WO2012093590A1

WO2012093590A1 - Curable epoxy resin composition

Info

Publication number: WO2012093590A1
Application number: PCT/JP2011/079688
Authority: WO
Inventors: 巽淳郎; 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: CN103168060A; TW201235375A; JPWO2012093590A1; KR20140009201A; JP5919200B2

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 and which exhibits excellent reflow-resistant properties (excellent heat resistance during reflow operations). This curable resin composition is characterized by comprising (A) an alicyclic epoxy compound, (B) a monoallyl diglycidyl isocyanurate compound represented by formula (1), (C) a polycarbonate polyol, and (D) a curing agent or (E) a curing catalyst. 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, a resin composition for optical semiconductor encapsulation comprising the curable epoxy resin composition, and the optical semiconductor encapsulation. The present invention relates to an optical semiconductor device in which an optical semiconductor element is sealed using a resin composition for use.

In recent years, the output of optical semiconductor devices has been increased, and high heat resistance and light resistance are required for resins used in such 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 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, even when the composition is used as a sealing resin for a high-power 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 is a problem that the luminous intensity of the light output from the optical semiconductor device is lowered.

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, the cured products of these alicyclic epoxy resins are vulnerable to various stresses, and when a thermal shock such as a cold cycle (repeating heating and cooling) is applied, cracks (cracks) occur. Had.

The optical semiconductor device usually undergoes a reflow process for joining the electrodes of the optical semiconductor device to the wiring board by soldering. In recent years, lead-free solder having a high melting point has been used as a solder as a bonding material, and the heat treatment in the reflow process has become a higher temperature (for example, the peak temperature is 240 to 260 ° C.). . Under such circumstances, in the conventional optical semiconductor device, there is a problem of deterioration such that the sealing resin is peeled off from the lead frame of the optical semiconductor device due to the heat treatment in the reflow process, or the sealing resin is cracked. Was found to occur.

For this reason, as a sealing resin in an optical semiconductor device, a transparent sealing resin that has high heat resistance, light resistance, and crack resistance and also has excellent reflow resistance is currently required. . In this specification, “reflow resistance” refers to a characteristic that does not cause peeling or cracking of the sealing resin from the lead frame when the optical semiconductor device is heat-treated in the reflow process.

Accordingly, an object of the present invention is to provide a curable epoxy resin composition that has a high transparency, heat resistance, light resistance, and crack resistance, and gives a cured product excellent in reflow resistance.
Another object of the present invention is a cured product obtained by curing the above curable epoxy resin composition, having high transparency, heat resistance, light resistance, and crack resistance, and having excellent reflow resistance. Is to provide.
Another object of the present invention is to provide an optical semiconductor sealing resin composition comprising the above-mentioned curable epoxy resin composition, which provides an optical semiconductor device in which deterioration due to heat treatment in the reflow process and a decrease in light intensity over time are suppressed. To provide things.
Another object of the present invention is to suppress degradation due to heat treatment in the reflow process and decrease in light intensity over time, which are obtained by sealing an optical semiconductor element using the above resin composition for optical semiconductor sealing. Another object is to provide an optical semiconductor device.

As a result of intensive studies to solve the above problems, the inventors of the present invention include an alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, and a polycarbonate polyol as essential components, and further includes a curing agent or a curing catalyst. An optical semiconductor device in which an epoxy resin composition provides a cured product having high transparency, heat resistance, light resistance, crack resistance, and reflow resistance, and an optical semiconductor element is sealed with the cured product is a reflow process. As a result, it was found that deterioration due to heat treatment and a decrease in light intensity over time hardly occur.

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 curable epoxy resin composition comprising a monoallyl diglycidyl isocyanurate compound (B) represented by the following formula, a polycarbonate polyol (C), and a curing agent (D) or a curing catalyst (E): To do.

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.

Furthermore, the said curable epoxy resin composition containing a hardening accelerator (F) is provided.

Furthermore, the curable epoxy resin composition containing rubber particles is provided.

Furthermore, the curable epoxy resin composition containing an acrylic block copolymer 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, it has high heat resistance, light resistance, transparency, and crack resistance by curing the resin composition, and also has reflow resistance. An excellent cured product can be obtained. In addition, the optical semiconductor device in which the optical semiconductor element is sealed using the curable epoxy resin composition of the present invention is excellent because it is not easily deteriorated by high-temperature treatment in the reflow process and the light intensity is not easily lowered over time. It has quality and durability.

FIG. 1 is a schematic view showing an embodiment of an optical semiconductor device in which an element (optical semiconductor element) is sealed with a curable epoxy resin composition of the present invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. FIG. 2 is an example of the surface temperature profile of the optical semiconductor device in the solder heat resistance test of the example (temperature profile in one of the two heating operations).

<Curable epoxy resin composition>
The curable epoxy resin composition of the present invention comprises 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]
It contains the monoallyl diglycidyl isocyanurate compound (B) represented by these, a polycarbonate polyol (C), and a hardening | curing agent (D) or a curing catalyst (E), It is characterized by the above-mentioned. If necessary, the curable epoxy resin composition of the present invention may further contain a curing accelerator (F).

<Alicyclic epoxy compound (A)>
The alicyclic epoxy compound (A) used in the present invention includes (i) a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and (ii) an alicyclic ring. Includes compounds in which an epoxy group is directly bonded by a single bond.

(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. Especially, as an alicyclic epoxy group, a cyclohexene oxide group is preferable.

(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 resins are preferred.

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 resin in which X in the formula (I) is a single bond include compounds represented by the following formula.

As such an alicyclic epoxy resin, for example, a commercially available product such as Celoxide 8000 (manufactured by Daicel Corporation) can also be used.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. 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 two of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include the aforementioned groups.

Typical examples of the alicyclic epoxy compound represented by the 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 compounds represented by the following formula (II).

In the formula (II), R ′ is a group obtained by removing p —OH from a p-valent alcohol; 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 50 to 99% 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 formula, 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. Among these, linear or branched alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl and isopropyl groups are preferable. In particular, R ¹ and R ² are preferably hydrogen atoms.

Typical 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, monoallyl diglycidyl isocyanurate compound (B) can be used individually by 1 type 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 solubility.

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) is not particularly limited, but is 50 to 50% based on the total amount (100% by weight) of the epoxy resin (compound having an epoxy group). It is preferably 100% by weight.

<Polycarbonate polyol (C)>
The polycarbonate polyol (C) is a polycarbonate having two or more hydroxyl groups in the molecule. Among these, as the polycarbonate polyol (C), a polycarbonate diol having two terminal hydroxyl groups in the molecule is preferable. The hydroxyl group in the polycarbonate polyol (C) may be an alcoholic hydroxyl group or a phenolic hydroxyl group.

Polycarbonate polyol (C) can be prepared by the same phosgene method or carbonate exchange reaction using dialkyl carbonate or diphenyl carbonate such as dimethyl carbonate and diethyl carbonate (for example, JP 62-187725 A). JP-A-2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420, etc.). Since the carbonate bond of the polycarbonate polyol (C) is hardly subject to thermal decomposition, the cured resin containing the polycarbonate polyol exhibits excellent stability even under high temperature and high humidity. In addition, a polycarbonate polyol (C) can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyol used in the carbonate exchange reaction together with the dialkyl carbonate or diphenyl carbonate include 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,8-octanediol, 1,9-nonanediol, 1,12 -Dodecanediol, butadiene diol, neopentyl glycol, tetramethylene glycol, propylene glycol, dipropylene glycol and the like.

The number average molecular weight of the polycarbonate polyol (C) is not particularly limited, but is preferably 200 to 10,000, more preferably 300 to 5,000, and still more preferably 400 to 4,000. If the number average molecular weight is less than 200, it may be difficult to obtain the effects of lowering the elastic modulus and improving the bending strength. On the other hand, when the number average molecular weight exceeds 10,000, it may not be liquid at normal temperature (25 ° C.) and may be difficult to handle. The number average molecular weight can be calculated from the following formula using the hydroxyl value of polycarbonate polyol.
[Number average molecular weight] = 56.11 × n / [hydroxyl value] × 1000
However, n represents the number of hydroxyl groups contained in one molecule of polycarbonate polyol. For example, in the case of polycarbonate diol, the number average molecular weight is calculated with n = 2.

Examples of the polycarbonate polyol (C) include Plaxel CD205, CD210, CD220, CD205PL, CD205HL, CD210PL, CD210HL, CD220PL, CD220HL, CD220EC, CD221T (manufactured by Daicel Corp.), ETERNACOLL UH-CARB50, UH-CARB100, UH -CARB300, UH-CARB90 (1/3), UH-CARB90 (1/1), UH-CARB100 (above, Ube Industries, Ltd.), Duranol T6002, T5652, T4672, T4692, G3452 (above, Asahi Kasei Chemicals) Commercially available products such as Kuraray Polyol ND, MPD (above, Kuraray Co., Ltd.) can also be used.

The use amount (content) of the polycarbonate polyol (C) is not particularly limited, but is preferably 1 to 50 parts by weight with respect to the total amount (100 parts by weight) of the component (A) and the component (B). The amount is preferably 1.5 to 30 parts by weight, more preferably 2 to 20 parts by weight. When the blending amount of the polycarbonate polyol (C) exceeds 50 parts by weight, the Tg of the cured product is excessively lowered, the volume change due to heating is increased, and problems such as non-lighting of the optical semiconductor device may occur. Moreover, although bending strength improves, transparency may fall. When the blending amount of the polycarbonate polyol (C) is less than 1 part by weight, the reflow resistance is lowered, and the heat treatment in the reflow process causes peeling or cracking of the sealing resin from the lead frame in the optical semiconductor device. There is a case.

<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), acid anhydrides that are liquid at 25 ° C. are preferable, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, and methylendomethylenetetrahydrophthalic anhydride. 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 curable epoxy resin composition of 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 by 1 type or in combination of 2 or more types.

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 also be used. .

The content of the curing agent (D) is not particularly limited, but is preferably 50 to 200 parts by weight with respect to 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 100 to 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 the compounds having epoxy groups contained in the curable epoxy resin composition. When the amount of the curing agent (D) used is less than 50 parts by weight, curing tends to be insufficient, and the toughness of the cured product tends to decrease, while the amount of the curing agent (D) used exceeds 200 parts by weight. When the cured product is colored, the hue may deteriorate.

<Curing catalyst (E)>
In the present invention, as the curing catalyst (E), a cationic catalyst that initiates polymerization by generating cationic species by performing ultraviolet irradiation or heat treatment may be used. In addition, a curing catalyst (E) can be used individually by 1 type or in combination of 2 or more types.

Examples of the cation catalyst that generates cation species by ultraviolet irradiation include hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, hexafluoroarsenate salt, and the like. UVACURE 1590 (Daicel Cytec) (Commercially available), CD-1010, CD-1011, CD-1012 (manufactured by Sartomer, USA), Irgacure 264 (manufactured by Ciba Japan), CIT-1682 (manufactured by Nippon Soda Co., Ltd.) Can be preferably used.

Examples of the cation catalyst that generates a 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) Commercially available products such as Kogyo Co., Ltd. and CG-24-61 (Ciba Japan Co., Ltd.) 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.

The content of the curing catalyst (E) is not particularly limited, but is preferably 0.01 to 15 parts by weight with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. More preferred is 0.01 to 12 parts by weight, still more preferred is 0.05 to 10 parts by weight, and particularly preferred is 0.1 to 10 parts by weight. By using the curing catalyst (E) within this range, a cured product having excellent heat resistance, light resistance and transparency can be obtained.

<Curing accelerator (F)>
The curable epoxy resin composition of the present invention may contain a curing accelerator (F). A hardening accelerator (F) 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. In particular, it is often used in combination with a curing agent (D). As the curing accelerator (F), 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. The said hardening accelerator (F) can be used individually or in mixture of 2 or more types.

In the present invention, U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 410, U-CAT 18X, 12XD (development products) (all developed products) are used as curing accelerators (F). Commercially available products such as San Apro Co., Ltd., TPP-K, TPP-MK (both from Hokuko Chemical Co., Ltd.) and PX-4ET (Nippon Chemical Industry Co., Ltd.) can also be used.

The content of the curing accelerator (F) is not particularly limited, but is 0.05 to 5 parts by weight with respect to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. More preferred is 0.1 to 3 parts by weight, still more preferred is 0.2 to 3 parts by weight, and particularly preferred is 0.25 to 2.5 parts by weight. When the usage-amount of a hardening accelerator (F) 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 (F) exceeds 5 weight part, hardened | cured material may color and a hue may deteriorate.

<Acrylic block copolymer>
The curable epoxy resin composition of the present invention preferably further contains an acrylic block copolymer from the viewpoint of suppressing a decrease in luminous intensity with time of the optical semiconductor device. More specifically, when the curable epoxy resin composition of the present invention contains an acrylic block copolymer, the optical semiconductor device encapsulated with the curable epoxy resin composition has a particularly high brightness and high output. However, the light intensity tends not to decrease. That is, by using the acrylic block copolymer, a cured product obtained by curing the curable epoxy resin composition of the present invention can exhibit higher levels of heat resistance, light resistance, and crack resistance.

The acrylic block copolymer is a block copolymer containing an acrylic monomer as an essential monomer component. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylic acid. (Meth) acrylic acid alkyl esters such as t-butyl acid, 2-ethylhexyl methacrylate, lauryl methacrylate and stearyl methacrylate; (meth) acrylic acid esters having an alicyclic structure such as cyclohexyl acrylate and cyclohexyl methacrylate; methacryl (Meth) acrylic acid ester having an aromatic ring such as benzyl acid; (fluoro) alkyl ester of (meth) acrylic acid such as 2-trifluoroethyl methacrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, etc. Min A carboxyl group-containing acrylic monomer having a carboxyl group therein; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacryl Hydroxyl group-containing acrylic monomer having hydroxyl group in molecule such as 4-hydroxybutyl acid, mono (meth) acrylic acid ester of glycerin; molecule such as glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate Acrylic monomer having epoxy group in it; Allyl group-containing acrylic monomer having allyl group in molecule such as allyl acrylate and allyl methacrylate; γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyl Silane group-containing acrylic monomer having hydrolyzable silyl group in the molecule such as oxypropyltriethoxysilane; benzotriazole such as 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole And UV-absorbing acrylic monomers having a UV-absorbing group.

In the acrylic block copolymer, a monomer other than the acrylic monomer may be used as a monomer component. Examples of the monomer other than the acrylic monomer include aromatic vinyl compounds such as styrene and α-methylstyrene, conjugated dienes such as butadiene and isoprene, and olefins such as ethylene, propylene and isobutene.

Although it does not specifically limit as said acrylic block copolymer, For example, the diblock copolymer which consists of two polymer blocks, the triblock copolymer which consists of three polymer blocks, four or more polymer blocks And a multi-block copolymer composed of these.

Among these, as the acrylic block copolymer, from the viewpoint of improving heat resistance, light resistance, and crack resistance, a polymer block (S) (soft block) having a low glass transition temperature (Tg) and a polymer block ( A block copolymer in which polymer blocks (H) (hard blocks) having a higher Tg than S) are alternately arranged is preferred, more preferably a polymer block (S) in the middle and a polymer at both ends thereof. A triblock copolymer having an HSH structure having a block (H) is preferred. In addition, although Tg of the polymer which comprises the polymer block (S) of the said acrylic block copolymer is not specifically limited, Less than 30 degreeC is preferable. Moreover, Tg of the polymer which comprises a polymer block (H) is although it does not specifically limit, 30 degreeC or more is preferable. When the said acrylic block copolymer has a some polymer block (H), each polymer block (H) may have the same composition and may differ. Similarly, also when the said acrylic block copolymer has a some polymer block (S), each polymer block (S) may have the same composition and may differ.

The monomer component constituting the polymer block (H) in the acrylic block copolymer (such as the triblock copolymer having the HSH structure) is not particularly limited. For example, the Tg of the homopolymer is Examples thereof include monomers having a temperature of 30 ° C. or higher, and more specifically, methyl methacrylate, styrene, acrylamide, acrylonitrile and the like. On the other hand, the monomer component constituting the polymer block (S) in the acrylic block copolymer is not particularly limited, and examples thereof include monomers having a Tg of a homopolymer of less than 30 ° C., and more specifically, Acrylic acid C _2-10 alkyl ester such as butyl acrylate and 2-ethylhexyl acrylate, butadiene (1,4-butadiene) and the like.

As a preferable specific example of the acrylic block copolymer in the curable epoxy resin composition of the present invention, for example, the polymer block (S) is a polymer composed of butyl acrylate (BA) as a main monomer, Polymethyl methacrylate-block-polybutyl acrylate-block-polymethyl methacrylate terpolymer (PMMA-b-PBA-b-), wherein the polymer block (H) is a polymer composed mainly of methyl methacrylate (MMA). PMMA) and the like. The PMMA-b-PBA-b-PMMA is preferable from the viewpoint of improving heat resistance, light resistance, and crack resistance. The PMMA-b-PBA-b-PMMA is a hydrophilic group (eg, hydroxyl group, carboxyl group, amino group) for the purpose of improving compatibility with the component (A) and the component (B), if necessary. Etc.) such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid and the like may be copolymerized with PMMA blocks and / or PBA blocks. .

The number average molecular weight of the acrylic block copolymer is not particularly limited, but is preferably 3000 to 500,000, more preferably 10,000 to 300,000, and still more preferably 30,000 to 400,000. If the number average molecular weight is less than 3000 (particularly less than 10,000), the toughness of the cured product may not be sufficient, and crack resistance may be reduced. On the other hand, when the number average molecular weight exceeds 500,000, the compatibility with the alicyclic epoxy compound (A) is lowered, and the transparency of the cured product may be lowered. The number average molecular weight can be calculated, for example, from a molecular weight in terms of standard polystyrene measured by a gel permeation chromatography method (GPC method).

The acrylic block copolymer can be produced by a known or commonly used block copolymer production method. As the method for producing the acrylic block copolymer, in particular, living polymerization (living radical polymerization, living anion polymerization, living room polymerization, etc., from the viewpoint of easy control of the molecular weight, molecular weight distribution, terminal structure, etc. of the acrylic block copolymer. Cationic polymerization etc.) are preferred. The living polymerization can be carried out by a known or conventional method.

Examples of the acrylic block copolymer include, for example, trade names “Nanostrength M52N”, “Nanostrength M22N”, “Nanostrength M51”, “Nanostrength M52”, “Nanostrength M53” (manufactured by Arkema Co., Ltd.) , PMMA-b-PBA-b-PMMA), commercial names such as “NanoStrength E21”, “NanoStrength E41” (manufactured by Arkema Co., Ltd., PSt (polystyrene) -b-PBA-b-PMMA) It can also be used.

The amount of the acrylic block copolymer used (content) is not particularly limited, but is preferably 1 to 30 parts by weight with respect to the total amount (100 parts by weight) of the component (A) and the component (B). The amount is more preferably 3 to 15 parts by weight, still more preferably 5 to 10 parts by weight. When the usage-amount of an acrylic block copolymer is less than 1 weight part, the toughness of hardened | cured material may not be enough, and heat resistance and light resistance may fall. On the other hand, when the usage-amount of an acrylic block copolymer exceeds 30 weight part, compatibility with an alicyclic epoxy compound (A) may fall, and transparency of hardened | cured material may fall.

<Rubber particles>
The curable epoxy resin composition of the present invention may further contain rubber particles. Examples of the rubber particles include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). The rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion. The rubber particles are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component, and react with a compound having an epoxy group such as an alicyclic epoxy resin (A) on the surface. Rubber particles having a hydroxyl group and / or a carboxyl group (either one or both of a hydroxyl group and a carboxyl group) as the functional group to be obtained are preferred. When there is no hydroxyl group and / or carboxyl group on the surface of the rubber particles, the cured product becomes clouded by a thermal shock such as a cold cycle and the transparency is lowered, which is not preferable.

The polymer constituting the core portion having rubber elasticity in the rubber particles is not particularly limited, but (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are used. The essential monomer component is preferred. The polymer constituting the core portion having rubber elasticity includes, for example, aromatic vinyl such as styrene and α-methylstyrene; nitrile such as acrylonitrile and methacrylonitrile; conjugated diene such as butadiene and isoprene; ethylene, propylene, Olefin such as isobutene may be included as a monomer component.

Especially, the polymer which comprises the said core part which has the rubber elasticity contains 1 type, or 2 or more types selected from the group which consists of aromatic vinyl, a nitrile, and a conjugated diene with a (meth) acrylic acid ester as a monomer component. It is preferable to include it in combination. That is, as the polymer constituting the core part, for example, (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene and other binary copolymers; (meth) acrylic acid ester / aromatic And terpolymers such as group vinyl / conjugated dienes. The polymer constituting the core part may contain silicone such as polydimethylsiloxane and polyphenylmethylsiloxane, polyurethane, and the like.

The polymer constituting the core part includes, as other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc. One monomer (one molecule) may contain a reactive crosslinking monomer having two or more reactive functional groups.

The core part of the rubber particles is a core part composed of a (meth) acrylic ester / aromatic vinyl binary copolymer (particularly butyl acrylate / styrene). It is preferable in that the rate can be easily adjusted.

The core portion of the rubber particles can be manufactured by a commonly used method, for example, by a method of polymerizing the monomer by an emulsion polymerization method. In the emulsion polymerization method, the whole amount of the monomer may be charged at once and may be polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently to polymerize, Furthermore, a polymerization method using seed particles may be used.

The polymer constituting the shell layer of the rubber particles is preferably a polymer different from the polymer constituting the core portion. In addition, as described above, the shell layer preferably has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as the alicyclic epoxy compound (A). Thereby, especially with respect to the hardened | cured material which can improve adhesiveness in an interface with an alicyclic epoxy compound (A), and hardened | cured the curable epoxy resin composition containing the rubber particle which has this shell layer. , Excellent crack resistance can be exhibited. Moreover, the fall of the glass transition temperature of hardened | cured material can also be prevented.

The polymer constituting the shell layer preferably contains a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component. For example, when butyl acrylate is used as the (meth) acrylic acid ester in the core part, (meth) acrylic acid esters other than butyl acrylate (for example, (meth) acrylic) It is preferable to use methyl acid, ethyl (meth) acrylate, butyl methacrylate and the like. Examples of the monomer component that may be contained in addition to the (meth) acrylic acid ester include aromatic vinyl such as styrene and α-methylstyrene, and nitrile such as acrylonitrile and methacrylonitrile. In the rubber particles, as a monomer component constituting the shell layer, it is preferable to contain the monomer alone or in combination of two or more, together with (meth) acrylic acid ester, and particularly at least aromatic vinyl. Is preferable in that the refractive index of the rubber particles can be easily adjusted.

Further, the polymer constituting the shell layer forms a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component. , Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, α, β-unsaturated acids such as (meth) acrylic acid, α, β-unsaturated acid anhydrides such as maleic anhydride, etc. It is preferable to contain the monomer.

The polymer constituting the shell layer in the rubber particles preferably contains one or more selected from the above monomers in combination with (meth) acrylic acid ester as a monomer component. That is, the shell layer is composed of, for example, a ternary copolymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / α, β-unsaturated acid. A shell layer composed of a polymer or the like is preferable.

Further, the polymer constituting the shell layer includes, as the other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, trimethyl, as well as the above-described monomer. A reactive crosslinking monomer having two or more reactive functional groups may be contained in one monomer (one molecule) such as allyl cyanurate, diallyl phthalate, or butylene glycol diacrylate.

The rubber particles (rubber particles having a core-shell structure) can be obtained by covering the core portion with a shell layer. Examples of the method of coating the core part with a shell layer include a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a copolymer constituting the shell layer, and the above method Examples thereof include a graft polymerization method in which the core portion having rubber elasticity obtained by the above is used as a trunk component, and each component constituting the shell layer is used as a branch component.

The average particle diameter of the rubber particles is not particularly limited, but is preferably 10 to 500 nm, more preferably 20 to 400 nm. The maximum particle size of the rubber particles is not particularly limited, but is preferably 50 to 1000 nm, more preferably 100 to 800 nm. If the average particle diameter exceeds 500 nm or the maximum particle diameter exceeds 1000 nm, the dispersibility of the rubber particles in the cured product may be reduced, and crack resistance may be reduced. On the other hand, if the average particle size is less than 10 nm or the maximum particle size is less than 50 nm, the effect of improving the crack resistance of the cured product may be difficult to obtain.

The refractive index of the rubber particles is not particularly limited, but is preferably 1.40 to 1.60, more preferably 1.42 to 1.58. The difference between the refractive index of the rubber particles and the refractive index of the cured product obtained by curing the curable epoxy resin composition (the curable epoxy resin composition of the present invention) containing the rubber particles is ± 0.00. It is preferably within 03 (−0.03 to 0.03). When the difference in refractive index exceeds ± 0.03, the transparency of the cured product decreases, sometimes it becomes cloudy, and the light intensity of the optical semiconductor device tends to decrease, thereby losing the function of the optical semiconductor device. There is a case.

The refractive index of the rubber particles is, for example, by casting 1 g of rubber particles into a mold and compression molding at 210 ° C. and 4 MPa to obtain a flat plate having a thickness of 1 mm. From the obtained flat plate, a test piece having a length of 20 mm × width of 6 mm And using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate solution, It can be determined by measuring the refractive index at 20 ° C. and sodium D line.

The refractive index of the cured product of the curable epoxy resin composition of the present invention is, for example, 20 mm long × 6 mm wide × 1 mm thick from a cured product obtained by the heat curing method described in the section of the optical semiconductor device below. Using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) with the test piece cut out and the prism and the test piece in close contact using monobromonaphthalene as an intermediate solution And it can obtain | require by measuring the refractive index in 20 degreeC and a sodium D line | wire.

The content (blending amount) of the rubber particles in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. On the other hand, the amount is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the content of the rubber particles is less than 0.5 parts by weight, the crack resistance of the cured product tends to decrease. On the other hand, when the content of the rubber particles exceeds 30 parts by weight, the heat resistance of the cured product tends 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, it is possible to obtain a cured product having excellent physical properties such as heat resistance, light resistance, transparency, and crack resistance, and also excellent reflow resistance. it can. The heating temperature (curing temperature) at the time of curing is not particularly limited, but is preferably 45 to 200 ° C, more preferably 100 to 190 ° C, 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. The curing conditions depend on various conditions, but can be appropriately adjusted by shortening the curing time when the curing temperature is high, and increasing the curing time when the curing temperature is low.

<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 sealing an optical semiconductor element using the resin composition for optical semiconductor encapsulation of the present invention, it is excellent in various physical properties such as heat resistance, light resistance, transparency, and crack resistance, and further in reflow resistance. In addition, an optical semiconductor device in which the optical semiconductor element is sealed with an excellent cured product can be obtained.

<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 the same as described above. The optical semiconductor device of the present invention is less likely to be deteriorated by heat treatment in the reflow process, and the light intensity is less likely to decrease with time.

Generally, in an optical semiconductor device, an optical semiconductor element 102 is fixed to a lead frame by a die bond material 105 as shown in FIG. The present inventors have found that the reflow resistance can also be improved by optimizing the die bond material in the optical semiconductor device. More specifically, when the optical semiconductor device is heat-treated in the reflow process, a die bond material (high adhesiveness / durability) that prevents the optical semiconductor element from being peeled off from the lead frame due to stress caused by the volume change of the sealing resin. It is important to select a die bond material. This is because when the optical semiconductor element is peeled from the lead frame, the sealing resin around the semiconductor element is easily peeled or cracked, and the optical semiconductor device is significantly deteriorated due to the heat treatment in the reflow process. Therefore, in order to improve the reflow resistance and prevent deterioration of the optical semiconductor device due to the heat treatment in the reflow process, the curable epoxy resin composition of the present invention is used as a sealing resin (sealing resin), In addition, it is effective to use the above-described high adhesiveness / durability as the die bond material. Examples of the die bond material include a die bond material in which conductive particles or the like (eg, silver particles) are contained in a base polymer such as a polyimide resin, an epoxy resin, or a silicone resin. Examples of such a die bond material include KER-3000 M2, KER-3100 O2, KER-3100 (manufactured by Shin-Etsu Chemical Co., Ltd.), EH1600-G2 (manufactured by Inabata Sangyo Co., Ltd.), CT200, CT284, CT265. (Made by Kyocera Chemical Co., Ltd.).

The curable epoxy resin composition of the present invention is not limited to the above-described optical semiconductor sealing application, and includes, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, a resist, a composite material, and a transparent base. It can also be used as a material, transparent sheet, transparent film, optical element, optical lens, optical member, optical modeling, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, and the like.

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
(Manufacture of rubber particles)
In a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. A monomer mixture consisting of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion is added here. After stirring for 20 minutes to emulsify, 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour for initial seed polymerization. Subsequently, 180.5 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, the remaining amount (about 95% by weight) of butyl acrylate 180.5 g, styrene 48.89 g, divinylbenzene 7.33 g and 0.95 g of sodium dioctyl sulfosuccinate were added to form the core part. The dissolved monomer mixture was continuously added over 2 hours to perform the second seed polymerization, and then aged for 1 hour to obtain a core part.
Next, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, 0.3 g of sodium dioctylsulfosuccinate was dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid and 0.3 g of allyl methacrylate. The monomer mixture was continuously added over 30 minutes to perform seed polymerization. Then, it aged for 1 hour and formed the shell layer which coat | covers a core part.
Next, the mixture was cooled to room temperature (25 ° C.) and filtered through a plastic mesh having an opening of 120 μm to obtain a latex containing rubber particles having a core-shell structure. The obtained latex was frozen at −30 ° C., dehydrated and washed with a suction filter, and then blown and dried at 60 ° C. overnight to obtain rubber particles. The resulting rubber particles had an average particle size of 254 nm and a maximum particle size of 486 nm.

The average particle size and the maximum particle size of the rubber particles are determined based on a nanotrac ^™ particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle. ) Was used to measure the sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is 0 The maximum particle size at the time of exceeding 0.000 was defined as the maximum particle size. In addition, as said sample, what disperse | distributed 1 weight part of rubber particle dispersion | distribution epoxy compounds obtained by the following manufacture example 2 to 20 weight part of tetrahydrofuran was used.

Production Example 2
(Manufacture of rubber particle-dispersed epoxy compounds)
Using a dissolver (1000 rpm, 60 minutes) with 10 parts by weight of the rubber particles obtained in Production Example 1 heated to 60 ° C. under a nitrogen stream, the product name “Celoxide 2021P” (3,4-epoxy) Disperse in 70 parts by weight of cyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (manufactured by Daicel Corp.) and vacuum deaerate to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C .: 624 mPa · s). It was.
The viscosity (viscosity at 25 ° C.) of the rubber particle-dispersed epoxy compound obtained in Production Example 2 (10 parts by weight of rubber particles dispersed in 70 parts by weight of celoxide 2021P) is a digital viscometer (trade name) “DVU-EII type” (manufactured by Tokimec Co., Ltd.).

Production Example 3
(Production of epoxy resin: Examples 1 to 7, Comparative Examples 2 and 3)
Monoaridiglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation), obtained in Production Example 2 A rubber particle-dispersed epoxy resin and a bisphenol A type epoxy resin (trade name “YD-128”, manufactured by Nippon Steel Chemical Co., Ltd.) are mixed according to the formulation (mixing ratio) (unit: parts by weight) shown in Table 1. Then, monoallyl diglycidyl isocyanurate is dissolved by stirring at 80 ° C. for 1 hour, and then a polycarbonate diol (trade name “CD220PL”, manufactured by Daicel Corporation) is blended as shown in Table 1 (unit: parts by weight) Was mixed at 60 ° C. for 1 hour to obtain an epoxy resin (mixture). “-” In Table 1 indicates that the component was not blended, and the same applies to Tables 2 and 3.

Production Example 4
(Production of curing agent composition containing at least curing agent: Examples 1 to 7, Comparative Examples 1 to 3)
Curing agent (acid anhydride) (trade name “Licacid MH-700”, manufactured by Shin Nippon Rika Co., Ltd.) 100 parts by weight, curing accelerator (trade name “U-CAT 18X”, manufactured by San Apro Co., Ltd.) 5 parts by weight, 1 part by weight of additives (trade name “ethylene glycol”, manufactured by Wako Pure Chemical Industries, Ltd.), self-revolving stirrer (trade name “Awatori Netaro AR-250”, Shinki Co., Ltd.) The mixture was uniformly mixed and defoamed to obtain a curing agent composition.

Examples 1 to 7, Comparative Examples 1 to 3
(Manufacture of curable epoxy resin composition)
The epoxy resin obtained in Production Example 3 and the curing agent composition obtained in Production Example 4 were mixed with a self-revolving stirrer (trade name “Awa” so as to have the blending ratio (unit: parts by weight) shown in Table 1. Tori Netaro AR-250 "(manufactured by Shinky Co., Ltd.) was mixed uniformly and defoamed to obtain a curable epoxy resin composition. In the case of Comparative Example 1, the trade name “Celoxide 2021P” (manufactured by Daicel Corporation) was used as the epoxy resin.

(Manufacture of optical semiconductor devices)
The curable epoxy resin composition obtained above is cast into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of an optical semiconductor shown in FIG. 1, and then 5 in a 120 ° C. oven (resin curing oven). An optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured product) heated for a time was obtained. In FIG. 1, 100 is a reflector (light reflecting resin composition), 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, 104 is a transparent sealing resin (cured product), and 105 is a die bond material. Show.

Production Example 5
(Production of epoxy resin: Examples 8 to 14, Comparative Examples 5 and 6)
Monoaridiglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation), obtained in Production Example 2 A rubber particle-dispersed epoxy resin and a bisphenol A type epoxy resin (trade name “YD-128”, manufactured by Nippon Steel Chemical Co., Ltd.) are mixed according to the formulation (mixing ratio) (unit: parts by weight) shown in Table 2. The monoallyl diglycidyl isocyanurate is dissolved by stirring at 80 ° C. for 1 hour, and then a polycarbonate diol (trade name “CD220PL”, manufactured by Daicel Corporation) is blended as shown in Table 2 (unit: parts by weight) Was mixed at 60 ° C. for 1 hour to obtain an epoxy resin (mixture).

Examples 8-14, Comparative Examples 4-6
(Manufacture of curable epoxy resin composition)
The epoxy resin obtained in Production Example 5 and the curing catalyst (trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd.) were prepared so that the blending ratio (unit: parts by weight) shown in Table 2 was obtained. Using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), the mixture was uniformly mixed and defoamed to obtain a curable epoxy resin composition. In the case of Comparative Example 4, the trade name “Celoxide 2021P” (manufactured by Daicel Corporation) was used as the epoxy resin.

(Manufacture of optical semiconductor devices)
The curable epoxy resin composition obtained above is cast into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of an optical semiconductor shown in FIG. 1, and then 5 in a 120 ° C. oven (resin curing oven). An optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured product) heated for a time was obtained.

<Evaluation>
The optical semiconductor devices obtained in Examples 1 to 14 and Comparative Examples 1 to 6 were evaluated by the following method.

[Solder heat resistance test]
The optical semiconductor devices obtained in Examples 1 to 14 and Comparative Examples 1 to 6 (two used for each curable epoxy resin composition) were allowed to stand for 168 hours at 30 ° C. and 70% RH to absorb moisture. I let you. Next, the optical semiconductor device was placed in a reflow furnace (UNI-5016F, manufactured by Nippon Antom Co., Ltd.) and heated under the following heating conditions. Thereafter, the optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then placed in a reflow furnace again and heated under the same conditions. That is, in the solder heat resistance test, the thermal history under the following heating conditions was given twice to the optical semiconductor device.
[Heating conditions (based on surface temperature of optical semiconductor device)]
(1) Preheating: 150 to 190 ° C. for 60 to 120 seconds (2) Main heating after preheating: 217 ° C. or more for 60 to 150 seconds, maximum temperature 260 ° C.
However, the rate of temperature increase when shifting from preheating to main heating was controlled to 3 ° C./second at the maximum.
FIG. 2 shows an example of the surface temperature profile of the optical semiconductor device during heating in the reflow furnace (temperature profile in one of the two heating operations).
Then, the optical semiconductor device was observed using a digital microscope (VHX-900, manufactured by Keyence Corporation), and peeling of the resin was observed on the electrode surface in one or both of the two optical semiconductor devices. The case where the test was performed was determined to be “defective” (defective reflow resistance), and the case where no peeling was observed in any of the two optical semiconductor devices subjected to the test was determined to be “good” (good reflow resistance). The results are shown in Tables 1 and 2.

[Energization test]
The total luminous flux of the optical semiconductor devices obtained in Examples 1 to 14 and Comparative Examples 1 to 6 was measured using a total luminous flux measuring machine.
Further, the total luminous flux after a current of 70 mA was passed through the optical semiconductor device for 1000 hours in a constant temperature bath of 60 ° C. and 90% RH was measured. The luminous intensity retention was calculated from the following equation. The results are shown in Tables 1 and 2.
{Luminance retention (%)}
= {Total luminous flux after 1000 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

[Thermal shock test]
The optical semiconductor devices obtained in Examples 1 to 14 and Comparative Examples 1 to 6 (two used for each curable epoxy resin composition) were subjected to 15 minutes at −40 ° C., followed by 15 minutes at 120 ° C. The thermal shock made into the cycle was added for 1000 cycles using the thermal shock tester. Thereafter, a current of 20 mA was applied to the optical semiconductor device to confirm lighting, and the number of optical semiconductor devices that did not light (the number of non-lighting occurrences) was measured. The results are shown in Tables 1 and 2.

[Comprehensive judgment]
When the determination of the solder heat resistance test was poor, it was determined to be comprehensive determination x (inferior). Out of those judged as good in the solder heat resistance test, those with a luminous intensity retention rate of 90% or more and zero non-lighting occurrence in the thermal shock test were evaluated as a comprehensive judgment ○ (very good), otherwise Was judged as a comprehensive judgment Δ (excellent).

Production Example 6
(Production of epoxy resin: Examples 15 to 18)
Monoalidiglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Chemicals Co., Ltd.), alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation), acrylic block copolymer (product) The name “Nanostrength M52N” (manufactured by Arkema Co., Ltd.) was mixed according to the formulation (mixing ratio) (unit: parts by weight) shown in Table 3 and stirred at 80 ° C. for 1 hour to monoallyl diglycidyl isocyanurate (And acrylic block copolymer) are dissolved, and then polycarbonate diol (trade name “CD220PL”, manufactured by Daicel Corporation) is mixed according to the formulation (unit: parts by weight) shown in Table 3, and 1 at 60 ° C. An epoxy resin (mixture) was obtained by stirring for a period of time.

Examples 15 to 18, Comparative Examples 7 and 8
(Manufacture of curable epoxy resin composition)
The epoxy resin obtained in Production Example 6, the curing agent composition obtained in Production Example 4, and the curing catalyst (trade name “Sun-Aid SI-100L”) so as to have the blending ratio (unit: parts by weight) shown in Table 3 , Manufactured by Sanshin Chemical Industry Co., Ltd.) using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.), defoamed and cured. An epoxy resin composition was obtained. In Comparative Examples 7 and 8, the trade name “Celoxide 2021P” (manufactured by Daicel Corporation) was used as the epoxy resin.

<Evaluation>
The optical semiconductor devices obtained in Examples 15 to 18 and Comparative Examples 7 and 8 were subjected to an energization test by the following method.

[Energization test]
The total luminous fluxes of the optical semiconductor devices obtained in Examples 15 to 18 and Comparative Examples 7 and 8 were measured using a total luminous flux measuring machine. Further, the total luminous flux after a current of 60 mA was passed through the optical semiconductor device for 300 hours in a thermostatic chamber at a temperature of 85 ° C. was measured. The luminous intensity retention was calculated from the following equation. The results are shown in Table 3.
{Luminance retention (%)}
= {Total luminous flux after 300 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

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 Multispectral Radiation Measurement System OL771 manufactured by Optronic Laboratories, USA
・ Thermal shock tester Espec Co., Ltd. Small thermal shock device TSE-11-A

100: Reflector (resin composition for light reflection)
DESCRIPTION OF SYMBOLS 101: Metal wiring 102: LED element 103: Bonding wire 104: Transparent sealing resin 105: Die bond material

The curable epoxy resin composition of the present invention can be preferably used for optical semiconductor sealing applications. 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]
The curable epoxy resin composition characterized by including the monoallyl diglycidyl isocyanurate compound (B) represented by these, a polycarbonate polyol (C), and a hardening | curing agent (D) or a hardening catalyst (E).
The curable epoxy resin composition according to claim 1, 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 claim 2, which is a compound represented by the formula:
The curable epoxy resin composition according to any one of claims 1 to 3, further comprising a curing accelerator (F).
The curable epoxy resin composition according to any one of claims 1 to 4, further comprising rubber particles.
The curable epoxy resin composition according to any one of claims 1 to 5, further comprising an acrylic block copolymer.
A cured product obtained by curing the curable epoxy resin composition according to any one of claims 1 to 6.
A resin composition for encapsulating an optical semiconductor comprising the curable epoxy resin composition according to any one of claims 1 to 6.
An optical semiconductor device in which an optical semiconductor element is sealed with the resin composition for optical semiconductor sealing according to claim 8.