KR101683891B1

KR101683891B1 - Resin composition for encapsulating optical semiconductor element

Info

Publication number: KR101683891B1
Application number: KR1020100042788A
Authority: KR
Inventors: 요시히라 하마모또; 츠또무 가시와기
Original assignee: 신에쓰 가가꾸 고교 가부시끼가이샤
Priority date: 2009-05-08
Filing date: 2010-05-07
Publication date: 2016-12-07
Also published as: JP5251919B2; CN101880461A; KR20100121435A; TWI480338B; CN101880461B; JP2010280885A; TW201041975A

Abstract

The present invention provides a resin composition for sealing an optical semiconductor device. (B) a second silicone resin having an epoxy group-containing nonaromatic group and a diorganosiloxane unit, (C) a curing agent, and (D) a second silicone resin having a diorganosiloxane unit, wherein the first silicone resin is a mixture of (A) a first silicone resin having a nonaromatic group containing an epoxy group and a linear diorganopolysiloxane segment, ) Curing catalyst. The composition is excellent in curability, and the resulting cured product is excellent in heat discoloration resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to resin compositions for optical semiconductor device encapsulation,

TECHNICAL FIELD The present invention relates to a composition for sealing an optical semiconductor element, and more particularly to a composition for sealing an optical semiconductor element which is excellent in heat discoloration resistance and curability wherein the main agent is substantially composed of a silicone resin.

BACKGROUND ART Conventionally, an epoxy resin composition is widely used for sealing an optical semiconductor element. The epoxy resin composition usually contains a subject alicyclic epoxy resin, a curing agent and a curing catalyst. The optical semiconductor element is sealed by pouring the composition into a mold in which the optical semiconductor element is disposed by casting, transfer molding or the like and curing the composition. However, discoloration and deterioration of the epoxy resin have been a problem due to the luminance and power-up of the LED. Particularly, since the alicyclic epoxy resin is yellowed by blue light or ultraviolet light, there is a problem that the lifetime of the LED element is shortened.

Therefore, although a silicone resin having excellent heat resistance and light resistance is used, there is a problem that the strength of the cured resin is weaker than that of the epoxy resin. To solve this problem, it has been proposed to use a high hardness rubber-like silicone resin for sealing applications (Patent Document 1). However, the high-hardness silicone resin is insufficient in adhesiveness, and in a device in which a light emitting element is disposed in a case-type light emitting semiconductor device, that is, a ceramic and / or a plastic case and the inside of the case is filled with silicone resin, There is a problem that the silicone resin is peeled off from the case of ceramic or plastic.

A silicone resin having an epoxy group has been proposed in order to improve adhesiveness and thermal shock resistance (Patent Document 2). The silicone resin is synthesized by condensing a silanol having an epoxy group with a silanol, but the elasticity of the cured product is low and is fragile. Therefore, there is a problem that cracks tend to occur in the resin in the temperature cycle test of the LED sealed with the resin.

As a material for solving this problem, a composition comprising an epoxy resin and silsesquioxane having at least two epoxy rings (Patent Document 3), and a composition comprising a silicone resin having an epoxy resin and an isocyanuric acid derivative group as a low- A composition (Patent Document 4) is known. However, since all of them show cracking in the temperature cycle test of the cured product, the thermal shock resistance can not be said to be satisfactory.

Japanese Patent Application Laid-Open No. 2002-314143 Japanese Patent Laid-Open No. 7-97433 Japanese Patent Application Laid-Open No. 2005-263869 Japanese Patent Application Laid-Open No. 2004-99751

An object of the present invention is to solve the above problems and to provide a resin composition for optical semiconductor device encapsulation which is capable of forming a sealing material having high hardness, excellent in light resistance and thermal shock resistance and excellent in heat discoloration resistance, And the like.

As a result of various investigations, the present inventors have found that a second epoxy-modified silicone resin obtained by bonding an epoxy-modified silicone resin having a straight-chain polysiloxane structure with two kinds of organosilanes and having an epoxy equivalent smaller than that of the epoxy- The present invention has been accomplished on the basis of these findings.

That is, the present invention is a composition for sealing optical semiconductor devices comprising the following components (A), (B), (C) and (D)

(A) 50 to 90 parts by mass of a first silicone resin having an epoxy group-containing non-aromatic group represented by the following average composition formula (1)

In the (expression ^(1), R 1 is a group that is an epoxy group-containing non-aromatic group, R ² is independently a hydroxyl group, C ₁ _-20 ₁ is selected from a hydrocarbon group and a C ₁ _-6 alkoxy group each other, R ³ is Independently of _one another are a C ₁ _-20 monovalent hydrocarbon group,

x and y are independently of each other an integer of 0, 1 or 2,

a is a number from 0.25 to 0.75,

b is a number from 0.25 to 0.75,

c is a number from 0 to 0.3, with the proviso that a + b + c = 1,

and n is an integer of 2 to 20)

(B) 10 to 50 parts by mass of a second silicone resin having an epoxy group-containing nonaromatic group represented by the following average formula (2)

(In the formula (2), R ¹ and R ² And R < ³ > are as defined above, z is independently of each other an integer of 0, 1 or 2,

d is a number from 0.5 to 0.8,

e is a number from 0.2 to 0.5,

However, d + e = 1)

(C) a curing agent having a functional group reactive with an epoxy group, wherein the amount of the functional group reactive with the epoxy group is 0.4 to 1.5 moles per mole of the total of the epoxy groups in the component (A) and the component (B)

(D) 0.01 to 3 parts by weight relative to 100 parts by weight of the total of the curing catalyst (A) and the component (B)

Since the resin composition of the present invention contains the second silicone resin, it provides a cured product having high hardness. In addition, since the second silicone resin is rich in reactivity, it is possible to provide an optical semiconductor package having excellent heat discoloration resistance in a short time.

Fig. 1 shows a measurement chart of ²⁹ Si-NMR obtained for the first silicone resin obtained in Synthesis Example 1. Fig.

&Lt; Component (A) >

In the composition of the present invention, the first silicone resin (A) having an epoxy group-containing non-aromatic group is represented by the following average composition formula (1).

In the formula (1), n is an integer of 2 to 20, preferably 3 to 20, more preferably 3 to 10. x and y are independently of each other an integer of 0, 1 or 2; In each of the first structural unit attached with the subscript a and the third structural unit attached with the suffix c constituting the first silicone resin, a unit in which x or y is 0 (T unit), a unit in which x or y is 1 ( D units) and units in which x or y is 2 (M units) are usually present together in one molecule. The presence ratio of the T unit, the D unit and the M unit in each of the first structural unit and the third structural unit depends on the kind of R ² in the monomer used in the production method described later and the progress of the hydrolysis and bonding . The molar ratio of T units: D units: M units is preferably 10:30:60 to 98: 1: 1, more preferably 40:30:30 to 98: 1: 1, more preferably 60: 20:20 to 96: 2: 2, even more preferably 80:10:10 to 95: 3: 2.

In the (R ³ ₂ Si0) _n unit in the formula (1), for example, a unit in which n is 3 has the following structure.

The (R ³ ₂ Si0) _n unit may be a main chain thereof when the silicone resin is linear, or may be bonded to any branch if it is branched. By including the (R ³ ₂ Si0) _n unit, a cured product having excellent heat shock resistance can be obtained.

In the formula (1), R ¹ is an epoxy group-containing nonaromatic group, and examples thereof include a linear or branched aliphatic group containing an epoxy group such as a? -Glycidoxyalkyl group such as a? -Glycidoxypropyl group, 4-epoxycyclohexyl) ethyl group, and epoxy group-containing heterocyclic ring-containing groups such as monoglycidylisocyanuryl group and diglycidylisocyanuryl group. Of these, an epoxy group-containing alicyclic group, particularly? - (3,4-epoxycyclohexyl) ethyl group is preferable. It is also conceivable to use a non-aromatic group having an oxetanyl group in place of the epoxy group, but it is excellent in epoxy group from the viewpoint of curability. It is preferable that at least 1, and more preferably 2 to 100 R ¹ are present in one molecule. Further, it is preferable to be present at the terminal of the molecule. For example, when the molecular structure is linear, it is more preferable that one molecule is present at both ends of the molecule.

R ² is a group selected from a hydroxyl group, a C ₁ _-20 monovalent hydrocarbon group and a C ₁ _-6 alkoxy group. Examples of the hydrocarbon group include an alkyl group such as methyl group, ethyl group, propyl group and butyl group, a cycloalkyl group such as cyclopentyl group and cyclohexyl group, an aryl group such as phenyl group, an alkaryl group such as tolyl group, Lt; / RTI > _{Examples of the} C _1-6 alkoxy group include a methoxy group and an ethoxy group. Preferably, R ² is a methyl group or a phenyl group.

R ³ is independently of each other a C _1-20 monovalent hydrocarbon group, and the groups mentioned above for R ² are exemplified.

a is a number from 0.25 to 0.75, preferably from 0.4 to 0.7. When the value of a is less than the above lower limit, the curing degree of the composition is low because the amount of the epoxy group is small, and the amount of the epoxy group is larger than the upper limit value, so that the synthesized resin is gelled, which is not preferable. b is a number of 0.25 to 0.75, preferably 0.3 to 0.6. c is a number from 0 to 0.3, preferably from 0 to 0.2. If c exceeds the upper limit value, the light resistance of the cured product tends to deteriorate. Formula (1) is a composition formula representing the average existing ratio of each structural unit, and a + b + c = 1.

(A) is obtained by reacting a straight-chain organopolysiloxane represented by the following formula (3) with an epoxy group-containing silane represented by the following formula (4), optionally with a silane represented by the formula (5) And a condensation reaction.

(Wherein R ³ is as defined above, X is a hydrolyzable group such as an alkoxy group and a halogen atom, and m is an integer of 0 to 18)

(In the formula, R ¹ and R ² is at least one of the same as described above, R ² a hydroxyl group or a C ₁ _-6 alkoxy dogs group)

(In the formula, R ² and R ³ is at least one of the same as described above, R ² a hydroxyl group or a C ₁ _-6 alkoxy dogs group)

The component (A) has a weight average molecular weight in terms of polystyrene of 3000 to 10,000, preferably 3000 to 6,000. The epoxy equivalent is 200 to 800 g / mol, preferably 300 to 600 g / mol.

&Lt; Component (B) >

(B) a second silicone resin having an epoxy group-containing non-aromatic group is represented by the following average composition formula (2).

In the formula (2), R ¹ , R ² and R ³ are as described above. and z is an integer of 0, 1 or 2 independently of each other. In the first structural unit attached with the subscript d constituting the second silicone resin, a unit (z unit) of z (Z unit) (z unit) and a unit z Are present together in the molecule. The presence ratio of the T unit, the D unit and the M unit in the above structural unit depends on the kind of R ² in the monomer used in the production method described later and the degree of progress of the hydrolysis and condensation. The molar ratio of T units: D units: M units is preferably 10:30:60 to 98: 1: 1, more preferably 40:30:30 to 98: 1: 1, more preferably 60: 20:20 to 96: 2: 2, even more preferably 80:10:10 to 95: 3: 2. d is a number of 0.5 to 0.8, preferably 0.5 to 0.7. When d is less than the above lower limit, the composition becomes poor in curing, and the resin exceeding the upper limit value tends to be difficult to synthesize, and the composition tends to gel, which is not preferable. e is a number from 0.2 to 0.5, preferably from 0.3 to 0.5, provided that d + e = 1.

The difference in the method for producing the component (A) of the method for producing the component (B) is that an organosilane represented by R ³ ₂ X ₂ Si is used in place of the straight-chain organopolysiloxane represented by the formula (3) , And applying the organosilane to the hydrolysis-condensation reaction with the epoxy group-containing silane represented by the formula (4). Therefore, it is considered that the component (B) substantially does not contain the (R ³ ₂ SiO) _n unit of the component (A) and exerts the same action as the crosslinking point in the cured product to increase the strength of the cured product. Thus, the composition of the present invention can form a cured product excellent in hardness, heat resistance, impact resistance, and the like, without using an epoxy resin, particularly an alicyclic epoxy resin widely used for sealing optical semiconductor elements. Since the cured product does not contain such an epoxy resin, there is no discoloration due to heat.

The component (B) has a weight average molecular weight in terms of styrene of 3000 to 10,000, preferably 3000 to 7000. The epoxy equivalent of the component (B) is 100 to 600 g / mol, preferably 250 to 400 g / mol. More preferably, the epoxy equivalent of the component (B) is smaller than the epoxy equivalent of the component (A) by 30 to 300 g / mole.

The blending amount of the component (B) is 10 to 50 parts by mass, preferably 10 to 30 parts by mass based on 100 parts by mass of the total of the components (A) and (B). When the amount of the component (B) exceeds the upper limit value, when the light emitting element emits ultraviolet light, the cured product of the resin composition tends to be deteriorated by ultraviolet light. Further, cracks and the like due to heat for a long time tend to occur.

&Lt; Component (C) >

Examples of the curing agent (C) include an amine curing agent, a phenol curing agent and an acid anhydride curing agent, among which an acid anhydride curing agent is preferred.

Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, - a mixture of hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride, a mixture of tetrahydrophthalic anhydride, nornic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane -2,3-dicarboxylic acid anhydride and the like. The compounding amount of the curing agent is preferably such that the epoxy group and the reactive group (an acid anhydride group represented by -CO-O-CO- in the case of the acid anhydride-based curing agent) are added to the total of 1 mole of the epoxy group in the component (A) Is 0.4 to 1.5 moles, preferably 0.5 to 1.2 moles.

&Lt; Component (D) >

Examples of the curing catalyst (D) include quaternary phosphonium salt-based curing catalysts such as tetrabutylphosphonium-0,0-diethylphosphorothioate and tetraphenylphosphonium-tetraphenylborate, triphenylphosphine-based curing catalysts such as triphenylphosphine, An organic phosphine-based curing catalyst such as a pin, a tertiary amine-based curing catalyst such as 1,8-diazabicyclo (5,4,0) undecene-7, triethanolamine and benzyldimethylamine, (5,4,0) undecene-7, octylate of 1,8-diazabicyclo (5,4,0) undecene-7, 1,8-diazabicyclo ) Undecene-7, an imidazole-based curing catalyst such as 2-methylimidazole and 2-phenyl-4-methylimidazole, and the like, and preferably Are quaternary phosphonium salts and quaternary ammonium salts.

The blending amount of the (D) curing catalyst is 0.01 to 3 parts by mass, preferably 0.05 to 0.5 parts by mass based on 100 parts by mass of the total of the components (A) and (B). If the compounding amount of the curing catalyst is lower than the above lower limit value, there is a possibility that the effect of accelerating the reaction between the epoxy resin and the curing agent can not be sufficiently obtained. On the other hand, if the compounding amount of the curing catalyst is higher than the upper limit value, there is a fear of causing discoloration during curing or reflow test.

An inorganic filler such as a phosphor, silica, and a fine titanium oxide powder, a silane-based coupling agent, a thermoplasticizer, a diluting agent, a dispersing agent or the like may be added in addition to the above- Etc. may be used in combination as occasion demands. As the antioxidant, hindered phenol-based antioxidants and phosphorus-based antioxidants are preferable. As the ultraviolet absorber, a hindered amine-based ultraviolet absorber is preferable. As the silane coupling agent, mercapto silane coupling is preferable.

The composition of the present invention can be easily prepared by blending one or more of the additives described above according to the components (A) to (D) and the purpose and melt-mixing at a temperature at which curing at about 60 ° C does not proceed . The melt mixing may be a known method, for example, the above components may be put into a reactor and melt blended in a batch manner, or the above components may be added to a kneader such as a kneader or a thermal three-axis roll, And melt-mixed.

The obtained resin composition for optical semiconductor device encapsulation can be used after being injected into a mold or case in which the light emitting device is mounted in the state of the molten mixture obtained in the above-mentioned process, and solidified after being made into a B stage at a predetermined temperature.

In addition, the composition may be applied by potting, printing, transfer molding, injection molding, compression molding or the like to an LED having the substrate mounted thereon. When a light-emitting semiconductor device such as an LED is coated and protected by potting or injection, the composition of the present invention is preferably in a liquid phase. The viscosity of the resin composition is preferably from 10 to 1,000,000 mPa · S, more preferably from 100 to 1,000,000 mPa · S as measured by a rotational viscometer at 25 ° C. On the other hand, when the light emitting semiconductor device is manufactured by transfer molding or the like, the above liquid resin can be used. However, the liquid resin can be solidified (B-stage) by pouring the liquid resin and then molded.

[Example]

Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Synthesis of component (A)

In the following Synthesis Examples, the average value of n in the average composition formula representing the product was calculated by multiplying the sum of the products of the n and n peak areas in the chart of molecular weight distribution by GPC measurement as the sum of the total peak areas Divided by the value obtained. For example, when n of a certain product is an integer of 2 to 20, [2 x (peak area of n = 2) + 3 x (peak area of n = 3) + + 20 占 (peak area of n = 20)] / [(peak area of n = 2) + (peak area of n = 3) + + (peak area of n = 20)].

&Lt; Synthesis Example 1 &

1695.6 g (5.966 moles) of MeO (Me) ₂ SiO (Me ₂ SiO) _m Si (Me) ₂ OMe (m is an integer from 0 to 8 with an average of 1.5), 3000 ml of isopropyl alcohol, 1470 g (5.966 moles) of tetramethylammonium tetraethylammonium hydroxide (KBM303, manufactured by Shin-Etsu Chemical Co., Ltd.) And the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 3000 ml of toluene was added to the system. The organic layer was neutralized with an aqueous solution of sodium hydrogen phosphate and the organic layer separated using a separatory funnel was washed with hot water. The toluene was removed under reduced pressure to obtain the desired resin (Resin 1) having a structure represented by the following average composition formula.

The weight average molecular weight in terms of polystyrene measured by GPC was 4,300. The epoxy equivalent was 403 g / mol.

The results of measurement by ²⁹ Si-NMR are shown in Fig. The peak near -68 ppm reflects Si forming T unit, and the peak near -57 to -58 ppm reflects Si forming D unit and M unit. From these results, it was found that the first structural unit (left unit) constituting the above average composition formula contained about 90 mol% of T unit and about 10 mol% of D unit and M unit in total.

(Provided that n is an integer of 2 to 10 and the average of n is 3.5 and that x is 0, 1 or 2 in the first unit)

&Lt; Synthesis Example 2 &

_{H0 (Me) 2 Si0 [(} Me) 2 Si0] m Si (Me) 2 0H (m is an integer from 3 to 18, the average is 8) 1500 g (1.975 mol) of 3- (3,4-epoxy cyclo 973.2 g (3.950 mol) of ethyltrimethoxysilane (KBM303, manufactured by Shin-Etsu Chemical Co., Ltd.) and 2300 ml of isopropyl alcohol were charged. Then, 49.90 g of 25% aqueous solution of tetramethylammonium hydroxide and 449.10 g And the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 2300 ml of toluene was added to the system, 49.90 g of a 25% aqueous solution of tetramethylammonium hydroxide and 449.10 g of water were added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 2300 ml of toluene was added to the system, and neutralized with an aqueous solution of sodium hydrogen dihydrogenphosphate. The separated organic layer was washed with hot water using a separatory funnel. The toluene was removed under reduced pressure to obtain a desired resin (referred to as " resin 2 ") having a structure represented by the following average composition formula. The weight average molecular weight in terms of polystyrene measured by GPC was 5,600. The epoxy equivalent was 570 g / mol.

(Provided that n is an integer of 5 to 20 and the average of n is 10, and in the first unit, x is 0, 1 or 2)

&Lt; Synthesis Example 3 &

3-glycidoxypropyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd. Preparation 80) 933.30 g (3.950 _{mol), HO (Me) 2 SiO} [(Me) 2 SiO] m Si (Me) 2 0H 1500 g (1.975 mol) of m-xylylenediamine (m is an integer of 3 to 18, average 8) and 2300 ml of isopropyl alcohol were charged. Then, 92.15 g of 25% aqueous solution of tetramethylammonium hydroxide and 444.96 g of water were added thereto, And the mixture was stirred for 3 hours. After completion of the reaction, 2300 ml of toluene was added to the system, and neutralized with an aqueous solution of sodium hydrogen dihydrogenphosphate. The separated organic layer was washed with hot water using a separatory funnel. The toluene was removed under reduced pressure to obtain a desired resin (referred to as " resin 3 ") having a structure represented by the following average composition formula. The weight average molecular weight in terms of polystyrene measured by GPC was 4,300. The epoxy equivalent was 570 g / mol.

[Synthesis of component (B)] [

&Lt; Synthesis Example 4 &

187.00 g (1.566 mol) of dimethyldimethoxysilane (KBM-22, Shin-Etsu Chemical Co., Ltd.), 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM303, Shinetsu Chemical Industries ) And 900 ml of isopropyl alcohol. 21.69 g of a 25% aqueous solution of tetramethylammonium hydroxide and 195.21 g of water were added, followed by stirring at room temperature for 3 hours. After completion of the reaction, 1000 ml of toluene was added to the system, and neutralized with an aqueous solution of sodium hydrogen dihydrogenphosphate. The separated organic layer was washed with hot water using a separatory funnel. The toluene was removed under reduced pressure to obtain a desired resin (referred to as " resin 4 ") having a structure represented by the following average composition formula. The weight average molecular weight in terms of polystyrene measured by GPC was 4200. The epoxy equivalent was 267 g / mol.

(Provided that x is 0, 1 or 2 in the first unit)

&Lt; Synthesis Example 5 &

187.00 g (1.566 mol) of dimethyldimethoxysilane (KBM-22, Shin-Etsu Chemical Co., Ltd.), 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM303, Shinetsu Chemical Industries ), 540 ml of isopropyl alcohol was added thereto, 12.97 g of 25% aqueous solution of tetramethylammonium hydroxide and 203.93 g of water were added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 1000 ml of toluene was added to the system, and neutralized with an aqueous solution of sodium hydrogen dihydrogenphosphate. The separated organic layer was washed with hot water using a separatory funnel. The toluene was removed under reduced pressure to obtain a desired resin (referred to as " resin 5 ") having a structure represented by the following average composition formula. The weight average molecular weight in terms of polystyrene measured by GPC was 3100. The epoxy equivalent was 359 g / mol.

(Provided that x is 0, 1 or 2 in the first unit)

&Lt; Synthesis Example 6 &

187.00 g (1.566 mol) of methyldimethoxysilane (KBM-22, Shin-Etsu Chemical Co., Ltd.) and 735.24 g of 3-glycidoxypropyltrimethoxysilane (KBM403, Shin-Etsu Chemical Co., 3.111 moles) and 900 ml of isopropyl alcohol were added thereto, 20.98 g of 25% aqueous solution of tetramethylammonium hydroxide and 188.82 g of water were added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 1000 ml of toluene was added to the system, and neutralized with an aqueous solution of sodium hydrogen dihydrogenphosphate. The separated organic layer was washed with hot water using a separatory funnel. The toluene was removed under reduced pressure to obtain a desired resin having a structure represented by the following average composition formula (" Resin 6 "). The weight average molecular weight in terms of polystyrene measured by GPC was 3500. The epoxy equivalent was 295 g / mol.

(Provided that x is 0, 1 or 2 in the first unit)

&Lt; Examples 1 to 6, Comparative Example 1, Reference Examples 1 and 2 >

Using the respective resins obtained, the respective compositions shown in Table 1 were prepared. In the same table, numerical units other than the curing agent are parts by mass, and the respective components are as follows.

(C) Hardener: 4-methylhexahydrophthalic anhydride (Ricaside MH, Shin-Nippon Chemical Co., Ltd.)

(D) a curing catalyst; Quaternary phosphonium salt (UCAT5003, manufactured by San-Aro Co., Ltd.)

ㆍ Silane coupling agent: 3-mercaptopropylmethyldimethoxysilane (KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd.)

Epoxy resin: 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate (Celloxide 2021P, manufactured by Daicel Chemical Industries, Ltd.)

&Lt; Example 1 >

80 parts by mass of the resin 1, 20 parts by mass of the resin 4, and 1 part by mole of the total of the epoxy groups of the resin 1 and the resin 4 were mixed with the curing agent in an amount of 1 mole of the acid anhydride group, 0.39 parts by mass of a curing catalyst and 0.25 parts by mass of a silane coupling agent were melt-mixed with 100 parts by mass of the mixture of the curing agent to obtain a composition. In the melt mixing, first, the curing agent and the curing catalyst were melted in an oven at 60 ° C and mixed with other components at 2000 rpm for 1 minute using a stirrer ("Thinky Mixer" (Shin Kisa) , Followed by defoaming at 2200 rpm for 1 minute.

&Lt; Example 2 >

80 parts by mass of Resin 1, 20 parts by mass of Resin 5, and a curing agent in an amount of 1 mole of the acid anhydride group per 1 mole in total of the epoxy groups of Resin 1 and Resin 5, 0.39 parts by mass of a curing catalyst and 0.25 parts by mass of a silane coupling agent were melt-mixed in the same manner as in Example 1 to obtain a composition.

&Lt; Example 3 >

80 parts by mass of Resin 2, 20 parts by mass of Resin 4, and a curing agent in an amount of 1 mole of the acid anhydride group per 1 mole in total of the epoxy groups of Resin 2 and Resin 4, 0.39 parts by mass of a curing catalyst and 0.25 parts by mass of a silane coupling agent were melt-mixed in the same manner as in Example 1 to 100 parts by mass of the mixture of the curing agent to obtain a composition.

80 parts by mass of the resin 2, 20 parts by mass of the resin 5, and 1 part by mole of the total of the epoxy groups of the resin 2 and the resin 5 were mixed with the curing agent in an amount of 1 mole of the acid anhydride group, 0.39 parts by mass of a curing catalyst and 0.25 parts by mass of a silane coupling agent were melt-mixed in the same manner as in Example 1 to 100 parts by mass of the mixture of the curing agent to obtain a composition.

&Lt; Example 5 >

, 80 parts by mass of Resin 3, 20 parts by mass of Resin 6, and a curing agent in an amount of 1 mole of the acid anhydride group per 1 mole in total of the epoxy groups of Resin 3 and Resin 6, 0.39 parts by mass of a curing catalyst and 0.25 parts by mass of a silane coupling agent were melt-mixed in the same manner as in Example 1 to 100 parts by mass of the mixture of the curing agent to obtain a composition.

&Lt; Example 6 >

80 parts by mass of the resin 1, 20 parts by mass of the resin 4, and 1 part by mole of the total of the epoxy groups of the resin 1 and the resin 4 were mixed with the curing agent in an amount of 1 mole of the acid anhydride group, 0.39 parts by mass of a curing catalyst was melt-mixed in the same manner as in Example 1 to 100 parts by mass of the mixture of the curing agent to obtain a composition.

&Lt; Comparative Example 1 &

100 parts by mass of Resin 1, 0.39 parts by mass of a curing catalyst per 100 parts by mass of a mixture of the resin 1 and the curing agent in an amount such that the amount of the acid anhydride group was 1 mole based on 1 mole of the epoxy group of the resin 1, And 0.25 parts by mass of a ring agent were melt-mixed in the same manner as in Example 1 to obtain a composition.

&Lt; Reference Example 1 &

78 parts by mass of the resin 1, 22 parts by mass of the epoxy resin, and 1 part by mass of the total amount of the epoxy resin of the resin 1 and the epoxy resin, the amount of the curing agent being 1 mole of the acid anhydride group, 0.39 parts by mass of a curing catalyst and 0.25 parts by mass of a silane coupling agent were melt-mixed in the same manner as in Example 1 to 100 parts by mass of the mixture of the curing agent to obtain a composition.

90 parts by mass of the resin 2, 10 parts by mass of the epoxy resin, the curing agent in an amount of 1 mole of the acid anhydride group per 1 mole of the total of the resin 2 and the epoxy group of the epoxy resin, 0.39 parts by mass of a curing catalyst and 0.25 parts by mass of a silane coupling agent were melt-mixed in the same manner as in Example 1 to 100 parts of the above mixture of the curing agent to obtain a composition.

(Note in Table 1) The units of components other than the (C) curing agent are parts by mass.

The following tests were carried out for each composition, and the results are shown in Table 2.

(1) Physical properties: The composition was cured by heating at 100 占 폚 for 2 hours, and post-curing was performed at 150 占 폚 for 4 hours to obtain a bar-shaped cured product having a thickness of 5 mm. The appearance, hardness (Shore D), flexural modulus and flexural strength (JIS K-6911) of the rod-shaped cured product were measured.

(2) Heat discoloration resistance: The appearance of the rod-shaped cured product prepared in the same manner as in (1) was examined after high-temperature aging (150 DEG C, 1000 hours).

(3) In-Vitro Test: The composition was molded into a cured piece (6 cm x 6 cm) having a thickness of 2 mm by press molding at 100 DEG C for 30 minutes, followed by post curing at 150 DEG C for 4 hours to prepare a test piece . The light transmittance of the test piece after 2 hours of UV irradiation (high-pressure mercury lamp 30 mW / cm ² , 365 nm) was measured. The transmittance was measured by scanning from 800 to 300 nm, and the transmittance was determined when the initial transmittance at 400 nm was taken as 100%.

(4) Microhardness of the surface: A polytetrafluoroethylene tape (180 μm in thickness) was adhered to the slide glass along the outer periphery of the slide glass, the composition was poured into the formed recess, Further post curing was performed at 150 캜 for 4 hours to make a thin film cured product. The microhardness of the thin-film cured product was measured using a micro-hardness meter (DUH-W201S, Shimadzu Corporation).

(Note in Table 2)

* 1: The cured product is weak, and the bending strength can not be measured.

* 2: The cured product is rubbery, and the bending strength can not be measured.

The following tests were carried out for each composition, and the results are shown in Table 3.

ㆍ Manufacture and evaluation of LED devices

Using the compositions of Examples 1 and 3 and Comparative Example 1, three LED devices were produced in the following manner. The InGaN-based blue light emitting device was fixed by silver paste to a preformed package for LED with a thickness of 1 mm, a side of 3 mm, an opening of 2.6 mm in diameter, and a bottom side coated with silver. Next, the external electrode and the light emitting element were connected with a gold wire. Each composition was injected into the package opening. The LED device was prepared by curing the composition at 100 DEG C for 1 hour and further at 150 DEG C for 2 hours. The LED device thus manufactured was subjected to a temperature cycle test under the following conditions and an LED lighting test (wavelength of LED: 450 nm) under a condition of 65 ° C / 95% RH for 500 hours to evaluate adhesion failure, cracking, Were visually observed. The results are shown in Table 3.

ㆍ Temperature cycle test condition:

One cycle: Leave at -40 ° C for 20 minutes and then at 125 ° C for 20 minutes.

Number of iterations: 1000

ㆍ Adhesive strength:

Using the compositions of Examples 1 and 3 and Comparative Example 1, an adhesive test piece was prepared in the following manner. Each of the compositions was thinly coated on a copper-plated copper plate, and thereafter a silicon chip of 2 mm square was placed and cured at 100 ° C for 1 hour and further at 150 ° C for 2 hours to prepare an adhesive test piece. The adhesive specimens thus prepared were cut using a die bond tester (device name: Dage Series 4000 Bond tester, test speed: 200 μm / s, test height: 10.0 μm, measurement temperature: 25 ° C.) Was measured.

As can be seen from the results shown in Tables 2 and 3, the cured product obtained from the composition of Comparative Example 1 in which the component (B) was omitted had poor bending strength and heat discoloration resistance and was discolored by LED light. Further, the cured product obtained from the reference composition containing an epoxy resin instead of the component (B) was yellowed by heat. In contrast, the cured product obtained from the composition of the Example had a high hardness and had almost no discoloration. Further, as can be seen from the microhardness values in Table 2, it was confirmed that the compositions of the Examples provided cured products having higher hardness than the compositions of Comparative Examples and Reference Examples which were cured under the same conditions, and had a faster curing rate.

The composition of the present invention is fast curing, and its cured product is excellent in heat discoloration resistance, UV resistance, and is useful for optical device sealing resin.

Claims

Wherein the epoxy equivalent of the component (A) is from 200 to 800 g / mol, the epoxy equivalent of the component (B) is the equivalent of the component (A) An epoxy equivalent of at least 30 g / mole;
(A) 50 to 90 parts by mass of a first silicone resin having an epoxy group-containing non-aromatic group represented by the following average composition formula (1)

In the (expression ^(1), R 1 is a non-aromatic group containing an epoxy group, R ² is a group with each other are independently a hydroxyl group, C _1-20 1 is selected from a hydrocarbon group and a C _1-6 alkoxy group, R ³ is Independently of one another, a C _1-20 monovalent hydrocarbon group,
x and y are independently of each other an integer of 0, 1 or 2,
a is a number from 0.25 to 0.75,
b is a number from 0.25 to 0.75,
c is a number from 0 to 0.3, with the proviso that a + b + c = 1,
and n is an integer of 2 to 20)
(B) 10 to 50 parts by mass of a second silicone resin having an epoxy group-containing nonaromatic group represented by the following average formula (2)

(In the formula (2), R ¹ , R ² and R ³ are as defined above, z is independently an integer of 0, 1 or 2,
d is a number from 0.5 to 0.8,
e is a number from 0.2 to 0.5,
However, d + e = 1)
(C) a curing agent having a functional group reactive with an epoxy group, wherein the amount of the functional group reactive with the epoxy group is 0.4 to 1.5 moles per mole of the total of the epoxy groups in the component (A) and the component (B)
(D) 0.01 to 3 parts by weight based on 100 parts by weight of the total of the curing catalyst (A) and the component (B).

The composition of claim 1, wherein n is an integer from 3 to 20.

The composition according to claim 1, wherein the component (A) has a weight average molecular weight of 3,000 to 10,000 in terms of polystyrene.

The composition according to claim 1, wherein R ¹ is a β- (3,4-epoxycyclohexyl) ethyl group or a γ-glycidoxyalkyl group.

2. The composition of claim 1 wherein R < ³ > is a methyl group.

The composition according to claim 1, wherein the component (A) has an epoxy equivalent of 300 to 600 g / mol and the component (B) has an epoxy equivalent of 250 to 400 g / mol.

The composition of claim 1, wherein component (C) is an acid anhydride.

The composition of claim 1, further comprising a mercaptan-based silane coupling agent.

A semiconductor device comprising a photosemiconductor element and a cured product obtained by curing the composition according to any one of claims 1 to 8 and sealing the optical semiconductor element.

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