JP6722129B2 - Epoxy/silicone hybrid resin composition for optical semiconductor element encapsulation and optical semiconductor device using the same - Google Patents

Description

The present invention relates to an epoxy/silicone hybrid resin composition for encapsulating an optical semiconductor element and an optical semiconductor device using the composition.

As a sealing material for sealing various optical semiconductor elements such as LEDs (Light Emitting Diodes), bisphenol A has excellent transparency, moisture resistance, heat resistance, and light resistance, and at the same time, it has a low cost. A composition containing an epoxy resin having no UV absorption, such as a type epoxy resin, a hydrogenated bisphenol A type epoxy resin, or an alicyclic epoxy resin, a curing agent, and a curing catalyst is often used. Such a composition is liquid at room temperature, and its use is limited to casting and potting (Patent Document 1).

In recent years, due to the trend toward higher output and higher brightness of LED elements, polyfunctional epoxy resins and alicyclic epoxy resins have been used to improve heat resistance and light resistance. Those materials that are solid at room temperature can be manufactured, and transfer molding and compression molding can be performed, so that even a package having a complicated shape can be molded (Patent Documents 2 and 3).

Further heat resistance and light resistance are required for such an epoxy resin, and a hybrid resin of epoxy/silicone has been reported to solve these problems (Patent Document 4, 5, 6). However, since the resins described in Patent Documents 4 and 5 are liquid at room temperature, the shape of the package used is limited. The resin described in Patent Document 6 is a material having transparency by adjusting the refractive index of the epoxy resin and the silicone resin, but stable adjustment is expected to be difficult in terms of compatibility. To be done.

JP, 07-309927, A JP-A-02-222165 JP 2008-285591 A JP2012-057006A JP, 2013-064087, A JP, 2006-274249, A

The present invention has been made in view of the above circumstances, since it is a solid at room temperature, it is easy to handle and can be tableted by pressure molding, and its cured product has high strength, high transparency, and heat resistance, An object of the present invention is to provide an epoxy-silicone hybrid resin composition for encapsulating an optical semiconductor element, which is also excellent in light resistance, and an optical semiconductor device using the same.

（式中、Ｒ^１及びＲ^３は独立して炭素数６〜１２の１価芳香族炭化水素基、又は炭素数１〜１２の１価脂肪族炭化水素基であり、Ｒ^２は炭素数４〜５０の１価脂肪族エポキシ基であり、１分子中、１個以上のＲ^３が１価芳香族炭化水素基であり、０≦ｌ＜０．４、０．１≦ｍ≦０．５、０．１≦ｎ≦０．８であり、ｌ＋ｍ＋ｎ＝１である。）
（Ａ−２）１分子中にエポキシ基を２つ以上有するエポキシ樹脂であって、トリアジン誘導体エポキシ樹脂、ビスフェノール型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、及び脂環式エポキシ樹脂からなる群から選択される少なくとも１つのエポキシ樹脂、及び
（Ａ−３）酸無水物系硬化剤、
の反応生成物であって、前記（Ａ−１）及び（Ａ−２）成分中のエポキシ基１個に対する前記（Ａ−３）成分中の酸無水物基の個数が０．３〜１．０個となる量のプレポリマー、並びに
（Ｂ）硬化触媒
を含有し、２５℃で固体であることを特徴とする光半導体素子封止用エポキシ・シリコーンハイブリッド樹脂組成物を提供する。 In order to solve the above problems, in the present invention,
(A) (A-1) An organopolysiloxane represented by the following formula (1),

(In the formula, R ¹ and R ³ are independently a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ² is 4 carbon atoms. To 50 monovalent aliphatic epoxy groups, one or more R ³ in one molecule is a monovalent aromatic hydrocarbon group, 0≦l<0.4, 0.1≦m≦0.5 , 0.1≦n≦0.8, and l+m+n=1.)
(A-2) An epoxy resin having two or more epoxy groups in one molecule, which is selected from the group consisting of a triazine derivative epoxy resin, a bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, and an alicyclic epoxy resin. At least one epoxy resin, and (A-3) an acid anhydride-based curing agent,
The number of acid anhydride groups in the component (A-3) per one epoxy group in the components (A-1) and (A-2) is 0.3 to 1. Provided is an epoxy-silicone hybrid resin composition for optical semiconductor element encapsulation, which comprises 0 prepolymer and (B) a curing catalyst and is solid at 25°C.

Since such an epoxy/silicone hybrid resin composition is solid at room temperature, it is easy to handle and can be formed into tablets by pressure molding, and its cured product has high strength, high transparency, heat resistance, Excellent light resistance.

（式中、Ｒ’は水素原子又は炭素数１〜６のアルキル基であり、Ｒ^４は炭素数１〜２０の２価の炭化水素基である。） At this time, in the formula (1), R ² is preferably represented by the following formula (2).

(In the formula, R′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms.)

Any component having such a structure is preferably used as the component (A-1).

Further, the component (A-2) is preferably a triazine derivative epoxy resin.

With such a component (A-2), an epoxy-silicone hybrid resin composition is obtained which is more excellent in heat resistance and UV resistance, and a cured product having a high glass transition temperature (Tg) can be obtained.

Moreover, it is preferable that the epoxy-silicone hybrid resin composition further contains (C) an antioxidant and (D) a silane coupling agent.

The inclusion of the antioxidant can improve the heat resistance and transparency of the cured product of the epoxy-silicone hybrid resin composition. Further, the inclusion of the silane coupling agent can improve the adhesiveness and the like of the composition.

Further, the component (C) is preferably a combination of a phenolic antioxidant and a phosphorus antioxidant.

If it is such a thing, it can be conveniently used as a (C)component.

Furthermore, the present invention provides an optical semiconductor device comprising a cured product of the above epoxy-silicone hybrid resin composition.

The cured product of the epoxy-silicone hybrid resin composition of the present invention is transparent, has mechanical strength, and is excellent in heat resistance and light resistance. Therefore, the optical semiconductor device using the epoxy-silicone hybrid resin composition of the present invention has excellent reliability.

The epoxy-silicone hybrid resin composition of the present invention is a solid at room temperature, so it is easy to handle and can be formed into a tablet by pressure molding. The cured product thereof has high strength, high transparency, heat resistance and light resistance. Is also excellent. Therefore, the epoxy-silicone hybrid resin composition of the present invention can be suitably used as a resin composition for encapsulating an optical semiconductor element. Further, an optical semiconductor device obtained by encapsulating an optical semiconductor element with such an epoxy/silicone hybrid resin composition has excellent reliability.

As mentioned above, since it is solid at room temperature, it is easy to handle, it can be made into tablets by pressure molding, and the cured product has high strength, high transparency, and excellent heat resistance and light resistance. There has been a demand for the development of a stopping epoxy-silicone hybrid resin composition.

As a result of earnest studies on the above problems, the present inventor has found that a D unit (R ¹ R ² SiO _2/2 unit) containing an aliphatic epoxy group and a T unit (R ³ SiO) containing an aromatic hydrocarbon group. _The epoxy-silicone hybrid resin composition containing a prepolymer obtained by using an organopolysiloxane having _3/2 units) and a specific epoxy resin in combination is solid at room temperature, so that it can be tableted by pressure molding. Therefore, they have found that a cured product having high transparency, mechanical strength, Tg, and excellent heat resistance and light resistance can be provided, and thus the present invention has been accomplished.

（式中、Ｒ^１及びＲ^３は独立して炭素数６〜１２の１価芳香族炭化水素基、又は炭素数１〜１２の１価脂肪族炭化水素基であり、Ｒ^２は炭素数４〜５０の１価脂肪族エポキシ基であり、１分子中、１個以上のＲ^３が１価芳香族炭化水素基であり、０≦ｌ＜０．４、０．１≦ｍ≦０．５、０．１≦ｎ≦０．８であり、ｌ＋ｍ＋ｎ＝１である。）
（Ａ−２）１分子中にエポキシ基を２つ以上有するエポキシ樹脂であって、トリアジン誘導体エポキシ樹脂、ビスフェノール型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、及び脂環式エポキシ樹脂からなる群から選択される少なくとも１つのエポキシ樹脂、及び
（Ａ−３）酸無水物系硬化剤、
の反応生成物であって、前記（Ａ−１）及び（Ａ−２）成分中のエポキシ基１個に対する前記（Ａ−３）成分中の酸無水物基の個数が０．３〜１．０個となる量のプレポリマー、並びに
（Ｂ）硬化触媒
を含有し、２５℃で固体である光半導体素子封止用エポキシ・シリコーンハイブリッド樹脂組成物である。 That is, the present invention is
(A) (A-1) An organopolysiloxane represented by the following formula (1),

(In the formula, R ¹ and R ³ are independently a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ² is 4 carbon atoms. To 50 monovalent aliphatic epoxy groups, one or more R ³ in one molecule is a monovalent aromatic hydrocarbon group, 0≦l<0.4, 0.1≦m≦0.5 , 0.1≦n≦0.8, and l+m+n=1.)
(A-2) An epoxy resin having two or more epoxy groups in one molecule, which is selected from the group consisting of a triazine derivative epoxy resin, a bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, and an alicyclic epoxy resin. At least one epoxy resin, and (A-3) an acid anhydride-based curing agent,
The number of acid anhydride groups in the component (A-3) per one epoxy group in the components (A-1) and (A-2) is 0.3 to 1. An epoxy-silicone hybrid resin composition for optical semiconductor element encapsulation, which contains 0 prepolymer and (B) a curing catalyst and is solid at 25°C.

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

<Epoxy/silicone hybrid resin composition>
The epoxy-silicone hybrid resin composition of the present invention is a solid composition containing the components (A) and (B) described below and solid at room temperature (25°C). Hereinafter, each component will be described.

[(A) Prepolymer]
The component (A) of the epoxy-silicone hybrid resin composition of the present invention is a prepolymer composed of reaction products of components (A-1) to (A-3) described later.

（式中、Ｒ^１及びＲ^３は独立して炭素数６〜１２の１価芳香族炭化水素基、又は炭素数１〜１２の１価脂肪族炭化水素基であり、Ｒ^２は炭素数４〜５０の１価脂肪族エポキシ基であり、１分子中、１個以上のＲ^３が１価芳香族炭化水素基であり、０≦ｌ＜０．４、０．１≦ｍ≦０．５、０．１≦ｎ≦０．８であり、ｌ＋ｍ＋ｎ＝１である。） [(A-1) Organopolysiloxane]
The component (A-1) is an organopolysiloxane represented by the following formula (1).

(In the formula, R ¹ and R ³ are independently a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ² is 4 carbon atoms. To 50 monovalent aliphatic epoxy groups, one or more R ³ in one molecule is a monovalent aromatic hydrocarbon group, 0≦l<0.4, 0.1≦m≦0.5 , 0.1≦n≦0.8, and l+m+n=1.)

In the above formula (1), R ¹ is independently a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms. The monovalent aromatic hydrocarbon group represented by R ¹ has 6 to 12, preferably 6 to 9 carbon atoms, and specifically, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and benzyl. And aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group. Of these, a phenyl group, a benzyl group, a 2-phenylethyl group, and a 2-phenylpropyl group are preferable, and a phenyl group is more preferable.

In addition, at least 1 or more, more preferably 2 to 6, of all R ^{1 in} the molecule are monovalent aromatic hydrocarbon groups, and further preferably phenyl groups.

The monovalent aliphatic hydrocarbon group represented by R ¹ has 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n group. -Alkyl group such as butyl group, t-butyl group, heptyl group, 2-ethylhexyl group and octyl group, alkenyl such as vinyl group, allyl group, isopropenyl group, butenyl group and 2-(3-cyclohexenyl)ethyl group Groups and the like. Among them, an alkyl group is preferable, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and a heptyl group are particularly preferable, and a methyl group is more preferable.

（式中、Ｒ’は水素原子又は炭素数１〜６のアルキル基であり、Ｒ^４は炭素数１〜２０の２価の炭化水素基である。） In the above formula (1), R ² is a monovalent aliphatic epoxy group having 4 to 50 carbon atoms, preferably 6 to 40 carbon atoms, and more preferably 7 to 30 carbon atoms. Examples of the aliphatic epoxy group include structures represented by the following formula (2).

(In the formula, R′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms.)

In the above formula (2), R'is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include alkylene groups such as methylene group, ethylene group and propylene group.

（式中、Ｒ^５は炭素数１〜２０のアルキレン基であり、好ましくはプロピレン基である。） Among them, R ² is preferably an aliphatic epoxy group represented by the following formula (3).

(In the formula, R ⁵ is an alkylene group having 1 to 20 carbon atoms, and preferably a propylene group.)

R ² is particularly preferably an aliphatic epoxy group ((3-glycidoxy)propyl group) having the following structure.

In the above formula (1), R ³ is independently a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ³ is 1 in one molecule. R ³ or more is a monovalent aromatic hydrocarbon group. Preferable examples of R ³ include the same as those shown for R ¹ above.

In the present invention, the above formula (1) is a composition formula, and l, m and n represent the number ratio (molar ratio) of each siloxane unit. 0≦l<0.4, 0.1≦m≦0.5, 0.1≦n≦0.8, and l+m+n=1. In addition, the bonding order of each siloxane unit in the parentheses in the above formula (1) is not limited.

In the above formula (1), l represents the content of ^R ₁ 2 _{SiO 2/2} units (molar ratio). The range of l is 0≦l<0.4, and preferably 0≦l<0.35.

In the above formula (1), m represents the content (molar ratio) of the D unit containing an aliphatic epoxy group, that is, the R ¹ R ² SiO _2/2 unit. The range of m is 0.1≦m≦0.5, preferably 0.1≦m≦0.4, and particularly preferably 0.1≦m≦0.35.

In the above formula (1), n represents the content (molar ratio) of the T unit containing an aromatic hydrocarbon group, that is, the R ³ SiO _3/2 unit. The range of n is 0.1≦n≦0.8, preferably 0.1≦n≦0.75, particularly preferably 0.1≦n≦0.7.
In addition, at least one or more, preferably 2 to 6 of all R ³ in the T unit are monovalent aromatic hydrocarbon groups, and more preferably phenyl groups.

The organopolysiloxane preferably has a weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of 1,200 or more and 6,000 or less, more preferably 1,200 or more and 5 or less. It is less than 1,000. When the weight average molecular weight (Mw) is within the above range, the composition has good workability and is easy to handle when sealing an optical semiconductor element. The cured product obtained from this composition has sufficient mechanical properties as an optical semiconductor element encapsulant.

上記式中、ｌ、ｍ、ｎは上述の通りである。上記括弧内にある各シロキサン単位の結合順序は制限されない。Ｍｅはメチル基を示す。 Examples of the organopolysiloxane represented by the above formula (1) include the structures represented by the following formulas.

In the above formula, l, m, and n are as described above. The bonding order of the siloxane units in the parentheses is not limited. Me represents a methyl group.

The method for producing the organopolysiloxane represented by the above formula (1) is not particularly limited. For example, the organopolysiloxane represented by the above formula (1) is a silanol group or an alkoxy group which is a raw material of R ¹ ₂ SiO _2/2 unit, R ¹ R ² SiO _2/2 unit, R ³ SiO _3/2 unit. It can be obtained by carrying out a condensation reaction in the presence of a catalyst with at least one organosilicon compound having at least two silyl groups in one molecule. The reaction ratio of the raw material compounds may be appropriately adjusted so that the molar ratios l, m, and n of the siloxane units are in the above ranges.

（式中、Ｒ^１は上述の通りであり、Ｘは水素原子又は炭素数１〜１０のアルキル基であり、好ましくはメチル基である。ｅは１〜２０の整数である。） The organic silicon compound as a raw material for R ¹ ₂ SiO _2/2 units, for example, organo (poly) siloxane represented by the following formula (4).

(In the formula, R ¹ is as described above, X is an alkyl group hydrogen atom or a C1-10, preferably a methyl group .e is an integer of 1 to 20.)

（式中、Ｘ及びＲ^１は上述の通りである。）
特には、Ｘが水素原子又はメチル基であり、Ｒ^１がメチル基又はフェニル基であるものが好ましい。より好ましくはジメトキシシランである。 Examples of the silane compound (e=1) represented by the above formula (4) include methyldialkoxysilane represented by the following formula.

(In the formula, X and R ¹ are as described above.)
Particularly, those in which X is a hydrogen atom or a methyl group and R ¹ is a methyl group or a phenyl group are preferable. More preferably dimethoxysilane.

（式中、Ｘ及びＲ^１は上述の通りであり、ｅ’は２〜１０の整数である。）
特には、Ｘが水素原子又はメチル基であり、Ｒ^１がメチル基又はフェニル基であるものが好ましい。上記オリゴマーの中でも、反応性、作業性、低ガス透過性の観点から、ジメトキシシランのオリゴマーが特に好適である。 Examples of the organopolysiloxane (e=2 to 20) represented by the above formula (4) include dialkoxysilane oligomers represented by the following formula.

(In the formula, X and R ¹ are as described above, and e′ is an integer of 2 to 10.)
Particularly, those in which X is a hydrogen atom or a methyl group and R ¹ is a methyl group or a phenyl group are preferable. Among the above oligomers, dimethoxysilane oligomers are particularly preferable from the viewpoints of reactivity, workability, and low gas permeability.

Examples of the organic silicon compound as a raw material of R ¹ R ² SiO _2/2 unit include an aliphatic epoxy group-containing silane compound represented by the following formula.

_{Examples of the} organosilicon compound as a raw material of R ³ SiO _3/2 unit include a phenyl group-containing silane compound represented by the following formula.

The condensation reaction for obtaining the organopolysiloxane represented by the above formula (1) can be performed using a conventionally known catalyst. For example, as a condensation reaction between an organo(poly)siloxane having a phenyl group-containing silanol group and/or an alkoxy group at both ends and an alkoxysilane compound having a substituent such as an alicyclic epoxy group, sodium hydroxide, water There is a method using strong bases such as potassium oxide, tetramethylammonium hydroxide, diazabicycloundecene, and 1,4-diazabicyclo[2.2.2]octane.

[(A-2) Epoxy resin having two or more epoxy groups in one molecule]
The component (A-2) is an epoxy resin having two or more epoxy groups in one molecule and comprises a triazine derivative epoxy resin, a bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, and an alicyclic epoxy resin. At least one epoxy resin selected from the group. The component (A-2) is preferably a triazine derivative epoxy resin from the viewpoint of heat resistance, UV resistance and high Tg.

The epoxy resin as the component (A-2) preferably contains three monovalent aliphatic epoxy groups represented by the above formula (2), and in these monovalent aliphatic epoxy groups, R ^4's are different from each other. You can Specific examples include 1-methyl-3,5-diglycidyl isocyanurate and 1,3,5-triglycidyl isocyanurate. Particularly, 1,3,5-triglycidyl isocyanurate represented by the following formula (5) is preferable.

The compounding amount of the epoxy resin as the component (A-2) is preferably 10 to 100 parts by mass, and more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the component (A-1). When the amount is 10 parts by mass or more, a sufficient Tg can be obtained. When the blending amount is 100 parts by mass or less, heat resistance and UV resistance do not decrease.

[(A-3) Acid Anhydride Curing Agent]
The component (A-3) is an acid anhydride group-based curing agent having reactivity with an epoxy group. The acid anhydride group in the acid anhydride-based curing agent is represented by -CO-O-CO-.

Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, and 4-methyl-hexahydroanhydride. Phthalic acid, a mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic acid anhydride, methylnadic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl Examples thereof include norbornane-2,3-dicarboxylic acid anhydride, 2,4-diethylglutaric acid anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. Among them, an acid anhydride having an alicyclic hydrocarbon structure is preferable, and it is more preferable to use two or more kinds of acid anhydrides in combination, and 4-methyl-hexahydrophthalic anhydride and a derivative thereof, particularly 4-methyl-hexahydro. It is more preferable to use phthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride together.

The amount of the acid anhydride-based curing agent as the component (A-3) is such that the amount of the acid anhydride group in the component (A-3) relative to one epoxy group in the components (A-1) and (A-2). The number, that is, the ratio of the number of acid anhydride groups in the component (A-3) to the total number of epoxy groups in the components (A-1) and (A-2) is 0.3 to 1.0. Is an amount, preferably 0.4 to 0.8. If the above ratio is less than 0.3, the heat resistance and transparency of the cured product will decrease. Moreover, when the said ratio is larger than 1.0, the mechanical property of hardened|cured material will fall.

(Method for producing prepolymer)
The prepolymer which is the component (A) of the present invention contains, for example, the above components (A-1), (A-2), and (A-3) at 60 to 120°C, preferably 70 to 110°C. It can be obtained by reacting for 2 to 20 hours, preferably 2 to 15 hours.

At this time, either the component (A-1) or the component (A-2) and the component (A-3) may be prepolymerized and the remaining components may be added later. Furthermore, the target prepolymer may be produced by adding each component other than the component (B) described below. At this time, the components may be added in any order.

Thus, the prepolymer of the component (A) can be obtained as a solid product having a softening point of 40 to 100°C, preferably 60 to 80°C. When the softening point of this prepolymer is 40° C. or higher, the resulting composition becomes solid at room temperature (25° C.), and pressure molding becomes easy at room temperature. Further, when the softening point of the prepolymer is 100° C. or lower, gelation does not proceed excessively and the composition can have the fluidity required at the time of molding.

[(B) Curing catalyst]
The curing catalyst that is the component (B) of the epoxy-silicone hybrid resin composition of the present invention is not particularly limited and may be selected from the curing catalysts that have been conventionally used in epoxy resin compositions. For example, quaternary phosphonium salts such as tetrabutylphosphonium-o,o-diethylphosphorodithioate and tetraphenylphosphonium tetraphenylborate, organic phosphine-based curing catalysts such as triphenylphosphine and diphenylphosphine, 1,8- Tertiary amine curing catalysts such as diazabicyclo[5.4.0]undecene-7, triethanolamine, benzyldimethylamine, 1,8-diazabicyclo[5.4.0]undecene-7 phenol salt, 1,8- Diazabicyclo[5.4.0]undecene-7 octylate, 1,8-diazabicyclo[5.4.0]undecene-7 p-toluenesulfonate, 1,8-diazabicyclo[5.4.0]undecene -7 Quaternary ammonium salts such as formate salts, organic carboxylic acid salts such as zinc octylate and zinc naphthylate, aluminum chelate compounds such as aluminum bisethylacetoacetate/monoacetylacetonate, aluminum ethylacetoacetate/diisopropylate , 2-methylimidazole, 2-phenyl-4-methylimidazole, and other imidazoles. Of these, quaternary phosphonium salts and quaternary ammonium salts are preferable.

The compounding amount of the curing catalyst is not particularly limited as long as it is an effective amount (catalyst amount) for promoting the reaction of the component (A). It is preferably 0.01 to 3 parts by mass, and more preferably 0.05 to 1.5 parts by mass, relative to 100 parts by mass of the component (A). When the amount of the curing catalyst is 0.01 part by mass or more, the effect of promoting the reaction between the epoxy resin and the curing agent can be sufficiently obtained. Further, when the compounding amount of the curing catalyst is 3 parts by mass or less, discoloration does not occur during curing of the composition or during the reflow test.

[(C) Antioxidant]
The epoxy-silicone hybrid resin composition of the present invention preferably further contains an antioxidant as the component (C). Examples of the antioxidant include phosphorous acid compounds and hindered phenol antioxidants. A hindered phenolic antioxidant is particularly preferable. Examples of the hindered phenol antioxidant include pentaerythritol tetrakis[3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate, N,N′-propane-1,3-. Diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide], thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl- 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 6,6'-di-t-butyl-2,2'-thiodi-p-cresol, N,N'-hexane-1 ,6-Diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7 -C9 side chain alkyl ester, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 2,2'-ethylidenebis[4,6-di-t-butylphenol ], 3,3′,3″,5,5′,5″-hexa-t-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri-p-cresol, calcium Diethylbis[[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate], 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis( Dodecylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di- t-Butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-trione , 1,3,5-Tris[(4-t-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)- Trione, 6,6'-di-t-butyl-4,4'-thiodi-m-cresol, diphenylamine, reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene, 2,6-di -T-Butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 3,4-dihydro-2,5,7,8-tetramethyi Le-2-(4,8,12-trimethyltridecyl)-2H-1-benzopyran-6-ol, 2′,3-bis[[3-[3,5-di-t-butyl-4-hydroxy] Examples include phenyl]propionyl]]propionohydrazide, didodecyl 3,3′-thiodipropionate, and dioctadecyl 3,3′-thiodipropionate. Of these, phenolic antioxidants and phosphorus antioxidants are preferable, and it is more preferable to use them in combination.

The compounding amount of the component (C) is preferably 0.1 to 0.5 part by mass, more preferably 0.1 to 0.3 part by mass, relative to 100 parts by mass of the component (A). If the compounding amount of the antioxidant is 0.5 parts by mass or less, there is no fear that the remaining antioxidant will be deposited on the surface of the cured resin. Further, when the blending amount is 0.1 part by mass or more, the heat resistance and transparency of the obtained cured product are improved.

[(D) Silane coupling agent]
The epoxy-silicone hybrid resin composition of the present invention preferably further contains a silane coupling agent as the component (D). Examples of the silane coupling agent include epoxy group-containing silanes, vinyl group-containing silanes, methacryloxy group-containing silanes, amino group-containing silanes, and mercapto group-containing silane compounds. Among them, epoxy group-containing silane or mercapto group-containing silane is preferable.

The compounding amount of the component (D) is preferably 0.1 to 0.5 part by mass, more preferably 0.2 to 0.3 part by mass, relative to 100 parts by mass of the component (A).

[(E) Release Agent]
The epoxy-silicone hybrid resin composition of the present invention may further contain a release agent as the component (E). The mold release agent as the component (E) is added in order to enhance the mold releasability during molding. Release agents include natural waxes such as carnauba wax, acid waxes, polyethylene waxes, and synthetic waxes such as fatty acid esters. Generally, they easily yellow under high-temperature conditions or under light irradiation. In many cases, it loses releasability due to deterioration with time or deterioration. Further, generally, the release agent oozes out on the resin surface, and if used in a small amount, the transparency of the cured product is often greatly reduced. Therefore, as the component (E) of the present invention, it is preferable to use a glycerin derivative or a fatty acid ester in terms of compatibility of transparency and releasability.

The blending amount of the component (E) is preferably 0.20 to 10.0% by mass, and more preferably 1.0 to 7.0% by mass with respect to the component (A). When the blending amount is 0.20 mass% or more, sufficient releasability can be obtained. When the blending amount is 10.0% by mass or less, sufficient transparency can be obtained, and there is no fear of defective drawing out, poor adhesion, and the like.

[Other ingredients]
Further, the epoxy-silicone hybrid resin composition of the present invention includes a flexibility-imparting agent such as polycaprolactone polyol or polycarbonate polyol for strengthening and improving crack resistance, a glass filler or a glass filler in a range not losing transparency. An inorganic filler such as silica or a low molecular weight polyol such as ethylene glycol, diethylene glycol or glycerin may be added to moderate the curing.

(Method for producing composition)
As the method for producing the epoxy-silicone hybrid resin composition of the present invention, for example, the components (A-1) to (A-3) are blended in a predetermined composition ratio, and the mixture is heat-mixed with a gate mixer or the like to obtain a pre-mixed product. To the prepolymer of the component (A) obtained by polymerizing, the components (B) and, if necessary, the additives such as the components (C) to (E) are melted at a predetermined ratio, cooled and solidified, and then appropriately added. Examples of the method include pulverizing into various sizes to obtain a molding material for an epoxy-silicone hybrid resin composition. At this time, the order of adding the components is not limited, and, for example, when the components (A-1) to (A-3) are prepolymerized, the component (C) may be added in advance.

Further, the prepolymer of the component (A) obtained by prepolymerizing only the components (A-1) to (A-3) is cooled and solidified, and pulverized to an appropriate size to obtain the component (B). The curing catalyst of, and other additives as required are blended in a predetermined composition ratio, and after sufficiently mixing them with a mixer or the like, melt mixing treatment with a heat roll, a kneader, an extruder or the like is performed, and then, It is also possible to solidify by cooling and pulverize to an appropriate size to obtain a molding material of the epoxy-silicone hybrid resin composition.

<Optical semiconductor device>
Next, the optical semiconductor device of the present invention will be described. The optical semiconductor device of the present invention comprises a cured product of the epoxy-silicone hybrid resin composition, and can be obtained by encapsulating an optical semiconductor element using the composition. As a method for manufacturing an optical semiconductor device, a known method may be adopted depending on the type of optical semiconductor element.

The encapsulation of an optical semiconductor element using the epoxy-silicone hybrid resin composition of the present invention can be performed by transfer molding or compression molding, but transfer molding is preferable. The sealing may be performed by a known molding method other than transfer molding or compression molding.

As conditions for the transfer molding method, a transfer molding machine is used, molding pressure is 5 to 20 N/mm ² , molding temperature is 120 to 190° C., molding time is 30 to 500 seconds, particularly molding temperature is 150 to 185° C., molding time is 90 to 300. It is preferable to carry out in seconds. Further, secondary curing may be performed at 150 to 185° C. for 0.5 to 20 hours.

The conditions for compression molding are preferably a molding temperature of 120 to 180° C. and a molding time of 30 to 900 seconds, particularly a molding temperature of 130 to 150° C. and a molding time of 60 to 600 seconds. Further, secondary curing may be performed at 150 to 185° C. for 0.5 to 20 hours.

The epoxy-silicone hybrid resin composition of the present invention is a solid at room temperature, so it is easy to handle and can be formed into a tablet by pressure molding. The cured product thereof has high strength, high transparency, heat resistance and light resistance. Is also excellent. Therefore, the epoxy-silicone hybrid resin composition of the present invention can be suitably used as a resin composition for encapsulating an optical semiconductor element, and an optical semiconductor device having excellent reliability can be provided.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, Me represents a methyl group.

The weight average molecular weight (Mw) shown in the following examples and comparative examples is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are shown below.
[GPC measurement conditions]
Developing solvent: Tetrahydrofuran Flow rate: 0.6 mL/min
Column: TSK Guardcolumn SuperH-L
TSKgel Super H4000 (6.0 mm ID x 15 cm x 1)
TSKgel Super H3000 (6.0 mm ID x 15 cm x 1)
TSKgel Super H2000 (6.0 mm ID x 15 cm x 2)
(All made by Tosoh Corporation)
Column temperature: 40°C
Sample injection amount: 20 μl (sample concentration: 0.5 wt%-tetrahydrofuran solution)
Detector: Differential Refractometer (RI)

上記括弧内に示す各単位の結合順序は特に制限されない。
得られたオルガノポリシロキサン１のＧＰＣ測定によるポリスチレン換算の重量平均分子量は５，６００であり、エポキシ当量は５０５ｇ／ｅｑであった。 (Synthesis of (A-1) Organopolysiloxane)
[Synthesis Example 1] Synthesis of organopolysiloxane 1 397 g of phenyltrimethoxysilane, 165 g of (3-glycidoxy)propylmethyldimethoxysilane, 500 g of isopropyl alcohol, and 750 g of toluene were mixed and stirred, and then tetramethylammonium hydroxide was used as a catalyst. 25% by weight aqueous solution of 25 g and 182 g of water were added and reacted for 3 hours. After completion of the reaction, the solution is neutralized with an aqueous solution of sodium dihydrogen phosphate, washed with hot water, and then toluene is distilled off under reduced pressure to obtain a linear organopolysiloxane 1 represented by the following formula (6). Got

The bonding order of each unit shown in the above parentheses is not particularly limited.
The polystyrene-converted weight average molecular weight of the obtained organopolysiloxane 1 by GPC measurement was 5,600, and the epoxy equivalent was 505 g/eq.

得られたオルガノポリシロキサン２のＧＰＣ測定によるポリスチレン換算の重量平均分子量は４，０００であり、エポキシ当量は８３０ｇ／ｅｑであった。 Synthesis of Synthesis Example 2] Organopolysiloxane _{2 X'O- (Me 2 SiO) a} -X '(X' is a hydrogen atom or a methyl group, a is an integer from 1 to 8 on average 3.5 139 g, phenyltrimethoxysilane 297 g, (3-glycidoxy)propylmethyldimethoxysilane 110 g, isopropyl alcohol 500 g, and toluene 900 g, and after stirring, 24 g of a 25 mass% aqueous solution of tetramethylammonium hydroxide as a catalyst and Water (176 g) was added and reacted for 3 hours. After completion of the reaction, the solution is neutralized with an aqueous solution of sodium dihydrogen phosphate, washed with hot water, and toluene is distilled off under reduced pressure to obtain a linear organopolysiloxane 2 represented by the following formula (7). Got

The obtained organopolysiloxane 2 had a polystyrene-equivalent weight average molecular weight of 4,000 as measured by GPC and an epoxy equivalent of 830 g/eq.

得られたオルガノポリシロキサン３のＧＰＣ測定によるポリスチレン換算の重量平均分子量は４，０００であり、エポキシ当量は４１４ｇ／ｅｑであった。 Synthesis of Comparative Synthesis Example 1] Organopolysiloxane _{3 X'O- (Me 2 SiO) a} -X '(X' is a hydrogen atom or a methyl group, a is an integer from 1 to 8 Mean 3.5 277 g , ( 3-glycidoxy)propylmethyldimethoxysilane 220 g, and isopropyl alcohol 500 g are mixed and stirred, and then 25 g of a 25% by mass aqueous solution of tetramethylammonium hydroxide as a catalyst and 180 g of water are added and reacted for 3 hours. Let After completion of the reaction, 900 g of toluene is added and stirred, neutralized with an aqueous solution of sodium dihydrogen phosphate, washed with hot water, and then toluene is distilled off under reduced pressure, which is represented by the following formula (8). A linear organopolysiloxane 3 was obtained.

The polystyrene-converted weight average molecular weight of the obtained organopolysiloxane 3 by GPC measurement was 4,000, and the epoxy equivalent was 414 g/eq.

[Examples 1 to 4, Comparative Examples 1 and 2]
An epoxy-silicone hybrid resin composition was prepared with the composition and formulation (parts by mass) shown in Table 1 below. Each component shown in Table 1 is as follows.
(A-2) Epoxy resin having two or more epoxy groups in one molecule:
Epoxy resin 1: 1,3,5-triglycidyl isocyanurate (TEPIC-S, Nissan Chemical Co., Ltd., epoxy equivalent 100, melting point 100° C.)
(A-3) Acid anhydride type curing agent: 4-methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., RIKACID MH)
(B) Curing catalyst: quaternary phosphonium salt (manufactured by San-Apro Ltd., U-CAT5003)
(C) Antioxidant:
Antioxidant 1: Phenolic antioxidant, compound name: pentaerythritol tetrakis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate] (ADEKA CORPORATION, ADEKA STAB AO) -60)
Antioxidant 2: phosphorus-based antioxidant, compound name: isodecyldiphenylphosphite (ADEKA STAB 135A, manufactured by ADEKA Corporation)
(D) Silane coupling agent: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)

The components (A-1), (A-2), (A-3), and (C) shown in Table 1 below were mixed in the proportions shown in the same table, and melt-mixed in a gate mixer heated to 85°C. , A prepolymer was obtained. The components (B) and (D) are further added to the obtained prepolymer in the ratios shown in the same table, and the mixture is melt-mixed for 5 minutes, cooled, solidified and pulverized to obtain the target powdery epoxy-silicone hybrid. A resin composition was obtained.

-Evaluation of properties of composition and cured product-
The characteristics of the obtained composition and its cured product were evaluated by the following methods. The cured product was obtained by subjecting each composition to transfer molding under the conditions of molding temperature: 175° C., molding pressure: 6.9 N/mm ² , and molding time of 120 seconds, and then curing at 180° C. for 1 hour.

(1) Hardness A plate-like cured product of 55 mm×15 mm×4 mmt was produced by the above method. The hardness (type D) of each cured product was measured according to JIS K6253-3:2012. The results are shown in Table 1.

(2) Heat resistance A sheet-like cured product having a thickness of 1 mm was produced by the above method. The initial light transmittance (T ₀ ) at a wavelength of 450 nm of the obtained cured product was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Co., Ltd.). Then, the cured product was heated at 180° C. for 72 hours, and the light transmittance (T ₁ ) of each cured product after the heat treatment was measured by the same method as T ₀ . Table 1 shows the values of T ₁ /T ₀ (%).

(3) Light resistance A sheet-like cured product having a thickness of 1 mm was produced by the above method. The initial light transmittance (T ₀ ) at a wavelength of 450 nm of the obtained cured product was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Co., Ltd.). Next, the cured product was irradiated with a 450 nm blue laser at 150° C. for 48 hours, and the light transmittance (T ₁ ) of each cured product after irradiation was measured by the same method as T ₀ . Table 1 shows the values of T ₁ /T ₀ (%).

(4) Glass transition temperature (Tg)
A plate-like cured product of 40 mm×6 mm×1 mmt was produced by the above method, DMA (Dynamic Mechanical Analysis) was measured under the following conditions, and the obtained storage elastic modulus (E′) and loss elastic modulus (E″) were measured. The temperature at the maximum point of the loss coefficient (tan δ=E″/E′) represented by the quotient was obtained, and the value was taken as Tg.
<DMA measurement conditions>
Model: Q800-1494-DMA Q-800 (TA INSTRUMENT JAPAN Co., Ltd.)
Measurement temperature: 25°C to 300°C
Temperature rising rate: 5°C/min
Frequency: 1 Hz
Measurement mode: Tensile vibration

(5) Bending strength and flexural modulus A plate-like cured product having a size of 10 mm×120 mm×4 mmt was produced by the above method. The flexural strength and flexural modulus of the obtained cured product were measured using Autograph AG-IS (manufactured by Shimadzu Corporation) in accordance with JIS K7171. The results are shown in Table 1.

As shown in Table 1, in the epoxy-silicone hybrid resin composition of Comparative Example 1 in which the organopolysiloxane did not have a phenyl group, the obtained cured product had low hardness and bending strength. Further, the epoxy-silicone hybrid resin composition of Comparative Example 2 containing no epoxy resin as the component (A-2) has excellent heat resistance and light resistance of the obtained cured product, but has low hardness, flexural strength and flexural elasticity. The rate was too low to measure.

On the other hand, since the epoxy-silicone hybrid resin compositions of the present invention (Examples 1 to 4) are solid at room temperature, they can be formed into tablets by pressure molding, and their cured products are transparent and mechanical. It has strength, excellent heat resistance and light resistance, and has high hardness and 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 It is included in the technical scope of.

Claims (6)

(A) (A-1) An organopolysiloxane represented by the following formula (1),

(In the formula, R ¹ and R ³ are independently a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ² is 4 carbon atoms. To 50 monovalent aliphatic epoxy groups, one or more R ³ in one molecule is a monovalent aromatic hydrocarbon group, 0≦l<0.4, 0.1≦m≦0.5 , 0.1≦n≦0.8, and l+m+n=1.)
(A-2) An epoxy resin having two or more epoxy groups in one molecule, which is selected from the group consisting of a triazine derivative epoxy resin, a bisphenol type epoxy resin, a hydrogenated bisphenol type epoxy resin, and an alicyclic epoxy resin. At least one epoxy resin, and (A-3) an acid anhydride-based curing agent,
The number of acid anhydride groups in the component (A-3) per one epoxy group in the components (A-1) and (A-2) is 0.3 to 1. An epoxy-silicone hybrid resin composition for optical semiconductor element encapsulation, which comprises 0 prepolymer and (B) a curing catalyst and is solid at 25°C. In the formula (1), R ² is represented by the following formula (2), and the epoxy-silicone hybrid resin composition according to claim 1.

(In the formula, R′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms.) The epoxy-silicone hybrid resin composition according to claim 1 or 2, wherein the component (A-2) is a triazine derivative epoxy resin. The epoxy-silicone hybrid resin composition according to any one of claims 1 to 3, further comprising (C) an antioxidant and (D) a silane coupling agent. The epoxy-silicone hybrid resin composition according to claim 4, wherein the component (C) is a combination of a phenolic antioxidant and a phosphorus antioxidant. An optical semiconductor device comprising a cured product of the epoxy-silicone hybrid resin composition according to any one of claims 1 to 5 , wherein the organopolysiloxane represented by the formula (1) has the R ³ is an optical semiconductor device characterized by being a phenyl group, a benzyl group, a 2-phenylethyl group, and a 2-phenylpropyl group .