WO2013047620A1

WO2013047620A1 - Curable resin composition for sealing optical semiconductor element, and cured material of same

Info

Publication number: WO2013047620A1
Application number: PCT/JP2012/074789
Authority: WO
Inventors: 直房宮川; 智江佐々木; 義浩川田
Original assignee: 日本化薬株式会社
Priority date: 2011-09-27
Filing date: 2012-09-26
Publication date: 2013-04-04
Also published as: JP2013071950A; TW201323469A; JP6150415B2

Abstract

Provided is a curable resin composition having excellent heat cycle resistance, for sealing an optical semiconductor element. The present invention is characterized in that the glass transition temperature (Tg) of the cured material as measured by the DMA method ranges from −10 to 10°C, and the storage modulus at 0°C as measured by the DMA method ranges form 0 to 150 MPa; the present invention contains an epoxy resin (A) and an epoxy resin curing agent, and the epoxy resin (A) is preferably a silicone backbone epoxy resin.

Description

Curable resin composition for optical semiconductor element sealing and cured product thereof

The present invention relates to a curable resin composition suitable for optical semiconductor element sealing applications, and a cured product thereof.

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 a 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 the phenomenon that the silver plating surface used in the LED is corroded due to the permeation of sulfur-based gas, resulting in blackening due to silver sulfide, and reducing the illuminance of the LED. Therefore, the countermeasure is urgent. This is done by increasing the crosslink density of the cured product or increasing the aromatic organic groups such as phenyl groups in the molecule, but inevitably increases the elastic modulus at low temperatures of the cured product. The heat cycle (thermal cycle) resistance is inferior, and there are concerns about adverse effects such as cracks and peeling from the substrate.

In order to solve these problems, a sealing material excellent in sulfidation resistance has been studied using a condensate of a silicon compound having an epoxy group and a phenyl group and a liquid acid anhydride (see Patent Document 3). ). However, a sealing material satisfying heat cycle resistance and sulfur gas corrosion resistance (sulfur resistance) has not yet been completed.

Japanese Unexamined Patent Publication No. 2003-277473 Japanese Patent No. 4636242 Japanese Unexamined Patent Publication No. 2011-063799

An object of the present invention is to provide a curable resin composition for encapsulating an optical semiconductor element that is extremely excellent in heat cycle resistance.

As a result of intensive studies in view of the above-described actual situation, the present inventors have found that the cured product has a glass transition temperature (Tg) measured by the DMA method in the range of −10 to 10 ° C., and is 0 measured by the DMA method. In order to complete the present invention, it has been found that a curable resin composition using an epoxy resin having a specific skeleton that gives a cured product having a storage elastic modulus in the range of 0 to 150 MPa at 0 ° C. solves the above-mentioned problems. It came.

That is, the present invention
(1)
The optical semiconductor device encapsulated product has a glass transition temperature (Tg) measured by DMA method in the range of −10 to 10 ° C. and a storage elastic modulus at 0 ° C. measured in DMA range of 0 to 150 MPa. Curable resin composition for stopping,
(2)
The curable resin composition for optical semiconductor element sealing according to (1), comprising an epoxy resin (A) and an epoxy resin curing agent (B),
(3)
The curable resin composition for optical semiconductor element encapsulation according to (2), wherein the epoxy resin (A) is a silicone skeleton epoxy resin,
(4)
The silicone skeleton epoxy resin is a polymer of a silanol-terminated silicone oil represented by formula (1) and an epoxy group-containing silicon compound represented by formula (2) obtained through the following production steps 1 and 2, The curable resin composition for sealing an optical semiconductor element according to (3), wherein the epoxy equivalent measured by the method described in JIS K-7236 is 300 to 1500 g / eq,
Manufacturing process 1
A step of condensing a silanol group of a silanol-terminated silicone oil and an alkoxy group of an epoxy group-containing silicon compound 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.

(In Formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 10 carbon atoms, and m represents an average value of 3 to 200. In the formula, a plurality of R ₁ are present. They may be the same or different)

(In the formula (2), X represents an organic group containing an epoxy group, R ₂ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and R ₃ represents a straight chain having 1 to 10 carbon atoms. A chain, branched or cyclic alkyl group, p is an integer from 0 to 2, and r is an integer and represents (3-p).)
(5)
Curing property for optical semiconductor elements according to (2), wherein the epoxy resin curing agent (B) is a carboxylic acid resin obtained by modifying a carboxylic acid anhydride and / or a carboxylic acid anhydride with an alcoholic hydroxyl group. Resin composition,
(6)
Furthermore, as a curing accelerator, zinc carboxylate is contained, (4) or (5) curable resin composition for optical semiconductor element sealing according to (5),
(7)
The curable resin composition for sealing an optical semiconductor element according to (6), wherein the zinc carboxylate is one or more selected from zinc 2-ethylhexanoate, zinc stearate, zinc behenate, and zinc myristylate,
(8)
(1) to a cured product obtained by curing the curable resin composition for sealing an optical semiconductor element according to any one of (7),
(9)
LED comprising the cured product according to (8),
About.

According to the present invention, the cured product obtained by curing the curable resin composition of the present invention has a glass transition temperature (Tg) measured by DMA method in the range of −10 to 10 ° C., and 0 ° C. measured by DMA method. A curable resin composition using an epoxy resin having a specific skeleton, which gives a cured product having a storage elastic modulus in the range of 0 to 150 MPa, is extremely excellent in heat cycle resistance, so that it is encapsulated in an optical semiconductor device (LED) It is extremely useful as a material.

The curable resin composition for an optical semiconductor element sealing material of the present invention has a glass transition temperature (Tg) measured by the DMA method in the range of −10 to 10 ° C., and 0 ° C. measured by the DMA method. Is preferably in the range of 0 to 150 MPa, particularly a glass transition point of −5 to 8 ° C. and a storage modulus of 0 to 100 MPa.

The DMA (Dynamic Mechanical Analysis) method in the present invention is a measurement of dynamic viscoelasticity (tensile vibration) described in JIS K7244 and JIS K7244-4 using the test piece prepared as follows. It is a method to do.
<Method for making DMA test piece>
After carrying out the vacuum defoaming for 5 minutes, the optical semiconductor element sealing material is gently cast on a glass substrate on which a dam is created with a heat-resistant tape so as to be 30 mm × 20 mm × height 0.8 mm. The casting is cured under predetermined conditions (specifically, conditions of curing at 120 ° C. for 1 hour and then curing at 150 ° C. for 3 hours) to obtain a cured product having a thickness of 0.8 mm. The obtained cured product is molded into a width of 5 mm and a length of 25 mm to obtain a DMA test piece.
<DMA measurement conditions>
Measurement temperature: -50 ° C to 150 ° C
Temperature increase rate: 2 ° C / min
Frequency: 10Hz
Measurement mode: Tensile vibration

In the present invention, the glass transition temperature (Tg) is a loss coefficient (tan δ = E ″ / E ′) represented by a quotient of storage elastic modulus (E ′) and loss elastic modulus (E ″) measured by the DMA method. ) Is the temperature at which the maximum point is shown.
The cured product of the curable resin composition for optical semiconductor encapsulating material of the present invention has a glass transition temperature (Tg) measured by DMA method of −10 to 10 ° C., particularly preferably −5 to 8 ° C. If it is lower than −10 ° C., it may be inferior in sulfidation resistance, and if it is higher than 10 ° C., it may be inferior in heat cycle resistance.
The cured product of the curable resin composition for an optical semiconductor element sealing material of the present invention has a storage elastic modulus at 0 ° C. measured by the DMA method of 0 to 150 MPa, particularly preferably 0 to 100 MPa. If it exceeds 150 MPa, cracks may occur during the heat cycle test.

The heat cycle test (also referred to as a thermal shock test or a heat shock test) is a test piece in a low temperature region of about −50 to −30 ° C. and a high temperature region of about 80 to 120 ° C. for about 5 to 30 minutes in each region. Is repeatedly used, and is widely used as a reliability confirmation test for optical semiconductor encapsulants.

From here, the curable resin composition of this invention is demonstrated.
The curable resin composition of the present invention is a curable resin composition for sealing an optical semiconductor element, and the cured product has a glass transition temperature (Tg) measured by DMA method of −10 to 10 ° C., The storage elastic modulus at 0 ° C. measured by the DMA method is 0 to 150 MPa.
Examples of the curable resin composition include a silicone resin composition and an epoxy resin composition.
The curable resin composition of the present invention is preferably a curable resin composition (epoxy resin composition) containing an epoxy resin (A) from the viewpoint of resistance to sulfide.

From here, the epoxy resin (A) of this invention is demonstrated.
The epoxy resin (A) is a compound having two or more epoxy groups in the same molecule, such as a silicone skeleton epoxy resin, an epoxy resin that is a glycidyl etherified product of a phenol compound, and a glycidyl etherified product of various novolac resins. Certain epoxy resins, cycloaliphatic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, polymerization with epoxy groups A copolymer of a polymerizable unsaturated compound and another polymerizable unsaturated compound, and the like, and a silicone skeleton epoxy resin is preferable because of its heat resistance and light resistance.

The silicone skeleton epoxy resin is a resin having an epoxy group having a silicone bond (Si—O bond) as a main skeleton, and can be obtained, for example, by polymerizing an epoxy group-containing silicon compound and other silicon compounds. Examples thereof include a 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. Moreover, an addition polymerization product 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.

The epoxy resin (A) in the present invention is made from a silanol-terminated silicone oil (a) and an epoxy group-containing silicon compound (b) (and, if necessary, an alkoxysilicon compound (c)) among the silicone skeleton epoxy resins. A silicone skeleton epoxy resin obtained through a two-stage production process described later is most preferable.

From here, the silanol-terminated silicone oil (a), the epoxy group-containing silicon compound (b), and the alkoxysilicon compound (c) will be described.
First, the silanol-terminated silicone oil (a) will be described.
Examples of the silanol-terminated silicone oil (a) in the present invention include a silicone resin represented by the following formula (1) and having silanol groups at both ends.

In the formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a hexyl group, or a carbon number of 5 to 5 such as a phenyl group, a benzyl group or a naphthyl group. 10 aryl groups are shown. A plurality of R ₁ may be the same or different, but preferably contain a phenyl group from the viewpoint of compatibility with other resins, high refractive index, and improvement in sulfur resistance.
From the viewpoint of reducing the glass transition temperature of the cured product and the storage elastic modulus at 0 ° C., it preferably contains a methyl group.

The proportion of the phenyl group 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, per 1 mol of the substituted methyl group. Particularly preferred is 0.15 to 0.2 mol. If the amount is less than 0.05 mol, the compatibility with other raw materials in the composition may decrease, the refractive index of the cured product may decrease, the light extraction efficiency of the LED may decrease, and the sulfidation resistance may decrease. When the amount exceeds 2.0 mol, the light resistance (UV resistance) of the cured product may decrease, the storage elastic modulus at 0 ° C. in the DMA method may increase excessively, or the heat cycle resistance may decrease. .

In the formula (1), m represents an average value of 3 to 200, preferably 3 to 100, more preferably 3 to 50. When m is less than 3, the cured product becomes too hard, and the storage elastic modulus at 0 ° C. in the DMA method may increase. When m exceeds 200, the mechanical strength of the cured product tends to decrease.

The weight average molecular weight (Mw) of the silanol-terminated silicone oil (a) is preferably in the range of 400 to 3000 (GPC). If the weight average molecular weight is less than 400, the silicone part is less likely to exhibit the characteristics of heat resistance and light resistance, and if it exceeds 3000, it has a severe layer separation structure, so that it can be used for optical semiconductor element sealing. May be less permeable.
In the present invention, the molecular weight of the silanol-terminated silicone oil (a) 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 (a) is produced, for example, by hydrolyzing and condensing dimethyl dialkoxysilane, methylphenyldichlorosilane, diphenylalkoxysilane, dimethyldichlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane. it can.

Specific examples of preferable silanol-terminated silicone oil (a) include the following product names. For example, PRX413, BY16-873 manufactured by Toray Dow Corning Co., Ltd., X-21-5841, KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd., XC96-723, TSR160, YR3370, YF3800, manufactured by Momentive Co., Ltd. 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 a large molecular weight in order to give the silicone segment flexibility characteristics. These silanol-terminated silicone oils (a) may be used alone or in combination of two or more.

Next, the epoxy group-containing silicon compound (b) will be described.
The epoxy group-containing silicon compound (b) in the present invention is an alkoxy silicon 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 4-epoxycyclohexyl) pentyl group. Among these, as an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group and 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 are preferable, and since β- (3,4-epoxycyclohexyl) ethyl group can be particularly suppressed in coloration Is preferred.

R ₂ in the formula (2) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group, a cyclohexyl group, etc. And an alkyl group having 5 to 8 carbon atoms having an alicyclic structure and an alkyl group having 5 to 8 carbon atoms having an aromatic ring structure such as a phenyl group.

R ₃ in the formula (2) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₃ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of reaction conditions such as compatibility and reactivity.

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

Specific preferred examples of the epoxy group-containing silicon compound (b) 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- Po carboxymethyl) ethyl cyclohexyl dimethoxysilane, and the like, especially 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferable. These epoxy group-containing silicon compounds (b) may be used alone or in combination of two or more, and may be used in combination with the alkoxysilicon compound (c) shown below.

In the silicone skeleton epoxy resin of the present invention, an alkoxysilicon compound (c) represented by the following formula (3) can be used in combination with the epoxy group-containing silicon compound (b). By using the alkoxysilicon compound (c) in combination, the viscosity, refractive index, Tg in the DMA method of the cured product, and storage elastic modulus of the silicone skeleton epoxy resin can be adjusted.

R ₂ , R ₃ , p and r in the formula (3) have the same contents as described above.

Preferred examples of the alkoxysilicon compound (c) that can be used in combination include methyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and diphenyl. Examples include dimethoxysilane and diphenyldidiethoxysilane. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and diphenyldimethoxysilane are preferable.

In the present invention, at least one of the silanol-terminated silicone oil (a) and the epoxy group-containing silicon compound (b) (and optionally the alkoxysilicon compound (c)) to be used 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 a compound having a phenyl group is particularly preferable. In particular, the silanol-terminated silicone oil (a) preferably has a phenyl group. This is because the silanol-terminated silicone oil (a) introduced with a phenyl group can suppress an excessive increase in viscosity of the silicone skeleton epoxy resin, while an epoxy group-containing silicon compound with a phenyl group (b) ) (And if necessary, the alkoxysilicon compound (c)), the increase in viscosity becomes large and workability may be inferior.

In the production of the silicone skeleton epoxy resin, the alkoxy group-containing silicon compound (b) (and, if necessary, the alkoxy group of the alkoxysilicon compound (c)) is added to 1 equivalent of the silanol group of the silanol-terminated silicone oil (a). When reacted in an amount less than 1.5 equivalents, two or more alkoxy groups in the epoxy group-containing silicon compound (b) (and optionally the alkoxysilicon compound (c)) are terminated with silanol-terminated silicone oil (a ) And the silanol group, the polymer becomes too high at the end of the production step 1 and gelation may occur. 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. From the viewpoint of reaction control, 2.0 equivalents or more are preferable.

Next, manufacturing steps 1 and 2 will be described.
(Manufacturing process 1)
A step of obtaining a modified silicone oil (d) by condensing a silanol group of a silanol-terminated silicone oil (a) and an alkoxy group of an epoxy group-containing silicon compound (b) (and, if necessary, an alkoxysilicon compound (c)). .
(Manufacturing process 2)
A step of adding water after the production step 1 to hydrolyze and condense the remaining alkoxy groups.
Through the production steps 1 and 2, the silanol-terminated silicone oil (a) and the epoxy group-containing silicon compound (b) (and the alkoxysilicon compound (c) as necessary) are polymerized.

By dividing the production process into two stages, the silanol group of the silanol-terminated silicone oil (a) and the alkoxy group of the epoxy group-containing silicon compound (b) (and the alkoxy silicon compound (c) if necessary) are surely obtained. After the modified silicone oil (d) is obtained by reacting with the above, it is possible to obtain a uniform and stable product by subjecting the remaining alkoxy groups to dealcoholic hydrolysis and condensation.

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 (a) 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 alcohols that can be used include alcohols having 1 to 10 carbon atoms, such as 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 view of the problem of removal performance later, a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol and t-butanol is preferred. These alcohols may be used as a mixture. When they are mixed, they are preferably two or more selected from primary alcohols and secondary alcohols, and at least one component contains primary alcohols. It is preferable because the solubility of the catalyst described later is excellent. The amount of primary alcohol is preferably 5% by weight or more, more preferably 10% by weight or more of the total alcohol amount.
By using a secondary alcohol in combination with this reaction, the amount of change in the weight average molecular weight per unit time 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 (a) and the epoxy group-containing silicon compound (b) (and, if necessary, the alkoxysilicon compound (c)). It is preferable to contain. It is more preferably 2 to 100% by weight, further preferably 3 to 50% by weight, particularly preferably 4 to 40% by 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. In some cases, the problem of an increase in the elastic modulus that makes it difficult to achieve the problem occurs.
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. Can be illustrated.

Although the reaction in the production process 1 can be carried out without a catalyst, the reaction proceeds slowly with no catalyst, so that it is preferably carried out in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst that can be used, any compound that exhibits acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Inorganic bases such as alkali metal carbonates and organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used.
Among these, a basic catalyst is particularly preferable, and an inorganic base is preferable in terms of easy catalyst removal from the product. Specifically, alkali metal salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, or alkaline earth metal salts, particularly hydroxides are preferable.
The amount of the catalyst added is usually 0.001 to 5% by weight based on the total weight of the silanol-terminated silicone oil (a) and the epoxy group-containing silicon compound (b) (and the alkoxysilicon compound (c) if necessary). Preferably, it is 0.01 to 2% by weight.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol. 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 (b) (and, if necessary, Since the polycondensation of the alkoxy group of the alkoxysilicon compound (c)) proceeds unilaterally, the reaction product produced thereby may not be compatible with the silanol-terminated silicone oil (a) and may become cloudy. is necessary.
In this case, the allowable range of moisture is preferably 0.5% by weight based on the total weight of the silanol-terminated silicone oil (a) and the epoxy group-containing silicon compound (b) (and, if necessary, the alkoxysilicon compound (c)). % Or less, more preferably 0.3% by weight or less, and it is more preferable that there is as little water as possible.

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

Thus, it is thought that the modified silicone oil (d) obtained by the manufacturing process 1 has a structure as shown in the following formula (4) as a main component (it is difficult to confirm the structure and accurately Cannot be identified.)

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

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 (d) are polymerized (sol-gel reaction). At this time, the silicon compound (b) containing the above-described epoxy group (and the alkoxysilicon compound (c) if necessary) and the catalyst may be added within the above-mentioned amount as necessary. This reaction is performed between (1) the modified silicone oils (d) and / or (2) the silicon compound (b) containing an epoxy group (and the alkoxysilicon compound (c) if used). And / or (3) a silicon compound (b) containing an epoxy group (and an alkoxy silicon compound (c), if used), and (4) a silicon compound (b) 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 (c)) and modified silicone oil (d). The polymerization reactions (1) to (4) are considered to proceed simultaneously in parallel.
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 alcohols that can be used include alcohols having 1 to 10 carbon atoms, such as 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 view of the problem of removal performance later, a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol and t-butanol is preferred. These alcohols may be used as a mixture. The presence of these alcohols contributes to molecular weight control and stability.
With respect to the total amount of the silanol-terminated silicone oil (a) and the silicon compound (b) containing an epoxy group (and, if necessary, the alkoxysilicon compound (c)) charged in the production process 1 as the addition amount of the alcohol, Usually 20 to 200% by weight, preferably 20 to 150% by weight, 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, particularly preferably 0.65 to 2.0 equivalents relative to the amount of remaining alkoxy groups. is there.
When the amount of water is less than 0.5 equivalent, the progress of the reaction is slow and the silicon compound (b) containing an epoxy group (and the alkoxysilicon compound (c) if necessary) 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 will occur even after the subsequent curing of the curable 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.

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

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

In this reaction, the catalyst may be removed only by washing with water, but the reaction is carried out under acidic or basic conditions. It is preferable to remove the adsorbent by filtration after adsorbing the catalyst using
Any compound that is acidic or basic can be used for the neutralization reaction. Examples of the compound exhibiting acidity include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Inorganic bases such as alkali metal carbonates, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, phosphates such as polyphosphoric acid, sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, Organic bases such as dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base or an inorganic acid is particularly 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, Toshin Kasei Co., Ltd., activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168 are manufactured by Mizusawa Chemical Co., Ltd. Galeon Earth, Mizuka Ace, etc. are listed. As the activated carbon, for example, CL-H, Y-10S, Y-10SF manufactured by Ajinomoto Fine Techno Co., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR manufactured by Phutamura Chemical Co., Ltd. , CW130AR, GM130A, and the like. Examples of zeolite include, for example, molecular sieves 3A, 4A, 5A, and 13X, manufactured by Union Showa. As a synthetic adsorbent, for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., Amberlist 15JWET, 15DRY, manufactured by Rohm and Haas Co., Ltd. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, manufactured by Dow Chemical Company, Dowex 66, HCR-S, HCR-W2, MAC-3, etc. may be mentioned.
The adsorbent is added to the reaction solution, followed by treatment such as stirring and heating to adsorb the catalyst, and then the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.

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

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

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

The appearance of the silicone skeleton epoxy resin of the present invention thus obtained is usually colorless and transparent and is a liquid having fluidity at 25 ° C. Further, 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 at the time of solder reflow of the LED element encapsulated using the weight average molecular weight.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.

The epoxy equivalent (measured by the method described in JIS K-7236) of the silicone skeleton epoxy resin of the present invention is 300 to 1500 g / eq. Preferably 320 to 1400 g / eq, more preferably 350 to 1200 g / eq, and particularly preferably 350 to 1000 g / eq. When the epoxy equivalent is less than 300 g / eq, the cured product is hard and the elastic modulus and the glass transition temperature tend to be too high, and when it exceeds 1500 g / eq, the mechanical properties of the cured product tend to decrease.
The silicone skeleton epoxy resin of the present invention may be a single silicone skeleton epoxy resin or a mixture of two or more silicone skeleton epoxy resins. Here, from the viewpoint of imparting a low glass transition temperature and a storage elastic modulus of 0 ° C. to the cured product, if the epoxy equivalent of the epoxy resin is a single silicone skeleton epoxy resin, two or more types of silicone skeleton epoxy resins are used. In this case, the total epoxy equivalent of the epoxy equivalent of the specific silicone skeleton epoxy resin × (content of the specific silicone skeleton epoxy resin / total amount of the silicone skeleton epoxy resin) is 300 to 1500 g / eq. It is preferably 350 to 1000 g / eq.

The viscosity of the silicone skeleton epoxy resin of the present invention (E-type viscometer, measured at 25 ° C.) is preferably 50 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, particularly 800 to 5 1,000 mPa · s is preferred. When the viscosity is less than 50 mPa · s, the viscosity is too low and may not be suitable as an optical semiconductor sealing material. When it exceeds 20,000 mPa · s, the viscosity is too high and workability is reduced. There is.

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

As described above, as the most preferable example of the epoxy resin (A) in the present invention, a silicon compound containing a silanol-terminated silicone oil (a) and an epoxy group, which is a silicone skeleton epoxy resin, obtained through production steps 1 and 2 ( b) (and condensates with alkoxysilicon compounds (c) if necessary) have been described.

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

In this case, the silicon compound (b) containing an epoxy group represented by the above formula (2) (and optionally represented by the above formula (3) can be produced by a one-step reaction. The alkoxysilicon compound (c)) can be obtained by adding water dropwise in the presence of a catalyst and a solvent as described above and condensing under the conditions of 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 (b) containing an epoxy group (and, if necessary, the alkoxysilicon compound (c)) 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 that the glass transition temperature and the storage elastic modulus at 0 ° C. of the present invention satisfy the required characteristics and has excellent sulfidation resistance is as follows.
(I) A silicone skeleton epoxy resin in which the ratio of the phenyl group in the substituent linked to silicon is 0.05 to 2.0 mol with respect to 1 mol of the substituted methyl group.
(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 any one of (i) and (ii), wherein a 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 any one of (i) and (ii), wherein a 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 types of silicone skeleton epoxy resins, the epoxy equivalent of the specific silicone skeleton epoxy resin × (the content of the specific silicone skeleton epoxy resin / the total amount of the silicone skeleton epoxy resin) The silicone skeleton epoxy resin mixture according to any one of (i) to (iv), wherein an epoxy equivalent is 350 to 1000 g / eq.

Next, other epoxy resins will be described.
Other epoxy resins 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 esters. Epoxy resins, glycidylamine 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. .

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'-methylene -Bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phloroglucinol, di Examples thereof include phenols having an isopropylidene 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 naphthols. Examples include novolak resins made from various phenols, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, fluorene skeleton-containing phenol novolak resins, and other glycidyl etherified products. It is done.

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. And a formula epoxy resin.
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 other polymerizable unsaturated compounds, Marproof G-0115S, G-0130S and G-0250S are commercially available products. 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, glycidyl methacrylate, 4 -Vinyl-1-cyclohexene-1,2-epoxide and the like. Examples of other polymerizable unsaturated compounds include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane and the like.

The aforementioned epoxy resin (A) may be used alone or in combination of two or more.

Among the above-described epoxy resins (A), a silicone skeleton epoxy resin is the most preferable example from the viewpoints of transparency, heat-resistant transparency, light-resistant transparency, heat cycle resistance, and the like. In the present invention, an alicyclic epoxy is used. The combined use of the resin is preferable from the viewpoint of adjusting the mechanical strength of the cured product. In the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and transesterification of cyclohexene carboxylic acid ester (Japan) Examples thereof include a product obtained by oxidizing a compound that can be produced by a method described in Japanese Patent Laid-Open No. 2006-052187, etc. (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- Pentanediol, 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, and tetraols such as pentaerythritol and ditrimethylolpropane. 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 body 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, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to them (reference: review epoxy resin basic edition I p76-85, the entire contents of which are incorporated herein by reference).

When the silicone skeleton epoxy resin is used in combination with another epoxy resin, 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 it is less than 60 parts by weight, the light resistance (UV resistance) of the cured product may be inferior.

Next, the epoxy resin curing agent (B) will be described.
Examples of the epoxy resin curing agent (B) include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and polycarboxylic acids.
In the present invention, as the epoxy resin curing agent (B), acid anhydride (Ba) and polyvalent carboxylic acid (Bb) are particularly preferable from the viewpoints of hardness, workability (being liquid at room temperature), and transparency of the cured product. preferable.

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

The polyvalent carboxylic acid (Bb) is a compound having at least two carboxyl groups.
The polyvalent carboxylic acid (Bb) is preferably a bi- to hexafunctional carboxylic acid, such as butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, Linear alkyl diacids such as malic acid, alkyltricarboxylic acids such as 1,3,5-pentanetricarboxylic acid, citric acid, phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid , Cycloaliphatic tricarboxylic acid, nadic acid, aliphatic cyclic polyvalent carboxylic acid such as methyl nadic acid, multimers of unsaturated fatty acids such as linolenic acid and oleic acid, and dimer acids that are reduced products thereof, bifunctional to hexafunctional polyfunctional And compounds obtained by the reaction of a monohydric alcohol and an acid anhydride. Compounds obtained by reaction with anhydrides, heat resistance, and more preferable from the viewpoint of workability. Furthermore, the polyhydric carboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable from a transparency viewpoint.
The bi- to hexafunctional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol and norbornene diol, triols such as glycerin, trimethylol ethane, trimethylol propane, trimethylol butane, 2-hydroxymethyl-1,4-butanediol, and teto such as pentaerythritol and ditrimethylol propane Ols, and the like hexa-ols, such as dipentaerythritol.

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

Examples of acid anhydrides to be reacted with polyhydric alcohols include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2, 2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4- Anhydrides and the like are preferable, and methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are particularly preferable from the viewpoints of heat resistance, transparency, and workability.
The conditions for the addition reaction can be used without any particular limitation as long as they are known methods. Specific reaction conditions include, for example, acid anhydrides and polyhydric alcohols in the absence of a catalyst and in the absence of a solvent. A method of reacting at 150 ° C. and heating, and taking out as it is after completion of the reaction can be mentioned.

As the epoxy resin curing agent (B) of the present invention, both terminal carbinol-modified silicone oil (e) (and, if necessary, terminal alcohol polyester (f)) and one or more carboxylic anhydride groups in the molecule. A polyvalent carboxylic acid (Bb) produced by a reaction with the compound (g) having the above can also be used.
As both-end carbinol-modified silicone oil (e), the following formula (5)

(In Formula (5), R ₆ represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 10 carbon atoms, R ₇ represents an alkylene group having 1 to 10 carbon atoms in total, an alkylene group having an ether bond, and n Represents an average value of 1 to 100.)
The compound shown by these is preferable.

In the formula (5), specific examples of R ₆ include a methyl group, an ethyl group, an isopropyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, and a naphthyl group. The polyvalent carboxylic acid (Bb) obtained by the addition reaction of the both-end carbinol-modified silicone oil (e) and the compound (g) having one or more carboxylic anhydride groups in the molecule is liquid at room temperature. For this purpose, a methyl group is preferred.

In formula (5), specific examples of R ₇ include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups, ethoxyethylene group, propoxyethylene group, Examples include an alkylene group having an ether bond such as a propoxypropylene group and an ethoxypropylene group. Particularly preferred are propoxyethylene group and ethoxypropylene group.

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

The both-end carbinol-modified silicone oil (e) represented by the formula (5) is, for example, X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-201, BY16-004. SF8427 (both manufactured by Toray Dow Corning Co., Ltd.) XF42-B0970, XF42-C3294 (both manufactured by Momentive Performance Materials Japan GK), and the like are all available from the market. These two terminal carbinol-modified silicone oils can be used alone or in combination. Among these, X-22-160AS, KF6001, KF6002, BY16-201, and XF42-B0970 are preferable.

The terminal alcohol polyester (f) represented by the following formula (6) can be used in combination with the above-mentioned both-end carbinol-modified silicone oil (e) as necessary.

(In Formula (6), R ₈ and R ₉ each independently represents an alkylene group having 1 to 10 carbon atoms, and k represents an average value of 1 to 100)

In the formula (6), specific examples of R ₈ 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 an alkylene group having a branched chain having 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene, and an alkylene group 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. It is preferable from the viewpoint.

In the formula (6), specific examples of R ₉ 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 an alkylene group having a branched chain having 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene, and an alkylene group 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 (6), k is an average value of 1 to 100, preferably 2 to 40, more preferably 3 to 30.

The weight average molecular weight (Mw) of the terminal alcohol polyester (f) is usually 500 to 20000, preferably 500 to 5000, and more preferably 500 to 3000. If the weight average molecular weight is less than 500, the cured product hardness of the curable resin composition of the present invention may be too high and cracks may occur in a heat cycle test or the like, and if the weight average molecular weight is more than 20000, the cured product becomes sticky. May occur. 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 (f) represented by the formula (6) include polyester polyols having an alcoholic hydroxyl group at the terminal. Specific examples thereof are polyester polyols, Kyowapol 1000 PA, 2000 PA, 3000 PA, 2000 BA (all manufactured by Kyowa Hakko Chemical Co., Ltd.); Adeka New Ace Y9-10, YT-101 (all ADEKA ( Plaxel 220EB, 220EC (both manufactured by Daicel Chemical Industries); Polylite 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-2523, OD-X-2555 (all IC Co., Ltd.); HS2H-201AP, HS2H-351A, HS2H-451A, HS2H-851A, HS2N-221A, HS2N-521A, HS2H-220S, HS2N-220S, HS2N-226P, HS2B-222A, HOKOKU-OL 110, HT-210, HT-12, HT-250, HT-310, HT-40M (all manufactured by Toyokuni Oil Co., Ltd.), etc., all of which are commercially available. These polyester compounds can be used alone or in combination of two or more. Of these, Kyowapol 1000PA, Adeka New Ace Y9-10, and HS2N-221A are preferable.

When used in combination, the amount of terminal alcohol polyester (f) used is usually 0.5 to 200 parts by weight, preferably 5 to 50 parts by weight, more preferably 100 parts by weight of carbinol-modified silicone oil (e) at both ends. Is 10 to 30 parts by weight. If the amount is less than 0.5 part by weight, the mechanical strength of the cured product may be reduced. If the amount is more than 200 parts by weight, the heat-resistant transparency of the cured product is lowered and the viscosity of the polyvalent carboxylic acid (Bb) to be obtained is significantly increased. Sometimes.
From the viewpoint of lowering the glass transition temperature and lowering the storage elastic modulus at 0 ° C., 15 to 30 parts by weight is preferable.

The compound (g) having one or more carboxylic anhydride groups in the molecule includes, for example, succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, 2,3-butanedicarboxylic anhydride, 2,4 -Saturated aliphatic carboxylic anhydrides such as pentanedicarboxylic anhydride, 3,5-heptanedicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, maleic anhydride, dodecyl succinic acid Unsaturated aliphatic carboxylic anhydrides such as anhydrides, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,3-cyclohexanedicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl Norbornane-2,3-dicarboxylic acid anhydride, nadic acid anhydride, methyl nadic acid anhydride, bicyclo [2,2,2] octane-2,3-dicar Acid anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydrides, cyclic saturated aliphatic carboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, methyl Cyclic unsaturation such as nadic acid anhydride, 4,5-dimethyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -5-octene-2,3-dicarboxylic acid anhydride Aromatic carboxylic anhydrides such as aliphatic carboxylic anhydride, phthalic anhydride, isophthalic anhydride, terephthalic anhydride, trimellitic anhydride, pyromellitic anhydride In addition, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl ) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride and the like, saturated aliphatic carboxylic acid anhydride, cyclic saturated carboxylic acid anhydride, cyclic unsaturated carboxylic acid anhydride Examples thereof include polycarboxylic acid compounds possessed.
The compound (g) having one or more carboxylic acid anhydride groups in the molecule can be used alone or in combination. Among these, since the polyvalent carboxylic acid (Bb) is liquid at room temperature and the cured product obtained by curing the polyvalent carboxylic acid (Bb) and the epoxy resin is excellent in transparency, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 1,2 3,4-butanetetracarboxylic dianhydride is preferred. More preferred are methylhexahydrophthalic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and particularly preferred is methylhexahydrophthalic anhydride.

The reaction between the both-end carbinol-modified silicone oil (e) (and optionally the terminal alcohol polyester (f)) and the compound (g) having one or more carboxylic acid anhydride groups in the molecule is not conducted in a solvent. It can also be performed with a solvent. As the solvent, the both-end carbinol-modified silicone oil (e) represented by the formula (5) (and the terminal alcohol polyester (f) if necessary) and one or more carboxylic anhydride groups in the molecule Any solvent that does not react with the compound (g) can be used without particular limitation. Examples of solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, toluene and xylene. An aromatic hydrocarbon etc. are mentioned, Among these, an aromatic hydrocarbon and ketones are preferable. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but the above-mentioned carbinol-modified silicone oil (e) (and optionally terminal alcohol polyester (f) if necessary) and a compound having one or more carboxylic anhydride groups ( It is usually preferable to use 0.1 to 300 parts by weight per 100 parts by weight of the total weight of g).

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

There are no particular restrictions on the amount of catalyst used, but both terminal carbinol-modified silicone oil (e) represented by formula (5) (and terminal alcohol polyester (f) if necessary) and one in the molecule. It is usually preferable to use 0.1 to 100 parts by weight as necessary with respect to 100 parts by weight of the total weight of the compound (g) having a carboxylic acid anhydride group.

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

When a curing agent other than the aforementioned acid anhydride (Ba) and / or polyvalent carboxylic acid (Bb) is used in combination as the epoxy resin curing agent, the acid anhydride (Ba) and / or the polyvalent carboxylic acid (Bb) The proportion of the total amount 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 (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, etc. 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 curable resin composition of the present invention, the blending ratio of the epoxy resin (A) and the epoxy resin curing agent (B) is 0.5 to 1.2 equivalents of the curing agent with respect to 1 equivalent of the epoxy groups of all epoxy resins. It is preferable to use it. When the curing agent is less than 0.5 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

In the curable resin composition of the present invention, a curing accelerator can be used together with the epoxy resin curing agent (B). Since the curing accelerator is excellent in transparency, an ammonium salt-based curing accelerator, a phosphonium salt-based curing accelerator, and a metal soap-based curing accelerator are particularly excellent. Examples of the ammonium salt curing accelerator include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide. , Trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate and the like. Examples of the phosphonium salt-based curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, methyltributylphosphonium diethylphosphate, and the like. Examples of the metal soap-based curing accelerator include tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, and potassium octylate. These curing accelerators may be used alone or in combination of two or more. Among these curing accelerators, trimethyl cetyl ammonium hydroxide, methyl tributyl phosphonium dimethyl phosphate, tin octylate, zinc octylate, and manganese octylate are preferable.
Among them, in order to obtain a cured product excellent in transparency and sulfidation resistance, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylate) and zinc phosphate ester ( Zinc compounds such as zinc octyl phosphate and zinc stearyl phosphate are preferably used.
The curing accelerator is usually used in the range of 0.001 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin (A).

In the curable 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, neoalkoxy tris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxy tris (ethylenediaminoethyl) zirconate, neoalco Examples thereof include zitris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, zirconium such as Al-methacrylate, Al-propionate, and aluminum coupling agents.
These coupling agents may be used alone or in combination of two or more.
In the curable resin composition of the present invention, the coupling agent is usually contained in an amount of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight as required.

In the curable resin composition of the present invention, it is possible to supplement mechanical strength without impairing transparency by using a nano-order level inorganic filler as necessary. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is preferably an amount occupying 0 to 95% by weight in the curable resin composition of the present invention.

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

In the curable resin composition of the present invention, a thixotropic imparting agent such as fine silica powder (also referred to as “aerosil” or “aerosol”) can be added for the purpose of preventing sedimentation of various phosphors during curing. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, AerosilR202, AerosilR202, AerosilR202 Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

For the purpose of preventing coloration, the curable resin composition of the present invention can contain an amine compound as a light stabilizer, 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- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetrame Ru-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] bu Lumalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine- , 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate And 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, 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-piperidinyl) Hindered amines such as octabenzone, benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, -Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5-methylphenyl Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl)- Benzotriazole compounds such as 6-dodecyl-4-methylphenol, 2,4 Benzoates such as di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- Examples include triazine compounds such as [(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound as the light stabilizer.
The commercially available amine compound is not particularly limited. For example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, and ADEKA manufactured by Ciba Specialty Chemicals, LA-52, LA-57, LA- 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

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) Hos 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'- Biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenedi Phosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butyl) Ruphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl -Phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl Examples include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. .

Commercially available products can also be used as the phosphorus compound. The commercially available phosphorus compounds are not particularly limited. For example, as ADEKA, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, Adekas tab TPP and the like.

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

Commercially available products can also be used as the phenolic compound. The commercially available phenolic compounds are not particularly limited. , ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, Sumitizer GA-80 manufactured by Sumitomo Chemical Co., Ltd. , Sumilizer MDP-S, Sumil izer BBM-S, SumizerｚGM, SumizerｉｌGS (F), SumizerGP, and the like.

In addition, commercially available additives can be used as resin coloring inhibitors. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like can be mentioned as manufactured by Ciba Specialty Chemicals.

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

The curable resin composition of the present invention is obtained by sufficiently mixing additives such as an epoxy resin (A), an epoxy resin curing agent (B), a curing accelerator, a coupling agent, an antioxidant, and a light stabilizer. A curable resin composition can be prepared and used as a sealing material. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

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

As a molding method of the sealing material, an injection method in which the sealing material is injected into the mold frame in which the optical semiconductor element is fixed is inserted and then heat-cured and then molded, and the sealing material is injected on the mold in advance. A compression molding method is used in which an optical semiconductor element fixed on a substrate is immersed therein and heat-cured and then released from a mold.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used. For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat-curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
In the present specification, ratios, percentages, parts and the like are based on weight unless otherwise specified. In this specification, the expression “X to Y” indicates a range from X to Y, and the range includes X and Y.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, 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 a silicone skeleton epoxy resin in which silanol-terminated silicone oil (a) and epoxy group-containing silicon compound (b) are produced through a two-stage production process)
(Manufacturing process 1)
394 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) 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 a 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, the organic phase was removed at 100 ° C. under reduced pressure to obtain 731 parts of a silicone skeleton epoxy resin (A-1). 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 2 (Synthesis Example of Silicone Skeleton Epoxy Resin Produced by Silanol-Terminated Silicone Oil (a) and Epoxy Group-Containing Silicon Compound (b) Through Two-Step Manufacturing Process)
(Manufacturing process 1)
197 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) 534 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 576 parts of methanol, 86.4 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 a 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 660 parts of MIBK was added for washing, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 648 parts of a silicone skeleton epoxy resin (A-2). The epoxy equivalent of the obtained resin was 857 g / eq, the weight average molecular weight was 1860, the viscosity was 390 mPa · s, and the appearance was a colorless and transparent liquid.

Synthesis Example 3 (Synthesis Example of Silicone Skeleton Epoxy Resin Made from Silanol-Terminated Silicone Oil (a) and Epoxy Group-Containing Silicon Compound (b) Through Two-Step Manufacturing Process)
(Manufacturing process 1)
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 74 parts, 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) 52 Part, 0.5 part of a KOH methanol solution and 9 parts of isopropyl alcohol were charged into a reaction vessel and heated to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours.
(Manufacturing process 2)
After adding 83 parts of methanol, 60.5 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 a 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 120 parts of MIBK was added for washing, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 100 parts of a silicone skeleton epoxy resin (A-3). The epoxy equivalent of the obtained resin was 364 g / eq, the weight average molecular weight was 2310, the viscosity was 67070 mPa · s, and the appearance was a colorless and transparent liquid.

Synthesis Example 4 (Synthesis example of polyvalent carboxylic acid having silicone skeleton)
In a glass separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, 50 parts of both-end carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), Ricacid MH (methyl hexahydrophthalic anhydride, 15.4 parts (manufactured by Shin Nippon Rika Co., Ltd.) were charged into a reaction vessel, heated to 80 ° C., and GPC was measured after 4 hours. The peak of Ricacid MH disappeared. Thereafter, the mixture was further reacted for 2 hours to obtain 65.0 parts of polyvalent carboxylic acid (B-1). The acid value of the obtained compound was 80.0 mgKOH / g, the weight average molecular weight was 1700, the viscosity was 750 mPa · s, and the appearance was a colorless and transparent liquid.

Synthesis Example 5 (Synthesis example of polyvalent carboxylic acid having silicone skeleton and polyester skeleton)
A glass separable flask equipped with a stirrer, a Dimroth condenser and a thermometer, 47.1 parts carbinol-modified silicone X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.), Adeka New Ace Y9- which is a polyester polyol 10 (polyester polyol manufactured by ADEKA Corporation, wherein R ₈ is a neopentylene group and R ₉ is a butylene group in the above formula (6)), Ricacid BT-100 (1,2,3,4-butanetetra) Carrying out 2.5 parts of carboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd.) and 16.6 parts of Ricacid MH (methylhexahydrophthalic anhydride, Shin Nippon Rika Co., Ltd.) at 140 ° C. for 10 hours By reacting, 77.5 parts of the polyvalent carboxylic acid resin (B-2) of the present invention was obtained. At this time, the peaks of Ricacid BT-100 and Ricacid MH disappeared in the GPC measurement. This polycarboxylic acid resin was a colorless and transparent liquid at the end of the reaction, but became a cloudy liquid as the temperature of the reaction liquid decreased. The acid value of the obtained compound was 88.8 mgKOH / g, the weight average molecular weight was 3452, the viscosity was 5730 mPa · s, and the appearance was a white liquid.

Synthesis Example 6 (Synthesis Example of Mixture of Acid Anhydride and Multivalent Carboxylic Acid)
A glass separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, 12 parts of tricyclodecane dimethanol (TCD-AL, manufactured by Oxea), RIKACID MH (methylhexahydrophthalic anhydride, Shin Nippon Rika Co., Ltd.) )) 73 parts were charged into a reaction vessel (a glass four-necked flask equipped with a stirrer, Dimroth, and thermometer), heated to 40 ° C. for 1 hour, and then reacted at 60 ° C. for 1 hour, and GPC was measured. However, the peak of tricyclodecane dimethanol disappeared. After completion of the reaction, a curing agent (B-3), which is a mixture of a polyvalent carboxylic acid having a cyclic aliphatic hydrocarbon group (tricyclodecanedimethyl) as a main skeleton and an acid anhydride (methylhexahydrophthalic anhydride). ) Was obtained 100 parts. The functional group equivalent of the obtained curing agent (B-3) was 171 g / eq. (The carboxylic acid and acid anhydride groups are each considered as one functional group). The viscosity was 15000 mPa · s, and the appearance was a colorless and transparent liquid.

Example 1
100 parts of silicone skeleton epoxy resin (A-1) obtained in Synthesis Example 1, 5 parts of ERL-4221 (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, manufactured by Dow Chemical), epoxy 74 parts of polyvalent carboxylic acid (B-1) obtained in Synthesis Example 4 as a resin curing agent, 8 parts of PRIPOL 1009 (dimer acid which is a reduced product of unsaturated fatty acid multimer, manufactured by Claude Japan Co., Ltd.), curing 1 part of zinc 2-ethylhexanoate was added as an accelerator, mixed and defoamed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation of the present invention.

Example 2
70 parts of silicone skeleton epoxy resin (A-1) obtained in Synthesis Example 1, 30 parts of silicone skeleton epoxy resin (A-3) obtained in Synthesis Example 3, ERL-4221 (3,4-epoxycyclohexylmethyl- 5 parts of (3,4-epoxy) cyclohexyl carboxylate, manufactured by Dow Chemical), 71 parts of polycarboxylic acid (B-2) obtained in Synthesis Example 5 as an epoxy resin curing agent, 2-ethylhexane as a curing accelerator 0.5 parts of zinc acid was added, mixed and degassed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation of the present invention.

Comparative Example 1
40 parts of silicone skeleton epoxy resin (A-1) obtained in Synthesis Example 1, 60 parts of silicone skeleton epoxy resin (A-3) obtained in Synthesis Example 3, ERL-4221 (3,4-epoxycyclohexylmethyl- 5 parts of (3,4-epoxy) cyclohexyl carboxylate, manufactured by Dow Chemical), 87 parts of polycarboxylic acid (B-2) obtained in Synthesis Example 5 as an epoxy resin curing agent, PRIPOL 1009 (multimer of unsaturated fatty acids) 10 parts of dimer acid, a product of Cloda Japan Co., Ltd.) and 1.2 parts of zinc 2-ethylhexanoate as a curing accelerator, mixed and degassed for 5 minutes to cure for optical semiconductor encapsulation A functional resin composition was obtained.

Comparative Example 2
50 parts of silicone skeleton epoxy resin (A-1) obtained in Synthesis Example 1, 50 parts of silicone skeleton epoxy resin (A-2) obtained in Synthesis Example 2, ERL-4221 (3,4-epoxycyclohexylmethyl- 5 parts of (3,4-epoxy) cyclohexyl carboxylate, manufactured by Dow Chemical), 23 parts of a mixture of acid anhydride and polycarboxylic acid obtained in Synthesis Example 6 as an epoxy resin curing agent (B-3), curing acceleration 0.2 parts of 2-ethylhexanoic acid zinc was added as an agent, mixed and defoamed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation.

Comparative Example 3
50 parts of silicone skeleton epoxy resin (A-1) obtained in Synthesis Example 1, 50 parts of silicone skeleton epoxy resin (A-2) obtained in Synthesis Example 2, obtained in Synthesis Example 6 as an epoxy resin curing agent 26 parts of the resulting acid anhydride and polycarboxylic acid mixture (B-3) and 0.8 part of zinc 2-ethylhexanoate as a curing accelerator were added, mixed and degassed for 5 minutes to seal the optical semiconductor. A curable resin composition was obtained.

Evaluation test The blending ratio of the curable resin compositions for sealing an optical semiconductor obtained in Examples 1 and 2 and Comparative Examples 1 to 3, and the storage modulus of the cured product at 0 ° C. measured by the DMA method, DMA Table 1 shows the results of the glass transition temperature (Tg), heat cycle resistance, and sulfidation resistance measured by the method. The test in Table 1 was performed as follows.

(1) Storage elastic modulus at 0 ° C. measured by DMA method;
After carrying out vacuum defoaming for 5 minutes with the curable resin composition for sealing an optical semiconductor obtained in Examples 1 and 2 and Comparative Examples 1 to 3, heat-resistant tape was used so that the height would 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 and then cured at 150 ° C. for 3 hours to obtain a cured film having a thickness of 0.8 mm. The obtained cured product was molded into a width of 5 mm and a length of 25 mm, DMA (Dynamic Mechanical Analysis) was measured under the following conditions, and the storage elastic modulus at 0 ° C. was read.
<DMA measurement conditions>
Measuring equipment: DMS6100 manufactured by Seiko Instruments Inc.
Measurement temperature: -50 ° C to 150 ° C
Temperature increase rate: 2 ° C / min
Frequency: 10Hz
Measurement mode: Tensile vibration

(2) Glass transition temperature (Tg) measured by DMA method;
The maximum point of the loss coefficient (tan δ = E ″ / E ′) represented by the quotient of the storage elastic modulus (E ′) and the loss elastic modulus (E ″) when the DMA of (1) is measured. The temperature was read.
(3) Heat cycle test The curable resin composition for sealing an optical semiconductor obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was vacuum degassed for 5 minutes, then filled into a syringe, and a precision dispensing device was used. A surface-mounted LED in which a light-emitting element having an emission wavelength of 450 nm is mounted on a surface-mounted LED package of 5 mm × 5 mm × 1.4 mm (sealing portion 0.6 mm) having a copper electrode with silver plating on the bottom surface In addition, casting was performed so that the opening was a flat surface. After pre-curing at 120 ° C. for 1 hour, it was cured at 150 ° C. for 3 hours to seal the surface-mounted LED. After sealing in this way, the heat cycle test shown below was performed, and the change in the appearance was observed.
<Heat cycle test conditions>
Test equipment: 1 cycle manufactured by ESPEC; -40 ° C. 30 minutes to 100 ° C. 30 minutes Taken every 100 cycles, and changes in appearance were observed up to 300 cycles.

(4) Sulfur resistance test Two surface-mounted LEDs, sealed in the same manner as in the heat cycle test, were made of two polyethylene containers with an opening diameter of 2 cm and a height of 1.5 cm containing 6 ml of 20% ammonium sulfide aqueous solution (lids) Was opened) and placed in a polypropylene sealed container of about 3.2 liters and allowed to stand at room temperature (20-27 ° C.) for 10 hours. After standing, the discoloration of the silver-plated portion on the bottom surface was visually confirmed. In the table, ○: no discoloration, Δ: slightly discolored, ×: severely discolored.

As is apparent from the results shown in Table 1, Comparative Examples 1 to 3 in which the storage elastic modulus at 0 ° C. by the DMA method exceeds 150 MPa and the glass transition temperature exceeds 10 ° C. are excellent in resistance to sulfidation. In the cycle test, cracks (cracks) are confirmed in the cured product near the wire by 300 cycles, and the reliability of the optical semiconductor is inferior. On the other hand, Examples 1 and 2 in which the storage elastic modulus at 0 ° C. by the DMA method is in the range of 0 to 150 MPa and the glass transition temperature is in the range of −10 to 10 ° C. are not only excellent in sulfidation resistance but also heat In the cycle test, the appearance did not change even after 300 cycles, and the reliability of the optical semiconductor was excellent.

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.
The present application is based on a Japanese patent application (Japanese Patent Application No. 2011-210118) filed on September 27, 2011, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

The curable resin composition of the present invention has a glass transition temperature (Tg) measured by DMA method in the range of −10 to 10 ° C. and a storage elastic modulus at 0 ° C. measured by DMA method in the range of 0 to 150 MPa. By giving a certain cured product, it is extremely useful as a sealing material for an optical semiconductor element (LED) because it has excellent heat cycle resistance.

Claims

The optical semiconductor device encapsulated product has a glass transition temperature (Tg) measured by DMA method in the range of −10 to 10 ° C. and a storage elastic modulus at 0 ° C. measured in DMA range of 0 to 150 MPa. Curable resin composition for stopping.
The curable resin composition for optical semiconductor element sealing of Claim 1 containing an epoxy resin (A) and an epoxy resin hardening | curing agent (B).
The curable resin composition for optical semiconductor element sealing according to claim 2, wherein the epoxy resin (A) is a silicone skeleton epoxy resin.
The silicone skeleton epoxy resin is a polymer of a silanol-terminated silicone oil represented by formula (1) and an epoxy group-containing silicon compound represented by formula (2) obtained through the following production steps 1 and 2, The curable resin composition for optical semiconductor element encapsulation according to claim 3, wherein the epoxy equivalent measured by the method according to JIS K-7236 is 300 to 1500 g / eq.
Manufacturing process 1
A step of condensing a silanol group of a silanol-terminated silicone oil and an alkoxy group of an epoxy group-containing silicon compound 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.

(In Formula (1), R 1 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 5 to 10 carbon atoms, and m represents an average value of 3 to 200. In the formula, a plurality of R 1 are present. They may be the same or different)

(In the formula (2), X represents an organic group containing an epoxy group, R 2 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and R 3 represents a straight chain having 1 to 10 carbon atoms. A chain, branched or cyclic alkyl group, p is an integer from 0 to 2, and r is an integer and represents (3-p).)
The curable resin for sealing an optical semiconductor element according to claim 2, wherein the epoxy resin curing agent (B) is a carboxylic acid resin obtained by modifying a carboxylic acid anhydride and / or a carboxylic acid anhydride with an alcoholic hydroxyl group. Resin composition.
Furthermore, zinc carboxylate is included as a hardening accelerator, The curable resin composition for optical semiconductor element sealing of Claim 4 or Claim 5 characterized by the above-mentioned.
The curable resin composition for sealing an optical semiconductor element according to claim 6, wherein the zinc carboxylate is at least one selected from zinc 2-ethylhexanoate, zinc stearate, zinc behenate, and zinc myristylate.
A cured product obtained by curing the curable resin composition for sealing an optical semiconductor element according to any one of claims 1 to 7.
LED which comprises the hardened | cured material of Claim 8.