JP2019023316A - Curable epoxy resin composition - Google Patents

Abstract

To provide a curable epoxy resin composition which enables formation of a cured article having high transparency, heat resistance and light resistance and particularly having a high adhesion property and excellent thermal shock resistance, and which can be used as a sealing agent in an optical semiconductor device to improve durability of the optical semiconductor device.SOLUTION: The present invention relates to a curable epoxy resin composition characterized by containing (A) an alicyclic epoxy compound, (B) an isocyanuric acid derivative having at least one oxirane ring in a molecule, and (C) an oxetane compound having at least one oxetane ring in a molecule.SELECTED DRAWING: None

Description

  The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, and an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition About. This application claims the priority of Japanese Patent Application No. 2013-111060 for which it applied to Japan on June 3, 2013, and uses the content here.

  In recent years, the output of optical semiconductor devices has been increased, and in such an optical semiconductor device, a resin (encapsulant) that covers the optical semiconductor element is required to have high heat resistance and light resistance. Conventionally, as a sealing agent for forming a sealing material having high heat resistance, for example, a composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin is known (see Patent Document 1). However, when the composition is used as a sealant for a high-output blue / white light semiconductor, the coloring of the sealant proceeds by light and heat emitted from the optical semiconductor element and should be output originally. As a result, the light is absorbed, and as a result, the intensity of the light output from the optical semiconductor device is lowered with time.

  3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4 as a sealing agent that forms a cured product (sealing material) that has high heat resistance and light resistance and is not easily yellowed -Liquid alicyclic epoxy resins having an alicyclic skeleton such as an adduct of epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and ε-caprolactone and 1,2,8,9-diepoxylimonene are known. ing. However, the cured products of these alicyclic epoxy resins are susceptible to various stresses, and cracks are generated when a thermal shock such as a cooling cycle (repeating heating and cooling periodically) is applied. Etc. had occurred.

JP 2000-344867 A

  The sealing material for the optical semiconductor element in the optical semiconductor device is high enough not to be peeled off from the lead frame or electrode of the optical semiconductor device even when a stimulus such as high temperature or long-time heating or thermal shock is applied. It is required to have adhesion. This is because if the sealing material is peeled off from the lead frame or electrode of the optical semiconductor device, the quality of the optical semiconductor device is significantly deteriorated.

Accordingly, the object of the present invention is to have high transparency, heat resistance, and light resistance, particularly high adhesion, and thermal shock resistance (characteristic that does not easily cause defects such as cracks when a thermal shock is applied). An object of the present invention is to provide a curable epoxy resin composition that can form a cured product excellent in the optical semiconductor device and can improve the durability of the optical semiconductor device by being used as a sealant in the optical semiconductor device.
Another object of the present invention is to provide a cured product having high transparency, heat resistance and light resistance, particularly high adhesion and excellent thermal shock resistance.
Another object of the present invention is to provide an optical semiconductor device with excellent durability that is less likely to cause a decrease in luminous intensity even when a thermal shock or high-temperature heat is applied.

  As a result of intensive studies to solve the above problems, the present inventors have found that an alicyclic epoxy compound, an isocyanuric acid derivative having one or more oxirane rings in the molecule, and one or more oxetane rings in the molecule. The curable epoxy resin composition containing an oxetane compound as an essential component has high transparency, heat resistance, and light resistance, and can form a cured product having particularly high adhesion and excellent thermal shock resistance. It has been found that the durability of an optical semiconductor device can be improved by using it as a sealant in an optical semiconductor device, and the present invention has been completed.

  That is, the present invention relates to an alicyclic epoxy compound (A), an isocyanuric acid derivative (B) having one or more oxirane rings in the molecule, and an oxetane compound (C) having one or more oxetane rings in the molecule. And a curable epoxy resin composition.

［式中、Ｒ¹、Ｒ²は、同一又は異なって、水素原子又は炭素数１〜８のアルキル基を示す。］
で表される化合物である前記の硬化性エポキシ樹脂組成物を提供する。 Furthermore, the isocyanuric acid derivative (B) is represented by the following formula (1-1):

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
The said curable epoxy resin composition which is a compound represented by these is provided.

  Furthermore, the curable epoxy resin composition is provided wherein the oxetane compound (C) is an oxetane compound (C1) having one or more oxetane rings and one hydroxyl group in the molecule.

  Furthermore, the curable epoxy resin composition is provided in which the alicyclic epoxy compound (A) is a compound having a cyclohexene oxide group.

で表される化合物である前記の硬化性エポキシ樹脂組成物を提供する。 Furthermore, 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 curing catalyst (D) is provided.

  Furthermore, the said curable epoxy resin composition containing a hardening | curing agent (E) and a hardening accelerator (F) is provided.

  Furthermore, the said curable epoxy resin composition containing an inorganic filler (G) is provided.

  Furthermore, the said curable epoxy resin composition whose inorganic filler (G) is a glass filler is provided.

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

  Furthermore, the said curable epoxy resin composition which is a resin composition for optical semiconductor sealing is provided.

  Moreover, this invention provides the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the said curable epoxy resin composition.

［式中、Ｒ¹、Ｒ²は、同一又は異なって、水素原子又は炭素数１〜８のアルキル基を示す。］
で表される化合物である（１）に記載の硬化性エポキシ樹脂組成物。
（３）オキセタン化合物（Ｃ）が、分子内に１個以上のオキセタン環及び１個の水酸基を有するオキセタン化合物（Ｃ１）である（１）又は（２）に記載の硬化性エポキシ樹脂組成物。
（４）脂環式エポキシ化合物（Ａ）が、シクロヘキセンオキシド基を有する化合物である（１）〜（３）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（５）脂環式エポキシ化合物（Ａ）が、下記式（Ｉ−１）

で表される化合物である（１）〜（４）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（６）脂環式エポキシ化合物（Ａ）の含有量が、硬化性エポキシ樹脂組成物（１００重量％）に対して、好ましくは５〜９５重量％、より好ましくは１０〜９０重量％、さらに好ましくは１５〜８５重量％である（１）〜（５）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（７）硬化性エポキシ樹脂組成物に含まれるカチオン硬化性化合物の全量（全カチオン硬化性化合物）に対する脂環式エポキシ化合物（Ａ）の割合が、好ましくは１０〜９５重量％、より好ましくは２０〜９０重量％、さらに好ましくは３０〜８０重量％である（１）〜（６）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（８）イソシアヌル酸誘導体（Ｂ）の含有量が、脂環式エポキシ化合物（Ａ）１００重量部に対して、好ましくは５〜１００重量部、より好ましくは８〜８０重量部、さらに好ましくは１０〜６０重量部である（１）〜（７）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（９）硬化性エポキシ樹脂組成物に含まれるカチオン硬化性化合物の全量（１００重量％）に対するイソシアヌル酸誘導体（Ｂ）の割合が、好ましくは１〜４０重量％、より好ましくは５〜３０重量％、さらに好ましくは８〜２５重量％である（１）〜（８）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（１０）オキセタン化合物（Ｃ）が、３，３−ビス（ビニルオキシメチル）オキセタン、３−メチル−３−（ヒドロキシメチル）オキセタン、３−エチル−３−（２−エチルヘキシルオキシメチル）オキセタン、３−エチル−３−（ヒドロキシメチル）オキセタン、３−エチル−３−［（フェノキシ）メチル］オキセタン、３−エチル−３−（ヘキシルオキシメチル）オキセタン、３−エチル−３−（クロロメチル）オキセタン、３，３−ビス（クロロメチル）オキセタン、１，４−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］ベンゼン、ビス｛［１−エチル（３−オキセタニル）］メチル｝エーテル、４，４'−ビス［（３−エチル−３−オキセタニル）メトキシメチル］ビシクロヘキシル、１，４−ビス［（３−エチル−３−オキセタニル）メトキシメチル］シクロヘキサン、１，４−ビス｛〔（３−エチル−３−オキセタニル）メトキシ〕メチル｝ベンゼン、及び３−エチル−３｛〔（３−エチルオキセタン−３−イル）メトキシ〕メチル｝オキセタンからなる群より選択される少なくとも１つである（１）〜（９）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（１１）オキセタン化合物（Ｃ）が、３−エチル−３−（ヒドロキシメチル）オキセタン及び３−メチル−３−（ヒドロキシメチル）オキセタンからなる群より選択される少なくとも１つである（１）〜（９）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（１２）オキセタン化合物（Ｃ）の含有量が、脂環式エポキシ化合物（Ａ）１００重量部に対して、好ましくは１０〜１５０重量部、より好ましくは１５〜１２５重量部、さらに好ましくは２０〜１２０重量部である（１）〜（１１）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（１３）さらに硬化触媒（Ｄ）を含む（１）〜（１２）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（１４）硬化触媒（Ｄ）が、光カチオン重合開始剤、熱カチオン重合開始剤、ルイス酸・アミン錯体、ブレンステッド酸塩類、及びイミダゾール類からなる群より選択される少なくとも一つである（１３）に記載の硬化性エポキシ樹脂組成物。
（１５）硬化触媒（Ｄ）の含有量が、硬化性エポキシ樹脂組成物に含まれるカチオン硬化性化合物の全量１００重量部に対して、好ましくは０．０１〜１５重量部、より好ましくは０．０１〜１２重量部、さらに好ましくは０．０５〜１０重量部、特に好ましくは０．０５〜８重量部である（１３）又は（１４）に記載の硬化性エポキシ樹脂組成物。
（１６）さらに硬化剤（Ｅ）及び硬化促進剤（Ｆ）を含む（１）〜（１５）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（１７）硬化剤（Ｅ）が、酸無水物類（酸無水物系硬化剤）、アミン類（アミン系硬化剤）、ポリアミド樹脂、イミダゾール類（イミダゾール系硬化剤）、ポリメルカプタン類（ポリメルカプタン系硬化剤）、フェノール類（フェノール系硬化剤）、ポリカルボン酸類、ジシアンジアミド類、及び有機酸ヒドラジドからなる群より選択される少なくとも一つである（１６）に記載の硬化性エポキシ樹脂組成物。
（１８）硬化剤（Ｅ）が、酸無水物類(酸無水物系硬化剤)である（１６）又は（１７）に記載の硬化性エポキシ樹脂組成物。
（１９）硬化剤（Ｅ）の含有量が、硬化性エポキシ樹脂組成物に含まれるカチオン硬化性化合物の全量１００重量部に対して、好ましくは５０〜２００重量部、より好ましくは８０〜１５０重量部である（１６）〜（１８）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（２０）硬化促進剤（Ｆ）が、１，８−ジアザビシクロ［５．４．０］ウンデセン−７（ＤＢＵ）又はその塩（例えば、フェノール塩、オクチル酸塩、ｐ−トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩など）；１，５−ジアザビシクロ［４．３．０］ノネン−５（ＤＢＮ）又はその塩（例えば、フェノール塩、オクチル酸塩、ｐ−トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩など）；ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ−ジメチルシクロヘキシルアミンなどの３級アミン；２−エチル−４−メチルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾールなどのイミダゾール；リン酸エステル；トリフェニルホスフィン、トリス（ジメトキシ）ホスフィンなどのホスフィン類；テトラフェニルホスホニウムテトラ（ｐ−トリル）ボレートなどのホスホニウム化合物；オクチル酸亜鉛、オクチル酸スズ、ステアリン酸亜鉛などの有機金属塩；及びアルミニウムアセチルアセトン錯体などの金属キレートからなる群より選択される少なくとも一つである（１６）〜（１９）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（２１）硬化促進剤（Ｆ）の含有量が、硬化性エポキシ樹脂組成物に含まれるカチオン硬化性化合物の全量１００重量部に対して、好ましくは０．０１〜５重量部、より好ましくは０．０３〜３重量部、さらに好ましくは０．０３〜２重量部である（１６）〜（２０）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（２２）さらに無機フィラー（Ｇ）を含む（１）〜（２１）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（２３）無機フィラー（Ｇ）が、シリカフィラー及びガラスフィラーからなる群より選択される少なくとも一つである（２２）に記載の硬化性エポキシ樹脂組成物。
（２４）無機フィラー（Ｇ）がガラスフィラーである（２２）に記載の硬化性エポキシ樹脂組成物。
（２５）無機フィラー（Ｇ）の含有量が、カチオン硬化性化合物の全量１００重量部に対して、好ましくは１〜２５重量部、より好ましくは３〜２０重量部、さらに好ましくは５〜１５重量部である（２２）〜（２４）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（２６）無機フィラー（Ｇ）の含有量が、脂環式エポキシ化合物（Ａ）１００重量部に対して、好ましくは１〜５０重量部、より好ましくは２〜４０重量部、さらに好ましくは３〜３０重量部である（２２）〜（２５）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（２７）（１）〜（２６）のいずれか一つに記載の硬化性エポキシ樹脂組成物を硬化させて得られる硬化物。
（２８）光半導体封止用樹脂組成物である（１）〜（２６）のいずれか一つに記載の硬化性エポキシ樹脂組成物。
（２９）（２８）に記載の硬化性エポキシ樹脂組成物の硬化物により光半導体素子が封止された光半導体装置。 That is, the present invention relates to the following.
(1) An alicyclic epoxy compound (A), an isocyanuric acid derivative (B) having one or more oxirane rings in the molecule, and an oxetane compound (C) having one or more oxetane rings in the molecule. A curable epoxy resin composition comprising:
(2) Isocyanuric acid derivative (B) is represented by the following formula (1-1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
The curable epoxy resin composition as described in (1) which is a compound represented by these.
(3) The curable epoxy resin composition according to (1) or (2), wherein the oxetane compound (C) is an oxetane compound (C1) having one or more oxetane rings and one hydroxyl group in the molecule.
(4) The curable epoxy resin composition according to any one of (1) to (3), wherein the alicyclic epoxy compound (A) is a compound having a cyclohexene oxide group.
(5) The alicyclic epoxy compound (A) is represented by the following formula (I-1)

The curable epoxy resin composition according to any one of (1) to (4), which is a compound represented by:
(6) The content of the alicyclic epoxy compound (A) is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and still more preferably based on the curable epoxy resin composition (100% by weight). Is 15 to 85% by weight, The curable epoxy resin composition according to any one of (1) to (5).
(7) The ratio of the alicyclic epoxy compound (A) to the total amount of the cationic curable compound (total cationic curable compound) contained in the curable epoxy resin composition is preferably 10 to 95% by weight, more preferably 20%. -90 weight%, More preferably, it is 30-80 weight%, The curable epoxy resin composition as described in any one of (1)-(6).
(8) The content of the isocyanuric acid derivative (B) is preferably 5 to 100 parts by weight, more preferably 8 to 80 parts by weight, and still more preferably 10 to 100 parts by weight of the alicyclic epoxy compound (A). The curable epoxy resin composition according to any one of (1) to (7), which is -60 parts by weight.
(9) The ratio of the isocyanuric acid derivative (B) to the total amount (100% by weight) of the cationic curable compound contained in the curable epoxy resin composition is preferably 1 to 40% by weight, more preferably 5 to 30% by weight. The curable epoxy resin composition according to any one of (1) to (8), more preferably 8 to 25% by weight.
(10) Oxetane compound (C) is 3,3-bis (vinyloxymethyl) oxetane, 3-methyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3 -Ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, 4,4 '-Bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [(3-ethyl-3 -Oxetanyl) methoxymethyl] cyclohexane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] The curable epoxy resin composition according to any one of (1) to (9), which is at least one selected from the group consisting of methyl} oxetane.
(11) The oxetane compound (C) is at least one selected from the group consisting of 3-ethyl-3- (hydroxymethyl) oxetane and 3-methyl-3- (hydroxymethyl) oxetane (1) to ( The curable epoxy resin composition according to any one of 9).
(12) The content of the oxetane compound (C) is preferably 10 to 150 parts by weight, more preferably 15 to 125 parts by weight, and still more preferably 20 to 100 parts by weight of the alicyclic epoxy compound (A). The curable epoxy resin composition according to any one of (1) to (11), which is 120 parts by weight.
(13) The curable epoxy resin composition according to any one of (1) to (12), further including a curing catalyst (D).
(14) The curing catalyst (D) is at least one selected from the group consisting of a photocationic polymerization initiator, a thermal cationic polymerization initiator, a Lewis acid / amine complex, a Bronsted acid salt, and an imidazole (13 ) Curable epoxy resin composition.
(15) The content of the curing catalyst (D) is preferably from 0.01 to 15 parts by weight, more preferably from 0.1 to 15 parts by weight, based on 100 parts by weight of the total amount of the cationic curable compounds contained in the curable epoxy resin composition. The curable epoxy resin composition according to (13) or (14), which is from 01 to 12 parts by weight, more preferably from 0.05 to 10 parts by weight, and particularly preferably from 0.05 to 8 parts by weight.
(16) The curable epoxy resin composition according to any one of (1) to (15), further comprising a curing agent (E) and a curing accelerator (F).
(17) The curing agent (E) is an acid anhydride (acid anhydride curing agent), an amine (amine curing agent), a polyamide resin, an imidazole (imidazole curing agent), or a polymercaptan (polymercaptan). Curable epoxy resin composition according to (16), which is at least one selected from the group consisting of (system curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, and organic acid hydrazides.
(18) The curable epoxy resin composition according to (16) or (17), wherein the curing agent (E) is an acid anhydride (an acid anhydride-based curing agent).
(19) The content of the curing agent (E) is preferably 50 to 200 parts by weight, more preferably 80 to 150 parts by weight with respect to 100 parts by weight of the total amount of the cationic curable compound contained in the curable epoxy resin composition. The curable epoxy resin composition according to any one of (16) to (18), which is a part.
(20) The curing accelerator (F) is 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, phenol salt, octylate, p-toluenesulfonate, formic acid Salt, tetraphenylborate salt, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, octylate, p-toluenesulfonate, formate, Tetraphenylborate salts, etc.); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; 2-ethyl-4-methylimidazole, 1-cyanoethyl Imidazoles such as 2-ethyl-4-methylimidazole; phosphate esters; triphenylphosphine, tris (dimeth A) phosphines such as phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organometallic salts such as zinc octylate, tin octylate and zinc stearate; and metal chelates such as aluminum acetylacetone complex The curable epoxy resin composition according to any one of (16) to (19), which is at least one selected from the group.
(21) The content of the curing accelerator (F) is preferably 0.01 to 5 parts by weight, more preferably 0 with respect to 100 parts by weight of the total amount of the cationic curable compounds contained in the curable epoxy resin composition. The curable epoxy resin composition according to any one of (16) to (20), which is 0.03 to 3 parts by weight, more preferably 0.03 to 2 parts by weight.
(22) The curable epoxy resin composition according to any one of (1) to (21), further including an inorganic filler (G).
(23) The curable epoxy resin composition according to (22), wherein the inorganic filler (G) is at least one selected from the group consisting of a silica filler and a glass filler.
(24) The curable epoxy resin composition according to (22), wherein the inorganic filler (G) is a glass filler.
(25) The content of the inorganic filler (G) is preferably 1 to 25 parts by weight, more preferably 3 to 20 parts by weight, and further preferably 5 to 15 parts by weight with respect to 100 parts by weight of the total amount of the cationic curable compound. The curable epoxy resin composition according to any one of (22) to (24), which is a part.
(26) The content of the inorganic filler (G) is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and still more preferably 3 to 100 parts by weight of the alicyclic epoxy compound (A). The curable epoxy resin composition according to any one of (22) to (25), which is 30 parts by weight.
(27) A cured product obtained by curing the curable epoxy resin composition according to any one of (1) to (26).
(28) The curable epoxy resin composition according to any one of (1) to (26), which is a resin composition for sealing an optical semiconductor.
(29) An optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition according to (28).

  Since the curable epoxy resin composition of the present invention has the above configuration, it is cured to form a cured product having high transparency, heat resistance, and light resistance, particularly high adhesion and excellent thermal shock resistance. it can. For this reason, by using the curable epoxy resin composition of the present invention as a sealing agent (an optical semiconductor sealing resin composition) in an optical semiconductor device, the luminous intensity is lowered even when thermal shock or high temperature heat is applied. It is possible to obtain an optical semiconductor device excellent in durability, which is less likely to occur.

It is the schematic which shows one Embodiment of the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of 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) (sometimes referred to as “component (A)”) and an isocyanuric acid derivative (B) having one or more oxirane rings in the molecule. ) (Sometimes referred to as “isocyanuric acid derivative (B)” or “component (B)”) and an oxetane compound (C) having one or more oxetane rings in the molecule (“oxetane compound (C)” or A composition (which may be referred to as “component (C)”) as an essential component (curable composition).

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (A) in 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). As the alicyclic epoxy compound (A), specifically, (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, (Ii) A compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and the like. However, the isocyanuric acid derivative (B) described later is not included in the alicyclic epoxy compound (A).

  The compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (i) is arbitrarily selected from known or commonly used compounds. Can be used. Especially, as said alicyclic epoxy group, a cyclohexene oxide group is preferable.

As the compound (i) having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, a compound having a cyclohexene oxide group from the viewpoint of transparency and heat resistance of the cured product In particular, a compound (alicyclic epoxy compound) represented by the following formula (I) is preferable.

  In the above 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 divalent hydrocarbon groups, alkenylene groups in which some or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected.

  Examples of the compound in which X in the above formula (I) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as a cyclohexylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like, and straight chain or branched chain alkenylene groups having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

  The linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation. An alkenylene group; a group in which a plurality of these groups are linked; 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-10), bis (3,4-epoxycyclohexylmethyl). ) Ether, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2 -Bis (3,4-epoxycyclohexane-1-yl) propane and the like. In the following formulas (I-5) and (I-7), l and m each represent an integer of 1 to 30. R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene. And linear or branched alkylene groups such as a group, a heptylene group, and an octylene group. Among these, C1-C3 linear or branched alkylene groups, such as a methylene group, ethylene group, a propylene group, an isopropylene group, are preferable. N1 to n6 in the following formulas (I-9) and (I-10) each represent an integer of 1 to 30.

Examples of the compound (ii) 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 in the structural formula, and p and n each represent a natural number. Examples of the p-valent alcohol [R ′-(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (such as alcohols having 1 to 15 carbon atoms). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each () (inside parenthesis) may be the same or different. Specifically, as the above-mentioned compound, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, trade name “EHPE3150”, ( Manufactured by Daicel Corporation).

  In the curable epoxy resin composition of the present invention, the alicyclic epoxy compound (A) can be used singly or in combination of two or more. In addition, as the alicyclic epoxy compound (A), for example, commercially available products such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) may be used.

  Among them, as the alicyclic epoxy compound (A), 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate represented by the above formula (I-1) [for example, trade name “Celoxide 2021P” (Daicel Co., Ltd.) etc. are particularly preferred.

  Although content (blending amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, it is 5 to 95 with respect to the curable epoxy resin composition (100% by weight). % By weight is preferable, more preferably 10 to 90% by weight, and still more preferably 15 to 85% by weight. By controlling the content of the alicyclic epoxy compound (A) within the above range, the heat resistance, light resistance, and thermal shock resistance of the cured product tend to be further improved.

  The ratio of the alicyclic epoxy compound (A) to the total amount (total cation curable compound) of the cation curable compound (for example, components (A) to (C)) contained in the curable epoxy resin composition is not particularly limited. However, it is preferably 10 to 95% by weight, more preferably 20 to 90% by weight, and still more preferably 30 to 80% by weight. By controlling the ratio of the alicyclic epoxy compound (A) to the above range, the heat resistance, light resistance, and thermal shock resistance of the cured product tend to be further improved.

[Isocyanuric acid derivative (B)]
The isocyanuric acid derivative (B) in the curable epoxy resin composition of the present invention is a derivative of isocyanuric acid and is a compound having at least one oxirane ring in the molecule. The number of oxirane rings in the molecule of the isocyanuric acid derivative (B) may be one or more, and is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

As an isocyanuric acid derivative (B), the compound represented by following formula (1) is mentioned, for example.

In the formula (1), R ^{X to} R ^Z are the same or different and each represents a hydrogen atom or a monovalent organic group. However, at least one of R ^{X to} R ^Z is a monovalent organic group containing an oxirane ring. Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group); a monovalent aromatic hydrocarbon group (for example, an aryl group); A cyclic group; a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The monovalent organic group may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom). Examples of the monovalent organic group containing an oxirane ring include groups having an oxirane ring such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group, and a cyclohexene oxide group.

More specifically, as the isocyanuric acid derivative (B), a compound represented by the following formula (1-1) (monoallyl diglycidyl isocyanurate compound), a compound represented by the following formula (1-2) ( Diallyl monoglycidyl isocyanurate compound), a compound represented by the following formula (1-3) (triglycidyl isocyanurate compound), and the like.

In said formula (1-1)-(1-3), R < ¹ >, R < ² > is the same or different and shows a hydrogen atom or a C1-C8 alkyl group. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and octyl groups. Examples thereof include a chain or branched alkyl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable. R ¹ and R ² in the above formulas (1-1) to (1-3) are particularly preferably hydrogen atoms.

  Representative examples of the compound represented by the above formula (1-1) include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2 -Methylpropenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, and the like.

  Representative examples of the compound represented by the formula (1-2) include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3-bis ( 2-methylpropenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5- (2-methylepoxypropyl) isocyanurate, and the like.

  Typical examples of the compound represented by the above formula (1-3) include triglycidyl isocyanurate, tris (2-methylepoxypropyl) isocyanurate, and the like.

  The isocyanuric acid derivative (B) may be modified in advance by adding a compound that reacts with an oxirane ring such as an alcohol or an acid anhydride.

  Especially, as an isocyanuric acid derivative (B), the compound represented by the said Formula (1-1)-(1-3) is preferable, More preferably, it is a compound represented by the said Formula (1-1). In the curable epoxy resin composition of the present invention, the isocyanuric acid derivative (B) can be used alone or in combination of two or more. In addition, a commercial item can also be used as an isocyanuric acid derivative (B), For example, a brand name "TEPIC" (made by Nissan Chemical Industries Ltd.), a brand name "MA-DGIC" as such a commercial item. (Shikoku Kasei Kogyo Co., Ltd.), trade name "DA-MGIC" (Shikoku Kasei Kogyo Co., Ltd.), etc. are mentioned.

  Although content (blending amount) of the isocyanuric acid derivative (B) in the curable epoxy resin composition of the present invention is not particularly limited, it is 5 to 100 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). Is preferable, more preferably 8 to 80 parts by weight, still more preferably 10 to 60 parts by weight. By setting the content of the isocyanuric acid derivative (B) to 5 parts by weight or more, the adhesiveness and thermal shock resistance of the cured product tend to be further improved. On the other hand, when the content of the isocyanuric acid derivative (B) exceeds 100 parts by weight, the solubility of the isocyanuric acid derivative (B) in the curable epoxy resin composition is lowered, and the physical properties of the cured product may be adversely affected. .

  The ratio of the isocyanuric acid derivative (B) to the total amount (100% by weight) of the cationically polymerizable compound (cationic curable compound) contained in the curable epoxy resin composition of the present invention is not particularly limited, but is 1 to 40% by weight. Is more preferable, more preferably 5 to 30% by weight, still more preferably 8 to 25% by weight. By setting the proportion of the isocyanuric acid derivative (B) to 1% by weight or more, the adhesion and thermal shock resistance of the cured product tend to be further improved. On the other hand, if the proportion of the isocyanuric acid derivative (B) exceeds 40% by weight, the solubility of the isocyanuric acid derivative (B) in the curable epoxy resin composition is lowered, and the physical properties of the cured product may be adversely affected.

[Oxetane compound (C)]
The oxetane compound (C) in the curable epoxy resin composition of the present invention is a compound having one or more oxetane rings in the molecule. The number of oxetane rings in the molecule of the oxetane compound (C) may be one or more and is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4.

  As the oxetane compound (C), known or conventional oxetane compounds can be used, and are not particularly limited. For example, 3,3-bis (vinyloxymethyl) oxetane, 3-methyl-3- (hydroxymethyl) Oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- ( Hexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-Ethyl (3-oxetanyl)] methyl} ether, 4,4′-bis [(3-ethyl-3- Oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, And 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane.

  Among them, the oxetane compound (C) may be referred to as a compound having one hydroxyl group in the molecule (“oxetane compound (C1)” in terms of further improving the adhesion and thermal shock resistance of the cured product; A compound having one or more oxetane rings and one hydroxyl group in the molecule is preferred. Examples of the oxetane compound (C1) include 3-ethyl-3- (hydroxymethyl) oxetane and 3-methyl-3- (hydroxymethyl) oxetane.

  In the curable epoxy resin composition of the present invention, the oxetane compound (C) can be used singly or in combination of two or more. In addition, a commercial item can also be used as an oxetane compound (C), As such a commercial item, brand name "Aron oxetane OXT-101", "Aron oxetane OXT-221" (above, Toagosei ( Etc.).

  Although content (blending amount) of the oxetane compound (C) in the curable epoxy resin composition of the present invention is not particularly limited, it is 10 to 150 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). More preferably, it is 15-125 weight part, More preferably, it is 20-120 weight part. By setting the content of the oxetane compound (C) to 10 parts by weight or more, the adhesiveness and thermal shock resistance of the cured product tend to be further improved. On the other hand, when the content of the oxetane compound (C) is 150 parts by weight or less, the transparency, heat resistance, and weather resistance of the cured product tend to be further improved.

[Curing catalyst (D)]
The curable epoxy resin composition of the present invention may further contain a curing catalyst (D). The curing catalyst (D) starts and / or accelerates a curing reaction (polymerization reaction) of a cationic curable compound such as an alicyclic epoxy compound (A), an isocyanuric acid derivative (B), or an oxetane compound (C). And a compound having a function of curing the curable epoxy resin composition. The curing catalyst (D) is not particularly limited. For example, a cationic polymerization initiator (photocation polymerization initiator, thermal cation polymerization, which initiates polymerization by generating cationic species by applying light irradiation or heat treatment). Initiators, etc.), Lewis acid / amine complexes, Bronsted acid salts, imidazoles and the like.

  Examples of the photocationic polymerization initiator as the curing catalyst (D) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically. For example, triarylsulfonium hexafluorophosphate (for example, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate), sulfonium salt such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salt); diaryl iodonium hexafluorophosphate Diaryl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodine Iodonium salts such as nium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; pyridinium salts such as N-hexylpyridinium tetrafluoroborate It is done. Moreover, as a photocationic polymerization initiator, for example, trade name “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, the United States) Commercial products such as Sartomer); trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.

  Examples of the thermal cationic polymerization initiator as the curing catalyst (D) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33” and “CP-66”. "CP-77" (manufactured by ADEKA); trade name "FC-509" (manufactured by 3M); trade name "UVE1014" (manufactured by GE); trade name "Sun-Aid SI-60L", “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-150L” (manufactured by Sanshin Chemical Industry Co., Ltd.); trade name “CG-24-61” ( Commercial products such as BASF) can be preferably used. Further, as the thermal cationic polymerization initiator, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketones and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketone Examples thereof include a compound of a chelate compound with a phenol and a phenol such as bisphenol S.

As the Lewis acid / amine complex as the curing catalyst (D), a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited. For example, BF ₃ .n-hexylamine, BF ₃ · monoethylamine, BF ₃ · benzylamine, BF ₃ · diethylamine, BF ₃ · piperidine, BF ₃ · triethylamine, BF ₃ · aniline, BF ₄ - n-hexylamine, BF ₄ - monoethylamine, BF ₄ - benzylamine , BF ₄ · diethylamine, BF ₄ · piperidine, BF ₄ · triethylamine, BF ₄ · aniline, PF ₅ · ethylamine, PF ₅ · isopropylamine, PF ₅ · butylamine, PF ₅ · laurylamine, PF ₅ · benzylamine, AsF _5. Laurylamine etc. are mentioned.

  As the Bronsted acid salts as the curing catalyst (D), known or commonly used Bronsted acid salts can be used, and are not particularly limited. For example, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphoniums. Examples include salts.

  As the imidazole as the curing catalyst (D), known or conventional imidazoles can be used, and are not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl Imidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4 - Mino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine, etc. Is mentioned.

  In the curable epoxy resin composition of the present invention, the curing catalyst (D) can be used singly or in combination of two or more. In addition, as above-mentioned, a commercial item can also be used as a curing catalyst (D).

  The content (blending amount) of the curing catalyst (D) in the curable epoxy resin composition of the present invention is not particularly limited, but is 100 parts by weight based on the total amount of the cationic curable compound contained in the curable epoxy resin composition. 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0.05 to 8 parts by weight. By using the curing catalyst (D) within the above range, the curing rate of the curable epoxy resin composition is increased, and the heat resistance and transparency of the cured product tend to be improved in a balanced manner.

[Curing agent (E)]
The curable epoxy resin composition of the present invention may further contain a curing agent (E) (for example, instead of the curing catalyst (D)). The curing agent (E) works to cure the curable epoxy resin composition by reacting with a cationic curable compound such as an alicyclic epoxy compound (A), an isocyanuric acid derivative (B), or an oxetane compound (C). It is a compound which has this. As the curing agent (E), a known or conventional curing agent can be used as a curing agent for epoxy resin, and is not particularly limited. For example, acid anhydrides (acid anhydride curing agents), amines ( Amine curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, etc. Can be mentioned.

  As the acid anhydrides (acid anhydride-based curing agents) as the curing agent (E), known or commonly used acid anhydride-based curing agents can be used, and are not particularly limited. For example, methyltetrahydrophthalic anhydride Acids (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl anhydride Acid, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride Product, nadic anhydride, methyl nadic anhydride, water Methyl nadic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether Examples thereof include maleic anhydride copolymers and alkylstyrene maleic anhydride copolymers. Among these, acid anhydrides [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] that are liquid at 25 ° C. are preferable from the viewpoint of handleability. On the other hand, for a solid acid anhydride at 25 ° C., for example, by dissolving in a liquid acid anhydride at 25 ° C. to form a liquid mixture, the curing agent (E in the curable epoxy resin composition of the present invention (E ) Tends to be improved. As the acid anhydride curing agent, saturated monocyclic hydrocarbon dicarboxylic acid anhydrides (including those in which a substituent such as an alkyl group is bonded to the ring) are preferable from the viewpoint of heat resistance and transparency of the cured product.

  As the amines (amine-based curing agent) as the curing agent (E), known or conventional amine-based curing agents can be used, and are not particularly limited. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene Aliphatic polyamines such as pentamine, dipropylenediamine, diethylaminopropylamine, polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, Cycloaliphatic polyamines such as N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro (5,5) undecane; m-phenylenediamine, p-phenylene Amine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2, Mononuclear polyamines such as 6-diamine; aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.

  As the phenols (phenolic curing agent) as the curing agent (E), known or commonly used phenolic curing agents can be used, and are not particularly limited. For example, novolac type phenol resins, novolac type cresol resins, Examples include paraxylylene-modified phenol resins, aralkyl resins such as paraxylylene / metaxylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.

  Examples of the polyamide resin as the curing agent (E) include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.

  As the imidazole (imidazole curing agent) as the curing agent (E), a known or commonly used imidazole curing agent can be used, and is not particularly limited. For example, 2-methylimidazole, 2-ethyl-4 -Methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenyl Imidazolium Sosocyanurate, 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]- Examples thereof include ethyl-s-triazine.

  Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (E) include liquid polymercaptan and polysulfide resin.

  Examples of the polycarboxylic acids as the curing agent (E) include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxyl group-containing polyester, and the like.

  Especially, as a hardening | curing agent (E), an acid anhydride (acid anhydride type hardening | curing agent) is preferable from a heat resistant and transparent viewpoint of hardened | cured material. In addition, the hardening | curing agent (E) can also be used individually by 1 type in the curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type. Moreover, a commercial item can also be used as a hardening | curing agent (E). For example, commercially available acid anhydride-based curing agents include trade names “Licacid MH-700”, “Licacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.); trade name “HN-5500” (Hitachi). Kasei Kogyo Co., Ltd.).

  The content (blending amount) of the curing agent (E) in the curable epoxy resin composition of the present invention is not particularly limited, but is 100 parts by weight based on the total amount of the cationic curable compound contained in the curable epoxy resin composition. 50 to 200 parts by weight, more preferably 80 to 150 parts by weight. More specifically, when acid anhydrides are used as the curing agent (E), 0.5% per equivalent of epoxy group in the compound having all epoxy groups contained in the curable epoxy resin composition of the present invention. It is preferable to use it at a ratio of ˜1.5 equivalents. By making content of a hardening | curing agent (E) into 50 weight part or more, it can fully harden | cure and there exists a tendency for the toughness of hardened | cured material to improve more. On the other hand, by setting the content of the curing agent (E) to 200 parts by weight or less, coloring tends to be suppressed and a cured product excellent in hue tends to be obtained.

[Curing accelerator (F)]
The curable epoxy resin composition of the present invention preferably further contains a curing accelerator (F), particularly when it contains a curing agent (E). The curing accelerator (F) is a compound having a function of accelerating the reaction rate when a cationic curable compound (particularly a compound having an epoxy group) reacts with the curing agent (E). As the curing accelerator (F), known or conventional curing accelerators can be used, and are not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or its Salts (for example, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or salts thereof ( For example, phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexyl Tertiary amines such as amines; 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole Phosphines such as triphenylphosphine and tris (dimethoxy) phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organic compounds such as zinc octylate, tin octylate and zinc stearate Metal salts; metal chelates such as aluminum acetylacetone complex.

  In addition, a hardening accelerator (F) can also be used individually by 1 type in the curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type. Further, as the curing accelerator (F), trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “U-CAT 12XD” ( (Developed product) (San Apro Co., Ltd.); trade names "TPP-K", "TPP-MK" (Hokuko Chemical Co., Ltd.); trade name "PX-4ET" (Nippon Chemical Industry ( It is also possible to use a commercial product such as a product manufactured by Co.

  The content (blending amount) of the curing accelerator (F) in the curable epoxy resin composition of the present invention is not particularly limited, but is based on 100 parts by weight of the total amount of the cationic curable compound contained in the curable epoxy resin composition. The amount is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, and still more preferably 0.03 to 2 parts by weight. By setting the content of the curing accelerator (F) to 0.01 parts by weight or more, a more efficient curing promoting effect tends to be obtained. On the other hand, by setting the content of the curing accelerator (F) to 5 parts by weight or less, coloring tends to be suppressed and a cured product excellent in hue tends to be obtained.

[Inorganic filler (G)]
The curable epoxy resin composition of the present invention may further contain an inorganic filler (G). As the inorganic filler (G), known or conventional inorganic fillers can be used, and are not particularly limited, but silica filler (such as nano silica), alumina filler, mica, synthetic mica, talc, calcium oxide, calcium carbonate, oxidation Zirconium (such as nano zirconia), titanium oxide (such as nano titania), barium titanate, kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, glass filler, glass fiber Graphite, carbon nanotubes, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, cellulose and the like.

  The inorganic filler (G) may have a surface modified with a surface modifier. Examples of the surface modifier include known and commonly used surface modifiers, and are not particularly limited. Examples thereof include saturated or unsaturated mono- and polycarboxylic acids having 1 to 12 carbon atoms; esters of the polycarboxylic acids. Amides; β-dicarbonyl compounds; silane coupling agents and the like.

  In addition, in the curable epoxy resin composition of this invention, an inorganic filler (G) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Moreover, as an inorganic filler (G), a commercial item can also be used.

  Among the inorganic fillers (G), a silica filler and a glass filler are preferable, and a glass filler is more preferable from the viewpoint of achieving both high transparency of the cured product and thermal shock resistance.

  As the silica filler, known or conventional silica fillers can be used, and are not particularly limited, and examples thereof include fused silica, crystalline silica, and high-purity synthetic silica.

  The shape of the silica filler is not particularly limited, and examples thereof include a spherical shape, a crushed shape, a fiber shape, a needle shape, a scale shape, and a whisker shape.

  The silica filler can be produced by a known or conventional method. Moreover, as a silica filler, a commercial item can also be used, for example, a brand name "Furex RD-8" (made by Tatsumori), a brand name "HPS-0500" (made by Toagosei Co., Ltd.). ) And the like.

  As the glass filler, known or conventional glass fillers can be used, and are not particularly limited. For example, glass beads, glass flakes, glass powder, milled glass, glass fiber, glass fiber cloth (for example, glass cloth, glass cloth) Non-woven fabric etc.).

  Although it does not specifically limit as a kind of glass which comprises a glass filler, For example, T glass, E glass, C glass, A glass, S glass, L glass, D glass, NE glass, quartz glass, low dielectric constant glass, Examples include high dielectric constant glass. Among these, E glass, T glass, and NE glass are preferable because they have few ionic impurities and are excellent in heat resistance and electrical insulation. In addition, a glass filler can also be used individually by 1 type in the curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type.

  Although the refractive index of the sodium D line | wire (light of wavelength 589.29nm) of a glass filler is not specifically limited, 1.40-2.10 are preferable, More preferably, it is 1.45-1.60. By controlling the refractive index within the above range, the transparency of the cured product tends to be improved. In addition, the refractive index of the sodium D line | wire of a glass filler can be measured using an Abbe refractometer (measurement temperature: 25 degreeC), for example.

  The glass filler may be surface-treated with various known or commonly used surface treatment agents. Examples of the surface treatment agent include silane coupling agents such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltriethoxysilane, surfactants, and inorganic acids. The surface treatment may improve wettability, affinity, and adhesion at the interface of the glass filler with other components (for example, a cationic curable compound).

  The said glass filler can be manufactured by a well-known thru | or usual method. Moreover, as a glass filler, a commercial item can also be used, for example, a brand name "Glass beads CF0018WB15C" (made by Nippon Frit Co., Ltd.), a brand name "Glass beads CF0018WB15" (made by Nippon Frit Co., Ltd.), Product name “Glass powder L-BSL7” (manufactured by OHARA INC.), Trade name “Glass powder L-LAH81” (manufactured by OHARA INC.), And the like.

  The content (blending amount) of the inorganic filler (G) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 1 to 25 parts by weight with respect to 100 parts by weight of the total amount of the cationic curable compound, More preferably, it is 3-20 weight part, More preferably, it is 5-15 weight part. By setting the content of the inorganic filler (G) to 1 part by weight or more, the thermal shock resistance of the cured product tends to be further improved. On the other hand, when the content of the inorganic filler (G) is 25 parts by weight or less, the transparency of the cured product tends to be further improved.

  Although content (blending amount) of the inorganic filler (G) in the curable epoxy resin composition of the present invention is not particularly limited, it is 1 to 50 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). The amount is preferably 2 to 40 parts by weight, more preferably 3 to 30 parts by weight. By setting the content of the inorganic filler (G) to 1 part by weight or more, the thermal shock resistance of the cured product tends to be further improved. On the other hand, when the content of the inorganic filler (G) is 50 parts by weight or less, the transparency of the cured product tends to be further improved.

[Additive]
In addition to the above, the curable epoxy resin composition of the present invention may contain various additives within a range that does not impair the effects of the present invention. For example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained as the additive, the reaction can be allowed to proceed slowly. In addition, as long as the effect of the present invention is not adversely affected, curing aids, organosiloxane compounds, metal oxide particles, rubber particles, silicone-based and fluorine-based antifoaming agents, silane coupling agents, fillers, Conventional additives such as plasticizers, leveling agents, antistatic agents, mold release agents, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments and dyes can be used.

  Although the curable epoxy resin composition of this invention is not specifically limited, It can prepare by stirring and mixing each above-mentioned component in the state heated as needed. In addition, the curable epoxy resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance. For example, components divided into two or more (each component The component may be a mixture of two or more components) and may be used as a multi-liquid composition (for example, a two-liquid system) that is used by mixing at a predetermined ratio before use. The stirring / mixing method is not particularly limited, and for example, known or commonly used stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.

<Hardened product>
By curing the curable epoxy resin composition of the present invention, a cured product having high transparency, heat resistance and light resistance, particularly high adhesion and excellent thermal shock resistance (the curable epoxy of the present invention). A cured product obtained by curing the resin composition may be referred to as “cured product of the present invention”). As the curing means, known or conventional means such as heat treatment or light irradiation treatment can be used. Although the temperature (curing temperature) at the time of making it harden | cure by heating is not specifically limited, 45-200 degreeC is preferable, More preferably, it is 50-190 degreeC, More preferably, it is 55-180 degreeC. In addition, 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 still more 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. Moreover, hardening can also be performed in one step and can also be performed in two or more steps.

<Resin composition for optical semiconductor encapsulation>
The curable epoxy resin composition of the present invention is a resin composition for sealing an optical semiconductor (optical semiconductor element) in an optical semiconductor device, that is, a resin composition for optical semiconductor sealing (an optical semiconductor element in an optical semiconductor device). Can be preferably used. By using it as the optical semiconductor sealing resin composition, an optical semiconductor device in which an optical semiconductor element is sealed with a cured product having high transparency, heat resistance and light resistance and excellent thermal shock resistance can be obtained. . The optical semiconductor device is less likely to cause a decrease in light intensity even when a thermal shock or high-temperature heat is applied, and has high durability.

<Optical semiconductor device>
The optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of 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 heat-curing under predetermined conditions. Thereby, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the curable epoxy resin composition is obtained. The curing temperature and the curing time can be appropriately set within the same range as when the cured product is prepared.

  The curable epoxy resin composition of the present invention is not limited to the above-mentioned optical semiconductor element sealing application, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, a resist, a composite material, It can also be used for applications such as transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members, optical modeling, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc. .

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, Examples 1-4, 6-12, and 14-16 are reference examples. Moreover, "-" in Tables 1 and 2 means that the component was not blended.

Example 1
First, with the blending ratio (unit: parts by weight) shown in Table 1, the trade name “Celoxide 2021P” (manufactured by Daicel Corporation) and the trade name “TEPIC” (manufactured by Nissan Chemical Industries, Ltd.) The mixture was uniformly mixed using a stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinkey Co., Ltd.). In addition, the said mixing was implemented by stirring at 80 degreeC for 1 hour. After cooling, the product name “Aron Oxetane OXT-101” (manufactured by Toagosei Co., Ltd.) and the product name “Sun-Aid SI-100L” (curing catalyst, manufactured by Sanshin Chemical Industry Co., Ltd.) A curable epoxy resin composition was produced by uniformly mixing and defoaming using an apparatus (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.).
Further, the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1, and then in an oven (resin curing oven) at 150 ° C. By heating for 2 hours, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable epoxy resin composition 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, and 104 is a cured product (sealing material).

Examples 2-8, Comparative Examples 1-6
A curable epoxy resin composition was prepared in the same manner as in Example 1 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 1. In addition, when not using an isocyanuric acid derivative (B), it mixed at room temperature.
Further, an optical semiconductor device was fabricated in the same manner as in Example 1.

Production Example 1
(Production of curing agent composition (K agent))
In the blending ratio (unit: parts by weight) shown in Table 2, the trade name “Rikacid MH-700” (curing agent, manufactured by Shin Nippon Rika Co., Ltd.), the trade name “U-CAT 18X” (curing accelerator, San Apro ( Co., Ltd.), and ethylene glycol (additive, manufactured by Wako Pure Chemical Industries, Ltd.) using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.) The mixture was uniformly mixed and defoamed to produce a curing agent composition (sometimes referred to as “K agent”).

Example 9
First, the product name “Celoxide 2021P” (manufactured by Daicel Corporation) and the product name “TEPIC” (manufactured by Nissan Chemical Industries, Ltd.) with the mixing ratio shown in Table 2 (unit: parts by weight) Using an apparatus (trade name “Awatori Nertaro AR-250”, manufactured by Shinkey Co., Ltd.), the mixture was uniformly mixed. In addition, the said mixing was implemented by stirring at 80 degreeC for 1 hour. After cooling, the product name “Aron Oxetane OXT-101” (manufactured by Toagosei Co., Ltd.) is used, and a self-revolving stirrer (product name “Awatori Nerita AR-250”, manufactured by Shinky Corp.) is used. Mixing uniformly and defoaming produced a mixture (mixture of cationically curable compounds).
Next, the mixture obtained as described above and the curing agent composition (K agent) obtained in Production Example 1 were mixed in a self-revolving stirrer (commodity) so that the blending ratio (unit: parts by weight) shown in Table 2 was obtained. Using the name “Awatori Netaro AR-250” (manufactured by Sinky Corporation), the mixture was uniformly mixed and defoamed to obtain a curable epoxy resin composition.
Further, the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1, and then in an oven (resin curing oven) at 120 ° C. By heating for 5 hours, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the said curable epoxy resin composition was obtained.

Examples 10-16, Comparative Examples 7-12
A curable epoxy resin composition was prepared in the same manner as in Example 9 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 2. In Examples 15 and 16, the inorganic filler (G) was blended when the mixture of the cationic curable compound and the curing agent composition were mixed.
Further, an optical semiconductor device was fabricated in the same manner as in Example 9.

<Evaluation>
The following evaluation tests were carried out on the optical semiconductor devices obtained in the examples and comparative examples.

[High temperature energization test]
The total luminous flux of the optical semiconductor devices obtained in the examples and comparative examples was measured using a total luminous flux measuring machine, and this was defined as “total luminous flux for 0 hour”. Further, the total luminous flux after flowing a current of 20 mA through the optical semiconductor device for 100 hours in a constant temperature bath at 85 ° C. was measured, and this was defined as “total luminous flux after 100 hours”. And luminous intensity retention was computed from the following formula. The results are shown in the column of “Luminance retention rate [%]” in Tables 1 and 2.
{Luminance retention (%)}
= {Total luminous flux after 100 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

[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 to 30 minutes was applied for 200 cycles using a thermal shock tester.
Then, the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), and cracks with a length of 90 μm or more occurred in the cured product (sealing material). It was confirmed whether or not electrode peeling (peeling of the cured product (encapsulant) from the electrode surface) occurred. Of the two optical semiconductor devices, the number of optical semiconductor devices with a crack of 90 μm or more in the cured product is shown in the column of “thermal shock test [number of cracks]” in Tables 1 and 2, and electrode peeling occurred. The number of optical semiconductor devices thus prepared is shown in the column of “Thermal Shock Test [Number of Detachment]” in Tables 1 and 2.

[Comprehensive judgment]
As a result of each test, what satisfy | filled all the following (1)-(3) was determined as (circle) (good). On the other hand, when any of the following (1) to (3) was not satisfied, it was determined as x (defective).
(1) High-temperature energization test: luminous intensity retention of 90% or more (2) Thermal shock test: No. of optical semiconductor devices having cracks of 90 μm or more in cured product (encapsulant) (3) Thermal shock test: The number of optical semiconductor devices in which electrode peeling occurred was 0. The results are shown in the column “Comprehensive judgment” in Tables 1 and 2.

In addition, the component used by the Example and the comparative example is as follows.
(Alicyclic epoxy compound (A))
Celoxide 2021P: Trade name “Celoxide 2021P” [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate], manufactured by Daicel Corporation (isocyanuric acid derivative (B))
TEPIC: trade name “TEPIC” [triglycidyl isocyanurate], manufactured by Nissan Chemical Industries, Ltd. MA-DGIC: trade name “MA-DGIC” [monoallyl diglycidyl isocyanurate], manufactured by Shikoku Kasei Kogyo Co., Ltd. DA- MGIC: Trade name “DA-MGIC” [diallyl monoglycidyl isocyanurate], manufactured by Shikoku Chemicals Co., Ltd. (oxetane compound (C))
OXT-101: Trade name “Aron oxetane OXT-101” [3-ethyl-3-hydroxymethyloxetane], manufactured by Toagosei Co., Ltd. OXT-221: Trade name “Aron oxetane OXT-221” [3-ethyl {[ (3-ethyloxetane-3-yl) methoxy] methyl} oxetane], manufactured by Toagosei Co., Ltd. (inorganic filler (G))
Silica filler: Trade name "Furex RD-8" [Silica filler], manufactured by Tatsumori Co., Ltd. Glass filler: Trade name "Glass beads CF0018WB15C" [Glass beads, with surface treatment (3-methacryloxypropyltriethoxysilane) , Refractive index 1.52, average particle diameter 20 μm], manufactured by Nippon Frit Co., Ltd. (curing catalyst (D))
Sun-Aid SI-100L: Trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd. (cured product (E))
MH-700: Trade name “Licacid MH-700” [4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30], manufactured by Shin Nippon Rika Co., Ltd. (curing accelerator (F))
U-CAT 18X: Trade name “U-CAT 18X”, manufactured by San Apro (additive)
Ethylene glycol: Wako Pure Chemical Industries, Ltd.

Test equipment ・ Resin curing oven ESPH Co., Ltd. GPH-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

100: Reflector (resin composition for light reflection)
DESCRIPTION OF SYMBOLS 101: Metal wiring 102: Optical semiconductor element 103: Bonding wire 104: Hardened | cured material (sealing material)

  Since the curable epoxy resin composition of the present invention has the above configuration, it is cured to form a cured product having high transparency, heat resistance, and light resistance, particularly high adhesion and excellent thermal shock resistance. it can. For this reason, by using the curable epoxy resin composition of the present invention as a sealing agent (an optical semiconductor sealing resin composition) in an optical semiconductor device, the luminous intensity is lowered even when thermal shock or high temperature heat is applied. It is possible to obtain an optical semiconductor device excellent in durability, which is less likely to occur.

Claims (10)

An alicyclic epoxy compound (A), an isocyanuric acid derivative (B) having one or more oxirane rings in the molecule, and an oxetane compound (C) having one or more oxetane rings in the molecule,
The alicyclic epoxy compound (A) is represented by the following formula (I-1)

A compound represented by
The isocyanuric acid derivative (B) is represented by the following formula (1-1):

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
A compound represented by
The oxetane compound (C) is at least one selected from the group consisting of 3-ethyl-3- (hydroxymethyl) oxetane and 3-methyl-3- (hydroxymethyl) oxetane;
Content of oxetane compound (C) is 10-150 weight part with respect to 100 weight part of alicyclic epoxy compound (A), The curable epoxy resin composition characterized by the above-mentioned.   The curable epoxy resin composition according to claim 1, wherein the ratio of the alicyclic epoxy compound (A) to the total amount of the cationic curable compound contained in the curable epoxy resin composition is 10 to 95% by weight.   3. The curable epoxy resin composition according to claim 1, wherein a ratio of the isocyanuric acid derivative (B) to the total amount of the cationic polymerizable compound contained in the curable epoxy resin composition is 1 to 40 wt%.   Furthermore, the curable epoxy resin composition as described in any one of Claims 1-3 containing a curing catalyst (D).   Furthermore, the curable epoxy resin composition as described in any one of Claims 1-4 containing a hardening | curing agent (E) and a hardening accelerator (F).   Furthermore, the curable epoxy resin composition as described in any one of Claims 1-5 containing an inorganic filler (G).   The curable epoxy resin composition according to claim 6, wherein the inorganic filler (G) is a glass filler.   Hardened | cured material obtained by hardening the curable epoxy resin composition as described in any one of Claims 1-7.   It is a resin composition for optical semiconductor sealing, The curable epoxy resin composition as described in any one of Claims 1-7.   An optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition according to claim 9.

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