JP5730852B2 - Method for producing organopolysiloxane, organopolysiloxane obtained by the production method, and composition containing the organopolysiloxane - Google Patents

Description

  The present invention relates to a method for producing an organopolysiloxane containing an epoxy group suitable for use in electrical and electronic materials, particularly for optical semiconductors, an organopolysiloxane obtained by the production method, and a composition containing the organopolysiloxane.

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, an alicyclic epoxy resin represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate is more transparent than a glycidyl ether type epoxy resin composition having an aromatic ring. Since it is excellent in terms, 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 Patent No. 4205368

Because of the problem of durability of the epoxy resin, a resin having a siloxane skeleton (specifically, a skeleton having a Si—O bond) introduced as a silicone resin or a silicone-modified epoxy resin is used as a sealing material. (Patent Document 3).
Such a compound containing a siloxane skeleton has been reported to have problems such as poor thermal stability of the resin itself and gelation during long-term storage as compared with ordinary epoxy resins (Patent Document 4). This is due to the reaction between the remaining alkoxy groups and silanol groups, and when left at a high temperature, the molecular weight increases, eventually resulting in gelation or increased viscosity. Considering safety and stability, it is urgent to solve this problem.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
Step 1:
A step of obtaining a modified silicone oil by reacting a silicone having a silanol structure at the terminal having a weight average molecular weight of 1000 to 3000 with an alkoxysilane compound; and
Step 2:
In the method for producing an organopolysiloxane (A) including a step of polymerizing modified silicone oils and / or an alkoxysilane compound by hydrolysis reaction,
(A) At least one of the alkoxysilane compounds to be used has a glycidyl group and / or an epoxycyclohexyl group in the molecule,
(B) The epoxy group obtained by reacting in the presence of 2 to 100% by weight of an alcohol having 1 to 10 carbon atoms with respect to the total weight of the silicone oil having a silanol structure and the alkoxysilane compound in Step 1 Containing organopolysiloxane (A).
(2)
Step 1:
A step of reacting a silicone oil having a silanol structure at the terminal having a weight average molecular weight of 1000 to 3000 with an alkoxysilane compound to obtain a modified silicone oil Step 2:
In the method for producing an organopolysiloxane (A) including a step of polymerizing modified silicone oils and / or an alkoxysilane compound by hydrolysis reaction,
(A) At least one of the alkoxysilane compounds to be used has a glycidyl group and / or an epoxycyclohexyl group in the molecule,
(B) An epoxy group that is reacted in the presence of 2 to 100% by weight of an alcohol having 1 to 10 carbon atoms with respect to the total amount of the silicone oil having a silanol structure and the alkoxysilane compound in Step 1; A method for producing an organopolysiloxane.
(3)
The organopolysiloxane according to (1), wherein the reaction is performed in the presence of an alcohol having 1 to 10 carbon atoms in Step 2.
(4)
The organopolysiloxane according to (1) or (3), wherein the alcohol having 1 to 10 carbon atoms is a primary alcohol.
(5)
The organopolysiloxane according to (1) or (3), wherein the alcohol having 1 to 10 carbon atoms is a mixture of a primary alcohol and a secondary alcohol.
(6)
The organopolysiloxane according to any one of (1) and (3) to (5), wherein at least one of a silicone oil having a silanol structure at the terminal and an alkoxysilane compound has a phenyl group. .
(7)
The epoxy equivalent of the resulting organopolysiloxane (A) is 300-1500 g / eq. The organopolysiloxane according to any one of (1) and (3) to (6), wherein
(8)
(1) An epoxy resin composition comprising the organopolysiloxane (A) according to any one of (3) to (7) and an acid anhydride (B).
(9)
(1) The polyvalent carboxylic acid having the organopolysiloxane (A) according to any one of (3) to (7) and two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton An epoxy resin composition comprising (C).
(10)
A cured product obtained by curing the epoxy resin composition according to (8) or (9).

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition containing the epoxy resin (organopolysiloxane containing an epoxy group) which has the siloxane structure excellent in thermal stability can be provided, and hardening containing this epoxy resin composition The resin composition is useful in a wide range of applications such as electrical / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, etc., and particularly for materials that require optical properties, such as for optical semiconductors. It is extremely useful as an adhesive or sealing material for LED products and the like.

In the manufacturing method of the organopolysiloxane (A) containing an epoxy group of the present invention, the following steps 1 and 2 are performed.
(Process 1)
A process of obtaining a modified silicone oil by reacting a silicone oil having a silanol structure at the terminal with an alkoxysilane compound (process 2)
Step of polymerizing by hydrolysis reaction between modified silicone oils and / or alkoxysilane compound In the present invention, the reaction is carried out in two steps (feature 1), and particularly in step 1, the reaction is carried out in the presence of alcohol. (Feature 2) is characteristic.
In the feature 1, by dividing the reaction into two stages, it is possible to form a structure in which as many functional groups as possible are introduced into the molecular chain of the modified silicone oil. Although this reaction is possible even in one step, the reaction between silanol and alkoxy group and the polymerization reaction between alkoxysilanes become a competitive reaction, resulting in heterogeneous compounds due to differences in reaction rates and product compatibility. May be obtained, or the silicone oil having no functional group may be left behind to adversely affect the product. According to the present invention, a block-type oligosiloxane structure having a structure in which a silicone oil segment in which silicone oil is incorporated and a polymer of an alkoxysilane compound enters each in order is performed by performing a reaction in two steps. Thus, these problems can be avoided.
In Feature 2, since the reaction between the silanol and the alkoxysilane compound is a dealcoholization reaction, the presence of the alcohol has a function of suppressing the reaction and is not preferable.
However, in the present invention, there is an effect that the excessive progress of the dealcoholization reaction can be controlled and the increase in the excessive molecular weight can be suppressed by intentionally adding alcohol. Such control of the reaction is industrially useful from the viewpoint of stabilizing the quality. By using the organopolysiloxane containing epoxy groups thus obtained, the present inventors succeeded in obtaining a cured product with extremely high flexibility. Furthermore, by suppressing the molecular weight from becoming too large, a cured product that hardly peeled off from the substrate during reflow could be obtained.

Hereinafter, it describes in detail about the manufacturing method (process 1) of the epoxy resin of this invention.
The silicone oil having a silanol structure at the end is represented by the following formula (1)

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

  M of the compound of General formula (1) 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 having a silanol structure at the terminal is preferably in the range of 1000 to 3000 (GPC). When the weight average molecular weight is less than 1000, the properties of the chain silicone part of the characteristic segment are difficult to be obtained. When the weight average molecular weight exceeds 3000, it has a severe layer separation structure. It becomes difficult.
In the present invention, the molecular weight of the silicone oil having a silanol structure at the terminal is a weight average molecular weight (Mw) calculated in terms of polystyrene based on a value measured under the following conditions using GPC (gel permeation chromatography). Means.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  Specific examples of preferable silicone oil having a silanol structure at the terminal include the following product names. For example, as manufactured by Toray Dow Corning, PRX413, BY16-873, manufactured by Shin-Etsu Chemical Co., Ltd. as X-21-5841, KF-9701, manufactured by Momentive as XC96-723, TSR160, YR3370, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, YF3804, XF3905, manufactured by Gelest, DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS- S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-1615, PDS-9931 and the like. Among these, PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21 from the viewpoint of molecular weight and kinematic viscosity PDS-1615 is preferred. Among these, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight in order to give the silicone segment flexibility characteristics. These silicone oils having a silanol structure at their ends may be used alone or in combination of two or more.

  The alkoxysilane compound is a compound represented by the following formula (2) or a mixture of a plurality of types of alkoxysilane compounds containing a compound represented by the following formula (2) as an essential component.

一般式（２）中のＸとしては、エポキシ基を有する有機基であれば特に制限はない。例えば、β−グリシドキシエチル、γ−グリシドキシプロピル、γ−グリシドキシブチル等のグリシドオキシ基で置換された炭素数１〜４のアルキル基、グリシジル基、β−（３，４−エポキシシクロヘキシル）エチル基、γ−（３，４−エポキシシクロヘキシル）プロピル基、β−（３，４−エポキシシクロヘプチル）エチル基、４−（３，４−エポキシシクロヘキシル）ブチル基、５−（３，４−エポキシシクロヘキシル）ペンチル基等のオキシラン基を持った炭素数５〜８のシクロアルキル基で置換された炭素数１〜５のアルキル基が挙げられる。これらの中で、グリシドオキシ基で置換された炭素数１〜３のアルキル基、エポキシ基を有する炭素数５〜８のシクロアルキル基で置換された炭素数１〜３のアルキル基として、例えば、β−グリシドキシエチル基、γ−グリシドキシプロピル基、β−（３，４−エポキシシクロヘキシル）エチル基が好ましく、特にβ−（３，４−エポキシシクロヘキシル）エチル基が好ましい。

X in the general formula (2) is not particularly limited as long as it is an organic group having an epoxy group. For example, an alkyl group having 1 to 4 carbon atoms substituted with a glycidoxy group such as β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, glycidyl group, β- (3,4-epoxy (Cyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, 4- (3,4-epoxycyclohexyl) butyl group, 5- (3, And an alkyl group having 1 to 5 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as a 4-epoxycyclohexyl) pentyl group. Among these, as an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group, an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy group, for example, β A glycidoxyethyl group, a γ-glycidoxypropyl group, and a β- (3,4-epoxycyclohexyl) ethyl group are preferable, and a β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable.

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

  Specific preferred examples of the alkoxysilane compound include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like are mentioned, and in particular, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is used. preferable. These alkoxysilane compounds may be used alone or in combination of two or more kinds, and may be used in combination with the alkoxysilane compound shown below.

The alkoxysilane compound that can be used in the present invention has the structure of the following formula (3).

一般式（３）中のＲ_３は、メチル基、シクロヘキシル基、フェニル基を示す。

R ₃ in the general formula (3) represents a methyl group, a cyclohexyl group, or a phenyl group.

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

  Specific examples of preferred alkoxysilane compounds that can be used in combination include methyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Of these, methyltrimethoxysilane and phenyltrimethoxysilane are preferred.

  In the present invention, it is possible to increase the refractive index and reduce the gas permeability by using a compound having an aromatic skeleton for at least one of the silicone oil having a silanol structure and the alkoxysilane compound at the terminal to be used. From the viewpoint, it is preferable to use a compound having a phenyl group. In particular, it is preferable that the silicone oil having a silanol structure at the terminal has a phenyl group. This is because by using a silicone oil introduced with a phenyl group, an excessive increase in viscosity of the organopolysiloxane can be suppressed, whereas when an alkoxysilane compound with a phenyl group is used, the increase in viscosity increases. This is because workability may be inferior.

  In step 1, when 1 alkoxyl silanol group having a silanol structure at the terminal is reacted with an alkoxy group in an amount smaller than 1.5 equivalents, two or more alkoxy groups in the alkoxysilane compound are converted to silanol at the terminal. It will react with the silanol group of the silicone oil having the structure, and at the end of Step 1, it becomes too high in polymer and gelation occurs. For this reason, it is necessary to make an alkoxy group react with 1.5 equivalent or more with respect to 1 equivalent of silanol groups. From the viewpoint of reaction control, 2.0 equivalents or more are preferable.

This reaction is characterized in that the reaction is carried out in the presence of an alcohol in Step 1. Examples of the alcohol that can be used include alcohols having 1 to 10 carbon atoms, specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, and cyclopentanol. Etc. In the present invention, primary alcohols and secondary alcohols are preferable, and it is particularly preferable to use primary alcohols or a mixture of primary alcohols and secondary alcohols. Examples of primary alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, nonane alcohol, decane alcohol, propylene glycol, and the like. Examples of secondary alcohols include isopropanol, cyclohexanol, propylene glycol. Etc. Moreover, from the problem of subsequent removal performance, low molecular weight alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol are preferable. These alcohols may be used as a mixture. When they are mixed, they are preferably two or more selected from primary alcohols and secondary alcohols, and at least one component contains primary alcohols. It is preferable because the solubility of the catalyst described later is excellent. The amount of primary alcohol is preferably 5% by weight or more, more preferably 10% by weight or more of the total alcohol amount.
By using a secondary alcohol in combination with this reaction, the amount of change in the weight average molecular weight per unit time of the reaction system in Step 1 is smaller than when only the primary alcohol is used, so that the reaction can be controlled more easily. is there. In general, in the case of large-scale reactions such as industrial production, it becomes difficult to strictly control the reaction time and reaction temperature, so the combined use of secondary alcohols is particularly important for large-scale reactions such as industrial production from the viewpoint of reaction control. Useful for.
In step 1, the amount of alcohol used is preferably 2% by weight or more based on the total weight of the silicone oil having a silanol structure at the terminal and the alkoxysilane compound. More preferably, it is 2 to 100 weight%, More preferably, it is 3 to 50 weight%, Especially preferably, it is 4 to 40 weight%.
When the amount exceeds 100% by weight, the progress of the reaction becomes extremely slow. When the amount is less than 2% by weight, the reaction other than the target reaction proceeds, the molecular weight increases, gelation, increase in viscosity, and use as a cured product. As a result, there arises a problem that the elastic modulus increases so that it becomes difficult.
In this reaction, other solvents may be used in combination as necessary.
Examples of solvents that can be used in combination include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene, and xylene. However, the addition of these solvents is not preferred in this reaction.

Although the production of the organopolysiloxane (A) containing an epoxy group of the present invention can be carried out without a catalyst, the reaction proceeds slowly with no catalyst. Therefore, 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, a basic catalyst is particularly preferable, and an inorganic base is preferable in terms of easy catalyst removal from the product. Specifically, alkali metal salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, or alkaline earth metal salts, particularly hydroxides are preferable.
The addition amount of the catalyst is usually 0.001 to 5% by weight, preferably 0.01 to 2% by weight, based on the total weight of the silicone oil having a silanol structure at the terminal and the alkoxysilane compound.
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 a sol-gel reaction other than the target reaction to proceed competitively, causing the polycondensation of the alkoxysilane compound to proceed unilaterally, and thereby generated. Care must be taken because the reactant and the silicone oil may become incompatible and become cloudy.
The allowable range of moisture at this time is 0.5% by weight or less, more preferably 0.3% by weight or less, based on the total weight of the silicone oil having a silanol structure at the terminal and the alkoxysilane compound, and there is no water as much as possible. Is more preferable.

  The reaction temperature in Step 1 is usually 20 to 160 ° C., preferably 40 to 100 ° C., particularly preferably 50 to 95 ° C., although it depends on the amount of catalyst and the solvent used. The reaction time is usually 1 to 20 hours, preferably 3 to 12 hours.

  Thus, the modified silicone oil obtained in step 1 is considered to have a structure as shown in the following formula (4) as a main component (the structure is difficult to confirm and can be accurately identified. Can not.).

一般式Ｒ_１、Ｒ_２、Ｘは前記と同様の置換基を表す。

General formula R < ₁ >, R < ₂ >, X represents the same substituent as the above.

Hereafter, it describes in detail about the manufacturing method (process 2) of the epoxy resin of this invention.
After completion of the reaction in Step 1, water is added, and polymerization (sol-gel reaction) of the remaining alkoxy groups of the modified silicone oil obtained in Step 1 is performed. At this time, if necessary, the above-mentioned alkoxysilane compound and catalyst may be added within the range of the above-mentioned amounts. This reaction can be performed by (1) modified silicone oils and / or (2) modified silicone oils and alkoxysilane compounds, and / or (3) alkoxysilane compounds, and (4) alkoxysilanes. In this step, a polymerization reaction is performed between a partially polymerized compound and a modified silicone oil. The polymerization reactions (1) to (4) are considered to proceed in parallel at the same time.
In particular, in the step 2, as in the previous case, the basic inorganic catalyst is preferable as the catalyst, and a necessary amount may be added in the step 1 in advance. However, it is not preferable to exceed the range described as a preferred embodiment in Step 1.

In step 2, it is preferable to add a solvent.
As in Step 1, alcohol is preferably used as the solvent in Step 2. Examples of the alcohol that can be used include alcohols having 1 to 10 carbon atoms, specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, and cyclopentanol. Etc. In the present invention, primary alcohols and secondary alcohols are particularly preferred, and primary alcohols are particularly preferred. Moreover, from the problem of subsequent removal performance, low molecular weight alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol are preferable. These alcohols may be used as a mixture. The presence of these alcohols contributes to molecular weight control and stability.
The amount of alcohol added is 20 to 200% by weight, preferably 20 to 150% by weight, particularly preferably 30 to 120% by weight based on the total weight of the silicone oil having a silanol structure at the terminal and the alkoxysilane compound charged in Step 1. %.

In step 2, water is added. (Ion exchange water, distilled water, and clean water can be used)
The amount of water used is 0.5 to 8.0 equivalents, more preferably 0.6 to 5.0 equivalents, and particularly preferably 0.65 to 2.0 equivalents relative to the amount of remaining alkoxy groups.
When the amount of water is less than 0.5 equivalent, the progress of the reaction slows down, causing problems such as the alkoxysilane compound remaining unreacted, or a sufficient network cannot be formed. There is a possibility of causing poor curing even after curing. On the other hand, if it exceeds 8.0 equivalents, the molecular weight control is not effective and the molecular weight becomes higher than necessary. Furthermore, there is a possibility of inhibiting the stability of the epoxy resin.

  The reaction temperature in step 2 is usually 20 to 160 ° C., preferably 40 to 100 ° C., particularly preferably 50 to 95 ° C., although it depends on the amount of catalyst and the solvent used. The reaction time is usually 1 to 20 hours, preferably 3 to 12 hours.

  After completion of the reaction, the catalyst is removed by quenching and / or washing with water as necessary. When washing with water, depending on the type of solvent used, it is preferable to add a solvent that can be separated from water. Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.

In this reaction, the catalyst may be removed only by washing with water. However, since the reaction is carried out under acidic or basic conditions, the washing is carried out after quenching by a neutralization reaction, or the adsorbent. It is preferable to remove the adsorbent by filtration after adsorbing the catalyst using
Any compound that is acidic or basic can be used for the neutralization reaction. Examples of the compound exhibiting acidity include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Inorganic bases such as alkali metal carbonates, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphates, phosphates such as sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, Organic bases such as dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, in particular, inorganic bases or inorganic acids are preferable because they can be easily removed from the product, and phosphates that can more easily adjust the pH to near neutral are more preferable.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
As the activated clay, for example, Toshin Kasei Co., Ltd., activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168, manufactured by Mizusawa Chemical Industry, Galeon Earth, Mizuka Ace, etc. are listed. As the activated carbon, for example, CL-H, Y-10S, Y-10SF manufactured by Ajinomoto Fine-Techno Co., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR are manufactured by Phutamura Chemical Co., Ltd. , CW130AR, GM130A, and the like. Examples of zeolite include, for example, molecular sieves 3A, 4A, 5A, and 13X, manufactured by Union Showa. As a synthetic adsorbent, for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., Amberlist 15JWET, 15DRY, manufactured by Rohm and Haas Co., Ltd. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, manufactured by Dow Chemical Company, Dowex 66, HCR-S, HCR-W2, MAC-3 and the like can be mentioned.
The adsorbent is added to the reaction solution, followed by treatment such as stirring and heating to adsorb the catalyst, and then the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.

  After completion of the reaction or after quenching, it can be purified by conventional separation and purification means other than washing with water and filtration. Examples of the purification means include column chromatography, vacuum concentration, distillation, extraction and the like. These purification means may be performed singly or in combination.

  When the reaction is performed using a solvent mixed with water as a reaction solvent, the reaction solvent mixed with water is removed from the system by distillation or vacuum concentration after quenching, and then washed with a solvent that can be separated from water. It is preferable.

  After washing with water, the epoxy resin of the present invention can be obtained by removing the solvent by vacuum concentration or the like.

The appearance of the organopolysiloxane containing the epoxy group of the present invention thus obtained (hereinafter also referred to as “the epoxy resin of the present invention”) is usually a colorless and transparent liquid having a fluidity at 25 ° C. The molecular weight is preferably 800 to 3000, more preferably 1000 to 3000, and particularly preferably 1500 to 2800 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the heat resistance may be lowered. When the weight average molecular weight is more than 3000, the encapsulant may be peeled from the substrate at the time of solder reflow of the LED element encapsulated using the weight average molecular weight.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The epoxy equivalent (measured by the method described in JIS K-7236) of the produced epoxy resin of the present invention is 300 to 1500 g / eq. The thing of 400-1400 g / eq is more preferable, and the thing of 400-1200 g / eq is especially preferable. When the epoxy equivalent is less than 300 g / eq, the cured product is hard and the elastic modulus tends to be too high, and when it exceeds 1500 g / eq, the mechanical properties of the cured product tend to deteriorate.

  The viscosity of the epoxy resin of the present invention (E-type viscometer, measured at 25 ° C.) is preferably 50 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, and particularly 800 to 5,000 mPa · s. -The thing of s is preferable. If the viscosity is less than 50 mPa · s, the viscosity may be too low to be suitable for use as an optical semiconductor encapsulant, and if it exceeds 20,000 mPa · s, the viscosity may be too high and workability may be poor. is there.

In the epoxy resin of the present invention, the ratio of silicon atoms to which three oxygen atoms are bonded to the total silicon atoms is preferably 3 to 50 mol%, more preferably 5 to 30 mol%, and particularly preferably 6 to 15 mol%. When the ratio of silicon atoms bonded to three oxygen atoms derived from silsesquioxane with respect to all silicon atoms is less than 3 mol%, the cured product tends to be too soft as a characteristic of the chain silicone segment, and the surface There are concerns about tack and scratches. On the other hand, if it exceeds 50 mol%, the properties of the silicone oil are liable to be impaired, and the cured product becomes too hard.
The proportion of silicon atoms present can be determined by ¹ H NMR, ²⁹ Si NMR, elemental analysis, etc. of the epoxy resin.

Hereinafter, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing agent as essential components.
In the present invention, as the curing agent, acid anhydride (B) and polyvalent carboxylic acid (C) are particularly preferable from the viewpoints of hardness and workability.

Specific examples of the acid anhydride (B) include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2 , 3-dicarboxylic acid anhydride, and acid anhydrides such as cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.
In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid Acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and the like. It is preferable from the viewpoint of workability.

The polyvalent carboxylic acid (C) is a compound having at least two carboxyl groups.
As the polyvalent carboxylic acid (C), a bifunctional to hexafunctional carboxylic acid is preferable, and a compound obtained by a reaction of a bifunctional to hexafunctional polyhydric alcohol and an acid anhydride is more preferable. Furthermore, the polyhydric carboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.
The 2- to 6-functional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane and 2-hydroxymethyl-1,4-butanediol, and tet such as pentaerythritol and ditrimethylolpropane Ols, and the like hexa-ols, such as dipentaerythritol.

  Preferred polyhydric alcohols are alcohols having 5 or more carbon atoms, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2,4 -Compounds such as diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol are preferred, among which 2-ethyl-2-butyl-1,3 -Alcohols having a branched chain structure or a cyclic structure such as propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol, Preferred from the viewpoint of transparency. In addition, tricyclodecane dimethanol is preferred.

Examples of acid anhydrides to be reacted with polyhydric alcohols include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2, 2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4- Anhydrides and the like are preferable, and methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are particularly preferable from the viewpoints of heat resistance, transparency, and workability.
The conditions for the addition reaction can be used without particular limitation as long as they are known methods, but specific reaction conditions include, for example, acid anhydrides and polyhydric alcohols in a catalyst-free and solvent-free condition, A method of reacting at 150 ° C. and heating, and taking it out as it is after completion of the reaction can be mentioned.
As the polyvalent carboxylic acid (C) of the present invention, a compound produced by a reaction between the silicone compound (a) and the acid anhydride (b) can also be used.
As a silicone compound (a), following formula (5)

（式（５）において、Ｒ_６は炭素総数１〜１０のアルキレン基を、Ｒ_５はメチル基又はフェニル基を、ｎは平均値で１〜１００をそれぞれ表す。）
に示される化合物が好ましい。

(In Formula (5), R ₆ represents an alkylene group having 1 to 10 carbon atoms, R ₅ represents a methyl group or a phenyl group, and n represents an average value of 1 to 100.)
The compound shown by these is preferable.

In the formula (5), specific examples of R ₆ include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups, ethoxyethylene group, propoxyethylene group propoxy A propylene group, an ethoxypropylene group, etc. are mentioned. Particularly preferred are propoxyethylene group and ethoxypropylene group.

Next, R ₅ represents a methyl group or a phenyl group, which may be the same or different, and an addition reaction between the silicone compound (a) and a compound (b) having one or more carboxylic anhydride groups in the molecule. In order that the carboxylic acid compound (C) obtained by making it be a liquid at room temperature, a methyl group is preferable compared with a phenyl group.

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

  Examples of the silicone compound (a) represented by the formula (5) include silicone compounds having alcoholic hydroxyl groups at both ends. As specific examples, X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-201, BY16-004, SF8427 (all manufactured by Toray Industries, Inc.) are carbinol-modified silicone oils at both ends. -Dow Corning Co., Ltd.) XF42-B0970, XF42-C3294 (both manufactured by Momentive Performance Materials Japan GK) and the like are all available from the market. These modified silicone oils having alcoholic hydroxyl groups at both ends can be used alone or in combination of two or more. Among these, X-22-160AS, KF6001, KF6002, BY16-201, and XF42-B0970 are preferable.

Next, the compound (b) having one or more carboxylic anhydride groups in the molecule includes, for example, succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, 2,3-butanedicarboxylic anhydride, , 4-pentanedicarboxylic acid anhydride, 3,5-heptanedicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride and other saturated aliphatic carboxylic acid anhydrides, maleic acid anhydride, dodecyl Unsaturated aliphatic carboxylic anhydrides such as succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride , Methylnorbornane-2,3-dicarboxylic acid anhydride, nadic acid anhydride, methylnadic acid anhydride, bicyclo [2,2,2] octane-2,3-di Rubonic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydrides, cyclic saturated aliphatic carboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, methyl Cyclic unsaturation such as nadic acid anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -5-octene-2,3-dicarboxylic acid anhydride No aromatic carboxylic acid such as aliphatic carboxylic acid anhydride, phthalic acid anhydride, isophthalic acid anhydride, terephthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride In addition, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride and the like, saturated aliphatic carboxylic acid anhydride, cyclic saturated carboxylic acid anhydride, cyclic unsaturated carboxylic acid anhydride Examples thereof include polycarboxylic acid compounds having a product.
The compound (b) having one or more carboxylic acid anhydride groups in the molecule can be used alone or in combination. Among these, since the carboxylic acid compound (C) is liquid at room temperature and the transparency of the cured product obtained by curing the carboxylic acid compound (C) and the epoxy resin is excellent, hexahydrophthalic anhydride, methylhexahydro Phthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2,3 1,4-butanetetracarboxylic dianhydride is preferred. More preferred are methylhexahydrophthalic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and particularly preferred is methylhexahydrophthalic anhydride.

  The reaction between the silicone compound (a) and the compound (b) having one or more carboxylic anhydride groups in the molecule can be carried out either in a solvent or without a solvent. Any solvent that does not react with the silicone compound (a) represented by the formula (5) and the compound (b) having one or more carboxylic acid anhydride groups in the molecule can be used without particular limitation. Examples of solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, toluene and xylene. An aromatic hydrocarbon etc. are mentioned, Among these, an aromatic hydrocarbon and ketones are preferable. These solvents may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount of a solvent, Usually, 0.1-300 with respect to 100 weight part of total weights of the said silicone compound (a) and the compound (b) which has one or more carboxylic anhydride groups. It is preferable to use parts by weight.

  A catalyst may be used for the reaction. Examples of usable catalysts include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, water Metal hydroxides such as sodium oxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, amine compounds such as triethylamine, tripropylamine, tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4. 0] heterocyclic compounds such as undec-7-ene, imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tri Tylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium Examples include quaternary ammonium salts such as acetate and trioctylmethylammonium acetate. These catalysts may be used alone or in combination of two or more. Of these, triethylamine, pyridine, and dimethylaminopyridine are preferred.

  The amount of the catalyst used is not particularly limited, but the total weight of the silicone compound (a) represented by the formula (5) and the compound (b) having one or more carboxylic anhydride groups in the molecule is 100 wt. It is preferably used in an amount of usually 0.1 to 100 parts by weight per part.

  In the epoxy resin composition of the present invention, two or more acid anhydrides (B) and polyvalent carboxylic acids (C) can be used in combination. In particular, when solid polycarboxylic acid (C) is used in applications where liquid is required at room temperature (25 ° C) such as sealing of optical semiconductors, liquid acid anhydride (B) is used in combination and used as a liquid mixture It is desirable to do. When used together, the acid anhydride (B) can be used at a ratio of 0.5 to 99.5% by weight of the total of the acid anhydride (B) and the polyvalent carboxylic acid (C).

  The epoxy resin composition of the present invention contains an organopolysiloxane (A) containing the epoxy group of the present invention as an epoxy resin, and a curing agent as essential components, but further contains other epoxy resins and other curing agents. It can also be made.

  When another epoxy resin is used in combination, the proportion of the organopolysiloxane (A) containing an epoxy group of the present invention in the total epoxy resin is preferably 60% by weight or more, particularly preferably 70% by weight or more.

  Other epoxy resins that can be used include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Solid or liquid epoxy resins such as chemical compounds, alicyclic epoxy resins, 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.

In particular, the epoxy resin composition of the present invention is mainly used for optical applications. When used for optical applications, the combined use of alicyclic epoxy resins is preferred. In the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and further transesterification reaction of cyclohexene carboxylic acid ester (Japan) Examples thereof include those obtained by oxidizing a compound that can be produced by a method described in Japanese Patent Laid-Open No. 2006-052187 (the entire contents of these references are incorporated herein by reference).
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

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

When another curing agent is used in combination as the curing agent, the proportion of the total amount of the above-mentioned acid anhydride (B) and / or polyvalent carboxylic acid (C) in the total curing agent is preferably 30% by weight or more, In particular, 40% by weight or more is preferable.
Examples of the curing agent that can be used in combination include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of curing agents that can be used include amines and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, etc.) , Reaction product of acid anhydride and silicone alcohol (phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, anhydrous Nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] Hep Reaction products of acid anhydrides such as cyclohexane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and silicone alcohols such as carbinol-modified silicone ), Polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, Phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydride Xylbenzene, 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.) This It is not limited to these. These may be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the curing agent is preferably 0.5 to 1.2 equivalents of the curing agent with respect to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.5 equivalent or more than 1.2 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the epoxy resin composition of the present invention, a curing catalyst can be used together with the curing agent. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl- 4′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 ( '-Methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5- Various imidazoles of dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 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) Diaza compounds such as undecene-7 and their compounds Salts such as raphenyl borate and phenol novolak, salts with the above polyvalent carboxylic acids or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide, ammonium salts such as trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) ) Phosphines such as phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts, tin octylate, and the like, and Examples thereof include a microcapsule-type curing catalyst in which these curing catalysts are made into microcapsules. Which of these curing catalysts is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A curing catalyst is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.

  The epoxy 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 Contains phosphorus obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

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

  If necessary, an inorganic filler can be added to the epoxy resin composition of the present invention. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the epoxy resin composition of the present invention. 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 epoxy resin composition of the present invention. be able to.

  When the epoxy resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, as the particle size of the inorganic filler used, the transparency can be improved by using a nano-order level filler. It is possible to supplement mechanical strength 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 the epoxy resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, a phosphor can be added as necessary. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to the resin component, Preferably it is 5-60 weight part.

  When the epoxy resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, thixo including silica fine powder (also called Aerosil or Aerosol) is used for the purpose of preventing sedimentation of various phosphors upon curing. A tropicity-imparting 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 epoxy resin composition of the present invention contains an optical material, particularly an optical semiconductor encapsulant, which contains an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant for the purpose of preventing coloring. Can do.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetrame Ru-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] bu Lumalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine- , 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate And 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa- 3,20-diazadispiro [5 · 1 · 11 · 2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa 3,20-diazadispiro [5,1,11,2] heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) Hindered amines such as octabenzone, benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, -Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl)- Benzotriazole compounds such as 6-dodecyl-4-methylphenol, 2,4 Benzoate series such as di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 Examples include triazine compounds such as [(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited, and for example, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, and ADEKA, LA-52, LA-57, LA-, manufactured by Ciba Specialty Chemicals. 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4 -Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenyl Range phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis ( 2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butyl) Phenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl -Phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl Examples include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, made by Adeka, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, Adekas tab TPP and the like.

  The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) 2), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), bis [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-pentyl Phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4 ′ -Hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

  A commercial item can also be used for the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, AGANOX 1520L, Adeka 1520L, and AGANOX 1520L manufactured by Ciba Specialty Chemicals , ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, Sumitizer GA-80 , Sumilizer MDP-S, Sumil zer BBM-S, Sumilizer GM, Sumilizer GS (F), and the like Sumilizer GP.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like can be cited as those manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0 with respect to the total weight of the epoxy resin composition of the present invention. 0.005 to 5.0% by weight.

  The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy 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, and a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, a compounding agent, and the like, if necessary, uniformly using an extruder, kneader, roll, planetary mixer, etc. Mix thoroughly until the epoxy resin composition is obtained. If the resulting epoxy resin composition is liquid, impregnate the composition into the substrate by potting or casting, or pour into a mold and cast. Or cured by heating. When the obtained epoxy resin composition is solid, it is molded using a cast after casting or a transfer molding machine, and further cured by heating. The curing temperature and time are 80 to 200 ° C. and 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.

  In addition, the epoxy 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, which contains glass fiber, -Making the cured product of the epoxy resin composition of the present invention by hot press molding a prepreg obtained by impregnating a base material such as bon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. Can do. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight, based on the total weight of the mixture of the epoxy 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 epoxy resin composition of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, the curable resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and a B-stage adhesive is formed. Get. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.
Next, the case where the epoxy resin composition of the present invention is used as an optical semiconductor sealing material or die bonding material will be described in detail.

  When the epoxy resin composition of the present invention is used as a sealing material or die bond material for an optical semiconductor such as a high-intensity white LED, an addition of an epoxy resin, a curing agent, a coupling agent, an antioxidant, a light stabilizer, etc. An epoxy resin composition is prepared by thoroughly mixing the materials, and is used as a sealing material or as both a die bond material and a sealing material. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

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

  As a method of adhering a semiconductor chip to a substrate using the epoxy resin composition of the present invention, the epoxy resin composition of the present invention is applied by a dispenser, potting, or screen printing, and then the semiconductor chip is placed and heat-cured. Yes, the semiconductor chip can be bonded. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.

  The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and 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. For example, the heating condition is preferably 80 to 230 ° C. and about 1 minute to 24 hours. 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, general applications in which a curable resin such as an epoxy resin is used include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed boards, electric wires). In addition to the encapsulating material, the encapsulating material, a cyanate resin composition for the substrate, an acrylic ester resin as a curing agent for the resist, an additive to other 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 plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.
In the present specification, ratios, percentages, parts and the like are based on weight unless otherwise specified. In the present specification, the expression “X to Y” indicates a range from X to Y, and the range includes X and Y.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, Example 1 shall be read as Reference Example 1.
Each physical property value in the examples was measured by the following method.
(1) Molecular weight: Polystyrene conversion and weight average molecular weight measured under the following conditions were calculated by the GPC method.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
(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.
(4) Transmittance: A light transmittance of 400 nm was measured using U-3300 manufactured by Hitachi, Ltd.

Example 1
As Step 1, 158 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 546 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (GPC measurement value) (silanol equivalent: 850, measured using GPC) Calculated as half the weight average molecular weight.), 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel (a glass four-necked flask equipped with a stirrer, Dimroth condenser, thermometer), The reaction was carried out for 8 hours under reflux. The weight average molecular weight at this time was 2230.
In Step 2, after adding 598 parts of methanol, 69.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted 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. Next, 700 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, 634 parts of organopolysiloxane (S-1) of the present invention were obtained. The epoxy equivalent of the obtained compound was 1015 g / eq, the weight average molecular weight was 2290, and the appearance was a colorless and transparent liquid resin.

Example 2
As step 1, 139.4 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 136.6 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (measured by GPC) (silanol equivalent 850, GPC) Calculated as half of the weight average molecular weight measured by using a 10% solution of 0.5% potassium hydroxide (KOH) in methanol and 140 parts of methanol in a reaction vessel (stirrer, Dimroth condenser, thermometer equipped with glass) 4 necked flask) and allowed to react for 8 hours under reflux. The weight average molecular weight at this time was 1770.
As Step 2, 17.3 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted 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. Next, 160 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, 151 parts of the organopolysiloxane (S-2) of the present invention were obtained. The epoxy equivalent of the obtained compound was 1042 g / eq, the weight average molecular weight was 2050, and the appearance was a colorless and transparent liquid resin.

Example 3
As Step 1, it was measured using 59 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 131 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (GPC measurement value) (silanol equivalent 850, GPC). Calculated as half of the weight average molecular weight.), 10 parts of 0.5% potassium hydroxide (KOH) methanol solution (0.05 parts as KOH parts) was placed in a reaction vessel (stirrer, Dimroth condenser, thermometer) Glass 4-neck flask), 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. The weight average molecular weight at this time was 1540.
In Step 2, after adding 135 parts of methanol, 25.9 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was 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. 170 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, 162 parts of organopolysiloxane (S-3) of this invention were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. The obtained compound was a liquid resin having an epoxy equivalent of 729 g / eq, a weight average molecular weight of 2200, and an appearance having a colorless and transparent appearance.

Example 4
As Step 1, 296 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 505 parts of silanol-terminated methylphenylsilicone oil having a weight average molecular weight of 1700 (measured GPC value) (silanol equivalent 850, measured using GPC) Calculated as half of the weight average molecular weight.), 40 parts of 0.5% potassium hydroxide (KOH) methanol solution (0.2 parts as KOH parts) were placed in a reaction vessel (stirrer, Dimroth condenser, thermometer). Glass 4-neck flask), 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. The weight average molecular weight at this time was 1380.
As Step 2, after adding 510 parts of methanol, 129.6 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. 704 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, the organic phase was removed under reduced pressure at 100 ° C. to obtain 692 parts of organopolysiloxane (S-4) of the present invention. The epoxy equivalent of the obtained compound was 611 g / eq, the weight average molecular weight was 2120, and the appearance was a colorless and transparent liquid resin.

Example 5
As Step 1, 355 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 487 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (GPC measurement value) (silanol equivalent: 850, measured using GPC) Calculated as half the weight average molecular weight.), 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into a reaction vessel (a glass four-necked flask equipped with a stirrer, Dimroth condenser, thermometer), The reaction was carried out for 10 hours under reflux. The weight average molecular weight at this time was 1130.
In Step 2, after adding 640 parts of methanol, 155.6 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted 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. Next, 757 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. 724 parts of organopolysiloxane (S-5) of this invention were obtained by removing a solvent at 100 degreeC under pressure reduction of the obtained organic phase. The resulting compound was a liquid resin having an epoxy equivalent of 526 g / eq, a weight average molecular weight of 2200, and an appearance having a colorless and transparent appearance.

Example 6 As step 1, 394 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (measured by GPC) (silanol equivalent 850, GPC was used) Calculated as half of the weight average molecular weight measured in the above) and 40 parts of 0.5% potassium hydroxide (KOH) methanol solution in a reaction vessel (a glass four-necked flask equipped with a stirrer, Dimroth condenser, thermometer). And reacted under reflux for 10 hours. The weight average molecular weight at this time was 960.
As Step 2, after adding 656 parts of methanol, 172.8 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted 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. Next, 782 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, 741 parts of the organopolysiloxane (S-6) of the present invention were obtained. The epoxy equivalent of the obtained compound was 487 g / eq, the weight average molecular weight was 2250, and the appearance was a colorless and transparent liquid resin.

Example 7
As Step 1, 394 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (GPC measurement value) (silanol equivalent: 850, measured using GPC) Calculated as half the weight average molecular weight.), 4 parts of 0.5% potassium hydroxide (KOH) methanol solution and 36 parts of isopropyl alcohol were added to a reaction vessel (agitator, Dimroth condenser, thermometer equipped with four necks) Flask) and reacted under reflux for 4 hours. The weight average molecular weight at this time was 840. Thereafter, the mixture was further reacted under reflux for 6 hours (total 10 hours). The weight average molecular weight at this time was 940.
As step 2, after adding 656 parts of methanol, 172.8 parts of 50% distilled water methanol solution was added dropwise over 60 minutes and reacted for 10 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. Next, 782 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. The organic phase obtained was removed at 100 ° C. under reduced pressure to obtain 731 parts of the organopolysiloxane (S-10) of the present invention. The obtained compound was a liquid resin having an epoxy equivalent of 491 g / eq, a weight average molecular weight of 2090, and a colorless and transparent appearance.

Example 8 As Step 1, 197 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 534 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (measured GPC value) (silanol equivalent 850, GPC was used) Calculated as half the weight average molecular weight measured in the above), 4 parts of 0.5% potassium hydroxide (KOH) methanol solution and 36 parts of isopropyl alcohol were made into a reaction vessel (stirrer, Dimroth condenser, thermometer equipped with glass). A four-necked flask) and reacted under reflux for 4 hours. The weight average molecular weight at this time was 1570. Thereafter, the mixture was further reacted under reflux for 6 hours (total 10 hours). The weight average molecular weight at this time was 1520.
As step 2, after adding 576 parts of methanol, 86.4 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted for 10 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. Next, 660 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. 648 parts of organopolysiloxane (S-11) of this invention were obtained by removing a solvent at 100 degreeC under pressure reduction of the obtained organic phase. The epoxy equivalent of the obtained compound was 857 g / eq, the weight average molecular weight was 1860, and the appearance was a colorless and transparent liquid resin.

Comparative Example 1
As Step 1, 118 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 262 parts of silanol-terminated methylphenylsilicone oil having a weight average molecular weight of 1700 (GPC measurement value) (silanol equivalent 850, measured using GPC) Calculated as half the weight average molecular weight.), 0.1 part of potassium hydroxide (KOH, added as a solid) was charged into a reaction vessel (a glass four-necked flask equipped with a stirrer, Dimroth condenser, thermometer). 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. The weight average molecular weight at this time was 2140.
As Step 2, after adding 170 parts of methanol, 51.8 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. 340 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, 320 parts of organopolysiloxane (S-7) was obtained by removing a solvent at 100 degreeC under pressure reduction of the organic phase. The epoxy equivalent of the obtained compound was 710 g / eq, the weight average molecular weight was 3100, and the appearance was a colorless and transparent liquid resin.

Comparative Example 2
As Step 1, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 59.7 parts, weight average molecular weight 1700 (GPC measured value) silanol-terminated methylphenyl silicone oil 130.6 parts (silanol equivalent 850, GPC Calculated as half of the weight average molecular weight measured using the above), 10 parts of 0.5% potassium hydroxide (KOH) methanol solution in a reaction vessel (stirrer, Dimroth condenser, thermometer, Dean-Stark apparatus) In a four-necked flask), the bath temperature was set to 75 ° C., and the temperature was raised. By 1 hour after the temperature rise, 9.8 g of methanol was extracted from the Dean Stark from the reaction system. Further, 6.1 g of methanol was extracted from the reaction system by 3 hours and 30 minutes after the temperature was raised. The reaction was allowed to proceed for 8 hours. The weight average molecular weight at this time was 2740.
In Step 2, after adding 135 parts of methanol, 25.9 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was 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. 170 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, 158 parts of organopolysiloxane (S-8) were obtained by removing a solvent at 100 degreeC under pressure reduction of the organic phase. The epoxy equivalent of the obtained compound was 715 g / eq, the weight average molecular weight was 3600, and the appearance was a colorless and transparent liquid resin.

Comparative Example 3
As step 1, 139.4 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 136.6 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (measured by GPC) (silanol equivalent 850, GPC) Calculated as half of the weight average molecular weight measured using the above), 10 parts of 0.5% potassium hydroxide (KOH) methanol solution in a reaction vessel (stirrer, Dimroth condenser, thermometer, Dean-Stark apparatus) In a four-necked flask), the bath temperature was set to 75 ° C., and the temperature was raised. By 1 hour after the temperature rise, 5.8 g of methanol was extracted from the Dean Stark from the reaction system. Further, 4.0 g of methanol was extracted from the reaction system by 2 hours after the temperature was raised. The reaction was allowed to proceed for 8 hours. The weight average molecular weight at this time was 3460.
As Step 2, after adding 140 parts of methanol, 17.3 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was 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. 158 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, 152 parts of organopolysiloxane (S-9) were obtained by removing a solvent at 100 degreeC under pressure reduction of the organic phase. The epoxy equivalent of the obtained compound was 1045 g / eq, the weight average molecular weight was 3660, and the appearance was a colorless and transparent liquid resin.

＊１）化合物中の、３つの酸素原子に結合しているケイ素原子の全ケイ素原子に対する割合（モル％）
＊２）添加したメタノールと共に、工程１の反応により生成したメタノールも系中から除いたため、工程１時の最終的なアルコール量（重量％）
Table 1 summarizes the properties of the resins S-1 to S11 obtained in Examples 1 to 6 and Comparative Examples 1 to 3.

* 1) Ratio of silicon atoms bonded to three oxygen atoms in the compound to all silicon atoms (mol%)
* 2) Since the methanol produced by the reaction in Step 1 was removed from the system together with the added methanol, the final alcohol amount (% by weight) in Step 1

  As is clear from Table 1, Examples 1 to 8 (compounds S-1 to S-6, S-10, and the like) in which the amount of alcohol added by the alcohol present in the system during Step 1 is 2% by weight or more. S-11) has a weight average molecular weight of less than 3000, whereas Comparative Examples 1 to 3 (compounds S-7 to S-9) having an alcohol content of less than 2% by weight have a weight average molecular weight of more than 3000, Therefore, the cured product may be peeled off from the substrate during reflow.

Synthesis Example 1 (Synthesis of polyvalent carboxylic acid (C) having polysiloxane as main skeleton)
50 parts of both ends hydroxyethoxypropyl modified polydimethylsiloxane (X22-160AS manufactured by Shin-Etsu Chemical Co., Ltd.) and 15.4 parts of methylhexahydrophthalic acid (Licacid MH manufactured by Shin Nippon Rika Co., Ltd.) were added to a reaction vessel (stirrer, Dimroth, temperature). When the GPC was measured after 4 hours, the methyl hexahydrophthalic acid peak disappeared. Thereafter, the reaction was further continued for 2 hours. After completion of the reaction, 65.4 parts of polycarboxylic acid (C-1) having polysiloxane as the main skeleton was obtained. The weight average molecular weight of the obtained compound was 1700, and the functional group equivalent was 700 g / eq. The appearance was a colorless and transparent liquid resin.

Synthesis Example 2 (Preparation of mixture of acid anhydride (B) and polycarboxylic acid (C))
12 parts of tricyclodecane dimethanol (Ocsea's TCD-AL), 73 parts of methylhexahydrophthalic acid (Rikacid MH manufactured by Shin Nippon Chemical Co., Ltd.), 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride ( H-TMAn (manufactured by Mitsubishi Gas Chemical Co., Inc.) is charged into a reaction vessel (a glass four-necked flask equipped with a stirrer, a Dimroth, and a thermometer), heated to 40 ° C. for 1 hour, and then at 60 ° C. for 1 hour. When GPC was measured, the peak of tricyclodecane dimethanol disappeared. After completion of the reaction, a curing agent (H-1) which is a mixture of a polyvalent carboxylic acid (C-2) having a cyclic aliphatic hydrocarbon group (tricyclodecanedimethyl) as a main skeleton and an acid anhydride (B) 100 parts were obtained. The functional group equivalent of the obtained curing agent (H-1) was 171 g / eq. (The carboxylic acid and acid anhydride groups are each considered as one functional group). The appearance was a colorless and transparent liquid.

Example 9
100 parts of the organopolysiloxane (S-10) containing the epoxy group obtained in Example 7 and 128 parts of the polyvalent carboxylic acid (C-1) obtained in Synthesis Example 1 were mixed and degassed for 20 minutes. An epoxy resin composition was obtained.

Example 10
50 parts of the organopolysiloxane (S-10) containing the epoxy group obtained in Example 7, 50 parts of the organopolysiloxane (S-11) containing the epoxy group obtained in Example 8, and Synthesis Example 2 19 parts of the resulting curing agent (H-1) was mixed and defoamed for 20 minutes to obtain an epoxy resin composition.

  Table 2 shows the compounding ratio of the epoxy resin compositions obtained in Examples 9 and 10, the transmittance of the cured product, and the results of the reflow test. The test in Table 2 was performed as follows.

(1) Permeability of cured product The epoxy resin composition obtained in Examples 9 and 10 was 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 0.8 mm. did. The cast was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a test piece for transmittance having a thickness of 0.8 mm.
(2) Reflow test A surface-mounted LED (external 5 mm square) in which the epoxy resin composition obtained in Examples 9 and 10 is filled into a syringe and a light-emitting element having an emission wavelength of 465 nm is mounted using a precision discharge device. , Inner diameter 4.4 mm, outer wall height 1.25 mm). The cast was cured at 150 ° C. for 3 hours after preparatory preparation at 120 ° C. for 1 hour, and the surface-mounted LED was sealed. The LED thus sealed was subjected to solder reflow using the IR-type reflow apparatus with the following profile, and the change in appearance when observed was fixed to the aluminum substrate. In the table, ◯: no peeling occurs between the encapsulant and the LED after reflow, and X: peeling occurs between the encapsulant and the LED after reflow.
Reflow profile;
The temperature is raised from room temperature (30 ° C. or lower) to 180 ° C. at 2 ° C./second and held at 180 ° C. for 2 minutes (preheating). Thereafter, the temperature is raised to 260 ° C. at 2 ° C./second, maintained at 260 ° C. for 10 seconds, and then air-cooled to 40 ° C. or lower.

 As is clear from Table 2, in Examples 9 and 10, the cured product had excellent transmittance, and the sealing material was not peeled off from the LED substrate during reflow.

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.
Note that this application is based on a Japanese patent application filed on March 2, 2010 (Japanese Patent Application No. 2010-045891), the entirety of which is incorporated herein by reference. The documents cited in this specification are incorporated as a whole.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition containing the epoxy resin (organopolysiloxane containing an epoxy group) which has the siloxane structure excellent in thermal stability can be provided, and hardening containing this epoxy resin composition The resin composition is useful in a wide range of applications such as electrical / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, etc., and particularly for materials that require optical properties, such as for optical semiconductors. It is extremely useful as an adhesive or sealing material for LED products and the like.

Claims (12)

Step 1:
A step of reacting a silicone oil having a silanol structure at the terminal having a weight average molecular weight of 1000 to 3000 with an alkoxysilane compound to obtain a modified silicone oil having a weight average molecular weight of 1770 or less ; and
Step 2:
The hydrolysis reaction, modified silicone oils each other, and / or the alkoxysilane compound is polymerized with a weight average molecular weight of Ru to give organopolysiloxane (A) is 2050 or more steps of the following formula (2) In the manufacturing method of organopolysiloxane (A) containing,
(A) At least one of the alkoxysilane compounds to be used has a glycidyl group and / or an epoxycyclohexyl group in the molecule,
(B) In step 1, the silicone oil having a silanol structure at the end is a chain silicone oil represented by the following formula (1), and is 2 to 100% by weight based on the total weight of the silicone oil and the alkoxysilane compound. An organopolysiloxane containing an epoxy group obtained by reacting in the presence of an alcohol having 1 to 10 carbon atoms.

(In the formula (1), a plurality of R ₁ may be the same or different from each other, and are 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. And at least one of R ₁ is a phenyl group, and m is an average value of 3 to 200.)

(In the formula (2), X represents an organic group having an epoxy group, and a plurality of R _{2 s} may be the same or different from each other, and are linear, branched or Represents a cyclic alkyl group.)   The organopolysiloxane (A) according to claim 1, wherein the silicone oil having a silanol structure at the terminal used in Step 1 is a silanol-terminated methylphenyl silicone oil. Step 1:
Process step 2: obtaining a modified silicone oil having a weight average molecular weight of 1770 or less by reacting a silicone oil having a silanol structure at the terminal having a weight average molecular weight of 1000 to 3000 with an alkoxysilane compound.
The hydrolysis reaction, modified silicone oils each other, and / or the alkoxysilane compound is polymerized with a weight average molecular weight of Ru to give organopolysiloxane (A) is 2050 or more steps of the following formula (2) In the manufacturing method of organopolysiloxane (A) containing,
(A) At least one of the alkoxysilane compounds to be used has a glycidyl group and / or an epoxycyclohexyl group in the molecule,
(B) In step 1, the silicone oil having a silanol structure at the end is a chain silicone oil represented by the following formula (1), and is 2 to 100% by weight based on the total weight of the silicone oil and the alkoxysilane compound. A process for producing an organopolysiloxane containing an epoxy group, wherein the reaction is carried out in the presence of an alcohol having 1 to 10 carbon atoms.

(In the formula (1), a plurality of R ₁ may be the same or different from each other, and are 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. And at least one of R ₁ is a phenyl group, and m is an average value of 3 to 200.)

(In the formula (2), X represents an organic group having an epoxy group, and a plurality of R _{2 s} may be the same or different from each other, and are linear, branched or Represents a cyclic alkyl group.)   The method for producing an organopolysiloxane according to claim 3, wherein the silicone oil having a silanol structure at the terminal used in step 1 is a silanol-terminated methylphenyl silicone oil.   3. The organopolysiloxane according to claim 1, wherein the reaction is carried out in the presence of an alcohol having 1 to 10 carbon atoms in Step 2.   The organopolysiloxane according to any one of claims 1 to 2 and 5, wherein the alcohol having 1 to 10 carbon atoms is a primary alcohol.   6. The organopolysiloxane according to claim 1, wherein the alcohol having 1 to 10 carbon atoms is a mixture of a primary alcohol and a secondary alcohol.   The organopolysiloxane according to any one of claims 1 to 2 and 5 to 7, wherein the alkoxysilane compound has a phenyl group. The epoxy equivalent of the resulting organopolysiloxane (A) is 300-1500 g / eq. The organopolysiloxane according to any one of claims 1 to 2 and claims 5 to 7. Claim 1-2, an epoxy resin composition comprising an organopolysiloxane (A) with an acid anhydride according to any one of claims 5 ~9 (B). A polyvalent carboxylic acid having the organopolysiloxane (A) according to any one of claims 1 to 2 and claims 5 to 9 and having two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton. An epoxy resin composition comprising (C).   The hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 10 or Claim 11.