JP2009019205A - Thermosetting composition for optical semiconductor, sealant for optical semiconductor element, and optical semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition for an optical semiconductor capable of giving a thermoset product which is excellent in transparency, heat resistance and light resistance, and which is excellent in adhesiveness to a housing material and does not cause problems such as yellowing or the like under long-term use conditions, when used as a sealant for an optical semiconductor element; to provide the sealant for the optical semiconductor element, made from the thermosetting composition; and to provide the optical semiconductor element. <P>SOLUTION: The thermosetting composition for the optical semiconductor comprises a silicone resin having a cyclic ether-containing group in the molecule thereof, a thermosetting agent capable of reacting with the cyclic ether-containing group, an antioxidant and a thermosetting accelerator having a structure represented by the general formula (1): X<SP>+</SP>[BR<SP>1</SP>R<SP>2</SP>R<SP>3</SP>R<SP>4</SP>]<SP>-</SP>, wherein R<SP>1</SP>-R<SP>4</SP>may be the same or different and represent each fluoro, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aralkyl, optionally substituted aryl or optionally substituted alicyclic; and X<SP>+</SP>represents a cation having N, S or P as a central element. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

In the present invention, the cured product is excellent in transparency, heat resistance and light resistance, and when used as a sealant for an optical semiconductor element, it has excellent adhesion to a housing material and is used for a long time. The present invention relates to a thermosetting composition for optical semiconductors that does not cause problems such as yellowing underneath, and relates to an encapsulant for optical semiconductor elements using the thermosetting composition for optical semiconductors, and an optical semiconductor element .

Light-emitting elements such as light-emitting diodes (LEDs) are usually sealed with a sealant because their light-emitting characteristics rapidly deteriorate due to moisture in the atmosphere or floating dust when they come into direct contact with the atmosphere. It has a structure. As a resin constituting a sealant for sealing such a light emitting element, epoxy resin such as bisphenol type epoxy resin and alicyclic epoxy resin is used because of its high adhesive strength and excellent mechanical durability. It was.

However, in recent years, LEDs have come to be used for applications that require high brightness such as automotive headlights and lighting, and as a result, the sealant that seals the light emitting element has high brightness. In addition to the high light resistance that prevents the accompanying light deterioration, extremely high heat resistance that can withstand the increase in the amount of heat generated during lighting has been required.
However, the conventional sealant made of epoxy resin has advantages such as high adhesion and low moisture permeability, but it is difficult to say that it has sufficient heat resistance and light resistance. In applications that require high brightness, such as, there is a problem of coloring.

For such problems, for example, addition of a compound has been studied in order to increase the heat resistance of the epoxy resin (see, for example, Patent Document 1). However, in recent years, the brightness of optical semiconductor elements such as LEDs has been increased. On the other hand, it did not satisfy sufficient heat resistance.

On the other hand, a method using a silicone resin as a sealant for sealing a light emitting element of an LED instead of an epoxy resin is known (see, for example, Patent Document 2).
However, the sealant made of silicone resin has high transparency to short-wavelength light in the blue to ultraviolet region and is excellent in heat resistance and light resistance, but has surface tackiness. There is a problem that the light emitting surface is easily damaged. In addition, the sealant made of silicone resin has a problem of poor reliability due to poor adhesion to a housing material or the like.
On the other hand, the silicone resin sealant with increased crosslink density eliminates the tackiness of the surface and prevents adhesion of foreign substances and damage to the light emitting surface, but has good adhesion to the housing material that encloses the light emitting element. In addition, there was a problem that the mechanical strength was remarkably lowered.

Furthermore, the sealing agent made of silicone resin has a problem that the light-emitting characteristics of the light-emitting element deteriorate due to high moisture permeability and long-term use.
In addition, the sealant made of silicone resin has a problem that the refractive index is low and the light extraction efficiency is not sufficient when the light-emitting element of the optical semiconductor is sealed, and these problems also occur when used in combination with an epoxy resin. It was not possible to achieve sufficient performance to solve the problem.

On the other hand, for example, Patent Document 3 discloses that R ⁴ R ¹ R ¹ SiO _1/2 (R ¹ R ¹ SiO _2/2 ) _x (R ¹ R ² SiO _2/2 ) _y (R ¹ R ³ SiO _{2 / 2} ) _z OSiR ¹ R ¹ R ⁴ (R ¹ is a hydrogen group or an aliphatic hydrocarbon having 1 to 6 carbon atoms, R ² is an epoxy group-containing group, and R ³ is an alicyclic carbonization. An encapsulant containing an epoxy-modified silicone resin having a structure represented by a hydrogen group and R ⁴ is any one of R ^{1 to} R ³ has been proposed. However, the sealant containing the epoxy silicone resin having such a structure has high transparency to light of a short wavelength in the blue to ultraviolet region and is excellent in light resistance, but has insufficient heat resistance and requires optical properties. However, it has been difficult to use for automotive headlights and lighting applications.
JP 2003-73452 A JP 2002-314142 A JP 2004-155865 A

In view of the above situation, the present invention has a cured product that is excellent in transparency, heat resistance and light resistance, and when used as a sealant for an optical semiconductor element, has excellent adhesion to a housing material, It aims at providing the thermosetting composition for optical semiconductors which does not produce problems, such as yellowing, on use conditions for a long time. Moreover, it aims at providing the sealing compound for optical semiconductor elements which uses this thermosetting composition for optical semiconductors, and an optical semiconductor element.

一般式（１）中、Ｒ^１〜Ｒ^４は、フルオロ基、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアラルキル基、置換されていてもよいアリール基、置換されていてもよい脂環基を表し、これらは、互いに同一であってもよく、異なっていてもよい。また、Ｘ^＋は、Ｎ、Ｓ又はＰを中心元素として有するカチオンを表す。
以下、本発明を詳述する。 The present invention relates to a silicone resin having a cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, an antioxidant, and a curing having a structure represented by the following general formula (1) It is a thermosetting composition for optical semiconductors containing an accelerator.

In the general formula (1), R ^{1 to} R ⁴ are a fluoro group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aralkyl group, and optionally substituted. An aryl group and an alicyclic group which may be substituted are represented, and these may be the same or different. X ⁺ represents a cation having N, S or P as a central element.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have found that a silicone resin having a cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, an antioxidant, and a borate salt system having a specific structure. A thermosetting composition containing a curing accelerator has a cured product that has excellent transparency and light resistance, and is extremely excellent in heat resistance. When used as a stopper, it was found that yellowing hardly occurs under the conditions of use, and that it has excellent adhesion to a substrate or the like, and the present invention has been completed.

The thermosetting composition for optical semiconductors of this invention contains the hardening accelerator (henceforth the hardening accelerator which concerns on this invention) which has a structure represented by the said General formula (1).
By containing such a curing accelerator according to the present invention, the curable composition for optical semiconductors of the present invention has a cured product that has extremely excellent long-term heat resistance, and has long-term heat. Even when placed in an environment, the coloring (yellowing) is very small. This is considered to be due to the following reasons.

That is, as used in the sealing agent containing a conventional epoxy-modified silicone resin, a curing accelerator, Br ^- to contain those which the halogen such as the anion, the cyclic ether-containing group in which the anion is described below Since it reacts with the cyclic ether-containing group in the silicone resin it has, only the counter cation remains, and a yellowing substance is generated by the reaction with this counter cation, and the heat resistance is considered to deteriorate. On the other hand, the curing accelerator according to the present invention has a bulky anion having a structure represented by [BR ¹ R ² R ³ R ⁴ ] ^- (hereinafter, also simply referred to as a borate salt), and therefore a cyclic ether described later. The reactivity of the silicone resin having a containing group with the cyclic ether-containing group is considered to be relatively low, and it is presumed that the production of the yellowing substance as described above is extremely reduced.

In the curing accelerator according to the present invention, R ^{1 to} R ⁴ in the general formula (1) may be a fluoro group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted. An aralkyl group, an optionally substituted aryl group, and an optionally substituted alicyclic group are represented, and these may be the same or different.

As the alkyl group which may be substituted, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms is preferable. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 3-methoxypropyl group, 4-chlorobutyl group, 2-diethylaminoethyl group and the like.

The alkenyl group which may be substituted is preferably a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, for example, a vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group. , Dodecynyl group, prenyl group and the like.

Examples of the optionally substituted aryl group include phenyl group, tolyl group, xylyl group, 4-ethylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-methoxyphenyl group, 4 -A diethylaminophenyl group, 2-methylphenyl group, 2-methoxyphenyl group, naphthyl group, 4-methylnaphthyl group, etc. are mentioned.

Examples of the optionally substituted aralkyl group include a benzyl group, a phenethyl group, a propiophenyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, and a p-methoxybenzyl group.

Examples of the alicyclic group which may be substituted include a cyclohexyl group, a 4-methylcyclohexyl group, a cyclopentyl group, and a cycloheptyl group.

In the curing accelerator according to the present invention, the borate salt is not particularly limited. For example, tetrafluoroborate, tetraphenylborate, tetraethylborate, tetrabutylborate, tetrakis (4-methylphenyl) borate, tetrakis (4 -Tert-butylphenyl) borate, tetrakis (4-fluorophenyl) borate, tetrakis (4-methoxyphenyl) borate, tetrakis (2,3,4,5,6-pentafluorophenyl) borate, tetrakis [3,5- Bis (trifluoromethyl) phenyl] borate, n-butyltriphenylborate, n-butyltris-4-tert-butylphenylborate, n-butyltrinaphthylborate and the like.

Among these, the borate salt is an aryl group that may be substituted as described above, and one of the alkyl groups that is substituted as described above, among R ^{1 to} R ⁴ , It is preferable because it is considered that it traps radical species that are eliminated as radicals and cause yellowing substances.
Specific examples of such a borate salt include n-butyltriphenylborate, n-butyltris-4-tert-butylphenylborate, n-butyltrinaphthylborate and the like.

In the curing accelerator according to the present invention, X ⁺ in the general formula (1) represents a cation having N, S, or P as a central element. Examples of such cations include ammonium cation, phosphonium cation, sulfonium cation, imidazolium cation, pyridinium cation, pyrrolidinium cation, piperidinium cation, and 1,5-diazabicyclo [4,3,0] nonene-5. The quaternary nitrogen cation of 6-dibutylamino-1,8-diazabicyclo [5,4,0] undecene-7, 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,4 , 0] undecene-7 quaternary nitrogen cation and the like.

Examples of the ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetra-n-propylammonium cation, tetra-n-butylammonium cation, tetra-n-pentylammonium cation, tetra-n-octylammonium cation, tetra -N-dodecyl ammonium cation, tetra-n-tetradecyl ammonium cation, tetra-n-octadecyl ammonium cation, tetrakis-2-hydroxyethylammonium cation, tetrakis-3-hydroxypropylammonium cation, tetrakis-2-cyanoethylammonium cation, Triethyloctylammonium cation, tri-n-butylmethylammonium cation, tri-n-butyl Ruoctylammonium cation, tri-n-butyldodecylammonium cation, tri-n-hexadecylammonium cation, tri-2-hydroxyethyloctylammonium cation, tri-2-hydroxyethyldodecylammonium cation, tri-2-hydroxyethylhexa Decyl decyl ammonium cation, tri-3-hydroxyethyl octyl ammonium cation, tri-3-hydroxyethyl dodecyl ammonium cation, tri-3-hydroxyethyl hexadecyl decyl ammonium cation, tri-2-cyanoethyl octyl ammonium cation, tri-2- Cyanoethyl dodecyl ammonium cation, tri-2-cyanoethyl hexadecyl decyl ammonium cation, allyltriethylan Nium cation, allyltri-n-propylammonium cation, allyltri-n-butylammonium cation, allyltri-n-octylammonium cation, trimethyl [3- (triethoxysilyl) propyl] ammonium cation, cyclohexyltrimethylammonium cation, tetraphenylammonium cation Benzyltrimethylammonium cation, benzyltriethylammonium cation, benzyltri-n-butylammonium cation, 3- (trifluoromethyl) phenyltrimethylammonium cation, phenyltrimethylammonium cation, benzyltriphenylammonium cation and the like.

Examples of the phosphonium cation include a tetramethylphosphonium cation, a tetraethylphosphonium cation, a tetra-n-propylphosphonium cation, a tetra-n-butylphosphonium cation, a tetra-n-pentylphosphonium cation, a tetra-n-octylphosphonium cation, and a tetra -N-dodecylphosphonium cation, tetra-n-tetradecylphosphonium cation, tetra-n-octadecylphosphonium cation, tetrakis-2-hydroxyethylphosphonium cation, tetrakis-3-hydroxypropylphosphonium cation, tetrakis-2-cyanoethylphosphonium cation, Triethyloctylphosphonium cation, tri-n-butylmethylphosphonium cation, tri-n-butyl Ruoctylphosphonium cation, tri-n-butyldodecylphosphonium cation, tri-n-hexadecylphosphonium cation, tri-2-hydroxyethyloctylphosphonium cation, tri-2-hydroxyethyldodecylphosphonium cation, tri-2-hydroxyethylhexa Decylphosphonium cation, tri-3-hydroxyethyloctylphosphonium cation, tri-3-hydroxyethyldodecylphosphonium cation, tri-3-hydroxyethylhexadecylphosphonium cation, tri-2-cyanoethyloctylphosphonium cation, tri-2-cyanoethyldodecyl Phosphonium cation, tri-2-cyanoethylhexadecylphosphonium cation, allyltriethylphosphonium cation, Riltri-n-propylphosphonium cation, allyltri-n-butylphosphonium cation, allyltri-n-octylphosphonium cation, tetraphenylphosphonium cation, benzyltrimethylphosphonium cation, benzyltriethylphosphonium cation, benzyltri-n-butylphosphonium cation, 3- ( (Trifluoromethyl) phenyltrimethylphosphonium cation, phenyltrimethylphosphonium cation, benzyltriphenylphosphonium cation and the like.

Examples of the sulfonium cation include a triphenylsulfonium cation, a trimethylsulfonium cation, and a dimethylphenylsulfonium cation.
Examples of the imidazolium cation include 1,3-dimethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, and 1-butyl-3-methylimidazolium cation. 1-ethyl-3-hexylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-hexadecyl-3 -Methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-vinyl-3-methylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-propyl-2,3-dimethyl Imidazolium cation, -Butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, 1-methyl-3- (3,3,4,4,5,5,6,6,7, 7,8,8,8-tridecafluorooctyl) imidazolium cation, 1-butyl-3- (3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctyl) imidazolium cation, 1-methyl-3-allylimidazolium cation, 1-ethyl-3-allylimidazolium cation, 1-propyl-3-allylimidazolium cation, 1-butyl-3-allylimidazolo Rium cation, 1-pentyl-3-allylimidazolium cation, 1-methyl-3-allylimidazolium cation, 1-hexylpyridinium cation, 1-helium Chill 3 allylimidazolium cation, 1-octyl-3-allylimidazolium cation, 1-allyl-3-allylimidazolium cation, and the like.

Examples of the pyridinium cation include 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-ethyl-3-methylpyridinium cation, and 1-ethyl-3- (hydroxymethyl). Examples thereof include a pyridinium cation, a 1-propyl-3-methylpyridinium cation, and a 1-butyl-3-methylpyridinium cation.
Examples of the pyrrolidinium cation include 1-butyl-1-methylpyrrolidinium cation.
Examples of the piperidinium cation include 1-methyl-1-propylpiperidinium cation.

In particular, X ⁺ in the general formula (1) preferably has a cation structure represented by the following general formula (2). By using the curing accelerator having such a cation structure, the thermosetting composition for optical semiconductors of the present invention is more excellent in heat resistance. This is presumably because even if cations are thermally decomposed during curing, the basicity of amines and phosphines generated is relatively low, so that the generation of substances that cause coloring during the curing reaction is suppressed.

In the general formula (2), Y ⁺ represents N, S or P, n is 3 or 4, and a plurality of R ⁵ are an optionally substituted alkyl group or an optionally substituted alkenyl. Represents an optionally substituted aralkyl group, an optionally substituted aryl group, an optionally substituted heterocyclic group, an optionally substituted alicyclic group, and an optionally substituted silyl group. These may be the same as or different from each other.

As the alkyl group which may be substituted, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms is preferable. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 3-methoxypropyl group, 4-chlorobutyl group, 2-diethylaminoethyl group and the like.

The alkenyl group which may be substituted is preferably a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, for example, a vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group. , Dodecynyl group, prenyl group and the like.

Examples of the optionally substituted aryl group include phenyl, tolyl, xylyl, 4-ethylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-diethylaminophenyl, and 2-methyl. Examples include phenyl, 2-methoxyphenyl, naphthyl, 4-methylnaphthyl group and the like.

Examples of the optionally substituted aralkyl group include a benzyl group, a phenethyl group, a propiophenyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, and a p-methoxybenzyl group.

Examples of the optionally substituted heterocyclic group include a pyridyl group, a quinolyl group, a methylpyridyl group, an indolyl group, and the like.

Examples of the alicyclic group which may be substituted include a cyclohexyl group, a 4-methylcyclohexyl group, a cyclopentyl group, and a cycloheptyl group.

Examples of the optionally substituted heterocyclic group include a 3- (triethoxysilyl) propyl group.

Specific examples of the cation structure represented by the general formula (2) are not particularly limited, and examples thereof include an ammonium cation, a phosphonium cation, and a sulfonium cation.

Examples of the ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetra-n-propylammonium cation, tetra-n-butylammonium cation, tetra-n-pentylammonium cation, tetra-n-octylammonium cation, tetra -N-dodecyl ammonium cation, tetra-n-tetradecyl ammonium cation, tetra-n-octadecyl ammonium cation, tetrakis-2-hydroxyethylammonium cation, tetrakis-3-hydroxypropylammonium cation, tetrakis-2-cyanoethylammonium cation, Triethyloctylammonium cation, tri-n-butylmethylammonium cation, tri-n-butyl Ruoctylammonium cation, tri-n-butyldodecylammonium cation, tri-n-hexadecylammonium cation, tri-2-hydroxyethyloctylammonium cation, tri-2-hydroxyethyldodecylammonium cation, tri-2-hydroxyethylhexa Decyl decyl ammonium cation, tri-3-hydroxyethyl octyl ammonium cation, tri-3-hydroxyethyl dodecyl ammonium cation, tri-3-hydroxyethyl hexadecyl decyl ammonium cation, tri-2-cyanoethyl octyl ammonium cation, tri-2- Cyanoethyl dodecyl ammonium cation, tri-2-cyanoethyl hexadecyl decyl ammonium cation, allyltriethylan Nium cation, allyltri-n-propylammonium cation, allyltri-n-butylammonium cation, allyltri-n-octylammonium cation, trimethyl [3- (triethoxysilyl) propyl] ammonium cation, cyclohexyltrimethylammonium cation, tetraphenylammonium cation Benzyltrimethylammonium cation, benzyltriethylammonium cation, benzyltri-n-butylammonium cation, 3- (trifluoromethyl) phenyltrimethylammonium cation, phenyltrimethylammonium cation, benzyltriphenylammonium cation and the like.

Examples of the phosphonium cation include tetramethylphosphonium cation, tetraethylphosphonium cation, tetra-n-propylphosphonium cation, tetra-n-butylphosphonium cation, tetra-n-pentylphosphonium cation, tetra-n-octylphosphonium cation, tetra -N-dodecylphosphonium cation, tetra-n-tetradecylphosphonium cation, tetra-n-octadecylphosphonium cation, tetrakis-2-hydroxyethylphosphonium cation, tetrakis-3-hydroxypropylphosphonium cation, tetrakis-2-cyanoethylphosphonium cation, Triethyloctylphosphonium cation, tri-n-butylmethylphosphonium cation, tri-n-butyl Ruoctylphosphonium cation, tri-n-butyldodecylphosphonium cation, tri-n-hexadecylphosphonium cation, tri-2-hydroxyethyloctylphosphonium cation, tri-2-hydroxyethyldodecylphosphonium cation, tri-2-hydroxyethylhexa Decylphosphonium cation, tri-3-hydroxyethyloctylphosphonium cation, tri-3-hydroxyethyldodecylphosphonium cation, tri-3-hydroxyethylhexadecylphosphonium cation, tri-2-cyanoethyloctylphosphonium cation, tri-2-cyanoethyldodecyl Phosphonium cation, tri-2-cyanoethylhexadecylphosphonium cation, allyltriethylphosphonium cation, Riltri-n-propylphosphonium cation, allyltri-n-butylphosphonium cation, allyltri-n-octylphosphonium cation, tetraphenylphosphonium cation, benzyltrimethylphosphonium cation, benzyltriethylphosphonium cation, benzyltri-n-butylphosphonium cation, 3- ( (Trifluoromethyl) phenyltrimethylphosphonium cation, phenyltrimethylphosphonium cation, benzyltriphenylphosphonium cation and the like.
Examples of the sulfonium cation include a triphenylsulfonium cation, a trimethylsulfonium cation, and a dimethylphenylsulfonium cation.

In the curing accelerator according to the present invention, particularly preferable combinations of the above-described borate salt and cation include, for example, tetraethylammonium u-butyltriphenylborate, tetraethylammonium u-butyltris-4-tert-butylphenylborate, tetraethyl Ammonium n-butyltrisnaphthyl borate, tetra-n-butylammonium n-butyltriphenylborate, tetra-n-butylammonium n-butyltris-4-tert-butylphenylborate, tetra-n-butylammonium n-butyltrisnaphthyl Borate, tetraethylphosphonium n-butyltriphenylborate, tetraethylphosphonium n-butyltris-4-tert-butylphenylborate, tetraethylphosphonium n Butyltrisnaphthylborate, tetra-n-butylphosphonium n-butyltriphenylborate, tetra-n-butylphosphonium n-butyltris-4-tert-butylphenylborate, tetra-n-butylphosphonium n-butyltrisnaphthylborate, etc. Can be mentioned.

In the thermosetting composition for optical semiconductors of the present invention, the content of the curing accelerator according to the present invention is a silicone resin having a cyclic ether-containing group in the molecule described later (containing a bifunctional silicone resin described later). In this case, a preferable lower limit is 0.01 part by weight and a preferable upper limit is 5 parts by weight with respect to 100 parts by weight of a total of a later-described silicone resin and a later-described bifunctional silicone resin. When the content of the curing accelerator is less than 0.01 parts by weight, the heat resistance of the cured product of the curable composition for optical semiconductors of the present invention may be insufficient. When the amount of outgas resulting from the curing accelerator according to the present invention generated from the cured product of the curable composition for optical semiconductor of the present invention is increased and used as a sealant for an optical semiconductor element such as an LED, the outgas As a result, the light emission performance of the optical semiconductor element may be deteriorated or deteriorated. The minimum with more preferable content of the said hardening accelerator is 0.05 weight part, and a more preferable upper limit is 2 weight part.

The thermosetting composition for optical semiconductors of the present invention contains a silicone resin having a cyclic ether-containing group in the molecule.
In the thermosetting composition for optical semiconductors of the present invention, the silicone resin is not particularly limited as long as it is a silicone resin having one or more cyclic ether-containing groups in the molecule. What contains the resin component represented by Formula (3) is preferable.

In the general formula (3), a, b, c and d are a / (a + b + c + d) = 0 to 0.2, b / (a + b + c + d) = 0.3 to 1.0, c / (a + b + c + d) = 0 to 0.5 and d / (a + b + c + d) = 0 to 0.3 are satisfied, and at least one of R ^{6 to} R ¹¹ represents a cyclic ether-containing group, and R ^{6 to} R ¹¹ other than the cyclic ether-containing group. Represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different.

When the silicone resin contains a resin component having an average composition formula represented by the general formula (3), the thermosetting composition for an optical semiconductor according to the present invention is suitable for light having a short wavelength in a blue to ultraviolet region. Light-emitting element for optical semiconductor elements such as light-emitting diodes, which has high transparency and is excellent in heat resistance and light resistance without causing heat generation or discoloration due to light emission of the light-emitting element to be sealed when used as a sealing agent for optical semiconductor elements. When this is sealed, the optical semiconductor element has excellent adhesion to the housing material or the like.
In addition, the said average composition formula is represented with the said Formula (3) not only when the thermosetting composition for optical semiconductors of this invention contains only the resin component represented by the said Formula (3). In the case of a mixture containing resin components having various structures, the average of the composition of the resin components contained also means the case represented by the above formula (3).

In the general formula (3), at least one of R ^{6 to} R ¹¹ represents a cyclic ether-containing group.
The cyclic ether-containing group is not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane group. Of these, a glycidyl group and / or an epoxycyclohexyl group are preferable.
In the present specification, the cyclic ether-containing group only needs to contain a cyclic ether group as at least a part of the group, and includes, for example, other skeletons such as an alkyl group and an alkyl ether group and a cyclic ether group. Means a group which may be

The glycidyl group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl Group, 4-glycidoxybutyl group and the like.

The epoxycyclohexyl group is not particularly limited, and examples thereof include 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, and the like.

In the silicone resin, a preferable lower limit of the content of the cyclic ether-containing group is 0.1 mol%, and a preferable upper limit is 50 mol%. When the content of the cyclic ether-containing group is less than 0.1 mol%, the reactivity between the silicone resin and the thermosetting agent described later is remarkably lowered, and the thermosetting composition for optical semiconductors of the present invention is cured. May be insufficient. When the content of the cyclic ether-containing group exceeds 50 mol%, the number of cyclic ether-containing groups not involved in the reaction between the silicone resin and the thermosetting agent increases, and the heat resistance of the thermosetting composition for optical semiconductors of the present invention. May decrease. The more preferable lower limit of the content of the cyclic ether-containing group is 1 mol%, the more preferable upper limit is 40 mol%, the still more preferable lower limit is 5 mol%, and the still more preferable upper limit is 30 mol%.
In addition, in this specification, content of the said cyclic ether containing group means the quantity of the said cyclic ether containing group contained in the average composition of the said silicone resin component.

In the silicone resin represented by the general formula (3), R ^{6 to} R ¹¹ other than the cyclic ether-containing group are linear, branched or cyclic hydrocarbons having 1 to 8 carbon atoms or fluorinated products thereof. To express.

The linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n- Hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, phenyl group Etc.

In the silicone resin represented by the general formula (3), the structural unit represented by (R ⁹ R ¹⁰ SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following general formula (3-2) That is, a structure in which one of oxygen atoms bonded to a silicon atom in a bifunctional structural unit constitutes a hydroxyl group or an alkoxy group.

In the general formula (3-2), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the silicone resin represented by the general formula (3), the structural unit represented by (R ¹¹ SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following general formula (3-3). Or a structure represented by (3-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxyl group or an alkoxy group, or silicon in a trifunctional structural unit It includes a structure in which one of oxygen atoms bonded to an atom constitutes a hydroxyl group or an alkoxy group.

In the general formulas (3-3) and (3-4), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the silicone resin represented by the general formula (3), the structural unit represented by (SiO _4/2 ) (hereinafter also referred to as tetrafunctional structural unit) is represented by the following general formula (3-5), ( 3-6) or (3-7), that is, a structure in which three or two oxygen atoms bonded to a silicon atom in the tetrafunctional structural unit constitute a hydroxyl group or an alkoxy group, or four It includes a structure in which one of oxygen atoms bonded to a silicon atom in the functional structural unit constitutes a hydroxyl group or an alkoxy group.

In the general formulas (3-5), (3-6) and (3-7), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. To express.

In the general formulas (3-2) to (3-7), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, and an n-propoxy group. N-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

In the general formula (3), a is a numerical value that satisfies the relationship that the lower limit of a / (a + b + c + d) is 0 and the upper limit is 0.2. When it exceeds 0.2, the heat resistance of the thermosetting composition for optical semiconductors of the present invention may deteriorate. A more preferred upper limit is 0.15, and a more preferred upper limit is 0.1.

In the general formula (3), b is a numerical value that satisfies the relationship that the lower limit of b / (a + b + c + d) is 0.3 and the upper limit is 1.0. If it is less than 0.3, the cured product of the thermosetting composition for optical semiconductors of the present invention becomes too hard, and when used as a semiconductor peripheral member such as a sealant, die bonding material, underfill, etc. Cracks or the like may occur between the adherends. A more preferred lower limit is 0.4, and even more preferred is 0.5.

In the general formula (3), c is a numerical value that satisfies the relationship that c / (a + b + c + d) has a lower limit of 0 and an upper limit of 0.5. If it exceeds 0.5, it may be difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention, and adhesion may be deteriorated. A more preferred upper limit is 0.4, and even more preferred is 0.3.

Furthermore, in the general formula (3), d is a numerical value that satisfies the relationship that the lower limit of d / (a + b + c + d) is 0 and the upper limit is 0.3. When it exceeds 0.3, it may be difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention, or adhesion may be deteriorated. A more preferred upper limit is 0.2, and even more preferred is 0.1.

When the ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) is performed on the silicone resin represented by the general formula (3) based on tetramethylsilane (hereinafter referred to as TMS), there is a slight variation depending on the type of substituent. Although seen, a peak corresponding to the structural unit represented by (R ⁶ R ⁷ R ⁸ SiO _1/2 ) _a in the general formula (3) appears in the vicinity of +10 to 0 ppm, and ( R ⁹ R ¹⁰ SiO _2/2 ) Each peak corresponding to the bifunctional structural unit of ( _b ) and (3-2) appears in the vicinity of −10 to −30 ppm, and (R ¹¹ SiO _{3/2 of the} above general formula (3)). ) Each peak corresponding to the trifunctional structural units of _c , (3-3) and (3-4) appears in the vicinity of −50 to −70 ppm, and (SiO _4/2 ) _{d of} the above general formula (3), ( 3-5), tetrafunctionality of (3-6) and (3-7) Each peak corresponding to a granulation unit appears in the vicinity of -90 to-120 ppm.
Therefore, it is possible to measure the ratio of the general formula (3) by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.
However, when the ²⁹ Si-NMR measurement based on the TMS cannot be distinguished from the functional structural unit of the general formula (3), not only the ²⁹ Si-NMR measurement result but also ¹ H-NMR or By using the results measured by ¹⁹ F-NMR or the like as necessary, the ratio of structural units can be identified.

The silicone resin preferably has a structural unit of R ¹² R ¹³ SiO _{2/2 and} a structural unit of R ¹⁴ SiO _3/2 and / or a structural unit of SiO _4/2 . By having a structural unit of R ¹² R ¹³ SiO _2/2, a structural unit of R ¹⁴ SiO _3/2 and / or a structural unit of SiO _4/2 , the thermosetting composition for optical semiconductors of the present invention is Furthermore, it has the outstanding heat resistance, and can prevent problems, such as film loss under use conditions. In addition, it is preferable to appropriately include the SiO _4/2 structural unit because the viscosity of the thermosetting composition for optical semiconductors of the present invention can be easily adjusted to a desired range. The above silicone resin, if it contains only structural units of R ¹² R ¹³ SiO _2/2, for an optical semiconductor thermosetting composition of the present invention, or a insufficient heat resistance and three-dimensional Crosslinking is likely to be insufficient, and film loss may occur after curing.

At least one of the above R ^{12 to} R ¹⁴ is a cyclic ether-containing group, and R ^{12 to} R ¹⁴ other than the cyclic ether-containing group is a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or It represents the fluorinated product, and these may be the same or different. Such ^R 12 ^{to R 14,} for example, include the same ^R 9 ^{to R 11} described above. Furthermore, the structural unit of R ¹² R ¹³ SiO _2/2 , the structural unit of R ¹⁴ SiO _3/2 , and the structural unit of SiO _4/2 include the above general formulas (3-2) to (3-7). The same structure as the bifunctional structural unit, trifunctional structural unit and tetrafunctional structural unit represented by
In addition, the film reduction in this specification means the phenomenon in which the thickness of hardened | cured material reduces gradually when exposed to a high temperature state.

In the thermosetting composition for optical semiconductors of the present invention, having a structural unit of R ¹² R ¹³ SiO _2/2, a structural unit of R ¹⁴ SiO _3/2 and / or a structural unit of SiO _4/2 A resin having a structural unit of R ¹² R ¹³ SiO _{2/2 and} a structural unit of R ¹⁴ SiO _3/2 and / or a structural unit of SiO _4/2 in a skeleton of one molecule in an uncured state A mixture of a resin having a structural unit of only R ¹² R ¹³ SiO _2/2 and a resin having a structural unit of R ¹⁴ SiO _3/2 and / or a resin having a structural unit of SiO _4/2 may be used. May be. Among them, a resin having a structural unit of R ¹² R ¹³ SiO _{2/2 and} a structural unit of R ¹⁴ SiO _3/2 in the skeleton of one molecule of the resin is preferable.

The resin having a structural unit of R ¹² R ¹³ SiO _{2/2 and} a structural unit of R ¹⁴ SiO _3/2 in the skeleton of one molecule is represented by a = d = 0 in the general formula (3). Can be used.
In this case, the preferable lower limit of b / (a + b + c + d) is 0.5, the preferable upper limit is 0.95, the more preferable lower limit is 0.6, and the more preferable upper limit is 0.9 (hereinafter, condition (1)) Also called). The preferable lower limit of c / (a + b + c + d) is 0.05, the preferable upper limit is 0.5, the more preferable lower limit is 0.1, and the more preferable upper limit is 0.4 (hereinafter also referred to as condition (2)).

The silicone resin preferably contains a resin component whose average composition formula is represented by the following general formula (4), (5) or (6). In addition, when the said silicone resin contains the resin component by which an average composition formula is represented by the following general formula (4), (5) or (6), the sealing compound for optical semiconductors of this invention is the following as a silicone resin. Not only the case of containing only the resin component represented by the general formula (4), (5) or (6), but also a mixture containing resin components of various structures, When the average is taken, it also means a case represented by the following general formula (4), (5) or (6).

In general formula (4), e and f satisfy e / (e + f) = 0.5 to 0.95, f / (e + f) = 0.05 to 0.5, and R ^{15 to} R ¹⁷ are at least 1 represents a cyclic ether-containing group, and R ^{15 to} R ¹⁷ other than the cyclic ether-containing group represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. They may be the same or different.

In the general formula (5), g, h and i satisfy (g + h) / (g + h + i) = 0.5 to 0.95, i / (g + h + i) = 0.05 to 0.5, and R ^{18 to} R ²² represents at least one cyclic ether-containing group, and R ^{18 to} R ² other than the cyclic ether-containing group represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, These may be the same as each other or different. However, (R ¹⁸ R ¹⁹ SiO _2/2 ) and (R ²⁰ R ²¹ SiO _2/2 ) have different structures.

In the general formula (6), j, k and l satisfy j / (j + k + l) = 0.5 to 0.95, (k + l) / (j + k + l) = 0.05 to 0.5, and R ^{23 to} R ²⁶ represents at least one cyclic ether-containing group, and R ^{23 to} R ²⁶ other than the cyclic ether-containing group represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, These may be the same as each other or different. However, (R ²⁵ SiO _3/2 ) and (R ²⁶ SiO _3/2 ) have different structures.

In the general formulas (4) to (6), the cyclic ether-containing group preferably contains either one of a glycidyl group or an epoxycyclohexyl group.

The silicone resin preferably has a cyclic ether-containing group in the trifunctional structural unit among the structural units represented by the general formulas (4) to (6). That is, R ^{17 in} the general formula (4), R ²² in the general formula (5), and R ²⁵ and / or R ²⁶ in the general formula (6) are preferably cyclic ether-containing groups.
When the cyclic ether-containing group is contained in the trifunctional structure, the cyclic ether-containing group is likely to be exposed outside the polysiloxane skeleton of the silicone resin, and the cured product of the encapsulant for optical semiconductors of the present invention is sufficiently three-dimensional. Thus, it is possible to suitably prevent the film from being reduced in the cured product.

In the thermosetting composition for optical semiconductors of the present invention, the silicone resin preferably has a cyclic ether-containing group and a polysiloxane skeleton bonded via a silicon-carbon bond. Since the cyclic ether-containing group and the polysiloxane skeleton are bonded via a silicon-carbon bond, the thermosetting composition for an optical semiconductor of the present invention is excellent in heat resistance, light resistance, and film reduction. This is preferable. For example, when a resin obtained by an addition reaction in which an OH group is reacted is used, a cyclic ether-containing group and a polysiloxane skeleton are bonded via a silicon-oxygen bond. In addition to the fact that sufficient light resistance and light resistance may not be obtained, film loss may be deteriorated.

The silicone resin preferably contains an alkoxy group with a lower limit of 0.5 mol% and an upper limit of 10 mol%. By containing such an alkoxy group, heat resistance and light resistance are drastically improved. This is presumably because the curing rate can be drastically improved by containing an alkoxy group in the silicone resin, thereby preventing thermal degradation during curing.

Further, since the curing speed is dramatically improved as described above, sufficient curability can be obtained even when the amount of the curing accelerator added is relatively small.

When the content of the alkoxy group is less than 0.5 mol%, the curing rate may not be sufficiently obtained, and the heat resistance may be deteriorated. When the content exceeds 10 mol%, the storage stability of the silicone resin or the composition is increased. May deteriorate or heat resistance may deteriorate. The minimum with more preferable content of the said alkoxy group is 1 mol%, and a more preferable upper limit is 5 mol%.

In the present specification, the content of the alkoxy group means the amount of the alkoxy group contained in the average composition of the silicone resin component.

The silicone resin preferably does not contain a silanol group. The silanol group is not preferable because the storage stability of the polymer is remarkably deteriorated and the storage stability when the resin composition is obtained is also remarkably deteriorated. Such silanol groups can be reduced by heating under vacuum, and the amount of silanol groups can be measured using infrared spectroscopy or the like.

In the thermosetting composition for optical semiconductors of the present invention, the preferable lower limit of the number average molecular weight (Mn) of the silicone resin is 1000, and the preferable upper limit is 50,000. When the number average molecular weight (Mn) of the silicone resin is less than 1000, the volatile component increases at the time of thermosetting, and the film loss increases when used as a sealant, which is not preferable. When the number average molecular weight (Mn) of the silicone resin exceeds 50,000, it is not preferable because it becomes difficult to adjust the viscosity. The minimum with a more preferable number average molecular weight (Mn) of the said silicone resin is 1500, and a more preferable upper limit is 15000.
In this specification, the number average molecular weight (Mn) is a value obtained by using polystyrene as a standard using gel permeation chromatography (GPC), and is a measuring device manufactured by Waters (manufactured by Showa Denko KK as a column). It means a value measured using two Shodex GPC LF-804 (length: 300 mm), measurement temperature is 40 ° C., flow rate is 1 mL / min, solvent is tetrahydrofuran, and standard material is polystyrene.

The method for synthesizing the silicone resin is not particularly limited. For example, (1) a method of introducing a substituent by a hydrosilation reaction of a silicone resin (a) having a SiH group and a vinyl compound having a cyclic ether group, (2) A method in which a siloxane compound and a siloxane compound having a cyclic ether-containing group are subjected to a condensation reaction may be mentioned.

In the above method (1), the hydrosilylation reaction is a method of reacting a SiH group and a vinyl group in the presence of a catalyst as necessary.

As the silicone resin (a) having the SiH group, after reacting the vinyl compound having a SiH group in the molecule and the cyclic ether-containing group, the structure represented by the general formula (3) described above, Preferably, a structure having a structure represented by any one of the above general formulas (4) to (6) may be used.

The vinyl compound having a cyclic ether-containing group is not particularly limited as long as it is a vinyl compound having one or more cyclic ether-containing groups in the molecule. For example, vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate , Epoxy group-containing compounds such as butadiene monooxide, vinylcyclohexene oxide, and allylcyclohexene oxide. In addition, the said (meth) acryl means acryl or methacryl.

Examples of the catalyst used as necessary during the hydrosilylation reaction include, for example, a simple substance of Group 8 metal, a metal solid supported on a carrier such as alumina, silica, carbon black, and the like. Examples include salts and complexes. Specifically, as the metal of Group 8 of the periodic table, for example, platinum, rhodium, and ruthenium are preferable, and platinum is particularly preferable.
As the hydrosilation reaction catalyst using platinum, for example, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone complex, platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, And dicarbonyldichloroplatinum.

The reaction conditions during the hydrosilylation reaction are not particularly limited, but the reaction temperature is preferably 10 ° C. and the preferred upper limit is 200 ° C. in consideration of the reaction rate and yield. A more preferred lower limit is 30 ° C., a more preferred upper limit is 150 ° C., a still more preferred lower limit is 50 ° C., and a still more preferred upper limit is 120 ° C.

Moreover, the said hydrosilylation reaction may be performed without a solvent and may be performed using a solvent.
The solvent is not particularly limited. For example, ether solvents such as dioxane, tetrahydrofuran and propylene glycol monomethyl ether acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, hydrocarbon solvents such as toluene, xylene and cyclohexane, acetic acid Examples thereof include ester solvents such as ethyl and butyl acetate, and alcohol solvents such as butyl cellosolve and butyl carbitol. Of these, ether solvents, ester solvents, ketone solvents, and hydrocarbon solvents are preferred. preferable.

In the method (2), examples of the siloxane compound include alkoxysilanes having a siloxane unit represented by the following general formulas (7), (8), (9), and (10), or partial hydrolysates thereof.

In the general formulas (7) to (10), R ^{27 to} R ³² represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR is linear or branched. Represents an alkoxy group having 1 to 4 carbon atoms.

In the general formulas (7) to (10), when R ^{27 to} R ³² are linear or branched hydrocarbons having 1 to 8 carbon atoms, specifically, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group Group, t-pentyl group, isohexyl group, cyclohexyl group, phenyl group and the like.

In the general formulas (7) to (10), the linear or branched alkoxy group having 1 to 4 carbon atoms represented by OR is specifically, for example, a methoxy group, an ethoxy group, or n -Propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

Specific examples of the compound represented by the general formula (7) include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane.

Specific examples of the compound represented by the general formula (8) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, isopropyl (methyl) dimethoxysilane, and cyclohexyl (methyl) dimethoxy. Silane, methyl (phenyl) dimethoxysilane, etc. are mentioned.

Specific examples of the compound represented by the general formula (9) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, Examples thereof include phenyltrimethoxysilane.

Specific examples of the compound represented by the general formula (10) include tetramethoxysilane and tetraethoxysilane.

Examples of the siloxane compound having a cyclic ether-containing group include an alkoxysilane having a cyclic ether-containing group represented by the following general formula (11), (12) or (13) or a partial hydrolyzate thereof.

In the general formulas (11), (12) and (13), at least one of R ³³ , R ³⁴ and R ³⁵ , R ³⁶ and / or R ³⁷ and R ³⁸ is a cyclic ether group, and a cyclic ether-containing group R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ other than those represent a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR represents a linear or branched alkoxy having 1 to 4 carbon atoms. Represents a group.

In general formulas (11), (12) and (13), the cyclic ether-containing group represented by at least one of R ³³ , R ³⁴ and R ³⁵ , R ³⁶ and / or R ³⁷ and R ³⁸ is particularly limited. For example, a glycidyl-containing group, an epoxycyclohexyl-containing group, an oxetane-containing group and the like can be mentioned. Of these, a glycidyl-containing group and / or an epoxycyclohexyl-containing group are preferable.

The glycidyl-containing group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy A propyl group, 4-glycidoxybutyl group, etc. are mentioned.

The epoxycyclohexyl-containing group is not particularly limited, and examples thereof include 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group.

In the general formulas (11) and (12), R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ other than the cyclic ether-containing group are specifically, for example, a methyl group, an ethyl group, and n-propyl. Group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t -A pentyl group, an isohexyl group, a cyclohexyl group, a phenyl group, etc. are mentioned.

In the general formulas (11), (12), and (13), the linear or branched alkoxy group having 1 to 4 carbon atoms represented by OR is specifically, for example, a methoxy group, Examples include ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

Specific examples of the compound represented by the general formula (11) include 3-glycidoxypropyl (dimethyl) methylmethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (dimethyl) methoxysilane, and the like. Is mentioned.

Specific examples of the compound represented by the general formula (12) include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycidoxy. Propyl (methyl) dibutoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl ) Diethoxysilane and the like.

Specific examples of the compound represented by the general formula (13) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl). Examples include ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

In the method (2), as a specific method for the condensation reaction of the siloxane compound and the siloxane compound having a cyclic ether-containing group, for example, the siloxane compound and the compound having a cyclic ether group are mixed with water and an acid. Or the method of making it react in presence of a basic catalyst and synthesize | combining a silicone resin is mentioned.
The siloxane compound may be reacted in advance in the presence of water and an acid or basic catalyst, and then the siloxane compound having a cyclic ether group may be reacted.

The blending amount of the water is not particularly limited as long as it is an amount capable of hydrolyzing the alkoxy group bonded to the silicon atom in the siloxane compound having the cyclic ether-containing group, and is appropriately adjusted.

The acidic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having a cyclic ether-containing group, and examples thereof include inorganic acids, organic acids, acid anhydrides or derivatives thereof, and the like.
Examples of the inorganic acid include phosphoric acid, boric acid, carbonic acid, and the like.
Examples of the organic acid include formic acid, acetic acid, propionic acid, lactic acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, olein An acid etc. are mentioned.

The basic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having a cyclic ether-containing group, and examples thereof include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds. It is done. Of these, potassium-based catalysts and cesium-based catalysts are preferred.
Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, cesium hydroxide and the like.
Examples of the alkali metal alkoxide include sodium-t-butoxide, potassium-t-butoxide, cesium-t-butoxide, and the like.
Examples of the alkali metal silanol compound include a sodium silanolate compound, a potassium silanolate compound, a cesium silanolate compound, and the like.

The addition amount of the acid or basic catalyst is not particularly limited, but the preferred lower limit is 10 ppm and the preferred upper limit is 10,000 ppm with respect to the total amount of the siloxane compound and the siloxane compound having a cyclic ether-containing group, A more preferred lower limit is 100 ppm, and a more preferred upper limit is 5000 ppm.
The acid or basic catalyst may be added as it is, or may be added after dissolving in a small amount of water or the siloxane compound.

In the condensation reaction of the siloxane compound and the siloxane compound having a cyclic ether-containing group, the silicone resin to be synthesized can be prevented from precipitating from the reaction system, and the water and free water due to the condensation reaction can be removed by azeotropic distillation. In view of the above, an organic solvent may be used.
Examples of the organic solvent include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as acetone and methyl isobutyl ketone, and aliphatic organic solvents such as hexane, heptane, and octane. Of these, aromatic organic solvents are preferably used.

Although it does not specifically limit as reaction temperature at the time of the said condensation reaction, A preferable minimum is 40 degreeC and a preferable upper limit is 200 degreeC, A more preferable minimum is 50 degreeC and a more preferable upper limit is 150 degreeC. Moreover, when using the said organic solvent, the said condensation reaction can be easily performed at reflux temperature by using what has a boiling point in the range of 40-200 degreeC as this organic solvent.

From the viewpoint of adjusting the amount of alkoxy groups, it is preferable to synthesize a silicone resin by the above method (2).
In order to bring the alkoxy group into an appropriate range, the above method (2) can bring the alkoxy group into an appropriate range by adjusting the reaction temperature, reaction time, amount of catalyst and amount of water. is there.

The thermosetting composition for optical semiconductors of the present invention preferably contains a bifunctional silicone resin having one or more glycidyl-containing groups in the molecule.
By containing such a bifunctional silicone resin, the thermosetting composition for optical semiconductors of the present invention significantly improves the crack resistance of the cured product. This is because the bifunctional silicone resin has a flexible skeleton compared to the silicone resin in the gap between the crosslinking points generated by the reaction of the cyclic ether-containing group of the silicone resin having a cyclic ether-containing group in the molecule in the cured product. It is guessed that this is because

In the present specification, the glycidyl-containing group only needs to contain a glycidyl group as at least a part of the group, and may contain, for example, another skeleton such as an alkyl group or an alkyl ether group and a glycidyl group. Means group.
The glycidyl-containing group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy A propyl group, 4-glycidoxybutyl group, etc. are mentioned.

As the bifunctional silicone resin, for example, a resin represented by a = c = d = 0 in the general formula (3) can be used. Specifically, the average composition formula is represented by the following general formula (14 It is preferable that the resin component represented by (15) or (15) is contained. When the bifunctional silicone resin contains a resin component represented by the following general formula (14) or (15), the thermosetting composition for optical semiconductors of the present invention has a moderate flexibility. Therefore, the crack resistance is extremely excellent. The bifunctional silicone resin has an average composition formula represented by the following general formula (14) or (15). The thermosetting composition for optical semiconductors of the present invention is represented by the following general formula. When it is a mixture containing not only the resin component represented by (14) or (15) but also a resin component having various structures, the following generality is obtained by taking the average of the composition of the resin component contained: It also means the case represented by formula (14) or (15).
Furthermore, the structure represented by (3-2) is included in the following general formula (14) or (15) having an average composition formula.

In the general formula (14), R ⁴¹ and / or R ⁴² is a glycidyl-containing group, and R ³⁹ and R ⁴⁰ are linear, branched or cyclic hydrocarbons having 1 to 8 carbon atoms or a fluorinated product thereof. These may be the same as or different from each other. When only one of R ^{41 and} R ⁴² is a glycidyl-containing group, the other represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit of m / (m + n) is 0.6, the preferred upper limit is 0.95, the more preferred lower limit is 0.7, the more preferred upper limit is 0.9, and the preferred lower limit of n / (m + n) is 0. 0.05, the preferred upper limit is 0.4, the more preferred lower limit is 0.1, and the more preferred upper limit is 0.3.

In the general formula (15), R ⁴⁷ and / or R ⁴⁸ is a glycidyl-containing group, and R ⁴³ , R ⁴⁴ , R ⁴⁵ , and R ⁴⁶ are linear, branched, or cyclic having 1 to 8 carbon atoms. It represents a hydrocarbon or a fluorinated product thereof, and these may be the same as or different from each other. When only one of R ^{47 and} R ⁴⁸ is a glycidyl-containing group, the other represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit of o + p / (o + p + q) is 0.6, the preferred upper limit is 0.95, the more preferred lower limit is 0.7, the more preferred upper limit is 0.9, and the preferred lower limit of q / (o + p + q) is 0. 0.05, the preferred upper limit is 0.4, the more preferred lower limit is 0.1, and the more preferred upper limit is 0.3.

The preferable lower limit of the number average molecular weight (Mn) of the bifunctional silicone resin is 1500, and the preferable upper limit is 50,000. When the number average molecular weight (Mn) of the bifunctional silicone resin is less than 1500, the cured product of the thermosetting composition for optical semiconductors of the present invention may have insufficient crack resistance, which exceeds 50,000. And, it may be difficult to adjust the viscosity of the thermosetting composition for optical semiconductors of the present invention. The minimum with more preferable number average molecular weight (Mn) of the said bifunctional silicone resin is 2000, and a more preferable upper limit is 20,000.

A method for synthesizing such a bifunctional silicone resin is not particularly limited, and examples thereof include a method similar to the method for synthesizing the above-described silicone resin. That is, a method of introducing a substituent by a hydrosilylation reaction between a silicone resin (b) having a SiH group and a vinyl compound having a glycidyl-containing group (method (3)), having an alkoxysilane compound and a glycidyl-containing group Examples thereof include a method (method (4)) for causing a condensation reaction with an alkoxysilane compound.

When the bifunctional silicone resin is synthesized by the above method (3), the silicone resin (b) having the SiH group may be reacted with a vinyl compound having a SiH group in the molecule and the glycidyl-containing group, for example. Then, the structure represented by the general formula (14) or (15) described above is used.

When the bifunctional silicone resin is synthesized by the method (4), the alkoxysilane compound is not particularly limited, and examples thereof include the same compounds as those of the general formula (8).
Moreover, as an alkoxysilane compound which has the said glycidyl containing group, the thing similar to the compound of the said General formula (12) mentioned above is mention | raise | lifted, for example.

Specific examples of the condensation reaction of the alkoxysilane compound and the alkoxysilane compound having a glycidyl-containing group include, for example, an alkoxysilane compound having a cyclic ether-containing group and an alkoxysilane compound in the case of synthesizing the above-described silicone resin. The same method as that in the case of reacting is mentioned.

In the encapsulant for optical semiconductors of the present invention, the blending amount of the bifunctional silicone resin with respect to the above-described silicone resin is not particularly limited, but a preferred lower limit is 10 parts by weight and a preferred upper limit with respect to 100 parts by weight of the silicone resin. Is 120 parts by weight. When the blending amount of the bifunctional silicone resin is less than 10 parts by weight, the crack resistance of the cured product of the encapsulant for optical semiconductors of the present invention may not be sufficiently exhibited. The hardened | cured material of the sealing compound for optical semiconductors of this invention is inferior in heat resistance, and this hardened | cured material may become easy to yellow in a thermal environment. A more preferable lower limit of the amount of the bifunctional silicone resin is 15 parts by weight, and a more preferable upper limit is 100 parts by weight.

In the encapsulant for optical semiconductors of the present invention, the total of the silicone resin and the bifunctional silicone resin is preferably 90 parts by weight when all resin components are 100 parts by weight. The more preferable lower limit of the total of the silicone resin and the bifunctional silicone resin is 95 parts by weight, the still more preferable lower limit is 97 parts by weight, and the particularly preferable lower limit is 99 parts by weight.

In the sealing compound for optical semiconductors of the present invention, in addition to the resin described above, a curable compound capable of reacting with an epoxy group may be further contained as long as the effects of the present invention are not hindered. Examples of such a compound include compounds having an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, and an epoxy group. Among these, an epoxy compound is preferable. The epoxy compound is not particularly limited, and various conventionally known epoxy compounds can be used.

The blending amount of the other curable compound capable of reacting with the epoxy group is not particularly limited, but a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the total silicone resin described above. A more preferable upper limit of the amount of the other curable compound capable of reacting with the epoxy group is 5 parts by weight, a further preferable upper limit is 3 parts by weight, and a particularly preferable upper limit is 1 part by weight.

The thermosetting composition for optical semiconductors of the present invention contains a thermosetting agent. When a thermosetting agent is contained, the occurrence of yellowing-causing substances can be efficiently prevented as compared with the case where the thermosetting composition for optical semiconductors is cured using only the curing accelerator.
The thermosetting agent is not particularly limited as long as it can react with the cyclic ether-containing group of the silicone resin. For example, ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylamino Aliphatic amines such as piperazine and isophoronediamine, metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenormethane, Aromatic amines such as 4,4'-diaminodiphenol ether, mercaptans such as mercaptopropionic acid esters, terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ) Methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, bromine Phenolic resins such as bisphenol A novolac, polyols hydrogenated aromatic rings of these phenolic resins, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydride Phthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3- Dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride 3-alkylglutaric anhydride having an optionally branched alkyl group having 1 to 8 carbon atoms, such as alicyclic acid anhydrides, 3-methylglutaric anhydride, etc., 2-ethyl-3- 2,3-dialkylglutaric anhydride, 2,4-diethylglutar having a C1-C8 alkyl group which may be branched, such as propylglutaric anhydride Alkyl-substituted glutaric anhydrides such as 2,4-dialkylglutaric anhydride having an alkyl group having 1 to 8 carbon atoms which may be branched, such as anhydride, 2,4-dimethylglutaric anhydride, anhydrous Aromatic acid anhydrides such as phthalic acid, trimellitic anhydride, pyromellitic anhydride, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and salts thereof, the above aliphatic Amines, aromatic amines, and / or amine adducts obtained by reaction of imidazoles with epoxy resins, hydrazines such as adipic acid dihydrazide, dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] Tertiary amines such as undecene-7, organic phosphines such as triphenylphosphine, dicyandiamide, etc. Can be mentioned. Among these, acid anhydrides such as alicyclic acid anhydrides, alkyl-substituted glutaric acid anhydrides, and aromatic acid anhydrides are preferable, and alicyclic acid anhydrides and alkyl-substituted glutaric acid anhydrides are more preferable. And particularly preferably methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, cyclohexane-1,2. , 3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride, 2,4-diethylglutaric anhydride. These thermosetting agents may be used independently and 2 or more types may be used together.

Although it does not specifically limit as a compounding quantity of the said thermosetting agent, The preferable minimum with respect to 100 weight part of the said silicone resin (When the said bifunctional silicone resin is contained, the said silicone resin and the said bifunctional silicone resin are the sum total). Is 1 part by weight, and the preferred upper limit is 200 parts by weight. When the blending amount of the thermosetting agent is within this range, the thermosetting composition for optical semiconductors of the present invention sufficiently undergoes a crosslinking reaction, is excellent in heat resistance and light resistance, and has a sufficiently low moisture permeability. It will be a thing. A more preferable lower limit of the amount of the thermosetting agent is 5 parts by weight, and a more preferable upper limit is 120 parts by weight.

The thermosetting composition for optical semiconductors of the present invention contains an antioxidant. The thermosetting composition for optical semiconductors of the present invention contains a curing accelerator that hardly generates a yellowing cause substance as described above, and further prevents the occurrence by using a thermosetting agent in combination. Yes. However, it cannot be said that the generation of the yellowing cause substance can be completely eliminated in order to obtain better heat resistance. By containing the antioxidant, it is possible to prevent the occurrence of yellowing cause substances more remarkably, and in some cases, the yellowing cause substances that have been generated can be decomposed, and the yellow of the cured product can be decomposed. Changes can be prevented more effectively.
As the antioxidant, for example, a sulfur-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, a phenol-based antioxidant, and the like are preferably used.

Examples of the sulfur-based antioxidant include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), and thiobis (N- Phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryltrithiophosphite, etc. .

Examples of the hindered amine antioxidant include 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)] phenyl-s-triazine, 2,4-diphenyl-6- [2-Hydroxy-4- (2-acryloyloxypropoxy)] phenyl-s-triazine, 2,4-bis (2-hydroxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)] Phenyl-s-triazine, 2,4-bis (2-hydroxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxypropoxy)] phenyl-s-triazine, 2,4-bis (2-methyl) Phenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)] phenyl-s-triazine, 2,4-bis (2 Methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxypropoxy)] phenyl-s-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2 -Acryloyloxyethoxy)] phenyl-s-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxypropoxy)] phenyl-s-triazine, 2,4 -Bis (2-ethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)] phenyl-s-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy -4- (2-acryloyloxyethoxy)] phenyl-s-triazine, 2,4-diphenyl-6- [2-hydroxy-4- (2- Tacryloyloxyethoxy)] phenyl-s-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy)] phenyl-s-triazine, 2,4 -Bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy)] phenyl-s-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy -4- (2-methacryloyloxyethoxy)] phenyl-s-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy)] phenyl-s- Triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) )] Phenyl-s-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)] phenyl-s-triazine, 2,4-bis (2,4-diethoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)] phenyl-s-triazine and 2,4-bis (2,4-diethylphenyl) -6 -[2-hydroxy-4- (2-acryloyloxyethoxy)] phenyl-s-triazine and the like.

Among these antioxidants, phosphorus-based antioxidants and / or phenol-based antioxidants are preferable, and it is preferable to use them together.
As the phosphorus antioxidant, a phosphorus compound having at least one skeleton selected from the group consisting of a phosphite skeleton, a phosphonite skeleton, a phosphate skeleton, and a phosphinate skeleton (hereinafter also simply referred to as a phosphorus compound) is preferable. Used for.
As the phenolic antioxidant, a phenolic compound (hereinafter also simply referred to as a phenolic compound) which is a substituted phenol derivative having an alkyl group at least at the second position is preferably used.
By containing the above phosphorus compound and phenol compound as an antioxidant, the thermosetting composition for optical semiconductors of the present invention is excellent in heat resistance without causing yellowing in the cured product under the use environment. It will be. This is considered to be due to the following reasons.

That is, yellowing that occurs in a cured product of a thermosetting composition containing a conventional epoxy silicone resin is a substance that causes yellowing that is generated from radicals, peroxides, and the like that are generated in a high-temperature environment (use conditions). On the other hand, the phenolic compound has a function of stabilizing radicals generated under a high temperature environment (use conditions), and the phosphorus compound has a function of decomposing the peroxide. . When the thermosetting composition for optical semiconductors of the present invention is used in combination with the phosphorus compound and the phenol compound as an antioxidant, a synergistic effect of the functions of the phenol compound and the phosphorus compound is born, and It is considered that yellowing substances can be efficiently stabilized or decomposed.
More specifically, in the thermosetting composition for optical semiconductors of the present invention, since the phosphorus compound has an oxygen atom adjacent to the phosphorus atom as will be described later, the oxygen atom and the phenol compound. By forming a hydrogen bond with the hydroxyl group, the interaction between the phenol compound and the phosphorus compound is increased. As a result, it is considered that the function of stabilizing and decomposing the yellowing cause substance is enhanced, and the heat resistance is extremely excellent as compared with a thermosetting composition containing a conventional epoxy silicone.
Moreover, it is thought that the phosphorus type compound and the phenol type compound can efficiently prevent the yellowing cause substance derived from the above-described curing accelerator.
Furthermore, when the phosphorus compound has a structure having an aromatic ring, which will be described later, an interaction occurs with the aromatic ring of the phenol compound, and the function of stabilizing and decomposing the yellowing cause substance is further enhanced. It is thought that it is raised.

The phosphorus compound has at least one skeleton selected from the group consisting of a phosphite skeleton, a phosphonite skeleton, a phosphate skeleton, and a phosphinate skeleton. By having these skeletons, the phosphorus compound has an oxygen atom adjacent to the phosphorus atom, and efficiently decomposes the yellowing-causing substance generated in the thermal composition for optical semiconductors of the present invention. Can do. Of these, phosphorus compounds having a phosphite skeleton and / or a phosphonite skeleton are preferable.

The phosphorus compound having the phosphite skeleton is not particularly limited. For example, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol Diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A penta Erythritol diphosphite, dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-) tert Butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di) -Tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) ) Phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6) -Tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

The phosphorus compound having the phosphonite skeleton is not particularly limited, and examples thereof include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert). -Butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-fe Ru-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, Bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, tetrakis (2,4- And di-tert-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite.

The phosphorus compound having the above phosphate skeleton is not particularly limited, and examples thereof include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate. , Tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like.

The phosphorus compound having the phosphinate skeleton is not particularly limited, and examples thereof include 9,10-di-hydro-9-oxa-10-phosphaphenanthroline-10-oxide.

The phosphorus compound is preferably a compound having one or more aromatic rings in the molecule. Such a phosphorus-based antioxidant having one or more aromatic rings in the molecule causes an interaction between the aromatic ring in the molecule and the aromatic ring of the phenolic compound described later, and the phosphorus-based compound described above. The interaction between the compound and the phenolic compound is further increased. As a result, the function of stabilizing or decomposing the yellowing cause substance described above can be further enhanced, and the heat resistance of the thermosetting composition for optical semiconductors of the present invention can be further enhanced.

A commercial item can also be used for the said phosphorus compound. Examples of commercially available phosphorus compounds include, but are not limited to, for example, Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260, Adeastab 522A, Adeastab 1178, Adeastab 1500, Adeastab C, Adeastab 135A, Adeastab 3010, Adeastab TPP (all are made by ADEKA) Sandstub P-EPQ, Hostanox PAR24 (all are made by Clariant) JP-312L, JP- 318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, JPH-3800 (all of which are manufactured by Johoku Chemical Industry Co., Ltd.) That.

Although it does not specifically limit as a compounding quantity of the said phosphorus compound, When the said silicone resin (The said bifunctional silicone resin is contained, the said silicone resin and the said bifunctional silicone resin are added with respect to 100 weight part. Is 0.01 part by weight, and the preferred upper limit is 2.0 parts by weight. When the amount of the phosphorus compound is less than 0.01 parts by weight, the effect of adding the phosphorus compound may not be obtained. Therefore, it is not preferable. A more preferable lower limit of the compounding amount of the phosphorus compound is 0.05 parts by weight, and a more preferable upper limit is 1.0 part by weight.
In addition, in the thermosetting composition for optical semiconductors of this invention, the phosphorus compound mentioned above may be used independently, and 2 or more types may be used together.

The phenolic compound is a substituted phenol derivative having an alkyl group at least at the second position. If the phenolic compound does not have an alkyl group at the second position, the function of stabilizing radicals generated in a high temperature environment will not be observed.
In the present specification, the position numbers of the substituents such as alkyl groups in the substituted phenol derivatives are the second, third, and fourth positions clockwise or counterclockwise with the carbon bonded to the OH group as the first position. , 5 and 6 means the number when numbered. Therefore, it does not necessarily match the IUPAC nomenclature.

The alkyl group in the substituted phenol derivative may have a branch point, and is preferably an alkyl group having 1 to 8 carbon atoms.
Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a tert-pentyl group, and a tert-octyl group. Can be mentioned. Of these, a methyl group, a tert-butyl group, or a tert-pentyl group is preferable.

The substituted phenol derivative having an alkyl group at least at the second position is not particularly limited. For example, a substituted phenol derivative having an alkyl group at the second position and the sixth position, an alkyl group at the second position, At least one selected from the group consisting of a substituted phenol derivative having a methylene group or a methine group at the position and a substituted phenol derivative having an alkyl group at the 2nd and 5th positions is preferably used.

The substituted phenol derivative having an alkyl group at the second position and the sixth position is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl -6-methylphenol, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4 -Hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- -Hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert- Butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and the like.

The substituted phenol derivative having an alkyl group at the 2nd position and a methylene group or a methine group at the 6th position is not particularly limited. For example, 2,2′-butylidenebis (4,6-di-tert-butylphenol ), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6) -Tert-butylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5 -Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate and the like.

The substituted phenol derivative having an alkyl group at the second position and the fifth position is not particularly limited. For example, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis ( 3-methyl-6-tert-butylphenol) and the like.

Moreover, it is preferable that the said phenol type compound is a substituted phenol derivative which does not have an alkyl group in 6th position. By containing such a substituted phenol derivative, the heat resistance of the thermosetting composition for optical semiconductors of the present invention is further improved. This is because the substituted phenol derivative having no alkyl group at the 6-position has a structure having an alkyl group only at one ortho position with respect to the OH group, so that steric hindrance around the OH group can be removed. It is considered that a hydrogen bond between the oxygen atom adjacent to the phosphorus atom of the phosphorus compound and the OH group of the phenol compound is likely to be formed. As a result, it is considered that the interaction between the phosphorus compound and the phenol compound is increased, and the function of stabilizing or decomposing the yellowing cause substance is enhanced.

The substituted phenol derivative having no alkyl group at the 6-position is not particularly limited, and examples thereof include 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di -Tert-pentylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), bis- [3,3-bis -(4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

The phenolic compound preferably has a quaternary carbon-containing group at the fourth position. By containing such a phenolic compound, the heat resistance of the thermosetting composition for optical semiconductors of the present invention is further improved. This is because a phenolic compound having no quaternary carbon at the 4th position generates a yellowing cause substance having a quinone skeleton by an intramolecular reaction or an intermolecular reaction during use under severe conditions. While this may occur, the phenolic compound having a quaternary carbon-containing group at the fourth position is considered to be able to prevent generation of the yellowing cause substance.

The phenolic compound having a quaternary carbon-containing group at the fourth position is not particularly limited. For example, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4′-hydroxy-3′-tert) -Butylphenyl) -butanoic acid] -glycol ester and the like.

Among the phenolic compounds mentioned above, in particular, bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2- [1- ( 2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate is preferably used.

A commercial item can also be used for the said phenolic compound. Commercially available phenolic compounds are not particularly limited. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295 (all of these are manufactured by Ciba Specialty Chemicals), Adeka Stub AO-30, Adeka Stub AO-30 -40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330 (all of which are manufactured by ADEKA), Sumizer GA-80, and Sumizer MDP-S Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumil zer GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, HOSTANOX O3 (all of which are manufactured by Clariant), ANTAGE BHT, ANTAGE W-300, ANTAGE W-400, ANTAGE W500 (above, all manufactured by Kawaguchi Chemical Industry Co., Ltd.), SEENOX 224M, SEENOX 326M (above, both manufactured by Sipro Kasei Co., Ltd.), and the like.

Although it does not specifically limit as a compounding quantity of the said phenolic compound, A preferable minimum is with respect to 100 weight part of the said silicone resin (When the said bifunctional silicone resin is contained, the said silicone resin and the said bifunctional silicone resin are the sum total). Is 0.01 part by weight, and the preferred upper limit is 2.0 parts by weight. When the blending amount of the phenolic compound is less than 0.01 parts by weight, the effect of adding the phenolic compound may not be obtained. When the blending amount exceeds 2.0 parts by weight, the light resistance is significantly lowered. Therefore, it is not preferable. A more preferable lower limit of the compounding amount of the phenol compound is 0.05 parts by weight, and a more preferable upper limit is 1.0 part by weight. In addition, in the thermosetting composition for optical semiconductors of this invention, the phenolic compound mentioned above may be used independently, and 2 or more types may be used together.

When the thermosetting composition for optical semiconductors of the present invention contains the phosphorus compound and the phenol compound, the mixing ratio of the phosphorus compound and the phenol compound is not particularly limited. The preferable lower limit of the “phenolic compound” (weight ratio) is 0.1, and the preferable upper limit is 20. If the “phosphorus compound / phenol compound” (weight ratio) is less than 0.1, the effect of adding the phosphorus compound may not be obtained, and if it exceeds 20, the effect of adding the phenol compound may be obtained. It may not be obtained. A more preferable lower limit of “phosphorus compound / phenolic compound” (weight ratio) is 0.5, and a more preferable upper limit is 10.

The thermosetting composition for optical semiconductors of the present invention may further contain fine particles having a metal element. By containing the fine particles, the refractive index of the thermosetting composition for optical semiconductors of the present invention is increased, and light extraction of an optical semiconductor element such as an LED using the thermosetting composition for optical semiconductors of the present invention is performed. Excellent in properties.

A preferable upper limit of the average primary particle diameter of the fine particles is 20 nm. When the average primary particle diameter of the fine particles exceeds 20 nm, light scattering due to the fine particles occurs in the thermosetting composition for optical semiconductors of the present invention, and the thermosetting composition for optical semiconductors of the present invention becomes cloudy. There are things to do. The more preferable lower limit of the average primary particle diameter of the fine particles is 3 nm, and the more preferable upper limit is 15 nm.

The fine particles have a metal element.
The fine particles are preferably at least one selected from the group represented by Al, In, Ge, Sn, Ti, Zr and Hf in which 80% or more of the metal elements present in the fine particles are present. When the proportion of these metal elements is less than 80%, the refractive index of the thermosetting composition for optical semiconductors of the present invention is not so high, and the thermosetting composition for optical semiconductors of the present invention is used. The light extraction property of the optical semiconductor element may be inferior.

The fine particles are not particularly limited as long as the fine particles have the above metal elements. However, since the refractive index of the thermosetting composition for optical semiconductors of the present invention is excellent, the fine particles containing zirconium are particularly preferred to have a refractive index. It is preferable because of improvement and excellent light transmission.

The blending amount of the fine particles is not particularly limited, but the preferred lower limit is 1 with respect to 100 parts by weight of the silicone resin (when the bifunctional silicone resin is contained, the total of the silicone resin and the bifunctional silicone resin). Part by weight, the preferred upper limit is 100 parts by weight. When the blending amount of the fine particles is less than 1 part by weight, the refractive index of the thermosetting composition for optical semiconductors of the present invention may hardly be improved, and when it exceeds 100 parts by weight, it is difficult to adjust the viscosity. . A more preferable lower limit of the amount of the fine particles is 5 parts by weight, and a more preferable upper limit is 80 parts by weight.

A preferable lower limit of the refractive index of the fine particles is 1.50. If the refractive index of the fine particles is less than 1.50, the refractive index of the thermosetting composition for optical semiconductors of the present invention does not increase, and the optical semiconductor using the thermosetting composition for optical semiconductors of the present invention. The light extraction performance of the device may be insufficient.
In addition, in this specification, the said refractive index is the value which measured the refractive index with respect to sodium D line | wire (589.3 nm) using the refractometer (Abbe type | formula) at the measurement temperature of 20 degreeC.

The thermosetting composition for optical semiconductors of the present invention may contain a coupling agent for imparting adhesion.
The coupling agent is not particularly limited, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, Examples thereof include silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane. These coupling agents may be used independently and 2 or more types may be used together.

As a blending ratio of the coupling agent, a preferable lower limit is 0.1 with respect to 100 parts by weight of the silicone resin (when the bifunctional silicone resin is contained, the total of the silicone resin and the bifunctional silicone resin). Part by weight, the preferred upper limit is 5 parts by weight. If the blending ratio of the coupling agent is less than 0.1 parts by weight, the blending effect of the coupling agent may not be sufficiently exhibited. If the blending ratio exceeds 5 parts by weight, the excess coupling agent volatilizes, and the present invention. When the thermosetting composition for optical semiconductors is cured, film loss may occur.

In addition, the thermosetting composition for optical semiconductors of the present invention may contain silica fine powder, high molecular weight silicone resin, or the like in order to adjust the viscosity. In particular, the silica fine powder not only has a thickening action but also acts as a thixotropic agent, so that the fluidity control of the thermosetting composition for optical semiconductors of the present invention and the effect of preventing the precipitation of the phosphor also occur. Therefore, it is preferable.

Although it does not specifically limit as an average particle diameter of the said silica fine powder, A preferable upper limit is 100 nm. When the average particle diameter of the silica fine powder exceeds 100 nm, the transparency of the thermosetting composition for optical semiconductors of the present invention may be lowered.

Moreover, the said silica fine powder has a preferable minimum of a BET specific surface area of 30 m < ² > / g, and a preferable upper limit of 500 m < ² > / g on performance. When the BET specific surface area of the silica fine powder is less than 30 m ² / g, the thickening effect and thixotropy improvement effect are insufficient, and when the silica fine powder exceeds 500 m ² / g, the silica fine powder is strongly agglomerated and dispersed. This is not preferable.

Examples of such silica fine powder include Aerosil 50 (specific surface area 50 m ² / g), Aerosil 90 (specific surface area 90 m ² / g), Aerosil 130 (specific surface area 130 m ² / g), Aerosil 200 ( Specific surface area is 200 m ² / g), Aerosil 300 (specific surface area is 300 m ² / g), Aerosil 380 (specific surface area is 380 m ² / g), Aerosil OX50 (specific surface area is 50 m ² / g), Aerosil TT600 (specific surface area) Is 200 m ² / g), Aerosil R972 (specific surface area is 110 m ² / g), Aerosil R974 (specific surface area is 170 m ² / g), Aerosil R202 (specific surface area is 100 m ² / g), Aerosil R812 (specific surface area is 260 m) ² / g) Aerosil R812S (specific surface area of ^{220m 2 / g), Aerosil R805} ( specific surface area of 150m ² / g), RY200 (specific surface area of 100m ² / g), RX200 (specific surface area of 140m ² / g) (both Nippon Aerosil Etc.).

The thermosetting composition for optical semiconductors of the present invention has additives such as an antifoaming agent, a colorant, a phosphor, a modifying agent, a leveling agent, a light diffusing agent, a thermally conductive filler, and a flame retardant as necessary. It may be blended.

Although it does not specifically limit as a viscosity of the thermosetting composition for optical semiconductors of this invention, A preferable minimum is 500 mPa * s and a preferable upper limit is 50,000 mPa * s. When the viscosity of the thermosetting composition for optical semiconductors of the present invention is less than 500 mPa · s, when used as a sealing agent for optical semiconductor elements, liquid dripping may occur and the optical semiconductor elements may not be sealed, If it exceeds 50,000 mPa · s, the optical semiconductor element may not be sealed uniformly and accurately. The minimum with a more preferable viscosity of the thermosetting composition for optical semiconductors of this invention is 1000 mPa * s, and a more preferable upper limit is 10,000 mPa * s.
In addition, in this specification, the said viscosity is the value measured on 25 degreeC and 5 rpm conditions using the E-type viscosity meter (the Toki Sangyo company make, TV-22 type | mold).

The thermosetting composition for optical semiconductors of the present invention preferably has an initial light transmittance of 90% or more. If the initial light transmittance is less than 90%, the optical characteristics of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention will be insufficient. In addition, the said initial light transmittance uses the hardened | cured material of thickness 1mm which hardened | cured the thermosetting composition for optical semiconductors of this invention, and the transmittance | permeability of light with a wavelength of 400 nm made from Hitachi Ltd. "U-4000. It is the value measured using "."

Moreover, it is preferable that the decreasing rate of the light transmittance after a light resistance test is less than 10% in the thermosetting composition for optical semiconductors of this invention. If the rate of decrease in light transmittance after the light resistance test is 10% or more, the optical characteristics of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention will be insufficient. In addition, the light resistance test is a 100mW filter in which a filter that cuts light having a wavelength of 340nm or less is attached to a cured product having a thickness of 1mm obtained by curing the thermosetting composition for optical semiconductors of the present invention. the examination of irradiating / cm ² at 24 hours, the light transmittance after light resistance test using the above cured product after the light resistance test, manufactured by Hitachi, Ltd. and the transmittance of light having a wavelength of 400nm "U- It is a value measured using "4000".

Moreover, it is preferable that the decreasing rate of the light transmittance after a heat resistance test is less than 10% in the thermosetting composition for optical semiconductors of this invention. If the rate of decrease in light transmittance after the heat resistance test is 10% or more, the optical characteristics of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention will be insufficient. The heat resistance test is a test in which a cured product having a thickness of 1 mm obtained by curing the thermosetting composition for optical semiconductors of the present invention is left in an oven at 150 ° C. for 2000 hours. The light transmittance is a value obtained by measuring the transmittance of light having a wavelength of 400 nm using “U-4000” manufactured by Hitachi, Ltd., using the cured product after the heat resistance test.

Since the thermosetting composition for optical semiconductors of this invention contains the hardening accelerator which has a structure represented by the said General formula (1), the hardened | cured hardened | cured material has the outstanding transparency and light resistance. In addition, it becomes extremely excellent in heat resistance, and when used as a sealant for optical semiconductor elements such as LEDs, yellowing hardly occurs under the conditions of use, and it has excellent adhesion to substrates and the like. It will be.

The method for producing the thermosetting composition for optical semiconductors of the present invention is not particularly limited, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three-roll, a bead mill, Examples thereof include a method of mixing the above-mentioned curing accelerator, silicone resin, and, if necessary, each predetermined amount of the above-described thermosetting agent, antioxidant, and the like at room temperature or under heating.

Although it does not specifically limit as a use of the thermosetting composition for optical semiconductors of this invention, For example, optical semiconductor elements, such as a sealing agent, a housing material, die bond material for connecting to a lead electrode, a heat sink, etc., 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 the optical semiconductor device which can take out the light by the light emission from an optical semiconductor element efficiently can be manufactured, it can use suitably as a sealing agent, an underfill material, and a die-bonding material.

An encapsulant for optical semiconductor elements using the thermosetting composition for optical semiconductors of the present invention is also one aspect of the present invention.
An optical semiconductor element can be manufactured by sealing a light emitting element using the sealing agent for optical semiconductor elements of this invention.

The light emitting element is not particularly limited. For example, when the optical semiconductor element is a light emitting diode, for example, a semiconductor material stacked on a substrate can be used. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.
Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. In addition, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the buffer layer include GaN and AlN.

The method for laminating the semiconductor material on the substrate is not particularly limited, and examples thereof include MOCVD, HDVPE, and liquid phase growth.
Examples of the structure of the light emitting element include a homojunction having a MIS junction, a PN junction, and a PIN junction, a heterojunction, and a double heterostructure. Moreover, it can also be set as a single or multiple quantum well structure.

When sealing the said light emitting element using the sealing compound for optical semiconductor elements of this invention, you may use another sealing agent together. In this case, after sealing the light emitting element with the sealant for optical semiconductor elements of the present invention, the periphery thereof may be sealed with the other sealant, and the light emitting element may be sealed with the other sealant. Then, the periphery thereof may be sealed with the optical semiconductor element sealing agent of the present invention.
The other sealing agent is not particularly limited, and examples thereof include an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, and glass. Moreover, when a surface modifier is contained, a liquid can be applied to provide a protective layer on the surface.

The method for sealing the light emitting element with the encapsulant for optical semiconductor elements of the present invention is not particularly limited. For example, the encapsulant for optical semiconductor elements of the present invention is pre-injected into a mold frame, and light is emitted there. Examples include a method in which a lead frame to which an element is fixed is immersed and then cured, and a method in which the sealing agent for optical semiconductor elements of the present invention is injected into a mold in which a light emitting element is inserted and cured.
Examples of the method for injecting the sealant for optical semiconductor elements of the present invention include injection by a dispenser, transfer molding, injection molding and the like. Furthermore, as another sealing method, the sealing agent for optical semiconductor elements of the present invention is dropped on the light emitting element, stencil printing, screen printing, or a method of applying and curing through a mask, and the light emitting element is formed at the bottom. The method etc. which inject | pour the sealing agent for optical semiconductor elements of this invention with a dispenser etc. to the arrange | positioned cup etc. and harden | cure.

An optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention and / or the encapsulant for optical semiconductor elements of the present invention is also one aspect of the present invention.

1 and 2 are cross-sectional views schematically showing an example of an optical semiconductor element using the encapsulant for optical semiconductor elements and the die bonding material for optical semiconductor elements of the present invention, and FIG. It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing agent for optical semiconductor elements, and the underfill material for optical semiconductor elements.

In the optical semiconductor element shown in FIG. 1, the light emitting element 11 is installed on the heat sink 16 via the die bonding material 10 for the optical semiconductor element, and extends from the upper surface of the light emitting element 11 to the bottom surface through the side surface of the housing material. The two lead electrodes 14 are electrically connected to each other by a gold wire 13. And the light emitting element 11, the die-bonding material 10 for optical semiconductor elements, and the gold wire 13 are sealed with the sealing compound 12 for optical semiconductor elements of this invention.

FIG. 2 shows an optical semiconductor device in which the die bond material for an optical semiconductor device has high conductivity by containing particles containing at least one selected from the group consisting of gold, silver, and copper described above.
In the optical semiconductor element shown in FIG. 2, the light emitting element 21 is installed via the die bonding material 20 for an optical semiconductor element, and two lead electrodes 24 extended from the upper surface of the housing material 25 to the bottom surface through the side surface. Among them, the end of one lead electrode 24 is formed between the optical semiconductor element die-bonding material 20 and the housing material 25 and is electrically connected to the light-emitting element 21 through the optical semiconductor element die-bonding material 20. The lead electrode 24 is electrically connected to the light emitting element 21 by a gold wire 23. And the light emitting element 21, the die-bonding material 20 for optical semiconductor elements, and the gold wire 23 are sealed with the sealing compound 22 for optical semiconductor elements of this invention.

In the optical semiconductor element of the present invention shown in FIG. 3, the light emitting element 31 is installed via the bump 33, and the optical semiconductor element underfill material 30 is formed between the light emitting element 31 and the housing material 35. . The two lead electrodes 34 extended from the upper surface of the housing material 35 to the bottom surface through the side surfaces are formed between the bumps 33 and the housing material 35 and are electrically connected to the light emitting element 31. ing. And the light emitting element 31 and the underfill material 30 for optical semiconductor elements are sealed with the sealing agent 32 for optical semiconductor elements of this invention.
In the optical semiconductor element of the present invention shown in FIG. 3, the underfill material 30 for an optical semiconductor element is connected to a space formed below the light emitting element 31 after the light emitting element 31 and the lead electrode 34 are connected by the bump 33. It is formed by filling from the gap.

Specific examples of the optical semiconductor element of the present invention include a light emitting diode, a semiconductor laser, and a photocoupler. Such an optical semiconductor element of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copy machine, a vehicle measuring instrument light source, a signal light, a display light, a display device, and a planar light emission It can be suitably used for body light sources, displays, decorations, various lights, switching elements and the like.

According to the present invention, the cured product is excellent in transparency, heat resistance and light resistance, and when used as a sealant for an optical semiconductor element, it has excellent adhesion to a housing material and has a long time. It is possible to provide a thermosetting composition for optical semiconductors which does not cause problems such as yellowing under use conditions. Moreover, the sealing compound for optical semiconductor elements which uses this thermosetting composition for optical semiconductors, and an optical semiconductor element can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples.

(Synthesis Example 1)
Dimethyldimethoxysilane (750 g) and 3-glycidoxypropylmethyldimethoxysilane (150 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Into this, potassium hydroxide (1.9 g) / water (250 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (2.1g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer A. The molecular weight of the polymer A is Mn = 11000 and Mw = 25000. From ²⁹ Si-NMR, (Me ₂ SiO _2/2 ) _0.90 (GEpMeSiO _2/2 ) _0.10
3-glycidoxypropyl group content (GEp) is 14 mol%, epoxy equivalent is 760 g / eq. Met. The molecular weight was stirred until tetrahydrofuran (1 mL) was added and dissolved in polymer A (10 mg), and a measuring device manufactured by Waters (column is Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK) Measurement was performed by GPC measurement using a measurement temperature of 40 ° C., a flow rate of 1 mL / min, a solvent of tetrahydrofuran, and a standard material of polystyrene. Moreover, the epoxy equivalent was calculated | required based on JISK-7236.

(Synthesis Example 2)
Dimethyldimethoxysilane (440 g) and 3-glycidoxypropyltrimethoxysilane (160 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Potassium hydroxide (1.2 g) / water (170 g) was slowly added dropwise thereto, and after the addition was completed, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer B. The molecular weight of the polymer B is Mn = 2000, Mw = 3800, and (Me ₂ SiO _2/2 ) _0.83 (GEpSiO _3/2 ) _0.17 from ²⁹ Si-NMR.
3-glycidoxypropyl group content (GEp) is 22 mol%, epoxy equivalent is 550 g / eq. Met. The molecular weight and epoxy equivalent of polymer B were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 3)
Dimethyldimethoxysilane (440 g) and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (160 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Potassium hydroxide (1.2 g) / water (170 g) was slowly added dropwise thereto, and after the addition was completed, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer C. The molecular weight of the polymer C is Mn = 2300, Mw = 4800, and (Me ₂ SiO _2/2 ) _0.84 (EpSiO _3/2 ) _0.16 from ²⁹ Si-NMR.
2- (3,4-epoxycyclohexyl) ethyl group content (Ep) is 22 mol%, epoxy equivalent is 550 g / eq. Met.
The molecular weight and epoxy equivalent of polymer C were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 4)
Dimethyldimethoxysilane (400 g), trimethoxymethylsilane (100 g), and 3-glycidoxypropyltrimethoxysilane (100 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Into this, potassium hydroxide (1.3 g) / water (180 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.4g) was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer D. The molecular weight of the polymer D is Mn = 3200, Mw = 5400, and (Me ₂ SiO _2/2 ) _0.71 (MeSiO _3/2 ) _0.18 (GEpSiO _3/2 ) _0.11 from ²⁹ Si-NMR.
3-glycidoxypropyl group content (GEp) is 15 mol%, epoxy equivalent is 780 g / eq. Met. The molecular weight and epoxy equivalent of polymer D were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 5)
In a separable flask equipped with a 2000 mL thermometer and a dropping device, dimethyldimethoxysilane (350 g), trimethoxymethylsilane (125 g), and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (125 g) are placed at 50 ° C. Stir. Potassium hydroxide (1.2 g) / water (190 g) was slowly added dropwise thereto, and after completion of the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The polymer obtained was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer E. The molecular weight of the polymer E is Mn = 2900, Mw = 4600, and (Me ₂ SiO _2/2 ) _0.65 (MeSiO _3/2 ) _0.22 (EpSiO _3/2 ) _0.13 from ²⁹ Si-NMR.
2- (3,4-epoxycyclohexyl) ethyl group content (Ep) is 19 mol%, epoxy equivalent is 660 g / eq. Met. The molecular weight and epoxy equivalent of polymer E were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 6)
Put a dimethyldimethoxysilane (400 g), trimethoxymethylsilane (50 g), tetramethoxysilane (50 g), 3-glycidoxypropyltrimethoxysilane (100 g) in a separable flask with a 2000 mL thermometer and dropping device. Stir at ° C. Into this, potassium hydroxide (1.3 g) / water (180 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.4g) was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer F. The molecular weight of the polymer F is Mn = 2600, Mw = 3600, and (Me ₂ SiO _2/2 ) _0.73 (MeSiO _3/2 ) _0.09 (GEpSiO _3/2 ) _0.10 from ²⁹ Si-NMR. SiO _4/2 ) _0.08
3-glycidoxypropyl group content (GEp) is 14 mol%, epoxy equivalent is 760 g / eq. Met. The molecular weight and epoxy equivalent of polymer F were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 7)
Dimethyldimethoxysilane (365 g), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (165 g), and trimethylmethoxysilane (70 g) are placed in a separable flask equipped with a 2000 mL thermometer and a dropping device and stirred at 50 ° C. did. To the solution, potassium hydroxide (1.2 g) / water (160 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water and volatile components were removed under reduced pressure to obtain polymer G. The molecular weight of the polymer G is Mn = 2000, Mw = 3500, and (Me ₃ SiO _1/2 ) _0.12 (Me ₂ SiO _2/2 ) _0.71 (EpSiO _3/2 ) from ²⁹ Si-NMR _{. 17}
The 2- (3,4-epoxycyclohexyl) ethyl group content (Ep) was 23 mol%, and the epoxy equivalent was 560 g / eq. Met. The molecular weight and epoxy equivalent of polymer G were determined in the same manner as in Synthesis Example 1.

(Example 1)
Polymer A (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), 1,5-diazabicyclo [4,3,0] nonene-5 tetraphenylborate salt (DBN-K, cured) Accelerator, Hokuko Chemical Co., Ltd., 0.5 g), HOSTANOX O3 (phenolic compound, Clariant Co., 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant Co., 0.5 g) Then, defoaming was performed to obtain a thermosetting composition for optical semiconductors. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Example 2)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), 1,5-diazabicyclo [4,3,0] nonene-5 tetraphenylborate salt (DBN-K, cured) Accelerator, Hokuko Chemical Co., Ltd., 0.5 g), HOSTANOX O3 (phenolic compound, Clariant Co., 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant Co., 0.5 g) Then, defoaming was performed to obtain a thermosetting composition for optical semiconductors. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Example 3)
Polymer B (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), 2-ethyl-4-methylimidazolium tetraphenylborate (EMZ-K, curing accelerator, manufactured by Hokuko Chemical Co., Ltd.) 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g), mixed, defoamed, light A thermosetting composition for semiconductor was obtained. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

Example 4
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), tetraphenylphosphonium tetra-p-tolylborate (TPP-MK, curing accelerator, manufactured by Hokuko Chemical Co., Ltd.) 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g), mixed, defoamed, light A thermosetting composition for semiconductor was obtained. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Example 5)
Polymer B (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), tetra-n-butylammonium tetraphenylborate (curing accelerator, manufactured by Aldrich, 0.5 g), HOSTANOX O3 ( Phenol compound, Clariant Co., 0.5g), Sandstub P-EPQ (Phosphorus compound, Clariant Co., 0.5g) was added and mixed, defoamed, and the thermosetting composition for optical semiconductors. Obtained. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Example 6)
Polymer B (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), tetra-n-butylammonium n-butyltriphenylborate (P3B, curing accelerator, manufactured by Showa Denko KK, 0. 5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g) and sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) are mixed and defoamed for an optical semiconductor. A thermosetting composition was obtained. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Example 7)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Rika Co., Ltd., 30 g), tetra-n-butylammonium n-butyltris-4-tert-butylphenylborate (BP3B, curing accelerator, Showa Denko) 0.5 g), HOSTANOX O3 (phenolic compound, Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, 0.5 g, 0.5 g) are mixed and defoamed. And a thermosetting composition for optical semiconductors was obtained. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Example 8)
Polymer C (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), BP3B (curing accelerator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, manufactured by Clariant) 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was mixed and defoamed to obtain a thermosetting composition for optical semiconductors. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

Example 9
Polymer D (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), BP3B (curing accelerator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, manufactured by Clariant) 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was mixed and defoamed to obtain a thermosetting composition for optical semiconductors. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Example 10)
Polymer E (100 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g), BP3B (curing accelerator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, manufactured by Clariant) 0.5 g), sand stub P-EPQ (phosphorus compound, manufactured by Clariant, 0.5 g) was mixed and defoamed to obtain a thermosetting composition for optical semiconductors. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

Example 11
Polymer F (100 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g), BP3B (curing accelerator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, manufactured by Clariant) 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was mixed and defoamed to obtain a thermosetting composition for optical semiconductors. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

Example 12
Polymer G (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), BP3B (curing accelerator, Showa Denko, 0.5 g), HOSTANOX O3 (phenolic compound, manufactured by Clariant) 0.5 g), sand stub P-EPQ (phosphorus compound, manufactured by Clariant, 0.5 g) was mixed and defoamed to obtain a thermosetting composition for optical semiconductors. This thermosetting composition for optical semiconductors was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Comparative Example 1)
Polymer A (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), tetra-n-butylammonium bromide (curing accelerator, manufactured by Aldrich, 0.5 g), HOSTANOX O3 (phenolic system) Compound, Clariant, 0.5 g) and sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) were mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Comparative Example 2)
Polymer A (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), sodium tetraphenylborate (curing accelerator, manufactured by Aldrich, 0.5 g), HOSTANOX O3 (phenolic compound, Clariant) 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5 g) was added and mixed, defoamed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Comparative Example 3)
Polymer A (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), 1,8-diazabicyclo (5.4.0) undecene-7 octylate (U-CAT SA 102, Curing accelerator, San Apro, 0.5g), HOSTANOX O3 (phenolic compound, Clariant, 0.5g), sand stub P-EPQ (phosphorus compound, Clariant, 0.5g) Then, defoaming was performed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Comparative Example 4)
Polymer A (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), 1,5-diazabicyclo [4,3,0] nonene-5 tetraphenylborate salt (DBN-K, cured) An accelerator, manufactured by Hokuko Chemical Co., Ltd., 0.5 g) was added and mixed, defoamed, and an encapsulant for optical semiconductor elements was obtained. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Comparative Example 5)
Celoxide 2021 (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, 100 g), Ricacid MH-700G (manufactured by Shin Nippon Chemical Co., Ltd., 100 g), BP3B (curing accelerator, manufactured by Showa Denko KK, 0.5 g), HOSTANOX O3 ( Phenol compound, Clariant Inc., 0.5 g), sand stub P-EPQ (phosphorus compound, Clariant Inc., 0.5 g) was added and mixed, defoamed, and an optical semiconductor element sealant. Obtained. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The cured product was colorless and transparent visually.

(Comparative Example 6)
YX-8000 (hydrogenated bisphenol A epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., 100 g), Ricacid MH-700G (manufactured by Nippon Nippon Chemical Co., Ltd., 64 g), BP3B (curing accelerator, Showa Denko Co., Ltd., 0.5 g), HOSTANOX O3 (phenolic compound, manufactured by Clariant, 0.5 g), sand stub P-EPQ (phosphorus compound, manufactured by Clariant, 0.5 g) was mixed and degassed, and sealed for optical semiconductor elements. A stop was obtained. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The cured product was reddish brown visually.

(Comparative Example 7)
VDT-431 (polysiloxane having a vinyl group, manufactured by Gelest, 45 g), HMS-031 (organohydrogenpolysiloxane, manufactured by Gelest, 55 g), octyl alcohol-modified solution of chloroplatinic acid (Pt concentration: 2% by weight, 0.05 g) was mixed and defoamed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 100 ° C. for 3 hours and 150 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm. The obtained cured product was colorless and transparent visually.

(Evaluation)
The following evaluation was performed about the sealing agent produced by the Example and the comparative example, and its hardened | cured material. The results are shown in Tables 1 and 2.

(1) Initial light transmittance A light transmittance of 400 nm was measured using a U-4000 manufactured by Hitachi, Ltd. using a cured product having a thickness of 1 mm.

(2) Light transmittance after light resistance test A cured product with a thickness of 1 mm is attached to a high-pressure mercury lamp with a filter that cuts 340 nm or less, irradiated at 100 mW / cm ² for 24 hours, and has a light transmittance of 400 nm. The measurement was performed using U-4000 manufactured by the company. In Table 1, “◎” indicates a decrease in light transmittance from the initial stage of less than 5%, “◯” indicates less than 10%, “Δ” indicates less than 10 to 40%, and 40%. The above case was set as “x”.

(3) Light transmittance after heat resistance test A cured product having a thickness of 1 mm was left in an oven at 150 ° C. for 2000 hours, and a light transmittance of 400 nm was measured using U-4000 manufactured by Hitachi, Ltd. In Table 1, “◎” indicates a decrease in light transmittance from the initial stage of less than 5%, “◯” indicates less than 10%, “△” indicates less than 10-20%, and 20%. The above case was set as “x”.

(4) Adhesion test Sealants for optical semiconductor elements prepared in Examples and Comparative Examples were applied to aluminum, polyphthalamide resin (PPA), and polybutylene terephthalate resin (PBT), and 100 ° C. × 3 hours, 130 Cured at ℃ x 3 hours (Comparative Example 7 is 100 ℃ x 3 hours, 150 ℃ x 3 hours) to produce a thin film, in accordance with JIS K-5400, with a clearance of 1 mm and a grid of 100 grids The adhesion test was performed using this method.
In Table 1, the case where the peel number was 0 was “◯”, the case where the peel number was 1 to 70 was “Δ”, and the case where the peel number was 71 to 100 was “x”.

According to the present invention, the cured product is excellent in transparency, heat resistance and light resistance, and when used as a sealant for an optical semiconductor element, it has excellent adhesion to a housing material and has a long time. It is possible to provide a thermosetting composition for optical semiconductors that does not cause problems such as yellowing under use conditions. Moreover, the sealing compound for optical semiconductor elements which uses this thermosetting composition for optical semiconductors, and an optical semiconductor element can be provided.

It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing compound for optical semiconductors of this invention, and the die-bonding material for optical semiconductor elements. It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing compound for optical semiconductors of this invention, and the die-bonding material for optical semiconductor elements. It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing agent for optical semiconductors of this invention, and the underfill material for optical semiconductor elements.

Explanation of symbols

10, 20 Die bond material for optical semiconductor element 11, 21, 31 Light emitting element 12, 22, 32 Sealant for optical semiconductor 13, 23 Gold wire 14, 24, 34 Lead electrode 15, 25, 35 Housing material 16 Heat sink 30 Underfill material 33 for optical semiconductors Bump

Claims (7)

A silicone resin having a cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, an antioxidant, and a curing accelerator having a structure represented by the following general formula (1) A thermosetting composition for optical semiconductors, comprising:

In the general formula (1), R ^{1 to} R ⁴ are a fluoro group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aralkyl group, and optionally substituted. An aryl group and an alicyclic group which may be substituted are represented, and these may be the same or different. X ⁺ represents a cation having N, S or P as a central element. The curing accelerator having a structure represented by the general formula (1) is characterized in that X ⁺ in the general formula (1) has a structure represented by the following general formula (2). The thermosetting composition for optical semiconductors.

In the general formula (2), Y ⁺ represents N, S or P, n is 3 or 4, and a plurality of R ⁵ are an optionally substituted alkyl group or an optionally substituted alkenyl. Represents an optionally substituted aralkyl group, an optionally substituted aryl group, an optionally substituted heterocyclic group, an optionally substituted alicyclic group, and an optionally substituted silyl group. These may be the same as or different from each other. The curing accelerator having the structure represented by the general formula (1) is an aryl group in which three of R ^{1 to} R ^{4 in} the general formula (1) may be substituted, and one is substituted. The thermosetting composition for optical semiconductors according to claim 1, wherein the thermosetting composition is an alkyl group. The thermosetting composition for optical semiconductors according to claim 1, wherein the thermosetting agent is an acid anhydride. The silicone resin having a cyclic ether-containing group in the molecule contains a resin component whose average composition formula is represented by the following general formula (3), and the content of the cyclic ether-containing group is 0.1 to 50 mol. 5. The thermosetting composition for optical semiconductors according to claim 1, wherein the composition is%.

In the general formula (3), a, b, c and d are a / (a + b + c + d) = 0 to 0.2, b / (a + b + c + d) = 0.3 to 1.0, c / (a + b + c + d) = 0, respectively. -0.5, d / (a + b + c + d) = 0-0.3 is satisfied, and R ^{6 to} R ¹¹ each represents at least one cyclic ether-containing group, and R ^{6 to} R ¹¹ other than the cyclic ether-containing group are Represents a linear, branched or cyclic hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different. An encapsulant for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4 or 5. An optical semiconductor element comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4 or 5, or the sealant for optical semiconductor elements according to claim 6.

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