JP2016069485A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that has heat resistance and UV resistance in combination with high refractive index, has improved thermal shock resistance by virtue of a low elastic modulus and high elongation and is excellent in reliability as a sealing material for LED.SOLUTION: The thermosetting resin composition comprises (A), (B) and (C) as given below: (A) a thermosetting resin which is a reaction product of a silsesquioxane having an SiH group with an organopolysiloxane having two alkenyl groups and has an SiH group and an alkenyl group; (B) a linear organopolysiloxane compound having an SiH group each at both terminals; and (C) a Pt catalyst.SELECTED DRAWING: None

Description

  The present invention is a thermosetting resin composition comprising a thermosetting resin composed of silsesquioxane and organopolysiloxane, which has heat resistance, high refractive index, and cold thermal shock resistance, the thermosetting resin composition A cured product obtained by curing a product, a composition for an optical semiconductor and an optical semiconductor element using the cured product are provided.

  As LEDs are used in a wide range of applications such as lighting and the output of white LEDs is increased, the required characteristics for LED sealing materials are becoming increasingly severe. Therefore, a thermosetting resin composition having both a high refractive index and heat resistance that can cope with a large output of a white LED and also having cold and thermal shock resistance has been desired.

  Silsesquioxane materials having excellent heat resistance and UV (ultraviolet) resistance have attracted attention, and LED sealing materials using such materials have been reported.

  Patent Document 1 discloses a sealing material for LED using a thermosetting resin composition of a thermosetting resin having a SiH group introduced into a cage-type octasilsesquioxane and an organopolysiloxane having an alkenyl group. .

  Patent Document 2 discloses a thermosetting resin composition using an incomplete cage-type silsesquioxane called a so-called double-decker type. The silsesquioxane is a structure-controlled compound obtained by hydrolytic condensation of phenyltrimethoxysilane. Since the position of the Si-Ph group is not random but the structure is controlled, it has high refractive index and heat resistance. Excellent light resistance.

  Patent Document 2 discloses a thermosetting containing a SiH group and a vinyl group obtained by reacting a silanol group part of silsesquioxane having an incomplete cage structure with a SiH group-modified compound and an organopolysiloxane having an alkenyl group. A functional resin is disclosed. And what hardened this thermosetting resin has high heat resistance in spite of being high refractive index, and also has good adhesiveness with the polyphthalamide resin base material or silver base material which is the package material of LED. It is shown.

  Patent Document 3 describes a silicone gel composition containing an organopolysiloxane having SiH groups at both ends as a component, which is heated under reduced pressure to remove volatile low-molecular siloxane.

JP 2012-102167 A International Publication No. 2011/145638 JP 2008-231247 A

Since the composition of Patent Document 1 is basically composed of units of -Me ₂ Si-O, the refractive index is not high. Further, the properties of the composition are solid at room temperature, and can be applied to the sealing of the LED by the molding method, but cannot be applied to the sealing of the LED of the dispenser method.

  A thermosetting resin containing a SiH group and a vinyl group obtained from the reaction of a double-decker silsesquioxane having four SiH groups described in Patent Document 2 and an organopolysiloxane having two vinyl groups was used. The cured product has a problem that when the double-decker silsesquioxane content is low, the adhesion performance is weakened.

  On the other hand, when the silsesquioxane content is high, the adhesion performance is improved, but the resin may be too hard. As a result, the stress cannot be relieved and peeling from the LED package may occur in the thermal shock test. Furthermore, in the wire bonding type package system, there is a problem that wire cutting is likely to occur.

  The present invention provides a thermosetting resin composition excellent in reliability as an LED encapsulant that has both a high refractive index and heat resistance and also has a higher thermal shock resistance than ever.

  The present inventors have intensively studied to solve the above problems. As a result, a thermosetting resin containing SiH groups and alkenyl groups obtained from a reaction between a silsesquioxane having SiH groups and an organopolysiloxane having two alkenyl groups, and an organopolysiloxane having SiH groups at both ends. It has been found that the above problems can be solved by including a siloxane compound and a Pt catalyst in the thermosetting resin composition, and the present invention has been completed.

式（１）において、Ｘは独立して、下記式（Ｘ−Ｉ）、式（Ｘ−ＩＩ）または式（Ｘ−ＩＩＩ）で表される基であり、式（１）で表される化合物１分子あたり［該化合物が式（Ｘ−Ｉ）で表される基と式（Ｘ−ＩＩ）で表される基と式（Ｘ−ＩＩＩ）で表される基の割合が異なる化合物の混合物である場合は該化合物１分子平均］の式（Ｘ−Ｉ）で表される基の数をａ、式（Ｘ−ＩＩ）で表される基の数をｂ、式（Ｘ−ＩＩＩ）で表される基の数をｃとした場合に、ａ＋２ｂ＋ｃ＝４であり、０＜ａ≦３であり、０≦ｂ≦１であり、０＜ｃ≦３である。
Ｒ^１は独立して、炭素数１〜４のアルキル、シクロペンチル及びシクロヘキシルから選択される基であり、ｍは１〜１００を満たす平均値である。

式（Ｘ−ＩＩ）において、Ｒ^２及びＲ^３は独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり、ｒは−ＯＳｉ（Ｒ^３）_２−の繰り返しの数であり、２〜２０を満たす平均値である。

式（Ｘ−ＩＩＩ）において、Ｒ^４及びＲ^５は独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり、ｓは−ＯＳｉ（Ｒ^５）_２−の繰り返しの数であり、２〜２０を満たす平均値である。
Ｒ^０は炭素数２〜５の１つの二重結合を有する不飽和炭化水素基を表す。
Ｒ^０’は、Ｒ^０と同じ炭素数をもつ、炭素数２〜５の飽和炭化水素基を表す。
６．両末端にＳｉＨ基を有する直鎖状のオルガノポリシロキサン化合物（Ｂ）が下記式（２）で示される化合物であることを特徴とする前項１〜５のいずれか１項に記載の熱硬化性樹脂組成物。

Ｒ^６は独立して、炭素数１〜４のアルキル、シクロペンチル及びシクロヘキシルから選択される基であり、ｍは−ＯＳｉ（Ｒ⁶）_２−の繰り返しの数であり、１〜２０を満たす平均値である。
７．（Ｄ）で定義される化合物が、下記式（Ｄ１）で示される化合物であることを特徴とする前項３〜６のいずれか１項に記載の熱硬化性樹脂組成物。

式（Ｄ１）において、Ｘ’は独立して、下記式（ａ）、式（ｂ）、式（ｃ−ｉ）、式（ｃ−ｉｉ）、式（ｃ−ｉｉｉ）、式（ｄ−ｉ）、式（ｄ−ｉｉ）または式（ｄ−ｉｉｉ）で表される基であり、式（Ｄ１）で表される化合物１分子あたり［該化合物が式（ａ）で表される基と式（ｂ）、式（ｃ−ｉ）、式（ｃ−ｉｉ）、式（ｃ−ｉｉｉ）、式（ｄ−ｉ）、式（ｄ−ｉｉ）または式（ｄ−ｉｉｉ）で表される基の割合が異なる化合物の混合物である場合は該化合物１分子平均］の、式（ａ）で表される基の数をＡ’、式（ｂ）で表される基の数をＢ’、式（ｃ−ｉ）、式（ｃ―ｉｉ）または式（ｃ−ｉｉｉ）で表される基の数をＣ’、式（ｄ−ｉ）、式（ｄ−ｉｉ）または式（ｄ−ｉｉｉ）で表される基の数をＤ’とした場合に、Ａ’＋２Ｂ’＋Ｃ’＋Ｄ’＝４であり、０．５≦Ａ’≦３．０であり、０．５≦２Ｂ’≦２．０であり、０．１≦Ｃ’≦２．０であり、０≦Ｄ’≦１．０である。
Ｒ^１’は独立して、炭素数１〜４のアルキル、シクロペンチル及びシクロヘキシルから選択される基であり、ｍ’は１〜１００を満たす平均値である。

式（ｂ）において、Ｒ^２’及びＲ^３’は独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり、ｔは−ＯＳｉ（Ｒ^３’）_２−の繰り返しの数であり、１〜２０を満たす平均値である。

式（ｄ−ｉ）におけるＲ^４、式（ｄ−ｉｉ）におけるＲ^４’および式（ｄ−ｉｉｉ）におけるＲ^４’’は独立して、メチル、エチル、ブチルおよびイソプロピルから選択される基である。
式（ｄ−ｉｉ）におけるｘは−ＯＳｉ（Ｒ^４’）_２−の繰り返しの数であり、１〜２０を満たす平均値である。式（ｄ−ｉｉｉ）におけるｙは−ＯＳｉ（Ｒ^４’’）_２−の繰り返しの数であり、１〜１０を満たす平均値である。
式（ｄ−ｉｉｉ）におけるＲ^０は炭素数２〜５の１つの二重結合を有する不飽和炭化水素基を表す。
８．（Ｄ）で定義される化合物が、下記式（Ｄ２）で示される化合物であることを特徴とする前項３〜６のいずれか１項に記載の熱硬化性樹脂組成物。

式（Ｄ２）において、Ｒ’’は独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり、ｒは０〜１００の整数である。ａｉｉは、０．１≦ａｉｉ≦３．５、Ｘｉｉは、０≦２Ｘｉｉ≦２．０、Ｙｉｉは、０≦Ｙｉｉ≦３．０、Ｚｉｉは、０．１≦Ｚｉｉ≦３．５である。
９．アルケニル基を２個以上有するオルガノポリシロキサン化合物（Ｅ）が式（３）で示される化合物であることを特徴とする前項４〜８のいずれか１項に記載の熱硬化性樹脂組成物。

式（３）において、Ｒ^７及びＲ^８は独立して、炭素数１〜４のアルキル、シクロペンチル、およびシクロヘキシルから選択される基であり、ｎは、−ＯＳｉ（Ｒ^８）_２−の繰り返しの数であり、１〜５０を満たす平均値である。
Ｒ^０は炭素数２〜５の１つの二重結合を有する不飽和炭化水素基を表す。
１０．熱硬化性樹脂組成物全量基準で、（Ａ）で定義される熱硬化性樹脂の配合割合が５０〜９５質量％、化合物（Ｂ）の配合割合が２〜２０質量％である前項１〜９のいずれか１項に記載の熱硬化性樹脂組成物。
１１．さらに化合物（Ｄ）を１〜５０質量％の割合で含有する前項３〜１０のいずれか１項に記載の熱硬化性樹脂組成物。
１２．さらに化合物（Ｅ）を１〜１０質量％の割合で含有する前項４〜１１のいずれか１項に記載の熱硬化性樹脂組成物。
１３．さらに無機化合物が分散された前項１〜１２のいずれか１項に記載の熱硬化性樹脂組成物。
１４．無機化合物が蛍光体または金属酸化物の少なくとも一方である、前項１３に記載の熱硬化性樹脂組成物。
１５．前項１〜１４のいずれか１項記載の熱硬化性樹脂組成物を成型して得られるプリプレグ。
１６．前項１〜１４のいずれか１項に記載の熱硬化性樹脂組成物、または前項１５に記載のプリプレグを硬化させて得られる硬化物。
１７．前項１〜１４のいずれか１項に記載の熱硬化性樹脂組成物、または前項１５に記載のプリプレグを含有する光半導体用組成物。
１８．前項１７に記載の光半導体用組成物を封止剤として含む光半導体素子。
１９．塗膜状またはシート状であり、厚みが０．１μｍ〜３，０００μｍである、前項１６に記載の硬化物。 That is, the present invention is as follows.
1. A thermosetting resin composition containing the following (A), (B) and (C).
(A) A reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, the thermosetting resin having a SiH group and an alkenyl group (B) having SiH groups at both ends. 1. Linear organopolysiloxane compound (C) Pt catalyst having 2. The thermosetting resin composition according to item 1 above, wherein the silsesquioxane is a double-decker silsesquioxane.
3. Furthermore, the thermosetting resin composition of the preceding clause 1 or 2 containing (D).
(D) A compound having a SiH group obtained by reacting a silsesquioxane having a SiH group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group, and a silyl compound having an alkenyl group. Furthermore, the thermosetting resin composition of any one of the preceding clauses 1-3 containing (E).
(E) an organopolysiloxane compound having two or more alkenyl groups; The thermosetting resin composition according to any one of items 1 to 4, wherein the thermosetting resin defined by (A) is a compound represented by the following formula (1).

In formula (1), X is independently a group represented by the following formula (XI), formula (X-II) or formula (X-III), and a compound represented by formula (1) Per molecule [a mixture of compounds in which the ratio of the group represented by the formula (XI), the group represented by the formula (X-II), and the group represented by the formula (X-III) is different. The number of groups represented by the formula (XI) of the compound (average of one molecule of the compound) is a, the number of groups represented by the formula (X-II) is b, and the formula (X-III) When the number of groups to be formed is c, a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3.
R ¹ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and m is an average value satisfying 1 to 100.

In the formula (X-II), R ² and R ³ are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is —OSi (R ³ ) ₂ —. It is the number of repetitions and is an average value satisfying 2-20.

In the formula (X-III), R ⁴ and R ⁵ are each independently a group selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R ⁵ ) ₂ —. It is the number of repetitions and is an average value satisfying 2-20.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.
R ⁰ ′ represents a C 2-5 saturated hydrocarbon group having the same carbon number as R ⁰ .
6). 6. The thermosetting property according to any one of items 1 to 5, wherein the linear organopolysiloxane compound (B) having SiH groups at both ends is a compound represented by the following formula (2): Resin composition.

R ⁶ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, m is the number of repeating -OSi (R ⁶ ) _2- , and an average value satisfying 1 to 20 It is.
7). 7. The thermosetting resin composition according to any one of items 3 to 6, wherein the compound defined by (D) is a compound represented by the following formula (D1).

In the formula (D1), X ′ is independently the following formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (d-i) ), A group represented by formula (d-ii) or formula (d-iii), and per molecule of the compound represented by formula (D1) [the group and the formula represented by formula (a) A group represented by (b), formula (ci), formula (c-ii), formula (c-iii), formula (d-i), formula (d-ii) or formula (d-iii) In the case of a mixture of compounds having different ratios, the number of groups represented by the formula (a) is A ′, the number of groups represented by the formula (b) is B ′, and the formula The number of groups represented by (ci), formula (c-ii) or formula (c-iii) is C ′, formula (di), formula (d-ii) or formula (d-iii) A ′ + 2B ′ + C ′ where D ′ is the number of groups represented by D ′ = 4, 0.5 ≦ A ′ ≦ 3.0, 0.5 ≦ 2B ′ ≦ 2.0, 0.1 ≦ C ′ ≦ 2.0, 0 ≦ D ′ ≦ 1.0.
R ^{1 ′} is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m ′ is an average value satisfying 1 to 100.

In the formula (b), R ^{2 ′} and R ^{3 ′} are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and t is —OSi (R ^{3 ′} ) ₂ —. The average value satisfying 1-20.

^{R 4} in Formula ^{(d-i), 'R} 4 in and Formula ^(d-iii)' R ⁴ in Formula (d-ii) ^'are independently a group selected from methyl, ethyl, butyl and isopropyl is there.
X in the formula (d-ii) is the number of repetitions of -OSi (R ^{4 '} ) _2- and is an average value satisfying 1 to 20. Y in the formula (d-iii) is the number of repetitions of -OSi (R ^{4 ''} ) _2- and is an average value satisfying 1 to 10.
R ⁰ in formula (d-iii) represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.
8). 7. The thermosetting resin composition according to any one of items 3 to 6, wherein the compound defined by (D) is a compound represented by the following formula (D2).

In the formula (D2), R ″ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100. aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, and Zii is 0.1 ≦ Zii ≦ 3.5.
9. 9. The thermosetting resin composition according to any one of items 4 to 8, wherein the organopolysiloxane compound (E) having two or more alkenyl groups is a compound represented by the formula (3).

In Formula (3), R ⁷ and R ⁸ are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and n is a repeating group of —OSi (R ⁸ ) ₂ —. It is a number and is an average value satisfying 1-50.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.
10. The preceding items 1 to 9 wherein the blending ratio of the thermosetting resin defined in (A) is 50 to 95% by mass and the blending ratio of the compound (B) is 2 to 20% by mass based on the total amount of the thermosetting resin composition. The thermosetting resin composition according to any one of the above.
11. Furthermore, the thermosetting resin composition of any one of the preceding clauses 3-10 which contains a compound (D) in the ratio of 1-50 mass%.
12 Furthermore, the thermosetting resin composition of any one of the preceding clauses 4-11 which contain a compound (E) in the ratio of 1-10 mass%.
13. Furthermore, the thermosetting resin composition of any one of the preceding clauses 1-12 by which the inorganic compound was disperse | distributed.
14 14. The thermosetting resin composition according to item 13, wherein the inorganic compound is at least one of a phosphor and a metal oxide.
15. A prepreg obtained by molding the thermosetting resin composition according to any one of items 1 to 14.
16. 15. A cured product obtained by curing the thermosetting resin composition according to any one of items 1 to 14 or the prepreg according to item 15.
17. The composition for optical semiconductors containing the thermosetting resin composition of any one of the preceding clauses 1-14, or the prepreg of the preceding clause 15.
18. 18. An optical semiconductor element comprising the optical semiconductor composition according to item 17 as a sealing agent.
19. Hardened | cured material of the preceding clause 16 which is a coating-film form or a sheet form, and whose thickness is 0.1 micrometer-3,000 micrometers.

  The cured product obtained by curing the thermosetting resin composition of the present invention can reduce the elastic modulus and increase the elongation while maintaining the advantages of high refractive index and high heat resistance. Therefore, the cured product sealed with the thermosetting resin composition of the present invention has excellent stress relaxation capability, and the optical semiconductor device manufactured using the thermosetting resin composition can withstand strict reliability tests. It can be an optical semiconductor device. Furthermore, it is possible to provide an optical semiconductor device that has low hardness but low surface tack, can be diced, and has excellent moldability.

  Since the thermosetting resin composition of the present invention has a double-decker silsesquioxane skeleton as a main component, the cured product is excellent in heat resistance and UV resistance.

  In the thermosetting resin composition of the present invention, the SiH group at one end of the compound (B) reacts with the alkenyl group of the thermosetting resin (A) which is the main agent, so that the hardness can be reduced. It will be a thing. Furthermore, even when the SiH groups at both ends of the compound (B) react with the alkenyl groups of the two compounds (A), respectively, the stress can be relaxed and kept in a low hardness state despite the higher molecular weight. Is possible.

  Hereinafter, the present invention will be described in detail. In the present application, the thermosetting resin defined in (A) may be referred to as a thermosetting resin (A) or simply (A). Moreover, the compound defined by (B) may be described as the compound (B) or simply (B). The same applies to the compounds defined by (D) and (E). (C) The Pt catalyst may be referred to as a Pt catalyst (C) or simply (C).

The thermosetting resin composition of the present invention is characterized by containing the following (A), (B) and (C).
(A) A reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, the thermosetting resin containing a SiH group and an alkenyl group (B) having SiH groups at both ends The linear organopolysiloxane compound (C) Pt catalyst having each component will be described below.

  The thermosetting resin defined by (A) is a reaction product of silsesquioxane having SiH groups and organopolysiloxane having two alkenyl groups. Examples of silsesquioxanes having SiH groups include double-decker silsesquioxanes and cage-type silsesquioxanes having a T8 structure. The cage silsesquioxane having a T8 structure has eight functional groups, whereas the double-decker silsesquioxane used in the present invention has only four functional groups. Easy to control the structure. Unlike the fully condensed cage silsesquioxane, the double-decker silsesquioxane preferably used in the present invention is incompletely condensed, has a relatively high degree of molecular freedom, and is excellent in flexibility. . From such a viewpoint, double-decker silsesquioxane is preferable.

  As a thermosetting resin (A), the compound represented by following formula (1) is mentioned, for example.

In the formula (1), X is independently a group represented by the following formula (XI), formula (X-II) or formula (X-III). R ¹ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m is an average value satisfying 1 to 100. Among these, m is preferably 1.

In the formula (X-II), R ² and R ³ are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is —OSi (R ³ ) ₂ —. It is the number of repetitions, is an average value satisfying 2-20, and 2-10 is more preferable.

In the formula (X-III), R ⁴ and R ⁵ are each independently a group selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R ⁵ ) ₂ —. It is the number of repetitions and is an average value satisfying 2-20. As for s, 2-10 are preferable and 2-4 are more preferable.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.
R ⁰ ′ represents a C 2-5 saturated hydrocarbon group having the same carbon number as R ⁰ .

  Per molecule of the compound represented by the formula (1) [the compound is represented by the group represented by the formula (XI), the group represented by the formula (X-II), and the formula (X-III) In the case of a mixture of compounds having different group ratios, the number of groups represented by the formula (XI) of the compound 1 molecule average] is a, and the number of groups represented by the formula (X-II) is b When the number of groups represented by formula (X-III) is c, a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3. .

  In the present invention, a compound in a range where a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3 will be described.

  If a> c, the compound represented by formula (1) has on average more SiH groups than alkenyl groups, and can be defined as a so-called SiH group type thermosetting resin.

  The alkenyl group is not particularly limited as long as it is a group containing a carbon-carbon double bond, and is an aliphatic unsaturated hydrocarbon group having 2 to 5 carbon atoms. The alkenyl group may be in the middle or at the end of the molecular chain of the hydrocarbon group, but from the viewpoint of the curing speed of the resulting composition and the physical properties after curing, particularly the silicon at the molecular chain end. It is preferably bonded to an atom.

  As the thermosetting resin (A), it is preferable to use a SiH-based thermosetting resin. From the viewpoint of making the excellent properties of the cured product remarkable, a is preferably 1.0 to 3.0, and more preferably 1.5 to 2.5. A, b, and c in the compound represented by the formula (1) can be adjusted by the inventor's discretion, for example, by conforming to the production method described in International Publication No. 2011/145638.

  The thermosetting resin composition of the present invention preferably contains 50 to 95% by mass of the thermosetting resin (A), more preferably 80 to 90% by mass, based on the total amount of the thermosetting resin composition. preferable. By setting the blending ratio of the thermosetting resin (A) to 50% by mass or more, the characteristics possessed by the double-decker silsesquioxane, that is, the characteristics such as heat resistance, UV resistance, and high refractive index are maintained. The heat resistance is further improved when the content is 80% by mass or more. Moreover, the hardness of hardened | cured material can be D45 or less by making the mixture ratio of a thermosetting resin (A) into 95 mass% or less.

The compound defined by (B) is a linear organopolysiloxane compound having SiH groups at both ends, and examples thereof include a compound represented by the following formula (2).

In the formula (2), R ⁶ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and preferably methyl or butyl. m is the number of repetitions of -OSi (R ⁶ ) _2- . m is an average value satisfying 1 to 20, and preferably an average value satisfying 2 to 15.

  The compound (B) is used for reducing the hardness. That is, it can be made to react with the alkenyl group which (A) which is a thermosetting resin has, and low hardness can be achieved by the effect of a linear organopolysiloxane compound.

  The more compound (B) is blended, the lower the hardness of the cured product. The content of the compound (B) in the thermosetting resin composition of the present invention is preferably such a content that the cured product can maintain a refractive index of 1.5 or more. By setting the content such that the refractive index of the cured product can maintain 1.5 or more, the light extraction efficiency is improved as an LED sealing material.

  The number average molecular weight of the compound (B) is preferably 134 to 2000. When the number average molecular weight of the compound (B) is 400 or more, the volatility becomes low, and volatilization at the stage of blending and curing the cured composition can be suppressed. Further, by setting the number average molecular weight of the compound (B) to 2000 or less, a reaction product of silsesquioxane having SiH group and organopolysiloxane having two alkenyl groups, wherein SiH group and alkenyl group It is possible to maintain compatibility with the thermosetting resin containing, and maintain the transparency of the cured product.

  The compounding ratio of the compound (B) is preferably 2 to 20% by mass and more preferably 5 to 15% by mass in the total thermosetting resin composition of the present invention. By setting the compounding ratio of the compound (B) to 2% by mass or more, the hardness of the cured product can be lowered to D45 or less. Moreover, by setting the blending ratio of the compound (B) to 20% by mass or less, it is possible to effectively obtain a cured product having a low hardness while maintaining various properties such as heat resistance and UV resistance of the cured product. is there.

The Pt catalyst of (C) means a catalyst containing platinum, and platinum may or may not be oxidized. Examples of oxidized platinum include platinum oxide. Examples of the partially oxidized platinum include an Adams catalyst.

  Examples of the Pt catalyst (C) include a Karstedt catalyst, a Spear catalyst, and hexachloroplatinic acid. These are generally well known catalysts. Of these, a non-oxidized type Karsted catalyst is preferably used.

  The blending ratio of the Pt catalyst (C) is preferably an amount sufficient to promote the curing of the curable resin composition of the present invention, specifically 0.01 ppm to 10 ppm, preferably 0 More preferably, the content is 0.05 ppm to 1 ppm. Curing can be advanced by setting the blending ratio of the Pt catalyst (C) to 0.01 ppm or more. By setting the blending ratio of the Pt catalyst (C) to 0.05 ppm or more, the curing can be rapidly advanced. Moreover, the heat resistance of hardened | cured material can be hold | maintained by the compounding ratio of Pt catalyst (C) being 10 ppm or less.

The thermosetting resin composition of this invention may further contain the compound defined by (D) as needed. The compound (D) is a compound that has a SiH group and may or may not have an alkenyl group.
The compound (D) can be obtained by reacting a silsesquioxane having a SiH group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group, and a silyl compound having an alkenyl group. Examples of the compound (D) include compounds represented by the following formula (D1).

  In the formula (D1), X ′ is independently the following formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (d-i) ), A group represented by formula (d-ii) or formula (d-iii), and per molecule of the compound represented by formula (D1) [the group and the formula represented by formula (a) A group represented by (b), formula (ci), formula (c-ii), formula (c-iii), formula (d-i), formula (d-ii) or formula (d-iii) In the case of a mixture of compounds having different ratios, the number of groups represented by the formula (a) is A ′, the number of groups represented by the formula (b) is B ′, and the formula The number of groups represented by (ci), formula (c-ii) or formula (c-iii) is C ′, formula (di), formula (d-ii) or formula (d-iii) When the number of groups represented by D is D ′, A ′ + 2 '+ C' + D '= 4, 0.5 ≦ A ′ ≦ 3.0, 0.5 ≦ 2B ′ ≦ 2.0, 0.1 ≦ C ′ ≦ 2.0, 0 ≦ D ′ ≦ 1.0.

R ^{1 ′} is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m ′ is an average value satisfying 1 to 100.

式（ｂ）において、Ｒ^２’及びＲ^３’は独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから選択される基であり、ｔは−ＯＳｉ（Ｒ^３’）_２−の繰り返しの数であり、１〜２０を満たす平均値である。

In the formula (b), R ^{2 ′} and R ^{3 ′} are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and t is —OSi (R ^{3 ′} ) ₂ —. The average value satisfying 1-20.

^{R 4} in Formula ^{(d-i), 'R} 4 in and Formula ^(d-iii)' R ⁴ in Formula (d-ii) ^'are independently a group selected from methyl, ethyl, butyl and isopropyl is there. X in the formula (d-ii) is the number of repetitions of -OSi (R ^{4 '} ) _2- and is an average value satisfying 1 to 20. Y in the formula (d-iii) is the number of repetitions of -OSi (R ^{4 ''} ) _2- and is an average value satisfying 1 to 10.
R ⁰ in formula (d-iii) represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.

  The group represented by the formula (a) is a group derived from silsesquioxane having a SiH group, the compound corresponding to the group represented by the formula (b), and the formulas (ci) to (c- The epoxy derivative corresponding to the group represented by iii), the SiH group residue after the reaction with the compound corresponding to the group represented by the formulas (di) to (d-iii) used as necessary It is a group. Accordingly, the group represented by the formula (a) can react with a thermosetting resin that is a reaction product of silsesquioxane and an organopolysiloxane to which the compound of the present invention is applied as an adhesion-imparting material. It has the role of strengthening the function as an adhesion-imparting material for these compounds.

  The group represented by the formula (b) is a crosslinking component of silsesquioxane, and can give flexibility to the compound of the present invention. Specifically, for example, by crosslinking with the formula (D1), a polymer structure such as a compound represented by the following formula (1-1) is given.

In Formula (1-1), X1 is independently represented by Formula (a), Formulas (ci) to (c-iii), or Formulas (di) to (d-iii) described above. X2 is a group represented by the formula (b) described above. R ¹⁷ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and is preferably methyl. u is an average value satisfying 0 to 100.

  The larger the value of B ′, the number of groups represented by formula (b), the more cross-linking components between molecules, and the compound of the present invention becomes a high molecular weight compound. If B ′ = 0, there is no crosslinking component. In the range of 0 <B ′ ≦ 1, the crosslinking component increases and the molecular weight increases as the value of B ′ increases. In the range of B ′> 1, the cross-linking of molecules is very advanced and it becomes a gel and cannot be used as a thermosetting resin. By changing the value of B ′ within the range of 0 <B ′ ≦ 1, the molecular weight of the compound of the present invention can be adjusted.

  The groups represented by the formulas (c-i) to (c-iii) are epoxy groups bonded to SiH residues in the crosslinked product of silsesquioxane and organopolysiloxane, and Has a role to improve adhesion. The component (ci) is a group having an isocyanuric ring skeleton in addition to an epoxy group, and also has a role of improving adhesion with a metal.

The groups represented by the formulas (di) to (d-iii) are an alkoxysilyl group, a trialkylsilyl group or an alkenylsilyl bonded to a SiH residue in a crosslinked product of silsesquioxane and an organopolysiloxane. It is a group.
The group represented by the following formula (di) is a group derived from (D) and is an optional component.
The group represented by the formula (d-i) is used for the purpose of improving the adhesion with a metal or the compatibility with a resin.

In the formula (di), R ⁴ is independently a group selected from methyl, ethyl, butyl and isopropyl.

The group represented by the following formula (d-ii) is a group derived from (D) and is an optional component. The group represented by the formula (d-ii) is used for the purpose of improving the compatibility with the resin, the purpose of adjusting the viscosity, or the purpose of adjusting the hardness after curing the curable resin composition.

In the formula (d-ii), R ^{4 ′} is independently a group selected from methyl, ethyl, butyl and isopropyl, preferably methyl. x is an average value satisfying 1 to 20 by the number of repetitions of -OSi (R ^{4 '} ) _2- , and more preferably an average value satisfying 1 to 10.

The group represented by the following formula (d-iii) is a group derived from (D) and is an optional component. The group represented by the formula (d-iii) is used for the purpose of improving the compatibility with the resin, the purpose of adjusting the viscosity, or the purpose of adjusting the hardness after curing the curable resin composition.

In formula (d-iii), R ^{4 ″} is independently a group selected from methyl, ethyl, butyl and isopropyl, preferably methyl. y is the number of repetitions of -OSi (R ^{4 ''} ) _2- , more preferably an average value satisfying 1 to 10.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.

  A ′ + 2B ′ + C ′ + D ′ = 4, 0.5 ≦ A ′ ≦ 3.0, 0.5 ≦ 2B ′ ≦ 2.0, and 0.1 ≦ C ′ ≦ 2.0. Yes, 0 ≦ D ′ ≦ 1.0. The values of A ′ to D ′ can be arbitrarily adjusted according to the properties of the thermoplastic resin composition to which the compound of the present invention is applied as an adhesion promoter.

  The group derived from (D) will be further described. A reaction reagent and a reaction method for obtaining a group represented by formula (d-ii) or formula (d-iii) will be described.

  First, a reaction reagent for obtaining a group represented by the formula (d-ii) or a group represented by the formula (d-iii) will be described.

  As shown in the following reaction formula, an equimolar reaction of excess moles of divinyltetradisiloxane (DVDS) and hexamethyldisiloxane (MM) in the presence of an acid catalyst with respect to cyclic octamethyltetracyclosiloxane (D4). And an equilibrated mixture of compound a, compound b, and compound c is obtained, and used as a reaction reagent for obtaining a group represented by formula (d-ii) or a group represented by formula (d-iii).

In the reaction formula, a is 1 to 20, b is 1 to 20, and c is 1 to 20.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.

  The molar ratio of the combined reaction of DVDS and MM with respect to D4 is preferably 2 or more. If the molar ratio is 2 or more, the molecular weight of the resulting siloxane chain is short and becomes a component that can be removed by distillation, and in the subsequent purification step, excess compound a, compound b, and compound c that were not involved in the reaction. Easy to remove.

It describes about the method of reaction in order to obtain group represented by a formula (d-ii) or a formula (d-iii).
As a reaction having the isocyanuric ring skeleton of the present invention and having an epoxy group and a group represented by the formula (d-ii) or the formula (d-iii), the group derived from (D) is The case where it is a group represented by the formula (ci) will be described.

  As shown in the following reaction formula, in the first reaction, DD-4H which is a double-decker compound having four SiH groups and MA-DGIC which is (ci) are first hydrosilylated. First, a compound having a group represented by the formula (ci) is obtained. The compound of the formula (ci) is sold as MA-DGIC by Shikoku Kasei Co., Ltd. DD-4H can be synthesized according to the method described in International Publication No. 2004/024741.

  In the reaction formula, ai is 0.1 ≦ ai ≦ 3.5.

  Next, as shown in the following reaction formula, in the second-stage reaction, the number of moles of vinyl groups in the mixture of compound a, compound b, and compound c with respect to the number of moles of SiH groups in the first-stage compound. The following product is obtained by carrying out a hydrosilylation reaction so that is excessive.

In the reaction formula, ai is 0.1 ≦ ai ≦ 3.5, Xi is 0 ≦ 2Xi ≦ 2.0, Yi is 0 ≦ Yi ≦ 3.0, Zi is 0.1 ≦ Zi ≦ 3.5, Wi is 0 ≦ Wi ≦ 3.0.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.

  The hydrosilylation reaction is performed so that the number of moles of vinyl groups is excessive, but the remaining SiH groups remain without disappearing even in a high temperature region of 100 ° C. or higher, and further 120 ° C. or higher.

  Excess compound a, compound b, and compound c not involved in the reaction can be distilled off by distillation using a thin film evaporator. Alternatively, it can be removed by a solvent extraction method. Alternatively, it may be left as it is at the discretion of the inventor. The temperature when distilling off excess compound a, compound b, and compound c in distillation using a thin film evaporator is preferably in the range of 120 ° C. to 180 ° C., and the operating pressure is preferably 0.13 kPa or less.

  A preferable solvent for removing excess compound a, compound b, and compound c in the solvent extraction method is a solvent having a large dissolving power and a relatively low boiling point. A preferred solvent is a lower alcohol. A particularly preferred solvent is methanol. In order to further increase the degree of purification, the number of repeated solvent extraction operations may be increased.

  Next, a method for obtaining only the group represented by the formula (d-iii) will be described in detail.

  As shown in the following reaction formula, in the first stage reaction, DD-4H and MA-DGIC are first hydrosilylated to obtain a compound having a group represented by the formula (ci).

  In the reaction formula, aii is 0.1 ≦ aii ≦ 3.5.

  As a reactant used in the second stage reaction, a compound represented by the formula (F) is used.

In the formula (F), R ′ and R ″ are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100. R ′ and R ″ are preferably methyl. r is preferably 1 to 100, and more preferably 2 to 20.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.

  As shown in the following reaction formula, the hydrosilylation reaction is performed so that the number of moles of the vinyl group of the compound represented by the formula (F) is excessive with respect to the number of moles of the SiH group in the first-stage compound. This gives the following product:

In the reaction formula, aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, Zii is 0.1 ≦ Zii ≦ 3.5, r is 1-20.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.

  Hydrosilylation reaction is performed so that the number of moles of the vinyl group of the compound represented by the formula (F) is excessive, but it does not disappear even in a high temperature region of 100 ° C. or higher, more preferably 120 ° C. or higher. Remains.

  Since the excess organopolysiloxane not involved in the reaction is a compound having a vinyl group, it may be left as it is as a thermosetting resin component. Or you may remove by solvent extraction etc. suitably. A preferred solvent for removing excess organopolysiloxane is a solvent having a high dissolving power and a relatively low boiling point. A preferred solvent is a lower alcohol. A particularly preferred solvent is methanol. In order to further increase the degree of purification, the number of repeated solvent extraction operations may be increased.

Moreover, as a compound (D), the compound represented by a following formula (D2) is mentioned, for example.

  In formula (D2), R ″ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100. aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, and Zii is 0.1 ≦ Zii ≦ 3.5.

  The thermosetting resin composition of the present invention preferably contains 1 to 50% by mass, more preferably 1 to 15% by mass, of the compound (D) based on the total amount of the thermosetting resin composition. By setting the compounding ratio of the compound (D) to 1% by mass or more, it is possible to improve the adhesion strength with the LED housing substrate.

  In addition, since the epoxy part in the compound (D) can be used arbitrarily, the part by which the total of the epoxy part is 0.01 to 10% by mass based on the total amount of the thermosetting resin composition. It is preferable to contain by mass part which becomes 0.05 to 5 mass% preferably.

  The thermosetting resin composition of the present invention may further contain an organosiloxane compound having two or more alkenyl groups defined by (E) (hereinafter referred to as compound (E)) as necessary. As a compound (E), the compound shown, for example by following formula (3) is mentioned.

In the formula (3), R ⁷ and R ⁸ are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and n is the number of repeating -OSi (R ⁸ ) ₂ —. And is an average value satisfying 1 to 50.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.

The compound (E) is a component for adjusting the viscosity of the cured composition of the present invention and assisting the cured product with strength or flexibility. In the formula (3), when R ⁷ and R ⁸ are all alkyl having 1 to 4 carbon atoms, methyl is preferably used and is represented by the following formula (4).

In Formula (4), n ′ is an average value satisfying 1-20. When n ′ is 20 or less, the compatibility with the cured composition of the present invention is good, which is preferable. In terms of imparting flexibility, 5 or more is preferable, and 10 or less is preferable from the viewpoint of a gas barrier. 5 to 8 is particularly preferable from the viewpoints of flexibility and gas barrier.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.

  Compound (E) can be produced by a known method. The organosiloxane compound represented by the formula (4) is obtained by, for example, equilibrating tetramethylvinyldisiloxane and octamethylcyclotetrasiloxane in the presence of a solid acid catalyst such as activated clay, and then filtering the solid acid catalyst. It can be manufactured by removing it and then cutting it at a low boiling point under a vacuum condition of about 0.13 kPa and a temperature condition of 100 to 120 ° C. It is also industrially available from GELEST.

  The compounding ratio of the compound (E) is preferably 10% by mass or less in the total thermosetting resin composition of the present invention. It is preferable that the compounding ratio of the compound (E) is 10% by mass or less because heat resistance is improved and resin strength is increased.

  The thermosetting resin composition of the present invention may further contain the following components.

<Curing inhibitor>
As the curing inhibitor, known ones used in addition-type curable compositions with hydrosilylation catalysts can be used. Specific examples include compounds containing two or more alkenyl groups, compounds containing aliphatic unsaturated bonds, organophosphorus compounds, tin compounds, and organic peroxides. These may be used alone or in combination of two or more.

  Examples of the compound containing two or more alkenyl groups include disiloxanes containing both vinyl groups, trisiloxanes, and vinyl group-containing cyclic siloxanes such as 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane. Can be mentioned.

  Examples of the compound containing an aliphatic unsaturated bond include 2-methyl-3-butyn-2-ol, 3-methyl-1-dodecin-3-ol, 3,5-dimethyl-1-hexyne-3- Ol, propargyl alcohols such as 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic esters such as maleic anhydride and dimethyl maleate.

  Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Of these, 1,3-divinyldisiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 2-methyl-3-butyn-2-ol or 1-ethynyl-1-cyclohexanol is preferred. .

  By mix | blending a hardening inhibitor with the thermosetting resin composition of this invention, the viscosity increase at room temperature can be suppressed and a pot life can be ensured. The content of the curing inhibitor in the thermosetting resin composition of the present invention is preferably 0.001 to 5% by mass, and more preferably 0.01 to 3% by mass.

<Inorganic compounds>
The thermosetting resin composition of the present invention can be used by further dispersing an inorganic compound in accordance with any purpose such as imparting thixotropy or imparting optical properties. There is no limitation in the inorganic compound to be used, A well-known material can be used. Further, the structure of the inorganic compound may be amorphous or may be crystallized. The combination of inorganic compounds to be dispersed is not limited. As the inorganic compound, various phosphors and metal oxides can be suitably used. Of course, phosphors and metal oxides may be used in combination.

  First, a case where the inorganic compound is a phosphor will be described. By dispersing the phosphor in the thermosetting resin composition of the present invention, the phosphor has a light emitting function and can be used as a composition for LED. The phosphor content in the thermosetting resin composition of the present invention is preferably 1 to 90% by mass, and more preferably 2 to 50% by mass.

  There is no restriction | limiting in the fluorescent substance which can be used for the thermosetting resin composition of this invention. Further, the concentration distribution of the phosphor in the composition may be uniform or different. The type of phosphor to be used, the presence / absence of the phosphor concentration distribution, and the conditions for the distribution may be determined according to the use environment, application, and purpose of the LED.

  The phosphor absorbs blue light, violet light, and ultraviolet light emitted from the LED chip, converts the wavelength, and emits red, orange, yellow, green, and blue light with wavelengths different from those of the LED chip. To be released. Thereby, a part of the light emitted from the LED chip and a part of the light emitted from the phosphor are mixed to obtain a multicolor LED including white. Specifically, a white LED can be emitted using a single LED chip by optically combining a blue LED with a phosphor that emits a yellow emission color by light from the LED.

  The phosphors as described above include various phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light. Specific phosphors used in the present invention include known phosphors such as organic phosphors, inorganic phosphors, fluorescent pigments, and fluorescent dyes. Examples of organic phosphors include allylsulfoamide / melamine formaldehyde co-condensed dyes and perylene phosphors. Perylene phosphors are preferably used because they can be used for a long period of time. Examples of the fluorescent material that is particularly preferably used in the present invention include inorganic phosphors. The inorganic phosphor used in the present invention is described below.

Examples of phosphors that emit green light include [SrAl ₂ O ₄ : Eu], [Y ₂ SiO ₅ : Ce, Tb], [MgAl ₁₁ O ₁₉ : Ce, Tb], and [Sr ₇ Al ₁₂ O ₂₅ : Eu. ] [(At least one of Mg, Ca, Sr, Ba) Ga ₂ S ₄ : Eu].

Examples of phosphors that emit blue light include [Sr ₅ (PO ₄ ) ₃ Cl: Eu], [(SrCaBa) ₅ (PO ₄ ) ₃ Cl: Eu], and [(BaCa) ₅ (PO ₄ ) ₃ Cl: Eu], [(at least one of Mg, Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu, Mn], [(at least one of Mg, Ca, Sr, Ba) (PO ₄ ) ₆ Cl ₂ : Eu, Mn].

As phosphors emitting green to yellow, at least cerium-activated yttrium / aluminum oxide phosphors, at least cerium-enriched yttrium / gadolinium / aluminum oxide phosphors, at least cerium-activated yttrium / aluminum There are garnet oxide phosphors and at least cerium activated yttrium gallium aluminum oxide phosphors (so-called YAG phosphors). Specifically, [Ln ₃ M ₅ O ₁₂ : R (Ln is at least one selected from Y, Gd, La, M includes at least one of Al and Ca, and R is a lanthanoid a _{system)], [(Y1-xGax} ) 3 (Al1-yGay) 5 O 12:. R (R is at least one or more of Ce, Tb, Pr, Sm, Eu, Dy, selected from Ho, 0 <Rx <0.5, 0 <y <0.5))].
Examples of phosphors that emit red light include [Y ₂ O ₂ S: Eu], [La ₂ O ₂ S: Eu], [Y ₂ O ₃ : Eu], and [Gd ₂ O ₂ S: Eu]. .

Moreover, as a fluorescent substance corresponding to the blue LED currently in the mainstream, [Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : YAG phosphor such as Ce, Y ₃ Al ₅ O ₁₂ : Ce], TAG phosphor such as [Tb ₃ Al ₅ O ₁₂ : Ce], [(Ba, Sr) ₂ SiO ₄ : Eu] phosphor Body, [Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce] phosphor, silicate phosphor such as [(Sr, Ba, Mg) ₂ SiO ₄ : Eu], [(Ca, Sr) ₂ Si ₅ N ₈ : Eu], [(Ca, Sr) AlSiN ₃ : Eu], nitride phosphors such as [CaSiAlN ₃ : Eu], and oxy such as [Cax (Si, Al) ₁₂ (O, N) ₁₆ : Eu] Nitride phosphors, and [ _{Ba, Sr, Ca) Si 2} O 2 N 2: Eu] _{phosphor, [Ca 8 MgSi 4 O 16} Cl 2: Eu] _{phosphor, [SrAl 2 O 4: Eu} , Sr 4 Al 14 O 25: And a phosphor such as Eu].

  Among these, YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors are preferably used in terms of light emission efficiency and luminance. In addition to these, known phosphors can be used depending on the intended use and the intended emission color.

  Next, a case where the inorganic compound is a metal oxide will be described. As the metal oxide, silica, alumina, yttrium oxide, zinc oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide and the like are preferably used.

  When titanium oxide or aluminum oxide is used for the thermosetting resin composition of the present invention, it can also be suitably used as a reflector material. Moreover, it is preferable to add a silica to the thermosetting resin composition of this invention in order to prevent sedimentation of fluorescent substance.

  It is preferable that the ratio of the silica in the thermosetting resin composition of this invention is 0.1 to 40% by weight ratio with respect to the thermosetting resin composition whole quantity, More preferably, it is 1 to 20%, More preferably, it is 1 -10%.

  Silica may be obtained by refining naturally produced silica (natural silica) or industrially synthesized silica (synthetic silica). Since natural silica is a crystal, it has a crystal axis. For this reason, although the optical characteristic derived from a crystal | crystallization can be anticipated, since specific gravity is a little high compared with a synthetic silica, it may influence the dispersion | distribution in a thermosetting resin composition. Moreover, when a natural product is pulverized, it may be an irregularly shaped particle or a material having a wide particle size distribution.

  Synthetic silica includes wet synthetic silica and dry synthetic silica, but the use is not particularly limited in the present invention. However, synthetic silica may have water of crystallization regardless of the production method, and if this water of crystallization may affect the thermosetting resin composition or cured product, LED element, etc., the number of water of crystallization It is preferable to select in consideration of the above.

  Since synthetic silica is amorphous rather than crystalline, it has no crystal axis and optical characteristics derived from crystals cannot be expected. However, in addition to controlling the particle distribution, it is possible to take advantage of features such as extremely small particle size.

  In particular, fumed silica has a nano-order particle size and excellent particle dispersibility. Furthermore, when compared with the same weight, the smaller the particle diameter, the larger the total surface area, so that the light reflection direction becomes more diversified, so that it can be used more preferably.

  In general, silica has a large surface area and is a hydrophilic material (hydrophilic silica) due to the effect of silanol present on the surface, but can also be made into hydrophobic silica by chemical modification. Which type of silica is used is selected depending on the purpose, but in the present invention, it is preferable to use hydrophilic silica in experimental verification.

  The method for producing the thermosetting resin composition of the present invention is not particularly limited. Examples include a method of mixing the above-described curing accelerator, silicone resin, and, if necessary, each predetermined amount of the thermosetting agent, antioxidant, and the like under heating.

  The thermosetting resin composition of the present invention can be molded into a desired shape by molding it in a soft state (semi-cured state). There is no restriction | limiting in a shaping | molding method, For example, printing methods, such as forming machines, such as a hot press molding, a film coater, and extrusion molding, screen printing, gravure printing, lithographic printing, are mentioned. Further, the molded product is reworked and can be used in the next step. For example, it can be formed into a flat shape such as a coating film or a sheet, and can be cut into pieces to form a chip-like shape for sealing or adhesion. Further, by using an injection molding or a compression molding method, it is possible to obtain an LED housing material or a reflector material having a reflection function. In addition, in this specification, what shape | molded the thermosetting resin composition regardless of the shape is expressed as a prepreg.

  In the case where the prepreg is molded into a planar shape such as a coating or sheet, the thickness is determined from the phosphor content and desired optical properties. Specifically, it is 0.1 μm or more in the case of a coating film, and about 10 μm to 3000 μm can be molded in the case of a sheet. When the thickness after curing changes, the thickness is determined in consideration of this. From the viewpoint of improving optical properties and heat resistance, the thickness of the phosphor sheet is preferably 1000 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. By setting the phosphor sheet to a film thickness of 1000 μm or less, light absorption and light scattering by the binder resin can be proposed, so that the phosphor sheet is optically excellent.

The thermosetting resin composition of this invention or this prepreg is heat-processed, and the target hardened | cured material (article) is obtained. As conditions for obtaining a cured product, the temperature is preferably 60 to 200 ° C, more preferably 80 to 160 ° C. Moreover, it is preferable that time is 1 to 24 hours, and it is more preferable that it is 2 to 5 hours from an economical viewpoint.
In addition to articles that function as a single product, articles that exist in a specific structure such as a sealing material and are cured as part of a member are also included.

  The use of the thermosetting resin composition or the prepreg of the present invention is not particularly limited. For example, a die bonding material for connecting to a sealant, a housing material, a lead electrode, a heat sink, or the like, an optical semiconductor element such as a light emitting diode When the light emitting element is flip-chip mounted, it can be used as an underfill material or a passivation film on the light emitting element. Especially, since an optical semiconductor device capable of efficiently extracting light generated by light emission from the optical semiconductor element can be manufactured, it can be suitably used as a sealant, a reflector material, a phosphor sheet, an underfill material, or a die bond material. .

  The hardness of the cured product obtained by curing the thermosetting resin composition of the present invention is preferably in the range of 45 or less in D hardness and 30 or more in A hardness. The refractive index is preferably a high refractive index of 1.5 or more. When the refractive index is 1.5 or more, the cured product is excellent in LED light extraction efficiency.

  The method for sealing the light emitting element with the composition for optical semiconductors of the present invention is not particularly limited. For example, the composition for optical semiconductor of the present invention is previously injected into a mold mold, and the light emitting elements are fixed thereto. Examples include a method of curing after immersing a lead frame or the like, and a method of injecting and curing the composition for optical semiconductors of the present invention into a mold in which a light emitting element is inserted.

  Examples of the method for injecting the composition for optical semiconductor of the present invention include injection by a dispenser, transfer molding, and injection molding. Further, as other sealing methods, for example, the optical semiconductor composition of the present invention is dropped onto a light emitting device, stencil printing, screen printing, a method of applying and curing through a mask, and a light emitting device on the bottom. A method of injecting the composition for optical semiconductor of the present invention into a cup or the like with a dispenser or the like and curing it.

  An optical semiconductor element comprising the composition for optical semiconductor elements of the present invention as a sealant is also one aspect of the present invention.

  The present invention will be described in more detail based on examples. The present invention is not limited to the following examples.

<Measurement of number average molecular weight and weight average molecular weight>
The number average molecular weight and the weight average molecular weight of the polymer synthesized in the present invention were measured as follows. Using a high-performance liquid chromatograph system CO-2065plus manufactured by JASCO Corporation, 20 μL of a THF solution having a sample concentration of 1% by mass is used as an analysis sample. Column: Shodex KF804L [manufactured by Showa Denko KK] , Column temperature: 40 ° C., detector: RI, eluent: THF, and eluent flow rate: 1.0 mL per minute, measured by GPC method, and determined by polystyrene conversion.

The reagents used in the examples are as follows.
Silaplane FM-2205 (trade name; polydimethylsiloxane having a vinyl group at both ends and a number average molecular weight of 700): manufactured by JNC Corporation, MA-DGIC (monoallyl diglycidyl isoannulate): Shikoku Kasei Kogyo Co., Ltd. Manufactured by Sila Ace S210 (trade name; vinyltrimethoxysilane): manufactured by JNC Corporation

(A) Thermosetting resin comprising a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, which is a component (A) of the present invention. The following silsesquioxane derivative base polymer 1 produced by the method disclosed in International Publication No. 2011/145638 was used as a thermosetting resin containing a SiH group and an alkenyl group.

[Silsesquioxane derivative base polymer 1]
In formula (1), a [formula (XI)] = 2.34, b [formula (X-II)] = 0, c [formula (X-III)] = 1.66, The compound represented by the chemical formula was designated as silsesquioxane derivative base polymer 1.

(B) A linear organopolysiloxane compound having SiH groups at both ends. SiH silicones having a number average molecular weight of 200, 500 and 1000 were prepared by a known method.

[SiH silicone at both ends with a number average molecular weight of 200]
In the formula (2), R ⁶ = methyl, m = 2, and a both-end SiH silicone having a number average molecular weight of 200 represented by the following formula was used.

[SiH silicone at both ends with a number average molecular weight of 500]
In the formula (2), R ⁶ = methyl, m = 6, and a both-end SiH silicone having a number average molecular weight of 500 represented by the following formula was used.

[SiH silicone at both ends with a number average molecular weight of 1000]
In the formula (2), ^{R 6} = methyl, m = 13, with both ends SiH silicone having a number average molecular weight of 1000 represented by the following formula.

(C) Pt catalyst As a Pt catalyst which is the component (C) of the present invention, Karsted catalyst trade name Pt-VTS-3.0X [3 wt% xylene solution, manufactured by Umicore] was used.

(D) Silsesquioxane having SiH group, organopolysiloxane having two alkenyl groups, epoxy compound having alkenyl groups, and silyl compound having alkenyl groups, a compound having SiH groups [sil Sesquioxane derivative base polymer 2]
As a compound having a SiH group as component (D) of the present invention, in formula (D1), A ′ [formula (a)] = 1.32, B ′ [formula (b)] = 0.69, C ′ The silsesquioxane derivative base polymer 2 represented by the following formula where [formula (ci)] = 0.65 and D ′ [formula (di)] = 0.65 was used.

  The silsesquioxane derivative base polymer 2 was synthesized by the following method according to the following reaction formula. 50 g of silsesquioxane derivative (DD-4H) and 18.6 g (0.0266 mol) of vinyl silicone (FM-2205) in a 300 mL internal reaction vessel equipped with a thermometer, reflux condenser, and stirrer Then, 7.47 g (0.0252 mol) of monoallyl diepoxy isocyanurate (MA-DGIC), 3.7 g (0.0252 mol) of S210, and 50 g of toluene as a solvent were added.

  Heating and stirring were started under a nitrogen atmosphere. After the contents reached 100 ° C., an amount that the Pt concentration became 1 ppm with respect to DD-4H was added, and the mixture was heated and stirred as it was for 5 hours. The reaction was completed after confirming the disappearance of MA-DGIC from GC. After cooling to room temperature, 1.6 g of activated carbon was added and stirred for 3 hours or more, and then the activated carbon was removed by filtration. Toluene, which is a solvent, was distilled off from the filtrate under reduced pressure conditions of 90 ° C. and 0.13 kPa using an evaporator. 74 g of a water-like colorless and transparent liquid was obtained.

  When the molecular weight of the obtained product was analyzed by GPC, it was number average molecular weight: Mn = 3900 and weight average molecular weight: Mw = 18200.

(E) Organopolysiloxane compound having two or more alkenyl groups
As a compound having two or more alkenyl groups as the component (E) of the present invention, referring to the method described in International Publication No. 2011/145638, in formula (3), R ⁷ = methyl, R ⁸ = Methyl, n = 8, a vinyl silicone having both ends having a number average molecular weight of 700 represented by the following chemical formula was used.

Curing inhibitor 2-methyl-3-butyn-2-ol [manufactured by Tokyo Chemical Industry Co., Ltd.] was used as a curing inhibitor.

Epoxy group-containing silane coupling agent Further, in the reference example, glycidyl ether trimethoxysilane: trade name S510 [manufactured by JNC Corporation] was used as an epoxy group-containing silane coupling agent as an adhesion promoter.

<Preparation of thermosetting resin composition>
The compound synthesized in the above example or a mixture of organopolysiloxane was placed in a screw tube. The screw tube was set in a rotating / revolving mixer ["Awatori Nertaro (registered trademark) ARE-250" manufactured by Sinky Co., Ltd.] and mixed and defoamed.

  Called catalyst (trade name Pt-VTS-3.0X: xylene solution having a Pt concentration of 3%) manufactured by Umicore Co., Ltd. Curing retarder: MVS-H [trade name, 1,3,5,7-tetravinyl-1 , 3,5,7-tetramethylcyclotetrasiloxane: manufactured by JNC Co., Ltd.] 10 times diluted so that the Pt concentration becomes a predetermined amount, and mixed and defoamed again with a rotation / revolution mixer The composition ak which is a thermosetting resin composition and the reference composition yz were obtained. Table 1 shows the mass% of each thermosetting resin composition.

<Viscosity>
The viscosity of the cured product was measured at 25 ° C. using a TV-22 viscometer cone plate type manufactured by Toki Sangyo Co., Ltd. The measurement results are shown in Table 2.

<Light transmittance>
A cured product having a thickness of 4 mm was prepared, and the light transmittance at a wavelength of 400 nm was measured with an ultraviolet-visible spectrophotometer V-650 manufactured by JASCO Corporation. The measurement results are shown in Table 2.

<Heat resistant transmittance>
The heat resistance test was performed and evaluated by the following method. A cured product having a thickness of 4 mm was prepared, and the light transmittance at a wavelength of 400 nm was measured with an ultraviolet-visible spectrophotometer V-650 manufactured by JASCO Corporation to obtain an initial transmittance. The cured product was put in an oven at 180 ° C. [constant temperature dryer: DX302 manufactured by Yamato Scientific Co., Ltd.] and heat-treated for a certain time (1000 hours in Table 2).

  The light transmittance of the cured product after the heat resistance test was measured with an ultraviolet-visible spectrophotometer, and the retention at this wavelength from the transmittance at a wavelength of 400 nm (transmittance after heat treatment for a certain time / initial transmittance at each wavelength × 100) Was calculated and evaluated. When the transmittance retention at 400 nm after a heat resistance test of 180 ° C. after 1000 hours was 85% or more, it was evaluated as ◯, when it was 75% or more, and when it was less than 75%, it was rated as x. The measurement results are shown in Table 2.

<Refractive index>
The test piece cut the hardened | cured material with the band saw, and produced the test piece according to JISK7142 (2008). Using this test piece, the refractive index was measured with an Abbe refractometer [NAR-2T manufactured by Atago Co., Ltd.] using a D line (586 nm) of a sodium lamp. The intermediate solution was methylene iodide. The measurement results are shown in Table 2.

<Hardness>
In accordance with the provisions of JIS K6253 (2006), the D hardness was measured with a durometer WR-105D manufactured by Nishitokyo Seimitsu Co., Ltd., and the A hardness was measured with a WR-104A. The measurement results are shown in Table 2.

<Film tensile test>
In accordance with JIS K6251 (2010), a dumbbell-shaped test piece was prepared and tested. The test piece was heat-cured under the condition of pouring a resin on a SUS plate with a Teflon (registered trademark) film attached thereto to give a thickness of 0.9 mm, heating at 120 ° C. for 1 hour, and then heating at 160 ° C. for 3 hours. The cured resin was peeled off from the SUS plate and punched with a dumbbell punching machine to obtain a dumbbell-type test piece. The film tensile test was measured using a 1 kN load cell with a tensile and compression tester [manufactured by Shimadzu Corporation Autograph AGS-500B]. The measurement temperature was a room temperature of 25 ° C. Table 2 shows the measurement results of stress, elongation and elastic modulus.

<Cool Thermal Shock Test PPA>
The thermosetting resin composition was injected into 48 PPA resin packages [Model No. 5050 D / G, manufactured by Enomoto Co., Ltd.] whose silver base was plated with a bottom portion with a dispenser [Model No. MPP-1 manufactured by Musashi Engineering Co., Ltd.]. Then, after heating at 120 ° C. for 1 hour, it was cured by heating at 160 ° C. for 3 hours. These PPA resin packages were reflowed once with a simulated reflow machine [model SRS-1C manufactured by Malcolm Co., Ltd.] under temperature conditions (260 ° C.) according to JEDEC standards. Then, it put into the test area of the thermal shock apparatus [Espec Co., Ltd. model number TSE-11], and exposed by -40 degreeC for 30 minutes, and exposing to 105 degreeC for 30 minutes was implemented by repeating 300 cycles. In addition, the movement time between both exposure temperatures was 2 minutes. The occurrence of peeling and cracking was observed with a microscope. The defective rate among 48 pieces is shown. The measurement results are shown in Table 2.

  As shown in Table 2, the cured product ak using the composition ak of the present invention has a hardness of D45 or less and a low hardness, and a refractive index of 1.5 or more and a high refractive index. Furthermore, the heat-resistant transmittance of silsesquioxane is maintained. Furthermore, it was revealed that the thermal shock resistance was excellent.

  Regarding the thermal shock resistance, it was revealed that the reference cured product yz had a defect rate of 100% at the 300th cycle, whereas the cured product ak significantly improved.

  The thermosetting resin composition of the present invention is very useful as a sealing material for optical semiconductor elements such as LEDs because it provides a cured product having high heat resistance and excellent cold-heat shock resistance.

Claims (19)

A thermosetting resin composition containing the following (A), (B) and (C).
(A) A reaction product of a silsesquioxane having a SiH group and an organopolysiloxane having two alkenyl groups, the thermosetting resin having a SiH group and an alkenyl group (B) having SiH groups at both ends. Linear organopolysiloxane compound (C) Pt catalyst having   The thermosetting resin composition according to claim 1, wherein the silsesquioxane is a double-decker silsesquioxane. Furthermore, the thermosetting resin composition of Claim 1 or 2 containing (D).
(D) A compound having a SiH group obtained by reacting a silsesquioxane having a SiH group, an organopolysiloxane having two alkenyl groups, an epoxy compound having an alkenyl group and a silyl compound having an alkenyl group Furthermore, the thermosetting resin composition of any one of Claims 1-3 containing (E).
(E) Organopolysiloxane compound having two or more alkenyl groups The thermosetting resin defined by (A) is a compound shown by following formula (1), The thermosetting resin composition of any one of Claims 1-4 characterized by the above-mentioned.

In formula (1), X is independently a group represented by the following formula (XI), formula (X-II) or formula (X-III), and a compound represented by formula (1) Per molecule [a mixture of compounds in which the ratio of the group represented by the formula (XI), the group represented by the formula (X-II), and the group represented by the formula (X-III) is different. The number of groups represented by the formula (XI) of the compound (average of one molecule of the compound) is a, the number of groups represented by the formula (X-II) is b, and the formula (X-III) When the number of groups to be formed is c, a + 2b + c = 4, 0 <a ≦ 3, 0 ≦ b ≦ 1, and 0 <c ≦ 3.
R ¹ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and m is an average value satisfying 1 to 100.

In the formula (X-II), R ² and R ³ are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is —OSi (R ³ ) ₂ —. It is the number of repetitions and is an average value satisfying 2-20.

In the formula (X-III), R ⁴ and R ⁵ are each independently a group selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl, and s is —OSi (R ⁵ ) ₂ —. It is the number of repetitions and is an average value satisfying 2-20.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.
R ⁰ ′ represents a C 2-5 saturated hydrocarbon group having the same carbon number as R ⁰ . The thermosetting according to any one of claims 1 to 5, wherein the linear organopolysiloxane compound (B) having SiH groups at both ends is a compound represented by the following formula (2). Resin composition.

R ⁶ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, m is the number of repeating -OSi (R ⁶ ) _2- , and an average value satisfying 1 to 20 It is. The thermosetting resin composition according to claim 3, wherein the compound defined by (D) is a compound represented by the following formula (D1).

In the formula (D1), X ′ is independently the following formula (a), formula (b), formula (ci), formula (c-ii), formula (c-iii), formula (d-i) ), A group represented by formula (d-ii) or formula (d-iii), and per molecule of the compound represented by formula (D1) [the group and the formula represented by formula (a) A group represented by (b), formula (ci), formula (c-ii), formula (c-iii), formula (d-i), formula (d-ii) or formula (d-iii) In the case of a mixture of compounds having different ratios, the number of groups represented by the formula (a) is A ′, the number of groups represented by the formula (b) is B ′, and the formula The number of groups represented by (ci), formula (c-ii) or formula (c-iii) is C ′, formula (di), formula (d-ii) or formula (d-iii) A ′ + 2B ′ + C ′ where D ′ is the number of groups represented by D ′ = 4, 0.5 ≦ A ′ ≦ 3.0, 0.5 ≦ 2B ′ ≦ 2.0, 0.1 ≦ C ′ ≦ 2.0, 0 ≦ D ′ ≦ 1.0.
R ^{1 ′} is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl and cyclohexyl, and m ′ is an average value satisfying 1 to 100.

In the formula (b), R ^{2 ′} and R ^{3 ′} are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and t is —OSi (R ^{3 ′} ) ₂ —. The average value satisfying 1-20.

^{R 4} in Formula ^{(d-i), 'R} 4 in and Formula ^(d-iii)' R ⁴ in Formula (d-ii) ^'are independently a group selected from methyl, ethyl, butyl and isopropyl is there.
X in the formula (d-ii) is the number of repetitions of -OSi (R ^{4 '} ) _2- and is an average value satisfying 1 to 20. Y in the formula (d-iii) is the number of repetitions of -OSi (R ^{4 ''} ) _2- and is an average value satisfying 1 to 10.
R ⁰ in formula (d-iii) represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms. The thermosetting resin composition according to any one of claims 3 to 6, wherein the compound defined by (D) is a compound represented by the following formula (D2).

In the formula (D2), R ″ is independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl, and r is an integer of 0 to 100. aii is 0.1 ≦ aii ≦ 3.5, Xii is 0 ≦ 2Xii ≦ 2.0, Yii is 0 ≦ Yii ≦ 3.0, and Zii is 0.1 ≦ Zii ≦ 3.5. The thermosetting resin composition according to any one of claims 4 to 8, wherein the organopolysiloxane compound (E) having two or more alkenyl groups is a compound represented by the formula (3).

In Formula (3), R ⁷ and R ⁸ are independently a group selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, and cyclohexyl, and n is a repeating group of —OSi (R ⁸ ) ₂ —. It is a number and is an average value satisfying 1-50.
R ⁰ represents an unsaturated hydrocarbon group having one double bond having 2 to 5 carbon atoms.   The blending ratio of the thermosetting resin defined in (A) is 50 to 95% by mass and the blending ratio of the compound (B) is 2 to 20% by mass based on the total amount of the thermosetting resin composition. 10. The thermosetting resin composition according to any one of 9 above.   Furthermore, the thermosetting resin composition of any one of Claims 3-10 which contains a compound (D) in the ratio of 1-50 mass%.   Furthermore, the thermosetting resin composition of any one of Claims 4-11 which contains a compound (E) in the ratio of 1-10 mass%.   Furthermore, the thermosetting resin composition of any one of Claims 1-12 in which the inorganic compound was disperse | distributed.   The thermosetting resin composition according to claim 13, wherein the inorganic compound is at least one of a phosphor and a metal oxide.   The prepreg obtained by shape | molding the thermosetting resin composition of any one of Claims 1-14.   The hardened | cured material obtained by hardening the thermosetting resin composition of any one of Claims 1-14, or the prepreg of Claim 15.   The composition for optical semiconductors containing the thermosetting resin composition of any one of Claims 1-14, or the prepreg of Claim 15.   The optical-semiconductor element which contains the composition for optical semiconductors of Claim 17 as a sealing agent.   The hardened | cured material of Claim 16 which is a coating-film form or a sheet form, and thickness is 0.1 micrometer-3,000 micrometers.