JP7021049B2 - Additive-curable silicone resin composition, cured product thereof, and optical semiconductor device - Google Patents

Description

The present invention relates to an addition-curable silicone resin composition, a cured product thereof, and an optical semiconductor device using these.

Recently, as a sealing material and a die bond material for a light emitting diode (hereinafter referred to as "LED") element, a silicone resin having good durability is used because the heat generation of the element has increased due to an improvement in the brightness of the LED element. (Patent Documents 1 and 2). In particular, in the case of a die-bonding material, if the resin is too soft, a problem occurs in which bonding cannot be performed in the wire bonding step performed after the die-bonding step, so that a die-bonding material having a high hardness is required.

Further, LED devices have been miniaturized in recent years, and there is a demand for a die bond material having higher adhesiveness. If the adhesive strength of the die-bonding material is insufficient, chip peeling may occur in the wire bonding process in LED manufacturing, which is a fatal problem in terms of manufacturing. Although the conventional silicone die bond materials have excellent durability, they have insufficient adhesiveness, and a material having higher die share strength is desired.

Japanese Unexamined Patent Publication No. 2006-342200 Japanese Unexamined Patent Publication No. 2010-285571

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an addition-curable silicone resin composition that gives a cured product having excellent hardness and die shear strength.

In order to solve the above problems, in the present invention,
(A) A branched organopolysiloxane represented by the following average composition formula (1) and having a viscosity at 25 ° C. of 100 mPa · s or less.
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² SiO _3/2 ) _c (R ¹ SiO _3/2 ) _d (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, respectively, and R ² is an alkenyl group which may be the same or different, respectively. a, b, c, d are numbers that satisfy a ≧ 0, b ≧ 0, c ≧ 0, and d ≧ 0, respectively, except that a + b> 0, b + c> 0, c + d> 0, and a + b + c + d. = A number that satisfies 1.)
(B) Branched organopolysiloxane represented by the following average composition formula (2): 60 to 90 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B).
(R ¹ ₃ SiO _1/2 ) _e (R ² R ¹ ₂ SiO _1/2 ) _f (R ² R ¹ SiO) _g (R ¹ ₂ SiO) _h (R ² SiO _3/2 ) _i (R ¹ SiO) _3/2 ) _j (SiO _4/2 ) _k (2)
(In the equation, R ¹ and R ² are the same as described above. E, f, g, h, i, j, k are e ≧ 0, f ≧ 0, g ≧ 0, h ≧ 0, i ≧, respectively. It is a number that satisfies 0, j ≧ 0 and k ≧ 0, except that f + g + i> 0, i + j + k> 0, and e + f + g + h + i + j + k = 1).
(C) Organohydrogenpolysiloxane, which is represented by the following average composition formula (3) and has at least two hydrogen atoms bonded to silicon atoms in one molecule.
R ³ _l H _m SiO _{(4-lm) / 2} (3)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, respectively, and l and m are 0.7 ≦ l ≦ 2.1, 0. .001 ≤ m ≤ 1.0 and 0.8 ≤ l + m ≤ 3.0.)
as well as,
(D) Provided is an addition-curable silicone resin composition comprising a platinum group metal-based catalyst.

The addition-curable silicone resin composition of the present invention can provide a cured product having excellent hardness and die shear strength.

In the present invention, it is preferable that 80 mol% or more of R ¹ and R ³ are methyl groups.

With such an addition-curable silicone resin composition, it is possible to provide a cured product having higher hardness and die shear strength.

Further, in the present invention, it is preferable that a = c = 0 in the component (A) in the composition.

With such an addition-curable silicone resin composition, it is possible to provide a cured product having further excellent hardness and die shear strength.

The present invention also provides a silicone cured product which is a cured product of the addition-curable silicone resin composition.

Such a cured silicone product is useful as a composition having excellent hardness and die shear strength and high adhesive strength to a substrate, an LED chip, or the like, and particularly as a die bonding material used for die bonding of an LED element or the like.

The present invention also provides an optical semiconductor device in which an optical semiconductor element is die-bonded with the cured silicone product.

Such an optical semiconductor device is highly reliable because the cured silicone material is used as a die bond material having excellent hardness and die shear strength and high adhesive strength to a substrate, an LED chip, or the like.

As described above, the addition-curable silicone resin composition of the present invention provides a silicone cured product having excellent hardness and die shear strength, and is particularly useful as a die-bonding material used for die-bonding of LED elements and the like. .. In the wire bonding process performed after the die bonding process, problems such as chip peeling and bonding failure are unlikely to occur. Therefore, the optical semiconductor device in which the optical semiconductor element is die-bonded with this cured silicone material is reliable. It is expensive and its productivity is also improved.

As described above, there has been a demand for the development of a silicone composition which gives a cured product having excellent hardness and die shear strength and gives a silicone cured product which is a die bonding material used for die bonding of LED elements and the like.

As a result of diligent studies on the above-mentioned problems, the present inventors have solved the above-mentioned problems in the case of an addition-curable silicone composition containing the components (A), (B), (C), and (D) described later. We found that it could be solved and completed the present invention.

That is, the present invention
(A) A branched organopolysiloxane represented by the following average composition formula (1) and having a viscosity at 25 ° C. of 100 mPa · s or less.
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² SiO _3/2 ) _c (R ¹ SiO _3/2 ) _d (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, respectively, and R ² is an alkenyl group which may be the same or different, respectively. a, b, c, d are numbers that satisfy a ≧ 0, b ≧ 0, c ≧ 0, and d ≧ 0, respectively, except that a + b> 0, b + c> 0, c + d> 0, and a + b + c + d. = A number that satisfies 1.)
(B) Branched organopolysiloxane represented by the following average composition formula (2): 60 to 90 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B).
(R ¹ ₃ SiO _1/2 ) _e (R ² R ¹ ₂ SiO _1/2 ) _f (R ² R ¹ SiO) _g (R ¹ ₂ SiO) _h (R ² SiO _3/2 ) _i (R ¹ SiO) _3/2 ) _j (SiO _4/2 ) _k (2)
(In the equation, R ¹ and R ² are the same as described above. E, f, g, h, i, j, k are e ≧ 0, f ≧ 0, g ≧ 0, h ≧ 0, i ≧, respectively. It is a number that satisfies 0, j ≧ 0 and k ≧ 0, except that f + g + i> 0, i + j + k> 0, and e + f + g + h + i + j + k = 1).
(C) Organohydrogenpolysiloxane, which is represented by the following average composition formula (3) and has at least two hydrogen atoms bonded to silicon atoms in one molecule.
R ³ _l H _m SiO _{(4-lm) / 2} (3)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, respectively, and l and m are 0.7 ≦ l ≦ 2.1, 0. .001 ≤ m ≤ 1.0 and 0.8 ≤ l + m ≤ 3.0.)
as well as,
(D) An addition-curable silicone resin composition comprising a platinum group metal-based catalyst.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[Additionally curable silicone composition]
The addition-curable silicone composition of the present invention contains the components (A) to (D) described later.
Hereinafter, each component will be described in detail.

<Ingredient (A)>
The component (A) is a component for increasing the strength of the cured product of the composition and improving the adhesive strength, that is, the die shear strength, and 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 SiO _3/2 ) _c (R ¹ SiO _3/2 ) _d (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, respectively, and R ² is an alkenyl group which may be the same or different, respectively. a, b, c, d are numbers that satisfy a ≧ 0, b ≧ 0, c ≧ 0, and d ≧ 0, respectively, except that a + b> 0, b + c> 0, c + d> 0, and a + b + c + d. = A number that satisfies 1.)

The viscosity of the component (A) is preferably 100 mPa · s or less and preferably 30 mPa · s or less as measured by a rotational viscometer at 25 ° C. If it exceeds 100 mPa · s, the viscosity of the composition becomes high, which causes a problem that the stamping property deteriorates. Unless otherwise specified below, the viscosity is a value measured by a rotational viscometer at 25 ° C.

The substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ is not particularly limited as long as it does not have an alkenyl group, but is substituted or substituted with 1 to 8 carbon atoms. Unsubstituted monovalent hydrocarbons are preferred. The monovalent hydrocarbon includes an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, an aryl group such as a phenyl group, a trill group and a xylyl group, and a benzyl group. , Alkyl group such as phenylethyl group, halogenated hydrocarbon group such as chloromethyl group, chloropropyl group, chlorocyclohexyl group and the like are exemplified. Alkyl groups are preferred, and methyl groups are particularly preferred.

The alkenyl group represented by ^R2 is not particularly limited, but an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, an allyl group and an ethynyl group, particularly 2 to 6 alkenyl groups is preferable, and a vinyl group is particularly preferable. preferable.

Specific examples of the component (A) include those represented by the following formulas.
(CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _0.5 ((CH ₃ ) SiO _3/2 ) _0.5 ,
(CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _0.5 ((CH ₂ = CH) SiO _3/2 ) _0.5 ,
(CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _0.5 ((CH ₃ ) SiO _3/2 ) _0.3 ((CH ₂ = CH) SiO _3/2 ) _0.2 ,
((CH ₃ ) ₃ SiO _1/2 ) _0.4 ((CH ₂ = CH) SiO _3/2 ) _0.6 ,
((CH ₃ ) ₃ SiO _1/2 ) _0.4 ((CH ₃ ) SiO _3/2 ) _0.3 ((CH ₂ = CH) SiO _3/2 ) _0.3 ,
The component (A) may be used alone or in combination of two or more.

<Ingredient (B)>
The component (B) is a branched organopolysiloxane represented by the following average composition formula (2).
(R ¹ ₃ SiO _1/2 ) _e (R ² R ¹ ₂ SiO _1/2 ) _f (R ² R ¹ SiO) _g (R ¹ ₂ SiO) _h (R ² SiO _3/2 ) _i (R ¹ SiO) _3/2 ) _j (SiO _4/2 ) _k (2)
(In the equation, R ¹ and R ² are the same as described above. E, f, g, h, i, j, k are e ≧ 0, f ≧ 0, g ≧ 0, h ≧ 0, i ≧, respectively. It is a number that satisfies 0, j ≧ 0 and k ≧ 0, except that f + g + i> 0, i + j + k> 0, and e + f + g + h + i + j + k = 1).

Examples of R ¹ include the same as those exemplified in the above component (A), preferably an alkyl group, and particularly preferably a methyl group.

Examples of ^R2 are the same as those exemplified in the above component (A), preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly a vinyl group. Is preferable.

In the above average composition formula (2), e is 0 to 0.65, f is 0 to 0.65, g is 0 to 0.5, h is 0 to 0.5, i0 to 0.8, and j is 0. It is preferable that ~ 0.8 and k are numbers of 0 to 0.6. Further, f + g + i is preferably 0.1 to 0.8, particularly preferably a number of 0.2 to 0.65, and i + j + k is preferably 0.05 or more, more preferably 0.1 to 0. It is 9, and particularly preferably a number of 0.2 to 0.6.

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

The organopolysiloxane of the component (B) preferably has a weight average molecular weight in the range of 500 to 100,000 from the viewpoint of ease of isolation.

The organopolysiloxane of the component (B) is a component for obtaining the reinforcing property of the cured product and has a branched structure. The organopolysiloxane of the component (B) requires a branched structure consisting of SiO _4/2 unit and / or SiO _3/2 unit, but further SiO _2/2 (SiO) such as methyl vinyl syloxy unit and dimethyl syroxy unit. ) Units, SiO _1/2 units such as dimethylvinyl syroxy units and trimethyl syroxy units may be included. The content of SiO _4/2 units and / or SiO _3/2 units is preferably 5 mol% or more, more preferably 10 mol to 90 mol%, of the total siloxane units in the organopolysiloxane resin of the component (B). Particularly preferably, it is 20 to 60 mol%.

The blending amount of the component (B) is 60 to 90 parts by mass, preferably 65 to 80 parts by mass, and more preferably 65 to 75 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B). It is a department. If the blending amount of the component (B) is less than 60 parts by mass, the adhesiveness may be poor or a cured product having high hardness may not be obtained, and if it exceeds 90 parts by mass, the viscosity of the composition is remarkably high. It becomes expensive, it becomes difficult to transfer, and it becomes difficult to handle the composition when it is used as a die bond material or the like.

Specific examples of the branched organopolysiloxane of the component (B) include the following.
(CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _0.1 ((CH ₃ ) ₃ SiO _1/2 ) _0.4 (SiO ₂ ) _0.5 ,
(CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _0.2 ((CH ₃ ) ₂ SiO) _0.25 ((CH ₃ ) SiO _3/2 ) _0.55 ,
(CH ₂ = CH (CH ₃ ) SiO) _0.4 ((CH ₃ ) ₂ SiO) _0.15 ((CH ₃ ) SiO _3/2 ) _0.45
The component (B) may be used alone or in combination of two or more.

<Ingredient (C)>
The component (C) acts as a cross-linking agent that crosslinks the alkenyl group contained in the component (A) and the component (B) by a hydrosilylation reaction. The component (C) is an organohydrogenpolysiloxane represented by the following average composition formula (3) and having at least two hydrogen atoms (Si—H groups) bonded to silicon atoms in one molecule.

R ³ _l H _m SiO _{(4-lm) / 2} ... (3)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, respectively, and l and m are 0.7 ≦ l ≦ 2.1. 0.001 ≦ m ≦ 1.0 and 0.8 ≦ l + m ≦ 3.0, preferably 1.0 ≦ l ≦ 2.0, 0.01 ≦ m ≦ 1.0, and 1.5 ≦ l + m ≦ It is a number that satisfies 2.5.)

The viscosity of the component (C) at 25 ° C. is not particularly limited, but is preferably in the range of 100 mPa · s or less, and more preferably 5 to 100 mPa · s.

Examples of R ³ include the same components as those exemplified as R ¹ in the above component (A), preferably an alkyl group, and particularly preferably a methyl group.

The number of methyl groups in the total number of monovalent hydrocarbon groups bonded to silicon atoms other than the alkenyl groups represented by R ¹ and R ³ in the composition of the present invention is 80 mol% or more (that is,). , 80 mol% or more of R ¹ and R ³ is a methyl group), and in particular, 90 mol% or more is heat resistance, light resistance (ultraviolet resistance), heat, ultraviolet rays, etc. It is preferable because it has excellent resistance to deterioration such as discoloration due to stress.

The component (C) has at least two hydrogen atoms (that is, Si—H groups) bonded to silicon atoms in one molecule, preferably 2 to 200, more preferably 3 to 100, and particularly preferably. There are 4 to 50 pieces.

The molecular structure of the organohydrogenpolysiloxane as a 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. The number is, more preferably 3 to 200.

Examples of the organohydrogenpolysiloxane as the component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, and tris. (Hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both-terminal trimethylsiloxy group-blocked dimethylsiloxane / methyl Hydrogensiloxane copolymer, both-ended dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both-ended dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, both-ended dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane Combined, double-ended trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, double-ended trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, double-ended trimethylsiloxy group-blocked methylhydrogensiloxane / Methylphenylsiloxane / dimethylsiloxane copolymer, both-ended dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both-ended dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / methylphenyl Siloxane copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _1/2 unit and SiO _4/2 unit copolymer, (CH ₃ ) ₂ HSiO _1/2 unit Examples include a copolymer composed of _4/2 units of SiO, a copolymer composed of (CH ₃ ) ₂ HSiO _1/2 unit, a SiO _4/2 unit, and (C ₆ H ₅ ) ₃ SiO _1/2 unit. In addition, those represented by the following general formula (4) or (5) can be mentioned.
R ³ ₃ SiO [SiR ³ (H) O] _r SiR ³ ₃ (4)
Circular [SiR ³ (H) O] _s (5)
(In the equation, R ³ is as described above, r is an integer of 2 to 40, preferably 8 to 35, and s is an integer of 6 to 8).

（式中、括弧内のシロキサン単位の配列順は任意である。）
（Ｃ）成分のオルガノハイドロジェンポリシロキサンは、一種単独で用いても二種以上を併用してもよい。 Specific examples of the component (C) include those represented by the following general formula (6).
Me ₃ SiO [SiMe (H) O] _r SiMe ₃ (6)
(In the formula, r is as described above. Me is a methyl group.)
Those expressed by the following formulas can be mentioned.

(In the formula, the arrangement order of the siloxane units in parentheses is arbitrary.)
The organohydrogenpolysiloxane of the component (C) may be used alone or in combination of two or more.

From the viewpoint of the balance of cross-linking, the blending amount of the component (C) was bonded to the silicon atom in the component (C) with respect to the total number of alkenyl groups bonded to the silicon atom in the components (A) and (B). The number of hydrogen atoms (Si—H groups) is preferably 0.5 to 5.0 times, more preferably 0.7 to 3.0 times. Within such a range, cross-linking proceeds sufficiently, and a cured product having excellent hardness can be obtained.

<(D) component>
The platinum group metal-based catalyst of the component (D) is a component for advancing and promoting the hydrosilylation reaction of the components (A) to (C).

The platinum group metal-based catalyst is not particularly limited, and for example, a platinum group metal such as platinum, palladium, and rhodium; a combination of platinum chloride acid, alcohol-modified platinum chloride acid, platinum chloride acid and olefins, vinylsiloxane, or acetylene compound. Examples thereof include platinum compounds such as position compounds, platinum group metal compounds such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, and the compatibility with the components (A) to (C) is good. Since it contains almost no chlor impurities, it is preferably a silicone-modified product of platinum chloride.
The component (D) may be used alone or in combination of two or more.

The blending amount of the component (D) may be an effective amount as a catalyst, but is preferably 1 to 500 ppm, preferably 1 to 500 ppm in terms of mass of the platinum group metal element, relative to the total of the components (A) to (C). It is 3 to 100 ppm, more preferably 5 to 40 ppm. When this blending amount is appropriate, the hydrosilylation reaction can be promoted more effectively.

<Other ingredients>
In addition to the above-mentioned components (A) to (D), the composition of the present invention may contain other components exemplified below.

Reaction inhibitor:
In the composition of the present invention, a conventionally known reaction inhibitor (reaction control agent), which is a compound having a curing inhibitory effect on the addition reaction catalyst of the component (D), can be used, if necessary. .. Examples of this reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; sulfur-containing compounds; acetylene-based compounds; hydroperoxy compounds; maleic acid derivatives and the like. Will be done.

Since the degree of the curing inhibitory effect of the reaction inhibitor varies greatly depending on the chemical structure of the reaction inhibitor, it is preferable to adjust the blending amount of the reaction inhibitor to an optimum amount for each reaction inhibitor to be used. Usually, 0.001 to 5 parts by mass is preferable with respect to a total of 100 parts by mass of the component (A), the component (B), the component (C) and the component (D).

Adhesive improver:
An adhesiveness improver may be added to the composition in order to enhance the adhesiveness to the resin. The adhesiveness improving agent is an organosilicon compound such as silane or siloxane containing a functional group that imparts adhesiveness, or a non-silicone type, from the viewpoint of imparting self-adhesiveness to the composition of the present invention which is an addition reaction curing type. Organic compounds and the like are used.

Specific examples of the functional group that imparts adhesiveness include a vinyl group bonded to a silicon atom, an alkenyl group such as an allyl group, a hydrogen atom; and an epoxy group bonded to a silicon atom via a carbon atom (for example, γ-glycid). Xypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, etc.), acryloxy group (eg, γ-acryloxypropyl group, etc.) or metharoxy group (eg, γ-methacryloxypropyl group, etc.); alkoxysilyl An alkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, or a methyldimethoxysilyl group bonded to a silicon atom via an alkylene group which may contain one or two groups (for example, an ester structure, a urethane structure, or an ether structure). Basics, etc.) and the like.

Organic silicon compounds containing a functional group that imparts adhesiveness include silane coupling agents, siloxanes having an alkoxysilyl group and an organic functional group, and compounds in which an alkoxysilyl group is introduced into an organic compound having a reactive organic group. Illustrated.

Examples of the non-silicone organic compound include an organic acid allyl ester, an epoxy group ring opening catalyst, an organic titanium compound, an organic zirconium compound, and an organic aluminum compound.

Organic peroxides:
In the present invention, further improvement in resin strength can be achieved by adding an organic peroxide.

Examples of the organic peroxide include benzoyl peroxide, t-butyl peroxide, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, dicumyl peroxide, and 1,1-bis (t-butyl peroxide). -3,3,3-trimethylcyclohexane, di (4-methylbenzoylperoxy) hexamethylene biscarbonate and the like can be mentioned. The amount to be added may be an effective amount, but usually 0.01 to 5 parts by mass, particularly 0.05 to 3 parts by mass, is added to 100 parts by mass of the total amount of organopolysiloxane of the components (A) and (B). Is preferable. These can be used alone or in combination of two or more.

filler:
In the composition of the present invention, an inorganic filler such as crystalline silica, a hollow filler, and silsesquioxane, and these fillers may be used as an organoalkoxysilane compound, an organochlorosilane compound, an organosilazane compound, a low molecular weight siloxane compound, or the like. Fillers and the like whose surface has been hydrophobized with an organic silicon compound; silicone rubber powder, silicone resin powder and the like can be filled. As this component, it is particularly preferable to use a filler capable of imparting chixo property, and by imparting chixo property, a cured product having excellent workability and die-share strength can be obtained.

These other components may be used alone or in combination of two or more.

The viscosity of the addition-curable silicone resin composition of the present invention is preferably 5 to 100 Pa · s, more preferably 20 to 50 Pa · s at 25 ° C. in order to improve workability in die bonding (transfer method). Is.

[Cursed product]
Furthermore, the present invention provides a cured product of an addition curable silicone composition.
The addition-curing silicone composition of the present invention may be cured under known conditions, and as an example, it can be cured at 100 to 180 ° C. for 10 minutes to 5 hours.

The cured product of the addition-curable silicone composition of the present invention is useful as a composition having high adhesive strength to a substrate / LED chip, particularly as a die-bonding material used for die-bonding of LED elements and the like. As described above, the cured silicone product of the present invention can be used as an adhesive having high adhesive strength to the substrate / LED chip.

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

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but these do not limit the present invention in any way. The molecular weight is a weight average molecular weight in terms of standard polystyrene in gel permeation chromatography (GPC). The viscosity at 25 ° C. is a measured value by a rotational viscometer.
The meaning of the abbreviations for each siloxane unit is as follows.
M: (CH ₃ ) ₃ SiO _1/2
M ^Vi : (CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2
D: (CH ₃ ) ₂ SiO _2/2
DH: ^H (CH ₃ ) S iO _2/2
D ^Vi : (CH = CH ₂ ) (CH ₃ ) SiO
T: (CH ₃ ) SiO _3/2
T ^Vi : (CH ₂ = CH) SiO _3/2
Q: SiO _4/2

[Synthesis Example 1]
In a 1,000 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer [(CH ₃ ) (CH ₃ O) ₂ SiO _1/2 ] ₂ [(CH ₃ ) (CH ₃ O) 733 g of organopolysiloxane represented by [SiO] ₂ , 528 g of 1,3-divinyltetramethyldisiloxane, and 170 g of isopropanol were added, and 14.0 g of methanesulfonic acid was added dropwise with stirring. Then, 144 g of water was added dropwise, and the mixture was mixed at 65 ° C. for 2 hours to carry out a reaction. Further, 7.0 g of baking soda was added and mixed at 65 ° C. for 2 hours to carry out a neutralization reaction. The temperature was further raised to 85 ° C., alcohol was removed in this process, and then the mixture was cooled to room temperature. After cooling, the mixture was washed with water and concentrated under reduced pressure at ₁₇₀ ° _C. and 10 ^mmHg or less for 1 hour. 1) was obtained.

[Synthesis example 2]
Put 136 g of methyltrimethoxysilane, 93.2 g of 1,3-divinyltetramethyldisiloxane and 61.2 g of isopropanol in a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, and stir. 3.0 g of methanesulfonic acid was added dropwise. Then, 28.9 g of water was added dropwise, and the mixture was mixed at 65 ° C. for 2 hours to carry out a reaction. Further, 6.0 g of baking soda was added and mixed at 65 ° C. for 2 hours to carry out a neutralization reaction. The temperature was further raised to 85 ° C., alcohol was removed in this process, and then the mixture was cooled to room temperature. After cooling, the mixture was washed with water and concentrated under reduced pressure at ₁₇₀ ° _C. and 10 ^mmHg or less for 1 hour. 2) was obtained.

[Synthesis Example 3]
Put 150.0 g of vinyltrimethoxysilane, 93 g of 1,3-divinyltetramethyldisiloxane and 60.8 g of isopropanol in a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, and stir. 2.9 g of methanesulfonic acid was added dropwise. Then, 30.6 g of water was added dropwise, and the mixture was mixed at 65 ° C. for 2 hours to carry out a reaction. Further, 5.8 g of baking soda was added and mixed at 65 ° C. for 2 hours to carry out a neutralization reaction. The temperature was further raised to 85 ° C., alcohol was removed in this process, and then the mixture was cooled to room temperature. After cooling, the mixture was washed with water and concentrated under reduced pressure at 170 ° C. and 10 mmHg or less for 1 hour. As a result, a branched organopolysiloxane having a viscosity of 21 mPa · s, an average structure of M ^Vi _0.5 T ^Vi _0.5 and a molecular weight of 1,450 ( A-3) was obtained.

[Comparative synthesis example 1]
Put 136 g of methyltrimethoxysilane, 45 g of 1,3-divinyltetramethyldisiloxane, and 45.2 g of isopropanol in a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, and methanesulfone while stirring. 2.2 g of acid was added dropwise. Then, 28.4 g of water was added dropwise, and the mixture was mixed at 65 ° C. for 2 hours to carry out a reaction. Further, 4.4 g of baking soda was added and mixed at 65 ° C. for 2 hours to carry out a neutralization reaction. The temperature was further raised to 85 ° C., alcohol was removed in this process, and then the mixture was cooled to room temperature. After cooling, the mixture was washed with water and concentrated under reduced pressure at 170 ° C. and 10 mmHg or less for 1 hour to obtain a branched organopolysiloxane (A) having a viscosity of 153 mPa · s, an average structure of M ^Vi _0.32 T _0.68 , and a molecular weight of 9,730. -5) was obtained.

[Synthesis Example 4]
The reaction product of platinum hexachloride and 1,3-divinyltetramethyldisiloxane is directly expressed as M ^Vi ₂ D ₄₀ with a viscosity of 60 mPa · s so that the platinum content is 0.004% by mass. A platinum catalyst (D) was prepared by diluting with chain dimethylpolysiloxane.

[Examples 1 to 3, Comparative Examples 1 and 2]
The following components were mixed in the blending amounts shown in Table 1 to prepare an addition-curable silicone composition.
The numerical values of each component in Table 1 represent parts by mass. The [Si—H] / [Si—Vi] value is the hydrogen atom bonded to the silicon atom in the component (C) with respect to the total number of alkenyl groups bonded to the silicon atom in the component (A) and the component (B). Represents the ratio (molar ratio) of the number of Si—H groups).

(A) Ingredient:
(A-1) Branched organopolysiloxane obtained in Synthesis Example 1 (A-2) Branched organopolysiloxane obtained in Synthesis Example 2 (A-3) Branched organopoly obtained in Synthesis Example 3 Siloxane

Comparative component:
(A-4) Linear organopolysiloxane (viscosity 8.7 mPa at 25 ° C.) represented by M ^Vi _0.167 D _0.833 (M ^Vi ₂ D ₁₀ ) with both ends sealed with vinyl groups.・ S)
(A-5) Branched organopolysiloxane obtained in Comparative Synthesis Example 1

Ingredients (B) to (D):
(B) Branched form represented by M ^Vi _0.064 M _0.398 Q _0.538 (M ^Vi _1.2 M _7.4 Q ₁₀ ) in which the amount of vinyl group with respect to solid content is 0.085 mol / 100 g. Platinum obtained in Methylhydrogenpolysiloxane (D) Synthesis Example 4 represented by Organopolysiloxane (C) M _0.037 D _0.266 ^DH _0.697 (M ₂ D _14.5 ^DH ₃₈ ) catalyst

Other ingredients:
(E) Reaction inhibitor: 1-ethynylcyclohexanol (F-1) Adhesive improver: Cyclic polysiloxane (F- ₂ ) represented by ^DV4 Adhesive improver: Triallyl isocyanurate (F-3) ) Adhesive improver: Compound represented by the following formula

The addition-curable silicone resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 2.

[hardness]
The composition was poured into a mold to a thickness of 2 mm, and the Type D hardness of the cured product cured under the conditions of 150 ° C. × 4 hours was measured according to JIS K6253.
[Die share strength]
The composition was quantitatively transferred by stamping to the silver-plated electrode portion of the SMD5050 package (manufactured by I-CHIUN PRESSION INDUSTRY CO., Resin portion: polyphthalamide) using a die bonder (manufactured by ASM, AD-830). , An optical semiconductor element (EV-B35A, 35 mil manufactured by SemiLEDs) was mounted on it. The prepared package was heated in an oven at 150 ° C. for 2 hours to cure the composition, and then the die shear strength was measured using a bond tester (Series 4000 manufactured by Dage).

As shown in Table 2, in Examples 1 to 3, all of the cured products were excellent in hardness and die shear strength, and were excellent as die bond materials.
On the other hand, in Comparative Example 1, since the component (A) is a linear organopolysiloxane, the die share strength of the cured product is inferior.
Further, in Comparative Example 2, although the component (A) was a branched organopolysiloxane, it was inferior in transferability due to its high viscosity, and die bonding could not be performed.

As described above, the addition-curable silicone resin composition of the present invention provides a cured silicone product having excellent hardness and die shear strength, and is particularly useful as a die-bonding material used for die-bonding of optical semiconductor devices and the like. In particular, due to this feature, in the wire bonding process performed after the die bonding process, problems such as chip peeling and bonding failure are unlikely to occur. In addition to increasing reliability, the productivity of the equipment is also improved. Therefore, the addition-curable silicone resin composition of the present invention and the cured product thereof have high utility value in the technical field of optical semiconductor devices.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and the present invention can be anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same function and effect. Is included in the technical scope of.

Claims (5)

(A) A branched organopolysiloxane represented by the following average composition formula (1) and having a viscosity at 25 ° C. of 100 mPa · s or less.
(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² SiO _3/2 ) _c (R ¹ SiO _3/2 ) _d (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, respectively, and R ² is an alkenyl group which may be the same or different, respectively. a, b, c, d are numbers that satisfy a ≧ 0, b ≧ 0, c ≧ 0, and d ≧ 0, respectively, except that a + b> 0, b + c> 0, c + d> 0, and a + b + c + d. = A number that satisfies 1.)
(B) Branched organopolysiloxane represented by the following average composition formula (2 ' ): 60 to 90 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B).
(R ¹ ₃ SiO _1/2 ) _e (R ² R ¹ ₂ SiO _1/2 ) _f (R ² R ¹ SiO) _g (R ¹ ₂ SiO) _h ( SiO _4/2 ) _k (2 ' )
(In the equation, R ¹ and R ² are the same as described above. E, f, g, h , k are e ≧ 0, f ≧ 0, g ≧ 0, h ≧ 0 , and k > 0, respectively. It is a number that satisfies, however, f + g> 0 and e + f + g + h + k = 1.)
(C) Organohydrogenpolysiloxane, which is represented by the following average composition formula (3) and has at least two hydrogen atoms bonded to silicon atoms in one molecule.
R ³ _l H _m SiO _{(4-lm) / 2} (3)
(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group containing no alkenyl group, which may be the same or different, respectively, and l and m are 0.7 ≦ l ≦ 2.1, 0. .001 ≤ m ≤ 1.0 and 0.8 ≤ l + m ≤ 3.0.)
as well as,
(D) An addition-curable silicone resin composition comprising a platinum group metal-based catalyst. The addition-curable silicone resin composition according to claim 1, wherein 80 mol% or more of R ¹ and R ³ are methyl groups. The addition-curable silicone resin composition according to claim 1 or 2, wherein in the component (A) in the composition, a = c = 0. A silicone cured product, which is a cured product of the addition-curable silicone resin composition according to any one of claims 1 to 3. An optical semiconductor device according to claim 4, wherein the optical semiconductor element is die-bonded with the cured silicone product.