Thermosetting silicone composition, die bonding material, and optical semiconductor device

Abstract

The present invention is a thermosetting silicone composition characterized by containing the following components (A)-(D): (A) an organopolysiloxane having an average constituent unit ratio represented by formula (1), (R1 3SiO1 / 2)a(R2 3-nR3 nSiO1 / 2)b(R1 2SiO2 / 2)c(R1SiO3 / 2)d(SiO4 / 2)e …(1), (B) an organic peroxide, (C) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms per molecule, and (D) a platinum group metal catalyst. As a result, provided are: a thermosetting silicone composition that provides a cured product having excellent hardness and die shear strength; a die bonding material comprising said composition; and an optical semiconductor device in which an optical semiconductor element is die-bonded with a cured product of said die bonding material.

Description

Thermosetting silicone composition, die bond material and optical semiconductor device

[0001] The present invention relates to a thermosetting silicone composition, a die bond material comprising the composition, and an optical semiconductor device using a cured product of the die bond material.

[0002] Optical semiconductor elements such as light-emitting diodes (LEDs) have the excellent property of low power consumption, and are therefore used in optical semiconductor devices for outdoor lighting and automotive applications. The optical semiconductor elements in optical semiconductor devices are adhered and fixed to the housing using a die bond material. As LED elements have become increasingly bright and powerful, silicone resins, which have excellent durability, are used as die bond material compositions. The die bond material must hold the element in place during the wire bonding process that follows the die bonding process. If the die bond material is not strong enough, bonding will not be possible, so a highly hard material is generally used.

[0003] As LED chips have become smaller in recent years, die bonds used for bonding are required to exhibit high adhesive strength even in small areas. If the adhesive strength is insufficient, problems such as chip peeling during the wire bonding process and bonding failure occur.

[0004] While silicone resins used as die-bonding materials have a wide variety of curing mechanisms, the most widely used is the addition reaction of SiH groups and alkenyl groups via hydrosilylation using a platinum catalyst. Components that react with platinum catalysts (sulfur compounds, nitrogen compounds, phosphorus compounds, etc.) may be present on the LED package. In such cases, the curing reaction may be inhibited, resulting in reduced hardness and adhesion. Peroxide curing using (meth)acrylic groups and other such groups is also commonly used as a curing mechanism, but peroxide curing consumes radicals due to oxygen, inhibiting the surface curing reaction. In response to this, the use of a thermosetting silicone composition has been proposed, which combines peroxide-based radical curing of (meth)acrylic groups with the addition reaction of SiH groups and aliphatic unsaturated bonds to produce a cured product resistant to reaction inhibition of hydrosilylation (addition) curing and oxygen inhibition of peroxide curing (Patent Document 1). However, die shear strength is insufficient, and materials with higher die shear strength are desired.

[0005] Japanese Patent Application Laid-Open No. 2018-076415

[0006] The present invention has been made in view of the above circumstances, and has as its object to provide a thermosetting silicone composition that gives a cured product that has excellent hardness and die shear strength, a die bond material comprising said composition, and an optical semiconductor device in which an optical semiconductor element is die-bonded with a cured product of said die bond material.

[0007] In order to solve the above problems, the present invention provides a composition comprising the following components (A) to (D): (A) an organopolysiloxane having an average structural unit ratio represented by the following formula (1), (R １ ３ SiO １／２ ) ａ (R ２ ３－ｎ R ３ ｎ SiO １／２ ) ｂ (R １ ２ SiO ２／２ ) ｃ (R １ SiO ３／２ ) ｄ (SiO４／２ ) ｅ ...(1) (wherein, R １ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; R ２ each independently represents an alkenyl group having 2 to 10 carbon atoms; R ３ each independently represents a group represented by the following formula (2), n is a number from 1.5 to 3, and a, b, c, d, and e are numbers that satisfy a≧0, b>0, c≧0, d≧0, and e≧0, with the proviso that d+e>0 and a+b+c+d+e=1. (In the formula, R ４ is a hydrogen atom or a methyl group, and R ５ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; Z １ is an alkylene or oxyalkylene group having 1 to 10 carbon atoms, Z ２ is an alkylene group having 2 to 10 carbon atoms, and m is an integer from 0 to 20. Note that a wavy line represents a bond.) Provided is a thermosetting silicone composition comprising: (B) an organic peroxide; (C) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms per molecule; and (D) a platinum group metal catalyst.

[0008] In the case of the thermosetting silicone composition of the present invention, not only does the addition reaction occur, but the organopolysiloxane with a specific structure having multiple (meth)acrylic groups at its terminals also increases the crosslink density during the curing reaction, making it possible to give a cured product with excellent hardness and die shear strength.

[0009] Furthermore, the thermosetting silicone composition of the present invention is such that R １ is a methyl group, and R ２ is a vinyl group, and R ３ is preferably a group represented by the following formula (3): (In the formula, the wavy line represents a bond.)

[0010] A thermosetting silicone composition of the present invention that contains such component (A) will have superior curability and the die shear strength of the cured product will be superior.

[0011] In the thermosetting silicone composition of the present invention, it is preferable that b in the above formula (1) is a number from 0.05 to 0.2, and n is a number from 2 to 3.

[0012] When the thermosetting silicone composition of the present invention contains this type of component (A), the crosslinking density increases, and the hardness and die shear strength of the cured product can be further improved.

[0013] In the thermosetting silicone composition of the present invention, it is preferable that c and d in the above formula (1) are 0.

[0014] A thermosetting silicone composition of the present invention that contains component (A) can further improve the hardness and die shear strength of the cured product.

[0015] Furthermore, the heat-curable silicone composition of the present invention preferably contains component (E), an organosiloxane having an average structural unit ratio represented by the following formula (4): (R １ ３ SiO １／２ ) ｆ (R ２ R １ ２ SiO １／２ ) ｇ (R ３ R １ ２ SiO １／２ ) ｈ (R １ ２ SiO ２／２ ) ｉ (R １ SiO ３／２ ) ｊ (SiO ４／２ ) ｋ ...(4) (In the formula, R １ , R ２ and R ３is the same as the above formula (1). f, g, h, i, j, and k are numbers that satisfy f≧0, g≧0, h>0, i≧0, j≧0, and k≧0, and f+g+h+i+j+k=1.

[0016] By using this type of component (E) in combination, the die shear strength of the cured product of the thermosetting silicone composition of the present invention can be further improved.

[0017] The present invention provides a die bond material characterized by comprising the thermosetting silicone composition of the present invention.

[0018] A die bond material characterized by comprising the thermosetting silicone composition of the present invention can be suitably used as a die bond material for mounting an LED chip onto a wiring board.

[0019] The present invention also provides a cured silicone product, which is a cured product of the thermosetting silicone composition of the present invention.

[0020] Such a cured silicone product has excellent hardness and die shear strength, and has high adhesive strength to substrates, LED chips, etc., making it particularly useful for die bonding of LED elements, etc.

[0021] Furthermore, the present invention provides an optical semiconductor device characterized by comprising the silicone cured product of the present invention.

[0022] Such optical semiconductor devices are highly reliable because they are die-bonded with the silicone cured product of the present invention, which has excellent hardness and die shear strength and strong adhesive strength to substrates, LED chips, etc.

[0023] As described above, the thermosetting silicone composition of the present invention provides a silicone cured product that exhibits excellent hardness and die shear strength, making it particularly useful as a die-bonding material for use in die-bonding LED elements, etc. Furthermore, in the wire-bonding step that follows the die-bonding step, problems such as chip peeling or bonding failure are unlikely to occur, and optical semiconductor devices in which optical semiconductor elements are die-bonded using this silicone cured product are highly reliable and also offer improved productivity.

[0024] As described above, there has been a need for the development of a thermosetting silicone composition that provides a cured silicone product with excellent hardness and die shear strength, which can be used as a die bonding material for die bonding of LED elements and the like.

[0025] As a result of extensive research into the above-mentioned problems, the present inventors discovered that the above-mentioned problems could be solved by a thermosetting silicone composition that contains components (B), (C), and (D) in addition to component (A) having a specific structure, as described below, and thus completed the present invention.

[0026] That is, the present invention provides a composition comprising the following components (A) to (D): (A) an organopolysiloxane having an average ratio of structural units represented by the following formula (1), (R １ ３ SiO １／２ ) ａ (R ２ ３－ｎ R ３ ｎ SiO １／２ ) ｂ (R １ ２ SiO ２／２ ) ｃ (R １ SiO ３／２ ) ｄ (SiO ４／２ ) ｅ ...(1) (wherein, R １ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; R ２ each independently represents an alkenyl group having 2 to 10 carbon atoms; R ３each independently represents a group represented by the following formula (2), n is a number from 1.5 to 3, and a, b, c, d, and e are numbers that satisfy a≧0, b>0, c≧0, d≧0, and e≧0, with the proviso that d+e>0 and a+b+c+d+e=1. (In the formula, R ４ is a hydrogen atom or a methyl group, and R ５ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; Z １ is an alkylene or oxyalkylene group having 1 to 10 carbon atoms, Z ２ is an alkylene group having 2 to 10 carbon atoms, and m is an integer from 0 to 20. Note that a wavy line represents a bond.) A thermosetting silicone composition comprising: (B) an organic peroxide; (C) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule; and (D) a platinum group metal catalyst.

[0027] The present invention will be described in detail below, but the present invention is not limited thereto.

[0028] [Thermosetting Silicone Composition] The thermosetting silicone composition of the present invention contains the following components (A) to (D), each of which will be described in detail below.

[0029] <Component (A)> Component (A) is an organopolysiloxane having an average structural unit ratio represented by the following formula (1), and is a component for increasing the strength of the cured product and improving the adhesive strength, i.e., die shear strength. (R １ ３ SiO １／２ ) ａ (R ２ ３－ｎ R ３ ｎ SiO １／２ ) ｂ (R １ ２ SiO ２／２ ) ｃ (R １ SiO ３／２ ) ｄ (SiO４／２ ) ｅ ...(1) (wherein, R １ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; R ２ each independently represents an alkenyl group having 2 to 10 carbon atoms; R ３ independently represent a group represented by the following formula (2), n is a number from 1.5 to 3, and a, b, c, d, and e are numbers that satisfy a≧0, b>0, c≧0, d≧0, and e≧0, provided that d+e>0 and a+b+c+d+e=1.) If n is less than 1.5, the crosslink density of the cured product will be low, resulting in inferior die shear strength, which is not preferred. Also, since b>0, R ３ and has a methacrylic group at the end. Furthermore, since d+e>0, this organopolysiloxane has a branched or three-dimensional network structure. (In the formula, R ４ is a hydrogen atom or a methyl group, and R ５ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; Z １ is an alkylene or oxyalkylene group having 1 to 10 carbon atoms, Z ２ is an alkylene group having 2 to 10 carbon atoms, and m is an integer from 0 to 20. The wavy line represents a bond.

[0030] In the above formula (1), R １ The monovalent hydrocarbon group having 1 to 12 carbon atoms, which does not have an aliphatic unsaturated bond and which may be substituted with a halogen atom, is not particularly limited as long as it does not have an aliphatic unsaturated bond, and examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl and cyclopentyl groups, aryl groups such as phenyl, tolyl, and xylyl groups, aralkyl groups such as benzyl and phenylethyl groups, and halogenated hydrocarbon groups such as chloromethyl, chloropropyl, and chlorocyclohexyl groups. An alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group is more preferred.

[0031] In the above formula (1), R ２ Examples of the alkenyl group having 2 to 10 carbon atoms represented by the formula (I) include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and an octenyl group, and preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably a vinyl group.

[0032] R in the above formula (1) ３ In the group represented by the above formula (2), Z １ Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, an isobutylene group, a dimethylethylene group, a pentamethylene group, a 2,2-dimethyltrimethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decylene (decamethylene) group, and examples of the oxyalkylene group having 1 to 10 carbon atoms include an oxyethylene group and an oxypropylene group. Of these, a trimethylene group is preferred.

[0033] In the above formula (2), Z ２ Examples of the alkylene group having 2 to 10 carbon atoms include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, an isobutylene group, a dimethylethylene group, a pentamethylene group, a 2,2-dimethyltrimethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decylene (decamethylene) group. An alkylene group having 2 to 6 carbon atoms is preferred, and an ethylene group is more preferred.

[0034] In the above formula (2), R ５ The monovalent hydrocarbon group having 1 to 12 carbon atoms and no aliphatic unsaturated bond, which may be substituted with a halogen atom, is represented by the above R １ Examples of the methyl group include the same groups as those exemplified as above, and a methyl group is preferred.

[0035] In the above formula (2), m is an integer of 0 to 20, preferably an integer of 0 to 10, and more preferably 0 or 1. If m is an integer exceeding 20, the hardness of the cured product may be reduced, which is not preferred.

[0036] R ３Specific examples of the group represented by the formula (3) include those represented by the following formulas (3) and (5) to (7), and the group represented by the following formula (3) is particularly preferred. (In the formula, the wavy line represents a bond.)

[0037] In terms of curability and the hardness and die shear strength of the cured product, a, b, c, d, e, and n in formula (1) are preferably in the following ranges.

[0038] a is preferably a number from 0 to 0.65, and more preferably a number from 0.10 to 0.50.

[0039] b is preferably a number from 0.05 to 0.20, and more preferably a number from 0.07 to 0.14.

[0040] c is preferably a number of 0 to 0.30, and more preferably 0.

[0041] d is preferably a number of 0 to 0.60, and more preferably 0.

[0042] The value e is preferably a number from 0.05 to 0.90, and more preferably a number from 0.40 to 0.70.

[0043] The sum of d and e is preferably a number between 0.05 and 0.90, and more preferably a number between 0.40 and 0.70.

[0044] Preferably, n is a number of 2 or 3.

[0045] Component (A) can be obtained, for example, as the product of a hydrosilylation reaction between component (a), an organopolysiloxane having an average structural unit ratio represented by the following formula (8), and component (b), a compound represented by the following general formula (9), using a platinum group metal as a catalyst. (R １ ３ SiO １／２ ) ａ (R ２ ３ SiO １／２ ) ｂ (R １ ２ SiO ２／２ )ｃ (R １ SiO ３／２ ) ｄ (SiO ４／２ ) ｅ ...(8) (wherein, R １ , R ２ , a, b, c, d and e are the same as in formula (1) above. (In the formula, R ４ , R ５ , Z １ and m are the same as in the above formula (2).

[0046] Component (b) is preferably a siloxane compound represented by the following formula (10), which can be obtained as the product of a hydrosilylation reaction between allyl methacrylate and 1,1,3,3-tetramethyldisiloxane using a platinum group metal as a catalyst.

[0047] Examples of platinum group metal catalysts used in the hydrosilylation reaction between component (a) and component (b) and in the hydrosilylation reaction when obtaining component (b) include platinum metal-supported carbon powder, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of platinum and vinylsiloxanes such as divinyltetramethyldisiloxane, complexes of chloroplatinic acid and olefins, platinum-based catalysts such as platinum bisacetoacetate, palladium-based catalysts, and rhodium-based catalysts, and among these, those containing platinum are preferred from the viewpoint of reactivity.Furthermore, the addition reaction conditions, the use of solvents, etc. are not particularly limited and may be the usual ones.

[0048] Specific examples of component (A) include, but are not limited to, those represented by the following formula: Me is a methyl group, Vi is a vinyl group, and MA is a group represented by the above formula (3). (Me ３ SiO １／２ ) ０．４ ((Vi) ０．６ (MA) ２．４ SiO １／２ ) ０．０７ (SiO ４／２ ) ０．５３ (Me ３ SiO １／２ )０．３３ ((Vi) ０．６ (MA) ２．４ SiO １／２ ) ０．１４ (SiO ４／２ ) ０．５３ (Me ３ SiO １／２ ) ０．２ (MA ３ SiO １／２ ) ０．２ (SiO ４／２ ) ０．６ (Me ３ SiO １／２ ) ０．２ ((Vi) １．５ (MA) １．５ SiO １／２ ) ０．２ (SiO ４／２ ) ０．６ (Me ３ SiO １／２ ) ０．２ ((Vi)(MA) ２ SiO １／２ ) ０．２ (SiO ４／２ ) ０．６ ,

[0049] The organopolysiloxane of component (A) preferably has a weight-average molecular weight in the range of 500 to 100,000. The weight-average molecular weight is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0050] The component (A) may be used alone or in combination of two or more types.

[0051] <Component (B)> Component (B) is an organic peroxide that generates radicals upon heating. Component (B) is not particularly limited as long as it is capable of polymerizing the (meth)acrylic groups of component (A) through a radical reaction, and examples thereof include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxydicarbonates, peroxyketals, hydroperoxides, and silyl peroxides.

[0052] The present invention achieves excellent hardness and die shear strength by both curing through peroxide radical polymerization of component (B) and addition curing through component (D).

[0053] Examples of diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoylperoxytoluene, and benzoyl peroxide.

[0054] Examples of peroxyesters include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,6-bis(t-butylperoxycarbonyloxy)hexane, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, and t-hexyl peroxy-2-ethylhexanone. t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, t-butylperoxyacetate, and bis(t-butylperoxy)hexahydroterephthalate. These may be used alone or in combination of two or more.

[0055] Examples of dialkyl peroxides include α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and t-butylcumyl peroxide.

[0056] Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, bis(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, and bis(3-methyl-3-methoxybutylperoxy)dicarbonate.

[0057] Examples of peroxyketals include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-(t-butylperoxy)cyclododecane, and 2,2-bis(t-butylperoxy)decane.

[0058] Examples of hydroperoxides include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

[0059] Examples of silyl peroxides include t-butyltrimethylsilyl peroxide, bis(t-butyl)dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis(t-butyl)divinylsilyl peroxide, tris(t-butyl)vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis(t-butyl)diallylsilyl peroxide, and tris(t-butyl)allylsilyl peroxide.

[0060] Taking into consideration the temperature at which the thermosetting silicone composition is thermally cured and storage stability, component (B) preferably has a 10-hour half-life temperature in benzene of at least 40° C., and more preferably at least 60° C. There is no particular upper limit, but it is usually no higher than 200° C.

[0061] The component (B) can be used alone or in appropriate combination of two or more types, and these may be diluted with a solvent before use.

[0062] The amount of component (B) to be blended may be any amount sufficient to initiate the crosslinking reaction upon heating, but from the viewpoints of curability and storage stability of the composition, the amount is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A).

[0063] <Component (C)> The organohydrogenpolysiloxane of component (C) functions as a crosslinking agent that reacts with the alkenyl groups and (meth)acrylic groups contained in component (A) via a hydrosilylation reaction.

[0064] Component (C) has at least two silicon-bonded hydrogen atoms (i.e., Si—H groups) per molecule, preferably 2 to 200, more preferably 3 to 100, and particularly preferably 4 to 50. Fewer than two are undesirable because crosslinking cannot be formed. Furthermore, the Si—H groups may be located at either the molecular chain terminals or non-terminal positions, or may be located at both positions.

[0065] The molecular structure of the organohydrogenpolysiloxane of component (C) may be linear, cyclic, branched, or a three-dimensional network structure, but the number of silicon atoms in one molecule is preferably 2 to 300, and more preferably 3 to 200.

[0066] Examples of the organohydrogenpolysiloxane of component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(hydrogendimethylsiloxy)methylsilane, tris(hydrogendimethylsiloxy)phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, methylhydrogenpolysiloxane capped at both ends with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer capped at both ends with trimethylsiloxy groups, dimethylpolysiloxane capped at both ends with dimethylhydrogensiloxy groups, methylhydrogenpolysiloxane capped at both ends with dimethylhydrogensiloxy groups, Dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both-end trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both-end trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-end trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both-end dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both-end dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / methylphenylsiloxane copolymer, (CH ３ ) ２ HSiO １／２ Units and (CH ３ ) ３ SiO １／２ Units and SiO ４／２ a copolymer consisting of (CH ３ ) ２ HSiO １／２ Units and SiO ４／２ a copolymer consisting of (CH ３ ) ２ HSiO １／２ Units and SiO ４／２ Units and (C ６ H ５ ) ３ SiO１／２ and copolymers consisting of units.

[0067] Specific examples of the component (C) include those represented by the following formula: (In the formula, the siloxane units may be arranged in any order.)

[0068] (In the formula, the siloxane units may be arranged in any order.)

[0069] (In the formula, the siloxane units may be arranged in any order.)

[0070] (In the formula, the siloxane units in the parentheses may be arranged in any order.)

[0071] The organohydrogenpolysiloxane of component (C) may use either a single compound, or a combination of two or more different compounds.

[0072] The amount of component (C) to be blended is such that the number of silicon-bonded hydrogen atoms (Si—H groups) in component (C) is preferably 0.5 to 5.0 times, and more preferably 0.7 to 3.0 times, the total number of alkenyl groups and (meth)acrylic groups in component (A).Within this range, crosslinking proceeds sufficiently, and a cured product with excellent surface curability and hardness can be obtained.

[0073] <Component (D)> The platinum group metal catalyst of component (D) is a component for promoting and accelerating the hydrosilylation reaction between components (A) and (C). Examples of platinum group metal catalysts include the same catalysts as those exemplified for use in the addition reaction of components (a) and (b) in component (A), and among these, those containing platinum are preferred.

[0074] The platinum group metal catalyst used in the synthesis of component (A) may be used as is and may remain in the composition, or may be further added to the composition.

[0075] The component (D) may use either a single compound or a combination of two or more compounds.

[0076] The amount of component (D) to be blended may be any amount that is effective as a catalyst, but is preferably an amount that results in a platinum group metal content of 0.01 to 500 ppm, and more preferably 0.1 to 100 ppm, relative to the total mass of the composition. Within such a range, the hydrosilylation reaction can be more effectively promoted.

[0077] <Component (E)> The thermosetting silicone composition of the present invention preferably further contains component (E), an organosiloxane having an average structural unit ratio represented by the following formula (4). By using such component (E) in combination, the die shear strength of the cured product can be further improved. (R １ ３ SiO １／２ ) ｆ (R ２ R １ ２ SiO １／２ ) ｇ (R ３ R １ ２ SiO １／２ ) ｈ (R １ ２ SiO ２／２ ) ｉ (R １ SiO ３／２ ) ｊ (SiO ４／２ ) ｋ ...(4) (In the formula, R １ , R ２ and R ３ is the same as the above formula (1). f, g, h, i, j, and k are numbers that satisfy f≧0, g≧0, h>0, i≧0, j≧0, k≧0, and f+g+h+i+j+k=1.

[0078] The value f is preferably a number from 0 to 0.65, and more preferably a number from 0.10 to 0.50.

[0079] The letter g is preferably a number from 0 to 0.65, and more preferably a number from 0.01 to 0.50.

[0080] h is preferably a number from 0.01 to 0.65, and more preferably a number from 0.05 to 0.50.

[0081] i is preferably a number from 0 to 0.30, and more preferably 0.

[0082] j is preferably a number from 0 to 0.60, and more preferably 0.

[0083] k is preferably a number from 0.05 to 0.90, and more preferably a number from 0.40 to 0.70.

[0084] Specific examples of component (E) include, but are not limited to, organopolysiloxanes having an average structural unit ratio represented by the following formula:

[0085] (Me ３ SiO １／２ ) ０．４ ((Vi)(Me) ２ SiO １／２ ) ０．０１４ ((MA) (Me) ２ SiO １／２ ) ０．０５６ (SiO ４／２ ) ０．５３ (Me ３ SiO １／２ ) ０．２ ((Vi)(Me) ２ SiO １／２ ) ０．１ ((MA) (Me) ２ SiO １／２ ) ０．１ (SiO ４／２ ) ０．６ (Me ３ SiO １／２ ) ０．２ ((MA) (Me) ２ SiO １／２ ) ０．２ (SiO ４／２ ) ０．６ ((Vi)(Me) ２ SiO １／２ ) ０．２５ ((MA) (Me) ２ SiO １／２ ) ０．２５ (MeSiO ３／２ ) ０．５ ((MA) (Me) ２ SiO １／２ )０．５ (SiO ４／２ ) ０．５

[0086] The component (E) may use either a single compound or a combination of two or more compounds.

[0087] When component (E) is used, the blending amount is preferably 10 to 80 mass %, and more preferably 20 to 70 mass %, based on the total mass of components (A) and (E).

[0088] <Other Components> In addition to the above components (A) to (E), the thermosetting silicone composition of the present invention may also contain other components, such as fillers, adhesion improvers, radical reaction inhibitors, and addition reaction inhibitors, depending on the intended purpose.

[0089] Specific examples of fillers include inorganic fillers such as finely powdered silica, crystalline silica, hollow fillers, and silsesquioxanes; fillers obtained by subjecting the surface of these fillers to hydrophobic treatment with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low-molecular-weight siloxane compounds; silicone rubber powder; and silicone resin powder.

[0090] Among these, the specific surface area measured by the BET method is preferably 50 m ２ / g or more, more preferably 120 to 400m ２ / g, and examples of finely powdered silica include fumed silica (dry silica), precipitated silica (wet silica), and gel-process silica (wet silica) with a high specific surface area, with fumed silica being particularly preferred.

[0091] The finely powdered silica may be a finely powdered silica whose surface has been hydrophobized with a surface treatment agent such as a (usually hydrolyzable) organic silicon compound, for example, chlorosilane, alkoxysilane, or organosilazane.

[0092] When a filler is used, the amount blended is preferably 1 to 50 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the total of components (A) and (E).

[0093] Examples of the radical reaction inhibitor include phenol-based radical reaction inhibitors such as dibutylhydroxytoluene, and amine-based radical reaction inhibitors such as diphenylamine derivatives.

[0094] Examples of the addition reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine, nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole, sulfur-containing compounds, acetylene compounds, hydroperoxy compounds, and maleic acid derivatives, and specific examples thereof include 3-methyl-1-dodecyn-3-ol, 1-ethynylcyclohexanol, and 3,5-dimethyl-1-hexyn-3-ol.

[0095] The degree of curing inhibition effect of these reaction inhibitors varies depending on the chemical structure of the reaction inhibitor, so it is desirable to adjust the amount of these reaction inhibitors to an optimal amount for each reaction inhibitor used. Usually, the amount is preferably 0.01 to 10% by mass based on the mass of the total composition.

[0096] From the perspective of imparting self-adhesive properties to the curable silicone composition of the present invention, the adhesion improver may be an organosilicon compound such as a silane or siloxane, or a non-silicon organic compound, which contains a functional group that imparts adhesiveness.

[0097] Specific examples of functional groups that impart adhesiveness include vinyl groups bonded to silicon atoms, alkenyl groups such as allyl groups, or hydrogen atoms; epoxy groups bonded to silicon atoms via carbon atoms (e.g., γ-glycidoxypropyl group, β-(3,4-epoxycyclohexyl)ethyl group, etc.); acryloxy groups (e.g., γ-acryloxypropyl group, etc.); methacryloxy groups (e.g., γ-methacryloxypropyl group, etc.); and alkoxysilyl groups (e.g., trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, etc., bonded to silicon atoms via alkylene groups which may contain 1 to 2 ester structures, urethane structures, or ether structures).

[0098] Specific examples of such organosilicon compounds include, but are not limited to, compounds represented by the following structural formulas: (In the formula, the siloxane units may be arranged in any order.) (In the formula, the siloxane units may be arranged in any order.)

[0099] Examples of non-silicon organic compounds include unsaturated carboxylic acid allyl esters such as acrylic acid, methacrylic acid, and vinylacetic acid; aromatic carboxylic acid allyl esters such as benzoic acid allyl ester, phthalic acid diallyl ester, and pyromellitic acid tetraallyl ester; saturated fatty acid allyl esters such as acetate allyl ester, propionate allyl ester, butyrate allyl ester, valerate allyl ester, and laurate allyl ester; and triallyl isocyanurate.

[0100] When an adhesion improver is used, the blending amount is preferably 1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the combined total of components (A) and (E). With blending amounts like these, the thermosetting silicone composition of the present invention and its cured product effectively improve adhesion to substrates and are less likely to become discolored.

[0101] The thermosetting silicone composition of the present invention can be produced by mixing the above-mentioned components using a known mixing method, for example, a mixer, a roll, etc. Furthermore, the thermosetting silicone composition of the present invention preferably has a viscosity, measured at 25°C using a rotational viscometer, for example, an E-type viscometer, of 5 to 100 Pa s, particularly 20 to 50 Pa s. A viscosity in this range improves workability in die bonding (transfer method).

[0102] [Silicone Cured Product] The present invention further provides a silicone cured product, characterized by being a cured product of the thermosetting silicone composition of the present invention. The thermosetting silicone composition of the present invention can be cured by a known curing method under known curing conditions. Specifically, the composition can be cured by heating at a temperature of typically 80 to 200°C, preferably 100 to 160°C. The heating time may be about 0.5 minutes to 5 hours, and particularly about 1 minute to 3 hours. This can be selected appropriately taking into account the balance between working conditions, productivity, and the heat resistance of the light-emitting element and the housing.

[0103] The thermosetting silicone composition of the present invention can provide a cured product that overcomes the problem of surface uncuring due to oxygen inhibition by undergoing both peroxide curing of the (meth)acrylic groups and an addition reaction of the SiH groups with unsaturated groups. Furthermore, the thermosetting silicone composition of the present invention can provide a cured product that has excellent adhesive strength and high hardness.

[0104] [Die Bond Material] The present invention also provides a die bond material comprising the thermosetting silicone composition of the present invention, particularly a die bond material that can be used to connect a semiconductor element to a wiring board.

[0105] The thermosetting silicone composition of the present invention can be suitably used to secure an LED chip to a package, and can also be suitably used for other optical semiconductor elements such as organic electroluminescent devices (organic EL), laser diodes, and LED arrays.

[0106] The thermosetting silicone composition of the present invention can provide a cured silicone product with excellent hardness and die shear strength. Therefore, a die bond material made from the thermosetting silicone composition of the present invention can be suitably used as a die bond material for mounting an LED chip to a wiring board.

[0107] The method for applying the die bond material is not particularly limited, and examples thereof include spin coating, printing, and compression molding. The thickness of the die bond material may be appropriately selected and is usually 5 to 50 μm, particularly 10 to 30 μm. For example, the die bond material may be applied using a dispenser at a temperature of 23°C and a pressure of 0.5 to 5 kgf / cm. ２ It can be easily applied by discharging it at a pressure of 1000 kJ / min. It can also be easily applied by using a stamping device to transfer a predetermined amount of die bond material onto a substrate.

[0108] The mounting method for the optical semiconductor element is not particularly limited, and examples include die bonders. Factors that determine the thickness of the die bond material include the viscosity of the die bond material, as well as the pressure load, pressure bonding time, and pressure bonding temperature of the optical semiconductor element. These conditions can be appropriately selected depending on the external shape of the optical semiconductor element and the desired thickness of the die bond material. The pressure load is generally 1 gf or more and 1 kgf or less. Preferably, it is 10 gf or more and 100 gf or less. A pressure load of 1 gf or more can sufficiently bond the die bond material. Furthermore, using a pressure load of 1 kgf or less does not damage the light-emitting layer on the surface of the optical semiconductor element. The pressure bonding time can be appropriately selected taking into account the productivity of the process, and is generally more than 0 msec and 1 sec or less. Preferably, it is 1 msec or more and 30 msec. A pressure of 1 sec or less is preferable in terms of productivity. There are no particular restrictions on the compression temperature, and it may be in accordance with the temperature range in which the die bond material is used, but it is generally preferable that it be 15°C or higher and 100°C or lower. If the compression stage of the die bonder does not have a heating facility, it may be used in a temperature range around room temperature. If the temperature is 15°C or higher, the viscosity of the die bond material does not become too high, and sufficient compression bonding can be achieved. If the temperature is 100°C or lower, the die bond material does not begin to harden, and the desired thickness of the die bond material can be achieved.

[0109] [Optical semiconductor device] The present invention further provides an optical semiconductor device characterized by comprising the above-described silicone cured product of the present invention.

[0110] The optical semiconductor device of the present invention is obtained by curing a die bond material made from the thermosetting silicone composition of the present invention, and is an optical semiconductor device having a cured product with excellent hardness and die shear strength.

[0111] The optical semiconductor device of the present invention can be produced by applying a die bond material made from the thermosetting silicone composition of the present invention to a substrate, and then die bonding an optical semiconductor element thereto using a conventional method.

[0112] The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these. The molecular weights are weight-average molecular weights calculated using standard polystyrene standards by gel permeation chromatography (GPC). The viscosity at 25°C is measured using a rotational viscometer.

[0113] The abbreviations for each siloxane unit have the following meanings: Me represents a methyl group, Vi represents a vinyl group, and MA represents a group represented by the following formula (3). (In the formula, the wavy line represents a bond.) M: (CH ３ ) ３ SiO １／２ M Ｖｉ :(CH ２ =CH)(CH ３ ) ２ SiO １／２ M ３Ｖｉ :(CH ２ =CH) ３ SiO １／２ D: (CH ３ ) ２ SiO ２／２ D Ｈ : H(CH ３ ) SiO ２／２ D Ｖｉ : (CH=CH ２ ) (CH ３ )SiOT:(CH ３ ) SiO ３／２ T Ｖｉ :(CH ２ =CH)SiO ３／２ Q: SiO ４／２

[0114] Synthesis Example 1 A 500 mL four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer was charged with 100 mL of ammonium hydroxide, 100 mL of ammonium hydroxide, and 100 mL of ammonium hydroxide. ０．４ M ３Ｖｉ ０．０７ Q ０．５３144.93 g of a 34.5 mass % xylene solution of an organopolysiloxane having a molecular weight of 3,300 and 29.80 g of the siloxane compound represented by the above formula (10) were added, and the temperature was raised to 70° C. with stirring. A platinum group metal catalyst was added to the mixture so that the concentration was 3 ppm by mass, and the mixture was stirred at 95° C. for 4 hours, after which it was cooled to room temperature, activated carbon was added, the mixture was stirred for 30 minutes, filtered, and concentrated under reduced pressure at 110° C. and 1,000 Pa or less for 2 hours to give a product with a viscosity of 1,316 mPa s and an average constitutional unit ratio (Me ３ SiO １／２ ) ０．４ ((Vi) ０．６ (MA) ２．４ SiO １／２ ) ０．０７ (SiO ４／２ ) ０．５３ As a result, an organopolysiloxane (A-1) having a weight average molecular weight of 4,100 was obtained.

[0115] Synthesis Example 2 A 500 mL four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer was charged with 100 mL of ammonium hydroxide, 100 mL of ammonium hydroxide, and 100 mL of ammonium hydroxide. ０．３２ M ３Ｖｉ ０．１４ Q ０．５３ 123.46 g of a 40.5% xylene solution of organopolysiloxane having a molecular weight of 3,900 and 59.08 g of the siloxane compound represented by the above formula (10) were added, and the temperature was raised to 70° C. with stirring. A platinum group metal catalyst was added to the mixture so that the concentration was 3 ppm by mass, and the mixture was stirred at 95° C. for 4 hours, after which it was cooled to room temperature, activated carbon was added, the mixture was stirred for 30 minutes, filtered, and concentrated under reduced pressure at 110° C. and 1,000 Pa or less for 2 hours to give a product with a viscosity of 505 mPa s and an average constitutional unit ratio (Me ３ SiO １／２ ) ０．３３ ((Vi) ０．６ (MA) ２．４ SiO １／２ ) ０．１４ (SiO ４／２ ) ０．５３ As a result, organopolysiloxane (A-2) having a weight average molecular weight of 4,700 was obtained.

[0116] Synthesis Example 3 A 2000 mL four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer was charged with 1000 mL of ammonium hydroxide, ... and 1000 mL of ammonium hydroxide. ０．４ M Ｖｉ０．０７ Q ０．５３ 800 g of a 51.5% xylene solution of organopolysiloxane having a molecular weight of 5,300 and 71.89 g of the siloxane compound represented by the above formula (10) were added, and the temperature was raised to 70° C. with stirring. A platinum group metal catalyst was added thereto so as to give a concentration of 3 ppm by mass, and the mixture was stirred at 95° C. for 2 hours, then cooled to room temperature, activated carbon was added, and the mixture was stirred for 30 minutes, filtered, and the average constitutional unit ratio (Me ３ SiO １／２ ) ０．４ ((Vi)(Me) ２ SiO １／２ ) ０．０１４ ((MA) (Me) ２ SiO １／２ ) ０．０５６ (SiO ４／２ ) ０．５３ Thus, a 55.4% xylene solution of organopolysiloxane (E-1) was obtained.

[0117] Synthesis Example 4 A 500 mL four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer was charged with 100 mL of acetic acid, 100 mL of acetic acid, and 100 mL of acetic acid. Ｖｉ ０．５ T ０．５ 100 g of organopolysiloxane having a molecular weight of 3,700 was added, and the temperature was raised to 70° C. with stirring. A platinum group metal catalyst was added to the mixture so that the concentration was 3 ppm by mass, and 68.8 g of the siloxane compound represented by formula (10) was added dropwise with stirring. After stirring at 95° C. for 3 hours, the mixture was cooled to room temperature, activated carbon was added, and the mixture was stirred for 30 minutes, followed by filtration. A viscosity of 100 mPa s and an average structural unit ratio ((Vi)(Me)) was obtained. ２ SiO １／２ ) ０．２５ ((MA) (Me) ２ SiO １／２ ) ０．２５ (MeSiO ３／２ ) ０．５ As a result, organopolysiloxane (E-2) having a molecular weight of 2,100 was obtained.

[0118] Examples 1 to 5, Comparative Examples 1 to 3 Thermosetting silicone compositions were prepared by mixing the following components in the amounts shown in Table 1. The numerical values ​​for each component in Table 1 represent parts by mass. The [Si-H] / [Vi] value represents the ratio (molar ratio) of the number of hydrogen atoms bonded to silicon atoms (Si-H groups) in components (C) and (H-3) to the total number of alkenyl groups and (meth)acrylic groups in components (A) and (E).

[0119] Component (A): (A-1) Organopolysiloxane obtained in Synthesis Example 1 (A-2) Organopolysiloxane obtained in Synthesis Example 2

[0120] Component (B): (B-1) 70% by mass solution of 1,6-bis(t-butylperoxycarbonyloxy)hexane in tributyl acetate citrate (manufactured by Kayaku Nouryon Co., Ltd., trade name: Kayalene 6-70, 10-hour half-life temperature at 0.2 mol / L in benzene: 97°C)

[0121] (C) Component: (C-1)M ２ D Ｈ ８ Methylhydrogenpolysiloxane (C-2)M ２ D ２８ D Ｈ ７０ Methylhydrogenpolysiloxane represented by

[0122] Component (D): (D-1) Toluene solution of reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane (platinum content: 0.5% by mass)

[0123] Component (E): (E-1) 55.4% xylene solution of organopolysiloxane obtained in Synthesis Example 3 (E-2) Organopolysiloxane obtained in Synthesis Example 4

[0124] (F) Filler: (F-1) Fumed silica (manufactured by Tokuyama Corporation, product name: Reolosil DM-30S)

[0125] Component (G): Reaction inhibitor (G-1) 3-methyl-1-dodecyn-3-ol

[0126] Component (H): Adhesion improver (H-1) triallyl isocyanurate (H-2) 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) (H-3) compound represented by the following structural formula

[0127] The resulting thermosetting silicone composition was evaluated as follows, and the results are shown in Table 2.

[0128] [Hardness] The resulting thermosetting silicone composition was molded to a thickness of 2 mm and cured for 2 hours at 120° C. After that, the hardness was measured using a Durometer Type D manufactured by Ueshima Seisakusho.

[0129] [Die Shear Strength] The obtained thermosetting silicone composition was quantitatively transferred by stamping using a die bonder (AD-830 manufactured by ASM Corporation) onto the silver-plated electrode portion of an SMD5050 package (I-CHIUN PRECSION INDUSTRY CO., resin portion: polyphthalamide), and an optical semiconductor element (0.25 × 0.25 mm) was mounted thereon. The produced package was heated in an oven at 120°C for 4 hours to cure the thermosetting silicone composition, and then the die shear strength was measured using a bond tester (Series 4000 manufactured by Dage Corporation).

[0130]

[0131]

[0132] As shown in Table 2, the cured silicone products obtained from the thermosetting silicone compositions of Examples 1 to 5, which contained component (A) with a specific structure, exhibited excellent hardness and die shear strength at 25°C and 150°C.

[0133] On the other hand, the silicone cured products obtained from the thermosetting silicone compositions of Comparative Examples 1 to 3, which did not contain component (A), had low crosslink density and inferior die shear strength. Furthermore, it was also not possible to increase die shear strength in Comparative Example 2, in which component (C) in Comparative Example 1 was changed, or in Comparative Example 3, in which the amount of peroxide (component (B-1)) was increased.

[0134] As described above, the thermosetting silicone composition of the present invention provides a cured silicone product that exhibits excellent hardness and die shear strength, and is therefore particularly useful as a die-bonding material for use in die-bonding LED elements and the like.

[0135] This specification encompasses the following aspects: [1]: The following components (A) to (D): (A) an organopolysiloxane having an average structural unit ratio represented by the following formula (1), (R １ ３ SiO １／２ ) ａ (R ２ ３－ｎ R ３ ｎ SiO １／２ ) ｂ (R １ ２ SiO ２／２ ) ｃ (R １ SiO ３／２ ) ｄ (SiO ４／２ ) ｅ ...(1) (wherein, R １ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; R ２ each independently represents an alkenyl group having 2 to 10 carbon atoms; R ３ each independently represents a group represented by the following formula (2), n is a number from 1.5 to 3, and a, b, c, d, and e are numbers that satisfy a≧0, b>0, c≧0, d≧0, and e≧0, with the proviso that d+e>0 and a+b+c+d+e=1. (In the formula, R ４ is a hydrogen atom or a methyl group, and R ５ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; Z １ is an alkylene or oxyalkylene group having 1 to 10 carbon atoms, Z ２is an alkylene group having 2 to 10 carbon atoms, and m is an integer of 0 to 20. The wavy line represents a bond.) A thermosetting silicone composition comprising: (B) an organic peroxide; (C) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule; and (D) a platinum group metal catalyst. [2]: R in the above formula (1) １ is a methyl group, and R ２ is a vinyl group, and R ３ is a group represented by the following formula (3): (In the formula, the wavy line represents a bond.) [3]: The heat-curable silicone composition according to the above [1] or [2], characterized in that in the above formula (1), b is a number from 0.05 to 0.2, and n is a number from 2 to 3. [4]: ​​The heat-curable silicone composition according to the above [1], [2], or [3], characterized in that in the above formula (1), c and d are 0. [5]: The heat-curable silicone composition according to the above [1], [2], [3], or [4], characterized in that it further contains, as component (E), an organosiloxane having an average structural unit ratio represented by the following formula (4): (R １ ３ SiO １／２ ) ｆ (R ２ R １ ２ SiO １／２ ) ｇ (R ３ R １ ２ SiO １／２ ) ｈ (R １ ２ SiO ２／２ ) ｉ (R １ SiO ３／２ ) ｊ (SiO ４／２ ) ｋ ...(4) (In the formula, R １ , R ２ and R ３is the same as formula (1) above. f, g, h, i, j, and k are numbers that satisfy f≧0, g≧0, h>0, i≧0, j≧0, k≧0, and f+g+h+i+j+k=1.) [6]: A die-bonding material comprising the thermosetting silicone composition according to any one of [1] to [5] above. [7]: A silicone cured product, which is a cured product of the thermosetting silicone composition according to any one of [1] to [5] above. [8]: An optical semiconductor device comprising the silicone cured product according to [7] above.

[0136] 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. The following components (A) to (D): (A) an organopolysiloxane having an average structural unit ratio represented by the following formula (1), (R １ ３ SiO １／２ ) ａ (R ２ ３－ｎ R ３ ｎ SiO １／２ ) ｂ (R １ ２ SiO ２／２ ) ｃ (R １ SiO ３／２ ) ｄ (SiO ４／２ ) ｅ ...(1) (wherein, R １ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; R ２ each independently represents an alkenyl group having 2 to 10 carbon atoms; R ３ each independently represents a group represented by the following formula (2), n is a number from 1.5 to 3, and a, b, c, d, and e are numbers that satisfy a≧0, b>0, c≧0, d≧0, and e≧0, with the proviso that d+e>0 and a+b+c+d+e=1. (In the formula, R ４ is a hydrogen atom or a methyl group, R ５ each independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which has no aliphatic unsaturated bond and which may be substituted with a halogen atom; Z １ is an alkylene or oxyalkylene group having 1 to 10 carbon atoms; Z ２ is an alkylene group having 2 to 10 carbon atoms, and m is an integer from 0 to 20. The wavy line represents a bond.) A thermosetting silicone composition comprising: (B) an organic peroxide; (C) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in each molecule; and (D) a platinum group metal catalyst.

2. R in the above formula (1) １ is a methyl group, R ２ is a vinyl group, R ３ is a group represented by the following formula (3): (In the formula, the wavy line represents a bond.) 3. The thermosetting silicone composition according to claim 1, wherein b in formula (1) is a number from 0.05 to 0.2, and n is a number from 2 to 3.

4. The heat-curable silicone composition according to claim 1, wherein c and d in formula (1) are 0.

5. The heat-curable silicone composition according to claim 1, further comprising an organosiloxane having an average ratio of structural units represented by the following formula (4) as component (E). (R １ ３ SiO １／２ ) ｆ (R ２ R １ ２ SiO １／２ ) ｇ (R ３ R １ ２ SiO １／２ ) ｈ (R １ ２ SiO ２／２ ) ｉ (R １ SiO ３／２ ) ｊ (SiO ４／２ ) ｋ ...(4) (In the formula, R １ , R ２ and R ３ is the same as the above formula (1). f, g, h, i, j, and k are numbers that satisfy f≧0, g≧0, h>0, i≧0, j≧0, k≧0, and f+g+h+i+j+k=1.

6. A die-bonding material comprising the thermosetting silicone composition according to any one of claims 1 to 5.

7. A silicone cured product, which is a cured product of the heat-curable silicone composition according to any one of claims 1 to 5.

8. An optical semiconductor device comprising the silicone cured product according to claim 7.

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