JP6006725B2 - Curable resin composition for optical semiconductor element sealing and cured product thereof - Google Patents

Description

  The present invention relates to a curable resin composition suitable for optical semiconductor element sealing applications, and a cured product thereof.

Liquid epoxy resin composition using bisphenol-type epoxy resin, alicyclic epoxy resin, etc. as a resin for sealing optical semiconductor elements such as LED (Light Emitting Diode), because of its excellent mechanical strength and adhesive strength Has been used (see Patent Document 1). In recent years, LEDs have been used in fields that require high brightness, such as automotive headlamps and lighting applications. Accordingly, resins that encapsulate optical semiconductor elements are particularly resistant to UV and heat. It has come to be required. However, it is difficult to say that bisphenol-type epoxy resins and alicyclic epoxy resins have sufficient UV resistance and heat resistance as described above, and may not be used in fields where high luminance is required. Therefore, as a sealing material having high UV resistance, heat resistance, etc., a silicone resin sealing material using an unsaturated hydrocarbon group-containing organopolysiloxane and an organohydrogenpolysiloxane is used (see Patent Document 2). ). However, although the sealing material using such a silicone resin is excellent in UV resistance and heat resistance, it has a problem that the sealing surface becomes sticky or gas permeability is high.
The problem of high gas permeability is the phenomenon that the silver plating surface used in the LED is corroded by the permeation of sulfur-based gas, and becomes black by turning into silver sulfide, thereby reducing the illumination intensity of the LED. Therefore, countermeasures (improvement of sulfidation resistance) are urgent. This is done by increasing the crosslink density of the cured silicone resin or increasing the aromatic organic groups such as phenyl groups in the molecule, but inevitably increases the hardness of the cured product. There is a concern that heat cycle (thermal cycle) resistance is inferior, adverse effects such as cracking and peeling from the substrate, and UV resistance is inferior because aromatic organic groups are increased. In addition, satisfactory sulfidation resistance has not yet been achieved.
In order to solve these problems, a condensate using a silicon compound condensate having an epoxy group or a phenyl group and an epoxy resin curing agent has been studied, but it is still not satisfactory. Furthermore, since the viscosity increase (pot life) after mixing these two liquids is fast, there is a problem that workability is inferior.

Japanese Unexamined Patent Publication No. 2003-277473 Japanese Patent No. 4636242

  An object of this invention is to provide the curable resin composition for optical semiconductor element sealing excellent in pot life and sulfidation resistance, and its hardened | cured material.

As a result of intensive studies in view of the actual situation as described above, the present inventors have found a curable resin composition containing a curing catalyst having a melting point of 40 to 200 ° C. and an epoxy resin and / or an epoxy resin curing agent. Has been found to solve the problem, and the present invention has been completed.
That is, the present invention

(1) A curable resin composition for optical semiconductor encapsulation containing a curing catalyst having a melting point of 40 to 200 ° C. and an epoxy resin and / or an epoxy resin curing agent.
(2) An epoxy resin curing agent is an addition reaction product of a carbinol-modified silicone oil (a) having both terminals represented by the formula (1) and a compound (d) having one carboxylic anhydride group in the molecule; A polycarboxylic acid resin (A) comprising an addition reaction product of a polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule and a compound (d) having one carboxylic anhydride group in the molecule The curable resin composition for optical semiconductor encapsulation according to (1).

(In the formula (1), an alkylene group containing _{R 1} is independently an ether bond 1-10 alkylene group or a carbon number of 1 to 10 carbon atoms, _{R 2} is 1 to 3 carbon atoms each independently (M represents an average value of 1 to 100 for an alkyl group or a phenyl group.)
(3) The epoxy resin curing agent is a carbinol-modified silicone oil (a) having both ends represented by the formula (1), a polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, A curable resin composition for encapsulating an optical semiconductor according to (1), which is a polyvalent carboxylic acid resin (A) obtained by addition reaction with a compound (d) having one carboxylic acid anhydride group object.

(In the formula (1), an alkylene group containing _{R 1} is independently an ether bond 1-10 alkylene group or a carbon number of 1 to 10 carbon atoms, _{R 2} is 1 to 3 carbon atoms each independently (M represents an average value of 1 to 100 for an alkyl group or a phenyl group.)
(4) The polyvalent carboxylic acid resin (A) is obtained by addition reaction including a compound (c) having two or more carboxylic acid anhydride groups in the molecule as a reaction raw material. (3) The curable resin composition for optical semiconductor sealing.
(5) The light according to any one of (2) to (4), wherein the polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule is a terminal alcohol polyester compound represented by the formula (2): A curable resin composition for semiconductor encapsulation.

(In Formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and m represents an average value of 1 to 100.)
(6) The curable resin composition for optical semiconductor encapsulation according to any one of (1) to (5), wherein the epoxy resin is a silicone skeleton epoxy resin (B).
(7) Silanol-terminated silicone oil represented by formula (3) and epoxy group-containing silicon represented by formula (4), wherein the silicone skeleton epoxy resin (B) is obtained through the following production steps 1 and 2. The curable resin composition for sealing an optical semiconductor element according to (6), which is a polymer of the compound and has an epoxy equivalent of 300 to 1500 g / eq measured by the method described in JIS K-7236.
Manufacturing process 1
A step of condensing a silanol group of a silanol-terminated silicone oil and an alkoxy group of an epoxy group-containing silicon compound to obtain a modified silicone oil.
Manufacturing process 2
A step of adding water after the production step 1 to hydrolyze and condense the remaining alkoxy groups.

(In Formula (3), R ₅ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and p represents an average value of 3 to 200. In the formula, a plurality of R ₅ may be the same as each other. May be different)

(In Formula (4), X is an organic group containing an epoxy group, R ₆ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ₇ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, q represents an integer of 0 to 2, and r represents an integer of (3-q).)
(8) The curable resin composition for optical semiconductor encapsulation according to any one of (1) to (7), wherein the curing catalyst having a melting point of 40 to 200 ° C. is a metal soap-based curing catalyst.
(9) The curable resin composition for optical semiconductor encapsulation according to (8), wherein the metal soap is a zinc salt comprising a carboxylic acid compound.
(10) The curable resin composition for optical semiconductor encapsulation according to (9), wherein the zinc salt composed of a carboxylic acid compound is a zinc salt composed of a C10-30 monocarboxylic acid compound having a hydroxyl group.
(11) The curable resin composition for optical semiconductor encapsulation according to (10), wherein the C10-30 monocarboxylic acid compound having a hydroxyl group is 12-hydroxystearic acid.
(12) The curable resin composition for optical semiconductor encapsulation according to (10), wherein the C10-30 monocarboxylic acid compound having a hydroxyl group is stearic acid.
(13) A cured product obtained by curing the curable resin composition for optical semiconductor encapsulation according to any one of (1) to (12).
(14) An LED comprising the cured product according to (13).

  According to the present invention, since a curable resin composition containing a curing catalyst having a melting point of 40 to 200 ° C. and an epoxy resin and / or an epoxy resin curing agent is extremely excellent in sulfidation resistance and pot life, an optical semiconductor element. (LED) Very useful as a sealing material.

  The curable resin composition for an optical semiconductor element sealing material of the present invention contains a curing catalyst having a melting point of 40 to 200 ° C., and an epoxy resin and / or an epoxy resin curing agent.

The curing catalyst in the present invention starts curing of epoxy groups, epoxy groups and carboxyl groups, epoxy groups and carboxylic anhydride groups, epoxy groups and amine groups, epoxy groups and thiol groups, epoxy groups and amide groups, or the like. It is a compound that promotes.
The resin composition for encapsulating an optical semiconductor of the present invention contains a curing catalyst having a melting point of 40 to 200 ° C. among the curing catalysts.
In general, a resin composition for optical semiconductor encapsulation is liquid at room temperature, and the molding method is to heat cure after injecting a sealing material into a mold in which a substrate to which an optical semiconductor element is fixed is inserted. An injection method for molding, a compression molding method in which a sealing material is pre-injected onto a mold, an optical semiconductor element fixed on the substrate is immersed in the mold, and then heat-cured and then released from the mold are used. ing.
A dispenser or the like is used as an injection method.
The injected sealing resin is heated and cured. For heating for curing, methods such as hot air circulation, infrared rays, and high frequency are used. The heating condition is preferably about 80 to 200 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing at 120 to 180 ° C. for 30 minutes to 10 hours. It is common.
When a curable resin composition for sealing an optical semiconductor is a solid catalyst at room temperature (25 ° C.), there is a problem that the cured product becomes cloudy and the illuminance of the LED is inferior, so select a liquid catalyst. Has become commonplace. However, when a curing catalyst that is liquid at room temperature (25 ° C.) is used, the appearance of the cured product is excellent, but since it is compatible with the epoxy resin and epoxy resin curing agent that are liquid at room temperature (25 ° C.), after mixing them, It has been regarded as a problem that it functions as a curing catalyst even before heat curing, causing an excessive increase in viscosity and inferior workability.
However, a catalyst that is solid at room temperature (25 ° C.) does not completely adapt to an epoxy resin and an epoxy resin curing agent at room temperature (25 ° C.), and therefore does not cause an excessive increase in viscosity. Moreover, in the case of heat-curing, those solid catalysts melt | dissolve, express catalytic ability, and since it hardens | cures as it is, the external appearance of hardened | cured material also does not become a problem.
A catalyst that is solid at room temperature (25 ° C.) is preferably one having a melting point of 40 to 200 ° C. from the viewpoint of workability and melting during heat curing to exhibit catalytic ability. In this case, from the viewpoint of suppressing an excessive increase in viscosity, it is more preferable to use a curing catalyst having a melting point of 100 to 160 ° C, and it is particularly preferable to use a curing catalyst having a melting point of 120 to 160 ° C.

As the catalyst having a melting point of 40 to 200 ° C., an ammonium salt-based curing catalyst, a phosphonium salt-based curing catalyst, and a metal soap-based curing catalyst are particularly preferable because of excellent transparency. Examples of the ammonium salt-based curing catalyst include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, Examples include trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, and trioctylmethylammonium acetate. Examples of the phosphonium salt-based curing catalyst include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, methyltributylphosphonium diethylphosphate, and the like. Examples of metal soap curing catalysts include calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, barium stearate, lithium stearate, sodium stearate, potassium stearate, 12-hydroxycalcium phosphate, 12-hydroxystearic acid. Zinc, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, barium 12-hydroxystearate, lithium 12-hydroxystearate, sodium 12-hydroxystearate, calcium montanate, zinc montanate, magnesium montanate, montan Aluminum oxide, lithium montanate, sodium montanate, calcium behenate, zinc behenate, magnesium behenate , Lithium behenate, sodium behenate, silver behenate, calcium laurate, zinc laurate, barium laurate, lithium laurate, zinc undecylenate, zinc ricinoleate, barium ricinoleate, zinc myristate, zinc palmitate, etc. It is done. These catalysts may be used alone or in combination of two or more.
In order to obtain a cured product with a high melting point of the curing catalyst and excellent transparency and sulfidation resistance, especially zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate Zinc salts made of a monocarboxylic acid compound having 10 to 30 carbon atoms such as zinc carboxylate having 10 to 30 carbon atoms such as zinc palmitate and zinc 12-hydroxystearate can be preferably used. Among these, from the viewpoint of excellent pot life and sulfidation resistance, a zinc salt composed of a monocarboxylic acid compound having 10 to 20 carbon atoms such as zinc stearate and zinc undecylenate, and a hydroxyl group such as 12-hydroxyzinc stearate. A zinc salt composed of a monocarboxylic acid compound having 15 to 20 carbon atoms is preferably used, more preferably zinc stearate, zinc undecylenate, zinc 12-hydroxystearate, particularly preferably zinc stearate, 12- Zinc hydroxystearate can be used.
The curing catalyst having a melting point of 40 to 200 ° C. is usually used in the range of 0.001 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin described later.
The curing catalyst having a melting point of 40 to 200 ° C. can be pulverized for use. As the pulverization method, a jet mill, a planetary ball mill, a spiral mill or the like can be used.

  In the curable resin composition of the present invention, an epoxy resin and / or an epoxy resin curing agent is used.

From here, the epoxy resin curing agent will be described.
Examples of the epoxy resin curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and polycarboxylic acids.
In the present invention, the epoxy resin curing agent is particularly preferably an acid anhydride or a polyvalent carboxylic acid from the viewpoints of hardness, workability (being liquid at room temperature), and transparency of the cured product. Carbinol-modified silicone oil (a), polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, compound (d) having one carboxylic anhydride group in the molecule, and as necessary The polyvalent carboxylic acid resin (A) obtained by addition reaction of the compound (c) having two or more carboxylic anhydride groups in the molecule is most preferable.

Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3- And acid anhydrides such as dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.
In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid Acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and the like. It is preferable from the viewpoint of workability.

The polyvalent carboxylic acid is a compound having at least two carboxyl groups.
The polyvalent carboxylic acid is preferably a bifunctional to hexafunctional carboxylic acid, such as butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, malic acid, etc. Linear alkyl diacids, alkyl tricarboxylic acids such as 1,3,5-pentanetricarboxylic acid, citric acid, phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid An aliphatic cyclic polycarboxylic acid such as acid, nadic acid and methyl nadic acid; a multimer of unsaturated fatty acids such as linolenic acid and oleic acid; and dimer acids which are reduced products thereof; Examples include compounds obtained by reaction with acid anhydrides, 2-6 functional polyhydric alcohols and acid anhydrides Compounds obtained by the reaction of, heat resistance, and more preferable from the viewpoint of workability. Furthermore, the polyhydric carboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable from a transparency viewpoint.
The 2- to 6-functional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane and 2-hydroxymethyl-1,4-butanediol, and tet such as pentaerythritol and ditrimethylolpropane Ols, and the like hexa-ols, such as dipentaerythritol.

  Preferred polyhydric alcohols are alcohols having 5 or more carbon atoms, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2,4 -Compounds such as diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol are preferred, among which 2-ethyl-2-butyl-1,3 -Alcohols having a branched chain structure or a cyclic structure such as propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol, Preferred from the viewpoint of transparency. In addition, tricyclodecane dimethanol is preferred.

Examples of acid anhydrides to be reacted with polyhydric alcohols include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2, 2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4- Anhydrides and the like are preferable, and methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are particularly preferable from the viewpoints of heat resistance, transparency, and workability.
The conditions for the addition reaction can be used without particular limitation as long as they are known methods, but specific reaction conditions include, for example, acid anhydrides and polyhydric alcohols in a catalyst-free and solvent-free condition, A method of reacting at 150 ° C. and heating, and taking it out as it is after completion of the reaction can be mentioned.

As the epoxy resin curing agent used in the curable resin composition for encapsulating an optical semiconductor of the present invention, a preferable polyvalent carboxylic acid resin (A) includes two or more carbinol-modified silicone oils (a) and two or more in the molecule. A polyhydric alcohol compound (i) having a hydroxyl group, a compound (d) having one acid anhydride group in the molecule, and a compound (c) having two or more acid anhydride groups in the molecule as necessary. ) And a polyvalent carboxylic acid resin (A) obtained by performing an addition reaction.
Usually, polyvalent carboxylic acids composed of only low molecular weight C, H, and O atoms are often in a solid state at room temperature (25 ° C.), and as it is, a curable resin composition for sealing an optical semiconductor composed of an epoxy resin. It is difficult to use as a curing agent for objects. However, when the component contains a polysiloxane compound having a repeating unit of Si—O bond, it can exist in a liquid state at room temperature (25 ° C.) due to its low intermolecular force. A polyvalent carboxylic acid resin (A) that is preferable as an epoxy resin curing agent used in the curable resin composition for encapsulating an optical semiconductor of the present invention can also be used at room temperature by using the both-end carbinol-modified silicone oil (a) as a reaction raw material. It can exist in liquid form at (25 ° C.).
Addition reaction of both terminal carbinol-modified silicone oil (a), polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, and compound (d) having one acid anhydride group in the molecule Thus, the hydroxyl group of the carbinol of the both-end carbinol-modified silicone oil (a) and the acid anhydride group of the compound (d) having one acid anhydride group in the molecule can be converted into a polyhydric alcohol compound (i The acid anhydride group of the compound (d) having a hydroxyl group and an acid anhydride group is subjected to an addition reaction involving ring opening of the acid anhydride group, and is a mixture of polyvalent carboxylic acids each having a carboxyl group at both ends. A carboxylic acid resin (A) is obtained.
Further, by using a compound (c) having two or more acid anhydride groups in the molecule as a reaction raw material, two or more carbinol-modified silicone oils (a) and / or two or more in the molecule are used. The polyhydric alcohol compounds (i) having two hydroxyl groups and / or the carbinol-modified silicone oil (a) at both ends and the polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule are polymerized as the same molecule. .
In particular, the compatibility between both terminal acid anhydride adducts of both ends carbinol-modified silicone oil (a) and acid anhydride adducts of polyhydric alcohol compounds (i) having two or more hydroxyl groups in the molecule is present. When it is bad and separated, by using the compound (c) having two or more acid anhydride groups in the molecule, the carbinol-modified silicone oil (a) at both ends and two or more hydroxyl groups in the molecule are used. The polyhydric alcohol compound (i) possessed can be polymerized as the same molecule and can be obtained as a uniform liquid substance at room temperature (25 ° C.).

  From here, the both-terminal carbinol-modified silicone oil (a), which is a raw material for the polycarboxylic acid resin (A), a polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, The compound (c) having two or more acid anhydride groups and the compound (d) having one acid anhydride group in the molecule will be described.

First, the both terminal carbinol-modified silicone oil (a) will be described.
Examples of the both-end carbinol-modified silicone oil (a) are silicone compounds having alcoholic hydroxyl groups at both ends represented by the following formula (1).

(In the formula (1), R ₁ is an alkylene group having 1 to 10 carbon atoms and an alkylene group having an ether bond, R ₂ is an alkyl group or phenyl group having 1 to 3 carbon atoms, and m is an average value of 1 to 1) 100 represents each.)

In the formula (1), specific examples of R ₁ include alkylene groups such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene, ethoxyethylene group, propoxyethylene group, Examples include an alkylene group having an ether bond such as a propoxypropylene group and an ethoxypropylene group. Particularly preferred are propoxyethylene group and ethoxypropylene group.

Next, R ₂ represents an alkyl group having 1 to 3 carbon atoms such as a methyl group or a phenyl group, and may be the same or different, but both ends carbinol-modified silicone oil (a) and two or more in the molecule A polyhydric alcohol compound (i) having a hydroxyl group, a compound (d) having one acid anhydride group in the molecule, and a compound (c) having two or more acid anhydride groups in the molecule as necessary. In order to make the polyvalent carboxylic acid resin (A) obtained by the addition reaction with) a liquid at room temperature, a methyl group is preferable compared to a phenyl group.

  In the formula (1), m is an average value of 1 to 100, preferably 2 to 80, more preferably 5 to 30.

  The both-end carbinol-modified silicone oil (a) represented by the formula (1) is, for example, X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-201, BY16-004. SF8427 (both manufactured by Toray Dow Corning Co., Ltd.) XF42-B0970, XF42-C3294 (both manufactured by Momentive Performance Materials Japan Godo Kaisha), etc., are all available from the market. These two terminal carbinol-modified silicone oils can be used alone or in combination. Among these, X-22-160AS, KF6001, KF6002, BY16-201, and XF42-B0970 are preferable.

Next, the polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule will be described.
Examples of the polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule include a terminal alcohol polyester compound (b), a hydrocarbon polyhydric alcohol compound (j), and a terminal alcohol polycarbonate compound.

  Although it does not specifically limit as a terminal alcohol polyester compound (b), For example, the polyester compound etc. which have a hydroxyl group at the terminal shown by following formula (2) are mentioned.

(In Formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and n represents an average value of 1 to 100.)

In Formula (2), specific examples of R ₃ include linear alkylene groups having 1 to 10 carbon atoms such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isopropylene, ethylbutylpropylene, isobutylene, Examples thereof include alkylene groups having a branched chain of 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene, and alkylene groups having a cyclic structure such as cyclopentanedimethylene and cyclohexanedimethylene. Among these, an alkylene group having a branched chain having 1 to 10 carbon atoms or an alkylene group having a cyclic structure is preferable, and in particular, ethylbutylpropylene, isobutylene, neopentylene, diethylpentylene, cyclohexanedimethylene is a heat-resistant transparency of a cured product. It is preferable from the viewpoint.

In the formula (2), specific examples of R ₄ include linear alkylene groups having 1 to 10 carbon atoms such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isopropylene, ethylbutylpropylene, isobutylene, Examples thereof include alkylene groups having a branched chain of 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene, and alkylene groups having a cyclic structure such as cyclopentanedimethylene and cyclohexanedimethylene. Among these, a linear alkylene group having 1 to 10 carbon atoms is preferable, and propylene, butylene, pentylene, and hexylene are particularly preferable from the viewpoint of adhesion of a cured product to a substrate or the like.

  In formula (2), n is an average value of 1 to 100, preferably 2 to 40, more preferably 3 to 30.

  Although the weight average molecular weight (Mw) of a terminal alcohol polyester compound (b) is 500-20000, Preferably it is 500-5000, More preferably, it is 500-3000. If the weight average molecular weight is less than 500, the cured product hardness of the curable resin composition of the present invention may be too high and cracks may occur in a heat cycle test or the like, and if the weight average molecular weight is more than 20000, the cured product becomes sticky. May occur. In the present invention, the weight average molecular weight means a weight average molecular weight (Mw) calculated in terms of polystyrene based on a value measured under the following conditions using GPC (gel permeation chromatography).

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  Examples of the terminal alcohol polyester compound (b) represented by the formula (2) include polyester polyols having an alcoholic hydroxyl group at the terminal. Specific examples thereof include polyester polyols, Kyowapol 1000 PA, 2000 PA, 3000 PA, 2000 BA (all manufactured by Kyowa Hakko Chemical Co., Ltd.); Adeka New Ace Y9-10, YT-101 (all ADEKA ( Plaxel 220EB, 220EC (both manufactured by Daicel Chemical Industries); Polylite OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2554, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555 (all D HS Co., Ltd.); HS2H-201AP, HS2H-351A, HS2H-451A, HS2H-851A, HS2N-221A, HS2N-521A, HS2H-220S, HS2N-220S, HS2N-226P, HS2B-222A, HOKKUOL 110, the same HT-210, the same HT-12, the same HT-250, the same HT-310, the same HT-40M (all manufactured by Toyokuni Oil Co., Ltd.) and the like, all of which are available from the market. These polyester compounds can be used alone or in combination of two or more. Among these, Kyowapol 1000PA, Adeka New Ace Y9-10, and HS2N-221A are preferable.

Next, the hydrocarbon polyhydric alcohol compound (j) will be described.
The hydrocarbon polyhydric alcohol compound (j) is a hydrocarbon compound having two or more hydroxyl groups in the molecule, such as ethylene glycol, propylene glycol, propanediol, butanediol, dimethylethanol, pentanediol, neopentyl glycol, Hexanediol, dimethylbutanediol, heptanediol, dimethylpentanediol, diethylpropanediol, octanediol, dimethylhexanediol, diethylbutanediol, nonanediol, dimethylheptanediol, diethylpentanediol, decanediol, dimethyloctanediol, diethylhexanediol , Ethylbutylpropanediol, 3-methylol-1,5-pentanediol, diglycerin, dipentaerythritol, tri Chain hydrocarbon polyhydric alcohol compounds such as tyrolpropane and ditrimethylolpropane, cyclopentanediol, cyclopentanedimethanol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethanol, norbornanediol, norbornane And cyclic hydrocarbon polyhydric alcohol compounds such as methanol. These hydrocarbon polyhydric alcohol compounds (j) can be used alone or in combination of two or more. Among these, tricyclodecane dimethanol, ditrimethylolpropane, and diglycerin are preferable from the viewpoint of the strength of the cured product and the transparency of the cured product.

Next, the terminal alcohol polycarbonate compound will be described.
Although it does not specifically limit as a terminal alcohol polycarbonate compound, For example, the polycarbonate compound etc. which have a hydroxyl group at the terminal shown by following formula (7) are mentioned.

(In Formula (7), R ₈ represents an alkylene group having 1 to 10 carbon atoms, and s represents 1 to 100 on average.)

In the formula (7), as specific examples of R ₈ , methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and other linear alkylene groups having 1 to 10 carbon atoms, isopropylene, ethylbutylpropylene, Examples include an alkylene group having a branched chain having 1 to 10 carbon atoms such as isobutylene, isopentylene, neopentylene, and diethylpentylene, and an alkylene group having a cyclic structure such as cyclopentanedimethylene and cyclohexanedimethylene. Among these, linear alkylene groups having 4 to 7 carbon atoms such as butylene, pentylene, hexylene, and heptylene are preferable from the viewpoint of workability because the viscosity of the terminal alcohol polycarbonate compound is not too high.

A plurality of R ₈ present in the formula (7) may be the same or different.

  In the formula (7), s is an average value of 1 to 100, preferably 2 to 40, more preferably 3 to 30.

  Although the weight average molecular weight (Mw) of a terminal alcohol polycarbonate compound becomes like this. Preferably it is 500-20000, More preferably, it is 500-5000, More preferably, it is 500-3000. If the weight average molecular weight is 500 or more, the cured product hardness of the curable resin composition for encapsulating an optical semiconductor of the present invention is not excessively high, and there is no concern that cracks may occur in a heat cycle test or the like. Moreover, if a weight average molecular weight is 20000 or less, there is no fear that stickiness of hardened | cured material generate | occur | produces and it is preferable. In the present invention, the weight average molecular weight means a weight average molecular weight (Mw) calculated in terms of polystyrene based on a value measured under the following conditions using GPC (gel permeation chromatography).

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  Although the usage-amount of the polyhydric alcohol compound (i) which has a 2 or more hydroxyl group in a molecule | numerator is not specifically limited, Preferably it is 0.5-200 with respect to 100 weight part of both terminal carbinol modified silicone oil (a). Parts by weight, more preferably 5 to 50 parts by weight, still more preferably 10 to 30 parts by weight. If it is 0.5 parts by weight or more, it is preferable because the mechanical strength of the cured product is further improved. This is preferable because the viscosity becomes more appropriate.

Next, the compound (c) having two or more carboxylic anhydride groups in the molecule will be described.
Compound (c) having two or more carboxylic acid anhydride groups in the molecule is, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid. Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic anhydride, 5- (2,5- Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene- 1,2-dicarboxylic anhydride and the like.
The compound (c) having two or more carboxylic acid anhydride groups in the molecule can be used alone or in combination. Among these, since the transparency of the cured product obtained by curing the polyvalent carboxylic acid resin (A) and the epoxy resin described later is excellent, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is preferred. In particular, 1,2,3,4-butanetetracarboxylic dianhydride is preferred.

Next, the compound (d) having one carboxylic anhydride group in the molecule will be described.
Compound (d) having one carboxylic acid anhydride group in the molecule includes succinic acid anhydride, methyl succinic acid anhydride, ethyl succinic acid anhydride, 2,3-butanedicarboxylic acid anhydride, 2,4-pentanedicarboxylic acid. Anhydride, saturated aliphatic carboxylic acid anhydride such as 3,5-heptanedicarboxylic acid anhydride, unsaturated aliphatic carboxylic acid anhydride such as maleic acid anhydride, dodecyl succinic acid anhydride, hexahydrophthalic acid anhydride, Methylhexahydrophthalic anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, nadic acid anhydride, methylnadic acid anhydride , Bicyclo [2,2,2] octane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2 -Cyclic saturated aliphatic carboxylic acid anhydride such as anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, nadic acid anhydride, methyl nadic acid anhydride, 4,5-dimethyl-4-cyclohexene-1, 2-dicarboxylic acid anhydride, cyclic unsaturated aliphatic carboxylic acid anhydride such as bicyclo [2.2.2] -5-octene-2,3-dicarboxylic acid anhydride, phthalic acid anhydride, isophthalic acid anhydride, And aromatic carboxylic acid anhydrides such as terephthalic acid anhydride and trimellitic acid anhydride.
The compound (d) having one carboxylic anhydride group in the molecule can be used alone or in combination. Among these, since the transparency of the cured product obtained by curing the polyvalent carboxylic acid resin (A) and the epoxy resin is excellent, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, Norbornane-2,3-dicarboxylic acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride are preferable. More preferred are methylhexahydrophthalic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and particularly preferred is methylhexahydrophthalic anhydride.

  When used, the amount of the compound (c) having two carboxylic anhydride groups in the molecule is usually 5 to 1000 per 100 parts by weight of the compound (d) having one carboxylic anhydride group in the molecule. Parts by weight, preferably 10 to 500 parts by weight, more preferably 15 to 300 parts by weight. When it is larger than 300 parts by weight, the polyvalent carboxylic acid resin (A) may have a too high molecular weight, resulting in poor workability.

  Both ends carbinol-modified silicone oil (a), polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, compound (c) having two or more carboxylic anhydride groups in the molecule, intramolecular The amount of the compound (d) having one carboxylic acid anhydride group is the total alcohol of the carbinol-modified silicone oil (a) at both ends and the polyhydric alcohol compound (e) having two or more hydroxyl groups in the molecule. When the compound (d) having one carboxylic acid anhydride group in the molecule is used per 1 equivalent of the functional hydroxyl group, the total carboxylic acid with the compound (c) having two or more carboxylic acid anhydride groups in the molecule The acid anhydride group is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents. If it is 0.5 equivalent or more, it is preferable because the mechanical strength of the cured product is good, and if it is 2.0 equivalent or less, a large amount of carboxylic acid anhydride groups do not remain and storage stability becomes good.

  The production of the polyvalent carboxylic acid resin (A) can be performed with or without a solvent. As the solvent, carbinol-modified silicone oil (a) at both ends, a polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, a compound (d) having one carboxylic anhydride group in the molecule, Any solvent that does not react with the compound (c) having two or more carboxylic acid anhydride groups in the molecule can be used without particular limitation. Examples of solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, toluene and xylene. An aromatic hydrocarbon etc. are mentioned, Among these, an aromatic hydrocarbon and ketones are preferable. These solvents may be used alone or in combination of two or more. When a solvent is used, the amount used is that the carbinol-modified silicone oil (a) at both ends, a polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, and one carboxylic anhydride group in the molecule. 0.5 to 300 parts by weight is preferable with respect to a total of 100 parts by weight of the compound (d) having, and when used, the compound (c) having two or more carboxylic anhydride groups in the molecule.

The polyvalent carboxylic acid resin (A) can be produced without a catalyst or with a catalyst. When a catalyst is used, usable catalysts are hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, potassium hydroxide, water Metal hydroxides such as calcium oxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, Heterocyclic compounds such as imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium Roxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctyl Quaternary ammonium salts such as methylammonium acetate, orthotitanic acid such as tetraethyl orthotitanate, tetramethyl orthotitanate, tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, Examples include metal soaps such as potassium octylate.
When using a catalyst, it can also be used 1 type or in mixture of 2 or more types.
When a catalyst is used, the amount used thereof is as follows: carbinol-modified silicone oil (a) at both ends, polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, and one carboxylic anhydride group in the molecule. 0.05 to 10 parts by weight is preferable with respect to 100 parts by weight in total of the compound (d) having, and the compound (c) having two or more carboxylic anhydride groups in the molecule when used.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. At this time, using an alcoholic solvent such as methanol or ethanol or water means that the unreacted compound (c) having two or more carboxylic acid anhydride groups in the molecule or one carboxylic acid anhydride in the molecule. Since it reacts with the compound (d) having a physical group, it is preferable to avoid it.

  The reaction temperature during the production of the polyvalent carboxylic acid resin (A) is usually 20 to 160 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 145 ° C., although it depends on the amount of catalyst and the solvent used. The total reaction time is usually 1 to 20 hours, preferably 3 to 12 hours. The reaction may be carried out in two or more stages, for example, after reacting at 20 to 100 ° C. for 1 to 8 hours, it may be reacted at 100 to 160 ° C. for 1 to 12 hours. In particular, the compound (d) having one carboxylic acid anhydride group in the molecule is often highly volatile, and when such a compound is used, it is reacted at 20 to 100 ° C. in advance and then 100 to 160. By reacting at ℃, volatilization can be suppressed. Thereby, not only can the diffusion of harmful substances into the atmosphere be suppressed, but also the polyvalent carboxylic acid resin (A) as designed can be obtained.

In the case of production using a catalyst, the catalyst can be removed by quenching and / or washing with water as necessary, but it is left as it is and used as a curing accelerator of the curable resin composition of the present invention. You can also
When performing a water washing process, it is preferable to add the solvent which can be isolate | separated from water depending on the kind of solvent currently used. Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.
When a solvent is used for the reaction or washing with water, it can be removed by vacuum concentration or the like.

The polycarboxylic acid resin (A) thus obtained is normally a liquid having fluidity at 25 ° C. Further, the molecular weight is preferably 800 to 80000, more preferably 1000 to 10000, and particularly preferably 1500 to 8000 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the fluidity at 25 ° C. may decrease, and when it exceeds 80,000, when it is used as a curable resin composition, the compatibility with the epoxy resin described later is increased. May be inferior.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The acid value (measured by the method described in JIS K-2501) of the produced polyvalent carboxylic acid resin (A) is preferably 35 to 200 mgKOH / g, more preferably 50 to 180 mgKOH / g. The thing of 60-150 mgKOH / g is preferable. When the functional group equivalent is less than 35 mgKOH / g, the mechanical properties of the cured product tend to deteriorate, and when it exceeds 150 mgKOH / g, the cured product tends to be hard and the elastic modulus tends to be too high.

  The viscosity of the polyvalent carboxylic acid resin (A) (E-type viscometer, measured at 25 ° C.) is preferably 50 to 800,000 mPa · s, more preferably 500 to 100,000 mPa · s, particularly 800 to Those having a viscosity of 30,000 mPa · s are preferred. When the viscosity is less than 50 mPa · s, the viscosity may be too low to be suitable as an optical semiconductor encapsulant, and when it exceeds 800,000 mPa · s, the viscosity may be too high and workability may be poor. is there.

  In the curable resin composition of the present invention, an acid anhydride, a polyvalent carboxylic acid, and a polyvalent carboxylic acid resin (A) can be used in combination of two or more. In particular, when using a solid polyvalent carboxylic acid in an application where a liquid state is required at room temperature (25 ° C.) such as sealing of an optical semiconductor, a liquid acid anhydride and / or a polyvalent carboxylic acid resin (A) is used in combination, It is desirable to use it as a liquid mixture. When used together, the acid anhydride and / or the polyvalent carboxylic acid resin (A) can be used at a ratio of 0.5 to 99.5% by weight of the total epoxy resin curing agent.

When the curing agent other than the above-mentioned acid anhydride and / or polyvalent carboxylic acid and / or polyvalent carboxylic acid resin (A) is used in combination as the epoxy resin curing agent, the acid anhydride and / or the polyvalent carboxylic acid and / or Alternatively, the proportion of the total amount of the polyvalent carboxylic acid resin (A) in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.
Examples of the curing agent that can be used in combination include amine compounds, amide compounds, phenol compounds, and the like. Specific examples of curing agents that can be used include amines and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, etc.) Polyphenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, fe Alcohol (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, Dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloro Methyl) benzene, polycondensates with 1,4′-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols, etc. Imidazole, trifluoroborane -. Amine complex, guanidine derivatives, etc.) and the like, but the invention is not limited to these may be used alone, or two or more may be used.

  From here, the epoxy resin contained in the curable resin composition for optical semiconductor sealing of this invention is demonstrated. Examples of the epoxy resin include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester. Epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having epoxy groups with other silicon compounds, polymerizable unsaturated compounds having epoxy groups and others And other copolymers with other polymerizable unsaturated compounds. Among these, the silicone skeleton epoxy resin (B) which is one embodiment of the condensate of the silicon compound having an epoxy group and the other silicon compound is preferable from the viewpoint of transparency of the cured product and heat-resistant transparency.

From here, the silicone skeleton epoxy resin (B) will be described.
The silicone skeleton epoxy resin (B) of the present invention is a resin having an epoxy group having a silicone bond (Si-O bond) as a main skeleton. For example, by polymerizing an epoxy group-containing silicon compound and other silicon compounds. Hydrolysis condensation polymer of an alkoxysilane compound having an epoxy group and an alkoxysilane having a methyl group or a phenyl group, or a condensation polymer of an alkoxysilane compound having an epoxy group and a silanol-terminated silicone oil can be obtained. Can be mentioned. Moreover, an addition polymerization product of a silicone resin having a hydrosilyl group (SiH group) and an epoxy compound having an unsaturated hydrocarbon group such as a vinyl group can be exemplified.

  Among them, the silicone skeleton epoxy resin (B) in the present invention includes, as raw materials, a silanol-terminated silicone oil (e) and an epoxy group-containing silicon compound (f) (and, if necessary, an alkoxysilicon compound (g)). The silicone skeleton epoxy resin obtained through the two-stage manufacturing process is most preferable.

From here, the silanol-terminated silicone oil (e), the epoxy group-containing silicon compound (f), and the alkoxysilicon compound (g) will be described.
First, the silanol-terminated silicone oil (e) will be described.
The silanol-terminated silicone oil (e) is a silicone resin represented by the following formula (3) and having silanol groups at both ends.

In the formula (3), R ₅ represents an alkyl group having 1 to 3 carbon atoms such as a methyl group or a phenyl group. A plurality of R ₅ may be the same or different, but it is preferable to contain a phenyl group from the viewpoint of compatibility with other resins, high refractive index, and improvement in sulfur resistance.
From the viewpoint of adjusting the viscosity of the silicone skeleton epoxy resin (B), it is preferable to contain a methyl group.

  The proportion of the phenyl group to be contained is preferably 0.05 to 2.0 mol, more preferably 0.1 to 1.0 mol, and still more preferably 0.15 to 0.3 mol, with respect to 1 mol of the substituted methyl group. Particularly preferred is 0.15 to 0.2 mol. If it is less than 0.05 mol, not only the compatibility with other raw materials in the composition is inferior, but also the refractive index of the cured product is low, the light extraction efficiency of the LED may deteriorate, and the sulfidation resistance may be inferior. If the amount exceeds 2.0 mol, the light resistance (UV resistance) of the cured product may be inferior or the heat cycle resistance may be inferior.

  In the formula (3), p represents an average value of 3 to 200, preferably 3 to 100, more preferably 3 to 50. When p is less than 3, the cured product becomes too hard and the heat cycle resistance may be lowered. When p exceeds 200, the mechanical strength of the cured product may decrease.

The weight average molecular weight (Mw) of the silanol-terminated silicone oil (e) is preferably in the range of 400 to 3000 (GPC). When the weight average molecular weight is less than 400, there is a concern that the properties of the silicone part are difficult to be obtained and the heat resistance and light resistance are inferior. Permeability may be reduced.
In the present invention, the molecular weight of the silanol-terminated silicone oil (e) is the weight average molecular weight (Mw) calculated in terms of polystyrene based on the value measured under the following conditions using GPC (gel permeation chromatography). means.

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  Silanol-terminated silicone oil (e) is produced, for example, by hydrolyzing and condensing dimethyldialkoxysilane, methylphenyldichlorosilane, diphenylalkoxysilane, dimethyldichlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane. it can.

  Specific examples of preferable silanol-terminated silicone oil (e) include the following product names. For example, as manufactured by Toray Dow Corning, PRX413, BY16-873, manufactured by Shin-Etsu Chemical Co., Ltd. as X-21-5841, KF-9701, manufactured by Momentive as XC96-723, TSR160, YR3370, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, YF3804, XF3905, manufactured by Gelest, DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS- S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-1615, PDS-9931 and the like. Among these, PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21 from the viewpoint of molecular weight and kinematic viscosity PDS-1615 is preferred. Among these, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight. These silanol-terminated silicone oils (a) may be used alone or in combination of two or more.

Next, the epoxy group-containing silicon compound (f) will be described.
The epoxy group-containing silicon compound (f) in the present invention is an alkoxysilicon compound represented by the formula (4).

In formula (4), X is not particularly limited as long as X is an organic group having an epoxy group.
For example, an alkyl group having 1 to 4 carbon atoms substituted with a glycidoxy group such as β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, glycidyl group, β- (3,4-epoxy (Cyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, 4- (3,4-epoxycyclohexyl) butyl group, 5- (3, And an alkyl group having 1 to 5 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as a 4-epoxycyclohexyl) pentyl group. Among these, as an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group, an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy group, for example, β -Glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group is preferable, and β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable because coloration can be suppressed. Is preferred.

In formula (4), R ₆ represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, phenyl Group, naphthyl group and the like. R ₆ is preferably a methyl group or a phenyl group from the viewpoints of compatibility and heat-resistant transparency of the cured product.

R ₇ in Formula (4) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₇ is preferably a methyl group or an ethyl group, particularly preferably a methyl group, from the viewpoint of reaction conditions such as compatibility and reactivity.

  Q in the formula (4) is an integer representing 0, 1, 2, and r represents (3-q). In view of the viscosity of the silicone skeleton epoxy resin (B) and the mechanical strength of the cured product, q is preferably 0 or 1.

  Specific preferred examples of the epoxy group-containing silicon compound (f) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxy. Propyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylcyclohexyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylphenyldimethoxysilane, 2- (3 4-D Carboxymethyl) ethyl cyclohexyl dimethoxysilane, and the like, especially 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferable. These epoxy group-containing silicon compounds (f) may be used alone or in combination of two or more, and may be used in combination with the alkoxysilicon compound (g) shown below.

  In the silicone skeleton epoxy resin (B), an alkoxysilicon compound (g) represented by the following formula (5) can be used in combination with the epoxy group-containing silicon compound (f). By using the alkoxysilicon compound (g) in combination, the viscosity, refractive index and the like of the silicone skeleton epoxy resin can be adjusted.

In the formula (5), R ₆ and R ₇ have the same contents as described above, s is an integer, 0, 1, 2, 3 and t represents (4-s).

  Specific examples of preferred alkoxysilicon compounds (g) that can be used in combination include methyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and diphenyl. Examples include dimethoxysilane and diphenyldidiethoxysilane. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and diphenyldimethoxysilane are preferable.

  In the present invention, at least one of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and the alkoxysilicon compound (g) if necessary) has an aromatic skeleton. It is preferable to use a compound having a phenyl group from the viewpoint of an increase in refractive index and a reduction in sulfur resistance, and it is particularly preferable to use a compound having a phenyl group. In particular, the silanol-terminated silicone oil (e) preferably has a phenyl group. This is because by using a silanol-terminated silicone oil (e) having a phenyl group introduced, an excessive increase in viscosity of the silicone skeleton epoxy resin (B) can be suppressed, while an epoxy group-containing silicon having a phenyl group is attached. This is because when the compound (f) (and the alkoxysilicon compound (g) if necessary) is used, the increase in viscosity becomes large and workability may be deteriorated.

  In the production of the silicone skeleton epoxy resin (B), the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)) with respect to 1 equivalent of the silanol group of the silanol-terminated silicone oil (e). When the alkoxy group is reacted in an amount less than 1.5 equivalents, two or more alkoxy groups in the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxy silicon compound (g)) are terminated with a silanol-terminated silicone. It will react with the silanol group of oil (e), and it will become a polymer | macromolecule at the end of the manufacturing process 1 mentioned later, and will gelatinize. For this reason, it is necessary to make an alkoxy group react with 1.5 equivalent or more with respect to 1 equivalent of silanol groups. From the viewpoint of reaction control, 2.0 equivalents or more are preferable.

Next, manufacturing steps 1 and 2 will be described.
(Manufacturing process 1)
A step of obtaining a modified silicone oil (h) by condensing the silanol group of the silanol-terminated silicone oil (e) and the alkoxy group of the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)). .
(Manufacturing process 2)
A step of adding water after the production step 1 to hydrolyze and condense the remaining alkoxy groups.
The present invention is characterized by polymerizing the modified silicone oil (h) and the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)) through the above production steps 1 and 2. To do.

  By dividing the production process into two stages, the silanol group of the silanol-terminated silicone oil (e) and the alkoxy group of the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxy silicon compound (g)) are ensured. To obtain a modified silicone oil (h), and then subjecting the remaining alkoxy group to dealcohol hydrolysis hydrolysis, a uniform and stable product can be obtained.

  When water is added from the beginning of the manufacturing process in one step, the condensation reaction between the silanol group and the alkoxy group and the polymerization reaction between the alkoxysilanes become a competitive reaction, resulting in a difference in the reaction rate between the products and the compatibility of the products. Due to the difference, a heterogeneous compound can be obtained, or a large amount of silanol-terminated silicone oil (e) having no epoxy group can be adversely affected.

In the production process 1, the reaction is preferably performed in the presence of a solvent, and alcohol is particularly preferable among the solvents from the viewpoint of reaction control. Examples of the alcohol that can be used include alcohols having 1 to 10 carbon atoms, specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, and cyclopentanol. Etc. In the present invention, primary alcohols and secondary alcohols are preferable, and it is particularly preferable to use primary alcohols or a mixture of primary alcohols and secondary alcohols. Examples of primary alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, nonane alcohol, decane alcohol, propylene glycol, and the like. Examples of secondary alcohols include isopropanol, cyclohexanol, propylene glycol. Etc. Moreover, from the problem of subsequent removal performance, low molecular weight alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol are preferable. These alcohols may be used as a mixture. When they are mixed, they are preferably two or more selected from primary alcohols and secondary alcohols, and at least one component contains primary alcohols. It is preferable because the solubility of the catalyst described later is excellent. The amount of primary alcohol is preferably 5% by weight or more, more preferably 10% by weight or more of the total alcohol amount.
By using a secondary alcohol in combination with this reaction, the amount of change in the weight average molecular weight per unit time in the reaction system of production process 1 is smaller than when only the primary alcohol is used, so the reaction is more easily controlled. It is. In general, in the case of large-scale reactions such as industrial production, it becomes difficult to strictly control the reaction time and reaction temperature, so the combined use of secondary alcohols is particularly important for large-scale reactions such as industrial production from the viewpoint of reaction control. Useful for.
In the production process 1, the amount of alcohol used is 2% by weight or more based on the total weight of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)). It is preferable to contain. More preferably, it is 2 to 100 weight%, More preferably, it is 3 to 50 weight%, Especially preferably, it is 4 to 40 weight%.
When the amount exceeds 100% by weight, the progress of the reaction is extremely slow, and when it is less than 2% by weight, the reaction other than the intended reaction proceeds, the molecular weight increases, gelation, increase in viscosity, An increase in modulus may occur.
In this reaction, other solvents may be used in combination as necessary.
Examples of solvents that can be used in combination include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene, and xylene. Can be illustrated.

The reaction in the production step 1 can be performed without a catalyst. However, since the reaction proceeds slowly with no catalyst, it is preferably performed in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst that can be used, any compound that exhibits acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Inorganic bases such as alkali metal carbonates, and organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used.
Among these, a basic catalyst is particularly preferable, and an inorganic base is preferable in terms of easy catalyst removal from the product. Specifically, alkali metal salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, or alkaline earth metal salts, particularly hydroxides are preferable.
The amount of the catalyst added is usually 0.001 to 5% by weight based on the total weight of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)). Preferably, it is 0.01 to 2% by weight.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol. In this case, adding as an aqueous solution using water or the like causes a sol-gel reaction other than the target reaction to proceed competitively, and the epoxy group-containing silicon compound (f) (and, if necessary, Since the polycondensation of the alkoxy group of the alkoxysilicon compound (g)) proceeds unilaterally, the reaction product produced thereby may not be compatible with the silanol-terminated silicone oil (e) and may become cloudy. is necessary.
In this case, the allowable range of moisture is usually 0.5% by weight or less based on the total weight of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)). More preferably, it is 0.3% by weight or less, and it is more preferable that there is as little moisture as possible.

  Although the reaction temperature of the manufacturing process 1 is based also on a catalyst amount and a use solvent, it is 20-160 degreeC normally, Preferably it is 40-100 degreeC, Most preferably, it is 50-95 degreeC. The reaction time is usually 1 to 20 hours, preferably 3 to 12 hours.

  Thus, the modified silicone oil (h) obtained in the production process 1 is considered to have a structure represented by the following formula (6) as a main component (the confirmation of the structure is difficult and accurate Cannot be identified.)

In the formula (6), R ₅ and p have the same meaning as described above. R ₈ represents any one of the aforementioned X, R ₆ , and —OR ₇ , and R ₉ represents R ₆ and / or —OR ₇ , respectively.

Next, the manufacturing process 2 will be described in detail.
After completion of the reaction in the production step 1, water is added, and the alkoxy groups remaining in the resulting modified silicone oil (h) are polymerized (sol-gel reaction). At this time, the silicon compound (f) containing the above-mentioned epoxy group (and the alkoxysilicon compound (g) if necessary) and the catalyst may be added within the above-mentioned range as necessary. This reaction is performed between (1) the modified silicone oils (h) and / or (2) the silicon compound (f) containing an epoxy group (and the alkoxysilicon compound (g) if used). And / or (3) a silicon compound (f) containing an epoxy group (and an alkoxy silicon compound (g) if used), and (4) a silicon compound (f) containing an epoxy group ( And when using, it is the process of performing a polymerization reaction between the partial polymer of an alkoxy silicon compound (g)) and modified silicone oil (h). The polymerization reactions (1) to (4) are considered to proceed in parallel at the same time.
In particular, in the production process 2, as described above, a basic inorganic catalyst is preferable as the catalyst, and a necessary amount may be added in the production process 1 in advance. However, it is not preferable to exceed the range described as a preferred embodiment in the production process 1.

In the production process 2, it is preferable to add a solvent.
As in the production process 1, alcohol is preferably used as the solvent in the production process 2. Examples of the alcohol that can be used include alcohols having 1 to 10 carbon atoms, specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, and cyclopentanol. Etc. In the present invention, primary alcohols and secondary alcohols are particularly preferred, and primary alcohols are particularly preferred. Moreover, from the problem of subsequent removal performance, low molecular weight alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol are preferable. These alcohols may be used as a mixture. The presence of these alcohols contributes to molecular weight control and stability.
As the addition amount of the alcohol, the total weight of the silanol-terminated silicone oil (e) and the silicon compound (f) containing an epoxy group (and the alkoxysilicon compound (g) if necessary) charged in the production process 1, It is 20 to 200% by weight, preferably 20 to 150% by weight, particularly preferably 30 to 120% by weight.

In the production process 2, water is added (ion exchange water, distilled water, or clean water can be used). The amount of water used is usually 0.5 to 8.0 equivalents, more preferably 0.6 to 5.0 equivalents, particularly preferably 0.65 to 2.0 equivalents, relative to the amount of remaining alkoxy groups. .
When the amount of water is less than 0.5 equivalent, the reaction proceeds slowly, and the silicon compound (f) containing an epoxy group (and, if necessary, the alkoxysilicon compound (g)) remains without reacting. There is a possibility that a problem such as the above will occur, a sufficient network may not be formed, and a curing failure will occur even after the subsequent curing of the curable resin composition. On the other hand, if it exceeds 8.0 equivalents, the molecular weight control is not effective and the molecular weight becomes higher than necessary. Furthermore, there is a possibility of inhibiting the stability of the silicone skeleton epoxy resin (B).

  The reaction temperature in production step 2 is usually 20 to 160 ° C, preferably 40 to 100 ° C, particularly preferably 50 to 95 ° C, although it depends on the amount of catalyst and the solvent used. The reaction time is usually 1 to 20 hours, preferably 3 to 12 hours.

  After completion of the reaction, the catalyst is removed by quenching and / or washing with water as necessary. When washing with water, depending on the type of solvent used, it is preferable to add a solvent that can be separated from water. Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.

In this reaction, the catalyst may be removed only by washing with water. However, since the reaction is carried out under acidic or basic conditions, the washing is carried out after quenching by a neutralization reaction, or the adsorbent. It is preferable to remove the adsorbent by filtration after adsorbing the catalyst using
Any compound that is acidic or basic can be used for the neutralization reaction. Examples of the compound exhibiting acidity include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Inorganic bases such as alkali metal carbonates, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphates, phosphates such as sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, Organic bases such as dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, in particular, inorganic bases or inorganic acids are preferable because they can be easily removed from the product, and phosphates that can more easily adjust the pH to near neutral are more preferable.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
As the activated clay, for example, Toshin Kasei Co., Ltd., activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168, manufactured by Mizusawa Chemical Industry, Galeon Earth, Mizuka Ace, etc. are listed. As the activated carbon, for example, CL-H, Y-10S, Y-10SF, manufactured by Ajinomoto Fine Techno Co., S, Y, FC, DP, SA1000, K, A, KA, M, manufactured by Phutamura Chemical Co., Ltd. Examples thereof include CW130BR, CW130AR, and GM130A. Examples of zeolite include, for example, molecular sieves 3A, 4A, 5A, and 13X, manufactured by Union Showa. As a synthetic adsorbent, for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., Amberlist 15JWET, 15DRY, manufactured by Rohm and Haas Co., Ltd. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, manufactured by Dow Chemical Company, Dowex 66, HCR-S, HCR-W2, MAC-3 and the like can be mentioned.
The adsorbent is added to the reaction solution, followed by treatment such as stirring and heating to adsorb the catalyst, and then the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.

  After completion of the reaction or after quenching, it can be purified by conventional separation and purification means other than washing with water and filtration. Examples of the purification means include column chromatography, vacuum concentration, distillation, extraction and the like. These purification means may be performed singly or in combination.

  When the reaction is performed using a solvent mixed with water as a reaction solvent, the reaction solvent mixed with water is removed from the system by distillation or vacuum concentration after quenching, and then washed with a solvent that can be separated from water. It is preferable.

  After washing with water, the silicone skeleton epoxy resin (B) of the present invention can be obtained by removing the solvent by vacuum concentration or the like.

The appearance of the silicone skeleton epoxy resin (B) thus obtained is usually a colorless and transparent liquid having a fluidity at 25 ° C. The molecular weight is preferably 800 to 3000, more preferably 1000 to 3000, and particularly preferably 1500 to 2800 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the heat resistance may be lowered. When the weight average molecular weight is more than 3000, the encapsulant may be peeled off from the substrate at the time of solder reflow of the LED element encapsulated using the weight average molecular weight.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

The epoxy equivalent (measured by the method described in JIS K-7236) of the silicone skeleton epoxy resin (B) is 300 to 1500 g / eq. Are preferred, those with 320 to 1400 g / eq are more preferred, those with 350 to 1200 g / eq, particularly 350 to 1000 g / eq are preferred. When the epoxy equivalent is less than 300 g / eq, the cured product tends to be too hard, and when it exceeds 1500 g / eq, the mechanical properties of the cured product tend to deteriorate.
The silicone skeleton epoxy resin (B) may be a single silicone skeleton epoxy resin (B) or a mixture of two or more kinds of silicone skeleton epoxy resins (B). Here, from the viewpoint of appropriate mechanical strength of the cured product, if the epoxy resin is a single silicone skeleton epoxy resin (B), the epoxy resin is a mixture of two or more types of silicone skeleton epoxy resins (B). The epoxy equivalent of the sum of the epoxy equivalent of the specific silicone skeleton epoxy resin (B) × (content of the specific silicone skeleton epoxy resin (B) / total amount of the silicone skeleton epoxy resin (B) fat) is 300 to 1500 g. / Eq is preferable, and 350 to 1000 g / eq is particularly preferable.

  The viscosity of the silicone skeleton epoxy resin (B) (E-type viscometer, measured at 25 ° C.) is preferably 50 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, particularly 800 to 5 1,000 mPa · s is preferred. When the viscosity is less than 50 mPa · s, the viscosity is too low and may not be suitable as an optical semiconductor sealing material. When it exceeds 20,000 mPa · s, the viscosity is too high and workability is reduced. There is.

In the silicone skeleton epoxy resin (B), the ratio of silicon atoms to which three oxygen atoms are bonded to the total silicon atoms is preferably 3 to 50 mol%, more preferably 5 to 30 mol%, and particularly preferably 6 to 15 mol%. preferable. When the ratio of silicon atoms bonded to three oxygen atoms derived from silsesquioxane with respect to all silicon atoms is less than 3 mol%, the cured product tends to be too soft and may cause surface tack and scratches. . Moreover, when it exceeds 50 mol%, hardened | cured material may become hard too much.
The proportion of silicon atoms present can be determined by ¹ H NMR, ²⁹ Si NMR, elemental analysis, etc. of the silicone skeleton epoxy resin (B).

  As described above, the silanol-terminated silicone oil (e) obtained through the production steps 1 and 2, which is a preferable embodiment of the silicone skeleton epoxy resin (B) in the present invention, and the silicon compound (f) containing an epoxy group (and The condensate with the alkoxysilicon compound (g)) was described as necessary.

  As the silicone skeleton epoxy resin (B), the above silanol-terminated silicone oil (e) is not used, and a silicon compound (f) containing an epoxy group (and an alkoxy silicon compound (g) if necessary) is condensed. Polymers can also be exemplified.

  In this case, the silicon compound (f) containing an epoxy group represented by the above formula (4) (and optionally represented by the above formula (5) can be produced by a one-step reaction. The alkoxysilicon compound (g)) can be obtained by adding water dropwise in the presence of a catalyst and a solvent as described above and condensing under a reaction temperature of 40 to 100 ° C. and a reaction time of 1 to 24 hours.

  After the condensation, a condensate of the silicon compound (f) containing an epoxy group (and, if necessary, the alkoxysilicon compound (g)) can be obtained by quenching, removing, washing with water, and concentrating as described above. .

An embodiment of the silicone skeleton epoxy resin (B) that is particularly preferable from the viewpoint of excellent sulfidation resistance and excellent pot life of the present invention is as follows.
(I) The silicone frame | skeleton epoxy resin (B) whose ratio of the phenyl group in the substituent linked to silicon is 0.05-2.0 mol with respect to 1 mol of substituted methyl groups.
(Ii) A silicone skeleton epoxy resin (B) in which the ratio of the phenyl group in the substituent linked to silicon is 0.15 to 0.2 mol relative to 1 mol of the substituted methyl group.
(Iii) The silicone skeleton epoxy resin (B) according to (i) or (ii), wherein the ratio of silicon atoms to which three oxygen atoms are bonded to all silicon atoms is 3 to 50 mol%.
(Iv) The silicone skeleton epoxy resin (B) according to (i) or (ii), wherein the ratio of silicon atoms to which three oxygen atoms are bonded to all silicon atoms is 6 to 15 mol%.
(V) The silicone skeleton epoxy resin (B) according to any one of (i) to (iv), wherein an epoxy equivalent is 350 to 1000 g / eq.
(Vi) In the case of a mixture of two or more types of silicone skeleton epoxy resins (B), the epoxy equivalent of the specific silicone skeleton epoxy resin × (content of the specific silicone skeleton epoxy resin (B) / silicone skeleton epoxy resin The silicone skeleton epoxy resin (B) mixture according to any one of (i) to (iv), wherein the total epoxy equivalent of (the total amount of (B)) is 350 to 1000 g / eq.

In the resin composition for encapsulating an optical semiconductor of the present invention, an epoxy resin can be used alone or in combination with the silicone skeleton epoxy resin (B) described above.
Other epoxy resins that can be used include epoxy resins that are glycidyl etherification products of phenolic compounds, epoxy resins that are glycidyl etherification products of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, Glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, copolymers of polymerizable unsaturated compounds having an epoxy group and other polymerizable unsaturated compounds, etc. Can be mentioned.

  Examples of the epoxy resin that is a glycidyl etherified product of a phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3 -Hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, Dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) Ethyl) phenyl] propane, 2,2′-methylene- Bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglicinol, diisopropyl Examples thereof include phenols having a redene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

  Examples of epoxy resins that are glycidyl etherified products of various novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols. And glycidyl etherified products of various novolac resins such as a novolak resin, a phenol novolac resin containing a xylylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolac resin containing a fluorene skeleton.

Examples of the alicyclic epoxy resin include alicyclic rings having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. An epoxy resin is mentioned.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester-based epoxy resin include epoxy resins made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
Examples of epoxy resins obtained by glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like. An epoxy resin obtained by glycidylating any of the halogenated phenols.

  As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, Marproof G-0115S, G-0130S, and G-0250S are commercially available products. G-1010S, G-0150M, G-2050M (manufactured by NOF Corporation), etc., and examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4 -Vinyl-1-cyclohexene-1,2-epoxide and the like. Examples of other polymerizable unsaturated compound copolymers include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and vinylcyclohexane.

  The aforementioned epoxy resins may be used alone or in combination of two or more.

Among the above-mentioned epoxy resins, the combined use of an alicyclic epoxy resin is preferable from the viewpoints of transparency, heat-resistant transparency, and light-resistant transparency. In the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and further transesterification reaction of cyclohexene carboxylic acid ester (Japan) Examples thereof include those obtained by oxidizing a compound that can be produced by a method described in Japanese Patent Laid-Open No. 2006-052187 (the entire contents of these references are incorporated herein by reference).
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (reference: review epoxy resin basic edition I p76-85, the entire contents of which are incorporated herein by reference).

  When the silicone skeleton epoxy resin (B) and another epoxy resin are used in combination, the ratio of the silicone skeleton epoxy resin (B) to the total epoxy resin composition is preferably 60 to 99 parts by weight, 90 -97 parts by weight are particularly preferred. If it is less than 60 parts by weight, the light resistance (UV resistance) of the cured product may be lowered.

  In the curable resin composition of the present invention, the blending ratio of the total epoxy resin containing the silicone skeleton epoxy resin (B) and the epoxy resin curing agent is 0.5 to 1.2 with respect to 1 equivalent of the epoxy groups of the total epoxy resin. It is preferred to use an equivalent amount of curing agent. When the amount is less than 0.5 equivalent or 1 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

In the curable resin composition of the present invention, a curing catalyst having a melting point of 40 to 200 ° C. and a liquid curing catalyst at room temperature (25 ° C.) is used as long as the pot life characteristics of the curable resin composition are not impaired. be able to. As a curing catalyst that is liquid at room temperature (25 ° C.), zinc octylate is mentioned because of its excellent transparency and sulfidation resistance.
When a liquid curing catalyst is mixed with a catalyst having a melting point of 40 to 200 ° C. at room temperature (25 ° C.), the curing catalyst having a melting point of 40 to 200 ° C. is 60 to 99 parts by weight among all the curing catalysts. Preferably there is. If it is less than 60 parts by weight, the pot life may be reduced. The total curing catalyst is usually used in the range of 0.001 to 15 parts by weight with respect to 100 parts by weight of all epoxy resins.

By using a coupling agent in the curable resin composition of the present invention as necessary, it is possible to supplement the viscosity adjustment of the composition and the hardness of the cured product.
Examples of coupling agents that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalco Examples include zirconium such as xylitol (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum coupling agent.
These coupling agents may be used alone or in combination of two or more.
A coupling agent is 0.05-20 weight part normally in the curable resin composition of this invention, Preferably 0.1-10 weight part is contained as needed.

In the curable resin composition of the present invention, it is possible to supplement mechanical strength and the like without impairing transparency by using a nano-order level inorganic filler as necessary. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention.

A phosphor can be added to the curable resin composition of the present invention as necessary. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, but the average particle size is usually 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part normally with respect to 100 weight part with respect to the resin component, Preferably it is 5-60 weight part.

  A thixotropic imparting agent such as silica fine powder (also called aerosil or aerosol) can be added to the curable resin composition of the present invention for the purpose of preventing sedimentation of various phosphors during curing. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

For the purpose of preventing coloration, the curable resin composition of the present invention can contain an amine compound as a light stabilizer, or a phosphorus compound and a phenol compound as an antioxidant.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetrame Ru-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] bu Lumalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine- , 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate And 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa- 3,20-diazadispiro [5 · 1 · 11 · 2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa 3,20-diazadispiro [5,1,11,2] heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) Hindered amines such as octabenzone, benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, -Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl)- Benzotriazole compounds such as 6-dodecyl-4-methylphenol, 2,4 Benzoate series such as di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 Examples include triazine compounds such as [(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited, and for example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, ADEKA manufactured by Ciba Specialty Chemicals, LA-52, LA-57, LA- 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-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 pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (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-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, 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'-biphenyl Range phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis ( 2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butyl) Phenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl -Phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl Examples include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, the product made from ADEKA, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, Adekas tab TPP and the like.

  The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and 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-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-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], 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), 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, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 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, 2,4-di-tert-butylphenol, 2,4-di-tert-pentyl Phenol, 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.

  A commercial item can also be used for the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, AGANOX 1520L, Adeka 1520L, and AGANOX 1520L manufactured by Ciba Specialty Chemicals , ADK STAB AO-30, ADK STAB AO-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, Sumitizer GA-80 , Sumilizer MDP-S, Sumil zer BBM-S, Sumilizer GM, Sumilizer GS (F), and the like Sumilizer GP.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like can be cited as those manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one or more of the phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but with respect to the total weight of the curable resin composition of the present invention, It is in the range of 0.005 to 5.0% by weight.

  The curable resin composition of the present invention is sufficiently mixed with additives such as a curing catalyst having a melting point of 40 to 200 ° C., an epoxy resin, an epoxy resin curing agent, a coupling agent, an antioxidant, and a light stabilizer. Thus, a curable resin composition can be prepared and used as a sealing material. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

  Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like. Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to pass an electric current. The semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens. The curable resin composition of this invention can be used for this sealing material.

As a molding method of the sealing material, an injection method in which the sealing material is injected into the mold frame in which the optical semiconductor element is fixed is inserted and then heat-cured and then molded, and the sealing material is injected on the mold in advance. A compression molding method is used in which an optical semiconductor element fixed on a substrate is immersed therein and heat-cured and then released from a mold.
Examples of the injection method include a dispenser.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used. The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
In the present specification, ratios, percentages, parts and the like are based on weight unless otherwise specified. In the present specification, the expression “X to Y” indicates a range from X to Y, and the range includes X and Y.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, Example 2 shall be read as Reference Example 2.
In addition, each physical-property value in a synthesis example was measured with the following method.
○ Weight average molecular weight: Polystyrene conversion and weight average molecular weight measured under the following conditions were calculated by the GPC method.

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
○ Epoxy equivalent: Measured by the method described in JIS K-7236.
○ Acid value: measured by the method described in JIS K-2501.
○ Viscosity: Measured using an E-type viscometer at 25 ° C.

Synthesis Example 1 (Synthesis Example of Silicone Skeleton Epoxy Resin (B) in which Silanol-Terminated Silicone Oil (e) and Epoxy Group-Containing Silicon Compound (f) are Manufactured Through Two-Step Manufacturing Process)
(Manufacturing process 1)
394 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, polydimethyldiphenylsiloxane having a silanol group having a molecular weight of 1700 (measured by GPC) (having 0.18 mol of phenyl group per 1 mol of methyl group) 475 Part, 4 parts of 0.5% KOH methanol solution and 36 parts of isopropyl alcohol were charged into a reaction vessel, and the temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours.
(Manufacturing process 2)
After adding 656 parts of methanol, 172.8 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux.
After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 780 parts of MIBK was added for washing, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 731 parts of a silicone skeleton epoxy resin (B-1). The epoxy equivalent of the obtained resin was 491 g / eq, the weight average molecular weight was 2090, the viscosity was 3530 mPa · s, and the appearance was a colorless and transparent liquid.

Synthesis Example 2 (Synthesis Example of Silicone Skeleton Epoxy Resin (B) in which Silanol-Terminated Silicone Oil (e) and Epoxy Group-Containing Silicon Compound (f) are Manufactured Through Two-Step Manufacturing Process)
(Manufacturing process 1)
444 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, polydimethyldiphenylsiloxane having a silanol group with a molecular weight of 1700 (measured by GPC) (having 0.18 mol of phenyl group per 1 mol of methyl group) 400 Part, 3.6 parts of 0.5% KOH methanol solution and 32.4 parts of isopropyl alcohol were charged into a reaction vessel, and the temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours.
(Manufacturing process 2)
After adding 480 parts of methanol, 194.4 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux.
After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 724 parts of MIBK was added for washing, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 658 parts of a silicone skeleton epoxy resin (B-2). The epoxy equivalent of the obtained resin was 410 g / eq, the weight average molecular weight was 2713, the viscosity was 15680 mPa · s, and the appearance was a colorless and transparent liquid.

Synthesis Example 3 (both ends carbinol-modified silicone oil (a), terminal alcohol polyester compound (b), compound (c) having two or more carboxylic anhydride groups in the molecule, and one in the molecule Synthesis Example of Polycarboxylic Acid Resin (A) Obtained by Addition Reaction with Compound (d) Having Carboxylic Anhydride Group)
In a glass separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, 47.1 parts of both-end carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), Adeka New Ace Y9- which is a polyester polyol 10 (manufactured by ADEKA Corporation, polyester polyol in which R ₃ is a neopentylene group and R ₄ is a butylene group in the above formula (2)), 11.8 parts of Ricacid BT-100 (1,2,3,4-butanetetra Carrying out 2.5 parts of carboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd.) and 16.6 parts of Ricacid MH (methylhexahydrophthalic anhydride, Shin Nippon Rika Co., Ltd.) at 140 ° C. for 10 hours The reaction was performed to obtain 77.5 parts of a polyvalent carboxylic acid resin (A-1). At this time, the peaks of Ricacid BT-100 and Ricacid MH disappeared in the GPC measurement. This polycarboxylic acid resin was a colorless and transparent liquid at the end of the reaction, but became a cloudy liquid as the temperature of the reaction liquid decreased. The acid value of the obtained compound was 88.8 mgKOH / g, the weight average molecular weight was 3452, the viscosity was 5730 mPa · s, and the appearance was a white liquid.

Synthesis example 4
(Obtained by addition reaction of a carbinol-modified silicone oil (a) at both ends, a hydrocarbon polyhydric alcohol compound (j), and a compound (c) having two or more carboxylic anhydride groups in the molecule) Synthesis Example of Polycarboxylic Acid Resin (A)
In a glass separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, 589 parts of both ends carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), a tricyclode which is a hydrocarbon polyhydric alcohol compound 74 parts of candimethanol and 337 parts of Ricacid MH (Methylhexahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd.) were charged and reacted at 90 ° C. for 10 hours to obtain a polyvalent carboxylic acid resin (A-2) part. It was. At this time, the peak of Ricacid MH disappeared in the GPC measurement. The acid value of the obtained compound was 111.1 mgKOH / g, the weight average molecular weight was 1216, the viscosity was 7870 mPa · s, and the appearance was a colorless and transparent liquid.

Example 1
40 parts of silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 60 parts of silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, ERL-4221 (3,4-epoxycyclohexylmethyl- 5 parts of (3,4-epoxy) cyclohexyl carboxylate, manufactured by Dow Chemical), 72.4 parts of polycarboxylic acid resin (A-1) obtained in Synthesis Example 3 as an epoxy resin curing agent, and stearic acid as a curing catalyst 1.1 parts of zinc (melting point: 120 to 126 ° C.) was added, mixed and degassed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation of the present invention.

Example 2
40 parts of silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 60 parts of silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, ERL-4221 (3,4-epoxycyclohexylmethyl- 5 parts of (3,4-epoxy) cyclohexyl carboxylate, manufactured by Dow Chemical), 72.4 parts of polycarboxylic acid resin (A-1) obtained in Synthesis Example 3 as an epoxy resin curing agent, undecylenic acid as a curing catalyst 1.1 parts of zinc (melting point: 115 to 125 ° C.) was added, mixed and degassed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation of the present invention.

Example 3
40 parts of silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 60 parts of silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, ERL-4221 (3,4-epoxycyclohexylmethyl- 5 parts of (3,4-epoxy) cyclohexyl carboxylate, manufactured by Dow Chemical), 72.4 parts of polycarboxylic acid resin (A-1) obtained in Synthesis Example 3 as an epoxy resin curing agent, and 12- as a curing catalyst 1.6 parts of zinc hydroxystearate (melting point: 145 to 155 ° C.) was added, mixed and defoamed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation of the present invention.

Example 4
40 parts of silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 60 parts of silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, ERL-4221 (3,4-epoxycyclohexylmethyl- 5 parts of (3,4-epoxy) cyclohexyl carboxylate, manufactured by Dow Chemical), 72.4 parts of polycarboxylic acid resin (A-1) obtained in Synthesis Example 3 as an epoxy resin curing agent, and 12- as a curing catalyst 1.1 parts of zinc hydroxystearate (melting point: 145 to 155 ° C.) was added, mixed and defoamed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation of the present invention.

Example 5
60 parts of silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, 5 parts of ERL-4221 (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, manufactured by Dow Chemical), epoxy 59.9 parts of the polycarboxylic acid resin (A-2) obtained in Synthesis Example 4 as a resin curing agent and 1.1 parts of zinc stearate (melting point 120 to 126 ° C.) as a curing catalyst are mixed and mixed for 5 minutes. Defoaming was performed to obtain a curable resin composition for optical semiconductor encapsulation of the present invention.

Comparative Example 1
40 parts of silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 60 parts of silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, ERL-4221 (3,4-epoxycyclohexylmethyl- 5 parts of (3,4-epoxy) cyclohexyl carboxylate, manufactured by Dow Chemical), 72.4 parts of polycarboxylic acid resin (A-1) obtained in Synthesis Example 3 as an epoxy resin curing agent, and octylic acid as a curing catalyst 0.5 parts of zinc (liquid at room temperature (25 ° C.)) was added, mixed and degassed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation.

Comparative Example 2
60 parts of silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, 5 parts of ERL-4221 (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, manufactured by Dow Chemical), epoxy 59.9 parts of the polycarboxylic acid resin (A-2) obtained in Synthesis Example 4 as a resin curing agent, and 1.1 parts of zinc octylate (liquid at room temperature (25 ° C.)) as a curing catalyst were mixed, Defoaming was performed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation.

Evaluation test Pot life test, sulfidation resistance test, durometer hardness, cured product of blending ratio of curable resin composition for optical semiconductor encapsulation obtained in Examples 1 to 5 and Comparative Examples 1 and 2 and cured products thereof The transmittance results are shown in Table 1. The test in Table 1 was performed as follows.
(1) Pot life test;
The curable resin composition for optical semiconductor encapsulation obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was filled in a 10 cc syringe made of polypropylene, and after vacuum degassing for 2 minutes, in an environment of 25 ° C. and 65% RH. And the viscosity at 25 ° C. was measured using an E-type viscometer after 0 hours, 8 hours, and 24 hours. The increase rate from the initial viscosity of the obtained viscosity at each standing time was calculated.
(2) Sulfur resistance test;
After carrying out the vacuum degassing for 5 minutes with the curable resin composition for optical semiconductor encapsulation obtained in Examples 1 to 5 and Comparative Examples 1 to 2, the syringe was filled and the emission wavelength was set to 450 nm using a precision discharge device. The surface-mounted LED on which the light-emitting element having the same was mounted was cast so that the opening was flat. After pre-curing at 120 ° C. for 1 hour, it was cured at 150 ° C. for 3 hours to seal the surface-mounted LED. Place the surface-mount type LED in a sealed polyethylene container of about 3.2 liters together with two polyethylene containers (open lid) with a diameter of 2 cm and a height of 2 cm containing 6 ml of 20% ammonium sulfide aqueous solution. It was left at room temperature (20-27 ° C.). After standing, the discoloration of the silver-plated portion on the bottom surface was visually confirmed. In the table, ◎: No discoloration even after standing for 6 hours, ○: No discoloration after standing for 4 hours, Δ: Discolored slightly after standing for 4 hours, X: Left for 4 hours Those that are discolored severely.
(3) durometer hardness;
Aluminum foil was used so that it might be 30 mm in diameter and 70 mm in height after carrying out vacuum defoaming for 5 minutes for the curable resin composition for optical semiconductor sealing obtained in Examples 1-5 and Comparative Examples 1-2. Cast into mold. The cast was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a test piece for durometer hardness having a thickness of 7 mm. The durometer hardness (type A) of the obtained test piece was measured by the method described in JIS K-6253.
(4) cured product transmittance;
The glass substrate which made the dam with the heat resistant tape so that it might become 30 mm x 20 mm x height 0.8mm after carrying out vacuum defoaming for 5 minutes for the epoxy resin composition obtained in Examples 1-5 and Comparative Examples 1-2. Cast gently on top. The cast was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a test piece for transmittance having a thickness of 0.8 mm. The obtained specimen was measured for light transmittance at 400 nm under the following conditions.

Spectrophotometer measurement conditions Manufacturer: Hitachi High-Technologies Corporation Model: U-3300
Slit width: 2.0nm
Scan speed: 300 nm / min

As is clear from the results shown in Table 1, Comparative Examples 1 and 2 using the curing catalyst zinc octylate which is liquid at room temperature (25 ° C.) are excellent in sulfidation resistance, but are allowed to stand for 8 hours in the pot life test. Later, the viscosity increased 1.7 times to 2.0 times from the initial viscosity, and the workability was poor. On the other hand, Examples 1 to 5 using each curing catalyst that is solid at room temperature (25 ° C.) having a melting point of 40 to 200 ° C. not only have excellent sulfidation resistance, but also 8 hours in the pot life test. The workability is excellent since the viscosity remains 1.2 to 1.4 times the initial viscosity after standing. Furthermore, the durometer hardness is moderate hardness, the cured product transmittance is excellent, and it is suitable as a resin composition for optical semiconductor encapsulation.
In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2011-196936) for which it applied on September 9, 2011, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

  The curable resin composition of the present invention is extremely useful as an optical semiconductor element (LED) encapsulant because it is extremely excellent in sulfidation resistance and pot life.

Claims (9)

  A curable resin composition for sealing an optical semiconductor containing a curing catalyst having a melting point of 40 to 200 ° C. and an epoxy resin and / or an epoxy resin curing agent, wherein the curing catalyst is zinc stearate or zinc montanate. , Zinc behenate, zinc laurate, zinc ricinoleate, zinc myristate, zinc palmitate and at least one metal selected from the group consisting of zinc salts having a C10-30 monocarboxylic acid compound having a hydroxyl group A curable resin composition for sealing an optical semiconductor, which is a soap-based curing catalyst. An epoxy resin curing agent is obtained by adding an addition reaction product of a carbinol-modified silicone oil (a) having both terminals represented by the formula (1) and a compound (d) having one carboxylic anhydride group in the molecule; A polycarboxylic acid resin (A) comprising an addition reaction product of a polyhydric alcohol compound (i) having two or more hydroxyl groups and a compound (d) having one carboxylic anhydride group in the molecule. Item 2. A curable resin composition for sealing an optical semiconductor according to Item 1.

(In the formula (1), an alkylene group containing _{R 1} is independently an ether bond 1-10 alkylene group or a carbon number of 1 to 10 carbon atoms, _{R 2} is 1 to 3 carbon atoms each independently (M represents an average value of 1 to 100 for an alkyl group or a phenyl group.) The epoxy resin curing agent includes a carbinol-modified silicone oil (a) having both ends represented by the formula (1), a polyhydric alcohol compound (i) having two or more hydroxyl groups in the molecule, and one in the molecule. The curable resin composition for optical semiconductor encapsulation according to claim 1, which is a polyvalent carboxylic acid resin (A) obtained by addition reaction with a compound (d) having a carboxylic acid anhydride group.

(In the formula (1), an alkylene group containing _{R 1} is independently an ether bond 1-10 alkylene group or a carbon number of 1 to 10 carbon atoms, _{R 2} is 1 to 3 carbon atoms each independently (M represents an average value of 1 to 100 for an alkyl group or a phenyl group.)   The polyvalent carboxylic acid resin (A) is obtained by addition reaction including a compound (c) having two or more carboxylic acid anhydride groups in the molecule as a reaction raw material. The curable resin composition for optical semiconductor encapsulation according to 1. The hardening for optical semiconductor sealing in any one of Claims 2-4 whose polyhydric alcohol compound (i) which has a 2 or more hydroxyl group in a molecule | numerator is a terminal alcohol polyester compound represented by Formula (2). Resin composition.

(In Formula (2), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and m represents an average value of 1 to 100.) The curable resin composition for optical semiconductor encapsulation according to any one of claims 1 to 5, wherein the epoxy resin is a silicone skeleton epoxy resin (B) .   The curable resin composition for optical semiconductor encapsulation according to claim 1, wherein the monocarboxylic acid compound having 10 to 30 carbon atoms having a hydroxyl group is 12-hydroxystearic acid. A cured product obtained by curing the optical semiconductor sealing resin composition according to any one of claims 1-7. LED which comprises the hardened | cured material of Claim 8 .