JP2012087249A - Curable resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel curable resin composition capable of providing a cured product with little tackiness and excellent light resistance, heat resistance and corrosive gas permeability resistance.SOLUTION: The curable resin composition includes as its essential components (A) an organopolysiloxane, (B) a polyhydric carboxylic acid, (C) an organic metal salt and/or an organic metal complex, and (D) a light stabilizer. (A) The organopolysiloxane, (B) the polyhydric carboxylic acid, (C) the organic metal salt and/or the organic metal complex, and (D) the light stabilizer satisfy the following conditions. (A) The organopolysiloxane is an epoxy resin including at least a glycidyl group and/or an epoxy cyclohexyl group in the molecule. (B) The polyhydric carboxylic acid includes at least two or more carboxyl groups with an aliphatic hydrocarbon group and/or a siloxane as the main skeleton. (D) The light stabilizer is a specific compound including a methacrylate group and a piperidyl group.

Description

  The present invention relates to an epoxy resin composition suitable for use in electrical and electronic materials, particularly for use in optical semiconductors, and a cured product.

Conventionally, an epoxy resin composition has been adopted as a sealing material for optical semiconductor elements such as LED products in terms of a balance between performance and economy. In particular, glycidyl ether type epoxy resin compositions typified by bisphenol A type epoxy resins having excellent balance of heat resistance, transparency and mechanical properties have been widely used.
However, as a result of the shortening of the emission wavelength of LED products (mainly the case of LED products emitting blue light of 480 nm or less), the sealing material is colored on the LED chip due to the influence of light of short wavelengths. However, it has been pointed out that the illuminance will eventually decrease as an LED product.
Therefore, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3 ′, 4 ′ epoxycyclohexyl carboxylate are more transparent than glycidyl ether type epoxy resin compositions having an aromatic ring. Since it is excellent, it has been actively studied as an LED sealing material. (Patent Documents 1 and 2)

  In recent years, LED products have become increasingly brighter for lighting, TV backlights, and the like, and when LEDs are turned on, they generate a lot of heat. Therefore, a resin composition using the alicyclic epoxy resin is used. Even an object causes coloring on the LED chip, and as a result, the illuminance is lowered as an LED product, leaving a problem in terms of durability. (Patent Document 3)

Because of the problem of durability of the epoxy resin, a resin having a siloxane skeleton (specifically, a skeleton having a Si—O bond) introduced as a silicone resin or a silicone-modified epoxy resin is used as a sealing material. Considerations are being made. (Patent Document 3)
In general, it is known that a resin having a siloxane skeleton introduced therein is more stable to light than an epoxy resin, but it is still not sufficient and further improvement has been a problem. As a means for solving this problem, a method of adding a light stabilizer is known (Japanese Patent Laid-Open No. 2009-275206). However, although the light resistance is improved by the addition of the light stabilizer, the resin deteriorates due to heat generated from the LED chip.

JP-A-9-213997 Japanese Patent No. 3618238 International Publication No. 2005/100445

  It is an object of the present invention to provide a novel curable resin composition that gives a cured product with less tack and excellent light resistance, heat resistance, and corrosion gas permeability.

（ただし、Ｒ₁は水素原子、炭素数１〜３のアルキル基、アリール基、アルコキシ基を表す。）
（２）
有機金属塩および／または有機金属錯体（Ｃ）が亜鉛塩、および／または亜鉛錯体であることを特徴とする（１）記載の硬化性樹脂組成物、
（３）
酸無水物を含有することを特徴とする前項（１）または（２）のいずれか一項に記載の硬化性樹脂組成物、
（４）
多価カルボン酸（Ｂ）が炭素数５以上の２〜６官能の多価アルコールと飽和脂肪族環状酸無水物との反応により得られた化合物であることを特徴とする前項（１）〜（３）いずれか一項に記載の硬化性樹脂組成物、
（５）
多価カルボン酸（Ｂ）が分岐鎖構造または環状構造を有する炭素数５以上の２〜６官能の多価アルコールまたはシロキサン構造を有する多価アルコールと、メチルヘキサヒドロ無水フタル酸またはシクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物との反応により得られた化合物であることを特徴とする前項（１）〜（４）のいずれか一項に記載の硬化性樹脂組成物、
（６）
酸化防止剤を含有することを特徴とする前項（１）〜（３）のいずれか一項に記載の硬化性樹脂組成物、
（７）
前項（１）〜（３）のいずれか一項に記載の硬化性樹脂組成物を硬化してなる硬化物、
に関する。 As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
A curable resin composition comprising an organopolysiloxane (A) and a polyvalent carboxylic acid (B), an organic metal salt and / or an organic metal complex (C), and a light stabilizer (D) as essential components;
However, organopolysiloxane (A), polyvalent carboxylic acid (B), organometallic salt and / or organometallic complex (C), and light stabilizer (D) satisfy the following conditions.
Organopolysiloxane (A):
Polyvalent carboxylic acid (B), which is an epoxy resin having at least a glycidyl group and / or an epoxycyclohexyl group in the molecule:
A light stabilizer (D) having at least two or more carboxyl groups and having an aliphatic hydrocarbon group and / or siloxane as a main skeleton:
It is a compound represented by the structural formula (1)

(However, R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group, or an alkoxy group.)
(2)
The curable resin composition according to (1), wherein the organometallic salt and / or the organometallic complex (C) is a zinc salt and / or a zinc complex,
(3)
The curable resin composition according to any one of (1) and (2) above, which comprises an acid anhydride,
(4)
(1) to (1) above, wherein the polyvalent carboxylic acid (B) is a compound obtained by reacting a bifunctional or hexafunctional polyhydric alcohol having 5 or more carbon atoms with a saturated aliphatic cyclic acid anhydride. 3) The curable resin composition according to any one of the above,
(5)
A polyhydric carboxylic acid (B) having a branched chain structure or a cyclic structure and having 2 or 6 carbon atoms and a polyhydric alcohol having a siloxane structure and methylhexahydrophthalic anhydride or cyclohexane-1, The curable resin composition according to any one of (1) to (4), wherein the curable resin composition is a compound obtained by a reaction with 3,4-tricarboxylic acid-3,4-anhydride,
(6)
The curable resin composition according to any one of (1) to (3) above, which contains an antioxidant.
(7)
Hardened | cured material formed by hardening | curing curable resin composition as described in any one of (1)-(3) of the preceding clause,
About.

Since the curable resin composition of the present invention has less tack and is excellent in heat resistance, light resistance, and corrosion gas resistance, among optical materials, especially for optical semiconductors (LED products) used in a living environment such as lighting. Etc.) are extremely useful as adhesives and sealing materials.

Hereinafter, it describes about the curable resin composition of this invention.
The epoxy resin composition of the present invention contains an organopolysiloxane (A) and a polyvalent carboxylic acid (B), an organic metal salt and / or an organic metal complex (C), and a light stabilizer (D) as essential components.
Organopolysiloxane (A) is an epoxy resin having at least a glycidyl group and / or an epoxycyclohexyl group in the molecule, and is generally a sol--using a trialkoxysilane having a glycidyl group or an epoxycyclohexyl group as a raw material. Obtained by gel reaction.
Specifically, JP-A No. 2004-256609, JP-A No. 2004-346144, WO 2004/072150, JP-A 2006-8747, WO 2006/003990, JP-A 2006-104248. Three-dimensional networks described in Japanese Patent Laid-Open No. 2007/135909, Japanese Patent Laid-Open No. 2004-10849, Japanese Patent Laid-Open No. 2004-359933, International Publication No. 2005/100445, Japanese Patent Laid-Open No. 2008-174640, and the like. Silsesquioxane type organopolysiloxane having the following structure.
In the present invention, the structure is not particularly limited. However, since a siloxane compound having a simple three-dimensional network structure is too hard, a structure that relaxes the hardness is desired. In the present invention, a block structure having a silicone segment and the aforementioned silsesquioxane structure of the coupling material in one molecule is particularly preferable (hereinafter referred to as a block type siloxane compound (E)).

  The block type siloxane compound (E) is not a compound having a repeating unit in a straight chain like a normal block copolymer, but has a three-dimensional network structure and a silsesquioxane structure as a core. The chain-like silicone segment is elongated and connected to the next silsesquioxane structure. This structure is effective in the sense of giving a balance between hardness and flexibility to the cured product of the curable composition of the present invention.

  The block type siloxane compound (E) can be produced using, for example, the alkoxysilane compound (a) represented by the general formula (2) and the silicone oil (b) represented by the general formula (3) as raw materials, If necessary, the alkoxysilane compound (c) represented by the general formula (4) can be used as a raw material. The chain-type silicone segment of the block type siloxane compound (E) is formed from the silicone oil (b), and the three-dimensional network of silsesquioxane segments is an alkoxysilane (a) (optionally alkoxysilane (c) ). Hereinafter, each raw material will be described in detail.

The alkoxysilane compound (a) is represented by the following formula (2).

XSi (OR ₂ ) ₃ (2)

X in the general formula (2) is not particularly limited as long as it is an organic group having an epoxy group. For example, β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl and other glycidoxy having 1 to 4 carbon atoms, glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ -(3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group 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 β- (3,4-epoxycyclohexyl) pentyl group. Among these, 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- A glycidoxyethyl group, a γ-glycidoxypropyl group, and a β- (3,4-epoxycyclohexyl) ethyl group are preferable, and β- (3,4-epoxycyclohexyl) ethyl is particularly preferable from the viewpoint of improving heat resistance colorability. Groups are preferred.

R ₂ in the general formula (2) 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 ₂ 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.

  Specific preferred examples of the alkoxysilane (a) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxy. Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like, particularly β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane is preferred. These alkoxysilane compounds (a) may be used independently, may use 2 or more types, and can also be used together with the alkoxysilane (c) mentioned later.

Silicone oil (b) is represented by the following formula (3)

Is a chain silicone oil having a silanol group at the end having a structure represented by:
In the formula of the general formula (3), a plurality of R ₃ may be the same as or different from each other, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 to 10 carbon atoms. An alkenyl group of
Examples of the alkyl group having 1 to 10 carbon atoms include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group and the like. Among these, considering light resistance, a methyl group, an ethyl group, and a cyclohexyl group are preferable.
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylyl group.
Examples of the alkenyl group having 2 to 10 carbon atoms include alkenyl groups such as vinyl group, 1-methylvinyl group, allyl group, propenyl group, butenyl group, pentenyl group, and hexenyl group.
R ₃ is preferably a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group from the viewpoints of light resistance and heat resistance, and particularly preferably a methyl group or a phenyl group. The phenyl group can be suitably used from the viewpoint of improving the corrosion gas resistance.

  M of the compound of General formula (3) shows 3-200 by an average value, Preferably it is 3-100, More preferably, it is 3-50. When m is less than 3, the cured product becomes too hard and the low elastic modulus characteristics are deteriorated. If m exceeds 200, the mechanical properties of the cured product tend to deteriorate, which is not preferable.

The weight average molecular weight (Mw) of the silicone oil (b) is preferably in the range of 300 to 18,000 (GPC measurement value). Among these, those having a molecular weight of 300 to 10,000 are preferable in consideration of the elastic modulus at low temperature, and those having a molecular weight of 300 to 5,000 are more preferable in consideration of compatibility at the time of forming the composition. 1,000 is preferred. If the weight average molecular weight is less than 300, the properties of the chain silicone portion of the characteristic segment are difficult to be obtained, and the properties as a block type may be impaired. If it exceeds 18,000, a severe layer separation structure will be formed. When used as a material, the permeability becomes poor, making it difficult to use. In the present invention, as the molecular weight of the silicone oil (b), polystyrene conversion and weight average molecular weight (Mw) measured under the following conditions were calculated 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)

  The kinematic viscosity of the silicone oil (b) is preferably in the range of 10 to 200 cSt, more preferably 30 to 90 cSt. When the viscosity is less than 10 cSt, the viscosity of the block type siloxane compound (E) becomes too low and may not be suitable as an optical semiconductor sealing material. When the viscosity exceeds 200 cSt, the viscosity of the block type siloxane compound (E) Is unfavorable because it tends to cause an adverse effect on workability.

  Specific examples of preferable silicone oil (b) include the following product names. For example, as manufactured by Toray Dow Corning Silicone, PRX413, BY16-873, as manufactured by Shin-Etsu Chemical Co., Ltd., X-21-5841, KF-9701, as manufactured by Momentive, 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, from the viewpoint of molecular weight and kinematic viscosity, PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21 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 in order to give the silicone segment flexibility characteristics. These silicone oils (b) may be used alone or in combination of two or more.

Next, the alkoxysilane (c) will be described in detail. The alkoxysilane (c) has a structure of the following formula (4). R ₄ Si (OR ₅ ) ₃ (4)
R ₄ in the general formula (4) represents a methyl group or a phenyl group.

R ₅ in the general formula (4) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₅ is preferably a methyl group or an ethyl group from the viewpoint of reaction conditions such as compatibility and reactivity.

  Specific examples of preferred alkoxysilane (c) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Of these, methyltrimethoxysilane and phenyltrimethoxysilane are preferred because of their good reactivity and easy control of the reaction.

  In the present invention, the alkoxysilane (c) adjusts the molecular weight of the block-type siloxane compound (E), the compatibility with the composition, the heat resistance of the cured product, light resistance, low moisture permeability, low gas permeability, and the like. Therefore, it can be used in combination with alkoxysilane (a).

  When the alkoxysilane (c) is used in combination with the alkoxysilane (a), it is preferably used in the range of 5 to 70 mol% of the total of the alkoxysilanes (a) and (c), more preferably 5 to 50 mol%, 10-40 mol% is especially preferable. If it is larger than 70 mol%, the crosslink density of the cured product is lowered and the mechanical strength is lowered, which is not preferable.

The reaction ratio of alkoxysilane (a), silicone oil (b), and alkoxysilane (c) is based on 1 equivalent of silanol groups of silicone oil (b), with alkoxysilane (a) (optionally alkoxysilane ( It is preferable to carry out the reaction between 1.5 and 200, preferably 2 to 200, particularly preferably 2 to 100, with the alkoxy group in c) used in combination) as an equivalent value.
When the equivalent value exceeds 200, the cured product using the block type siloxane compound (E) becomes too hard, and the desired low elastic modulus characteristic is lowered.

Hereinafter, a preferred method for producing the block type siloxane compound (E) will be specifically described.

As a manufacturing method of block type siloxane compound (E), it is preferable to pass through the manufacturing process shown by the following (i) and (ii).
Production step (i): Step of dealcoholization condensation of silanol-terminated silicone oil and silicon compound having alkoxy group Production step (ii): Hydrolysis condensation between alkoxy groups of silicon compound having alkoxy group by adding water In the process manufacturing process (i) (ii), the reaction may be performed in any order as long as it goes through each process.

Specific examples of preferred production methods include the following three production methods.
<Manufacturing method (I)>
First, as a production process (i), a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) and / or alkoxysilane (c) which is a silicon compound having an alkoxy group are subjected to a dealcoholization condensation reaction. A step of obtaining an alkoxysilane-modified product (d) is performed by modifying the oil terminal with alkoxysilane.
Subsequently, alkoxysilane (a) which is a silicon compound having an alkoxy group as production step (ii) (optionally alkoxysilane (c)), and an alkoxysilane-modified product of silicone oil obtained in production step (i) ( A method for producing a block-type siloxane compound (E) by passing through a step of adding water to d) and performing a hydrolysis-condensation reaction between alkoxy groups.
<Manufacturing method (b)>
First, as a production process (ii), molecules are obtained by performing a hydrolysis-condensation reaction between alkoxy groups by adding water to alkoxysilane (a) (optionally alkoxysilane (c)), which is a silicon compound having an alkoxy group. A step of obtaining silsesquioxane (e) having an alkoxy group therein is performed.
Next, as a production process (i), a reaction between the silanol group-containing silicone oil (b) and the silsesquioxane (e) causes a dealcoholization condensation reaction between the alkoxy group remaining in the silsesquioxane structure and the silanol group. Method of producing block-type siloxane compound (E) by passing through the steps <Production method (c)>
First, as a production process (i), a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) and / or alkoxysilane (c) which is a silicon compound having an alkoxy group are subjected to a dealcoholization condensation reaction. After making the alkoxysilane modified body (d) by modifying the oil end with alkoxysilane, water is added to the system and remains as a manufacturing step (ii) in one pot (a) (if necessary (c)) And a method for producing a block-type siloxane compound (E) by carrying out a hydrolysis-condensation reaction between alkoxy groups in (d)

In the present invention, from the viewpoint of shortening the production process, it is preferable to use the above production method (c) in which the reaction is sequentially carried out in one pot.
Hereinafter, the production method (c) will be described more specifically.
When the reaction is carried out in one pot, the silanol having an alkoxy group formed in the production step (ii) is performed in the reverse order of the production method (c) described above, that is, when the production step (ii) is performed after the production step (ii). There is a high possibility that the sesquioxane oligomer and the silicone oil (b) are not compatible with each other, the dealcoholization condensation polymerization does not proceed in the subsequent production step (i), and the silicone oil is left behind. On the other hand, if a method in which the production step (ii) is performed in one pot after the production step (i) as in the production method (c) is used, the phase between the silicone oil (b) and the alkoxysilane (a) or (c) Since the solubility is relatively high, the problem that the reaction does not proceed without being compatible as described above can be avoided. Furthermore, since a large amount of unreacted low-molecular alkoxysilane is present with respect to the silanol group, it is preferable from the viewpoint of reactivity. Assuming that the production process (i) in the one pot is the first stage reaction and the production process (ii) is the second stage reaction, first, in the first stage reaction (production process (i)), the silicone oil (b) and alkoxy The dealcohol condensation of silane (a) (alkoxysilane (c) if necessary) is performed, and the terminal of the silicone oil is alkoxysilyl-modified to obtain an alkoxysilane-modified product (d). Since water is not added in the first stage reaction, hydrolysis condensation between alkoxy groups does not occur, and when the reaction is carried out using 3 equivalents or more of alkoxy groups per 1 equivalent of silanol groups, a modified alkoxysilane (D) is considered to exist in a structure represented by the following formula (5).

In formula (5), R ₃ and m have the same meaning as described above, and R ₆ represents X and / or R ₄ . R ₇ represents R ₂ and / or R ₅ .

  In the first stage reaction, if the alkoxy group is reacted in an amount less than 1.0 equivalent with respect to 1 equivalent of the silanol group, the alkoxy group does not exist at the end of the first stage reaction. Moreover, when an alkoxy group is made to react between 1.0-1.5 equivalent, two or more alkoxy groups in alkoxysilane (a) (the alkoxysilane (c) as needed) will become silanol of silicone oil (b). It will react with the group and become a polymer at the end of the first stage reaction, causing gelation. 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.

After the completion of the first stage reaction, a second stage reaction (production process (ii)) is performed in which water is added as it is to hydrolyze and condense alkoxy groups. Further, in the second stage reaction, the following reactions (I) to (III) occur.
(I) Condensation reaction between alkoxy groups of alkoxysilane (a) (optionally alkoxysilane (c)) remaining in the system.
(II) A condensation reaction between alkoxy groups of the alkoxysilane-modified product (d) obtained in the first stage reaction and the alkoxysilane (a) (optionally alkoxysilane (c)).
(III) between the alkoxy groups of the partial condensate of the alkoxysilane modified product (d) obtained in the first step reaction and the alkoxysilane (a) (optionally alkoxysilane (c)) produced by (I) Condensation reaction.
In the second stage reaction, the above reaction occurs in combination, and the formation of the silsesquioxane segment and the condensation with the silicone oil-derived chain silicone segment are simultaneously performed.

Although the production of the block type siloxane compound (E) can be carried out without a catalyst, the reaction progress is slow with no catalyst, and it is preferably carried out 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, an inorganic base is particularly preferable in terms of easy catalyst removal from the product, and sodium hydroxide and potassium hydroxide are particularly preferable. The amount of the catalyst added is usually 0.001 to 7.5% by weight, preferably 0.01 to 5%, based on the total weight of alkoxysilane (a) (optionally alkoxysilane (c)) in the reaction system. % 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. At this time, as an aqueous solution using water or the like, as described above, the condensation of alkoxysilane (a) (if necessary, alkoxysilane (c)) was unilaterally proceeded and produced thereby. There is a possibility that the silsesquioxane oligomer and the silicone oil (b) are incompatible and become cloudy.

  The production of the block type siloxane compound (E) can be carried out without a solvent or in a solvent. Moreover, a solvent can also be added in the middle of a manufacturing process. The solvent for use is not particularly limited as long as it is a solvent that dissolves alkoxysilane (a), silicone oil (b) (optionally alkoxysilane (c)), and modified alkoxysilane (d). Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, and tetrahydrofuran, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and butanoic acid. Examples thereof include esters such as isopropyl, alcohols such as methanol, ethanol, propanol and butanol, hydrocarbons such as hexane, cyclohexane, toluene and xylene. In the present invention, reaction in alcohols is preferable from the viewpoint of reaction control, and methanol and ethanol are more preferable. The amount of solvent used is not particularly limited as long as the reaction proceeds smoothly, but the total weight of the alkoxysilane (a), silicone oil (b), and (optionally alkoxysilane (c)) compounds. About 0 to 900 parts by weight is usually used for 100 parts. The reaction temperature is usually 20 to 160 ° C., preferably 40 to 140 ° C., particularly preferably 50 to 140 ° C., although it depends on the amount of catalyst. Moreover, reaction time is 1 to 40 hours normally in each manufacturing process, Preferably it is 5 to 30 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, but the reaction is carried out under acidic or basic conditions. 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, an inorganic base or an inorganic acid is preferable because it can be easily removed from the product, and phosphates that can more easily adjust the pH to near neutrality 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, Examples include Galeon Earth and Mizuka Ace. 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, 13X, etc., 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, Dow Chemical Co., Dowex 66, HCR-S, HCR-W2, MAC-3, etc. may 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 block siloxane compound (E) can be obtained by removing the solvent by vacuum concentration or the like.

The appearance of the block-type siloxane compound (E) thus obtained is usually colorless and transparent and is a liquid having fluidity at 25 ° C. The molecular weight is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,500 to 6,000 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 20,000, the viscosity is increased and the workability is adversely affected.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The epoxy equivalent (measured by the method described in JIS K-7236) of the block type siloxane compound (E) is preferably 300 to 1,600 g / eq, more preferably 400 to 1,000 g / eq, The thing of 450-900 g / eq is especially preferable. When the epoxy equivalent is less than 300 g / eq, the cured product is hard and the elastic modulus tends to be too high, and when it exceeds 1,600 g / eq, the mechanical properties of the cured product tend to deteriorate.

  The viscosity of the block-type siloxane compound (E) (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.

The ratio of silicon atoms bonded to three oxygens derived from silsesquioxane in the block-type siloxane compound (E) to the total silicon atoms is preferably 5 to 50 mol%, more preferably 8 to 30 mol%, 10-20 mol% is especially preferable. When the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to the total silicon atoms is less than 5 mol%, the cured product tends to be too soft as a characteristic of the chain silicone segment, and surface tack There are concerns about injury. On the other hand, if it exceeds 50 mol%, the cured product becomes too hard as a feature of the silsesquioxane segment, which is not preferable.
The proportion of silicon atoms present can be determined by ¹ H NMR, ²⁹ Si NMR, elemental analysis, etc. of the block siloxane compound (E).
By using organopolysiloxane, which is an epoxy resin having a glycidyl group and / or an epoxycyclohexyl group in the molecule, a cured product having no tack property and excellent corrosion gas permeability compared to a silicone resin can be obtained. A resin composition that can be provided can be obtained.

（式（６）において、Ａ_１はエーテル結合を介しても良い炭素総数１〜１０アルキレン基を表し、Ａ_２はメチル基又はフェニル基を表す。また、ｎは繰り返し数であり平均値を意味し、１〜１００である。）
酸無水物としては特にメチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、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、ブタンテトラカルボン酸無水物、ビシクロ［２，２，１］ヘプタン−２，３−ジカルボン酸無水物、メチルビシクロ［２，２，１］ヘプタン−２，３−ジカルボン酸無水物、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物等が好ましく、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。照度保持率を特に向上させる観点からメチルヘキサヒドロ無水フタル酸の使用が好ましく、硬度を向上させる観点からはシクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物が好適に使用することができる。
付加反応の条件としては特に指定はないが、具体的な反応条件の１つとしては酸無水物、多価アルコールを無触媒、無溶剤の条件下、４０〜１５０℃で反応させ加熱し、反応終了後、そのまま取り出す。という手法である。ただし、本反応条件に限定されない。 The polyvalent carboxylic acid (B) is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group and / or siloxane as a main skeleton. 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.
As the polyvalent carboxylic acid (B), a bifunctional to hexafunctional carboxylic acid is particularly preferable, and a reaction between a polyhydric alcohol having 2 or 6 carbon atoms or a polyhydric alcohol having a siloxane structure and an acid anhydride. The obtained compound is more preferred. Furthermore, the polycarboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.
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, 2-hydroxymethyl-1,4-butanediol, tetraaus such as pentaerythritol and ditrimethylolpropane Kind, hexa-ols such as dipentaerythritol, and the like.
Particularly preferred polyhydric alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, Examples include 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol, among others 2-ethyl-2-butyl -1.3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol and other alcohols having a branched chain structure or a cyclic structure More preferred. From the viewpoint of particularly improving the illuminance retention rate, 2,4-diethylpentanediol and tricyclodecane dimethanol can be preferably used.
Although the polyhydric alcohol which has a siloxane structure is not specifically limited, For example, the silicone oil represented by following formula (6) can be used.

(In Formula (6), A ₁ represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond, A ₂ represents a methyl group or a phenyl group, and n represents the number of repetitions, which means an average value. 1 to 100.)
Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methyl nadic 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-anhydride and the like are preferable, Of these, methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are preferable. Methylhexahydrophthalic anhydride is preferably used from the viewpoint of particularly improving illuminance retention, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferably used from the viewpoint of improving hardness. Can do.
Although there is no particular designation as a condition for the addition reaction, one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted in a non-catalytic and solvent-free condition at 40 to 150 ° C. and heated to react. After completion, take it out as it is. It is a technique. However, it is not limited to this reaction condition.

  The polycarboxylic acid thus obtained is particularly represented by the following formula (7)

（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 polyhydric alcohol described above. .)
The compound represented by these is preferable.

The curable 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- Examples thereof include 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.
Especially the following formula (8)

（式中、存在するＺ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, Z 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 (B) 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 (B), 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 (B) and acid anhydride are used in combination, the polyhydric carboxylic acid (B) is produced in an excess of acid anhydride at the time of producing polyhydric carboxylic acid (B), and a mixture of polyvalent carboxylic acid (B) and acid anhydride The method of making is also preferable from the viewpoint of simplicity of operation.

The curable resin composition of the present invention contains an organometallic salt and / or an organometallic complex (C).
Examples of the metal of the organometallic salt and / or organometallic complex (C) include aluminum, manganese, iron, cobalt, nickel, copper, zinc, zirconium, tin, lead, and the like.
Examples of the organometallic salt and / or organometallic complex (C) include aluminum 2-ethylhexanoate, manganese 2-ethylhexanoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, 2-ethylhexane. Nickel oxide, copper 2-ethylhexanoate, zinc 2-ethylhexanoate, zirconium 2-ethylhexanoate, tin 2-ethylhexanoate, lead 2-ethylhexanoate, aluminum naphthenate, manganese naphthenate, iron naphthenate, Cobalt naphthenate, nickel naphthenate, copper naphthenate, zinc naphthenate, zirconium naphthenate, tin naphthenate, lead naphthenate, aluminum stearate, manganese stearate, iron stearate, cobalt stearate, nickel stearate, stearic acid Copper, stearic acid , Zirconium stearate, tin stearate, lead stearate, aluminum-acetylacetone complex, manganese-acetylacetone complex, iron-acetylacetone complex, cobalt-acetylacetone complex, nickel-acetylacetone complex, copper-acetylacetone complex, zinc-acetylacetone complex, zirconium- Acetylacetone complex, tin-acetylacetone complex, lead-acetylacetone complex, etc., phosphoric acid aluminum complex and / or salt, phosphoric acid manganese complex and / or salt, phosphoric acid iron complex and / or salt, phosphoric acid cobalt complex and And / or salt, nickel complex and / or salt of phosphoric acid, copper complex and / or salt of phosphoric acid, zinc complex and / or salt of phosphoric acid, zirconium complex and / or salt of phosphoric acid, Tin complexes and / or salts of acids, lead complexes and / or salts of phosphoric acids, aluminum complexes and / or salts of 2-ethylhexyl phosphate, manganese complexes and / or salts of 2-ethylhexyl phosphate, 2-ethylhexyl phosphate Iron complexes and / or salts thereof, cobalt complexes and / or salts of 2-ethylhexyl phosphate, nickel complexes and / or salts of 2-ethylhexyl phosphate, copper complexes and / or salts of 2-ethylhexyl phosphate, phosphoric acid 2 -Zinc complex and / or salt of ethylhexyl, zirconium complex and / or salt of 2-ethylhexyl phosphate, tin complex and / or salt of 2-ethylhexyl phosphate, lead complex and / or salt of 2-ethylhexyl phosphate, etc. Can be mentioned. From the viewpoint of improving the corrosion gas permeability and heat resistance, it is preferable to use a zinc salt and / or a zinc complex.

  Here, the ratio of the organometallic salt and / or organometallic complex (C) is 0.01 to 8% by weight, more preferably 0.05 to 5% by weight, and more preferably 0.05% to 5% by weight, based on the organopolysiloxane (A). Is 0.1 to 4% by weight. Further, it is particularly preferably 0.1 to 2% by weight.

（ただし、Ｒ₁は水素原子、炭素数１〜３のアルキル基、アリール基、アルコキシ基を表す。）
ここで、耐光性、耐熱性の向上の観点からＲ_１は水素であることが好ましい。
前記式（１）で表せられる、光安定剤としては市販のものを使用することができ、具体的には、日本化薬株式会社製 ＩＭ−００７２が挙げられる。 The epoxy resin composition of the present invention contains a light stabilizer (D).
The light stabilizer (D) is preferably a compound represented by the following general formula (1).

(However, R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group, or an alkoxy group.)
Here, from the viewpoint of improving light resistance and heat resistance, R ₁ is preferably hydrogen.
As the light stabilizer represented by the formula (1), commercially available products can be used, and specifically, IM-0072 manufactured by Nippon Kayaku Co., Ltd. can be mentioned.

Here, the ratio of the light stabilizer (D) is 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight with respect to the organopolysiloxane (A). It is.
When the ratio of the light stabilizer (D) is less than 0.005% by weight based on the organopolysiloxane (A), the effect of improving light resistance is insufficient. On the other hand, if it is more than 5% by weight, the cured resin is colored, which causes a decrease in illuminance.

  The light stabilizer (D) is used in combination with the organopolysiloxane (A), the polyvalent carboxylic acid (B), and the organometallic salt and / or organometallic complex (C). It can be significantly improved. In particular, as an organic metal salt and / or an organic metal complex (C), a zinc salt and / or a zinc complex, and as a light stabilizer (D), heat resistance and light resistance are improved, and compatibility is good and bleed-out hardly occurs. From this viewpoint, 2-[(2,2,6,6-tetramethyl-4-piperidyloxy) carbonylamino] ethyl methacrylate is preferable, and it is preferable to use these in combination.

  The light stabilizer (D) can be used in combination with other light stabilizers. Examples of the light stabilizer that can be used include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6, 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, bis (2,2) decanedioate , 6,6-tetramethyl-4-piperidyl) sebacate, 2,2,6,6, -tetramethyl-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) se Kate, 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] butyl malonate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-pi Lysinyl) 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 Polycondensate of '-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine , Poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4- Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], a polymer of 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] heneicosane-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] heneicosan-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, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, Hins such as N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) and bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate Benzophenone compounds such as dartamine and octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1 3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5 -Methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) Benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol reaction product, 2- (2H-benzotriazole-2- Yl) -6-dodecyl-4-methylphenol and other benzotriazole compounds, , 4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) And triazine compounds such as -5-[(hexyl) oxy] phenol.

  When using the curable resin composition of this invention for an optical material, especially an optical semiconductor sealing material, it is preferable to contain the phosphorus compound as antioxidant as a particularly preferable component.

  The phosphorus compound is not particularly limited. 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) Ho Phyto, 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 ' -Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenyl Rangephosphonite, 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) Ruphenyl) -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 thereof include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like.

  A commercial item can also be used for the said phosphorus compound. For example, as ADK, 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, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, and ADK STAB C 135A, ADK STAB 3010, and ADK STAB TPP.

  Here, the ratio of the phosphorus compound is 0.005 to 5% by weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight with respect to the organopolysiloxane (A).

  The curable resin composition of the present invention comprises an organopolysiloxane (A) as an epoxy resin, a polyvalent carboxylic acid compound (B) as a curing agent, an organometallic salt and / or an organometallic complex (C) as an additive, and a light stabilizer. It contains (D) as an essential component, an acid anhydride as a curing agent, and a phosphorus-containing antioxidant as an additive as a preferred optional component. These may be used in combination with other epoxy resins, curing agents, and various additives. it can.

  The organopolysiloxane (A) can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the component (A) in the total epoxy resin is preferably 60% by weight or more, and particularly preferably 70% by weight or more.

  Other epoxy resins that can be used in combination with the organopolysiloxane (A) include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, 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, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) It has a glycidyl group and / or an epoxycyclohexane structure Epoxy resins) include solid or liquid epoxy resins such as, but not limited thereto. These may be used alone or in combination of two or more.

In particular, the curable resin composition of the present invention is mainly used for optical applications. When used for optical applications, combined use with an alicyclic epoxy resin is preferred. 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 JP-A-2003-170059, JP-A-2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester (JP-A-2006-052187). And the like obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Publication No.
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. Examples include diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, and tetraols such as pentaerythritol and ditrimethylolpropane. It is. 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).
These may be used alone or in combination of two or more.

As the curing agent, the polyvalent carboxylic acid compound (B) can be used alone or in combination with an acid anhydride, and further in combination with other curing agents. When used in combination, the proportion of the total amount of the polyvalent carboxylic acid compound (B) and the acid anhydride 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, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. 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.) , Reaction product of acid anhydride and silicone alcohol (phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, anhydrous Nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] Heptane A reaction product of an acid anhydride such as 2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like and a silicone alcohol such as carbinol-modified silicone), 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, phenols (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxyben , 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 (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene and the like Polycondensates and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols), and others (imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc.) and the like. But limited to these Is not something These may be used alone or in combination of two or more.

  In the curable resin composition of the present invention, the blending ratio of the epoxy resin having the organopolysiloxane (A) as an essential component and the curing agent having the polyvalent carboxylic acid (B) as an essential component is an organopolysiloxane ( A polyvalent carboxylic acid (B) having a functional group number of 0.7 to 1.2 equivalents, particularly preferably 0.75 to 1.10 equivalents, is essential with respect to 1 equivalent of epoxy group of the epoxy resin having A) as an essential component. It is preferable to use a curing agent as a component. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the curable resin composition of the present invention, the organic metal salt and / or organic metal complex (C), which is an essential component, acts as a curing accelerator (curing catalyst) as it is, and therefore a curing accelerator is added separately. However, other curing accelerators may be used in combination. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 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′-methyl Imidazole (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-dihydroxymethyl Various imidazoles such as imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid Acids, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as 7 and their tetra Salts such as phenyl borate and phenol novolac, salts with the above polycarboxylic acids, or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide, ammonium salts such as trioctylmethylammonium bromide, triphenylphosphine, tri (tolyl) phosphine Phosphines and phosphonium compounds such as tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, and curing thereof Examples thereof include a microcapsule-type curing accelerator having a microcapsule as an accelerator. 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.

  The curable resin composition of the present invention can be added with various additives and auxiliary materials as listed below. For example, when provided in two liquids, either one of an epoxy resin and a curing agent, or It can be added to both, and it is also possible to add after mixing the epoxy resin and the curing agent.

  The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / epoxy resin = 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, binder resin can also be mix | blended with the curable resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 100 parts by weight of the curable resin component. Up to 20 parts by weight are used as needed.

  An inorganic filler can be added to the curable resin composition of the present invention as necessary. 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. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable resin composition of the present invention. can do.

  When the curable resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, the particle size of the inorganic filler used is transparent by using a nano-order level filler. It is possible to supplement mechanical strength and the like without hindering. 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.

When using the curable resin composition of this invention for an optical material, especially an optical semiconductor sealing material, fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, 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, 5-60 weight part is preferable.

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

  The curable resin composition of the present invention can contain a phenolic compound as an antioxidant.

  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-pentylphenol, 2 -[1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4'-hydroxy- 3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

  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, Adekas 1520L 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, SUMITOMO CHEMICAL INDUSTRIES, SUMITIZER GA-80, SUMILIZER MDP-S, Sumili er BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, and the like.

  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.

  When adding the said phenol type compound, it is although it does not specifically limit as the compounding quantity, It is the range of 0.005-5.0 weight% with respect to this curable resin composition of this invention.

  The curable resin composition of this invention is obtained by mixing each component uniformly. The curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent until uniform using an extruder, kneader, roll, planetary mixer, etc. as necessary After thoroughly mixing to obtain a curable resin composition, if the curable resin composition is in liquid form, potting, casting, impregnation into the substrate, casting mold casting, and curing by heating To do. In addition, when the curable resin composition is solid, there is a method in which it is molded using a cast after casting or a transfer molding machine, and further cured by heating. The curing temperature and time are 80 to 200 ° C., and the curing time is 2 to 10 hours. As a curing method, it can be hardened at a high temperature at a stretch, but it is preferable to raise the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed between 80 and 150 ° C., and post-curing is performed between 100 and 200 ° C. As the curing stage, the temperature is preferably divided into 2 to 8 stages, more preferably 2 to 4 stages.

  Further, the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, glass fiber, A prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heat-dried is subjected to hot press molding, thereby obtaining a cured product of the curable resin composition of the present invention. can do. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

Moreover, the curable resin composition of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, the curable resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and a B-stage adhesive is formed. Get. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.
Next, the case where the curable resin composition of the present invention is used as an optical semiconductor sealing material or die bond material will be described in detail.

  When the curable resin composition of the present invention is used as a sealing material or die bond material for an optical semiconductor such as a high-intensity white LED, an epoxy resin, a curing agent, a coupling material, an antioxidant, a light stabilizer, etc. The epoxy resin composition is prepared by thoroughly mixing the additive, and is used as a sealing material or for both a die bond material and 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 epoxy resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition of the present invention for both the die bond material and the sealing material.

  As a method of adhering a semiconductor chip to a substrate using the curable resin composition of the present invention, the epoxy resin composition of the present invention is applied by a dispenser, potting, or screen printing, and then the semiconductor chip is placed and heat cured. The semiconductor chip can be bonded. 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.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and then molded, and the sealing material is formed on the mold. A compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
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.

  Furthermore, the curable resin composition of the present invention can be used for various applications, and specific examples include general applications in which a curable resin such as an epoxy resin is used. , Coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, resists Examples of the curing agent include additives to other resins such as acrylic ester resins.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die-bonding materials, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films (ACFs) ) And an adhesive for mounting such as anisotropic conductive paste (ACP).

  Sealing materials include capacitors, transistors, diodes, light emitting diodes, potting, dipping, transfer mold sealing for IC, LSI, potting sealing such as IC, LSI COB, COF, TAB, etc., flip chip For example, underfill for IC packages such as QFP, BGA, and CSP (including a reinforcing underfill).

  The cured product obtained in the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications in which light such as visible light, infrared light, ultraviolet light, X-rays, and laser passes through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. In the display field, liquid crystal display device peripheral materials, including liquid crystal display field substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, liquid crystal films such as polarizer protective films, Also, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, and LEDs that are expected as next-generation flat panel displays LED molding materials used in display devices, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, plasma address liquid crystal (PALC) display substrate materials, light guide plates, prism sheets, Deflector plate, retardation plate, viewing angle correction film, adhesive, polarizer protective film In addition, protective film for front glass of organic EL (electroluminescence) display, front glass substitute material, adhesive, various film substrates of field emission display (FED), protective film for front glass, substitute for front glass, adhesive, etc. It is. In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the field of optical equipment, they are still camera lens materials, finder prisms, target prisms, finder covers, light receiving sensor sections, etc., and video camera photographing lenses and finders. Further, they are projection lens for projection television, protective film, sealing material, adhesive, etc., lens material for optical sensing equipment, sealing material, adhesive, film, etc. In the optical component field, fiber materials, lenses, waveguides, element sealants, adhesives, etc. around optical switches in optical communication systems, and optical fiber materials, ferrules, sealants, adhesives, etc., around optical connectors In addition, for optical passive components and optical circuit components, lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, etc., and substrate materials, fiber materials, and elements around the optoelectronic integrated circuit (OEIC) Sealing materials, adhesives and the like. In the field of optical fibers, it is an optical fiber for industrial use sensors, displays / signs, etc. for illumination and light guides for decorative displays, and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel sheets, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass substitutes, and multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

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 an Example was measured with the following method.
(1) Molecular weight: Polystyrene conversion and weight average molecular weight measured under the following conditions were calculated by gel permeation chromatography (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)
(2) Epoxy equivalent: measured by the method described in JIS K-7236.
(3) Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.
Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. In the synthesis examples and examples, “part” means part by weight, and “%” means% by weight.

Synthesis example 1
As the first step reaction, 106 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 234 parts of silanol-terminated methylphenylsilicone oil having a weight average molecular weight of 1700 (GPC measurement value) (silanol equivalent: 850, measured using GPC) Was calculated as half the weight average molecular weight.), 18 parts of 0.5% potassium hydroxide (KOH) methanol solution (0.09 parts as KOH parts) was charged into the reaction vessel, and the bath temperature was set to 75 ° C. Then, the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As the second stage reaction, after adding 305 parts of methanol, 86.4 parts of 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, 300 parts of organopolysiloxane compounds (A-1) which have a reactive functional group were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. The epoxy equivalent of the obtained compound was 718 g / eq, the weight average molecular weight was 2200, the appearance was liquid and colorless and transparent.

Synthesis example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, 20 parts of tricyclodecane dimethanol, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH or less, acid anhydride 100 parts of the product (referred to as product H-1) was added, reacted at 40 ° C. for 3 hours, and then heated and stirred at 70 ° C. for 1 hour (disappearance of tricyclodecane dimethanol (1 area% or less) by GPC). ) 120 parts of a curing agent composition (B-1) containing a polyvalent carboxylic acid (I-1) and an acid anhydride (H-1) were obtained. The obtained curing agent composition is a colorless liquid resin, and the purity by GPC is 55 area% for polyvalent carboxylic acid (I-1; the following formula (9)) and 45 area% for methylhexahydrophthalic anhydride. Met. The functional group equivalent was 201 g / eq. Met.
Formula (9)

Synthesis example 3
To a flask equipped with a stirrer, reflux condenser, and stirrer, 20 parts of 2,4-diethylpentanediol and 100 parts of acid anhydride (H-1) were added while purging with nitrogen, and reacted at 40 ° C. for 3 hours. By heating and stirring at 70 ° C. for 1 hour (disappearance of 2,4-diethylpentanediol (1 area% or less) was confirmed by GPC). Polycarboxylic acid (I-2) and acid anhydride (H— 120 parts of curing agent composition (B-2) containing 1) was obtained. The obtained hardening | curing agent composition is a colorless liquid resin, The purity by GPC is 50 area% of polyhydric carboxylic acid (I-2; following formula (10)), and an acid anhydride (H-1) is 50 area. %Met. The functional group equivalent was 201 g / eq. Met.
Formula (10)

Example 1, Comparative Example 1, Comparative Example 2
Organopolysiloxane compound (A-1) obtained in Synthesis Example 1 as an epoxy resin, and curing agent composition (B-1) obtained in Synthesis Example 2 as a curing agent (organopolysiloxane (A) and curing agent The ratio of the composition (B) is 1: 0.8 in terms of functional group equivalent, zinc salt (zinc complex) (XC-9206 manufactured by Enomoto Kasei Co., Ltd., hereinafter referred to as catalyst C-1) as a curing accelerator, and 2- [(2,2,6,6-tetramethyl-4-piperidyloxy) carbonylamino] ethyl methacrylate (manufactured by Nippon Kayaku, IM-0072 hereinafter D-1), bis (1-undecanoxy-2,2,6 , 6-Tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81 or less D-2) manufactured by ADEKA, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) as a phosphorus compound (Ludi-tridecyl phosphite) (ADEKA ADEKA STAB 260 or less E-1) is used and blended at the blending ratio (parts by weight) shown in Table 1 below, defoamed for 20 minutes, and used in the present invention or for comparison. A curable resin composition was obtained.

Example 2, Comparative Example 3, Comparative Example 4
Organopolysiloxane compound (A-1) obtained in Synthesis Example 1 as an epoxy resin, and curing agent composition (B-2) obtained in Synthesis Example 3 as an curing agent (organopolysiloxane (A) and curing agent The ratio of the composition (B) is 1: 1.0 in terms of functional group equivalent, zinc salt (zinc complex) (XC-9206, hereinafter referred to as Catalyst C-1) as a curing accelerator, and 2- [(2,2,6,6-tetramethyl-4-piperidyloxy) carbonylamino] ethyl methacrylate (manufactured by Nippon Kayaku, IM-0072 hereinafter D-1), bis (1-undecanoxy-2,2,6 , 6-Tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81 or less, D-2) manufactured by ADEKA, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) as a phosphorus compound (Ludi-tridecyl phosphite) (ADEKA ADEKA STAB 260 or less, E-1), and blended at the blending ratio (parts by weight) shown in Table 2 below, defoamed for 20 minutes, and used for the present invention or for comparison A curable resin composition was obtained.

Example 3, Comparative Example 5, Comparative Example 6
Organopolysiloxane compound (A-1) obtained in Synthesis Example 1 as an epoxy resin, Curing agent composition (B-1) obtained in Synthesis Example 2 as a curing agent, Ricacid MH (manufactured by Shin Nippon Rika Co., Ltd., below) B-3) (The ratio of the organopolysiloxane (A) to the curing agent composition and (B) is 1: 0.8 in terms of functional group equivalent), and zinc salt (zinc complex) (XC- manufactured by Enomoto Kasei) as the curing accelerator 9206 or less, catalyst C-1), 2-[(2,2,6,6-tetramethyl-4-piperidyloxy) carbonylamino] ethyl methacrylate (Nippon Kayaku IM-0072 or less D- 1), bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81 or less D-2) manufactured by ADEKA, 4,4′- The Tylidenebis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite) (ADEKA ADEKA STAB 260 or less E-1) was used and blended at the blending ratio (parts by weight) shown in Table 3 below. 20 Defoaming was performed for a minute to obtain a curable resin composition of the present invention or for comparison.

  The obtained curable resin composition was gently poured into a test piece mold, and the cast was cured under conditions of 150 ° C. × 3 hours after pre-curing at 120 ° C. × 1 hour for various tests. A cured product was obtained. The obtained cured product was evaluated for the following hardness and thermal durability transmittance test under the conditions described below (the results are shown in Tables 1, 2 and 3 below).

(Thermal durability transmission test)
Heat test conditions: Standing in a 180 ° C. oven for 72 hours Size: 1.0 mm thickness
Evaluation conditions: Transmittance of 460 nm is measured with a spectrophotometer. Calculate the rate of change.

(Light resistance test)
Testing machine: Super UV tester (EYE SUPER UV TESTER SUV-WII, manufactured by Iwasaki Electric Co., Ltd.)
Light resistance test conditions: temperature 60 ° C., humidity 60 ° C., irradiance 60 mW / cm ² left for 100 hours,
Specimen size: Thickness 1.0mm
Evaluation conditions: Transmittance of 460 nm is measured with a spectrophotometer. Calculate the rate of change.

By comparing Examples 1-3 and Comparative Examples 1-6, it turns out that the curable resin composition of this invention is excellent in heat-resistant coloring (heat-resistant transmittance | permeability test) and light resistance.

Claims (7)

A curable resin composition comprising an organopolysiloxane (A) and a polyvalent carboxylic acid (B), an organic metal salt and / or an organic metal complex (C), and a light stabilizer (D) as essential components.
However, organopolysiloxane (A), polyvalent carboxylic acid (B), organometallic salt and / or organometallic complex (C), and light stabilizer (D) satisfy the following conditions.
Organopolysiloxane (A):
Polyvalent carboxylic acid (B), which is an epoxy resin having at least a glycidyl group and / or an epoxycyclohexyl group in the molecule:
A light stabilizer (D) having at least two or more carboxyl groups and having an aliphatic hydrocarbon group and / or siloxane as a main skeleton:
It is a compound represented by the structural formula (1)

(However, R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group, or an alkoxy group.) The curable resin composition according to claim 1, wherein the organometallic salt and / or organometallic complex (C) is a zinc salt and / or a zinc complex. An acid anhydride is contained, The curable resin composition as described in any one of Claim 1 or 2 characterized by the above-mentioned. The polyhydric carboxylic acid (B) is a compound obtained by reaction of a C6-C6 bifunctional polyhydric alcohol and a saturated aliphatic cyclic acid anhydride. The curable resin composition according to claim 1. A polyhydric carboxylic acid (B) having a branched chain structure or a cyclic structure and having 2 or 6 carbon atoms and a polyhydric alcohol having a siloxane structure and methylhexahydrophthalic anhydride or cyclohexane-1, The curable resin composition according to any one of claims 1 to 4, which is a compound obtained by a reaction with 3,4-tricarboxylic acid-3,4-anhydride. Antioxidant is contained, The curable resin composition as described in any one of Claims 1-3 characterized by the above-mentioned. Hardened | cured material formed by hardening | curing the curable resin composition as described in any one of Claims 1-3.