JP2017155145A - Curable epoxy resin composition for optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable epoxy resin composition for an optical material, which gives a cured product having good optical characteristics as well as crack resistance.SOLUTION: The curable epoxy resin composition comprises: an alicyclic epoxy compound (A) (excluding a compound of the following siloxane derivative (C)); a specific monoallyldiglycidyl isocyanurate compound (B) having specific sites which may be identical or different and have H or a 1-8C alkyl group; and a siloxane derivative (C) represented by formula (IV-1). In formula (IV-1), Reach independently represents a group containing an epoxy group, or an alkyl group, in which at least one Ris a group containing an epoxy group; and n represents an integer of 1-1000.SELECTED DRAWING: None

Description

  The present invention relates to a curable epoxy resin composition for optical materials, a cured product of the curable epoxy resin composition for optical materials, and an optical semiconductor device including the cured product.

  In recent years, the output of optical semiconductor devices has been increased, and as a resin used in optical semiconductor devices, cured products that give good optical properties (for example, transparency and light reflectivity) and crack resistance can be formed. There is a need for resins.

  In an optical semiconductor device, for the purpose of protecting an optical semiconductor element or the like, a cured product of the above resin may be used as a sealing material for covering the optical semiconductor element. In such a sealing material, the light that is supposed to be output is absorbed as the sealing material is colored by light or heat emitted from the optical semiconductor element, and as a result, the output from the optical semiconductor device is absorbed. There has been a problem that the luminous intensity of the emitted light decreases with time.

  In addition, the substrate in the optical semiconductor device (substrate for mounting an optical semiconductor element) has the above resin as a member for reflecting light (light reflecting material; reflector) in order to increase the extraction efficiency of light emitted from the optical semiconductor element. May be used. Such a light reflecting material is required to have high light reflectivity. However, like the sealing material, the light reflectivity decreases with time due to light and heat emitted from the optical semiconductor element. There has been a problem that the luminous intensity of light output from the semiconductor device decreases with time.

  So far, a resin composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin is known as a resin composition that imparts good optical properties to a cured product (see Patent Document 1). However, even when these compositions (cured products) are used as a sealing material or a light reflecting material, the light intensity of light output from a high-output optical semiconductor device decreases with time, so that optical properties are imparted. As a resin composition to be used, it was not sufficient.

  Moreover, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate as resins imparting good optical properties to the cured product Liquid alicyclic epoxy resins having an alicyclic skeleton such as adduct of ε-caprolactone and 1,2,8,9-diepoxylimonene are known. 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.

  In addition, the optical semiconductor device generally undergoes a reflow process for joining the electrodes of the optical semiconductor device to the wiring board by soldering. However, in recent years, lead-free solder having a high melting point has been used as a solder as a bonding material. The heat treatment in the reflow process is becoming higher (for example, the peak temperature is 240 to 260 ° C.). Under such circumstances, in the conventional optical semiconductor device, the encapsulant is peeled off from the lead frame of the optical semiconductor device by the heat treatment in the reflow process, or cracks are generated in the encapsulant or the light reflecting material (reflector). There was a problem of deterioration such as.

  For this reason, in addition to good optical characteristics, the sealing material and light reflecting material (reflector) in the optical semiconductor device are resistant to cracking even when a thermal shock is applied (referred to as “thermal shock resistance”). And properties that are unlikely to cause cracking or peeling even when heat-treated in the reflow process (this property is sometimes referred to as “reflow resistance”). The thermal shock resistance and the reflow resistance are sometimes collectively referred to as “crack resistance”.

  For this reason, the light intensity output from the optical semiconductor device (particularly, the optical semiconductor device provided with a high-output, high-brightness optical semiconductor element) is suppressed (that is, has good optical characteristics) and high. At present, there is a demand for a resin composition having crack resistance.

JP 2000-344867 A

  Therefore, the objective of this invention is providing the curable epoxy resin composition for optical materials which gives the hardened | cured material which has a favorable optical characteristic and crack resistance. Another object of the present invention is to provide a cured product having good optical properties and crack resistance. Another object of the present invention is to provide an optical semiconductor device including a cured product having both good optical characteristics and crack resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable epoxy resin composition for optical materials containing a specific alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, and a siloxane derivative is good. The present invention was completed by finding that a cured product having excellent optical properties and crack resistance was obtained.

［式中、Ｒ⁴及びＲ⁵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］
で表されるモノアリルジグリシジルイソシアヌレート化合物（Ｂ）と、下記式（ＩＶ−１）

［式中、２ｎ個のＲ^aは、互いに同一又は異なって、エポキシ基を含有する基、又はアルキル基を示す。ただし、Ｒ^aの少なくとも１つはエポキシ基を含有する基である。ｎは、１〜１０００の整数を示す。］
で表されるシロキサン誘導体（Ｃ）とを含むことを特徴とする光学材料用硬化性エポキシ樹脂組成物を提供する。 That is, the present invention includes an alicyclic epoxy compound (A) (excluding those corresponding to the siloxane derivative (C)) and the following formula (III-1):

[Wherein, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
And a monoallyl diglycidyl isocyanurate compound (B) represented by the following formula (IV-1)

[Wherein, 2n R ^{a s} are the same or different from each other and each represents a group containing an epoxy group or an alkyl group. However, at least one of R ^a is a group containing an epoxy group. n shows the integer of 1-1000. ]
The curable epoxy resin composition for optical materials characterized by including the siloxane derivative (C) represented by these.

  Moreover, the curable epoxy resin composition for optical materials in which the alicyclic epoxy group of the alicyclic epoxy compound (A) is a cyclohexene oxide group is provided.

で表される化合物である前記光学材料用硬化性エポキシ樹脂組成物を提供する。 Moreover, the said alicyclic epoxy compound (A) is a following formula (I-1).

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

  Moreover, the said curable epoxy resin composition for optical materials containing a white pigment (G) and an inorganic filler (H) is provided.

  Moreover, the said curable epoxy resin composition for optical materials which contains a hardening | curing agent (D) and a hardening accelerator (E), or contains a hardening catalyst (F) is provided.

  Moreover, the said curable epoxy resin composition for optical materials which is a resin composition for optical semiconductor sealing, or is a resin composition for light reflection is provided.

  Moreover, the hardened | cured material of the said curable epoxy resin composition for optical materials is provided.

  Moreover, the optical member containing the said hardened | cured material is provided.

  Also provided is an optical semiconductor device in which an optical semiconductor element is sealed with the cured product.

  Moreover, the optical semiconductor device provided with the reflector which consists of the said hardened | cured material at least is provided.

  Since the curable epoxy resin composition for optical materials of the present invention has the above-described configuration, a cured product having good optical characteristics and crack resistance can be obtained by curing the resin composition. In particular, when used as an optical semiconductor sealing application, it is possible to obtain a cured product having high transparency as optical characteristics, and when used as an optical reflection application, high light reflectivity is obtained. A cured product can be obtained.

  In addition, an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition for optical materials of the present invention exhibits good optical characteristics and crack resistance, and particularly has high transparency. In addition, the light intensity is less likely to decrease over time, and excellent quality and durability can be exhibited. In addition, the optical semiconductor device including a reflector made of a cured product of the curable epoxy resin composition for an optical material of the present invention exhibits good optical characteristics and crack resistance, and particularly has high light reflectivity and over time. Light reflectivity is unlikely to decrease, and excellent quality and durability can be exhibited. In particular, the curable epoxy resin composition for optical materials of the present invention may be used as a sealing material or a light reflecting material (reflector) of an optical semiconductor device provided with a high-output, high-brightness optical semiconductor element. Therefore, it is possible to suppress a decrease in light intensity of the optical semiconductor device over time.

It is the schematic which shows an example of the board | substrate for optical semiconductor element mounting in the optical semiconductor device of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. It is the schematic (sectional drawing) which shows an example of the optical semiconductor device of this invention. It is the schematic (sectional drawing; when it has a heat sink) which shows another example of the optical semiconductor device of this invention. It is the schematic (when it has a heat sink (radiation fin)) which shows another example of the optical semiconductor device of this invention. The left figure (a) is a top view, and the right figure (b) is a cross-sectional view along line AA 'in (a).

<Curable epoxy resin composition for optical material>
The curable epoxy resin composition for optical materials of the present invention comprises an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B) represented by the formula (III-1), and the formula ( It contains the siloxane derivative (C) represented by IV-1). The curable epoxy resin composition of the present invention may further contain a curing agent (D), a curing accelerator (E), a curing catalyst (F), a white pigment (G), and an inorganic filler (H). good. That is, an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B) represented by the formula (III-1), a siloxane derivative (C) represented by the formula (IV-1), It may be a curable epoxy resin composition for an optical material containing a curing agent (D) and a curing accelerator (E), or an alicyclic epoxy compound (A), which is represented by the formula (III-1). A curable epoxy resin composition for an optical material comprising a monoallyldiglycidyl isocyanurate compound (B) represented by formula (IV-1), a siloxane derivative (C) represented by formula (IV-1), and a curing catalyst (F). Further, it may be a curable epoxy resin composition for optical materials containing a white pigment (G) and an inorganic filler (H).

  In addition, the curable epoxy resin composition for optical materials of the present invention may be simply referred to as the curable epoxy resin composition of the present invention. In addition, the monoallyl diglycidyl isocyanurate compound (B) represented by the formula (III-1) may be simply referred to as “isocyanurate compound (B)”. Further, the siloxane derivative (C) represented by the formula (IV-1) may be simply referred to as “siloxane derivative (C)”.

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (alicyclic epoxy resin) (A), which is an essential component of the curable epoxy resin composition of the present invention, has an alicyclic (aliphatic hydrocarbon ring) structure in the molecule (in one molecule). It is a compound which has an epoxy group (oxiranyl group) at least, A well-known thru | or usual alicyclic epoxy compound can be used. However, those corresponding to the siloxane derivative (C) are excluded from the alicyclic epoxy compound (A). More specifically, as the alicyclic epoxy compound (A), for example, a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (alicyclic epoxy group) ( And a compound having an epoxy group that is directly bonded to the alicyclic ring with a single bond (sometimes referred to as “compound (A-2)”).

As said compound (A-1), the well-known thru | or usual compound which has 1 or more of alicyclic epoxy groups in a molecule | numerator can be used, It does not specifically limit. The alicyclic epoxy group is preferably a cyclohexene oxide group from the viewpoint of the optical properties of the cured product. In particular, the compound (A-1) is preferably a compound having two or more cyclohexene oxide groups in the molecule, more preferably a compound represented by the following formula (I), from the viewpoint of the optical properties of the cured product. is there.

  In formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized (sometimes referred to as an “epoxidized alkenylene group”), a carbonyl group, Examples include an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (I).

  Examples of the compound in which X in the formula (I) is a single bond include (3,4,3 ′, 4′-diepoxy) bicyclohexyl and the like.

  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, Examples thereof include cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (epoxidized alkenylene group) include, for example, vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene. Group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group and the like, and a linear or branched alkenylene group 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.

  As the linking group in X, a linking group containing an oxygen atom is particularly preferable. Specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-, epoxy 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 compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10), 2,2-bis (3,4-epoxycyclohexane- 1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, Bis (3,4-epoxycyclohexylmethyl) ether and the like can be mentioned. 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.

As a compound (A-2), the compound (epoxy resin) represented by following formula (II) is mentioned, for example.

In the above formula (II), R ¹ represents a p-valent organic group. p shows the integer of 1-20. Examples of the p-valent organic group include a p-valent organic group having a structure formed by removing p hydroxy groups from the structural formula of an organic compound having p hydroxy groups described later.

  In formula (II), q represents an integer of 1 to 50. In addition, when p is an integer greater than or equal to 2, several q may be the same and may differ. The sum (total) of q in Formula (II) is an integer of 3 to 100.

In the formula (II), R ² is a substituent on the cyclohexane ring shown in the formula and represents any of the groups represented by the following formulas (IIa) to (IIc). The bonding position of R ² on the cyclohexane ring is not particularly limited. Usually, when the positions of the two carbon atoms of the cyclohexane ring bonded to the oxygen atom are the 1st and 2nd positions, the 4th or 5th carbon atom It is. When the compound represented by the formula (II) has a plurality of cyclohexane rings, the bonding positions of R ² in each cyclohexane ring may be the same or different. At least one R ² in the formula (II) is a group (epoxy group) represented by the formula (IIa). In the case where the compound represented by the formula (II) has two or more R ^2, to a plurality of R ² may be the same or different.

In formula (IIc), R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl. Examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms such as a group. Examples of the alkylcarbonyl group include methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl. Examples thereof include a linear or branched alkyl-carbonyl group having 1 to 20 carbon atoms such as a carbonyl group. Examples of the arylcarbonyl group include arylcarbonyl groups having 6 to 20 carbon atoms such as phenylcarbonyl group (benzoyl group), 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, and the like.

Examples of the substituent that the above-described alkyl group, alkylcarbonyl group, and arylcarbonyl group may have include a substituent having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms). Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Preferably C _1-6 alkoxy group, more preferably C _1-4 alkoxy group); alkenyloxy group such as allyloxy group (preferably C _2-6 alkenyloxy group, more preferably C _2-4 alkenyloxy group) An acyloxy group such as an acetyloxy group, a propionyloxy group and a (meth) acryloyloxy group (preferably a C _1-12 acyloxy group); a mercapto group; an alkylthio group such as a methylthio group and an ethylthio group (preferably a C _1-6 alkylthio group) group, more preferably a C _1-4 alkylthio group); allyl alkenylthio such groups (Preferably C _2-6 alkenylthio group, more preferably C _2-4 alkenylthio group); carboxy; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, an alkoxycarbonyl group (preferably C such as butoxycarbonyl group _1-6 alkoxy-carbonyl group); amino group; mono- or dialkylamino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group (preferably mono- or di-C _1-6 alkylamino group); acetyl An acylamino group such as an amino group or a propionylamino group (preferably a C _1-11 acylamino group); an oxetanyl group-containing group such as an ethyl oxetanyloxy group; an acyl group such as an acetyl group or a propionyl group; an oxo group; It includes groups attached via a C _1-6 alkylene group optionally It is. In addition, examples of the substituent that the above-described arylcarbonyl group may have include the above-described substituted or unsubstituted alkyl group and the above-described substituted or unsubstituted alkylcarbonyl group.

The ratio of the group (epoxy group) represented by the formula (IIa) to the total amount (100 mol%) of R ^{2 in} the compound represented by the formula (II) is not particularly limited, but is 40 mol% or more (for example, 40 to 100 mol%) is preferable, more preferably 60 mol% or more, and still more preferably 80 mol% or more. When the ratio is 40 mol% or more, the optical properties (particularly, transparency and light reflectivity) of the cured product and mechanical properties tend to be further improved. The ratio can be calculated by, for example, ¹ H-NMR spectrum measurement or oxirane oxygen concentration measurement.

The compound represented by the formula (II) is not particularly limited. For example, an organic compound [R ¹ (OH) _p ] having p hydroxy groups in the molecule is used as an initiator (ie, the hydroxy group of the compound). (Starting with active hydrogen)), 1,2-epoxy-4-vinylcyclohexane (3-vinyl-7-oxabicyclo [4.1.0] heptane) is subjected to ring-opening polymerization (cationic polymerization), and then Manufactured by epoxidation with an oxidizing agent.

Examples of the organic compound [R ¹ (OH) _p ] having p hydroxy groups in the molecule include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol; ethylene glycol, diethylene glycol , Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, neopentyl glycol ester, cyclohexanedi Methanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, water Polyhydric alcohol such as bisphenol S; polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, acrylic polyol resin, styrene-allyl alcohol copolymer resin, polyester polyol, polycaprolactone polyol, polypropylene polyol, polytetramethylene glycol, polycarbonate polyol Examples thereof include oligomers or polymers having a hydroxy group such as polybutadiene having a hydroxy group, cellulose, cellulose acetate, cellulose acetate butyrate, and cellulose-based polymers such as hydroxyethyl cellulose.

  The 1,2-epoxy-4-vinylcyclohexane can be produced by a known or conventional method, and is not particularly limited. For example, 4-vinylcyclohexene obtained by a dimerization reaction of butadiene is replaced with an oxidizing agent such as peracetic acid. Obtained by partial epoxidation using. Moreover, as 1,2-epoxy-4-vinylcyclohexane, a commercial item can also be used.

  The oxidant may be a known or conventional oxidant such as hydrogen peroxide or organic peracid, and is not particularly limited. Examples of the organic peracid include performic acid, peracetic acid, peroxygen. Examples include benzoic acid and trifluoroperacetic acid. Among them, peracetic acid is preferable because it is industrially available at low cost and has high stability.

  More specifically, the ring-opening polymerization and epoxidation can be carried out according to well-known and conventional methods described in, for example, JP-A-60-161973.

  Although the weight average molecular weight of the compound represented by Formula (II) in terms of standard polystyrene is not particularly limited, it is preferably 300 to 100,000, more preferably 1000 to 10,000. If the weight average molecular weight is 300 or more, the optical properties and mechanical strength of the cured product tend to be improved. On the other hand, when the weight average molecular weight is 100,000 or less, the viscosity does not become too high and the fluidity during molding tends to be maintained low. The weight average molecular weight is measured by a gel permeation chromatography (GPC) method.

  Although the equivalent (epoxy equivalent) of the epoxy group of the compound represented by Formula (II) is not specifically limited, 50-1000 are preferable, More preferably, it is 100-500. When the epoxy equivalent is 50 or more, the cured product tends not to be brittle. On the other hand, when the epoxy equivalent is 1000 or less, the mechanical strength of the cured product tends to be improved. The epoxy equivalent is measured according to JIS K7236: 2001.

  As an alicyclic epoxy compound (A), a compound (A-1) and a compound (A-2) are preferable from a viewpoint of the optical characteristic (especially transparency and light reflectivity) of hardened | cured material. Especially, it is preferable that the curable epoxy resin composition of this invention contains a compound (A-1) at least from a viewpoint of optical characteristics (especially transparency and light reflectivity), and also contains a compound (A-2). It is more preferable. Moreover, as a compound (A-1), from a viewpoint of the optical characteristic of cured | curing material, and crack resistance, the compound [3,4-epoxy cyclohexyl methyl (3,4-) represented by the said formula (I-1) is shown. Epoxy) cyclohexanecarboxylate; for example, trade name “Celoxide 2021P” (manufactured by Daicel Corporation)] is particularly preferable.

  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. The alicyclic epoxy compound (A) can also be produced by a known or conventional method. For example, commercial names such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) are available. Can also be used.

  The content (blending amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is 0.1% with respect to the curable epoxy resin composition (100% by weight). -80 wt% is preferable, more preferably 0.5-75 wt%, still more preferably 1.0-70 wt%. By using the alicyclic epoxy compound (A) within the above range, the optical properties and crack resistance of the cured product tend to be improved. In addition, in this specification, each component (for example, an alicyclic epoxy compound (A), an isocyanurate compound (B), a siloxane derivative (C), a hardening | curing agent (D) contained in the curable epoxy resin composition of this invention. ), A curing accelerator (E), a curing catalyst (F), a white pigment (G), an inorganic filler (H), etc.), and the content thereof is such that the total is 100% by weight or less. It can select suitably from the inside.

  The ratio of the alicyclic epoxy compound (A) to the total amount of 100 parts by weight of the compound having an epoxy group contained in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 1 to 90 parts by weight, for example. More preferably, it is 3-80 weight part, More preferably, it is 5-70 weight part. By using the alicyclic epoxy compound (A) within the above range, the optical properties and crack resistance of the cured product tend to be improved. In addition, the compound which has an epoxy group contained in the curable epoxy resin composition of this invention is an alicyclic epoxy compound (A), an isocyanurate compound (B), a siloxane derivative (C), and the other mentioned later, for example. Of epoxy compounds.

[Monoallyl diglycidyl isocyanurate compound (B)]
The isocyanurate compound (B) which is an essential component of the curable epoxy resin composition of the present invention is a compound represented by the following formula (III-1). When the curable epoxy resin composition contains the isocyanurate compound (B), the crack resistance of the cured product tends to be improved.

In said formula (III-1), R < ⁴ > and R < ⁵ > are the same or different and show 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, and a hydrogen atom is particularly preferable.

  Representative examples of the isocyanurate compound (B) include monoallyldiglycidyl 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 can be mentioned.

  In addition, the said isocyanurate compound (B) can also be modified | denatured beforehand by adding the compound which reacts with epoxy groups, such as alcohol and an acid anhydride.

  In addition, in the curable epoxy resin composition of this invention, an isocyanurate compound (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, as an isocyanurate compound (B), commercial items, such as "DA-MGIC" (Shikoku Chemicals Co., Ltd. product), can also be used, for example.

  The use amount (blending amount) of the isocyanurate compound (B) in the curable epoxy resin composition of the present invention is preferably 0.5 to 60% by weight with respect to the curable epoxy resin composition (100% by weight), More preferably, it is 1.0 to 40 weight%, More preferably, it is 2.0 to 30 weight%. By using the isocyanurate compound (B) within the above range, the optical properties and crack resistance of the cured product tend to be improved.

  Although content (blending amount) of the isocyanurate compound (B) in the curable epoxy resin composition of the present invention is not particularly limited, the total amount of compounds having epoxy groups contained in the curable epoxy resin composition is 100 parts by weight. On the other hand, 1-80 weight part is preferable, More preferably, it is 3-50 weight part, More preferably, it is 5-30 weight part. By using the isocyanurate compound (B) within the above range, the optical properties and crack resistance of the cured product tend to be improved.

[Siloxane derivative (C)]
The siloxane derivative (C), which is an essential component of the curable epoxy resin composition of the present invention, is a siloxane derivative represented by the following formula (IV-1). When the curable epoxy resin composition contains the siloxane derivative (C), the optical properties and crack resistance (particularly heat-resistant peelability) of the cured product tend to be improved.

In formula (IV-1), 2n R ^{a s} are the same or different from each other, and represent an epoxy group-containing group or an alkyl group. However, at least one of R ^a is a group containing an epoxy group. The group containing an epoxy group is a group containing at least one epoxy group (oxirane ring), for example, a linear or branched aliphatic group having a carbon-carbon unsaturated double bond such as an alkenyl group. A group in which at least one double bond of a hydrocarbon group is epoxidized, or a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond (for example, cycloalkenyl group; cyclohexenylethyl group, etc. A group in which at least one double bond of the alkenylalkyl group or the like is epoxidized. More specifically, for example, 1,2-epoxyethyl group (epoxy group), 1,2-epoxypropyl group, 2,3-epoxypropyl group (glycidyl group), 2,3-epoxy-2-methylpropyl Group (methylglycidyl group), 3,4-epoxybutyl group, 3-glycidyloxypropyl group, 3,4-epoxycyclohexylmethyl group, 2- (3,4-epoxycyclohexyl) ethyl group and the like. Examples of the alkyl group include straight chain or branched chain groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group. An alkyl group etc. are mentioned. Especially, a C1-C10 linear or branched alkyl group is preferable.

  The group containing an epoxy group contained in the siloxane derivative (C) is not particularly limited, but from the viewpoint of improving the optical properties of the cured product and crack resistance (particularly heat-resistant peelability), the adjacent 2 constituting the alicyclic ring. A group containing an epoxy group (alicyclic epoxy group) composed of two carbon atoms and an oxygen atom is preferred, and among them, a group containing a cyclohexene oxide group is particularly preferred.

  In formula (IV-1), n represents an integer of 1 to 1000. In particular, from the viewpoint of improving optical characteristics (particularly transparency and light reflectivity), n is preferably 1 to 500, more preferably 5 to 300, and still more preferably 10 to 200.

  The number of epoxy groups that the siloxane derivative (C) has in the molecule is not particularly limited, but from the viewpoint of improving the optical properties (particularly transparency and light reflectivity) of the cured product, 1 to 50 is preferable, more preferably. 2 to 30, more preferably 3 to 10.

  Moreover, the siloxane derivative (C) is preferably a siloxane derivative represented by the following formula (IV-2) from the viewpoints of transparency of the cured product, light reflectivity, and crack resistance (particularly heat-resistant peelability).

In formula (IV-2), l A's are the same as or different from each other, and represent an epoxy group-containing group, specifically the same as those exemplified for ^Ra in formula (IV-1). Things. In addition, (l + 2m) R ^{b s} are the same or different from each other and represent an alkyl group, and specifically, the same as those exemplified for R ^a in Formula (IV-1) can be given.

  In formula (IV-2), l represents an integer of 1 to 50. In particular, from the viewpoint of improving the optical properties of the cured product, 1 to 30 is preferable, and 3 to 10 is more preferable. Moreover, m shows the integer of 1-500, and 10-300 are preferable from a viewpoint of improving the optical characteristic of hardened | cured material, More preferably, it is 50-200.

  Although the weight average molecular weight of a siloxane derivative (C) is not specifically limited, From a viewpoint of improving the optical characteristic of hardened | cured material, 300-100000 are preferable, More preferably, it is 350-50000, More preferably, it is 400-30000. In addition, the said weight average molecular weight of a siloxane derivative (C) is computed from the molecular weight of standard polystyrene conversion measured by GPC (gel permeation chromatography) method.

  Although the epoxy equivalent of a siloxane derivative (C) is not specifically limited, From a viewpoint of improving the optical characteristic of hardened | cured material, 100-10000 are preferable, More preferably, it is 120-3000, More preferably, it is 150-1000. The epoxy equivalent is a value measured according to JIS K7236.

  In addition, in the curable epoxy resin composition of this invention, a siloxane derivative (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type. The siloxane derivative (C) can be produced by a known or conventional method.

  The use amount (blending amount) of the siloxane derivative (C) in the curable epoxy resin composition of the present invention is preferably 0.1 to 95% by weight relative to the curable epoxy resin composition (100% by weight). Preferably it is 0.5 to 90 weight%, More preferably, it is 1.0 to 85 weight%. By controlling the content of the siloxane derivative (C) within the above range, the optical properties (particularly transparency and light reflectivity) of the cured product tend to be further improved.

  The content (blending amount) of the siloxane derivative (C) 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 compounds having epoxy groups contained in the curable epoxy resin composition. The amount is preferably 5 to 98 parts by weight, more preferably 10 to 95 parts by weight, and still more preferably 15 to 90 parts by weight. By controlling the content of the siloxane derivative (C) within the above range, the optical properties (particularly transparency and light reflectivity) of the cured product tend to be further improved.

[Curing agent (D)]
The curable epoxy resin composition of the present invention may contain a curing agent (D). The curing agent (D) is a compound having a function of curing the curable epoxy resin composition by reacting with a compound having an epoxy group such as the alicyclic epoxy compound (A). As the curing agent (D), known or conventional epoxy resin curing agents can be used, and are not particularly limited. For example, acid anhydrides (acid anhydride curing agents), amines (amine curing) Agents), polyamide resins, imidazoles (imidazole-based curing agents), polymercaptans (polymercaptan-based curing agents), phenols (phenol-based curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides and the like.

  As acid anhydrides (acid anhydride-based curing agents) in the curing agent (D), known or conventional acid anhydride-based curing agents can be used, and are not particularly limited. For example, methyltetrahydrophthalic anhydride (4- Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride), dodecenyl succinic anhydride, methyl end Methylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride Acid, methyl nadic anhydride, methyl hydride Dic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride Examples include acid copolymers and alkylstyrene-maleic anhydride copolymers. Among them, from the viewpoint of efficiently preparing a uniform curable epoxy resin composition, from the viewpoint of easily mixing with the alicyclic epoxy compound (A) to form a liquid mixture (curing agent composition) at 25 ° C, Preference is given to acid anhydrides [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] which are liquid at 25 ° C. 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 (D in the curable epoxy resin composition of the present invention (D ) Tends to be improved. As the acid anhydride curing agent, from the viewpoint of heat resistance and transparency of the cured product, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those having a substituent such as an alkyl group bonded to the ring) are preferable.

  As the amines (amine-based curing agent) in the curing agent (D), known or conventional amine-based curing agents can be used, and are not particularly limited. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylene Aliphatic polyamines such as propylenediamine, diethylaminopropylamine, polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethyl Alicyclic polyamines such as piperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; m-phenylenediamine, p-phenylenediamine, tri 2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6- Examples include mononuclear polyamines such as diamine, aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.

  As the phenols (phenolic curing agent) in the curing agent (D), 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, 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 in the curing agent (D) 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) in the curing agent (D), 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-methylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)] -Ethyl-s-triazine and the like.

  Examples of the polymercaptans (polymercaptan-based curing agent) in the curing agent (D) include liquid polymercaptans and polysulfide resins.

  Examples of the polycarboxylic acids in the curing agent (D) include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxy group-containing polyester, and the like.

  Especially, as a hardening | curing agent (D), an acid anhydride (acid anhydride type hardening | curing agent) is preferable from a viewpoint of the optical characteristic of hardened | cured material. In addition, the hardening | curing agent (D) 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. The curing agent can be produced by a known or commonly used method. For example, trade names “Ricacid MH-700”, “Ricacid MH-700F”, “Ricacid MH-700G”, “Ricacid TH”, “Ricacid” "HH", "Licacid HNA-100" (manufactured by Shin Nippon Rika Co., Ltd.); trade name "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.); trade names "H-TMAn-S", "H Commercially available products such as “-TMAn” (manufactured by Mitsubishi Gas Chemical Co., Inc.); trade name “YH1120” (manufactured by Mitsubishi Chemical Co., Ltd.) can also be used.

  When the curable epoxy resin composition of the present invention contains a curing agent (D), the content (blending amount) of the curing agent (D) is not particularly limited, but the curable epoxy resin composition (100% by weight). The content is preferably 0.1 to 80% by weight, more preferably 1 to 70% by weight, and still more preferably 5 to 60% by weight. By setting the content of the curing agent (D) to 0.1% by weight or more, the curing becomes more sufficient, and the crack resistance of the cured product tends to be improved. On the other hand, by setting the content of the curing agent (D) to 80% by weight or less, there is a tendency that a cured product that is suppressed in coloring and excellent in hue is easily obtained.

  When the curable epoxy resin composition of the present invention contains a curing agent (D), the content (blending amount) of the curing agent (D) is not particularly limited, but is an epoxy group contained in the curable epoxy resin composition. 40 to 200 parts by weight is preferable, more preferably 60 to 160 parts by weight with respect to 100 parts by weight of the total amount of the compounds having bismuth. More specifically, when acid anhydrides are used as the curing agent (D), 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 setting the content of the curing agent (D) to 40 parts by weight or more, the curing becomes more sufficient, and the crack resistance of the cured product tends to be improved. On the other hand, by setting the content of the curing agent (D) to 200 parts by weight or less, there is a tendency that a cured product that is suppressed in coloring and excellent in hue is easily obtained.

[Curing accelerator (E)]
The curable epoxy resin composition of the present invention may contain a curing accelerator (E). The curing accelerator (E) is a compound having a function of accelerating the reaction rate when the compound having an epoxy group contained in the curable epoxy resin composition of the present invention reacts with a curing agent such as the curing agent (D). It is. As the curing accelerator (E), a known or conventional curing accelerator can be used. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, phenol) Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, Octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, etc. Secondary amines; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Ether, phosphines such as triphenyl phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p- tolyl) borate, organic metal salts such as zinc octylate and tin octylate; metal chelate and the like.

  A hardening accelerator (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.

  The curing accelerator (E) can also be produced by a known or conventional method. For example, trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, "U-CAT 18X", "12XD" (developed product) (San Apro Co., Ltd.); trade names "TPP-K", "TPP-MK" (Hokuko Chemical Co., Ltd.); Commercial products such as the name “PX-4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) can also be used.

  When the curable epoxy resin composition of the present invention contains a curing accelerator (E), the content (blending amount) of the curing accelerator (E) is not particularly limited, but the curable epoxy resin composition (100 weight) %) To 0.001 to 5% by weight, more preferably 0.01 to 3% by weight. By setting the content of the curing accelerator (E) to 0.001% by weight or more, the curing reaction tends to proceed more efficiently. On the other hand, by setting the content of the curing accelerator (E) to 5% by weight or less, there is a tendency that a cured product having suppressed hue and excellent hue can be easily obtained.

  When the curable epoxy resin composition of the present invention contains a curing accelerator (E), the content (blending amount) of the curing accelerator (E) is not particularly limited, but is included in the curable epoxy resin composition. 0.05-10 weight part is preferable with respect to 100 weight part of whole quantity of the compound which has an epoxy group, More preferably, it is 0.1-5 weight part. By setting the content of the curing accelerator to 0.05 parts by weight or more, the curing reaction tends to proceed more efficiently. On the other hand, by setting the content of the curing accelerator to 10 parts by weight or less, there is a tendency that a cured product having suppressed hue and excellent hue can be easily obtained.

[Curing catalyst (F)]
The curable epoxy resin composition of the present invention may contain a curing catalyst (F). The curing catalyst (F) has a function of curing the curable epoxy resin composition by initiating and / or accelerating the curing reaction (polymerization reaction) of a cationically polymerizable compound such as the alicyclic epoxy compound (A). A compound. The curing catalyst (F) is not particularly limited. For example, a cationic polymerization initiator (photo cationic polymerization initiator, thermal cationic polymerization) that initiates polymerization by generating cationic species by performing light irradiation, heat treatment, or the like. Initiators, etc.), Lewis acid / amine complexes, Bronsted acid salts, imidazoles and the like.

  Examples of the photocationic polymerization initiator in the curing catalyst (F) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically, For example, triarylsulfonium hexafluorophosphate (for example, p-phenylthiophenyl diphenylsulfonium hexafluorophosphate, etc.), sulfonium salts such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salts); diaryl iodonium hexafluorophosphate, Diaryliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodo Iodonium salts such as um [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 in the curing catalyst (F) 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" (BASF Commercially available products such as those manufactured by Kogyo Co., Ltd. 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 diketone 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 in the curing catalyst (F), 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 in the curing catalyst (F), 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, phosphonium salts. Etc.

  As the imidazoles in the curing catalyst (F), known or conventional imidazoles can be used, and are not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-undecylimidazole. 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4- The 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 (F) can be used alone or in combination of two or more. In addition, as above-mentioned, a commercial item can also be used as a curing catalyst (F).

  When the curable epoxy resin composition of the present invention contains a curing catalyst (F), the content (blending amount) of the curing catalyst (F) is not particularly limited, but the curable epoxy resin composition (100% by weight). Is preferably 0.001 to 5% by weight, more preferably 0.01 to 3% by weight. By using the curing catalyst (F) within the above range, the curing reaction can be efficiently advanced, and the resulting cured product tends to have high transparency.

  When the curable epoxy resin composition of the present invention contains a curing catalyst (F), the content (blending amount) of the curing catalyst (F) in the curable epoxy resin composition of the present invention is not particularly limited. 0.001 to 15 parts by weight is preferable with respect to 100 parts by weight of the total amount of the compound having an epoxy group contained in the conductive epoxy resin composition, more preferably 0.01 to 12 parts by weight, and still more preferably 0.05 to 10 parts by weight. By using the curing catalyst (F) within the above range, the curing reaction can be efficiently advanced, and the resulting cured product tends to have high transparency.

[White pigment (G)]
When the curable epoxy resin composition of the present invention is used as a resin composition for light reflection, it preferably contains a white pigment (G), and contains a white pigment (G) and an inorganic filler (H) described later. Is more preferable. The white pigment (G) mainly has a function of imparting high light reflectivity to the cured product (reflector). As the white pigment, a known or conventional white pigment can be used, and is not particularly limited. For example, glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acid clay, activated clay, boehmite. Inorganic white pigments such as pseudoboehmite, inorganic oxides, metal salts [for example, alkaline earth metal salts]; styrene resins, benzoguanamine resins, urea-formalin resins, melamine-formalin resins, amide resins, etc. White pigments such as resin pigments (plastic pigments); hollow particles having a hollow structure (balloon structure), and the like.

  As the white pigment (G), it is preferable to use a white pigment having a high refractive index in order to increase the reflectance of the reflector. For example, a white pigment having a refractive index of 1.5 or more is preferable. However, since the white pigment having a hollow particle structure contains a gas having a low refractive index inside (core) and has a very high surface reflectance, the shell portion may be made of a material having a refractive index lower than 1.5. . Of those exemplified as the white pigment (G), those corresponding to the inorganic filler (H) are those having a refractive index of 1.5 or more as the white pigment (G) and having a refractive index of 1.5. The smaller one is the inorganic filler (H).

  Examples of the inorganic oxide include aluminum oxide (alumina), magnesium oxide, antimony oxide, titanium oxide [eg, rutile titanium oxide, anatase titanium oxide, brookite titanium oxide, etc.], zirconium oxide, zinc oxide, and the like. Can be mentioned. Examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, and sulfuric acid. Barium etc. are mentioned. Examples of the metal salt other than the alkaline earth metal salt include aluminum silicate, aluminum hydroxide, and zinc sulfide.

  Although it does not specifically limit as said hollow particle, For example, inorganic glass [For example, silicate glass, aluminum silicate glass, sodium borosilicate glass, quartz, etc.], metal oxides, such as silica and alumina, calcium carbonate, barium carbonate, Inorganic hollow particles composed of inorganic materials such as nickel carbonate and calcium silicate (including natural products such as Shirasu Balloon); styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride -Based resins, vinylidene chloride-based resins, amide-based resins, urethane-based resins, phenol-based resins, styrene-conjugated diene-based resins, acrylic-conjugated diene-based resins, olefin-based polymers (including cross-linked products of these polymers), etc. Organic hollow particles composed of organic materials; hybrid materials of inorganic and organic materials Configured inorganic - organic hollow particles, and the like. In addition, the said hollow particle may be comprised from the single material, and may be comprised from 2 or more types of materials. The hollow portion of the hollow particles (the space inside the hollow particles) may be in a vacuum state or may be filled with a medium. In particular, from the viewpoint of improving the reflectance, the refractive index is high. Hollow particles filled with a low medium (for example, an inert gas such as nitrogen or argon or air) are preferred.

  The white pigment (G) is subjected to a known or conventional surface treatment [for example, a surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone]. It may be what was done. By performing such a surface treatment, there are cases where compatibility and dispersibility with other components in the curable epoxy resin composition can be improved.

  Among them, the white pigment (G) is preferably an inorganic oxide or an inorganic hollow particle, more preferably from the viewpoints of availability and a high reflectance of a cured product (reflector) and an increase in light reflectivity with respect to the addition amount. Aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, barium sulfate, inorganic hollow particles, more preferably titanium oxide, zirconium oxide, zinc oxide, barium sulfate. In particular, the white pigment (G) is preferably titanium oxide because it has a higher refractive index.

  The shape of the white pigment (G) is not particularly limited, and examples thereof include a spherical shape, a crushed shape, a fibrous shape, a needle shape, and a scale shape. Among these, spherical titanium oxide is preferable from the viewpoint of dispersibility, and particularly spherical titanium oxide (for example, spherical titanium oxide having an aspect ratio of 1.2 or less) is preferable.

  Although the center particle diameter of a white pigment (G) is not specifically limited, 0.1-50 micrometers is preferable from a viewpoint of the light reflectivity improvement of hardened | cured material (reflector). In particular, when titanium oxide is used as the white pigment (G), the center particle diameter of the titanium oxide is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, and still more preferably 0. 0.1-20 μm, particularly preferably 0.1-10 μm, most preferably 0.1-5 μm. On the other hand, when hollow particles (particularly inorganic hollow particles) are used as the white pigment (G), the center particle diameter of the hollow particles is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 0.1 μm. 30 μm. In addition, the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.

  In the curable epoxy resin composition of the present invention, the white pigment (G) can be used alone or in combination of two or more. The white pigment (G) can also be produced by a known or conventional method. For example, trade names “SR-1”, “R-42”, “R-45M”, “R-650”, “R-32”, “R-5N”, “GTR-100”, “R-62N”, “R-7E”, “R-44”, “R-3L”, “R-11P”, “R -21 "," R-25 "," TCR-52 "," R-310 "," D-918 "," FTR-700 "(above, manufactured by Sakai Chemical Industry Co., Ltd.) -50 "," CR-50-2 "," CR-60 "," CR-60-2 "," CR-63 "," CR-80 "," CR-90 "," CR-90-2 " "," CR-93 "," CR-95 "," CR-97 "(manufactured by Ishihara Sangyo Co., Ltd.), trade names" JR-301 "," JR-403 " JR-405, JR-600A, JR-605, JR-600E, JR-603, JR-805, JR-806, JR-701, JRNC , “JR-800”, “JR” (manufactured by Teika Co., Ltd.), trade names “TR-600”, “TR-700”, “TR-750”, “TR-840”, “TR-900” "(Fuji Titanium Industry Co., Ltd.), trade names" KR-310 "," KR-380 "," KR-380N "," ST-410WB "," ST-455 "," ST-455WB " , “ST-457SA”, “ST-457EC”, “ST-485SA15”, “ST-486SA”, “ST-495M” (above, manufactured by Titanium Industry Co., Ltd.), etc .; A-110 "," TCA-123 "," A-190 "," A-197 "," SA-1 "," SA-1L "," SSP series "," CSB series "(above, manufactured by Sakai Chemical Industry Co., Ltd.) JA-1 "," JA-C "," JA-3 "(manufactured by Teika Co., Ltd.), trade names" KA-10 "," KA-15 "," KA-20 "," STT-65C " -S "," STT-30EHJ "(above, manufactured by Titanium Industry Co., Ltd.), trade names" DCF-T-17007 "," DCF-T-17008 "," DCF-T-17050 "(above, Resino Color Industries) Commercial products such as anatase-type titanium oxide such as (manufactured by Co., Ltd.) can also be used.

  Among these, as the white pigment (G), particularly from the viewpoint of light reflectivity of a cured product (reflector), trade names “R-62N”, “CR-60”, “DCF-T-17007”, “DCF-T” -17008 "," DCF-T-17050 "," FTR-700 "are preferable.

  When using the curable epoxy resin composition of the present invention as a resin composition for light reflection, the content (blending amount) of the white pigment (G) is not particularly limited, but the curable epoxy resin composition (100% by weight). ) To 0.1 to 50% by weight, more preferably 1 to 40% by weight, still more preferably 3 to 35% by weight. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more by making content of a white pigment (G) into the said range. Moreover, the fluidity | liquidity fall of the curable epoxy resin composition by addition of a white pigment (G) is suppressed, and there exists a tendency for workability | operativity to improve more.

  When the curable epoxy resin composition of the present invention is used as a resin composition for light reflection, the content (blending amount) of the white pigment (G) is not particularly limited, but the epoxy contained in the curable epoxy resin composition. The amount is preferably 10 to 600 parts by weight, more preferably 30 to 500 parts by weight, and still more preferably 50 to 400 parts by weight with respect to 100 parts by weight of the total amount of the compound having a group. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more by making content of a white pigment (G) into the said range. Moreover, the fluidity | liquidity fall of the curable epoxy resin composition by addition of a white pigment (G) is suppressed, and there exists a tendency for workability | operativity to improve more.

  When titanium oxide is contained in the curable epoxy resin composition of the present invention, the ratio of titanium oxide to the total amount (100% by weight) of the white pigment (G) and the inorganic filler (H) is not particularly limited. From the viewpoint of the balance between the heat resistance (yellowing resistance) of the (reflector) and the light reflectivity, it is preferably 5 to 70% by weight, more preferably 10 to 60% by weight. By making the ratio of titanium oxide 5% by weight or more, the light reflectivity of the cured product (reflector) tends to be further improved. Moreover, there exists a tendency for heat resistance (especially yellowing resistance) and light resistance to improve more. On the other hand, by setting the proportion of titanium oxide to 70% by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.

  When the curable epoxy resin composition of the present invention is used as a resin composition for encapsulating an optical semiconductor, it may contain a white pigment (G), but its content does not lose the transparency of the cured product. It is preferable that Specifically, the content (blending amount) of the white pigment (G) is preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of the compound having an epoxy group contained in the curable epoxy resin composition. Preferably it is 5 weight part or less, More preferably, it is 1 weight part or less.

[Inorganic filler (H)]
When using the curable epoxy resin composition of this invention as a resin composition for light reflections, it is preferable that an inorganic filler (H) is included. The inorganic filler (H) imparts excellent optical properties to the cured product. Moreover, it has the function to reduce the linear expansion coefficient of hardened | cured material.

  As the inorganic filler (H), a known or conventional inorganic filler can be used, and is not particularly limited. For example, silica, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, Silicon nitride, aluminum nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, fosterite, steatite, spinel, clay, kaolin, dolomite , Hydroxyapatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, talc and the like, or moldings thereof (for example, spherical beads). Examples of the inorganic filler (H) include those obtained by subjecting the above-described inorganic filler to a known or conventional surface treatment. Among these, as the inorganic filler (H), silica, alumina, silicon nitride, aluminum nitride, and boron nitride are preferable from the viewpoint of optical properties and fluidity of the cured product.

  The silica is not particularly limited, and for example, known or commonly used silica such as fused silica, crystalline silica, high-purity synthetic silica or the like can be used. Silica has been subjected to a known or conventional surface treatment [for example, surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone]. Can also be used.

  The shape of silica is not particularly limited, and examples thereof include powder, spherical shape, crushed shape, fibrous shape, needle shape, scale shape, and the like. Among these, spherical silica is preferable from the viewpoint of dispersibility, and spherical silica (for example, spherical silica having an aspect ratio of 1.2 or less) is particularly preferable.

  The center particle diameter of silica is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm from the viewpoint of improving the light reflectivity of the cured product (reflector). In addition, the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.

  In the curable epoxy resin composition of the present invention, the inorganic filler (H) can be used alone or in combination of two or more. The inorganic filler (H) can also be produced by a known or conventional production method. For example, trade names “FB-910”, “FB-940”, “FB-950”, “FB-105”. , “FB-105FD”, “FB-5D”, “FB-8S”, “FB-7SDC”, “FB-5SDC”, “FB-3SDC”, “FB-9FDC”, “FB-7FDC”, FB series such as “FB-5FDC”, “FB-970FD”, “FB-975FD”, “FB-950FD”, “FB-40RFD”, trade names “DAW-03DC”, “DAW-0525”, “DAW DAW series such as “-1025”, trade name “SGP” (manufactured by Denka Corporation), trade name “HF-05” (manufactured by Tokuyama Corporation), trade name “10 μm SE-CC5” (manufactured by Admatech) ), Trade names "MSR-2212", "MSR-25" (above, manufactured by Tatsumori Co., Ltd.), trade names "HS-105", "HS-106", "HS-107" (above, Micron) Commercially available products such as those manufactured by the company may also be used.

  When the curable epoxy resin composition of the present invention is used as a resin composition for light reflection, the content (blending amount) of the inorganic filler (H) is not particularly limited, but the curable epoxy resin composition (100 weight) %) To 10 to 90% by weight, more preferably 13 to 80% by weight, still more preferably 15 to 70% by weight. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more by making content of an inorganic filler (H) into 10 weight% or more. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and defects such as warping of the lead frame in the optical semiconductor element mounting substrate using the reflector tend not to occur. On the other hand, when the content of the inorganic filler (H) is 90% by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.

  When using the curable epoxy resin composition of the present invention as a resin composition for light reflection, the content (blending amount) of the inorganic filler (H) is not particularly limited, but is included in the curable epoxy resin composition. The amount is preferably 10 to 1500 parts by weight, more preferably 50 to 1200 parts by weight, and still more preferably 70 to 1000 parts by weight with respect to 100 parts by weight of the total amount of the compound having an epoxy group. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more because content of an inorganic filler (H) is 10 weight part or more. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and defects such as warping of the lead frame in the optical semiconductor element mounting substrate using the reflector tend not to occur. On the other hand, when the content of the inorganic filler (H) is 1500 parts by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.

  When the curable epoxy resin composition of the present invention is used as a resin composition for encapsulating an optical semiconductor, it may contain an inorganic filler (H), but its content does not lose the transparency of the cured product. It is preferable that it is a grade. Specifically, the content (blending amount) of the inorganic filler (H) is preferably 20 parts by weight or less with respect to 100 parts by weight of the total amount of the compound having an epoxy group contained in the curable epoxy resin composition, More preferably, it is 10 parts weight or less, More preferably, it is 5 parts weight or less.

  The maximum particle size of the white pigment (G) and the inorganic filler (H) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 200 μm or less, more preferably 185 μm or less, still more preferably 175 μm or less, Particularly preferably, it is 150 μm or less. When the maximum particle size is 200 μm or less, there is a tendency that the optical properties (light reflectivity) and crack resistance of the cured product are more excellent than when a white pigment or an inorganic filler having a maximum particle size exceeding 200 μm is used. is there. In addition, by using the white pigment (G) and the inorganic filler (H) having a small maximum particle size, it is possible to increase the content thereof, and the light reflectivity and crack resistance of the cured product are further improved. Tend to. The lower limit of the maximum particle size is, for example, 0.01 μm or more. The maximum particle size is the total maximum particle size of the white pigment (G) and the inorganic filler (H) contained in the curable epoxy resin composition of the present invention. The maximum particle size means the maximum particle size in the particle size distribution measured by the laser diffraction / scattering method.

[Other epoxy compounds]
The curable epoxy resin composition of the present invention further includes an epoxy compound other than the alicyclic epoxy compound (A), the isocyanurate compound (B), and the siloxane derivative (C) (sometimes referred to as “other epoxy compounds”). May be included). As said other epoxy compound, the well-known thru | or usual compound which has 1 or more epoxy groups (oxirane ring) in a molecule | numerator can be used, Although it does not specifically limit, For example, an aromatic epoxy compound (aromatic epoxy resin) ), Aliphatic epoxy compounds (aliphatic epoxy resins), heterocyclic epoxy compounds other than isocyanurate compounds (B) (heterocyclic epoxy resins), and at least one epoxy group in the molecule other than the siloxane derivative (C) Examples thereof include siloxane derivatives. The said other epoxy compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The curable epoxy resin composition of the present invention may contain a heterocyclic epoxy compound other than the above isocyanurate compound (B) (hereinafter sometimes simply referred to as “other isocyanurate compound”), Examples thereof include diallyl monoglycidyl isocyanurate compounds represented by the following formula (III-2) and triglycidyl isocyanurate compounds represented by the following formula (III-3).

In the above formulas (III-2) and (III-3), R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include 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, and a hydrogen atom is particularly preferable.

  Representative examples of the compound represented by the formula (III-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. Further, representative examples of the compound represented by the above formula (III-3) include triglycidyl isocyanurate, tris (2-methylepoxypropyl) isocyanurate, and the like.

  In addition, the said other isocyanurate compound can also be modified | denatured beforehand by adding the compound which reacts with epoxy groups, such as alcohol and an acid anhydride.

  In addition, in the curable epoxy resin composition of this invention, another isocyanurate compound can also be used individually by 1 type, and can also be used in combination of 2 or more type. As other isocyanurate compounds, for example, commercially available products such as trade name “TEPIC” (manufactured by Nissan Chemical Industries, Ltd.); trade name “DA-MGIC” (manufactured by Shikoku Kasei Kogyo Co., Ltd.) are used. You can also.

[Rubber particles]
The curable epoxy resin composition of the present invention may contain rubber particles. Examples of the rubber particles include particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, particulate SBR (styrene-butadiene rubber), and the like. The rubber particle has a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion, and a functional group capable of reacting with an alicyclic epoxy compound on the surface. Rubber particles having a hydroxyl group and / or a carboxyl group, an average particle diameter of 10 nm to 500 nm, and a maximum particle diameter of 50 nm to 1000 nm, wherein the refractive index of the rubber particles and the curable epoxy resin composition Rubber particles having a difference from the refractive index of the cured product within ± 0.02 may be used. The blending amount of the rubber particles can be appropriately adjusted as necessary, and is not particularly limited.

[Release agent]
When the curable epoxy resin composition of the present invention is used as a resin composition for light reflection, it may further contain a release agent. By including a release agent, continuous molding by a molding method using a mold such as transfer molding is facilitated, and a cured product (reflector) can be produced with high productivity. As the release agent, known or commonly used release agents can be used, and are not particularly limited. For example, fluorine release agents (fluorine atom-containing compounds; such as fluorine oil and polytetrafluoroethylene), Silicone release agents (silicone compounds; for example, silicone oil, silicone wax, silicone resin, polyorganosiloxane having a polyoxyalkylene unit), wax release agents (waxes; for example, plant waxes such as carnauba wax) Animal waxes such as wool wax, paraffins such as paraffin wax, polyethylene wax, oxidized polyethylene wax, etc.), higher fatty acids or salts thereof (for example, metal salts), higher fatty acid esters, higher fatty acid amides, mineral oils, etc. .

  In addition, in the curable epoxy resin composition of this invention, a mold release agent can also be used individually by 1 type, and can also be used in combination of 2 or more type. Moreover, a mold release agent can also be manufactured by a well-known thru | or usual method, and a commercial item can also be used for it.

  When the curable epoxy resin composition of the present invention contains a release agent, the content (mixing amount) of the release agent is not particularly limited. In addition, when using the curable epoxy resin composition of this invention as a resin composition for optical semiconductor sealing, it may contain the mold release agent, but does not need to contain it.

[Antioxidant]
The curable epoxy resin composition of the present invention may contain an antioxidant. By containing an antioxidant, it becomes possible to produce a cured product having further excellent heat resistance (particularly yellowing resistance). As the antioxidant, known or commonly used antioxidants can be used, and are not particularly limited. For example, phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), phosphorus System antioxidants (phosphorus compounds), sulfur antioxidants (sulfur compounds), and the like.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl- 6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro 5.5] Bisphenols such as undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [ 3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl-4 ′ -Hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, polymer type phenols such as tocophenol, and the like.

  Examples of the hindered amine antioxidant include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl. ] Butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine and the like can be mentioned.

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2 , 4-di-tert-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. Fights; 9,10-di Dro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene Examples include oxaphosphaphenanthrene oxides such as -10-oxide.

  Examples of the sulfur-based antioxidant include dodecanethiol, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. Is mentioned.

  In the curable epoxy resin composition of the present invention, the antioxidant can be used alone or in combination of two or more. The antioxidant can also be produced by a known or conventional method. For example, the trade name “Irganox 1010” (manufactured by BASF, a phenolic antioxidant), trade names “AO-60”, “AO-80”. ”(Manufactured by ADEKA Corporation, phenolic antioxidant), trade name“ Irgafos168 ”(manufactured by BASF, phosphorous antioxidant), trade names“ Adekastab HP-10 ”,“ Adekastab PEP-36 ”(Co., Ltd.) Commercial products such as ADEKA (phosphorus antioxidant) and trade name “HCA” (manufactured by Sanko Co., Ltd., phosphorus antioxidant) can also be used.

  When the curable epoxy resin composition of the present invention contains an antioxidant, the content (blending amount) of the antioxidant is not particularly limited, but the compound having an epoxy group contained in the curable epoxy resin composition is not limited. 0.1-5 weight part is preferable with respect to 100 weight part of whole quantity, More preferably, it is 0.5-3 weight part. By setting the content of the antioxidant to 0.1 parts by weight or more, oxidation of the cured product is efficiently prevented, and heat resistance and yellowing resistance tend to be further improved. On the other hand, by setting the content of the antioxidant to 5 parts by weight or less, coloring tends to be suppressed and a cured product having a better hue tends to be obtained.

[Additive]
In addition to the above, various additives can be used in the curable epoxy resin composition of the present invention as long as the effects of the present invention are not impaired. As the additive, for example, when a compound having a hydroxy group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is used, the reaction can be allowed to proceed slowly. In addition, as long as the viscosity and transparency are not impaired, an antifoaming agent, a leveling agent, a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, a surfactant, Conventional additives such as flame retardants, colorants, ion adsorbents, ultraviolet absorbers, light stabilizers, and pigments other than white pigments can be used. The content of these additives is not particularly limited and can be appropriately selected.

  The curable epoxy resin composition of the present invention is obtained by heating and reacting part of the alicyclic epoxy compound (A) and the curing agent (D) in the curable epoxy resin composition, B A staged curable epoxy resin composition (a curable epoxy resin composition in a B-stage state) may be used.

  The curable epoxy resin composition of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components in a heated state as necessary. 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, two or more stored separately. These components can also be used as a multi-liquid composition (for example, a two-liquid system) that is used by mixing them at a predetermined ratio before use. The stirring / mixing method is not particularly limited, and for example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.

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

<Light reflection resin composition>
The curable epoxy resin composition of the present invention may be used as a light reflecting resin composition. That is, the cured product may be used for a light reflecting material such as a reactor. By using the resin composition for light reflection, an optical semiconductor device using a cured product excellent in various physical properties such as initial light reflectivity, light resistance, heat resistance, and crack resistance as a reflector can be obtained. Even if the optical semiconductor device includes an optical semiconductor element with high output and high brightness, the light intensity is unlikely to decrease with time.

<Hardened product>
By curing the curable epoxy resin composition of the present invention, a cured product having excellent optical properties and various physical properties such as crack resistance can be obtained (hereinafter referred to as the cured product of the present invention). is there). Although the heating temperature (curing temperature) in the case of hardening 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.

  The cured product of the present invention has high transparency and light reflectivity, and is excellent in crack resistance (heat resistance and light resistance). Therefore, the curable epoxy resin composition of the present invention can be used for optical semiconductor sealing (for example, LED sealing material) or LED package (for LED package components, for example, a reflector material in an optical semiconductor device, a housing). Material). In addition to the above, adhesives, electrical insulating materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members, light Modeling, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, chip parts, bare chip mounting, optical fiber, optical pickup sensor (for example, optical pickup sensor in DVD recorder, Blue Ray recorder, etc.), photoelectric sensor (For example, a photoelectric sensor in a non-contact switch), a color sensor (for example, a color sensor in a camera, a printer, etc.), an illuminance sensor (for example, an illuminance sensor in a mobile terminal, a television, etc.), a proximity sensor (for example, a mobile terminal, etc.) Proximity sensor) Composite sensor (e.g., a composite sensor in the portable terminal and the like), an image sensor (e.g., an image sensor in a camera or the like), AF sensor (e.g., AF sensor in the camera, etc.) can also be used for various applications such as MEMS implementation.

[Luminance retention]
Although the luminous intensity retention of the cured product of the present invention is not particularly limited, for example, it is preferably 75% or more, more preferably 80% or more, and further preferably 85% or more.

In addition, as a measuring method of luminous intensity retention, after casting a curable epoxy resin composition to the lead frame (InGaN element, 3.5 mm x 2.8 mm) of an optical semiconductor, 120 degreeC oven (resin hardening oven) By heating for 5 hours, an optical semiconductor device in which the LED element is sealed with a cured resin can be created and measured by the following procedure.
[Energization test (measurement of luminous intensity retention)]
The total luminous flux of the optical semiconductor device is measured using a total luminous flux measuring instrument (“total luminous flux for 0 hour”), and a constant temperature bath of 85 ° C. (small high temperature chamber: trade name “ST-120B1, Espec Corp.) The total luminous flux after applying a current of 60 mA to the optical semiconductor device for 750 hours is measured ("total luminous flux after 750 hours"), and the luminous intensity retention is calculated from the following equation.
{Luminance retention (%)}
= {Total luminous flux after 750 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

[Initial reflectance]
The reflectance (initial reflectance) of the cured product of the present invention is not particularly limited. For example, the reflectance of light having a wavelength of 450 nm is preferably 85% or more, and more preferably 90% or more. In particular, the reflectance of light at 450 to 800 nm is preferably 85% or more, more preferably 90% or more.

[Reflectivity retention ratio (1)]
Retention rate of the cured product of the present invention at a wavelength of 450 nm after heating at 120 ° C. for 100 hours (sometimes referred to as “reflectance after heating aging”) relative to the initial reflectance ([heating aging (Reflectance after) / [Initial reflectance] × 100) is not particularly limited, but is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. In particular, the retention in the case of 450 to 800 nm light is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.

[Reflectance retention rate (2)]
Retention rate of the cured product of the present invention at a wavelength of 450 nm after heating at 150 ° C. for 100 hours (sometimes referred to as “reflectance after heating aging”) with respect to the initial reflectance ([heating aging The “reflectance after” / [initial reflectance] × 100) is not particularly limited, but is preferably 85% or more, and more preferably 90% or more. In particular, the retention in the case of 450 to 800 nm light is preferably 85% or more, and more preferably 90% or more.

[Reflectance retention rate (3)]
Retention of the reflectance of the cured product of the present invention with respect to light having a wavelength of 450 nm after irradiation with ultraviolet rays having an intensity of 10 mW / cm ² for 120 hours (sometimes referred to as “reflectance after ultraviolet ray aging”) relative to the initial reflectance. The rate ([reflectance after ultraviolet ray aging] / [initial reflectance] × 100) is not particularly limited, but is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more. . In particular, the retention in the case of 450 to 800 nm light is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more.

  The reflectance is measured, for example, using a cured product of the present invention (thickness: 3 mm) as a test piece and using a spectrophotometer (trade name “Spectrophotometer UV-2450”, manufactured by Shimadzu Corporation). can do.

  When the curable epoxy resin composition of the present invention is a curable epoxy resin composition for a reflector in an optical semiconductor device, the curable epoxy resin composition of the present invention is a substrate of an optical semiconductor element (optical semiconductor) in the optical semiconductor device. This is a molding material (material used for molding with a mold or the like) used for forming a reflector (light reflecting member) included in the element mounting substrate. Therefore, by molding (and curing) the curable epoxy resin composition of the present invention, it has high light reflectivity, excellent heat resistance and light resistance, and further has a reflector having excellent crack resistance. It is possible to manufacture a substrate for mounting an optical semiconductor element (for example, highly durable). The reflector is a member for reflecting light emitted from the optical semiconductor element in the optical semiconductor device to increase the directivity and luminance of the light and improve the light extraction efficiency. A substrate used for mounting an optical semiconductor element having at least a reflector formed of the cured product of the present invention may be referred to as “optical semiconductor element mounting substrate of the present invention”.

<Optical member>
Since the hardened | cured material of this invention has a favorable optical characteristic, it is used also for optical members other than the optical semiconductor sealing material mentioned above and the material for light reflection. For example, as an optical member including the cured product of the present invention (using a cured product), it can be used as an optical lens, electronic paper, a touch panel, an optical waveguide, and the like.

<Optical semiconductor device mounting substrate>
The optical semiconductor device of the present invention may have an optical semiconductor element mounting substrate. Moreover, the optical semiconductor element mounting substrate of the present invention is a substrate that may have a reflector (white reflector) formed of a cured product of the curable epoxy resin composition of the present invention. FIG. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention, where (a) is a perspective view and (b) is a cross-sectional view. In FIG. 1, 100 is a white reflector, 101 is a metal wiring (lead frame), 102 is an optical semiconductor element mounting region, and 103 is a package substrate. A metal wiring 101 and a white reflector 100 are attached to the package substrate 103. An optical semiconductor element 107 is placed in the center (optical semiconductor element mounting region 102) and die-bonded. And the metal wiring 101 on the package substrate 103 are connected by wire bonding. As the material of the package substrate 103, resin, ceramic, or the like is used, but it may be the same as the white reflector. The upper white reflector 100 in the optical semiconductor element mounting substrate of the present invention has a concave shape that surrounds the optical semiconductor element mounting region 102 in an annular shape and is inclined so that the diameter of the ring increases upward. Have. The substrate for mounting an optical semiconductor element of the present invention only needs to have at least the inner surface of the concave shape formed of a cured product of the curable epoxy resin composition of the present invention. Further, as shown in FIG. 1, the portion surrounded by the metal wiring 101 (the lower part of 102) may be the package substrate 103 or the white reflector 100 (that is, “100/103 in FIG. 1). "Means the white reflector 100 or the package substrate 103). However, the optical semiconductor element mounting substrate of the present invention is not limited to the embodiment shown in FIG.

  As a method for forming a white reflector in the substrate for mounting an optical semiconductor element of the present invention, a known or conventional molding method (for example, compression molding or the like) can be used, and is not particularly limited. And a method of subjecting the conductive epoxy resin composition to various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and dam molding by dispensing. The curing conditions for forming the reflector can be appropriately selected from, for example, the conditions for forming the cured product. In the present invention, in particular, it is possible to prevent foaming due to a rapid curing reaction, to relieve stress strain due to curing and to improve crack resistance, and to perform heat treatment in multiple stages and cure in stages. It is preferable to make it.

  The optical semiconductor device of the present invention is obtained by using the optical semiconductor element mounting substrate of the present invention as a substrate in an optical semiconductor device and mounting the optical semiconductor element on the substrate.

<Optical semiconductor device>
The optical semiconductor device of the present invention is an optical semiconductor device comprising at least an optical semiconductor element as a light source and a sealing material and / or a reflector (reflecting material) made of a cured product of the curable epoxy resin composition of the present invention. . More specifically, 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 of the present invention, or the curable epoxy of the present invention. An optical semiconductor device comprising at least a reflector made of a cured product of a resin composition.

  FIG. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention. In FIG. 2, 100 is a white reflector, 101 is a metal wiring (lead frame), 103 is a package substrate, 104 is a bonding wire, 105 is a sealing material, 106 is die bonding, and 107 is an optical semiconductor element (LED element). In the optical semiconductor device shown in FIG. 2, the light emitted from the optical semiconductor element 107 is reflected by the surface (reflecting surface) of the white reflector 100, so that the light from the optical semiconductor element 107 is extracted with high efficiency. As shown in FIG. 2, the optical semiconductor element in the optical semiconductor device of the present invention is usually sealed with a transparent sealing material (105 in FIG. 2).

  3 and 4 are diagrams showing another example of the optical semiconductor device of the present invention. Reference numeral 108 in FIGS. 3 and 4 denotes a heat sink (case heat sink), and by having such a heat sink 108, the heat radiation efficiency in the optical semiconductor device is improved. FIG. 3 is an example in which the heat dissipation path of the heat sink is located immediately below the optical semiconductor element, and FIG. 4 is an example in which the heat dissipation path of the heat sink is positioned in the lateral direction of the optical semiconductor device [(a) is a top view, (B) shows an AA ′ cross-sectional view in (a)]. The heat sink 108 protruding from the side surface of the optical semiconductor device in FIG. 4 may be referred to as a heat radiating fin. Further, reference numeral 109 in FIG. 4 denotes a cathode mark. However, the optical semiconductor device of the present invention is not limited to the embodiment shown in FIGS.

  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, the unit of the compounding quantity of each component of the curable epoxy resin composition in Tables 1-4 is a weight part. Moreover, "-" in Tables 1-4 means that the said component was not mix | blended.

Production Example 1 / Production of Curing Agent Composition (K Agent) In the blending ratio (unit: parts by weight) shown in Table 1, the trade name “Rikacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.) -CAT 18X "(manufactured by San Apro Co., Ltd.) and ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), a revolving stirrer (trade name" Awatori Neritaro AR-250 ", manufactured by Shinky Co., Ltd.) ) To obtain a curing agent composition (hereinafter referred to as K agent).

Production Example 2
(Production of Siloxane Derivative 1)
100 g of methylhydrosiloxane-dimethylsiloxane copolymer (Poly (dimethylsiloxane-co-methylhydrosiloxane), trimethylsilyl terminated, molecular weight 950, manufactured by Sigma-Aldrich), 30.5 g of Celoxide 2000 (manufactured by Daicel Corporation), and 18 g Of tetramethylammonium hydroxide was charged into a reaction vessel, and 80 g of a 50% distilled water methanol solution was added dropwise over 60 minutes, followed by reaction for 3 hours under reflux. Then, it neutralized with 5% sodium dihydrogen phosphate aqueous solution, and methanol was removed at 80 ° C. Further, 300 g of methyl isobutyl ketone was added, and washing with water was repeated three times. Next, the solvent was removed from the organic layer under reduced pressure at 100 ° C., to obtain 95 g of an organopolysiloxane compound having a reactive functional group (epoxy group) (sometimes referred to as “siloxane derivative 1”). The epoxy equivalent of the obtained siloxane derivative 1 was 280 g / eq, and the viscosity at 25 ° C. was 300 mPa · s.

Example 1
According to the formulation (unit: parts by weight) shown in Table 1, alicyclic epoxy compound (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate: trade name “Celoxide 2021P”, manufactured by Daicel Corporation )), Isocyanuric acid derivative (monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and stirred at 80 ° C. for 1 hour, and then the siloxane obtained in Production Example 2 The derivative 1 was mixed to obtain an epoxy resin (composition). Next, this epoxy resin and the K agent obtained in Production Example 1 are uniformly mixed using a self-revolving stirrer so as to have the blending ratio shown in Table 1, defoamed, and cured. An epoxy resin composition was obtained.
Further, the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) illustrated in FIG. 1, and then 5 in a resin curing oven at 120 ° C. By heating for an hour, an optical semiconductor device in which the optical semiconductor element was sealed with a cured product of the curable epoxy resin composition was obtained.

Examples 2-6, Comparative Examples 1-4
A curable epoxy resin composition and an optical semiconductor device were obtained in the same manner as in Example 1 except that the blending composition was changed as shown in Table 1.

Example 7
According to the formulation (unit: parts by weight) shown in Table 2, alicyclic epoxy compound (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate: trade name “Celoxide 2021P”, manufactured by Daicel Corporation )), Isocyanuric acid derivative (monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and stirred at 80 ° C. for 1 hour, and then the siloxane obtained in Production Example 2 The derivative 1 was mixed to obtain an epoxy resin (composition). Next, this epoxy resin and the trade name “Sun-Aid SI-100L” (manufactured by Sanshin Chemical Industry Co., Ltd.) are mixed uniformly using a self-revolving stirrer so that the blending ratio shown in Table 2 is obtained. 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) illustrated in FIG. By heating at 140C for 3 hours and then at 140C for 4 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.

Examples 8-12, Comparative Examples 5-8
A curable epoxy resin composition and an optical semiconductor device were obtained in the same manner as in Example 7 except that the blending composition was changed as shown in Table 2.

<Evaluation (Examples 1-12 and Comparative Examples 1-8)>
About the optical semiconductor device obtained in Examples 1-12 and Comparative Examples 1-8, the evaluation test was done with the following method.

[Energization test (measurement of luminous intensity retention)]
The total luminous fluxes of the optical semiconductor devices obtained in Examples 1 to 12 and Comparative Examples 1 to 8 were measured using a total luminous flux measuring machine (OL771, multispectral radiation measurement system, manufactured by Optronic Laboratories). It was defined as “0 hour total luminous flux”. Furthermore, the total luminous flux after flowing a current of 60 mA to the optical semiconductor device was measured for 750 hours in an 85 ° C. constant temperature bath (small high temperature chamber: trade name “ST-120B1, manufactured by Espec Corp.”). Was “total luminous flux after 750 hours”. And luminous intensity retention was computed from the following formula. The results are shown in the column of “Luminance retention [%]” in Tables 1 and 2.
{Luminance retention (%)}
= {Total luminous flux after 750 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

[Solder heat resistance test (JEDEC standard level 1)]
The optical semiconductor devices obtained in Examples 1-12 and Comparative Examples 1-8 (two were used for each curable epoxy resin composition) were allowed to stand for 168 hours at 85 ° C. and 85% RH. To absorb moisture. Subsequently, the said optical semiconductor device was put into the reflow furnace, and it heat-processed on the following heating conditions. Thereafter, the optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then again placed in a reflow furnace and heat-treated under the same conditions. That is, in the solder heat resistance test, the thermal history under the following heating conditions was given to the optical semiconductor device three times.
[Heating conditions (based on surface temperature of optical semiconductor device)]
(1) Preheating: 150 to 190 ° C. for 60 to 120 seconds (2) Main heating after preheating: 230 ° C. or more and 60 to 150 seconds, maximum temperature 260 ° C.
However, the rate of temperature increase during the transition from preheating to main heating was controlled to 3 ° C./second at the maximum.
FIG. 2 shows an example of a surface temperature profile (temperature profile in one of the two heat treatments) of the optical semiconductor device when heated by the reflow furnace.
Thereafter, the optical semiconductor device was observed using a digital microscope, and whether or not a crack having a length of 90 μm or more occurred in the cured product, and electrode peeling (peeling of the cured product from the electrode surface) occurred. It was evaluated whether or not. Of the two optical semiconductor devices, the number of optical semiconductor devices having a crack of 90 μm or longer in the cured product is shown in the column of “Solder heat resistance test [number of cracks]” in Tables 1 and 2, The number of the generated optical semiconductor devices is shown in the column of “Solder heat resistance test [electrode peeling number]” in Tables 1 and 2.

[Thermal shock test]
The optical semiconductor devices obtained in Examples 1 to 12 and Comparative Examples 1 to 8 (two were used for each curable epoxy resin composition) were exposed in an atmosphere of −40 ° C. for 30 minutes, followed by A thermal shock with one cycle of exposure to an atmosphere of 120 ° C. for 30 minutes was applied for 500 cycles using a thermal shock tester (Espec Co., Ltd., small thermal shock apparatus TSE-11-A). Thereafter, the length of the crack generated in the sealing resin of the optical semiconductor device (cured product of the curable epoxy resin composition) was observed using a digital microscope (VHX-900, manufactured by Keyence Corporation), Of the two optical semiconductor devices, the number of optical semiconductor devices having cracks having a length of 90 μm or more was measured. The results are shown in the column of “thermal shock test [number of cracks]” in Tables 1 and 2.

[Comprehensive judgment]
As a result of each test, what satisfy | filled all the following (1)-(4) was determined as (circle) (good). On the other hand, when any of the following (1) to (4) was not satisfied, it was determined as x (defective).
(1) Current test: luminous intensity retention of 85% or more (2) Solder heat resistance test (number of cracks): No. of optical semiconductor devices with cracks of 90 μm or more in cured product (3) Solder Heat resistance test (number of electrode peeling): No. of optical semiconductor devices with electrode peeling occurred (4) Thermal shock test: No. of optical semiconductor devices with a crack of 90 μm or longer in cured product The results are shown in the “overall determination” column of Tables 1 and 2.

Example 13
Aliphatic epoxy compounds (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate: trade name “Celoxide 2021P”, manufactured by Daicel Corporation)), isocyanuric acid derivatives at the blending ratios shown in Table 3 (Monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was stirred at 80 ° C. for 1 hour, and then the siloxane derivative 1 obtained in Production Example 2 was mixed. An epoxy resin (composition) was obtained. Next, Table 3 shows the epoxy resin, white pigment (trade name “TCR-52”, manufactured by Sakai Chemical Industry Co., Ltd.) and inorganic filler (trade name “FB-970FD”, manufactured by Denka Co., Ltd.). According to the blending ratio shown, they were uniformly mixed using a dissolver, and kneaded by a roll mill under predetermined conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3 passes). Thereafter, the composition after kneading and the K agent obtained in Production Example 1 are uniformly mixed using a self-revolving stirrer so as to have the blending ratio shown in Table 3, defoamed, and cured. An epoxy resin composition was obtained.
Further, the curable epoxy resin composition is cast into a mold (5.0 cm × 10.0 cm; the same applies hereinafter), placed in a resin curing oven, and heated at 120 ° C. for 5 hours to obtain a cured product. It was.

Example 14
Aliphatic epoxy compounds (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate: trade name “Celoxide 2021P”, manufactured by Daicel Corporation)), isocyanuric acid derivatives at the blending ratios shown in Table 4 (Monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was stirred at 80 ° C. for 1 hour, and then the siloxane derivative 1 obtained in Production Example 2 was mixed. An epoxy resin (composition) was obtained. Next, Table 3 shows the epoxy resin, white pigment (trade name “TCR-52”, manufactured by Sakai Chemical Industry Co., Ltd.) and inorganic filler (trade name “FB-970FD”, manufactured by Denka Co., Ltd.). According to the blending ratio shown, they were uniformly mixed using a dissolver, and kneaded by a roll mill under predetermined conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3 passes). Thereafter, the composition after kneading and the trade name “Sun-Aid SI-100L” (manufactured by Sanshin Chemical Industry Co., Ltd.) are uniformly mixed using a self-revolving stirrer so that the mixing ratio shown in Table 4 is obtained The mixture was mixed and degassed to obtain a curable epoxy resin composition.
Further, the curable epoxy resin composition is cast into a mold (5.0 cm × 10.0 cm; the same applies hereinafter), placed in a resin curing oven, and heated at 120 ° C. for 5 hours to obtain a cured product. It was.

<Evaluation (Examples 13 and 14)>
The cured products obtained in Examples 13 and 14 were evaluated as follows.

[Initial reflectance]
The cured product obtained in the example was cut to prepare a test piece having a length of 30 mm, a width of 30 mm, and a thickness of 3 mm. Next, using a spectrophotometer (trade name “Spectrophotometer UV-2450”, manufactured by Shimadzu Corporation), the reflectance of each test piece with respect to light having a wavelength of 450 nm (referred to as “initial reflectance”) is measured. did. The results are shown in the column of “initial reflectance” in Tables 3 and 4.
If the initial reflectance is 90% or more, it can be said that the material is particularly excellent as a light reflecting material.

[Reflectivity retention before and after heating aging-1]
Using a test piece (cured product; length 30 mm × width 30 mm × 3 mm thickness) on which the initial reflectance was evaluated, the test piece was placed in a dryer at 120 ° C. and allowed to stand for 100 hours (heat resistance test). After the measurement, the reflectance of light having a wavelength of 450 nm was measured in the same manner as the initial reflectance, and the reflectance (reflectance after heating aging-1) was obtained. And the reflectance holding | maintenance rate (before and after heating aging -1) was computed by the following formula. The results are shown in the columns of “before and after heating aging-1” in Tables 3 and 4.
[Reflectance retention ratio (before and after heating aging-1)] = ([Reflectance after heating aging-1] / [Initial reflectance]) × 100
It is suggested that the higher the reflectance retention, the better the cured product is in heat resistance. In addition, if the reflectance retention after heating at 120 ° C. for 100 hours is 95% or more, it can be said that the material is particularly excellent in heat resistance as a light reflecting material.

[Reflectivity retention before and after heating aging-2]
Using a test piece (cured product: length 30 mm × width 30 mm × 3 mm thickness) on which the initial reflectance was evaluated, the test piece was placed in a dryer at 150 ° C. and allowed to stand for 100 hours (heat resistance test). After the measurement, the reflectivity of light having a wavelength of 450 nm was measured in the same manner as the initial reflectivity to obtain the reflectivity (reflectance -2 after heating aging). And the reflectance holding | maintenance rate (before and after heating aging -2) was computed by the following formula. The results are shown in the column of “before and after heating aging-2” in Tables 3 and 4.
[Reflectance retention ratio (before and after heating aging-2)] = ([Reflectance after heating aging-2] / [Initial reflectance]) × 100
It is suggested that the higher the reflectance retention, the better the cured product is in heat resistance. In addition, if the reflectance retention after heating at 150 ° C. for 100 hours is 90% or more, it can be said that the material is particularly excellent in heat resistance as a light reflecting material.

[Reflectance retention before and after UV aging]
Using a test piece (cured product; length 30 mm × width 30 mm × 3 mm thickness) for which the initial reflectance was evaluated, the test piece was irradiated with ultraviolet light having an intensity of 10 mW / cm ² for 120 hours (light resistance test) ), The reflectance of light having a wavelength of 450 nm was measured in the same manner as the initial reflectance. And the reflectance retention (before and after ultraviolet ray aging) was computed by the following formula. The results are shown in the columns “before and after UV aging” in Tables 3 and 4.
[Reflectance retention (before and after ultraviolet aging)] = ([Reflectance after ultraviolet aging] / [Initial reflectance]) × 100
It is suggested that the higher the reflectance retention, the more excellent the light resistance of the cured product. In addition, it can be said that it is especially excellent in light resistance as a light-reflecting material if intensity | strength is 10 mW / cm < ² > and the reflectance retention rate after 250-hour irradiation is 95% or more.

[Evaluation of crack presence during cutting (crack resistance evaluation)]
The cured product obtained in the example was cut to prepare a test piece having a width of 5 mm, a length of 5 mm, and a thickness of 3 mm. For cutting of the cured product, a micro cutting machine (trade name “BS-300CL”, manufactured by Meiwa Forsys Co., Ltd.) is used. This was observed and confirmed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation). In Tables 3 and 4, 10 test pieces are prepared for each sample, and the number [pieces / 10 pieces] of the test pieces in which the occurrence of cracks is confirmed is shown as an evaluation result.

[Evaluation of crack presence during reflow (crack resistance evaluation)]
Using a reflow furnace (trade name “UNI-5016F”, manufactured by Nippon Antom Co., Ltd.) for the test piece (width 5 mm × length 5 mm × thickness 3 mm) obtained by the above cutting, the maximum is 260 ° C. The reflow treatment was performed at a temperature of 5 seconds and a total reflow time of 90 seconds. Thereafter, whether or not the test piece was cracked by the reflow treatment was observed and confirmed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation). Tables 3 and 4 show the number of test pieces [pieces / 10 pieces] in which the occurrence of cracks was confirmed as an evaluation result after reflow treatment of 10 test pieces per sample.

[Comprehensive judgment]
As a result of each test, what satisfy | filled all the following (1)-(6) was determined as (circle) (good). On the other hand, when any of the following (1) to (6) was not satisfied, it was determined as x (defective).
(1) Initial reflectance: light reflectance is 90% or more (2) Reflectivity retention ratio before and after heating aging-1: Reflectivity retention ratio is 95% or more (3) Reflectivity retention ratio before and after heating aging-2: Reflectivity retention ratio is 90% or more (4) Reflectivity retention ratio before and after UV aging: Reflectivity retention ratio is 95% or more (5) Evaluation of crack existence at the time of cutting: Number of cracks is 0 (6) Evaluation of presence / absence of cracks during reflow: The number of cracks generated is 0. The results are shown in the “Comprehensive judgment” column of Tables 3 and 4.

In addition, the component shown to Tables 1-4 is demonstrated below.
(Epoxy resin)
Celoxide 2021P: Trade name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate), manufactured by Daicel Corporation EHPE3150: Trade name “EHPE3150” (2,2-bis (hydroxymethyl) ) -1-Butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct), manufactured by Daicel Corporation (isocyanurate compound)
MA-DGIC: Trade name “MA-DGIC” [monoallyl diglycidyl isocyanurate], manufactured by Shikoku Chemicals Co., Ltd. (siloxane derivative)
Siloxane derivative 1: Siloxane derivative obtained in Production Example 2 X-40-2670: Trade name “X-40-2670” (cyclic siloxane derivative having four epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd. Made (curing agent composition (K agent))
MH-700: Trade name “Licacid MH-700” (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride), manufactured by Shin Nippon Rika Co., Ltd. 18X: Trade name “U-CAT 18X” (curing accelerator) , San Apro Co., Ltd. Ethylene glycol: Trade name "Ethylene glycol", Wako Pure Chemical Industries, Ltd. (curing catalyst)
SI-100L (Sun-Aid SI-100L): Arylsulfonium salt, manufactured by Sanshin Chemical Industry Co., Ltd. (white pigment)
TCR-52: Trade name “TCR-52” (titanium oxide), manufactured by Sakai Chemical Industry Co., Ltd. (inorganic filler)
FB-970FD: trade name “FB-970FD” (silica, no surface treatment, average particle size 16.7 μm, maximum particle size 70 μm), manufactured by Denka Corporation

100: White reflector 101: Metal wiring (electrode)
102: Mounting area of optical semiconductor element 103: Package substrate 104: Bonding wire 105: Sealing material for optical semiconductor element 106: Die bonding 107: Optical semiconductor element 108: Heat sink 109: Cathode mark

Claims (10)

Alicyclic epoxy compound (A) (excluding those corresponding to siloxane derivative (C)) and the following formula (III-1)

[Wherein, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]
And a monoallyl diglycidyl isocyanurate compound (B) represented by the following formula (IV-1)

[Wherein, 2n R ^{a s} are the same or different from each other and each represents a group containing an epoxy group or an alkyl group. However, at least one of R ^a is a group containing an epoxy group. n shows the integer of 1-1000. ]
The curable epoxy resin composition for optical materials characterized by including the siloxane derivative (C) represented by these.   The curable epoxy resin composition for optical materials according to claim 1, wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is a cyclohexene oxide group. The alicyclic epoxy compound (A) is represented by the following formula (I-1)

The curable epoxy resin composition for optical materials according to claim 1, wherein the curable epoxy resin composition is represented by the formula:   The curable epoxy resin composition for optical materials according to any one of claims 1 to 3, further comprising a white pigment (G) and an inorganic filler (H).   Furthermore, curable epoxy resin composition for optical materials of any one of Claims 1-4 which contains a hardening | curing agent (D) and a hardening accelerator (E), or contains a hardening catalyst (F).   It is a resin composition for optical semiconductor sealing, or is a resin composition for light reflection, The curable epoxy resin composition for optical materials of any one of Claims 1-5.   Hardened | cured material of the curable epoxy resin composition for optical materials of any one of Claims 1-6.   An optical member comprising the cured product according to claim 7.   An optical semiconductor device in which an optical semiconductor element is sealed with the cured product according to claim 7.   An optical semiconductor device comprising at least a reflector made of the cured product according to claim 7.

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