JP6279830B2 - Curable resin composition 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, the sealing material using such a silicone resin is excellent in UV resistance and heat resistance, but because the hardness is insufficient, the gold wire is likely to break, or the adhesion is poor and easily peeled off. The problem is that the sealing surface is sticky.
Therefore, hardened cured products with increased crosslink density of the cured silicone resin or increased aromatic organic groups such as phenyl groups in the molecule are also used, but the heat cycle resistance is poor. There are concerns that there are adverse effects such as cracks and peeling from the substrate, and that UV resistance is inferior due to an increase in aromatic organic groups.
In order to solve these problems, a curable resin composition for sealing an optical semiconductor element using a condensate of a silicon compound having an epoxy group or a phenyl group and an epoxy resin curing agent has been proposed. However, these methods improve the heat resistance and light resistance, but the effect is insufficient. When the LED package is sealed with a resin and evaluated, the illuminance decreases, peels off, cracks are generated, and no lighting is produced. Such a problem may occur.
Among such problems, as a method for preventing a decrease in illuminance, in particular, a metal frame on which an optical semiconductor is fixed is immersed in a surfactant and dried by heating. A casting method has been proposed (Japanese Patent Laid-Open No. 06-132330). However, it is difficult to completely remove the solvent used in the surfactant without yellowing the package during drying by heating, so that it is not suitable for practical use. Met.

JP 2003-277473 A Japanese Patent No. 4636242

  An object of the present invention is to provide a curable resin composition for encapsulating an optical semiconductor element that is free from cracking, peeling, or non-lighting during lighting and has excellent lighting durability.

（上記式（１）において、Ｘは下記部分構造（１ａ）

（上記式中、Ｒ^１はメチル基または水素原子を、Ｒ^２は炭素数１〜１５のアルキル基、炭素数１〜９のアルコキシ基、または水酸基を、ｙは１〜２０の整数を、ｎは０〜５０の整数を、ｍは１〜３の整数をそれぞれ表す。）
及び、下記部分構造（１ｂ）

（上記式中、ｘは１〜１００の整数を表す。）
とからなる残基を示す。）

（４）前記ポリエーテル変性ポリシロキサンが式（１’）で表されるポリエーテル変性ポリシロキサンであることを特徴とする（１）〜（３）のいずれか一項に記載の光半導体封止用硬化性樹脂組成物、

（式（１’）において、Ｒ^１はメチル基または水素を、Ｒ^２は炭素数１〜１５のアルキル基、炭素数１〜９のアルコキシ基、または水酸基を、ｘは１〜１００の整数を、ｙは１〜２０の整数を、ｎは０〜５０の整数を、ｍは１〜３の整数をそれぞれ表す。）

（５）（１）記載の界面活性剤が下記式（２）の部分構造を有するアクリル重合体であることを特徴とする（１）に記載の光半導体封止用硬化性樹脂組成物、

（式（２）において、Ｒ^１はメチル基または水素原子を表し、Ｒ^２は各々独立に、炭素数１〜１５のアルキル基、ヘテロ環基、ポリエステル、ポリエーテル、またはアミン塩を、zは１〜２００の整数を表す。）
（６）前記アクリル重合体が、下記式（２’）で表されるアクリル重合体であることを特徴とする（５）に記載の光半導体封止用硬化性樹脂組成物、

（式（２’）において、Ｒ^１はメチル基または水素原子を表し、Ｒ^２、Ｒ^３、Ｒ^４
は、各々独立に、炭素数１〜１５のアルキル基、ヘテロ環基、ポリエステル、ポリエーテル、またはアミン塩を、ｘ、ｙ、ｚは０〜２００の整数を表し、ｘ、ｙ及びｚが全て０となることはない。）
ここで、前記アクリル重合体が、式（２’）の部分構造においてＲ^２、Ｒ^３、Ｒ^４の少なくとも一つは、炭素数４のアルキル基であり、炭素数４のアルキル基からなるＲ^２、Ｒ^３、またはＲ^４の少なくとも一つが炭素数４のアルキル基である部分構造がアクリル重合体の１５〜９５質量％を構成するアクリル重合体であることを特徴とする（１）又は（４）に記載の光半導体封止用硬化性樹脂組成物、
（７）（１）記載の界面活性剤が含フッ素界面活性剤であることを特徴とする（１）に記載の光半導体封止用硬化性樹脂組成物、
（８）（７）記載の含フッ素界面活性剤が、アクリル構造を有する含フッ素界面活性剤であることを特徴とする（１）又は（７）に記載の光半導体封止用硬化性樹脂組成物、
（９）（７）記載の含フッ素界面活性剤が、パーフルオロアルキル基を有する含フッ素界面活性剤であることを特徴とする（１）もしくは（７）に記載の光半導体封止用硬化性樹脂組成物、
（１０）（６）記載の含フッ素界面活性剤が、パーフルオロアルケニル基を有する含フッ素界面活性剤であることを特徴とする（１）もしくは（７）に記載の光半導体封止用硬化性樹脂組成物、
（１１）エポキシ樹脂に対し、前記界面活性剤が０．００１〜１０重量％含有されていることを特徴とする（１）〜（１０）のいずれか一項に記載の光半導体封止用硬化性樹脂組成物、
（１２）さらに、エポキシ樹脂硬化剤を含有し、エポキシ樹脂硬化剤が、多価カルボン酸（Ａ１）および／または多価カルボン酸樹脂（Ａ２）である、（１）〜（１１）のいずれか一項に記載の光半導体封止用硬化性樹脂組成物、
（１３）前記エポキシ樹脂がシリコーン骨格エポキシ樹脂（Ｂ）である（１）〜（１１）のいずれか一項に記載の光半導体封止用硬化性樹脂組成物、
（１４）前記シリコーン骨格エポキシ樹脂（Ｂ）が、下記製造工程１、２を経て得られた、下記式（３）で表されるシラノール末端シリコーンオイルと下記式（４）で表されるエポキシ基含有ケイ素化合物の重合物であり、エポキシ当量が３００〜１５００ｇ／ｅｑである、（２）に記載の光半導体素子封止用硬化性樹脂組成物、
製造工程１
シラノール末端シリコーンオイルのシラノール基と、エポキシ基含有ケイ素化合物のアルコキシ基を縮合させ、変性シリコーンオイルを得る工程。
製造工程２
製造工程１の後に、水を加え、残存するアルコキシ基の加水分解縮合を行なう工程。

（式（３）において、Ｒ_５は炭素数１〜３のアルキル基又はフェニル基を、ｐは平均値で３〜２００をそれぞれ表す。式中、複数存在するＲ_５は互いに同一であっても異なっていても良い）

（式（３’）において、Ｘはエポキシ基を含有する有機基を、Ｒ_６は炭素数１〜１０の直鎖状、分岐状、環状のアルキル基又は炭素数６〜１０の芳香族炭化水素基を有するアリール基を、Ｒ_７は炭素数１〜１０の直鎖状、分岐状、環状のアルキル基を、ｑは整数で０〜２を、ｒは整数で（３−ｑ）をそれぞれ表す。）
（１５）（１）〜（１４）のいずれか一項に記載の光半導体封止用硬化性樹脂組成物を硬化してなる硬化物、
（１６）（１５）に記載の硬化物を具備するＬＥＤ、
に関する。 As a result of intensive investigations in view of the actual situation as described above, the present inventors have found that a curable resin composition containing an epoxy resin and / or an epoxy resin curing agent and a surfactant solves the above-described problems. The invention has been completed.
That is, the present invention
(1)
A curable resin composition for sealing an optical semiconductor containing an epoxy resin and a surfactant,

(2) The curable resin composition for optical semiconductor encapsulation according to (1), wherein the surfactant is a polyether-modified polysiloxane,

(3) The curable resin composition for optical semiconductor encapsulation according to (1) or (2), wherein the polyether-modified polysiloxane is a polyether-modified polysiloxane represented by the formula (1): ,

(In the above formula (1), X represents the following partial structure (1a)

(In the above formula, R ¹ represents a methyl group or a hydrogen atom, R ² represents an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or a hydroxyl group, y represents an integer of 1 to 20, n Represents an integer of 0 to 50, and m represents an integer of 1 to 3.)
And the following partial structure (1b)

(In the above formula, x represents an integer of 1 to 100.)
The residue which consists of is shown. )

(4) The optical semiconductor encapsulation according to any one of (1) to (3), wherein the polyether-modified polysiloxane is a polyether-modified polysiloxane represented by the formula (1 ′): Curable resin composition,

(In Formula (1 ′), R ¹ represents a methyl group or hydrogen, R ² represents an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or a hydroxyl group, and x represents an integer of 1 to 100. Y represents an integer of 1 to 20, n represents an integer of 0 to 50, and m represents an integer of 1 to 3.)

(5) The curable resin composition for sealing an optical semiconductor according to (1), wherein the surfactant according to (1) is an acrylic polymer having a partial structure represented by the following formula (2):

(In Formula (2), R ¹ represents a methyl group or a hydrogen atom, R ² each independently represents an alkyl group having 1 to 15 carbon atoms, a heterocyclic group, a polyester, a polyether, or an amine salt; Represents an integer of 1 to 200.)
(6) The curable resin composition for optical semiconductor encapsulation according to (5), wherein the acrylic polymer is an acrylic polymer represented by the following formula (2 ′):

(In the formula (2 ′), R ¹ represents a methyl group or a hydrogen atom, R ² , R ³ , R ⁴
Each independently represents an alkyl group having 1 to 15 carbon atoms, a heterocyclic group, a polyester, a polyether, or an amine salt, and x, y, and z each represents an integer of 0 to 200, and x, y, and z are all It will never be zero. )
Here, in the partial structure of the formula (2 ′), at least one of R ² , R ³ , and R ⁴ is an alkyl group having 4 carbon atoms, and the acrylic polymer is an R having an alkyl group having 4 carbon atoms. ^The partial structure in which at least one of ² , R ³ and R ⁴ is an alkyl group having 4 carbon atoms is an acrylic polymer constituting 15 to 95% by mass of the acrylic polymer (1) or ( 4) curable resin composition for optical semiconductor encapsulation,
(7) The curable resin composition for sealing an optical semiconductor according to (1), wherein the surfactant according to (1) is a fluorine-containing surfactant,
(8) The curable resin composition for sealing an optical semiconductor according to (1) or (7), wherein the fluorine-containing surfactant according to (7) is a fluorine-containing surfactant having an acrylic structure object,
(9) The curable surfactant for optical semiconductors according to (1) or (7), wherein the fluorine-containing surfactant described in (7) is a fluorine-containing surfactant having a perfluoroalkyl group. Resin composition,
(10) The curable surfactant for optical semiconductor encapsulation according to (1) or (7), wherein the fluorine-containing surfactant described in (6) is a fluorine-containing surfactant having a perfluoroalkenyl group. Resin composition,
(11) The curing for optical semiconductor encapsulation according to any one of (1) to (10), wherein the surfactant is contained in an amount of 0.001 to 10% by weight with respect to the epoxy resin. Functional resin composition,
(12) Any of (1) to (11), further comprising an epoxy resin curing agent, wherein the epoxy resin curing agent is a polyvalent carboxylic acid (A1) and / or a polyvalent carboxylic acid resin (A2). The curable resin composition for optical semiconductor encapsulation according to one item,
(13) The curable resin composition for optical semiconductor encapsulation according to any one of (1) to (11), wherein the epoxy resin is a silicone skeleton epoxy resin (B),
(14) The silanol-terminated silicone oil represented by the following formula (3) and the epoxy group represented by the following formula (4), wherein the silicone skeleton epoxy resin (B) is obtained through the following production steps 1 and 2. A curable resin composition for sealing an optical semiconductor element according to (2), which is a polymer of a silicon-containing compound and has an epoxy equivalent of 300 to 1500 g / eq,
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 the formula (3 ′), 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 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). .)
(15) A cured product obtained by curing the curable resin composition for optical semiconductor encapsulation according to any one of (1) to (14),
(16) LED comprising the cured product according to (15),
About.

  According to the present invention, a curable resin composition containing an epoxy resin and a surfactant is extremely excellent in lighting durability, and thus is useful as an optical semiconductor element (LED) sealing material.

  As described above, the curable resin composition for an optical semiconductor element sealing material of the present invention contains a surfactant and an epoxy resin.

The resin composition for encapsulating an optical semiconductor of the present invention contains a surfactant. Accordingly, the surfactant will be described.
The surfactant that can be used in the present invention is at least one selected from the group consisting of an anionic surfactant, a cationic surfactant, and a nonionic surfactant, and a mixture of two or more types is used. May be. Among these, preferable surfactants include polyether-modified polysiloxane which is a nonionic surfactant.

First, the surfactant contained in the present invention will be described.

（上記式（１）において、Ｘは下記部分構造（１ａ）

（上記式中、Ｒ^１はメチル基または水素原子を、Ｒ^２は炭素数１〜１５のアルキル基、炭素数１〜９のアルコキシ基、または水酸基を、ｙは１〜２０の整数を、ｎは０〜５０の整数を、ｍは１〜３の整数をそれぞれ表す。）
及び、下記部分構造（１ｂ）

（上記式中、ｘは１〜１００の整数を表す。）
とからなる残基を示す。）

より具体的には、式（１’）で表されるポリエーテル変性ポリシロキサンがあげられる。

（式（１’）において、Ｒ^１はメチル基または水素を、Ｒ^２は炭素数１〜１５のアルキル基、炭素数１〜９のアルコキシ基、または水酸基を、ｘは１〜１００の整数を、ｙは１〜２０の整数を、ｎは０〜５０の整数を、ｍは１〜３の整数をそれぞれ表す。）
式（１）ないし式（１’）において、ｘは通常１〜１００であり、２０〜３０が好ましく、ｙは通常１〜２０の整数であり、２〜１０が好ましい。
また、式（１）ないし式（１’）において、ｎは通常０〜５０の整数であり、好ましくは２０〜３０である。 The polyether group of the polyether-modified polysiloxane is composed of alkylene oxide such as methylene oxide, ethylene oxide, propylene oxide, butylene oxide, and mixed components thereof. Examples of the structure include those having a polyether group at one end, both ends, and side chains. Among these, a preferable structure has a polyether group in the side chain, and the polyether group is composed of ethylene oxide, propylene oxide, and a mixed component thereof. Such a polyether-modified polysiloxane is represented by the following formula (1).

(In the above formula (1), X represents the following partial structure (1a)

(In the above formula, R ¹ represents a methyl group or a hydrogen atom, R ² represents an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or a hydroxyl group, y represents an integer of 1 to 20, n Represents an integer of 0 to 50, and m represents an integer of 1 to 3.)
And the following partial structure (1b)

(In the above formula, x represents an integer of 1 to 100.)
The residue which consists of is shown. )

More specifically, polyether-modified polysiloxane represented by the formula (1 ′) can be mentioned.

(In Formula (1 ′), R ¹ represents a methyl group or hydrogen, R ² represents an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or a hydroxyl group, and x represents an integer of 1 to 100. Y represents an integer of 1 to 20, n represents an integer of 0 to 50, and m represents an integer of 1 to 3.)
In Formula (1) thru | or Formula (1 '), x is 1-100 normally, 20-30 are preferable, y is an integer of 1-20 normally, and 2-10 are preferable.
Moreover, in Formula (1) thru | or Formula (1 '), n is an integer of 0-50 normally, Preferably it is 20-30.

The polyether-modified polysiloxane is preferably a solventless type. This is because when used by blending in a curable resin composition, the solvent volatilizes during heat-curing, resulting in a problem that a dent is formed in the cured product.
Here, as the solventless type, in the polyether-modified polysiloxane-containing additive used as the surfactant, the non-volatile component content is preferably 90% or more, more preferably 95% or more. When the resin composition is less than 90%, when the resin composition is cured to seal the package, the solvent is volatilized, a dent is generated in the sealing portion, the wire or other package member is exposed, or the illuminance value is This is because it may cause defects such as variations.
The polyether-modified polysiloxane may be mixed with other nonionic surfactant poly (oxyethylene) alkyl ether. When mixed and used, the mixture ratio of the polyether-modified polysiloxane is preferably 30% or more, more preferably 40% or more. This is because if it is less than 30%, the properties of the polyether-modified polysiloxane are hardly exhibited.
For this reason, BYK-302 (manufactured by Big Chemie Japan Co., Ltd.) and the like can be mentioned as a preferred commercially available polyether-modified silicone.

（式（２）において、Ｒ^１はメチル基または水素原子を表し、Ｒ^２は各々独立に、炭素数１〜１５のアルキル基、ヘテロ環基、ポリエステル、ポリエーテル、またはアミン塩を、zは１〜２００の整数を表す。）
より具体的には、下記式（２’）で表されるアクリル重合体があげられる。

（式（２’）において、Ｒ^１はメチル基または水素原子を表し、Ｒ^２、Ｒ^３、Ｒ^４
は、各々独立に、炭素数１〜１５のアルキル基、ヘテロ環基、ポリエステル、ポリエーテル、またはアミン塩を、ｘ、ｙ、ｚは０〜２００の整数を表す。但し、ｘ、ｙ、ｚが全て０となることはない。）
上記式（２）ないし式（２’）において、Ｒ^２、Ｒ^３、Ｒ^４の少なくとも一つは、炭素数４のアルキル基であり、炭素数４のアルキル基からなるＲ^２、Ｒ^３またはＲ^４、またはこれらの混成成分が、アクリル重合体の１５〜９５質量％を構成することが好ましい。上記式（２’）のＲ^２〜Ｒ^４の少なくとも一つが炭素数４のアルキル基である部分構造がアクリル重合体の１５〜９５質量％を構成することがより好ましい。また、アクリル重合体の混合物においては、上記式（２’）のＲ^２〜Ｒ^４の少なくとも一つが炭素数４のアルキル基である部分構造を有するアクリル重合体が、アクリル重合体混合物の１５〜９５質量％を構成することが好ましい。
好ましいアクリル重合体の市販品としては、ＢＹＫ−３５２（ビックケミー・ジャパン株式会社製）等が挙げられる。 Another preferable surfactant is an acrylic polymer having a partial structure represented by the following formula (2).

(In Formula (2), R ¹ represents a methyl group or a hydrogen atom, R ² each independently represents an alkyl group having 1 to 15 carbon atoms, a heterocyclic group, a polyester, a polyether, or an amine salt; Represents an integer of 1 to 200.)
More specifically, an acrylic polymer represented by the following formula (2 ′) is exemplified.

(In the formula (2 ′), R ¹ represents a methyl group or a hydrogen atom, R ² , R ³ , R ⁴
Each independently represents an alkyl group having 1 to 15 carbon atoms, a heterocyclic group, a polyester, a polyether, or an amine salt, and x, y, and z each represents an integer of 0 to 200. However, x, y, and z are not all zero. )
In the above formulas (2) to (2 ′), at least one of R ² , R ³ , and R ⁴ is a C ⁴ alkyl group, and R ² , R ^3, R ⁴ or a mixed component thereof preferably constitutes 15 to 95% by mass of the acrylic polymer. More preferably, the partial structure in which at least one of R ^{2 to} R ^{4 in} the above formula (2 ′) is a C 4 alkyl group constitutes 15 to 95% by mass of the acrylic polymer. In the acrylic polymer mixture, an acrylic polymer having a partial structure in which at least one of R ^{2 to} R ^{4 in} the above formula (2 ′) is an alkyl group having 4 carbon atoms is 15 to 15% of the acrylic polymer mixture. It is preferable to constitute 95% by mass.
As a preferable commercial product of the acrylic polymer, BYK-352 (manufactured by Big Chemie Japan Co., Ltd.) and the like can be mentioned.

  Other preferred surfactants include fluorine-containing surfactants. Among these, preferred structures include a fluorine-containing surfactant having an acrylic structure, a fluorine-containing surfactant having a perfluoroalkyl group, and a fluorine-containing surfactant having a perfluoroalkenyl group.

As a commercial product of a fluorine-containing surfactant having an acrylic structure, Polyflow KL600 (manufactured by Kyoeisha Chemical Co., Ltd.), and as a commercial product of a fluorine-containing surfactant having a perfluoroalkyl group, Polyfox PF651 (manufactured by Omninova) Examples of commercially available fluorine-containing surfactants having a perfluoroalkenyl group include FTX-710LL (manufactured by Neos).
Among these surfactants, BYK-302 (manufactured by Big Chemie Japan Co., Ltd.) and FTX-710LL (manufactured by Neos Co., Ltd.) are preferable because they have an effect in a small amount.
Also in the fluorine-containing surfactant having an acrylic structure, for the same reason as above, a solventless type is preferable. As the solventless type, in the polyether-modified polysiloxane-containing additive used as the surfactant, The content is preferably 90% or more, more preferably 95% or more.

The surfactant that can be used in the present invention has a surface tension of 14 to 45 mN / m as measured by the Wilhelmy method in an environment of 25 ° C. and adjusted to a 0.1 wt% aqueous solution. Is preferred. When the surface tension is in a more preferable range of 14.0 to 35.0 mN / m, the effect of preventing defects such as cracking, peeling, or non-lighting during lighting is remarkable, and the lighting durability is remarkably improved.
Further, in terms of surface tension, the wettability is excellent, and the effect of addition of the surfactant is more easily exhibited, so that it is preferably 14.0 to 25.0 mN / m. On the other hand, the thing of 30-45 mN / m is also preferable.
Furthermore, a water-insoluble surfactant is preferable from the viewpoint of excellent compatibility with the resin and the ability to obtain a uniform cured product. Examples of water-insoluble surfactants include Polyfox PF651 (Omnova), FTX-710LL (Neos), BYK-352 (Bic Chemie Japan).

One kind of these surfactants can be contained in the composition of the present invention, or two or more kinds thereof can be contained in combination. The preferable content of these surfactants in the curable resin composition of the present invention is 0.005 to 5% by weight of the surfactant with respect to the epoxy resin and / or the epoxy resin curing agent. This is because if the amount is too small, the effect is impaired, and if the amount is too large, the effect reaches a peak, and in addition to mechanical properties, transparency and heat resistance are impaired.

Since the ultraviolet curable resin composition for optical semiconductor encapsulation of the present invention can contain an epoxy resin curing agent, 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, as the epoxy resin curing agent, particularly from the viewpoint of hardness, workability (being liquid at room temperature), and transparency of the cured product, acid anhydride, polyvalent carboxylic acid (A1), polyvalent carboxylic acid resin ( A2) is preferable, and among them, a polycarboxylic acid (A1) having at least two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton, or a both-end carbinol described later Modified silicone oil (a), terminal alcohol polyester compound (b), compound (c) having two or more carboxylic anhydride groups in the molecule, and compound having one carboxylic anhydride group in the molecule The polyvalent carboxylic acid resin (A2) obtained by addition reaction of (d) 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 alcohols are alcohols having 5 or more carbon atoms, particularly 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 or cyclic structure such as propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol are heat resistant and transparent From the viewpoint of sex, 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 out as it is after completion of the reaction can be mentioned.
In the present invention, the polyvalent carboxylic acid 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 composition. In the present invention, these are collectively referred to as polyvalent carboxylic acids.

  The polycarboxylic acid thus obtained is particularly represented by the following formula (4)

（式中、複数存在するＱは、水素原子、メチル基、カルボキシル基の少なくとも１種以上を表す。Ｐは前述の多価アルコール由来の炭素数２〜２０の鎖状、環状の脂肪族基である。）
で表される化合物が好ましい。

(In the formula, plural Qs represent at least one of a hydrogen atom, a methyl group, and a carboxyl group. P is a chain-like, cyclic aliphatic group having 2 to 20 carbon atoms derived from the above-mentioned polyhydric alcohol. is there.)
The compound represented by these is preferable.

The epoxy resin composition of the present invention preferably contains an acid anhydride. 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 An acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like are preferable.
Particularly preferably, the following formula (5)

（式中、存在するＱは、水素原子、メチル基、カルボキシル基の少なくとも１種以上を表す。）
で表されるヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好ましく、中でもメチルヘキサヒドロ無水フタル酸、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好ましい。

(In the formula, Q present represents at least one of a hydrogen atom, a methyl group, and a carboxyl group.)
And preferably hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride represented by the formula: methylhexahydrophthalic anhydride, cyclohexane-1,3, 4-Tricarboxylic acid-3,4-anhydride is preferred.

The polyvalent carboxylic acid (A1) and the acid anhydride are preferably used in combination, and when used in combination, the use ratio is preferably in the following range.

W1 / (W1 + W2) = 0.05-0.70

However, W1 shows the compounding weight part of polyhydric carboxylic acid (A1), and W2 shows the compounding weight part of an acid anhydride. The range of W1 / (W1 + W2) is more preferably 0.05 to 0.60, still more preferably 0.10 to 0.55, and particularly preferably 0.15 to 0.4. If it is less than 0.05, the volatilization of the acid anhydride tends to increase during curing, which is not preferable. If it exceeds 0.70, the viscosity becomes high and handling becomes difficult. When the acid anhydride is not contained (except when it remains in a small amount), there is no problem because the shape becomes a solid, a solid state or a crystal.
When polyhydric carboxylic acid (A1) and acid anhydride are used in combination, the polyhydric carboxylic acid (A1) is produced in an excess of acid anhydride at the time of producing polyhydric carboxylic acid (A1), and a mixture of polycarboxylic acid (A1) and acid anhydride The method of making is also preferable from the viewpoint of simplicity of operation.

  A polyvalent carboxylic acid resin (A2) preferable as an epoxy resin curing agent that can be used in the curable resin composition for sealing an optical semiconductor of the present invention is a carbinol-modified silicone oil (a) at both ends and a terminal alcohol polyester compound. It can be obtained by performing an addition reaction between (b), a compound (c) having two or more acid anhydride groups in the molecule, and a compound (d) having one acid anhydride group in the molecule. It is a compound having a polysiloxane structure in the molecule (polysiloxane composed of Si—O bonds as the main skeleton) and two or more carboxylic acids (carboxyl groups) in the same molecule having a polyester structure. Carboxylic acid is an alcoholic hydroxyl group of both end carbinol-modified silicone oil (a) and terminal alcohol polyester compound (b) described later, compound (c) having two or more acid anhydride groups in the molecule, and in the molecule. This is caused by the addition reaction of the acid anhydride group of the compound (d) having one acid anhydride group. By addition reaction of the compound (c) having two or more acid anhydride groups in the molecule, both terminal carbinol-modified silicone oils (a), and / or terminal alcohol polyester compounds (b), and / or Or both terminal carbinol modified silicone oil (a) and terminal alcohol polyester compound (b) polymerize as the same molecule.

  From here, the both-terminal carbinol-modified silicone oil (a), the terminal alcohol polyester compound (b), and two or more acid anhydride groups in the molecule, which are raw materials for the polyvalent carboxylic acid resin (A2), are used. The compound (c) having a compound 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.
Both terminal carbinol-modified silicone oil (a) is a silicone compound having an alcoholic hydroxyl group at both terminals represented by the following formula (6).

（式（６）において、Ｒ_１は炭素総数１〜１０のアルキレン基、エーテル結合を有するアルキレン基を、Ｒ_２は炭素数１〜３のアルキル基又はフェニル基を、ｍは平均値で１〜１００をそれぞれ表す。）

In (Equation (6), _{R 1} is an alkylene group having carbon atoms in total 1 to 10, an alkylene group having an ether bond, _{R 2} is an alkyl group or a phenyl group having 1 to 3 carbon atoms, m is 1 to the mean value 100 represents each.)

In the formula (1), specific examples of R ₁ include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups, ethoxyethylene group, propoxyethylene group propoxy Examples include an alkylene group having an ether bond such as a propylene 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 terminal carbinol-modified silicone oil (a) and terminal alcohol polyester compound (b ), A compound (c) having two or more acid anhydride groups in the molecule, and a compound (d) having one acid anhydride group in the molecule are subjected to an addition reaction. In order for the resin (A) to be liquid at room temperature, a methyl group is preferred compared to a phenyl group.

  In the formula (6), m is an average value of 1 to 100, preferably 2 to 80, more preferably 5 to 30.

  For example, X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-201, BY16-004 are used as the both-end carbinol-modified silicone oil (a) represented by the formula (6). 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 terminal alcohol polyester compound (b) will be described.
The terminal alcohol polyester compound (b) is a polyester compound having a hydroxyl group at the terminal represented by the following formula (7).

（式（７）において、Ｒ_３、Ｒ_４はそれぞれ独立して炭素数１〜１０のアルキレン基を、ｎは平均値で１〜１００をそれぞれ表す。）

(In Formula (7), 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 (7), 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 (7), 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.

  In the formula (7), 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 terminal alcohol polyester (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 is too high, and there is a concern that cracks may occur in a heat cycle test or the like. There is a concern that will 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 (b) represented by the formula (7) include polyester polyols having an alcoholic hydroxyl group at the terminal. Specific examples thereof are 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 IC Co., Ltd.); HS2H-201AP, HS2H-351A, HS2H-451A, HS2H-851A, HS2N-221A, HS2N-521A, HS2H-220S, HS2N-220S, HS2N-226P, HS2B-222A, HOKOKUOL 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.

  The amount of the terminal alcohol polyester (b) used is 0.5 to 200 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of both terminal carbinol-modified silicone oils (a). Part. If the amount is less than 0.5 parts by weight, the mechanical strength of the cured product may be inferior, and if it exceeds 200 parts by weight, the heat resistant transparency of the cured product may be inferior.

Next, the 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-cyclobutanetetra. Carboxylic 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-tetrahydro And naphthalene-1,2-dicarboxylic anhydride.
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 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-pentane. Saturated aliphatic carboxylic acid anhydrides such as dicarboxylic acid anhydrides, 3,5-heptanedicarboxylic acid anhydrides, unsaturated aliphatic carboxylic acid anhydrides such as maleic acid anhydrides and dodecyl succinic acid anhydrides, hexahydrophthalic acid anhydrides , 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 acid anhydride, 1,2,4-cyclohexanetricarboxylic acid- Cyclic saturated aliphatic carboxylic acid anhydride such as 1,2-anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, nadic acid anhydride, methyl nadic acid anhydride, 4,5-dimethyl-4-cyclohexene- Cyclic unsaturated aliphatic carboxylic acid anhydrides such as 1,2-dicarboxylic acid anhydride and bicyclo [2.2.2] -5-octene-2,3-dicarboxylic acid anhydride, phthalic acid anhydride, isophthalic acid anhydride Products, aromatic carboxylic acid anhydrides such as terephthalic acid anhydride and trimellitic acid anhydride.
The compound (d) can be used alone or in combination of two or more with one carboxylic anhydride group in the molecule. 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.

  The amount of the compound (d) having one carboxylic anhydride group in the molecule is 5 to 1000 parts by weight, preferably 10 to 10 parts by weight based on 100 parts by weight of the compound (c) having two carboxylic acids in the molecule. 500 parts by weight, more preferably 50 to 300 parts by weight. If the amount is less than 5 parts by weight, the polyvalent carboxylic acid resin (A2) may be too high in molecular weight and workability may be inferior, and if it is more than 300 parts by weight, the mechanical strength of the cured product may be inferior.

  Both terminal carbinol-modified silicone oil (a), terminal alcohol polyester (b), compound (c) having two or more carboxylic acid anhydride groups in the molecule, one or more carboxylic acid anhydride groups in the molecule The amount of the compound (d) used is such that two or more carboxylic anhydride groups are present in the molecule with respect to 1 equivalent of the total alcoholic hydroxyl groups of the carbinol-modified silicone oil (a) and the terminal alcohol polyester (b). The total carboxylic anhydride group of the compound (c) having one or more carboxylic anhydride groups in the molecule is 0.5 to 2.0 equivalents, preferably 0.8 to 1.5. Is equivalent. If it is less than 0.5 equivalent, the mechanical strength of the cured product may be inferior, and if it is more than 2.0, a large amount of acid anhydride groups may remain, resulting in poor storage stability.

  The production of the polyvalent carboxylic acid resin (A2) can be performed with or without a solvent. Solvents include carbinol-modified silicone oil (a) at both terminals, terminal alcohol polyester (b), compound (c) having two or more carboxylic anhydride groups in the molecule, and one or more carboxylic acids in the molecule. Any solvent that does not react with the compound (d) having an anhydride group 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 as follows: Carbinol-modified silicone oil (a) at both ends, terminal alcohol polyester (b), compound (c) having two or more carboxylic anhydride groups in the molecule, 0.5-300 weight part is preferable with respect to a total of 100 weight part of the compound (d) which has a 1 or more carboxylic anhydride group.

The polyvalent carboxylic acid resin (A2) 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, terminal alcohol polyester (b), compound (c) having two or more carboxylic anhydride groups in the molecule, 0.05-10 weight part is preferable with respect to a total of 100 weight part of compound (d) which has one carboxylic anhydride group.
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 (A2) 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 (A2) 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 (A2) thus obtained is usually 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 a curable resin composition using the same is used, the compatibility with the epoxy resin described later is low. 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)

Acid value (JIS) of manufactured polycarboxylic acid resin (A2)
(Measured by the method described in K-2501) is preferably from 35 to 200 mgKOH / g, more preferably from 50 to 180 mgKOH / g, particularly preferably from 60 to 150 mgKOH / g. 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 (A2) (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. If the viscosity is less than 50 mPa · s, the viscosity may be too low to be suitable for use as an optical semiconductor encapsulant, and if 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, two or more types of acid anhydride, polyvalent carboxylic acid (A1), and polyvalent carboxylic acid resin (A2) may be used in combination. 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 (A2) 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. Examples thereof include addition polymerization products of a silicone resin having a hydrosilyl group (SiH group) and an epoxy compound having an unsaturated hydrocarbon group such as a vinyl group.

  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 (2) and having silanol groups at both ends.

(In 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 other resins From the viewpoints of compatibility with the above, high refractive index, and improvement in sulfur resistance, it is preferable to contain a phenyl group.
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 be deteriorated, and the sulfidation resistance may be inferior. If it 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, which may be inferior in heat cycle resistance. If p exceeds 200, the mechanical strength of the cured product tends to decrease, which is not preferable.

The silanol-terminated silicone oil (e) preferably has a weight average molecular weight (Mw) 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 heat resistance and light resistance are inferior, and when it exceeds 3000, it has a severe layer separation structure, so that it can be used for sealing an optical semiconductor element. The permeability becomes poor and it is difficult to use.
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 (b) in the present invention is an alkoxysilicon compound represented by the formula (3).

In formula (3 ′), 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 (3 ′), R ₆ represents an aryl group having 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 the formula (3 ′) 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 (3 ') is an integer representing 0, 1, or 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), together with the epoxy group-containing silicon compound (f), an alkoxysilicon compound (g) represented by the following formula (8) can be used in combination. 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 (8), R ₆ and R ₇ are the same as those described above, s is an integer, 0, 1, 2, 3 and t is (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, it is preferable to react in the presence of a solvent. Among the solvents, alcohol is particularly preferable 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 becomes extremely slow. When the amount is less than 2% by weight, the reaction other than the target reaction proceeds, the molecular weight increases, gelation, increase in viscosity, and use as a cured product. As a result, there arises a problem that the elastic modulus increases so that it becomes difficult.
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, addition 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 alkoxysilicon as necessary) Care must be taken because the polycondensation of the alkoxy group of the compound (g)) proceeds unilaterally and the resulting reaction product and the silanol-terminated silicone oil (e) may become incompatible and cloudy. is there.
The allowable range of moisture at this time is 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 water 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 formula (9), 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.
The amount of alcohol added is based on the total weight of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and the alkoxysilicon compound (g) as required) charged in the production step 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 0.5 to 8.0 equivalents, more preferably 0.6 to 5.0 equivalents, and 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., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR are manufactured by Phutamura Chemical Co., Ltd. , CW130AR, GM130A, and the like. 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 normally colorless and transparent and is a liquid having 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 during reflow soldering 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)

Epoxy equivalent of silicone skeleton epoxy resin (B) (JIS
K-7236, measured by the method described in K-7236) 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 (A) or a mixture of two or more 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. If the viscosity is less than 50 mPa · s, the viscosity may be too low to be suitable for use as an optical semiconductor encapsulant, and if it exceeds 20,000 mPa · s, the viscosity may be too high and workability may be poor. is there.

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 there is a concern of surface tack and scratches. . Moreover, since it will become hard too hard when it exceeds 50 mol%, it is not preferable.
The proportion of silicon atoms present can be determined by 1H NMR, 29Si 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 with respect 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 (A) 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 (A), the epoxy equivalent of the specific silicone skeleton epoxy resin × (content of the specific silicone skeleton epoxy resin (A) / 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 (total amount of (A)) 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 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.

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

Among the above-described epoxy resins, the combined use of an alicyclic epoxy resin is preferable from the viewpoint 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-pentane. Diol, 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, ditrimethylolpropane, etc. 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 the amount is less than 60 parts by weight, the light resistance (UV resistance) of the cured product may be inferior.

  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 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.

  In the curable resin composition of the present invention, a curing catalyst can be used as necessary. Specific examples of curing catalysts that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 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 (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2' -Methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxy Various imidazoles of methylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, Salts with polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7 and their teto Salts such as phenyl borate and phenol novolak, salts with the above polycarboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) Phosphines such as phosphine, tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, and the like Examples thereof include a microcapsule type curing accelerator in which a curing accelerator is used as a microcapsule. 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. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of 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 YAG phosphors, TAG phosphors, orthosilicate phosphors, thiogallate phosphors, sulfide phosphors, and the like can be mentioned. YAlO ₃ : Ce, Y ₃ Al ₅ O1 ₂ : 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, 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.

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
R812, Aerosil R812S, 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, 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 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
Examples thereof include MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and 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 includes an epoxy resin, an epoxy resin curing agent, a surfactant, a curing catalyst, a coupling agent, an inorganic filler, a phosphor, a thixotropic agent, an antioxidant, a light stabilizer, and the like. Are sufficiently mixed to prepare a curable resin composition, which can be 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, 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: JIS
It measured by the method of 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)
β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 106 parts, weight average molecular weight 1700 (GPC measured value) silanol-terminated methylphenyl silicone oil 234 parts (silanol equivalent 850, half weight average molecular weight measured using GPC ), 18 parts of 0.5% potassium hydroxide (KOH) methanol solution (0.09 parts as KOH parts) was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
(Manufacturing process 2)
After adding 305 parts of methanol, 86.4 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 380 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, the organic phase was removed under reduced pressure at 100 ° C. to obtain 300 parts of an organopolysiloxane compound (B-1) having a reactive functional group. The epoxy equivalent of the obtained compound was 718 g / eq, the weight average molecular weight was 2200, and the appearance was colorless and transparent.

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) were 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. Subsequently, 731 parts of silicone frame | skeleton epoxy resins (B-2) were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. 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 transparent liquid.

Synthesis example 3
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, 20 parts of tricyclodecane dimethanol, 100 parts of acid anhydride (H-1), cyclohexane-1,2,4-tricarboxylic acid- 1.2 parts of 1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd. H-TMAn) was added and reacted at 40 ° C for 3 hours, followed by heating and stirring at 70 ° C for 1 hour (disappearance of tricyclodecanedimethanol by GPC (1 area% or less) was confirmed.) 100 parts of a curing agent composition (A-1) containing a polycarboxylic acid (I-1; the following formula (10)) and an acid anhydride (H-1). Obtained. The obtained curing agent composition is a colorless liquid resin, and the purity by GPC is 45 area% of polyvalent carboxylic acid (I-1), cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. Was 1 area%, and the acid anhydride (H-1) was 54 area%. The functional group equivalent was 200 g / eq. Met.

Synthesis Example 4 (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-2) 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, 13.8 parts of a polyester polyol in which R ₃ is a neopentyl group and R ₄ is a butyl group in the above formula (2)), 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-2). 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.

Example 1
50 parts of the silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 50 parts of the silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, and obtained in Synthesis Example 3 as an epoxy resin curing agent 25.9 parts of polyvalent carboxylic acid resin (A-1), zinc-based metal soap (Hope Pharmaceutical Co., Ltd., Octopus 18% zinc or less C-1) 0.6 parts as a curing catalyst, and bis (1- Undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81 or less D-1 manufactured by ADEKA, 0.3 parts below), 4,4′-butylidenebis (3 -Methyl-6-tert-butylphenyl-di-tridecyl phosphite) (manufactured by ADEKA, Adeka Stub 260 or less E-1), 0.3 parts, polyether-modified polyester as a surfactant Siloxane (BYK Japan KK BYK-302 or less F-1) were placed 0.6 parts of a mixture, for 5 minutes defoaming, to obtain a photosemiconductor encapsulating resin composition of the present invention.

Example 2
The same procedure as in Example 1 was performed except that 1.2 parts of an acrylic leveling agent (BYK-352 or less, F-2, manufactured by Big Chemie Japan Co., Ltd.) was added as a surfactant.

Example 3
The same procedure as in Example 1 was performed except that 1.2 parts of a fluorine-containing surfactant (Polyfox PF651 or less F-3 manufactured by Omninova) was added as a surfactant.

Example 4
It was the same as Example 1 except that 1.2 parts of a fluorine-containing surfactant (Kyoeisha Chemical Co., Ltd., Polyflow KL600 or less F-4) was added as a surfactant.

Example 5
The same procedure as in Example 1 was performed except that 0.6 part of a fluorine-containing surfactant (FTX-710LL or less F-5 manufactured by Neos Co., Ltd.) was added as a surfactant.

Example 6
50 parts of the silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 50 parts of the silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, and obtained in Synthesis Example 4 as an epoxy resin curing agent 81.8 parts of polyvalent carboxylic acid resin (A-2), zinc-based metal soap (Hope Pharmaceutical Co., Ltd., Octopus 18% zinc or less C-1) 0.6 part as a curing catalyst, and bis (1- Undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81 or less D-1 manufactured by ADEKA, 0.3 parts below), 4,4′-butylidenebis (3 -Methyl-6-tert-butylphenyl-di-tridecyl phosphite) (manufactured by ADEKA, Adeka Stub 260 or less E-1), 0.3 parts, polyether-modified polyester as a surfactant Siloxane (BYK Japan KK BYK-302 or less F-1) were placed 0.6 parts of a mixture, for 5 minutes defoaming, to obtain a photosemiconductor encapsulating resin composition of the present invention.

Example 7
The same procedure as in Example 6 was performed except that 0.9 part of an acrylic leveling agent (BYK-352 or less, F-2, manufactured by Big Chemie Japan Co., Ltd.) was added as a surfactant.

Example 8
The same procedure as in Example 6 was conducted except that 1.8 parts of a fluorine-containing surfactant (Polyfox PF651 or less F-3 manufactured by Omninova) was added as a surfactant.

Example 9
The same procedure as in Example 6 was conducted except that 1.8 parts of a fluorine-containing surfactant (polyflow KL600 or less F-4 manufactured by Kyoeisha Chemical Co., Ltd.) was added as the surfactant.

Example 10
The same procedure as in Example 1 was conducted except that 0.9 part of a fluorine-containing surfactant (FTX-710LL or less F-5 manufactured by Neos Co., Ltd.) was added as a surfactant.

Comparative Example 1
50 parts of the silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 50 parts of the silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, and obtained in Synthesis Example 3 as an epoxy resin curing agent 25.9 parts of polyvalent carboxylic acid resin (A-1), zinc-based metal soap (Hope Pharmaceutical Co., Ltd., Octopus 18% zinc or less C-1) 0.6 parts as a curing catalyst, and bis (1- Undecanooxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81 or less D-2) manufactured by ADEKA 0.3 parts, 4,4′-butylidenebis (3 -Methyl-6-tert-butylphenyl-di-tridecyl phosphite) (Adeka Adeka Stub 260 or less E-1) 0.3 part was added, mixed, degassed for 5 minutes, It was obtained for body sealing the curable resin composition.

Comparative Example 2
50 parts of the silicone skeleton epoxy resin (B-1) obtained in Synthesis Example 1, 50 parts of the silicone skeleton epoxy resin (B-2) obtained in Synthesis Example 2, and obtained in Synthesis Example 4 as an epoxy resin curing agent 81.8 parts of polyvalent carboxylic acid resin (A-2), zinc-based metal soap (Hope Pharmaceutical Co., Ltd., Octopus 18% zinc or less C-1) 0.6 part as a curing catalyst, and bis (1- Undecanooxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81 or less D-2) manufactured by ADEKA 0.3 parts, 4,4′-butylidenebis (3 -Methyl-6-tert-butylphenyl-di-tridecyl phosphite) (Adeka Adeka Stub 260 or less E-1) 0.3 part was added, mixed, degassed for 5 minutes, It was obtained for body sealing the curable resin composition.

Evaluation Test Table 1 shows the lighting test evaluation results of the curable resin compositions for sealing an optical semiconductor obtained in Examples 1 to 10 and Comparative Examples 1 and 2. The tests in Table 1 were performed as follows.
After carrying out vacuum defoaming for 5 minutes with the curable resin composition for sealing an optical semiconductor obtained in Examples 1 to 10 and Comparative Examples 1 and 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.
Thereafter, a lighting test for 1000 hours was performed in a constant current method, a driving method of 60 mA (light emitting element defining current is 30 mA), and a driving environment of 100 ° C. The illuminance before and after the test was measured using an integrating sphere, the illuminance retention rate was calculated, and the presence or absence of cracks, discoloration, etc. was observed.

As is clear from the results shown in Table 1, in Comparative Examples 1 and 2 in which no surfactant was blended, the illuminance decreased after the test. On the other hand, Examples 1 to 10 containing a surfactant are suitable as a resin composition for encapsulating an optical semiconductor because they retain a higher illuminance than Comparative Example 1 or Comparative Example 2 and are excellent in lighting durability. It is.

Claims (10)

A hindered amine light stabilizer which is an epoxy resin, a polyether-modified polysiloxane represented by the formula (1) , and bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate A curable resin composition for sealing an optical semiconductor.

(In the above formula (1), X represents the following partial structure (1a)

(In the above formula, R ¹ represents a methyl group or a hydrogen atom, R ² represents an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, y represents an integer of 1 to 20, n represents an integer of 0 to 50, m Represents an integer of 1 to 3, respectively.
And the following partial structure (1b)

(Wherein x represents an integer of 1 to 100). ) 2. The curable resin composition for optical semiconductor encapsulation according to claim 1, wherein the polyether-modified polysiloxane is a polyether-modified polysiloxane represented by the formula (1 ′).

(In the formula (1 '), the ^{R 1} is a methyl group or hydrogen, ^{R 2} is an alkyl Motoma other hydroxyl groups of 1 to 15 carbon atoms, x is an integer of 1 to 100, y is an integer from 1 to 20 , N represents an integer of 0 to 50, and m represents an integer of 1 to 3.) The polyether-modified polysiloxane has a surface tension of 14 to 25 mN / m of a surfactant adjusted to a 0.1 wt% aqueous solution, measured by a Wilhelmy method in an environment at 25 ° C. Curable resin composition for optical semiconductor encapsulation.   The curable resin composition for optical semiconductor encapsulation according to any one of claims 1 to 3, wherein the polyether-modified polysiloxane is a solventless type. The curable composition for optical semiconductor encapsulation according to any one of claims 1 to 4, wherein the polyether-modified polysiloxane is contained in an amount of 0.001 to 10 wt% with respect to the epoxy resin. Resin composition. Furthermore, it contains an epoxy resin curing agent, and the epoxy resin curing agent is a polyvalent carboxylic acid (A1) and / or a polyvalent carboxylic acid resin (A2). The curable resin composition for optical semiconductor sealing of description. The said epoxy resin is a silicone frame | skeleton epoxy resin (B), The curable resin composition for optical semiconductor sealing as described in any one of Claims 1-6. The silicone skeleton epoxy resin (B) has a silanol-terminated silicone oil residue represented by the following formula (3A) and an epoxy group-containing silicon compound residue represented by the following formula (3′A). The curable resin composition for optical semiconductor element sealing as described in any one of Claims 1-7 whose equivalent is 300-1500 g / eq.

(In Formula (3A), 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 the formula (3′A), X represents an organic group containing an epoxy group, R ₆ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic carbon atom having 6 to 10 carbon atoms. An aryl group having a hydrogen group, q is an integer of 0 to 2, r is an integer of (3-q), and-represents a bond to an oxygen atom in the formula (3A). Hardened | cured material formed by hardening | curing the curable resin composition for optical semiconductor sealing as described in any one of Claims 1-8. LED which comprises the hardened | cured material of Claim 9.