JP6141095B2 - Silicone hybrid resin composition and optical semiconductor device - Google Patents

Description

  The present invention relates to a silicone hybrid resin composition having higher reliability than before and an optical semiconductor device using the same.

  Conventionally, epoxy-silicone hybrid resins and silicone resin compositions have been widely used as sealing materials for sealing optical semiconductor elements. Since these sealing materials for optical semiconductor devices are directly sealed on the upper part of the element, they are susceptible to resin deterioration due to light and heat from the element.

  Among these, epoxy resins (Patent Document 1 and Patent Document 2) used for sealing materials for medium-brightness optical semiconductor devices are very susceptible to deterioration by strong light and heat due to the structure of the resin. Resin is likely to be colored over time, and cracks and peeling are likely to occur in temperature cycle tests and the like. Therefore, when an epoxy resin is used as a sealing material in a high-brightness LED or an LED with a strong applied current that is required today, the lifetime of the element is shortened. Therefore, a silicone resin is often used as a sealing material for high brightness optical semiconductor devices.

  However, in a sealing material using a silicone resin, silver discoloration used as a lead frame is a problem. As a cause of discoloration, due to the high gas permeability of silicone resin, sulfide gas etc. existing outside the sealing material permeates the resin and penetrates into the sealing material, causing the silver surface to turn black. It has been found.

  In order to prevent discoloration of lead frames, new hybrid resins have been developed by various companies. Patent Documents 3, 4, and 5 show an addition curing type hybrid resin using allyl isocyanurate. However, in a resin obtained by reacting allyl isocyanurate and hydrogenorganosiloxane, a portion bonded by an addition reaction is cut by oxidative degradation, and resin degradation such as discoloration occurs. For this reason, attempts have been made to prevent deterioration by adding a hindered phenol-based or hindered amine-based antioxidant, but this is only a life-prolonging treatment and cannot be said to be a fundamental solution.

  In addition, synthesis of isocyanuric acid using isocyanate is conventionally known (Patent Document 6), but the synthesized isocyanuric acid derivative is used in a condensed form.

JP 2013-018921 A JP 2012-184394 A JP 2012-0823303 A JP 2012-224742 A JP 2003-268239 A Special table 2008-531634 gazette

  Therefore, the present invention is a highly reliable silicone hybrid resin composition that is excellent in heat resistance, light resistance, and discoloration resistance, that is, is resistant to resin deterioration, has low gas permeability, and is a cured product excellent in impact resistance. The purpose is to provide goods.

The present invention has been made to solve the above problems,
(A) an organopolysiloxane having an isocyanuric acid skeleton, an N—CH ₂ —Si bond, and two or more alkenyl groups in one molecule;
(B) one or more hydrogen organopolysiloxanes of the following (B1) and (B2),
(B1) Average composition formula R ¹ ′ _x SiO _{(4-x) / 2} (1)
(R ¹ ′ is, independently of each other, a monovalent hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, at least one of R ¹ ′ is a hydrogen atom, and x is 0.7 to 3.3. Hydrogenorganopolysiloxane represented by:
(B2) hydrogen organopolysiloxane having an isocyanuric acid skeleton, N—CH ₂ —Si bond and SiH group in one molecule;
(C) addition reaction catalyst,
The present invention provides a silicone hybrid resin composition comprising:

Such a silicone hybrid resin composition has a siloxane structure having both an N—CH ₂ —Si bond and an isocyanuric acid skeleton, and thus is excellent in heat resistance, light resistance, and discoloration resistance, that is, resistant to resin degradation, Further, the cured product has low gas permeability and excellent impact resistance.

  Furthermore, the silicone hybrid resin composition preferably includes (D) an adhesion-imparting agent.

  Thereby, hardened | cured material with higher adhesiveness can be obtained.

  Moreover, it is preferable that ratio of the alkenyl group contained in the said (A) component with respect to SiH group contained in the said (B) component is 0.5-4.0.

  Thereby, it becomes a silicone hybrid resin composition which is hard to become a more uncured state and hardened | cured material does not foam easily.

（Ｒ^１は互いに独立に、炭素数１〜１０の一価炭化水素基であり、Ｒ^２、Ｒ^３は炭素数１〜１０の一価炭化水素基であり、Ｒ^４はアルケニル基である。ａは０、１、又は２、ｂは０〜２．０、ｃは０〜２．０、ｄは０．０２〜１．０であり、ｂ＋ｃ＋ｄ＝０．５〜３．０である。ｍは０．１〜０．９、ｎは０．１〜０．９である。）

（Ｒ^１、Ｒ^２、Ｒ^３、ａ、ｂ、及びｃは前記と同様である。ｅは０．０２〜１．０であり、ｂ＋ｃ＋ｅ＝０．５〜３．０である。ｐは０．１〜０．９、ｑは０．１〜０．９である。） The component (A) is an organopolysiloxane represented by the following average composition formula (2), and the component (B2) is a hydrogen organopolysiloxane represented by the following average composition formula (3). Is preferred.

(R ¹ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms , R ² and R ³ are monovalent hydrocarbon groups having 1 to 10 carbon atoms , and R ⁴ is an alkenyl group. a is 0, 1, or 2, b is 0 to 2.0, c is 0 to 2.0, d is 0.02 to 1.0, and b + c + d = 0.5 to 3.0. Is 0.1 to 0.9, and n is 0.1 to 0.9.)

(R ¹ , R ² , R ³ , a, b, and c are the same as described above. E is 0.02 to 1.0, and b + c + e = 0.5 to 3.0. P is 0. .1-0.9, q is 0.1-0.9.)

  With such components (A) and (B2), it is possible to obtain a silicone hybrid resin composition that is a cured product that is more resistant to resin degradation, lower gas permeability, and more excellent impact resistance. .

  The present invention also provides an optical semiconductor device that is sealed with the silicone hybrid resin composition.

  Such an optical semiconductor device is excellent in heat resistance, light resistance, and discoloration resistance without adding an antioxidant or the like to the encapsulant, that is, it is resistant to resin deterioration, low gas permeability, Since the impact property is also excellent, the sealing material and the optical semiconductor element are less deteriorated and have high reliability.

  As described above, if it is the present invention, it is excellent in heat resistance, light resistance, and discoloration resistance, that is, it is resistant to resin deterioration, has low gas permeability, and becomes a cured product excellent in impact resistance. A highly reliable silicone hybrid resin composition can be provided. Further, by using the composition as a sealing material, it is possible to provide a highly reliable optical semiconductor device with little deterioration of the sealing material and the optical semiconductor element.

  Hereinafter, the present invention will be described in detail. As described above, particularly in high-intensity optical semiconductor devices, development of a silicone resin composition that is resistant to resin degradation, has low gas permeability, and is excellent in impact resistance is required. It was.

In order to achieve the above-mentioned problems, the present inventors impart a silmethylene bond excellent in heat resistance as a reactive functional group other than an allyl group to an isocyanuric acid skeleton excellent in impact resistance, and a siloxane structure having both of them. As a result of intensive research, the silicone hybrid resin composition that is addition-curable and has both an isocyanuric acid skeleton and an N—CH ₂ —Si bond is resistant to resin deterioration and has gas permeability. The present inventors have found that an encapsulant for optical semiconductor devices that is low and excellent in impact resistance can be obtained, and the present invention has been completed.

That is, the silicone hybrid resin composition of the present invention is
(A) an organopolysiloxane having an isocyanuric acid skeleton, an N—CH ₂ —Si bond, and two or more alkenyl groups in one molecule;
(B) one or more hydrogen organopolysiloxanes of the following (B1) and (B2),
(B1) Average composition formula R ¹ ′ _x SiO _{(4-x) / 2} (1)
(R ¹ ′ is, independently of each other, a monovalent hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, at least one of R ¹ ′ is a hydrogen atom, and x is 0.7 to 3.3. Hydrogenorganopolysiloxane represented by:
(B2) hydrogen organopolysiloxane having an isocyanuric acid skeleton, N—CH ₂ —Si bond and SiH group in one molecule;
(C) addition reaction catalyst,
Is included.
Hereinafter, the present invention will be described in more detail.

（Ｒ^１は互いに独立に、炭素数１〜１０の一価炭化水素基であり、Ｒ^２、Ｒ^３は炭素数１〜１０の一価炭化水素基であり、Ｒ^４はアルケニル基である。ａは０、１、又は２、ｂは０〜２．０、ｃは０〜２．０、ｄは０．０２〜１．０であり、ｂ＋ｃ＋ｄ＝０．５〜３．０である。ｍは０．１〜０．９、ｎは０．１〜０．９である。） [(A) Organopolysiloxane]
The organopolysiloxane (A) used in the present invention has an isocyanuric acid skeleton, an N—CH ₂ —Si bond, and two or more alkenyl groups in one molecule. As such an organopolysiloxane, those represented by the following average composition formula (2) are preferable.

(R ¹ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms , R ² and R ³ are monovalent hydrocarbon groups having 1 to 10 carbon atoms , and R ⁴ is an alkenyl group. a is 0, 1, or 2, b is 0 to 2.0, c is 0 to 2.0, d is 0.02 to 1.0, and b + c + d = 0.5 to 3.0. Is 0.1 to 0.9, and n is 0.1 to 0.9.)

In the above formula (2), R ¹ is independently a substituted or unsubstituted monovalent organic group, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and having 1 to 6 carbon atoms. It is more preferably a monovalent hydrocarbon group. Examples of such R ¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group and the like. Alkyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl.

In the above formula (2), R ⁴ is an alkenyl group. Examples of such R ⁴ include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, and an octenyl group, and among them, a vinyl group or an allyl group is desirable.

[(B) Hydrogen Organopolysiloxane]
The hydrogen organopolysiloxane (B) used in the present invention is one or more hydrogen organopolysiloxanes of the following (B1) and (B2). The SiH group in the component (B) and the alkenyl group in the component (A) undergo an addition reaction in the presence of a metal catalyst to form a crosslinked structure.

The hydrogen organopolysiloxane (B1) used in the present invention is represented by the following average composition formula (1).
R ¹ ′ _x SiO _{(4-x) / 2} (1)
( R ¹ ′ is the same as described above, and x represents 0.7 to 3.3.)

（Ｒ^１、Ｒ^２、Ｒ^３、ａ、ｂ、及びｃは前記と同様である。ｅは０．０２〜１．０であり、ｂ＋ｃ＋ｅ＝０．５〜３．０である。ｐは０．１〜０．９、ｑは０．１〜０．９である。） The hydrogen organopolysiloxane (B2) used in the present invention has an isocyanuric acid skeleton, an N—CH ₂ —Si bond and a SiH group in one molecule. As such hydrogen organopolysiloxane, those represented by the following average composition formula (3) are preferable.

(R ¹ , R ² , R ³ , a, b, and c are the same as described above. E is 0.02 to 1.0, and b + c + e = 0.5 to 3.0. P is 0. .1-0.9, q is 0.1-0.9.)

  (B) As a compounding quantity of a component, the molar ratio of the alkenyl group contained in (A) component with respect to the total number of SiH groups contained in (B1) and (B2) component is 0.5-4.0. The amount that becomes 0.5 to 2.0 is more preferable, and the amount that becomes 0.7 to 1.5 is more preferable. If the molar ratio is greater than 0.5, it is easy to cure because there are sufficient functional groups to cure the composition. If the molar ratio is less than 4.0, the amount of SiH groups remaining after curing is appropriate, and dehydrogenation reaction is unlikely to occur during curing, and as a result, foaming of the cured product can be suppressed.

[(C) Catalyst for addition reaction]
The addition reaction catalyst (C) used in the present invention is blended in order to promote the addition reaction between the alkenyl group in the component (A) and the SiH group in the component (B). As such a component (C), platinum-based, palladium-based and rhodium-based catalysts can be used, but platinum group metal-based catalysts are desirable from the standpoint of cost. Examples of the platinum group metal catalyst include H ₂ PtCl ₆ · mH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · mH ₂ O, PtO ₂ · mH ₂ O (m represents a positive integer). Further, a complex of the platinum group metal catalyst with a hydrocarbon such as an olefin, an alcohol, or a vinyl group-containing organopolysiloxane can be used. The above catalysts may be used alone or in combination of two or more.

  (C) A component should just be mix | blended with what is called a catalyst amount, Usually, platinum group metal conversion (mass) with respect to 100 mass parts of total amounts of (A) component and (B) component, Preferably 0.0001- It is used in an amount of 2 parts by mass, more preferably 0.0001 to 0.05 parts by mass.

[(D) Adhesive agent]
The silicone hybrid resin composition of the present invention may further contain an adhesion-imparting agent (D) in addition to the components (A) to (C). Adhesive agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, N 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-A Silane coupling agents such as nopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxylane, 3-mercaptopropyltrimethoxysilane, trimethoxysilane, tetramethoxysilane, and the like 1 type or 2 types or more of hydrolytic condensates chosen from among these.

  An organic compound having one or more groups selected from a vinyl group, an epoxy group, an alkoxy group bonded to a silicon atom, and a hydroxyl group bonded to a silicon atom in one molecule represented by the following average composition formula A silicon compound is mentioned.

上記式において、Ｒは水素原子、又は置換もしくは非置換の一価炭化水素基であり、好ましくは炭素数１〜６の一価炭化水素基である。このようなＲとしては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基が挙げられ、ｊ、ｋ、ｈ、ｉは自然数で、ｊは１又は２、ｋ及びｈは１〜３、ｉは１〜４である。ｓ、ｔ、ｕは０≦ｓ≦１、０≦ｔ≦１、０≦ｕ≦１であり、ｓ＋ｔ＋ｕ＝１を満たす数である。ｒは単位数を示す自然数で、１≦ｒ≦１００を満たす数である。分子量はゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算の重量平均分子量で１，０００〜２０，０００が好ましく、１，０００〜１０，０００がより好ましく、１，０００〜６，０００がさらに好ましい。

In the above formula, R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of such R include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, nonyl, and decyl. Group, j, k, h and i are natural numbers, j is 1 or 2, k and h are 1 to 3, and i is 1 to 4. s, t, and u are 0 ≦ s ≦ 1, 0 ≦ t ≦ 1, 0 ≦ u ≦ 1, and s + t + u = 1. r is a natural number indicating the number of units and is a number satisfying 1 ≦ r ≦ 100. The molecular weight is preferably 1,000 to 20,000, more preferably 1,000 to 10,000, and even more preferably 1,000 to 6,000, in terms of polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC).

The weight average molecular weight referred to in the present invention refers to a weight average molecular weight using polystyrene by GPC measured under the following conditions as a standard substance.
[Measurement condition]
Developing solvent: THF
Flow rate: 0.6mL / min
Detector: Differential refractive index detector (RI)
Column: TSK Guardcolom SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H3000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH2000 (6.0 mm ID × 15 cm × 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (0.5% by weight THF solution)

（Ｒ、ｊ、ｋは前記と同様である。）
これらの接着付与剤は、１種単独でも２種以上混合して使用しても良い。 Among these, it is preferable to use an adhesion-imparting agent represented by the following average composition formula.

(R, j, and k are the same as described above.)
These adhesion-imparting agents may be used alone or in combination of two or more.

  When mix | blending an adhesion | attachment imparting agent, it is preferable to mix | blend with the quantity used as 0.01-10 mass% with respect to the total mass of (A)-(C) component, and mix | blend with the quantity used as 1-5 mass%. It is more preferable. By mix | blending an adhesion | attachment imparting agent with said quantity, generation | occurrence | production of a crack is suppressed and the reliability as a sealing material improves.

[Other ingredients]
In addition to the components (A) to (D), the silicone hybrid resin composition of the present invention can appropriately contain various known additives as necessary. Various additives include reinforcing inorganic fillers such as fumed silica and fumed titanium dioxide, non-reinforcing inorganic fillers such as calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, and zinc oxide. Inorganic fillers, photodegradation inhibitors such as hindered amines, vinyl ethers, vinyl amides, epoxy resins, oxetanes, allyl phthalates, and reactive diluents such as vinyl adipate.

  Moreover, the silicone hybrid resin composition of this invention can mix | blend organosiloxane other than (A) component and (B) component suitably other than the said (A)-(D) component. Examples of such organosiloxanes include those having a vinyl group at the terminal and those having a SiH group, and specifically include terminal vinylmethylorganosiloxane.

[Method for preparing silicone hybrid resin composition]
The silicone hybrid resin composition of the present invention can be prepared by, for example, stirring, dissolving, mixing and dispersing the above-mentioned components simultaneously or separately while applying heat treatment as necessary. In order to prevent the curing reaction from proceeding, the components (A) and (C) and the component (B) are stored separately in two liquids, and the two liquids are mixed and cured at the time of use. . At this time, it is preferable to store the component (B) and the component (C) separately so that the dehydrogenation reaction does not occur. Acetylene alcohol, 2-methyl-3-buten-1-ol, 1-ethynyl-1-cyclohexanol, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane It can also be used as one liquid by adding a small amount of a curing inhibitor such as.

  Although the apparatus used for operations, such as stirring, is not specifically limited, A raikai machine provided with stirring and a heating apparatus, 3 rolls, a ball mill, a planetary mixer etc. can be used. Moreover, you may combine these apparatuses suitably. In addition, it is preferable that the viscosity in 25 degreeC measured with the rotational viscometer of the obtained silicone hybrid resin composition is 100-10,000,000 mPa * s, and it is about 300-500,000 mPa * s. More preferred.

[Hardened product of silicone hybrid resin composition]
The silicone hybrid resin composition of the present invention is cured immediately by heating as necessary, and becomes a cured product having high transparency. The composition can be used after being cured by a method such as dispensing, compression molding, transfer molding or injection molding. About the temperature at the time of hardening this composition by heating, 60-200 degreeC is preferable, 60-180 degreeC is more preferable, 80-160 degreeC is further more preferable. Moreover, it becomes possible to prevent the crack and peeling of the LED device due to thermal expansion by performing multi-stage curing instead of curing at a constant temperature.

  The cured product of the composition is excellent in heat resistance, light resistance, and discoloration resistance in terms of chemical structure, that is, resistant to resin deterioration, low gas permeability, and excellent impact resistance. Therefore, an optical semiconductor device using such a cured product as a sealing material is a highly reliable optical semiconductor device with little deterioration of the sealing material and the optical semiconductor element.

  In addition, since such a cured product has high transparency and adheres very well to a package material such as LCP or a metal substrate, the type of element is not particularly limited. For example, LED, photodiode, CCD , CMOS, photocoupler, and the like, particularly as a sealing material for LEDs.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following formulae, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

ジメチルジクロロシラン４５．２ｇ（０．３５ｍｏｌ）、ビニルジメチルクロロシラン２１．１ｇ（０．１７ｍｏｌ）、キシレン１００ｇを混合したものを滴下して、加水分解を行った。水洗後、水酸化カリウムを加えて１５０℃で加熱還流を終夜で行い、中和、ろ過を経て溶剤留去を行い、下記平均組成式で表される樹脂１を得た。この樹脂１のビニル価は０．０９１ｍｏｌ／１００ｇであった。

[Synthesis Example 1]
The flask was charged with 300 g of water and 150 g of xylene, 200 g (0.35 mol) of an isocyanuric acid skeleton-containing organochlorosilane represented by the following structural formula,

Hydrolysis was performed by adding dropwise a mixture of 45.2 g (0.35 mol) of dimethyldichlorosilane, 21.1 g (0.17 mol) of vinyldimethylchlorosilane, and 100 g of xylene. After washing with water, potassium hydroxide was added, and the mixture was heated and refluxed at 150 ° C. overnight. After neutralization and filtration, the solvent was distilled off to obtain Resin 1 represented by the following average composition formula. The vinyl value of this resin 1 was 0.091 mol / 100 g.

ジメチルジクロロシラン５０．５９ｇ（０．３９ｍｏｌ）、ビニルジメチルクロロシラン２３．６６ｇ（０．１９ｍｏｌ）、キシレン１５０ｇを混合したものを滴下して、加水分解を行った。水洗後、水酸化カリウムを加えて１５０℃で加熱還流を終夜で行い、中和、ろ過を経て溶剤留去を行い、下記平均組成式で表される樹脂２を得た。この樹脂２のビニル価は０．１０７ｍｏｌ／１００ｇであった。

[Synthesis Example 2]
The flask was charged with 300 g of water and 100 g of xylene, 200 g (0.39 mol) of an isocyanuric acid skeleton-containing organochlorosilane represented by the following structural formula,

Hydrolysis was performed by adding dropwise a mixture of 50.59 g (0.39 mol) of dimethyldichlorosilane, 23.66 g (0.19 mol) of vinyldimethylchlorosilane, and 150 g of xylene. After washing with water, potassium hydroxide was added and heated to reflux at 150 ° C. overnight. After neutralization and filtration, the solvent was distilled off to obtain Resin 2 represented by the following average composition formula. The vinyl value of this resin 2 was 0.107 mol / 100 g.

ジメチルジクロロシラン５７．４９ｇ（０．４５ｍｏｌ）、ビニルジメチルクロロシラン２６．８８ｇ（０．２２ｍｏｌ）、キシレン１５０ｇを混合したものを滴下して、加水分解を行った。水洗後、水酸化カリウムを加えて１５０℃で加熱還流を終夜で行い、中和、ろ過を経て溶剤留去を行い、下記平均組成式で表される樹脂３を得た。この樹脂３のビニル価は０．１０３ｍｏｌ／１００ｇであった。

[Synthesis Example 3]
The flask was charged with 300 g of water and 100 g of xylene, 200 g (0.45 mol) of an isocyanuric acid skeleton-containing organochlorosilane represented by the following structural formula,

A mixture of 57.49 g (0.45 mol) of dimethyldichlorosilane, 26.88 g (0.22 mol) of vinyldimethylchlorosilane and 150 g of xylene was added dropwise for hydrolysis. After washing with water, potassium hydroxide was added, and the mixture was heated and refluxed at 150 ° C. overnight. After neutralization and filtration, the solvent was distilled off to obtain Resin 3 represented by the following average composition formula. The vinyl value of this resin 3 was 0.103 mol / 100 g.

ジメチルジクロロシラン５７．４９ｇ（０．４５ｍｏｌ）、トルエン１００ｇを混合したものを滴下して、加水分解を行った。中和し水洗後、濃硫酸２ｇ、（Ｍｅ_２ＨＳｉＯ _１／２ ）_２ １４．９６ｇ（０．１１ｍｏｌ）を添加し、室温で終夜攪拌を行った。水洗後溶剤留去を行い、下記平均組成式で表されるハイドロジェンオルガノシロキサン１を得た。このハイドロジェンオルガノシロキサン１の水素ガス発生量は０．１０５ｍｏｌ／１００ｇであった。

[Synthesis Example 4]
The flask was charged with 250 g of water and 100 g of toluene, and 200 g (0.45 mol) of an isocyanuric acid skeleton-containing organochlorosilane represented by the following structural formula.

Hydrolysis was performed by adding dropwise a mixture of 57.49 g (0.45 mol) of dimethyldichlorosilane and 100 g of toluene. After neutralizing and washing with water, 2 g of concentrated sulfuric acid and 14.96 g (0.11 mol) of (Me ₂ HSiO _1/2 ) ₂ were added and stirred overnight at room temperature. After washing with water, the solvent was distilled off to obtain hydrogen organosiloxane 1 represented by the following average composition formula. The hydrogen gas generation amount of this hydrogen organosiloxane 1 was 0.105 mol / 100 g.

  Each component was blended in the following procedure in the parts by mass shown below to prepare a silicone hybrid resin composition.

（Ｒ’は水素原子、メチル基又はイソプロピル基であり、ｊ、ｋは自然数で、ｊは１又は２、ｋは１〜３である。） [Example 1]
To 100 parts by mass of the isocyanuric acid-modified silicone represented by Resin 1, 0.02 part by mass of a terminal vinylmethylsiloxane complex of chloroplatinic acid (1 wt% in terms of platinum) is added as a platinum catalyst and stirred well. 2.5 parts by mass of a mixture of compounds represented by the formula (adhesion imparting agent 1), 0.1 part by mass of 1-ethynyl-1-cyclohexanol as a curing inhibitor, and 95.3 parts by mass of hydrogen organosiloxane 1 In addition, they were mixed to obtain an isocyanuric acid skeleton / N—CH ₂ —Si bond-containing silicone hybrid resin composition.

(R ′ is a hydrogen atom, a methyl group or an isopropyl group, j and k are natural numbers, j is 1 or 2, and k is 1 to 3).

[Example 2]
Example 2 was prepared in the same amount as shown in Table 1 except that the terminal vinylmethylorganosiloxane having the following general formula was added before adding the catalyst.
(ViMe ₂ SiO _1/2 ) _0.02 (Me ₂ SiO) _0.70 (Ph ₂ SiO) _0.28

Example 3
In Example 3, the same operation as in Example 1 was performed except that the resin 2 was added instead of the resin 1, and the preparation was carried out with the blending amounts shown in Table 1.

Example 4
In Example 4, the same operation as in Example 1 was performed except that the resin 3 was added instead of the resin 1, and the preparation was carried out with the blending amounts shown in Table 1.

[Comparative Example 1]
As epoxy resin, 70 parts by mass of CEL2021P (alicyclic epoxy resin manufactured by Daicel Corp.) and 30 parts by mass of MA-DGIC (manufactured by monoallyl diglycidyl isocyanurate Shikoku Kasei Co., Ltd.), Ricacid MH700 (Shin Nippon) Compounding was performed using 130 parts by mass of acid anhydride (Rika Co., Ltd.), 0.5 parts by mass of U-CAT 18X (manufactured by San Apro) and 1 part by mass of ethylene glycol as a curing catalyst.

ＴＡＩＣ１００質量部に、白金触媒として塩化白金酸の末端ビニルメチルシロキサン錯体（白金換算１ｗｔ％）０．２５質量部、接着付与剤としてＫＢＭ−４０３（グリシドキシプロピルトリメトキシシラン 信越化学工業（株）製）１２．４質量部及びアルミニウムトリスエチルアセトアセテート２．４質量部、硬化抑制剤として１−エチニル−１−シクロヘキサノール０．２５質量部、ハイドロジェンオルガノシロキサン２を１４８．８質量部加えて混合し、アリルイソシアヌル酸変性シリコーン樹脂を得た。 [Comparative Example 2]
1 mol of triallyl isocyanurate (TAIC) is subjected to addition reaction of 3 mol of 1,3,5,7-tetramethylcyclotetrasiloxane with a platinum catalyst, and a SiH group-containing isocyanuric acid-modified silicone (hydrogen) represented by the following structural formula Organosiloxane 2) was obtained.

100 parts by mass of TAIC, 0.25 parts by mass of a terminal vinylmethylsiloxane complex of chloroplatinic acid as platinum catalyst (1 wt% in terms of platinum), and KBM-403 (glycidoxypropyltrimethoxysilane) as an adhesion-imparting agent Shin-Etsu Chemical Co., Ltd. 12.4 parts by mass and 2.4 parts by mass of aluminum trisethyl acetoacetate, 0.25 parts by mass of 1-ethynyl-1-cyclohexanol as a curing inhibitor, and 148.8 parts by mass of hydrogen organosiloxane 2 By mixing, an allyl isocyanuric acid-modified silicone resin was obtained.

The composition of the above-mentioned Examples and Comparative Examples is shown in Table 1 below.

[Production of cured product]
Each resin composition blended as Examples 1 to 4 and Comparative Examples 1 and 2 was cured at 150 ° C./4 hr to produce a cured product of 110 mm × 120 mm × 2 mm. In addition, hardness (measured using a durometer type D spring type), bending strength, and bending elastic modulus were measured according to JIS K 6253. These results are shown in Table 2 below.

[Production of LED device]
A cup-shaped pre-mold package for LED (3 mm × 3 mm × 1 mm, opening diameter 2.6 mm) is subjected to Ar plasma (output 100 W, irradiation time 10 seconds) under reduced pressure, and a lead frame on the bottom of the package The InGaN blue light emitting device electrode is connected to the silver lead (conductive adhesive) and the counter electrode of the light emitting device is connected to the counter lead frame with a gold wire, and various resin compositions are opened in the package. It was filled in a portion and cured by sealing at 60 ° C. for 1 hour and further at 150 ° C. for 4 hours and sealed. The LED device thus obtained was left to stand at 150 ° C. for 500 hours while being lit with a current of 50 mA, and then the degree of discoloration in the vicinity of the silver plating surface in the package was visually observed to obtain an initial luminous efficiency ( The degree of deterioration from (lm / W) was measured with an initial value of 100%. Further, a thermal shock test of −40 ° C. to 120 ° C. was performed on 20 packages. Furthermore, the water vapor transmission rate was measured by the Lyssy method (apparatus name: Lyssy Corporation L80-5000) in accordance with JIS K 7129. These results are shown in Table 2 below.

  As shown in Table 2, the cured product of the resin composition formulated as an example of the present invention is a very strong cured product similar to a pure epoxy cured product. Resin deterioration such as lowering is less likely to occur, and the thermal shock resistance is excellent. Moreover, gas permeability was also lower than the comparative example. On the other hand, the cured products of the resin compositions formulated as Comparative Example 1 and Comparative Example 2 show resin deterioration such as discoloration in the high-temperature lighting test and reduced luminous efficiency, and cracks also occur in the thermal shock test. It was.

  From the above, it is clear that the resin composition of the present invention is a highly reliable silicone hybrid resin composition that is resistant to resin degradation, has low gas permeability, and is a cured product with excellent impact resistance. It became. Moreover, it became clear that the optical semiconductor device which has high reliability can be provided by using the resin composition of this invention as a sealing material.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (4)

(A) an organopolysiloxane having an isocyanuric acid skeleton, an N—CH ₂ —Si bond, and two or more alkenyl groups in one molecule;
(B) one or more hydrogen organopolysiloxanes of the following (B1) and (B2),
(B1) Average composition formula R ¹ ′ _x SiO _{(4-x) / 2} (1)
(R ¹ ′ is, independently of each other, a monovalent hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, at least one of R ¹ ′ is a hydrogen atom, and x is 0.7 to 3.3. Hydrogenorganopolysiloxane represented by:
(B2) hydrogen organopolysiloxane having an isocyanuric acid skeleton, N—CH ₂ —Si bond and SiH group in one molecule;
(C) addition reaction catalyst,
Including
The component (A) is an organopolysiloxane represented by the following average composition formula (2), and the component (B2) is a hydrogen organopolysiloxane represented by the following average composition formula (3). A silicone hybrid resin composition.

(R ¹ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ⁴ is an alkenyl group. a is 0, 1, or 2, b is 0 to 2.0, c is 0 to 2.0, d is 0.02 to 1.0, and b + c + d = 0.5 to 3.0. Is 0.1 to 0.9, and n is 0.1 to 0.9.)

(R ¹ , R ² , R ³ , a, b, and c are the same as described above. E is 0.02 to 1.0, and b + c + e = 0.5 to 3.0. P is 0. .1-0.9, q is 0.1-0.9.)   The silicone hybrid resin composition according to claim 1, further comprising (D) an adhesion-imparting agent.   The ratio of the alkenyl group contained in said (A) component with respect to SiH group contained in said (B) component is 0.5-4.0, The claim 1 or 2 characterized by the above-mentioned. Silicone hybrid resin composition.   An optical semiconductor device sealed with the silicone hybrid resin composition according to any one of claims 1 to 3.