WO2012093589A1

WO2012093589A1 - Curable epoxy resin composition

Info

Publication number: WO2012093589A1
Application number: PCT/JP2011/079686
Authority: WO
Inventors: 鈴木弘世
Original assignee: 株式会社ダイセル
Priority date: 2011-01-07
Filing date: 2011-12-21
Publication date: 2012-07-12
Also published as: JP2012184394A; TWI535748B; JP5764432B2; MY161464A; CN103154073A; KR101864462B1; CN103154073B; TW201237059A; KR20140009200A

Abstract

The purpose of the present invention is to provide a curable epoxy resin composition capable of yielding a cured product which has high transparency, heat resistance, light resistance and crack resistance. This curable epoxy resin composition is characterized by comprising (A) an alicyclic epoxy compound, (B) a monoallyl diglycidyl isocyanurate compound represented by formula (1), (C) a siloxane derivative which has two or more epoxy groups in the molecule, (D) a curing agent, and (E) a cure accelerator. In formula (1), R¹ and R² are each a hydrogen atom or C_1-8 alkyl.

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, an optical semiconductor sealing resin composition comprising the curable epoxy resin composition, and the curable epoxy resin. The present invention relates to an optical semiconductor device in which an optical semiconductor element is sealed using a composition.

In recent years, output of optical semiconductor devices has been increased, and high heat resistance and light resistance are required for resins used in optical semiconductor devices. For example, in a sealing material (sealing resin) for a blue / white optical semiconductor, yellowing of the sealing resin due to light and heat emitted from the optical semiconductor element is a problem. Since the yellowing sealing resin absorbs light emitted from the optical semiconductor element, the luminous intensity of the light output from the optical semiconductor device decreases with time.

So far, a cured product of a composition containing monoallyl diglycidyl isocyanurate and bisphenol A type epoxy resin is known as a sealing resin having high heat resistance (see Patent Document 1). However, when the cured product is used as a sealing resin for a high-output blue / white light semiconductor, coloring proceeds due to light and heat emitted from the optical semiconductor element, and light that should be output is absorbed, As a result, there has been a problem that the luminous intensity of the light output from the optical semiconductor device decreases with time.

JP 2000-344867 A

3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) as sealing resins that have high heat resistance and light resistance and are resistant to yellowing A liquid alicyclic epoxy resin having an alicyclic skeleton such as an adduct of cyclohexanecarboxylate and ε-caprolactone and 1,2,8,9-diepoxylimonene is known. However, these alicyclic epoxy resin cured products are vulnerable to various stresses, and when subjected to a thermal shock such as a cold cycle (repeating heating and cooling) or a high temperature process such as a reflow process In addition, there are problems such as the occurrence of cracks. The occurrence of such cracks also causes problems such as a decrease in light intensity of light output from the optical semiconductor device over time.

For this reason, high heat resistance, light resistance, and crack resistance that suppress a decrease in light intensity over time of light output from an optical semiconductor device (particularly, an optical semiconductor device including a high-output, high-brightness optical semiconductor element) Under the present circumstances, there is a demand for a transparent sealing resin having both properties.

Accordingly, an object of the present invention is to provide a curable epoxy resin composition that provides a cured product having high transparency, heat resistance, light resistance, and crack resistance.
Another object of the present invention is to provide a cured product having high transparency, heat resistance, light resistance, and crack resistance obtained by curing the curable epoxy resin composition.
Another object of the present invention is to provide a resin composition for encapsulating an optical semiconductor comprising the above curable epoxy resin composition, from which an optical semiconductor device in which a decrease in light intensity over time is suppressed can be obtained.
Another object of the present invention is to provide high heat resistance, light resistance, transparency, and crack resistance obtained by sealing an optical semiconductor element using the above resin composition for optical semiconductor sealing. Another object of the present invention is to provide an optical semiconductor device in which an optical semiconductor element is sealed with a cured product and a decrease in luminous intensity with time is suppressed.

As a result of intensive studies to solve the above problems, the present inventor includes an alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, and a siloxane derivative having two or more epoxy groups in the molecule, and further includes a curing agent and A curable epoxy resin composition containing a curing accelerator or a curing catalyst gives a cured product having excellent heat resistance, light resistance, transparency and crack resistance, and encapsulates an optical semiconductor element with the cured product. As a result, the present inventors have found that the optical semiconductor device is less likely to decrease in light intensity over time.

That is, the present invention relates to an alicyclic epoxy compound (A) and the following formula (1).

[Wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A monoallyl diglycidyl isocyanurate compound (B) represented by the formula, a siloxane derivative (C) having two or more epoxy groups in the molecule, a curing agent (D), and a curing accelerator (E). A curable epoxy resin composition is provided.

Further, the present invention provides an alicyclic epoxy compound (A) and the following formula (1):

[Wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A curable epoxy resin comprising a monoallyl diglycidyl isocyanurate compound (B) represented by the formula: a siloxane derivative (C) having two or more epoxy groups in the molecule; and a curing catalyst (F). A composition is provided.

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

Furthermore, the curable epoxy resin composition is provided wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is a cyclohexene oxide group.

Further, the alicyclic epoxy compound (A) is represented by the following formula (I-1)

The said curable epoxy resin composition which is a compound represented by these is provided.

The present invention also provides a cured product obtained by curing the curable epoxy resin composition.

The present invention also provides a resin composition for sealing an optical semiconductor comprising the curable epoxy resin composition.

The present invention also provides an optical semiconductor device in which an optical semiconductor element is sealed with the above-described resin composition for sealing an optical semiconductor.

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, an optical semiconductor device in which an optical semiconductor element is encapsulated with the curable epoxy resin composition (an optical semiconductor encapsulating resin composition) of the present invention is less likely to have a decrease in light intensity over time, and has excellent quality and durability. Can be demonstrated. In particular, even when the curable epoxy resin composition of the present invention is used as a sealing resin for an optical semiconductor device provided with a high-output, high-brightness optical semiconductor element, A decrease in luminous intensity can be suppressed.

It is the schematic which shows one Embodiment of the optical semiconductor device which sealed the element (optical semiconductor element) with the curable epoxy resin composition of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view.

<Curable epoxy resin composition>
The curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A) and the following formula (1).

[In formula (1), R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
At least a monoallyl diglycidyl isocyanurate compound (B) represented by the formula, a siloxane derivative (C) having two or more epoxy groups in the molecule, a curing agent (D), and a curing accelerator (E). . The curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B) represented by the above formula (1), and two or more in the molecule. It contains at least a siloxane derivative (C) having an epoxy group 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 (in one molecule). More specifically, the alicyclic epoxy compound (A) includes (i) a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and (ii) a fatty acid. A compound in which an epoxy group is directly bonded to the ring by a single bond is included. However, the alicyclic epoxy compound (A) does not include a siloxane derivative (C) having two or more epoxy groups in the molecule described later.

(I) A compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring is arbitrarily selected from known or commonly used compounds. be able to. The alicyclic epoxy group is preferably a cyclohexene oxide group.

(I) Especially as a compound which has an epoxy group comprised by two adjacent carbon atoms and oxygen atoms which comprise an alicyclic ring, the fat represented by the following formula (I) in terms of transparency and heat resistance Cyclic epoxy compounds (alicyclic epoxy resins) are desirable.

In 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, an amide group, and a group in which a plurality of these are linked.

Examples of the alicyclic epoxy compound in which X in the formula (I) is a single bond include compounds represented by the following formula. As such an alicyclic epoxy compound, for example, a commercially available product such as Celoxide 8000 (manufactured by Daicel Corporation) can be used.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1, And divalent cycloalkylene groups (including cycloalkylidene groups) such as 4-cyclohexylene and cyclohexylidene groups.

The linking group X is preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—; A group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include those exemplified above.

Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-8). For example, commercially available products such as Celoxide 2021P and Celoxide 2081 (manufactured by Daicel Corporation) can also be used. In the following formulas (I-1) to (I-8), l and m each represents an integer of 1 to 30. R is an alkylene group having 1 to 8 carbon atoms, and is a linear or branched alkylene group such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, s-butylene, pentylene, hexylene, heptylene, octylene group or the like. Can be mentioned. Among these, linear or branched alkylene groups having 1 to 3 carbon atoms such as methylene, ethylene, propylene, and isopropylene groups are preferable.

(Ii) Examples of the compound in which the epoxy group is directly bonded to the alicyclic ring with a single bond include a compound represented by the following formula (II).

In the formula (II), R ′ is a group obtained by removing p —OH from a p-valent alcohol, and p and n represent natural numbers. Examples of the p-valent alcohol [R ′-(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms, etc.). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each () (in parentheses) may be the same or different. Specific examples of the compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, EHPE 3150 (manufactured by Daicel Corporation). Etc.

These alicyclic epoxy compounds (A) can be used alone or in combination of two or more. As the alicyclic epoxy compound (A), 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate represented by the above formula (I-1) and ceroxide 2021P are particularly preferable.

The amount of use (content) of the alicyclic epoxy compound (A) is not particularly limited, but the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B). On the other hand, it is preferably 50 to 90% by weight, more preferably 60 to 90% by weight, still more preferably 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 monoallyl diglycidyl isocyanurate compound (B) is not sufficient, and it may be easily precipitated when placed at room temperature. On the other hand, if the amount of the alicyclic epoxy compound (A) used exceeds 90% by weight, cracks may easily occur when an optical semiconductor device is produced. Sum of contents of alicyclic epoxy compound (A) and monoallyl diglycidyl isocyanurate compound (B) in the total amount (100% by weight) of component (A), component (B), and component (C) (total amount) ) Is not particularly limited, but is preferably 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) with respect to the total amount (100% by weight) of the curable epoxy resin composition is particularly limited. However, it is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, and 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 content of the alicyclic epoxy compound (A) with respect to the total amount of the curable epoxy resin composition (100% by weight) is: Although not particularly limited, it is preferably 25 to 90% by weight, more preferably 30 to 85% by weight, and still more preferably 35 to 80% by weight.

<Monoallyl diglycidyl isocyanurate compound (B)>
The monoallyl diglycidyl isocyanurate 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 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, and octyl groups. It is done. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl and isopropyl groups is preferred. R ¹ and R ² in the above formula (1) are particularly preferably hydrogen atoms.

Representative examples of the monoallyl diglycidyl isocyanurate compound (B) include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methyl And propenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, and the like. In addition, a monoallyl diglycidyl isocyanurate compound (B) can be used individually or in combination of 2 or more types.

The monoallyl diglycidyl isocyanurate compound (B) can be arbitrarily mixed as long as it dissolves in the alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B). The ratio of the alicyclic epoxy compound (A): monoallyl diglycidyl isocyanurate compound (B) is preferably 50:50 to 90:10 (weight ratio). Outside this range, it becomes difficult to obtain the solubility of the monoallyl diglycidyl isocyanurate compound (B).

The monoallyl diglycidyl isocyanurate compound (B) may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.

The total amount of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) with respect to the total amount (100% by weight) of the epoxy resin (compound having an epoxy group) is not particularly limited, From the viewpoint of improving light resistance and crack resistance, it is preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 70% by weight or more.

<Siloxane derivative (C) having two or more epoxy groups in the molecule>
The siloxane derivative having two or more epoxy groups in the molecule (in one molecule), which is the component (C) of the curable epoxy resin composition of the present invention, improves the heat resistance and light resistance of the cured product, and is an optical semiconductor. It plays a role of suppressing a decrease in luminous intensity of the device.

The siloxane skeleton in the siloxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited. For example, a cyclic siloxane skeleton; a linear silicone, a cage-type or ladder-type polysilsesquioxane And a polysiloxane skeleton. Among these, as the siloxane skeleton, a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the decrease in luminous intensity. That is, the siloxane derivative (C) having two or more epoxy groups in the molecule is preferably a cyclic siloxane having two or more epoxy groups in the molecule or a linear silicone having two or more epoxy groups in the molecule. In addition, the siloxane derivative (C) which has 2 or more epoxy groups in a molecule | numerator can be used individually or in combination of 2 or more types.

When the siloxane 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 the siloxane ring (the number of silicon atoms forming the siloxane ring) Although it is not particularly limited, it is preferably 2 to 12 and more preferably 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 siloxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited, but is preferably 100 to 3000, more preferably 180 from the viewpoint of improving the heat resistance and light resistance of the cured product. ~ 2000.

The number of epoxy groups in one molecule of the siloxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited as long as it is two or more, but the viewpoint of improving the heat resistance and light resistance of the cured product 2 to 4 (2, 3, or 4) is preferable.

The epoxy equivalent (based on JIS K7236) of the siloxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, 180 to 400 It is preferably 240 to 400, more preferably 240 to 350.

The epoxy group in the siloxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, adjacent two carbons constituting the aliphatic ring. An epoxy group composed of an atom and an oxygen atom (alicyclic epoxy group) is preferable, and among them, a cyclohexene oxide group is particularly preferable.

Specific examples of the siloxane derivative (C) having two or more epoxy groups in the molecule include 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl. ] -2,4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,2 , 4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6,8-dipropyl-2, 4,6,8-tetramethyl-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,6-dipropyl-2,4 6,8-tetramethyl-cyclotetrasiloxane, 2,4,8- Li [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tri [2- ( 3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetra [2- ( 3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,8-tetramethyl-cyclotetrasiloxane, silsesquioxane having an epoxy group, and the like. More specifically, for example, cyclic siloxane having two or more epoxy groups in one molecule represented by the following formula.

Examples of the siloxane derivative (C) having two or more epoxy groups in the molecule include alicyclic epoxy group-containing silicone resins described in JP-A-2008-248169 and JP-A-2008-19422. An organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule can also be used.

Examples of the siloxane derivative (C) having two or more epoxy groups in the molecule include a trade name “X-40-2678” (Shin-Etsu Chemical Co., Ltd.), which is a cyclic siloxane having two or more epoxy groups in the molecule. )), Trade name “X-40-2670” (manufactured by Shin-Etsu Chemical Co., Ltd.), and trade name “X-40-2720” can also be used.

Although the amount (content) of the siloxane derivative (C) having two or more epoxy groups in the molecule is not particularly limited, the total amount (100 weight) of the component (A), the component (B), and the component (C). %) To 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight, and particularly preferably 15 to 40% by weight. When the amount of the siloxane 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 usage-amount of the siloxane derivative (C) which has 2 or more epoxy groups in a molecule | numerator exceeds 60 weight%, the crack resistance of hardened | cured material may fall.

<Curing agent (D)>
The curing agent (D) has a function of curing the compound having an epoxy group. As a hardening | curing agent (D) in this invention, a well-known thru | or usual hardening | curing agent can be used as a hardening | curing agent for epoxy resins. As the curing agent (D) in the present invention, an acid anhydride which is liquid at 25 ° C. is preferable, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride. An acid etc. can be mentioned. In addition, solid acid anhydrides at room temperature (about 25 ° C.) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride are liquid at room temperature (about 25 ° C.). It can be used as the curing agent (D) in the present invention by dissolving in an acid anhydride to form a liquid mixture. In addition, a hardening | curing agent (D) can be used individually or in combination of 2 or more types. As described above, as the curing agent (D), from the viewpoint of heat resistance, light resistance and crack resistance of the cured product, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (a substituent such as an alkyl group is bonded to the ring) Are also preferable).

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

Although it does not specifically limit as usage-amount (content) of a hardening | curing agent (D), It is 50 with respect to the whole quantity (100 weight part) of the compound which has an epoxy group contained in the curable epoxy resin composition of this invention. The amount is preferably -200 parts by weight, more preferably 100-145 parts by weight. More specifically, it is preferably used in a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in all compounds having an epoxy group contained in the curable epoxy resin composition of the present invention. . When the usage-amount of a hardening | curing agent (D) is less than 50 weight part, hardening will become inadequate and there exists a tendency for the toughness of hardened | cured material to fall. On the other hand, when the usage-amount of a hardening | curing agent (D) exceeds 200 weight part, hardened | cured material may color and a hue may deteriorate.

<Curing accelerator (E)>
The curable epoxy resin composition of the present invention further contains a curing accelerator (E). A hardening accelerator (E) is a compound which has a function which accelerates | stimulates a cure rate, when the compound which has an epoxy group hardens | cures with a hardening | curing agent. As the curing accelerator (E), known or conventional curing accelerators can be used. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and salts thereof (for example, Phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), and salts thereof (eg, phosphonium salts) , Sulfonium salts, quaternary ammonium salts, iodonium salts); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; 2-ethyl-4- Imidazoles such as methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphate ester, triphenyl Phosphines such as phosphine; tetraphenylphosphonium tetra (p- tolyl) phosphonium compounds such as borate, tin octylate, organic metal salts such as zinc octylate; metal chelate and the like. A hardening accelerator (E) can be used individually or in mixture of 2 or more types.

In the present invention, as the curing accelerator (E), U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X, 12XD (developed products) (all manufactured by San Apro Co., Ltd.) ), TPP-K, TPP-MK (both manufactured by Hokuko Chemical Co., Ltd.), PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.) and the like can also be used.

The amount of use (content) of the curing accelerator (E) is not particularly limited, but is 0.05 to 0.004 based on the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. The amount is preferably 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight. When the usage-amount of a hardening accelerator (E) is less than 0.05 weight part, the hardening promotion effect may become inadequate. On the other hand, when the usage-amount of a hardening accelerator (E) exceeds 5 weight part, hardened | cured material may color and a hue may deteriorate.

<Curing catalyst (F)>
In the curable epoxy resin composition of the present invention, a curing catalyst (F) may be used instead of the above-described curing agent (D) and curing accelerator (E). Similarly to the case of using the curing agent (D) and the curing accelerator (E), the curing reaction of the compound having an epoxy group can be advanced by using the curing catalyst (F) to obtain a cured product. Although it does not specifically limit as said hardening catalyst (F), The cationic catalyst (cationic polymerization initiator) which generate | occur | produces a cationic seed | species by performing ultraviolet irradiation or heat processing, and starts superposition | polymerization can be used.

Examples of the cation catalyst that generates cation species by ultraviolet irradiation include hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, and hexafluoroarsenate salt. These cationic catalysts can be used alone or in combination of two or more. Examples of the cationic catalyst include trade names “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.), trade names “CD-1010”, “CD-1011”, “CD-1012” (above, manufactured by Sartomer, USA), Commercial products such as trade name “Irgacure 264” (manufactured by Ciba Japan Co., Ltd.) and trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can also be preferably used.

Examples of the cation catalyst that generates cation species by heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, and the like. PP-33, CP-66, CP -77 (manufactured by ADEKA), FC-509 (manufactured by 3M), UVE1014 (manufactured by GE), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L (Sanshin Chemical) Kogyo Co., Ltd.), CG-24-61 (Ciba Japan) and other commercial products can be preferably used. Furthermore, a chelate compound of a metal such as aluminum or titanium and a acetoacetate or diketone compound and a silanol such as triphenylsilanol, or a chelate compound of a metal such as aluminum or titanium and acetoacetate or diketone and bisphenol S The compound with phenols, such as these, may be sufficient. These cationic catalysts can be used alone or in combination of two or more.

The use amount (content) of the curing catalyst (F) is not particularly limited, but is 0.01 to 15 with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. Part by weight is preferable, more preferably 0.01 to 12 parts by weight, still 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) within this range, a cured product having excellent heat resistance, light resistance and transparency can be obtained.

<Rubber particles>
The curable epoxy resin composition of the present invention may contain rubber particles. Examples of rubber particles include particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, particulate SBR (styrene-butadiene rubber), and the like. The rubber particle has a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion, and a functional group capable of reacting with an alicyclic epoxy compound on the surface. Rubber particles having a hydroxyl group and / or a carboxyl group, an average particle size of 10 nm to 500 nm, and a maximum particle size of 50 nm to 1000 nm, wherein the refractive index of the rubber particles and the curable epoxy resin composition Rubber particles having a difference from the refractive index of the cured product within ± 0.02 may be used. The blending amount of the rubber particles can be appropriately adjusted as necessary and is not particularly limited, but with respect to the total amount of the compound having an epoxy group contained in the curable epoxy resin composition (100 parts by weight), The amount is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight. If the amount of rubber particles used is less than 0.5 parts by weight, the crack resistance of the cured product tends to be reduced. On the other hand, if the amount of rubber particles used exceeds 30 parts by weight, the heat resistance and transparency of the cured product are reduced. Tend to decrease.

<Additives>
In addition to the above, various additives can be used in the curable epoxy resin composition of the present invention as long as the effects of the present invention are not impaired. For example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is used as the additive, the reaction can be allowed to proceed slowly. In addition, silicone and fluorine antifoaming agents, leveling agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, surfactants, silica, alumina, as long as viscosity and transparency are not impaired. Conventional additives such as inorganic fillers, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, mold release agents and the like can be used.

<Hardened product>
By curing the curable epoxy resin composition of the present invention, a cured product having excellent physical properties such as transparency, heat resistance, light resistance, and crack resistance can be obtained. The heating temperature (curing temperature) during curing is not particularly limited, but is preferably 45 to 200 ° C, more preferably 100 to 190 ° C, and still more preferably 100 to 180 ° C. Further, the heating time (curing time) for curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and further preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit value in the above range, curing is insufficient. On the contrary, when the curing temperature and the curing time are higher than the upper limit value in the above range, the resin component may be decomposed. Although the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased.

<Resin composition for optical semiconductor encapsulation>
The resin composition for optical semiconductor encapsulation of the present invention comprises the curable epoxy resin composition of the present invention. By using the resin composition for encapsulating an optical semiconductor of the present invention, the optical semiconductor element was sealed over time with a cured product excellent in various properties such as transparency, heat resistance, light resistance, and crack resistance. An optical semiconductor device in which the luminous intensity is unlikely to decrease can be obtained. Even if the optical semiconductor device includes an optical semiconductor element with high output and high brightness, the light intensity is unlikely to decrease with time.

<Optical semiconductor device>
The optical semiconductor device of the present invention is obtained by sealing an optical semiconductor element with the curable epoxy resin composition (resin composition for optical semiconductor sealing) of the present invention. The optical semiconductor element is sealed by injecting the curable epoxy resin composition prepared by the above-described method into a predetermined mold and heating and curing under predetermined conditions. Thereby, an optical semiconductor device in which the optical semiconductor element is sealed with the curable epoxy resin composition is obtained. The curing temperature and the curing time can be set in the same range as described above.

The curable epoxy resin composition of the present invention is not limited to the optical semiconductor (optical semiconductor element) sealing application described above, and includes, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, and a resist. , Composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc. Can do.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Example 1
(A mixture of curing agent, curing accelerator and additive, hereinafter referred to as K agent)
Curing agent (Shin Nippon Rika Co., Ltd., Ricacid MH-700): 100 parts by weight Curing accelerator (San Apro Co., Ltd., U-CAT 18X): 0.5 parts by weight, additive (Wako Pure Chemical Industries, Ltd.) (Ethylene glycol, manufactured by Co., Ltd.): 1 part by weight was mixed evenly using a self-revolving stirrer (manufactured by Shinky Co., Ltd., Narataro Awatori AR-250), defoamed to obtain K agent. Obtained.

Production Example 2
(Epoxy resin)
Monoallyl diglycidyl isocyanurate (Shikoku Kasei Kogyo Co., Ltd., MA-DGIC), alicyclic epoxy compound (manufactured by Daicel Corporation, Celoxide 2021P), and siloxane derivatives having two or more epoxy groups in the molecule (Shin-Etsu) Tables 1 and 2 show Chemical Industry Co., Ltd., X-40-2678; Shin-Etsu Chemical Co., Ltd., X-40-2720; Shin-Etsu Chemical Co., Ltd., X-40-2670). The mixture was mixed according to the formulation (unit: parts by weight), and stirred at 80 ° C. for 1 hour to dissolve monoallyl diglycidyl isocyanurate to obtain an 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 subjected to self-revolving stirring according to the formulation (unit: parts by weight) shown in Table 1. Using a device (manufactured by Shinky Co., Ltd., Awatori Nertaro AR-250), the mixture was 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 (Dacel Chemical Industries, Ltd., Celoxide 2021P) was used as an epoxy resin, and in Comparative Examples 2 to 4, an epoxy resin containing 2 in the molecule. Siloxane derivatives having the above epoxy groups (Shin-Etsu Chemical Co., Ltd., X-40-2678; Shin-Etsu Chemical Co., Ltd., X-40-2720; Shin-Etsu Chemical Co., Ltd., X-40-2670) ) Was used in the same manner as above to obtain a curable epoxy resin composition.
The curable epoxy resin composition is cast on an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1 and then heated in an oven (resin curing oven) at 120 ° C. for 5 hours. Thus, an optical semiconductor device in which the LED element was sealed with the cured resin was obtained. In FIG. 1, 100 is a reflector (a resin composition for reflecting light), 101 is a metal wiring, 102 is an LED element, 103 is a bonding wire, and 104 is a transparent sealing resin (cured product).

Examples 13 to 24, Comparative Examples 5 to 8
In Examples 13 to 24, the epoxy resin obtained in Production Example 2 and a curing catalyst (manufactured by Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-100L) were added according to the formulation (unit: parts by weight) shown in Table 2. Each component was uniformly mixed using a self-revolving stirrer (manufactured by Shinky Co., Ltd., Awatori Nertaro AR-250) and defoamed to obtain a curable epoxy resin composition. Further, as shown in Table 2, in Comparative Example 5, only an alicyclic epoxy compound (Delcel Chemical Industries, Ltd., Celoxide 2021P) was used as an epoxy resin, and in Comparative Examples 6 to 8, 2 in the molecule as an epoxy resin. Siloxane derivatives having the above epoxy groups (Shin-Etsu Chemical Co., Ltd., X-40-2678; Shin-Etsu Chemical Co., Ltd., X-40-2720; Shin-Etsu Chemical Co., Ltd., X-40-2670) ) Was used in the same manner as above to obtain a curable epoxy resin composition.
The curable epoxy resin composition is cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1, and then heated at 110 ° C. for 3 hours using an oven (resin curing oven). Then, the optical semiconductor device which sealed the LED element with the hardened resin was obtained by heating at 140 degreeC for 4 hours.

<Evaluation>
About the curable epoxy resin composition and optical semiconductor device obtained by the Example and the comparative example, the evaluation test was done with the following method.

[Energization test]
The total luminous fluxes of the optical semiconductor devices obtained in the examples and comparative examples were measured using a total luminous flux measuring instrument (referred to as “zero hour total luminous flux”). Furthermore, the total luminous flux after flowing a current of 60 mA through the optical semiconductor device in a thermostat at 85 ° C. for 100 hours was measured (referred to as “total luminous flux after 100 hours”). And luminous intensity retention was computed from the following formula. The results are shown in Tables 1 and 2.
{Luminance retention (%)}
= {Total luminous flux after 100 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

[Solder heat resistance test]
The optical semiconductor devices (two used for each curable epoxy resin composition) obtained in Examples and Comparative Examples were absorbed for 168 hours under the conditions of 30 ° C. and 70% RH, and then reflow oven was used. Heat treatment was performed twice at 260 ° C. for 10 seconds. Thereafter, the length of cracks generated in the sealing resin of the optical semiconductor device (cured product of the curable epoxy resin composition) was observed using a digital microscope (VHX-900, manufactured by Keyence Corporation), Of the two optical semiconductor devices, the number of optical semiconductor devices having cracks having a length of 90 μm or more was measured. The results are shown in Tables 1 and 2.

[Thermal shock test]
The optical semiconductor devices obtained in Examples and Comparative Examples (two used for each curable epoxy resin composition) were exposed in an atmosphere of −40 ° C. for 30 minutes, and then in an atmosphere of 100 ° C. A thermal shock with one cycle of exposure for 30 minutes was applied for 200 cycles using a thermal shock tester. Thereafter, the length of cracks generated in the sealing resin of the optical semiconductor device (cured product of the curable epoxy resin composition) was observed using a digital microscope (VHX-900, manufactured by Keyence Corporation), Of the two optical semiconductor devices, the number of optical semiconductor devices having cracks having a length of 90 μm or more was measured. The results are shown in Tables 1 and 2.

[Comprehensive judgment]
In the energization test, the luminous intensity retention was 90% or more, and in both the solder heat resistance test and the thermal shock test, the number of optical semiconductor devices in which cracks of 90 μm or more occurred was zero. Judgment ○ (good). Other than this, the overall judgment was x (defective). The results are shown in Tables 1 and 2.

In addition, the component used by the Example and the comparative example is as follows.
(Epoxy resin)
CEL2021P (Celoxide 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, manufactured by Daicel Corporation MA-DGIC: monoallyl diglycidyl isocyanurate, manufactured by Shikoku Kasei Kogyo Co., Ltd. X-40 -2678: Siloxane derivative having two epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd. X-40-2720: Siloxane derivative having three epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd. X -40-2670: Siloxane derivative having 4 epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd. (K agent)
Rikacid MH-700: 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Rika Co., Ltd. U-CAT 18X: curing accelerator, manufactured by San Apro Co., Ltd. Ethylene glycol: Wako Pure Chemicals Industrial Co., Ltd. (curing catalyst)
SI-100L (Sun-Aid SI-100L): Arylsulfonium salt, manufactured by Sanshin Chemical Industry Co., Ltd.

Test equipment ・ Resin curing oven Espec Co., Ltd. GPHH-201
-Thermostatic chamber ESPEC Co., Ltd. Small high temperature chamber ST-120B1
・ Total luminous flux measuring machine Optronic Laboratories Multi-spectral Radiation Measurement System OL771
・ Thermal shock tester Espec Co., Ltd. Small thermal shock device TSE-11-A
・ Reflow furnace manufactured by Nippon Antom Co., Ltd., UNI-5016F

100: Reflector (resin composition for light reflection)
101: Metal wiring 102: LED element 103: Bonding wire 104: Transparent sealing resin

The curable epoxy resin composition of the present invention can be preferably used for sealing an optical semiconductor element. In addition, the curable epoxy resin composition of the present invention includes an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, a resist, a composite material, a transparent substrate, a transparent sheet, a transparent film, an optical element, and an optical element. It can also be used for lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and the like.

Claims

Alicyclic epoxy compound (A) and the following formula (1)

[Wherein R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A monoallyl diglycidyl isocyanurate compound (B) represented by the formula, a siloxane derivative (C) having two or more epoxy groups in the molecule, a curing agent (D), and a curing accelerator (E). A curable epoxy resin composition characterized by the above.
Alicyclic epoxy compound (A) and the following formula (1)

[Wherein R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
A curable epoxy resin comprising a monoallyl diglycidyl isocyanurate compound (B) represented by the formula: a siloxane derivative (C) having two or more epoxy groups in the molecule; and a curing catalyst (F). Composition.
The content of the siloxane derivative (C) having two or more epoxy groups in the molecule is from 5 to 5 with respect to the total amount (100% by weight) of the component (A), the component (B), and the component (C). The curable epoxy resin composition according to claim 1 or 2, which is 60% by weight.
The curable epoxy resin composition according to any one of claims 1 to 3, wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is a cyclohexene oxide group.
The alicyclic epoxy compound (A) is represented by the following formula (I-1)

The curable epoxy resin composition according to any one of claims 1 to 4, which is a compound represented by the formula:
A cured product obtained by curing the curable epoxy resin composition according to any one of claims 1 to 5.
A resin composition for optical semiconductor encapsulation comprising the curable epoxy resin composition according to any one of claims 1 to 5.
An optical semiconductor device in which an optical semiconductor element is sealed with the resin composition for sealing an optical semiconductor according to claim 7.