Curable organopolysiloxane composition and semiconductor device for wearable device

Abstract

To provide a curable organopolysiloxane composition which has excellent adhesiveness to a urethane resin substrate and exhibits stretchability equivalent to that of a polyurethane resin, and a semiconductor device for a wearable device including a cured product thereof.SOLUTION: Provided is a curable organopolysiloxane composition which contains: (A) 100 pts.mass of an organopolysiloxane having at least two alkenyl groups in one molecule; (B) an organohydrogenpolysiloxane; (C) a platinum group metal-based catalyst; and (D) an organosilicon compound which has at least one hydrogen atom bonded to a silicon atom and has at least one organic group having an epoxy group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable organopolysiloxane composition that has excellent adhesion to substrates for wearable devices, and to a semiconductor device for use in a wearable device. [Background technology]

[0002] Silicone resin compositions have low elasticity and low stress, and are highly reliable in terms of heat resistance and electrical insulation properties, and are therefore widely used in electronic parts and semiconductor applications.

[0003] In recent years, various studies have been conducted on materials for wearable devices, such as smartwatches and smart glasses worn on the wrist, arm, or head. Polyurethane resins have begun to be used as materials for wearable devices due to their excellent elasticity and toughness (Patent Documents 1 and 2). When polyurethane resins are used as substrate materials for wearable devices to encapsulate semiconductor elements mounted on the substrate, the encapsulant must also have elasticity equivalent to that of the polyurethane resin and good adhesion to the polyurethane resin. Furthermore, because the heat resistance of polyurethane resins limits their curing temperature to 120°C or below, they must also be cured at low temperatures. When addition-curable silicone resins are used as encapsulants, there have been issues with the addition-curable silicone resins not curing sufficiently on polyurethane resin substrates, or with insufficient adhesive strength even after curing. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2015-515287 [Patent Document 2] Patent Publication No. 2021-89287 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to provide a curable organopolysiloxane composition that has excellent adhesion to urethane resin substrates for wearable devices and exhibits elasticity equivalent to that of polyurethane resins, and a semiconductor device for wearable devices that includes a cured product of the cured organopolysiloxane composition. [Means for solving the problem]

[0006] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the curable organopolysiloxane composition described below has excellent adhesion to urethane resin substrates for wearable devices and gives a cured product that exhibits elasticity equivalent to that of polyurethane resin, thereby completing the present invention.

[0007] That is, the present invention is (A) 100 parts by mass of an organopolysiloxane having at least two alkenyl groups per molecule, (B1) an organohydrogenpolysiloxane represented by the following formula (1) or (2): [ka] [ka] (In the formula, R 1 and R 2 are each independently a substituted or unsubstituted saturated aliphatic hydrocarbon group or saturated cyclic hydrocarbon group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, provided that R 1 and R 2 At least one of the groups is an aromatic hydrocarbon group, x is an integer of 0 to 4, n is an integer of 1 to 3, and s is an integer of 3 to 4, provided that the group does not have an epoxy group. (B2) an organohydrogenpolysiloxane represented by the following formula (3): [ka] (In the formula, R 3are each independently a substituted or unsubstituted saturated aliphatic hydrocarbon group or saturated cyclic hydrocarbon group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, y is an integer of 0 to 300, and z is an integer of 5 to 300, provided that they do not have an epoxy group. (C) a platinum group metal catalyst in a catalytic amount; and (D) an organosilicon compound having 4 to 200 silicon atoms, which has at least one hydrogen atom bonded to a silicon atom and at least one organic group having an epoxy group: 0.01 to 10 parts by mass per 100 parts by mass of the total of the components (A), (B1), and (B2); Including, The curable organopolysiloxane composition is characterized in that the ratio of the total number of hydrosilyl groups in components (B1) and (B2) to the number of alkenyl groups in component (A) is 0.5 to 6, and the ratio of the total number of hydrosilyl groups in components (B1), (B2), and (D) to the number of alkenyl groups in component (A) is 0.55 to 6.5. The present invention further provides a cured product of the curable organopolysiloxane composition, and a semiconductor device for a wearable device comprising the cured product. [Effects of the Invention]

[0008] The curable organopolysiloxane composition of the present invention has excellent adhesion to urethane resin substrates for wearable devices, and can give cured products that are generally transparent and have sufficient hardness, excellent adhesion, and stretchability.

[0009] The present invention will be described in detail below, but the present invention is not limited thereto.

[0010] [(A) Alkenyl Group-Containing Organopolysiloxane] The alkenyl group-containing organopolysiloxane (A) has at least two, preferably two to five, alkenyl groups per molecule and may be appropriately selected from known alkenyl group-containing organopolysiloxanes. The alkenyl groups are preferably capable of undergoing an addition reaction with hydrosilyl groups. The (A) component may be any of a linear organopolysiloxane, a branched organopolysiloxane, and a resinous (network-like) organopolysiloxane, each of which may be used alone or in combination of two or more. A linear organopolysiloxane is preferred.

[0011] The curable organopolysiloxane composition of the present invention preferably contains (A1) a linear or branched organopolysiloxane as component (A). The linear or branched organopolysiloxane preferably contains two or more alkenyl groups having 2 to 10 carbon atoms per molecule. This allows the viscosity and hardness to be adjusted to suit the application. There are no restrictions on the bonding position of the alkenyl group, but an alkenyl group bonded to a terminal silicon atom of the linear or branched organopolysiloxane is preferred.

[0012] In component (A1), the amount of alkenyl groups bonded to silicon atoms is typically 0.001 to 0.05 mol / 100 g, preferably 0.005 to 0.03 mol / 100 g, and more preferably 0.006 to 0.02 mol / 100 g. If the amount of alkenyl groups bonded to silicon atoms is 0.001 mol / 100 g or more, there will be enough crosslinking points for the composition to solidify, while if it is 0.05 mol / 100 g or less, there is no risk of the crosslink density becoming too high and losing toughness, which is preferable.

[0013] Component (A1) preferably has a viscosity of 10 to 100,000 mPa·s at 25°C, measured by the method described in JIS K 7117-1: 1999, more preferably 100 to 50,000 mPa·s, and even more preferably 1,000 to 30,000 mPa·s. A viscosity of 10 mPa·s or higher will prevent the composition from becoming brittle, while a viscosity of 100,000 mPa·s or lower will prevent poor workability.

[0014] The linear or branched organopolysiloxane (A1) is preferably represented by the following formula: [ka] In the formula, R 4 are each independently an alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkyl or cycloalkyl group having 1 to 10 carbon atoms, or an aryl or aralkyl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. 4 At least two of the groups are alkenyl groups.

[0015] Examples of substituted or unsubstituted alkyl or cycloalkyl groups having 1 to 10 carbon atoms include lower alkyl groups such as methyl, ethyl, propyl, and butyl; and cycloalkyl groups such as cyclohexyl, with methyl being preferred. Examples also include groups in which some or all of the hydrogen atoms in these groups have been substituted with halogen atoms such as fluorine, bromine, and chlorine, or with cyano groups, such as chloromethyl, cyanoethyl, and 3,3,3-trifluoropropyl. Examples of aryl groups having 6 to 10 carbon atoms include phenyl, tolyl, and xylyl. Examples of aralkyl groups include benzyl, phenylethyl, and phenylpropyl. Of these, phenyl is preferred.

[0016] Examples of alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, include vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and octenyl groups. Of these, vinyl is preferred. Preferably, one molecule contains two or more alkenyl groups, and more preferably two to five. In the above formula, x 1 is an integer of 10 to 1000, preferably an integer of 20 to 500, more preferably an integer of 30 to 200, and y 1 is an integer of 0 to 10, preferably an integer of 1 to 5, and z 1 is an integer of 0 to 1000, preferably an integer of 1 to 500.

[0017] Examples of the component (A1) include, but are not limited to, the following compounds. [ka] [ka] [ka] [ka] (In the formula, s, t, and u are each an integer of 0 or more, and are numbers that satisfy s+t+u≧1. 1 (The range satisfies the requirements of [ka] (In the above formula, s, t, u, and p are each an integer of 0 or more, and are numbers that satisfy s+t+u+p≧1. 1 , y 1 , z 1 (The range satisfies the requirements of

[0018] The component (A) preferably contains a resinous (chain-like) organopolysiloxane (A2) in addition to the component (A1). The amount of component (A1) blended is 5 parts by mass or more, i.e., 5 to 100 parts by mass, and preferably 30 to 100 parts by mass, per 100 parts by mass of the total amount of components (A1) and (A2).

[0019] The resinous organopolysiloxane (A2) contains 30 to 60 mol % of SiO 4 / 2 Unit (Q unit), 0-30 mol% R 4 SiO 3 / 2 Unit (T unit), 0~50mol% (R 4 )2SiO 2 / 2 units (D units), and 10 to 70 mol% of (R 4 )3SiO1 / 2 The SiO 4 / 2 Units and R 4 SiO 3 / 2 The sum of the units is 40 mol% or more based on the total moles of all siloxane units. It is preferable that the weight-average molecular weight is 2,000 to 10,000, that each molecule contains at least two silicon-bonded alkenyl groups, that the amount of silicon-bonded hydroxyl groups is 0.001 to 1.0 mol / 100 g, and that the amount of silicon-bonded alkoxy groups having 1 to 10 carbon atoms is 1.0 mol / 100 g or less.

[0020] More specifically, the component (A2) contains 30 to 60 mol %, preferably 35 to 55 mol % of SiO 4 / 2 units (Q units) and 0 to 30 mol%, preferably 0 to 20 mol% of R 4 SiO 3 / 2 units (T units) and usually 0 to 50 mol %, preferably 0 to 20 mol % of (R 4 )2SiO 2 / 2 units (D units), and usually 10 to 70 mol %, preferably 10 to 65 mol %, and preferably 10 to 30 mol % of (R 4 )3SiO 1 / 2 More preferably, component (A2) is an organopolysiloxane comprising 30 to 60 mol %, and preferably 35 to 55 mol % of SiO 2 . 4 / 2 units (Q units) and 40 to 70 mol %, preferably 45 to 65 mol % of (R 4 )3SiO 1 / 2 It is preferable that the organopolysiloxane is an organopolysiloxane consisting of a unit (M unit). In the above formula, R 4 are each independently a substituted or unsubstituted alkyl group or cycloalkyl group having 1 to 10 carbon atoms, preferably 2 to 5 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group or aralkyl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Preferably, (R 4 )3SiO 1 / 2 Substituent R bonded to the unit (M unit) 4 At least one of them is an alkenyl group having 2 to 10 carbon atoms.

[0021] Above R 4 Examples of the alkyl group include lower alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and octenyl; and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine, bromine, and chlorine, or with cyano groups, such as chloromethyl, cyanoethyl, and 3,3,3-trifluoropropyl. Of these, methyl, phenyl, and vinyl groups are preferred.

[0022] The amount of silicon-bonded alkenyl groups in component (A2) is typically 0.01 to 0.5 mol / 100 g, preferably 0.05 to 0.3 mol / 100 g, and more preferably 0.10 to 0.25 mol / 100 g. If the amount of silicon-bonded alkenyl groups is less than the above lower limit, the hardness of the composition may not be sufficiently increased. If it exceeds the above upper limit, the crosslink density of the resulting cured product may be too high, resulting in a loss of toughness.

[0023] The amount of hydroxyl groups bonded to silicon atoms in component (A2) is preferably 0.001 to 1.0 mol / 100 g, more preferably 0.005 to 0.8 mol / 100 g, and even more preferably 0.008 to 0.6 mol / 100 g.

[0024] In component (A2), the amount of alkoxy groups bonded to silicon atoms having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, is preferably 1.0 mol / 100 g or less, more preferably 0.8 mol / 100 g or less, and even more preferably 0.5 mol / 100 g or less. If the amount of alkoxy groups exceeds the upper limit, alcohol gas may be generated as a by-product during curing, which may leave voids in the cured product. Note that the amount of hydroxyl groups and alkoxy groups bonded to silicon atoms in the present invention is 1 H-NMR and29 The values ​​were measured by Si-NMR.

[0025] The resinous organopolysiloxane (A2) preferably has a weight-average molecular weight (Mw) of 2,000 to 10,000, more preferably 3,000 to 8,000. If the molecular weight is less than the lower limit, the composition may become brittle, while if the molecular weight exceeds the upper limit, the composition may become too viscous and not flow easily. The weight-average molecular weight (Mw) in the present invention refers to the weight-average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard, and may be measured under the following conditions: [Measurement conditions] Developing solvent: tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-L TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×2) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 20 μL (0.5% by mass THF solution)

[0026] SiO 4 / 2 Examples of materials for obtaining the units (Q units) include, but are not limited to, sodium silicate, tetraalkoxysilane, or condensation products thereof.

[0027] R 4 SiO 3 / 2 Examples of materials for obtaining units (T units) include, but are not limited to, organosilicon compounds such as organotrichlorosilane and organotrialkoxysilane represented by the following structural formulas, or condensation products thereof. [ka] (In the above formula, Me represents a methyl group.)

[0028] R 4 2SiO 2 / 2 Examples of materials for obtaining units (D units) include, but are not limited to, organosilicon compounds such as diorganodichlorosilane and diorganodialkoxysilane represented by the following structural formulas. [ka] (In the above formula, Me represents a methyl group, n represents an integer of 5 to 80, and m represents an integer of 5 to 80, provided that n+m≦78.)

[0029] [ka] [ka] (In the above formula, Me represents a methyl group.)

[0030] R 4 3SiO 1 / 2 Examples of materials for obtaining units (M units) include, but are not limited to, organosilicon compounds such as triorganochlorosilane, triorganoalkoxysilane, and hexaorganodisiloxane, which are represented by the following structural formulas: [ka] (In the above formula, Me represents a methyl group.)

[0031] [(B) Organohydrogenpolysiloxane] The curable organopolysiloxane composition of the present invention is characterized by comprising, as component (B), a combination of (B1) an organohydrogenpolysiloxane represented by the following formula (1) or (2) and (B2) an organohydrogenpolysiloxane represented by the following formula (3): The blending ratio of component (B1) to component (B2) is preferably 5 to 95 mass%, more preferably 10 to 80 mass%, of component (B1), where the total amount of components (B1) and (B2) is 100 mass%.

[0032] [ka] [ka] (In the formula, R 1 and R 2 are each independently a substituted or unsubstituted saturated aliphatic hydrocarbon group or saturated cyclic hydrocarbon group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, provided that R 1 and R 2 At least one of the groups is an aromatic hydrocarbon group, x is an integer of 0 to 4, n is an integer of 1 to 3, and s is an integer of 3 to 4, provided that the group does not have an epoxy group. [ka] (In the formula, R 3 are each independently a substituted or unsubstituted saturated aliphatic hydrocarbon group or saturated cyclic hydrocarbon group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, y is an integer of 0 to 300, preferably 1 to 100, and more preferably 2 to 50, and z is an integer of 5 to 300, preferably 6 to 150, and more preferably 7 to 100, and even more preferably 10 to 50, provided that it does not have an epoxy group.

[0033] The amount of component (B) is such that the total number of hydrosilyl groups in components (B1) and (B2) is 0.5 to 6.0 (number ratio) relative to the number of alkenyl groups in component (A). The amount is preferably 2.0 to 5.8, more preferably 3.0 to 5.5, and most preferably 4.0 to 5.0. If the amount of component (B) is less than the above-mentioned lower limit, the curing reaction of the composition of the present invention will not proceed, making it difficult to obtain a silicone cured product. Furthermore, the resulting cured product will have too low a crosslink density, resulting in insufficient mechanical strength and adversely affecting adhesive properties. On the other hand, if the amount of component (B) is greater than the above-mentioned upper limit, numerous unreacted hydrosilyl groups will remain in the cured product, causing changes in physical properties over time and a decrease in the crosslink density of the cured product, resulting in a decrease in strength and adversely affecting stretchability.

[0034] The amount of component (B1) is preferably such that the number of hydrosilyl groups in component (B1) relative to the number of alkenyl groups in component (A) is 0.3 to 5.5 (number ratio), preferably 1.0 to 5.0, and more preferably 1.5 to 4.0.The amount of component (B2) is preferably such that the number of hydrosilyl groups in component (B2) relative to the number of alkenyl groups in component (A) is 0.1 to 3.0 (number ratio), preferably 0.2 to 2.5, and more preferably 0.5 to 1.5.

[0035] Above R 1 and R 2 Examples of R include saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, and pentyl; saturated cyclic hydrocarbon groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; and aromatic hydrocarbon groups such as aralkyl groups such as benzyl, phenylethyl, and phenylpropyl; and groups in which some or all of the hydrogen atoms bonded to carbon atoms in these groups have been substituted with halogen atoms such as fluorine, bromine, or chlorine, such as halogenated hydrocarbon groups such as trifluoropropyl and chloropropyl. Among these, saturated hydrocarbon groups having 1 to 5 carbon atoms such as methyl, ethyl, and propyl, and phenyl are preferred.2 Preferably, each molecule contains one or more silicon-bonded aryl groups.

[0036] Above R 3 Examples of the alkyl group include saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, and pentyl groups, saturated cyclic hydrocarbon groups such as cyclopentyl and cyclohexyl groups, aryl groups such as phenyl, tolyl, and xylyl groups, and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups, as well as aromatic hydrocarbon groups in which some or all of the hydrogen atoms bonded to carbon atoms of these groups have been substituted with halogen atoms such as fluorine, bromine, and chlorine, for example, halogenated hydrocarbon groups such as trifluoropropyl and chloropropyl groups. Of these, saturated hydrocarbon groups having 1 to 5 carbon atoms such as methyl, ethyl, and propyl groups, and phenyl groups are preferred.

[0037] Examples of the organohydrogenpolysiloxane represented by (B1) above include, but are not limited to, compounds represented by the following formula: [ka] (x is an integer between 0 and 4) [ka] [ka] [ka]

[0038] Examples of the organohydrogenpolysiloxane represented by (B2) above include, but are not limited to, compounds represented by the following formula: [ka] [ka] [ka] [ka] (p and r are each independently an integer of 0 or greater, z is an integer of 5 or greater, and is a number that satisfies 0≦p+r≦300 and 5≦z≦300. Preferably, it is a number that satisfies 1≦p+r≦100 and 6≦z≦150.)

[0039] [(C) Platinum group metal catalyst] The platinum group metal catalyst is added to induce the addition curing reaction of the composition of the present invention. It may be appropriately selected from conventionally known addition reaction catalysts, such as platinum, palladium, and rhodium. Any platinum group metal catalyst known to promote hydrosilylation reactions can be used. Considering cost and other factors, examples include platinum, platinum black, and platinum-based catalysts such as HPtCl6·pH2O, K2PtCl6, KHPtCl6·pH2O, K2PtCl4, K2PtCl4·pH2O, PtO2·pH2O, PtCl4·pH2O, PtCl2, and HPtCl4·pH2O (where p is a positive integer), as well as complexes of these with hydrocarbons such as olefins, alcohols, or vinyl-containing organopolysiloxanes. The above catalysts may be used alone or in combination.

[0040] The amount of component (C) may be a catalytic amount (i.e., an amount effective for curing), and is generally in the range of 0.1 to 500 ppm, and particularly preferably 0.5 to 100 ppm, in terms of platinum group metal, based on the total amount of components (A), (B), and (C).

[0041] [(D) Organosilicon compounds] Component (D) is an organosilicon compound having 4 to 200 silicon atoms, which has at least one hydrogen atom bonded to a silicon atom and at least one organic group containing an epoxy group. Preferably, component (D) is represented by the following formula (4): HR 5 a R 6 b SiO (4-a-b) / 2 (4) In formula (4), R 5 are each independently a substituted or unsubstituted saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated cyclic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms; and R 6 are each independently an organic group having 5 to 20 carbon atoms and an epoxy group, and a and b are positive numbers satisfying 0.7≦a≦2.1, 0.08≦b≦1.1, and 0.8≦a+b≦3.0, preferably 1.0≦a≦2.0, 0.2≦b≦1.0, and 1.5≦a+b≦2.5.

[0042] Above R 5 Examples of the alkyl group include saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, and pentyl groups, saturated cyclic hydrocarbon groups such as cyclopentyl and cyclohexyl groups, aryl groups such as phenyl, tolyl, and xylyl groups, and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups, as well as aromatic hydrocarbon groups in which some or all of the hydrogen atoms bonded to carbon atoms of these groups have been substituted with halogen atoms such as fluorine, bromine, and chlorine, for example, halogenated hydrocarbon groups such as trifluoropropyl and chloropropyl groups. Of these, saturated hydrocarbon groups having 1 to 5 carbon atoms such as methyl, ethyl, and propyl groups, and phenyl groups are preferred.

[0043] The epoxy group-containing organic group is a monovalent hydrocarbon group having an ethylene oxide structure, preferably having 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms. Examples include a 3,4-epoxycyclohexylethyl group, a 2-glycidoxyethyl group, and a 3-glycidoxypropyl group.

[0044] The molecular structure of component (D) is not particularly limited and may be any of linear, cyclic, branched, or three-dimensional network (resin-like) molecular structures. The number of silicon atoms (or degree of polymerization) per molecule is typically 4 to 200, preferably 4 to 100, and more preferably 4 to 50. Epoxy-containing organosilicon resins that are liquid or solid at room temperature (25°C) are preferred. Component (D) is preferably a linear or cyclic organo(poly)siloxane, and may be a siloxane having a silphenylene structure or a silalkylene structure. The number of hydrogen atoms bonded to the silicon atom may be one or more, preferably 1 to 100. The number of epoxy-containing organic groups may be one or more, preferably 1 to 6, and more preferably 2 to 4.

[0045] Examples of the component (D) include compounds represented by the following formula: [ka] (In the formula, u and v are integers of 1 or more, and are numbers that result in 2 to 200 silicon atoms, preferably 4 to 100, more preferably 5 to 50, and even more preferably 8 to 30 silicon atoms.) [ka]

[0046] The amount of component (D) is 0.01 to 10 parts by mass, and preferably 0.02 to 2 parts by mass, per 100 parts by mass of the total of components (A), (B1) and (B2).

[0047] In the present invention, the ratio of the total number of hydrosilyl groups in components (B1) and (B2) to the number of alkenyl groups in component (A) is 0.5 to 6.0 (number ratio), preferably 2.0 to 5.8, more preferably 3.0 to 5.5, and even more preferably 4.0 to 5.0. Furthermore, the ratio of the total number of hydrosilyl groups in components (B1), (B2), and (D) to the number of alkenyl groups in component (A) is 0.55 to 6.5, preferably 1.1 to 5.6, and more preferably 2.1 to 5.1. Having hydrosilyl groups within this range is preferred in that it is less susceptible to cure inhibition and exhibits excellent adhesion.

[0048] In addition to the components (A) to (D), the curable organopolysiloxane composition of the present invention may contain, as necessary, known additives such as adhesion promoters, cure inhibitors, and pigments.

[0049] Examples of adhesion promoters include phenyltrimethoxysilane, trimethoxysilane, triethoxysilane, methyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, Examples of adhesion promoters include alkoxysilanes such as silane, 3-methacryloxypropyltriethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-cyanopropyltriethoxysilane, as well as oligomers thereof. These adhesion promoters can be used alone or in combination of two or more.

[0050] The amount of adhesion promoter is preferably 0 to 10 parts by mass, and more preferably 0 to 5 parts by mass, per 100 parts by mass of the total of components (A) and (B).

[0051] Examples of the cure inhibitor include compounds selected from the group consisting of triallyl isocyanurate, alkyl maleate, acetylene alcohols and their silane-modified and siloxane-modified products, hydroperoxide, tetramethylethylenediamine, benzotriazole, and mixtures thereof. The cure inhibitors can be used singly or in combination of two or more.

[0052] The amount of the cure inhibitor is usually 0.001 to 1.0 part by mass, and preferably 0.005 to 0.5 part by mass, per 100 parts by mass of the total of the components (A) and (B).

[0053] Examples of pigments include inorganic white pigments such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium carbonate, magnesium oxide, aluminum hydroxide, barium carbonate, magnesium silicate, zinc sulfate, and barium sulfate, as well as carbon black. The pigment can be appropriately blended in an amount of up to 600 parts by mass, preferably up to 400 parts by mass, more preferably up to 200 parts by mass, and even more preferably up to 100 parts by mass (for example, 0 to 600 parts by mass, typically 1 to 600 parts by mass, preferably 2 to 400 parts by mass, and even more preferably 10 to 100 parts by mass) per 100 parts by mass of the total of components (A) to (C).

[0054] Other additives include, for example, reinforcing inorganic fillers such as silica, glass fiber, and fumed silica; non-reinforcing inorganic fillers such as calcium silicate, ferric oxide, cerium fatty acid salts, barium fatty acid salts, cerium alkoxides, and barium alkoxides; aluminum oxide (alumina: Al2O3), iron oxide (FeO2), triiron tetroxide (Fe3O4), lead oxide (PbO2), tin oxide (SnO2), and cerium oxide (Ce2O 3、Examples of nanofillers include nanofillers such as CeO2), calcium oxide (CaO), trimanganese tetroxide (Mn3O4), and barium oxide (BaO), and these can be appropriately blended in an amount of 600 parts by mass or less (for example, 0 to 600 parts by mass, typically 1 to 600 parts by mass, and preferably 10 to 400 parts by mass) per 100 parts by mass of the above components (A) to (D) combined.

[0055] The curable organopolysiloxane composition of the present invention can be applied to a substrate of interest and then cured. Curing conditions are such that the composition cures sufficiently at room temperature (25°C), but may also be heated for curing if necessary. The heating conditions are not particularly limited as long as the resin is cured, but can be, for example, at a temperature of 60 to 200°C for 10 seconds to 24 hours.

[0056] The cured product obtained by heat-curing the curable organopolysiloxane composition of the present invention preferably has a refractive index in the range of 1.41 to 1.55 at 589 nm and 23°C, as measured according to JIS K 7142:2014 Method A. The cured product obtained from the curable organopolysiloxane composition of the present invention has low bleeding properties and excellent adhesion to various substrates such as urethane.

[0057] The present invention further provides a semiconductor device for wearable devices, in which a semiconductor element is encapsulated with the above-described cured product. As described above, the cured product obtained from the composition of the present invention has excellent transparency and heat resistance. Therefore, it is suitable for use as, for example, a lens material for light-emitting semiconductor devices used in wearable devices, a protective coating agent, a molding agent, etc., and is particularly useful for encapsulating LED elements such as blue LEDs, white LEDs, and ultraviolet LEDs.

[0058] When a semiconductor element is encapsulated with the cured product of the present invention, the semiconductor element can be encapsulated with the cured product by applying the curable organopolysiloxane composition of the present invention to an element mounted on an organic substrate made of a thermoplastic resin or a thermosetting resin, such as a polyurethane resin substrate or a polycarbonate resin substrate, and then curing the composition on the element.

[0059] Due to its excellent elasticity and adhesive properties, the curable organopolysiloxane composition of the present invention is an ideal material for use as a display material for wearable devices, an optical / electronic functional organic material, a semiconductor integrated circuit peripheral material, and the like. The cured product of the present invention can be used to encapsulate elements for wearable devices by any conventionally known method, including dispensing, jet dispensing, printing, spraying, molding, and the like. [Example]

[0060] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, "parts" means "parts by mass".

[0061] The component (A) used in the following examples and comparative examples is as follows: (A1) Ingredients: (A1-1) Organopolysiloxane represented by the following formula (5): [ka] (where t is 100 (average value), the weight-average molecular weight is 7560, and the viscosity is 1050 mPa·s) (A1-2) Organopolysiloxane represented by the following formula (6): [ka] (wherein p is 5 (average value), q is 90 (average value), the aryl group content is 5.1 mol%, the weight average molecular weight is 8200, and the viscosity is 1250 mPa s) (A1-3) Organopolysiloxane represented by the following formula (7): [ka] (wherein p = 15, q = 15 (average value), the aryl group content is 45.5 mol%, the weight-average molecular weight is 4300, the viscosity is 4910 mPa s, and the content of low-molecular-weight substances having a weight-average molecular weight of 500 or less is 9.3% by mass) (A2) Ingredients: (A2-1)SiO 4 / 2 Unit 50mol%, ViPhMeSiO 1 / 2 Unit 25mol%, and Me3SiO 1 / 2 Branched phenylmethylpolysiloxane consisting of 25 mol% units (The weight-average molecular weight is 5500, the content of low-molecular-weight compounds having a weight-average molecular weight of 500 or less is 3.2% by mass, the amount of hydroxyl groups bonded to silicon atoms is 0.01 mol / 100 g, the amount of methoxy groups bonded to silicon atoms is 0.04 mol / 100 g, and the amount of isopropoxy groups bonded to silicon atoms is 0.01 mol / 100 g) (A2-2)SiO 4 / 2 Unit: 50mol%, ViMe2SiO 1 / 2 Unit 20mol%, Me3SiO 1 / 2 Branched methylpolysiloxane consisting of 30 mol% units (The weight-average molecular weight is 6500, the content of low-molecular-weight substances with a weight-average molecular weight of 500 or less is 4.3% by mass, the amount of hydroxyl groups bonded to silicon atoms is 0.03 mol / 100 g, and the amount of methoxy groups bonded to silicon atoms is 0.01 mol / 100 g) (A2-3)SiO 4 / 2 Unit 50mol%, ViPhMeSiO 1 / 2 Unit 25mol%, PhMe2SiO 1 / 2 Branched phenylmethylpolysiloxane consisting of 25 mol% units (Weight average molecular weight: 5500, amount of hydroxyl groups bonded to silicon atoms: 0.05 mol / 100 g, amount of methoxy groups bonded to silicon atoms: 0.03 mol / 100 g, amount of isopropoxy groups: 0.02 mol / 100 g)

[0062] The catalyst (C) used in the following examples and comparative examples was an octyl alcohol-modified solution of chloroplatinic acid (elemental platinum content: 1% by mass).

[0063] [Example 1] 50 parts of the organopolysiloxane (A1-1) represented by the above formula (5) and 50 parts of the branched-chain phenylmethylpolysiloxane (A2-1) (hereinafter collectively referred to as component (A)), (B1) an organohydrogenpolysiloxane represented by the following formula (13) in such an amount that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A) is 1.5: [ka] (B2) an amount such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A) of the organohydrogenpolysiloxane represented by the following formula (14) is 1.5; [ka] (wherein q is 38 (average value)) 0.01 part of the (C) catalyst, and (D) an organosilicon compound represented by the following formula (15) in an amount such that the total number of hydrosilyl groups in component (D) relative to the total number of alkenyl groups in component (A) is 0.1 (3 parts per 100 parts of the combined total of components (A) and (B)): [ka] The mixture was thoroughly stirred to prepare a curable organopolysiloxane composition. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0064] [Example 2] 100 parts of the organopolysiloxane (A1-1) represented by the above formula (5), (B1) in an amount such that the ratio of the number of hydrosilyl groups in the component (B1) of the organohydrogenpolysiloxane represented by the above formula (13) to the total number of alkenyl groups in the component (A1-1) is 2.5, (B2) in an amount such that the ratio of the number of hydrosilyl groups in the component (B1) of the organohydrogenpolysiloxane represented by the above formula (14) to the total number of alkenyl groups in the component (A1-1) is 1.5, A curable organopolysiloxane composition was prepared by adding 0.01 parts of the (C) catalyst described above, and 0.01 parts of the (C) catalyst described above, and 0.3 parts of the organosilicon compound (D) represented by the above formula (15) such that the ratio of the number of hydrosilyl groups in component (D) to the total number of alkenyl groups in component (A1-1) was 2.5 (1 part per 100 parts of the combined total of components (A) and (B)). The mixture was thoroughly stirred. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0065] [Example 3] 50 parts of the organopolysiloxane (A1-2) represented by the above formula (6) and 50 parts of the branched-chain methylpolysiloxane (A2-2) (hereinafter collectively referred to as component (A)), (B1) an organohydrogenpolysiloxane represented by the following formula (16) in an amount such that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A) is 0.3, [ka] (B2) an amount such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A) of the organohydrogenpolysiloxane represented by the following formula (8) is 0.2; [ka] (wherein p=3, q=20, r=18 (average value), the aryl group content is 6.8 mol%, and the weight average molecular weight is 3300) 0.01 part of the (C) catalyst, and an organosilicon compound represented by the following formula (9) as component (D) in an amount such that the total number of hydrosilyl groups in component (D) relative to the total number of alkenyl groups in component (A) is 0.1 (2 parts per 100 parts of the total of component (A) and component (B)). [ka] The mixture was thoroughly stirred to prepare a curable organopolysiloxane composition. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0066] [Example 4] 30 parts of the organopolysiloxane (A1-3) represented by the above formula (7), 30 parts of the branched-chain phenylmethylpolysiloxane (A2-3) (hereinafter collectively referred to as component (A)), (B1) an organohydrogenpolysiloxane represented by the following formula (10): [ka] (B2) an organohydrogenpolysiloxane represented by the following formula (11): an amount such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A) is 0.5; [ka] (wherein p = 14, q = 14 (average value), the aryl group content is 45.2%, the molecular weight is 3640, and the content of low-molecular-weight compounds having a weight-average molecular weight of 500 or less is 9.2% by mass) Organohydrogenpolysiloxanes represented by the formula: 0.01 part of the above (C) catalyst, and an organosilicon compound (D) represented by the following formula (12) in an amount such that the total number of hydrosilyl groups in component (D) relative to the total number of alkenyl groups in components (A1) and (A2) is 0.06 (1 part per 100 parts of the total of components (A) and (B)). [ka] The mixture was thoroughly stirred to prepare a curable organopolysiloxane composition. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0067] [Example 5] 50 parts of the organopolysiloxane (A1-1) represented by the above formula (5) and 50 parts of the branched-chain phenylmethylpolysiloxane (A2-1) (hereinafter collectively referred to as component (A)), (B1) an organohydrogenpolysiloxane represented by the following formula (13) in such an amount that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A) is 1.5: [ka] (B2) an amount such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A) of the organohydrogenpolysiloxane represented by the following formula (14) is 1.5; [ka] (wherein q is 38 (average value)) 0.01 part of the (C) catalyst, and (D) an organosilicon compound represented by the following formula (15) in an amount such that the total number of hydrosilyl groups in component (D) relative to the total number of alkenyl groups in component (A) is 0.1 (3 parts per 100 parts of the combined total of components (A) and (B)): [ka] 100 parts of titanium oxide (CR-95, manufactured by Ishihara Sangyo Kaisha) was added and thoroughly stirred to prepare a curable organopolysiloxane composition. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0068] [Example 6] 50 parts of the organopolysiloxane (A1-1) represented by the above formula (5) and 50 parts of the branched-chain phenylmethylpolysiloxane (A2-1) (hereinafter collectively referred to as component (A)), (B1) an organohydrogenpolysiloxane represented by the following formula (13) in such an amount that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A) is 1.5: [ka] (B2) an amount such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A) of the organohydrogenpolysiloxane represented by the following formula (14) is 1.5; [ka] (wherein q is 38 (average value)) 0.01 part of the (C) catalyst, and (D) an organosilicon compound represented by the following formula (15) in an amount such that the total number of hydrosilyl groups in component (D) relative to the total number of alkenyl groups in component (A) is 0.1 (3 parts per 100 parts of the combined total of components (A) and (B)): [ka] Two parts of carbon black (DENKA BLACK Li-100, manufactured by Denka Co.) was added and thoroughly stirred to prepare a curable organopolysiloxane composition. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0069] [Comparative Example 1] A curable organopolysiloxane composition was prepared by adding 50 parts of the organopolysiloxane (A1-1) represented by the formula (5) above, 50 parts of the branched-chain phenylmethylpolysiloxane (A2-1) above (hereinafter collectively referred to as component (A)), (B1) the organohydrogenpolysiloxane represented by the formula (13) above in an amount such that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A) was 1.5, 0.01 parts of the (C) catalyst, and (D) the organosilicon compound represented by the formula (15) above in an amount such that the sum of the hydrosilyl groups in component (D) to the total number of alkenyl groups in component (A) was 0.2 (3 parts per 100 parts of the combined components (A) and (B)). The mixture was thoroughly stirred. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0070] Comparative Example 2 50 parts of the organopolysiloxane (A1-1) represented by the above formula (5) and 50 parts of the branched-chain phenylmethylpolysiloxane (A2-1) (hereinafter collectively referred to as component (A)), (B1) an amount such that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A) of the organohydrogenpolysiloxane represented by the above formula (13) is 0.2, and (B2) an organohydrogenpolysiloxane represented by the above formula (14): such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A) was 0.1, 0.01 part of the (C) catalyst, and (D) an organosilicon compound represented by formula (15) in an amount such that the sum of hydrosilyl groups in component (D) to the total number of alkenyl groups in component (A) was 0.1 (0.2 part per 100 parts of components (A) and (B) combined), and the mixture was thoroughly stirred to prepare a curable organopolysiloxane composition. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0071] Comparative Example 3 50 parts of organopolysiloxane (A1-1) represented by the above formula (5), (B1) an amount such that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A1-1) of the organohydrogenpolysiloxane represented by the above formula (13) is 1.5, (B2) an amount such that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A1-1) of the organohydrogenpolysiloxane represented by the above formula (14) is 1.5, A curable organopolysiloxane composition was prepared by adding an amount such that the ratio of the number of hydrosilyl groups in component B2) was 5.0, 0.01 part of the above (C) catalyst, and an amount such that the sum of the hydrosilyl groups in component (D) relative to the total number of alkenyl groups in component (A1-1) was 0.06 (1 part per 100 parts of the combined total of components (A1-1) and (B)), of an organosilicon compound (D) represented by the above formula (15). The mixture was thoroughly stirred. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0072] Comparative Example 4 A curable organopolysiloxane composition was prepared by adding 100 parts of organopolysiloxane (A1-1) represented by the formula (5) above, (B2) in an amount such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A1-1) of the organohydrogenpolysiloxane represented by the formula (14) above was 1.5, 0.01 part of the (C) catalyst, and (D) in an amount such that the sum of the hydrosilyl groups in component (D) to the total number of alkenyl groups in component (A1-1) was 0.8 (1 part per 100 parts of components (A1-1) and (B) combined). The mixture was thoroughly stirred. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0073] Comparative Example 5 A curable organopolysiloxane composition was prepared by adding 50 parts of the organopolysiloxane (A1-2) represented by the formula (6) above, 50 parts of the branched-chain methylpolysiloxane (A2-2) above (hereinafter collectively referred to as component (A)), (B1) in an amount such that the ratio of the number of hydrosilyl groups in component (B1) to the total number of alkenyl groups in component (A) of the organohydrogenpolysiloxane represented by the formula (13) above is 2.0, (B2) in an amount such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A) of the organohydrogenpolysiloxane represented by the formula (14) above is 0.5, and 0.01 part of the (C) catalyst above, and stirring thoroughly. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0074] Comparative Example 6 A curable organopolysiloxane composition was prepared by adding 50 parts of the organopolysiloxane (A1-2) represented by the formula (6) above, 50 parts of the branched-chain methylpolysiloxane (A2-2) represented by the formula (6) above (hereinafter collectively referred to as component (A)), (B2) the organohydrogenpolysiloxane represented by the formula (8) above in an amount such that the ratio of the number of hydrosilyl groups in component (B2) to the total number of alkenyl groups in component (A) was 1.0, 0.01 parts of the (C) catalyst, and (D) the organosilicon compound represented by the formula (15) above in an amount such that the sum of the hydrosilyl groups in component (D) to the total number of alkenyl groups in component (A) was 0.2 (3 parts per 100 parts of the combined components (A) and (B)). The mixture was thoroughly stirred. The resulting composition was heat-molded at 120° C. for 4 hours to form a cured product (120 mm×110 mm×1 mm), and the following physical properties were measured. The results are shown in Table 1.

[0075] The physical properties of the compositions prepared in the examples and comparative examples and their cured products were measured by the following methods.

[0076] (1) Appearance Each composition was cured at 120°C for 4 hours, and the color and transparency of the resulting cured product (thickness 1 mm) were visually inspected.

[0077] (2) Properties The fluidity of each composition before curing was confirmed. 50 g of the composition was added to a 100 ml glass bottle, which was then turned on its side and left to stand at 25°C for 10 minutes. If the resin flowed out during this time, it was considered to be in a liquid state.

[0078] (3) Viscosity The viscosity of each composition before curing at 25°C was measured by the method described in JIS K 7117-1:1999.

[0079] (4) Refractive index The refractive index of each composition before curing was measured at 25°C using a digital refractometer RX-9000α manufactured by ATAGO for light with a wavelength of 589 nm.

[0080] (5) Hardness (Type A) Each composition was cured at 120°C for 4 hours, and the hardness of the resulting cured product was measured using a Durometer A hardness tester in accordance with JIS K 6249:2003.

[0081] (6) Adhesiveness 0.25 g of each composition was placed on a 180 mm 2 The base area is 45mm on the urethane sheet. 2 The adhesive was then applied so that the adhesive strength was such ... (Judgment criteria) ○: Good adhesion (cohesive failure rate 60% or more) ×: Poor adhesion (less than 60% of the area is cohesively broken)

[0082] (7)Stretchability 0.25 g of each composition was applied to a urethane film measuring 1 cm in width, 10 cm in length, and 50 μm in thickness, with a base area of ​​45 mm 2Ten samples were molded with the coating applied so that the coating was as follows: 10 samples were molded and cured at 120°C for 4 hours. The urethane film was then repeatedly stretched lengthwise up to 30 cm 10 times. After the test, the ratio of samples in which the cured product had detached from the urethane film to the number of samples that remained adhered was calculated to assess the stretchability. (Judgment criteria) ○: The percentage of samples that adhere to the urethane substrate is 80% or more (8 or more out of 10 adhere to the urethane substrate). ×: Less than 80% of the samples adhered to the urethane substrate (more than 8 out of 10 samples detached)

[0083] (8) Results of sealing test of semiconductor elements for wearable devices Using SMC-788SE-AG11 (Shin-Etsu Chemical Co., Ltd., Ag paste), 1mm thick urethane film was applied to a 10cm wide, 10cm long, and 100µm thick urethane film. 3 Ten Si chips of this size were mounted at 0.5 cm intervals and heated at 120°C for 4 hours. Then, 0.1 g of each composition was dispensed, sealed to cover the Si chips, and cured at 120°C for 4 hours. The urethane film was then repeatedly stretched lengthwise to 15 cm 30 times, and the appearance of each composition after curing was observed. The presence or absence of cracks originating from the Si chips was evaluated according to the following criteria. (Crack resistance criteria) ○: No cracks (10 out of 10 samples had no cracks) △: Some cracks occurred (cracks occurred in 1 to 3 samples out of 10) ×: Cracks occurred (cracks occurred in 4 or more samples out of 10)

[0084] [Table 1]

[0085] [Table 2]

[0086] As shown in Table 2, the composition of Comparative Example 1, which did not contain component (B2), yielded a cured product with poor adhesion and stretchability. The composition of Comparative Example 2, in which the ratio of the total number of silicon-bonded hydrogen atoms in components (B) and (D) to the total number of silicon-bonded vinyl groups in component (A) was too low, yielded a cured product with poor adhesion and stretchability. The composition of Comparative Example 3, in which the ratio of the total number of silicon-bonded hydrogen atoms in components (B) and (D) to the total number of silicon-bonded vinyl groups in component (A) was too high, yielded a cured product with poor stretchability and crack resistance. The compositions of Comparative Examples 4 and 6, which did not contain component (B1), yielded cured products with poor adhesion and stretchability. The composition of Comparative Example 5, which did not contain component (D), yielded a cured product with poor adhesion, crack resistance, and stretchability. In contrast, the organopolysiloxane compositions of Examples 1 to 4 were generally transparent and gave cured products having sufficient hardness, excellent adhesion, crack resistance, and stretchability, as shown in Table 1. The organopolysiloxane compositions of Examples 5 and 6, which contained titanium oxide or carbon black, also gave cured products having sufficient hardness, excellent adhesion, crack resistance, and stretchability. [Industrial Applicability]

[0087] The curable organopolysiloxane composition of the present invention has excellent adhesion to urethane resin substrates for wearable devices, and can give cured products that are generally transparent and have sufficient hardness, excellent adhesion, and stretchability.

[0088] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A semiconductor device comprising: a substrate containing a polyurethane resin; a semiconductor element on the substrate containing the polyurethane resin; and a cured product of a curable organopolysiloxane composition, wherein the semiconductor element is encapsulated with the cured product of the curable organopolysiloxane composition, The curable organopolysiloxane composition comprises: (A) an organopolysiloxane having at least two alkenyl groups in each molecule; 100 parts by mass, (B1) an organohydrogenpolysiloxane represented by the following formula (1) or (2): 【Chemical 1】 【Chemistry 2】 (In the formula, R １ and R ２ are each independently a substituted or unsubstituted saturated aliphatic hydrocarbon group or saturated cyclic hydrocarbon group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, provided that R １ and R ２ at least one of the groups is an aromatic hydrocarbon group, x is an integer of 0 to 4, n is an integer of 1 to 3, and s is an integer of 3 to 4, provided that the group does not have an epoxy group. (B2) an organohydrogenpolysiloxane represented by the following formula (3): 【Chemistry 3】 (In the formula, R ３ are each independently a substituted or unsubstituted saturated aliphatic hydrocarbon group or saturated cyclic hydrocarbon group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, y is an integer of 0 to 300, and z is an integer of 5 to 300, provided that they do not contain an epoxy group. (C) a catalytic amount of a platinum group metal catalyst, and (D) an organosilicon compound having 4 to 200 silicon atoms, which has at least one hydrogen atom bonded to a silicon atom and at least one organic group having an epoxy group: 0.01 to 10 parts by mass per 100 parts by mass of the total of the components (A), (B1), and (B2); Including, a curable organopolysiloxane composition, characterized in that the ratio of the total number of hydrosilyl groups in components (B1) and (B2) to the number of alkenyl groups in component (A) is 0.5 to 6, and the ratio of the total number of hydrosilyl groups in components (B1), (B2), and (D) to the number of alkenyl groups in component (A) is 0.55 to 6.5; The semiconductor device.

2. A semiconductor device as described in claim 1, wherein in the curable organopolysiloxane composition, the amount of component (B1) is 5 to 95 parts by mass per 100 parts by mass of the total of components (B1) and (B2).

3. A semiconductor device as described in claim 1, wherein in the curable organopolysiloxane composition, the amount of component (B1) is 60 to 95 parts by mass per 100 parts by mass of the total of components (B1) and (B2).

4. A semiconductor device according to any one of claims 1 to 3, wherein the curable organopolysiloxane composition contains, as component (A), (A1) a linear or branched organopolysiloxane having two or more alkenyl groups having 2 to 10 carbon atoms per molecule and having a viscosity of 10 to 100,000 mPa·s at 25°C measured in accordance with JIS K 7117-1:1999.

5. The curable organopolysiloxane composition further comprises (A2) a resinous organopolysiloxane as the component (A), and the amount of the component (A1) is 5 parts by mass or more per 100 parts by mass of the total of the components (A1) and (A2), The component (A2) contains 30 to 60 mol% of SiO based on the total moles of siloxane units. ４／２ Units, 0 to 30 mol% R ４ SiO ３／２ unit, 0 to 50 mol% of (R ４ ) ２ SiO ２／２ units, and 10 to 70 mol % of (R ４ ) ３ SiO １／２ Units (wherein R ４ are each independently a substituted or unsubstituted alkyl group or cycloalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group or aralkyl group having 6 to 10 carbon atoms), and ４／２ Units and the R ４ SiO ３／２ the sum of the units is 40 mol% or more based on the total moles of all siloxane units, the weight average molecular weight is 2,000 to 10,000, there are at least two silicon atom-bonded alkenyl groups per molecule, the amount of hydroxyl groups bonded to silicon atoms is 0.001 to 1.0 mol / 100g, and the amount of alkoxy groups having 1 to 10 carbon atoms bonded to silicon atoms is 1.0 mol / 100g or less; 5. The semiconductor device according to claim 4.

6. The semiconductor device according to claim 1, wherein in the curable organopolysiloxane composition, the component (D) is represented by the following formula (4): HR ５ ａ R ６ ｂ SiO （４－ａ－ｂ）／２ (4) (In formula (4), R ５ are each independently a substituted or unsubstituted saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated cyclic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms; R ６ are each independently an organic group having 5 to 12 carbon atoms and an epoxy group, and a and b are positive numbers satisfying 0.7≦a≦2.1, 0.08≦b≦1.1, and 0.8≦a+b≦3.0).

7. A semiconductor device described in any one of claims 1 to 6, wherein the curable organopolysiloxane composition further contains an inorganic filler in an amount of 600 parts by mass or less per 100 parts by mass of the total of components (A) to (C).

8. 8. The semiconductor device according to claim 7, wherein the inorganic filler is at least one selected from the group consisting of silica, carbon black, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium carbonate, magnesium oxide, aluminum hydroxide, barium carbonate, magnesium silicate, zinc sulfate, and barium sulfate.

9. A wearable device having a semiconductor device described in any one of claims 1 to 8, wherein the semiconductor element is a semiconductor element for a wearable device, and the semiconductor element for a wearable device is sealed with a cured product of the curable organopolysiloxane composition.

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