JP2007070554A - Epoxy resin composition for encapsulation of optical semiconductor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for encapsulation of optical semiconductor free from deterioration in ultraviolet radiation and excellent in moisture resistance. <P>SOLUTION: The epoxy resin composition for encapsulation of optical semiconductor comprises (A) an epoxy resin obtained by cohydrolysis and condensation of an alkoxysilane compound having an epoxy group, (B) a hydrogenated epoxy resin obtained by hydrogenating an aromatic ring of an epoxy resin expressed by general formula (3), (C) a hardener, and (D) a hardening accelerator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition for optical semiconductor sealing excellent in transparency and an optical semiconductor device sealed with a cured product thereof.

Conventionally, epoxy resin-based sealing materials have been widely used as sealing materials for optical semiconductor elements such as LEDs, CCDs, and photocouplers because they are preferable in terms of balance between performance and economy. In particular, aromatic epoxy resins typified by bisphenol A type have been generally used for conventional optical semiconductor sealing materials.
In recent years, in the field of LEDs, LEDs that emit ultraviolet light (ultraviolet LEDs) have been developed in order to realize white LEDs. However, the aromatic epoxy resin has a problem of being deteriorated by ultraviolet light near 400 nm. there were. In order to solve this problem, Patent Document 1 proposes a method using a nuclear hydride of an aromatic epoxy resin, but it is still not sufficient.
Patent Document 2 describes a condensate of an alkoxysilicon compound having an epoxy group, but does not describe a composition containing a hydrogenated epoxy resin and used for an optical semiconductor sealing material.

JP 2003-82062 A JP-A-6-298940

  The present invention is an epoxy resin for encapsulating an optical semiconductor that is less deteriorated even in ultraviolet light and has excellent moisture resistance required from the viewpoint of solder reflow resistance when mounting an optical semiconductor and the reliability of an optical semiconductor device. An object is to provide a composition.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention relates to the following 1) to 3).
1) Cohydrolytic condensation of alkoxysilicon compounds represented by general formula (1), or an alkoxysilicon compound represented by general formula (1) and an alkoxysilicon compound represented by general formula (2) Epoxy resin (A) obtained by

[Chemical 1]
XSi (R ¹ ) _a (OR ² ) _3-a (1)
(In the formula, X represents a substituent containing an epoxy group, R ¹ represents a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenylcarboxy group having 2 to 5 carbon atoms. , R ² represents an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 2, when R ¹ is a plurality, the plurality of R ¹ may be the being the same or different.)

[Chemical 2]
_{^{X k (R 3) b Si}} (OR 4) 4- (k + b) (2)
(In the formula, X represents a substituent containing an epoxy group, R ³ represents a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ⁴ represents a group having 1 to ⁴ carbon atoms. an alkyl group, k and b are integer from 0 to 3, k + b is 0 to 3, when there are a plurality of R ^3, a plurality of R ³ may be be the same or different from each other.) ;

A hydrogenated epoxy resin (B) obtained by nuclear hydrogenation of the aromatic ring of the epoxy resin represented by the general formula (3),

Wherein R ⁵ may be the same or different and each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 1 to 4, and n is an average value of 1 to 6 Indicates a positive number.);
An epoxy resin composition for optical semiconductor encapsulation containing a curing agent (C) and a curing accelerator (D).

2) X in formula (1) is an alkyl group having 1 to 5 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms or an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or an epoxy group. The optical semiconductor encapsulation according to 1), wherein R ³ in the formula (2) is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms substituted with a (meth) acryloxy group Epoxy resin composition.

3) An optical semiconductor device sealed with a cured product of the epoxy resin composition described in 1) or 2) above.

  The cured product obtained by curing the resin composition for an optical semiconductor encapsulating material of the present invention is less deteriorated by ultraviolet light, so that, for example, the decrease in transparency over time that reduces the brightness of the LED is small, and the moisture resistance is improved. Therefore, high reliability is given to the optical semiconductor device. Therefore, the resin composition for sealing an optical semiconductor of the present invention is extremely useful as a sealing material for an optical semiconductor.

The epoxy resin composition for optical semiconductor encapsulation of the present invention has the general formula (1) (wherein X is a substituent containing an epoxy group, R ¹ is a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, It shows an alkenyl carboxy group of an aryl group or a 3 to 5 carbon atoms having 6 to 14 carbon atoms, ^{R 2} represents an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 2, ^{R 1} is more A plurality of R ^{1 s} may be the same or different from each other.) Or an alkoxysilicon compound represented by the general formula (1) and the above general formula (2) (In the formula, X represents a substituent containing an epoxy group, R ³ represents a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ⁴ represents a group having 1 to ⁴ carbon atoms. An alkyl group, k and b are integers from 0 to 3; b is 0 to 3, when there are a plurality of R ^3, the alkoxy silicon compound represented by a plurality of R ³ may be be the same or different from each other.) By engaging cohydrolysis condensation The resulting epoxy resin (A); the above general formula (3) (wherein R ⁵ may be the same or different and each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms; An integer of 1 to 4, n is an average value and represents a positive number of 1 to 6.) A hydrogenated epoxy resin (B) obtained by nuclear hydrogenation of an aromatic ring of an epoxy resin represented by: Curing agent (C) And a curing accelerator (D).

  Substituents having an epoxy group in the alkoxysilicon compounds of the general formula (1) and the general formula (2) used for producing the epoxy resin (A) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention As long as it has an epoxy group, it may be the same or different, for example, β-glycidoxyethyl group, γ-glycidoxypropyl group, γ-glycidoxybutyl group, etc. C1-C4 alkyl group to which glycidoxy group is bonded, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ) Ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) pe Epoxy group with cycloalkyl group-substituted alkyl group of 1 to 5 carbon atoms having a carbon number of 5-8 such as methyl group, a glycidyl group, and the like.

  Among these, as the substituent having an epoxy group as X in the general formula (1), a glycidoxyalkyl group in which a glycidoxy group is bonded to an alkyl group having 1 to 3 carbon atoms, or a carbon number having an epoxy group A C1-C3 alkyl group substituted with a 5-8 cycloalkyl group is preferable, and specifically, for example, β-glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4 -Epoxycyclohexyl) ethyl group is preferred.

As the ^{R 4 R 2,} in the general formula (2) in the general formula (1), a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- C1-C4 alkyl groups, such as a butyl group, are mentioned, From a viewpoint of reaction conditions, such as compatibility and reactivity, a methyl group or an ethyl group is preferable.

R ¹ in the compound represented by the general formula (1) used for producing the epoxy resin (A) contained in the epoxy resin composition for sealing an optical semiconductor of the present invention, represented by the general formula (2) R ³ in the compound includes methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n A linear or branched alkyl group having 1 to 14 carbon atoms such as an octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, and an n-tetradecyl group; An alkyl group having 6 to 14 carbon atoms such as a phenyl group and a naphthyl group.
As the alkenyl carboxy group of 3 to 5 carbon atoms in R ^1, for example, acryloxy group, methacryloxy group, and the like.

  Examples of the substituent in the alkyl group having a substituent include a halogen atom (chlorine atom, bromine atom, etc.), a vinyl group, an amino group, a nitro group, a methoxy group, an ethoxy group, and a (meth) acryloxy group.

When there are isomers depending on the substitution position, all these compounds can be used, and all compounds having 1 to the maximum number of substitutable groups can be used.
Among these, an alkyl group having 1 to 6 carbon atoms which is unsubstituted or substituted with a methacryloxy group, or a phenyl group is particularly preferable.

  The alkoxysilicon compound represented by the general formula (1) used for producing the epoxy resin (A) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention is preferably β-glycidoxyethyltri Methoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyl Examples include diethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. These alkoxysilicon compounds represented by the general formula (1) may be used alone or in combination of two or more.

  The alkoxy silicon compound represented by the general formula (2) used for producing the epoxy resin (A) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention is preferably β-glycidoxyethyl methyl. Dimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane and the like can be mentioned.

  A compound having no epoxy group can also be used (when k is 0). As such an alkoxysilicon compound, methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexyl are preferable. Methyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane Etc. These alkoxysilicon compounds represented by the general formula (2) may be used alone or in combination of two or more.

The epoxy resin (A) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention is an alkoxysilicon compound of the above general formula (1) or the above general formula (1) and the above general formula (2). The alkoxysilicon compound shown can be obtained by cohydrolytic condensation (hereinafter, the cohydrolytic condensation is simply referred to as condensation).
The ratio of each of the compound represented by the general formula (1) and the compound represented by the general formula (2) in the condensation reaction is appropriately determined according to the desired physical properties of the resin and the cured physical properties of the composition containing the resin. That's fine.
The amount of water used in the condensation reaction is usually about 0.1 to 1.5 mol, preferably about 0.2 to 1.2 mol, per 1 mol of alkoxy groups in the entire reaction system.

In the above condensation reaction, a catalyst is usually used, and the catalyst is not particularly limited as long as it is a compound that shows basicity in water. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, etc. Inorganic bases such as alkali metal carbonates, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; ammonia; triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, hydroxylated An organic base such as tetramethylammonium may be mentioned. Among these, an inorganic base or ammonia is preferable because the catalyst can be easily removed from the product.
The addition amount of the catalyst is usually 0.001 to 7.5% by weight, preferably 0.01 to 5% by weight, based on the total weight of the alkoxysilicon compound in the reaction system.

The condensation reaction can be carried out without a solvent or in a solvent. The solvent is not particularly limited as long as it is a solvent that dissolves the alkoxysilicon compound used in the reaction. For example, aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone, toluene And aromatic hydrocarbons such as xylene. Of these, aprotic polar solvents are preferred.
When the solvent is used, the amount used is not particularly limited as long as the reaction proceeds smoothly, but usually 50 to 100 parts per 100 parts by weight of the total weight of the compounds of the general formula (1) and the general formula (2). About 900 parts by weight.
While the reaction temperature depends on the amount of catalyst, it is generally 20 to 160 ° C, preferably 40 to 140 ° C. The reaction time is usually 1 to 12 hours.

  The molecular weight of the epoxy resin (A) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention is preferably 400 to 50000 in weight average molecular weight, more preferably 750 to 30000. When the weight average molecular weight is less than 400, the physical properties of the composition may decrease, such as a decrease in heat resistance, and when it is greater than 50,000, the viscosity of the composition may increase.

  Used for producing a hydrogenated epoxy resin (B) obtained by nuclear hydrogenation of the aromatic ring of the epoxy resin represented by the general formula (3) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention. The epoxy resin represented by the general formula (3) can be obtained, for example, by a method described in JP-A-5-117350 or a method analogous thereto. It is also possible to obtain a commercial product (trade name NC-3000, manufactured by Nippon Kayaku Co., Ltd.).

  The nuclear hydrogenation of the epoxy resin represented by the general formula (3) is usually performed by bringing the epoxy resin represented by the general formula (3) into contact with hydrogen gas in the presence of a hydrogenation catalyst. A catalyst having a platinum group element as an active component may be used as the hydrogenation catalyst. Of the platinum group elements, ruthenium or rhodium is preferred. Further, a catalyst obtained by supporting the active component on a carbon-based support is preferable. Examples of the carbon-based carrier include activated carbon, graphite, and carbon black.

  As these catalysts, those prepared by a known method such as an impregnation method may be used, or those commercially available as hydrogenation reaction catalysts may be used. Examples of commercially available products include “5% ruthenium / carbon catalyst”, “5% rhodium / carbon catalyst” (both manufactured by NV Chemcat). The amount of the catalyst used is not particularly limited. However, since the reaction takes a long time if the amount of the catalyst is small, it is usually 0.05% by weight or more in terms of ruthenium or rhodium with respect to the epoxy resin of the general formula (3). The range of 0.1 to 2% by weight is more preferable.

The hydrogenation reaction is usually performed in a solvent. Examples of the solvent include ether solvents, ester solvents, alcohol solvents (for example, methanol, ethanol, isopropanol, etc.), paraffin solvents (for example, hexane, heptane, etc.) that are stable to hydrogenation and are not toxic to the catalyst. , Octane, etc.). Among them, linear or cyclic ether solvents such as diethyl ether, isopropyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane and dioxolane, ester solvents such as ethyl acetate and butyl acetate, or ethylene glycol methyl ether An ether ester solvent such as acetate is preferably used.
These solvents can be used alone or in combination. Although the usage-amount of a solvent is not specifically limited, Usually, the solvent is 10-1000 weight% with respect to the epoxy resin of General formula (3), Preferably it is the range of 20-500 weight%.

  The conditions for the hydrogenation reaction may generally be those used for nuclear hydrogenation of the aromatic ring, and the reaction temperature and reaction pressure are not particularly limited as long as the hydrogenation reaction can be completed. Practical conditions include a reaction temperature in the range of 10 to 200 ° C., preferably 30 to 150 ° C., and a reaction pressure in the range of 0.5 to 30 MPa, preferably 1.5 to 15 MPa.

  The reaction time varies depending on the amount of catalyst used and the above reaction conditions, but is usually 0.5 to 20 hours. Further, the reaction mode of the hydrogenation reaction is not limited to a batch type, and it can be carried out by a flow type by forming a ruthenium or rhodium supported catalyst into an appropriate shape and filling it in a fixed bed reactor.

After completion of the reaction, the target hydrogenated epoxy resin (B) can be obtained as it is by separating the catalyst from the reaction solution by an appropriate means and then distilling off the solvent by an ordinary means such as distillation.
The nuclear hydrogenation rate in the hydrogenated epoxy resin (B) is 40 to 100%, preferably 60 to 100%.

  The weight ratio of the epoxy resin (A) and the epoxy resin (B) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention is preferably in the range of 90/10 to 10/90. When outside this range, the combined effect is small.

  In addition, the epoxy resin composition for optical semiconductor encapsulation of the present invention can be used in combination with an epoxy resin (E) other than the epoxy resin (A) and the epoxy resin (B) within a range that does not hinder physical properties. . When other epoxy resins (E) are used in combination, the total amount of the epoxy resin (A) and the epoxy resin (B) is a proportion of the total amount of the epoxy resin contained in the epoxy resin composition for optical semiconductor encapsulation. It is preferable to set it as 20 to 95 weight%, and 30 to 95 weight% is especially preferable.

Specific examples of other epoxy resins (E) include polyfunctional epoxy resins that are glycidyl etherified products of polyphenol compounds, polyfunctional epoxy resins that are glycidyl etherified products of various novolak resins, nuclear hydrides of aromatic epoxy resins, and fats. Examples thereof include cyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, and the like.
Polyfunctional epoxy resins that are glycidyl etherification products of polyphenol compounds include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetra Methyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- ( 4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol) , Trishydroxypheny Methane, resorcinol, hydroquinone, 2,6-di-t-butylhydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di (4-hydroxyphenyl) fluorene, phenol The polyfunctional epoxy resin which is the glycidyl etherification product of polyphenol compounds, such as chlorinated polybutadiene, is mentioned.

Polyfunctional epoxy resins that are glycidyl etherified products of various novolak resins are phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols and other various phenols. Examples thereof include glycidyl ethers of various novolak resins such as novolak resins, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins.
Examples of the nuclear hydride of the aromatic epoxy resin other than the epoxy resin (B) include glycidyl etherified products of phenol compounds (for example, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol) or various phenols (for example, phenol). , Cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) as a raw material.

Examples of the alicyclic epoxy resin include alicyclic epoxy resins having a cyclic aliphatic skeleton such as cyclohexane such as 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexylcarboxylate.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, and xylylene glycol derivatives.

Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester epoxy resin include epoxy resins made of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.

Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative.
Examples of epoxy resins obtained by glycidylation of halogenated phenols include halogens such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A. An epoxy resin obtained by glycidyl etherification of a fluorinated phenol is exemplified.

Among these epoxy resins (E), those having less colorability are more preferable from the viewpoint of transparency. Specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethyl-4,4 '-Biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, trishydroxyphenylmethane, resorcinol, 2,6-di- polyfunctional epoxy resins that are glycidyl etherified products of phenols having a fluorene skeleton such as t-butylhydroquinone, phenols having a diisopropylidene skeleton, 1,1-di (4-hydroxyphenyl) fluorene; phenols, cresols, Various types of bisphenol A, bisphenol S, naphthols, etc. Glycidyl etherified products of various novolak resins such as novolak resin using diol, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, fluorene skeleton-containing phenol novolak resin; phenol compounds (bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, etc.) or various phenols (phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) Nuclear hydride of glycidyl etherified product of novolak resin; 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexylcarboxylate Alicyclic epoxy resin having a cyclohexane skeleton of bets like; 1,6-hexanediol, polyethylene glycol, glycidyl ethers such as polypropylene glycol; triglycidyl isocyanurate; hexahydrophthalic acid diglycidyl ester.
Furthermore, these epoxy resins can be used as one kind or a mixture of two or more kinds as required for imparting heat resistance.

As the curing agent (C) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention, an amine compound, an amide compound, an acid anhydride compound, ordinarily used as a curing agent for an epoxy resin, Phenol compounds can be used without particular limitation.
Specifically, for example, an amine compound such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, ketimine compound, a dimer of linolenic acid and ethylenediamine Amide compounds such as polyamide resin to be synthesized, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, Acid anhydride compounds such as methylhexahydrophthalic anhydride, bisphenols or phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydr Roxybenzene, dihydroxynaphthalene, etc.) and polycondensates of various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol, bismethoxymethylbiphenyl and naphthols or phenols Condensates, phenols such as biphenols and modified products thereof, imidazoles, boron trifluoride-amine complexes, guanidine derivatives and the like.

The amount of the curing agent (C) used is preferably 0.2 to 1.5 equivalents, particularly 0.3 to 1.2 equivalents, based on 1 equivalent of epoxy groups in the epoxy resin composition for optical semiconductor encapsulation. preferable.
Moreover, when using tertiary amines, such as benzyldimethylamine, as a hardening | curing agent (C), the usage-amount is 0.3- with respect to the total amount of the epoxy resin contained in the epoxy resin composition for optical semiconductor sealing. About 20% by weight is preferable, and about 0.5 to 10% by weight is particularly preferable.

Examples of the curing accelerator (D) contained in the epoxy resin composition for optical semiconductor encapsulation of the present invention include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2 -Phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2- Undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s -Triazine, 2,4-diamino-6 (2'-ethyl-4-methylimidazole (1 ')) Til-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2- Of phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole Various imidazoles; salts of these imidazoles with polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid; amides such as dicyandiamide; 1 , 8-Diazabicyclo [5.4.0] undecene Diaza compounds such as -7; their tetraphenylboric acid, phenol novolac, etc., salts with the above-mentioned polycarboxylic acids or phosphinic acids; tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, etc. Ammonium salts; phosphines and phosphonium compounds such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate; phenols such as 2,4,6-trisaminomethylphenol; amine adducts It is also possible to use a microcapsule type curing accelerator in which these compounds are made into microcapsules. Which of these curing accelerators is used is appropriately selected depending on the characteristics required for the obtained epoxy resin composition for encapsulating a transparent optical semiconductor, such as transparency, curing speed, and working conditions.
The curing accelerator (D) is usually used in the range of about 0.01 to 15% by weight in the solid content of the epoxy resin for sealing an optical semiconductor.

An inorganic filler, a colorant, a coupling agent, a leveling agent, a lubricant and the like can be appropriately added to the epoxy resin composition for optical semiconductor encapsulation of the present invention depending on the purpose.
Examples of the inorganic filler include crystalline or amorphous silica, talc, silicon nitride, boron nitride, alumina, silica / titania mixed melt, and the like.

  Examples of the colorant include phthalocyanine series, azo series, disazo series, quinacridone series, anthraquinone series, flavantron series, perinone series, perylene series, dioxazine series, condensed azo series, various azomethine series organic dyes, titanium oxide, Inorganic pigments such as lead sulfate, chrome yellow, zinc yellow, chrome vermilion, valve shell, cobalt violet, bitumen, ultramarine, carbon black, chrome green, chrome oxide, cobalt green and the like can be mentioned.

  Examples of the leveling agent include oligomers composed of acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil, and titanium-based coupling agents. .

  Examples of the lubricant include hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, stearylamide, palmityl Higher fatty acid amide type lubricants such as amide, oleylamide, methylene bisstearamide, ethylene bisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri-, or Higher fatty acid ester lubricants such as tetra-) stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, arachizi Acid, behenic acid, ricinoleic acid, such as magnesium naphthenate, calcium, cadmium, barium, zinc, metallic soaps are metal salts such as lead, carnauba wax, candelilla wax, beeswax, and natural waxes such as montan wax.

  Examples of the coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropi Silane coupling agents such as trimethoxysilane, isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neoalkoxy Titanium coupling agents such as tri (p-N- (β-aminoethyl) aminophenyl) titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodecanoylzirco , Neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m -Aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al-propionate and other zirconium or aluminum coupling agents.

  The epoxy resin composition for optical semiconductor encapsulation of the present invention comprises an epoxy resin (A), an epoxy resin (B), a curing agent (C) and a curing accelerator (D), an epoxy resin (E) as necessary, and an optional component. Ingredients such as inorganic filler, coupling agent, colorant and leveling agent are mixed using a blender such as Henschel mixer and Nauter mixer if the compounding ingredients are solid, then kneader, extruder, heating It can knead | mix at 80-120 degreeC using a roll, can grind | pulverize after cooling, and can be obtained as a powder form. On the other hand, when the compounding component is liquid, it is uniformly dispersed using a planetary mixer or the like to obtain the epoxy resin composition for optical semiconductor encapsulation of the present invention.

  In order to obtain the optical semiconductor device included in the present invention, the optical semiconductor device obtained by sealing with the epoxy resin composition for optical semiconductor sealing thus obtained for use in LDs, photosensors, transceivers, etc. What is necessary is just to shape | mold by the conventional shaping | molding methods, such as a transfer mold, a compression mold, an injection mold, and a printing method.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part.
Each physical property value in the examples was measured by the following method.
(1) Weight average molecular weight: Measured by gel permeation chromatography (GPC) method.
(2) Epoxy equivalent: measured by the method described in JIS K-7236.
(3) Nuclear hydrogenation rate: measured with a spectrophotometer. Spectrophotometer: UV-2500PC (manufactured by Shimadzu Corporation)
(4) Viscosity: E-type viscometer: Measured with VISCONIC EHD (manufactured by Tokyo Keiki).

Synthesis example 1
A reaction vessel was charged with 94.4 parts of γ-glycidoxypropyltrimethoxysilane and 94.4 parts of methyl isobutyl ketone, and the temperature was raised to 80 ° C. After the temperature increase, 10.8 parts of a 0.1 wt% aqueous potassium hydroxide solution was continuously added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was reacted at 80 ° C. under reflux for 5 hours. After completion of the reaction, washing with water was repeated until the washing solution became neutral. Subsequently, 66 parts of epoxy resins (A-1) were obtained by removing a solvent under reduced pressure. The epoxy equivalent of the obtained epoxy resin was 171 g / eq, and the weight average molecular weight was 2200.

Synthesis example 2
100 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 100 parts of methyl isobutyl ketone were charged into a reaction vessel and heated to 80 ° C. After the temperature rise, 11 parts of a 0.1 wt% aqueous potassium hydroxide solution was continuously added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was reacted at 80 ° C. under reflux for 5 hours. After completion of the reaction, washing with water was repeated until the washing solution became neutral. Subsequently, 69 parts of epoxy resins (A-2) were obtained by removing a solvent under reduced pressure. The epoxy equivalent of the obtained compound was 184 g / eq, and the weight average molecular weight was 2500.

Synthesis example 3
A reaction vessel was charged with 47.3 parts of γ-glycidoxypropyltrimethoxysilane, 24 parts of dimethyldimethoxysilane, and 285.2 parts of methyl isobutyl ketone, and the temperature was raised to 80 ° C. After the temperature increase, 10.8 parts of a 0.1 wt% aqueous potassium hydroxide solution was continuously added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was reacted at 80 ° C. under reflux for 5 hours. After completion of the reaction, washing with water was repeated until the washing solution became neutral. Subsequently, 46 parts of epoxy resins (A-3) were obtained by removing a solvent under reduced pressure. The obtained compound had an epoxy equivalent of 240 g / eq, a weight average molecular weight of 1400, and a viscosity of 370 mPa · s.

Synthesis example 4
In an autoclave, phenol / biphenyl novolac type epoxy resin (trade name: NC-3000, manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent 276 g / eq) 50 parts, tetrahydrofuran 50 parts, ruthenium / carbon catalyst 6 parts (manufactured by N Chemcat Corporation) A ruthenium carrying amount of 5% by weight, a water-containing product) was charged, and the inside of the autoclave was purged with nitrogen and then purged with hydrogen gas. Thereafter, the contents were reacted at a hydrogen pressure of 8 MPa and a reaction temperature of 110 ° C. for 12 hours while stirring. After completion of the reaction, 50 parts of tetrahydrofuran was added to the reaction solution, followed by suction filtration using filter paper, and the filtrate was further dried under reduced pressure by a rotary evaporator to obtain a transparent epoxy resin (B-1) as a nonvolatile content. The epoxy equivalent of the obtained epoxy resin was 388 g / eq. The nuclear hydrogenation rate was 89%.

Examples 1-3, Comparative Example 1
The said epoxy resin and the raw material shown below were mixed by the weight ratio shown to the "composition of a compound" of Table 1, and the epoxy resin composition was obtained.
Curing agent: 4-methylhexahydrophthalic anhydride (“MH-700G” manufactured by Shin Nippon Rika Co., Ltd.)
Curing accelerator: Quaternary phosphonium bromide ("U-CAT 5003" manufactured by Sun Apro)

Table 1 Composition of the formulation
Example 1 Example 2 Example 3 Comparative Example 1
Epoxy resin A-1 50 100
Epoxy resin A-2 50
Epoxy resin A-3 50
Epoxy resin B-1 50 50 50
Curing agent 69 65 55 95
Curing accelerator 3 3 3 3

Test Example 1 Permeability Test For the epoxy resin compositions obtained in Examples 1 to 3 and Comparative Example 1, the permeability test shown below was performed, and the results are shown in Table 2.
Permeability test: A test piece having a thickness of 1 mm and 20 mm × 15 mm was obtained by casting the obtained epoxy resin composition (curing conditions at 120 ° C. × 2 hours). Using these test pieces, the transmittance (measurement wavelength: 400 nm) before and after ultraviolet irradiation for 7 hours was measured with a spectrophotometer.
The ultraviolet irradiation conditions are as follows.
Ultraviolet irradiation machine: Eye super UV tester SUV-W11
Temperature: 60 ° C
Irradiation energy: 65 mW / cm ²
Irradiation time: 7 hours

Table 2
Transmittance before UV irradiation (%) Transmittance after UV irradiation (7 hours) (%)
Example 1 91 86
Example 2 92 86
Example 3 92 87
Comparative Example 1 91 88

Test Example 2 Water Absorption Rate A resin molded body was prepared by casting (curing conditions: 120 ° C. × 2 hours) using the epoxy resin composition obtained above. The results of measuring the water absorption rate of the cured product thus obtained are shown in Table 3. The measurement was performed by the following method.
Water absorption: weight increase rate (%) after boiling a disk-shaped test piece having a diameter of 5 cm and a thickness of 4 mm in water at 100 ° C. for 24 hours

Table 3
Example 1 Example 2 Example 3 Comparative Example 1
Water absorption rate (%) 1.8 2.1 2.0 3.0

From the results of Tables 2 and 3, it was shown that the epoxy resin composition for encapsulating an optical semiconductor of the present invention gives a cured product with little deterioration against ultraviolet light and excellent in moisture resistance.

Claims (3)

Co-hydrolyzing and condensing the alkoxysilicon compounds represented by the general formula (1) or the alkoxysilicon compound represented by the general formula (1) and the alkoxysilicon compound represented by the general formula (2). Epoxy resin (A) obtained by
[Chemical 1]
XSi (R ¹ ) _a (OR ² ) _3-a (1)
(In the formula, X represents a substituent containing an epoxy group, R ¹ represents a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenylcarboxy group having 3 to 5 carbon atoms. , R ² represents an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 2, when R ¹ is a plurality, the plurality of R ¹ may be the being the same or different.)
[Chemical 2]
_{^{X k (R 3) b Si}} (OR 4) 4- (k + b) (2)
(In the formula, X represents a substituent containing an epoxy group, R ³ represents a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ⁴ represents a group having 1 to ⁴ carbon atoms. an alkyl group, k and b are integer from 0 to 3, k + b is 0 to 3, when there are a plurality of R ^3, a plurality of R ³ may be be the same or different from each other.) ;
A hydrogenated epoxy resin (B) obtained by nuclear hydrogenation of the aromatic ring of the epoxy resin represented by the general formula (3),

Wherein R ⁵ may be the same or different and each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 1 to 4, and n is an average value of 1 to 6 Indicates a positive number.);
An epoxy resin composition for optical semiconductor encapsulation containing a curing agent (C) and a curing accelerator (D). X in formula (1) is an alkyl group having 1 to 5 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an alkyl group having 1 to 3 carbon atoms or an epoxy group substituted with a glycidoxy group, 2. The epoxy for encapsulating an optical semiconductor according to claim 1, wherein R ^{3 in the} formula (2) is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms substituted with a (meth) acryloxy group. Resin composition. An optical semiconductor device sealed with a cured product of the epoxy resin composition according to claim 1.