KR20160072095A - Curable resin composition and cured product thereof - Google Patents

Abstract

An epoxy resin composition comprising a cyclic siloxane compound (A) having a specific structure having two or more epoxy groups in a molecule, an epoxy resin curing agent (B), and optionally an epoxy resin curing accelerator (C). Preferably, the epoxy resin curing agent (B) is a polycarboxylic acid resin or a polycarboxylic acid having a specific structure.

Description

CURABLE RESIN COMPOSITION AND CURED PRODUCT THEREOF [0002]

TECHNICAL FIELD The present invention relates to a curable resin composition and a cured product thereof, which are particularly suitable for use in areas where high transparency is required, such as for optical semiconductor encapsulation.

As a resin for optical semiconductor sealing such as an LED (Light Emitting Diode, light emitting diode) emitting white light, a silicone resin sealing material using an unsaturated hydrocarbon group-containing dimethylpolysiloxane and an organohydrogen dimethylpolysiloxane is excellent in transparency and transparency (See Patent Document 1).

BACKGROUND ART [0002] Silver plating having a high conductivity and a high light reflectance is widely used as a lead frame in order to energize the LED and improve the light extraction efficiency. However, since the silicone resin sealing material has high gas permeability, sulfur gas such as hydrogen sulfide present in the air permeates and the surface of the lead frame changes to black due to bonding with silver plating (silver sulfuration) , The reflectivity is lowered, and as a result, the LED brightness is lowered.

Therefore, a phenylsilicone resin sealing material improved in sulfide resistance by introducing a phenyl group into a dimethylsilicone resin in order to lower permeability of the sulfur gas as an improvement in sulfidation resistance has been used (see Patent Document 2).

On the other hand, in recent years, the thinness of the LED package is also progressing for the thinning of the liquid crystal display. The resin sealing portion is also thinned to make the LED package thinner, so that it is impossible to obtain resistance to sulfidation that can satisfy even a phenylsilicone resin sealing material.

In order to fix the surface mount LED package to the substrate, the lead frame solder reflow process in which the entire package is temporarily exposed to a high temperature needs to be performed. In this process, the sealant is peeled off from the package or crack There is a problem that cracks are introduced.

Japanese Patent No. 4636242 Japanese Patent No. 4676735

The present invention relates to an optical semiconductor device which is provided with a cured product having excellent transparency, moderate hardness and excellent mechanical strength and which does not cause cracking during reflow when the optical semiconductor is sealed, and which has excellent sulphide resistance and long- An epoxy resin composition for imparting a sealing material, and a cured product thereof.

The inventors of the present invention have made intensive studies in view of the above-mentioned circumstances and as a result, they have found that a curable resin composition containing a cyclic siloxane compound having a specific structure having two or more epoxy groups in a molecule and an epoxy resin curing agent, and optionally a curing accelerator, And have accomplished the present invention.

That is, the present invention relates to the following (1) to (13).

(1) An epoxy resin composition comprising a cyclic siloxane compound (A) having two or more epoxy groups in a molecule represented by the following formula (1) and an epoxy resin curing agent (B).

(Wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, X is an organic group containing an epoxy group or a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 3. When R ¹ , X may be the same or different, but may be different, with the proviso that at least two of the plural Xs present are organic groups containing an epoxy group.

(2) The method according to (1)

An epoxy resin composition wherein at least 90 mol% of X in the formula (1) is an organic group containing an epoxy group.

(3) The method according to (1) or (2)

Wherein the epoxy resin curing agent (B) is a polycarboxylic acid resin.

(4) The method according to (3)

Wherein the polycarboxylic acid resin is an addition polymer obtained by reacting at least (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule and (b) a compound containing at least one acid anhydride group in the molecule.

(5) The method according to (4)

(b) an epoxy resin composition wherein the compound containing at least one acid anhydride group in the molecule is at least one compound selected from methylhexahydrophthalic anhydride, glutaric anhydride and diethylglutaric anhydride.

(6) In the item (1) or (2)

An epoxy resin composition wherein the epoxy resin curing agent (B) is a polyfunctional carboxylic acid represented by the following formula (2).

Wherein Q represents a hydrogen atom, a methyl group, or a carboxyl group, P represents an aliphatic group having 2 to 20 carbon atoms in the form of a chain and / or cyclic structure, and m represents an integer of 2 to 4, .

(7) The method according to (6)

The epoxy resin curing agent (B) represented by the formula (2) contains at least one compound represented by the following formulas (3) to (6).

(8) In the item (1) or (2)

Wherein the epoxy resin curing agent (B) is a polyvalent carboxylic acid represented by the following formula (8).

(Wherein P and m have the same meanings as in the formula (2), and R ² represents a hydrogen atom or an ethyl group.)

(9) In (8)

The epoxy resin curing agent (B) represented by the formula (8) contains at least one compound represented by the following formulas (9) to (12).

(In the formulas (9) to (12), R ² has the same meanings as in the formula (8).)

(10) In any one of (1) to (9)

And an epoxy resin curing accelerator (C).

(11) In (10)

Wherein the epoxy resin curing accelerator (C) is a metal soap curing accelerator.

(12) A cured product obtained by curing the epoxy resin composition according to any one of (1) to (11).

(13) A resin composition for optical semiconductor encapsulation comprising the epoxy resin composition according to any one of (1) to (11).

(14) The optical semiconductor device in which the optical semiconductor element is sealed by the resin composition for optical semiconductor encapsulation described in (13).

(Effects of the Invention)

According to the present invention, a curable resin composition containing a cyclic siloxane compound having a specific structure having two or more epoxy groups in a molecule, an epoxy resin curing agent and, optionally, a curing accelerator is provided with a cured product of high transparency, Is very useful as a material requiring high transparency, particularly, a resin for sealing of optical semiconductors (LED, etc.) because of maintaining the illuminance at the time and maintaining the illuminance at the time of long-term lighting.

The curable resin composition of the present invention is characterized by containing a cyclic siloxane compound (A) having two or more epoxy groups in the molecule and an epoxy resin curing agent (B).

The cyclic siloxane compound (A) having two or more epoxy groups in the molecule in the present invention is a compound represented by the following formula (1).

In the formula (1), R ¹ represents a hydrocarbon group of 1 to 6 carbon atoms, X represents an organic group containing an epoxy group or a hydrocarbon group of 1 to 6 carbon atoms, and n represents an integer of 1 to 3, respectively. The plurality of R ¹ and X present in the formula may be the same or different. Provided that at least two of the plural Xs present are epoxy groups containing an epoxy group.

Specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a phenyl group. Among them, a methyl group and a phenyl group are preferable from the viewpoint of heat resistance and transparency of a cured product. .

The organic group in X represents a compound consisting of C, H, N, and O atoms. Specific examples of the organic group containing an epoxy group include 2,3-epoxycyclohexylethyl group and 3-glycidoxypropyl group, From the viewpoint of transparency, a 2,3-epoxycyclohexylethyl group is preferable. Here, the number of carbon atoms in the organic group is preferably 1 to 20, more preferably 3 to 15. Also preferred is a group in which a 2,3-epoxycyclohexylethyl group or a 3-glycidoxypropyl group is added via an alkylene group having 1 to 5 carbon atoms.

Specific examples of the hydrocarbon group having 1 to 6 carbon atoms in X include methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl groups. From the viewpoint of easiness, the methyl group is particularly preferable.

Of the Xs present in the molecule, at least two are organic groups containing an epoxy group, but an organic group containing at least 90 mol%, on the average, of X in the compound represented by the formula (1) Is preferable because it maintains the roughness retention ratio, and particularly preferably 96 mol% or more.

n is preferably 2 from the viewpoint of ease of preparation of the compound.

The cyclic siloxane compound (A) having two or more epoxy groups in the molecule represented by the formula (1) can be obtained by a hydrosilylation reaction between a cyclic hydrogen siloxane compound and an olefin compound having an epoxy group in the molecule.

Specific examples of the cyclic hydrogensiloxane compound include trimethyltricyclosiloxane, triphenyltricyclosiloxane, tetramethyltetracyclosiloxane, tetraphenyltetracyclosiloxane, pentamethylpentacyclosiloxane, pentaphenylpentacyclosiloxane, and the like, and the ease of manufacture Tetramethyltetrasiloxane is preferred.

Examples of the olefin compound having an epoxy group in the molecule include 4-vinyl-1,2-epoxycyclohexane and 3-glycidoxy-1,2-propane. From the viewpoint of heat resistance and transparency of the cured product, - Epoxycyclohexane is preferred.

As the catalyst for the hydrosilylation reaction, for example, known metal complexes such as rhodium, palladium, and platinum can be used. Specific examples thereof include tris (triphenylphosphine) rhodium chloride, hexachloroplatinic acid hexahydrate, divinyltetramethyldisiloxane platinum complex, tetravinyltetramethylcyclotetrasiloxane platinum complex, dichlorobis (triphenylphosphine) platinum complex, tetra There is exemplified a platinum catalyst immobilized on a solvent insoluble carrier such as commercially available polyethylene such as FibreCat (trademark) 4001 and FibreCat 4003 (both manufactured by Wako Pure Chemical Industries, Ltd.) in addition to kiss (triphenylphosphine) platinum complex, From the viewpoints of the transparency of the cyclic siloxane compound (A) having two or more epoxy groups in the resulting molecule and the transparency of the cured product, hexachloroplatinic acid hexahydrate, divinyltetramethyldisiloxane platinum complex, tetravinyltetramethylcyclotetrasiloxane platinum complex, Dichlorobis (triphenylphosphine) platinum complex, FibreCat 4003 is preferred .

The catalyst used in the hydrosilylation reaction is preferably dissolved in a solvent to be used as a solution from the viewpoint of workability. The catalyst that can be used can be used as long as it is a solvent that dissolves the catalyst, but from the viewpoints of solubility and workability, tetrahydrofuran and toluene are preferable.

When it is used as a solution, it may be added to the reaction solution by adjusting the catalyst to 0.05 to 50% by weight.

When a catalyst immobilized on polyethylene or the like is used, it can be directly added to the reaction solution.

The amount of the catalyst to be added is preferably the amount of metal used in the catalyst and is usually in the range of 0.1 to 1,000 ppm of the reaction substrate. More preferably from 1 to 100 ppm, and particularly preferably from 2 to 20 ppm, from the viewpoints of the transparency of the cyclic siloxane compound (A) having two or more epoxy groups in the resulting molecule and the transparency of the cured product. If the addition amount is less than 0.1 ppm, the addition reaction may be delayed. If the addition amount is more than 1,000 ppm, the coloration of the silicone-modified epoxy resin may be increased.

After the hydrosilylation reaction, it can be purified by a known method such as washing with water, distillation, recrystallization, column chromatography, adsorption (activated carbon, various minerals).

The solvent used for the reaction and / or the purification may be removed by distillation under reduced pressure or the like.

The epoxy equivalent (measured by the method described in JIS K7236) of the cyclic siloxane compound (A) having two or more epoxy groups in the molecule is preferably 180 to 400 g / eq, and particularly preferably 190 to 250 g / eq.

The viscosity of the cyclic siloxane compound (A) having two or more epoxy groups in the molecule at 25 占 폚 is preferably 1,500 to 10,000 mPa 占 퐏, more preferably 2,000 to 8,000 mPa 占 퐏, still more preferably 3,000 to 7,000 mPa 占 퐏 Particularly preferred.

The cyclic siloxane compound (A) having two or more epoxy groups in the molecule represented by the formula (1) specifically includes the compounds represented by the following formulas (1-1) to (1-6).

In addition to the cyclic siloxane compound (A) having two or more epoxy groups in the molecule, an epoxy resin may be mixed with the epoxy resin composition of the present invention.

Examples of other epoxy resins which can be used include epoxy resins which are glycidyl ether compounds of phenolic compounds, epoxy resins which are glycidyl ether compounds of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, A glycidylamine-based epoxy resin, a glycidylated halogenated phenol resin, a copolymer of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound other than the above, a silicon compound having an epoxy group, Condensation products of silicon compounds other than these, silicone-modified epoxy resins, and the like.

Examples of the epoxy resin which is a glycidyl ether compound of the phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- Bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetra Bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1- (4-hydroxyphenyl) -2- [4- (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl- 6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, fluoroglycinol, phenols having diisopropylidene skeleton, 1,1-di- Phenols having a fluorene skeleton such as fluorene, polyphenols such as phenolated polybutadiene Sum the like are exemplified water glycidyl ether solvate of the epoxy resin.

Examples of the epoxy resin which is the glycidyl etherified product of the various novolac resins include phenols such as phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenols such as bisphenol A, bisphenol F and bisphenol S, Phenolic novolak resins containing a dicyclopentadiene skeleton, phenol novolak resins containing a biphenyl skeleton, and phenol novolac resins containing a fluorene skeleton, and the like, Glycidyl ether compounds of various novolak resins, and the like.

Examples of the alicyclic epoxy resin include aliphatic cyclic skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. And an alicyclic epoxy resin.

Examples of the aliphatic epoxy resin include epoxy resins composed of 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 isocyanuric ring and hydantoin ring.

Examples of the glycidyl ester-based epoxy resin include epoxy resins composed 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 the epoxy resin obtained by glycidylating the halogenated phenols include halogenated phenols such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S and chlorinated bisphenol A For example, glycidylated epoxy resins.

As the copolymer of the polymerizable unsaturated compound having an epoxy group and the other polymerizable unsaturated compounds other than the above, there can be mentioned Murphuf (trade name) G-0115S, G-0130S, G-0250S, G- Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-vinyl-2-pyrrolidone, and the like. 1-cyclohexene-1,2-epoxide, and the like. Examples of the copolymer of other polymerizable unsaturated compounds include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane .

The condensation product of the silicon compound having an epoxy group and the silicon compound other than the epoxy compound can be obtained by, for example, a condensation product of an alkoxysilane compound having an epoxy group and a hydrolyzed condensate of an alkoxysilane having a methyl group or a phenyl group, an alkoxysilane compound having an epoxy group, A polydimethyldiphenylsiloxane having a silanol group, a condensate of a polyphenylsiloxane having a silanol group, or a condensed compound obtained by using them in combination. Examples of the alkoxysilane compound having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and the like. Examples of the alkoxysilane compound having a methyl group or a phenyl group include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, Ethoxy silane, and the like. Examples of polydimethyldiphenylsiloxane having a silanol group and polydimethyldiphenylsiloxane having a silanol group include X-21-5841 and KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) BY16- DMS-S14, DMS-S15, DMS-S21, DMS-S21, DMS-S21, DMS-S21, DMS- DMS-S27, DMS-S31, PDS-0338 and PDS-1615 (manufactured by Gelest).

The silicone-modified epoxy resin is a compound having two or more epoxy groups in the molecule and having a silicon (Si-O) bond as a main skeleton. For example, a hydrogensiloxane compound represented by the following formula (13) 1,2-epoxycyclohexane or 3-glycidoxy-1,2-propane by the hydrosilylation reaction.

In the formula (13), R ¹ represents the same meaning as in the formula (1), and s represents an average value of 1 to 100.

The above-mentioned epoxy resins may be used alone or in combination of two or more.

Among the above-mentioned epoxy resins, alicyclic epoxy resins, condensation products of silicon compounds having an epoxy group with other silicon compounds, and silicon-modified epoxy resins are preferably used in view of transparency, heat resistance transparency and light fastness. Among them, a compound having an epoxy cyclohexane structure in the skeleton is preferable.

When the cyclic siloxane compound (A) having two or more epoxy groups in the molecule is used in combination with another epoxy resin, the ratio of the cyclic siloxane compound (A) having two or more epoxy groups in the molecule to the whole epoxy resin is 30 to 99 parts by weight Particularly preferably 60 to 97 parts by weight. If the amount is less than 30 parts by weight, there is a possibility that the lightness maintenance ratio at the time of the resistance to sulphurization test and the crack resistance at the time of reflow may be lowered.

In the epoxy resin composition of the present invention, the ratio of the total epoxy resin containing the cyclic siloxane compound (A) having two or more epoxy groups in the molecule to the epoxy resin curing agent (B) is preferably 0.5 To 1.2 equivalents of a curing agent is preferably used. When the equivalent of 0.5 equivalents or more than 1.2 equivalents based on 1 equivalent of the epoxy group is exceeded, the curing is incomplete and there is a possibility that good curing properties are not obtained.

Next, the epoxy resin curing agent (B) will be described. The epoxy resin curing agent (B) is a curing agent for curing the epoxy resin, and examples thereof include amine curing agents, phenol curing agents, acid anhydride curing agents, polyvalent carboxylic acid resins and polycarboxylic acid curing agents, A curing agent, a polycarboxylic acid resin, and a polycarboxylic acid-based curing agent are preferable. Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, A mixture of hydrohalophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, anhydrous nadic acid, methylnadic anhydride, novaline-2,3-dicarboxylic acid anhydride, methylnorbornene- 3-dicarboxylic acid anhydride, 2,4-diethylglutaric acid anhydride and the like. Of these, hexahydrophthalic anhydride and derivatives thereof are preferable.

Next, the polycarboxylic acid resin will be described.

The polycarboxylic acid resin is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group or a siloxane skeleton as a main skeleton. In the present invention, the polyvalent carboxylic acid resin includes not only a polyvalent carboxylic acid compound having a single structure but also a mixture of a plurality of compounds having different substituent groups or different substituents, that is, a polyvalent carboxylic acid composition, In the present invention, they are collectively referred to as a polycarboxylic acid resin.

As the polycarboxylic acid resin, a carboxylic acid having 2 to 6 functional groups is particularly preferable, and (b) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule and (b) a compound containing at least one acid anhydride group in the molecule The compound obtained by the reaction is more preferable. Here, in the reactants of (a) and (b), other alcohol compounds may be further reacted, and two or more kinds of compounds corresponding to component (a) or (b) may be used.

(a) The polyhydric alcohol compound containing two or more hydroxyl groups in the molecule is not particularly limited as long as the polyhydric alcohol compound has two or more alcoholic hydroxyl groups in the molecule, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, , 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, Bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl- Diols such as 5-hydroxymethyl-1,3-dioxane, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane and 2-hydroxymethyl-1,4-butanediol, pentaerythritol, Tetraols such as ditrimethylolpropane, and hexanol such as dipentaerythritol, etc., terminal alcohol polyesters, terminal alcohol polycarbos Polyhydric alcohols having an isocyanuric ring structure such as polyhydric alcohols, polyhydric alcohols having a siloxane structure, trishydroxyethyl isocyanurate, and trishydroxypropyl isocyanurate are exemplified.

Particularly preferred alcohols are alcohols having 5 or more carbon atoms, and particularly preferred are alcohols having 1 to 6 carbon atoms, such as 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3- Butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol, 2,2'-bis (4-hydroxycyclohexyl) Propane and 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, among which 2-ethyl- 1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, norbornenediol, 2,2'-bis (1, 1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane and the like, Is more preferable. From the viewpoint of imparting high resistance to sulfidation, it is preferable to use 2,4-diethylpentanediol, tricyclodecane dimethanol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1- -Hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane and the like are particularly preferable. Among them, in particular, in the branched chain structure, it is preferable that the branched chain has two or more branched chains, and the branched chain preferably extends from other carbon atoms. Herein, the alcohols having a branched chain structure or a cyclic structure preferably have 5 to 25 carbon atoms, and particularly preferably 5 to 20 carbon atoms.

Further, a polyhydric alcohol compound having an isocyanuric ring structure, which is exemplified by trishydroxyethyl isocyanurate and tris hydroxypropyl isocyanurate, is preferable from the viewpoint of heat-resistant transparency, gas barrier property and mechanical strength of the cured product.

The polyhydric alcohol having a siloxane structure is not particularly limited, and for example, a silicone oil represented by the following formula (7) can be used.

(In the formula (7), A ₁ represents an alkylene group having 1 to 10 carbon atoms in total which may have an ether bond, A ₂ represents a methyl group or a phenyl group, n represents a repeating number and an average value, 100.)

The above polyhydric alcohol compounds containing two or more hydroxyl groups in the molecule (a) may be used alone or in combination of two or more.

The use of a polyhydric alcohol having the above-mentioned siloxane structure and alcohols having a branched structure of 5 to 25 carbon atoms or alcohols having a cyclic structure is used in order to obtain a high resistance to sulfidation by using the obtained polyvalent carboxylic acid resin in a liquid phase desirable.

When a polyhydric alcohol having a siloxane structure and a branched chain structure having 5 to 25 carbon atoms or an alcohol having a cyclic structure are mixed and used, the amount of the polyhydric alcohol having a siloxane structure (polyvalent alcohol having a siloxane structure) / To 25 branched alcohols having a branched structure or cyclic structure) is preferably from 1 to 20, more preferably from 5 to 15, particularly preferably from 6 to 10, from the viewpoints of the heat-resistant transparency of the cured product and the suitable viscosity of the polycarboxylic acid resin desirable.

Examples of the compound (b) containing at least one acid anhydride group in the molecule include methyl tetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, Cyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane- 2,4-diethylglutaric anhydride, succinic anhydride and the like are preferable, and among them, methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid, Butanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, Acid dianhydride is preferred. In order to increase the hardness, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable, and methylhexahydrophthalic anhydride anhydride is preferable for increasing the roughness retention ratio. In order to suppress excessive viscosity rise, 2,4-diethylglutaric acid and glutaric acid are preferable.

The conditions of the addition reaction are not particularly specified, but one of the specific reaction conditions is a method in which an acid anhydride and a polyhydric alcohol are reacted at 40 to 150 ° C under the conditions of a non-catalyst and a solvent and heated, do. However, the reaction conditions are not limited thereto.

Next, the polycarboxylic acid-based curing agent will be described.

The polybasic carboxylic acid is preferably a compound represented by the following formula (2).

(Wherein Q in the formula (2) represents at least one of a hydrogen atom, a methyl group and a carboxyl group, and P represents a chain and / or chain linkage of 2 to 20 carbon atoms derived from a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule An aliphatic group containing a cyclic structure, and m is an integer of 2 to 4.)

Among the compounds represented by the formula (2), the dicarboxylic acid compounds represented by the following formulas (3) to (6) are particularly preferred from the viewpoints of transparency and high resistance to sulfidization of the cured product.

As the polyvalent carboxylic acid resin, a compound represented by the following formula (8) is also preferable.

(In the formula (8), P and m have the same meanings as in the formula (2), and R ² is a hydrogen atom or an ethyl group.)

Among the compounds represented by the formula (8), the dicarboxylic acid compounds represented by the following formulas (9) to (12) are preferred because of the transparency, high sulfidation resistance and low viscosity of the cured product and excellent workability .

(In the formulas (9) to (12), R ² has the same meanings as in the formula (8).)

The blending amount of the epoxy resin curing agent (B) is preferably 0.3 to 1.0 (in terms of the total amount of the epoxy groups), the functional group having reactivity with the epoxy group (the acid anhydride group represented by -CO-O-CO- in the case of the acid anhydride- Mol, and more preferably 0.4 to 0.8 mol. When the amount of the functional group having reactivity with the epoxy group is 0.3 mole or more, the heat resistance and transparency of the cured product are more improved, and 1.0 mole or less is preferable because the mechanical properties of the cured product are further improved. Herein, the term " functional group having reactivity with an epoxy group " refers to an amino group possessed by an amine curing agent, a phenolic hydroxyl group of a phenolic curing agent, an acid anhydride group of a polyhydric carboxylic acid resin, Carboxyl group.

Next, the epoxy resin curing accelerator (C) will be described.

As the epoxy resin curing accelerator (C), any resin capable of promoting the curing reaction of the cyclic siloxane compound (A) having two or more epoxy groups in the molecule (and the epoxy resin in combination) and the epoxy resin curing agent (B) Examples of the hardening accelerator (C) which can be used but are usable include ammonium salt-based hardening accelerator, phosphonium salt-based hardening accelerator, metal soap hardening accelerator, imidazole hardening accelerator, Curing accelerators, Lewis acid-based curing accelerators and the like.

The mixing ratio of the epoxy resin curing accelerator (C) in the epoxy resin composition of the present invention is preferably 0.001 to 15 parts by weight of a curing accelerator based on 100 parts by weight of the epoxy resin composition.

Specific examples of the epoxy resin curing accelerator (C) that can be used in the epoxy resin composition of the present invention include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole Benzimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1- 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl- Triazine, 2,4-diamino-6 (2'-undecylimidazole (1 ')) ethyl-s-triazine, 2,4- (2 '-methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 2,4-diamino- -Methylimidazole is a 2: 3 adduct of isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl- - hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2- 3,5-dicyanoethoxymethylimidazole, and imidazoles of imidazoles thereof with at least one of phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, Diacid compounds such as 1,8-diaza-bicyclo [5.4.0] undecene-7, and their tetraphenylborates, phenol novolacs, Boric acid and the like, salts with polycarboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide and trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) phosphine , Tetraphenylphosphonium bromide, and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, and metals such as tin octylate Compounds and the like, and microcapsule type curing accelerators containing these curing accelerators as microcapsules. The use of these curing accelerators is appropriately selected depending on the properties required for the obtained transparent resin composition, such as transparency, curing rate, and working conditions.

Among them, the metal soap hardening accelerator is excellent from the viewpoints of the transparency and the resistance to sulfidization of the hardened product, and among the metal soap hardening accelerators, the zinc carboxylate compound is particularly preferable.

Examples of the metal soap hardening accelerator include tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, potassium octylate, calcium stearate, zinc stearate, magnesium stearate, Aluminum stearate, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxyphosphate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate Hydroxystearic acid, sodium 12-hydroxystearate, calcium montanate, zinc montanate, magnesium montanate, aluminum montanate, lithium montanate, sodium montanate, sodium montanate, Calcium laurate, zinc laurate, lithium barium laurate, lithium laurate, calcium laurate, calcium laurate, calcium laurate, barium laurate, magnesium laurate, Zinc decylate, zinc ricinolate, barium ricinoleate, zinc myristate, and zinc palmitate. These catalysts may be used alone or in combination of two or more.

In order to obtain a cured product having excellent transparency and sulfidization resistance, it is particularly preferable to use zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate and zinc palmitate A zinc salt of 10 to 30 carbon atoms, and a zinc salt of 10 to 30 carbon atoms having a hydroxyl group such as 12-hydroxystearic acid can be preferably used. Among them, zinc salts such as zinc stearate, zinc salts of monocarboxylic acid compounds having 10 to 20 carbon atoms, such as undecylenic acid zinc, and hydroxystearic acid, such as zinc 12-hydroxystearate, A zinc salt of a monocarboxylic acid compound having from 15 to 20 carbon atoms can be preferably used and zinc stearate, zinc undecylenic acid and zinc 12-hydroxystearate are more preferably used, Zinc stearate, and zinc 12-hydroxystearate can be used.

Examples of the ammonium salt-based curing accelerator include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethyl ethyl ammonium hydroxide, , Trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, etc. . Examples of the phosphonium salt-based curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate and methyltributylphosphonium diethylphosphate.

Other general-purpose applications include, in addition to the ammonium salt-based curing accelerator, the phosphonium salt-based curing accelerator, the metal soap-based curing accelerator, an imidazole-based curing accelerator, an amine-based curing accelerator, a heterocyclic compound-based curing accelerator, A curing accelerator, a Lewis acid-based curing accelerator, and the like.

The above-mentioned epoxy resin curing accelerator (C) can be used as a solid compound or a liquid compound at room temperature (25 캜). In the case where the epoxy resin composition of the present invention is used for optical semiconductor encapsulation, when a solid compound at room temperature (25 캜) is used as a curing accelerator, it may be dissolved in a resin beforehand.

In the epoxy resin composition of the present invention, the viscosity of the composition can be adjusted and the hardness of the cured product can be supplemented by using a coupling agent as required.

Examples of the coupling agent that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Methacryloxypropyltrimethoxysilane, ethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3- A silane-based coupling agent such as 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane and the like; (Dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neo alkoxy tri (meth) acrylate, (pN- (p-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neo Zirconium such as alkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Or an aluminum-based coupling agent.

These coupling agents may be used alone or in combination of two or more.

The coupling agent is contained in the epoxy resin composition of the present invention in an amount of usually 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, if necessary.

The epoxy resin composition of the present invention can supplement mechanical strength and the like without impairing transparency by using an inorganic filler having a nano-order level as required. It is preferable from the viewpoint of transparency to use a filler having an average particle diameter of 500 nm or less, particularly an average particle diameter of 200 nm or less as a reference as a nano order level. Examples of inorganic fillers include powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, titania, talc, Beads, and the like, but the present invention is not limited thereto. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers in the epoxy resin composition of the present invention is preferably from 0 to 95% by weight.

In the epoxy resin composition of the present invention, a phosphor may be added as required. The phosphor has a function of absorbing a part of blue light emitted from, for example, a blue LED element and emitting white light by emitting wavelength-converted yellow light. The phosphor is previously dispersed in the curable resin composition, and then the optical semiconductor is sealed. The phosphor is not particularly limited and conventionally known phosphors can be used, and examples thereof include aluminates, thiogalates, and orthosilicates of rare earth elements. Examples of the phosphor include fluorescent materials such as YAG fluorescent material, TAG fluorescent material, orthosilicate fluorescent material, thiogallate fluorescent material and sulfide fluorescent material, 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. As the particle diameter of such a fluorescent substance, those having a known particle diameter in this field are used, but the average particle diameter is preferably 1 to 250 占 퐉, particularly preferably 2 to 50 占 퐉. When these phosphors are used, the amount thereof is preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.

A thixotropic property-imparting agent including a fine silica powder (also referred to as an aerosol (trade name) or an aerosol) may be added to the epoxy resin composition of the present invention for the purpose of preventing settling of various phosphors upon curing. Examples of such fine silica powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, RY200, RX200 (manufactured by Nippon Aerosil Co., Ltd.), and the like.

For the purpose of preventing coloring, the epoxy resin composition of the present invention may 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-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 , 6-pentamethyl-4-piperidino and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin- Tetramethyl-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, Benzyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3, < Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert- Octyl] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6 (2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4- hydroxyphenyl] methyl] butyl malonate, decanedioic acid bis N, N ', N' '' - tetrakis (triphenylphosphine), the reaction product of 1,1-dimethylethyl hydroperoxide and octane, - (4,6-bis- (N-methyl- 2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin- Diamine, dibutylamine 1,3,5-triazine N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6- A polycondensate of hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, a poly [[6- (1,1,3,3-tetramethylbutyl) amino- 2,4,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetra Methyl-4-piperidylimino]], dimethyl succinate A polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, 2,2,4,4-tetramethyl-20- (beta -lauryloxycarbonyl) ethyl- -Oxa-3,20-diazadis pyrrolo [5.1.11.2] heneic acid-21-one, [beta] -alanine, N- (2,2,6,6-tetramethyl-4-piperidinyl) Ester / tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine- , 4-tetramethyl-7-oxa-3,20-diazabicyclo [5.1.11. 2] heneic acid-21-one, 2,2,4,4-tetramethyl- [(4-methoxyphenyl) -methylene] -bis (1, 2, 2, 6-dihydroxybenzoic acid) -dodecyl ester / tetradecyl ester, propanedioic acid, 6-pentamethyl-4-piperidinyl) ester, higher fatty acid esters of 2,2,6,6-tetramethyl-4-piperidino, 1,3-benzenedicarboxamide, N, N'-bis 2,2,6,6-tetramethyl-4-piperidinyl), and other hindered amine compounds such as octabenzone Benzophenone-based compounds, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) (2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole, 2- Methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol- 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol Benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- -1,3,5-triazin-2-yl) -5 - [(hexyl) oxy] phenol and the like are exemplified, and a hindered amine compound is particularly preferable.

As the amine compound as the light stabilizer, the following commercially available products can be used.

Examples of commercially available amine compounds include, but are not limited to, TINUVIN (trade name) 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB (trade name) 944, and ADEKA as a Ciba Specialty Chemicals LA-52, LA-62, LA-63P, LA-77Y, LA-81, LA-82 and LA-87.

The phosphorus compound is not particularly limited and examples thereof include 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, distearylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, dicyclohexyl penta (Di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (di-tert- butylphenyl) (2,6-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di- Butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert- butyl-4-methylphenyl) phosphite , 2,2'-methylene Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl- (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert- butylphenyl) Phenyl) -4,3'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphosphonite, tetrakis Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4- Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylene diphosphonite, tributylphosphate, trimethylphosphate, tricresylphosphate, triphenylphosphate, Trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoctalkenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like.

Commercially available phosphorus compounds may be used. Examples of commercially available phosphorus compounds include, but are not limited to, adekastab (trade name) PEP-4C, adekastab PEP-8, adekastab PEP-24G, adekastab PEP- 36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A and the like.

The phenolic compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3,5- Phenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythritol-tetrakis [ 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate], 3,9-bis- [2- [3- (3- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol-bis [3- (3- Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert- Butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylene Butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [ Tert-butylphenyl acrylate, 4,4'-thiobis (3-methyl-6-tert (tert- Butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2-tert- butyl-4-methylphenol, 2,4- , 4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6-tert- butylphenol), 4,4'-butylidenebis ), Bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di- tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -Bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester, It is.

Commercially available phenolic compounds may be used. Examples of commercially available phenol compounds include, but are not limited to, IRGANOX (trade name) 1010, IRGANOX1035, IRGANOX1076, IRGANOX11535, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098, IRGANOX1520L, AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, and Sumilizer (trade name) as Sumitomo Chemical Co., Ltd., Sumilizer GS (F), Sumilizer GP, and the like.

In addition, commercially available additives can be used as the coloring preventing agent for the resin. For example, THINUVIN (product name) 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB (trade name) 2020FDL, CHIMASSORB 119FL and the like are exemplified as Ciba Specialty Chemicals.

The amount of the phosphorus compound, amine compound, and phenol compound is not particularly limited, but is preferably 0.005 to 5.0% by weight, more preferably 0.005 to 5.0% by weight based on the total weight of the epoxy resin composition of the present invention. .

The epoxy resin composition of the present invention is obtained by uniformly mixing the above components at room temperature or under heating. For example, the mixture is thoroughly mixed using an extruder, a kneader, a three-roll mill, a universal mixer, a planetary mixer, a homomixer, a homodisper and a bead mill until uniformity is obtained. .

The epoxy resin composition of the present invention comprises a cyclic siloxane compound (A) having two or more epoxy groups in a molecule (another epoxy resin as required), an epoxy resin curing agent (B), and a curing accelerator (C) A light stabilizer, and the like, and can be used as a sealing material. As a mixing method, mixing can be performed at room temperature or by using a kneader, a three-roll mixer, an universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like.

When it is desired to use the epoxy resin composition of the present invention thus obtained for optical semiconductor encapsulation and to be liquid at room temperature (25 DEG C), the viscosity is preferably 100 to 20,000 mPa · s from the viewpoint of workability, More preferably from 12,000 mPa · s, and particularly preferably from 3,000 to 10,000 mPa · s.

BACKGROUND ART An optical semiconductor device such as a high-brightness white LED generally has a semiconductor chip such as GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN, etc. stacked on a substrate of sapphire, spinel, SiC, Is adhered to a lead frame, a heat sink or a package using an adhesive (die bond material). There is a type in which a wire such as a gold wire is connected to flow current. The semiconductor chip is sealed by a sealing material such as an epoxy resin in order to protect the semiconductor chip from heat and moisture and also to serve as a lens function. The epoxy resin composition of the present invention can be used in this sealing material.

As a molding method of the sealing material, there is a molding method in which a sealing material is injected into a mold in which a substrate on which an optical semiconductor element is fixed is injected, followed by heating and curing to form a mold, a sealing material is preliminarily injected onto a mold, A compression molding method in which a resin is dipped from a mold after heat curing is performed is used.

Examples of the injection method include a dispenser and the like.

Heating can be performed by a method of hot-air circulation, infrared, high frequency, or the like. The heating conditions are preferably, for example, 80 to 230 DEG C for about 1 minute to 24 hours. Cured at a temperature of 120 to 180 ° C for 30 minutes to 10 hours after pre-curing at 80 to 120 ° C for 30 minutes to 5 hours for the purpose of reducing the internal stress generated at the time of heat curing.

When a cured product obtained by curing the epoxy resin composition of the present invention thus obtained is used for optical semiconductor encapsulation, the hardness is preferably 40 to 80 in terms of durometer A, and more preferably 45 to 75 in terms of durometer A. When the value of the durometer A is less than 40, there is a risk of deterioration of workability during the manufacturing process due to tack (sticking). When the durometer A is larger than 80, cracks may be introduced during a heat cycle of cold heat, There is concern that this may fall.

The glass transition temperature (Tg) of the cured product is preferably 20 to 60 ° C, more preferably 30 to 50 ° C, as measured by DMA (Dynamic Mechanical Analysis). If the temperature is lower than 20 占 폚, there is a risk of tack (sticking), and if it is higher than 60 占 폚, cracks may enter during a heat cycle of cold heat, for example.

In addition, in the cured product having a cured product having a thickness of 0.8 mm, the transmittance of the cured product is preferably not less than 85%, more preferably not less than 90%. If it is less than 85%, there is a possibility that the light extraction efficiency from the optical semiconductor element is lowered.

The tensile elongation of the cured product is preferably 100% or more. If it is less than 100%, there is a possibility that a crack may enter during the reflow process when the LED package is mounted, and the reliability as a sealing material may be lowered.

In this specification, ratios, percentages, parts, etc. are by weight unless otherwise specified. In the present specification, the expression "X to Y" represents a range from X to Y, and the range includes X, Y.

Example

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. The physical properties of the synthetic examples and examples were measured by the following methods. Here, parts denote parts by weight unless otherwise specified.

Weight average molecular weight: Calculated by polystyrene conversion and weight average molecular weight measured by GPC (Gel Permeation Chromatography) under the following conditions.

Various conditions of GPC

Maker: Shimazu Seisakusho

Column: Guard column SHODEX GPC LF-G LF-804 (3 pieces)

Flow rate: 1.0 ml / min.

Column temperature: 40 ° C

Solvents used: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

? Epoxy equivalent: measured by the method described in JIS K7236.

Acid value: Measured by the method described in JIS K2501.

○ Viscosity: Measured at 25 ° C using an E-type viscometer (TV-20) manufactured by Toray Industries, Ltd.

≪ ¹ > H-NMR: Measured with a medium chloroform solvent using JNM-ECS400 manufactured by Nippon Denshikushi Co.,

Synthesis Example 1; Production example of cyclic siloxane compound having four epoxy groups in the molecule

In a 200 ml four-necked glass flask, 0.03 part of 4-vinyl-1,2-epoxycyclohexane and a tetrahydrofuran solution of 1% hexachloroplatinic acid · hexahydrate were charged, and a dim rod condenser, The flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 80 占 폚, 12 parts of 1,3,5,7-tetramethyltetracyclosiloxane was added dropwise thereto over 1 hour, and the mixture was allowed to react for 1 hour.

The resulting reaction solution was concentrated under reduced pressure at 110 DEG C while blowing nitrogen gas to remove tetrahydrofuran and excess 4-vinyl-1,2-epoxycyclohexane to obtain a cyclic siloxane compound (EP-1) having four epoxy groups in the molecule, 36 parts were obtained. The obtained compound had an epoxy equivalent of 190 g / eq, a viscosity of 2,800 mPa · s and a colorless transparent liquid.

Synthesis Example 2; Production Example of a condensate of an alkoxy silicon having a cyclohexyl epoxy and a silanol-terminated silicone oil as a condensate of a silicon compound having an epoxy group and other silicon compounds

394 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 300 parts of silanol terminated polydimethyldiphenylsilicone oil (weight average molecular weight 1,700, silanol equivalent 850, phenyl group content of 33 wt%) 475 parts of a silanol terminated silicone oil), 4 parts of a 5 wt% KOH methanol solution and 36 parts of isopropyl alcohol were placed and a dim rod condenser, a stirrer, and a thermometer were provided, and the flask was immersed in a water bath. The water bath was heated to maintain the internal temperature at 72 占 폚 and reacted for 10 hours.

Thereafter, 656 parts of methanol was added, 173 parts of a 50% by weight ion-exchanged water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at an internal temperature of 66 캜 for 10 hours.

Thereafter, 17.5 parts of a 5 wt% aqueous solution of sodium dihydrogenphosphate was added to neutralize, and then methanol was distilled and collected at a water bath temperature of 80 캜. Thereafter, 780 parts of methyl isobutyl ketone was added for washing, and the washing with water was repeated three times. Subsequently, the organic layer was removed under reduced pressure at 100 ° C to obtain 731 parts of an epoxy group-containing polysiloxane (EP-2) which was a condensation product of a silicon compound having an epoxy group and a silicon compound other than the silicon compound.

The obtained compound had an epoxy equivalent of 491 g / eq, a weight average molecular weight of 2,090, a viscosity of 3,328 mPa,, and a colorless transparent liquid.

Synthesis Example 3; (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, and a silicone oil represented by the formula (7) and a hydrogenated product of bisphenol A, (b) a compound having at least one acid anhydride group in the molecule Production Example of Polyvalent Carboxylic Acid Resin Using Hexahydrophthalic Anhydride

In a glass 1,000 ml separable flask, 294 parts of X22-160 AS (in the formula (7), A ₁ is a propyloxyethylene group and A ₂ is a methyl group, a silicone oil of Cabinol end manufactured by Shin-Etsu Chemical Co., , 42 parts of hydrogenated bisphenol A and 164 parts of ricaside (trade name) MH-T (manufactured by Shin-Nippon Rikagaku Co., Ltd., methyl hexahydrophthalic anhydride) were charged, and a dim rod condenser, The flask was immersed in a bath. The oil bath was heated to maintain the internal temperature at 80 to 90 占 폚 and reacted for 3 hours. Thereafter, the internal temperature was raised to 100 to 110 ° C and reacted for 4 hours to obtain 489 parts of the polyvalent carboxylic acid resin (B-1). The obtained polyvalent carboxylic acid resin had a viscosity of 19,700 mPa · s and a colorless transparent liquid.

Synthesis Example 4; (a) a silicone oil represented by the formula (7) and tricyclodecane dimethanol as a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, (b) a compound having at least one acid anhydride group in the molecule Production Example of Polyvalent Carboxylic Acid Resin Using Hexahydrophthalic Anhydride

In a glass 2,000 ml separable flask, 501 parts of X22-160AS (in the formula (7), A1 is a propyloxyethylene group and A2 is a methyl group, Shin-Etsu Chemical Co., Ltd., a carbynol-terminal silicone oil) 63 parts of decane dimethanol and 286 parts of ricaside MH-T were charged, a dim rod condenser, a stirrer and a thermometer were provided, and the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 40 to 50 占 폚 and reacted for 4 hours. Thereafter, the internal temperature was raised to 70 to 80 캜 and reacted for 4 hours to obtain 833 parts of the polycarboxylic acid resin (B-2). The obtained polyvalent carboxylic acid resin had a viscosity of 8,450 mPa · s, an acid value of 111 mgKOH / g, and a colorless and transparent liquid.

Synthesis Example 5; (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, the silicone oil represented by the formula (7) and dioxane glycol, (b) a compound containing at least one acid anhydride group in the molecule, Production Example of Polyvalent Carboxylic Acid Resin Using Phthalic Anhydride

59 parts of X22-160AS (in the above formula (7), A ₁ is a propyloxyethylene group and A ₂ is a methyl group, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to a 1,000-ml separable glass flask, 7.9 parts of dioxane glycol and 33.2 parts of ricaside MH-T were charged, and a dim rod condenser, a stirrer, and a thermometer were provided, and the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 70 to 80 캜 and reacted for 4 hours to obtain 98 parts of the polyvalent carboxylic acid resin (B-3). The obtained polyvalent carboxylic acid resin had a viscosity of 12,390 mPa · s, an acid value of 113 mgKOH / g, and a colorless and transparent liquid.

Synthesis Example 6; Production example of cyclic siloxane compound having four epoxy groups in the molecule, using Fibrecat (trademark) 4003 (manufactured by Wako Pure Chemical Industries, Ltd.), which is a platinum-immobilized catalyst, on the hydrosilylation catalyst

In a 200 ml four-necked flask made of glass, 0.032 parts of 4-vinyl-1,2-epoxycyclohexane, Fibrecat 4003 (platinum content 3.4 to 4.5%) and 50 parts of toluene were charged and a dimmer condenser, And the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 80 占 폚, 12 parts of 1,3,5,7-tetramethyltetracyclosiloxane was added dropwise thereto over 1 hour, and the mixture was allowed to react for 10 hours. As a result of ¹ H-NMR measurement of the reaction solution, the proton peak derived from the hydrogensiloxane disappeared.

Activated charcoal and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the resulting filtrate. The filtrate was dried at 60 占 폚 for 2 hours at room temperature (20 to 30 占 폚) After concentrating under reduced pressure, toluene and excess 4-vinyl-1,2-epoxycyclohexane were removed to obtain 36.7 parts of cyclic siloxane compound (EP-3) having four epoxy groups in the molecule. The obtained compound had an epoxy equivalent of 184.3 g / eq, a viscosity of 5,601 mPa · s and a colorless transparent liquid.

Synthesis Example 7; Production example of cyclic siloxane compound having two or more epoxy groups in the molecule of X in the formula (1) having 91 mol% of an organic group containing an epoxy group and 9% of a hexyl group

In a 200 ml four-necked flask made of glass, 0.047 part of 4-vinyl-1,2-epoxycyclohexane, 2.2 parts of 1-hexene, 0.047 part of Fibrecat 4003 (platinum content of 3.4 to 4.5%) and 50 parts of toluene were charged, A stirrer, and a thermometer, and the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 50 to 58 占 폚, 12 parts of 1,3,5,7-tetramethyltetracyclosiloxane was added dropwise thereto over 1 hour, and the mixture was allowed to react for 10 hours. Thereafter, the internal temperature was raised to 80 캜 and further reacted for 6 hours. As a result of ¹ H-NMR measurement of the reaction solution, the proton peak derived from the hydrogensiloxane disappeared.

Activated charcoal and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the resulting filtrate. The filtrate was dried at 60 占 폚 for 2 hours at room temperature (20 to 30 占 폚) The toluene and the excess of 4-vinyl-1,2-epoxycyclohexane and 1-hexene were removed to obtain 35.9 parts of a cyclic siloxane compound (EP-4) having two or more epoxy groups in the molecule. The obtained compound had an epoxy equivalent of 198.6 g / eq, a viscosity of 3,799 mPa · s and a colorless transparent liquid. As a result of ¹ H-NMR analysis, it was found that 91% by mole of the organic group containing an epoxy group and 9% by mole of the hexyl group in X of the formula (1).

Synthesis Example 8; Production example of cyclic siloxane compound having two or more epoxy groups in the molecule of the X of the formula (1) wherein the organic group containing an epoxy group is 81 mol% and the hexyl group is 19%

To a 200 ml four-necked glass flask, 0.047 part of 4-vinyl-1,2-epoxycyclohexane, 4.3 parts of 1-hexene, 0.047 part of Fibrecat 4003 (platinum content of 3.4 to 4.5%) and 50 parts of toluene were charged, A stirrer, and a thermometer, and the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 50 to 58 占 폚, 12 parts of 1, 3,5,7-tetramethyltetracyclosiloxane was added dropwise thereto over 1 hour, and the mixture was allowed to react for 37 hours. Thereafter, the inner temperature was raised to 80 DEG C and the reaction was further continued for 4 hours. As a result of ¹ H-NMR measurement of the reaction solution, the proton peak derived from the hydrogensiloxane disappeared.

Activated charcoal and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the resulting filtrate. The filtrate was dried at 60 占 폚 for 2 hours at room temperature (20 to 30 占 폚) After concentrating under reduced pressure, toluene and excess 4-vinyl-1,2-epoxycyclohexane and 1-hexene were removed to obtain 35.0 parts of a cyclic siloxane compound (EP-5) having two or more epoxy groups in the molecule. The obtained compound had an epoxy equivalent of 213.5 g / eq, a viscosity of 1,423 mPa · s and a colorless transparent liquid. As a result of ¹ H-NMR analysis, 81 mol% of an organic group containing an epoxy group and 19 mol% of a hexyl group in X of the formula (1).

Synthesis Example 9; Production example of a cyclic siloxane compound having at least two epoxy groups in a molecule of an X having an epoxy group-containing organic group of 76 mol% and a hexyl group of 24% in X of the formula (1)

Vinyl chloride-1,2-epoxycyclohexane, 6.5 parts of 1-hexene, 0.047 part of Fibrecat 4003 (platinum content: 3.4 to 4.5%) and 50 parts of toluene were put in a glass 200 ml four-necked flask, A stirrer, and a thermometer, and the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 50 to 58 占 폚, 12 parts of 1,3,5,7-tetramethyltetracyclosiloxane was added dropwise thereto over 1 hour, and the mixture was allowed to react for 24 hours. As a result of ¹ H-NMR measurement of the reaction solution, the proton peak derived from the hydrogensiloxane disappeared.

Activated carbon (manufactured by Ajinomoto Fine Techno Co., Ltd.) was added to the reaction solution and stirred at room temperature (20 to 30 ° C) for 3 hours. Then, activated carbon and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the obtained filtrate. , And toluene and excess of 4-vinyl-1,2-epoxycyclohexane and 1-hexene are removed to obtain 34.7 parts of a cyclic siloxane compound (EP-6) having two or more epoxy groups in the molecule. The obtained compound had an epoxy equivalent of 229.9 g / eq, a viscosity of 840 mPa · s and a colorless transparent liquid. As a result of ¹ H-NMR analysis, it was found that 76% by mole of an organic group containing an epoxy group and 24% by mole of a hexyl group were contained in X of the formula (1).

Synthesis Example 10; Production example of silicone-modified epoxy resin

In a 200 ml four-necked flask made of glass, 0.032 parts of 4-vinyl-1,2-epoxycyclohexane, Fibrecat 4003 (platinum content 3.4 to 4.5%) and 50 parts of toluene were charged and a dimmer condenser, And the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 80 to 85 占 폚, 13.4 parts of 1,1,3,3-tetramethyldisiloxane was added dropwise thereto over 40 minutes, and the mixture was allowed to react for 5 hours. As a result of ¹ H-NMR measurement of the reaction solution, the proton peak derived from the hydrogensiloxane disappeared.

Activated charcoal and Fibrecat 4003 were removed by filtration, and nitrogen gas was blown into the resulting filtrate. The filtrate was dried at 60 占 폚 for 2 hours at room temperature (20 to 30 占 폚) The mixture was concentrated under reduced pressure, and toluene and excess 4-vinyl-1,2-epoxycyclohexane were removed to obtain 36.3 parts of (EP-7) having two epoxy groups in the molecule. The obtained compound had an epoxy equivalent of 193.8 g / eq, a viscosity of 840 mPa · s and a colorless transparent liquid.

Synthesis Example 11; Production Example of a condensate of an alkoxy silicon having a cyclohexyl epoxy and a silanol-terminated silicone oil as a condensate of a silicon compound having an epoxy group and other silicon compounds

111 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 100 parts of polydimethyldiphenylsiloxane having a silanol group with a molecular weight of 1,700 (measured by GPC), 1 part of a 5% KOH methanol solution, Was charged into a reaction vessel, and the temperature was raised to 75 캜. After elevated temperature, reaction was carried out under reflux for 10 hours. After the reaction, 120 parts of methanol was added, and then 48.6 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted for further 10 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with a 5% aqueous solution of sodium hydrogenphosphate and distilled and collected at 80 ° C. Thereafter, 174 parts of MIBK was added for washing, and the washing with water was repeated three times. Subsequently, the solvent was removed from the organic phase under reduced pressure at 100 占 폚 to obtain 174 parts of an epoxy resin (EP-8). The obtained compound had an epoxy equivalent of 411 g / eq, a weight average molecular weight of 3,200, a viscosity of 15,140 mPa,, and a colorless and transparent appearance.

Synthesis Example 12; (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, and a silicone oil represented by the formula (7) and 2,2'-bis (4-hydroxycyclohexyl) Synthesis Example of a polyvalent carboxylic acid resin using methylhexahydrophthalic anhydride and anhydroglutaric acid as a compound containing at least two acid anhydride groups

A glass 500 ml separable flask was charged with 18.2 g of ricavinol HB (2,2'-bis (4-hydroxycyclohexyl) propane manufactured by Shin-Nippon Rika Kogyo Co., Ltd.), 20.1 g of anhydrous glutaric acid, KF-6000 (manufactured by Shin-Etsu Chemical Co., , 122.7 g of a carbinol-modified silicone oil of the formula (7) wherein A ₁ is a propyloxyethylene group, A ₂ is a methyl group, and p is 7.5, a carbino-terminated silicone oil manufactured by Shin-Etsu Chemical Co., 39.0 g of Ricaside MH-T (4-methylhexahydrophthalic anhydride, manufactured by Shin-Nippon Rikagaku) and 200 g of toluene were charged and a dim rod condenser, an agitator and a thermometer were provided, and the flask was immersed in an oil bath. The oil bath was heated at 130 캜 and reacted for 8 hours in a state where toluene was refluxed. After completion of the reaction, the reaction solution was confirmed by GPC. As a result, peaks of 4-methylhexahydrophthalic anhydride, anhydroglutaric anhydride, and 2,2'-bis (4-hydroxycyclohexyl) propane disappeared. The obtained reaction solution was distilled under reduced pressure to obtain toluene, whereby 195 g of a polycarboxylic acid resin (B-4) was obtained. The polycarboxylic acid resin (B-4) had an acid value of 113.4 mgKOH / g, a viscosity of 2,780 mPa.s, a polystyrene-reduced weight average molecular weight of 1,264 measured by GPC, and a colorless transparent liquid.

Synthesis Example 13; (a) a silicone oil represented by the formula (7) and tricyclodecane dimethanol as a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, (b) a compound containing two or more acid anhydride groups in the molecule , Production example of polyvalent carboxylic acid resin using 4-diethylglutaric anhydride

In a glass 500 ml separable flask, 91.8 parts of X22-160 AS (in the formula (7), A ₁ is a propyloxyethylene group and A ₂ is a methyl group, a silicone oil of Cabinol end manufactured by Shin-Etsu Chemical Co., 45.5 parts of cyclodecane dimethanol and 112.5 parts of YH1120 (2,4-diethylglutaric acid, manufactured by Mitsubishi Chemical Corp.) were charged, and a dim rod condenser, a stirrer and a thermometer were provided, and the flask was immersed in an oil bath . The oil bath was heated to maintain the internal temperature at 95 to 105 占 폚 and reacted for 6 hours. Thereafter, the internal temperature was raised to 115 to 120 캜 and reacted for 7 hours to obtain 248 parts of a polyvalent carboxylic acid resin (B-5). The obtained polyvalent carboxylic acid resin had a viscosity of 7,219 mPa s, an acid value of 146 mgKOH / g, and a colorless and transparent liquid.

Synthesis Example 14; (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, and a silicone oil represented by the formula (7) and 2,2'-bis (4-hydroxycyclohexyl) Production example of polyvalent carboxylic acid resin using 2,4-diethylglutaric anhydride as a compound containing more than two acid anhydride groups

In a 1,000 ml separable glass flask, 397.5 parts of X22-160 AS (in the formula (7), A ₁ is a propyloxyethylene group and A ₂ is a methyl group, a silicone oil of Cabinol end manufactured by Shin-Etsu Chemical Co., 149 parts of Ricavinol HB (2,2'-bis (4-hydroxycyclohexyl) propane manufactured by Shin-Nippon Rika KK), 353.6 parts of YH1120 (2,4-diethylglutaric acid, manufactured by Mitsubishi Chemical Corp.) , A dim rod condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 95 to 105 DEG C and reacted for 4 hours. Thereafter, the internal temperature was raised to 115 to 120 캜 and reacted for 18 hours to obtain 895 parts of the polyvalent carboxylic acid resin (B-6). The obtained polyvalent carboxylic acid resin had a viscosity of 7,859 mPa · s, an acid value of 123 mgKOH / g and a colorless and transparent liquid.

Synthesis Example 15; (a) a polyhydric alcohol compound containing two or more hydroxyl groups in a molecule, and (b) a silicone oil represented by the formula (7) and 2,4-diethyl-1,5-pentanediol, Production example of a polyvalent carboxylic acid resin using 2,4-diethylglutaric anhydride as a compound containing an acid anhydride group

In a glass 500 ml separable flask, 36.8 parts of X22-160 AS (in the formula (7), A ₁ is a propyloxyethylene group and A ₂ is a methyl group, a silicone oil of Cabinol end manufactured by Shin-Etsu Chemical Co., -9 (manufactured by Kyowa Hakko Kagaku Co., Ltd., 2,4-diethyl-1,5-pentanediol) and 47.2 parts of YH1120 (2,4-diethylglutaric acid manufactured by Mitsubishi Chemical Corporation) A dim rod condenser, a stirrer, and a thermometer were placed, and the flask was immersed in an oil bath. The oil bath was heated to raise the internal temperature to 115 to 120 DEG C and reacted for 8 hours to obtain 98 parts of the polycarboxylic acid resin (B-7). The obtained polyvalent carboxylic acid resin had a viscosity of 1,797 mPa s, an acid value of 155 mgKOH / g and a colorless and transparent liquid.

Synthesis Example 16; (a) a silicone oil represented by the formula (7) and tricyclodecane dimethanol as a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, (b) a compound containing two or more acid anhydride groups in the molecule , Production example of polyvalent carboxylic acid resin using 4-diethylglutaric anhydride

109.9 parts of X22-160AS (in the above formula (7), A ₁ is a propyloxyethylene group, A ₂ is a methyl group, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to a 500-ml separable glass flask, 36.6 parts of cyclodecane dimethanol and 103.5 parts of YH1120 (2,4-diethylglutaric acid, manufactured by Mitsubishi Chemical Corp.) were charged, a dim rod condenser, a stirring device and a thermometer were provided, and the flask was immersed in an oil bath . The oil bath was heated to maintain the internal temperature at 95 to 105 DEG C, and the reaction was carried out for 14 hours. Thereafter, the internal temperature was raised to 115 to 120 캜 and reacted for 1 hour to obtain 247 parts of a polyvalent carboxylic acid resin (B-8). The obtained polyvalent carboxylic acid resin had a viscosity of 3,077 mPa · s, an acid value of 136 mgKOH / g, and a colorless and transparent liquid.

Example 1; A cyclic siloxane compound (EP-1) having four epoxy groups in the molecule obtained in Synthesis Example 1, ERL-4221 (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate Ltd.), the polyvalent carboxylic acid resin (B-1) obtained in Synthesis Example 3 and zinc stearate as a curing accelerator were charged into a polypropylene container in the proportions shown in Table 1 below, mixed and defoamed for 5 minutes To obtain an epoxy resin composition of the present invention.

Examples 2 to 3; A cyclic siloxane compound (EP-1) having four epoxy groups in the molecule obtained in Synthesis Example 1, an epoxy resin (EP-2) obtained in Synthesis Example 2 as another epoxy resin, 3,4-epoxycyclohexylmethyl- , ERL-4221 (manufactured by Dow Chemical Co.), cycloaliphatic carboxylate, polyvalent carboxylic acid resin (B-1) obtained in Synthesis Example 2 and zinc stearate as a curing accelerator, The mixture was placed in a container made of polypropylene and degassed for 5 minutes to obtain an epoxy resin composition of the present invention.

Example 4; A cyclic siloxane compound (EP-1) having four epoxy groups in the molecule obtained in Synthesis Example 1, ERL-4221 (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate Ltd.), the polyvalent carboxylic acid resin (B-2) obtained in Synthesis Example 4, and zinc stearate as a curing accelerator were placed in a polypropylene container in the proportions shown in Table 1 below, mixed and defoamed for 5 minutes To obtain an epoxy resin composition of the present invention.

Examples 5 to 6; (EP-1) having four epoxy groups in the molecule obtained in Synthesis Example 1, the epoxy resin (EP-2) obtained in Synthesis Example 2 as another epoxy resin, and the polyvalent carboxylic acid resin ( B-2), and zinc stearate as a curing accelerator were charged into a container made of polypropylene in the ratio shown in Table 1 below, followed by mixing and defoaming for 5 minutes to obtain an epoxy resin composition of the present invention.

Example 7; An epoxy resin composition of the present invention was obtained in the same manner as in Example 1 except that the polyvalent carboxylic acid resin of Example 4 was changed to (B-3) obtained in Synthesis Example 5.

Examples 8 to 9; An epoxy resin composition of the present invention was obtained in the same manner as in Example 1 except that the polyvalent carboxylic acid resins of Examples 5 to 6 were changed to (B-3) obtained in Synthesis Example 5.

Comparative Example 1; (EP-2) obtained in Synthesis Example 2, ERL-4221 (manufactured by Dow Chemical) serving as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, (B-1) obtained in Example 1 and zinc stearate as a curing accelerator were placed in a polypropylene container in the proportions shown in Table 1 below, mixed and defoamed for 5 minutes to obtain an epoxy resin composition of the present invention .

Comparative Example 2; The epoxy resin (EP-2) obtained in Synthesis Example 2, the polyvalent carboxylic acid resin (B-2) obtained in Synthesis Example 4, and zinc stearate as a curing accelerator were placed in a polypropylene container in the proportions shown in Table 1 below, Followed by mixing and defoaming for 5 minutes to obtain an epoxy resin composition of the present invention.

Comparative Example 3; The epoxy resin (EP-2) obtained in Synthesis Example 2, the polyvalent carboxylic acid resin (B-3) obtained in Synthesis Example 5 and zinc stearate as a curing accelerator were placed in a polypropylene container in the proportions shown in Table 1 below, Followed by mixing and defoaming for 5 minutes to obtain an epoxy resin composition of the present invention.

(Evaluation test)

The compounding ratio and viscosity of the curable resin composition for optical semiconductor encapsulation obtained in Examples 1 to 9 and Comparative Examples 1 to 3, the hardness, the Tg, the transmittance, the tensile elongation percentage of the cured product, the crack after the reflow test , And the results of resistance to sulfidation are shown in Table 1. The tests in Table 1 were carried out as follows.

(1) Viscosity

The measurement was carried out at 25 占 폚 using an E-type viscometer (TV-20) manufactured by Toray Industries, Ltd.

(2) Hardness

The durometer A hardness was measured by the method described in JIS K7215.

(3) Tg (glass transition temperature)

The epoxy resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were subjected to vacuum degassing for 5 minutes, and then the glass substrate was subjected to a dipping test using a heat-resistant tape so as to have a size of 30 mm x 20 mm x 0.8 mm Gently. The preform was pre-cured at 120 ° C for 1 hour and cured at 150 ° C for 3 hours to obtain a test piece for transmittance having a thickness of 0.8 mm.

The obtained cured product was molded into a sheet having a width of 5 mm and a length of 25 mm, and Tg (glass transition temperature) was read by measuring DMA (Dynamic Mechanical Analysis) under the following conditions.

≪ DMA Measurement Condition >

Manufacturer: Seiko Instruments Inc.

Model: Viscoelastic spectrometer EXSTAR DMS6100

Measuring temperature: -50 ° C to 150 ° C

Heating rate: 2 캜 / min

Frequency: 10Hz

Measurement mode: Tensile vibration

Glass transition temperature (Tg) measured by DMA method:

The temperature at the maximum point of the loss coefficient (tan? = E "/ E ') represented by the quotient of the storage elastic modulus (E') and the loss elastic modulus (E") when DMA was measured was read.

(4) Cured product permeability

The epoxy resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were subjected to vacuum degassing for 5 minutes, and then the glass substrate was subjected to a dipping test using a heat-resistant tape so as to have a size of 30 mm x 20 mm x 0.8 mm Gently. The preform was pre-cured at 120 ° C for 1 hour and cured at 150 ° C for 3 hours to obtain a test piece for transmittance having a thickness of 0.8 mm. The obtained test piece was measured for the light transmittance at 400 nm under the following conditions.

≪ Spectrophotometer measurement conditions >

Manufacturer: Hitachi High-Technologies Corporation

Model: U-3300

Slit width: 2.0 nm

Scan speed: 120 nm / min

(5) Tensile elongation

The epoxy resin composition for optical semiconductor encapsulation obtained in Examples 1 to 9 and Comparative Examples 1 to 3 was subjected to vacuum degassing for 5 minutes and then a dam was made with a heat resistant tape so as to have a size of 50 mm x 30 mm x 0.8 mm And gently molded on one glass substrate. The preform was pre-cured at 120 ° C for 1 hour and then cured at 150 ° C for 3 hours to obtain a test piece having a thickness of 0.8 mm. The obtained test piece was processed to have a width of 5 mm and a length of 50 mm, and five test pieces for each cured product were measured for tensile elongation under the following conditions, and the average value thereof was calculated.

<Tensile test measurement conditions>

Manufacturer: A & D Co., Ltd.

Model: Tensilon universal material testing machine RTG-1210

Chuck distance: 15㎜

Test speed: 5.0 mm / min

The elongation was calculated by the chuck distance when the specimen was broken.

(6) Sulfurization test

The epoxy resin composition for optical semiconductor encapsulation obtained in Examples 1 to 9 and Comparative Examples 1 to 3 was subjected to vacuum defoaming for 5 minutes and then charged into a syringe and silver plating was performed on the bottom surface using an accurate discharging device A surface mount type LED having a light emitting element having an emission wavelength of 450 nm is mounted on a surface mount type LED package having a 3.0 mm x 1.4 mm x 1.4 mm t (sealing portion: 0.6 mm t) having copper electrodes, did. After preliminary curing at 120 ° C for 1 hour, curing was performed at 150 ° C for 3 hours to seal the surface mount type LED.

The illuminance of the sealed surface mount type LED was measured in advance and placed in a glass sealed container having a size of 170 mm x 170 mm x 50 mm with a glass chalet having a diameter of 9 cm into which 2 g of sulfur solid was put and left in a thermostatic chamber at 80 캜. After 3 hours of standing, the illuminance was measured again, and the rate of change from the illuminance before the test was calculated.

The illuminance of the LED was measured as follows.

A surface mount LED package used for the test was placed on the wall surface of an integrating sphere (FOIS-1, manufactured by Ocean Optics Co., Ltd.) under the conditions of 25 ° C and 65% RH, and a constant current of 20 mA was passed therethrough. (Manufactured by Asahi Denka Co., Ltd.).

(7) Reflow test

The epoxy resin composition for optical semiconductor encapsulation obtained in Examples 1 to 9 and Comparative Examples 1 to 3 was subjected to vacuum defoaming for 5 minutes and then charged into a syringe and silver plating was performed on the bottom surface using an accurate discharging device A surface mount type LED having a light emitting element having an emission wavelength of 450 nm is mounted on a surface mount type LED package having a 3.0 mm x 1.4 mm x 1.4 mm t (sealing portion: 0.6 mm t) having copper electrodes, did. After preliminary curing at 120 占 폚 for 1 hour, curing was performed at 150 占 폚 for 3 hours to seal the surface-mounted LED.

Each of the obtained three surface-mounted LED packages was dried in an oven at 150 캜 for 24 hours and then left in a constant temperature and humidity bath at 30 캜 and 70% RH for 168 hours. The hot-air circulation type reflow test device was passed once, Subsequently, the appearance of the cured product of the sealing material was counted for the number of cracks (cracks) confirmed.

<Reflow conditions>

Manufacturer: Kabushiki Kaisha Tamura Seisakusho

Model: TNR15-225LH-M

Atmosphere: Waiting

Temperature profile: The temperature was raised from room temperature of 25 占 폚 to 180 占 폚 to 4 占 폚 / sec and maintained at 180 to 200 占 폚 for 120 seconds. Thereafter, the temperature was raised to 260 占 폚 at 4 占 폚 / ).

As is clear from the results shown in Table 1, Comparative Examples (1) and (3), in which the cyclic siloxane compound (A) having two or more epoxy groups in the molecule was not used, . In Comparative Example (2) and Comparative Example (3), cracks were found in the reflow test. In addition, the comparative examples (1) to (3) were found to have a low tensile elongation and a low mechanical strength.

On the other hand, Examples (1) to (9) using the cyclic siloxane compound (A) having two or more epoxy groups in the molecule were excellent in cured product permeability and tensile elongation in addition to the appropriate viscosity, hardness and Tg. In addition, it is suitable as a resin composition for optical semiconductor encapsulation particularly in the field of high light transmittance retention even in the sulfidation test, in which cracking does not occur even in the reflow test and light transparency is required.

Example 10; (EP-3) having four epoxy groups in the molecule obtained in Synthesis Example 6, the polyvalent carboxylic acid resin (B-4) obtained in Synthesis Example 11, and zinc stearate as a curing accelerator, The mixture was placed in a container made of polypropylene in a mortar, defoamed for 5 minutes to obtain an epoxy resin composition of the present invention.

Example 11; An epoxy resin composition of the present invention was obtained in the same manner as in Example 10, except that EP-3 of Example 10 was changed to cyclic siloxane compound (EP-4) having two or more epoxy groups in the molecule obtained in Synthesis Example 7.

Example 12; An epoxy resin composition of the present invention was obtained in the same manner as in Example 10 except that EP-3 of Example 10 was changed to cyclic siloxane compound (EP-5) having two or more epoxy groups in the molecule obtained in Synthesis Example 8.

Example 13; An epoxy resin composition of the present invention was obtained in the same manner as in Example 10 except that EP-3 of Example 10 was changed to cyclic siloxane compound (EP-6) having two or more epoxy groups in the molecule obtained in Synthesis Example 9.

(Evaluation test)

The blending ratio and viscosity of the curable resin composition for optical semiconductor encapsulation obtained in Examples 10 to 13, the hardness of the cured product, the transmittance, the tensile elongation, the cracks after the reflow test as an LED test, and the results of the illuminance retention Are shown in Table 2. The tests in Table 2 were carried out as follows.

(1) Viscosity

The measurement was carried out at 25 占 폚 using an E-type viscometer (TV-20) manufactured by Toray Industries, Ltd.

(2) Hardness

The durometer A hardness was measured by the method described in JIS K7215.

(3) Cured product permeability

The epoxy resin compositions obtained in Examples 10 to 13 were subjected to vacuum degassing for 5 minutes and then smoothly molded on a glass substrate on which dams were formed with heat resistant tape so as to have a size of 30 mm x 20 mm x 0.8 mm height. The preform was pre-cured at 120 ° C for 1 hour and cured at 150 ° C for 3 hours to obtain a test piece for transmittance having a thickness of 0.8 mm. The obtained test piece was measured for the light transmittance at 400 nm under the following conditions.

&Lt; Spectrophotometer measurement conditions >

Manufacturer: Hitachi High-Technologies Corporation

Model: U-3300

Slit width: 2.0 nm

Scan speed: 120 nm / min

(4) Tensile elongation

The epoxy resin composition for optical semiconductor encapsulation obtained in Examples 10 to 13 was subjected to vacuum degassing for 5 minutes and then smoothly molded on a glass substrate on which a dam was formed with a heat resistant tape so as to have a size of 50 mm x 30 mm x 0.8 mm height. The preform was pre-cured at 120 ° C for 1 hour and then cured at 150 ° C for 3 hours to obtain a test piece having a thickness of 0.8 mm. The obtained test piece was processed to have a width of 5 mm and a length of 50 mm, and five test pieces for each cured product were measured for tensile elongation under the following conditions, and the average value thereof was calculated.

<Tensile test measurement conditions>

Manufacturer: A & D Co., Ltd.

Model: Tensilon universal material testing machine RTG-1210

Chuck distance: 15㎜

Test speed: 5.0 mm / min

The elongation was calculated by the chuck distance when the specimen was broken.

(5) Reflow test

The epoxy resin composition for optical semiconductor encapsulation obtained in Examples 10 to 13 was subjected to vacuum degassing for 5 minutes and then filled in a syringe and subjected to silver plating on the bottom surface using a precision ejecting apparatus. A surface mount type LED having a light emitting element having an emission wavelength of 450 nm was mounted on a surface mount type LED package of 0.4 mm x 1.4 mm (sealing portion: 0.4 mmt). Pre-curing at 120 ° C for 1 hour, and curing at 150 ° C for 3 hours to seal the surface-mounted LED.

Each of the obtained three surface-mounted LED packages was dried in an oven at 150 캜 for 24 hours and then left in a constant temperature and humidity bath at 30 캜 and 70% RH for 168 hours. The hot-air circulation type reflow test device was passed once, Subsequently, the appearance of the cured product of the sealing material was counted for the number of cracks (cracks) confirmed.

<Reflow conditions>

Manufacturer: Kabushiki Kaisha Tamura Seisakusho

Model: TNR15-225LH-M

Atmosphere: Waiting

Temperature profile: The temperature was raised from room temperature of 25 占 폚 to 180 占 폚 to 4 占 폚 / sec and maintained at 180 to 200 占 폚 for 120 seconds. Thereafter, the temperature was raised to 260 占 폚 at 4 占 폚 / ).

(6) Brightness maintenance rate at long-term lighting test

The epoxy resin composition for optical semiconductor encapsulation obtained in Examples 10 to 13 was subjected to vacuum degassing for 5 minutes and then filled in a syringe and subjected to silver plating on the bottom surface using a precision ejecting apparatus. A surface mount type LED having a light emitting element having an emission wavelength of 450 nm was mounted on a surface mount type LED package having a size of 0.4 mm x 1.4 mm (sealing portion: 0.4 mmt) so as to have openings parallel to each other. After preliminary curing at 120 ° C for 1 hour, curing was performed at 150 ° C for 3 hours to seal the surface mount type LED.

The initial surface roughness was measured for each of the surface mount type LED packages obtained, and a constant current of 20 mA was flown in an oven maintained at 100 캜, and the lamps were lighted for 600 hours. Thereafter, the illuminance after the test was taken out from the oven, the retention rate from the initial illuminance was calculated, and the average was used as the illuminance retention ratio at the long-term lighting test.

The illuminance of the LED was measured as follows.

A surface mount LED package used for the test was placed on the wall surface of an integrating sphere (FOIS-1, manufactured by Ocean Optics Co., Ltd.) under the conditions of 25 ° C and 65% RH, and a constant current of 20 mA was passed therethrough. (Manufactured by Asahi Denka Co., Ltd.).

As is clear from the results shown in Table 2, the epoxy resin compositions of Examples 10 to 13 using the cyclic siloxane compound (A) having two or more epoxy groups in the molecule have an appropriate viscosity, and the hardness, transmittance, The elongation was excellent. In addition, cracks do not enter even in the reflow test, and it is suitable as a resin composition for optical semiconductor encapsulation, particularly in a field requiring high transparency. In particular, the long-term lighting test of Examples 10 and 11 containing EP-3 and EP-4, in which the organic group containing epoxy groups in the formula (1) is 91 mol% or more, Is excellent.

Example 14; A cyclic siloxane compound (EP-3) having four epoxy groups in the molecule obtained in Synthesis Example 6, a silicone-modified epoxy resin (EP-7) obtained in Synthesis Example 10, and a polyvalent carboxylic acid resin ) And zinc stearate as a curing accelerator were placed in a polypropylene vessel in the proportions shown in Table 3 below, mixed and defoamed for 5 minutes to obtain an epoxy resin composition of the present invention.

Example 15; An epoxy resin composition of the present invention was obtained in the same manner as in Example 14 except that the polyvalent carboxylic acid resin (B-5) of Example 14 was changed to the polyvalent carboxylic acid resin (B-6) obtained in Synthesis Example 14 .

Example 16; (EP-3) having four epoxy groups in the molecule obtained in Synthesis Example 6, the polyvalent carboxylic acid resin (B-7) obtained in Synthesis Example 15, and zinc stearate as a curing accelerator, The mixture was placed in a container made of polypropylene in a mortar, defoamed for 5 minutes to obtain an epoxy resin composition of the present invention.

Example 17; The procedure of Example 16 was repeated except that the cyclic siloxane compound (EP-3) having four epoxy groups in the molecule of Example 16 was changed to the silicone-modified epoxy resin (EP-7) obtained in Synthesis Example 10 in part. To obtain an epoxy resin composition.

Example 18; An epoxy resin composition of the present invention was obtained in the same manner as in Example 14 except that the polyvalent carboxylic acid resin (B-5) of Example 14 was changed to the polyvalent carboxylic acid resin (B-8) obtained in Synthesis Example 16 .

Comparative Example 4; (EP-2) obtained in Synthesis Example 2, the epoxy resin (EP-8) obtained in Synthesis Example 11, the polyvalent carboxylic acid resin (B-5) obtained in Synthesis Example 13, zinc stearate as a curing accelerator The mixture was placed in a container made of polypropylene in the proportions shown in Table 3, followed by mixing and defoaming for 5 minutes to obtain an epoxy resin composition of Comparative Example.

Comparative Example 5; An epoxy resin composition of Comparative Example was obtained in the same manner as in Comparative Example 4 except that the polyvalent carboxylic acid resin (B-5) of Comparative Example 4 was changed to the polyvalent carboxylic acid resin (B-6) obtained in Synthesis Example 14.

Comparative Example 6; An epoxy resin composition of a comparative example was obtained in the same manner as in Comparative Example 4 except that the polyvalent carboxylic acid resin (B-5) of Comparative Example 4 was changed to the polyvalent carboxylic acid resin (B-7) obtained in Synthesis Example 15.

Comparative Example 7; An epoxy resin composition of a comparative example was obtained in the same manner as in Comparative Example 4 except that the polyvalent carboxylic acid resin (B-5) of Comparative Example 4 was changed to the polyvalent carboxylic acid resin (B-8) obtained in Synthesis Example 16.

(Evaluation test)

The compounding ratios and viscosity of the curable resin compositions for optical semiconductor encapsulation obtained in Examples 14 to 18 and Comparative Examples 4 to 7, the transmittance of the cured product, the tensile elongation, the sulfidization resistance thereof as an LED test, the cracking resistance after the reflow test The results are shown in Table 3. The tests in Table 3 were carried out as follows.

(1) Viscosity

The measurement was carried out at 25 占 폚 using an E-type viscometer (TV-20) manufactured by Toray Industries, Ltd.

(2) Cured product permeability

The epoxy resin compositions obtained in Examples 14 to 18 and Comparative Examples 4 to 7 were subjected to vacuum degassing for 5 minutes, and then, on a glass substrate on which dams were formed with heat-resistant tapes so as to have a size of 30 mm x 20 mm x height 0.8 mm Gently mold it. The preform was preliminarily cured at 120 ° C for 1 hour and cured at 150 ° C for 3 hours to obtain a test piece for transmittance having a thickness of 0.8 mm. The obtained test piece was measured for the light transmittance at 400 nm under the following conditions.

&Lt; Spectrophotometer measurement conditions >

Manufacturer: Hitachi High-Technologies Corporation

Model: U-3300

Slit width: 2.0 nm

Scan speed: 120 nm / min

(3) Tensile elongation

The epoxy resin composition for optical semiconductor encapsulation obtained in Examples 14 to 18 and Comparative Examples 4 to 7 was subjected to vacuum degassing for 5 minutes and then glass produced by forming a dam with heat resistant tape so as to have a size of 50 mm x 30 mm x 0.8 mm And gently molded on the substrate. The preform was pre-cured at 120 ° C for 1 hour and then cured at 150 ° C for 3 hours to obtain a test piece having a thickness of 0.8 mm. The obtained test piece was processed to have a width of 5 mm and a length of 50 mm, and five test pieces were measured for each cured product under the following conditions, and the average value thereof was calculated.

<Tensile test measurement conditions>

Manufacturer: A & D Co., Ltd.

Model: Tensilon universal material testing machine RTG-1210

Chuck distance; 15 mm

Test speed; 5.0 mm / min

The elongation was calculated by the chuck distance when the specimen was broken.

(4) Sulfurization test

The epoxy resin compositions for optical semiconductor encapsulation obtained in Examples 14 to 18 and Comparative Examples 4 to 7 were subjected to vacuum defoaming for 5 minutes and then filled in a syringe and silver plating was performed on the bottom surface using an accurate discharging device A surface mount type LED having a light emitting element having an emission wavelength of 450 nm is mounted on a surface mount type LED package having a 3.0 mm x 1.4 mm x 1.4 mm t (sealing portion: 0.6 mm t) having copper electrodes, did. After preliminary curing at 120 占 폚 for 1 hour, curing was performed at 150 占 폚 for 3 hours to seal the surface mount type LED.

The illuminance of the sealed surface mount type LED was measured in advance and placed in a glass sealed container having a size of 170 mm x 170 mm x 50 mm with a glass chalet having a diameter of 9 cm into which 2 g of sulfur solid was put and left in a thermostatic chamber at 80 캜. After 6 hours of standing, the illuminance was measured again, and the rate of change from the illuminance before the test was calculated.

The illuminance of the LED was measured as follows.

The surface mounted LED package used for the test was placed on the wall surface of an integrating sphere (FOIS-1, manufactured by Ocean Optics Co., Ltd.) under the condition of 25 ° C and 65% RH, and a constant current of 20 mA was flown. The optical measurement device (Wavelength Calibration USB4000 series, (Manufactured by Asahi Denka Co., Ltd.).

(5) Reflow test

The epoxy resin compositions for optical semiconductor encapsulation obtained in Examples 14 to 18 and Comparative Examples 4 to 7 were subjected to vacuum defoaming for 5 minutes and then filled in a syringe and silver plating was performed on the bottom surface using an accurate discharging device A surface mount type LED having a light emitting element having an emission wavelength of 450 nm is mounted on a surface mount type LED package having a 3.0 mm x 1.4 mm x 1.4 mm t (sealing portion: 0.6 mm t) having copper electrodes, did. After preliminary curing at 120 ° C for 1 hour, curing was performed at 150 ° C for 3 hours to seal the surface mount type LED.

The resulting surface-mounted LED package was dried in an oven at 150 ° C. for three hours in each of three samples, and then allowed to stand in a constant temperature and humidity bath at 30 ° C. and 70% RH for 168 hours. Thereafter, a hot air circulation type reflow test apparatus was passed once, And the number of cracks (cracks) confirmed in the cured product of the sealing material was counted.

<Reflow conditions>

Manufacturer: Kabushiki Kaisha Tamura Seisakusho

Model: TNR15-225LH-M

Atmosphere: Waiting

Temperature profile: The temperature was raised from room temperature of 25 占 폚 to 180 占 폚 to 4 占 폚 / sec, maintained at 180 to 200 占 폚 for 120 seconds, then raised to 260 占 폚 at 4 占 sec, maintained at 260 占 폚 for 10 seconds, Lt; 0 &gt; C).

As is clear from the results shown in Table 3, Comparative Examples (4) to Comparative Example (7), in which the cyclic siloxane compound (A) having two or more epoxy groups in the molecule was not used, And a crack was introduced in the reflow test. In addition, the comparative examples (4) to (7) were found to have a low tensile elongation and a low mechanical strength.

On the other hand, Examples (14) to (18) using the cyclic siloxane compound (A) having two or more epoxy groups in the molecule were excellent in tensile elongation. In addition, it is suitable as a resin composition for optical semiconductor encapsulation particularly in the field of high light transmittance retention even in the sulfidation test, in which cracking does not occur even in the reflow test and light transparency is required.

While the invention has been described in detail with reference to specific embodiments thereof, it is evident to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application (2013-215442) filed on October 16, 2013, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated by reference in their entirety.

(Industrial applicability)

The curable resin composition of the present invention has a suitable viscosity, and the cured product has a suitable hardness, Tg, and is excellent in light transmittance and tensile elongation, and therefore is suitable as a resin composition for optical semiconductor encapsulation Can be used.

Claims (14)

An epoxy resin composition comprising a cyclic siloxane compound (A) having two or more epoxy groups in a molecule represented by the following formula (1) and an epoxy resin curing agent (B).

(Wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, X is an organic group containing an epoxy group or a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 3. When R ¹ , X may be the same or different, but may be different, with the proviso that at least two of the plural Xs present are organic groups containing an epoxy group. The method according to claim 1,
An epoxy resin composition wherein at least 90 mol% of X in the formula (1) is an organic group containing an epoxy group. 3. The method according to claim 1 or 2,
The epoxy resin curing agent (B) is a polycarboxylic acid resin. The method of claim 3,
Wherein the polycarboxylic acid resin is an addition polymer obtained by reacting at least (a) a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule and (b) a compound containing at least one acid anhydride group in the molecule. 5. The method of claim 4,
(b) the epoxy resin composition, wherein the compound containing at least one acid anhydride group in the molecule is at least one compound selected from methylhexahydrophthalic anhydride, glutaric anhydride and diethylglutaric anhydride. 3. The method according to claim 1 or 2,
The epoxy resin curing agent (B) is a polyvalent carboxylic acid represented by the following formula (2).

Wherein Q represents a hydrogen atom, a methyl group, or a carboxyl group, P represents an aliphatic group having 2 to 20 carbon atoms in the form of a chain and / or cyclic structure, and m represents an integer of 2 to 4, . The method according to claim 6,
The epoxy resin curing agent (B) represented by the formula (2) contains at least one compound represented by the following formulas (3) to (6).

3. The method according to claim 1 or 2,
The epoxy resin curing agent (B) is a polyvalent carboxylic acid represented by the following formula (8).

(Wherein P and m have the same meanings as in the formula (2), and R ² represents a hydrogen atom or an ethyl group.) 9. The method of claim 8,
The epoxy resin curing agent (B) represented by the formula (8) contains at least one compound represented by the following formulas (9) to (12).

(In the formulas (9) to (12), R ² has the same meanings as in the formula (8).) 10. The method according to any one of claims 1 to 9,
And an epoxy resin curing accelerator (C). 11. The method of claim 10,
The epoxy resin curing accelerator (C) is a metal soap curing accelerator. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 11. A resin composition for optical semiconductor encapsulation, comprising the epoxy resin composition according to any one of claims 1 to 11. An optical semiconductor device in which an optical semiconductor element is sealed with the resin composition for optical semiconductor encapsulation according to claim 13.