TW201237059A - Curable epoxy resin composition - Google Patents

Abstract

The present invention provides a curable epoxy resin composition. The curable epoxy resin composition can provide cured products which have high transparency, heat resistance, light resistance and crack resistance. The curable epoxy resin composition is characterized by containing alicyclic epoxy compounds (A), monoallyl diglycidyl isocyanurate compounds (B) represented by following formula (1), siloxane derivatives having more than 2 epoxy groups in a molecule (C), curing agents (D) and curing accelerators (E).[In the formula, R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.]

Description

201237059 VI. [Technical Field] The present invention relates to a curable epoxy resin composition, a cured product obtained by hardening the curable epoxy resin composition, and a curable epoxy resin composition. Further, the resin composition for sealing the optical semiconductor and the optical semiconductor device in which the optical semiconductor element is sealed using the curable epoxy resin composition. [Prior Art] In recent years, high output of optical semiconductor devices has progressed, and resins used in optical semiconductor devices require high heat resistance and light resistance. For example, in the sealing material (sealing resin) for blue and white light semiconductors, the light emitted from the optical semiconductor element and the yellow of the sealing resin caused by heat become a problem. The yellowing sealing resin lowers the luminosity of light output from the optical semiconductor device with time as it absorbs light emitted from the optical semiconductor device. Hereto, a highly heat-resistant sealing resin is known to contain a cured product of a composition of a poly(octylic acid monoallyl diglycidyl ester) and a bisphenol A type epoxy resin (see Patent Document). When the cured product is used as a sealing resin for a blue or white photo-semiconductor which is rotated in a high direction, coloring is caused by light and heat emitted from the optical semiconductor element, and light which should originally be taken out is absorbed, and as a result, there is a light. The problem that the light output by the semiconductor device decreases with time. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2000-344867, JP-A No. 200037059 [Summary of the Invention] [Problems to be Solved by the Invention] There are: a seal that is rich in heat and light resistance and is not easily yellowed. Resin and Lu, known as 3,4-epoxycyclohexylfluorenyl (3 4 w 4 Niang) cyclohexane carboxylate, V-oxycyclohexyldecyl (3,4-epoxy) cyclohexane A liquid alicyclic epoxy resin having an alicyclic skeleton such as an acidified vinegar and a vinegar, an adduct, a di-epoxy lemon and the like. However, the hardened material of the alicyclic resin does not have various stresses, and when a thermal shock such as a thermal cycle (reverse heating and cooling) is applied, or a high temperature step such as a reflow step is performed, Cracks (cracks) and other issues. Due to such a crack, the luminosity of the light output from the photo-semiconductor is lowered with time. Therefore, the current state of the art requires an optical semiconductor device (especially an optical semiconductor device having a high-output, south-bright optical semiconductor device) to emit light with a reduced luminosity over time, which is highly resistant to heat, light, and cracking. Transparent sealing resin. Therefore, an object of the present invention is to provide a cured epoxy resin composition which can impart a cured product having high transparency, heat resistance, light resistance, and crack resistance. Further, another object of the present invention is to provide a cured product having high transparency, heat resistance, light resistance, and cracking property, which is obtained by curing the above-mentioned curable epoxy resin composition. Further, another object of the present invention is to provide an optical semiconductor sealing resin composition comprising the above-described hardened cerium oxide composition, which is capable of obtaining an optical semiconductor device in which luminosity reduction with time is suppressed. Further, another object of the present invention is to provide an optical semiconductor device 201237059" which is obtained by sealing a photo-semiconductor article using the resin composition for optical semiconductor sealing described above, and has high heat resistance, light resistance, transparency, and The crack-resistant hardened material seals the optical semiconductor element, and the luminosity reduction with time is suppressed. [Means for Solving the Problem] In order to solve the above problem, the inventors found that the results include an alicyclic epoxy compound and heterotrimerization. a cyanuric acid monoallyl diglycidyl 00 compound, and a decyl alkane derivative having two or more epoxy groups in the molecule, and further containing a curing agent, a hardening accelerator, or a hardening epoxy of a curing catalyst The resin composition can provide a cured product having excellent heat resistance, light resistance, transparency, and crack resistance, and an optical semiconductor device obtained by sealing the optical semiconductor element with the cured product, the luminosity is not easily lowered with time. The present invention has been completed. Also, the present invention provides a curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A) and the following formula (1). The isomeric glyceryl monoallyl diglycidyl ester compound (B), the oxirane derivative (C) having two or more epoxy groups in the molecule, and the hardener (D), and hardening Promoter (E);

[wherein R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. Further, the present invention provides a curable epoxy resin composition, which is packaged in 201237059

The alicyclic epoxy compound (A), the isoallyl cyanuric acid monoallyl diglycidyl ester compound (B) represented by the following formula (丨), and the epoxy group having two or more molecules in the molecule a decane derivative (C) and a hardening catalyst (F); wherein R' and R2 represent a hydrogen atom or a carbon number of 1 to 8. Furthermore, the content of the curable epoxy resin composition as described above, wherein the content of the oxoxane derivative (c) having two or more epoxy groups in the molecule is relative to the component (A) and the component (B) And the total amount of component (c) (1 〇〇 weight ° / 〇) is 5 to 60 weight. Furthermore, the above-mentioned curable epoxy resin composition is provided, wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is hexylene oxide. Furthermore, the above-mentioned curable epoxy resin composition is provided, wherein the above-mentioned alicyclic epoxy compound (A) is represented by the following formula (1-1): Ο 〆0 (I-1) ο A cured product obtained by hardening a curable epoxy resin composition. Further, the present invention provides a resin composition for optical semiconductor sealing comprising the above-mentioned curable epoxy resin composition. In addition, the present invention provides an optical semiconductor device in which an optical semiconductor element is sealed by the resin composition for optical semiconductor sealing. [Effects of the Invention] Since the curable epoxy resin composition of the present month has the above-described configuration, it is possible to obtain high transparency, heat resistance, light resistance, and crack resistance by curing the resin composition. Hardened matter. In addition, the optical semiconductor device obtained by sealing the optical semiconductor element using the curable epoxy resin composition of the present invention (resin composition for optical semiconductor sealing) has a low illuminance and can exhibit excellent quality and durability. In particular, when the curable epoxy resin composition of the present invention is used as a sealing resin for an optical semiconductor device having a high-output, high-luminance optical semiconductor device, the luminosity of the optical semiconductor device can be suppressed from decreasing with time. . [Embodiment] [Form of the invention] < Curable epoxy resin composition> The curable epoxy resin composition of the present month contains at least an alicyclic epoxy compound (A) and the following formula (1) ) is a monocyl monopropyl monoepoxypropane Sa compound (B) ' and has more than 2 epoxy groups in the molecule

1) 201237059 Further, the curable epoxy resin composition of the present invention contains at least the alicyclic epoxy compound (4) and the isomeric cyanide:monoallyl diglycidyl ester compound represented by the above formula (1) (B) And a halogenated alkane derivative (c) having two or more epoxy groups in the molecule, and a curing catalyst <alicyclic epoxy compound (A)> a fat constituting the curable epoxy resin composition of the present invention a compound (... is a compound having at least a lipid epoxide structure and an epoxy group in a molecule (in a molecule), and a substance (A), which comprises (1) and has a structure/ring 'in an alicyclic ring. A compound which oxidizes an epoxy group and an epoxy group which is bonded to an alicyclic ring. ^: The gas group directly uses the early bond to describe the intramolecular I, the substance (A)' does not contain the above or above epoxy group of the oxane derivative (〇. The ring of the ring constitutes the adjacent two of the alicyclic ring A compound having a carbon atom and an oxygen atom constituting an oxy group (alicyclic epoxy group), which is conventionally used. It is preferred to use a known or known ruthenium oxy group, and a cyclohexene group is preferred. The two carbon atoms and oxygen atoms adjacent to the alicyclic ring are conceived as an alicyclic epoxy compound (alicyclic epoxy resin) which is a lower core material from the viewpoint of transparency and finernity.

(I) 2 'base). The above-mentioned far: a single bond or a linking group (having one or more atoms, an ester bond, a cesium carbonate group, an ether group, an ether bond group, etc., alumina, amidino group, and a plurality of these are connected to each other 201237059 The alicyclic epoxy compound in which x is a single bond in the formula (i), for example, a compound represented by the following formula. For such an alicyclic epoxy compound, for example, a commercially available product such as CELL® XlDE 8000 (manufactured by Daicel Co., Ltd.) can also be used.

The above-mentioned divalent hydrocarbon group is, for example, a linear or branched alkyl group having a carbon number of 丨 18 or a divalent alicyclic hydrocarbon group. The linear or branched alkyl group having a carbon number of 丨 18 is, for example, an anthranylene group, a mercaptomethylene group, a dimethylmethylene group, an exoethyl group, a propyl group, a trimethylene group or the like. A divalent alicyclic hydrocarbon group 'for example: 1,2-cyclo-amyl, 1,3-cyclopentyl, cyclopentylene, 1,2-cyclohexyl, 1,3-cyclohexyl' ι, A bivalent cycloalkyl group (including a cycloalkylene group) such as a 4-cyclohexyl group or a cyclohexylene group. The above-mentioned linking group X' is preferably a linking group containing an oxygen atom, specifically, for example. CO- '-O-CO-0-, -COO-, -〇-, -CONH-; these groups are bonded to a plurality of groups; one or more of these groups and one of the divalent hydrocarbon groups Or a base obtained by linking two or more. A divalent hydrocarbon group such as the above exemplified. Representative examples of the alicyclic epoxy compound represented by the above formula (I) are, for example, compounds represented by the following formulas (1-1) to (1-8). For example, commercially available products such as CELLOXIDE 2021P and CELLOXIDE 20 81 (manufactured by Daicel Co., Ltd.) can be used. Further, in the following formulae (1-1) to (1-8), "b" represents an integer of 1 to 30. R represents an alkylene group having 1 to 8 carbon atoms, such as an anthracenylene group, an ethylidene group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a pentyl group, and a stretching group. A linear or branched alkyl group such as a hexyl group, a heptyl group or a octyl 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 or an exo-propyl group is preferred.

0

0 (1-6)

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

-〇

R'-

(Π) In the formula (II), R' is a group of p-type alcohols after p-OH is removed, and ρ, η is 201237059. The p-type alcohol [R, _(0H)p], for example, 2, 2_ bis (hydroxymethylbubu T-fermented polyol, etc. (carbon number 15 alcohol, etc.) β p should be b 6,11 Preferably, 1 to 30. When P is 2 or more, n of each of the groups (in parentheses) may be the same or different. The above compound 'specifically, t, for example, 2,2-bis(hydroxy fluorenyl) 1) 1-butanol 1) 2_epoxy_4·(2·oxiranyl)cyclohexane adduct, EHPE 3l5〇 (made by Daicel). These alicyclic epoxy compounds (A) may be used singly or in combination of two or more. The alicyclic epoxy compound (A) is preferably a 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate or a cell 〇xide 2 0 2 1P represented by the above formula (11). The amount (content) of the alicyclic epoxy compound (A) is not particularly limited with respect to the total amount of the alicyclic epoxy compound (A) and the isomeric cyanuric monoallyl propylene oxide compound (B) ( 100% by weight, preferably 50 to 90% by weight, more preferably 60 to 90% by weight. /. Further preferably, when the amount of the alicyclic epoxy compound (Α) is less than 5% by weight, the isocyanuric monoallyl propylene oxide compound (Β) is dissolved. Insufficient properties, if placed at room temperature, sometimes the valley is easy to precipitate. On the other hand, the amount of the alicyclic epoxy compound (Α) is more than 90% by weight. /〇' When a photo-semiconductor device is fabricated, cracks may easily occur. In the total amount (% by weight) of the component (Α), the component (Β), and the component (C), the alicyclic epoxy compound (Α) and the isomeric cyanuric acid monoallyl propylene oxide compound The sum (total amount) of the content of (Β) is not particularly limited to the weight %. When the hardening epoxy resin composition of this month contains a hardener (D) as an essential component, the content of the alicyclic epoxy compound (A) relative to the total amount (100% by weight) of the curable epoxy resin composition is not particularly Limited, should be 1〇~9〇-12- 201237059 重里/. More preferably, it is 1 5 to 80% by weight/〇, and more preferably 1 to 7 to 70% by weight. On the other hand, when the curable epoxy resin composition of the present invention contains a curing catalyst as an essential component, the alicyclic epoxy compound (A) is present in a total amount (1% by weight) relative to the curable epoxy resin composition. The content is not particularly limited to 25 to 9 % by weight, more preferably 30 to 85 by weight. /〇, and more preferably 35~8〇 weight%. &lt;Iso-di- cyanuric acid monoallyl diglycidyl ester compound (B)&gt; The isocyanuric acid monoallyl diglycidyl ester compound (B) used in the present invention can be used in the following formula (1) indicates.

In the above formula (1), R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropanol, butyl, isobutyl, first butyl, pentyl, hexyl, heptyl, octyl, etc. Or branched alkyl. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl 'propyl group is preferred. R1 and R2 in the above formula (1) are preferably a hydrogen atom. Representative examples of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B), such as isoallyl cyanurethane diglycidyl ester, isotrimer acid 1-allyl-3 ,5-bis(2·methylepoxypropyl)ester, decylpropenyl)-3,5-diglycidyl ester, isomeric cyanuric acid 1_(2-methacryloyl) -3,5-bis(2-methylepoxypropyl) ester, and the like. Also, 'iso-cyanuric acid single-grade -13- 201237059 propyl diglycidyl ester was used. The σ substance (B) may be used singly or in combination of two kinds of heteropoly silver to the above alicyclic cyclization=based diglycidyl acetate compound (B), and the soluble compound (4) may also be an arm/object (4). The range is arbitrarily mixed, and the ratio of the alicyclic epoxy compound, the polycyanic acid monoallyl diglycidyl ester compound (B) is not particularly limited to the allyl epoxide... the oxy-oxygen compound (4): iso-cyanuric acid single Preferably, the compound (B) is preferably 50:50 to 90: 1 Torr (by weight). When the ratio is outside the range _ s 罜罝 , ^ λ, the solubility of the isomeric cyanuric monoallyl diglycidyl ester compound (B) is not easily obtained. The iso-polycapric acid monoallyl diglycidyl ester compound (B) may be previously modified by adding a compound which reacts with an epoxy group such as an alcohol or an acid needle. The total amount (100% by weight) of the total amount of the epoxy compound (4) and the iso-Zt acid mono-propyl propylene glycol sulfonium sulfonate (8) relative to the epoxy resin (the compound having an epoxy group) It is not particularly limited, and is preferably 4 G% by weight or more and more preferably 50% from the viewpoint of improving heat resistance, light resistance, and crack resistance. /. More preferably, it is more than 7% by weight. <The oxoxane derivative (c) having two or more epoxy groups in the molecule> The component (c) of the curable epoxy resin composition of the present invention, that is, two or more molecules (in one molecule) The cyclooxyalkylene derivative of the epoxy group is responsible for improving the heat resistance and green resistance of the cured product and suppressing the decrease in the luminosity of the optical semiconductor device. In the oxoxane derivative (c) having two or more epoxy groups in the molecule, the fluorination skeleton is not particularly limited, and examples thereof include a cyclic siloxane skeleton; a linear polyoxy siloxane, or a cage type or Stepped type of polysesquioxanes and other polyfluorene-14- 201237059 2 skeleton. Among them, the upper-cut oxygen-fired skeleton is preferably a ring-shaped crucible frame or a linear polyanthracene oxygen skeleton from the viewpoint of improving the resistance to the cured product and the light resistance and suppressing the decrease in luminosity. Further, the p-oxane derivative (c) having two or more epoxy groups in the molecule is preferably a cyclic oxirane having two or more epoxy groups in the molecule, and two or more rings in the molecule. A linear polyoxyl group of an oxy group. Further, the oxane derivative (C) having two or more epoxy groups in the molecule may be used singly or in combination of two or more. The oxime-oxygen derivative (c) having two or more epoxy groups in the molecule is a ring-shaped oxime of the epoxy group, and the Si-Ο early is formed. The number of ruthenium (equal to the number of ruthenium atoms forming a siloxane ring) is not particularly limited, and is preferably from 2 to 12, more preferably from 4 to 8, from the viewpoint of improving the heat resistance and light resistance of the cured product. The weight average molecular weight of the fluorinated alkane derivative (C) having two or more epoxy groups in the molecule is not particularly limited, and is preferably from 100 to 3 Å from the viewpoint of improving heat resistance and light resistance of the cured product. More preferably 18〇~2〇〇〇. The oxoxane derivative (c) having two or more epoxy groups in the molecule is not particularly limited as long as the number of epoxy groups in one molecule is two or more, and the heat resistance and light resistance of the cured product are improved. From the point of view, 2 to 4 (2, 3, or 4) are preferred. The oxirane derivative (c) having two or more epoxy groups in the molecule is not particularly limited as long as it has an epoxy equivalent (according to JIS K7236), and is 180 to 400 from the viewpoint of improving the heat resistance and light resistance of the cured product. Preferably, it is preferably 240 to 400, and more preferably 24 to 35 inches. The epoxy group in the oxoxane derivative (c) having two or more epoxy groups in the molecule is not particularly limited, and the heat resistance and light resistance of the cured product are improved.

It is preferable that two carbon atoms and an oxygen atom of S -15-201237059 are in which the epoxy group is particularly preferable, and an adjacent epoxy group (alicyclic epoxy group) constituting the aliphatic ring is preferable.

-2,4,6,8-tetramethyl-cyclotetraoxane, 4,8•bis[2_(3_{oxabicyclo[4.1.0]heptyl})ethyl]-2,6- Dipropyl-2,4,6,8-tetradecyl-cyclotetraoxane, 2'4,8·tri[2-(3-{oxabicyclo[4.1〇]heptyl})ethyl] -2,4,6,6'8-pentamethyl-cyclotetraoxane, 24,8 trioxabicyclo[4.1.〇]heptyl})ethyl]_6_propyl-2,4,6 , 8-tetramethyl-cyclotetraoxane, 2,4,6,8-tetra[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl b 2,4,6, 8-tetramethyl-cyclotetraoxane, sesquioxane having an epoxy group, and the like. More specifically, for example, the following formula represents a cyclic oxirane having two or more epoxy groups in one molecule. -16- 201237059 \/

(c) In the case of a group of two or more ring gas groups in the scorpion, the sulphur-oxygen resin is used in Japan. A polysilsesquioxane resin having at least two epoxy functional groups in the molecule, which is described in JP-A No. 2,819,422, and a pyrithione derivative having two or more epoxy groups in the molecule (c) For example, it is also possible to use a ring-burning product name "X-40-2678" (manufactured by Shin-Etsu Chemical Co., Ltd.) and a commercial product having two or more epoxy groups in the sub-item. The name "X-40-2670" ( Commercial products such as Shin-Etsu Chemical Co., Ltd., under the trade name Χ-40·2720. -17- 201237059 The amount (content) of the oxy-oxygen derivative containing two or more epoxy groups in the molecule is not In particular, it is preferably 5 to 6 % by weight, more preferably 8 to 55% by weight, and even more preferably 10 to 5 %, based on the total amount (100% by weight) of the component (A) and the component (c). % by weight, particularly preferably 15 to 4 〇 〇 / ❶. The amount of the oxy-oxygen derivative (6) having two or more epoxy groups in the molecule is less than 5% by weight. On the other hand, if the amount of the oxoxane derivative (C) having two or more epoxy groups in the molecule is more than 60% by weight, the crack resistance of the cured product may be <The hardener (D)&gt; The hardener (D) has a function of hardening the epoxy group-containing compound. In the present invention, the hardener (D) can be used as the hardener for the epoxy resin. It is a known or customary hardener. In the present invention, the hardener (D) is preferably a 25. hydrazine-based acid anhydride, for example, mercaptotetrahydrophthalic anhydride, methylhexahydrophthalic acid f An acid anhydride, dodecenyl succinic anhydride, methyl intrinsic fluorenylene tetraisoproton benzoic acid needle, etc. Further, for example, phthalic acid needle, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Normal temperature (about 25. 〇 is a solid acid anhydride dissolved in normal temperature (about 25. 〇 is a liquid acid anhydride and becomes a liquid mixture, whereby it can also be used as the hardening of the present invention). Further, the curing agent (D) may be used singly or in combination of two or more. As described above, the curing agent is used. From the viewpoint of heat resistance, light resistance, and crack resistance of the compound, it is preferably a saturated monocyclic hydrocarbon dicarboxylic anhydride (including a substituent bonded to a ring such as a ring). Further, in the present invention, a hardener (D) It is also possible to use products such as Rikacid MH-700 (New 理 理 ( (), HN-5500 (曰立化成股份有限公司), etc. * 18 - 201237059. Use of hardener (D) The amount (content) is not particularly limited, and the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention is preferably 5 Torr to 2 Torr. It is 1 00~L 45 parts by weight. More specifically, the epoxy group in the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention is preferably used in an amount of from 0.5 to 1.5 equivalents per 1 part. When the amount of the curing agent (D) is less than 50 parts by weight, the curing is insufficient, and the toughness of the cured product tends to decrease. On the other hand, when the amount of the curing agent (D) is more than 2 parts by weight, the cured product is colored. Sometimes the hue is deteriorated. &lt;Curing accelerator (E)&gt; The curable epoxy resin composition of the present invention further contains a curing accelerator (E). The hardening accelerator (E) is a compound having a function of promoting the rate of hardening when the epoxy group-containing compound is hardened by a hardener. As the hardening accelerator (E), a known or conventional hardening accelerator such as hydrazine, 8_diazabicyclo[5.4.0]undecene-7 (DBU), and a salt thereof (for example, phenate, octanoic acid) can be used. Salt, p-toluenesulfonate, decanoate, tetraphenylborate); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and salts thereof (eg, scale salts, cesium) Salt, grade 4 ammonium salt, phosphonium salt); benzyl diamine, 2,4,6-g (diguanylamino) phenol, n, n-dimethylcyclohexylamine and other tertiary amines; Imidazole such as ethyl 4-4 methylimidazole, 1-cyanoethyl-2-ethyl-4-ylimidazole; phosphines such as phosphates and triphenylphosphine; An scaly compound such as borate; an organic metal salt such as tin octylate or zinc octoate; a metal chelate compound or the like. The hardening accelerator (Ε) may be used singly or in combination of two or more.

Further, in the present invention, the hardening accelerator (Ε) can also use U-CAT SA.

S -19 * 201237059 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X, 12XD (developed products) (all manufactured by San-apro), TPP-K, TPP-MK (all Commercial products such as Beixing Chemical Industry Co., Ltd. and Ρχ-4ΕΤ (Sakamoto Chemical Industry Co., Ltd.). The amount (content) of the hardening accelerator (Ε) is not particularly limited, and is 〇. 5 to 5 by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. Preferably, it is preferably from 1 to 3 parts by weight, and more preferably from 0.2 to 3 parts by weight, particularly preferably from 0.25 to 2.5 parts by weight. If the amount of the hardening accelerator (Ε) is less than 〇.〇5 parts by weight, the hardening promoting effect may sometimes be insufficient. On the other hand, if the amount of the curing accelerator (Ε) exceeds 5 parts by weight, the cured product may be colored, and the hue may be deteriorated. &lt;Curing Catalyst (F)&gt; In the curable epoxy resin composition of the present invention, a curing catalyst (F) may be used instead of the above curing agent (D) and a curing accelerator (E), and a curing agent may be used. (D) As in the case of the hardening accelerator, the hardening reaction of the compound having an epoxy group can be carried out by using the curing catalyst (F)' to obtain a cured product. The hardening catalyst is not particularly limited, and a cationic catalyst (cationic polymerization initiator) which generates a cationic substance by polymerization by ultraviolet irradiation or heat treatment and starts polymerization can be used. A cationic catalyst which generates a cationic substance by ultraviolet irradiation, for example, a hexa-a citrate, a pentafluorohydroxy decanoate, a hexafluorophosphate or a hexafluoroarsenate. These cationic catalysts may be used singly or in combination of two or more. The cation catalyst is, for example, trade name "UVACURE 1590" (Daicel · Cytec Co., Ltd.), trade name "CD_101〇", r cd-101 1 "CD-1012" (above, US sart〇inei^), trade name Commercial products such as "irgacure -20-201237059 264" (manufactured by Ciba Japan Co., Ltd.) and trade name "CIT-1682" (manufactured by Japan Soda Co., Ltd.) are preferred. The heat treatment may generate a cationic catalyst of a cationic substance, for example, an aryl diazonium salt, an aryl sulfonium salt, an aryl sulfonium salt, an arene ion ion complex, etc., and preferably, for example, pp_33 may be used. CP-66,

CP-77 (made by ADEKA), FC-509 (made by 3M), UVE1014 (made by GE), San-Aid SI-6 0L, San-Aid SI-8 0L, San-Aid SI-100L, San" Aid SI-1 l.〇L (Sanshin Chemical Industry Co., Ltd.), CG_24_61 (made by ciba Japan), and other metals such as aluminum or titanium and acetonitrile or diketone. A compound of a chelating compound such as a sterol such as triphenyl decyl alcohol or a chelating compound of a metal such as sulphur or titanium, an acetonitrile acetic acid or a diketone, or a phenol such as bisphenol S. The cationic catalyst may also be used. The amount (content) of the curing catalyst (F) is not particularly limited, and the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition (100 weight) The portion is preferably 0.01 to 15 parts by weight, more preferably 1 to 12 parts by weight, still more preferably 〇.05 to 1 part by weight, particularly preferably 7b (7) parts by weight. A cured product excellent in heat resistance, light resistance, and transparency can be obtained by using a curing catalyst (F). <Rubber particles> The curable epoxy resin composition of the present invention can also be used. The rubber particles are contained, for example, particulate NBR (acrylonitrile butadiene rubber), ^ terminal carboxyl group NBR (CTBN), metal-free nbr, particulate sbr (present ethylene-butadiene rubber). The rubber particles are a multi-layered-21-201237059 structure (nuclear sheath structure) composed of a core portion having rubber elasticity and a layer of at least one layer covering the core portion, and having a surface capable of reacting with an alicyclic epoxy compound The rubber particles having a hydroxyl group and/or a carboxyl group of a functional group and having an average particle diameter of 10 nm to 5 nm and a maximum particle diameter of 50 nm to 1000 nm may also be a refractive index of the rubber particle and the hardenable epoxy The rubber particles having a difference in the refracting time of the cured product of the resin composition are within ±0.02. The blending amount of the rubber particles is appropriately adjusted as needed, and is not particularly limited, and is contained in the curable epoxy resin composition. The total amount (100 parts by weight) of the epoxy group compound is preferably 0.5 to 30 parts by weight, more preferably 4 to 2 parts by weight. The rubber particles are used in an amount of less than 0.5 part by weight, and the crack resistance of the cured product Have a tendency to decrease, another When the amount of the rubber particles used exceeds 30 parts by weight, the heat resistance and transparency of the cured product tend to be lowered. &lt;Additives&gt; The curable epoxy resin composition of the present invention, in addition to the above, Various additives may be used as long as the effects of the present invention are not impaired. For example, if a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or glycerin is used as the above additive, the reaction can be carried out gently. In the range of viscosity and transparency, it may also contain a polysulfide-oxygen-based fluorinated antifoaming agent, a coating agent, and a gamma-glycidoxypropyltrimethoxy oxysulfide or the like. Conventional additives such as inorganic fillers such as surfactants, cerium oxide, and aluminum oxide, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, and mold release agents. &lt;Cured product&gt; By curing the curable epoxy resin composition of the present invention, a cured product having excellent transparency, such as heat resistance, light resistance, and crack resistance, can be obtained. The heating temperature (hardening temperature) at the time of hardening is not particularly limited,

S -22- 201237059 is preferably 45~200°C, more preferably 1〇〇~19(rc, and even more preferably ι〇〇~ΐ8〇ι. Also, the heating time (hardening time) during hardening is not special Preferably, 30 to 600 minutes is better, more preferably 45 to 54 minutes, and even more preferably 6 to 48 minutes. When the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening is insufficient, and vice versa. When the upper limit of the above range is 値, the sorrel component may be deficient in f, and it is not preferable. The curing conditions depend on various conditions. For example, when the curing temperature is increased, the curing time is shortened, and when the curing temperature is lowered, the curing time is lengthened. The resin composition for optical semiconductor sealing of the present invention is composed of the curable epoxy resin composition of the present invention. The light of the present invention is used. In the resin composition for semiconductor sealing, it is possible to obtain a cured product which is excellent in various physical properties such as transparency, rail resistance, light resistance, and resistance to turtles, etc., and the optical semiconductor is sealed, and the illuminance is less likely to decrease with time. Optical semiconductor device In the optical semiconductor device described above, even when a light semiconductor device having a high output and a high luminance is provided, the illuminance is less likely to decrease with time. <Optical semiconductor device> The optical semiconductor device of the present invention is cured by the present invention. = resin composition (resin composition for optical semiconductor sealing) is obtained by sealing an optical semiconductor element. The seal of the 夯 邋 — 灿 于 于 于 于 兀 兀 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于The material is injected into a predetermined forming mold, and the Π:: member is heat-hardened. Thereby, the optical semiconductor device can be obtained by using a hardened epoxy resin disk hard conductor member. The hardening temperature and the hardening time can be set to be the same as above. Scope. The hardening % oxygen resin composition of the moon is not limited to the above-mentioned light half-23-201237059 conductor (optical semiconductor component) sealing agent, electrical insulating material, laminated board, anti-synthesis agent, composite material, transparent Optical components, optical lenses, optical control panels, solar cell substrates, memory, etc. Uses can also be used, for example, for adhesive coating, ink, coatings, sealant substrates, Clear film, transparent film, member, optical shape, electronic paper, light-guided waveguide, light guide plate, hologram [Examples] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. 1 (mixture of hardener and hardening accelerator and additive, hereinafter referred to as κ agent) Hardener (Nippon Chemical and Chemical Co., Ltd., Rikacid ΜΗ-700): 100 parts by weight, hardening accelerator (SAN-APRO) ), U-CAT 18X): 0.5 parts by weight, additive (manufactured by Wako Pure Chemical Industries, Ltd., ethylene glycol): 1 part by weight using a self-revolving stirring device (THINKY), defoaming Ryotaro AR -250) uniformly mixed and defoamed to obtain a κ agent. Production Example 2 (Epoxy Resin) Isopropyl methacrylate (Isochemical Co., Ltd., MA-DGIC), alicyclic epoxy compound (Daicel Co., Ltd., CELLOXIDE 2021P) And a oxane derivative having two or more epoxy groups in the molecule (Shin-Etsu Chemical Co., Ltd., X-40-2678; Shin-Etsu Chemical Co., Ltd., X-40-2720; Shin-Etsu Chemical Co., Ltd. Industrial (stock) system, X-40-2670), mixed according to the blending formula shown in Table 1 and Table 2 (unit: weight -24 - 201237059 injury), stirred at 80 ° C for 1 hour, thereby making the three Polycyanate monoallyl diglycidyl ester dissolved 'obtained epoxy resin (mixture). Examples 1 to 1 2, Comparative Examples 1 to 4 Examples 1 to 12' are the epoxy resins obtained in Production Example 2 and the K agents obtained in Production Example 1, according to the blending formula shown in Table ( (Unit: Weight (Part I) The components were uniformly mixed and defoamed using a self-rotating stirring device (THINKY (manufactured by the company), defoamed and ritual AR_250) to obtain a curable epoxy resin composition. Further, as shown in Table 1, in Comparative Example 1, only the alicyclic epoxy compound (CaiOXIDE 20 2 1 P, manufactured by Daicel Chemical Industry Co., Ltd.) was used for the epoxy resin. Only oxoxane derivatives having two or more epoxy groups in the molecule (Shin-Etsu Chemical Co., Ltd., X-40-2678; Shin-Etsu Chemical Co., Ltd., χ_4〇_272〇; Shin-Etsu Chemical Co., Ltd.) Industrial Co., Ltd., X-40-26 70) 'A cured epoxy resin composition is obtained in the same manner as above.>> The above-mentioned curable epoxy resin composition is cast into a lead frame of an optical semiconductor as shown in Fig. 1. After the mold (InGaN element, 3.5 mm x 2.8 mm), the film was heated in an oven (resin-hardened oven) of 1 20 c for 5 hours to obtain an optical semiconductor device obtained by sealing the LED element with a cured resin. In Fig. 1, 1 〇〇 represents a reflecting member (resin composition for light reflection), 1 〇 1 represents a metal wiring, 102 represents an LED element, 103 represents a bonding wire, and 1 〇 4 represents a transparent sealing resin (cured material). Example 1 3 to 24, Comparative Examples 5 to 8 Example 1 3 to 24' The epoxy resin and hardening catalyst obtained in Production Example 2 (Sanshin Chemical Industry Co., Ltd., SAN-AID SI-100L) According to the blending formula (unit: parts by weight) shown in Table 2, the ingredients were uniformly mixed using a self-revolving type mixing device (THINKY (manufactured by the company), degassing and ritual AR-250). Defoaming, a hardenable epoxy resin composition is obtained. Further, as shown in Table 2, in Comparative Example 5, only an alicyclic epoxy compound (manufactured by Daicel Chemical Industry Co., Ltd., CELLOXIDE 2021P) was used for the epoxy resin, and Comparative Examples 6 to 8 were only for the epoxy resin. A nonoxyl derivative having two or more epoxy groups in the molecule (manufactured by Shin-Etsu Chemical Co., Ltd., χ40-2678; Shin-Etsu Chemical Co., Ltd., X-40-2720; Shin-Etsu Chemical Co., Ltd. , x_4〇-2670), a hardenable epoxy resin composition was obtained in the same manner as described above. The above-mentioned curable epoxy resin composition was cast on a lead frame (InGaN element, 3.5 mm x 2.8 mm) of an optical semiconductor as shown in Fig. 1, and then heated at 11 ° C for 3 hours in an oven (resin-hardened oven), followed by heating for 3 hours at 11 ° C. At 14〇.加热 Heating for 4 hours, thereby obtaining an optical semiconductor device obtained by sealing a led element with a hardened resin. &lt;Evaluation&gt; The curable epoxy resin composition obtained in the examples and the comparative examples and the optical semiconductor device were subjected to an evaluation test by the following method. [Electrification test] The total light beam of the optical semiconductor device obtained in the examples and the comparative examples was measured by a full beam measuring machine (determined as a full beam of Γ 〇 hours). Further, the total light beam (defined as "total light beam after 1 hour") was measured in the constant temperature bath for a current of 6 mA for the optical semiconductor device. The photometric retention rate is calculated by the following formula. The results are shown in Table 1 'Table 2. {Photometric retention rate (%)} = {full beam (100) after 100 hours} / {full beam of light (lm)} X 1〇〇-26- 201237059 [Solder heat resistance test] Examples and comparisons The obtained optical semiconductor device (two for each curable epoxy resin composition) was subjected to moisture absorption for 168 hours under conditions of 3 (TC, 70% RH, and then subjected to heat treatment at 26 (TC for 10 seconds). 2 times. Then, the length of the crack generated by the sealing resin (cured material of the curable epoxy resin composition) of the optical semiconductor device was observed using a digital microscope (VHX-900, KEYENCE), and two lights were measured. The number of the optical semiconductor devices having a crack of 90 μm or more in the semiconductor device is shown in Tables 1 and 2. [Thermal punching test] The optical semiconductor devices obtained in the examples and the comparative examples (each hardenable epoxy) The resin composition was used for 2 minutes) in a gas atmosphere exposed to -40 Torr: for 3 minutes, and then exposed to a gas atmosphere of 100 ° C for 30 minutes to be used as a thermal shock of one cycle, using a thermal shock tester. Give 2 cycles. Then 'use a digital microscope VHX-900, KEYENCE (manufacturing)) The length of the crack generated by the sealing resin (cured material of the curable epoxy resin composition) of the optical semiconductor device was measured, and the length of the two optical semiconductor devices was measured to be 90 μm or more. The number of cracked light semiconductor devices. The results are shown in Table 1, Table 2 » [Comprehensive judgment] The photometric retention rate of the energization test is 90% or more, and the solder is heat-resistant ['s ν test and thermal shock § test) The number of optical semiconductor devices having a crack of more than the length is one, and it is judged to be 〇 (good) in the overall judgment. In addition, the overall judgment is X (bad). The results are shown in Table 1 and Table 2. -27- 201237059 inch* 1 1 1 Ο § 〇&lt;NX 1 1 1 o 1 § 〇(NX anger A3 1 1 ο ^-1 1 1 § VO 〇〇〇&lt;NX Ϊ 〇1 1 1 1 § 〇CN &lt ;NX rj ί 〇〇1 1 § 〇Ο 〇Ϊ VO &gt;Λ inch 1 1 § 〇ο 〇〇i 3 VO 1 1 § 〇ο 〇〇\ 镩$xc CS 〇〇1 I 〇§ § 〇ο 〇 00 Ο 〇1 1 § 5; 〇ο 〇5'1 i' ^ 知|丨1&quot; 1 1 | 〇ο 〇v〇5 sv〇1 1 § 〇ο 〇 W *i (N 〇〇1 o « § § 〇ο 〇 inch 5 镩o 〇s 1 1 § § 〇ο 〇m ? Private NO ir> 1 1 § 〇ο 〇 (N 5 sv〇1 1 § S 〇ο 〇i pi 〇〇〇1 1 § § 〇ο 〇CL. su υ 5 Q &lt; s OO 5 (N 0 &quot;TX 卜&lt;N ό X 〇Ό CN 0 inch&gt;&lt; S g 冢m * m 冢 奄遝 奄遝 与 与 与 与 与 2012 2012 5 5 5 5 5 2012 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 370 &quot;Η 1 yrs 〇00 〇&lt;Ν X Comparative Example 6 1 1 〇1 1 d 3 〇&lt;Ν X Comparative Example 5 〇t 1 1 t yr\ 〇00 v〇(N &lt;Ν X Example 24 〇〇1 1 in o 5; 〇Ο 〇 Example 23 々t 1 o 〇Ο 〇 Example 22 v〇1 1 w-&gt; d (N ON 〇Ο 〇 Example 21 CS oo 1 1 Ο o § 〇 ο 〇 Example 20 〇o *—H 1 I o 〇ο 〇 Example 19 v 〇 t I o (N 〇 〇 〇 〇 Example 18 sv〇1 tdm 〇 〇 〇 〇 Example 17 CN OO rH 1 ο 1 〇〇ο 〇 Example 16 oo «—H 1 1 in o 窆〇ο 〇 Example 1 5 2 1 1 *T) om On 〇ο 〇Example 14 sv〇r—H 1 1 o (N 〇\ 〇ο 〇Example 13 &lt;N OO ο 1 1 md ON 〇ο 〇CEL2021P MA-DGIC Χ -40-2678 Χ-40-2720 X-40-2670 SI-100L Photometric retention rate [%] Solder heat resistance test [number] Thermal shock test [number] Comprehensive evaluation of epoxy resin hardening catalyst i) in Si 5 # ^ ^ Hardened material (optical semiconductor device) 201237059 Further, the components used in the examples and comparative examples are as follows. (Epoxy Resin) CEL2021P(CELLOXIDE2021P): 3,4^ Oxycyclohexyldecyl (3,4-epoxy) cyclohexanol oxalate, 〇3丨061 (stock) MA-DGIC: Iso-Cyanide Acid monoallyl diglycidyl ester, X-40-2678 manufactured by Shikoku Chemicals Co., Ltd.: a cyclooxygen derivative having two epoxy groups in the molecule, X-40 manufactured by Shin-Etsu Chemical Co., Ltd. -2720: a oxane derivative having three epoxy groups in the molecule, X-40-2670 manufactured by Shin-Etsu Chemical Co., Ltd.: a cyclooxygen derivative having four epoxy groups in the molecule, Shin-Etsu Chemical Industry ( Stock system (K agent).

Rikacid ΜΗ_7〇0 : 4-mercapto hexahydrophthalic acid field / hexaphthalic phthalic anhydride = 70/30, New Japan Physicochemical (stock) U-CAT 18X: hardening accelerator, SAN-APRO Ethylene glycol: Wako Pure Chemical Industries Co., Ltd. (hardening catalyst) SI-100L (SAN-AID SI-100L): aryl sulfonium salt, =e a chemical industry (stock) test equipment • Resin Hardening oven ESPEC (stock) GPHH-201 • Thermostatic chamber ESPEC (stock) small high temperature chamber ST-120B1 -30- 201237059 • Full beam measuring machine

Multi-spectral emission measurement system manufactured by Optronic Laboratories OL7 71 • Thermal shock tester

ESPEC (stock) small thermal shock device TSE-11-A * reflow furnace

曰本 ANTOM (share) system, UNI-5016F

[Industrial Applicability] The curable epoxy resin composition of the present invention can be preferably used for sealing applications of optical semiconductor elements. Moreover, the curable epoxy resin composition of the present invention can also be used for an adhesive, an electrical insulating material, a laminated board, a coated ink, a coating, a potting agent, a resist, a composite material, a transparent substrate, Transparent sheets, transparent films, optical elements, optical lenses, optical members, optical shapes, electronic paper, touch panels, solar cell substrates, optical waveguides, light guides, holographic memories, and the like. [Brief Description of the Drawings] Fig. 1 is a schematic view showing an embodiment of an optical semiconductor device obtained by sealing a member (optical semiconductor element) of the curable epoxy resin composition of the present invention. The left side view (a) is a perspective view, and the right side view (b) is a cross-sectional view. [Description of main component symbols] 100 Reflector (resin composition for light reflection) 101 Metal wiring 102 LED component 103 Bonding wire 104 Transparent sealing resin -31-

Claims (1)

201237059 VII. Patent application scope: 1. A curable epoxy resin composition' characterized by: an alicyclic epoxy compound (A), and an isomeric cyanuric acid monoallyl group represented by the following formula (1) a glycidyl ester compound (B), a oxoxane derivative (c) having two or more molecules in the molecule, a hardener (D), and a hardening accelerator (Ε); [wherein R1 and R2 represent an argon atom or an alkyl group having 1 to 8 carbon atoms]. 2. A curable epoxy resin composition, characterized by comprising: an alicyclic epoxy compound (Α), and a mono-l-propyl propylene carbonate compound represented by the following formula (1) ( Β), an oxy-oxygen derivative (C) having two or more epoxy groups in the molecule, and a curing catalyst (f); [wherein R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. The curable epoxy resin composition according to claim 1 or 2, wherein the content of the oxoxane derivative (C) having two or more epoxy groups in the molecule is relative to the component (Α), the component (Β), and the combination of the components (c) S - 32 - 201237059 The metering (100% by weight) is 5 to 60% by weight. 4. The sclerosing epoxy resin composition according to any one of the claims s= 丄 to 3, wherein the alicyclic epoxy group of the lipid oxime compound (A) is epoxy hexene base. 5. If you apply for a patent range! The sclerosing epoxy resin composition according to any one of items 1 to 4, wherein the alicyclic s $ 阳*% oxygen compound (A) is a compound represented by the following formula; y' Ο A cured product obtained by hardening a curable epoxy resin composition according to any one of claims 5 to 5. A resin composition for sealing a photo-semiconductor comprising the curable epoxy resin composition according to any one of the first to fifth aspects of the invention. An optical semiconductor device obtained by sealing an optical semiconductor element with a resin composition for optical semiconductor sealing according to claim 7 of the patent application. , -33-