JP5626856B2 - Curable resin composition and cured product thereof - Google Patents

Description

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

Conventionally, an epoxy resin composition has been employed 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 light emission wavelength of LED products (mainly 480 nm or less for LED products that emit blue light), the sealing material is colored on the LED chip under the influence of short wavelength light, and finally Has been pointed out that illuminance decreases as an LED product.
Therefore, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′epoxycyclohexylcarboxylate 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)

Furthermore, due to the durability problem of epoxy resin, a resin having a siloxane skeleton (specifically, a skeleton having a Si-O bond) typified by silicone resin or silicone-modified epoxy resin as a sealing material is used. Consideration to use has been made. (Patent Document 3)
In general, a resin having a siloxane skeleton introduced is known to be more stable to light than an epoxy resin, but it is still not sufficient, and further improvement is 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 JP 2005-100445

  An object of this invention is to provide the novel curable resin composition which gives the hardened | cured material excellent in light-coloring resistance, heat-resistant coloring property, and corrosion gas resistance.

（ただし、Ｘ₁，Ｘ₂は水素原子、炭素数１〜５０のアルキル基、アラルキル基、アリール基、炭素数１〜２０のアルキル基を有するアリール基、アルコキシ基または構造式（２）であり、Ｘ₁，Ｘ₂の少なくとも一方は構造式（２）である。

（式（２）中、＊印で構造式（２）は構造式（１）の酸素原子と結合する。また、Ｙは水素原子、炭素数１〜５０のアルキル基、アリール基、アルコキシ基を表す。））
（２）
構造式（２）のＹが炭素数１〜２０のアルコキシ基である構造式（１）の化合物を含む前項（１）に記載の硬化性樹脂組成物、
（３）
有機金属塩および／または有機金属錯体（Ｃ）が燐酸エステル、燐酸の亜鉛塩、および／またはこれらの酸あるいはエステルを配位子として有する亜鉛錯体であ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）
構造式（１）のＸ₁、Ｘ₂がともに構造式（２）であり、かつ、構造式（２）のＹが
−ＯＣ₁₁Ｈ₂₃
である化合物を含む前項（１）〜（３）のいずれか一項に記載の硬化性樹脂組成物、
（５）
酸無水物を含有す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）
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）〜（５）のいずれか一項に記載の硬化性樹脂組成物、
（７）
酸化防止剤を含有することを特徴とする前項（１）〜（６）のいずれか一項に記載の硬化性樹脂組成物、
（８）
前項（１）〜（７）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 containing an organopolysiloxane (A) and a polyvalent carboxylic acid (B), an organometallic salt and / or an organometallic complex (C), and a light stabilizer (D);
However, organopolysiloxane (A), polyvalent carboxylic acid (B), and light stabilizer (D) satisfy the following conditions.
Organopolysiloxane (A):
Organopolysiloxane polycarboxylic acid (B) having at least a glycidyl group and / or an epoxycyclohexyl group in the molecule:
Light stabilizer (D) having at least two carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton:
Compound represented by structural formula (1)

(Where X ₁ and X ₂ are a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an aralkyl group, an aryl group, an aryl group having an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a structural formula (2). , at least one of X _1, X ₂ is a structural formula (2).

(In the formula (2), the structural formula (2) is bonded to the oxygen atom of the structural formula (1) at the mark *. Y represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an aryl group, or an alkoxy group. Represents)))
(2)
The curable resin composition according to the above item (1), comprising a compound of the structural formula (1), wherein Y in the structural formula (2) is an alkoxy group having 1 to 20 carbon atoms,
(3)
(1) or (1) above, wherein the organometallic salt and / or organometallic complex (C) is a phosphoric ester, a zinc salt of phosphoric acid, and / or a zinc complex having these acids or esters as ligands. The curable resin composition according to any one of 2),
(4)
X ₁ and X _{2 in} the structural formula (1) are both the structural formula (2), and Y in the structural formula (2) is —OC ₁₁ H _23.
The curable resin composition according to any one of (1) to (3) above, comprising a compound that is:
(5)
The curable resin composition according to any one of (1) to (4) above, which contains an acid anhydride,
(6)
(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. 5) The curable resin composition according to any one of
(7)
The curable resin composition according to any one of (1) to (6) above, which contains an antioxidant.
(8)
A cured product obtained by curing the curable resin composition according to any one of (1) to (7) above,
About.

  Since the curable resin composition of the present invention is excellent in corrosion gas resistance, heat-resistant colorability, and light-colorable property, among optical materials, particularly for optical semiconductors (LED products, etc.) used in a living environment such as lighting. It is extremely useful as an adhesive and sealing material.

Hereinafter, it describes about the curable resin composition of this invention.
The curable resin composition of the present invention contains an organopolysiloxane (A), a polyvalent carboxylic acid (B), an organometallic salt and / or an organometallic complex (C), and a light stabilizer (D).
As the organopolysiloxane (A), an organopolysiloxane having a glycidyl group and / or an epoxycyclohexyl group in its molecule is used.
The organopolysiloxane is an organopolysiloxane having at least a glycidyl group and / or an epoxycyclohexyl group in the molecule, and is generally a sol-gel using a trialkoxysilane having a glycidyl group or an epoxycyclohexyl group as a raw material. Obtained by 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 Patent 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 chain-like silicone segment and the aforementioned silsesquioxane structure 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, an alkoxysilane (a) represented by the following general formula (3) and a silicone oil (b) represented by the general formula (4) as raw materials, The alkoxysilane (c) represented by the general formula (5) can be used as a raw material as necessary. 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 (a) is represented by the following general formula (3).
XSi (OR ₁ ) ₂ (3)
X in the general formula (3) is not particularly limited as long as it is an organic group having an epoxy group. For example, an alkyl group having 1 to 4 carbon atoms substituted with a glycidoxy group such as β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, glycidyl group, β- (3,4-epoxy (Cyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3, C1-C5 alkyl groups substituted by C5-C8 cycloalkyl groups having an oxirane group such as 4-epoxycyclohexyl) butyl group and β- (3,4-epoxycyclohexyl) pentyl group. It is done. 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 a β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable.

A plurality of R ₁ present in the general formula (3) may be the same or different from each other, and represent 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 ₁ 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 alkoxysilanes (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 general formula (4)

Is a chain silicone oil having a silanol group at the end having a structure represented by:
In the formula of the general formula (4), a plurality of R ₂ may be the same or different from each other, and may be 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 M represents the number of repeating units.
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, 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 ₂ 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 average number m of repeating units of the compound of the general formula (4) is 3 to 200, preferably 3 to 100, more preferably 3 to 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 (measured value by GPC (gel permeation chromatography)). 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 agent. 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, PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21 from the viewpoint of molecular weight and kinematic viscosity PDS-1615 is preferred. Among these, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight 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 represented by the following general formula (5).
R ₃ Si (OR ₄ ) ₃ (5)
R ₃ in the general formula (5) represents a methyl group or a phenyl group.

A plurality of R ₄ present in the general formula (5) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, which may be the same or different. 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 ₄ 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.

  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), the alkoxysilane (c) is preferably used in the range of 5 to 70 mol% of the total of the alkoxysilane (a) and the alkoxysilane (c). 5-50 mol% is still more preferable, and 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 ( When c) is used in combination, the reaction is carried out between 1.5 to 200, preferably 2 to 200, particularly preferably 2 to 100, with the alkoxy group in alkoxysilane (a) and alkoxysilane (c)) as an equivalent value. It is preferable to carry out.
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 (1) and (2).
Production step (1): Step of dealcoholization condensation of silanol-terminated silicone oil and silicon compound having alkoxy group Production step (2): Hydrolysis condensation between alkoxy groups of silicon compound having alkoxy group by adding water In the process manufacturing steps (1) and (2), the reaction may be carried out in any order as long as it goes through each step.

Specific examples of preferred production methods include the following three production methods.
<Manufacturing method (I)>
First, as a production process (1), a silicone oil (b) having a silanol group at the terminal and an alcohol silane (a) and / or an 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.
Next, alkoxysilane (a) (alkoxysilane (c) as required) which is a silicon compound having an alkoxy group as production step (2), and alkoxysilane-modified product of silicone oil obtained in production step (1) ( 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 (2), a molecule is 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 (1), 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 (1), a dealcoholization condensation reaction between a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) (which is an alkoxysilane (c) if necessary) which is a silicon compound having an alkoxy group To form an alkoxysilane-modified product (d) by modifying the terminal of the silicone oil with alkoxysilane, and then adding water to the system to leave the alkoxysilane (a) (if necessary) as a production step (2) in one pot. The alkoxysilane (c)) and the method for producing the block siloxane compound (E) by carrying out hydrolysis condensation reaction between the alkoxy groups of the modified alkoxysilane (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 reverse of the manufacturing method (c) described above, that is, when the manufacturing process (1) is performed after the manufacturing process (2) as shown in (b), it is formed in the manufacturing process (2). There is a possibility that the silsesquioxane oligomer having an alkoxy group and the silicone oil (b) are not compatible with each other, the dealcoholization condensation polymerization does not proceed in the subsequent production step (1), and an unreacted silicone oil remains. Is expensive. On the other hand, if the method of performing the manufacturing process (2) in one pot after the manufacturing process (1) as in the manufacturing method (c) is used, the silicone oil (b) and the alkoxysilane (a) or the alkoxysilane (c) Since the compatibility is relatively high, the problem that the reaction does not proceed without compatibility as described above can be avoided. Furthermore, a low molecular weight alkoxysilane that does not cause a condensation reaction between alkoxysilanes is present in a large amount with respect to the silanol group, which is preferable from the viewpoint of reactivity. Assuming that the production process (1) in the one-pot is the first stage reaction and the production process (2) is the second stage reaction, first, in the first stage reaction (production process (1)), the silicone oil (b) and the 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 (6).

In formula (6), R ₂ and m have the same meaning as described above, and R ₅ represents X and / or R ₃ . R ₆ represents R ₁ when R ₅ is X, and R ₄ when R ₅ is R ₃ .

  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, and 3.0 equivalents or more are more preferable.

After the completion of the first stage reaction, the second stage reaction (production process (2)) in which water is added as it is to carry out hydrolysis condensation between alkoxy groups is performed. 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 compound (acid 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 compounds (basic catalysts) include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate Inorganic bases such as alkali metal carbonates such as potassium hydrogen carbonate, 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, condensation of alkoxysilane (a) (optionally alkoxysilane (c) if necessary) was unilaterally progressed 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) (optionally alkoxysilane (c)), silicone oil (b), 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 the solvent used is not particularly limited as long as the reaction proceeds smoothly, but the total weight of alkoxysilane (a) (alkoxysilane (c) if necessary) and silicone oil (b) is 100. Usually, about 0 to 900 parts by weight are used per part. The reaction temperature is usually 20 to 160 ° C, preferably 40 to 140 ° C, particularly preferably 50 to 150 ° 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, in particular, inorganic bases or inorganic acids are preferable because they can be easily removed from the product, and phosphates that can more easily adjust the pH to near neutral are more preferable.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
As the activated clay, for example, Toshin Kasei Co., Ltd., activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168, manufactured by Mizusawa Chemical Industry, Galeon Earth, Mizuka Ace, etc. are listed. As the activated carbon, for example, CL-H, Y-10S, Y-10SF manufactured by Ajinomoto Fine-Techno Co., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR are manufactured by Phutamura Chemical Co., Ltd. , CW130AR, GM130A, and the like. Examples of zeolite include, for example, molecular sieves 3A, 4A, 5A, and 13X, manufactured by Union Showa. As a synthetic adsorbent, for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., Amberlist 15JWET, 15DRY, manufactured by Rohm and Haas Co., Ltd. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, 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 type siloxane compound (E).

The polyvalent carboxylic acid (B) is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group 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 bi- to hexa-functional carboxylic acid is particularly preferable, and a compound obtained by reacting a bi- or polyfunctional alcohol having 5 or more carbon atoms with an acid anhydride is more preferable. Furthermore, the polycarboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.
As the 2- to 6-functional polyhydric alcohol, the alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, Diols such as tricyclodecane dimethanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, ditrimethylo Tetraols such as propane, and the like hexaol such as dipentaerythritol.
Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, Compounds such as 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol are preferred, and among them, heat resistance and light resistance are imparted and high From the viewpoint of maintaining the illuminance retention, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol Branched chain structure such as norbornenediol Alcohols having a structure or a cyclic structure are more preferred.
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, Among them, methyl hexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are preferable because of high transparency.
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種以上を表す。Ｐは前述の多価アルコール由来の炭素数２〜２０の鎖状、分岐状、環状の脂肪族基である。ｍは、多価アルコールの官能基数であり、好ましくは２〜６の整数である。）
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, branched, or cyclic fat having 2 to 20 carbon atoms derived from the aforementioned polyhydric alcohol. M is the number of functional groups of the polyhydric alcohol, preferably an integer of 2 to 6.)
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- And acid anhydrides such as dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.
In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid An acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like are preferable.
Particularly preferably, the following formula (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、中でも透明性が高いため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.)
Preferred are hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride represented by the formula. -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 to 0.65
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 preferably 0.05 to 0.65, more preferably 0.10 to 0.65, and particularly preferably 0.3 to 0.6. If it is less than 0.05, there is a strong tendency of acid volatilization to increase during curing, which is not preferable. If it exceeds 0.65, 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, zinc undecylate, zinc laurate, zinc pehenate, zinc 12-hydroxystearate, zinc montanate, zinc myristate, zinc palmitate, zinc naphthenate, zinc hexate Zinc octylate, aluminum-acetylacetone complex, manganese-acetylacetone complex, iron-acetylacetone complex, cobalt-acetylacetone complex, nickel-acetylacetone complex, copper-acetylacetone complex, zinc-acetylacetone complex, zinc complex of phosphoric acid (2-ethylhexyl) , Zirconium-acetylacetone complex, tin-acetylacetone complex, lead-acetylacetone complex and the like.
Here, from the viewpoint of imparting corrosion resistance, zinc salts and / or zinc complexes are preferable. Specifically, zinc 2-ethylhexanoate, zinc complexes of phosphoric acid (2-ethylhexyl) and / or salts thereof, Zinc stearate, zinc undecylenate, zinc laurate, zinc pehenate, zinc 12-hydroxystearate, zinc montanate, zinc myristate, zinc palmitate, zinc naphthenate, zinc hexoate and zinc octylate are preferred.
Among them, from the viewpoint of compatibility, zinc 2-ethylhexanoate, zinc complex of phosphoric acid (2-ethylhexyl) and / or a salt thereof, zinc stearate, and zinc undecylate are more preferable, and considering transparency, Zinc 2-ethylhexanoate, zinc complex of phosphoric acid (2-ethylhexyl) and / or a salt thereof are particularly preferred.
As such a zinc carboxylate, commercially available products include Zn-St, Zn-ST 602, Zn-St NZ, ZS-3, ZS-6, ZS-8, ZS-7, ZS-10, ZS-. 5, ZS-14, ZS-16 (manufactured by Nitto Kasei Kogyo), XK-614 (manufactured by King Industry), 18% octope Zn, 12% octope Zn, 8% octope Zn (manufactured by Hope Pharmaceutical), phosphate ester and / or Or as a zinc phosphate body, LBT-2000B (product made from SC organic chemistry) and XC-9206 (product made from King Industry) are mentioned.

  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、Ｘ₁，Ｘ₂は同一もしくは異なり水素原子、炭素数１〜５０のアルキル基、アラルキル基、アリール基、炭素数１〜２０のアルキル基を有するアリール基、アルコキシ基または構造式（２）であり、Ｘ₁，Ｘ₂の少なくとも一方は構造式（２）である

前記式中、＊印で構造式（２）は式（１）の酸素原子と結合する。また、Ｙは水素原子、炭素数１〜５０のアルキル基、アリール基、アルコキシ基を表す
一般式（１）で表される化合物の好適な具体例としては、Ｙ＝水素原子である構造式（２）をＸ₁およびＸ₂とするビス（２,２,６,６−テトラメチルピペリジン−４−イル）カーボネート、Ｙ＝メチル基である構造式（２）をＸ₁およびＸ₂とするビス（１,２,２,６,６−ペンタメチルピペリジン−４−イル）カーボネート、Ｙ＝プロポキシ基である構造式（２）をＸ₁およびＸ₂とするビス（２,２,６,６−テトラメチル−プロポキシピペリジン−４−イル）カーボネート、Ｙ＝ウンデシロキシ基である構造式(2)を置換基Ｘ₁およびＸ₂とするビス（１−ウンデカンオキシ−２,２,６,６−テトラメチルピペリジン−４−イル）カーボネート、Ｙ＝メチル基である構造式（２）をＸ₁とし、ｔｅｒｔ−ペンチルオキシ基をＸ₂とする１,２,２,６,６−ペンタメチルピペリジン−４−イルｔｅｒｔ−ペンチルカルボノペルオキシアート等がある。特に好ましい化合物として、Ｙ＝ウンデシロキシ基である構造式(2)を置換基Ｘ₁およびＸ₂とするビス（１−ウンデカンオキシ−２,２,６,６−テトラメチルピペリジン−４−イル）カーボネートが挙げられる。 The curable 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, X _1, X ₂ are the same or different hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an aralkyl group, an aryl group, an aryl group having an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or structural formula (2) And at least one of X ₁ and X ₂ is the structural formula (2)

In the above formula, the structural formula (2) is bonded to the oxygen atom of the formula (1) at *. Y represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an aryl group, or an alkoxy group. As a preferable specific example of the compound represented by the general formula (1), a structural formula in which Y is a hydrogen atom ( bis to 2) and X ₁ and X ₂ (2,2,6,6-tetramethyl-piperidin-4-yl) carbonate, bis Y = structural formula is a methyl group and (2) and X ₁ and X ₂ (1,2,2,6,6-pentamethylpiperidin-4-yl) carbonate, bis (2,2,6,6-) wherein X = X ₂ is X ₁ and X ₂ is the structural formula (2) where Y = propoxy group Tetramethyl-propoxypiperidin-4-yl) carbonate, bis (1-undecanoxy-2,2,6,6-tetramethyl) having the structural formula (2) where Y = undecyloxy group as substituents X ₁ and X ₂ Piperidin-4-yl) carbonate, Y = methyl group. Concrete formula (2) and X _1,-4-tert- pentyloxy group and a X ₂ 1,2,2,6,6 pentamethylpiperidine yl tert- pentyl carbonitrile Roh has peroxy art like. As a particularly preferred compound, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate having the structural formula (2) where Y = undecyloxy group as substituents X ₁ and X ₂ Is 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 still more preferably 0.1 to 4% by weight with respect to the organopolysiloxane (A). 2% by weight.
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, zinc salts and / or zinc complexes as organometallic salts and / or organometallic complexes (C), and bis (1-undecanoxy-2,2,6,6-tetramethylpiperidine as light stabilizers (D) -4-yl) carbonate is preferred, and these are preferably used in combination. This is because when used in the combination, it is excellent in light resistance and heat resistance, hardly colored by light or heat, and excellent in corrosion gas resistance.

  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-tetramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4- Mixed esterified product of piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, decanedioic acid bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate, 2,2,6,6, -tetramethyl-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) seba 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-pipe decanedioate Dinyl) 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- Tet Lamethyl-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, N , N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) and other hindered amines, octabenzone and other benzophenone compounds, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotria 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- Methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5 tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol reaction product, benzotriazole compounds such as 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2,4- Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. Benzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 - [(hexyl) oxy] triazine such as phenol-based compounds and the like.

  When using the curable resin composition of this invention for an optical material, especially an optical semiconductor sealing agent, it is preferable to contain the phosphorus compound as an 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 include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as an Adeka product, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, and Adekas tab 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 (B) as a curing agent, an organometallic salt and / or organometallic complex (C) as an additive, and a light stabilizer ( D) is an essential component, and an acid anhydride as a curing agent and an antioxidant as a preferred optional component are included as optional components, but these can be used in combination with other epoxy resins, curing agents, and various additives.

  In the epoxy resin, the organopolysiloxane (A) can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 60% by weight or more, 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 , Glycidylamine epoxy resin, alicyclic 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.

The curable resin composition of the present invention is mainly intended for use in 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 cyclohexane structure is particularly preferable.
These alicyclic epoxy resins include esterification reaction of cyclohexene carboxylic acid with alcohols or esterification reaction of cyclohexene methanol with carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) )), Or Tyschenko reaction of cyclohexene aldehyde (method described in JP 2003-170059 A, JP 2004-262871 A, etc.), and transesterification of cyclohexene carboxylic acid ester (JP A And a compound obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Application Publication No. 2006-052187.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.

As the curing agent, the polycarboxylic acid (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 (such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and polyamide resins synthesized from linolenic acid dimer and ethylenediamine). , 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] Hepta -Reaction products of acid anhydrides such as 2,3-dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and silicone alcohols 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, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydro Sibenzene, 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.) But this It is not limited to that. These may be used alone or in combination of two or more.

  In the curable resin composition of the present invention, the mixing ratio of the curing agent containing the organopolysiloxane (A) and the polyvalent carboxylic acid (B) as essential components is the epoxy group 1 of the organopolysiloxane (A). It is preferable to use a curing agent containing, as an essential component, 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 based on equivalents. 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 the organic metal complex (C), which are essential components, exhibit the action as a curing catalyst as it is, and therefore it is not necessary to add a curing catalyst separately. However, other curing catalysts can 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 tetrafes Salts such as ruborate and phenol novolac, salts with the above polycarboxylic acids, or phosphinic acids, ammonium salts such as tetrabutyl ammonium bromide, cetyltrimethyl ammonium bromide, trioctylmethyl ammonium 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 curing catalyst 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, both are organopolysiloxane (A) and polyvalent carboxylic acid. It can be added to either or both of (B), and can also be added after mixing organopolysiloxane (A) and polyvalent carboxylic acid (B).

  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 with 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 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, 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 the 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 optical semiconductor sealing agent, a 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) such as _{O · A} l2 _{O 3} is 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 for an optical material, particularly an optical semiconductor encapsulant, for the purpose of preventing sedimentation of various phosphors upon curing, silica fine powder (also called Aerosil or Aerosol) is used. 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 CO., LTD., Sumilizer GA-80, Sumizer MDP-S, Sumili er BBM-S, Sumilizer GM, Sumilizer GS (F), and the like Sumilizer GP.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477, TINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like are 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, the curable resin composition of the present invention, another epoxy resin and a curing agent, and if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler and a compounding agent as necessary, an extruder, a kneader, a roll, Mix thoroughly until uniform using a planetary mixer, etc. to obtain a curable resin composition. If the curable resin composition is in liquid form, potting or casting, impregnating the base material, curable on the mold For example, the resin composition may be poured and cast, and cured by heating. In the case of a solid, it may be cast after melting or molded using a transfer molding machine, and further cured by heating. The curing temperature and time are 80 to 200 ° C. and 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 to obtain 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 curable resin hardened | cured material which contains 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 for an optical semiconductor such as a high-intensity white LED or a die bond material, an organopolysiloxane (A), a polyvalent carboxylic acid (B), an organic metal salt, and / Or thoroughly mix additives such as organometallic complex (C), light stabilizer (D), and other epoxy resins, curing agents, coupling agents, antioxidants, light stabilizers, etc. as necessary. The curable resin composition is prepared by the method described above and 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 curable 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 for adhering a semiconductor chip to a substrate using the curable resin composition of the present invention, the curable resin composition of the present invention is applied by dispenser, potting, or screen printing, and then heated by placing the semiconductor chip thereon. Curing can be performed to bond the semiconductor chip. 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 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.

  Applications of the curable resin composition of the present invention include general applications in which curable resins such as epoxy resins are used. For example, adhesives, paints, coating agents, molding materials (sheets, films, FRP, etc.) ), Insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, and other resins such as acrylic ester resins as resist curing agents And the like.

  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 agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

  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 that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. 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 optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., 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 plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a 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 stage reaction, 114 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 234 parts of silanol-terminated methylphenylsilicone oil having a weight average molecular weight of 1700 (GPC measured value) (measured using silanol equivalent 850, 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, the organic phase was removed under reduced pressure at 100 ° C. to obtain 303 parts of an organopolysiloxane compound (A-1) having a reactive functional group. The epoxy equivalent of the obtained compound was 677 g / eq, the weight average molecular weight was 2200, and the appearance was colorless and transparent.

Synthesis example 2
As the first stage reaction, 257 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 505 parts of silanol-terminated methylphenyl silicone 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.), 40 parts of a 0.5% potassium hydroxide (KOH) methanol solution (0.2 parts as the KOH part) 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 a second stage reaction, after adding 510 parts of methanol, 130 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. under reflux for 8 hours. 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. 704 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, the organic phase was removed at 100 ° C. under reduced pressure to obtain 663 parts of an organopolysiloxane compound (A-2) having a reactive functional group. The epoxy equivalent of the obtained compound was 659 g / eq, the weight average molecular weight was 2370, and the appearance was colorless and transparent.

Synthesis example 3
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 20 parts of tricyclodecane dimethanol, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH or less, acid anhydride) 100 parts of this 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 (by GPC, the disappearance of tricyclodecane dimethanol (1 area% or less) was confirmed. ) 120 parts of a curing agent composition (T-1) containing a polycarboxylic acid (B-1) and an acid anhydride (H-1) were obtained. The obtained colorless liquid resin had a GPC purity of 55 area% for polycarboxylic acid (B-1; the following formula (9)) and 45 area% for methylhexahydrophthalic anhydride. The functional group equivalent was 201 g / eq. Met.
Formula (9)

Synthesis example 4
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). Polyvalent carboxylic acid (B-2) and acid anhydride (H— 120 parts of curing agent composition (T-2) containing 1) was obtained. It was the obtained colorless liquid resin, and the purity by GPC was 50 area% for polycarboxylic acid (B-2; the following formula 8) and 50 area% for acid anhydride (H-1). The functional group equivalent was 201 g / eq. Met.
Formula (10)

Example 1, Comparative Examples 1 and 2
The organopolysiloxane compound (A-1) obtained in Synthesis Example 1 as an epoxy resin, and the curing agent composition (T-1) obtained in Synthesis Example 3 (organopolysiloxane (A) and a curing agent as a curing agent. The ratio of the composition (B) is 1: 0.8 in terms of functional group equivalent, a zinc salt (zinc complex) (XC-9206 or below, C-1) as an organometallic complex, and bis (1 as a light stabilizer. -Undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (ADEKA STAB LA-81 or less D-1 manufactured by ADEKA), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINVAIN 770DF manufactured by Ciba Japan, hereinafter referred to as D-2), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) (TI manufactured by Ciba Japan) UVIN123 or less, D-3), 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl-di-tridecylphosphite) (manufactured by ADEKA, Adeka Stub 260 or less as a phosphorus compound as an antioxidant E- 1) was used and blended at a blending ratio (parts by weight) shown in Table 1 below, and defoamed for 20 minutes to obtain a curable resin composition for the present invention or for comparison.

Example 2, Comparative Examples 3, 4
Organopolysiloxane compound (A-2) obtained in Synthesis Example 2 as an epoxy resin, and curing agent composition (T-2) obtained in Synthesis Example 4 (organopolysiloxane (A) and a curing agent as a curing agent The ratio of the composition (B) is 1: 0.8 in terms of functional group equivalent), zinc salt (zinc complex) as an organometallic complex (18% octope Zn, hereinafter C-2), and bis ( 1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (Adeka ADEKA STAB LA-81 or less D-1), bis (2,2,6,6-tetramethyl-4-piperidyl) Sebacate (TINUVIN770DF manufactured by Ciba Japan, hereinafter referred to as D-2), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) (Ciba Japan) Made TINUVIN123 Hereinafter, D-3) was used and blended at a blending ratio (parts by weight) shown in Table 2 below, followed by defoaming for 20 minutes to obtain a curable resin composition of the present invention or for comparison.

(Thermal durability transmission test)
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. A cured product was obtained. About the obtained hardened | cured material, the heat durability transmittance | permeability test was implemented on the conditions described below, and evaluation was performed (a result is shown in following Table 1 and Table 2).
Measurement conditions Test conditions: In a 180 ° C oven, left for 72 hours Test piece size: Thickness 0.8mm
Evaluation conditions: A transmittance of 400 nm is measured with a spectrophotometer. Calculate the rate of change.

  It can be seen from Examples 1-2 and Comparative Examples 1-4 that the curable resin composition of the present invention is excellent in heat-resistant coloring (heat-resistant transmittance test).

(LED lighting test)
Using the obtained curable resin composition, it was filled into a syringe and cast into a surface mount LED package having an outer diameter of 5 mm square on which a chip having a center emission wave of 465 nm was mounted using a precision discharge device. The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour, further at 150 ° C. for 3 hours to produce an LED package. In the lighting test, a lighting test was performed at 60 mA which is twice the specified current of 30 mA (acceleration test). In the measurement, the illuminance retention before and after lighting for 1000 hours was measured using an integrating sphere, and the average value of three samples was recorded. Detailed conditions are shown below (results are shown in Table 3 below).
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 60 mA (light emitting element regulation current is 30 mA)
Driving environment: 85 ° C, 85%

  From Example 1 and Comparative Examples 1-2, it can be seen that the curable resin composition of the present invention is excellent in illuminance retention.

Comparative Examples 5 and 6
Organopolysiloxane compounds (A-1) and (A-2) obtained in Synthesis Examples 1 and 2 as epoxy resins, (T-1) and (T-2) as curing agents, and zinc salts as organometallic complexes (Zinc Complex) (C-1), (C-2), Quaternary Phosphonium Salt (Nippon Chemical Industry Hishicolin PX4MP, hereinafter referred to as C-3), Light Stabilizer (D-1), Antioxidant (E-1) was used and blended at a blending ratio (parts by weight) shown in Table 4 below, followed by defoaming for 20 minutes to obtain a curable resin composition for the present invention or for comparison.

(Corrosion gas permeability test)
Using the obtained curable resin composition, it was filled into a syringe and cast into a surface mount LED package having an outer diameter of 5 mm square on which a chip having a center emission wave of 465 nm was mounted using a precision discharge device. The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour, further at 150 ° C. for 3 hours, and an LED package was prepared. The LED package was left in a corrosive gas under the following conditions, and the change in the color of the lead-plated silver-plated part inside the seal was observed (the results are shown in Table 4 below).
Measurement conditions Corrosion gas: Ammonium sulfide 20% aqueous solution (turns black when sulfur component reacts with silver)
Contact method: A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered to bring the volatilized ammonium sulfide gas into contact with the LED package in a sealed state.
Judgment of corrosion: The time when the lead frame inside the LED package was discolored black (referred to as blackening) was observed, and it was determined that the longer the discoloration time, the better the corrosion gas resistance.
The observation was taken out after 10 hours for confirmation, and the evaluation was indicated as ◯ for those with no discoloration and × for those that were blackened.

  From Examples 1-2 and Comparative Examples 5-6, it turns out that the curable resin composition of this invention is excellent in corrosion-resistant gas resistance.

Comparative Examples 7 and 8
Organopolysiloxane compounds (A-1) and (A-2) obtained in Synthesis Examples 1 and 2 as epoxy resins, (T-1) and (T-2) as curing agents, and zinc salts as organometallic complexes (Zinc complex) (C-1), (C-2), (D-1) as a light stabilizer, (E-1) as an antioxidant, and the blending ratio (parts by weight) shown in Table 5 below And defoaming for 20 minutes to obtain a curable resin composition for the present invention or for comparison.

(Light durability transmission test)
Using the obtained curable resin composition, the test piece 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. A cured product was obtained. About the obtained hardened | cured material, the light durability transmittance | permeability test was implemented on the conditions described below, and evaluation was performed (a result is shown in following Table 5).
Measuring condition tester: Super UV tester (Iwasaki Electric Co., Ltd.)
Test conditions: 60 mW / cm 2 · nm, 200 hr
Test piece size: Thickness 0.8mm
Evaluation conditions: A transmittance of 400 nm is measured with a spectrophotometer. Calculate the rate of change.

  It can be seen from Examples 1-2 and Comparative Examples 7-8 that the curable resin composition of the present invention is excellent in light-coloring resistance.

Claims (7)

A curable resin composition for an optical semiconductor containing 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);
However, the organopolysiloxane (A) , the polyvalent carboxylic acid (B) , and the light stabilizer (D) satisfy the following conditions.
Organopolysiloxane (A):
Organopolysiloxane having at least a glycidyl group and / or an epoxycyclohexyl group in the molecule
Polyvalent carboxylic acid (B): having at least two carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton Light stabilizer (D):
Compound represented by structural formula (1)

(Where X ₁ and X ₂ are a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an aralkyl group, an aryl group, an aryl group having an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a structural formula (2). , X ₁ , X ₂ is structural formula (2).

(In the formula (2), the structural formula (2) is bonded to the oxygen atom of the structural formula (1) at the mark *. Y represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, an aryl group, or an alkoxy group. Represent. The curable resin composition for optical semiconductors of Claim 1 containing the compound of Structural formula (1) whose Y of Structural formula (2) is a C1-C20 alkoxy group. The organometallic salt and / or organometallic complex (C) is a phosphoric acid ester, a zinc salt of phosphoric acid, and / or a zinc complex having these acids or esters as ligands. The curable resin composition for optical semiconductors as described in any one of 2 . X ₁ and X _{2 in} the structural formula (1) are both the structural formula (2), and Y in the structural formula (2) is —OC ₁₁ H _23.
The curable resin composition for optical semiconductors as described in any one of Claims 1-3 containing the compound which is. An acid anhydride is contained, The curable resin composition for optical semiconductors as described in any one of Claims 1-4 characterized by the above-mentioned. The polyhydric carboxylic acid (B) is a compound obtained by a reaction of a C6-C6 bifunctional polyhydric alcohol and a saturated aliphatic cyclic acid anhydride. The curable resin composition for optical semiconductors according to any one of 5 . Hardened | cured material formed by hardening | curing the curable resin composition for optical semiconductors as described in any one of Claims 1-6 .