JP2020125430A - Organic modified silicone resin composition for die bonding, and cured product thereof and optical semiconductor element - Google Patents

Abstract

To provide an organic modified silicone resin composition for die bonding that can give a cured product having excellent adhesive force between an LED element and a substrate at high temperature.SOLUTION: An organic modified silicone resin composition for die bonding contains (A) a vinyl group-containing branched organopolysiloxane that is liquid at 25°C, (B) a component that has a cyclic siloxane structure and serves as a crosslinker and crosslinks with an alkenyl group in the (A) component by hydrosilylation, and (C) a platinum group metal catalyst.SELECTED DRAWING: None

Description

The present invention relates to an organic silicone resin composition for die bonding such as a light emitting diode element, a cured product thereof, and an optical semiconductor element.

Silicone resins and organically modified silicone resins are mainly used as die-bonding materials for light emitting diode (LED) elements (Patent Documents 1 to 3). However, in recent years, due to the advent of blue LED elements and the miniaturization of LED elements, when the conventional silicone die-bonding material is used for wire bonding, the adhesive force between the LED element and the substrate at a high temperature is insufficient, and a bonding defect occurs. There was a problem.

JP, 2006-342200, A JP, 2011-086844, A JP, 2015-140372, A

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an organically modified silicone resin composition for die bonding, which can provide a cured product having excellent adhesion between the LED element and the substrate at high temperatures. To aim.

（式中、Ｒ^３は独立に非置換または置換のシロキサン結合を有しない２価の基を表し、ｈは独立に０または１であり、ｎは０〜５の整数である。）及び
（Ｃ）白金族金属系触媒
を含有するダイボンディング用有機変性シリコーン樹脂組成物を提供する。
このような有機変性シリコーン樹脂組成物は、高硬度かつ高温時におけるＬＥＤ素子と基板との接着力に優れる硬化物を与えることができるものである。 In order to achieve the above object, in the present invention,
(A) a branched organopolysiloxane represented by the following average unit formula (1), which is a liquid at 25° C.,
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and R ² is an alkenyl group. a, b, c, d, e, f, and g are numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, respectively, provided that b+c+e>0, e+f+g. >0 and a number satisfying a+b+c+d+e+f+g=1.)
(B) Compound represented by the following formula (2): The number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.5 with respect to one total silicon atom-bonded alkenyl group in the component (A). ~ 5.0 pieces,

(In the formula, R ³ independently represents a divalent group having no unsubstituted or substituted siloxane bond, h is 0 or 1, and n is an integer of 0 to 5) and (C The present invention provides an organically modified silicone resin composition for die bonding, which contains a platinum group metal-based catalyst.
Such an organically modified silicone resin composition can give a cured product having high hardness and excellent adhesion between the LED element and the substrate at high temperatures.

At least 10 mol% of all R ¹ in the above formula (1) is preferably an aryl group.
The presence of the aryl group can improve the refractive index, improve the light extraction efficiency in the LED package, and impart sulfidation resistance for suppressing the blackening of the silver substrate.

In the above formula (1), it is preferable that c=d=0, 0.4≦a+b≦0.8, and 0.2≦e+f+g≦0.6.
When a to g are as described above, the effects of the present invention are more easily exhibited.

（式中、アスタリスク（＊）は隣接するケイ素原子との結合を表す。）
上記式（２）におけるＲ^３が上記特定の２価の基のいずれか１つ以上から選択されるものであると、本発明の効果がより奏されやすくなる。 R ³ in the above formula (2) is preferably selected from any one or more divalent groups represented by the following formulas (3) to (8).

(In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)
When R ³ in the above formula (2) is selected from any one or more of the above specific divalent groups, the effect of the present invention is more easily exhibited.

Further, the present invention provides a cured product obtained by curing the above organic modified silicone resin composition for die bonding.
Since such a cured product has excellent adhesiveness at high temperatures, it is particularly useful as a die bond material used for die bonding of LED elements and the like.

Furthermore, the present invention provides an optical semiconductor device die-bonded with the above cured product.
Such an optical semiconductor element is highly reliable because the optical semiconductor element such as an LED and the substrate are bonded to each other by a cured product having high hardness and excellent adhesive strength at high temperature.

INDUSTRIAL APPLICABILITY The organically modified silicone resin composition of the present invention can give a cured product having high hardness and excellent adhesion between the LED element and the substrate at high temperatures. Therefore, a cured product obtained from such an addition-curable silicone composition is particularly useful as a die-bonding material used for die-bonding a small LED element or the like.

（式中、Ｒ^３は独立に非置換または置換のシロキサン結合を有しない２価の基を表し、ｈは独立に０または１であり、ｎは０〜５の整数である。）及び
（Ｃ）白金族金属系触媒
を含有することを特徴とするダイボンディング用有機変性シリコーン樹脂組成物である。 As a result of intensive studies on the above problems, the present inventors have found that an organically modified silicone resin composition containing components (A) to (C) described below can achieve the above objects, and completed the present invention.
That is, the present invention is
(A) a branched organopolysiloxane represented by the following average unit formula (1), which is a liquid at 25° C.,
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and R ² is an alkenyl group. a, b, c, d, e, f, and g are numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, respectively, provided that b+c+e>0, e+f+g. >0 and a number satisfying a+b+c+d+e+f+g=1.)
(B) Compound represented by the following formula (2): The number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.5 with respect to one total silicon atom-bonded alkenyl group in the component (A). ~ 5.0 pieces,

(In the formula, R ³ independently represents a divalent group having no unsubstituted or substituted siloxane bond, h is 0 or 1, and n is an integer of 0 to 5) and (C ) An organically modified silicone resin composition for die bonding, which comprises a platinum group metal-based catalyst.

Further, the present invention is a cured product obtained by curing the above organic modified silicone resin composition for die bonding.

Furthermore, the present invention is an optical semiconductor element characterized by being die-bonded with the above cured product.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
The organic modified silicone resin composition for die bonding of the present invention contains the following components (A) to (C). Hereinafter, each component will be described in detail.

<(A) component>
The component (A) in the organically modified silicone resin composition of the present invention is a branched organopolysiloxane represented by the following average composition formula (1).
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and at least 10 mol% of all R ¹ are aryl groups. Preferably, R ² is an alkenyl group, and a, b, c, d, e, f, and g are a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, respectively. , And g≧0, provided that b+c+e>0, e+f+g>0, and a+b+c+d+e+f+g=1.)

The component (A) is a component necessary for obtaining the reinforcing property of the organically modified silicone resin composition and has a branched structure. Therefore, at least the component (A) is composed of SiO _4/2 units and/or SiO _3/2 units (that is, SiO _4/2 units, R ² SiO _3/2 units _, and/or R ¹ SiO _3/2 units). Although a branched structure containing any one of them is essential, it may further contain SiO _2/2 units such as methylvinylsiloxy units and dimethylsiloxy units, and SiO _1/2 units such as dimethylvinylsiloxy units and trimethylsiloxy units. The content of the SiO _4/2 unit and/or the SiO _3/2 unit is preferably 5 mol% or more, more preferably 10 mol to 95 mol% of all siloxane units in the organopolysiloxane resin of the component (A). It is particularly preferably 20 to 60 mol %.

The component (A) is a liquid organopolysiloxane at 25°C. “Liquid” means a state of showing self-fluidity at 25° C. and having a viscosity of 100,000 mPa·s or less, particularly 10,000 mPa·s or less as measured by a rotational viscometer.

In the above average composition formula (1), 10 mol% or more of all R ¹ is preferably an aryl group, and more preferably 20 mol% or more. The presence of the aryl group can improve the refractive index, improve the light extraction efficiency in the LED package, and impart sulfidation resistance for suppressing the blackening of the silver substrate. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like, and a phenyl group is particularly preferable.

In R ¹ above, the group other than the aryl group is not particularly limited as long as it is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, Alkyl groups such as pentyl group, hexyl group, heptyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group And the like, usually, a monovalent hydrocarbon group having 1 to 12, preferably 1 to 10 and more preferably 1 to 8 carbon atoms, which is unsubstituted or halogen-substituted. A methyl group is particularly preferable.

R ² is an alkenyl group, preferably a C 2-10 alkenyl group such as a vinyl group, an allyl group or an ethynyl group, more preferably a C 2-6 alkenyl group, and particularly preferably a vinyl group.

The content of the alkenyl group bonded to the silicon atom in the component (A) is preferably 0.01 to 1 mol, and more preferably 0.05 to 0.5 mol, per 100 g of the component (A). Is more preferable. When the content of the alkenyl group is in the range of 0.01 to 1 mol based on 100 g of the component (A), the crosslinking reaction proceeds sufficiently and a cured product having a higher hardness can be obtained.

a+b is preferably in the range of 0.4 to 0.8, and more preferably 0.45 to 0.7. c+d is preferably in the range of 0 to 0.4, e+f+g is preferably in the range of 0.2 to 0.6, and more preferably 0.3 to 0.55.

Specific examples of the component (A) include the following branched organopolysiloxanes. In addition, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.
(Me ₃ SiO _1/2 ) _0.33 (ViMePhSiO _1/2 ) _0.33 (SiO _4/2 ) _0.34
(ViMePhSiO _1/2 ) _0.66 (SiO _4/2 ) _0.34
(ViMe ₂ SiO _1/2 ) _0.5 (PhSiO _3/2 ) _0.5
(ViMePhSiO _1/2 ) _0.45 (PhSiO _3/2 ) _0.25 (SiO _4/2 ) _0.3
As the component (A), one type may be used alone, or two or more types may be used in combination.

（式中、Ｒ^３は独立に非置換または置換のシロキサン結合を有しない２価の基を表し、ｈは独立に０または１であり、ｎは０〜５の整数である。） <(B) component>
The component (B) is a component that acts as a crosslinking agent that crosslinks with the alkenyl group in (A) by a hydrosilylation reaction, and is a compound represented by the following formula (2).

(In the formula, R ³ independently represents a divalent group having no unsubstituted or substituted siloxane bond, h is independently 0 or 1, and n is an integer of 0 to 5.)

（式中、アスタリスク（＊）は隣接するケイ素原子との結合を表す。） Examples of the divalent group having no siloxane bond represented by R ³ include a divalent organic group in which a carbon atom may be replaced by a silicon atom, and are represented by the following formulas (3) to (8): It is preferred to be selected from any one or more of the valent groups.

(In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)

Specific examples of the component (B) include compounds represented by the following structural formulas.

（Ｂ）成分は、一種単独で用いても二種以上を併用してもよい。

As the component (B), one type may be used alone, or two or more types may be used in combination.

The blending amount of the component (B) is such that the number of silicon atom-bonded hydrogen atoms in the component (B) is 0.5 to 5.0, preferably 1 to one alkenyl group bonded to the silicon atom in the component (A). Is an amount within the range of 0.7 to 3.0. If it is out of this range, it may not be possible to impart high strength to the obtained cured product.

Further, it is preferable that the number of the silicon atom-bonded hydrogen atoms in the component (B) is 0.6 to 3.0 with respect to one silicon atom-bonded alkenyl group in the composition. It is more preferable that the amount be in the range of 0.7 to 2.5. When such a range is satisfied, a composition having a viscosity range suitable for use and a desired cured product having high hardness can be obtained.

<(C) component>
The platinum group metal-based catalyst of the component (C) is not particularly limited as long as it is a component that promotes the addition reaction between the alkenyl group in the component (A) and the silicon atom-bonded hydrogen atom in the component (B). Specific examples thereof include platinum group metals such as platinum, palladium and rhodium; platinum-based compounds such as chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid with olefins, vinyl siloxanes or acetylene compounds; tetrakis. Examples thereof include platinum group metal compounds such as (triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Platinum compounds are preferable, and coordination compounds of chloroplatinic acid and vinylsiloxane are particularly preferable.
As the component (C), one type may be used alone, or two or more types may be used in combination.

The blending amount of the component (C) may be an effective amount as a catalyst, but is usually 3 to 100 ppm in terms of mass of the platinum group metal element with respect to the total of the components (A) and (B). It is preferably present, and more preferably 5 to 40 ppm. When such a range is satisfied, the reaction rate of the addition reaction becomes appropriate, and a cured product having high strength can be obtained.

<Other ingredients>
Components such as an organic peroxide, an antioxidant, an adhesion improver and a reaction inhibitor may be added to the organically modified silicone resin composition of the present invention depending on the purpose.

Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, o-methyl benzoyl peroxide, p-methyl benzoyl peroxide, dicumyl peroxide, and 1,1-bis(t-butyl peroxy). Examples include -3,3,3-trimethylcyclohexane, di(4-methylbenzoylperoxy)hexamethylene biscarbonate and the like.
The addition amount of the organic peroxide is preferably 0.01 to 5 parts by mass, and particularly preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the total of the components (A) to (C). .. Within such a range, further improvement in resin strength can be achieved. These may be used alone or in combination of two or more.

Examples of the antioxidant include hindered amine and hindered phenol compounds, and the addition amount thereof is preferably 500 to 3,000 ppm with respect to the total mass of the components (A) to (C).

As the adhesion improver, from the viewpoint of imparting self-adhesiveness to the composition of the present invention which is an addition reaction curable type, an organic silicon compound such as silane or siloxane having a functional group imparting adhesiveness, a non-silicone type An organic compound or the like is used.

Specific examples of the functional group imparting adhesiveness include a vinyl group bonded to a silicon atom, an alkenyl group such as an allyl group, or a hydrogen atom; an epoxy group bonded to a silicon atom through a carbon atom (for example, γ-glycid Xoxypropyl group, β-(3,4-epoxycyclohexyl)ethyl group, etc., acryloxy group (eg, γ-acryloxypropyl group), or methacryloxy group (eg, γ-methacryloxypropyl group); alkoxysilyl Group (for example, alkoxysilyl such as trimethoxysilyl group, triethoxysilyl group, and methyldimethoxysilyl group bonded to a silicon atom through an alkylene group which may contain 1 to 2 ester structures, urethane structures, and ether structures) Groups and the like).

Examples of the organosilicon compound having a functional group that imparts adhesiveness include a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, and a compound obtained by introducing an alkoxysilyl group into an organic compound having a reactive organic group. Is exemplified.

Examples of non-silicone organic compounds include organic acid allyl esters, epoxy group ring-opening catalysts, organic titanium compounds, organic zirconium compounds, organic aluminum compounds, and the like.

Examples of the 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; maleic acid derivatives; 1-ethynyl Cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylcarbinol, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples of the known compound have a curing suppressing effect on the hydrosilylation catalyst of the component (C).

Since the degree of the curing inhibitory effect of the reaction inhibitor varies depending on the chemical structure of the reaction inhibitor, it is desirable to adjust the compounding amount of the reaction inhibitor to an optimum amount for each reaction inhibitor used. It is preferably 0.001 to 5 parts by mass with respect to a total of 30 parts by mass of the component (A), the component (B), and the component (C). When the amount is 0.001 part by mass or more, long-term storage stability of the composition at room temperature can be sufficiently obtained. When the compounding amount is 5 parts by mass or less, there is no fear that curing of the composition will be hindered.

In addition, in order to improve the reinforcing property, the composition of the present invention includes, for example, fine powder silica, crystalline silica, hollow fillers, inorganic fillers such as silsesquioxane, and organoalkoxysilanes of these fillers. A compound, an organochlorosilane compound, an organosilazane compound, a filler surface-hydrophobicized with an organosilicon compound such as a low molecular weight siloxane compound, and the like; silicone rubber powder, silicone resin powder, and the like may be added.

The fine powder silica preferably has a specific surface area (BET method) of 50 m ² /g or more, more preferably 50 to 400 m ² /g, and particularly preferably 100 to 300 m ² /g. When the specific surface area is 50 m ² /g or more, the cured product can be provided with sufficient reinforcement.

As such fine powder silica, known ones which have been conventionally used as a reinforcing filler for silicone rubber can be used, and examples thereof include fumed silica (dry silica) and precipitated silica (wet silica). Can be mentioned. Although finely divided silica may be used as it is, methylchlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane, dimethylpolysiloxane, hexamethyldisilazane, and divinyl are used to impart good fluidity to the composition. It is preferable to use those treated with an organosilicon compound such as hexaorganodisilazane such as tetramethyldisilazane and dimethyltetravinyldisilazane. Such reinforcing silica may be used alone or in combination of two or more.

The organic modified silicone resin composition of the present invention can be prepared by mixing the components (A) to (C) and, if necessary, other components. For example, from the components (A) and (C), It is also possible to separately prepare the above-mentioned part and the part consisting of the component (B) and the other component, and then mix and use the two parts. Further, the component (A) and the component (B) and, if necessary, a part composed of other components and the component (C) may be mixed.

[Cured product]
Furthermore, the present invention is a cured product of the above organic modified silicone resin composition for die bonding.

The organic modified silicone resin composition of the present invention may be cured under known conditions, for example, heating at 60 to 180° C. for 10 minutes to 3 hours. In particular, the Shore D hardness of the cured product obtained by curing the composition is preferably 30 or more, more preferably 50 or more, and the curing conditions for adjusting the Shore D hardness to 30 or more are usually the composition of the present invention. It can be obtained by heating and curing the product at 120 to 180° C. for 30 minutes to 3 hours.

The cured product of the organic modified silicone resin composition for die bonding of the present invention is excellent in adhesiveness at high temperatures, and thus is particularly useful as a die bonding material used for die bonding of LED elements and the like.

[Optical semiconductor element]
Further, the present invention is an optical semiconductor element which is die-bonded with the above cured product.

As an example of a method for die-bonding an optical element using the composition of the present invention, a syringe is filled with the composition of the present invention, and a dispenser is used to dry a substrate having a thickness of 5 to 100 μm on a substrate such as a package. After applying the composition as described above, an optical element (for example, a light emitting diode) is arranged on the applied composition, and the composition is cured to die-bond the optical element onto a substrate. Further, the composition is placed on a squeegee dish, and while being squeegeeed, it is applied on a substrate by a method by stamping so as to have a thickness of 5 to 100 μm in a dry state, and then an optical element is arranged on the applied composition. Alternatively, a method of die-bonding the optical element onto the substrate by curing The curing conditions for the composition may be as described above. Thus, a highly reliable light-emitting diode element die-bonded with the cured product of the silicone composition for die bonding of the present invention can be obtained.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Further, in the following, the viscosity is a value measured at 25° C. using a rotational viscometer, “SiH group” is a hydrogen atom bonded to a silicon atom, “Me” is a methyl group, “Vi” is a vinyl group, "Ph" represents a phenyl group.

[Example 1]
As the component (A), an organopolysiloxane represented by an average unit formula (ViMe ₂ SiO _1/2 ) _0.5 (PhSiO _3/2 ) _0.5 (vinyl group content 0.47 mol/100 g, at 25° C.) Liquid, viscosity 130 mPa·s) 100 parts by mass, compound (B) represented by the following average structural formula (9) (SiH group amount: 0.0053 mol/g) 130 parts by mass, surface-hydrophobicized silica particles ( Reoroseal DM-30S, particle diameter of about 7 nm, 5 parts by mass of Tokuyama Corp., 5 parts by mass of tetramethyltetravinyltetracyclosiloxane, 0.3 parts by mass of ethynylcyclohexanol, and the following structural formula (10). 2 parts by weight of the adhesion-imparting component to be mixed were mixed to obtain a transparent liquid mixture.
For this liquid mixture, a toluene solution of a platinum catalyst having 1,3-divinyltetramethyldisiloxane derived from chloroplatinic acid as a component (C) as a ligand was prepared from the components (A) and (B). A composition was prepared by adding 10 ppm in terms of mass of platinum to the total mass and stirring and mixing.
The number of SiH groups in the component (B) was 1.46 per one silicon atom-bonded vinyl group in the component (A) of the obtained composition, and the number of SiH groups in the composition was one. The number of SiH groups in the component (B) was 1.3.

[Example 2]
As the component (A), an organopolysiloxane represented by an average unit formula (ViMe ₂ SiO _1/2 ) _0.5 (PhSiO _3/2 ) _0.5 (vinyl group content 0.47 mol/100 g, at 25° C.) Liquid, viscosity 130 mPa·s) 100 parts by mass, (B) component represented by the following average structural formula (11) (SiH group amount: 0.007 mol/g) 130 parts by mass, surface-hydrophobicized silica particles ( Reoroseal DM-30S, particle diameter of about 7 nm, 5 parts by mass of Tokuyama Corp., 5 parts by mass of tetramethyltetravinyltetracyclosiloxane, 0.3 parts by mass of ethynylcyclohexanol, and the following structural formula (12). 2 parts by weight of the adhesion-imparting component to be mixed were mixed to obtain a transparent liquid mixture.
For this liquid mixture, a toluene solution of a platinum catalyst having 1,3-divinyltetramethyldisiloxane derived from chloroplatinic acid as a component (C) as a ligand was prepared from the components (A) and (B). A composition was prepared by adding 10 ppm in terms of mass of platinum to the total mass and stirring and mixing.
The number of SiH groups in the component (B) was 1.5 for one silicon atom-bonded vinyl group in the component (A) of the obtained composition, and for one silicon atom-bonded vinyl group in the composition. The number of SiH groups in the component (B) was 1.3.

[Comparative Example 1]
It is composed of Me ₃ SiO _1/2 unit, ViMe ₂ SiO _1/2 unit and SiO _4/2 unit, and the sum of Me ₃ SiO _1/2 unit and ViMe ₂ SiO _1/2 unit with respect to SiO _4/2 unit. A toluene solution of 75 parts by mass of a branched organopolysiloxane having a molar ratio of 0.8 (vinyl group content: 0.074 mol/100 g, solid at 23° C.), and both ends were blocked with dimethylvinylsiloxy groups. 25 parts by mass of linear dimethylpolysiloxane having a viscosity of 70 mPa·s at 25° C. was mixed. Toluene was removed from the obtained liquid mixture at 120° C. under reduced pressure of 10 mmHg or less to obtain a viscous liquid at room temperature. With respect to 100 parts by mass of this viscous liquid, methylhydrogenpolysiloxane represented by the following formula (13) having both ends blocked with trimethylsiloxy groups (SiH group content: 0.015 mol/g) 4 Parts by mass, surface-hydrophobicized silica particles (Rheoroseal DM-30S, particle diameter of about 7 nm, manufactured by Tokuyama Corp.) 5 parts by mass, tetramethyltetravinyltetracyclosiloxane 3 parts by mass, ethinylcyclohexanol 0.3 parts by mass, and 7 parts by mass of the adhesion-imparting component represented by the following structural formula (14) were mixed to obtain a transparent liquid mixture.

To this liquid mixture, a toluene solution of a platinum catalyst having 1,3-divinyltetramethyldisiloxane derived from chloroplatinic acid as a ligand was added in an amount of 10 ppm in terms of platinum mass based on the total mass of polysiloxane. The mixture was stirred and mixed to prepare a composition.
The number of SiH groups in the methylhydrogenpolysiloxane component relative to one silicon-bonded vinyl group in the branched organopolysiloxane component and both-end dimethylvinylsiloxy group-blocked linear dimethylpolysiloxane component of the obtained composition. Was 1.67, and the number of SiH groups in the methylhydrogenpolysiloxane component was 1.12 with respect to one silicon-bonded vinyl group in the composition.

[Comparative Example 2]
100 parts by mass of a compound represented by the following structural formula (15) (addition-reactive carbon-carbon double bond amount 0.35 mol/100 g, viscosity at 25° C. 12,000 mPa·s), the average structural formula (9) Compound (SiH group amount: 0.0053 mol/g) 100 parts by mass, surface-hydrophobicized silica particles (Rheoroseal DM-30S, particle size about 7 nm, manufactured by Tokuyama Corp.) 5 parts by mass, tetramethyl tetra 5 parts by mass of vinyltetracyclosiloxane, 0.3 parts by mass of ethynylcyclohexanol, and 2 parts by mass of the adhesion-imparting component represented by the structural formula (10) were mixed to obtain a transparent liquid mixture.
To this liquid mixture, a toluene solution of a platinum catalyst having 1,3-divinyltetramethyldisiloxane derived from chloroplatinic acid as a component (C) was used as a component (A) and a component (B). A composition was prepared by adding 10 ppm in terms of mass of platinum to the total mass and stirring and mixing.
In the resulting composition, the number of SiH groups in the compound represented by the above average structural formula (9) per one addition-reactive carbon-carbon double bond in the compound represented by the following structural formula (15). Was 1.5, and the number of SiH groups in the compound represented by the above average structural formula (9) was 1.3 with respect to one addition-reactive carbon-carbon double bond in the composition. ..

<Measurement method>
The physical properties of cured products made of the organically modified silicone resin compositions obtained in Examples and Comparative Examples were measured according to the following measuring methods. The results obtained are shown in Table 1.
[Hardness of cured product]
The hardness of a 2 mm-thick plate-shaped molded product obtained by pouring the composition into a mold and heating at 150° C. for 3 hours was measured by a Shore D hardness meter according to JIS K 6253.

[Adhesive strength (die shear strength)]
Using a die bonder (AD-830, manufactured by ASM), each composition was dispensed on the silver-plated electrode part of the SMD5050 package (polyphthalamide resin, manufactured by I-CHIUN PRECISION INDUSTRY Co.), and an optical semiconductor was formed thereon. The device (0.4×0.24 mm) was mounted and heated at 150° C. for 3 hours. After curing, the bond shear (Series 4000, manufactured by Dage) was used to measure the die shear strength at 25°C and 150°C.

As shown in Table 1, Example 1 and Example 2 are different from Comparative Example 1 and Comparative Example 2 in which the organic modified silicone resin composition of the present invention is not used, and have high hardness, and especially die shear at 150° C. It was confirmed to give a cured product having excellent strength.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the invention having substantially the same configuration as the technical idea described in the scope of the claims of the present invention and exhibiting the same action and effect is the present invention Within the technical scope of.

Claims (6)

(A) a branched organopolysiloxane represented by the following average unit formula (1), which is a liquid at 25° C.,
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, and R ² is an alkenyl group. a, b, c, d, e, f, and g are numbers that satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, respectively, provided that b+c+e>0, e+f+g. >0 and a number satisfying a+b+c+d+e+f+g=1.)
(B) Compound represented by the following formula (2): The number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.5 with respect to one total silicon atom-bonded alkenyl group in the component (A). ~ 5.0 pieces,

(In the formula, R ³ independently represents a divalent group having no unsubstituted or substituted siloxane bond, h is independently 0 or 1, and n is an integer of 0 to 5.)
And (C) a platinum group metal-based catalyst, which is an organic modified silicone resin composition for die bonding. The organically modified silicone resin composition for die bonding according to claim 1, wherein at least 10 mol% of all R ¹ is an aryl group. The organic modified silicone resin composition for die bonding according to claim 1 or 2, wherein c=d=0, 0.4≦a+b≦0.8, and 0.2≦e+f+g≦0.6. R ³ is selected from any one or more of the divalent groups represented by the following formulas (3) to (8). An organically modified silicone resin composition for die bonding.

(In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) A cured product obtained by curing the organic modified silicone resin composition for die bonding according to any one of claims 1 to 4. An optical semiconductor element, which is die-bonded with the cured product according to claim 5.