JP2010248446A - Optical semiconductor sealing silicone resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical semiconductor sealing silicone resin composition which excels in curability in a sealed system, adhesion, wet heat adhesion resistance, and wet heat coloring stability. <P>SOLUTION: The optical semiconductor sealing silicone resin composition contains (A) a (meth)acrylic-modified organopolysiloxane which has two or more functional groups represented by formula (I) (wherein R<SP>1</SP>is hydrogen or a methyl group and R<SP>4</SP>is a 1-8C divalent hydrocarbon group) and one or more alkoxysilyl groups in one molecule and a weight average molecular weight of 10,000-150,000, (B) a radical initiator, and (C) a bis(alkoxysilyl)alkane. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a silicone resin composition for sealing an optical semiconductor.

  Conventionally, a curable silicone resin composition containing (meth) acryl-modified organopolysiloxane and silicone oil or a radical polymerizable monomer such as N, N-dialkyl-substituted acrylamide or acryloylmorpholine has been proposed (Patent Literature). 1, 2).

Japanese Patent Publication No. 6-51774 JP 2008-31307 A

However, in the case of curing by condensation of silanol groups and alkoxy groups, the present inventor found that in the case of a closed system, alcohol as a by-product of the condensation reaction does not escape from the system and becomes uncured, and (meth) acryl-modified organo It has been found that when the polysiloxane does not have an alkoxysilyl group and when the weight average molecular weight of the (meth) acryl-modified organopolysiloxane is less than 10,000, the adhesion to glass is low and cracks are likely to occur.
Furthermore, the present inventors have found that (meth) acryl-modified organopolysiloxane has poor wet heat resistance, (meth) acryl-modified organopolysiloxane and radical polymerizable monomers such as N, N-dialkyl-substituted acrylamide or acryloylmorpholine. It has been found that a composition containing the colorant is inferior in heat-resistant coloring stability.
Then, an object of this invention is to provide the silicone resin composition for optical semiconductor sealing excellent in sclerosis | hardenability in a closed system, adhesiveness, heat-and-moisture-resistant adhesiveness, and heat-resistant coloring stability.

（式中、Ｒ¹は水素原子またはメチル基であり、Ｒ⁴は炭素原子数１〜８の２価の炭化水素基である。） As a result of diligent research to solve the above-mentioned problems, the present inventor has (A) two or more functional groups represented by the following formula (I) and one or more alkoxysilyl groups in one molecule. (Meth) acryl-modified organopolysiloxane having an average molecular weight of 10,000 to 150,000,
(B) Light excellent in curability, adhesiveness, moist heat and heat resistance, and heat resistant coloring stability in a closed system by adding (C) bis (alkoxysilyl) alkane to a composition containing a radical initiator It discovered that the silicone resin composition for semiconductor sealing was obtained, and completed this invention.

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms.)

（式中、Ｒ¹は水素原子またはメチル基であり、Ｒ⁴は炭素原子数１〜８の２価の炭化水素基である。）
２． 前記（メタ）アクリル変性オルガノポリシロキサンが、下記式（２）で表される上記１に記載の光半導体封止用シリコーン樹脂組成物。

（式中、Ｒ¹はそれぞれ水素原子またはメチル基であり、Ｒ²、Ｒ³はそれぞれアルキル基であり、Ｒ⁴はそれぞれ炭素原子数１〜８の２価の炭化水素基であり、ｎはそれぞれ１または２であり、ｍは100〜2000である。）
３． 前記ビス（アルコキシシリル）アルカンが、ビス−（３−トリメトキシシリルプロピル）アミン、１，２−ビス（トリエトキシシリル）エタン、１，６−ビス（トリメトキシシリル）ヘキサン、１，７−ビス（トリメトキシシリル）ヘプタン、１，８−ビス（トリメトキシシリル）オクタン、１，９−ビス（トリメトキシシリル）ノナンおよび１，１０−ビス（トリメトキシシリル）デカンからなる群から選ばれる少なくとも１種である上記１または２に記載の光半導体封止用シリコーン樹脂組成物。
４． 前記ビス（アルコキシシリル）アルカンの量が、前記（メタ）アクリル変性オルガノポリシロキサン１００質量部に対して、0.01〜10質量部である上記１〜３のいずれかに記載の光半導体封止用シリコーン樹脂組成物。 That is, this invention provides the following 1-4.
1. (A) (meth) acryl having 2 or more functional groups represented by the following formula (I) and 1 or more alkoxysilyl groups in one molecule and having a weight average molecular weight of 10,000 to 150,000 Modified organopolysiloxane,
(B) a radical initiator;
(C) A silicone resin composition for encapsulating an optical semiconductor containing bis (alkoxysilyl) alkane.

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms.)
2. 2. The silicone resin composition for sealing an optical semiconductor according to 1 above, wherein the (meth) acryl-modified organopolysiloxane is represented by the following formula (2).

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group, R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is Each is 1 or 2, and m is 100-2000.)
3. The bis (alkoxysilyl) alkane is bis- (3-trimethoxysilylpropyl) amine, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis. At least one selected from the group consisting of (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane 3. The silicone resin composition for sealing an optical semiconductor according to 1 or 2 above, which is a seed.
4). The silicone for optical semiconductor encapsulation according to any one of 1 to 3 above, wherein the amount of the bis (alkoxysilyl) alkane is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acryl-modified organopolysiloxane. Resin composition.

  The silicone resin composition for optical semiconductor encapsulation of the present invention is excellent in curability, adhesion, wet heat resistance, and heat resistant coloration stability in a closed system.

FIG. 1 is a cross-sectional view schematically showing a mold used for curing the silicone resin composition for sealing an optical semiconductor of the present invention in Examples.

（式中、Ｒ¹は水素原子またはメチル基であり、Ｒ⁴は炭素原子数１〜８の２価の炭化水素基である。）
本発明の光半導体封止用シリコーン樹脂組成物を以下「本発明の組成物」ということがある。 The present invention will be described in detail below.
The silicone resin composition for optical semiconductor encapsulation of the present invention is
(A) (meth) acryl having 2 or more functional groups represented by the following formula (I) and 1 or more alkoxysilyl groups in one molecule and having a weight average molecular weight of 10,000 to 150,000 Modified organopolysiloxane,
(B) a radical initiator;
(C) A composition containing bis (alkoxysilyl) alkane.

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms.)
The silicone resin composition for encapsulating an optical semiconductor of the present invention may be hereinafter referred to as “the composition of the present invention”.

（式中、Ｒ¹は水素原子またはメチル基であり、Ｒ⁴は炭素原子数１〜８の２価の炭化水素基である。）
なお、本発明において（メタ）アクリルは、アクリルおよびメタクリルのうちの一方または両方を意味する。 (A) The (meth) acryl-modified organopolysiloxane will be described below.
The (meth) acryl-modified organopolysiloxane contained in the composition of the present invention has a main chain of organopolysiloxane, two or more functional groups represented by formula (I) and an alkoxysilyl group in one molecule. The (meth) acryl-modified organopolysiloxane has a weight average molecular weight of 10,000 to 150,000.

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms.)
In the present invention, (meth) acryl means one or both of acrylic and methacrylic.

  The organopolysiloxane as the main chain is not particularly limited. Examples thereof include dimethylpolysiloxane and diethylpolysiloxane. The organopolysiloxane as the main chain may be either linear or branched.

In the functional group represented by the formula (I), the divalent hydrocarbon group having 1 to 8 carbon atoms as R ⁴ is not particularly limited. For example, an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentylene group; and a cycloalkylene group such as a cyclohexylene group.
The alkoxysilyl group of the (meth) acryl-modified organopolysiloxane is not particularly limited. Examples thereof include a trialkoxysilyl group, a divalent silyl group having a dialkoxy group, a divalent silyl group having a monoalkoxy group and a monoalkyl group. Examples of the alkoxy group in the alkoxysilyl group include a methoxy group, an ethoxy group, and a propyl group. Examples of the alkyl group that the alkoxysilyl group can have include a methyl group, an ethyl group, and a propyl group.

The functional group represented by the formula (I) can be bonded to the side chain and / or terminal of the organopolysiloxane as the main chain. The functional group represented by the formula (I) can be bonded to both ends of the organopolysiloxane as the main chain.
The alkoxysilyl group can be bonded to the side chain and / or terminal of the organopolysiloxane as the main chain. The alkoxysilyl group can be bonded to both ends of the organopolysiloxane as the main chain.

（式中、Ｒ¹は水素原子またはメチル基であり、Ｒ²、Ｒ³はそれぞれアルキル基であり、Ｒ⁴は炭素原子数１〜８の２価の炭化水素基であり、ｎは１または２である。）
式（Ｉ）で示される官能基は、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れるという観点から、式（１）で表されるものが好ましい。 In the present invention, the silicon atom in the formula (I) can be an alkoxysilyl group of the (meth) acryl-modified organopolysiloxane.
When the silicon atom in the formula (I) is an alkoxysilyl group, examples of the functional group represented by the formula (I) include those represented by the following formula (1).

Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group, R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is 1 or 2)
The functional group represented by the formula (I) is preferably the one represented by the formula (1) from the viewpoint that it is more excellent in curability, adhesion, wet heat and heat resistance, and heat resistant coloring stability in a closed system.

  The group represented by the formula (1) can be bonded to the side chain and / or terminal of the organopolysiloxane as the main chain. The group represented by the formula (1) can be bonded to both ends of the organopolysiloxane as the main chain.

In the group represented by the formula (1), alkyl groups as R ² and R ³ are not particularly limited. Examples thereof include a methyl group and an ethyl group.
In formula (1), the divalent hydrocarbon group having 1 to 8 carbon atoms as R ⁴ is not particularly limited. Examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentylene group.
n is preferably 2 from the viewpoint that it is more excellent in curability, adhesion, wet heat and heat resistance and heat resistant coloration stability in a closed system.

（式中、Ｒ¹はそれぞれ水素原子またはメチル基であり、Ｒ²、Ｒ³はそれぞれアルキル基であり、Ｒ⁴はそれぞれ炭素原子数１〜８の２価の炭化水素基であり、ｎは１または２であり、ｍは１００〜２，０００である。）
Ｒ¹〜Ｒ⁴、ｎは式（１）と同義である。
ｍは、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れ、作業性に優れるという観点から、１００〜１，３５０であるのが好ましい。 Examples of the (meth) acryl-modified organopolysiloxane include those represented by the following formula (2).

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group, R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is 1 or 2 and m is 100 to 2,000.)
R < ¹ > -R < ⁴ >, n is synonymous with Formula (1).
m is preferably 100 to 1,350 from the viewpoints of excellent curability, adhesiveness, moist heat and heat resistance and heat-resistant coloring stability in a closed system, and excellent workability.

  The (meth) acryl-modified organopolysiloxane is preferably represented by the formula (2) from the viewpoint that it is more excellent in curability, adhesion, wet heat resistance, and heat resistant coloration stability in a closed system.

In the present invention, the (meth) acryl-modified organopolysiloxane has a weight average molecular weight of 10,000 to 150,000.
The weight average molecular weight of the (meth) acryl-modified organopolysiloxane is 10,000 to 100,000 from the viewpoint that it is excellent in curability, adhesion, wet heat and heat resistance, heat resistant color stability in a closed system, and excellent workability. 000 is preferred.
When n in the formula (2) is 2, the weight average molecular weight of the (meth) acryl-modified organopolysiloxane is 10,000 to 100,000 from the viewpoint of excellent heat-resistant coloring stability and excellent transparency. Is preferred.
In the present invention, the weight average molecular weight of the (meth) acryl-modified organopolysiloxane is expressed in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
The (meth) acryl-modified organopolysiloxane can be used alone or in combination of two or more.

（式中、Ｒ¹はそれぞれ水素原子またはメチル基であり、Ｒ²、Ｒ³はそれぞれアルキル基であり、Ｒ⁴はそれぞれ炭素原子数１〜８の２価の炭化水素基であり、ｎは２または３であり、ｍは100〜2000である。）
Ｒ¹〜Ｒ⁴は式（１）と同義である。ｍは式（２）と同義である。
密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れ、加熱減量の抑制、硬化性に優れるという観点から、両末端にヒドロキシ基を有するオルガノポリシロキサン１モルに対して、式（４）で表される化合物を２モルを超える量で反応させるのが好ましい。 The (meth) acryl-modified organopolysiloxane is not particularly limited for its production. For example, it can be produced by reacting an organopolysiloxane having hydroxy groups at both ends (for example, an organopolysiloxane represented by the formula (3)) with a compound represented by the formula (4).

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group, R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is 2 or 3 and m is 100 to 2000.)
R < ¹ > -R < ⁴ > is synonymous with Formula (1). m is synonymous with Formula (2).
From the viewpoints of excellent curability, adhesiveness, moist heat resistance and heat-resistant coloring stability in a closed system, suppression of heat loss, and excellent curability, with respect to 1 mol of an organopolysiloxane having hydroxy groups at both ends. It is preferable to react the compound represented by the formula (4) in an amount exceeding 2 mol.

(B) The radical initiator will be described below.
The radical initiator contained in the composition of the present invention is not particularly limited as long as it allows radical polymerization of a (meth) acryloyl group by heat and / or light.
The radical initiator is preferably one that does not contain a nitrogen atom, a sulfur atom, or a benzene ring from the viewpoint of excellent curability in a closed system, heat-resistant coloring stability, and excellent light resistance, and includes a carbon atom, a hydrogen atom, and an oxygen atom. More preferably, it consists of

Examples of the thermal radical initiator (thermal radical initiator) include organic oxides and azo compounds. Examples of the organic oxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. For example, methyl ethyl ketone peroxide, 1,1-di (t-hexylperoxy) cyclohexane, 2,2- (t-butylperoxy) butane, 2,2-di- (t-amylperoxy) butane, p-men Tamperoxide, di-t-butyl peroxide, diamyl peroxide, dilauryl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2- Aliphatic hydrocarbon peroxides such as ethylhexyl monocarbonate and di- (2 ethylhexyl) peroxydicarbonate, cumene hydroperoxide, dicumyl peroxide, dibenzoyl peroxide, cumylperoxyneodecanate, t-butyl Aromatic or acid such as peroxybenzoate Thing, and the like.
Examples of the azo compound include 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2methylpionate), and 2,2′-azobis (2,4,4-trimethylpentate). ) And the like.

  Examples of radical initiators by light (photo radical initiators) include carbonyl compounds such as acetophenone compounds, benzoin ether compounds, and benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, and phosphine oxide compounds. Can be mentioned.

  Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenylketone, etc. Carbonyl compounds; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobisisobutyronitrile and azobis-2,4-dimethylvalero Compounds; benzoyl peroxide, include peroxide compounds such as di-tertiary butyl peroxide.

Among them, from the viewpoint of excellent curability in a closed system and heat-resistant coloring stability, a thermal radical initiator is preferable, an aliphatic hydrocarbon peroxide is more preferable, and 1,1,3,3-tetramethylbutyl peroxide is preferable. Oxy-2-ethylhexanoate, 2,2-di- (t-amylperoxy) butane, and t-butylperoxy-2-ethylhexyl monocarbonate are more preferable.
The radical initiators can be used alone or in combination of two or more.

  The amount of the radical initiator is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (meth) acryl-modified organopolysiloxane, from the viewpoint of excellent curability in the closed system and heat-resistant coloring stability.

(C) The bis (alkoxysilyl) alkane will be described below.
The bis (alkoxysilyl) alkane contained in the composition of the present invention is a divalent alkane having two alkoxysilyl groups in one molecule.
The alkoxy group in the alkoxysilyl group is not particularly limited. Examples thereof include a methoxy group, an ethoxy group, and an isopropoxy group.
The alkoxysilyl group can have 1 to 3 alkoxy groups. Examples of the group other than the alkoxy group that can be bonded to the alkoxysilyl group include alkyl groups such as a methyl group and an ethyl group.
The divalent alkane (alkylene group) is not particularly limited. The divalent alkane can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. The number of carbon atoms of the divalent alkane is not particularly limited. The number of carbon atoms of the divalent alkane is preferably 2 to 3 from the viewpoint of excellent curability, adhesiveness, wet heat resistance, and heat resistant coloration stability in a closed system.

式中、Ｒ⁷〜Ｒ⁸はそれぞれアルキル基であり、Ｒ⁹は２価の炭化水素基であり、ａはそれぞれ１〜３の整数である。アルキル基としては、例えば、メチル基、エチル基が挙げられる。Ｒ⁹としての２価の炭化水素基は上記の２価のアルカンと同義である。 Examples of the bis (alkoxysilyl) alkane include those represented by the following formula (II).

In the formula, R ^{7 to} R ⁸ are each an alkyl group, R ⁹ is a divalent hydrocarbon group, and a is an integer of 1 to 3, respectively. Examples of the alkyl group include a methyl group and an ethyl group. The divalent hydrocarbon group as R ⁹ has the same meaning as the above divalent alkane.

  Examples of the bis (alkoxysilyl) alkane include 1,2bis (triethoxylyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl-4-trimethoxysilylbutane, 1,4 -Bis (methyldimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5-trimethoxysilylpentane, 1,5- Bis (methyldimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxysilyl) hexane, 2,5-bis ( Trimethoxysilyl) hexane, 1,6-bis (methyldimethoxysilyl) hexane, 1,7-bis ( Limethoxysilyl) heptane, 2,5-bis (trimethoxysilyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 2,5-bis (trimethoxy Silyl) octane, 2,7-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1,10-bis (trimethoxysilyl) Examples include decane, 3,8-bis (trimethoxysilyl) decane, and those having a nitrogen atom such as bis- (3-trimethoxysilylpropyl) amine.

The bis (alkoxysilyl) alkane is preferably represented by the formula (II) from the viewpoint of excellent curability, adhesion, heat-and-moisture resistance and heat-resistant coloring stability in a closed system, and bis (trialkoxysilyl). ) Alkanes are more preferred, bis- (3-trimethoxysilylpropyl) amine, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxy) At least one selected from the group consisting of (silyl) heptane, 1,8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane. 1,6-bis (trimethoxysilyl) hexane and 1,2bis (triethoxylyl) ethane are more preferable.
Bis (alkoxysilyl) alkanes can be used alone or in combination of two or more.

  The amount of bis (alkoxysilyl) alkane is based on 100 parts by weight of (meth) acryl-modified organopolysiloxane from the viewpoint of excellent curability, adhesion, wet heat resistance, and heat resistant color stability in a closed system. It is preferable that it is 0.01-10 mass parts, and it is more preferable that it is 0.1-3 mass parts.

  The composition of the present invention has a (meth) acryl-modified organopolysiloxane, a radical initiator, a bis (alkoxy) from the viewpoint of being excellent in curability, adhesion, wet heat resistance, and heat resistant color stability in a closed system. A composition composed of (silyl) alkane (a composition containing only the above three components) can be used.

The composition of the present invention further contains additives as necessary within a range not impairing the object and effect of the present invention, in addition to (meth) acryl-modified organopolysiloxane, radical initiator, and bis (alkoxysilyl) alkane. be able to.
Examples of additives include inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, inorganic phosphors, Anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductive Examples include property-imparting agents, phosphorus peroxide decomposers, pigments, metal deactivators, and physical property modifiers. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

From the viewpoint that the composition of the present invention is excellent in storage stability, it is mentioned as one of preferred embodiments that substantially does not contain water. In the present invention, “substantially free of water” means that the amount of water in the composition of the present invention is 0.1% by mass or less.
In addition, the composition of the present invention can be mentioned as one of preferred embodiments that substantially does not contain a solvent from the viewpoint of excellent work environment properties. The phrase “substantially free of solvent” in the present invention means that the amount of the solvent in the composition of the present invention is 1% by mass or less.

The composition of the present invention is not particularly limited for its production. For example, it can be produced by mixing (meth) acryl-modified organopolysiloxane, a radical initiator, bis (alkoxysilyl) alkane, and an additive that can be used as necessary.
The composition of the present invention can be produced as a one-pack type or a two-pack type.

The composition of this invention can be used as a composition for optical semiconductor sealing.
The optical semiconductor to which the composition of the present invention can be applied is not particularly limited. For example, a light emitting diode (LED, for example, white LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array can be mentioned.

As a method of using the composition of the present invention, for example, the composition of the present invention is applied to an adherend (for example, an optical semiconductor, glass), and the adherend to which the composition of the present invention is applied is heated and / or Alternatively, light irradiation may be performed to cure the composition of the present invention.
For example, a glass laminate can be obtained by applying and curing the composition of the present invention between a plurality of glasses and bonding the plurality of glasses through the composition of the present invention.
Also, an optical semiconductor is disposed between a plurality of glasses, the composition of the present invention is applied between the glasses and cured, and the plurality of glasses are bonded via the composition of the present invention to seal the optical semiconductor. Can do.

  The method for applying the composition of the present invention to the adherend is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

  The temperature at which the composition of the present invention is heated is excellent in curability, adhesiveness, moisture-resistant adhesive heat resistance, heat-resistant coloring stability in a closed system, excellent in thin film curability, and has an appropriate long curing time and pot life From the viewpoint of being able to suppress cracks in the cured product and being excellent in the smoothness, moldability, and physical properties of the cured product, it is preferably cured at around 80 ° C. to 150 ° C., more preferably around 150 ° C.

When the composition of the present invention is cured by light irradiation, for example, ultraviolet rays and electron beams can be used.
Curing can be performed under substantially anhydrous conditions from the viewpoint of excellent curability and transparency. In the present invention, the phrase “curing is performed under substantially anhydrous conditions” means that the atmospheric humidity of the environment in heating and / or light irradiation is 10% RH or less.

  A cured product obtained by using the composition of the present invention (when the thickness of the cured product is 2 mm) is an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation, the same applies hereinafter) according to JIS K0115: 2004. The transmittance measured at a wavelength of 400 nm is preferably 80% or more, and more preferably 85% or more.

  In addition, the cured product obtained using the composition of the present invention is subjected to a heat resistance test after initial curing (a test in which the cured product after initial curing is placed at a temperature of 150 ° C. for 1,000 hours), and then cured product ( (Thickness: 2 mm), the transmittance measured at a wavelength of 400 nm using an ultraviolet / visible spectrum measuring apparatus according to JIS K0115: 2004 is preferably 80% or more, more preferably 85% or more. .

  The cured product obtained using the composition of the present invention preferably has a permeability retention ratio (transmittance after heat test / transmittance at initial curing × 100) of 70 to 100%, 80 More preferably, it is -100%.

  In addition to optical semiconductors, the composition of the present invention is used for applications such as display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials. Can be used.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Production of modified organopolysiloxane (1) Modified organopolysiloxane 1
100 parts by mass of polydimethylsiloxane having hydroxy groups at both ends (weight average molecular weight 28,000, trade name ss70, manufactured by Shin-Etsu Chemical Co., Ltd.), methacryloxypropyltrimethoxysilane (trade name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd., and so on) .) 4 parts by mass and 0.01 part by mass of 2-ethylhexanoate tin (manufactured by Kanto Chemical Co., Ltd.) as a catalyst were placed in a reaction vessel and reacted for 6 hours while maintaining the pressure at 10 mmHg and the temperature at 60 ° C.
The obtained reaction product was subjected to ¹ H-NMR analysis, and it was confirmed that the silanol groups at both ends of the polydimethylsiloxane disappeared to be methacryloxypropyldimethoxysilyl groups.
The obtained polydimethylsiloxane is referred to as modified organopolysiloxane 1.
The weight average molecular weight of the modified organopolysiloxane 1 was 35,000 in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent (hereinafter the same).

(2) Modified organopolysiloxane 2
Except that the polydimethylsiloxane as a raw material was replaced with 100 parts by mass of polydimethylsiloxane having hydroxy groups at both ends (weight average molecular weight 60,000, trade name x-21-5848, manufactured by Shin-Etsu Chemical Co., Ltd.), modified organo In the same manner as polysiloxane 1, polydimethylsiloxane having methacryloxypropyldimethoxysilyl groups on both ends was produced.
The obtained polydimethylsiloxane is referred to as modified organopolysiloxane 2.
The modified organopolysiloxane 2 had a weight average molecular weight of 63,000.

2. Production of Silicone Resin Composition for Optical Semiconductor Encapsulation Using the components shown in Table 1 below in the amounts (parts by mass), uniformly mixing them with a stirrer equipped with a vacuum machine, A composition was prepared.

・ポリシロキサン３：Ｍｗ＝3０００での両末端シラノール（KF−9701，信越化学社製）１００ｇとＫＢＭ５０３を２５ｇ投入した。あとの製造法は変性ポリシロキサン１，２に同じであり、製造後の重量平均分子量は８，０００であった。
・（Ｂ）ラジカル開始剤１：熱ラジカル開始剤、化合物名１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、商品名パーオクタO（日本油脂社製）
・（Ｂ）ラジカル開始剤２：光ラジカル開始剤、商品名イルガキュア５００（１−ヒドロキシ−シクロヘキシル−フェニルケトンとベンゾフェノンとの１：１混合物）（チバスペシャル社製）
・（Ｂ）ラジカル開始剤３：熱ラジカル開始剤、商品名パーヘキシルD（日本油脂社製）（ジ−ｔ−ヘキシルパーオキサイド）
・（Ｂ）ラジカル開始剤４：熱ラジカル開始剤、商品名カヤケタールAM−c55（化薬アクゾ社製）（２，２−ジ（ｔ−アミルパーオキシ）ブタン
・（Ｂ）ラジカル開始剤５：熱ラジカル開始剤、商品名トリゴノックス１１７（化薬アクゾ社製）（ｔ−ブチルパーオキシ２−エチルヘキシルカーボネート）
・（Ｃ）ビス（アルコキシシリル）アルカン１：下記式で表される１，６ビス（トリメトキシシリル）へキサン（商品名Ｚ−６８３０、東レダウコーニング社製）

・（Ｃ）ビス（アルコキシシリル）アルカン２：下記式で表される１，２ビス(トリエトキシシリル)エタン（ＫＢＥ３０２６，信越化学工業社製）

・（Ｅ）ジメチルポリシロキサン１：下記式で表される化合物（商品名ｓｓ−１０、信越化学工業社製、Ｍｗ＝４２，０００）

・（Ｆ）アルコキシオリゴマー：商品名ｘ−４０−９２４６、信越化学工業社製、（Ｍｗ＝６０００）
・（Ｇ）ナフテン酸ジルコニル：日本化学産業社製
・（Ｈ）エポキシシリコーン：エポキシ変性ポリシロキサン（商品名：ＫＦ１０１、信越化学工業社製）
・（Ｉ）カチオン重合触媒：ＢＦ₃・Ｅｔ₂Ｏ（ＢＦ₃エチルエテラート錯体、東京化成工業社製）
・（Ｊ）シリコーンオイル：末端トリメチルシリル基末端シリコーンオイル、商品名KF96-5000cs(信越化学工業社製）
・（Ｋ）アクリロイルモルホリン：ACMO、興人社製
・（Ｌ）Ｎ，Ｎ−ジメチルアクリルアミド：関東化学社製 Each component shown in Table 1 is as follows.
(A) Modified polysiloxane 1: Modified polysiloxane 1 produced as described above
(A) Modified polysiloxane 2: Modified polysiloxane 2 produced as described above
Polysiloxane 1: Trade name x-22-164AS, manufactured by Shin-Etsu Chemical Co., Ltd. A methacryl-modified dimethylpolysiloxane represented by the following formula (5), wherein R ⁶ is a methyl group, and there is no alkoxysilyl group in the molecule. Mw = 900
Polysiloxane 2: represented by the following formula (5), R ⁶ in the formula is a methyl group, a weight average molecular weight of 1,720, a compound functional group equivalent of methacryloyl group is 860 g / mol (manufactured by Shin-Etsu (Made by Chemical Industries)

Polysiloxane 3: 100 g of both-end silanol (KF-9701, manufactured by Shin-Etsu Chemical Co., Ltd.) and MBM = 503 at 25 Mw were added. The subsequent production method was the same as that for the modified polysiloxanes 1 and 2, and the weight average molecular weight after production was 8,000.
(B) radical initiator 1: thermal radical initiator, compound name 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, trade name perocta O (manufactured by NOF Corporation)
(B) Radical initiator 2: Photoradical initiator, trade name Irgacure 500 (1: 1 mixture of 1-hydroxy-cyclohexyl-phenyl ketone and benzophenone) (manufactured by Ciba Special)
(B) Radical initiator 3: Thermal radical initiator, trade name Perhexyl D (manufactured by NOF Corporation) (di-t-hexyl peroxide)
(B) radical initiator 4: thermal radical initiator, trade name Kayaketal AM-c55 (manufactured by Kayaku Akzo) (2,2-di (t-amylperoxy) butane) (B) radical initiator 5: Thermal radical initiator, trade name Trigonox 117 (manufactured by Kayaku Akzo) (t-butylperoxy 2-ethylhexyl carbonate)
(C) bis (alkoxysilyl) alkane 1: 1,6 bis (trimethoxysilyl) hexane represented by the following formula (trade name Z-6830, manufactured by Toray Dow Corning)

(C) Bis (alkoxysilyl) alkane 2: 1,2-bis (triethoxysilyl) ethane represented by the following formula (KBE3026, manufactured by Shin-Etsu Chemical Co., Ltd.)

(E) Dimethylpolysiloxane 1: Compound represented by the following formula (trade name ss-10, manufactured by Shin-Etsu Chemical Co., Ltd., Mw = 42,000)

(F) Alkoxy oligomer: trade name x-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd. (Mw = 6000)
・ (G) Zirconyl naphthenate: manufactured by Nippon Chemical Industry Co., Ltd. (H) Epoxy silicone: Epoxy-modified polysiloxane (trade name: KF101, manufactured by Shin-Etsu Chemical Co., Ltd.)
(I) Cationic polymerization catalyst: BF ₃ · Et ₂ O (BF ₃ ethyl etherate complex, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ (J) Silicone oil: Terminal trimethylsilyl group-terminated silicone oil, trade name KF96-5000cs (manufactured by Shin-Etsu Chemical Co., Ltd.)
(K) acryloylmorpholine: ACMO, manufactured by Kojin Co., Ltd. (L) N, N-dimethylacrylamide: manufactured by Kanto Chemical Co.

3. Evaluation About the silicone resin composition for optical semiconductor encapsulation obtained as described above, in the following manner, a sealed initial curing state, transmittance, transmittance retention, heat-resistant coloring stability, glass adhesiveness during curing, wet heat Adhesion and heat crack resistance were evaluated. The results are shown in Table 1.
<Preparation of sample>
The production of the sample will be described below with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view schematically showing a mold used for curing the silicone resin composition for sealing an optical semiconductor of the present invention in Examples.
In FIG. 1, a mold 8 has a silicon mold spacer 1 (vertical 5 cm, lateral 5 cm, height 2 mm) between a glass 2 (vertical 5 cm, lateral 5 cm, thickness 4 mm) and an aluminum plate 4. Between the aluminum plate 4 and the spacer 1, there is PET3 (polyethylene terephthalate film is used as a release paper). The mold 8 is fixed with a jig (not shown).
The composition obtained as follows is applied directly to the glass 2, the composition on the glass 2 is sandwiched between the glass 2 and the PET 3, and the interior 6 is filled with the composition. After filling, the inside 6 was sealed (not shown), and the composition 6 was cured under the following curing conditions to obtain a cured product 6.

<Curing conditions>
(1) When the composition contains a photo-radical initiator A light irradiation device (trade name: GS UVSYSTEM TYPE S250-01, manufactured by GS Yuasa Lighting Co., Ltd., using a metal hydrolamp as a light source, integrated light quantity 1 , 800 mJ / cm ² ) was irradiated for 40 seconds at a light amount of 120 mW / cm with a wavelength of 250 to 380 nm to obtain a cured product with an integrated light amount of 1800 mJ / cm ² .

(2) When the composition contains a thermal radical initiator The mold 8 was put in an electric oven and heated at 150 ° C. for 3 hours to obtain a cured product.

(3) When the composition contains a cationic polymerization catalyst The mold 8 was placed in an electric oven and heated at 80 ° C. for 1 hour and then at 150 ° C. for 1 hour to obtain a cured product.

<Evaluation conditions>
(1) Sealed initial curing state The composition was cured using the mold 8 under the above conditions, and the initial curing state was evaluated.
As the evaluation criteria, it was confirmed whether or not there was a surface tack after curing, and “O” was given when there was no tack, and “X” was given when tack was present or not cured. The case where the composition became cloudy was designated as “cloudy”.

(2) Transmittance, Transmittance Retention Rate In the transmittance evaluation test, an initial cured product obtained by curing the composition using the mold 8 under the above conditions, and a heat resistance test (the initial cured product is further heated at 150 ° C. 400 nm wavelength using a UV / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corp.) according to JIS K0115: 2004 for each cured product (each having a thickness of 2 mm) after 1,000 hours of heating under conditions) The transmittance was measured. Moreover, the retention with respect to the initial transmittance of the transmittance after the heat test was obtained by the following calculation formula.
Transmittance retention rate (%) = (Transmittance after heat resistance test) / (Initial transmittance) × 100

(3) Heat-resistant coloring stability Initial cured product obtained by curing the composition under the above conditions using the mold 8, and a heat resistance test (a test in which the initial cured product is heated at a temperature of 150 ° C. for 1,000 hours) ) Regarding the cured product after, it was visually observed whether the cured product after the heat resistance test was yellow compared with the initial cured product.

(4) Glass adhesiveness during curing An initial cured product obtained by curing the composition using the mold 8 under the above conditions (spacer 1, PET3 and aluminum plate 4 are removed from the mold 8 in advance of the hand peeling test. A hand peeling test (conditions: room temperature 23 ° C., 55% RH) was performed, and the adhesiveness at the time of curing (initial curing stage) was evaluated according to the fracture form of the cured product after the test.
The evaluation criteria for glass adhesiveness during curing were “◯” when the fracture mode was cohesive failure and “x” when the fracture mode was interfacial fracture.

(5) Moisture and heat-resistant adhesion Cured at 150 ° C. for 3 hours using a mold 8 (the same method as glass adhesion during curing), and the spacer 1, PET3 and aluminum plate 4 are removed from the mold 8 at 121 ° C. and 100%. It was left for 24 hours under the condition of RH. Thereafter, it was rated as ○ when cohesive failure (CF) was obtained by the hand peeling test, and x when interfacial peeling (AF) occurred.

(6) Heat-resistant cracking property An initial cured product obtained by curing the composition under the above conditions using the mold 8 was placed under a condition of 150 ° C. for 500 hours. When the cured product obtained after heating had no cracks, “◯” was given, and when there were cracks, “x” was given.

As is apparent from the results shown in Table 1, Comparative Examples 1 and 2 containing no bis (alkoxysilyl) alkane were inferior in wet heat resistance. Comparative Example 3 containing no (meth) acryl-modified organopolysiloxane, radical initiator, or bis (alkoxysilyl) alkane (curing only by condensation of silanol groups and alkoxy groups) is a side effect of the condensation reaction when cured in a closed system. Since the product alcohol did not escape from the system, it was uncured. Comparative Examples 4 and 5 [when the (meth) acryl-modified organopolysiloxane has no alkoxysilyl group], Comparative Example 6 [when the weight average molecular weight of the (meth) acryl-modified organopolysiloxane is less than 10,000] Low adhesion to glass and inferior heat-resistant cracks. Comparative Example 7 containing epoxy silicone was inferior in heat-resistant coloring stability. Comparative Example 8, which did not contain bis (alkoxysilyl) alkane and contained silicone oil instead, was inferior in adhesion. Comparative Examples 9 and 10 containing a radical polymerizable monomer without containing bis (alkoxysilyl) alkane were not compatible and became cloudy and inferior in transparency and curability.
On the other hand, Examples 1-6 are excellent in sclerosis | hardenability in a closed system, adhesiveness (adhesion with glass, adhesiveness between glass / glass), heat-and-moisture resistance, and heat-resistant coloring stability.

1 Spacer 2 Glass 3 PET
4 Aluminum plate 6 Composition of the present invention (internal 6 and cured product 6 after curing)
Type 8

Claims (4)

(A) (meth) acryl having 2 or more functional groups represented by the following formula (I) and 1 or more alkoxysilyl groups in one molecule and having a weight average molecular weight of 10,000 to 150,000 Modified organopolysiloxane,
(B) a radical initiator;
(C) A silicone resin composition for encapsulating an optical semiconductor containing bis (alkoxysilyl) alkane.

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms.) The silicone resin composition for optical semiconductor encapsulation according to claim 1, wherein the (meth) acryl-modified organopolysiloxane is represented by the following formula (2).

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each an alkyl group, R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is Each is 1 or 2, and m is 100-2000.)   The bis (alkoxysilyl) alkane is bis- (3-trimethoxysilylpropyl) amine, 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis. At least one selected from the group consisting of (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane The silicone resin composition for optical semiconductor encapsulation according to claim 1 or 2, which is a seed.   The amount of the bis (alkoxysilyl) alkane is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acryl-modified organopolysiloxane. Silicone resin composition.

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