JPWO2014157552A1 - Epoxy resin composition for optical semiconductor encapsulation, cured product thereof and optical semiconductor device - Google Patents

Abstract

The epoxy resin composition for optical semiconductor sealing containing a silicone frame | skeleton epoxy resin (A) and a cationic polymerization initiator (B). The epoxy resin composition may further contain an epoxy resin curing agent. The silicone skeleton epoxy resin (A) may be a hydrolysis condensate of a polymer of a specific silanol-terminated silicone oil and a specific epoxy group-containing silicon compound having an epoxy equivalent of 300 to 1500 g / eq.

Description

  The present invention relates to a curable epoxy resin composition suitable for optical semiconductor sealing applications, a cured product thereof, and an optical semiconductor device sealed with the cured product.

Liquid epoxy resin composition using bisphenol-type epoxy resin, alicyclic epoxy resin, etc. as a resin for sealing optical semiconductor elements such as LED (Light Emitting Diode), because of its excellent mechanical strength and adhesive strength Has been used (see Patent Document 1). In recent years, LEDs have been used in fields that require high brightness, such as automotive headlamps and lighting applications. Accordingly, resins that encapsulate optical semiconductor elements are particularly resistant to UV and heat. It has come to be required. However, it is difficult to say that bisphenol-type epoxy resins and alicyclic epoxy resins have sufficient UV resistance and heat resistance as described above, and may not be used in fields where high luminance is required. Therefore, as a sealing material having high UV resistance, heat resistance, etc., a silicone resin sealing material using an unsaturated hydrocarbon group-containing organopolysiloxane and an organohydrogenpolysiloxane is used (see Patent Document 2). ). However, although the sealing material using such a silicone resin is excellent in UV resistance and heat resistance, it has a problem that the sealing surface becomes sticky or gas permeability is high.
The problem of high gas permeability is that the silver plating surface of the member constituting the LED is corroded by the intrusion of sulfur-based gas, etc., and becomes black due to silver sulfide or the like, which reduces the LED light extraction efficiency. Cause the event.
As measures for improving gas corrosion resistance, a sealing material using a silicone resin having a phenyl group, or a sealing material using a condensate of an epoxy group or a silicon compound having a phenyl group and an epoxy resin curing agent Is being studied. All of the sealing materials increase the crosslinking density of the cured product or introduce an aromatic organic group such as a phenyl group into the molecule. However, this increases the hardness of the cured product, causing adverse effects such as cracking and peeling from the substrate in the heat cycle test, and UV resistance due to the influence of the introduced aromatic organic group. There is concern that it will be inferior. Therefore, a sealing material that still satisfies the gas corrosion resistance has not been obtained.

Japanese Unexamined Patent Publication No. 2012-001592 Japanese Unexamined Patent Publication No. 2012-076933

  The present invention has been made in view of the above circumstances, and an epoxy resin composition for optical semiconductor encapsulation that gives a cured product excellent in heat resistance, light resistance, curability, hardness, heat cycle property, and corrosion gas resistance, and curing thereof. An object is to provide a semiconductor device and an optical semiconductor device.

That is, the present invention relates to the following (1) to (9).
(1) An epoxy resin composition for encapsulating an optical semiconductor containing a silicone skeleton epoxy resin (A) and a cationic polymerization initiator (B).
(2) The epoxy resin composition for optical semiconductor encapsulation according to (1), further comprising an epoxy resin curing agent.
(3) A silicone skeleton epoxy resin (A) having an epoxy equivalent of 300 to 1500 g / eq, a silanol-terminated silicone oil represented by the following formula (1) and an epoxy group-containing silicon represented by the following formula (2) Hydrolyzed condensate of a polymer of the compound, or a silanol-terminated silicone oil represented by the following formula (1), an epoxy group-containing silicon compound represented by the following formula (2), and the following formula (3) An epoxy resin composition for sealing an optical semiconductor, which is a hydrolysis-condensation product of a polymer of an alkoxysilicon compound.

(In the formula, R ₅ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and p represents an average value of 3 to 200. In the formula, a plurality of R ₅ may be the same or different from each other. Is also good.)

(Wherein X is an organic group containing an epoxy group, R ₆ is an aryl having a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ₇ represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, q represents an integer of 0 to 2, and r represents an integer of (3-q).)

(Wherein R ₆ and R ₇ are the same as described above, s is an integer, 0, 1, 2, 3 and t represents (4-s).)
(4) The epoxy resin composition for sealing an optical semiconductor according to (3), wherein the silicone skeleton epoxy resin (A) is a silicone skeleton epoxy resin obtained through the following production steps 1 and 2:
(Manufacturing process 1)
A step of condensing the silanol group of the silanol-terminated silicone oil represented by the formula (1) and the alkoxy group of the epoxy group-containing silicon compound represented by the formula (2) to obtain a modified silicone oil;
(Manufacturing process 2)
A step of adding water after the production step 1 to hydrolyze and condense the remaining alkoxy groups.
(5) The cationic polymerization initiator (B) is composed of a cation represented by the following formula (4) and an anion represented by the following formula (5) or the following formula (6) (1) to (4) The epoxy resin composition for optical semiconductor sealing as described in any one of 1).

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and are a hydroxyl group, a halogen atom, a substituent or an unsubstituted alkyl group having 1 to 30 carbon atoms, an alkoxy group, an aralkyl group, an aryl group, or Represents an alkylaryl group, and R ₁ and R ₂ may combine with each other to form a ring.)

(In the formula, X represents Sb, As, or P. Y represents fluorine, chlorine, bromine, or iodine. In the formula, R ₄ may be the same or different, and fluorine, chlorine, bromine, or iodine. And b is an integer of 0 to 5.)

（式中、Ｙはフッ素、塩素、臭素、またはヨウ素を表す。Ｒ_５は同一でも異なっていてもよく、フッ素、塩素、臭素もしくはヨウ素で置換または無置換のアルキル基又はアリール基、あるいはフッ素原子である。）
（６）前記式（４）においてＲ_３が下記式（７）で表されるカチオンと、前記式（５）においてＸがリンであるアニオンとから構成されるカチオン重合開始剤を含有する（１）〜（５）のいずれか一つに記載の光半導体封止用エポキシ樹脂組成物。

(In the formula, Y represents fluorine, chlorine, bromine or iodine. R ₅ may be the same or different, and is an alkyl or aryl group substituted or unsubstituted by fluorine, chlorine, bromine or iodine, or a fluorine atom. .)
(6) A cationic polymerization initiator comprising R ₃ in the formula (4) represented by the following formula (7) and an anion in which X is phosphorus in the formula (5) (1) The epoxy resin composition for optical semiconductor sealing as described in any one of)-(5).

(R ₆ represents hydrogen, an alkyl group, a hydroxy group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an aralkylcarbonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and m is 0 to 5) Is an integer.)
(7) The epoxy resin composition for optical semiconductor encapsulation according to any one of (2) to (6), wherein the epoxy resin curing agent is a polyvalent carboxylic acid resin.
(8) A cured product obtained by curing the epoxy resin composition for optical semiconductor encapsulation according to any one of (1) to (7).
(9) An optical semiconductor device comprising the cured product according to (8).

  According to the present invention, an epoxy resin composition containing a silicone skeleton epoxy resin and a cationic polymerization initiator is extremely excellent in heat resistance, light resistance, curability, hardness, heat cycle resistance, and gas corrosion resistance, so that it is an optical semiconductor. It is extremely useful as an epoxy resin composition for sealing.

  The epoxy resin composition for optical semiconductor encapsulation of the present invention contains a silicone skeleton epoxy resin and a cationic polymerization initiator.

  The silicone skeleton epoxy resin in the present invention is a resin having an epoxy group having a silicone bond (Si—O bond) as a main skeleton, and is obtained by polymerizing, for example, an epoxy group-containing silicon compound and other silicon compounds. And hydrolytic condensation polymer of an alkoxysilane compound having an epoxy group and an alkoxysilane having a methyl group or a phenyl group, and a condensation polymer of an alkoxysilane compound having an epoxy group and a silanol-terminated silicone oil. In addition, addition polymers of a silicone resin having a hydrosilyl group (SiH group) and an epoxy compound having an unsaturated hydrocarbon group such as a vinyl group can be exemplified.

  Among them, the silicone skeleton epoxy resin in the present invention is a two-stage process described later using a silanol-terminated silicone oil (e) and an epoxy group-containing silicon compound (f) (and an alkoxysilicon compound (g) as required) as raw materials. The silicone skeleton epoxy resin obtained through the manufacturing process is most preferable.

From here, the silanol-terminated silicone oil (e), the epoxy group-containing silicon compound (f), and the alkoxysilicon compound (g) will be described.
First, the silanol-terminated silicone oil (e) will be described.
The silanol-terminated silicone oil (e) in the present invention is a silicone resin represented by the following formula (1) and having silanol groups at both ends.

In formula (1), R ₅ represents an alkyl group having 1 to 3 carbon atoms such as a methyl group or a phenyl group. A plurality of R ₅ may be the same or different, but it is preferable to contain a phenyl group from the viewpoint of compatibility with other resins, high refractive index, and improvement in sulfur resistance.
From the viewpoint of adjusting the viscosity of the silicone skeleton epoxy resin, it is preferable to contain a methyl group.

  The proportion of the phenyl group to be contained is preferably 0.05 to 2.0 mol, more preferably 0.1 to 1.0 mol, and still more preferably 0.15 to 0.3 mol, with respect to 1 mol of the substituted methyl group. Particularly preferred is 0.15 to 0.2 mol. If it is less than 0.05 mol, the compatibility with the other raw materials in the composition may be inferior, the refractive index of the cured product is low, the light extraction efficiency of the LED is deteriorated, and the sulfidation resistance is inferior. If the amount exceeds 2.0 moles, the light resistance (UV resistance) of the cured product may be inferior or the heat cycle resistance may be inferior.

  In Formula (1), p shows 3-200 by an average value, Preferably it is 3-100, More preferably, it is 3-50. When p is less than 3, the cured product becomes too hard, which may be inferior in heat cycle resistance. If p exceeds 200, the mechanical strength of the cured product tends to decrease, which is not preferable.

The range of the weight average molecular weight (Mw) of the silanol-terminated silicone oil (e) is preferably 400 to 3000 (GPC), more preferably 400 to 2000, and still more preferably 400 to 1500. When the weight average molecular weight is less than 400, the properties of the silicone part are difficult to be obtained and the heat resistance and light resistance may be inferior, and when it exceeds 3000, it may be difficult to use due to the severe layer separation structure .
In the present invention, the molecular weight of the silanol-terminated silicone oil (e) 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)

  Silanol-terminated silicone oil (e) is produced, for example, by hydrolyzing and condensing dimethyldialkoxysilane, methylphenyldichlorosilane, diphenylalkoxysilane, dimethyldichlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane. it can.

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

Next, the epoxy group-containing silicon compound (f) will be described.
The epoxy group-containing silicon compound (f) in the present invention is an alkoxysilicon compound represented by the formula (2).

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

In formula (2), R ₆ represents an aryl group having a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, phenyl Group, naphthyl group and the like. Among these, a methyl group and a phenyl group are preferable from the viewpoints of compatibility and heat-resistant transparency of the cured product.

In formula (2), R ₇ 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. Among these, from the viewpoint of reaction conditions such as compatibility and reactivity, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

  In formula (2), q is an integer representing 0, 1, 2 and r represents (3-q). In view of the viscosity of the silicone skeleton epoxy resin (A) and the mechanical strength of the cured product, q is preferably 0 or 1.

  Specific preferred examples of the epoxy group-containing silicon compound (f) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxy. Propyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylcyclohexyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylphenyldimethoxysilane, 2- (3, 4-D Carboxymethyl) ethyl cyclohexyl dimethoxysilane, and the like, especially 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferable. These epoxy group-containing silicon compounds (f) may be used alone or in combination of two or more, and may be used in combination with the alkoxy silicon compound (g) shown below.

  In the silicone skeleton epoxy resin, an alkoxy silicon compound (g) represented by the following formula (3) can be used in combination with the epoxy group-containing silicon compound (f). By using the alkoxysilicon compound (g) in combination, the viscosity, refractive index and the like of the silicone skeleton epoxy resin can be adjusted.

In formula (3), R ₆ and R ₇ are the same as described above, s is an integer, 0, 1, 2, 3 and t is (4-s).

  Specific examples of preferred alkoxysilicon compounds (g) that can be used in combination include methyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and diphenyl. Examples include dimethoxysilane and diphenyldiethoxysilane. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and diphenyldimethoxysilane are preferable.

  In the present invention, at least one of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and the alkoxysilicon compound (g) if necessary) has an aromatic skeleton. It is preferable to use a compound having a phenyl group from the viewpoint of an increase in refractive index and a reduction in sulfur resistance, and it is particularly preferable to use a compound having a phenyl group. In particular, the silanol-terminated silicone oil (e) preferably has a phenyl group. This is because the silanol-terminated silicone oil (e) introduced with a phenyl group can easily suppress an excessive increase in viscosity of the silicone skeleton epoxy resin, while an epoxy group-containing silicon compound with a phenyl group ( This is because when f) (and the alkoxysilicon compound (g) as required) is used, the increase in viscosity becomes large and workability may be inferior.

  In the production of the silicone skeleton epoxy resin, the alkoxy group of the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)) is added to one equivalent of the silanol group of the silanol-terminated silicone oil (e). When the reaction is carried out in an amount less than 1.5 equivalents, two or more alkoxy groups in the epoxy group-containing silicon compound (f) (and the alkoxy silicon compound (g) if necessary) are converted into the silanol-terminated silicone oil (e). It will react with a silanol group, and may become a polymer too much at the end of the production step 1 described later, resulting in gelation. For this reason, it is preferable to make an alkoxy group react with 1.5 equivalent or more with respect to 1 equivalent of silanol groups, and 2.0 equivalent or more is more preferable from a viewpoint of reaction control.

Next, manufacturing steps 1 and 2 will be described.
(Manufacturing process 1)
A step of obtaining a modified silicone oil (h) by condensing the silanol group of the silanol-terminated silicone oil (e) and the alkoxy group of the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)). .
(Manufacturing process 2)
A step of adding water after the production step 1 to hydrolyze and condense the remaining alkoxy groups.
In the present invention, the modified silicone oil (h) and the epoxy group-containing silicon compound (f) (and the alkoxysilicon compound (g) if necessary) are polymerized through the production steps 1 and 2 described above.

  By dividing the production process into two stages, the silanol group of the silanol-terminated silicone oil (e) and the alkoxy group of the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxy silicon compound (g)) are ensured. To obtain a modified silicone oil (h), and then subjecting the remaining alkoxy group to dealcohol hydrolysis hydrolysis, a uniform and stable product can be obtained.

  When water is added from the beginning of the manufacturing process in one step, the condensation reaction between the silanol group and the alkoxy group and the polymerization reaction between the alkoxysilanes become a competitive reaction, resulting in a difference in the reaction rate between the products and the compatibility of the products. Due to the difference, a heterogeneous compound can be obtained, or a large amount of silanol-terminated silicone oil (e) having no epoxy group can be adversely affected.

In the production process 1, the reaction is preferably performed in the presence of a solvent, and alcohol is particularly preferable among the solvents from the viewpoint of reaction control. Examples of the alcohol that can be used include alcohols having 1 to 10 carbon atoms, specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, and cyclopentanol. Etc. In the present invention, primary alcohols and secondary alcohols are preferable, and it is particularly preferable to use primary alcohols or a mixture of primary alcohols and secondary alcohols. Examples of primary alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, nonane alcohol, decane alcohol, propylene glycol, and the like. Examples of secondary alcohols include isopropanol, cyclohexanol, propylene glycol. Etc. In addition, from the viewpoint of subsequent removability, a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol is preferable. These alcohols may be used as a mixture. When they are mixed, it is preferable to use at least two kinds selected from primary alcohols and secondary alcohols, and that at least one component is a primary alcohol. It is more preferable because the solubility of the catalyst is excellent. The amount of primary alcohol is preferably 5% by weight or more, more preferably 10% by weight or more of the total alcohol amount.
By using a secondary alcohol in combination with this reaction, the amount of change in the weight average molecular weight per unit time in the reaction system of production process 1 is smaller than when only the primary alcohol is used, so the reaction is more easily controlled. It is. In general, in the case of large-scale reactions such as industrial production, it becomes difficult to strictly control the reaction time and reaction temperature, so the combined use of secondary alcohols is particularly important for large-scale reactions such as industrial production from the viewpoint of reaction control. Useful for.
In the production process 1, the amount of alcohol used is 2% by weight or more based on the total weight of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)). It is preferable that 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. There is a possibility that a problem such as an increase in elastic modulus that makes it difficult to occur.
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. It can be illustrated.

The reaction in the production step 1 can be performed without a catalyst. However, since the reaction proceeds slowly with no catalyst, it is preferably performed in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst that can be used, any compound that exhibits acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, alkali metals such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate. Inorganic bases such as carbonates, and organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, 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 are preferable, and hydroxides are particularly preferable.
The amount of the catalyst added is usually 0.001 to 5% by weight based on the total weight of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)). Is more preferable, and 0.01 to 2% by weight is more preferable.
The catalyst can be added directly or in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol. In this case, addition as an aqueous solution using water or the like causes a sol-gel reaction other than the target reaction to proceed competitively, and the epoxy group-containing silicon compound (f) (and alkoxysilicon as necessary) Care must be taken because the polycondensation of the alkoxy group of the compound (g)) proceeds unilaterally and the resulting reaction product and the silanol-terminated silicone oil (e) may become incompatible and cloudy. is there.
In this case, the allowable range of moisture is 0.5% by weight or less based on the total weight of the silanol-terminated silicone oil (e) and the epoxy group-containing silicon compound (f) (and, if necessary, the alkoxysilicon compound (g)). More preferably, it is 0.3% by weight or less, and it is further more preferable that there is as little water as possible.

  Although the reaction temperature of the manufacturing process 1 is based also on a catalyst amount and the solvent to be used, 20-160 degreeC is preferable normally, More preferably, it is 40-100 degreeC, Especially preferably, it is 50-95 degreeC. The reaction time is usually preferably 1 to 20 hours, more preferably 3 to 12 hours.

  Thus, it is thought that the modified silicone oil (h) obtained by the manufacturing process 1 has the structure shown by following formula (8) as a main component (it is difficult to confirm a structure and identifies correctly) I can't.)

In the formula (8), R ₅ and p have the same meaning as described above. R ₈ represents any one of the aforementioned X, R ₆ , and —OR ₇ , and R ₉ represents any one of R ₆ and —OR ₇ , respectively.

Next, the manufacturing process 2 will be described in detail.
After completion of the reaction in the production step 1, water is added, and the alkoxy groups remaining in the resulting modified silicone oil (h) are polymerized (sol-gel reaction). At this time, the silicon compound (f) containing the above-mentioned epoxy group (and the alkoxysilicon compound (g) if necessary) and the catalyst may be added within the above-mentioned range as necessary. This reaction is performed between (1) the modified silicone oils (h) and / or (2) the silicon compound (f) containing an epoxy group (and the alkoxysilicon compound (g) if used). And / or (3) a silicon compound (f) containing an epoxy group (and an alkoxy silicon compound (g) if used), and (4) a silicon compound (f) containing an epoxy group ( And when using, it is the process of performing a polymerization reaction between the partial polymer of an alkoxy silicon compound (g)) and modified silicone oil (h). The polymerization reactions (1) to (4) are considered to proceed in parallel at the same time.
In particular, in the production process 2, as described above, a basic inorganic catalyst is preferable as the catalyst, and a necessary amount may be added in the production process 1 in advance. However, it is not preferable to exceed the range described as a preferred embodiment in the production process 1.

In the production process 2, it is preferable to add a solvent.
As in the production process 1, alcohol is preferably used as the solvent in the production process 2. Examples of the alcohol that can be used include alcohols having 1 to 10 carbon atoms, specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, and cyclopentanol. Etc. In the present invention, primary alcohols and secondary alcohols are particularly preferred, and primary alcohols are particularly preferred. In addition, from the viewpoint of subsequent removability, a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol is preferable. These alcohols may be used as a mixture. The presence of these alcohols contributes to molecular weight control and stability.
As the addition amount of the alcohol, the total weight of the silanol-terminated silicone oil (e) and the silicon compound (f) containing an epoxy group (and the alkoxysilicon compound (g) if necessary) charged in the production process 1, It is preferably 20 to 200% by weight, more preferably 20 to 150% by weight, and particularly preferably 30 to 120% by weight.

In the production process 2, water is added (ion exchange water, distilled water, or clean water can be used). The amount of water used is preferably 0.5 to 8.0 equivalents, more preferably 0.6 to 5.0 equivalents, and particularly preferably 0.65 to 2.0 equivalents with respect to the amount of remaining alkoxy groups. is there.
When the amount of water is less than 0.5 equivalent, the reaction proceeds slowly, and the silicon compound (f) containing an epoxy group (and, if necessary, the alkoxysilicon compound (g)) remains without reacting. There is a possibility that a problem such as the above will occur, a sufficient network may not be formed, and a curing failure may occur even after curing after the subsequent epoxy resin composition. On the other hand, if it exceeds 8.0 equivalents, the molecular weight control is not effective, and the molecular weight may be higher than necessary. Furthermore, there is a possibility of inhibiting the stability of the silicone skeleton epoxy resin (A).

  Although the reaction temperature of the manufacturing process 2 is based also on a catalyst amount and a solvent to be used, 20-160 degreeC is preferable normally, More preferably, it is 40-100 degreeC, Especially preferably, it is 50-95 degreeC. The reaction time is usually preferably 1 to 20 hours, more 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. Examples of preferable 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. it can.

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 the basic compounds include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. Inorganic bases such as alkali metal carbonates, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid, sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol Organic bases such as triethanolamine and tetramethylammonium hydroxide can be used. Among these, an inorganic base or an inorganic acid is preferable because it can be easily removed from the product, and phosphates that can more easily adjust the pH to near 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, activated clay SA35, SA1, T, R-15, E, Nikkanite (trade names) G-36, G-153, G-168 manufactured by Toshin Kasei Co., Ltd. As a product made by the company, Galeon Earth (trade name), Mizuka Ace (trade name) and the like can be mentioned. As the activated carbon, for example, CL-H, Y-10S, Y-10SF, manufactured by Ajinomoto Fine Techno Co., S, Y, FC, DP, SA1000, K, A, KA, M, manufactured by Phutamura Chemical Co., Ltd. Examples thereof include CW130BR, CW130AR, and GM130A. Examples of the zeolite include, for example, molecular sieves (trade names) 3A, 4A, 5A, and 13X, manufactured by Union Showa. Examples of the synthetic adsorbent include Kyowa Chemical Co., Ltd., Kyoward (trade name) 100, 200, 300, 400, 500, 600, 700, 1000, 2000, and Rohm and Haas Co., Ltd. (Product Name) 15JWET, 15DRY, 16WET, 31WET, A21, Amberlite (Product Name) IRA400JCl, IRA403BLCl, IRA404JCl, manufactured by Dow Chemical Company, Dowex (Product Name) 66, HCR-S, HCR-W2, MAC- 3 etc. are 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 carried out using a solvent mixed with water as the reaction solvent, the reaction solvent mixed with water is removed from the system by distillation or vacuum concentration after quenching, and then washed with water in combination with a solvent that can be separated from water. It is preferable to do so.

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

The appearance of the silicone skeleton epoxy resin thus obtained is normally colorless and transparent and is a liquid having fluidity at 25 ° C. The molecular weight is preferably 800 to 3000, more preferably 1000 to 3000, and particularly preferably 1500 to 2800 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the heat resistance may be lowered. When the weight average molecular weight is more than 3000, the encapsulant may be peeled off from the substrate during reflow soldering of the LED element encapsulated using the weight average molecular weight.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured under the following conditions using GPC (gel permeation chromatography).

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

The epoxy equivalent (measured by the method described in JIS K-7236) of the silicone skeleton epoxy resin is 300 to 1500 g / eq. Are preferred, those with 320 to 1400 g / eq are more preferred, those with 350 to 1200 g / eq, particularly 350 to 1000 g / eq are preferred. When the epoxy equivalent is less than 300 g / eq, the cured product tends to be too hard, and when it exceeds 1500 g / eq, the mechanical properties of the cured product tend to deteriorate.
The silicone skeleton epoxy resin may be a single silicone skeleton epoxy resin or a mixture of two or more silicone skeleton epoxy resins. Here, from the viewpoint of appropriate mechanical strength of the cured product, when the silicone skeleton epoxy resin is a mixture of two or more kinds of silicone skeleton epoxy resins, the epoxy equivalent of the specific silicone skeleton epoxy resin × (the specific skeleton The total epoxy equivalent of (content of silicone skeleton epoxy resin / total amount of silicone skeleton epoxy resin) is preferably 300 to 1500 g / eq, and particularly preferably 350 to 1000 g / eq.

  The viscosity of the silicone skeleton epoxy resin (E-type viscometer, measured at 25 ° C.) is preferably 50 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, particularly 800 to 5,000 mPa · s. s is preferred. When the viscosity is less than 50 mPa · s, the viscosity is too low and may not be suitable when used as a sealing material or the like. When the viscosity exceeds 20,000 mPa · s, the viscosity is too high or the sealing material or the like. May be inferior in workability.

In the silicone skeleton epoxy resin, 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, and there is a concern of surface tack and scratches. . Moreover, when it exceeds 50 mol%, it exists in the tendency for hardened | cured material to become hard too much and is not preferable.
The proportion of silicon atoms present can be determined by 1H NMR, 29Si NMR, elemental analysis, etc. of the silicone skeleton epoxy resin.

  The silanol-terminated silicone oil (e) obtained through the production steps 1 and 2, which is a preferred embodiment of the silicone skeleton epoxy resin in the present invention, and the silicon compound (f) containing an epoxy group (and if necessary) The condensate with the alkoxysilicon compound (g)) has been described.

  As the silicone skeleton epoxy resin, the above silanol-terminated silicone oil (e) is not used, and a condensation polymer of an epoxy group-containing silicon compound (f) (and, if necessary, an alkoxysilicon compound (g)), Can also be illustrated.

  In this case, the silicon compound (f) containing an epoxy group represented by the above formula (4) (and optionally represented by the above formula (5) can be produced by a one-step reaction. The alkoxysilicon compound (g)) can be obtained by adding water dropwise in the presence of a catalyst and a solvent as described above and condensing under a reaction temperature of 40 to 100 ° C. and a reaction time of 1 to 24 hours.

  After the condensation, a condensate of the silicon compound (f) containing an epoxy group (and, if necessary, the alkoxysilicon compound (g)) can be obtained by quenching, removing, washing with water, and concentrating as described above. .

An embodiment of the silicone skeleton epoxy resin that is particularly preferable from the viewpoint of having an excellent pot life of the present invention is as follows.
(I) The silicone frame | skeleton epoxy resin whose ratio of the phenyl group in the substituent linked to silicon is 0.05-2.0 mol with respect to 1 mol of substituted methyl groups.
(Ii) A silicone skeleton epoxy resin in which the ratio of the phenyl group in the substituent linked to silicon is 0.15 to 0.2 mol with respect to 1 mol of the substituted methyl group.
(Iii) The silicone skeleton epoxy resin according to (i) or (ii), wherein the ratio of silicon atoms to which three oxygen atoms are bonded to all silicon atoms is 3 to 50 mol%.
(Iv) The silicone skeleton epoxy resin according to (i) or (ii), wherein the ratio of silicon atoms to which three oxygen atoms are bonded to all silicon atoms is 6 to 15 mol%.
(V) The silicone skeleton epoxy resin according to any one of (i) to (iv), wherein an epoxy equivalent is 350 to 1000 g / eq.
(Vi) In the case of a mixture of two or more kinds of silicone skeleton epoxy resins, the epoxy equivalent of the specific silicone skeleton epoxy resin × (content of the specific silicone skeleton epoxy resin (A) / silicone skeleton epoxy resin (A) (I) to (iv). The silicone skeleton epoxy resin mixture according to any one of (i) to (iv), wherein the total epoxy equivalent of (total amount) is 350 to 1000 g / eq.

The cationic polymerization initiator (B) in the present invention can be used without particular limitation as long as it can generate a Bronsted acid, a Lewis acid or the like by heating to initiate an epoxy group binding reaction. Examples of the thermal cationic polymerization initiator include onium salts such as sulphonium salts, ammonium salts, and phosphonium salts, and silanol / aluminum complexes.
In the present invention, the cationic polymerization initiator is not particularly limited, and any desired cationic polymerization initiator can be used to obtain the intended effect.
By using a cationic polymerization initiator, the calorific value can be increased. Due to the increase in the calorific value, it is possible to improve the hardness of the epoxy resin composition containing the epoxy group and / or the epoxy resin curing agent, and to exhibit a desired effect.
Moreover, it is thought that the improvement of physical properties, such as hardness, is influenced by superposition | polymerization of epoxy groups.

Specific examples of the thermal cationic polymerization initiator include arylsulfonium complex salts described in US Pat. No. 4,231,951; aromatic iodonium complex salts and aromatic sulfonium complex salts described in US Pat. No. 4,256,828; “Journal of Polymer Science” (Journal of Polymer Science), Polymer Chemistry. R. Bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (for example, phosphates, arsenates, antimonates, etc.) described in Watt et al., Vol. 22, p. 1789 (1984), USA Metal fluoroboron complex salts and boron trifluoride complex compounds described in US Pat. No. 3,379,653; Bis (perfluoroalkylsulfonyl) methane metal salts described in US Pat. No. 3,586,616; Aryl diazonium compounds described in US Pat. No. 3,708,296 An aromatic onium salt of a Group VIa element described in US Pat. No. 4,058,400; an aromatic onium salt of a Group Va element described in US Pat. No. 4069055; a di group of a Group IIIa-Va element described in US Pat. No. 4068091; A carbonyl chelate; a thiopyrylium salt described in US Pat. No. 4,139,655; Country Patent (here M phosphorus, antimony and is selected from arsenic) ^{MF 6-} anions described in No. 4,161,478 VIb group element form of; fluorinated alkyl phosphoric acid described in Japanese Patent 2012-56915 A sulfonium salt etc. can be mentioned.

  These thermal cationic polymerization initiators can be obtained as commercial products. For example, CI-2855, CI-2624 (all manufactured by Nippon Soda), CATEX-1 (manufactured by Daicel Chemical Industries), Adekaoptomer (trade name) ) CP-66, Adekaoptomer CP-67 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Sun Aid (trade name) SI-60L, Sun Aid SI-80L, Sun Aid SI-1000L (all manufactured by Sanshin Chemical Industry Co., Ltd.), NB -101, NB-201 (all manufactured by Midori Chemical), TA-100 (manufactured by San Apro), TA-120 (manufactured by San Apro), TA-160 (manufactured by San Apro), and the like.

As the cationic polymerization initiator contained in the epoxy resin composition of the present invention, a cation having a specific structure and an anion having a specific structure can be preferably used.
As the suitable compound, those composed of the following cation (K) and the following anion (AN) can be used.
Cation (K):

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and are a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkoxy group, an aralkyl group, an aryl group or an alkyl group. Represents an aryl group, and R ₁ and R ₂ may combine with each other to form a ring)

Anion (AN):
Following formula (5)

(In the formula, X represents Sb, As, or P. Y represents fluorine, chlorine, bromine, or iodine. In the formula, R ₄ may be the same or different, and fluorine, chlorine, bromine, or iodine. And b is an integer of 0 to 5.)
Or the following formula (6)

(In the formula, Y represents fluorine, chlorine, bromine, or iodine. R ₅ may be the same or different, and is an alkyl or aryl group substituted or unsubstituted with fluorine, chlorine, bromine, or iodine, or fluorine. (N is an integer of 0 to 5)

The cation (K) will be described in more detail.
In the above formula (4), R _{1 to} R ₃ are usually a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkoxy group, an aralkyl group, an aryl group, or an alkylaryl group. R ₁ and R ₂ may be bonded to each other to form a ring. Here, the substitution in the above formula (4) means that a hydrogen atom is replaced by a halogen atom or the like, specifically Includes a halogen atom and a hydroxyl group.
In addition, R ₁ and R ₂ being bonded to each other to form a ring specifically means a structure of the following formula.

(In the above formula, the cyclic part is connected to R ₁ and R ₂ and represents an alkylene group having 1 to 10 carbon atoms or an alkenylene group.)
Here, in _R 1, _{R 2} in the formula (4), an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylaryl group.

In the cation (K), R ₃ in the formula (4) is preferably the following formula (7).

(R ₆ represents a hydrogen atom, an alkyl group, a hydroxy group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an aralkylcarbonyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and m is 0 to 0. (It is an integer of 5.)
Here, R ₆ is preferably a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, a carboxy group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an aralkylcarbonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. More preferably a hydrogen atom, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, a carboxyl group, an alkoxy group or an aryloxy group, and particularly preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms and a carboxyl group. Group or alkoxy group.

Next, the anion will be described in more detail.
In the above formulas (5) and (6), R ₄ and R ₅ are a substituted, unsubstituted alkyl group or aryl group with fluorine, chlorine, bromine or iodine. The substitution in the formulas (5) and (6) in this specification means that a hydrogen atom is replaced by a halogen atom, and in both of them, 80% or more of the hydrogen atoms of R ₄ are fluorine. An alkyl group or an aryl group substituted with an atom is preferable.
Here, the alkyl group and the aryl group usually preferably have 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
X is preferably a phosphorus atom.

  In the cationic polymerization initiator of the present invention, a combination of preferred ones among the cations and anions detailed above can be used particularly suitably.

In the present invention, the cationic polymerization initiator is used as a composition with the silicone skeleton epoxy resin.
By using in this way, it becomes possible to obtain a well-balanced epoxy resin composition excellent in heat resistance, light resistance and corrosion gas resistance in addition to hardness.
Furthermore, by using together with the said epoxy resin and setting it as the epoxy resin composition containing the epoxy resin hardening | curing agent, the hardened | cured material excellent also in toughness can be obtained, implement | achieving high hardness.
Here, the suitable ratio of the cationic polymerization initiator, the epoxy resin curing agent, and the epoxy resin is such that the epoxy resin curing agent is 1.2 equivalents or less, more preferably 0.6 equivalents or less with respect to 1 equivalent of the epoxy group. Yes, it is a case where the cationic polymerization initiator is blended so as to be 0.0001 to 0.3 parts by weight, more preferably 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the epoxy resin.

In this invention, it becomes possible to obtain the hardened | cured material excellent in corrosion-gas resistance by using together the curing catalyst (curing accelerator) mentioned later with the said cationic polymerization initiator.
In this case, the content ratio of the cationic polymerization initiator and the curing accelerator is preferably such that the cationic polymerization initiator is 1 to 20% by weight of the curing accelerator.

  These may be used alone or as a mixture of two or more. The amount of the thermal cationic polymerization initiator contained in the epoxy resin composition of the present invention is preferably 0.0001 to 0.3 parts by weight, particularly preferably 0.01 to 0.00 parts by weight based on 100 parts by weight of the epoxy resin. 1 part by weight.

The epoxy resin composition of the present invention can be used by mixing an epoxy resin in addition to the silicone skeleton epoxy resin.
Other epoxy resins that can be used include epoxy resins that are glycidyl etherification products of phenolic compounds, epoxy resins that are glycidyl etherification products of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, Glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, copolymers of polymerizable unsaturated compounds having an epoxy group and other polymerizable unsaturated compounds, etc. Can be mentioned.

  Examples of the epoxy resin that is a glycidyl etherified product of the phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3, -Hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, Dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) Ethyl) phenyl] propane, 2,2'-methy -Bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglucinol, Examples thereof include phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

  Examples of epoxy resins that are glycidyl etherified products of various novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols. And glycidyl etherified products of various novolac resins such as a novolak resin, a phenol novolac resin containing a xylylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolac resin containing a fluorene skeleton.

Examples of the alicyclic epoxy resin include alicyclic rings having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. An epoxy resin is mentioned.
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.
Examples of 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 Laid-Open No. 2003-170059, Japanese Patent Laid-Open No. 2004-262871, etc.), and further transesterification 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).

Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester-based epoxy resin include epoxy resins made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
Examples of epoxy resins obtained by glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like. An epoxy resin obtained by glycidylating any of the halogenated phenols.

  As a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound other than that, there are Marproof (trade name) G-0115S, G-0130S, G-0250S, G-1010S, G-0150M, G-2050M (manufactured by NOF Corporation) and the like. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, methacrylic acid, and the like. Examples thereof include glycidyl acid, 4-vinyl-1-cyclohexene-1, 2-epoxide and the like. Examples of other polymerizable unsaturated compound copolymers include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and vinylcyclohexane.

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

When the silicone skeleton epoxy resin and another epoxy resin are used in combination, the above-described epoxy resin can be used, and among them, an alicyclic epoxy resin is preferable from the viewpoint of transparency.

  When the silicone skeleton epoxy resin and another epoxy resin are used in combination, the ratio of the silicone skeleton epoxy resin to the total epoxy resin composition is preferably 60 to 99 parts by weight, particularly 90 to 97 parts by weight. preferable. If the amount is less than 60 parts by weight, the light resistance (UV resistance) of the cured product may be inferior.

  An epoxy resin curing agent can be mixed and used in the epoxy resin composition of the present invention.

The epoxy resin curing agent will be described.
Examples of the epoxy resin curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polyvalent carboxylic acids, and polyvalent carboxylic acid resins.
The epoxy resin curing agent in the present invention is particularly an acid anhydride (C1), a polyvalent carboxylic acid (C2) having at least two carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton from the viewpoint of heat resistance. Or a polyhydric alcohol compound (a) having two or more hydroxyl groups in the molecule, a compound (b) having one carboxylic anhydride group in the molecule, and two or more carboxylic acids in the molecule, which will be described later. The polycarboxylic acid resin (C3) obtained by addition reaction with the compound (c) having an acid anhydride group is preferred.

Specific examples of the acid anhydride (C1) include succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, phthalic anhydride, naphthalenedicarboxylic anhydride, trimellit Acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, bicyclo [ 2.2.1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3, 4-anhydride, pentanedioic anhydride, 2,4-diethylpentanedioic anhydride, 2,2-dimethylpentanedioic anhydride 3,3-dimethylpentanedioic anhydride, 1,1-cyclopentanedioic anhydride, 1,1-cyclohexanedioic anhydride, diglycolic anhydride, maleic anhydride, itaconic anhydride, citraconic acid Anhydride, dodecyl succinic anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, bicyclo [2,2,2] Octane-2,3-dicarboxylic acid anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -5-octene-2,3-dicarboxylic acid anhydride And 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride.
In particular, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane -2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 2, 4-Diethylpentanedioic anhydride and the like are preferable from the viewpoints of light resistance, transparency, and workability.

The polyvalent carboxylic acid (C2) is a compound having at least two carboxyl groups.
The polyvalent carboxylic acid is preferably a bifunctional to hexafunctional carboxylic acid, such as butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, malic acid, etc. Linear alkyl diacids, alkyl tricarboxylic acids such as 1,3,5-pentanetricarboxylic acid and citric acid, phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid Examples include aliphatic cyclic polycarboxylic acids such as acid, nadic acid, and methyl nadic acid, multimers of unsaturated fatty acids such as linolenic acid and oleic acid, and dimer acids that are reduced products thereof, and the above acid anhydrides are saturated. A polyvalent carboxylic acid which is an aliphatic cyclic acid anhydride is preferred from the viewpoint of transparency.

  The polyvalent carboxylic acid resin (C3) preferred as an epoxy resin curing agent used in the epoxy resin composition of the present invention includes an alcoholic hydroxyl group of a polyhydric alcohol compound (a) having two or more hydroxyl groups in the molecule described below, The compound (b) having one carboxylic anhydride group in the molecule and / or the acid anhydride group of the compound (c) having two or more carboxylic anhydride groups in the molecule can be obtained by addition reaction. It is a compound and has two or more carboxylic acids in the molecule as functional groups.

From here, a polyhydric alcohol compound (a) having two or more hydroxyl groups in the molecule and a compound having one carboxylic anhydride group in the molecule (raw material), which are raw materials for the polyvalent carboxylic acid resin (C3) b) The compound (c) having two or more acid anhydride groups in the molecule will be described.
The polyhydric alcohol compound (a) having two or more hydroxyl groups in the molecule has 1 to 10 carbon atoms such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol. Alkylene diol, EO-modified bisphenol A, EO-modified bisphenol F, EO-modified bisphenol E, EO-modified naphthalene diol, PO-modified bisphenol A, both-end carbinol-modified silicone oil (a1), a chain alkylene diol having a branched structure (a2) A polyhydric alcohol having an alicyclic structure (a3), a polyhydric alcohol having three or more hydroxyl groups in the molecule (a4), a polyhydric alcohol having two or more hydroxyl groups in the molecule and having 2 to 8 carbon atoms. Lactones were subjected to ring-opening addition polymerization Polyhydric alcohol-modified lactone polymer (a5), polycyclic polyphenol compound (polycyclic polyphenol compound is a compound having two or more six-membered rings and having two or more phenolic hydroxyl groups Alcohol compound (a6) in which one or more aromatic rings having a hydroxyl group are hydrogenated, and at least one polyhydric alcohol compound selected from these groups can be used, Two or more types may be used in combination. Preferably, both terminal carbinol-modified silicone oil (a1), a branched alkylene diol (a2) having a branched structure, a polyhydric alcohol (a3) having an alicyclic structure, a polyhydric alcohol having three or more hydroxyl groups in the molecule (A4), polyhydric alcohol-modified lactone polymer (a5), and alcohol compound (a6) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyphenol compound are hydrogenated.

First, the both terminal carbinol-modified silicone oil (a1) will be described.
Both terminal carbinol-modified silicone oil (a1) is a silicone compound having an alcoholic hydroxyl group at both ends represented by the following formula (9).

In (Equation (9), the _{R 1} is an alkylene group having an alkylene group or an ether bond of carbon atoms in total 1 to 10, _{R 2} is an alkyl group or a phenyl group having 1 to 3 carbon atoms, m is 1 to the mean value 100 represents each.)

In the formula (9), specific examples of R ₁ include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups, ethoxyethylene group, propoxyethylene group propoxy Examples include an alkylene group having an ether bond such as a propylene group and an ethoxypropylene group. Particularly preferred are propoxyethylene group and ethoxypropylene group.

Next, R ₂ represents an alkyl group having 1 to 3 carbon atoms such as a methyl group or a phenyl group, and may be the same or different, but both ends carbinol-modified silicone oil (a1) and (if necessary) An addition reaction between another polyhydric alcohol compound, compound (c) having two or more acid anhydride groups in the molecule, and compound (b) having one acid anhydride group in the molecule In order for the obtained polyvalent carboxylic acid resin to be liquid at room temperature, a methyl group is preferred compared to a phenyl group.

  In formula (9), m is an average value of 1 to 100, preferably 2 to 80, more preferably 5 to 30.

  For example, X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-201, BY16-004 are used as the both-end carbinol-modified silicone oil (a1) represented by the formula (9). SF8427 (both manufactured by Toray Dow Corning Co., Ltd.) XF42-B0970, XF42-C3294 (both manufactured by Momentive Performance Materials Japan GK) Silaplane (trade names) FM-4411, FM-4421, FM-4425 (both manufactured by JNC Co., Ltd.) and the like can be mentioned, and all are available from the market. These two terminal carbinol-modified silicone oils can be used alone or in combination. Among these, X-22-160AS, KF6001, KF6002, BY16-201, XF42-B0970, and FM-4411 are preferable.

Next, the chain alkylene diol (a2) having a branched structure which is a polyhydric alcohol compound will be described. Specific examples of the branched alkylene diol (a2) having a branched structure include, for example, neopentyl glycol, 2-ethyl-2-butylpropylene-1,3-diol, 2,4-diethylpentane-1,5-diol, Examples include, but are not limited to, dimethylbutanediol, dimethylpentanediol, diethylpropanediol, dimethylhexanediol, diethylbutanediol, dimethylheptanediol, diethylpentanediol, dimethyloctanediol, diethylhexanediol, and ethylbutylpropanediol. There is nothing. These may be used alone or in combination of two or more.
Applying a chain alkylene diol having a branched structure is preferable because the gas permeation resistance of the cured product is improved.

Next, the polyhydric alcohol (a3) which has an alicyclic structure which is a polyhydric alcohol compound is demonstrated. Specific examples of the polyhydric alcohol having an alicyclic structure which is a particularly preferred polyhydric alcohol compound include cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, tricyclodecanediol, pentacyclodecane dimethanol, norbornanediol, norbornanedi. Examples thereof include, but are not limited to, methanol, dioxane glycol, and spiro glycol. These may be used alone or in combination of two or more.
It is preferable to apply a polyhydric alcohol having an alicyclic structure because gas permeability resistance is improved in the cured product.

Next, the polyhydric alcohol (a4) which has a 3 or more hydroxyl group in the molecule | numerator which is a polyhydric alcohol compound is demonstrated. Specific examples of polyhydric alcohols having three or more hydroxyl groups in the molecule which are particularly preferred polyhydric alcohol compounds include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, and isocyanuric acid tris (2-hydroxyethyl). , Pentaerythritol, ditrimethylolpropane, diglycerol, dipentaerythritol and the like, but are not limited thereto. These may be used alone or in combination of two or more.
Applying a polyhydric alcohol having three or more hydroxyl groups in the molecule is preferable because the hardness of the cured product is improved.

Next, the polyhydric alcohol (a5) obtained by ring-opening addition polymerization of a lactone having 2 to 8 carbon atoms to a polyhydric alcohol having two or more hydroxyl groups in the molecule, which is a polyhydric alcohol compound, will be described. It is used to obtain a polyhydric alcohol-modified lactone polymer obtained by ring-opening addition polymerization of a lactone having 2 to 8 carbon atoms to a polyhydric alcohol having two or more hydroxyl groups in the molecule, which is a particularly preferred polyhydric alcohol. Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and other alkylene diols having 1 to 10 carbon atoms, EO (ethylene oxide) modification Bisphenol A, EO-modified bisphenol F, EO-modified bisphenol E, EO-modified naphthalenediol, PO (propylene oxide) -modified bisphenol A, a branched alkylene diol having a branched structure, neopentyl glycol, 2-ethyl-2-butyl group Pyrene-1,3-diol, 2,4-diethylpentane-1,5-diol, dimethylbutanediol, dimethylpentanediol, diethylpropanediol, dimethylhexanediol, diethylbutanediol, dimethylheptanediol, diethylpentanediol, dimethyl Cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, tricyclodecanediol, pentacyclodecane dimethanol, norbornanediol, which is a polyhydric alcohol having an alicyclic structure, such as octanediol, diethylhexanediol, ethylbutylpropanediol, Norbornanedimethanol, dioxane glycol, spiroglycol, 2,2-bis (4-hydroxycyclohexyl) propane, etc. Terminals represented by formula (3) such as glycerin, trimethylolpropane, isocyanuric acid tris (2-hydroxyethyl), pentaerythritol, ditrimethylolpropane, diglycerol, dipentaerythritol, etc., which are polyhydric alcohols having a hydroxyl group above Examples include alcohol polyester compounds, but are not limited thereto. Among these, alkylene oxide modified bisphenol A such as EO modified bisphenol A, alkylene oxide modified bisphenol F such as EO modified bisphenol F, polyhydric alcohol having an alicyclic structure, and chain alkylene diol having a branched structure are preferable. These may be used alone or in combination of two or more.
The lactones used for obtaining the polyhydric alcohol-modified lactone polymer are lactones having 4 to 8 carbon atoms. Specific examples include γ-butyrolactone, β-methylpropiolactone, δ-valerolactone, ε -Caprolactone, 3-methylcaprolactone, 4-methylcaprolactone, trimethylcaprolactone, β-methyl-δ-caprolactone and the like.
The polyhydric alcohol-modified lactone polymer is usually preferably in the range of 0.1 to 10 mol, more preferably 0.2 to 5 mol, and still more preferably 0.3 to 2 mol with respect to 1 mol of the hydroxyl group of the polyhydric alcohol. Lactones are used, and catalysts such as alkali metal compounds, tin compounds, titanium compounds, zinc compounds, molybdenum compounds, aluminum compounds, tungsten compounds, etc. are usually preferably used at 80 to 230 ° C., more preferably 100 to 200 ° C. Preferably, it is obtained by reacting at 120 to 160 ° C.

Next, an alcohol compound (a6) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyhydric phenol compound which is a polyhydric alcohol compound is hydrogenated will be described. 1 having a hydroxyl group of a polycyclic polyhydric phenol compound (a polycyclic polyhydric phenol compound is a compound having two or more six-membered rings and having two or more phenolic hydroxyl groups). Examples of the alcohol compound (a6) in which at least one aromatic ring is hydrogenated include 2,2-bis (4-hydroxycyclohexyl) propane (= hydrogenated bisphenol A) and 1,1-bis (4-hydroxycyclohexyl). Ethane (= hydrogenated bisphenol E), 4,4′-bicyclohexanol (= hydrogenated biphenol), 3,3 ′, 5,5′-tetramethyl-4,4′-bicyclohexanol, methylene biscyclohexanol (= Hydrogenated bisphenol F), 4,4 ′, 4 ″ -methylidenetriscyclohexanol, 4,4 ′-[(4-hydroxycyclohexyl) Methylene] bis (2-methylhexanol) 4,4 ′-(1- {4- [1- (4-hydroxycyclohexyl) -1-methylethyl] phenyl} ethylidene) biscyclohexanol, 4,4 ′-[4 -(4-hydroxycyclohexyl) cyclohexylidene] bisphenol, 4,4 '-[4- (4-hydroxycyclohexyl) cyclohexylidene] bis (2-methylphenol), 4,4'-[4- (4- Hydroxycyclohexyl) cyclohexylidene] bis (2,6-dimethylphenol, dihydroxydecahydronaphthalene (= hydrogenated dihydroxynaphthalene), dihydroxytetradecahydroanthracene, 1,4-cyclohexylenebis (methylethanol), 5,5 '-(1-Methylethylidene) bis [1,1'-(bicyclohe Syl) -2-ol], 5,5 ′-(1,1′-cyclohexylidene) bis [1,1 ′-(bicyclohexyl) -2-ol], 5,5 ′-(cyclohexylmethylene) bis [1,1 ′-(bicyclohexyl) -2-ol], 1,1,2,2, -tetrakis (4-hydroxycyclohexyl) ethane, 1,1,2,2, -tetrakis (3,5-dimethyl) -4-hydroxycyclohexyl) ethane, but is not limited thereto, and one kind or a mixture of two or more kinds may be used.
Among these, hydrogenated bisphenol such as hydrogenated bisphenol A, hydrogenated biphenol, and hydrogenated dihydroxynaphthalene are preferable.

Next, the terminal alcohol polyester compound (a7) will be described.
The terminal alcohol polyester compound (a7) is a polyester compound having a hydroxyl group at the terminal represented by the following formula (10).

(In Formula (8), R ₃ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, and n represents an average value of 1 to 100.)

In Formula (10), specific examples of R ₃ include linear alkylene groups having 1 to 10 carbon atoms such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isopropylene, ethylbutylpropylene, isobutylene, Examples thereof include alkylene groups having a branched chain of 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene, and alkylene groups having a cyclic structure such as cyclopentanedimethylene and cyclohexanedimethylene. Among these, an alkylene group having a branched chain having 1 to 10 carbon atoms or an alkylene group having a cyclic structure is preferable, and in particular, ethylbutylpropylene, isobutylene, neopentylene, diethylpentylene, cyclohexanedimethylene is a heat-resistant transparency of a cured product. It is preferable from the viewpoint.

In the formula (10), specific examples of R ₄ include linear alkylene groups having 1 to 10 carbon atoms such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isopropylene, ethylbutylpropylene, isobutylene, Examples thereof include alkylene groups having a branched chain of 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene, and alkylene groups having a cyclic structure such as cyclopentanedimethylene and cyclohexanedimethylene. Among these, a linear alkylene group having 1 to 10 carbon atoms is preferable, and propylene, butylene, pentylene, and hexylene are particularly preferable from the viewpoint of adhesion of a cured product to a substrate.

  In the formula (10), n is an average value of 1 to 100, preferably 2 to 40, more preferably 3 to 30.

  Although the weight average molecular weight (Mw) of terminal alcohol polyester (a7) becomes like this. Preferably it is 500-20000, More preferably, it is 500-5000, More preferably, it is 500-3000. If the weight average molecular weight is less than 500, the cured product hardness of the epoxy resin composition of the present invention is too high, and there is a concern that cracks may occur in a heat cycle test or the like. There are concerns that arise. In the present invention, the weight average molecular weight means a weight average molecular weight (Mw) calculated in terms of polystyrene based on a value measured under the following conditions using GPC (gel permeation chromatography).

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  Examples of the terminal alcohol polyester (a7) represented by the formula (10) include polyester polyols having an alcoholic hydroxyl group at the terminal. Specific examples thereof include polyester polyols such as Kyowapol (trade name) 1000 PA, 2000 PA, 3000 PA, 2000 BA (all manufactured by Kyowa Hakko Chemical Co., Ltd.); Adeka New Ace (trade name) Y9-10, YT-101 (both manufactured by ADEKA); Plaxel (trade name) 220EB, 220EC (both manufactured by Daicel Chemical Industries); Polylite (trade name) OD-X-286, OD-X- 102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2554, OD-X-2108, OD-X-2376 OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2 23, OD-X-2555 (all manufactured by DIC Corporation); HS2H-201AP, HS2H-351A, HS2H-451A, HS2H-851A, HS2N-221A, HS2N-521A, HS2H-220S, HS2N-220S, HS2N-226P, HS2B-222A, HOKOKOOL HT-110, HT-210, HT-12, HT-250, HT-310, HT-40M (all manufactured by Toyokuni Oil Co., Ltd.) Both are available from the market. These polyester compounds can be used alone or in combination of two or more. Among these, Kyowapol 1000PA, Adeka New Ace Y9-10, and HS2N-221A are preferable.

  When both ends carbinol-modified silicone oil (a1) and other polyhydric alcohols are used in combination as the polyhydric alcohol, the other polyhydric alcohol (a) is used in the amount of both ends carbinol-modified silicone oil (a1). The amount is preferably 0.5 to 200 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 10 to 30 parts by weight with respect to 100 parts by weight. If the amount is less than 0.5 parts by weight, the mechanical strength of the cured product may be inferior, and if it exceeds 200 parts by weight, the heat resistant transparency of the cured product may be inferior.

Next, the compound (c) having two or more carboxylic acid anhydride groups in the molecule is, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetra. Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyromellitic anhydride, 5- (2, 5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydro And naphthalene-1,2-dicarboxylic acid anhydride.
The compound (c) having two or more carboxylic acid anhydride groups in the molecule can be used alone or in combination. Among these, since the transparency of the cured product obtained by curing the polyvalent carboxylic acid resin (A) and the epoxy resin described later is excellent, 1, 2, 3, 4-butanetetracarboxylic dianhydride, 1, 2 4,5-cyclohexanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is preferred. In particular, 1,2,3,4-butanetetracarboxylic dianhydride is preferred.

Next, the compound (b) having one carboxylic anhydride group in the molecule is, for example, succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, phthalic anhydride. , Naphthalene dicarboxylic anhydride, trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1, 3,4-tricarboxylic acid-3,4-anhydride, pentanedioic anhydride, 2,4-diethylpentanedioic anhydride, 2, -Dimethylpentanedioic anhydride, 3,3-dimethylpentanedioic anhydride, 1,1-cyclopentanedioic anhydride, 1,1-cyclohexanedioic anhydride, diglycolic anhydride, maleic anhydride , Itaconic anhydride, citraconic anhydride, dodecyl succinic anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, Bicyclo [2,2,2] octane-2,3-dicarboxylic anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -5-octene -2,3-dicarboxylic acid anhydride, 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, and the like.
The compound (b) having one carboxylic anhydride group in the molecule can be used alone or in combination of two or more. Among these, since the transparency of a cured product obtained by curing a polyvalent carboxylic acid resin and an epoxy resin is excellent, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, norbornane-2 3-dicarboxylic acid anhydride, methylnorbornane-2, 3-dicarboxylic acid anhydride, 1,2,4-cyclohexanetricarboxylic acid-1, 2-anhydride, and 2,4-diethylpentanedioic acid anhydride are preferred. More preferred are methylhexahydrophthalic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 2,4-diethylpentanedioic anhydride, and particularly preferred is methylhexahydrophthalic anhydride. It is a thing.

  The amount of the compound (b) having one carboxylic anhydride group in the molecule is 5 to 1000 parts by weight with respect to 100 parts by weight of the compound (c) having two or more carboxylic anhydride groups in the molecule. Is more preferable, more preferably 10 to 500 parts by weight, still more preferably 50 to 300 parts by weight. If the amount is less than 5 parts by weight, the polyvalent carboxylic acid resin (C3) may be too high in molecular weight and workability may be inferior, and if it is more than 300 parts by weight, the mechanical strength of the cured product may be inferior.

  The amount of the polyhydric alcohol compound (a), the compound (c) having two or more carboxylic anhydride groups in the molecule, and the compound (b) having one carboxylic anhydride group in the molecule is Compound (c) having two or more carboxylic anhydride groups in the molecule and compound (b) having one carboxylic anhydride group in the molecule for 1 equivalent of the total alcoholic hydroxyl group of the alcohol compound (a) The total carboxylic acid anhydride group is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents. If it is less than 0.5 equivalent, the mechanical strength of the cured product may be inferior, and if it is more than 2.0, a large amount of acid anhydride groups may remain, resulting in poor storage stability.

  The production of the polyvalent carboxylic acid resin can be performed in a solvent or without a solvent. The solvent does not react with the polyhydric alcohol compound (a), the compound (c) having two or more carboxylic anhydride groups in the molecule, and the compound (b) having one carboxylic anhydride group in the molecule. Any solvent 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, and aromatics such as toluene and xylene. A hydrocarbon etc. are mentioned, Among these, an aromatic hydrocarbon and ketones are preferable. These solvents may be used alone or in combination of two or more. When a solvent is used, the amount used is as follows: polyhydric alcohol compound (a), compound (c) having two or more carboxylic anhydride groups in the molecule, compound having one carboxylic anhydride group in the molecule 0.5-300 weight part is preferable with respect to a total of 100 weight part of (b).

The polyvalent carboxylic acid resin (C3) can be produced without a catalyst or with a catalyst. When a catalyst is used, usable catalysts are hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, potassium hydroxide, water Metal hydroxides such as calcium oxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, Heterocyclic compounds such as imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium Roxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctyl Quaternary ammonium salts such as methylammonium acetate, orthotitanic acid such as tetraethyl orthotitanate, tetramethyl orthotitanate, tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, Examples include metal soaps such as potassium octylate.
When using a catalyst, it can also be used 1 type or in mixture of 2 or more types.
When a catalyst is used, the amount used is a polyhydric alcohol compound (a), a compound having two or more carboxylic anhydride groups in the molecule (c), a compound having one carboxylic anhydride group in the molecule. 0.05-10 weight part is preferable with respect to a total of 100 weight part of (b).
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. At this time, using an alcoholic solvent such as methanol or ethanol or water means that the unreacted compound (c) having two or more carboxylic acid anhydride groups in the molecule or one carboxylic acid anhydride in the molecule. Since it reacts with the compound (b) having a physical group, it is preferable to avoid it.

  The reaction temperature during the production of the polyvalent carboxylic acid resin (C3) depends on the catalyst amount and the solvent used, but is usually preferably 20 to 160 ° C, more preferably 50 to 150 ° C, particularly preferably 60 to 145 ° C. is there. The total reaction time is usually preferably 1 to 20 hours, more preferably 3 to 12 hours. The reaction may be carried out in two or more stages, for example, after reacting at 20 to 100 ° C. for 1 to 8 hours, it may be reacted at 100 to 160 ° C. for 1 to 12 hours. In particular, the compound (b) having one carboxylic anhydride group in the molecule is often highly volatile. When such a compound is used, it is reacted at 20 to 100 ° C. in advance, and then 100 to 160. By reacting at ℃, volatilization can be suppressed. This is preferable because not only the diffusion of harmful substances into the atmosphere can be suppressed, but also the polyvalent carboxylic acid resin (C3) as designed can be obtained.

In the case of production using a catalyst, the catalyst can be removed by quenching and / or washing with water as necessary, but it is left as it is and used as a curing accelerator for the epoxy resin composition of the present invention. You can also.
When performing a water washing process, it is preferable to add the solvent which can be isolate | separated from water depending on the kind of solvent currently used. Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. It can be illustrated.
When a solvent is used for the reaction or washing with water, it can be removed by vacuum concentration or the like.

The polycarboxylic acid resin (C3) thus obtained is normally a liquid having fluidity at 25 ° C. Further, the molecular weight is preferably 800 to 80000, more preferably 1000 to 10000, and particularly preferably 1500 to 8000 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the fluidity at 25 ° C. may be lowered. When the weight average molecular weight is more than 80000, when the epoxy resin composition is used, the compatibility with the epoxy resin described later is poor. There is a fear.
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 acid value (measured by the method described in JIS K-2501) of the produced polyvalent carboxylic acid resin (C3) is preferably 35 to 200 mgKOH / g, more preferably 50 to 180 mgKOH / g. The thing of 60-150 mgKOH / g is preferable. When the functional group equivalent is less than 35 mgKOH / g, the mechanical properties of the cured product tend to deteriorate, and when it exceeds 150 mgKOH / g, the cured product tends to be hard and the elastic modulus tends to be too high.

  The viscosity of the polycarboxylic acid resin (C3) (E-type viscometer, measured at 25 ° C.) is preferably 50 to 800,000 mPa · s, more preferably 500 to 100,000 mPa · s, particularly 800 to The thing of 30,000 mPa * s is preferable. When the viscosity is less than 50 mPa · s, the viscosity is too low and may not be suitable when used as a sealing material or the like. When the viscosity exceeds 800,000 mPa · s, the viscosity is too high or the sealing material or the like. May be inferior in workability.

  In the epoxy resin composition of the present invention, two or more kinds of acid anhydride (C1), polyvalent carboxylic acid (C2), and polyvalent carboxylic acid resin (C3) can be used in combination. In particular, when a solid polyvalent carboxylic acid (C2) is used in a sealing material or the like that is required to be liquid at room temperature (25 ° C.), the liquid acid anhydride (C1) and / or the polyvalent carboxylic acid resin (C3) ) In combination, and is preferably used as a liquid mixture. When used in combination, the acid anhydride (C1) and / or the polyvalent carboxylic acid resin (C3) can be used in a proportion of 0.5 to 99.5% by weight of the total epoxy resin curing agent.

When the curing agent other than the above-mentioned acid anhydride (C1) and / or polyvalent carboxylic acid (C2) and / or polyvalent carboxylic acid resin (C3) is used in combination as the epoxy resin curing agent, the acid anhydride (C1) The proportion of the total amount of the polyvalent carboxylic acid (C2) and / or the polyvalent carboxylic acid resin (C3) in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.
Examples of the curing agent that can be used in combination include amine compounds, amide compounds, phenol compounds, and the like. Specific examples of curing agents that can be used include amines and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, etc.) Polyphenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4, 4′-biphenol, 2, 2′-biphenol, 3, 3 ′, 5, 5′-tetramethyl- [ 1, 1′-biphenyl] -4, 4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, fe Alcohol (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, Dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloro Methyl) benzene, polycondensates with 1,4′-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols, etc. Imidazole, trifluoroborane -. Amine complex, guanidine derivatives, etc.) and the like, but the invention is not limited to these may be used alone, or two or more may be used.

  In the epoxy resin composition of the present invention, another curing catalyst (curing accelerator) can be used in combination as necessary. Specific examples of the curing catalyst that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole) (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4 -Methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino- (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3, Various imidazoles of 5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the imidazoles and phthalic acid; Isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic 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 the like Salts such as tetraphenylborate and phenol novolak, salts with the above polycarboxylic acids, or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide and other ammonium salts, triphenylphosphine, triphenylphosphine (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, etc. And a microcapsule type curing accelerator obtained by making these curing accelerators into microcapsules. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. The curing catalyst (curing accelerator) can be used in the range of usually 0.001 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin.

  In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the epoxy resin curing agent is preferably 1.2 equivalents or less of the curing agent with respect to 1 equivalent of the epoxy groups of all epoxy resins. When it exceeds 1.2 equivalents with respect to 1 equivalent of epoxy group, there exists a possibility that hardening may become incomplete and favorable hardened | cured material property may not be obtained.

  In the epoxy resin composition of the present invention, another curing catalyst (curing accelerator) can be used in combination as necessary. Specific examples of the curing catalyst that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole) (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4 -Methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino- (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3, Various imidazoles of 5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the imidazoles and phthalic acid; Isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic 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 the like Salts such as tetraphenylborate and phenol novolak, salts with the above polycarboxylic acids, or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide and other ammonium salts, triphenylphosphine, triphenylphosphine (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, etc. And a microcapsule type curing accelerator obtained by making these curing accelerators into microcapsules. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A hardening accelerator can be normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.

In the epoxy resin composition of the present invention, it is possible to supplement the viscosity adjustment of the composition and the hardness of the cured product by using a coupling agent as necessary.
Examples of coupling agents that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalco Examples include zirconium such as xylitol (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum coupling agent.
These coupling agents may be used alone or in combination of two or more.
In the epoxy resin composition of the present invention, the coupling agent is usually preferably contained in an amount of 0.05 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight.

  The epoxy resin composition of the present invention can supplement mechanical strength and the like by using an inorganic filler as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. Examples thereof include, but are not limited to, beads formed by spheroidizing, phosphors, and the like. These fillers may be used alone or in combination of two or more. Content of these inorganic fillers can be made into the quantity which occupies 0 to 95 weight% in the epoxy resin composition of this invention.

For the purpose of preventing coloring, the epoxy resin composition of the present invention may contain an amine compound as a light stabilizer and / or a phosphorus compound and a phenol compound as an antioxidant.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6,- Tramethyl-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] me L) butyl malonate, 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) -triazine -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-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl Amino-1,3,5-tria -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7 -Oxa-3,20-diazadispiro [5 · 1 · 11 · 2] 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] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11, 2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4- Hindered amine compounds such as piperidinyl), benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1 3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5 -Methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) Benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol reaction product, 2- (2H-benzotriazole-2- Yl) -6-dodecyl-4-methylphenol and other benzotriazole compounds, 2 , 4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) Examples include triazine compounds such as -5-[(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

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

  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′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3 '-Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'- Biphenylene diphosphonite, 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-butylphenyl) -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 phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. It is below.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as an ADEKA product, ADK STAB (brand name) PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB 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-butyl) Enol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), Bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert -Pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- ( 4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, and the like.

  A commercial item can also be used for the said phenolic compound. The commercially available phenolic compound is not particularly limited. For example, IRGANOX (trade name) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 1598, IRGANOX 1598, IRGANOX 1520, manufactured by Ciba Specialty Chemicals, , ADK STAB AO-20, 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, manufactured by Sumitomo Chemical As Sumilizer (trade name) GA-80, Sumilizer M P-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), SumilizerGP the like.

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

  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. A range of 0.005 to 5.0% by weight is preferred.

  The epoxy resin composition of the present invention is obtained by thoroughly mixing additives such as a silicone skeleton epoxy resin, a cationic polymerization initiator, an epoxy resin curing agent, a coupling agent, an antioxidant, and a light stabilizer. Can be prepared and used as a sealing material. As a mixing method, mixing can be performed at room temperature or by heating using a kneader, a triple roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, or the like.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, each physical-property value in a synthesis example was measured with the following method.
○ Weight average molecular weight: Polystyrene conversion and weight average molecular weight measured under the following conditions were calculated by the GPC method.

Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

○ Epoxy equivalent: Measured by the method described in JIS K-7236.
○ Acid value: measured by the method described in JIS K-2501.
○ Viscosity: Measured using an E-type viscometer at 25 ° C.

Synthesis Example 1 (Synthesis Example of Silicone Skeleton Epoxy Resin (A-1) produced by Silanol-Terminated Silicone Oil (e) and Epoxy Group-Containing Silicon Compound (f) through Two-Step Manufacturing Process)
(Manufacturing process 1)
444 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, polydimethyldiphenylsiloxane having a silanol group with a molecular weight of 1700 (measured by GPC) (having 0.18 mol of phenyl group per 1 mol of methyl group) 400 Part, 3.6 parts of 0.5% KOH methanol solution and 32.4 parts of isopropyl alcohol were charged into a reaction vessel, and the temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours.

(Manufacturing process 2)
After adding 480 parts of methanol, 194.4 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux.
After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 724 parts of methyl isobutyl ketone (MIBK) was added for washing, and washing with water was repeated three times. Subsequently, 658 parts of silicone frame | skeleton epoxy resins (A-1) were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. The epoxy equivalent of the obtained resin was 410 g / eq, the weight average molecular weight was 2713, the viscosity was 15680 mPa · s, and the appearance was a colorless and transparent liquid.

Synthesis Example 2 (Synthesis Example of Silicone Skeleton Epoxy Resin (A-2) in which Silanol-Terminated Silicone Oil (e) and Epoxy Group-Containing Silicon Compound (f) were Manufactured Through Two-Step Manufacturing Process)
(Manufacturing process 1)
394 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, polydimethyldiphenylsiloxane having a silanol group having a molecular weight of 1700 (measured by GPC) (having 0.18 mol of phenyl group per 1 mol of methyl group) 475 Part, 4 parts of 0.5% KOH methanol solution and 36 parts of isopropyl alcohol were charged into a reaction vessel, and the temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours.

(Manufacturing process 2)
After adding 656 parts of methanol, 172.8 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux.
After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 780 parts of MIBK was added for washing, and washing with water was repeated three times. Subsequently, 731 parts of silicone frame | skeleton epoxy resins (A-2) were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. The epoxy equivalent of the obtained resin was 491 g / eq, the weight average molecular weight was 2090, the viscosity was 3530 mPa · s, and the appearance was a colorless and transparent liquid.

Synthesis Example 3 (Synthesis example of epoxy resin curing agent (H-1))
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 8.3 parts of 2,2-bis (4-hydroxycyclohexyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.), both ends carbinol-modified silicone X22-160AS (Shin-Etsu Chemical Co., Ltd.) 58.9 parts, MH-T (methylcyclohexanedicarboxylic acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd.) 32.8 parts was added, and nitrogen purge was performed at 80 ° C. for 3 hours, 120 When the reaction was carried out at 0 ° C. for 3 hours, 99 parts of an epoxy resin curing agent (H-1) which is a polyvalent carboxylic acid resin was obtained as a colorless transparent liquid. The obtained polyvalent carboxylic acid resin (H-1) had a viscosity of 17562 mPa · s and a transmittance at 400 nm of 97.6%.

Examples 1 and 2 and Comparative Example 1
The epoxy resin (A-1) obtained in Synthesis Example 1 as the silicone skeleton epoxy resin (A) and the epoxy resin (A-2) obtained in Synthesis Example 2 and ERL-4221P (3,4-epoxy) as the epoxy resin Cyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, manufactured by Dow Chemical), polyvalent carboxylic acid resin (H-1) obtained in Synthesis Example 3 as an epoxy resin curing agent, and cationic polymerization initiator (B) TA-100 (4-hydroxyphenyl-methyl-benzylsulfonium tris (pentafluoroethyl) trifluorophosphate, manufactured by San Apro), pale south wax (trade name) FZ (V) (zinc stearate, pale south chemical as a curing catalyst) Manufactured by Adeka Stab LA-81 (bis (1-undecanoxy-2,2, , 6-tetramethylpiperidin-4-yl) carbonate, manufactured by ADEKA), as an antioxidant, ADK STAB 260 (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), ADEKA) was used and blended at the blending ratios (parts by weight) shown in Table 1 below. After mixing, defoaming was performed for 5 minutes to obtain an epoxy resin composition of the present invention or for comparison.

<Evaluation test>
The mixing ratio (parts by weight) of each component of the curable epoxy composition for sealing an optical semiconductor obtained in Examples 1 and 2 and Comparative Example 1, and DSC measurement, durometer hardness, heat of each cured product Table 1 shows the results of the durability transmittance test, the light durability transmittance test, the heat cycle test, and the corrosion resistance gas test. Each evaluation test was performed as follows.

(1) DSC measurement manufacturer: Seiko Instruments Inc.
Model: Differential thermal scanning calorimeter (DSC6200)
Gas type: Nitrogen heating rate: 10 ° C / min

(2) Durometer hardness After carrying out the vacuum degassing for 5 minutes with the epoxy resin compositions obtained in Examples 1 and 2 and Comparative Example 1, the mold was made into a mold using an aluminum foil so that the diameter was 30 mm and the height was 70 mm. Cast. The casting was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a test piece for durometer hardness having a thickness of 7 mm. The durometer hardness of the obtained test piece was measured by the method described in JIS K-6253.

(3) Thermal durability transmission test Heated in a 180 ° C oven for 72 hours.
The preparation of the test piece and the measurement of the transmittance were in accordance with the procedure of “(5) Measurement of cured product transmittance” below.

(4) Light durability transmission tester: Super UV tester (EYE SUPER UV TESTER SUV-WII, manufactured by Iwasaki Electric Co., Ltd.)
Light irradiation was performed for 200 hours at a temperature of 60 ° C., a humidity of 60 ° C., and an irradiance of 60 mW / cm ² .
The preparation of the test piece and the measurement of the transmittance were in accordance with the procedure of “(5) Measurement of cured product transmittance” below.

(5) Measurement of cured product transmittance After heat-treating the epoxy resin composition obtained in Examples 1 and 2 and Comparative Example 1 for 5 minutes by vacuum defoaming, heat-resistant tape is used so as to be 30 mm × 20 mm × height 0.8 mm. The dam was gently cast on the glass substrate. 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. The obtained specimen was measured for light transmittance at 400 nm under the following conditions. A value obtained by dividing the transmittance after the test by the transmittance before the test was defined as the transmittance retention.
Spectrophotometer measurement conditions Manufacturer: Hitachi High-Technologies Corporation Model: U-3300
Slit width: 2.0nm
Scan speed: 300 nm / min

(6) Heat cycle test The test sample is a 5 mm square surface-mounted LED equipped with a light emitting element having an emission wavelength of 450 nm, and a resin is cast so that the opening is flat, and pre-cured at 120 ° C. for 1 hour. After that, it was cured at 150 ° C. for 3 hours to seal the surface-mounted LED.
The heat cycle test was carried out for 100 cycles at −40 ° C. for 30 minutes and at 100 ° C. for 30 minutes, and then the presence or absence of cracks was confirmed with a microscope.

(7) Corrosion-resistant gas test The epoxy resin compositions obtained in Examples 1 and 2 and Comparative Example 1 were vacuum degassed for 5 minutes, then filled into a syringe and used with a precision discharge device to have an emission wavelength of 450 nm. The surface-mounted LED on which the light-emitting element was mounted was cast so that the opening was flat. After pre-curing at 120 ° C. for 1 hour, it was cured at 150 ° C. for 3 hours to seal the surface-mounted LED. The surface-mounted LED was attached to the blue plate glass using a double-sided tape.
Using a spacer, 2 grams of sulfur and blue plate glass placed in a petri dish were placed in a glass test container so that the sample faced downward (sulfur side), and the lid was securely closed. The glass test vessel was placed in a preheated oven (80 ° C.). In the oven, nitrogen was flowed at 5 L / min.
The sample was taken out after 8 hours, allowed to cool in a fume hood, then the lid was opened and the sample was taken out in the fume hood, and observed and measured for illuminance. The value obtained by dividing the illuminance after the test by the illuminance before the test was defined as the illuminance retention rate.

  As is apparent from the results shown in Table 1, Examples 1 and 2 using a cationic polymerization initiator were cured because the amount of heat generated by DSC was larger than that of Comparative Example 1 using no cationic polymerization initiator. Excellent in hardness and the hardness of the cured product is also high. Furthermore, the illuminance retention rate in the corrosion-resistant gas test is also a high value, indicating that the corrosion-resistant gas is excellent. The results of the heat durability transmittance test, the light durability transmittance test, and the heat cycle test maintain the same characteristics.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is based on the Japan patent application (2013-068037) for which it applied on March 28, 2013, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

  The epoxy resin composition for optical semiconductor encapsulation of this invention is used suitably for LED etc.

Claims (9)

  The epoxy resin composition for optical semiconductor sealing containing a silicone frame | skeleton epoxy resin (A) and a cationic polymerization initiator (B).   Furthermore, the epoxy resin composition for optical semiconductor sealing of Claim 1 containing an epoxy resin hardening | curing agent. Polymerization of a silicone skeleton epoxy resin (A) having an epoxy equivalent of 300 to 1500 g / eq, a silanol-terminated silicone oil represented by the following formula (1) and an epoxy group-containing silicon compound represented by the following formula (2) Hydrolysis-condensation product of the product, or a silanol-terminated silicone oil represented by the following formula (1), an epoxy group-containing silicon compound represented by the following formula (2), and an alkoxysilicon compound represented by the following formula (3) The epoxy resin composition for optical semiconductor encapsulation according to claim 1, wherein the epoxy resin composition is a hydrolysis-condensation product of the polymer.

(In the formula, R ₅ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and p represents an average value of 3 to 200. In the formula, a plurality of R ₅ may be the same or different from each other. Is also good.)

(Wherein X is an organic group containing an epoxy group, R ₆ is an aryl having a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ₇ represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, q represents an integer of 0 to 2, and r represents an integer of (3-q).)

(Wherein R ₆ and R ₇ are the same as described above, s is an integer, 0, 1, 2, 3 and t represents (4-s).) The epoxy resin composition for optical semiconductor encapsulation according to claim 3, wherein the silicone skeleton epoxy resin (A) is a silicone skeleton epoxy resin obtained through the following production steps 1 and 2.
(Manufacturing process 1)
A step of condensing the silanol group of the silanol-terminated silicone oil represented by the formula (1) and the alkoxy group of the epoxy group-containing silicon compound represented by the formula (2) to obtain a modified silicone oil;
(Manufacturing process 2)
A step of adding water after the production step 1 to hydrolyze and condense the remaining alkoxy groups. The cationic polymerization initiator (B) is composed of a cation represented by the following formula (4) and an anion represented by the following formula (5) or the following formula (6). Item 4. An epoxy resin composition for optical semiconductor encapsulation according to the item.

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and are a hydroxyl group, a halogen atom, a substituent or an unsubstituted alkyl group having 1 to 30 carbon atoms, an alkoxy group, an aralkyl group, an aryl group, Or an alkylaryl group, and R ₁ and R ₂ may be bonded to each other to form a ring.)

(In the formula, X represents Sb, As, or P. Y represents fluorine, chlorine, bromine, or iodine. In the formula, R ₄ may be the same or different, and fluorine, chlorine, bromine, or iodine. And b is an integer of 0 to 5.)

(In the formula, Y represents fluorine, chlorine, bromine or iodine. R ₅ may be the same or different, and is an alkyl or aryl group substituted or unsubstituted by fluorine, chlorine, bromine or iodine, or a fluorine atom. .) A cationic polymerization initiator comprising R ₃ in the formula (4) represented by the following formula (7) and an anion in which X is phosphorus in the formula (5). The epoxy resin composition for optical semiconductor sealing as described in any one of these.

Wherein R ₆ represents hydrogen, an alkyl group, a hydroxy group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an aralkylcarbonyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, It is an integer from 0 to 5.)   The epoxy resin curing agent is a polyvalent carboxylic acid resin. The epoxy resin composition for optical semiconductor encapsulation according to any one of claims 2 to 6.   Hardened | cured material formed by hardening | curing the epoxy resin composition for optical semiconductor sealing as described in any one of Claims 1-7.   An optical semiconductor device comprising the cured product according to claim 8.