JPWO2011108588A1 - Curable resin composition and cured product thereof - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition that gives a cured product satisfying various physical properties required for electrical and electronic material use, particularly as a semiconductor encapsulating material. Provided is a curable resin composition that has excellent adhesion, light resistance, heat resistance, and gas permeability resistance, and gives a cured product that has little resin stress on the chip and does not cause illuminance deterioration when used as an LED encapsulant. It is to be. The curable resin composition according to the present invention contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B) and an acid anhydride (C), and an epoxycyclohexyl group-containing organopolysiloxane (A ) And the amount of the alicyclic epoxy resin (B) in the total amount of the alicyclic epoxy resin (B) is 1.5 to 40% by weight.

Description

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

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 emission wavelength of LED products (mainly the case of LED products emitting blue light of 480 nm or less), the sealing material is colored on the LED chip due to the influence of light of short wavelengths. However, it has been pointed out that the illuminance will eventually decrease as an LED product.
Therefore, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3 ′, 4 ′ epoxycyclohexyl carboxylate are more transparent than glycidyl ether type epoxy resin compositions having an aromatic ring. Since it is excellent, it has been actively studied as an LED sealing material (Patent Documents 1 and 2).

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

Japanese Unexamined Patent Publication No. 9-213997 Japanese Patent No. 3618238 Japan Special Reissue 2005-100445 Japanese Unexamined Patent Publication No. 2006-225515 Japanese Unexamined Patent Publication No. 2007-324256 Japanese Unexamined Patent Publication No. 2000-174347

  From the problem of durability of the epoxy resin, in Patent Document 3, an epoxy resin into which a siloxane skeleton (specifically, a skeleton having a Si—O bond) represented by a silicone resin or a silicone-modified epoxy resin is introduced. The use as a sealing material has been studied.

In general, it is known that an epoxy resin having a siloxane skeleton introduced is more stable to heat and light than an epoxy resin having no siloxane skeleton introduced. Therefore, when applied to a sealing material for LED products, it has been said that in terms of coloring on the LED chip, it is more durable than an epoxy resin that does not introduce a siloxane skeleton.
However, since the resin containing the siloxane skeleton has insufficient hardness of the cured product compared to a normal epoxy resin, the gold wire used for the wiring is cut by vibration, and the adhesion to the substrate is insufficient. Disadvantages such as easy peeling are pointed out (Patent Document 4).

In order to solve such a problem, Patent Document 4 discloses an epoxy resin having an organopolysiloxane structure having a high crosslinking density (containing silicon atoms having three bonded oxygen atoms in a proportion exceeding 40 mol% per total silicon atoms). Attempts have been made to use alicyclic epoxy resins in combination.
However, the composition described in Patent Document 4 has a high crosslinking density of the organopolysiloxane and a high content of the alicyclic epoxy resin, so that the cured product becomes too hard although it has excellent adhesion. It has been found that stress is easily applied to the chip when the LED is sealed. Further, it has been found that this causes a problem that illuminance deterioration during lighting is severe.

  On the other hand, LEDs using silicone resins or silicone-modified epoxy resins are generally inferior in gas permeability resistance. Therefore, when a silicone resin or a silicone-modified epoxy resin is used as the LED sealing material, coloring on the LED chip is not a problem, but there is a problem that internal components are deteriorated and coloring occurs. . In particular, when used in a living environment, various compounds are floating, and the penetration of such compounds into the interior triggers problems. For example, when used in lighting applications, gas in the environment or the like permeates the LED sealing material, so that the silver component plated on the metal lead frame, which is a component in the LED package (to increase reflectivity) (Which has been subjected to silver plating) is discolored or blackened, and ultimately has a problem of reducing the performance as an LED product (Patent Documents 5 and 6).

  In order to clear this gas permeation resistance problem, Patent Documents 5 and 6 use techniques such as coating a gas permeation-resistant protective agent and coating a metal part with an inorganic material. In addition to an increase in productivity and productivity, there is a problem in that light extraction efficiency is deteriorated due to a difference in refractive index between the covering portion and the sealant.

  The present invention has been made in view of the above prior art, and the object thereof is a curable resin capable of providing a cured product satisfying various physical properties required as an electrical semiconductor material application, particularly as an optical semiconductor sealing material. It is to provide a composition, specifically, it has excellent curability, adhesiveness, light resistance, heat resistance and gas permeability resistance, and resin stress to a chip when used as an LED sealing material An object of the present invention is to provide a curable resin composition that can provide a cured product that is low in illuminance and does not cause illuminance deterioration.

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention shown below.
(1) An epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B), and an acid anhydride (C), and an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin ( A curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount of B) is 1.5 to 40% by weight.
(2) Contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B) and an acid anhydride (C), and includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin ( A curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount of B) is 2 to 40% by weight.
(3) The content of the alicyclic epoxy resin (B) in the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) is 10 × (epoxycyclohexyl group-containing organopolysiloxane ( The curable resin composition according to (1) or (2), wherein the weight average molecular weight of A) / (epoxy equivalent of epoxycyclohexyl group-containing organopolysiloxane (A)) is not more than wt%.
(4) The curable resin composition according to any one of (1) to (3), further comprising a polyvalent carboxylic acid (D).
(5) The said polyvalent carboxylic acid (D) is a compound obtained by reaction of a C6-C6 bifunctional polyhydric alcohol and a saturated aliphatic cyclic acid anhydride. Curable resin composition as described in (4).
(6) The curable resin composition according to any one of (1) to (5) above, wherein the epoxycyclohexyl group-containing organopolysiloxane (A) has a phenyl group in its structure. .
(7) The epoxysiloxane group-containing organopolysiloxane (A) is a chain silicone moiety comprising dimethyl-substituted, diphenyl-substituted or a mixture thereof, and a three-dimensional condensate moiety having an epoxycyclohexyl group (silsesquioxane moiety). The curable resin composition according to any one of (1) to (6) above, wherein the curable resin composition is a block-type compound.
(8) Hardened | cured material formed by hardening | curing the curable resin composition as described in any one of said (1)-(7).
(9) A curable resin composition for optical semiconductor encapsulation, comprising the curable resin composition according to any one of (1) to (7) above.
(10) An optical semiconductor device obtained by curing and sealing with the curable resin composition for optical semiconductor encapsulation described in (9) above.

  The curable resin composition of the present invention is useful for electrical and electronic material applications, particularly as an optical semiconductor sealing material, and has excellent curability, adhesiveness, light resistance, heat resistance, and gas permeability resistance, and an LED sealing material. When used as a hardened material, the resin has little resin stress on the chip and does not cause illuminance deterioration.

Hereinafter, it describes about the curable resin composition of this invention.
The curable resin composition of the present invention contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B), and an acid anhydride (C).
The epoxycyclohexyl group-containing organopolysiloxane (A) is an epoxy resin having an epoxycyclohexyl group in at least its molecule, and is generally synthesized by a sol-gel reaction using trialkoxysilane having an epoxycyclohexyl group as a raw material. Can do. Specifically, Japanese Unexamined Patent Publication No. 2004-256609, Japanese Unexamined Patent Publication No. 2004-346144, WO 2004/072150, Japanese Unexamined Patent Publication No. 2006-8747, WO 2006/003990, Japanese Special JP 2006-104248, WO 2007/135909, JP 2004-10849, JP 2004-359933, WO 2005/100445, JP 2008-174640, etc. Examples thereof include silsesquioxane type organopolysiloxane having the three-dimensional network structure described above.

The structure of the organopolysiloxane in the present invention is not particularly limited, but a substance having an aromatic group in the structure is preferable in terms of compatibility.
Moreover, since the cured | curing material obtained with the normal siloxane compound of a simple three-dimensional network structure becomes hard too much, it is desired to set it as the structure which relaxes hardness. In the present invention, a block structure having a silicone segment and the silsesquioxane structure obtained by the sol-gel reaction in one molecule is preferable (hereinafter referred to as a block-type siloxane compound (A1)). ). That is, the block-type siloxane compound (A1) is a block structure having a chain silicone moiety and a three-dimensional condensate moiety composed of a silsesquioxane structure in one molecule.

  The block type siloxane compound (A1) is not a compound having a repeating unit in a straight chain like a normal block copolymer, but a silsesquioxane structure site that is a three-dimensional network structure is used as a core, A chain-like silicone site extends and bonds to the next silsesquioxane structure site. 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 (A1) is produced using, for example, an alkoxysilane compound (a) represented by the general formula (1) and a silicone oil (b) represented by the general formula (2) as raw materials as described below. If necessary, the alkoxysilane compound (c) represented by the general formula (3) can be used as a raw material. The chain-type silicone part of the block-type siloxane compound (A1) is formed from the silicone oil (b), and the three-dimensional network silsesquioxane part is the alkoxysilane (a) (and the alkoxysilane (c )).
Hereinafter, each raw material will be described in detail.

The alkoxysilane compound (a) is represented by the following formula (1).
XSi (OR ₂ ) ₃ (1)
X in the general formula (1) is not particularly limited as long as it is an organic group having an epoxycyclohexyl group. For example, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) Examples thereof include an alkyl group having 1 to 5 carbon atoms substituted with a cyclohexyl group having an epoxy group such as a butyl group. Among these, an alkyl group having 1 to 3 carbon atoms substituted with a cyclohexyl group having an epoxy group is preferable, and a β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable.

In the general formula (1), a plurality of R ₂ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₂ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of reaction conditions such as compatibility and reactivity.

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

  Silicone oil (b) has the following formula (2)

Is a chain silicone oil having a silanol group at the end having a structure represented by:
In the general formula (2), a plurality of R ₃ 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 an alkenyl having 2 to 10 carbon atoms. Indicates a group. In general formula (2), m represents the number of repetitions.
Examples of the alkyl group having 1 to 10 carbon atoms include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group and the like. Among these, considering light resistance, a methyl group, an ethyl group, a cyclohexyl group, and an n-propyl group are preferable.
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylyl group.
Examples of the alkenyl group having 2 to 10 carbon atoms include alkenyl groups such as vinyl group, 1-methylvinyl group, allyl group, propenyl group, butenyl group, pentenyl group, and hexenyl group.
R ₃ is preferably a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group from the viewpoints of light resistance and heat resistance, and particularly preferably a methyl group or a phenyl group. In the present invention, those having a phenyl group in at least a part of the substituents are particularly preferable from the viewpoint of compatibility.

  M of the compound of General formula (2) shows 3-200 by an average value, Preferably it is 3-100, More preferably, it is 3-50. When m is less than 3, the cured product becomes too hard and the low elastic modulus characteristics are deteriorated. If m exceeds 200, the mechanical properties of the cured product tend to deteriorate, which is not preferable.

  The weight average molecular weight (Mw) of the silicone oil (b) is preferably in the range of 300 to 18,000 (measured value by gel permeation chromatography (GPC)). 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. When 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. When the molecular weight exceeds 18,000, a severe layer separation structure is formed. When used as a material, the permeability becomes poor, making it difficult to use. In the present invention, the molecular weight of the silicone oil (b) can be calculated by polystyrene conversion and weight average molecular weight (Mw) measured under the following conditions using GPC.

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 (A1) 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 (A1) 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 part flexibility. These silicone oils (b) may be used alone or in combination of two or more.

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

In the general formula (3), R ₄ represents a methyl group, a phenyl group or a glycidyl group.
In the general formula (3), a plurality of R ₅ may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₅ is preferably a methyl group or an ethyl group from the viewpoint of reaction conditions such as compatibility and reactivity.

  Specific examples of preferred alkoxysilane (c) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Of these, methyltrimethoxysilane and phenyltrimethoxysilane are preferred.

  In the present invention, the alkoxysilane (c) adjusts the molecular weight of the block-type siloxane compound (A1), 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 using alkoxysilane (c), it is preferable to use alkoxysilane (c) in the range of 5-70 mol% among the total mol of alkoxysilane (a) and (c), and 5-50 mol% is further. Preferably, 10 to 40 mol% is particularly 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.

As a reaction ratio of alkoxysilane (a), silicone oil (b), and alkoxysilane (c), alkoxysilane (a) (and used as necessary) with respect to 1 equivalent of silanol group of silicone oil (b). It is preferable to carry out the reaction between 1.5 and 200, preferably 2 to 200, particularly preferably 2 to 100, with the alkoxy group in alkoxysilane (c)) as an equivalent value.
When the equivalent value exceeds 200, the cured product using the block-type siloxane compound (A1) becomes too hard and the desired low elastic modulus characteristic is lowered.

Hereinafter, a preferred method for producing the block type siloxane compound (A1) will be specifically described.
As a manufacturing method of a block type siloxane compound (A1), it is preferable to pass through the manufacturing process shown by the following (i) and (ii).
Production step (i): A step of carrying out dealcoholization condensation of silanol-terminated silicone oil (b) and alkoxysilane-containing alkoxysilane (a) (and alkoxysilane (c) added if necessary) (ii) : A step of hydrolyzing and condensing alkoxy groups of alkoxysilane (a) (and alkoxysilane (c) added if necessary) by adding water Production steps (i) and (ii) go through each step The reaction can be performed in any order.

Specific examples of preferred production methods include the following three production methods.
<Manufacturing method (I)>
First, as a production process (i), a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) which is a silicon compound having an alkoxy group (and an alkoxysilane (c) which is added if necessary) A step of obtaining an alkoxysilane-modified product (d) by performing alkoxysilane modification on the terminal of the silicone oil by a dealcoholization condensation reaction is performed.
Next, alkoxysilane (a) (and alkoxysilane (c) added as necessary) which is a silicon compound having an alkoxy group as production step (ii), and alkoxy of the silicone oil obtained in production step (i) A method of producing a block-type siloxane compound (A1) by passing water through the silane-modified product (d) and performing a hydrolysis-condensation reaction between alkoxy groups.
<Manufacturing method (b)>
First, as a production step (ii), an alkoxy group in the molecule is obtained by performing a hydrolysis condensation reaction between alkoxy groups by adding water of alkoxysilane (a) (and alkoxysilane (c) added as necessary). The process of obtaining silsesquioxane (e) which has this is performed.
Next, through a step of dealcoholization condensation reaction between the alkoxy group and the silanol group remaining in the silsesquioxane structure by the reaction of the silicone oil (b) and the silsesquioxane (e) as the production step (i), A method for producing a block-type siloxane compound (A1).
<Manufacturing method (c)>
First, as a production step (i), a silicone oil is obtained by a dealcoholization condensation reaction between a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) (and an alkoxysilane (c) added if necessary). After the terminal is changed to alkoxysilane-modified body (d) by modifying it with alkoxysilane, water is added to the system, and alkoxysilane (a) (and alkoxysilane (c)) remaining as a manufacturing step (ii) in one pot And a method of producing a block-type siloxane compound (A1) by carrying out a hydrolysis-condensation reaction between alkoxy groups of the alkoxysilane-modified product (d).

In the present invention, from the viewpoint of shortening the production process, it is preferable to use the above production method (c) in which the reaction is sequentially carried out in one pot.
Hereinafter, the production method (c) will be described more specifically.
When the reaction is carried out in one pot, the silanol having an alkoxy group formed in the production step (ii) is performed in the reverse order of the production method (c) described above, that is, when the production step (ii) is performed after the production step (ii). There is a high possibility that the sesquioxane oligomer and the silicone oil (b) are not compatible with each other, the dealcoholization condensation polymerization does not proceed in the subsequent production step (i), and the silicone oil is left behind. On the other hand, if the method of performing manufacturing process (ii) in one pot after manufacturing process (i) like manufacturing method (c) is used, silicone oil (b) and alkoxysilane (a) or alkoxylane (c) Since the compatibility is relatively high, the problem that the reaction does not proceed without compatibility as described above can be avoided. Furthermore, since a large amount of unreacted low-molecular alkoxysilane is present with respect to the silanol group, it is preferable from the viewpoint of reactivity. When performing in one pot, first, in the production step (i), dealcoholization condensation of silicone oil (b) and alkoxysilane (a) (and alkoxysilane (c) added if necessary) is performed, and the terminal of silicone oil is obtained. Is modified with alkoxysilyl to obtain an alkoxysilane-modified product (d). Since water is not added in the production step (i), hydrolysis condensation between alkoxy groups does not occur, and when the reaction is performed using 3 equivalents or more of alkoxy groups per 1 equivalent of silanol groups, the alkoxysilane modification The body (d) is considered to exist in a structure represented by the following formula (4).

(In the formula (4), R ₂ , R ₃ and m have the same meaning as described above, and R ₆ represents the above X and / or R _4. )

  In the production process (i), when an alkoxy group is reacted in an amount less than 1.0 equivalent with respect to 1 equivalent of a silanol group, since no alkoxy group exists at the end of the production process (i), the process proceeds to the production process (ii). Further, when the alkoxy group is reacted between 1.0 to 1.5 equivalents, two or more alkoxy groups in the alkoxysilane (a) (and the alkoxysilane (c) added as necessary) It will react with the silanol group of the silicone oil (b), and at the end of the production step (i), it will become a polymer and gelation will occur. For this reason, it is necessary to make an alkoxy group react with more than 1.5 equivalent with respect to 1 equivalent of silanol groups. From the viewpoint of reaction control, 2.0 equivalents or more are preferable.

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

The production of the block type siloxane compound (A1) can be carried out without a catalyst, but if it is no catalyst, the reaction proceeds slowly, and it is preferably carried out in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst that can be used, any compound that exhibits acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Inorganic bases such as alkali metal carbonates, and organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base is particularly preferable in terms of easy catalyst removal from the product, and sodium hydroxide and potassium hydroxide are particularly preferable. The amount of the catalyst added is usually 0.001 to 7.5% by weight, preferably 0, based on the total weight of the alkoxysilane (a) (and the alkoxysilane (c) added as necessary) in the reaction system. 0.01 to 5% 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, adding as an aqueous solution using water or the like causes the condensation of the alkoxysilane (a) (and the alkoxysilane (c) to be added as necessary) unilaterally as described above, The silsesquioxane oligomer produced thereby and the silicone oil (b) may not be compatible with each other and may become cloudy.

  The block type siloxane compound (A1) can be produced in the absence of 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), alkoxysilane (c), silicone oil (b), and alkoxysilane-modified product (d). Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, and tetrahydrofuran, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and butanoic acid. Examples thereof include esters such as isopropyl, alcohols such as methanol, ethanol, propanol and butanol, hydrocarbons such as hexane, cyclohexane, toluene and xylene. In the present invention, reaction in alcohols is preferable from the viewpoint of reaction control, and methanol and ethanol are more preferable. The amount of solvent used is not particularly limited as long as the reaction proceeds smoothly, but alkoxysilane (a) (and alkoxysilane (c) added if necessary), a compound of silicone oil (b) Usually, about 0 to 900 parts by weight is used per 100 parts by weight. 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 exhibits acidity or basicity 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. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, Dow Chemical Co., Dowex 66, HCR-S, HCR-W2, MAC-3 and the like can be mentioned.
The adsorbent is added to the reaction solution, followed by treatment such as stirring and heating to adsorb the catalyst, and then the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.

  After completion of the reaction or after quenching, it can be purified by conventional separation and purification means in addition to 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 (A1) can be obtained by removing the solvent by vacuum concentration or the like.

The appearance of the block-type siloxane compound (A1) 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 molecular weight is the equivalent ratio of alkoxysilane (a) (and optionally added alkoxysilane (c)) to silicone oil (b), the molecular weight of silicone oil (b), the amount of water added during the reaction, The reaction time and reaction temperature can be adjusted.
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 of the block type siloxane compound (A1) (measured by the method described in JIS K-7236) is 300 to 1,600 g / eq. Are preferable, and 400 to 1,200 g / eq. Are more preferred. Epoxy equivalent is 300 g / eq. Is less than 1,600 g / eq., The cured product is hard and the elastic modulus tends to be too high. If it exceeds 1, the mechanical properties of the cured product tend to deteriorate, which is not preferable.

  The viscosity of the block-type siloxane compound (A1) (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 (A1) to the total silicon atoms is preferably 8 to 30 mol%, and more preferably 8 to 25 mol%. When the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to the total silicon atoms is less than 8 mol%, the characteristics of the chain silicone sites appear and the cured product tends to be too soft. . Moreover, when it exceeds 30 mol%, the characteristic of the silsesquioxane structure site | part will express and a hardened | cured material will become hard too much. If the cured product becomes too hard, the resin stress on the chip at the time of LED sealing increases, so that the illuminance deterioration of the LED tends to occur.
The proportion of silicon atoms present can be determined by ¹ H NMR, ²⁹ Si NMR, elemental analysis, etc. of the block siloxane compound (A1).

  Moreover, it is desirable that the epoxycyclohexyl group-containing organopolysiloxane (A) and the block type siloxane compound (A1) in the present invention contain a phenyl skeleton in the structure. When the phenyl skeleton is introduced into the block-type siloxane compound (A1), it is contained in at least one of silicone oil (b) and alkoxysilane (a) (and alkoxysilane (c) added if necessary). It only has to be. By having a phenyl skeleton in the structure, the strength and refractive index of the cured product are improved. By improving the refractive index, the light extraction efficiency is improved when used as an optical semiconductor sealing material. The phenyl skeleton also has an effect of filling a space between molecules and preventing gas permeation.

  When a phenyl group is contained as a substituent of the epoxycyclohexyl group-containing organopolysiloxane, the phenyl group is preferably in the range of 1 to 45% by weight in terms of weight in the epoxycyclohexyl group-containing organopolysiloxane. It is particularly preferable to be in the range of ˜30% by weight. If it exceeds 45% by weight, the viscosity becomes high, and the functional group equivalent becomes too large, so that the heat resistance is poor.

The curable resin composition of the present invention contains an alicyclic epoxy resin (B). The alicyclic epoxy resin (B) is introduced in order to impart toughness to the cured product.
The alicyclic epoxy resin (B) is preferably a compound having an epoxycyclohexane structure in the skeleton, and particularly preferably an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and further transesterification reaction of cyclohexene carboxylic acid ester (Japan) And a compound obtained by oxidizing a compound that can be produced by a method described in Japanese Patent Laid-Open No. 2006-052187 or the like.
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. In the present invention, a compound having an epoxycyclohexane structure is also preferable from the viewpoint of improving gas permeability resistance.

  The epoxy equivalent (measured by the method described in JIS K-7236) of the alicyclic epoxy resin (B) is 100 to 500 g / eq. Are preferable, and 100 to 300 g / eq. Are more preferred.

  The molecular weight of the alicyclic epoxy resin (B) is preferably 200 to 1000, more preferably 200 to 600.

  In the curable resin composition of the present invention, the amount of the alicyclic epoxy resin (B) in the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) is 2.0 to 40 wt. Although it can mix | blend so that it may become a part, you may mix | blend so that it may become 1.5 to 40 weight%. If the content of the alicyclic epoxy resin (B) exceeds 40% by weight, the resulting cured product becomes too hard, and cracks are likely to occur when an LED sealing material is used, or the chip is too stressed. Illuminance degradation. On the other hand, when the content of the alicyclic epoxy resin (B) is less than 1.5% by weight, the resulting cured product is brittle, has a high linear expansion coefficient, and has poor adhesion, and as an optical semiconductor sealing material Inferior to suitability. The content of the alicyclic epoxy resin (B) is more preferably 1.7 to 20% by weight, and particularly preferably 1.8 to 20% by weight. Moreover, when increasing content of an alicyclic epoxy resin, content of an alicyclic epoxy resin (B) becomes like this. More preferably, it is 5-20 weight%, Especially preferably, it is 10-20 weight%.

  In addition, the present inventor has recently found that the epoxy resin contained in the epoxycyclohexyl group-containing organopolysiloxane (A) (preferably the block siloxane compound (A1)) has a balance between the hardness and flexibility of the resulting cured product and the light extraction efficiency. It was found that the dispersibility of the group largely depends. Although the epoxycyclohexyl group-containing organopolysiloxane (A) is an effective material from the viewpoints of heat resistance, light resistance, light extraction efficiency, etc., it is brittle and has high linear thermal expansion. Therefore, in the present invention, the alicyclic epoxy resin (B) is introduced in order to give toughness. Usually, in the reaction between epoxy compounds, in order to ideally react the epoxy resin that is the main component, the quantity ratio can be determined by the epoxy equivalent of each other. In addition, by considering the dispersibility of the epoxy group contained in the organopolysiloxane (A), it has been found that a cured product having a balance between hardness and flexibility and excellent light extraction efficiency can be obtained.

In the present invention, the epoxy group dispersibility of the epoxycyclohexyl group-containing organopolysiloxane (A) refers to the weight average molecular weight of the epoxycyclohexyl group-containing organopolysiloxane (A), and the epoxycyclohexyl group-containing organopolysiloxane (A). It means a value divided by an epoxy equivalent (amount of resin containing 1 g equivalent of epoxy (unit: g / eq.)), Whereby the average of epoxy groups contained in one molecule of epoxycyclohexyl group-containing organopolysiloxane (A) The amount can be estimated. The present inventor can determine the amount of alicyclic epoxy resin (B) introduced based on the amount of epoxy groups per molecule, specifically, epoxycyclohexyl group-containing organopolysiloxane (A) and alicyclic epoxy. The amount (% by weight) of the alicyclic epoxy resin (B) in the total amount of the resin (B) is correlated with the amount of epoxy groups per molecule of the epoxycyclohexyl group-containing organopolysiloxane (A). It came to know by experiment. That is, the content (% by weight) of the alicyclic epoxy resin (B) is 10 × (weight average molecular weight of the epoxycyclohexyl group-containing organopolysiloxane (A)) ÷ (epoxycyclohexyl group-containing organopolysiloxane (A). By setting the epoxy equivalent) to less than wt% (ratio P), the flexibility derived from the chain silicone moiety is not impaired, and a cured product having an even better balance between hardness and flexibility can be obtained. Furthermore, an alicyclic epoxy It has been found that when the content (% by weight) of the resin (B) satisfies the above formula (ratio P), the occurrence of resin turbidity can be suppressed and the light extraction efficiency is improved.
By containing at such a blending ratio, the epoxycyclohexyl group-containing organopolysiloxane (A) -acid anhydride (C) (and / or optionally added polyvalent carboxylic acid (D)) is cured during the curing. Cyclic epoxy resin (B) -acid anhydride (C) (and / or polyvalent carboxylic acid (D)) crosslinks can be included. When the alicyclic epoxy resin (B) is more than necessary in the system, a curing system of only the alicyclic epoxy resin (B) -acid anhydride (C) (and / or the polyvalent carboxylic acid (D)) is present. Since it occupies in the cured product, the flexibility derived from the chain silicone moiety is impaired, and there is a risk of becoming a brittle and weak cured product. In the cured product, the alicyclic epoxy resin (B) -acid anhydride (C) (and / or polyvalent carboxylic acid (D))-curing system is low in compatibility with other parts, This may cause a decrease in light extraction efficiency.
By blending the alicyclic epoxy resin (B) in the above proportion, the flexibility derived from the chain silicone moiety is effectively expressed, the cured product has a better balance between hardness and flexibility, and has improved light extraction efficiency. It is possible to obtain
According to the above formula, the greater the amount of epoxy groups per molecule, the greater the amount of alicyclic epoxy resin (B) introduced. On the other hand, the smaller the amount of epoxy groups per molecule, the smaller the amount of alicyclic epoxy resin (B) introduced.
The ratio P calculated from the above formula is desirably 40 or less (that is, the maximum content of the alicyclic epoxy resin (B) is 40% by weight or less). However, the ratio P is an amount within the range of 1.5 to 40% by weight described above. Preferably, the alicyclic epoxy resin (B) is 1.5 to 20% by weight and the ratio P is 40 or less.

The curable resin composition of the present invention contains an acid anhydride (C) as a curing agent. The acid anhydride (C) is excellent in transparency and is excellent in workability because it is liquid.
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-1,2,4-tricarboxylic acid-1,2-anhydride.
In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid Preference is given to acid anhydrides, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.
Further, among the acid anhydrides, the following formula (5)

(Wherein Q represents at least one of a hydrogen atom, a methyl group, and a carboxyl group.) Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid- 1,2-anhydride is preferable, and methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride are particularly preferable.

As for the usage-amount of the acid anhydride (C) in the curable resin composition of this invention, 0.7-1.2 equivalent is preferable with respect to 1 equivalent of epoxy groups of all the epoxy resins. 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. When used in combination with a curing agent such as a polyvalent carboxylic acid to be described later, the total amount of the curing agent used is preferably within the above range.
In the present invention, the acid anhydride (C) is preferably used in combination with the polyvalent carboxylic acid (D) which is another curing agent, and the content when used in combination with the polyvalent carboxylic acid (D) described later is It is desirable to be determined by a ratio, and the range of the following formula is preferable.
W1 / (W1 + W2) = 0.05-0.70
(W1 represents a blended part by weight of the polyvalent carboxylic acid (D), and W2 represents a blended part by weight of the acid anhydride (C).)
In the above, the range of W1 / (W1 + W2) is more preferably 0.05 to 0.60, further preferably 0.10 to 0.55, and particularly preferably 0.15 to 0.4. If it is less than 0.05, there is a strong tendency to increase the volatilization of the acid anhydride (C) during curing, which is not preferable. If it exceeds 0.70, the viscosity becomes high and handling becomes difficult.
When the acid anhydride (C) and the polyvalent carboxylic acid (D) are used in combination, the polyhydric carboxylic acid (D) is produced in excess of the acid anhydride (C) during the production of the polyvalent carboxylic acid (D). A method of making a mixture of acid and acid anhydride is also preferable from the viewpoint of easy operation.

  The polyvalent carboxylic acid (D) used in the present invention is desirably 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 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, they are collectively referred to as a polyvalent carboxylic acid.

As the polyvalent carboxylic acid (D), 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.
The 2- to 6-functional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol, norbornenediol, carbinol-modified silicone oil, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, pentaerythritol, dito Examples include tetraols such as limethylolpropane and hexaols such as dipentaerythritol.

  Particularly preferred polyhydric alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, , 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, carbinol-modified silicone oil, and the like are preferable. -Branched chain structures such as butyl-1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol, carbinol-modified silicone oil Or ring structure Polyhydric alcohols having a siloxane structure is more preferable.

  Here, the carbinol-modified silicone oil is specifically represented by the following formula (4A):

(In the formula (4A), R ₈ represents an alkylene group having 1 to 10 carbon atoms, R ₇ represents a methyl group or a phenyl group, and p represents an average value of 1 to 100.)
The compound shown by these is preferable.

In the formula (4A), specific examples of R ₈ include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups, ethoxyethylene group, propoxyethylene group, Examples thereof include a propoxypropylene group and an ethoxypropylene group. Particularly preferred are propoxyethylene group and ethoxypropylene group.

Next, R ₇ represents a methyl group or a phenyl group, and may be the same or different.

  In the formula (4A), p is an average value of 1 to 100, preferably 2 to 80, more preferably 5 to 30.

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-1,2,4-tricarboxylic acid-1,2-anhydride and the like are preferable, Of these, methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride are preferable.
Although there is no particular designation as a condition for the addition reaction, one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted in a non-catalytic and solvent-free condition at 40 to 150 ° C. and heated to react. Although the method of taking out as it is after completion | finish is mentioned, It is not limited to this reaction conditions.

  The polycarboxylic acid thus obtained is particularly represented by the following formula (6)

(In the formula, plural Qs represent at least one of a hydrogen atom, a methyl group, and a carboxyl group. P is a chain-like, cyclic aliphatic group having 2 to 20 carbon atoms derived from the polyhydric alcohol described above. .) Is preferred. m is preferably 1-7, particularly preferably 2-6.

  Since the polyvalent carboxylic acid (D) as the curing agent component has high crystallinity, there is a concern of causing an increase in viscosity of the epoxycyclohexyl group-containing organopolysiloxane (A) after long-term storage, but the curable resin composition of the present invention. Then, since an alicyclic epoxy resin (B) is an essential component, an increase in viscosity can be suppressed. This is because the alicyclic epoxy resin (B) can dissolve the polyvalent carboxylic acid so as to be compatible with the organopolysiloxane structure, and thus, a curable composition of the polyvalent carboxylic acid which is a curing agent. The amount of introduction of can be increased. Moreover, there exists an effect which improves the gas-permeation resistance of hardened | cured material more by using polyhydric carboxylic acid as a hardening | curing agent.

The curable resin composition of the present invention preferably contains a zinc salt and / or a zinc complex (E) as a curing accelerator.
The zinc salt and / or zinc complex (E) is a salt and / or complex having a zinc ion as a central element, and preferably has a phosphate ester or phosphoric acid as a counter ion and / or a ligand.
In particular, zinc salts and / or zinc complexes of phosphoric acid and phosphoric acid esters of a C 1-30 alkyl group (monoalkyl ester, dialkyl ester, trialkyl ester, or a mixture thereof) are preferred. Examples of the alkyl group include methyl, isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, decanyl, and cetyl groups.

In the present invention, a phosphoric ester of an alkyl group having 3 to 15 carbon atoms is particularly preferred, and the ester may be a mixture or a single product, but the main component is preferably a monoalkyl phosphate.
In particular, the molar ratio of monoalkyl ester, dialkyl ester, and trialkyl ester in the phosphoric acid ester contained (substitute with the purity of gas chromatography. However, since it is necessary to perform trimethylsilylation, there is a difference in sensitivity. In this case, the amount of the monoalkyl ester compound is preferably 50 area% or more at the stage of the trimethylsilylation treatment.
Furthermore, the zinc salt and / or zinc complex used for this invention are obtained by making the obtained phosphoric acid ester react with zinc carbonate, zinc hydroxide, etc. (patent document EP699708 gazette).

As the details of the zinc salt and / or zinc complex of such phosphate ester, the ratio of phosphorus atom to zinc atom (P / Zn) is preferably 1.2 to 2.3, more preferably 1.3 to 2.0. . Especially preferably, it is 1.4-1.9. That is, in a particularly preferred form, the amount of phosphate ester (or phosphate derived from phosphate ester) is 2.0 mol or less per mol of zinc ion, and not a simple ionic structure, some molecules are ion-bonded (or arranged). Those having a structure related by coordinate bond) are preferred. Such a zinc salt and / or zinc complex can also be obtained, for example, by the method described in Japanese National Publication No. 2003-51495.
In addition, as the zinc salt and / or zinc complex (E), zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate, etc.) can be used. 3-20 zinc alkylcarboxylates are preferred.

  In the curable resin composition of the present invention, the content of the zinc salt and / or the zinc complex (E) is zinc relative to the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B). The salt and / or zinc complex (E) is 0.01 to 8% by weight, more preferably 0.05 to 5% by weight, and further 0.1 to 4% by weight. Further, it is particularly preferably 0.1 to 2% by weight.

When the curable resin composition of the present invention is used in an optical material, particularly an optical semiconductor encapsulant, it contains a hindered amine compound as a light stabilizer and a phosphorus compound as an antioxidant as particularly preferable components. That is preferred.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetrame Ru-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] bu Lumalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Polymer of dimethyl acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7- Oxa-3,20-diazadispiro [5,1,11,2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetra Decyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7- Oki -3,20-diazadispiro [5,1,11,2] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11, 2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4- And hindered amine compounds such as piperidinyl).

The following commercially available products can be used as the amine compound that is the light stabilizer.
For example, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, and ADEKA manufactured by Ciba Specialty Chemicals, LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like can be mentioned.

  In the curable resin composition of the present invention, the light stabilizer is used in a weight ratio of 0.005 to 5 with respect to the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B). % By weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight.

  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.
For example, as ADK, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, and ADK STAB C 135A, ADK STAB 3010, and ADK STAB TPP.

  In the curable resin composition of the present invention, the phosphorus compound is used in an amount of 0.005 to 5 by weight with respect to the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B). % By weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight.

The curable resin composition of the present invention includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B) as an epoxy resin, and an acid anhydride (C) and a polyvalent carboxylic acid (D) as a curing agent. It is preferable to contain. The curable resin composition of the present invention comprises an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B) as an epoxy resin, and an acid anhydride (C) and a polyvalent carboxylic acid (as a curing agent). D) It is preferable to contain a zinc salt and / or a zinc complex (E) as an additive. Furthermore, the curable resin composition of the present invention preferably contains a hindered amine light stabilizer and a phosphorus-containing antioxidant as additives.
These can be used in combination with other epoxy resins, curing agents and various additives described below.

  As the epoxy resin component, other epoxy resins that can be used in combination with the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, A triphenylmethane type epoxy resin, a phenol aralkyl type epoxy resin, etc. are mentioned. 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 Solid or liquid epoxy resins such as chemical compounds, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like are not limited thereto. These may be used alone or in combination of two or more.

  When the epoxy cyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) are used in combination with another epoxy resin as the epoxy resin component, the epoxy cyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin The proportion of the total weight of (B) in the total epoxy resin is preferably 60% by weight or more, particularly preferably 70% by weight or more.

Curing agents that can be used in combination with acid anhydride (C) or polycarboxylic acid (D) as the curing agent component are, for example, amine compounds, acid anhydride compounds, amide compounds, phenol compounds, carboxylic acid compounds. Etc. Specific examples of curing agents that can be used include amines and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, etc.) , Reaction product of acid anhydride and silicone alcohol (phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, anhydrous Nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] Hepta Reaction products of acid anhydrides such as -2,3-dicarboxylic acid anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-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 these. These may be used alone or in combination of two or more.
When other curing agents are used in addition to the acid anhydride (C) and polyvalent carboxylic acid (D) as the curing agent component, the total weight of the total weight of the acid anhydride (C) and polyvalent carboxylic acid (D) The proportion in the agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

In the curable resin composition of the present invention, the epoxy resin component containing the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) as essential components, and the acid anhydride (C) as essential components The blending ratio of the curing agent component as a component is such that the curing agent component is 0.7 to 1.2 equivalents, particularly preferably 0.75 to 1.10 equivalents per 1 equivalent of the epoxy group of the epoxy resin component. It is preferable to use a curing agent.
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.

The curable resin composition of the present invention preferably further contains a curing catalyst. When the zinc salt and / or zinc complex (E) is contained in the curable composition, the zinc salt and / or zinc complex (E) itself acts as a curing catalyst, so that the curing catalyst is used. Although it does not need to be added separately, other curing catalysts can be used in combination.
Examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4-methyl) Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-methyl) Imidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole , 2-phenyl-4-hydroxymethyl-5-methylimidazole, various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid , 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-7 Diaza compounds and their tetrapheni Salts such as borates and phenol novolaks, salts with the above polycarboxylic acids, or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (tolyl) phosphine Phosphines and phosphonium compounds such as tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, and curing thereof Examples thereof include a microcapsule-type curing accelerator having a microcapsule as an accelerator. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resin components contained in a curable composition.

The curable resin composition of the present invention may contain various additives and auxiliary materials as listed below.
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 content of the phosphorus-containing compound is preferably an epoxy resin contained in the phosphorus-containing compound / curable composition = 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, there is a concern of adversely affecting 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 0.1% relative to 100 parts by weight of the epoxy resin component and the curing agent component contained in the curable resin composition. 05 to 50 parts by weight, preferably 0.05 to 20 parts by weight are used as necessary.

  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) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When these phosphors are used, the addition amount is 1 to 80 parts by weight, preferably 5 parts per 100 parts by weight of the organic component such as epoxycyclohexyl group-containing organopolysiloxane (A). -60 parts by weight is preferred.

  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.
For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114 IRGANOX 1098, IRGANOX 1520L, Adeka Tab AO-20A Adeka Stub AO-60, Adeka Stub AO-70, Adeka Stub AO-80, Adeka Stub AO-90, Adeka Stub AO-330, manufactured by Sumitomo Chemical Co., Ltd. r 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, although it does not specifically limit as the compounding quantity, In the curable resin composition of this invention, it can add in the quantity which occupies 0.005-5.0 weight%.

  The curable resin composition of this invention is obtained by mixing each component uniformly. The curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin component, a curing agent component, a zinc salt and / or a zinc complex are mixed thoroughly as necessary using an extruder, kneader, roll, planetary mixer, etc., to obtain a curable resin composition. When the obtained curable resin composition of the present invention is in a liquid state, potting, casting, impregnating the base material, pouring the curable resin composition into a mold, casting, and curing by heating Let Further, when the obtained curable resin composition of the present invention is solid, it is molded using a cast after casting or a transfer molding machine, and further cured by heating. In addition, what is necessary is just to add and mix the hardening accelerator, an amine compound, a phosphorus containing compound, a phenol compound, binder resin, an inorganic filler, etc. which are arbitrary components at the said mixing process. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours. As a curing method, curing can be performed at a high temperature at a stretch, but it is preferable to increase 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 epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

  Moreover, the curable resin composition of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, the curable resin composition of the present invention is applied to the release film by applying the varnish, removing the solvent under heating, and forming a B-stage to form a sheet-like adhesive. It can be formed as an agent. 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 epoxy resin, a curing agent, a coupling agent, an antioxidant, a light stabilizer, etc. The epoxy resin composition is prepared by thoroughly mixing the additive, and is used as a sealing material or for both a die bond material and a sealing material. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

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

  Furthermore, the curable resin composition of the present invention can be used for general applications in which curable resins such as epoxy resins are used. For example, adhesives, paints, coating agents, molding materials (sheets, films, FRPs) Etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, acrylic ester resins as resist curing agents, etc. Examples include additives to resins 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 plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute. 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 wire harnesses, 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 the following synthesis examples and examples, “parts” means parts by weight, and “%” means% by weight.

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.

(Synthesis Example 1)
As production step (i), 285 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (GPC measurement value) (silanol equivalent 950, using GPC) 40 parts of a 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), after adding 655 parts of methanol, 123 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 mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic phase under reduced pressure at 100 ° C., 620 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-1) was obtained. The epoxy equivalent of the obtained compound (S-1) was 605 g / eq. The weight average molecular weight was 2120, and the appearance was a colorless and transparent liquid resin. Further, the value of the ratio P was 35, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 18 mol%.

(Synthesis Example 2)
As production step (i), 375 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (GPC measurement value) (silanol equivalent 950, GPC) were used. 40 parts of a 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), after adding 655 parts of methanol, 144 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 mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic phase at 100 ° C. under reduced pressure, 647 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-2) was obtained. The epoxy equivalent of the obtained compound (S-2) was 541 g / eq. The weight average molecular weight was 2,100, and the appearance was a colorless and transparent liquid resin. Moreover, the value of the ratio P was 39, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 20 mol%.

(Synthesis Example 3)
As production step (i), 263 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (measured GPC value) (silanol equivalent 950, using GPC) 40 parts of a 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), after adding 655 parts of methanol, 115 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 mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic phase at 100 ° C. under reduced pressure, 605 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-3) was obtained. The epoxy equivalent of the obtained compound (S-3) was 636 g / eq. The weight average molecular weight was 2090, and the appearance was a colorless and transparent liquid resin. Moreover, the value of the ratio P was 33, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 17 mol%.

(Synthesis Example 4)
As production step (i), 106 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 234 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (measured GPC value) (silanol equivalent 850, using GPC) It was calculated as half the measured 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 75 ° C. Set and warm. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), 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. 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. 380 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 300 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-4). The epoxy equivalent of the obtained compound (S-4) was 729 g / eq. The weight average molecular weight was 2200, and the appearance was a colorless and transparent liquid resin. Further, the value of the ratio P was 30, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 15 mol%.

(Synthesis Example 5)
As the production step (i), 39.4 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 137 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (measured by GPC) (silanol equivalent: 950, GPC) 10 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 10 hours.
As a manufacturing process (ii), after adding 140 parts of methanol, 17.3 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 mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. Subsequently, 200 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. The obtained organic phase was removed at 100 ° C. under reduced pressure to obtain 152 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-5). The epoxy equivalent of the obtained compound (S-5) was 1040 g / eq. The weight average molecular weight was 2290, and the appearance was a colorless and transparent liquid resin. Further, the value of the ratio P was 22, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 10 mol%.

(Synthesis Example 6 (adjustment of curing agent composition (H-1)))
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, and 20 parts of tricyclodecane dimethanol (TCD-AlcholDM manufactured by OXEA), methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika, Ricacid MH) Hereinafter, 100 parts of acid anhydride CDA-1) is added, reacted at 40 ° C. for 3 hours, and then heated and stirred at 70 ° C. for 1 hour (disappearance of tricyclodecane dimethanol by GPC (1 area% or less)) 120 parts of a curing agent composition (H-1) containing a polyvalent carboxylic acid and an acid anhydride was obtained. The resulting colorless liquid resin had a GPC purity of 55 area% for polyvalent carboxylic acid (following formula (F)) and 45 area% for methylhexahydrophthalic anhydride. The functional group equivalent was 201 g / eq. Met.

Formula (F)

(Synthesis Example 7 (adjustment of curing agent composition (H-2)))
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 20 parts of 2,4-diethylpentanediol (Kyowa Hakko Chemical Kyowadiol PD-9), acid anhydride (CDA-1) 100 The reaction was carried out at 40 ° C. for 3 hours and then heated and stirred at 70 ° C. for 1 hour (disappearance of 2,4-diethylpentanediol (1 area% or less) was confirmed by GPC). 120 parts of hardening | curing agent compositions (H-2) containing an acid anhydride were obtained. It was the obtained colorless liquid resin, and the purity by GPC was 50 area% for polyvalent carboxylic acid (following formula (G)) and 50 area% for acid anhydride (CDA-1). The functional group equivalent was 201 g / eq. Met.

Formula (G)

  Epoxy resin (S-1) (S-2) (S-3) obtained in the synthesis example, alicyclic epoxy resin CAE-1 (Nippon Kayaku SEJ-01R (3,4-epoxycyclohexylmethyl-3) ', 4'-epoxycyclohexylcarboxylate))), the curing agent composition obtained in Synthesis Example 6 (a mixture of H-1 acid anhydride and polyvalent carboxylic acid), and a quaternary phosphonium salt as a curing accelerator ( C-1 Nippon Chemical Industry Hishicolin PX4MP) was blended at the blending ratio (parts by weight) shown in Table 1 below and defoamed for 20 minutes. A curable resin composition was obtained.

  Using the obtained curable resin composition, hardness measurement, a thermal durability test, and an adhesion test with silver were performed in the following manner. The results are shown in Table 1. The curing condition is 140 ° C. × 5 hours after 110 ° C. × 2 hours of preliminary curing.

(Hardness (Shore D))
The Shore D hardness was measured according to JIS K6253.

(Heat resistance test (DMA measurement))
The curable resin compositions obtained in the examples and comparative examples were vacuum defoamed for 20 minutes, and then gently poured into a test piece mold having a width of 7 mm, a length of 5 cm, and a thickness of about 800 μm, and then a polyimide film from above. Covered with. The cast was cured under the above conditions to obtain a dynamic viscoelastic test piece. Using these test pieces, a dynamic viscoelasticity test (DMA measurement) was performed under the conditions shown below.
Measurement conditions Dynamic viscoelasticity measuring instrument: TA-2 instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: A material cut into 5 mm × 50 mm was used (thickness was about 800 μm).
-Analysis conditions Tg: The peak point of Tan-δ in DMA measurement was defined as Tg.

(Silver adhesion test (tensile shear test))
Uniformly apply the curable resin compositions obtained in the examples and comparative examples to the end of an SUS base material of 25 mm × 50 mm × thickness 2 mm subjected to Ag plating so that the adhesion area is 25 mm × 10 mm. The same base material is bonded to the coated surface from above, the adhesive surface is fixed with a large clip, and heat cured for a predetermined curing time. A sample was used. Using these samples, a tensile shear test was performed under the conditions shown below.
・ Measurement conditions Tensilon: RTA-500 manufactured by Orientec
Measurement mode: Tensile Movement speed: 3 mm / min / Analysis conditions The tensile shear strength takes the maximum value of breakage, and is converted per bonded area.

In Table 1, when Comparative Example 1 and Example 1 and Example 2 and Comparative Example 3 are compared, the alicyclic epoxy resin is 1.5 to 40% by weight, preferably within the range of the ratio P (% by weight). It has been confirmed that the inclusion of contains not only the hardness (D) but also the heat resistance Tg and adhesive strength.
Comparative Example 2 was prepared in order to obtain a cured product having a hardness (D) equivalent to that of Example 1, but when both were compared, Tg, which is a heat resistant property, could be raised to the same extent. The adhesive strength of Example 1 is significantly higher. This can also be judged from the comparative evaluation of Comparative Example 1 and Example 2.
That is, by adding the alicyclic epoxy resin at 1.5 to 40% by weight, preferably within the range of the ratio P (% by weight), it is possible to develop a level of adhesive strength that cannot be achieved with a polysiloxane structure. Became clear.

For the epoxy resin (S-1) and alicyclic epoxy resin (CAE-1) obtained in the synthesis example, the curing agent composition (H-1) obtained in the synthesis example, and zinc phosphate phosphate as the curing accelerator A complex (XC-9206 manufactured by C-2 King Industry Corporation), hindered amine (TINUVIN 770DF manufactured by L-1 Ciba Specialty Chemical), an antioxidant (A-1 ADEKA ADEKA STAB 260) as a light stabilizer, and the following The curable resin compositions of Example 3 and Comparative Example 4 were obtained by blending at a blending ratio (parts by weight) shown in Table 2 and performing defoaming for 20 minutes.
Using the obtained curable resin composition, the stability of the curable resin composition and the hardness of the cured product were evaluated in the manner described below. The results are shown in Table 2. The curing conditions are 140 ° C. × 5 hours after 110 ° C. × 2 hours of preliminary curing.

(Stability test)
Viscosity at 25 ° C. (E-type rotary viscometer) was measured immediately after blending and after 6 hours, and the stability was evaluated by the degree of increase in the viscosity.

(Hardness (Shore D))
The Shore D hardness was measured according to JIS K6253.

  From this result, it can be seen that when one solution is used, the viscosity after 6 hours has a relatively low rate of increase in viscosity relative to the initial value, and is a more stable composition.

  For the epoxy resins (S-4) and (S-5) obtained in the synthesis examples and the alicyclic epoxy resin (CAE-1), the curing agent composition (H-1) obtained in synthesis example 6 and synthesis. Curing agent composition (H-2) obtained in Example 7, phosphate ester zinc complex (C-2) as curing accelerator, hindered amine (L-1) as light stabilizer, antioxidant (O-1) The curable resin compositions of Examples 4 to 6 and Comparative Example 5 were obtained by blending at a blending ratio (parts by weight) shown in Table 3 below and performing defoaming for 20 minutes. Furthermore, the obtained curable resin composition was cured in the following manner, and the transmittance and light resistance were evaluated.

(Transmissivity test)
The curable resin compositions of Examples and Comparative Examples were gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. The casting was cured at 110 ° C. for 1 hour after 110 ° C. × 3 hours of precuring to obtain a transmittance test piece having a thickness of 1 mm. The transmittance of each cured product at 460 nm was compared.

(UV durability transmission test)
The curable resin compositions of Examples and Comparative Examples were defoamed in a vacuum for 20 minutes, and then gently cast into an aluminum cup having a bottom diameter of 5 cm and a height of 2 cm. The cast was placed in an oven and cured under the same curing conditions as in the above transmittance test to obtain a 2 mm thick test piece for permeability. Using these test pieces, the transmittance (measurement wavelength: 375 nm, 400 nm, 465 nm) before and after ultraviolet irradiation was measured with a spectrophotometer, and the rate of change was calculated. The ultraviolet irradiation conditions are as follows.
Ultraviolet irradiation machine: Eye super UV tester SUV-W11
Temperature: 60 ° C
Irradiation energy: 50-60 mW / cm ²
Irradiation time: 100 hours

  From these results, the curable resin composition of the present invention has the same level of light resistance as an unmixed product in spite of containing an alicyclic epoxy resin, and has no inferior optical properties. It was confirmed that it was.

  For the epoxy resin (S-4) and alicyclic epoxy resin (CAE-1) obtained in Synthesis Example, the curing agent composition (H-1) obtained in Synthesis Example 6 and phosphate ester as a curing accelerator Zinc complex (C-2), hindered amine (L-1) and antioxidant (O-1) are used as light stabilizers and blended at the blending ratio (parts by weight) shown in Table 4 below for 20 minutes. By performing defoaming, the curable resin compositions of Examples 7 and 8 were obtained.

(LED lighting test)
Using the obtained curable resin composition, it was filled into a syringe and poured into a surface-mount LED package having an outer diameter of 5 mm square and an outer diameter of 3 mm square on which a chip having a central emission wave of 465 nm was mounted using a precision discharge device. . The casting was put into a heating furnace and cured at 120 ° C. for 1 hour and 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). Detailed conditions are shown below. As a measurement item, the illuminance before and after lighting for 200 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated. In this test, the driving environment was performed under high humidity and high temperature.

-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 the above results, it was confirmed that the curable resin composition of the present invention exhibited high illuminance retention even in an accelerated test in which an excessive current was passed at high temperature and high humidity, and had high characteristics as an LED.

  For the epoxy resin (S-4) and alicyclic epoxy resin (CAE-1) obtained in the synthesis examples, as a curing agent composition (H-1), an acid anhydride (CDA-1), and a curing accelerator. Quaternary phosphonium salt (C-1), hindered amine (L-2 Ciba Specialty Chemicals TINUVIN 144), antioxidant (O-2 Adeka Adeka Stub AO60) and additive (O-3 Adeka) The curable resin compositions of Examples 9 to 11 and Comparative Examples 6 and 7 are obtained by using Adeka Stub 3010) and defoaming for 20 minutes by blending at the blending ratio (parts by weight) shown in Table 5 below. It was.

(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 casting was put into a heating furnace and cured at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to produce an LED package. The LED package was left in a corrosive gas under the following conditions, and the color change of the silver-plated lead frame part inside the seal was observed. The results are shown in Table 5.
・ Measurement condition Corrosion gas: 20% aqueous solution of ammonium sulfide (discolors 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.
-Analysis conditions Corrosion judgment: The time when the lead frame inside the LED package was discolored black (referred to as blackening) was observed, and it was judged that the longer the discoloration time, the better the corrosion resistance. Observations were taken out after 10 minutes, 2 hours, and 6 hours, and confirmed, and evaluation was described as ○ for undiscolored products, × for brown-brown materials, and XX for completely blackened materials.

  From the above results, it is clear that the curable resin compositions of the examples do not discolor the lead frame silver plating as compared with the curable resin compositions of the comparative examples (containing a polysiloxane compound and an acid anhydride). It was found that it was excellent in long-term corrosion gas resistance.

Synthesis example A
Stirrer, reflux condenser, a flask equipped with a stirrer, while performing nitrogen purge both terminals carbinol-modified silicone (X22-160AS Shin-Etsu Chemical Co., Ltd., in the formula (4A), _{R 7} is a methyl group A compound in which R ₈ is a propoxyethylene group.) 500 parts and 168 parts of Ricacid MH (4-methylhexahydrophthalic anhydride, manufactured by Shin Nippon Chemical Co., Ltd.) were charged into a reaction vessel and reacted at 80 ° C. for 4 hours. As a result, 668 parts of a colorless transparent liquid polycarboxylic acid (H-4) was obtained.

Example A-F, Comparative Examples A and B
Using the polyvalent carboxylic acid (H-4) obtained in Synthesis Example A for the epoxy resin (S-2) and alicyclic epoxy resin (CAE-1) obtained in Synthesis Example, 2-ethylhexane Use of zinc oxide (Hope Pharmaceutical Co., Ltd., hereinafter referred to as C-3), hindered amine (LA-81 manufactured by Adeka, hereinafter referred to as L-3), phosphorus compound (Adeca 260, hereinafter referred to as O-4) And it mix | blended with the compounding ratio (weight part) shown in following Table 6, defoamed for 20 minutes, and obtained the curable resin composition for this invention or for a comparison.
Using the obtained curable resin composition, various tests were performed in the following manner. The results are shown in Table 6.

(1) Reflow test;
The resulting curable resin composition is vacuum degassed for 20 minutes, then filled into a syringe, and a precision discharge device is used to flatten the opening on a surface-mounted LED equipped with a light emitting device having an emission wavelength of 465 nm. So casted. After pre-curing at 120 ° C. for 3 hours, it was cured at 150 ° C. for 2 hours to seal the surface-mounted LED. The test LED obtained was subjected to moisture absorption at 30 ° C. and 70% × 72 Hr, and then a test LED reflector (made of polyamide) under the following reflow conditions using a high-temperature observation apparatus (manufactured by SMT Scope SK-5000, Sanyo Seiko Co., Ltd.) ) Was confirmed. The test is performed with n = 3, and the evaluation is performed by (number of NG) / (number of tests).
The temperature was raised from 25 ° C. to 150 ° C. at 2 ° C./second, then held at 150 ° C. for 2 minutes, further heated to 260 ° C. at 2 ° C./second, and maintained at 10 ° C., then 1.3 ° C. It cools to room temperature at / second.
(2) Heat cycle test The heat cycle test requires a cycle of −40 ° C. × 15 minutes to 120 ° C. × 15 minutes for temperature increase and decrease in the thermal shock test after blending, casting and curing as in (1). The time was repeated 2 times for 50 minutes, and the presence or absence of cracks in the test LED was visually observed. The test is performed with n = 5, and the evaluation result is expressed as (NG number) / (test number).

  From the above results, it can be seen that the curable resin composition of the present invention has higher toughness than the comparative example, has fewer cracks due to heat cycle, and can solve problems such as peeling from the reflector due to reflow.

Synthesis example B
To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean Stark tube, while purging with nitrogen, 150 parts of toluene, 2,4-diethyl-1,5-pentanediol (Kyowa Hakko Chemical Co., Ltd. Kyowa All PD9) ) 80 parts, 126 parts of 3-cyclohexenecarboxylic acid and 2 parts of paratoluenesulfonic acid were added, and the reaction was carried out under heating and refluxing for 10 hours while removing water. After completion of the reaction, the diolefin compound of the present invention is washed with 50 parts of 10% aqueous sodium hydrogen carbonate solution twice, the organic layer obtained is washed twice with 50 parts of water, and then the organic solvent is concentrated with a rotary evaporator. 187 parts of (D-1) was obtained. The shape was liquid, the purity by gas chromatography was 96%, and the result of analysis by gel permeation chromatography confirmed that the purity was> 98%.

Synthesis example C
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, di-cured tallow alkyldimethylammonium acetate 2.7 parts (50% hexane solution made by Lion Akzo, Acquard 2HT acetate) was added to form a tungstic acid catalyst, 120 parts of toluene and 94 parts of diolefin compound D-1 were added, and the mixture was stirred again. Thus, a liquid in an emulsion state was obtained. The temperature of this solution was raised to 50 ° C., and while stirring vigorously, 55 parts of 35% aqueous hydrogen peroxide was added and stirred as it was at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by GC, the substrate conversion after the completion of the reaction was> 99%, and the raw material peak disappeared.
Then, after neutralizing with 1% aqueous sodium hydroxide solution, 25 parts of 20% aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 20 parts of activated carbon (CAP SUPER made by NORIT) and 20 parts of montmorillonite (Kunimine Industries Kunipia F) were added, and the mixture was stirred at room temperature for 3 hours and then filtered. The obtained filtrate was washed with 100 parts of water three times, and 90 parts of alicyclic epoxy resin (CAE-2) was obtained by distilling off the organic solvent from the obtained organic layer. Epoxy equivalent was 216 g / eq. Met.

Synthesis example D
To a flask equipped with a stirrer, reflux condenser, stirrer, and Dean-Stark tube, while purging with nitrogen, 100 parts of toluene, 126 parts of 3-cyclohexene-1-carboxylic acid, 98 parts of tricyclopentadecane dimethanol, p-toluene 3 parts of sulfonic acid was added, and the reaction was carried out for 15 hours while dehydrating under a reflux condition using a Dean-Stark tube. After completion of the reaction, 5 parts of sodium tripolyphosphate was added and stirred at 100 ° C. for 1 hour. After cooling to room temperature, 300 parts of methyl isobutyl ketone was added, washed with 300 parts of water three times, 100 parts of silica gel and 1 part of activated carbon were added to the resulting organic layer, and the mixture was stirred at room temperature for 2 hours, followed by filtration. It was. 190 parts of diolefin compound D-2 was obtained by removing a solvent etc. from the obtained filtrate.

Synthesis example E
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 12 parts of water, 0.38 part of 12-tungstophosphoric acid, 0.56 part of phosphoric acid and sodium carbonate are added while purging with nitrogen, and the pH is 4.7. Adjusted. Furthermore, after adding 0.6 parts of trioctylmethylammonium chloride (manufactured by Tokyo Chemical Industry) to produce a tungstic acid catalyst, 50 parts of toluene and 41 parts of diolefin compound D-2 were added and stirred again. An emulsion was obtained. The solution was heated to 50 ° C., and 24.8 parts of 30% aqueous hydrogen peroxide was added with vigorous stirring, followed by stirring at 50 ° C. for 15 hours. Next, 20 parts of a 1% aqueous sodium hydroxide solution and 10 parts of a 20% aqueous sodium thiosulfate solution were added, stirred for 1 hour, and allowed to stand. The organic layer separated into two layers was taken out, and 30 parts of toluene was added to the obtained aqueous layer to extract organic substances in the aqueous layer. This was repeated twice more and the resulting organic layers were mixed. 20 parts of activated carbon (CAP SUPER made by NORIT) and 20 parts of montmorillonite (Kunimine Industries Kunipia F) were added thereto, and the mixture was stirred at room temperature for 3 hours and then filtered. The obtained filtrate was washed with 100 parts of water three times, and 40 parts of alicyclic epoxy resin (CAE-3) was obtained by distilling off the organic solvent from the obtained organic layer. Epoxy equivalent was 233 g / eq. Met.

Example G-K Comparative Example CD
Alicyclic epoxy resin (CAE-1), alicyclic epoxy resin (CAE-2) (CAE-3) obtained in Synthesis Examples C and E, and epoxy resin (S-) obtained in Synthesis Example 5 in the same manner 5) was used and blended at the blending ratio (parts by weight) shown in Table 7 below and defoamed for 20 minutes to obtain the epoxy resin compositions of Examples and Comparative Examples. The turbidity of the obtained epoxy resin composition was judged and evaluated visually. In addition, the epoxy equivalent of an epoxy resin (S-5) is 1040 g / eq. The weight average molecular weight is 2290, and the value of the ratio P is 22.

  From the above results, the blending amount (% by weight) of the alicyclic epoxy resin (B) is 1.5 to 40% by weight, and the ratio P is determined based on the dispersibility of the epoxycyclohexyl group-containing organopolysiloxane (A). By introducing it so as to satisfy, resin turbidity can also be suppressed.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2010-045927) for which it applied on March 2, 2010, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

Claims (10)

  It contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B) and an acid anhydride (C), and includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B). The curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount is 1.5 to 40% by weight.   It contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B) and an acid anhydride (C), and includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B). A curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount is 2 to 40% by weight.   The content of the alicyclic epoxy resin (B) in the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) is 10 × (epoxycyclohexyl group-containing organopolysiloxane (A). 3. The curable resin composition according to claim 1 or 2, wherein the weight average molecular weight) / (epoxy equivalent of epoxycyclohexyl group-containing organopolysiloxane (A)) is not more than wt%.   Furthermore, polyhydric carboxylic acid (D) is contained, The curable resin composition as described in any one of Claims 1-3 characterized by the above-mentioned.   5. The compound according to claim 4, wherein the polycarboxylic acid (D) is a compound obtained by a reaction of a bifunctional or polyfunctional alcohol having 5 or more carbon atoms with a saturated aliphatic cyclic acid anhydride. The curable resin composition described.   The said epoxy cyclohexyl group containing organopolysiloxane (A) has a phenyl group in the structure, The curable resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.   The epoxycyclohexyl group-containing organopolysiloxane (A) has a chain silicone moiety composed of dimethyl substitution, diphenyl substitution or a mixture thereof, and a three-dimensional condensate moiety (silsesquioxane moiety) having an epoxycyclohexyl group. It is a block type compound, The curable resin composition as described in any one of Claims 1-6 characterized by the above-mentioned.   Hardened | cured material formed by hardening | curing the curable resin composition as described in any one of Claims 1-7.   The curable resin composition for optical semiconductor sealing which consists of a curable resin composition as described in any one of Claims 1-7.   An optical semiconductor device obtained by curing and sealing with the curable resin composition for optical semiconductor encapsulation according to claim 9.