KR20200098411A - Organomodified silicone resin composition for die-bonding, cured product thereof, and optical semiconductor element - Google Patents

Abstract

The present invention relates to an organically modified silicone resin composition for die-bonding, which has a high Tg and can provide a cured product showing excellent adhesion between a LED device and a substrate at high temperature. The organically modified silicone resin composition for die-bonding includes: (A) a specific compound having two carbon-carbon double bonds capable of addition reaction per molecule; (B) a specific organopolysiloxane having an alkenyl group content of 0.2 mol/100 g or more; (C) a compound represented by the following Chemical Formula (3) and having a specific content of hydrogen atoms bound to silicon atoms; and (D) a platinum group metal catalyst. In Chemical Formula (3), R^5 independently represents a substituted or non-substituted divalent group having no siloxane bonding, f independently represents 0 or 1, and n is an integer of 0-5.

Description

Organic modified silicone resin composition for die bonding, cured product thereof, and optical semiconductor device TECHNICAL FIELD TECHNICAL FIELD OF THE INVENTION

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

Silicone resins and organic modified silicone resins are mainly used as die bonding materials for light emitting diode (LED) devices (Patent Documents 1 to 3). However, in recent years, due to the advent of blue LED devices and miniaturization of LED devices, when wire bonding with a conventional silicon-based die bonding material, the adhesion between the LED device and the substrate at high temperature is insufficient, resulting in a bonding problem. There was a problem.

In addition, since the LED wire bonding process is performed under high temperature, a die bonding material having a high glass transition point (Tg) and high heat strength is required. As a conventional silicon-based die bonding material, Tg is applied in the range of room temperature to 50°C. Because there is, it was not enough. That is, there is a need for a die-bonding agent having a higher glass transition point and excellent adhesion between an LED element and a substrate including at high temperatures.

Japanese Patent Publication No. 2006-342200 Japanese Patent Publication No. 2011-086844 Japanese Patent Publication No. 2015-140372

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic modified silicone resin composition for die bonding capable of providing a cured product having a high Tg and excellent adhesion between an LED element and a substrate at high temperature. .

In order to achieve the above object, in the present invention,

(A) (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following formula (1) in one molecule, and (b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule It is an addition reaction product of, and a compound having two addition reactive carbon-carbon double bonds in one molecule,

(In the formula, R ¹ is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, which does not contain an alkenyl group, and R ² is , A substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)

(B) an organopolysiloxane represented by the following formula (2) and having an alkenyl group content of 0.2 mol/100 g or more,

(R ³ ₃ SiO _1/2 ) _a (R ³ ₂ R ⁴ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ³ R ⁴ SiO) _d (R ³ SiO _3/2 ) _e (2)

(In the formula, R ³ is each independently a substituted or unsubstituted monovalent hydrocarbon group not including an alkenyl group, and R ⁴ is an alkenyl group. However, a, b, c, d, e are each, is a number that satisfies a≥0, b≥0, c≥0, d≥0 and e≥0, provided that b+d>0, c+d+e>0, and a+b+c+d It is a number that satisfies +e=1.)

(C) Compound represented by the following formula (3): 0.5 to 5.0 hydrogen atoms bonded to silicon atoms in component (C) per one addition reactive carbon-carbon double bond in component (A) and component (B) amount,

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

(D) It provides an organic-modified silicone resin composition for die bonding containing a platinum group metal catalyst.

The organic-modified silicone resin composition of the present invention has a high Tg and can provide a cured product having high hardness and excellent adhesion between the LED element and the substrate at the time of high temperature.

It is preferable that the component (A) is a compound represented by the following formula (4).

(In formula, m represents the integer of 0-50.)

When the component (A) is the specific compound described above, a cured product having particularly excellent hardness and strength can be provided.

It is preferable that R ⁵ in said formula (3) is a divalent group represented by following formula (5).

When R ⁵ is the specific divalent group described above, the effect of the present invention is more easily exhibited.

In the component (B), it is preferable that R ³ is a methyl group, R ⁴ is a vinyl group, and a cyclic organopolysiloxane satisfying a=b=c=e=0 and d=1.

In the component (B), when R ³ is a methyl group, R ⁴ is a vinyl group, and a to e are cyclic as described above, the effect of the present invention is more likely to be exhibited.

In the component (B), it is also preferable that R ³ is a methyl group or a phenyl group, R ⁴ is a vinyl group, and a branched organopolysiloxane satisfying a=c=d=0 and b+e=1.

If the component (B) is the specific branched organopolysiloxane, the effects of the present invention are more likely to be exhibited.

In addition, the present invention provides a cured product obtained by curing the silicone composition for die bonding.

The cured product of the present invention has a high Tg and excellent adhesion between the LED element and the substrate at high temperature.

In addition, the present invention provides an optical semiconductor device that is die-bonded with the cured product.

The optical semiconductor device of the present invention has high reliability since the LED device and the substrate are adhered by a cured product having a high Tg and excellent adhesion at high temperatures.

The organic-modified silicone resin composition of the present invention has a high Tg and can provide a cured product having high hardness and excellent adhesion between the LED element and the substrate at the time of high temperature. Therefore, a cured product obtained from such an addition curable silicone composition is particularly useful as a die bonding material used for die bonding of a small LED device or the like.

The inventors of the present invention have repeatedly studied the above problems, and found that an organic-modified silicone resin composition containing components (A) to (D) described later can achieve the above problems, and completed the present invention. .

That is, the present invention

(A) (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following formula (1) in one molecule, and (b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule It is an addition reaction product of, and a compound having two addition reactive carbon-carbon double bonds in one molecule,

(In the formula, R ¹ is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, which does not contain an alkenyl group, and R ² is , A substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)

(B) an organopolysiloxane represented by the following formula (2) and having an alkenyl group content of 0.2 mol/100 g or more,

(R ³ ₃ SiO _1/2 ) _a (R ³ ₂ R ⁴ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ³ R ⁴ SiO) _d (R ³ SiO _3/2 ) _e (2)

(In the formula, R ³ is each independently a substituted or unsubstituted monovalent hydrocarbon group not including an alkenyl group, and R ⁴ is an alkenyl group. However, a, b, c, d, e are each, is a number that satisfies a≥0, b≥0, c≥0, d≥0 and e≥0, provided that b+d>0, c+d+e>0, and a+b+c+d It is a number that satisfies +e=1.)

(C) Compound represented by the following formula (3): 0.5 to 5.0 hydrogen atoms bonded to silicon atoms in component (C) per one addition reactive carbon-carbon double bond in component (A) and component (B) amount,

(In the formula, R ⁵ independently represents a divalent group having no unsubstituted or substituted siloxane bond, f is independently 0 or 1, and n is an integer of 0 to 5.), and (D) a platinum group metal system catalyst

It is an organic-modified silicone resin composition for die bonding, characterized in that it contains.

Further, the present invention is a cured product characterized in that the silicone composition for die bonding of the present invention is cured.

In addition, the present invention is an optical semiconductor device characterized in that the die-bonded with the cured product of the present invention.

Hereinafter, although this invention is demonstrated in detail, this invention is not limited to these.

<(A) component>

Component (A) in the organic-modified silicone resin composition of the present invention comprises (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following formula (1) in one molecule, and (b) an addition reactive carbon -An addition reaction product of a polycyclic hydrocarbon having two carbon double bonds in one molecule, and an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule.

(In the formula, R ¹ is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, which does not contain an alkenyl group, and R ² is , A substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)

Specific examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n- Alkyl groups having 1 to 12 carbon atoms such as hexyl, n-octyl, n-decyl, cyclopentyl, and cyclohexyl groups; Aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups; Alkylaryl groups having 7 to 12 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, and hexylphenyl group; Aralkyl groups having 7 to 12 carbon atoms, such as benzyl and phenethyl group, etc. are mentioned.

Further, as specific examples of the alkoxy group having 1 to 6 carbon atoms, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyloxy , n-hexyloxy, cyclopentyloxy, cyclohexyloxy group, etc. are mentioned.

Among these, as R ¹ , an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group is more preferable.

On the other hand, as a specific example of the divalent hydrocarbon group having 1 to 12 carbon atoms of R ² , carbon such as methylene, ethylene, propylene, trimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene group, etc. A linear, branched or cyclic alkylene group having 1 to 12 atoms; Aralkylene groups having 6 to 12 carbon atoms such as phenylene, biphenylene, and naphthylene group, and aralkylene groups having 7 to 12 carbon atoms such as phenylene methylene and methylenephenylene methylene group.

Among these, an arylene group having 6 to 12 carbon atoms is preferable, and a phenylene group is more preferable.

As the component (a), it is particularly preferable that all R ¹ in General Formula (1) are methyl groups, and R ² is a phenylene group. As a specific example of such component (a), 1,4-bis(dimethylsilyl)benzene, 1,3-bis(dimethylsilyl)benzene, etc. are mentioned, for example.

In addition, component (a) may be used individually by 1 type, and may use 2 or more types together.

In addition, as a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule of the component (b), (i) among the carbon atoms forming the skeleton of the polycyclic hydrocarbon, addition between two adjacent carbon atoms A reactive carbon-carbon double bond is formed, (ii) a hydrogen atom bonded to a carbon atom forming the skeleton of a polycyclic hydrocarbon is substituted with an addition reactive carbon-carbon double bond-containing group, (iii) c Among the carbon atoms forming the skeleton of a cyclic hydrocarbon, an addition reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and a hydrogen atom bonded to a carbon atom forming the skeleton of a polycyclic hydrocarbon is additionally reactive. Those substituted with a carbon-carbon double bond-containing group can be used.

Specific examples of the component (b) include 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene represented by the following formula. , These may also be used as a mixture (hereinafter, when it is not necessary to distinguish them, they may be collectively referred to as "vinyl norbornene").

In addition, the substitution position of the vinyl group of the vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type), and there is no particular difference in the reactivity of the compound depending on the difference in these configurations. Therefore, it may be a combination of the isomers of both batches.

The addition reaction product of the component (A) can be synthesized, for example, by the method described in JP 2005-133073 A.

As an example, it can be prepared by addition reaction in the presence of a hydrosilylation reaction catalyst in an amount of more than 1 mol and 10 mol or less, preferably more than 1 mol and 5 mol or less of the component (b) with respect to 1 mol of the component (a). have.

In this case, a known hydrosilylation catalyst can be used, and specific examples thereof include carbon powder carrying platinum metal, platinum black, platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, chloroplatinic acid. Platinum-based catalysts such as complexes of and olefins and platinum bisacetoacetate; And platinum group metal catalysts such as palladium catalysts and rhodium catalysts. In addition, the addition reaction conditions, use of a solvent, etc. are not particularly limited and may be as known.

In the above reaction, when the addition reaction product of component (A) is synthesized, an excess molar amount of (b) polycyclic hydrocarbon is reacted with respect to the compound represented by formula (1). The addition reaction product (b) has two addition-reactive carbon-carbon double bonds derived from polycyclic hydrocarbons per molecule.

As the addition reaction product of the component (A), it is preferable that it is represented by the following formula (6), and in particular, it is more preferably represented by the following formula (4) in which R ¹ is a methyl group.

The addition reaction product containing such a polycyclic hydrocarbon and a phenylene group can be particularly suitably used in order to provide a cured product having excellent hardness and strength.

(Wherein, R ¹ can represent the same meaning as that of R ¹ in the formula (1), and preferably a methyl group. M is represent an integer from 0 to 50, preferably from 0 to 30 integer, and more preferably It is an integer from 0 to 20.)

(In the formula, m represents the same meaning as m in the formula (6).)

(A) The component may be used individually by 1 type, and may use 2 or more types together.

<(B) component>

The component (B) is a component that increases the crosslinking density of the resulting cured product and imparts high Tg and high strength, and is an organopolysiloxane represented by the following formula (2).

(R ³ ₃ SiO _1/2 ) _a (R ⁴ R ³ ₂ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ R ³ SiO) _d (R ³ SiO _3/2 ) _e (2)

(In the formula, R ³ is each independently a substituted or unsubstituted monovalent hydrocarbon group not including an alkenyl group, and R ⁴ is an alkenyl group. However, a, b, c, d, e are each, is a number that satisfies a≥0, b≥0, c≥0, d≥0 and e≥0, provided that b+d>0, c+d+e>0, and a+b+c+d It is a number that satisfies +e=1.)

The monovalent hydrocarbon group of R ³ is not particularly limited as long as it does not have an alkenyl group, but a substituted or unsubstituted monovalent hydrocarbon having 1 to 8 carbon atoms is preferable. Examples of the monovalent hydrocarbon include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, and cyclopentyl groups, aryl groups such as phenyl groups, tolyl groups, and xylyl groups, benzyl groups, and phenylethyl groups. Halogenated hydrocarbon groups, such as an aralkyl group, a chloromethyl group, a chloropropyl group, and a chlorocyclohexyl group, etc. are illustrated. Preferably, it is an alkyl group, and a methyl group is especially preferable.

The alkenyl group for R ⁴ is preferably an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, an allyl group, and an ethynyl group, more preferably 2 to 6 alkenyl groups, and particularly preferably a vinyl group. The alkenyl group bonded to this silicon atom may be present in either the molecular chain terminal or the side chain of the molecular chain in the organopolysiloxane molecule of the component (B), or may be present in both of them, and 3 or more silicon in one molecule. It is preferred to have an alkenyl group bonded to an atom.

In the component (B), the content of the alkenyl group bonded to the silicon atom is 0.2 mol/100 g or more, preferably 0.5 mol/100 g or more.

The dynamic viscosity of the component (B) is preferably 100 mm 2 /s or less at 25°C, and particularly preferably 50 mm 2 /s or less. If it is within the above range, the compatibility with the component (A) and the component (C) increases, and in addition to improving transparency, separation of each component can be suppressed when a die bonding material is applied to the LED substrate by a die bonder. . In addition, it is possible to improve the workability when applying the die bonding material.

As a specific example of the component (B), any structure of a linear organopolysiloxane, a cyclic organopolysiloxane, and a branched organopolysiloxane may be sufficient, but preferably, R ³ is a methyl group, R ⁴ is a vinyl group, a=b =c=e=0, cyclic organopolysiloxane satisfying d=1, or R ³ is a methyl group or a phenyl group, R ⁴ is a vinyl group, a=c=d=0, b+e=1 is satisfied Is a branched organopolysiloxane.

As a specific example of a component (B), the compound represented by following formula (7)-(9) is mentioned, for example. In addition, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

(B) component may be used individually by 1 type, and may use 2 or more types together.

<(C) component>

The component (C) is a component that acts as a crosslinking agent for crosslinking by a hydrosilylation reaction with an addition reactive carbon-carbon double bond in components (A) and (B). The component (C) is a compound represented by the following formula (3), having a hydrogen atom bonded to a silicon atom (ie, a SiH group) as a cyclic body, and bonded by a divalent organic group.

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

As R ⁵ , it is particularly preferable to have the following structure.

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

As a specific example of the organohydrogenpolysiloxane of component (C), the compound etc. which are represented by the following structural formula are mentioned, for example.

(C) component may be used individually by 1 type, and may use 2 or more types together.

The blending amount of component (C) is the number of silicon atom-bonded hydrogen atoms in component (C) per one addition-reactive carbon-carbon double bond in component (A) and component (B), 0.5 to 5.0, preferably It is an amount within the range of 0.7 to 3.0. When it is in this range, high strength can be provided to the hardened|cured material obtained.

In addition, it is preferable that the number of silicon atom-bonded hydrogen atoms in the component (C) per one addition reactive carbon-carbon double bond in the composition is 0.6 to 3.0, and more preferably 0.7 to 2.5. . When this range is satisfied, it is a composition having a viscosity range suitable for use, and a cured product having a high hardness for the purpose can be obtained.

<(D) component>

The platinum group metal catalyst of the component (D) is a component that accelerates the addition reaction of the addition reactive carbon-carbon double bond in the component (A) and the component (B) and the hydrogen atom bonded to the silicon atom in the component (C). It is not limited and specific examples thereof include platinum group metals such as platinum, palladium, and rhodium; Platinum-based compounds such as chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, vinylsiloxane or a coordination compound with an acetylene compound; And platinum group metal compounds such as tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine)rhodium, etc., preferably a platinum-based compound, particularly preferably a coordination compound of chloroplatinic acid and vinylsiloxane. .

(D) component may be used individually by 1 type, and may use 2 or more types together.

The blending amount of the component (D) may be an effective amount as a catalyst, but is preferably in the range of 1 to 500 ppm in terms of the mass of the platinum group metal element with respect to the total amount of the component (A), the component (B) and the component (C), 1 It is more preferably in the range of to 100 ppm. When this range is satisfied, the reaction rate of the addition reaction becomes appropriate, and a cured product having high strength can be obtained.

<(E) component>

In the organic-modified silicone resin composition of the present invention, in order to improve reinforcing properties, inorganic fillers such as fine powder silica, crystalline silica, hollow fillers, silsesquioxane, and these fillers are used as component (E). Fillers subjected to surface hydrophobic treatment with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds; Silicone rubber powder, silicone resin powder, or the like may be blended.

As the component (E), silica fine particles are particularly preferable, and as the silica fine particles, for example, those obtained by reacting a silanol group present on the surface of the hydrophilic silica fine particles with a surface modifier to make the surface hydrophobic may be used. Examples of the surface modifier include compounds of alkylsilanes, and specific examples thereof include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethyl silicone oil.

As a suitable example of silica fine particles, from the ease of availability, fumed silica (fumed silica) is mentioned, for example. Fumed silica is produced by oxidizing and hydrolyzing SiCl ₄ gas with a flame of 1,100 to 1,400°C in which a mixed gas of H ₂ and O ₂ is burned. The primary particles of fumed silica are spherical ultrafine particles mainly composed of amorphous silicon dioxide (SiO ₂ ) having an average particle diameter of about 5 to 50 nm, and these primary particles are aggregated to form 2 particles having a particle diameter of several hundred nm. Form secondary particles. Since fumed silica is produced by rapid cooling along with ultrafine particles, the structure of the surface is in a chemically active state.

Specifically, for example, Nippon Aerosil Co., Ltd. "Aerosil" (registered trademark) is mentioned, and examples of hydrophilic Aerosil (registered trademark) are "90", "130", "150", and " Examples of "200", "300", and hydrophobic aerosil (registered trademark) are "R8200", "R972", "R972V", "R972CF", "R974", "R202", "R805", "R812", and " R812S", "RY200", "RY200S" and "RX200" are mentioned. In addition, as "Reolosil" (registered trademark) manufactured by Tokuyama Corporation, "DM-10", "DM-20", and "DM-30S" are mentioned.

The blending amount of the component (E) is preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass with respect to 100 parts by mass in total of the components (A), (B), and (C). Within such a range, a composition having an appropriate viscosity having thixotropic properties will be obtained, and thus transfer properties will be good when used as a die bonding material.

<Other ingredients>

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

As an organic peroxide, for example, benzoyl peroxide, t-butyl perbenzoate, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, dicumyl peroxide, 1,1-bis(t-butylperoxy)- 3,3,3-trimethylcyclohexane, di(4-methylbenzoylperoxy)hexamethylene biscarbonate, etc. are mentioned.

The amount of the organic peroxide added is preferably 0.01 to 5 parts by weight, and particularly preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the total of the components (A), (B), and (C). If it is such a range, further improvement in resin strength can be achieved. These can be used alone or in combination of two or more.

Examples of antioxidants include hindered amines and hindered phenol compounds, and the amount added is 500 to 3,000 ppm based on the total mass of the component (A), component (B), and component (C). desirable.

As the adhesion improving agent, from the viewpoint of imparting self-adhesion to the composition of the present invention, which is an addition reaction curable type, an organosilicon compound such as a silane or siloxane containing a functional group that imparts adhesion, and a non-silicone-based organic compound are used.

As a specific example of the functional group which imparts adhesiveness, Alkenyl group, such as a vinyl group and an allyl group, or a hydrogen atom bonded to a silicon atom; An epoxy group bonded to a silicon atom through a carbon atom (e.g., a γ-glycidoxypropyl group, a β-(3,4-epoxycyclohexyl) ethyl group, etc.), an acrylicoxy group (e.g., γ-acryloxypropyl Group, etc.), or a methacryloxy group (eg, γ-methacryloxypropyl group, etc.); Alkoxysilyl group (e.g., a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group bonded to a silicon atom through an alkylene group that may contain 1 to 2 ester structures, urethane structures, ether structures, etc. Alkoxysilyl group, etc.).

Examples of the organosilicon compound containing a functional group imparting adhesiveness include a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, and a compound having an alkoxysilyl group introduced into an organic compound having a reactive organic group.

Moreover, as a non-silicone type organic compound, an organic acid allyl ester, an epoxy group ring opening catalyst, an organic titanium compound, an organic zirconium compound, an organic aluminum compound, etc. are mentioned, for example.

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-ethynylcyclohexanol, 3,5-dimethyl-1-hexin-3-ol, ethynylmethyldecylcarbinol, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl Known compounds having a curing inhibiting effect on the hydrosilylation catalyst of the component (D), such as cyclotetrasiloxane, are exemplified.

Since the degree of the curing inhibitory effect by the reaction inhibitor differs depending on the chemical structure of the reaction inhibitor, the amount of the reaction inhibitor is preferably adjusted to an optimum amount for each reaction inhibitor to be used. Preferably, it is 0.001-5 mass parts with respect to 30 mass parts in total of (A) component, (B) component, and (C) component. When the blending amount is 0.001 parts by mass or more, long-term storage stability of the composition at room temperature can be sufficiently obtained. If the blending amount is 5 parts by mass or less, there is no fear that curing of the composition is inhibited.

The organic-modified silicone resin composition of the present invention can be prepared by mixing components (A) to (D) and other components as necessary.

[Hardened cargo]

In addition, the present invention is a cured product of the organic modified silicone resin composition for die bonding.

The curing of the organic-modified silicone resin composition of the present invention may be performed under known conditions, and for example, curing can be performed at 100 to 180°C for 10 minutes to 5 hours. In particular, the Shore D hardness of the cured product obtained by curing the composition is preferably 60 or more, particularly 70 or more, and the curing conditions for setting the Shore D hardness to 60 or more are, usually, the composition of the present invention at 120 to 180°C for 30 It can be obtained by heating and curing under conditions of minutes to 5 hours.

Since the cured product of the organic-modified silicone resin composition for die bonding of the present invention has a high Tg and excellent adhesiveness at high temperatures, it is particularly useful as a die bonding material used for die bonding such as LED devices.

[Light-emitting diode device]

In addition, the present invention is a light emitting diode device that is die-bonded with the cured product.

As an example of a method of die bonding an optical element using the composition of the present invention, the composition of the present invention is filled in a syringe and applied to a thickness of 5 to 100 μm in a dry state on a substrate such as a package using a dispenser. Then, by disposing an optical element (for example, a light emitting diode) on the applied composition and curing the composition, a method of die-bonding the optical element onto the substrate is exemplified. In addition, the composition is placed on a squeegee dish, applied to a thickness of 5 to 100 μm in a dry state on a substrate by stamping while squeezing, and then an optical element is placed on the applied composition and the composition is cured, It may be a method of die bonding an optical element onto a substrate. The curing conditions of the composition may be as described above. In this way, it is possible to obtain a highly reliable light emitting diode device die-bonded with a cured product of the die-bonding silicone composition of the present invention.

[Example]

Hereinafter, the present invention will be specifically described using Examples and Comparative Examples, but the present invention is not limited thereto. In the following, the kinematic viscosity is a value at 25°C measured using a Canon-Penske viscometer, "Me" represents a methyl group, "Vi" represents a vinyl group, and "Ph" represents a phenyl group.

[Examples 1 to 3, Comparative Examples 1 and 2]

Each of the following components was mixed in the blending amount shown in Table 1 to prepare an addition curable silicone composition. In addition, the numerical value of each component in Table 1 represents a mass part. The value of [Si-H]/[additional reactive carbon-carbon double bond] is hydrogen bonded to a silicon atom in component (C) for one addition-reactive carbon-carbon double bond in component (A) and component (B) It represents the ratio of the number of atoms.

Component (A): An organic modified silicone compound represented by the following formula.

(B) component:

(B-1) Cyclic organopolysiloxane represented by the following structural formula (alkenyl group amount 1.16 mol/100 g, kinematic viscosity 3.4 mm 2 /s)

(B-2) Average unit formula (ViMe ₂ SiO _1/2 ) _0.5 (MeSiO _3/2 ) Organopolysiloxane represented by _0.5 (alkenyl group amount 0.51 mol/100 g, kinematic viscosity 32 mm 2 /s)

(C) component:

(C-1) a compound represented by the following structural formula

Comparative ingredients:

(C-2) Linear organohydrogenpolysiloxane represented by the following formula

(In the formula, the order of the siloxane units in parentheses is arbitrary)

(D) Component: Toluene solution of reaction product of platinum hexachloride and 1,3-divinyltetramethyldisiloxane (platinum content is 0.5% by mass)

(E) Reaction control agent: 1,6-bis(t-butylperoxycarbonyloxy)hexane

(F) adhesion imparting agent: compound represented by the following structural formula

(G) Fumed silica: Rheolosil DM-30S (manufactured by Tokuyama Corporation)

<Measurement method>

The physical properties of the cured product containing the organic-modified silicone resin composition obtained in Examples and Comparative Examples were measured according to the following measuring method. Table 2 shows the obtained results.

[Hardness of hardened material]

The composition was introduced into a mold, and the hardness of a 2 mm thick plate-shaped molded article cured by heating at 150° C. for 3 hours was measured according to JIS K 6253 by a Shore D hardness tester.

[Adhesion (die shear strength)]

Using a die bonder (manufactured by ASM, AD-830), each composition was transferred by stamping to the silver plated electrode portion of the SMD5050 package (manufactured by I-CHIUN PRECISION INDUSTRY Co., Ltd., polyphthalamide resin), and light A semiconductor device (manufactured by SemiLED, EV-B35A, 35mil) was mounted and heated at 150°C for 4 hours. After curing, the die shear strength was measured at 25°C and 150°C using a bond tester (manufactured by Dage, Series 4000).

[Glass transition point]

The cured product obtained by heating the composition at 150° C. for 4 hours was analyzed for the glass transition point using a thermomechanical analyzer (made by METTLER, TMA/SDTA841e).

As shown in the above table, in Examples 1 to 3, it was confirmed that Tg of the cured product was high, and the cured product having excellent die shear strength between the LED device and the substrate at 25°C and 150°C was provided.

On the other hand, in Comparative Example 1 in which the component (B) of the present invention was not contained, the crosslinking density was decreased, so that the resin strength was decreased, and the die shear strength and Tg were low. Further, in Comparative Example 2 in which organohydrogenpolysiloxane was used in place of the component (C) of the present invention, since the amount of organic groups was small, the resin strength was lowered, and the die shear strength and Tg were low.

In addition, this invention is not limited to the said embodiment. The above-described embodiment is an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same effects and effects is included in the technical scope of the present invention.

Claims (7)

(A) (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following formula (1) in one molecule, and (b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule It is an addition reaction product of, and a compound having two addition reactive carbon-carbon double bonds in one molecule,

(In the formula, R ¹ is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, which does not contain an alkenyl group, and R ² is It represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
(B) an organopolysiloxane represented by the following formula (2) and having an alkenyl group content of 0.2 mol/100 g or more,
(R ³ ₃ SiO _1/2 ) _a (R ³ ₂ R ⁴ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ³ R ⁴ SiO) _d (R ³ SiO _3/2 ) _e (2)
(In the formula, R ³ is each independently a substituted or unsubstituted monovalent hydrocarbon group not including an alkenyl group, and R ⁴ is an alkenyl group. However, a, b, c, d, e are each, is a number that satisfies a≥0, b≥0, c≥0, d≥0 and e≥0, provided that b+d>0, c+d+e>0, and a+b+c+d It is a number that satisfies +e=1.)
(C) Compound represented by the following formula (3): 0.5 to 5.0 hydrogen atoms bonded to silicon atoms in component (C) per one addition reactive carbon-carbon double bond in component (A) and component (B) amount,

(In the formula, R ⁵ independently represents a divalent group having no unsubstituted or substituted siloxane bond, f is independently 0 or 1, and n is an integer of 0 to 5.), and
(D) platinum group metal catalyst
Organic-modified silicone resin composition for die bonding, characterized in that it contains. The organic-modified silicone resin composition for die bonding according to claim 1, wherein the component (A) is a compound represented by the following formula (4).

(In formula, m represents the integer of 0-50.) The organic-modified silicone resin composition for die bonding according to claim 1 or 2, wherein R ⁵ is a divalent group represented by the following formula (5).

(In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) The cyclic organopolysiloxane according to claim 1 or 2, wherein in component (B), R ³ is a methyl group, R ⁴ is a vinyl group, and a=b=c=e=0, d=1. Organic-modified silicone resin composition for die bonding, characterized in that. The branched phase according to claim 1 or 2, wherein in the component (B), R ³ is a methyl group or a phenyl group, R ⁴ is a vinyl group, a=c=d=0, b+e=1. Organic-modified silicone resin composition for die bonding, characterized in that it is an organopolysiloxane. A cured product obtained by curing the silicone composition for die bonding according to claim 1 or 2. An optical semiconductor device, which is die-bonded with the cured product according to claim 6.