TWI535748B - Curable epoxy resin composition - Google Patents

Description

Curable epoxy resin composition

The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, a resin composition for optical semiconductor sealing comprising the curable epoxy resin composition, and a use thereof. The curable epoxy resin composition is an optical semiconductor device in which an optical semiconductor element is sealed.

In recent years, high output of optical semiconductor devices has progressed, and resins used in optical semiconductor devices require high heat resistance and light resistance. For example, in the sealing material (sealing resin) for blue and white light semiconductors, the light emitted from the optical semiconductor element and the yellow of the sealing resin caused by heat become a problem. The yellowing sealing resin absorbs light emitted from the optical semiconductor element, so that the luminosity of the light output from the optical semiconductor device decreases with time.

Hereto, a cured product containing a composition of isoallyl cetyl monoglycidyl epoxide and a bisphenol A type epoxy resin is known as a high heat-resistant sealing resin (see Patent Document 1). However, when the cured product is used as a sealing resin for a high-output blue and white photo-semiconductor, coloring is caused by light and heat emitted from the optical semiconductor element, and the light to be output is absorbed, and as a result, there is light. The problem that the luminosity of light output by a semiconductor device decreases with time.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-344867

3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, 3,4-, is known as a sealing resin having high heat resistance and light resistance and not easily yellowing. An adduct of epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate and ε-caprolactone, and an alicyclic skeleton such as 1,2,8,9-diepoxylimene Epoxy resin. However, the hardened materials of the alicyclic epoxy resins are not resistant to various stresses, and cracks may occur when hot-heat cycles such as heating and cooling cycles (repetitive heating and cooling) are applied, or when high-temperature steps such as a reflow step are performed. (Fracture) and other issues. Due to such cracking, problems such as a decrease in the illuminance of light output from the optical semiconductor device with time may occur.

Therefore, the current state of the art requires an optical semiconductor device (especially an optical semiconductor device having a high-output, high-intensity optical semiconductor device) to emit light with a reduced luminosity over time, and has high heat resistance, light resistance, and crack resistance. Transparent sealing resin.

Therefore, an object of the present invention is to provide a curable epoxy resin composition capable of imparting a cured product having high transparency, heat resistance, light resistance, and crack resistance.

Moreover, another object of the present invention is to provide a cured product having high transparency, heat resistance, light resistance, and crack resistance, which is obtained by curing the curable epoxy resin composition.

Moreover, another object of the present invention is to provide an optical semiconductor sealing resin composition comprising the above-mentioned curable epoxy resin composition, which is capable of obtaining an optical semiconductor device in which luminosity reduction with time is suppressed.

Moreover, another object of the present invention is to provide an optical semiconductor device obtained by sealing an optical semiconductor element using the resin composition for optical semiconductor sealing described above, and having high heat resistance, light resistance, transparency, and resistance. The cracked hardened material seals the optical semiconductor element, and the decrease in luminosity over time is suppressed.

In order to solve the above problems, the inventors of the present invention have intensively studied and found that an alicyclic epoxy compound, a monoallyl methallyl diglycidyl ester compound, and two or more epoxy groups in the molecule are contained. An oxyalkylene derivative, which further contains a curing agent, a curing accelerator, or a curing epoxy resin composition, and provides a cured product having excellent heat resistance, light resistance, transparency, and crack resistance. The optical semiconductor device obtained by sealing the optical semiconductor element with the cured product has a low illuminance with time, and has completed the present invention.

That is, the present invention provides a curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A) and an isomeric cyanuric acid monoallyl propylene glycol represented by the following formula (1) An ester compound (B), a oxoxane derivative (C) having two or more epoxy groups in the molecule, a curing agent (D), and a curing accelerator (E);

[wherein, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

Moreover, the present invention provides a curable epoxy resin composition comprising: an alicyclic epoxy compound (A), and a isocyanurate monoallyl diglycidyl compound represented by the following formula (1) ( B), a oxoxane derivative (C) having two or more epoxy groups in the molecule, and a hardening catalyst (F);

[wherein, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

Furthermore, the curable epoxy resin composition is provided, wherein the content of the oxoxane derivative (C) having two or more epoxy groups in the molecule is relative to the component (A) and the component (B). The total amount (100% by weight) of the component (C) is 5 to 60% by weight.

Furthermore, the curable epoxy resin composition according to the above aspect, wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is hexylene oxide.

Furthermore, the above-mentioned curable epoxy resin composition is provided, wherein the alicyclic epoxy compound (A) is represented by the following formula (I-1):

Moreover, the present invention provides a cured product obtained by curing the curable epoxy resin composition.

Moreover, the present invention provides a resin composition for optical semiconductor sealing comprising the above-mentioned curable epoxy resin composition.

Moreover, the present invention provides an optical semiconductor device obtained by sealing an optical semiconductor element with the resin composition for optical semiconductor sealing described above.

Since the curable epoxy resin composition of the present invention has the above-described configuration, a cured product having high transparency, heat resistance, light resistance, and crack resistance can be obtained by curing the resin composition. In addition, the optical semiconductor device obtained by sealing the optical semiconductor element using the curable epoxy resin composition of the present invention (the resin composition for optical semiconductor sealing) is less likely to have a decrease in illuminance with time, and exhibits excellent quality and durability. In particular, when the curable epoxy resin composition of the present invention is used as a sealing resin for an optical semiconductor device having a high-output, high-luminance optical semiconductor device, the luminosity of the optical semiconductor device can be suppressed from decreasing with time.

[Formation of the Invention] <Curable epoxy resin composition>

The curable epoxy resin composition of the present invention comprises at least an alicyclic epoxy compound (A), a isocyanuric acid monoallyl diglycidyl ester compound (B) represented by the following formula (1), and a oxoxane derivative (C) having two or more epoxy groups in the molecule, a curing agent (D), and a curing accelerator (E);

In the formula (1), R ¹ and R ^{2 each} represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Further, the curable epoxy resin composition of the present invention comprises at least an alicyclic epoxy compound (A) and a isocyanuric acid monoallyl diglycidyl ester compound represented by the above formula (1) (B) And a pyrithione derivative (C) having two or more epoxy groups in the molecule, and a curing catalyst (F).

<alicyclic epoxy compound (A)>

The alicyclic epoxy compound (A) constituting the curable epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in the molecule (within one molecule). More specifically, the alicyclic epoxy compound (A) comprises (i) a compound having an epoxy group constituting two adjacent carbon atoms and an oxygen atom of the alicyclic ring, and (ii) an epoxy group. A compound that is directly bonded to an alicyclic ring by a single bond. However, the alicyclic epoxy compound (A) does not contain a decane derivative (C) having two or more epoxy groups in the molecule to be described later.

(i) A compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring, and any one known or customary can be used. The above alicyclic epoxy group is preferably hexylene oxide.

(i) a compound having an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring, and particularly preferably an alicyclic epoxy represented by the following formula (I) from the viewpoint of transparency and heat resistance. Compound (alicyclic epoxy resin).

In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine group, and a group obtained by linking a plurality of these groups.

The alicyclic epoxy compound in which X in the formula (I) is a single bond, for example, a compound represented by the following formula. As such an alicyclic epoxy compound, for example, a commercially available product such as CELLOXIDE 8000 (manufactured by Daicel Co., Ltd.) can also be used.

The above-mentioned divalent hydrocarbon group is, for example, a linear or branched alkyl group having 1 to 18 carbon atoms or a divalent alicyclic hydrocarbon group. A linear or branched alkyl group having 1 to 18 carbon atoms, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylidene group, a propyl group, a trimethylene group or the like. a divalent alicyclic hydrocarbon group, for example, 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-cyclohexyl, 1,3-cyclohexyl, 1, A bivalent cycloalkyl group (including a cycloalkylene group) such as a 4-cyclohexyl group or a cyclohexylene group.

The linking group X is preferably a linking group containing an oxygen atom, specifically, for example, -CO-, -O-CO-O-, -COO-, -O-, -CONH-; A group obtained by linking one or two or more of the above-mentioned groups to one or more of the divalent hydrocarbon groups. A divalent hydrocarbon group such as the ones exemplified above.

Representative examples of the alicyclic epoxy compound represented by the above formula (I) are, for example, compounds represented by the following formulas (I-1) to (I-8). For example, commercially available products such as CELLOXIDE 2021P and CELLOXIDE 2081 (manufactured by Daicel Co., Ltd.) can be used. Further, in the following formulae (I-1) to (I-8), 1, m represents an integer of 1 to 30. R represents an alkylene group having 1 to 8 carbon atoms, such as methylene, ethyl, propyl, isopropyl, butyl, isobutyl, butyl, pentylene, and A linear or branched alkyl group such as a hexyl group, a heptyl group or a octyl group. Among these, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylidene group, a propyl group or an iso stretched propyl group is preferred.

(ii) a compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond, for example, a compound represented by the following formula (II).

In the formula (II), R' is a group of p-type alcohols after p-OH is removed, and p and n represent natural numbers. The p-valent alcohol [R'-(OH) _p ], for example, a polyhydric alcohol such as 2,2-bis(hydroxymethyl)-1-butanol or the like (an alcohol having 1 to 15 carbon atoms). p is preferably from 1 to 6, and n is preferably from 1 to 30. When p is 2 or more, n of each of the bases (in the parentheses) may be the same or different. The above compound, specifically, for example, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, EHBE 3150 (Daicel system) and so on.

These alicyclic epoxy compounds (A) may be used singly or in combination of two or more. The alicyclic epoxy compound (A) is preferably a 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate represented by the above formula (I-1), and CELLOXIDE 2021P.

The amount (content) of the alicyclic epoxy compound (A) is not particularly limited, and is relative to the total amount of the alicyclic epoxy compound (A) and the isomeric cyanuric acid monoallyl diglycidyl ester compound (B). (100% by weight), preferably from 50 to 90% by weight, more preferably from 60 to 90% by weight, still more preferably from 70 to 90% by weight. When the amount of the alicyclic epoxy compound (A) used is less than 50% by weight, the solubility of the isocyanurate monoallyl diglycidyl ester compound (B) is insufficient, and if it is left at room temperature, sometimes it may be Easy to precipitate. On the other hand, when the amount of the alicyclic epoxy compound (A) used exceeds 90% by weight, cracks may easily occur when an optical semiconductor device is produced. In the total amount (100% by weight) of the component (A), the component (B), and the component (C), the alicyclic epoxy compound (A) and the isocyanurate monoallyl diglycidyl ester compound ( The sum (total amount) of the content of B) is not particularly limited, and is preferably from 40 to 95% by weight.

When the curable epoxy resin composition of the present invention contains the curing agent (D) as an essential component, the content of the alicyclic epoxy compound (A) relative to the total amount (100% by weight) of the curable epoxy resin composition is not particularly limited. It is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, still more preferably 17 to 70% by weight. On the other hand, when the curable epoxy resin composition of the present invention contains a curing catalyst (F) as an essential component, the entire amount of the alicyclic epoxy compound (A) relative to the curable epoxy resin composition (100% by weight) The content is not particularly limited and is preferably from 25 to 90% by weight, more preferably from 30 to 85% by weight, still more preferably from 35 to 80% by weight.

<Iso-cyanuric acid monoallyl diglycidyl ester compound (B)>

The isomeric cyanuric acid monoallyl diglycidyl ester compound (B) used in the present invention can be represented by the following general formula (1).

In the above formula (1), R ¹ and R ^{2 each} represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, etc. Or branched alkyl. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. R ¹ and R ² in the above formula (1) are preferably a hydrogen atom.

Representative examples of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B), such as isoallyl cyanurethane diglycidyl ester, isomeric cyanuric acid 1-allyl-3 , 5-bis(2-methylepoxypropyl) ester, 1-(2-methylpropenyl)-3,5-diglycidyl isocyanate, 1-cyanuric acid 1-( 2-Methylpropenyl)-3,5-bis(2-methylepoxypropyl) ester or the like. Further, the isocyanuric acid monoallyl diglycidyl ester compound (B) may be used singly or in combination of two or more.

The isocyanuric acid monoallyl diglycidyl ester compound (B) can be optionally mixed in the range of the above alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) and isomeric cyanide The ratio of the acid monoallyl diglycidyl ester compound (B) is not particularly limited, and the alicyclic epoxy compound (A): the isocyanuric acid monoallyl diglycidyl ester compound (B) is preferably 50. : 50 to 90: 10 (weight ratio) is preferred. When it is outside this range, the solubility of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) is not easily obtained.

The isocyanuric acid monoallyl diglycidyl ester compound (B) may be previously modified by adding a compound which reacts with an epoxy group such as an alcohol or an acid anhydride.

The total amount of the alicyclic epoxy compound (A) and the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) relative to the total amount of the epoxy resin (the compound having an epoxy group) (100 weight) %) is not particularly limited, and is preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 70% by weight or more from the viewpoint of improving heat resistance, light resistance, and crack resistance.

<a oxane derivative (C) having two or more epoxy groups in the molecule>

The component (C) of the curable epoxy resin composition of the present invention, that is, a decane derivative having two or more epoxy groups in a molecule (in one molecule), is responsible for improving the heat resistance and light resistance of the cured product. The effect of suppressing the luminosity reduction of the optical semiconductor device is suppressed.

In the fluorinated alkane derivative (C) having two or more epoxy groups in the molecule, the siloxane skeleton is not particularly limited, and examples thereof include a cyclic siloxane skeleton; a linear polyoxy siloxane, or a cage type or A polyoxane skeleton such as a ladder type polysesquioxane or the like. Among them, the above-described siloxane skeleton is preferably a cyclic oxime skeleton and a linear polyfluorene skeleton from the viewpoint of improving heat resistance and light resistance of the cured product and suppressing reduction in luminosity. In other words, the fluorinated alkane derivative (C) having two or more epoxy groups in the molecule is preferably a cyclic oxirane having two or more epoxy groups in the molecule, and two or more rings in the molecule. A linear polyoxyl group of an oxy group. Further, the decane derivative (C) having two or more epoxy groups in the molecule may be used singly or in combination of two or more.

When the oxoxane derivative (C) having two or more epoxy groups in the molecule is a cyclic siloxane having two or more epoxy groups, the number of Si-O units forming a siloxane chain (and The number of the ruthenium atoms forming the oxime ring is not particularly limited, and is preferably from 2 to 12, more preferably from 4 to 8, from the viewpoint of improving the heat resistance and light resistance of the cured product.

The weight average molecular weight of the fluorinated alkane derivative (C) having two or more epoxy groups in the molecule is not particularly limited, and is preferably from 100 to 3,000, more preferably from the viewpoint of improving heat resistance and light resistance of the cured product. 180~2000.

The oxoxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited as long as the number of epoxy groups in one molecule is two or more, and the heat resistance and light resistance of the cured product are improved. From the viewpoint, 2 to 4 (2, 3, or 4) are preferred.

The oxirane derivative (C) having two or more epoxy groups in the molecule is not particularly limited as long as it has an epoxy equivalent (according to JIS K7236), and is 180 to 400 from the viewpoint of improving heat resistance and light resistance of the cured product. Preferably, it is preferably 240 to 400, and more preferably 240 to 350.

The epoxy group in the oxoxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited, and from the viewpoint of improving the heat resistance and light resistance of the cured product, it is adjacent to the aliphatic ring. An epoxy group (alicyclic epoxy group) composed of two carbon atoms and an oxygen atom is preferred, and an epoxyhexenyl group is particularly preferred.

a oxoxane derivative (C) having two or more epoxy groups in the molecule, specifically, for example, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl}) Ethyl]-2,4,6,6,8,8-hexamethyl-cyclotetraoxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl}) Ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetraoxane, 2,4-di[2-(3-{oxabicyclo[4.1.0]heptyl}) Ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 4,8-di[2-(3-{oxabicyclo[4.1.0] Heptyl})ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,8-tri[2-(3-{oxa) Bicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetraoxane, 2,4,8-tri[2-(3-{oxa) Bicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,6,8-tetra[2-( 3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetraoxane, sesquioxane having an epoxy group, and the like. More specifically, for example, the following formula represents a cyclic siloxane having two or more epoxy groups in one molecule.

In addition, the oxirane derivative (C) having two or more epoxy groups in the molecule may be, for example, an alicyclic epoxy group-containing polyfluorene-containing resin described in JP-A-2008-248169, or Japan. JP-A-2008-19422 discloses an organopolysesquioxane resin having at least two epoxy functional groups in a molecule.

As the oxoxane derivative (C) having two or more epoxy groups in the molecule, for example, a cyclic oxirane having two or more epoxy groups in the molecule may be used, and the trade name "X-40-2678" may be used. (Shin-Etsu Chemical Co., Ltd.), the trade name "X-40-2670" (Shin-Etsu Chemical Co., Ltd.), and the trade name "X-40-2720".

The amount (content) of the oxoxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited, and is a total amount of the component (A), the component (B), and the component (C) ( 100% by weight) is preferably 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight, still more preferably 15 to 40% by weight. When the amount of the oxoxane derivative (C) having two or more epoxy groups in the molecule is less than 5% by weight, the heat resistance and light resistance of the cured product may be lowered. On the other hand, when the amount of the oxoxane derivative (C) having two or more epoxy groups in the molecule is more than 60% by weight, the crack resistance of the cured product may be lowered.

<hardener (D)>

The hardener (D) has a function of hardening a compound having an epoxy group. In the present invention, as the curing agent (D), a curing agent which is known or conventionally used as a curing agent for an epoxy resin can be used. In the present invention, the hardener (D) is preferably an acid anhydride having a liquid state at 25 ° C, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, Methyl inward methylenetetrahydrophthalic anhydride or the like. Further, for example, an acid anhydride having a solid temperature (about 25 ° C) at a normal temperature (about 25 ° C) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or methylcyclohexene dicarboxylic anhydride is dissolved in a normal temperature ( About 25 ° C) is a liquid acid anhydride and becomes a liquid mixture, and can also be used as the hardener (D) of the present invention. Further, the curing agent (D) may be used singly or in combination of two or more. As described above, the curing agent (D) is a saturated monocyclic hydrocarbon dicarboxylic anhydride (also included in a ring-bonded substituent such as an alkyl group) from the viewpoint of heat resistance, light resistance, and crack resistance of the cured product. good.

Further, in the present invention, commercially available products such as Rikacid MH-700 (manufactured by Shin Nippon Chemical & Chemical Co., Ltd.) and HN-5500 (manufactured by Hitachi Chemical Co., Ltd.) can be used as the curing agent (D).

The amount (content) of the curing agent (D) is not particularly limited, and is 50 to 200 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention. More preferably, it is preferably 100 to 145 parts by weight. More specifically, the epoxy group in the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention is preferably used in an amount of from 0.5 to 1.5 equivalents per equivalent of the epoxy group. When the amount of the curing agent (D) used is less than 50 parts by weight, the curing is insufficient, and the toughness of the cured product tends to be lowered. On the other hand, when the amount of the curing agent (D) used exceeds 200 parts by weight, the cured product may be colored, and the hue may be deteriorated.

<hardening accelerator (E)>

The curable epoxy resin composition of the present invention further contains a hardening accelerator (E). The hardening accelerator (E) is a compound having a function of promoting the curing speed when the epoxy group-containing compound is cured by a curing agent. As the hardening accelerator (E), a known or conventional hardening accelerator such as 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and a salt thereof (for example, a phenate, Octanoic acid, p-toluenesulfonate, formate, tetraphenyl borate); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and salts thereof (eg, phosphonium salts, a phosphonium salt, a 4-grade ammonium salt, a phosphonium salt); a benzylamine, a 2,4,6-glycol (dimethylaminomethyl)phenol, a N-N-dimethylcyclohexylamine or the like; Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphates and triphenylphosphine; tetraphenylphosphonium tetra(p-tolyl) An antimony compound such as borate; an organic metal salt such as tin octylate or zinc octoate; a metal chelate compound or the like. The hardening accelerator (E) may be used singly or in combination of two or more.

Further, in the present invention, the hardening accelerator (E) may also be U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X, 12XD (developed product) (both San-apro) )), TPP-K, TPP-MK (both from Beixing Chemical Industry Co., Ltd.) and PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.).

The amount (content) of the hardening accelerator (E) is not particularly limited, and is preferably 0.05 to 5 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. More preferably, it is 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight. When the amount of the hardening accelerator (E) used is less than 0.05 parts by weight, the hardening promoting effect may be insufficient. On the other hand, when the amount of the curing accelerator (E) used exceeds 5 parts by weight, the cured product may be colored, and the hue may be deteriorated.

<hardening catalyst (F)>

In the curable epoxy resin composition of the present invention, a curing catalyst (F) may be used instead of the curing agent (D) and the curing accelerator (E). As in the case of using the hardener (D) and the hardening accelerator (E), by using the hardening catalyst (F), the hardening reaction of the epoxy group-containing compound can be carried out and a cured product can be obtained. The hardening catalyst (F) is not particularly limited, and a cationic catalyst (cationic polymerization initiator) which generates a cationic substance by polymerization by ultraviolet irradiation or heat treatment and starts polymerization can be used.

A cationic catalyst which generates a cationic substance due to ultraviolet irradiation, for example, hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, hexafluoroarsenate or the like. These cationic catalysts may be used alone or in combination of two or more. The cation catalyst is, for example, trade name "UVACURE 1590" (manufactured by Daicel‧Cytec Co., Ltd.), trade name "CD-1010", "CD-1011", "CD-1012" (above, Sartomer, USA), trade name Commercial products such as "Irgacure 264" (manufactured by Ciba Japan Co., Ltd.) and trade name "CIT-1682" (manufactured by Japan Soda Co., Ltd.) are preferred.

The heat treatment may produce a cationic catalyst of a cationic substance such as an aryldiazonium salt, an arylsulfonium salt, an arylsulfonium salt, an arene-ion complex, or the like, and preferably, for example, PP- may be used. 33. CP-66, CP-77 (made by ADEKA), FC-509 (made by 3M), UVE1014 (made by GE), San-Aid SI-60L, San-Aid SI-80L, San-Aid SI- Commercial products such as 100L, San-Aid SI-110L (manufactured by Sanshin Chemical Industry Co., Ltd.) and CG-24-61 (manufactured by Ciba Japan Co., Ltd.). Further, a compound of a metal such as aluminum or titanium and a chelating compound of acetonitrile acetic acid or a diketone, a sterol compound such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and a chelating compound of acetonitrile acetic acid or a diketone. A compound such as a phenol such as bisphenol S may also be used. These cationic catalysts may be used singly or in combination of two or more.

The amount (content) of the curing catalyst (F) is not particularly limited, and is preferably 0.01 to 15 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. More preferably, it is 0.01 to 12 parts by weight, more preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight. By using the curing catalyst (F) in this range, a cured product excellent in heat resistance, light resistance, and transparency can be obtained.

<Rubber Particles>

The curable epoxy resin composition of the present invention may also contain rubber particles. Examples of the rubber particles include particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). The rubber particles are a multi-layered structure (nuclear sheath structure) composed of a core portion having rubber elasticity and a sheath layer covering at least one layer of the core portion, and having a surface having a functional group capable of reacting with an alicyclic epoxy compound A rubber particle having a hydroxyl group and/or a carboxyl group and having an average particle diameter of 10 nm to 500 nm and a maximum particle diameter of 50 nm to 1000 nm may be a refractive index of the rubber particle and a cured product of the curable epoxy resin composition. The rubber particles are within ±0.02. The blending amount of the rubber particles is not particularly limited as long as it is necessary, and is 0.5 to 30 parts by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. Preferably, it is preferably 1 to 20 parts by weight. When the amount of the rubber particles used is less than 0.5 part by weight, the crack resistance of the cured product tends to be lowered. On the other hand, when the amount of the rubber particles used exceeds 30 parts by weight, the heat resistance and transparency of the cured product may be lowered. The tendency.

<additive>

In addition to the above, various additives may be used in the curable epoxy resin composition of the present invention within the range not impairing the effects of the present invention. For example, if a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or glycerin is used as the above additive, the reaction can be carried out gently. Further, a decane coupling agent such as a polyfluorene-based or fluorine-based antifoaming agent, a coating agent, or γ-glycidoxypropyltrimethoxydecane may be contained within a range that does not impair viscosity or transparency. Conventional additives such as inorganic fillers such as surfactants, cerium oxide, and aluminum oxide, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, and mold release agents.

<hardened matter>

By curing the curable epoxy resin composition of the present invention, a cured product excellent in physical properties such as transparency, heat resistance, light resistance, and crack resistance can be obtained. The heating temperature (hardening temperature) at the time of hardening is not particularly limited, and is preferably 45 to 200 ° C, more preferably 100 to 190 ° C, still more preferably 100 to 180 ° C. Further, the heating time (hardening time) at the time of hardening is not particularly limited, and is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. When the hardening temperature and the hardening time are less than the lower limit of the above range, the hardening is insufficient. On the other hand, when the curing temperature is higher than the upper limit of the above range, the resin component may be decomposed, which is not preferable. The hardening conditions depend on various conditions, for example, when the hardening temperature is raised, the hardening time is shortened, and when the hardening temperature is lowered, the hardening time is lengthened, etc., and can be appropriately adjusted.

<Resin composition for optical semiconductor sealing>

The resin composition for optical semiconductor sealing of the present invention comprises a curable epoxy resin composition of the present invention. By using the resin composition for optical semiconductor sealing of the present invention, it is possible to obtain a cured product excellent in physical properties such as transparency, heat resistance, light resistance, and crack resistance, and to seal the optical semiconductor element, and the luminosity is not easy to follow. Time-reduced optical semiconductor device. In the optical semiconductor device described above, even when a high-output, high-luminance optical semiconductor element is provided, the illuminance does not easily decrease with time.

<Optical semiconductor device>

The optical semiconductor device of the present invention is obtained by sealing the optical semiconductor element with the curable epoxy resin composition (resin composition for optical semiconductor sealing) of the present invention. In the sealing of the optical semiconductor element, the curable epoxy resin composition prepared by the above method is injected into a predetermined molding die, and heat-hardened under predetermined conditions. Thereby, the optical semiconductor device can be sealed with a curable epoxy resin composition to obtain an optical semiconductor device. The hardening temperature and the hardening time can be set to the same range as described above.

The curable epoxy resin composition of the present invention is not limited to the sealing use of the above-mentioned optical semiconductor (optical semiconductor element), and can be used, for example, for an adhesive, an electrical insulating material, a laminated plate, a coating, an ink, a coating, or the like. Sealing agent, resist, composite material, transparent substrate, transparent sheet, transparent film, optical element, optical lens, optical member, optical shape, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, Full image memory, etc.

[Examples]

The invention will be described in more detail below on the basis of examples, but the invention is not limited to the examples.

Manufacturing example 1 (mixture of hardener and hardening accelerator and additive, hereinafter referred to as K agent)

Hardener (Nippon Chemical and Chemical Co., Ltd., Rikacid MH-700): 100 parts by weight, hardening accelerator (SAN-APRO, U-CAT 18X): 0.5 parts by weight, additive (Wako Pure Chemical Industries, Ltd.) (Stock), ethylene glycol): 1 part by weight was uniformly mixed using a self-rotating stirring device (manufactured by THINKY Co., Ltd., defoaming Ryotaro AR-250), and defoaming was carried out to obtain a K agent.

Manufacturing Example 2 (epoxy resin)

Isocyanuric acid monoallyl diglycidyl ester (Four Countries Chemical Industry Co., Ltd., MA-DGIC), alicyclic epoxy compound (Daicel Co., Ltd., CELLOXIDE 2021P), and two molecules in the molecule The above-mentioned epoxy group-containing oxane derivative (Shin-Etsu Chemical Co., Ltd., X-40-2678; Shin-Etsu Chemical Co., Ltd., X-40-2720; Shin-Etsu Chemical Co., Ltd., X- 40-2670), mixed according to the blending formula (unit: parts by weight) shown in Tables 1 and 2, and stirred at 80 ° C for 1 hour, thereby dissolving isoallyl cyanuric propylene carbonate , obtained epoxy resin (mixture).

Examples 1 to 12 and Comparative Examples 1 to 4

In Examples 1 to 12, the epoxy resin obtained in Production Example 2 and the K agent obtained in Production Example 1 were used in accordance with the blending formula (unit: parts by weight) shown in Table 1, and each component was used in a self-revolving stirring device. (THINKY (stock) system, defoaming ritaro AR-250) uniformly mixed and defoamed to obtain a curable epoxy resin composition. Further, as shown in Table 1, in Comparative Example 1, only an alicyclic epoxy compound (manufactured by Daicel Chemical Industry Co., Ltd., CELLOXIDE 2021P) was used for the epoxy resin, and Comparative Examples 2 to 4 were used only for the epoxy resin. a decane derivative having two or more epoxy groups in the molecule (Shin-Etsu Chemical Co., Ltd., X-40-2678; Shin-Etsu Chemical Co., Ltd., X-40-2720; Shin-Etsu Chemical Industry Co., Ltd. , manufactured by X-40-2670), was obtained in the same manner as above to obtain a curable epoxy resin composition.

The curable epoxy resin composition was cast into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of an optical semiconductor as shown in Fig. 1, and then heated in an oven (resin-hardened oven) at 120 ° C for 5 hours. Thereby, an optical semiconductor device obtained by sealing an LED element with a hardened resin is obtained. In Fig. 1, 100 represents a reflecting member (resin composition for light reflection), 101 represents metal wiring, 102 represents an LED element, 103 represents a bonding wire, and 104 represents a transparent sealing resin (cured material).

Examples 13 to 24 and Comparative Examples 5 to 8

Examples 13 to 24 are the epoxy resin obtained in Production Example 2 and a hardening catalyst (manufactured by Sanshin Chemical Industry Co., Ltd., SAN-AID SI-100L) according to the blending formula shown in Table 2 (unit: Each component was uniformly mixed and defoamed using a self-rotating stirring device (manufactured by THINKY Co., Ltd., defoaming Ryotaro AR-250) to obtain a curable epoxy resin composition. Further, as shown in Table 2, in Comparative Example 5, only an alicyclic epoxy compound (CaiOXIDE 2021P, manufactured by Daicel Chemical Industry Co., Ltd.) was used for the epoxy resin, and Comparative Examples 6 to 8 were only for the epoxy resin. A oxoxane derivative having two or more epoxy groups in the molecule (manufactured by Shin-Etsu Chemical Co., Ltd., X-40-2678; Shin-Etsu Chemical Co., Ltd., X-40-2720; Shin-Etsu Chemical Industry ( (manufactured by X-40-2670), a curable epoxy resin composition was obtained in the same manner as described above.

The curable epoxy resin composition was cast on a lead frame (InGaN element, 3.5 mm × 2.8 mm) of an optical semiconductor as shown in Fig. 1, and then heated at 110 ° C for 3 hours in an oven (resin-hardened oven), and then, The film was heated at 140 ° C for 4 hours, whereby an optical semiconductor device obtained by sealing the LED element with a cured resin was obtained.

<evaluation>

The evaluation results of the curable epoxy resin composition obtained in the examples and the comparative examples and the optical semiconductor device were carried out in the following manner.

[Power-on test]

The total light flux of the optical semiconductor device obtained in the examples and the comparative examples was measured using a full beam measuring machine (determined as "total light beam of 0 hours"). Further, a total light beam (defined as "full beam after 100 hours") of a current of 60 mA was applied to the optical semiconductor device in a constant temperature bath at 85 ° C for 100 hours. The photometric retention rate is calculated by the following formula. The results are shown in Tables 1 and 2.

{Photometric retention rate (%)}={100 hours after full beam (lm)}/{0 hour full beam (lm)}×100

[Solder heat resistance test]

The optical semiconductor device obtained in the examples and the comparative examples (two for each curable epoxy resin composition) was allowed to absorb moisture at 30 ° C and 70% RH for 168 hours, and then subjected to a reflow furnace at 260 ° C for 10 hours. The heat treatment was performed twice in two seconds. After that, the length of the crack generated by the sealing resin (cured material of the curable epoxy resin composition) of the optical semiconductor device was observed with a digital microscope (VHX-900, manufactured by KEYENCE Co., Ltd.), and measured in two optical semiconductor devices. The number of optical semiconductor devices having cracks having a length of 90 μm or more. The results are shown in Tables 1 and 2.

[Hot rush test]

The optical semiconductor device obtained in the examples and the comparative examples (two for each curable epoxy resin composition) was exposed to a gas atmosphere at -40 ° C for 30 minutes, and then exposed to a gas atmosphere at 100 ° C for 30 minutes. This was treated as a hot cycle of one cycle, and 200 cycles were given using a hot press tester. After that, the length of the crack generated by the sealing resin (cured material of the curable epoxy resin composition) of the optical semiconductor device was observed with a digital microscope (VHX-900, manufactured by KEYENCE Co., Ltd.), and measured in two optical semiconductor devices. The number of optical semiconductor devices having cracks having a length of 90 μm or more. The results are shown in Tables 1 and 2.

[Comprehensive judgment]

The illuminance retention rate of the electric current test was 90% or more, and the number of optical semiconductor devices having a crack of 90 μm or more in the solder heat resistance test and the thermal squeezing test was zero, and it was judged as ○ (good). In addition to this, the overall judgment is × (bad). The results are shown in Tables 1 and 2.

Moreover, the components used in the examples and comparative examples are as follows.

(epoxy resin)

CEL2021P (CELLOXIDE 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, manufactured by Daicel

MA-DGIC: Isopropyl propylene glycol monoisopropyl epoxide, Siguo Chemical Industry Co., Ltd.

X-40-2678: a cyclooxygen derivative having two epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

X-40-2720: a trioxane derivative having three epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

X-40-2670: a cyclooxygen derivative having four epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

(K agent)

Rikacid MH-700: 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30, New Japan Physical and Chemical Co., Ltd.

U-CAT 18X: Hardening accelerator, SAN-APRO (share) system

Ethylene glycol: Wako Pure Chemical Industries Co., Ltd.

(hardening catalyst)

SI-100L (SAN-AID SI-100L): aryl sulfonium salt, Sanshin Chemical Industry Co., Ltd.

Test equipment

‧Resin hardening oven

ESPEC (share) system GPHH-201

‧Thermostat

ESPEC (stock) small high temperature chamber ST-120B1

‧Full beam measuring machine

Multi-spectral radiometry system manufactured by Optronic Laboratories OL771

‧Hot scouring test machine

ESPEC (stock) system small hot and cold flushing device TSE-11-A

‧Reflow furnace

Japan ANTOM (share) system, UNI-5016F

[Industrial availability]

The curable epoxy resin composition of the present invention can be preferably used for sealing applications of optical semiconductor elements. Moreover, the curable epoxy resin composition of the present invention can also be used for an adhesive, an electrical insulating material, a laminated board, a coating, an ink, a coating, a potting agent, a resist, a composite material, a transparent substrate. , transparent sheet, transparent film, optical element, optical lens, optical member, optical shape, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, and the like.

100. . . Reflector (resin composition for light reflection)

101. . . Metal wiring

102. . . LED component

103. . . Bonding wire

104. . . Transparent sealing resin

Fig. 1 is a schematic view showing an embodiment of an optical semiconductor device in which a device (optical semiconductor device) is sealed by a curable epoxy resin composition of the present invention, and a left side view (a) is a perspective view, and a right side view ( b) is a sectional view.

Claims (7)

A curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A) represented by the following formula (I) or the following formula (II), and an iso-cyanuric acid monoolefin represented by the following formula (1) a propyl diglycidyl ester compound (B), a cyclic siloxane derivative (C) having two or more epoxy groups in the molecule, a curing agent (D), and a curing accelerator (E); The content of the cyclic oxoxane derivative (C) having two or more epoxy groups in the molecule, and the total amount of the component (A), the component (B), and the component (C) (100% by weight) ) is 5 to 60% by weight; [In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms)]; [In the formula (II), R' is a group of p-membered alcohols after p-OH is removed, and p and n represent natural numbers]; [wherein, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. A curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A) represented by the following formula (I) or the following formula (II), and an iso-cyanuric acid monoolefin represented by the following formula (1) a propyl diglycidyl ester compound (B), a cyclic oxoxane derivative (C) having two or more epoxy groups in the molecule, and a curing catalyst (F); further, the molecule has 2 The content of the cyclic oxirane derivative (C) of the above epoxy group is 5 to 60 parts by weight based on the total amount (100% by weight) of the component (A), the component (B), and the component (C). %; [In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms)]; [In the formula (II), R' is a group of p-membered alcohols after p-OH is removed, and p and n represent natural numbers]; [wherein, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. The curable epoxy resin composition according to claim 1 or 2, wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is hexylene oxide. The curable epoxy resin composition according to claim 1 or 2, wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (I-1); A cured product obtained by hardening a curable epoxy resin composition according to any one of claims 1 to 4. A resin composition for optical semiconductor sealing comprising a curable epoxy resin composition according to any one of claims 1 to 4. An optical semiconductor obtained by sealing an optical semiconductor element with a resin composition for optical semiconductor sealing according to item 6 of the patent application.