance by using an organopolysiloxane with a high phenyl group content has been proposed for opto-semiconductor applications.

[0005] For example, Patent Document 1 discloses a hydrosilylation reaction-curable organicpolysiloxane composition comprising (A) a methyl-phenyl-alkenyl polysiloxane having at least two silicon atom-bonded alkenyl groups per molecule, wherein the diphenylsiloxane unit is 5 mol% or less of the total siloxane unit and at least 20 mol% of the total silicon atom-bonded organic groups in the molecule are phenyl groups; (B) a methyl-phenyl-hydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule, wherein the diphenylsiloxane unit is 5 mol% or less of the total siloxane unit and at least 20 mol% of the total silicon atom-bonded organic groups in the molecule are phenyl groups; and (C) a catalyst for a hydrosilylation reaction, wherein the composition is characterized in that the diphenylsiloxane unit is 5 mol% or less of the total siloxane unit.

[0006] Patent Document 2 contains at least (A) average structural formula: R 1 a SiO (4－a) / 2 (during food, R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group; provided that at least two Rs in one molecule 1 This is an alkenyl group, and the entire R 1 (B) an organopolysiloxane in which at least 30 mol% of the total silicon atom bonded organogroups are aryl groups; and “a” is a number ranging from 0.6 to 2.1; (B) an organopolysiloxane containing at least two silicon atom bonded hydrogen atoms in one molecule, wherein at least 15 mol% of the total silicon atom bonded organogroups are aryl groups; (C) average unit formula: (R 2 SiO 3 / 2 ) b (R 2 2SiO 2 / 2 ) c (R 2 3SiO 1 / 2 ) d (SiO 4 / 2 ) e (XO 1 / 2 ) f {In the formula, each R 2independently represents an alkyl group, an alkenyl group, an aryl group, or an epoxy-containing organic group; provided that the total R in one molecule 2 A branched-chain organopolysiloxane in which at least 5 mol% is an alkenyl group, at least 15 mol% is an aryl group, and at least 10 mol% is an epoxy-containing organic group; X represents a hydrogen atom or an alkyl group; b is positive, c is 0 or positive, d is 0 or positive, e is 0 or positive, f is 0 or positive, c / b is a number in the range of 0 to 10, d / b is a number in the range of 0 to 5, e / (b + c + d + e) ​​is a number in the range of 0 to 0.3, and f / (b+c+d+e) is a number in the range of 0 to 0.02; A curable organic polysiloxane composition comprising (D) a catalyst for hydrosilylation is disclosed, wherein the content of component (B) is an amount such that the molar ratio of silicon atom bonded hydrogen atoms contained in component (B) to alkenyl groups contained in component (A) and component (C) is in the range of 0.1 to 5, the content of component (C) is 0.1 to 20 parts by mass per 100 parts by mass of the total of component (A) and component (B), and the content of component (D) is an amount sufficient to accelerate the curing of the composition.

[0007] Patent document 3 describes a diorganopolysiloxane having at least two alkenyl groups in one molecule, wherein at least 70 mol% of the total siloxane units are methylphenylsiloxane units (provided that the total content of 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane is 5 weight% or less); and (B) an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, wherein at least 15 mol% of the silicon atom-bonded organic groups are phenyl groups {an amount such that the molar number of silicon atom-bonded hydrogen atoms of component (B) is 10 to 500% relative to the total molar number of alkenyl groups of component (A)}. A curable organopolysiloxane composition is disclosed, characterized by comprising (C) a catalyst for a hydrosilylation reaction (an amount sufficient to cure the composition).

[0008] Patent document 4 discloses a curable organopolysiloxane composition characterized by comprising: (A) an organopolysiloxane having at least two alkenyl groups in one molecule; (B) an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule; (C) a polyether-modified silicone having repeating units represented by a general formula and a number average molecular weight of 1,000 to 100,000; and (D) a catalyst for a hydrosilylation reaction.

[0009] However, conventional curable silicon compositions typically require high-temperature treatment for a long time to cure. Therefore, when used as encapsulating materials for semiconductor devices, the shape may shrink during curing, which may result in the flexible substrate bending, the accuracy of patterning during the semiconductor device mounting process being reduced, or the mounted electronic device being damaged by heat. Furthermore, if the amount of curing catalyst is increased to improve curability, the curability of the curable silicon composition improves, but there is a problem that the cured product may become discolored. In addition, conventional curable silicon compositions containing aryl groups and having a high refractive index may have insufficient wettability for organic substrates such as polycarbonate, and the cured product may have insufficient surface smoothness.

[0010] In addition, hydrosilylated reaction-curable organopolysiloxane compositions with high heat resistance, particularly at high temperatures, have also been developed in the past.

[0011] For example, Patent Document 5 describes (A) having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group per molecule, general formula: RSiO 3 / 2 (B) a branched organopolysiloxane having a siloxane unit represented by (wherein R is a substituted or unsubstituted monovalent hydrocarbon group); (B) a linear organopolysiloxane having at least one silicon-bonded aryl group per molecule, wherein both ends of the branched chain are blocked by silicon-bonded hydrogen atoms; (C) a catalyst for a hydrosilylation reaction; and (D) having at least one silicon-bonded alkenyl group per molecule, with the average formula: (R 5 3SiO 1 / 2 ) f (R 5 2SiO 2 / 2 ) ｇ (R 5 SiO 3 / 2 ) h (SiO 4 / 2 ) i (among the food, each R 5may be the same or different, is independently selected from substituted or unsubstituted monovalent hydrocarbon groups, and has at least one R per molecule 5 A curable organic polysiloxane composition is disclosed comprising a low molecular weight siloxane represented by an alkenyl group, wherein the ratio between the alkenyl group and the silicon atom is 0.3:1, and f, g, h, and i are independently 0 or positive) (wherein the weight average molecular weight Mw of the siloxane is less than 1,000 g / mol).

[0012] Additionally, Patent Document 6 discloses an addition-curing silicone composition comprising the following components (A) to (C): (A) an organopolysiloxane represented by a specific compositional formula, having at least two alkenyl groups in one molecule and having a network structure; (B) a branched organo-hydrogen polysiloxane represented by a specific formula and having at least two hydrosilyl groups in one molecule; and (C) a catalytic amount of a hydrosilylation catalyst.

[0013] Patent document 7 discloses a curable resin composition comprising (A) a straight-chain organicpolysiloxane having at least two silicon atom-bonded hydrogen atoms and at least one aryl group in one molecule and an average degree of polymerization greater than 10; (B) a branched-chain organicpolysiloxane having at least three alkenyl groups and at least one aryl group in one molecule; and (C) a catalyst for a hydrosilylation reaction (wherein the ratio of diphenylsiloxane units to the total siloxane units comprising the straight-chain organicpolysiloxane (A) and the branched-chain organicpolysiloxane (B) is 10 mol% or more).

[0014] However, in conventional high-heat-resistant curable silicone compositions, there is a problem that the pot life and curability of the curable silicone composition are insufficient. Prior art literature

[0015] Patent Document 1: JP 2012-507582 A Patent Document 2: JP 2010-1335 A Patent Document 3: JP 2010-84118 A Patent Document 4: WO 2019 / 026754 A1 Patent Document 5: JP 2019-524959 A Patent Document 6: JP 2016-204423 A Patent Document 7: WO 2015 / 136820 A1 The problem to be solved

[0016] The objective of the present invention is to provide a silicone composition capable of forming a cured product having excellent surface smoothness, transparency, and high hardness, while exhibiting a practically effective pot life and excellent curability at low temperatures.

[0017] Another objective of the present invention is to provide a silicone composition that exhibits a practically effective pot life and excellent curing properties at low temperatures, and can form a transparent and high-hardness cured product even when exposed to high temperatures for a long time.

[0018] Another object of the present invention is to provide an encapsulating material comprising the curable silicone composition of the present invention. A further object of the present invention is to provide an opto-semiconductor device encapsulated with the encapsulating material of the present invention. means of solving the problem

[0019] As a result of careful examination to solve the above problem, the inventors have arrived at the present invention by surprisingly discovering that a curable silicone composition comprising the following can be efficiently cured even at low temperatures and for a short time, and can form a cured product having excellent transparency, high hardness, and a smooth surface: (A) a dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule; (B) a dendritic organo-hydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule; (C) a molecular chain side-chain polyether-modified organopolysiloxane, a phenol-modified organopolysiloxane, a terminal hydroxyl group-containing dimethylpolysiloxane not containing an aryl group, and a phenolic antioxidant, and an additive having a wettability-improving effect selected from combinations thereof; and (D) a curing reaction inhibitor.

[0020] Accordingly, the present invention relates to a curable silicone composition comprising the following:

[0021] (A) Dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule;

[0022] (B) Dendritic organo-hydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule;

[0023] (C) an additive having a wettability improving effect selected from molecular chain side chain polyether-modified organopolysiloxane, phenol-modified organopolysiloxane, dimethylpolysiloxane containing terminal hydroxyl groups not containing aryl groups, and phenolic antioxidants, and combinations thereof; and

[0024] (D) Curing catalyst.

[0025] The curable silicone composition preferably further comprises a straight-chain organo-hydrogen polysiloxane.

[0026] The polyether group of the molecular chain side chain polyether-modified organopolysiloxane of component (C) preferably includes a polyoxyethylene unit.

[0027] The phenol-modified organopolysiloxane of component (C) is preferably straight-chain and contains phenol-containing organic groups at both ends of the molecular chain.

[0028] The terminal hydroxyl group-containing dimethylpolysiloxane that does not contain an aryl group of component (C) is preferably straight-chain and contains hydroxyl groups at both ends of the molecular chain.

[0029] The phenolic antioxidant of component (C) is preferably 2,6-di-tert-butyl-p-cresol.

[0030] The content of molecular chain side chain polyether modified organopolysiloxane (C) is preferably 0.01 mass% or more and 10 mass% or less of the total mass of alkenyl group-containing organopolysiloxane and organo-hydrogen polysiloxane.

[0031] The content of the dendritic organo-hydrogen polysiloxane (B) is preferably 1% by mass or more of the total mass of the alkenyl group-containing organo-hydrogen polysiloxane and the organo-hydrogen polysiloxane.

[0032] The curing catalyst (D) is preferably a platinum-based catalyst and contains platinum atoms of 0.01 ppm or more and 15 ppm or less with respect to the total mass of the curable silicon composition.

[0033] The molar ratio (H / Vi) of hydrogen atoms and alkenyl groups derived from the organopolysiloxane component is preferably 0.9 to 1.3.

[0034] The curable silicone composition preferably further comprises, other than component (A), an epoxy group-containing resinous organopolysiloxane, an alkenyl group-containing cyclic organopolysiloxane, and / or an alkenyl group-containing organopolysiloxane comprising only M units and Q units.

[0035] In addition, the present invention

[0036] (A) Dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule;

[0037] (F) Alkenyl group-containing organopolysiloxane containing only M and Q units;

[0038] (B) Dendritic organo-hydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule;

[0039] (E) Ethinylcyclohexanol; and

[0040] (D) Curing catalyst

[0041] (Here, the molar ratio (H / Vi) of hydrogen atoms and alkenyl groups derived from the organopolysiloxane component is 0.98 to 1.2, and

[0042] SiO 2 / 2 The present invention relates to a curable silicone composition comprising a dendritic organopolysiloxane containing an alkenyl group bonded to a silicon atom of a siloxane unit (D unit) represented by, wherein the content of the organopolysiloxane containing the alkenyl group is less than 50 mass% of the total mass of the organohydrogen polysiloxane and the alkenyl group-containing organopolysiloxane.

[0043] (F) The content of the alkenyl group-containing organopolysiloxane containing only M units and Q units is preferably 2% by mass or more and 20% by mass or less of the total mass of the alkenyl group-containing polysiloxane and the organo-hydrogen polysiloxane.

[0044] (B) The content of the dendritic organo-hydrogen polysiloxane is preferably 1% by mass or more and 15% by mass or less of the total mass of the alkenyl group-containing organo-hydrogen polysiloxane and the organo-hydrogen polysiloxane.

[0045] The curing catalyst (D) is preferably a platinum-based catalyst and contains platinum atoms of 0.01 ppm or more and less than 8 ppm with respect to the total mass of the curable silicon composition.

[0046] The content of straight-chain organo-hydrogen polysiloxane is preferably 25 mass% or more of the total mass of the dendritic alkenyl group-containing organopolysiloxane of component (A).

[0047] The present invention also relates to a sealing material comprising the curable silicone composition of the present invention.

[0048] The present invention also relates to an opto-semiconductor device comprising a cured encapsulant according to the present invention. Effects of the invention

[0049] According to one embodiment of the present invention, a curable silicone composition can form a cured article having a transparent, high hardness and a smooth surface shape, and can provide a silicone composition capable of exhibiting a practically effective pot life and excellent curability at low temperatures.

[0050] In addition, according to another embodiment of the present invention, a curable silicone composition can provide a silicone composition capable of exhibiting a practically effective pot life and excellent curability at low temperatures, and forming a cured product that exhibits excellent transparency even after prolonged heating. Specific details for implementing the invention

[0051] [Curable Silicone Composition]

[0052] The curable silicone composition of Embodiment 1 of the present invention comprises at least the following:

[0053] (A) Dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule;

[0054] (B) Dendritic organo-hydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule;

[0055] (C) an additive having a wettability improving effect selected from molecular chain side chain polyether-modified organopolysiloxane, phenol-modified organopolysiloxane, dimethylpolysiloxane containing terminal hydroxyl groups not containing aryl groups, and phenolic antioxidants, and combinations thereof; and

[0056] (D) Curing catalyst.

[0057] According to this embodiment 1 of the present invention, it is possible to provide a curable silicone composition that exhibits a practically effective pot life and excellent curability at low temperatures, and can form a cured product with a smooth surface shape on a substrate. In addition, the curable silicone composition of embodiment 1 of the present invention can form a cured product that also exhibits high hardness and excellent transparency after heating.

[0058] In addition, the curable silicone composition of Embodiment 2 of the present invention comprises the following:

[0059] (A) Dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule;

[0060] (F) Alkenyl group-containing organopolysiloxane containing only M and Q units;

[0061] (B) Dendritic organo-hydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule;

[0062] (E) Ethinylcyclohexanol; and

[0063] (D) Curing catalyst

[0064] (Here, the molar ratio (H / Vi) of hydrogen atoms and alkenyl groups derived from the organopolysiloxane component is 0.98 to 1.2, and

[0065] SiO 2 / 2The content of dendritic organopolysiloxane containing alkenyl groups bonded to silicon atoms of siloxane units (D units) represented by is less than 50 mass% of the total mass of alkenyl group-containing organopolysiloxane and organo-hydrogen polysiloxane).

[0066] According to this embodiment 2 of the present invention, it is possible to provide a curable silicone composition capable of forming a curable product that exhibits a practically effective pot life and excellent curability at low temperatures, and excellent transparency even after heating for a long time.

[0067] Hereinafter, each component of the curable silicone composition of the present invention is described in detail.

[0068] (A) Dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule

[0069] Component (A) is the main component of the present composition and is a dendritic organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule. The curable silicone composition of the present invention may include one type of alkenyl group-containing organopolysiloxane (A) or two or more types of alkenyl group-containing organopolysiloxanes (A).

[0070] The molecular structure of component (A) is dendritic. In this specification, "dendritic" means having a branched or three-dimensional network structure in the molecular structure, and, for example, at least one SiO 3 / 2 Siloxane units (T units) or SiO denoted by 4 / 2 It means including siloxane units (Q units) indicated by.

[0071] Examples of alkenyl groups that may be included in component (A) include C2-12 alkenyl groups, such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group and dodecenyl group, and vinyl group is preferred.

[0072] Examples of aryl groups included in component (A) include C6-20 aryl groups, such as phenyl, tolyl, xylyl, and naphthyl groups, and phenyl groups are preferred.

[0073] Silicon atom-bonded organic groups other than alkenyl and aryl groups included in component (A) comprise halogen-substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl and aryl groups; for example, C1-12 alkyl groups, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; C7-20 aralkyl groups, e.g., benzyl, phenethyl, and phenylpropyl groups; and the groups in which some or all of the hydrogen atoms are substituted with halogen atoms, e.g., fluorine, chlorine, or bromine atoms. It should also be noted that the silicon atoms in component (A) may have a small amount of hydroxyl or alkoxy groups, such as methoxy or ethoxy groups, to the extent that the purpose of the present invention is not impaired. The silicon atom bonding groups other than alkenyl and aryl groups in component (A) are preferably selected from C1-6 alkyl groups, particularly methyl groups and C6-20 aryl groups, particularly phenyl groups.

[0074] In the present specification, a dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule of component (A) may mean a dendritic alkenyl group-containing organopolysiloxane that does not include an epoxy group-containing organic group, wherein the epoxy group is an organic group bonded to a silicon atom.

[0075] In one embodiment of the present invention, component (A) can preferably be represented by the following average unit formula (I):

[0076] Average unit formula (I): (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b(R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e

[0077] (In Equation (I), R 1 is an identical or different halogen-substituted or unsubstituted monovalent hydrocarbon group, provided that at least two Rs in one molecule 1 is an alkenyl group, and at least one R 1 is an aryl group; 0≤a<1, 0≤b<1, 0≤c<0.9, 0≤d<0.5, and 0≤e<0.4, a+b+c+d=1.0, and c+d>0).

[0078] R in the above equation (I) 1 Examples of halogen-substituted or unsubstituted monovalent hydrocarbon groups as are C1-12 alkyl groups, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; C6-20 aryl groups, e.g., phenyl, tolyl, xylyl, and naphthyl groups; C7-20 aralkyl groups, e.g., benzyl, phenethyl, and phenylpropyl groups; C2-12 alkenyl groups, e.g., vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups; and includes the above group in which some or all of the hydrogen atoms are substituted with halogen atoms, such as fluorine, chlorine, or bromine atoms. R 1 It may be a small amount of hydroxyl or alkoxy groups, such as methoxy or ethoxy groups, within a range that does not impair the purpose of the present invention. 1 It is preferably selected from C1-6 alkyl groups, particularly methyl groups, C2-6 alkenyl groups, particularly vinyl groups, or C6-20 aryl groups, particularly phenyl groups.

[0079] X in the above formula (I) is a hydrogen atom or an alkyl group. The X alkyl group is preferably a C1-3 alkyl group, and specific examples include a methyl group, an ethyl group, and a propyl group.

[0080] In the above formula (I), a is preferably in the range of 0.1 ≤ a ≤ 0.8, more preferably in the range of 0.15 ≤ a ≤ 0.6, and even more preferably in the range of 0.2 ≤ a ≤ 0.4. In the above formula (I), b is preferably in the range of 0 ≤ b ≤ 0.6, more preferably in the range of 0 ≤ b ≤ 0.5, and particularly in the range of 0 ≤ b ≤ 0.4. In the above formula (I), c is preferably in the range of 0.2 ≤ c < 0.9, more preferably in the range of 0.4 ≤ c ≤ 0.85, and particularly in the range of 0.6 ≤ c ≤ 0.8. In the above formula (I), d is preferably in the range of 0 ≤ d ≤ 0.4, more preferably in the range of 0 ≤ d ≤ 0.25, and particularly in the range of 0 ≤ d ≤ 0.1. In the above formula (I), e is preferably in the range of 0≤e≤0.15, more preferably in the range of 0≤e≤0.1, and particularly in the range of 0≤e≤0.05.

[0081] In a preferred embodiment of the present invention, in the formula (I), c is greater than 0, that is, the dendritic alkenyl group-containing organopolysiloxane of component (A) is SiO 3 / 2 It includes siloxane units (T units) represented by . The dendritic organopolysiloxane of component (A) contains SiO 4 / 2 It may or may not include siloxane units (Q units) represented by, but preferably does not include.

[0082] In a preferred embodiment of the present invention, in the formula (I), the dendritic alkenyl group-containing organopolysiloxane of component (A) is SiO₂ 2 / 2 It may or may not include a siloxane unit (D unit) indicated by, but preferably does not include.

[0083] In a preferred embodiment of the present invention, the dendritic alkenyl group-containing organopolysiloxane of component (A) contains alkenyl groups at the molecular ends. The dendritic organopolysiloxane of component (A) is preferably SiO₂ 1 / 2 The siloxane unit (M unit) represented by has an alkenyl group, and the molecular chain side chain (i.e., SiO) 2 / 2 Siloxane units (D units) or SiO denoted by 3 / 2 The siloxane unit (T unit) represented by may or may not include an alkenyl group, but preferably does not include it.

[0084] There are no specific limitations on the content of alkenyl groups in the total silicon atom bonded organic groups of the dendritic alkenyl group-containing organopolysiloxane of component (A); however, for example, the content may be 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more of the total silicon atom bonded organic groups, and the content may be 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less of the total silicon atom bonded organic groups. It should be noted that in this specification, the content of alkenyl groups contained in the organopolysiloxane component may be determined by analytical methods such as Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), or the following titration method.

[0085] A method for determining the amount of alkenyl groups in each component by titration will be explained. The alkenyl group content in the organopolysiloxane component can be determined with excellent accuracy by a titration method generally known as the Wijs method. The principle is as follows. First, the alkenyl groups in the organopolysiloxane starting material and iodine monochloride are subjected to an addition reaction as shown in Equation (1). Next, the excess iodine monochloride is reacted with potassium iodide by the reaction shown in Equation (2) to release free iodine. Then, the free iodine is titrated with a sodium thiosulfate solution.

[0086] Equation (1) CH2=CH- + 2ICl → CH2I-CHCl- + ICl(excess)

[0087] Equation (2) ICl + KI → I2+ KCl

[0088] The amount of alkenyl groups in the components can be determined from the difference between the amount of sodium thiosulfate required for titration and the titration amount of a blank solution prepared separately.

[0089] The content of aryl groups of the dendritic organopolysiloxane of component (A) (mol% of aryl groups in the total silicon atom bonded functional groups of the dendritic organopolysiloxane) can be designed as desired, but said content is typically 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, preferentially 30 mol% or more, particularly preferably 35 mol% or more, said content may also be 80 mol% or less, preferably 70 mol% or less, even more preferably 65 mol% or less, preferentially 60 mol% or less, particularly preferably 55 mol% or less. It should be noted herein that the content of aryl groups contained in the organopolysiloxane component may be determined by analysis such as, for example, Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0090] The organopolysiloxane of component (A) is preferably solid or semi-solid at 25°C. The number average molecular weight of the organopolysiloxane of component (A) is not particularly limited, but is preferably in the range of 500 to 10,000.

[0091] Component (A) is the main agent of the curable silicone composition of the present invention, and its content is preferably 40 mass% or more, more preferably 50 mass% or more, even more preferably 55 mass% or more, and particularly preferably 60 mass% or more, based on the total mass of the alkenyl group-containing organic polysiloxane and organo-hydrogen polysiloxane included in the curable silicone composition of the present invention. In addition, the content of component (A) is preferably 90 mass% or less, more preferably 80 mass% or less, even more preferably 70 mass% or less, and particularly preferably 65 mass% or less, based on the total mass of the alkenyl group-containing organic polysiloxane and organo-hydrogen polysiloxane included in the curable silicone composition of the present invention.

[0092] (Other alkenyl group-containing organopolysiloxanes)

[0093] The curable silicone composition of the present invention may include, in addition to component (A) which is the subject of the curable silicone composition of the present invention, an alkenyl group-containing organopolysiloxane comprising at least two alkenyl groups per molecule. Such other alkenyl group-containing organopolysiloxanes are not particularly limited, but examples include epoxy group-containing resinous organopolysiloxanes, alkenyl group-containing cyclic organopolysiloxanes, and alkenyl group-containing organopolysiloxanes comprising only M units and Q units.

[0094] (Epoxy group-containing resinous organopolysiloxane)

[0095] In one embodiment of the present invention, the curable silicone composition of the present invention may include an epoxy group-containing resinous organicpolysiloxane. The curable silicone composition of the present invention may include one type of epoxy group-containing resinous organicpolysiloxane or a combination of two or more types of epoxy group-containing resinous organicpolysiloxanes.

[0096] The epoxy group-containing resinous organopolysiloxane is preferably of average unit formula (II):

[0097] (R 9 3SiO 1 / 2 ) a (R 10 2SiO 2 / 2 ) b (R 9 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e

[0098] (during food, R 9 Each is independently a halogen-substituted or unsubstituted monovalent hydrocarbon group, provided that at least two Rs 1 is an alkenyl group; R 10 Each is independently a halogen-substituted or unsubstituted monovalent hydrocarbon group or an epoxy-containing organic group, provided that at least one R 10 It can be represented as follows: 0≤a<1, 0≤b<1, 0≤c<0.9, 0≤d<0.5, and 0≤e<0.4, a+b+c+d+e=1.0, and c+d>0.

[0099] In the above formula (II), the halogen-substituted or unsubstituted monovalent hydrocarbon group R 9 and R 10 R is preferably selected from C1-12 alkyl groups, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; C6-20 aryl groups, e.g., phenyl, tolyl, xylyl, and naphthyl groups; C2-12 alkenyl groups, e.g., vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups; and the above groups in which some or all of the hydrogen atoms are substituted with halogen atoms, e.g., fluorine, chlorine, or bromine atoms. 9It is preferably selected from C1-6 alkyl groups, particularly methyl groups, C2-6 alkenyl groups, particularly vinyl groups, and C6-20 aryl groups, particularly phenyl groups.

[0100] In the above (II), the epoxy group-containing organic group R 10 It comprises, for example, glycidoxyalkyl groups, such as 2-glycidoxyethyl, 3-glycidoxypropyl, and 4-glycidoxybutyl groups; epoxycycloalkylalkyl groups, such as 2-(3,4-epoxycyclohexyl)-ethyl and 3-(3,4-epoxycyclohexyl)-propyl groups; and epoxyalkyl groups, such as 3,4-epoxybutyl and 7,8-epoxyoctyl groups, wherein the glycidoxyalkyl group is preferred, and the 3-glycidoxypropyl group is particularly preferred. R 10 R is preferably selected from C1-6 alkyl groups, particularly methyl groups, C2-6 alkenyl groups, particularly vinyl groups, C6-20 aryl groups, particularly phenyl groups, and 3-glycidoxypropyl groups. 10 It is preferably selected from C1-6 alkyl groups, in particular methyl groups and 3-glycidoxypropyl groups.

[0101] X in the above formula (II) is a hydrogen atom or an alkyl group. The X alkyl group is preferably a C1-3 alkyl group, and specific examples include a methyl group, an ethyl group, and a propyl group.

[0102] In the above formula (II), based on a+b+c+d+e=1.0, a is preferably in the range of 0.03≤a≤0.7, more preferably in the range of 0.06≤a≤0.5, and particularly in the range of 0.09≤a≤0.3. In the above formula (II), b is preferably in the range of 0.05≤b≤0.6, more preferably in the range of 0.1≤b≤0.5, and particularly in the range of 0.15≤b≤0.4. In the above formula (II), c is preferably in the range of 0.1≤c≤0.8, more preferably in the range of 0.25≤c≤0.7, and particularly in the range of 0.4≤c≤0.6. In the above formula (II), d is preferably in the range of 0≤d≤0.3, more preferably in the range of 0≤d≤0.2, and even more preferably in the range of 0≤d≤0.1. In Equation (II), e is preferably in the range of 0.05 ≤ e ≤ 0.4, more preferably in the range of 0.1 ≤ e ≤ 0.3, and particularly in the range of 0.15 ≤ e ≤ 0.25.

[0103] In one embodiment, in the above formula (II), e / (a+b+c+d) is greater than 0.05. Preferably, e / (a+b+c+d) is greater than 0.08, more preferably greater than 0.11, and even more preferably greater than 0.14. Also, e / (a+b+c+d) is typically less than 0.5, preferably less than 0.4, even more preferably less than 0.3, and particularly preferably less than 0.25.

[0104] In a preferred embodiment of the present invention, the epoxy group-containing resinous organicpolysiloxane is a siloxane unit in formula (II) where c is greater than 0, i.e., SiO 3 / 2 It contains siloxane units (T units) represented by . Epoxy group-containing resinous organopolysiloxanes contain SiO 4 / 2 It may or may not include siloxane units (Q units) represented by, but preferably does not include.

[0105] In a preferred embodiment of the present invention, the epoxy group-containing resinous organopolysiloxane contains alkenyl groups at the molecular ends. The epoxy group-containing resinous organopolysiloxane is preferably SiO₂ 1 / 2 The siloxane unit (M unit) represented by has an alkenyl group, and the molecular side chain (i.e., SiO) 2 / 2 Siloxane units (D units) and SiO represented by 3 / 2 The siloxane unit (T unit) represented by may or may not include an alkenyl group, but preferably does not include it.

[0106] In a preferred embodiment, there is no particular limitation on the amount of alkenyl groups among the total silicon atom bonded organic groups in the epoxy group-containing resinous organicpolysiloxane, but the amount may preferably be 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, particularly preferably 8 mol% or more; additionally, the amount may also be, for example, 30 mol% or less, preferably 20 mol% or less, more preferably 15 mol% or less.

[0107] There is no specific limit on the amount of epoxy-containing organic groups among the total silicon atom bonded organic groups in the epoxy-containing dendritic organopolysiloxane, but this is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 15 mol% or more, and said amount may also be, for example, 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less. It should be noted that the amount of epoxy-containing organic groups can be determined by analysis such as, for example, Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0108] In a preferred embodiment of the present invention, the epoxy group-containing resinous organopolysiloxane comprises an aryl group to the silicon atom-bonded organic group. More specifically, in formula (I), R 9and R 10 At least one of them may be an aryl group. In a preferred embodiment of the present invention, the epoxy group-containing dendritic organopolysiloxane contains a silicon atom bonded aryl group in a molecular side chain, i.e., a D unit or a T unit, preferably in a T unit. The epoxy group-containing dendritic organopolysiloxane may or may not contain an aryl group in a molecular end, i.e., a M unit, but preferably does not contain one. It should be noted that the aryl group includes C6-20 aryl groups, in particular phenyl, tolyl, xylyl, and naphthyl groups.

[0109] When the epoxy group-containing resinous organicpolysiloxane contains aryl groups, the content thereof (mol% of aryl groups in the total silicon atom bonded functional groups in the epoxy group-containing resinous organicpolysiloxane) can be designed as desired, but preferably 15 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, particularly preferably 30 mol% or more; said content may preferably be 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less.

[0110] In a preferred embodiment of the present invention, the epoxy group-containing dendritic organopolysiloxane comprises hydroxyl groups and / or alkoxy groups as silicon atom-bonded organic groups. Although there are no specific limitations on the content of hydroxyl groups and / or alkoxy groups among the total silicon atom-bonded organic groups in the epoxy group-containing dendritic organopolysiloxane, the content is preferably 2 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more; and the content is, for example, 30 mol% or less, preferably 20 mol% or less, and more preferably 15 mol% or less. It should be noted that the amount of hydroxyl groups and / or alkoxy groups can be determined by analysis such as, for example, Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0111] There are no specific limitations on the viscosity of the epoxy group-containing resinous organopolysiloxane, but it is, for example, in the range of 50 mPa·s to 20,000 mPa·s at 25°C. In this specification, the viscosity of the organopolysiloxane component at 25°C can be measured by a rotational viscometer in accordance with JIS K7117-1.

[0112] Although there are no specific limitations on the amount of epoxy group-containing resinous organicpolysiloxane, when the curable silicone composition of the present invention includes epoxy group-containing resinous organicpolysiloxane, the amount that may be included is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 0.7 mass% or more, based on the total mass of alkenyl group-containing organicpolysiloxane and organo-hydrogen polysiloxane; additionally, an amount of 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and particularly preferably 1.5 mass% or less may be included based on the total mass of alkenyl group-containing organicpolysiloxane and organo-hydrogen polysiloxane.

[0113] (Alkenyl group-containing cyclic organopolysiloxane)

[0114] In one embodiment of the present invention, the curable silicone composition of the present invention may include an alkenyl group-containing cyclic organosiloxane. The curable silicone composition of the present invention may include one type of alkenyl group-containing cyclic organopolysiloxane or a combination of two or more types of alkenyl group-containing cyclic organopolysiloxanes.

[0115] Alkenyl group-containing cyclic organosiloxanes can be represented by the following unit formula (III).

[0116] Unit formula (III): (R 3 2SiO) n

[0117] During the meal, R 3Each is independently a halogen-substituted or unsubstituted monovalent hydrocarbon group, provided that at least two Rs in one molecule 3 is an alkenyl group, and n is a number that produces a viscosity of 1000 mPa·s or less at 25°C. Note that viscosity can be measured by a rotational viscometer in accordance with JIS K7117-1.

[0118] R in the above equation (III) 3 Examples of halogen-substituted or unsubstituted monovalent hydrocarbon groups as are C1-12 alkyl groups, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; C6-20 aryl groups, e.g., phenyl, tolyl, xylyl, and naphthyl groups; C7-20 aralkyl groups, e.g., benzyl, phenethyl, and phenylpropyl groups; C2-12 alkenyl groups, e.g., vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups; and includes the above group in which some or all of the hydrogen atoms are substituted with halogen atoms, such as fluorine, chlorine, or bromine atoms. R 3 The amount may be a small amount of hydroxyl or alkoxy groups, such as methoxy or ethoxy groups, within a range that does not impair the purpose of the present invention.

[0119] In the above formula (III), n is a number that produces a viscosity of 1000 mPa·s or less at 25°C, for example, 4 to 15, preferably 4 to 10, more preferably 4 to 8. In this specification, the viscosity of the organopolysiloxane component at 25°C can be measured by a rotational viscometer in accordance with JIS K7117-1.

[0120] There is no specific limit on the amount of alkenyl groups in the total silicon atom bonded organic groups in the alkenyl group-containing cyclic organopolysiloxane, but the amount is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more; this is also, for example, 80 mol% or less, preferably 70 mol% or less, and more preferably 60 mol% or less.

[0121] When the curable silicone composition of the present invention comprises an alkenyl group-containing cyclic organopolysiloxane, the amount that may be included is preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 3 mass% or more, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane; additionally, the amount that may be included is 15 mass% or less, more preferably 10 mass% or less, and even more preferably 5 mass% or less, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane.

[0122] In a specific embodiment of the present invention, the curable silicone composition of the present invention comprises an alkenyl group-containing cyclic organopolysiloxane in an amount of 3 mass% or less, more preferably 2 mass% or less, and even more preferably 1.5 mass% or less, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane. Additionally, it may be permitted for the curable silicone composition of the present invention not to comprise an alkenyl group-containing cyclic organopolysiloxane.

[0123] (Alkenyl group-containing organopolysiloxane containing only M and Q units)

[0124] In one embodiment of the present invention, the curable silicone composition of the present invention may comprise an alkenyl group-containing organopolysiloxane comprising only M units and Q units. The curable silicone composition of the present invention may comprise one type of alkenyl group-containing organopolysiloxane comprising only M units and Q units, or may comprise a combination of two or more types of alkenyl group-containing organopolysiloxanes comprising only M units and Q units.

[0125] In this specification, the alkenyl group-containing organopolysiloxane comprising only M and Q units is SiO 1 / 2 Siloxane units (M units) and SiO represented by 4 / 2 It represents an organopolysiloxane containing only a siloxane unit (Q unit) represented by . Preferably, an alkenyl group-containing organopolysiloxane containing only M and Q units can be represented by the following unit formula (IV).

[0126] Unit Formula IV: (R 4 3SiO 1 / 2 ) n (SiO 4 / 2 ) m

[0127] During the meal, R 4 Each group is independently a halogen-substituted or unsubstituted monovalent hydrocarbon group, provided that at least two Rs in one molecule 4 is an alkenyl group, n is an integer in the range of 4 to 100, and m is an integer in the range of 1 to 100.

[0128] In the above equation (IV), R 4 The halogen-substituted or unsubstituted monovalent hydrocarbon group as R in the above formula (III) 3 It includes the same mechanism as described for.

[0129] In the above formula (IV), n and m are preferably numbers that produce a viscosity of 1000 mPa·s or less at 25°C; for example, n is 4 to 50, preferably 4 to 16, and m is 1 to 50, preferably 1 to 16.

[0130] In addition, in a specific embodiment, in the formula (IV), n and m are preferably numbers that produce a viscosity of 1000 mPa·s or less at 25°C, for example, n is 4 to 12, preferably 4 to 8, and m is 1 to 4, preferably 1 to 3, more preferably 1 to 2.

[0131] There is no specific limit on the amount of alkenyl groups in the total silicon atom bonded organic groups in an alkenyl group-containing organopolysiloxane containing only M units and Q units, but the amount is, for example, 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more; this is also, for example, 60 mol% or less, preferably 50 mol% or less, more preferably 40 mol% or less.

[0132] When the curable silicone composition of the present invention comprises an alkenyl group-containing organopolysiloxane comprising only M units and Q units, the amount that may be included is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane; additionally, the amount that may be included is 20 mass% or less, more preferably 15 mass% or less, and even more preferably 10 mass% or less, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane.

[0133] In the aforementioned embodiment 2 of the present invention, the curable silicone composition comprises an alkenyl group-containing organopolysiloxane comprising only M units and Q units. Although there is no particular limitation on the content of the alkenyl group-containing organopolysiloxane comprising only M units and Q units, the amount that may be included is preferably 1 mass% or more, more preferably 2 mass% or more, even more preferably 3 mass% or more, particularly preferably 5 mass% or more, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane; additionally, the amount that may be included is 20 mass% or less, more preferably 15 mass% or less, even more preferably 10 mass% or less, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane.

[0134] In a specific embodiment of the present invention, in the curable silicon composition of the present invention, SiO 2 / 2 The content of the dendritic organopolysiloxane containing an alkenyl group bonded to a silicon atom of the siloxane unit (D unit) represented by is less than 50 mass% based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane. Preferably, SiO 2 / 2 The content of the dendritic organopolysiloxane containing an alkenyl group bonded to a silicon atom of a siloxane unit (D unit) represented by is less than 40 mass%, more preferably less than 30 mass%, even more preferably less than 20 mass%, preferentially less than 10 mass%, and particularly preferably less than 5 mass%, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane. In addition, the curable silicone composition of the present invention is SiO 2 / 2 It may be permitted not to include a dendritic organopolysiloxane containing an alkenyl group bonded to a silicon atom of a siloxane unit (D unit) represented by .

[0135] In addition, in a specific embodiment of the present invention, in the curable silicon composition of the present invention, SiO 2 / 2 The content of the alkenyl group-containing dendritic organopolysiloxane containing a siloxane unit (D unit) represented by is less than 50 mass% based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane. Preferably, SiO 2 / 2 The content of the dendritic organopolysiloxane containing an alkenyl group bonded to a silicon atom of the siloxane unit (D unit) represented by is less than 40 mass%, more preferably less than 30 mass%, even more preferably less than 20 mass%, preferentially less than 10 mass%, and particularly preferably less than 5 mass%, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane.

[0136] (B) Dendritic organo-hydrogen polysiloxane having at least two silicon atoms bonded to hydrogen atoms per molecule

[0137] Component (B) acts as a crosslinking agent in a curable silicone composition by a hydrosilylation curing reaction and is a dendritic organo-hydrogen polysiloxane having at least two silicon atom bonded hydrogen atoms per molecule. The curable silicone composition of the present invention may include one type of dendritic organo-hydrogen polysiloxane (B) or two or more types of dendritic organo-hydrogen polysiloxane (B).

[0138] The silicon atom bonding group other than the silicon atom bonding hydrogen atom included in component (B) comprises a halogen-substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, examples of which include a C1-12 alkyl group, such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group; a C6-20 aryl group, such as a phenyl group, tolyl group, xylyl group and naphthyl group; a C7-20 aralkyl group, such as a benzyl group, phenethyl group and phenylpropyl group; and the group in which some or all of the hydrogen atoms are substituted with a halogen atom, such as a fluorine atom, a chlorine atom or a bromine atom. It should be noted that the silicon atoms in component (B) may have a small amount of hydroxyl or alkoxy groups, such as methoxy or ethoxy groups, to the extent that the purpose of the present invention is not impaired. The silicon atom bonding groups other than the hydrogen atoms bonded to the silicon atoms in component (B) are preferably selected from C1-6 alkyl groups, particularly methyl groups and C6-20 aryl groups, particularly phenyl groups.

[0139] In one embodiment of the present invention, the dendritic organo-hydrogen polysiloxane of component (B) can preferably be represented by the following average unit formula (V):

[0140] Average unit formula (V): (R 5 3SiO 1 / 2 ) a (R 5 2SiO 2 / 2 ) b (R 5 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e

[0141] In equation (V), R 5Each is independently a hydrogen atom or an identical or different halogen-substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, provided that at least two Rs in one molecule 5 is a hydrogen atom; 0≤a<1, 0≤b<1, 0≤c<0.9, 0≤d<0.7, and 0≤e<0.4, a+b+c+d=1.0, and c+d>0.

[0142] R in the above equation (V) 5 Halogen-substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups comprise C1-12 alkyl groups, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; C6-20 aryl groups, e.g., phenyl, tolyl, xylyl, and naphthyl groups; C7-20 aralkyl groups, e.g., benzyl, phenethyl, and phenylpropyl groups; and said groups in which some or all of the hydrogen atoms are substituted with halogen atoms, e.g., fluorine, chlorine, or bromine atoms. 5 It may be a small amount of hydroxyl group or alkoxy group, such as a methoxy group or an ethoxy group, within a range that does not impair the purpose of the present invention. 5 It is preferably selected from hydrogen atoms, C1-6 alkyl groups, particularly methyl groups or C6-20 aryl groups, particularly phenyl groups.

[0143] X in the above formula (V) is a hydrogen atom or an alkyl group. The X alkyl group is preferably a C1-3 alkyl group, and specific examples include a methyl group, an ethyl group, and a propyl group.

[0144] In the above formula (V), a is preferably in the range of 0.1 ≤ a ≤ 0.9, more preferably in the range of 0.3 ≤ a ≤ 0.8, and even more preferably in the range of 0.5 ≤ a ≤ 0.7. In the above formula (V), b is preferably in the range of 0 ≤ b ≤ 0.5, more preferably in the range of 0 ≤ b ≤ 0.3, and particularly in the range of 0 ≤ b ≤ 0.1. In the above formula (V), c is preferably in the range of 0 ≤ c ≤ 0.7, more preferably in the range of 0 ≤ c ≤ 0.6, and particularly in the range of 0 ≤ c ≤ 0.5. In the above formula (V), d is preferably in the range of 0 ≤ d ≤ 0.7, more preferably in the range of 0 ≤ d ≤ 0.6, and particularly in the range of 0 ≤ d ≤ 0.5. In the above formula (V), e is preferably in the range of 0≤e≤0.15, more preferably in the range of 0≤e≤0.1, and particularly in the range of 0≤e≤0.05.

[0145] In a preferred embodiment of the present invention, in the dendritic organo-hydrogen polysiloxane of component (B), in the formula (V), c is greater than 0, i.e., T unit is included. The dendritic organo-hydrogen polysiloxane of component (B) may or may not include Q unit.

[0146] In a preferred embodiment of the present invention, the dendritic organo-hydrogen polysiloxane of component (B) contains silicon atom-bonded hydrogen atoms at the molecular ends. The dendritic organo-hydrogen polysiloxane of component (B) preferably has silicon atom-bonded hydrogen atoms in the M unit and may or may not include silicon atom-bonded hydrogen atoms in the molecular chain side chains (i.e., D unit and T unit), but preferably does not include.

[0147] In a preferred embodiment of the present invention, the dendritic organo-hydrogen polysiloxane of component (B) may or may not include an aryl group in the silicon atom bonded organic group. Examples of aryl groups include C6-20 aryl groups, e.g., phenyl, tolyl, xylyl, and naphthyl groups, and phenyl groups are particularly preferred.

[0148] When the dendritic organo-hydrogen polysiloxane of component (B) contains aryl groups, the content thereof (mol% of aryl groups in the total silicon atom bonded functional groups in the dendritic organo-hydrogen polysiloxane) can be designed as desired, but is typically 1 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 13 mol% or more, particularly preferably 16 mol% or more; additionally, the content may be 50 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less, preferentially 30 mol% or less, particularly preferably 25 mol% or less.

[0149] In one embodiment of the present invention, the resinous organic polysiloxane of component (B) may be an MQ resin comprising only M units and Q units. In this embodiment, the ratio of the number of moles of M units and Q units is not particularly limited, but, for example, the molar ratio of M units to Q units may be in the range of 1:1 to 4:1, preferably in the range of 1.1:1 to 3:1, more preferably in the range of 1.2:1 to 2:1, and even more preferably in the range of 1.3:1 to 1.8:1.

[0150] There are no specific limitations on the viscosity of the dendritic organopolysiloxane of component (B), but the viscosity at 25°C is, for example, in the range of 10 mPa·s to 1000 mPa·s. In this specification, the viscosity of the organopolysiloxane component at 25°C can be measured by a rotational viscometer in accordance with JIS K7117-1.

[0151] In addition, in one embodiment of the present invention, the number average molecular weight (Mn) of the dendritic organopolysiloxane of component (B) is preferably in the range of 500 to 3000, more preferably in the range of 750 to 2000, even more preferably in the range of 1000 to 2000, and particularly preferably in the range of 1000 to 1500.

[0152] The content of the dendritic organo-hydrogen polysiloxane of component (B) is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 1 mass% or more, and particularly preferably 1.3 mass% or more, based on the total mass of the alkenyl group-containing organo-hydrogen polysiloxane and the organo-hydrogen polysiloxane. In addition, the content of component (B) is preferably 15 mass% or less, more preferably 10 mass% or less, even more preferably 8 mass% or less, and particularly preferably 5 mass% or less, based on the total mass of the alkenyl group-containing organo-hydrogen polysiloxane and the organo-hydrogen polysiloxane.

[0153] In addition, in a specific embodiment of the present invention, the content of the dendritic organo-hydrogen polysiloxane of component (B) is 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 1 mass% or more, particularly preferably 1.3 mass% or more, based on the total mass of the alkenyl group-containing organo-hydrogen polysiloxane and the organo-hydrogen polysiloxane; and the content is 15 mass% or less, preferably 12 mass% or less, more preferably 9 mass% or less, particularly preferably 6 mass% or less.

[0154] (Linear organo-hydrogen polysiloxane)

[0155] The curable silicone composition of the present invention may contain a straight-chain organo-hydrogen polysiloxane as the organo-hydrogen polysiloxane in addition to the dendritic organo-hydrogen polysiloxane of component (B). The curable silicone composition of the present invention may include one type of straight-chain organo-hydrogen polysiloxane, or it may include or not include a combination of two or more types of straight-chain organo-hydrogen polysiloxanes.

[0156] Linear organo-hydrogen polysiloxane is preferably

[0157] Average structural formula VI: R 5 3SiO(R 5 2SiO 2 / 2 ) m SiR 5 3

[0158] (Equation (VI), R 5 Each is independently a hydrogen atom or an identical or different halogen-substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, provided that at least two Rs in one molecule 5 It can be represented as (where m is a hydrogen atom and m is 1 to 100).

[0159] In the above equation (VI), R 5 Halogen-substituted or unsubstituted monovalent hydrocarbon groups other than the alkenyl group may be the same as those in Formula (V) above.

[0160] In the above formula (VI), m is preferably 1 to 50, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 5.

[0161] In a preferred embodiment of the present invention, the straight-chain organo-hydrogen polysiloxane contains silicon-bonded hydrogen atoms at both ends of the molecular chain. The straight-chain organo-hydrogen polysiloxane has silicon-bonded hydrogen atoms in the M unit, and may or may not include silicon-bonded hydrogen atoms in the D unit, but preferably does not include them.

[0162] In a preferred embodiment of the present invention, the straight-chain organo-hydrogen polysiloxane contains a silicon atom-bonded aryl group. The straight-chain organo-hydrogen polysiloxane preferably contains a silicon atom-bonded aryl group in a molecular chain side chain. The straight-chain organopolysiloxane may or may not contain an aryl group at the molecular chain end, but preferably does not.

[0163] In a more preferred embodiment of the present invention, the linear organo-hydrogen polysiloxane is a unit in which two aryl groups are bonded to a silicon atom of the D unit, namely Ar2SiO2 2 / 2 Includes structural units indicated by .

[0164] In one embodiment of the present invention, when the straight-chain organo-hydrogen polysiloxane contains aryl groups, there is no particular limitation on the content of the aryl groups in the total silicon atom-bonded organic groups, but the content is, for example, 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more of the total silicon atom-bonded organic groups; the content may also be 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less of the total silicon atom-bonded organic groups.

[0165] When the curable silicone composition of the present invention includes a straight-chain organo-hydrogen polysiloxane, there is no particular limitation on the content thereof, but the amount that may be included is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, preferentially 20 mass% or more, particularly preferably 25 mass% or more, based on the total mass of the alkenyl group-containing organic polysiloxane and the organo-hydrogen polysiloxane; additionally, the amount that may be included is 40 mass% or less, more preferably 35 mass% or less, even more preferably 30 mass% or less, based on the total mass of the alkenyl group-containing organic polysiloxane and the organo-hydrogen polysiloxane.

[0166] In addition, in one embodiment of the present invention, when the curable silicone composition of the present invention comprises a straight-chain organo-hydrogen polysiloxane, the content thereof may be preferably 25 mass% or more, more preferably 30 mass% or more, and even more preferably 35 mass% or more with respect to the total mass of the dendritic alkenyl group-containing organopolysiloxane of component (A).

[0167] In one embodiment of the present invention, in the curable silicone composition of the present invention, the total amount of the organo-hydrogen polysiloxane component including the dendritic organo-hydrogen polysiloxane of component (B) is, for every 1 mole of silicon atom bonded alkenyl group of the total alkenyl group-containing organopolysiloxane component including the dendritic alkenyl group-containing organopolysiloxane of component (A), preferably an amount in which the silicon atom bonded hydrogen atoms are 0.8 to 1.3 moles, more preferably an amount in which the silicon atom bonded hydrogen atoms are 0.85 to 1.25 moles, and particularly preferably an amount in which the silicon atom bonded hydrogen atoms are 0.9 to 1.2 moles. That is, in the curable silicone composition of the present invention, the molar ratio (H / Vi) of hydrogen atoms and alkenyl groups derived from the organopolysiloxane component may preferably be 0.8 to 1.3, more preferably 0.85 to 1.25, and particularly 0.9 to 1.2.

[0168] In a specific embodiment of the present invention, in the curable silicone composition of the present invention, the molar ratio (H / Vi) of hydrogen atoms and alkenyl groups derived from the organopolysiloxane component is 0.95 to 1.2, preferably 0.98 to 1.2, more preferably 1.0 to 1.2.

[0169] In another embodiment of the present invention, there is no particular limitation on the total amount of the organo-hydrogen polysiloxane component including the dendritic organo-hydrogen polysiloxane of component (B), but based on the total mass of the alkenyl group-containing organo-hydrogen polysiloxane and the organo-hydrogen polysiloxane, the amount is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, preferentially 20 mass% or more, particularly preferably 25 mass% or more; additionally, the amount may be 45 mass% or less, preferably 40 mass% or less, even more preferably 35 mass% or less.

[0170] (C) Additive having a wettability improving effect

[0171] The curable silicone composition of the present invention comprises, as component (C), an additive that improves the wettability of the curable silicone composition of the present invention. Such additive is selected from molecular chain side chain polyether-modified organopolysiloxane, phenol-modified organopolysiloxane, dimethylpolysiloxane containing terminal hydroxyl groups that does not contain aryl groups, and phenolic antioxidants, and combinations thereof.

[0172] One type of molecular chain side chain polyether-modified organopolysiloxane (C-1) may be used, or a combination of two or more types may be used.

[0173] Examples of molecular structures of the side-chain polyether-modified organopolysiloxane of component (C-1) include straight chain, partially branched straight chain, branched chain, dendritic, cyclic, and three-dimensional network structures, but a straight chain is preferred.

[0174] The molecular chain side chain polyether-modified organopolysiloxane of component (C-1) is preferably the following average structural formula (VII):

[0175] Average structural formula (VII): R 6 3SiO(R 6 2SiO 2 / 2 ) m (R 6 R 7 SiO 2 / 2 ) n SiR 6 3

[0176] (In Equation (VII), R 6 Each is independently a halogen-substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, and R 7 It can be represented as a polyoxyalkylene group-containing organic group, where m is a number in the range of 0 to 1000 and n is a number in the range of 1 to 1000.

[0177] R in the above equation (VII) 6Halogen-substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups comprise C1-12 alkyl groups, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; C6-20 aryl groups, e.g., phenyl, tolyl, xylyl, and naphthyl groups; C7-20 aralkyl groups, e.g., benzyl, phenethyl, and phenylpropyl groups; and said groups in which some or all of the hydrogen atoms are substituted with halogen atoms, e.g., fluorine, chlorine, or bromine atoms. 6 It may be a small amount of hydroxyl or alkoxy groups, such as methoxy or ethoxy groups, within a range that does not impair the purpose of the present invention. 6 It is preferably selected from C1-6 alkyl groups, particularly methyl groups or C6-20 aryl groups, particularly phenyl groups.

[0178] In formula (VII), the polyoxyalkylene group-containing organic group R 7 There are no specific restrictions on the structure of the oxyalkylene group, but examples of the structure include two or more oxyethylene units, oxypropylene units, or oxybutylene units, or a combination thereof. The polyoxyalkylene group-containing organic group preferably comprises four or more oxyalkylene units, more preferably six or more oxyalkylene units, and even more preferably eight or more oxyalkylene units; additionally, the polyoxyalkylene group-containing organic group comprises 100 or fewer oxyalkylene units, preferably 60 or fewer oxyalkylene units, more preferably 40 or fewer oxyalkylene units, and even more preferably 20 or fewer oxyalkylene units.

[0179] Note that the alkylene portion constituting the oxypropylene unit or oxybutylene unit may be a straight-chain alkylene group, or it may be a branched isoalkylene group such as an isopropylene group or an isobutylene group.

[0180] The polyoxyalkylene group-containing organic group R in the above formula (VII) 7 It can preferably be represented by the following formula (1):

[0181] Equation (1): -R 8 -O-(C2H4O) t1 (C3H6O) t2 (C4H8O) t3 -Y

[0182] Here, R 8 The silicon atom bond is a C1-6, preferably C1-3, 2 organic group; t1, t2 and t3 are numbers satisfying 0≤t1≤60, 0≤t2≤50, 0≤t3≤50, and 2≤t1+t2+t3≤110; and Y is a group selected from hydrogen atoms, C1-4 alkyl groups, and COCH3 groups.

[0183] In Equation (1), R 8 It includes, for example, alkylene groups, alkenylene groups, arylene groups, etc., and more specific examples include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, hexylene groups, and phenylene groups.

[0184] In formula (1), Y is a terminal group of a polyoxyalkylene structure and is selected from a hydrogen atom, a C1-4 alkyl group and a COCH3 group; Y can preferably be a hydrogen atom or a methyl group.

[0185] In formula (1), t1, t2, and t3 are the number of oxyethylene units, oxypropylene units, and oxybutylene units constituting the polyoxyalkylene structure, and are numbers satisfying 2≤t1+t2+t3≤110, preferably 6≤t1+t2+t3≤50, more preferably 8≤t1+t2+t3≤20.

[0186] In one embodiment of the present invention, in formula (1), t1 is a number of 2 or more, preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and is 50 or less, preferably 30 or less, more preferably 20 or less, even more preferably 15 or less. In one embodiment of the present invention, in formula (1), t2 is a number of 0 or more and 50 or less, preferably 30 or less, more preferably 10 or less, even more preferably 3 or less, and 0 may also be allowed. In one embodiment of the present invention, in formula (1), t3 is a number of 0 or more and 50 or less, preferably 30 or less, more preferably 10 or less, even more preferably 3 or less, and 0 may also be allowed.

[0187] In formula (VII), n and m are the degrees of siloxane polymerization of the straight-chain molecular-chain side-chain polyether-modified organopolysiloxane; m is a number in the range of 0 to 1000, and n is a number in the range of 1 to 1000. Preferably, m is a number in the range of 1 or more and 500 or less, more preferably 150 or less, even more preferably 100 or less, preferentially 50 or less, particularly preferably 10 or less. Preferably, n is a number in the range of 500 or less, more preferably 150 or less, even more preferably 100 or less, preferentially 50 or less, and particularly preferably 20 or less.

[0188] In a preferred embodiment, the molecular chain side chain polyether-modified organopolysiloxane of component (C) is straight-chain and has a polyoxyalkylene group selected from polyoxyethylene (POE) and polyoxypropylene (POP). The molecular chain side chain polyether-modified organopolysiloxane of component (C) can preferably be represented by the following general formula (2).

[0189] [Chemical Formula 1]

[0190]

[0191] In the above formula (2), m is 1 to 1000, preferably 5 to 500, and n is 1 to 40. Additionally, m:n is preferably 200:1 to 1:1. Also, a is 5 to 50, preferably 8 to 30, more preferably 10 to 20. b is 0 to 50, preferably 0 to 10, and 0 may be allowed. That is, the polyether-modified organopolysiloxane of component (C) comprises polyoxyethylene units and may comprise only polyoxyethylene units.

[0192] In a preferred embodiment, the molecular chain side chain polyether-modified organopolysiloxane is selected from molecules having an HLB(Si) of 4 to 15, preferably 7 to 15, more preferably 9 to 15, and even more preferably 11 to 15. The HLB(Si) mentioned herein is a value determined by the following formula.

[0193] [Formula 1]

[0194]

[0195] Preferred embodiments of the molecular chain side chain polyether-modified organopolysiloxane of component (C-1) include PEG / PPG-19 / 19 dimethicone, PEG / PPG-30 / 10 dimethicone, PEG-12 dimethicone, PEG-11 methyl ether dimethicone, etc.

[0196] Specific examples of commercially available products of molecular chain side chain polyether-modified organopolysiloxane of component (C-1) include the following:

[0197] · Trade name BY11-030 (Manufactured by Dow Corning Toray Co. Ltd., PEG / PPG-19 / 19 Dimethicone (HLB(Si)=7.7)),

[0198] · Trade name SH3773M (manufactured by Dow Corning Toray Co. Ltd., PEG-12 dimethicone (HLB(Si)=7.7)),

[0199] · Trade name BY25-339 (manufactured by Dow Corning Toray Co. Ltd., PEG / PPG-30 / 10 Dimethicone (HLB(Si)=12.2)),

[0200] · Product name KF6011 (manufactured by Shin-Etsu Chemical Co., Ltd., PEG-11 methyl ether dimethicone (HLB(Si)=14.5)).

[0201] The number average molecular weight of the side-chain polyether-modified organopolysiloxane of component (C-1) is not particularly limited, but is suitably in the range of 3,000 to 60,000, and particularly suitably in the range of 3,000 to 40,000.

[0202] One type of phenol-modified organopolysiloxane (C-2) may be used, or a combination of two or more types may be used.

[0203] Examples of molecular structures of phenol-modified organopolysiloxanes (C-2) include straight chain, partially branched straight chain, branched chain, dendritic, cyclic, and three-dimensional network structures, but straight chain is preferred.

[0204] The phenol-modified organopolysiloxane of component (C-2) is preferably the following average structural formula (VIII):

[0205] Average structural formula VIII: R 8 3SiO(R 8 2SiO 2 / 2 ) m SiR 8 3

[0206] (In Equation (VIII), R 8 Each is independently a halogen-substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, or a phenolic-containing organic group, provided that at least one R 8 It can be represented as an organic group containing a phenolic group, where m is a number in the range of 1 to 1000.

[0207] In Equation (VIII), R 8The halogen-substituted or unsubstituted monovalent hydrocarbon group other than the alkenyl group is R of the above formula (VII). 6 It could be the same as.

[0208] R in Equation (VIII) 8 The phenolic group-containing organic group is not particularly limited, but can be represented by the following formula (3):

[0209] [Chemical Formula 2]

[0210]

[0211] In formula (3), R is a C1-6 alkyl group, particularly a C1-4 alkyl group; n is 1 to 4, preferably 1; and * indicates a portion bonded to a silicon atom to which a phenolic group-containing organic group is bonded.

[0212] The phenol-containing organic group of the phenol-modified organopolysiloxane of component (C-2) may be included at the ends of the molecule or in the side chains of the molecule. In a preferred embodiment, the phenol-containing organic group is included at the ends of the molecular chain of the phenol-modified organopolysiloxane, particularly at both ends of the molecular chain.

[0213] Specific examples of commercially available products of phenol-modified organopolysiloxane of component (C-2) include product name KF2201 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0214] There are no specific limitations on the viscosity of the phenol-modified organopolysiloxane of component (C-2), but the viscosity at 25°C is, for example, 1×10⁻⁶ 4 Up to 1×10 8 St, especially suitable for 1×10 5 Up to 1×10 7 This is the range of St.

[0215] There is no specific limit on the refractive index of the phenol-modified organopolysiloxane of component (C-2), but it is, for example, within the range of 1.35 to 1.5, preferably within the range of 1.38 to 1.47, more preferably within the range of 1.40 to 1.45.

[0216] One type of (C-3) aryl group-free terminal hydroxyl group-containing dimethylpolysiloxane may be used, or a combination of two or more types may be used.

[0217] Examples of molecular structures of dimethylpolysiloxane containing terminal hydroxyl groups that do not contain aryl groups of component (C-3) include straight chain, partially branched straight chain, branched chain, dendritic, cyclic, and three-dimensional network structures, but a straight chain is preferred.

[0218] The terminal hydroxyl group-containing dimethylpolysiloxane that does not contain an aryl group of component (C-3) is preferably straight-chain and contains hydroxyl groups at both ends of the molecular chain. Accordingly, the terminal hydroxyl group-containing dimethylpolysiloxane that does not contain an aryl group of component (C-3) has the following average structural formula (IX):

[0219] Average structural formula IX: HOR 9 2SiO(R 9 2SiO 2 / 2 ) m SiR 9 2OH

[0220] (In Equation (IX), R 9 Each can be independently represented as a halogen-substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl or aryl group, OH is a hydroxyl group, and m is a number in the range of 1 to 1000.

[0221] R in the above equation (IX) 9The halogen-substituted or unsubstituted monovalent hydrocarbon group other than the alkenyl and aryl groups preferably comprises a C1-12 alkyl group, such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, and said group in which some or all of the hydrogen atoms are substituted with a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom. 9 It may be a small amount of hydroxyl group or alkoxy group, such as a methoxy group or an ethoxy group, within a range that does not impair the purpose of the present invention. 9 It is preferably selected from C1-6 alkyl groups, particularly methyl groups.

[0222] In formula (IX), m is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 20, and particularly preferably 1 to 12.

[0223] There are no specific limitations on the viscosity of the terminal hydroxyl group-containing dimethylpolysiloxane that does not contain an aryl group of component (C-3), but the viscosity at 25°C is, for example, in the range of 0.1 to 1000 St, particularly preferably 0.1 to 100 St.

[0224] One type of phenolic antioxidant (C-4) may be used, or a combination of two or more types may be used.

[0225] The phenolic antioxidant (C-4) is preferably selected from conventionally known phenolic primary antioxidants. For the phenolic antioxidant (C-4), a phenolic antioxidant having excellent compatibility with the organopolysiloxane component of the present invention, particularly the aryl-containing organopolysiloxane of component (A), is suitably used. These phenolic antioxidants preferably comprise alkylphenols, and specific examples thereof include: 2,6-di-tert-butyl-p-cresol (BHT), 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, nonylphenols having a straight chain or branched side chain (e.g., 2,6-di-nonyl-4-methylphenol). 2,4-dimethyl-6-(1'-methylundeca-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadeca-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltrideca-1'-yl)phenol and mixtures thereof, 4-hydroxylaoulanilide, 4-hydroxystearylanilide, and octyl N-(3,5-di-t-butyl-4-hydroxyphenyl)carbamate, 2,2'-methylenebis(6-t-butyl-4-methylphenol), 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(1-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-Methylenebis(6-nonyl-4-methylphenol), 2,2'-Methylenebis(4,6-di-t-butylphenol), 2,2'-Ethylidenebis(4,6-di-t-butylphenol), 2,2'-Ethylidenebis(6-t-butyl-4-isobutylphenol), 2,2'-Methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-Methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylenebis(2,6-di-t-butylphenol), 4,4'-Methylenebis(6-t-butyl-2-methylphenol), 1,1-Bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-Bis(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-Bis(5-t-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-t-butyl-4'-hydroxyphenyl)butylate], bis(3-t-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-t-butyl-2'-hydroxy-5'-methylbenzyl)-6-t-butyl-4-methylphenyl]terephthalate, 1,1-Bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, and 1,1,5,5-tetra(5-t-butyl-4-hydroxy-2-methylphenyl)pentane, etc. In terms of compatibility with the aryl-containing organopolysiloxane of component (A), 2,6-di-tert-butyl-p-cresol (BHT) is particularly preferred.

[0226] The content of the additive having a wetting effect of component (C) is not particularly limited, but the content is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, even more preferably 0.03 mass% or more, and particularly preferably 0.04 mass% or more, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane. In addition, the content of component (C) is preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and particularly preferably 1.5 mass% or less, based on the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane.

[0227] (D) Curing catalyst

[0228] The curing catalyst of component (D) is a curing catalyst for a hydrosilylation reaction to promote the curing of the curable silicone composition of the present invention. Examples of such component (D) include platinum-based catalysts such as chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a platinum-olefin complex, a complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and a platinum-supported powder; palladium-based catalysts such as tetrakis(triphenylphosphine)palladium, palladium black, and a mixture with triphenylphosphine; and also rhodium-based catalysts; platinum-based catalysts are particularly preferred.

[0229] The amount of component (D) is the amount of catalyst; more specifically, when a platinum-based catalyst is used as component (D), the amount of platinum atoms relative to the total mass of the curable silicon composition of the present invention is preferably 0.01 ppm or more, more preferably 0.1 ppm or more, and even more preferably 1 ppm or more, and additionally, the amount of platinum atoms relative to the total mass of the curable silicon composition of the present invention is preferably 20 ppm or less, more preferably 15 ppm or less, and even more preferably 12 ppm or less.

[0230] In a specific embodiment of the present invention, the amount of component (D) is such that when a platinum-based catalyst is used as component (D), the amount of platinum atoms relative to the total mass of the curable silicon composition of the present invention is less than 10 ppm, preferably less than 9 ppm, more preferably less than 8 ppm, and even more preferably less than 7 ppm.

[0231] The curable silicone composition of the present invention may include optional components within a range that does not impair the purpose of the present invention. Examples of such optional components include acetylene compounds, organic phosphorus compounds, vinyl group-containing siloxane compounds, inorganic fillers such as powdered quartz, silica, titanium oxide, magnesium carbonate, zinc oxide, iron oxide, and diatomaceous earth, inorganic fillers whose surfaces have been hydrophobically treated with an organosilicon compound, hydrosilylation reaction inhibitors, organopolysiloxanes that do not contain silicon atom-bonded hydrogen atoms and silicon atom-bonded alkenyl groups, tackifiers, heat retardants, cold retardants, thermally conductive fillers, flame retardants, thixotropic agents, phosphors, and solvents. If the curable silicone composition includes a tackifier, its content may be 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, and particularly preferably 1.5 parts by mass or less, per 100 parts by mass of the organopolysiloxane component.

[0232] Hydrosilylation reaction inhibitors are components for inhibiting the hydrosilylation reaction of a curable silicone composition. Examples of such curing reaction inhibitors include alkyne alcohols, such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexin-3-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol; en-phosphorus compounds, such as 3-methyl-3-pentene-1-phosphorus and 3,5-dimethyl-3-hexene-1-phosphorus; low molecular weight siloxanes containing alkenyl groups, such as tetramethyl-tetravinyl-cyclotetrasiloxane and tetramethyl-tetrahexenyl-cyclotetrasiloxane; and alkyneyloxysilanes, such as methyl-tris(1,1-dimethylpropynyloxy)silane and vinyl-tris(1,1-dimethylpropynyloxy)silane. The hydrosilylation reaction inhibitor is preferably selected from alkyne alcohols, and particularly preferably is 2-methyl-3-butyn-2-ol or 1-ethynyl-1-cyclohexanol. The amount of reaction inhibitor added is typically 0.001 to 5 parts by mass per 100 parts by mass of the organopolysiloxane component.

[0233] In one embodiment of the present invention, when the curable silicone composition comprises 2-methyl-3-butyn-2-ol as a reaction inhibitor, the content thereof is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, per 100 parts by mass of the organopolysiloxane component; this is typically 5 parts by mass or less.

[0234] In another embodiment of the present invention, when the curable silicone composition comprises 1-ethynyl-1-cyclohexanol as a reaction inhibitor, the content thereof is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, per 100 parts by mass of the organopolysiloxane component; this is typically 2 parts by mass or less.

[0235] In the aforementioned embodiment 2 of the present invention, the curable silicone composition comprises ethinylcyclohexanol as a reaction inhibitor. Ethynylcyclohexanol may be 1-ethynyl-1-cyclohexanol or 1-ethynyl-2-cyclohexanol, but 1-ethynyl-1-cyclohexanol is preferred. Its content is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, per 100 parts by mass of the organopolysiloxane component; this is typically 2 parts by mass or less, and preferably 1 part by mass or less.

[0236] There are no specific limitations on the viscosity of the curable silicone composition of the present invention, but the viscosity at 25°C is preferably in the range of 100 mPa·s to 700 mPa·s, more preferably in the range of 300 mPa·s to 600 mPa·s. The viscosity can be measured by a Type B rotational viscometer (MCR-302, manufactured by Anton Paar Co.) according to the method described in JIS K 7117-1:1999.

[0237] In a specific embodiment of the present invention, the viscosity of the curable silicone composition at 25°C is less than 1000 mPa·s, preferably in the range of 200 mPa·s to 700 mPa·s, more preferably in the range of 300 mPa·s to 650 mPa·s.

[0238] The curable silicone composition of the present invention can form a cured product having high hardness after curing. The cured product obtained by curing the curable silicone composition of the present invention preferably has a Type D dumeter hardness of D60 or higher at 25°C. It should be noted that such Type D dumeter hardness can be measured by a Type D dumeter in accordance with JIS K 6253-1997 "Method for testing the hardness of vulcanized rubber and thermoplastic rubber".

[0239] In a specific embodiment of the present invention, the cured product obtained by curing the curable silicone composition of the present invention preferably has a type D durometer hardness of D55 or higher at 25°C.

[0240] The curable silicone composition of the present invention can form a cured product having good transparency after curing. More specifically, the cured product of the curable silicone composition of the present invention can maintain high transparency and exhibit minimal yellowing even after heating. For example, it is preferable that a 2 mm thick cured product of the curable silicone composition of the present invention has a light transmittance of 95% or more for light with a wavelength of 400 nm to 700 nm even after being maintained at 150°C for 8 hours. It should be noted that the light transmittance of the cured product of the curable silicone composition of the present invention can be determined, for example, by measuring the cured product using a spectrophotometer.

[0241] The curable silicone composition of the present invention can be prepared by mixing each component. The method of mixing the components may be a conventionally known method without special limitations, but a uniform mixture is typically provided by simple stirring. Additionally, when a solid component, such as an inorganic filler, is included as an optional component, mixing using a mixing device is more preferable. There are no special limitations on such a mixing device, and examples include single-screw or twin-screw continuous mixers, double rolls, Ross mixers, Hobart mixers, dental mixers, planetary mixers, kneader mixers, Henschel mixers, etc.

[0242] [Bag material]

[0243] The present invention also relates to a semiconductor encapsulant comprising the curable silicon composition of the present invention. Furthermore, the present invention relates to a sealant obtained by curing the encapsulant of the present invention. That is, the sealant of the present invention comprises a cured product of the curable silicon composition of the present invention.

[0244] There are no special limitations on the shape of the sealing material of the present invention, but it is preferably in the form of a dome or a sheet. There are no special limitations on the semiconductor to be sealed by the encapsulating material, sealing material, or film of the present invention, and examples include semiconductors such as SiC and GaN, in particular power semiconductors or opto-semiconductors, such as light-emitting diodes.

[0245] According to the encapsulating material of the present invention, since the curable silicone composition of the present invention is used, a cured product having excellent surface smoothness, transparency, and high hardness can be formed.

[0246] [Opto-semiconductor device]

[0247] The present invention also relates to an opto-semiconductor device encapsulated by a cured encapsulation material of the present invention. That is, the opto-semiconductor device of the present invention comprises a cured encapsulation material of the present invention. The opto-semiconductor device may be, for example, a light-emitting diode (LED), a semiconductor laser, a photodiode, a phototransistor, a solid-state imaging device, a light-emitting device for a photocoupler, and a light-receiving device; this is particularly preferably a light-emitting diode (LED).

[0248] Since light is emitted from the top, bottom, left, and right sides of the opto-semiconductor element in a light-emitting diode (LED), the components constituting the light-emitting diode (LED) are preferably made of a material that does not absorb light and preferably has high light transmittance or high reflectance. Accordingly, the substrate on which the opto-semiconductor element is mounted is also preferably made of a material having high light transmittance or high reflectance. Such a substrate on which the opto-semiconductor element is mounted includes, for example, electrically conductive metals such as silver, gold, and copper; electrically non-conductive metals such as aluminum and nickel; thermoplastic resins such as PPA and LCP mixed with white pigment; thermosetting resins such as epoxy resin, BT resin, polyimide resin, and silicone resin containing white pigment; and ceramics such as alumina and alumina nitride.

[0249] Examples

[0250] The curable silicone composition of the present invention is described in detail below by way of examples and comparative examples.

[0251] Curable silicone compositions were prepared by mixing different components to provide the composition (parts by mass) shown in the table. It should be noted below that Me represents a methyl group, Vi represents a vinyl group, Ph represents a phenyl group, Ep represents a 3-glycidoxypropyl group, PE represents an organic functional group containing a polyether structure, and PH represents an organic functional group containing a phenol structure. Additionally, in the table, the structures of the organopolysiloxane components are presented in a simplified form, and functional groups other than Me among the M, D, or T units are exemplified in parentheses. Furthermore, H / Vi represents the molar ratio of hydrogen atoms (H) bonded to silicon atoms and vinyl groups (Vi) in the organopolysiloxane components.

[0252] (Component a: Alkenyl group-containing organopolysiloxane)

[0253] Component a-1: Average unit formula (ViMe2SiO2) 1 / 2 ) 25 (PhSiO 3 / 2 ) 75 Dendritic alkenyl group-containing organopolysiloxane represented by

[0254] Component a-2: Average unit formula (ViMe2SiO2) 1 / 2 ) 13 (EpMeSiO 2 / 2 ) 24 (PhSiO 3 / 2 ) 46 (OMe) 17 Epoxy group-containing resinous organopolysiloxane represented by

[0255] Component a-3: Cyclic alkenyl group-containing organopolysiloxane represented by the average structural formula (ViMeSiO)4

[0256] Component a-4: Dendritic alkenyl group-containing organopolysiloxane represented by the average structural formula (ViMe2SiO)4Si

[0257] Component a-5: Average unit formula (Me3SiO2) 1 / 2 )5(ViMe2SiO 1 / 2 ) 17 (MeSiO 3 / 2 )39 (PhSiO 3 / 2 ) 39 Dendritic alkenyl group-containing organopolysiloxane represented by

[0258] Component a-6: Average unit formula (ViMeSiO2) 2 / 2 ) 25 (Ph2SiO 2 / 2 ) 30 (PhSiO 3 / 2 ) 45 Dendritic alkenyl group-containing organopolysiloxane represented by

[0259] (Component b: Organo-hydrogen polysiloxane)

[0260] Component b-1: Average unit formula (HMe2SiO2) 1 / 2 ) 60 (PhSiO 3 / 2 ) 40 Dendritic organo-hydrogen polysiloxane represented by

[0261] Component b-2: Linear organo-hydrogen polysiloxane represented by the average structural formula HMe2SiO(Ph2SiO)SiMe2H

[0262] Component b-3: Average structural formula (HMe2SiO2) 1 / 2 ) 62 (SiO 4 / 2 ) 38 Dendritic organo-hydrogen polysiloxane represented by

[0263] (Ingredient c: Additive having a wetting effect)

[0264] Component c-1: Average structural formula Me3SiO(Me2SiO) n (Me(PE)SiO) m Molecular chain side chain polyether-modified organopolysiloxane denoted as SiMe3 (HLB value: 12.7)

[0265] Component c-2: Average structural formula PHMe2SiO(Me2SiO) n Molecular chain-terminal phenol-modified organopolysiloxane denoted as SiPHMe2 (refractive index: 1.42)

[0266] Component c-3: Hydroxy-terminated polydimethylsiloxane (HO(Me2SiO) n H: n=12, viscosity 50 cSt

[0267] Ingredient c-4: BHT(2,6-di-tert-butyl-p-cresol)

[0268] Component c'-1: Terminal hydroxyl phenyl silicone oil represented by the average structural formula HOMe2SiO(Ph2SiO)SiMe2OH

[0269] Component c'-2: Average unit formula (EpSiO 3 / 2 )(ViMeSiO 2 / 2 )(Me2SiO 2 / 2 Epoxy group-containing resinous organopolysiloxanes represented by ).

[0270] Component c'-3: Organopolysiloxane represented by the average structural formula (ViMe2SiO)(Me2SiO)3Si(OMe)3

[0271] Component c'-4: 1,6-bis(trimethoxysilyl)hexane

[0272] Ingredient C'-5: Methyltrimethoxysilane

[0273] Ingredient C'-6: Phenyltrimethoxysilane

[0274] Ingredient c'-7: (3-glycidoxypropyl)trimethoxysilane

[0275] Ingredient C'-8: Methacryltrimethoxysilane

[0276] Ingredient c'-9: Propyltrimethoxysilane

[0277] Ingredient c'-10: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane

[0278] Ingredient c'-11: Vinyltrimethoxysilane

[0279] Component c'-12: Propylene glycol monomethyl ether acetate (PGMEA) solvent

[0280] Component c'-13: PP solvent

[0281] Ingredient c'-14: 1-Butyl-3-methylimidazolium hexafluorophosphate

[0282] Ingredient C'-15: Epoxy-modified silicone oil

[0283] Component c'-16: An organopolysiloxane with both ends of the molecular chain modified to polyethers, represented by the average structural formula (PEG)Me2SiO(Me2SiO)2SiMe2(PEG).

[0284] (Component d: Curing catalyst)

[0285] Component d: Complex of platinum with a platinum concentration of 4.0 mass% and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane

[0286] (Ingredient e: Hydrosilylation reaction inhibitor)

[0287] Ingredient e-1: 2-methyl-3-butyn-2-ol

[0288] Ingredient e-2: 1-ethynyl-1-cyclohexanol

[0289] Ingredient e-3: 2-phenyl-3-butyn-2-ol

[0290] Component e-4: 3,5-dimethyl-1-hexine-3-ol

[0291] [Examples 1 to 14 and Comparative Examples 1 to 25]

[0292] Curable silicon compositions were prepared by mixing different components to provide the composition (parts by mass) shown in the table below. Note that the amount of curing catalyst of component d is expressed as the amount of platinum atoms (ppm) contained in component d. The following evaluations were performed, and the results are summarized in the table below.

[0293] [viscosity]

[0294] The viscosity of a curable silicone composition was measured at 25°C and 20 s using a viscoelasticity measuring device (MCR-302, manufactured by Anton Paar Co.) according to the method described in JIS K 7117-1:1999. -1 It was measured at.

[0295] [Hardness of hardened material]

[0296] The obtained curable silicone composition was heated at 90°C for 20 minutes to produce a cured product with a thickness of 10 mm. The hardness of this cured product was measured using a Type D durometer as specified in JIS K 7215-1986 "Durometer Hardness Test Method for Plastics".

[0297] [Light transmittance of cured material]

[0298] A test specimen was produced by heat-treating the obtained curable silicone composition (thickness of 2 mm) at 150°C for 8 hours. The light transmittance of this test specimen was measured at 25°C using a self-recording spectrophotometer capable of measuring at any wavelength in the visible light range (wavelengths 400 nm to 700 nm). A transmittance of 95% or higher at 450 nm was defined as "OK".

[0299] [Wetness]

[0300] About 2 mg of the obtained curable silicone composition was applied by dispenser molding onto a polycarbonate sheet (commercial product name: Iupilon Sheet, FE-2000, manufactured by Mitsubishi Gas Chemical Co., Inc.), the diameter of the applied material was measured immediately after application, and the material was measured again after standing at 25°C for 30 minutes. If the ratio of the diameter of the applied material after standing at 25°C for 30 minutes to the diameter of the applied material immediately after application (diameter of the applied material after standing at 25°C for 30 minutes / diameter of the applied material immediately after application) was less than 2.0, the result was given as "OK", and if the ratio was 2.0 or more, the result was given as "NG".

[0301] [Hardening]

[0302] The obtained curable silicone composition was measured at a temperature of 90°C using a curability tester (moving die rheometer (MDR)), and if the time from immediately after measurement until reaching saturation torque was 5 minutes or less, the result was rated as "OK," and if the time was 5 minutes or more, the result was rated as "NG."

[0303] [Lyrics Time]

[0304] The viscosity of the obtained curable silicone composition was measured after maintaining it at 40°C for 4 hours. If the increase rate of viscosity compared to the initial viscosity was less than 20%, it was classified as "OK," and if the increase rate was 20% or more, or if measurement was impossible, it was classified as "NG." The viscosity measurement was performed in the same manner as described in the viscosity section above.

[0305] [Table 1]

[0306]

[0307] [Table 2]

[0308]

[0309] [Table 3]

[0310]

[0311] [Table 4]

[0312]

[0313] [Table 5]

[0314]

[0315] [Table 6]

[0316]

[0317] According to the test results of the examples and comparative examples described above, the curable silicone composition of the present invention exhibited a practically effective pot life and excellent curability at low temperatures. In addition, because the curable silicone composition of the present invention exhibited excellent wettability on a base material, a cured product with a smooth surface shape could be formed. Furthermore, the curable silicone composition of the present invention could form a cured product exhibiting high hardness and excellent transparency even after heating.

[0318] [Examples 15 to 22 and Comparative Examples 1 and 18 to 36]

[0319] A curable silicone composition was prepared by mixing different components to provide the composition (parts by mass) shown in the table below. It is also noted that the amount of the curing catalyst of component d is presented as the amount of platinum atoms (ppm) contained in component d. Furthermore, it is noted that the compositions of Comparative Examples 1 and 18 to 25 are identical to the compositions of Comparative Examples 1 and 18 to 25.

[0320] The viscosity, hardness, curability, and pot life of the cured product were evaluated in the same manner as the evaluations of Examples 1 to 14 and Comparative Examples 1 to 25 in Tables 1 to 6 above. The light transmittance of the cured product was evaluated in the same manner as the light transmittance of the cured products of Examples 1 to 14 and Comparative Examples 1 to 25 in Tables 1 to 6 above, except that the heat treatment was performed at 150°C for 48 hours. More specifically, the evaluation was performed as follows.

[0321] [viscosity]

[0322] The viscosity of a curable silicone composition was measured at 25°C and 20 s using a viscoelasticity measuring device (MCR-302, manufactured by Anton Paar Co.) according to the method described in JIS K 7117-1:1999. -1 It was measured at.

[0323] [Hardness of hardened material]

[0324] The obtained curable silicone composition was heated at 90°C for 20 minutes to produce a cured product with a thickness of 10 mm. The hardness of this cured product was measured using a Type D durometer as specified in JIS K 7215-1986 "Durometer Hardness Test Method for Plastics".

[0325] [Light transmittance of cured material]

[0326] A test specimen was produced by heat-treating the obtained curable silicone composition (thickness of 2 mm) at 150°C for 48 hours. The light transmittance of this test specimen was measured at 25°C using a self-recording spectrophotometer capable of measuring at any wavelength in the visible light range (wavelengths 400 nm to 700 nm). A transmittance of 95% or higher at 450 nm was defined as "OK".

[0327] [Hardening]

[0328] The obtained curable silicone composition was measured at a temperature of 90°C using a curability tester (moving die rheometer (MDR)), and if the time from immediately after measurement until reaching saturation torque was 5 minutes or less, the result was rated as "OK," and if the time was 5 minutes or more, the result was rated as "NG."

[0329] [Lyrics Time]

[0330] The viscosity of the obtained curable silicone composition was measured after maintaining it at a temperature of 40°C for 4 hours. If the increase rate of viscosity compared to the initial viscosity was less than 20%, it was classified as "OK," and if the increase rate was 20% or more, or if measurement was impossible, it was classified as "NG." The viscosity measurement was performed in the same manner as described in the viscosity section above.

[0331] [Table 7]

[0332]

[0333] [Table 8]

[0334]

[0335] [Table 9]

[0336]

[0337] [Table 10]

[0338]

[0339] [Table 11]

[0340]

[0341] According to the test results of the examples and comparative examples described above, the curable silicone composition of the present invention exhibited a practically effective pot life and excellent curability at low temperatures. Furthermore, the curable silicone composition of the present invention was able to form a cured product having excellent hardness and excellent transparency even after prolonged heating. Industrial applicability

[0342] The curable silicone composition of the present invention exhibits a practically effective pot life and excellent curability at low temperatures, and can form a cured product having excellent surface smoothness, transparency, and high hardness. For this reason, the curable silicone composition of the present invention is very useful for encapsulation applications, for example, when manufacturing opto-semiconductor devices.

Claims

Claim 1 A curable silicone composition comprising: (A) a dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule; (B) a dendritic organo-hydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule; (C) an additive having a wettability-improving effect selected from molecular chain side-chain polyether-modified organopolysiloxane, phenol-modified organopolysiloxane, terminal hydroxyl group-containing dimethylpolysiloxane not containing an aryl group, and a phenolic antioxidant, and combinations thereof; (D) a curing catalyst; and a dendritic organopolysiloxane containing an epoxy group including an aryl group. Claim 2 A curable silicone composition according to claim 1, further comprising a straight-chain organo-hydrogen polysiloxane. Claim 3 In claim 1, the polyether group of the molecular chain side chain polyether-modified organopolysiloxane of component (C) comprises a polyoxyethylene unit, in a curable silicone composition. Claim 4 A curable silicone composition according to claim 1, wherein the phenol-modified organopolysiloxane of component (C) is a straight chain and contains phenol-containing organic groups at both ends of the molecular chain. Claim 5 A curable silicone composition according to claim 1, wherein the terminal hydroxyl group-containing dimethylpolysiloxane that does not contain an aryl group of component (C) is a straight chain and contains hydroxyl groups at both ends of the molecular chain. Claim 6 A curable silicone composition according to claim 1, wherein the phenolic antioxidant of component (C) is 2,6-di-tert-butyl-p-cresol. Claim 7 A curable silicone composition according to claim 1, wherein (C) the content of an additive having a wettability improving effect is 0.01 mass% or more and 10 mass% or less of the total mass of the alkenyl group-containing organopolysiloxane and the organo-hydrogen polysiloxane. Claim 8 A curable silicone composition according to claim 1, wherein the content of dendritic organo-hydrogen polysiloxane (B) is 1% by mass or more of the total mass of the dendritic alkenyl group-containing organic polysiloxane and the dendritic organo-hydrogen polysiloxane. Claim 9 In claim 1, the curing catalyst (D) is a platinum-based catalyst and the curable silicon composition comprises platinum atoms of 0.01 ppm or more and 15 ppm or less with respect to the total mass of the curable silicon composition. Claim 10 A curable silicone composition according to claim 1, wherein the molar ratio (H / Vi) of hydrogen atoms and alkenyl groups derived from the organopolysiloxane component is 0.9 to 1.

3. Claim 11 A curable silicone composition according to claim 1, further comprising, other than component (A), an alkenyl group-containing cyclic organopolysiloxane and / or an alkenyl group-containing organopolysiloxane comprising only M units and Q units. Claim 12 A curable silicone composition comprising: (A) a dendritic alkenyl group-containing organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule; (F) an alkenyl group-containing organopolysiloxane having only M units and Q units; (B) a dendritic organo-hydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule; (E) an ethynylcyclohexanol (D) curing catalyst; and a dendritic organopolysiloxane containing epoxy groups including an aryl group (wherein the molar ratio (H / Vi) of hydrogen atoms derived from the organopolysiloxane component to alkenyl groups is 0.98 to 1.2, and SiO₂ 2 / 2 The content of dendritic organopolysiloxane containing alkenyl groups bonded to silicon atoms of siloxane units (D units) represented by is less than 50 mass% of the total mass of (A) dendritic alkenyl group-containing organopolysiloxane, (F) alkenyl group-containing organopolysiloxane containing only M units and Q units, and (B) dendritic organo-hydrogen polysiloxane). Claim 13 A curable silicone composition according to claim 12, wherein the content of (F) an alkenyl group-containing organopolysiloxane containing only M units and Q units is 2% by mass or more and 20% by mass or less of the total mass of (A) a dendritic alkenyl group-containing organopolysiloxane, (F) an alkenyl group-containing organopolysiloxane containing only M units and Q units, and (B) a dendritic organo-hydrogen polysiloxane. Claim 14 A curable silicone composition according to claim 12, wherein the content of (B) dendritic organo-hydrogen polysiloxane is 1% by mass or more and 15% by mass or less of the total mass of (A) dendritic alkenyl group-containing organopolysiloxane, (F) alkenyl group-containing organopolysiloxane containing only M units and Q units, and (B) dendritic organo-hydrogen polysiloxane. Claim 15 In claim 12, the curing catalyst (D) is a platinum-based catalyst and the curable silicon composition contains platinum atoms of 0.01 ppm or more and less than 8 ppm with respect to the total mass of the curable silicon composition. Claim 16 A curable silicone composition according to claim 12, further comprising a straight-chain organo-hydrogen polysiloxane in an amount of at least 25 mass% with respect to the total mass of the dendritic alkenyl group-containing organopolysiloxane of component (A). Claim 17 A packaging material comprising a curable silicone composition according to any one of claims 1 to 16. Claim 18 An opto-semiconductor device comprising a cured encapsulant of claim 17.

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