WO2006083025A1

WO2006083025A1 - Optical semiconductor, sealing material therefor and sealing composition

Info

Publication number: WO2006083025A1
Application number: PCT/JP2006/302295
Authority: WO
Inventors: Toshiyuki Akiike
Original assignee: Jsr Corporation
Priority date: 2005-02-04
Filing date: 2006-02-03
Publication date: 2006-08-10
Also published as: TW200711060A

Abstract

Disclosed is a composition for optical semiconductor encapsulation containing a polyorganosiloxane (A), 100-1000 parts by weight of an aliphatic or alicyclic epoxy compound (B) per 100 parts by weight of the polyorganosiloxane (A), and a carboxylic acid anhydride curing agent (C). The composition may further contain a curing accelerator (D). The composition for optical semiconductor encapsulation is useful as a main component for optical semiconductor sealing materials which can be used for potting and enables to form an optical semiconductor sealing material which is excellent in transparency, UV resistance, heat resistance, and crack resistance to solder reflow and heat cycle.

Description

Optical semiconductor, sealing material and sealing composition

Technical field

The present invention relates to a composition for sealing an optical semiconductor such as blue LED and white LED, a preparation method thereof, an optical semiconductor sealing material, and an optical semiconductor. Light

Background technology.

Conventionally, bisphenol A glycidyl ether has been written as an optical semiconductor sealing resin.

Epoxy compounds as the main agent were generally used, but since such epoxy compounds have an aromatic ring, durability against ultraviolet rays (UV durability) is required to seal optical semiconductors that emit blue or ultraviolet light. ) Was insufficient.

Therefore, it has been proposed to use an alicyclic epoxy compound in order to improve the UV durability of the measurement for optical semiconductor encapsulation (refer to Japanese Patent Laid-Open No. 2000-082). Still, UV durability was not enough.

On the other hand, it is known that a resin having a siloxane skeleton is excellent in weather resistance, and in recent years, studies using a resin having polydimethylsiloxane as a main skeleton as an optical semiconductor encapsulant have been extensively conducted. However, in the case of this resin, the hardness of the cured product is inadequate, and it has been pointed out that the gold wire used for the wiring is broken by vibration, or the adhesion to the substrate is insufficient and it is easy to peel off. .

Therefore, silsesquioxane resins have been proposed as siloxane-based materials that are hard and have high adhesion properties in order to increase the hardness and adhesion of the cured product. In particular, silsesquioxane resins having an epoxy group were used. An optical semiconductor sealing material is disclosed in Japanese Patent Laid-Open No. 62-1060 632. However, in order to potting the silsesquioxane resin disclosed in Japanese Patent Application Laid-Open No. Sho 6 2-1 0 6 6 3 2, gelling occurs when the solvent is distilled off, making molding difficult. When the film thickness is increased, cracks and bubbles are generated, so that it cannot be practically used as an optical semiconductor sealing material. Moreover, as a method for producing an epoxy group-containing polyorganosiloxane, Japanese Patent Application Laid-Open No. 01-297421, Japanese Patent Application Laid-Open No. 02-0667290, Japanese Patent Application Laid-Open No. 04-252228, Japanese Patent Application Laid-Open No. 04-352793, Japanese Patent Application Laid-Open No. 08-041168. No. 2000 and Japanese Laid-Open Patent Publication No. 2000-103859, a method of adding an epoxy derivative having a vinyl group to a polyorganosiloxane having a Si—H bond using a platinum, rhodium or ruthenium catalyst is known. Yes. However, polyorganosiloxanes containing Si—H have the problem that they are unstable with respect to moisture, are difficult to handle, and the raw materials are expensive. There is also a problem that coloring may occur when the catalyst remains.

Japanese Patent Application Laid-Open No. 2004-289102 describes that an epoxy resin may be blended with a modified polysiloxane having an epoxy group, but the amount of epoxy added is 100 parts by weight of the modified polysiloxane. It is 0 to 100 parts by weight, and no description of blending epoxy is found in the examples.

In addition, the optical semiconductor encapsulating element needs to withstand solder reflow and a heat cycle of -40 ° C to 100 ° C. However, if the mechanical properties of the encapsulating resin are weak, cracks will occur and the light output will decrease. There's a problem. Disclosure of the invention

The present invention has been made in view of the above circumstances, and its problem is that it can be potted, is colorless and transparent, has excellent durability, and is an optical semiconductor encapsulating that is less prone to cracking due to solder reflow and heat cycle. An optical semiconductor sealing composition capable of forming a material, a method for preparing the same, an optical semiconductor sealing material, and an optical semiconductor sealed with the optical semiconductor sealing material.

Other objects and advantages of the present invention will become apparent from the following description.

The present invention, first,

(A) 100 parts by weight of a polyorganosiloxane having an epoxy equivalent of 1,600 gZ mol or less, (B) more than 100 parts by weight of an aliphatic or alicyclic epoxy compound and 1,000 parts by weight or less, and (C) a carboxylic anhydride or Containing polyvalent carboxylic acid It is composed of an m-semiconductor composition for sealing an optical semiconductor.

The present invention secondly,

It consists of the optical semiconductor sealing material which consists of hardened | cured material which heat-hardened the composition for optical semiconductor sealing of this invention.

Third, the present invention

It consists of an optical semiconductor sealed with the optical semiconductor sealing material of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below.

Polyorganosiloxane and process for producing the same

The polyorganosiloxane (α) used in the present invention has an epoxy equivalent of 1600 gZ mol or less, for example, a silane compound represented by the following formula (1) (hereinafter,

It is called “silane compound (ι)”. ) And z or a partial condensate thereof (hereinafter, the silane compound (1) and the partial condensate thereof are collectively referred to as “silane compound (1) etc.”) and a silane compound represented by the following formula (2) (hereinafter referred to as “silane compound (1)”). And / or a partial condensate thereof (hereinafter, the silane compound (2) and the partial condensate thereof are collectively referred to as “silane compound (2) etc.”). It is obtained by hydrolysis and condensation by heating in the presence of organic solvent, organic base and water.

[In the formula (1), X represents a monovalent organic group having at least one epoxy group, Y ¹ represents a chlorine atom, a bromine atom, an iodine atom, or a linear, branched or 1 to 20 carbon atom. Represents a cyclic alkoxyl group, R ¹ represents a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear or branched or cyclic group having 1 to 20 carbon atoms. A substituted alkyl group, a straight chain having 2 to 20 carbon atoms, branched or A cyclic alkenyl group, an aryl group having 6 to 20 carbon atoms, or a carbon number? Represents an aralkyl group of ˜20, and n is an integer of 0-2. ]

[In the formula (2), Y ² represents a chlorine atom, a bromine atom, an iodine atom or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom, a fluorine atom, a carbon number 1-20 straight chain, branched or cyclic alkyl group, 1-20 carbon straight chain, branched or cyclic substituted alkyl group, 2-20 carbon straight chain, branched, or cyclic Alkenyl group, aryl group with 6 to 20 carbon atoms, or carbon number? Represents an aralkyl group of ˜20, and m is an integer of 0-3. ]

In the formula (1), the monovalent organic group having one or more epoxy groups of X is not particularly limited, and examples thereof include glycidoxypropyl group, 3, 4 epoxycyclopentyl) methyl group , (3,4-epoxycyclohexyl) methyl group, 2- (3,4-epoxycyclopentyl) ethyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 2- (3,4) 1-epoxycyclopentyl) propyl group, 2- (3, 4-epoxycyclohexyl) propyl group, 3_ (3, 4-epoxycyclopentyl) propyl group, 3_ (3, 4-epoxycyclohexyl) propyl group, etc. And groups having 5 to 20 carbon atoms.

Of these monovalent organic groups having one or more epoxy groups, an aglycidoxypropyl group, a 2- (3,4-epoxycyclohexyl) ethyl group, etc. are preferable, and a 2- (3,4-epoxy group) is particularly preferable. (Cyclohexyl) ethyl group. In the formula (1), Y ¹ represents a chlorine atom, a bromine atom, an iodine atom or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms. These groups generate a silanol group in the course of a hydrolysis / condensation reaction in the presence of an organic base and water, and cause a condensation reaction between the silanol groups, or the silanol group and chlorine. It is a group that forms a siloxane bond by causing a condensation reaction with an atom, a bromine atom, an iodine atom, or a silicon atom having the alkoxyl group.

In the formula (1), examples of the linear, branched or cyclic alkyloxyl group having ¹ to 20 carbon atoms of Y ¹ include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n Examples include —butoxy group, i-butoxy group, sec-butoxy group, t—butoxy group, n-pentyloxy group, n-hexyloxy group, cyclopentyloxy group, hexoxy group.

Y ¹ in the formula (1) is preferably a chlorine atom, a methoxy group, an ethoxy group or the like. .

In the formula (1), examples of the linear, branched or cyclic alkyl group having ¹ to 20 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples thereof include n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.

Examples of the linear, branched or cyclic substituted alkyl group having ¹ to 20 carbon atoms of R ¹ include, for example, a fluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, (trifluoromethyl) Methyl group, Penufluoroethyl group, 3-Fluoro-n-propyl group, 2- (Trifluoromethyl) ethyl group, (Pentafluoroethyl) Methyl group, Heptafluorofluoro-n-propyl group, 4-Fluoro-n-butyl group Group, 3- (trifluoromethyl) —n-propyl group, 2— (pentafluoroethyl) ethyl group, (heptofluoro-n-propyl) methyl group, nonafluoro —n-butyl group, 5-fluoro-n— Pentyl group, 4- (Trifluoromethyl) _ n-Butyl group, 3-(Peneven fluoroethyl) — n-Propyl group, 2-(Heptafluoro-n-propyl) Tyl group, (nonafluoro-n-butyl) methyl group, perfluoro-n-pentyl group, 6-fluoro-n-hexyl group, 5-(trifluoromethyl) 1-n-pentyl group, 4- (pentafluoroethyl) 1-n-butyl Group, 3 _ (heptafluoro-n-propyl) 1 n-propyl group, 2-(nonafluoro n-butyl) ethyl group, (perfluoro-n-pentyl) methyl group, per Fluoro-n-hexyl group, '7- (trifluoromethyl) 1 η-heptyl group, 6 1 (pentufluorethyl) 1 η-hexyl group, 5- (heptofluoro-η-pap pill) —η —Pentyl group, 4-1- (Nonafluoro-η-butyl) 1-η-butyl group, 3- (Perfluoro-η-pentyl) _η-propyl group, 2 -— (Perfluoro-η-hexyl) ethyl group, (Perfluoro-η— Heptyl) methyl group, perfluoro η-octyl group, 9- (trifluoromethyl) 1-eta-nonyl group, 8-(pentafluoroethyl) 1-eta-octyl group, 7- (heptafluoro-η-propyl ) _ Η-heptyl group, 6- (nonafluoro-η-butyl) 1 η-hexyl group, 5- (perfluoro 1-pentyl) 1 η-pentyl group, 4 1 (perfluoro-η-hexyl) — η-Butyl group, 3- (Perfluoro-η-heptyl) — η-Pine pill group, 2- (Perfluoro-η-octyl) ethyl group, (Perfluoro-η-nonyl) methyl group, Perfluoro-η-decyl group A fluoroalkyl group such as 4-fluorofluoropropyl group, 4-fluorocyclohexyl group,

Chloromethyl group, 2_chloroethyl group, 3-chloro-η-propyl group, 4-chloro η-butyl group, 3-chlorocyclopentyl group, 4-chlorocyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group Group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group, 3- '(meth) acryloxypropyl group, 3-mercaptopropyl group

Etc.

Examples of the linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms of R ¹ include, for example, vinyl group, 1-methylvinyl group, 1-propenyl group, aryl group (2 -Propenyl group), 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-cyclopentenyl group, 3-cyclohexenyl group, etc. .

In addition, examples of the aryl group having 6 to 20 carbon atoms of R ¹ include, for example, phenyl group, ο —tolyl group, m-tolyl group, ρ-tolyl group, 2,3-xylyl group, 2,4-xylyl group. Group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 1-naphthyl group and the like. Moreover, examples of the aralkyl group having 7 to 20 carbon atoms of R ¹ include a benzyl group and a phenethyl group.

R ¹ in formula (1) is preferably a methyl group, an ethyl group or the like.

As a specific example of the silane compound (1),

Compounds with n = 0 include glycidoxypropyltrimethoxysilane, τ-glycidoxypropyl 卜 triethoxysilane, 2— (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2_ (3 , 4-Epoxycyclohexyl) Ethyltriethoxysilane, etc .;

As compounds of n = l, (τ-glycidoxypropyl) (methyl) dimethoxysilane, (a-glycidoxypropyl) (ethyl) dimethoxysilane, (aglycidoxypropyl) (methyl) diethoxysilane, (agr Sidoxypropyl)

(Ethyl) Jetoxysilane, [2— (3,4-Epoxycyclohexyl) Eth; 1 /] (Methyl) Dimethoxysilane, [2— (3, 4-Epoxycyclohexyl) Ethyl] (Ethyl ) Dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (methyl) jetoxysilane, [2_ (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, etc .;

As compounds of n = 2, (r-glycidoxydipropyl) (methoxy) dimethylsilane, (aglycidoxypropyl) (methoxy) jetylsilane, (τ-glycidoxypropyl) (ethoxy) dimethylsilane, (aglycid (Xypropyl) (ethoxy) jetylsilane, [2- (3, 4-epoxycyclohexyl) ethyl] (methoxy) dimethylsilane, [2- (3, 4-epoxycyclohexyl) ethyl] (methoxy) Jetylsilane, [2- (3, 4-Epoxycyclohexyl) ethyl] (Ethoxy) Dimethylsilane, [2-— (3, 4-Epoxycyclohexyl) Ethyl] (Ethoxy) Jetylsilane, etc.

Can be mentioned respectively.

The partial condensates of silane compound (1) are trade names such as ES 1 001 N, ES 1002T, ES 1023 (manufactured by Shin-Etsu Silicone Co., Ltd.); Methyl Silicate MSEP2 (Mitsubishi Chemical Corporation ) Made) and the like. In the present invention, the silane compound (1) and the partial condensate thereof can be used alone or in admixture of two or more.

In the formula (2), Y ² represents a chlorine atom, a bromine atom, an iodine atom or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms. These groups generate a silanol group in the process of hydrolysis / condensation reaction in the presence of an organic base and water, and cause a condensation reaction between the silanol groups, or the silanol group and a chlorine atom, It is a group that forms a siloxane bond by causing a condensation reaction with a bromine atom, an iodine atom, or a silicon atom having the alkoxyl group.

In the formula (2), examples of the linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms of Y ² are the same as those exemplified for the corresponding group of Y ¹ in the formula (1). And the like.

Y ² in the formula (2) is preferably a chlorine atom, methoxy group, ethoxy group, n_propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group or the like.

In formula (2), R ^{2 is} a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group, carbon Examples of the linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms include, for example, each of R ¹ in the above formula (1) Examples thereof include the same groups as those exemplified for the corresponding group.

R ² in the formula (2) includes a fluorine atom, a methyl group, an ethyl group, a 2- (trifluoromethyl) ethyl group, a 2- (perfluoro-n-hexyl) ethyl group, and a 2- (perfluoro-n— Octyl) ethyl group, hydroxymethyl group, 2-hydroxychetyl group, 3- (meth) acryloxypropyl group, 3-mercaptopropyl group, vinyl group, aryl group, phenyl group and the like are preferable.

As a specific example of the silane compound (2),

Compounds with m = 0 include tetrachlorosilane, tetramethoxysilane, tetraeth Toxisilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, etc .;

As compounds of m = l, trichlorosilane, trimethoxysilane, triethoxysilane, tree n-propoxysilane, tree i-propoxysilane, tri-n-butoxysilane, 卜 s e c-butoxysilane,

Fluorotrichlorosilane, Fluorotrimethoxysilane, Fluorotriethoxysilane, Fluorotri-n-Proxoxysilane, Fluorotri-i-propoxysilane, Fluorotri n-Butoxysilane, Fluorotri-sec-Butoxysilane, N, Methyltri_n-Proxoxysilane , Methyltri_i-propoxysilane, methyltri-n-butoxysilane, methyletry sec-butoxysilane,

2— (Trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethryltrioxysilane, 2- (trifluoromethyl) ethyltrisilane n-Propoxysilane , 2-(trifluoromethyl) ethryltri-i _propoxysilane, 2— (trifluoromethyl) ethyltri n-butoxysilane, 2— (trifluoromethyl) ethyltri sec sec-butoxysilane,

2-(Perfluoro-n-hexyl) ethyltrichlorosilane, 2— (Perfluoro n-hexyl) Ethyltrimethoxysilane, 2— (Perfluoro-n-hexyl) Ethyltriethoxysilane, 2— (Perfluoro-n —Hexyl) Ethyltri- n-Propoxysilane, 2— (Perfluoro-n-Hexyl) Ethyltri-i-Propoxysilane, 2 -— (Perfluoro-n-Hexyl) Ettilly n-Butoxysilane, 2-— (Perfluoro-n—) Xylyl) Ettilly sec — butoxysilane,

2— (Perfluoro-n-octyl) ethyltrichlorosilane, 2-— (Perfluoro-n-octyl) ethyltrimethoxysilane, 2-— (Perfluoro-n-octyl) ethyltriethoxysilane, 2— (Perfluoro-n— Octyl) Tiltly n—Proxoxy silane, 2 -— (Perfluoro-n-octyl) ethyl tree i-Proxoxy silane, 2-— (Perfluoro-n-octyl) Ethyl tri-n-butoxy silane, 2-— (Perfluoro-n-octyl) Ettilly sec- 卜Xylan,

Hydroxymethyltrichlorosilane, Hydroxymethyltrimethoxysilane, Hydroxystiltrimethoxysilane, Hydroxymethyltri-n-propoxysilane, Hydroxymethyltrii-i-Propoxysilane, Hydroxymethyltri-n-butoxysilane, Hydroxymethyltrisec sec-Butoxy Silane,

3-(Meth) acryloxypropyltrichlorosilane, 3-— (meth) acryloxypropyltrimethoxysilane, 3-— (meth) acryloxypropyltriethoxysilane, 3-— (meth) acryloxypropyltri-n— Proxoxysilane, 3— (meth) acryloxypropyltree i-Proxoxysilane, 3-— (meth) acryloxypropyltree n-butoxysilane, 3-— (meth) acryloxyl mouth pills sec-butoxysilane, silane, 3 _mercapto Propyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mergaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyl-pilutri _ se c. Monobutoxysilane,

Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltree i-propoxysilane, vinyltri-n-butoxysilane, Viertree sec-butoxysilane, n, allytree n-propoxysilane, valyltri-i- Propoxysilane, allyltri_n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrii-i-propoxysilane, phenyltri-n- Butoxysilane, phenyl sec sec-Butoki Sisilane, '

etc:

As compounds of m = 2, methylesichlorochlorosilane, methyldimethoxysilane, methyljetoxysilane, methylzie n-propoxysilane, methylzie i monopropoxysilane, methylzie n-butoxysilane, methylzie c-butoxysilane,

Dimethyldichlorosilane, dimethyldimethoxysilane, dimethyljetoxysilane, dimethylzie n-propoxysilane, dimethylzie i-propoxysilane, dimethylzie n-butoxysilane, dimethyldione sec-butoxysilane, (methyl) [2- (perfluoron -Cutyl) ethyl] dichlorosilane, '(methyl) [2- (perfluoron-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoron-octyl) ethyl] gemethoxysilane, (Methyl) [2- (perfluoro_n-octyl) ethyl] g-n-propoxysilane, (methyl) [2- (perfluoromono-octyl) ethyl] g-i-propoxysilane, (methyl) [2- Monofluoro-n-octyl) ethyl n-butoxysilane, (Methyl) [2- (perfluoron-octyl) ethyl] di_sec-butoxysilane,

(Methyl) (aglycidoxypropyl) dichlorosilane, (methyl) (aglycidoxypropyl) dimethoxysilane, (methyl) (aglycidoxypropyl) diethoxysilane, (methyl) (a Glycidoxypropyl) Di-n-propoxysilane, (Methyl) (A-glycidoxypropyl) Di-i-Monopropoxysilane, (Methyl) (r-Glycidoxypropyl) G-n-Butoxysilane, (Methyl) ( Diglycidoxypropyl) di-sec-butoxysilane,

(Methyl) (3-Mercaptopropyl) dichlorosilane, (Methyl) (3-Mercaptopropyl) Dimethoxysilane, (Methyl) (3-Mercaptopropyl) Dietoxysilane, (Methyl) (3-Mercaptopropyl) G-n-Propoxysilane, (Methyl) (3-Mercaptopropyl) di-i-monopropoxysilane, (Methyl) (3-Mercaptopropyl) G-n-Butoxysilane, (Methyl) (3-Mercap) Topropyl) G sec-butoxysilane,

(Methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl) (vinyl) di-n-propoxysilane, (methyl) (bier) di-i —Propoxy silane, (methyl) (vinyl) di- n-butoxy silane, (methyl) (vinyl) di-sec—butoxy silane, divinyl dichloro silane, divinyl dimethoxy silane, divinyl ethoxy silane, divinyl diol n-propoxy silane, divinyl diol i 1-propoxysilane, divinyldi-n-butoxysilane, divinyl-di-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyljetoxysilane, diphenylsilane n-propoxysilane, diphenyloxy i—propoxy Silane, diphenyl n-butoxysilane, diphenyl s e c-butoxysilane, etc .;

As compounds of m = 3, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane,

Chlorotrimethylsilane, promotrimethylsilane, odotrimethylsilane, butylsilane, i_propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane,

(Black mouth) (Vinyl). Dimethylsilane, (Methoxy) (Biel) Dimethylsilane, (Ethoxy) (Vinyl) Dimethylsilane,

(Black mouth) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilan, (ethoxy) '(methyl) diphenylsilane, etc.

Can be mentioned respectively.

Of these silane compounds (2), tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Allyltrimethoxysilane, Allyltriethoxysilane, Phenyltrimethoxy Silane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and the like are preferable.

In addition, as a partial condensate of the silane compound (2), for example, KC-

89, KC-89 S, X ― 2 1-315 3, X-21 1 5 841, X-2 1-5

842, X -21-58 4 3, X-21 -5844, X-21-5 845, X—

21 1 58 46, X -2 1 ― 5847, 84 8, X ― 22- 160

AS, X-22-1 70 B, X-22-170 BX, X-22-1 70D, x-

22-17 0DX, X-2 2-176B, X-22-17 6D, X 22-17

6DX, X -22-17 6 F, X— 40 -2308, X— 40-2 651, x-

40- 26 55 A, X- 4 0 -2671, X-40- 26 72, X -40 -92

20, X-40-9 22 5, X-40- 92 t 27, X -4 0-9 2 46, X-4

0-9 24 7, X- 40 ― 9 250.X -40- 193 23, x- 4 1-1 053,

X-4 1 1 1056, X ― 4 1-180 5, X-41-1 810, KF 6 001,

KF 6002, KF600, KR212, KR-213, KR-217, KR

220 L, KR 24 2 A, KR271, KR282, KR 300, KR 3 11,

KR4 01 N, KR 50 0, KR 510, KR 520 6, KR 5 2 30, KR 5

235, KR9218, KR 9706 (above, manufactured by Shin-Etsu Silicone); Dara Resin (manufactured by Showa Denko); SH804, SH805, SH806A, SH 840, SR240.0, SR2402, SR2405, SR2406, SR24 10, SR2411, SR2416, SR2420 (above, manufactured by Toray Dowco-Silicon Co., Ltd.); FZ 3711, FZ 3722 (above, made by Nippon Tunica Co., Ltd.); DMS—S 12, DMS—S 15, DMS—S 21, DMS-S 27, DMS—S 31, DMS-S 32, DMS-S 33, DMS-S 35, DM S—S 38, DMS-S 42, DMS-S 45, DMS-S 51, DMS—22 7, PDS-0332, PDS-1615, PDS—9931, XMS-502 5 (above, manufactured by Chisso Corporation); Methyl silicate MS 51, Methyl silicate MS 56 (above, Mitsubishi Chemical ( Co., Ltd.); Ethyl Silicate 28, Ethyl Silicate 40, Ethyl Silicate 48 (above, Colcoat Co., Ltd.); GR100, GR 6 5 0, GR 9 0 8, GR 9 5 0 (above, manufactured by Showa Denko KK) and the like.

In the present invention, the silane compound (2) and the partial condensate thereof can be used alone or in admixture of two or more.

Polyorganosiloxane (Q!) Is produced by heating and hydrolyzing and condensing silane compound (1), etc. and silane compound (2), etc. in the presence of an organic solvent, organic base and water. It is preferable.

As the organic solvent, for example, hydrocarbons, ketones, esters, ethers, alcohols and the like can be used, but a solvent that does not mix uniformly with water is preferable.

Examples of the hydrocarbon include toluene and xylene; Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, jetyl ketone, and cyclohexanone; and examples of the ester include Ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, lactic acid ethyl, etc .; for example, ethylene glycol dimethyl ether, ethylene glycol rugetyl Ethers, tetrahydrofuran, dioxane, etc .; examples of the alcohol include: 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl And glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono-ethyl ether, propylene glycol mono-n-propyl ether, and the like.

These organic solvents can be used alone or in admixture of two or more. The amount of the organic solvent used is preferably 10 parts per 100 parts by weight of the total silane compounds.

-10, 000 parts by weight, more preferably 50-5, 000 parts by weight.

Examples of the organic base include primary and secondary organic amines such as ethylamine and jetylamine; triethylamine, tri-n-propylamine, and tri-n-butyl. Examples include tertiary organic amines such as amine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide.

Among these organic bases, tertiary organic amines such as tritylamine, tri-n-propylamine, tri-n-ptylamine, pyridine, 4-dimethylaminopyridine; teramethyl ammonium hydroxide, etc. Quaternary organic amines are preferred.

When producing polyorganosiloxane (), by using an organic base as a catalyst, the desired polyorganosiloxane (ii) can be produced at a high hydrolysis-condensation rate without causing side reactions such as ring opening of epoxy groups. Therefore, it is possible to obtain a composition having good production stability and good curability.

The amount of organic amine used varies depending on the type of organic amine, reaction conditions such as temperature, etc., and is not particularly limited, but is preferably about 0.1 to 3 times moles, more preferably about all silane compounds. About 0.5 to 1 times mole. In addition, when using an organic base other than organic amines, an amount almost equivalent to that of organic amines is sufficient.

The amount of water used in the production of the polyorganosiloxane (α) is preferably about 0.5 to 100 times mole, more preferably about 1 to 30 times mole relative to the total silane compounds. .

The hydrolysis / condensation reaction in producing the polyorganosiloxane (α) involves dissolving the silane compound (1) and the silane compound (2) in an organic solvent and mixing the solution with an organic base and water. For example, it can be carried out by heating in an oil bath.

Hydrolysis During the condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 120, preferably about 0.5 to 12 hours, more preferably 1 to 8 hours. It is desirable to heat to a certain extent. During the heating operation, the mixed solution may be stirred or left under reflux.

Upon completion of the reaction, the organic solvent layer is separated from the reaction solution and preferably washed with water. This In this case, the washing operation is facilitated by washing with water containing a small amount of salt, for example, about 0.2 wt% ammonium nitrate aqueous solution. Washing is performed until the water after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then concentrated to obtain the desired poly Organosiloxane (iii) can be obtained.

The polyorganosiloxane thus obtained has less residual hydrolyzable groups (such as alkoxyl groups) and silanol groups, so it gels at room temperature for more than 1 month without dilution with a solvent. You can save without doing. Further, if desired, silanol groups can be further reduced by trimethylsilylating the remaining silanol groups with hexamethyldisilazane or the like after completion of the reaction.

In addition, the hydrolysis in the presence of organic base and water does not cause side reactions such as ring-opening reaction or polymerization reaction of the epoxy group in the silane compound (1). Compared with metal catalyst, polyorganosiloxane

(a) There is an advantage that metal impurities such as sodium, potassium, platinum, and ruthenium are reduced.

The weight average molecular weight (hereinafter referred to as “Mw”) of the polyorganosiloxane () is preferably 5 0 0 to 1, 0 0 0, 0 0 0, more preferably 1, 0 0 0 to 1 0 0. , 0 0 0,

The polyorganosiloxane () preferably satisfies at least one of the following conditions regarding the epoxy equivalent and the following conditions regarding the content of the structural unit derived from the silan compound (1).

That is, the epoxy equivalent is preferably 1, e o o gZ mol or less, more preferably

1 60 to 900 g nomol, more preferably 180 to 500 g / mol. In this case, if the epoxy equivalent exceeds 1,600 gZ mol, the resulting polyorganosiloxane may have problems such as reduced heat resistance and coloring.

Further, the content of the structural unit derived from the silane compound (1) is preferably 5 mol% or more of the total structural unit. In this case, if the content of the structural unit is less than 5 mol% of the total structural units, the resulting polyorganosiloxane has no heat resistance and no coloring. Any problems may occur.

Furthermore, the polyorganosiloxane () has an epoxy equivalent that satisfies the above-mentioned conditions, and the ratio of the key atoms bonded to three or more oxygen atoms to the total key atoms is preferably 10% or higher. Is desirable. In this case, if the ratio of the silicon atoms bonded to three or more oxygen atoms to the total gate atoms is less than 10%, the cured product obtained from each optical semiconductor sealing composition described later There is a risk of problems in hardness and adhesion to the substrate.

The polyorganosiloxane (α) can be used very suitably as a main component in each composition for encapsulating optical semiconductors described later, and can be used alone or mixed with a general polyorganosiloxane, for example, a molded product. It is also useful as a film, laminate, paint, etc.

Optical semiconductor sealing composition and method for preparing the same

The composition for optical semiconductor encapsulation of the present invention is:

[I] (Α) Polyorganosiloxane (iii) having an epoxy equivalent of 1,600 g / mol or less (hereinafter referred to as “(A) polyorganosiloxane”), (B) Aliphatic or A composition for encapsulating an optical semiconductor containing an alicyclic epoxy compound and (C) a carboxylic acid anhydride or a polyvalent carboxylic acid (hereinafter referred to as “the composition for encapsulating an optical semiconductor [I]”); or

[II] For optical semiconductor encapsulation containing (A) polyorganosiloxane, (B) aliphatic or alicyclic epoxy compound, (C) carboxylic acid anhydride or polyvalent carboxylic acid, and (D) curing accelerator Composition (hereinafter referred to as “photosemiconductor sealing composition [II]”)

Consists of.

In the composition for optical semiconductor encapsulation [I] and the composition for optical semiconductor encapsulation [I I], (A) polyorganosiloxane can be used alone or in admixture of two or more.

(B) Aliphatic or alicyclic epoxy compounds

In particular,. (Formula B) c)

(Formula D) ^ ⁰ ^ ⁰ ^ ⁶ 0 (Formula E)

(Formula F)

―. CHg CH3

CH ₃ CH ₃

(Formula H)

(Formula I)

R to (CH ₂ ) ₈

³ (Formula J)

Where R is a trivalent organic group,

(Formula K)

Where R is a tetravalent organic group,

(Expression)

Where R is a η-valent organic group and η is an integer greater than or equal to 1.

(Formula Μ)

0—one 0

0 (Formula N)

And so on. The above epoxy compound may be condensed.

(Formula B) is HBE 100 (Nippon Nippon Steel Co., Ltd.), YX8000 (Japan Epoxy Resin Co., Ltd.), (Formula C) is YL 7040, (Formula D) is YL 6753, (Formula E) is Y ED216D (above, Japan Epoxy Resin Co., Ltd.), (Formula F) is CE 2021 (Daicel Chemical Industries, Ltd.), (Formula G) is LS 797.0 (Shin-Etsu Chemical Co., Ltd.), (Formula HL) Are CE 2080, CE 3000, Epolide GT 300, Epolid GT400, EHPE 3150 (above, Daicel Chemical Industries, Ltd.), (Formula M) is SR—HHP A (Sakamoto Pharmaceutical Co., Ltd.), (Formula N) is available as Tepic (Nissan Chemical Industry Co., Ltd.). YL7170, YL 8034 (above, Japan Epoxy Resin Co., Ltd.), W-100 (Shin Nippon Rika Co., Ltd.) Etc. can also be used. In addition to these, alicyclic epoxy compounds obtained by hydrogenating the following aromatic epoxy compounds may be used. Examples include bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol A. Bisphenol-type epoxy tree glycidylated bisphenols such as, tetrafluorobisphenol A, and epoxy glycidylated divalent phenols such as dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Resin, 1, 1, 1 1-tris (4-hydroxyphenyl) methane, 4, 4— (1— (4 1 (1 — (4 -hydroxyphenyl) 1 1-methylethyl) phenyl) ethylidene) bisphenol, etc. , 1, 2, 2, an epoxy resin obtained by dalicidylation of trisphenols Tetrakis (4-hydroxyphenyl) ethane and other tetrakisphenols glycidylated epoxy resin, phenol nopolac, cresolol nopolac, bisphenol A nopolac, brominated bisphenol A novolak, etc. The nopolac type epoxy resin etc. which were made can be mentioned.

The aliphatic or alicyclic epoxy compound is in a ratio of more than 100 parts by weight and not more than 1,000 parts by weight, preferably from 100 parts by weight to 100 parts by weight of the polyorganosiloxane of (A). 800 parts by weight can be added.

Moreover, the aromatic epoxy compound as described above may be included as required.

-(C) Carboxylic anhydride or polycarboxylic acid

(C) Carboxylic acid anhydride or polyvalent carboxylic acid in optical semiconductor sealing composition [I] and optical semiconductor sealing composition [II] causes (A) polyorganosiloxane to undergo a curing reaction. It is an ingredient.

The (C) carboxylic acid anhydride or polyvalent carboxylic acid is not particularly limited, but an alicyclic carboxylic acid anhydride is preferable.

Examples of the alicyclic carboxylic acid anhydride include compounds represented by the following formulas (3) to (1 3):

)

In addition to 4-methyltetrahydrofuranic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, alicyclic compounds having conjugated double bonds such as terpinene and aroocimene, and maleic anhydride Examples include Diels-Alder reaction products and hydrogenated products thereof. 'In addition, as the Diels-Alder reaction product and hydrogenated product thereof, any structural isomer and any geometrically different isomer can be used.

In addition, the alicyclic carboxylic acid anhydride can be appropriately chemically modified and used as long as it does not substantially hinder the hard reaction.

Also, formula (14) can be used as a curing agent.

HOOC 0

R- _N A _N .R-COOH

Ο ^ Ν 0

HOOC ' ^R (14) (where R is a divalent organic group) Specific examples of formula (14) include formulas (15) to (19). O

HOOC ^-^ N 儿 N ^^^^ COOH

O N.

, COOH (15)

O

HOOC-C ₄ H ₈ - _N A _N .C ₄ H ₈ -COOH

C ₄ H ₈ -COOH (i 6)

HOOCC H ₄ C00, n

^{2 4} \ § OOCC ₂ H ₄ COOH

N in N—

OOCC ₂ H ₄ COOH (17)

o

HOOCn (H ₂ C) SC ₃ H ₆ , _N儿_N C ₃ H ₆ S (CH ₂ ) nCOOH

C ₃ H ₆ S (CH ₂ ) nCOOH (18) n = 1 to 10

O

HOOCC ₂ H ₄ SC ₂ H ₄ OC-OC ₂ H ₄ , _N儿_N .C ₂ H ₄₀ -COC ₂ H ₄ SC ₂ H ₄ COOH

0 (19)

C ₂ H ₄ 0-COC ₂ H ₄ SC ₂ H ₄ COOH

Among these cycloaliphatic sulfonic acid anhydrides, from the viewpoint of fluidity and transparency of the composition, the formula (3), formula (5), formula (7) or formula (8), formula (15) A compound represented by formula (3), a formula (5) or a formula (15) is particularly preferred.

In the present invention, the alicyclic carboxylic acid anhydride can be used alone or in admixture of two or more.

In addition, the composition for optical semiconductor encapsulation [I] and the composition for optical semiconductor encapsulation [II] (C) As the carboxylic acid anhydride, one or more aliphatic carboxylic acid anhydrides or aromatic carboxylic acid anhydrides can be used, but these are used in combination with alicyclic carboxylic acid anhydrides. It is preferable.

The aliphatic force sulfonic acid anhydride and the aromatic force sulfonic acid anhydride can also be used after being appropriately chemically modified as long as the curing reaction is not substantially hindered.

The total use ratio of the aliphatic carboxylic acid anhydride and the aromatic carboxylic acid anhydride is preferably 50% by weight or less, more preferably 30% by weight or less, based on the total amount with the alicyclic carboxylic acid anhydride. It is.

In the composition for optical semiconductor encapsulation [I] and the composition for optical semiconductor encapsulation [II], the amount of (C) carboxylic anhydride or polycarboxylic acid used is: (A) epoxy group in polyorganosiloxane 1 The equivalent ratio of the carboxylic acid anhydride group or the carboxyl group to the mole is preferably 0.1 to 1.5, more preferably 0.5 to 1.3. In this case, even if the corresponding amount ratio is less than 0.1 or more than 1.5, there is a risk that inconveniences such as a decrease in the glass transition point (Tg) and coloring of the resulting cured product may occur. Furthermore, in the composition for optical semiconductor encapsulation [I] and the composition for optical semiconductor encapsulation [II], in addition to (C) carboxylic acid anhydride or polyvalent carboxylic acid, the desired effect of the present invention Components known as curing agents for epoxy compounds and epoxy resins (hereinafter referred to as “other curing agents”), such as phenols, dicyandiamides, adipic acid hydrazide, phthalic acid hydrazide One or more organic hydrazides such as can be used in combination.

The proportion of the other curing agent used is preferably 50% by weight or less, more preferably 30% by weight or less, based on (C) the carboxylic acid anhydride or polyvalent carboxylic acid.

(D) Curing accelerator

The (D) curing accelerator in the composition for optical semiconductor encapsulation [I I] is a component that accelerates the curing reaction between (A) polyorganosiloxane and (C) a carboxylic acid anhydride or a polyvalent carboxylic acid.

Such (D) curing accelerator is not particularly limited, but for example, Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide , Tetraphenylphosphonium bromide, ethyltriphenylphosphonumide, ethyltriphenylphosphonium cetate, tetrabutylphosphonium acetate, tetra-n-butylphosphine o, o-jetylphosphoro Dithionate, Methyltributyl Phosphonium Dimethyl Phosphate, Tetra-n-Butylphosphonium Benzotriazolate, Tetra-n-Butylphosphonium Tetrafluoroporate, Tetra-I n-butylphosphonium tetraphenyl, tetraphenylphosphonium tetraphenyl, triphenylbenzylphosphonium tetraphenyl, tetra-n-butylphosphonium tetrafluoroporate 4th grade Phosphonium salt;

1,8-diazabicyclo [5.4.0] undecene-7 and diazabicycloalkenes such as their organic acid salts;

Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylethylacetone complexes;

Tetraethylammonium bromide, tetra-n-butylammonum bromide, the following formula (2 0)

R ₄ -NR ₂ (CH ₃ 0) ₂ POO ^Θ ... 0)

^A quaternary ammonium salt such as ^R 3 (where R i to R ₄ are alkyl groups of 1 to 8 carbon atoms);

Boron trifluoride, boron compounds such as triborate borate; metal octalogen compounds such as zinc chloride and stannic chloride,

High melting point dispersion type latent curing accelerators such as amine addition accelerators such as adducts of dicyandiamide and epoxy resin; the imidazoles, organophosphorus compounds and quaternary Micro-force type latent curing accelerator with the surface of curing accelerator such as phosphonium salt coated with polymer; amine salt type latent curing accelerator; high temperature such as Lewis acid salt and Bronsted acid salt Latent hardening accelerators such as dissociative thermal cationic polymerization type latent curing accelerators

Etc.

Of these (D) curing accelerators, imidazoles, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds and quaternary ammonium salts are colorless and transparent, and are hard to discolor even when heated for a long time. This is preferable in that a diced product is obtained.

The (D) curing accelerator can be used alone or in admixture of two or more.

In the composition for optical semiconductor encapsulation [II], the amount of (D) curing accelerator used is preferably 0-6 parts by weight, more preferably 100 parts by weight of (A) polyorganosiloxane. 0 to 4 parts by weight. In this case, if the amount of the (D) curing accelerator used exceeds 6 parts by weight, the resulting hard material may have problems such as coloring. One other additive

In addition, an adhesion aid can be added for the purpose of improving the adhesion to the lead frame. Examples of adhesion assistants include: [3- (3,4-epoxycyclohexyl) ethyl sidoxypropyltriethoxysilane, arglycidoxypropylmethyljetoxysilane, arglycidoxypropylmethyldimethoxysilane, N— i3 (aminoethyl) _r -aminopropylmethyldimethyloxysilane, N-j3 (aminoethyl) aminoprovir trimethoxysilane, Ν-β (aminoethyl) aminoaminopropyltriethoxysilane, N-phenyl (1) τ-aminopropyltrimethoxysilane, chloropropyltrimethoxysilane, (1) mercaptopropyl trimethoxysilane, dodecanedithiol, compounds of formula (2 1), (2 2).

In addition, titanate adhesion assistants such as formulas (23) and (24) can also be used.

0

H ₃ C-0-Ti (oCC ₁₇ H ₃₅ ] 3 _{(2 3)}

Among these, j3—. (3 4 _Epoxycyclohexyl) etyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropiyl

Methoxysilane, dodecanedithiol, and compounds of formulas (21) and (22) are preferred. The addition amount of the adhesion assistant is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight per 100 parts by weight of component (A).

A stress relaxation agent can be added for the purpose of preventing cracks and peeling from the lead frame. Examples of the stress relaxation agent include epoxy-modified silicone, carboxyl group-modified silicone, mercapto-modified silicone, and both-end carboxy-modified hydrogenated polybutadiene. Mention may be made of phenogen and both-end hydroxy-modified polybutadiene.

Epoxy-modified silicones such as KF-105, X-22-163 A, X-22-163B, X-22-163C, KF-1001, KF-101, -2 2-2000, X-22-169AS, X — 22— 169 B, KF— 102 (Shin-Etsu Chemical Co., Ltd.), SF 8421 (Toray Dow Co., Ltd.), X- 22— 162 C, X-22- 3701 E, X—22—371 0 (Shin-Etsu Chemical Co., Ltd.), Mercapto-modified silicones such as X—22—167 B, KF—2001, KF—2004 (Shin-Etsu Chemical Co., Ltd.), Examples of the both-end carboxy-modified hydrogenated polybutadiene include C 1 1000 (Nippon Soda Co., Ltd.) and examples of the both-end hydroxy-modified polybutadiene include G 1 2000 and GI 3000 (manufactured by Nippon Soda Co., Ltd.).

In addition, a surfactant can be added for the purpose of adjusting the surface tension of the resin. Specifically, F-474, F-479 (above, Dainippon Ink Industries, Ltd.), FC—4 430, FC-4432 (above, Sumitomo 3EM Ltd.), KP 323, ΚΡ 34 1 (above, Shin-Etsu Chemical Co., Ltd.), PAI NTAD32, PA I NTAD 54, D K8-8011 (Toray Dow Co., Ltd.), Emargen 104 P, Emargen 109 P, Emargen 123, Leodol 8 P (above,. 'Kao (Co., Ltd.)). In the composition for optical semiconductor encapsulation [I] and the composition for optical semiconductor encapsulation [II], for the purpose of further improving the UV durability and adjusting the viscosity, an inorganic oxide is used as necessary. Product particles can also be blended.

The inorganic oxide particles are not particularly limited, but are selected from the group of, for example, Si, Al, Zr, Ti, Zn, Ge, In, Sn, Sb, and Ce. Mention may be made of particles composed of oxides containing at least one element. More specifically, silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium-tin oxide (ITO), antimony oxide, antimony-tin oxide (ΑΤΟ) And particles such as cerium oxide.

Of these inorganic oxide particles, silica, alumina, zirconia, anti-oxide Fine particles such as mon are preferred. '

The inorganic oxide particles can also be used after appropriate surface treatment such as alkylation, polyoxylation, (meth) acryloxyalkylation, glycoxyalkylation, aminoalkylation and the like.

The inorganic oxide particles can be used alone or in admixture of two or more.

The primary average particle diameter of the inorganic oxide particles is preferably 100 η m or less, more preferably 1 to 80 nm. In this case, if the primary average particle diameter of the inorganic oxide particles exceeds 100 nm, the transparency of the resulting cured product may be impaired.

The amount of the inorganic oxide particles used is preferably 90 parts by weight or less, more preferably 80 parts by weight or less with respect to 100 parts by weight of (A) polyorganosiloxane. In this case, if the amount of inorganic oxide particles used exceeds 90 parts by weight, the composition may thicken and processing may become difficult.

In some cases, the inorganic oxide particles can be used as a dispersion dispersed in an appropriate solvent.

The solvent is inert to each component constituting the composition for sealing an optical semiconductor [I] and the composition for sealing an optical semiconductor [II] and a hard reaction, and has an appropriate volatility. Although not particularly limited, for example, methanol, ethanol, i

—Propanol, n-butanol, n-octanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propyl glycol monomethyl ether, propyl glycol monoester Alcohols such as tilether;

Ketones such as acetone, methylethylketone, methylisoptylketone, cyclohexanone;

Esters or lactones such as ethyl acetate, n-butyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, aptilolactone;

Aromatic hydrocarbons such as benzene, toluene, xylenes; Amides or lactams such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone

Etc.

These solvents can be used alone or in admixture of two or more. The solid content concentration of the dispersion of inorganic oxide particles is preferably 1 to 60% by weight, more preferably 5 to 50% by weight.

Further, if necessary, together with the inorganic oxide particles, for example, one or more dispersants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a polymer dispersant can be used in combination.

Inorganic oxide particles and dispersions thereof are commercially available, and these commercially available products can also be used.

Commercially available inorganic oxide particles and their dispersions (trade names) include, for example, silica particle dispersions such as methanol silica sol, IPA—ST, MEK—ST, NB A—ST, XBA—ST, DMAC. — ST, ST—UP, ST—OUP, ST—C, ST-N, ST—0, ST-OL, ST-20, ST—40, ST—50 (above, manufactured by Nissan Chemical Industries, Ltd.); Organosol PL-2PGME (Propylene glycol monomethyl ether dispersion, manufactured by Fuso Chemical Industry Co., Ltd.) etc. as silica particles, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT 600, Aerosil OX 50 (or more, Nippon Aerosil Co., Ltd.); Sildex H31, Sildex H32, Sildex H51, Sildex H52, Sildex H 121, Sildex H 122 (above, manufactured by Asahi Glass Co., Ltd.); E 2 2 OA, E 220 (The above is made by Nippon Silica Industry Co., Ltd.) S YLYS I A470 (manufactured by Fuji Silysia Co., Ltd.), SG flake (manufactured by Nippon Sheet Glass Co., Ltd.), etc. are used as alumina particle dispersions. Alumina sol-100, Alumina sol 200, Alumina sol 520 (or more, either AS- 1 501 (i-propanol dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd.); AS- 150 T (toluene dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd.) ) Etc. as a dispersion of zirconia particles — 110 JC (Toluene dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd.) Etc. as a dispersion of zinc antimonate particles, Celnax (aqueous dispersion, manufactured by Nissan Chemical Industries, Ltd.), etc. as a dispersion of cerium oxide particles, Nidral (moisture dispersion, Taki Chemical) Etc.) and the like.

In addition, the composition for optical semiconductor encapsulation [I] and the composition for optical semiconductor encapsulation [II] include an antioxidant, a light stabilizer and an ultraviolet absorber as necessary to suppress coloring of the cured product. A collecting agent can also be blended.

Examples of the antioxidant include trade names such as Sumi 1 izer BHT, Sum i 1 izer GM, Sumilize rGS, Sum i 1 izer MDP—S, Sum i 1 izer BBM—S, and Sum i. 1 ize rWX—R, Sumi 1 izer GA—80, Sum i 1 ize rTPL—R, Sumi 1 izer TP M, Sumi 1 izer TPS, Sumi 1 ize rTP-D (above, manufactured by Sumitomo Chemical Co., Ltd.) I rg anox l 076, I rg anox 565, I rgan ox l 520, I r ganox 245, I r ganox l 010, I rganoxl 098, I r ganoxl 330, I rganoxl 425, I rganox 3114, I rg an o xMD — 1024 (above, Ciba 'speciality' manufactured by Chemicals); Cy anox 1790 (produced by Cytec); TNP (produced by Yokkatsusei Co., Ltd.); Weston 618 (produced by V org Warner) ); I rgafos 168 (Ciba Specialty Chemicals); Ade kasta bPE P—36, Ade ka st abHP-10 (above, Asahi Denka Kogyo Co., Ltd.) and S and st abP—EPQ, U 1 tr an ox 626 etc. It can be mentioned. As the light stabilizer, for example, V ios 0 rb 04 (manufactured by Kyodo Pharmaceutical Co., Ltd.); T i nuv in 622, T i nuv in 765 (above, manufactured by Ciba Specialty Chemicals) Cyasor bUV-3346 (manufactured by Cytec); Ad ekast abLA-57 (manufactured by Asahi Denka Kogyo Co., Ltd.), Chimassorb 119, Chima ssorb 944, and the like.

Examples of the ultraviolet absorber include trade names such as Viosorb 80, Viosorbll O, Viosorb® 30, V iosorb 520, V iosorb 583, and Y iosorb 590 (above, manufactured by Kyodo Yakuhin Co., Ltd.); T inuvin P, T i nuv i n213, T i nuv i n234, T i nuv i n320, T i nu vin 326, T i nuv in 328 (above, manufactured by Ciba Specialty 'Chemicals); Ad e ka st abLA ~ 31 (manufactured by Asahi Denka Kogyo Co., Ltd.).

Furthermore, the composition for encapsulating an optical semiconductor [I] and the composition for encapsulating an optical semiconductor [II] include ethylene glycol and propylene diamine, if necessary, within a range that does not impair the intended effect of the present invention. Aliphatic polyols such as recall, carbon dioxide generation inhibitors such as aliphatic or aromatic carboxylic acids and phenol compounds; stress relaxation agents such as polyalkylene glycols and polydimethylsiloxane derivatives; various rubbers and organic polymers In addition to impact resistance improvers such as single beads, plasticizers, lubricants, other silane coupling agents. Flame retardants, antistatic agents, leveling agents, ion trap agents, sliding properties improving agents, far-modifying agents Other additives such as a surface tension reducing agent, an antifoaming agent, an anti-settling agent, an antioxidant, a release agent, a fluorescent agent, a coloring agent, and a conductive filler may be added.

The method for preparing the optical semiconductor encapsulating composition [I] and the optical semiconductor encapsulating composition [II] is not particularly limited, and can be prepared by mixing each component by a conventionally known method. . A preferred method for preparing the optical semiconductor encapsulating composition [I] was obtained by hydrolyzing and condensing the silane compound (1) and the like and the silane compound (2) and the like in the manner described above (A) Examples thereof include a method of mixing polyorganosiloxane with (B) an aliphatic or alicyclic epoxy compound and (C) a carboxylic acid anhydride or a polyvalent carboxylic acid. II] is preferably prepared by hydrolyzing and condensing the silane compound (1) and the like and the silane compound (2) and the like in the manner described above. (A) Polyorganosiloxane obtained by (B) Examples thereof include a method of mixing with an aliphatic or alicyclic epoxy compound, (C) a carboxylic acid anhydride or a polyvalent carboxylic acid, and (D) a curing accelerator.

The composition for optical semiconductor encapsulation [I] was prepared separately from a polyorganosiloxane liquid mainly composed of component (A) and a curing agent liquid mainly composed of component (B) and component (C). It may be prepared by mixing these at the time of use. The composition [II] is prepared by separately preparing a polyorganosiloxane liquid mainly composed of component (A), a component (B), and a curing agent liquid mainly composed of component (C) and component (D). These may be prepared by mixing at the time of use.

Optical semiconductor encapsulant

The optical semiconductor sealing material of the present invention comprises a hardened material obtained by heat-curing the optical semiconductor sealing composition [I] or the optical semiconductor sealing composition [I I].

When forming the optical semiconductor sealing material of the present invention, after applying each composition for optical semiconductor sealing to a predetermined portion of the substrate having the optical semiconductor layer, for example, by coating, potting, impregnation, etc. Heat to cure.

The construction method of each optical semiconductor sealing composition is not particularly limited. For example, a known method such as application or potting using a dispenser, application by screen printing under vacuum or normal pressure, reaction injection molding, or the like. Can be adopted.

Further, the method for curing each composition for optical semiconductor sealing after construction is not particularly limited. For example, a conventionally known curing apparatus such as a closed curing furnace or a tunnel furnace capable of continuous curing is used. Can be used.

The heating method for curing is not particularly limited, and conventionally known methods such as hot air circulation heating, infrared heating, and high-frequency heating can be employed.

The curing conditions are preferably, for example, 80 to 25 O and about 30 seconds to 15 hours. For the purpose of reducing the internal stress of the cured product at the time of curing, for example, after pre-curing at 80 to 120 ° C. for about 0.5 to 5 hours, for example, 120 It is preferable to perform post-curing at a temperature of about ~ 180 ° C. for about 0.1 to 15 hours. It is preferable to cure under the condition of about ~ 30 minutes.

Optical semiconductor

The optical semiconductor of the present invention comprises an optical semiconductor sealed with the optical semiconductor sealing material of the present invention. . When obtaining the optical semiconductor of the present invention, an optical semiconductor sealing material using the optical semiconductor sealing composition [I] and an optical semiconductor sealing using the optical semiconductor sealing composition [II] You may use both with material.

The film thickness of the optical semiconductor sealing material in the optical semiconductor of the present invention is preferably 0.05 mm or more, more preferably 0.1 mm or more. Note that the upper limit of the thickness of the optical semiconductor encapsulant is appropriately selected according to the use of the optical semiconductor to be encapsulated.

It also has excellent UV durability and can be used as a bonding material for optical semiconductors.

As described above, the polyorganosiloxane (α) of the present invention is particularly suitable as a main component of the optical semiconductor sealing composition [I] and the optical semiconductor sealing composition [II] of the present invention. Can be used.

(A) The composition for sealing an optical semiconductor [I] and the composition for sealing an optical semiconductor [II] of the present invention, which will be described later, comprising polyorganosiloxane as a main component, can be potted and molded. Even if the film thickness is thick, there is no generation of bubbles in the cured product, and it is possible to form an optical semiconductor encapsulant that is colorless and transparent and has excellent UV durability. For example, it emits light in the region below 500 nm. It can be used very favorably for sealing blue LEDs or white LEDs having a peak wavelength. Example

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

The methods for measuring the viscosity, Mw and epoxy equivalent of (A) polyorganosiloxane obtained in each synthesis example are as follows.

Viscosity measurement method:

The temperature was measured at 25 ° C with a TV viscometer.

Mw measurement method: Column: Tosohichi TSKg e 1 GRCXLH, Solvent: Tetrahydrofuran, Temperature: 40 ° C, Pressure: 68 kg f / cm ²

Method for measuring epoxy equivalent: Conforms to JISC 2105 hydrochloric acid-methylethyl ketone method.

Synthesis example 1

In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 2— (3,4-dimethyldimethylmethoxysilane (DMDS) 10.0 g., Methylisobutyl ketone (MI BK) 300 g, triethylamine 10. 00 g was added and mixed at room temperature Next, 80 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 4 hours while mixing under reflux. After that, the organic layer was taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain (A) polyorganosiloxane. Obtained as a viscous clear liquid.

As for this (A) polyorganosiloxane, as a result of NMR analysis, a peak based on the epoxy group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm according to the theoretical strength. It was confirmed that this did not happen.

The viscosity of this (A) polyorganosiloxane exceeded 10 OPa · s and exceeded the measurement limit. Mw was 2500 and the epoxy equivalent was 200.

The molding jig and curing conditions for the composition for optical semiconductor encapsulation, and the evaluation procedure for the appearance, UV durability and hardness of the cured product are as follows.

Hardened material creation (for light transmittance measurement):

Two glass plates with polyethylene terephthalate film attached to the surface were made to face each other, and a silicon rubber rod with a diameter of 5 mm was sandwiched between the ends of the glass plate in a U shape to form a molding jig. The composition for optical semiconductor sealing is poured into this molding jig, heated in an oven at 100 ° C for 2 hours, then heated in an oven at 120 ° C for 2 hours, and further in an oven at 140 ° C for 2 hours. Cured by heating for hours. A 5 mm thick sample for light transmittance measurement was obtained.

Hardened material creation (Tg, for measuring linear expansion coefficient):

Two stainless steel plates sprayed with a release agent face each other and the mold is hollowed between them lm A m-thick stainless steel plate was sandwiched to form a molding jig. The composition for optical semiconductor sealing is poured into this molding jig, heated in an oven at 100 ° C for 2 hours, then heated in an oven at 120 ° C for 2 hours, and further in an oven at 140 ° C for 2 hours. Heated to harden.

A sample for measuring Tg with a thickness of 1 mm was obtained.

Sample preparation for crack resistance evaluation:

A mold release agent was applied to a mold having a diameter of 5 mm and a depth of 5 mm, and a 2 X 2 X 0.2 mm ³ sapphire substrate was placed thereon. The resin composition of the present invention is poured from above, heated in an oven at 100 ° C for 2 hours, then heated in an oven at 120 ° C for 2 hours, and further heated in an oven at 140 ° C for 2 hours. I let you. Ten evaluation samples were prepared for one resin.

Solder reflow conditions:

After leaving the sample for crack resistance evaluation at 30 ° C and 70% for 1 week, preliminary overheating: 1 80 ~ 200 ° (:, heating temperature: within 120 seconds, soldering temperature: 260 ° C or less, soldering time: 10 Within a second, after 3 passes under nitrogen reflow conditions, the occurrence of cracks was observed with a microscope, and the number of samples that did not crack was counted out of 10 samples.

heat cycle:

The cycle of 40 ° CX for 30 minutes and 100 ° CX for 30 minutes was repeated 100 times with the apparatus, and the occurrence of cracks was observed with a microscope. Of the 10 samples, the number of samples that did not crack was counted.

Tg:

DMTA (RSA—I I, manufactured by Rheometrics Scientific) was scanned from 30 to 28 at a heating rate of 5 ° CZmin, and the maximum value of t an <5 was defined as Tg.

Linear expansion coefficient (also called CTE):

A TMA (TMA-S S 6100, manufactured by Seiko Instruments Inc.) was scanned from 30 to 150 ° C at a heating rate of 5 ° C / min.

Initial transmittance; The transmittance of the cured product at a wavelength of 4700 nm was measured with a spectrophotometer.

Evaluation procedure for UV durability:

Using UV long life fade meter (manufactured by Suga Test Instruments Co., Ltd.), the cured product was continuously irradiated with UV (UV) at 63 ° C for 100 hours, and at a wavelength of 4700 nm. The transmittance was measured with a spectrophotometer. It is sufficient if 90% or more of the initial transmittance is maintained.

Evaluation procedure for heat resistance:

The cured product was allowed to stand at 150 ° C. for 72 hours, and the transmittance at a wavelength of 47 nm was measured with a spectrophotometer. It is sufficient that 90% or more of the initial transmittance is maintained.

Example 1

As component (A), obtained in Synthesis Example 1 (A) 4.0 g of polyorganosiloxane,

(B) 6.0 g of YX800 as component, methylhexahydrophthalic anhydride as component (C) (see formula (3) above, trade name: MH700, manufactured by Shin Nippon Rika Co., Ltd.) 7. Add 5 g of U-CAT 5 0 0 3 0 .0 70 g (Sanpro Corporation) as component (D), mix evenly, degas, then inject into molding tool and cure. As a result, a cured product that was transparent and free from cracks and bubbles was obtained. Table 2 shows the evaluation results of this cured product.

Examples 2-5, Comparative Examples 1 and 2

A cured product was obtained in the same manner as in Example 1 except that each component shown in Table 1 was used. Table 2 shows the evaluation results for each cured product. (D) all components are U—C A T 5 0 0 3

(C) 1% by weight based on the component was added. In Examples 1 to 4, the transmittance did not change even when irradiated with UV, and the transmittance of 90% or more was maintained even when left at 1550 for 72 hours. As it can withstand practical use. Also, no cracks occurred after reflow or heat cycle. table 1

X 8.0 0 0 Made by Japan Epoxy Resin Co., Ltd.

YL 6 7 5 3 ⁰ Made by Japan Epoxy Resin Co., Ltd.

YED 2 1 6 D: <0 ( ^eH 2) ⁶ 0> Made by Japan Epoxy Resin Co., Ltd.

CE 2 0 2 1:

Daicel Chemical Industries Table 2

Synthesis example 2

In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 2— (3,4-dimethyldimethoxysilane (DMDS) 40.0 g, (MI BK) 500 g and triethylamine 10.0 g were added and mixed at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure. (A) Polyorgano Siloxane was obtained as a viscous transparent liquid.

For this (A) polyorganosiloxane — when NMR analysis was performed, a peak based on the epoxy group was obtained in the vicinity of the chemical shift (<5) = 3.2 ppm according to the theoretical intensity. It was confirmed that no reaction occurred.

Table 3 shows the viscosity, Mw and epoxy equivalent of this (A) polyorganosiloxane.

Synthesis examples 3-5

Each (A) polyorganosiloxane was obtained as a viscous transparent liquid in the same manner as in Synthesis Example 2 except that the charged raw materials were as shown in Table 3.

Table 3 shows the viscosity, Mw and epoxy equivalent of each (A) polyorganosiloxane. '

Table 3

Synthesis example 6

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 20 g of polyorganosiloxane of Synthesis Example 1, 6 g of methylisoptyl ketone, and 12 g of hexamethyldisilazane were uniformly dissolved. Subsequently, 0.23 acetic acid was added dropwise and the mixture was stirred for 1.5 hours at 60 ° (:. After completion of the reaction, it was washed with 3% aqueous nitric acid and water, and the solvent was distilled off under reduced pressure. A transparent viscous liquid was obtained. When the IR spectrum of this viscous liquid was examined, it was confirmed that the absorption peak at 3,400 cm- ¹ based on the silanol group disappeared and the silanol group was trimethylsilylated.

The molding jig and curing conditions for the composition for optical semiconductor encapsulation, and the evaluation procedures for the appearance, UV durability and hardness of the cured product are as follows.

Molding jig:

Two glass plates with a polyethylene terephthalate film affixed to the surface were made to face each other, and a silicon rubber rod with a diameter of 2 mm was sandwiched between the ends of the glass plate in a U shape to form a molding jig. .

Curing conditions:

The composition for optical semiconductor sealing was poured into the molding jig, and cured by heating in an oven at 120 ° C. for 1 hour and in an oven at 140 ° C. for 2 hours.

Evaluation procedure for UV durability:

Using a UV long life fade meter (manufactured by Suga Test Instruments Co., Ltd.), the cured product was irradiated with UV light (UV) continuously at 63 ° C for 2 weeks, and the transmittance at a wavelength of 470 nm before and after irradiation. Was measured with a spectrophotometer.

Heat resistance: The transmittance at 470 nm was measured at the initial stage of the cured product and after being left in an oven at 150 ° C. for 120 hours.

Crack · Peeling evaluation guidelines:

The semiconductor sealing composition was injected into a lead frame, and 10 samples were prepared by curing at 120 ° C. for 2 hours and at 140 ° C. for 2 hours. This sample was repeated 400 times at a heat cycle of 1-50 to 100 ° C., and then cracking and peeling were observed with a microscope. Crack · Peeling of 3 or less samples out of 10 ··· ◎

Crack '4-5 out of 10 samples with peeling'

Cracks 6 or more of 10 samples with peeling · X

Example 6

(A) As component, (A) Polyorganosiloxane 4.5 g obtained in Synthesis Example 2, (B) SR—HHPA 5.5 g as component, (C) Methylhexahydride as component Mouth fuuric anhydride (Refer to formula (3) above. Product name MH 700, manufactured by Shin Nippon Rika Co., Ltd.) 7. Add 7 g, mix uniformly, degas, and then inject into molding jig Then, it was hardened to obtain an uncolored transparent cured product. Table 5 shows the evaluation results of this cured product.

Examples 7 to 17

A cured product was obtained in the same manner as in Example 6 except that each component shown in Table 4 was used. Table 5 shows the evaluation results for each cured product.

Comparative Examples 3 and 4

The contents of the other components in Table 4 are as follows.

PX-4ET: Tetra n-butyl phosphonium o, o-Jetyl phosphoroditonate (trade name Hishicoline 4X-PET, manufactured by Nippon Chemical Industry Co., Ltd.)

S R— HH P A: Compound of formula (M)

Sakamoto Pharmaceutical Co., Ltd.

KBM403: key glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBM803: Armercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

(Made by Co., Ltd.)

DDS: Dodecanedithiol

I TM: Compound of formula (21)

Y 11597: compound of formula (22)

X—22—2000: Epoxy silicone (manufactured by Shin-Etsu Chemical Co., Ltd.) CI 100: Both-terminal carboxylic acid hydrogenated polybutadiene (manufactured by Nippon Soda Co., Ltd.) While maintaining sufficient UV durability and heat resistance by adding additives as shown in Examples and Comparative Examples It can be seen that the crack has sufficient resistance to peeling.

Table 4

(A) component (g) (B) component (g) (C content (g). Curing accelerator (g) additive (g) Example 6 Synthesis example 2 (4.5) SR-HHPA (5.5) H700 ( 7.7) PX-4ET (0.07) KB 403 (0.5) Example 7 Synthesis Example 3 (4.5) SR-HHPA (5.5) MH700 (7.3) PX-4ET (0.07) KB 403 (0.5) Example 8 Synthesis Example 4 ( 4.5) SR-HHPA (5.5) MH700 (6.9) PX-4ET (0.07) KBM403 (0.5) Example 9 Synthesis Example 5 (4.5) SR-HHPA (5.5) MH700 (6.6) PX-4ET (0.07) KBM403 (0.5 Example 10 Synthesis Example 3 (4.5) SR-HHPA (5.5) H700 (7.3) PX-4ET (0.07) KBM803 (0.5) Example 11 Synthesis Example 3 (4.5) SR- HHPA (5.5) MH700 (7.3) PX -4ET (0.07) DDS (0.5) Example 12 Synthesis Example 3 (4.5) SR-HHPA (5.5) MH700 (7.3) PX— 4ET (0.07) IT (0.5) Example 13 Synthesis Example 3 (4.5) SR-HHPA (5.5) MH700 (7.3) PX-4ET (0.07) Yl 1597 (0.5) Example 14 Synthesis Example 3 (4.5) SR-HHPA (5.5) H700 (7.3) PX-4ET (0.07) X-22- 2000 (0.5 Example 15 Synthesis Example 3 (4.5) SR-HHPA (5.5) MH700 (7.3) PX-4ET (0.07) CI1000 (0.5) Example 16 Synthesis Example 3 (4.5) SR-HHPA (5.5) MH700 (6.9) PX -4ET (0.03) KBM403 (0.5)

C3-CIC acid (0.4)

Example 17 Synthesis Example 5 (4.5) SR—HHPA (5.5) H700 (7.7) PX-4ET (0.07) None Comparative Example 3 Synthesis Example 3 (8) SR-HHPA (2) H700 (5.5) PX-4ET (0.06) ) KBM403 (0.5) Comparative Example 4 SR-HHPA (IO) MH700 (9.7) PX-4ET (0.10) KBM403 (0.5)

Table 5

Initial transmittance «) After UV irradiation (¾;) After 150 ° C for 120 hours Crack-peeling Example 6 89 88 86 ◎ Example 7 89 88 86 ◎ Example 8 89 88 86 ◎ Example 9 89 88 86 ◎ Example 1 0 89 88 86 ◎ Example 1 1 89 88 84 ◎ Example 1 2 89 88 86 ◎ Example 1 3 89 87 84 ◎ Example 1 4 89 88 86 ○ Example 1 5 89 88 86 ○ Example 1 6 89 89 88 ◎ Example 1 7 89. 87 84 ◎ Comparative example 3 90 89 87 X Comparative example 4 89 85 79 〇

Claims

The scope of the claims

1. (A) Polyorganosiloxane having an epoxy equivalent weight of not more than 1600 g / mole, 100 parts by weight, (B) Aliphatic or alicyclic epoxy compound exceeding 10.00, 1, 0 0 0 parts by weight And (C) a composition for encapsulating an optical semiconductor, which contains a carboxylic acid anhydride or a polyvalent carboxylic acid.

2. The component (A) comprises a silane compound and / or a partial condensate thereof represented by the following formula (1) and a silane compound and Z or a partial condensate represented by the following formula (2). A polyorganosiloxane having a polystyrene-reduced weight-average molecular weight of 5 0 0 to 1, 0 0 0, 0 0 0, obtained by hydrolysis and condensation by heating in the presence of a solvent, an organic base and water. An optical semiconductor sealing composition.

[In the formula (1), X is a monovalent organic group having one or more epoxy groups, Y ¹ is a chlorine atom, a bromine atom, an iodine atom, or a linear, branched or cyclic group having 1 to 20 carbon atoms. R ¹ is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms, or A cyclic substituted alkyl group, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and n is 0 It is an integer of ~ 2. ]

(R ² ) — Si— (丫² (2)

4-m [In the formula (2), Y ² represents a chlorine atom, a bromine atom, an iodine atom or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom, a fluorine atom, carbon A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms, a linear chain having 2 to 20 carbon atoms, branched Or cyclic alkenyl group, aryl group having 6 to 20 carbon atoms, or carbon number? Represents an aralkyl group of ˜20, and m is an integer of 0-3. ]

3. The composition for encapsulating an optical semiconductor according to claim 1, further comprising (D) a curing accelerator. .

4. An optical semiconductor sealing material comprising a cured product obtained by heat-curing the optical semiconductor sealing composition according to claim 1.

5. An optical semiconductor sealed with the optical semiconductor sealing material according to claim 4.

6. Use of the composition for optical semiconductor sealing according to any one of claims 1 to 3 for forming an optical semiconductor sealing material.