JP6319845B2 - Curable resin composition and cured product thereof - Google Patents

Description

The present invention relates to a curable resin composition suitable for use in a portion requiring high transparency, particularly for optical semiconductor sealing, and a cured product thereof.

Unsaturated hydrocarbon group-containing dimethylpolysiloxane and organohydrogendimethyl as a resin for encapsulating optical semiconductors such as LEDs (Light Emitting Diodes) that emit white light. A silicone resin sealing material using polysiloxane has been used (see Patent Document 1).
Silver plating having high conductivity and high light reflectance is widely used as a lead frame for energization for turning on the LED and improvement of light extraction efficiency. The silver-plated part is covered with a sealing material, but because of the high gas permeability of the silicone resin sealing material, sulfur-based gases such as hydrogen sulfide that are present in the air permeate and bond with silver plating (silver In recent years, it has been regarded as a problem that the surface of the lead frame is discolored black due to (sulfurization), the light reflectance is lowered, and as a result, the LED luminance is lowered.
Therefore, in order to reduce sulfur-based gas permeability as an improvement in sulfidation resistance, phenyl silicone resin encapsulants with improved sulfidation resistance introduced by introducing phenyl groups into dimethylsilicone resins have been used (patents). Reference 2).
On the other hand, recently, LED packages have been made thinner in order to make liquid crystal displays thinner. In order to reduce the thickness of the LED package, the resin sealing portion is also thinned, and even with a phenyl silicone resin sealing material, satisfactory sulfidation resistance cannot be obtained.
In recent years, especially for LEDs used in backlight units of liquid crystal displays, sialon fluorescence has been developed from YAG (Yttrium Aluminum Garnet) phosphors, which have been used for a long time, in order to improve color reproducibility. More and more products are changing to the body. The sialon phosphor needs to be added to the encapsulant in a larger amount than conventional YAG phosphors. Since a sealing material to which a large amount of phosphor is added has a high viscosity, there is a problem that workability is inferior, and there is an increasing demand for lowering the viscosity of the sealing material.

Japanese Patent No. 4636242 Japanese Patent No. 4676735

The present invention provides an epoxy resin composition that provides a cured product having excellent transparency while having a low viscosity, and provides an optical semiconductor encapsulant that is also excellent in sulfidation resistance when the optical semiconductor is encapsulated, and the cured product thereof The purpose is to provide.

（式（１）中、Ｒ^１は炭素数１〜６の炭化水素基を、Ｘはエポキシ基含有の有機基または下記式（２）で表される置換基を、nは１〜３の整数をそれぞれ表す。式中に複数存在するＲ^１、Ｘはそれぞれ同一であっても異なっていても構わない。ただし、複数存在するＸ中、平均で１モル％〜３０モル％が式（２）で表される（アルコキシシリル）アルキル基である。）

（式（２）中、Ｒ^２は炭素数２〜６のアルキレン基を、Ｒ^３は炭素数１〜６のアルキル基又はアルコキシ基をそれぞれ表す。式中に複数存在するＲ^３はそれぞれ同一であっても異なっていても構わないが、少なくとも一つはアルコキシ基である。）
（２）式（２）中のＲ^３が、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基から選択される一種以上である、（１）に記載のエポキシ樹脂組成物。
（３）エポキシ樹脂硬化剤（Ｂ）が、多価カルボン酸樹脂である、（１）、（２）のいずれか一項に記載のエポキシ樹脂組成物。
（４）多価カルボン酸樹脂が、少なくとも次の（ａ）（ｂ）を反応させることによって得られる付加重合体、多価カルボン酸樹脂である、（３）に記載のエポキシ樹脂組成物。
（ａ）；分子内に２つ以上の水酸基を含有する多価アルコール化合物
（ｂ）；分子内に１つ以上の酸無水物基を含有する化合物
（５）（ｂ）；分子内に１つ以上の酸無水物基を含有する化合物が、メチルヘキサヒドロフタル酸無水物、グルタル酸無水物、ジエチルグルタル酸無水物より一種以上選択される、（４）に記載のエポキシ樹脂組成物。
（６）さらにエポキシ樹脂硬化促進剤（Ｃ）を含有する、（１）〜（５）のいずれか一項に記載のエポキシ樹脂組成物。
（７）エポキシ樹脂硬化促進剤（Ｃ）が金属石鹸硬化促進剤である、（６）に記載のエポキシ樹脂組成物。
（８）（１）〜（７）のいずれか一項に記載のエポキシ樹脂組成物を硬化してなる硬化物。
（９）（１）〜（８）のいずれか一項に記載のエポキシ樹脂組成物からなる、光半導体封止用樹脂組成物。
（１０）（９）に記載の光半導体封止用樹脂組成物で光半導体素子を封止した光半導体装置。 As a result of intensive studies in view of the actual situation as described above, the present inventors have found that a curable compound containing a cyclic siloxane compound having an epoxy group and an (alkoxysilyl) silyl moiety in the molecule, an epoxy resin curing agent, and a curing accelerator. The present inventors have found that a resin composition solves the above problems and have completed the present invention.
That is, the present invention relates to the following (1) to (10).
(1) An epoxy resin composition comprising a cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group in the molecule and an epoxy resin curing agent (B) represented by the following formula (1).

(In formula (1), R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, X is an epoxy group-containing organic group or a substituent represented by the following formula (2), and n is an integer of 1 to 3) A plurality of R ¹ and X present in the formula may be the same or different from each other, but in the plurality of X present, an average of 1 mol% to 30 mol% is represented by formula (2) (Alkoxysilyl) alkyl group represented by

(In Formula (2), R ² represents an alkylene group having 2 to 6 carbon atoms, and R ³ represents an alkyl group or alkoxy group having 1 to 6 carbon atoms. Multiple R ^{3 s in the} formula are the same. Or at least one is an alkoxy group.
(2) The epoxy resin composition according to (1), wherein R ³ in formula (2) is one or more selected from a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
(3) The epoxy resin composition according to any one of (1) and (2), wherein the epoxy resin curing agent (B) is a polyvalent carboxylic acid resin.
(4) The epoxy resin composition according to (3), wherein the polyvalent carboxylic acid resin is an addition polymer obtained by reacting at least the following (a) and (b): a polyvalent carboxylic acid resin.
(A); a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule (b); a compound containing one or more acid anhydride groups in the molecule (5) (b); one in the molecule The epoxy resin composition according to (4), wherein the compound containing the above acid anhydride group is selected from one or more of methylhexahydrophthalic anhydride, glutaric anhydride, and diethylglutaric anhydride.
(6) The epoxy resin composition according to any one of (1) to (5), further containing an epoxy resin curing accelerator (C).
(7) The epoxy resin composition according to (6), wherein the epoxy resin curing accelerator (C) is a metal soap curing accelerator.
(8) A cured product obtained by curing the epoxy resin composition according to any one of (1) to (7).
(9) A resin composition for encapsulating an optical semiconductor, comprising the epoxy resin composition according to any one of (1) to (8).
(10) An optical semiconductor device in which an optical semiconductor element is sealed with the optical semiconductor sealing resin composition according to (9).

  According to the present invention, a curable resin composition containing a cyclic siloxane compound having an epoxy group and (alkoxysilyl) silyl moiety in the molecule, an epoxy resin curing agent, and a curing accelerator is a highly transparent cured product. In addition, since it is excellent in sulfidation resistance, it is extremely useful as a sealing resin for materials requiring high transparency, particularly optical semiconductors (LEDs, etc.).

  The curable resin composition of the present invention contains a cyclic siloxane compound (A) having an epoxy group and (alkoxysilyl) silyl moiety in the molecule, and an epoxy resin curing agent (B).

In the present invention, the cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group in the molecule is a compound represented by the following formula (1).

In formula (1), R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, X is an epoxy group-containing organic group or a substituent represented by the following formula (2), and n is an integer of 1 to 3. Represent each. A plurality of R ¹ and X present in the formula may be the same or different. However, in a plurality of X, 1 mol% to 30 mol% on average is an (alkoxysilyl) alkyl group represented by the following formula (2).

Specific examples of R ¹ in formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group. From the viewpoint of heat-resistant transparency of the cured product, methyl Group and phenyl group are preferred, and methyl group is particularly preferred from the viewpoint of ease of production.
The organic group in X represents a compound consisting of C, H, N, and O atoms, and specific examples of the epoxy group-containing organic group include 2,3-epoxycyclohexylethyl group, 3-glycidoxypropyl group, Examples include 5,6-epoxy normal hexyl group and 3,4-epoxy butyl group, and 2,3-epoxy cyclohexyl ethyl group is preferable from the viewpoint of heat-resistant transparency of the cured product. Here, the number of carbon atoms in the organic group is preferably 1-20, and more preferably 3-15.
In the X of the compound represented by the formula (1), an average of 1 mol% to 30 mol% is a substituent represented by the formula (2). From the viewpoint of If the content is less than 1 mol%, the sulfidation resistance is inferior, and if the content is more than 30 mol%, the mechanical strength of the cured product may be inferior. Here, in X of the compound represented by Formula (1), the average is 1 mol% to 20 mol%, and particularly preferably 1 mol% to 10 mol%. By using in the said range, it becomes possible to obtain the hardened | cured material which does not produce a dent at the time of hardening, improving a sulfidation resistance.
n is preferably 2 in view of ease of production of the compound.

In formula (2), R ² represents an alkylene group having 2 to 6 carbon atoms, and R ³ represents an alkyl group or alkoxy group having 1 to 6 carbon atoms. A plurality of R ³ present in the formula may be the same or different, but at least one is an alkoxy group.

Specific examples of R ² include an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and an ethylene group and a propylene group are preferable from the viewpoint of transparency of the cured product.
Specific examples of R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, cyclohexyl group, methoxy group, ethoxy group, Examples thereof include a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a neopentoxy group, a hexoxy group, an isohexoxy group, and a cyclohexoxy group. Among these, from the viewpoint of low viscosity of the cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group and an excellent gas barrier of the cured product, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group. Is preferred.

The cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group represented by the formula (1) includes a cyclic hydrogensiloxane compound, an olefin compound having an epoxy group in the molecule, and an alkoxy group in the molecule. It can be obtained by a hydrosilylation reaction with an olefin compound having a silyl group.
Specific examples of the cyclic hydrogensiloxane compound include trimethylcyclotrisiloxane, triphenylcyclotrisiloxane, tetramethylcyclotetrasiloxane, tetraphenylcyclotetrasiloxane, pentamethylcyclopentasiloxane, and pentaphenylcyclopentasiloxane. Tetramethylcyclotetrasiloxane is preferred because of ease of production.
Examples of the olefin compound having an epoxy group in the molecule include 4-vinyl-1,2-epoxycyclohexane, 3-glycidoxy-1,2-propene, 5,6-epoxy-1-hexene, 3,4-epoxybutene, and the like. 4-vinyl-1,2-epoxycyclohexane is preferable from the viewpoint of heat-resistant transparency of the cured product.
As the olefin compound having an alkyl and / or alkoxysilyl group in the molecule, a compound represented by the following formula (3) can be used.

In formula (3), R ³ represents the same meaning as described above, and R ⁴ represents an alkylene group having 0 to ⁴ carbon atoms. A plurality of R ³ present in the formula may be the same or different, but at least one is an alkoxy group.

Specific examples of the alkylene group having 0 to 4 carbon atoms represented by R ⁴ include a methylene group, an ethylene group, a propylene group, and a butylene group, and the compound represented by the formula (3) is represented by R ⁴ A vinylsilane compound which is an alkylene group having 0 carbon atoms is preferable.

In the hydrosilylation reaction, a known metal complex such as rhodium, palladium, or platinum can be used as the catalyst. Specifically, tristriphenylphosphine rhodium chloride, hexachloroplatinic acid hexahydrate, divinyltetramethyldisiloxane platinum complex, tetravinyltetramethylcyclotetrasiloxane platinum complex, dichlorobis (triphenylphosphine) platinum complex, tetrakis ( In addition to triphenylphosphine) platinum complexes, there are platinum catalysts immobilized on solvent-insoluble carriers such as polyethylene, such as FibreCat ^R 4001 and FibreCat ^R 4003 (both manufactured by Wako Pure Chemical Industries). From the viewpoint of the transparency of the cyclic siloxane compound (A) having an epoxy group and (alkoxysilyl) alkyl group in the molecule obtained, and the transparency of the cured product, hexachloroplatinic acid hexahydrate, divinyltetramethyl Preferred are tildisiloxane platinum complex, tetravinyltetramethylcyclotetrasiloxane platinum complex, dichlorobis (triphenylphosphine) platinum complex, and FibreCat ^R 4003.

The catalyst used for the hydrosilylation reaction is preferably dissolved in a solvent and used as a solution from the viewpoint of workability. Any solvent can be used as long as it can dissolve the catalyst. From the viewpoints of solubility and workability, tetrahydrofuran and toluene are preferable.
When used as a solution, the catalyst is adjusted to 0.05 to 50% by weight and added to the reaction solution.
When using a catalyst immobilized on polyethylene or the like, it is added to the reaction solution as it is.
The addition amount of the catalyst is added in the range of 0.1 to 1000 ppm of the reaction substrate as the amount of metal used in the catalyst. From the viewpoint of the transparency of the cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group in the obtained molecule and the transparency of the cured product, 1 to 100 ppm is preferable, and 2 to 20 ppm is particularly preferable. If the amount added is less than 0.1 ppm, the addition reaction may be delayed, and if it exceeds 1000 ppm, the cyclic siloxane compound (A) having an epoxy group and (alkoxysilyl) alkyl group in the molecule may be severely colored. .

After the hydrosilylation reaction, it can be purified by known methods such as washing with water, distillation, recrystallization, column chromatography, adsorption (activated carbon, various minerals) and the like.
The solvent used for the reaction and / or purification can be removed by distillation under reduced pressure or the like.

The epoxy equivalent (measured by the method described in JIS K7236: 2001) of the cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group in the molecule is preferably 180 to 400 g / eq, and 190 to 250 g / eq. Particularly preferred.
The viscosity (measured by the method described in JIS Z8803: 2011) at 25 ° C. of the cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group in the molecule is preferably 1000 to 10000 mPa · s, and preferably 1500 to 8000 mPa · s. s is more preferable, and 2000 to 7000 mPa · s is particularly preferable.

The cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group in the molecule represented by the formula (1) is specifically represented by the following formulas (1-1) to (1-16). Compounds.

The epoxy resin composition of the present invention can be used by mixing an epoxy resin in addition to the cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group in the molecule.
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 with other polymerizable unsaturated compounds, epoxy Examples thereof include condensates of silicon compounds having a group with other silicon compounds, silicone-modified epoxy resins, and the like.

  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 glycidylation of halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, 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.

  Examples of the condensate of the silicon compound having an epoxy group and another silicon compound include a hydrolysis condensate of an alkoxysilane compound having an epoxy group and an alkoxysilane having a methyl group or a phenyl group, or an epoxy group. It is a condensate of an alkoxysilane compound and a polydimethylsiloxane having a silanol group, a polydimethyldiphenylsiloxane having a silanol group, a polyphenylsiloxane having a silanol group, or a condensate obtained by using them in combination. Examples of the alkoxysilane compound having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldimethoxysilane and the like. Examples of the alkoxysilane compound having a methyl group or a phenyl group include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane. . As polydimethylsiloxane having a silanol group and polydimethyldiphenylsiloxane having a silanol group, for example, X-21-5841, KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-873 are available from the market. PRX413 (Toray Dow Corning Co., Ltd.) XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive Performance Materials Japan GK) DMS-S12, DMS-S14, DMS-S15, DMS-S21, Examples thereof include DMS-S27, DMS-S31, PDS-0338, and PDS-1615 (manufactured by Gelest).

  The silicone-modified epoxy resin is a compound having two or more epoxy groups in the molecule and having a silicone (Si—O) bond as a main skeleton. For example, hydrogen siloxane represented by the following formula (4) It can be obtained by a hydrosilylation reaction between the compound and 4-vinyl-1,2-epoxycyclohexane or 3-glycidoxy-1,2-propene.

In the formula (4), R ¹ represents the same meaning as described above, and s represents an average value of 1 to 100.

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

Among the above-mentioned epoxy resins, from the viewpoint of transparency, heat-resistant transparency, and light-resistant transparency, alicyclic epoxy resins, condensates of silicon compounds having an epoxy group with other silicon compounds, and combined use of silicone-modified epoxy resins Is preferred. Among these, a compound having an epoxycyclohexane structure in the skeleton is preferable.

  In the case where the cyclic siloxane compound (A) having an epoxy group and (alkoxysilyl) alkyl group in the molecule is used in combination with another epoxy resin, the epoxy group and (alkoxysilyl) alkyl group in the molecule with respect to all epoxy resins. The proportion of the cyclic siloxane compound (A) having a group is preferably 30 to 99 parts by weight, particularly preferably 60 to 97 parts by weight. If it is less than 30 parts by weight, the illuminance retention rate during the sulfidation resistance test and the crack resistance during reflow may be inferior.

  In the epoxy resin composition of the present invention, the blending ratio of the total epoxy resin containing the cyclic siloxane compound (A) having an epoxy group and (alkoxysilyl) alkyl group in the molecule and the epoxy resin curing agent is the epoxy group of all epoxy resins. It is preferable to use 0.5 to 1.2 equivalents of curing agent with respect to 1 equivalent. When less than 0.5 equivalent or more than 1.2 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.

Next, the epoxy resin curing agent (B) will be described. The epoxy resin curing agent (B) is a curing agent for curing the epoxy resin, and examples thereof include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polyvalent carboxylic acid resins, of which acid anhydrides. A system hardening agent and polyvalent carboxylic acid resin are preferable. Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, A mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2 , 3-dicarboxylic acid anhydride, 2,4-diethylglutaric acid anhydride, etc., among which hexahydrophthalic anhydride and its derivatives are preferred.

Next, the polyvalent carboxylic acid resin will be described.
The polycarboxylic acid resin is a compound having at least two carboxyl groups and having an aliphatic hydrocarbon group or a siloxane skeleton as a main skeleton. In the present invention, the polyvalent carboxylic acid resin is not only a polyvalent carboxylic acid compound having a single structure, but also a mixture of a plurality of compounds having different substituent positions or different substituents, that is, a polyvalent carboxylic acid. A composition is also included, and in the present invention, they are collectively referred to as a polyvalent carboxylic acid resin.

As the polyvalent carboxylic acid resin, a bi- to hexafunctional carboxylic acid is particularly preferable. (A); a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule; and (b); one or more in the molecule. More preferred are compounds obtained by reaction with compounds containing acid anhydride groups. Here, in the reactants (a) and (b), another alcohol compound may be reacted, and two or more compounds corresponding to the component (a) or (b) may be used. .
(A): The polyhydric alcohol compound containing two or more hydroxyl groups in the molecule is not particularly limited as long as it is a compound having two or more alcoholic hydroxyl groups in the molecule, 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, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) ) Diols such as 5-ethyl-5-hydroxymethyl-1,3-dioxane , Triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane, hexa such as dipentaerythritol Examples thereof include terminal alcohol polyester, terminal alcohol polycarbonate, terminal alcohol polyether, and polyhydric alcohol having a siloxane structure.
Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- And compounds such as (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, among which 2-ethyl-2-butyl-1,3-propanediol, Neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexane Sandimethanol, tricyclodecane dimethanol, norbornenediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl- Alcohols having a branched chain structure or a cyclic structure such as a compound such as 1,3-dioxane are more preferable. From the viewpoint of imparting high sulfidation resistance, 2,4-diethylpentanediol, tricyclodecane dimethanol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxy Compounds such as ethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane are particularly preferred. Among them, particularly in a branched chain structure, it is preferable to have two or more branched chains, and it is particularly preferable that the branched chains extend from different carbon atoms. Here, the alcohol having the branched chain structure or the cyclic structure preferably has 5 to 25 carbon atoms, and particularly preferably 5 to 20 carbon atoms.
Although the polyhydric alcohol which has a siloxane structure is not specifically limited, For example, the silicone oil represented by following formula (5) can be used.

In Formula (5), A ₁ represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond, and A ₂ represents a methyl group or a phenyl group. Moreover, m is the number of repetitions and means an average value, and is 1-100.

As described above, (a): the polyhydric alcohol compound containing two or more hydroxyl groups in the molecule may be used alone or in combination of two or more.
In order to use the obtained polycarboxylic acid resin in a liquid state and impart high resistance to sulfidation, the polyhydric alcohol having the siloxane structure described above and the alcohol having a branched chain structure or a cyclic structure having 5 to 25 carbon atoms. It is preferable to use a mixture.
When using a mixture of a polyhydric alcohol having a siloxane structure and an alcohol having a branched chain structure or a cyclic structure having 5 to 25 carbon atoms, the amount used is in the total alcohol compound (polyhydric alcohol having a siloxane structure). / (Alcohols having a branched chain structure or cyclic structure having 5 to 25 carbon atoms) is preferably 1 to 20, and 5 to 15 from the viewpoint of heat-resistant transparency of the cured product and appropriate viscosity of the polyvalent carboxylic acid resin. Is preferable, and 6 to 10 is particularly preferable.

(B); compounds containing one or more acid anhydride groups in the molecule include, in particular, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane Tetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3 , 4-tricarboxylic acid-3,4-anhydride, glutaric anhydride, 2,4-diethylglutaric anhydride, succinic anhydride and the like are preferred, and among them, methylhexahydrophthalic anhydride, cyclohexane-1,3, 4-tricarboxylic acid-3,4-anhydride, 2,4-diethylglutaric anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Cyclohexane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride is preferred. Here, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable for increasing hardness, and methylhexahydrophthalic anhydride is preferable for increasing illuminance retention. In order to suppress an excessive increase in viscosity of the polyvalent carboxylic acid resin, 2,4-diethylglutaric acid and glutaric acid are preferable.
Although there is no particular designation as a condition for the addition reaction, one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted in a non-catalytic and solvent-free condition at 40 to 150 ° C. and heated to react. After completion, take it out as it is. It is a technique. However, it is not limited to this reaction condition.

  The compounding amount of the epoxy resin curing agent (B) is a functional group having reactivity with the epoxy group with respect to a total of 1 mol of all epoxy groups (in the case of an acid anhydride curing agent, -CO-O-CO- Is an amount such that the acid anhydride group is 0.3 to 1.0 mol, preferably 0.4 to 0.8 mol. If the functional group having reactivity with the epoxy group is 0.3 mol or more, the heat resistance and transparency of the cured product are improved, and if it is 1.0 mol or less, the mechanical properties of the cured product are improved. ,preferable. Here, “functional group having reactivity with epoxy group” means an amino group possessed by an amine curing agent, a phenolic hydroxyl group possessed by a phenol curing agent, an acid anhydride group possessed by an acid anhydride curing agent, It is a carboxyl group possessed by a polyvalent carboxylic acid resin.

Next, the epoxy resin curing accelerator (C) will be described.
The epoxy resin curing accelerator (C) accelerates the curing reaction between the cyclic siloxane compound (A) having two or more epoxy groups in the molecule (and the epoxy resin when used in combination) and the epoxy resin curing agent (B). Any capable accelerator can be used. Examples of the curing accelerator (C) that can be used include ammonium salt-based curing accelerators, phosphonium salt-based curing accelerators, metal soap-based curing accelerators, and imidazoles. Examples thereof include a system curing accelerator, an amine-based curing accelerator, a phosphine-based curing accelerator, a phosphite-based curing accelerator, and a Lewis acid-based curing accelerator.
In the epoxy resin composition of the present invention, the epoxy resin curing accelerator (C) is preferably used in an amount of 0.001 to 15 parts by weight of the curing accelerator with respect to 100 parts by weight of the epoxy resin composition.

Specific examples of the epoxy resin curing accelerator (C) that can be used in the epoxy resin composition of the present invention include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl. -4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine 2,4-diamino-6 (2′-ethyl, 4-methylimidazole ( ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 2: 3 adduct of 2-methylimidazole isocyanuric acid 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxy Various imidazoles of methylimidazole, and salts of these imidazoles with polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid, dicyandiamide, etc. Amides of 1,8-diaza-bicyclo (5.4 0) Diaza compounds such as undecene-7 and salts thereof such as tetraphenylborate and phenol novolac, salts with the above polyvalent carboxylic acids or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide Ammonium salts such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate and other phosphines and phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, amines Examples thereof include metal compounds such as adducts, tin octylate and the like, and microcapsule type curing accelerators in which these curing accelerators are formed into microcapsules. . Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions.

Among these, from the viewpoints of transparency and sulfidation resistance of the cured product, a metal soap curing accelerator is excellent, and among the metal soap curing accelerators, a zinc carboxylate compound is particularly preferable.
Examples of the metal soap hardening accelerator include tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, potassium octylate, calcium stearate, zinc stearate, magnesium stearate, stearin Aluminum oxide, barium stearate, lithium stearate, sodium stearate, potassium stearate, 12-hydroxy calcium phosphate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, 12-hydroxystearic acid Barium, lithium 12-hydroxystearate, sodium 12-hydroxystearate, calcium montanate, zinc montanate, mon Magnesium phosphate, aluminum montanate, 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 undecylate, zinc ricinoleate, barium ricinoleate, zinc myristate, zinc palmitate and the like. These catalysts may be used alone or in combination of two or more.
Carbons such as zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate, and zinc palmitate are used to obtain cured products with excellent transparency and sulfidation resistance. A zinc salt composed of a monocarboxylic acid compound having 10 to 30 carbon atoms and having a hydroxyl group such as zinc carbonate having several tens to thirty or 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.

Examples of the ammonium salt curing accelerator include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide. , Trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate and the like. Examples of the phosphonium salt curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, methyltributylphosphonium diethylphosphate, and the like.

  In addition to the above-mentioned ammonium salt-based curing accelerators, phosphonium salt-based curing accelerators, metal soap-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators, and heterocyclic compound-based curing accelerators. A phosphine-based curing accelerator, a phosphite-based curing accelerator, a Lewis acid-based curing accelerator, or the like can be used.

  The epoxy resin curing accelerator (C) described above can be used as a solid compound or a liquid compound at room temperature (25 ° C.). When the epoxy resin composition of the present invention is used for optical semiconductor encapsulation, and a solid compound is used as a curing accelerator at room temperature (25 ° C.), it can be used by dissolving it in a resin in advance.

In the epoxy resin composition of the present invention, it is possible to supplement the viscosity adjustment of the composition and the hardness of the cured product by using a coupling agent as necessary.
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 epoxy resin composition of this invention, Preferably 0.1-10 weight part is contained as needed.

The epoxy resin composition of the present invention can be supplemented with 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 epoxy resin composition of the present invention.

If necessary, a phosphor can be added to the epoxy resin composition of the present invention. 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. The phosphor is not particularly limited, and a conventionally known phosphor can be used. For example, a rare earth element such as aluminate, thiogallate, orthosilicate, or silicon nitride, a part of the silicon atom is an aluminum atom. Examples thereof include substances in which a part of nitrogen atoms is replaced with oxygen atoms. More specifically, phosphors such as YAG phosphors, TAG phosphors, orthosilicate phosphors, thiogallate phosphors, sulfide phosphors, and sialon phosphors 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 , Si _{12- (m + n)} Al _{(m + n ) )} O _n N _{16-n and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to the resin component, Preferably it is 5-60 weight part.

  For the purpose of preventing settling of various phosphors during curing, thixotropic imparting agents such as silica fine powder (also referred to as aerosil or aerosol) can be added to the epoxy resin composition of the present invention. 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 coloring, the epoxy resin composition of the present invention may 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, as an ADEKA product, 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 , Adekas tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, 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 of the phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0 with respect to the total weight of the epoxy resin composition of the present invention. 0.005 to 5.0% by weight.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at room temperature or under heating. For example, mix thoroughly until uniform using an extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., and if necessary, filter with SUS mesh etc. Prepared.

  The epoxy resin composition of the present invention comprises a cyclic siloxane compound (A) having two or more epoxy groups in the molecule (other epoxy resins as required), an epoxy resin curing agent (B), and a curing accelerator (C ), An epoxy resin composition can be prepared by sufficiently mixing additives such as an antioxidant and a light stabilizer 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.

  When the epoxy resin composition of the present invention thus obtained is used for sealing an optical semiconductor, and further required to be liquid at room temperature (25 ° C.), its viscosity (measured according to JIS Z8803: 2011) Is preferably 100 to 2000 mPa · s from the viewpoint of workability, more preferably 2000 to 12000 mPa · s, and particularly preferably 3000 to 10000 mPa · s.

  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 epoxy 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.

  When the cured product obtained by curing the epoxy resin composition of the present invention thus obtained is used for optical semiconductor sealing, the transmittance at 400 nm is 85% or more in a cured product plate having a thickness of 0.8 mm. It is preferable that it is 88% or more. If it is less than 85%, the light extraction efficiency from the optical semiconductor element may be reduced.

  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, each physical-property value in a synthesis example and an Example was measured with the following method. Here, a part represents a mass part unless otherwise specified.
O Epoxy equivalent: Measured by the method described in JIS K7236: 2001.
○ Acid value: measured by the method described in JIS K2501: 2003.
Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd. according to JIS Z8803: 2011.
○ ¹ H-NMR: Measured with deuterated chloroform solvent using JNM-ECS400 manufactured by JEOL Ltd.

Synthesis Example 1: In X of formula (1), the epoxy group-containing organic group is 95 mol%, the 2- (trimethoxysilyl) ethyl group is 5%, and the epoxy group and the (alkoxysilyl) alkyl group in the molecule. Example of Production of Cyclic Siloxane Compound Having Glass In a 300 ml four-necked flask made of glass, 30.7 parts of 4-vinyl-1,2-epoxycyclohexane, 1.9 parts of trimethoxyvinylsilane, Fibrecat ^R 4003 (platinum content 3.4 -4.5%) was charged with 0.024 parts and toluene 50 parts, a Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated and the internal temperature was maintained at 70 to 80 ° C., and 12 parts of 2,4,6,8-tetramethyltetracyclosiloxane was added dropwise over 1 hour, and the reaction was allowed to proceed for 3.5 hours. When ¹ H-NMR measurement of the reaction solution was performed, the proton peak derived from hydrogensiloxane disappeared.
Activated carbon (manufactured by Ajinomoto Fine Techno Co., Ltd.) is added to the reaction solution, and after stirring for 3 hours at room temperature (20 to 30 ° C.), the activated carbon and Fibercat ^R 4003 are removed by filtration, and nitrogen gas is blown into the obtained filtrate. The cyclic siloxane compound (A-1) having two or more epoxy groups in the molecule by removing the toluene, excess 4-vinyl-1,2-epoxycyclohexane and trimethoxyvinylsilane by concentration under reduced pressure at 60 ° C. ) 36.4 parts were obtained. The epoxy equivalent of the obtained compound was 204.2 g / eq, the viscosity was 2222 mPa · s, and the appearance was a colorless transparent liquid. As a result of ¹ H-NMR analysis, in X in formula (1), the epoxy group-containing organic group was 95 mol% and the 2- (trimethoxysilyl) ethyl group was 5 mol%.

Synthesis Example 2: Production Example of Cyclic Siloxane Compound Having Two or More Epoxy Groups in a Molecule in which X in Formula (1) is 100 mol% of Epoxy Group-Containing Organic Group In a glass 200 ml four-necked flask , 4-vinyl-1,2-epoxycyclohexane 32.3 parts, Fibrecat ^R 4003 (platinum content 3.4-4.5%) 0.023 parts, toluene 50 parts, a Dimroth condenser, a stirrer, A thermometer was installed and the flask was immersed in an oil bath. The oil bath was heated, the internal temperature was kept at 80 ° C., and 12 parts of 2,4,6,8-tetramethyltetracyclosiloxane was added dropwise over 1 hour, and the reaction was allowed to proceed for 10 hours. When ¹ H-NMR measurement of the reaction solution was performed, the proton peak derived from hydrogensiloxane disappeared.
Activated carbon (manufactured by Ajinomoto Fine Techno Co., Ltd.) is added to the reaction solution, and after stirring for 3 hours at room temperature (20 to 30 ° C.), the activated carbon and Fibercat ^R 4003 are removed by filtration, and nitrogen gas is blown into the obtained filtrate. The solution was concentrated under reduced pressure at 60 ° C., and toluene and excess 4-vinyl-1,2-epoxycyclohexane were removed to obtain 36.7 parts of a cyclic siloxane compound (EP-1) having four epoxy groups in the molecule. Obtained. The epoxy equivalent of the obtained compound was 184.3 g / eq, the viscosity was 5601 mPa · s, and the appearance was a colorless transparent liquid.

Synthesis Example 3: (a) As a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, one or more silicone oils and neopentyl glycol represented by the formula (5) are contained in the molecule (b). Example of Synthesis of Polyvalent Carboxylic Acid Resin Using 2,4-Diethylglutaric Acid as a Compound Containing an Acid Anhydride Group In a 400 ml four-necked flask made of glass, 23.4 g of neopentyl glycol, YH1120 (Mitsubishi Chemical Corporation) Ltd., 2,4-diethyl glutaric acid) 102.1 g, KF-6000 (Shin-Etsu Chemical Co., Ltd., both terminals carbinol-modified silicone oils, the formula (5) medium _{A 1} is propyl oxyethylene group, _{A 2} is methyl , 74.4 g of carbinol-terminated silicone oil whose m is 7.5), a Dimroth condenser, a stirrer, and a thermometer are installed. I was immersed in a flask to the nest. The inner temperature was 95 to 105 ° C. and the reaction was carried out for 10 hours. Then, it was made to react at internal temperature 115-125 degreeC for 4 hours. When the reaction solution was confirmed by GPC after completion of the reaction, the peaks of neopentyl glycol and 2,4-diethylglutaric acid had disappeared. In this way, 193 g of a polycarboxylic acid resin (B-1) was obtained. The acid value of the polyvalent carboxylic acid resin (B-1) was 160.1 mgKOH / g, the viscosity was 2300 mPa · s, and the appearance was a colorless transparent liquid.

Example 1 In the X of the formula (1) obtained in Synthesis Example 1, the epoxy group-containing organic group is 95 mol%, and the 2- (trimethoxysilyl) ethyl group is 5%. And (cycloalkoxy) alkyl group-containing cyclic siloxane compound (A-1), the polyvalent carboxylic acid resin (B-1) obtained in Synthesis Example 3, and zinc stearate as a curing accelerator are listed in Table 1 below. The mixture was put into a polypropylene container at a quantitative ratio, mixed and degassed for 5 minutes to obtain an epoxy resin composition of the present invention.

Comparative Example 1; a cyclic siloxane compound (EP-1) having an epoxy group in which the organic group containing an epoxy group is 100 mol% in X of the formula (1) obtained in Synthesis Example 2, obtained in Synthesis Example 3 The polyvalent carboxylic acid resin (B-1) and zinc stearate as a curing accelerator are put in a polypropylene container at the quantitative ratio shown in Table 1 below, mixed and degassed for 5 minutes, and the epoxy resin of the present invention A composition was obtained.

(Evaluation test)
Table 1 shows the blending ratio of the curable resin composition for sealing an optical semiconductor obtained in Example 1 and Comparative Example 1, the viscosity thereof, the transmittance of the cured product, and the results of sulfidation resistance as an LED test. The test in Table 1 was performed as follows.
Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.
Hardened product transmittance Glass substrate on which a dam was made with heat-resistant tape so that the epoxy resin composition obtained in Example 1 and Comparative Example 1 was subjected to vacuum defoaming for 5 minutes and then 30 mm × 20 mm × height 0.8 mm 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
Scanning speed: 120 nm / min (3) Sulfurization resistance test The epoxy resin composition for optical semiconductor encapsulation obtained in Example 1 and Comparative Example 1 was vacuum degassed for 5 minutes, then filled into a syringe, and a precision dispensing device was used. A light-emitting element having a light emission wavelength of 450 nm is mounted on a 3.0 mm × 1.4 mm × 1.4 mmt (sealing portion 0.6 mmt) surface-mount LED package having a copper electrode with a silver plating on the bottom surface. The surface-mounted LED 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.
The illuminance of the sealed surface-mounted LED was measured in advance, placed in a 170 mm × 170 mm × 50 mmt glass sealed container together with a 9 cm diameter glass petri dish containing 2 g of sulfur solid, and left in a 70 ° C. constant temperature bath. The illuminance was measured again 12 hours later, and the rate of change from the illuminance before the test was calculated.
In addition, the illumination intensity of LED was measured as follows.
The surface mount type LED package used for the test was installed on the wall of an integrating sphere (FOIS-1, manufactured by Ocean Opto) at 25 ° C. and 65% RH, and a constant current of 20 mA was applied to measure the light (Wavelength Calibration USB4000 series, Radiant flux (W) was measured with Optocilius.

As is clear from the results shown in Table 1, Comparative Example 1 using a cyclic siloxane compound having an epoxy group and having no (alkoxysilyl) alkyl group represented by the formula (2) in the molecule is appropriate. The viscosity and excellent transmittance of the cured product were shown, but the illuminance retention was poor in the sulfidation resistance test.
On the other hand, Example 1 using a cyclic siloxane compound having an epoxy group and an (alkoxysilyl) alkyl group in the molecule exhibits an appropriate viscosity, excellent cured product transmittance, and further exhibits excellent sulfidation resistance. It is suitable for fields requiring optical transparency and high gas barrier properties, particularly as a resin composition for optical semiconductor encapsulation.

Claims (7)

An epoxy resin composition containing a cyclic siloxane compound (A) having an epoxy group and an (alkoxysilyl) alkyl group in the molecule represented by the following formula (1), and an epoxy resin curing agent (B) : An epoxy resin composition, wherein the epoxy resin curing agent (B) is a polyvalent carboxylic acid resin obtained by reacting at least the following (a) and (b).
(A): a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule
(B); a compound containing one or more acid anhydride groups in a molecule selected from one or more of methylhexahydrophthalic anhydride, glutaric anhydride, and diethylglutaric anhydride

(In the formula (1), R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, X is an epoxy group-containing organic group or a substituent represented by the following formula (2), and n is an integer of 1 to 3. A plurality of R ¹ and X present in the formula may be the same or different from each other, but in the plurality of X present, an average of 1 mol% to 30 mol% is represented by formula (2) (Alkoxysilyl) alkyl group represented by

(In Formula (2), R ² represents an alkylene group having 2 to 6 carbon atoms, and R ³ represents an alkyl group or alkoxy group having 1 to 6 carbon atoms. Multiple R ^{3 s in the} formula are the same. Or at least one is an alkoxy group. The epoxy resin composition according to claim 1, wherein R ³ in formula (2) is one or more selected from a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. Furthermore, the epoxy resin composition of Claim 1 or 2 containing an epoxy resin hardening accelerator (C). The epoxy resin composition of Claim 3 whose epoxy resin hardening accelerator (C) is a metal soap hardening accelerator. Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-4 . The resin composition for optical semiconductor sealing which consists of an epoxy resin composition as described in any one of Claims 1-4 . The optical semiconductor device which sealed the optical semiconductor element with the resin composition for optical semiconductor sealing of Claim 6 .