TW201307423A - Curable epoxy resin composition - Google Patents

Abstract

The present invention provides a curable epoxy composition, which has high photo reflectivity and excellent heat resistance and photo resistance, and is tenacious and its photo reflectivity is not easy to be declined during a period of time. The curable epoxy resin composition of the present application is characterized by containing alicyclic epoxy compound (A), monoally digylcidyl isocyanurate represented by the following formula (1), white pigment (C), curable agent (D), and curable enhancer (F), or is characterized by containing alicyclic epoxy compound (A), monoally digylcidyl isocyanurate represented by the following formula (1), white pigment (C), and curable catalyst (E), [in formula, R1 and R2 represent hydrogen atom or alkyl group having carbon number of 1 to 8].

Description

Curable epoxy resin composition

The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, a curable resin composition for light reflection comprising the curable epoxy resin composition, and An optical semiconductor device including at least an optical semiconductor element and a reflective material including the cured material.

In recent years, various types of indoor or outdoor display panels, light sources for image reading, traffic signals, components for large displays, and the like, and the use of light-emitting devices using optical semiconductor elements (LED elements) as light sources are progressing. In general, such a light-emitting device has an optical semiconductor element, a transparent resin that protects the periphery of the optical semiconductor element, and has an efficiency for extracting light emitted from the optical semiconductor element and reflecting the light. A light-emitting device of a reflector is widely used.

The above-mentioned reflective material is required to have high light reflectivity, and such high light reflectivity can continue to be exerted. In the case of the constituent material of the above-mentioned reflective material, a resin composition obtained by dispersing an inorganic filler or the like in a polyamine resin (polyamide resin) having a phthalic acid unit as an essential constituent unit is known. (Refer to Patent Documents 1 to 3).

In addition, a thermosetting resin composition for light reflection containing a thermosetting resin containing an epoxy resin and a refractive index of 1.6 to 3.0 is known as a constituent material of the above-mentioned reflective material. Inorganic oxide (refer to Patent Document 4). Further, a thermosetting resin composition for light reflection is known which contains a thermosetting resin component and one or more kinds thereof. The filler component is controlled to a specific range by the difference between the refractive index of the entire thermosetting resin component and the refractive index of each filler component, and the parameter calculated from the volume ratio of each filler component (see Patent Document 5).

Prior technical literature

Patent literature

Patent Document 1 JP-A-2000-204244

Patent Document 2, JP-A-2004-75994

Patent Document 3, JP-A-2006-257314

Patent Document 4, JP-A-2010-235753

Patent Document 5, JP-A-2010-235756

However, the reflective material of the above-mentioned polyimide resin described in Patent Documents 1 to 3 is particularly a light-emitting device using a blue semiconductor light having a high output and a white light semiconductor as a light source, and light emitted from the optical semiconductor element. The heat and the like cause yellowing or the like to deteriorate over time, and there is a problem that sufficient light reflectivity cannot be maintained. Further, with the use of lead-free solder, the heating temperature of the reflow step (solder reflow step) at the time of manufacture of the light-emitting device tends to be higher, and the above-mentioned reflective material is also present due to the heat applied in such a manufacturing step. It deteriorates over time and causes a problem of low light reflectivity.

In addition, in the reflective material of the cured product of the thermo-reflective resin composition for light reflection described in Patent Documents 4 and 5, triglycidyl isocyanurate is used as a main component of the thermosetting resin. The heat resistance is insufficient, and the heat generated from the optical semiconductor element or the heat in the reflow step causes a problem that the reflectance is lowered over time.

Further, in addition to the above-described heat resistance and light resistance, the above-mentioned reflective material may be subjected to stress caused by cutting processing or temperature change (for example, heating at a very high temperature such as a reflow step, low-temperature circulation, etc.). It is required to be less likely to be cracked (cracked) (the case where such a property is referred to as "crack resistance") and is strong. Since the light reflectivity is low (i.e., the light extraction efficiency is low) when the reflective material is cracked, it is difficult to secure the reliability of the light-emitting device.

Therefore, the current situation requires a material which is excellent in heat resistance and light resistance and is tough, and can form defects and light reflectance which are not deteriorated or cracked even at a higher output, short-wavelength light or high temperature. A reflective material that is not easily lowered by time.

Therefore, an object of the present invention is to provide a curable epoxy resin composition which has high light reflectivity, is excellent in heat resistance and light resistance, and is strong, and is capable of supplying a cured product which is less likely to be lowered in light reflectance over time.

Further, another object of the present invention is to provide a cured product obtained by curing the curable epoxy resin composition, having high light reflectivity, excellent heat resistance and light resistance, and being strong and light reflective. Because of the time and down.

Further, another object of the present invention is to provide a light-reflecting resin composition for light reflection, which is capable of obtaining an optical semiconductor device which suppresses a decrease in luminance due to passage of time.

Further, another object of the present invention is to provide an optical semiconductor device which is less likely to have low luminance and high signal reliability due to passage of time.

In order to solve the above problems, the inventors of the present invention have found that an alicyclic epoxy compound, an allyl cyanurate monoallyl diglycidyl ester compound and a white pigment are contained as essential components, and a hardener and a hardener are contained. The curing accelerator or the curing epoxy resin composition of the curing catalyst has high light reflectivity, is excellent in heat resistance and light resistance, and is strong and light reflectance is not easily lowered by time. Further, the present inventors have found that an alicyclic epoxy compound, an isoallyl cyanuric propylene carbonate compound, a cyclooxyalkylene derivative having two or more epoxy groups in the molecule, and an alicyclic ring have been found. A polyester resin and a white pigment as essential components, and a hardenable epoxy resin composition containing a curing agent and a curing accelerator or a curing catalyst, which are capable of supplying particularly high light reflectivity, heat resistance and light resistance. It is excellent, and it is tough and light-reflective is not easily hardened by the passage of time. The present invention has been accomplished based on such knowledge.

That is, the present invention provides a curable epoxy resin composition characterized in that it contains an alicyclic epoxy compound (A) and an isomeric cyanurate group represented by the following formula (1) a glycidyl ester compound (B), a white pigment (C), a hardener (D), and a hardening accelerator (F),

[wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

Further, the present invention provides a curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A) and an isomeric cyanuric acid monoallyl propylene glycol represented by the following formula (1) Ester compound (B), white pigment (C), and hardening catalyst (E),

[wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

Further, there is provided a curable epoxy resin composition as described above, wherein the alicyclic epoxy compound (A) is a compound having a cyclohexene oxide group.

Further, a curable epoxy resin composition as described above, wherein the alicyclic epoxy compound (A) is represented by the following formula (I-1)

Expressed as a compound.

The curable epoxy resin composition as described above is further provided, further comprising a hafnoxy derivative (G) having two or more epoxy groups in the molecule.

A curable epoxy resin composition as described above is further provided, which further contains an alicyclic polyester resin (H).

Further, a curable epoxy resin composition as described above is provided, wherein the alicyclic polyester resin (H) is further an alicyclic polyester resin having an alicyclic ring in the main chain.

A curable epoxy resin composition as described above is provided, which further contains rubber particles.

Furthermore, the curable epoxy resin composition as described above is further provided, and further comprising at least one selected from the group consisting of a polyfluorinated leveling agent and a fluorine-based leveling agent.

A curable epoxy resin composition as described above, which further contains a polyol compound.

A curable epoxy resin composition as described above is provided, which further contains an acrylic block copolymer.

Further, the present invention provides a cured product obtained by hardening the above-mentioned curable epoxy resin composition.

Moreover, the present invention provides a curable resin composition for light reflection, which comprises the above-described curable epoxy resin composition.

Furthermore, the present invention provides an optical semiconductor device comprising at least an optical semiconductor element and a reflective material comprising a cured product of the above-described light-reflecting curable resin composition.

The curable epoxy resin composition of the present invention has the above-described configuration, and the cured product obtained by curing the curable epoxy resin composition has high light reflectivity, is excellent in heat resistance and light resistance, and is strong and not It is prone to cracking, so light reflectivity is not easy to fall due to time. Therefore, the curable epoxy resin composition of the present invention is suitable for various applications related to optical semiconductor devices, and in particular, a curable resin composition for light reflection for LED packaging can be suitably used. In addition, since the reflector of the cured product containing the curable epoxy resin composition (curable resin composition for light reflection) of the present invention can continue to exhibit high light reflectivity for a long period of time, it is provided with at least an optical semiconductor element and The optical semiconductor device (light-emitting device) of the above-mentioned reflective material can exhibit high reliability as a long-life optical semiconductor device.

Form for implementing the invention <Curable epoxy resin composition>

The curable epoxy resin composition of the present invention which is an alicyclic epoxy compound (A) and an isomeric isocyanurate compound (B) represented by the following formula (1) ), the white pigment (C), the hardener (D), and the hardening accelerator (F) are provided as a resin composition containing the essential component, or the alicyclic epoxy compound (A) is represented by the following formula (1) a resin composition containing the isoallyl cyanuric acid monoallyl diglycidyl ester compound (B), a white pigment (C), and a curing catalyst (E) as essential components, [wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].

[Cycloaliphatic epoxy compound (A)]

The alicyclic epoxy compound (A) constituting the curable epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in a molecule (within one molecule). More specifically, the alicyclic epoxy compound (A) contains, for example, (i) an epoxy group having two carbon atoms and an oxygen atom constituting the adjacent alicyclic ring (referred to as "alicyclic epoxy group"). The compound of the case; and (ii) the epoxy group is a compound which is directly bonded to the alicyclic ring by a single bond or the like. However, the alicyclic epoxy compound (A) is a nonoxyalkylene derivative (G) which does not contain an epoxy group having two or more epoxy groups in the molecule which will be described later.

(i) A compound having an epoxy group (alicyclic epoxy group) constituting two carbon atoms and an oxygen atom adjacent to the alicyclic ring can be arbitrarily selected from known or commonly used ones. In particular, the above compound has an epoxy group containing two carbon atoms and an oxygen atom adjacent to each other of the cyclohexane ring, that is, a compound having an epoxycyclohexane group (alicyclic epoxy compound) is preferred. .

(i) a compound having an epoxy group (alicyclic epoxy group) constituting two carbon atoms and an oxygen atom adjacent to the alicyclic ring, particularly in terms of heat resistance and light resistance, is represented by the following formula ( The alicyclic epoxy compound (alicyclic epoxy resin) represented by I) is preferred.

In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the above-mentioned linking group include a divalent hydrocarbon group, a carbonyl group, an ether group (ether bond), a thioether group (thioether bond), and an ester group (ester). A bond), a carbonate group (carbonate bond), a guanamine group (a guanamine bond), and a plurality of such a bonded base.

The alicyclic epoxy compound in which X is a single bond in the formula (I) is a compound represented by the following formula. For the alicyclic epoxy compound, for example, a commercially available product such as "CELLOXIDE 8000" (manufactured by DAICEL Co., Ltd.) can be used.

Examples of the above-mentioned divalent hydrocarbon group include a linear or branched chain alkylene group having a carbon number of 1 to 18, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched chain alkylene group having a carbon number of 1 to 18 include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylidene group, and a propyl group. , trimethylene and so on. Examples of the divalent alicyclic hydrocarbon group include a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-cyclopentyl group, and 1,3. a divalent cycloalkylene group (including a cycloalkylene group) such as a cyclopentyl group, a 1,4-cyclopentyl group or a cyclohexylene group.

The above-mentioned linking group X is particularly preferably a linking group containing an oxygen atom, and specific examples thereof include -CO-(carbonyl), -O-CO-O-(carbonate group), and -COO-. (ester group), -O-(ether group), -CONH-(nonylamino group), a plurality of such groups, and one or more of the groups and one of the divalent hydrocarbon groups Or two or more links to form a base. The divalent hydrocarbon group may, for example, be exemplified above.

Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10). on For the above-mentioned compounds, for example, commercially available products such as "CELLOXIDE 2021P" and "CELLOXIDE 2081" (manufactured by DAICEL Co., Ltd.) can be used. Further, l and m in the following formulae (I-5) and (I-7) each represent an integer of 1 to 30. In the following formula (I-5), R is an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an exoethyl group, a propyl group, an exo-propyl group, a butyl group, and an isobutylene group. a linear or branched chain alkyl group having a second butyl group, a pentyl group, a hexyl group, a heptyl group, a thiol group, and the like. These are preferably linear or branched chain alkyl groups having 1 to 3 carbon atoms such as methylene, ethyl, propyl and isopropyl. Further, n1 to n6 in the following formulae (I-9) and (I-10) each represent an integer of 1 to 30.

(ii) The compound represented by the following formula (II) is exemplified as the compound in which the epoxy group is directly bonded to the alicyclic ring by a single bond.

In the formula (II), R' is a group obtained by removing p-OH from a p-valent alcohol, and p and n each represent a natural number. The p-valent alcohol [R'-(OH) _p ] may, for example, be an alcohol having 1 to 15 carbon atoms, and more specifically, 2,2-bis(hydroxymethyl)-1-butanol Such as polyols and the like. The p system is preferably 1 to 6, and the n system is preferably 1 to 30. When p is 2 or more, the n-systems in the respective ( ) (in parentheses) may be the same or different. Specific examples of the above compound include 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. The product name is "EHPE3150" (DAICEL (share) system).

The alicyclic epoxy compound (A) can be used singly or in combination of two or more. Among the above, the alicyclic epoxy compound (A) is a 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane represented by the above formula (I-1). The carboxylic acid ester and the trade name "CELLOXIDE 2021P" are particularly excellent.

The amount (content) of the alicyclic epoxy compound (A) is not particularly limited, and when the curable epoxy resin composition of the present invention contains a curing agent (D) as an essential component, the white pigment (C) is used. The total amount (100% by weight) of the curable epoxy resin composition to be removed is preferably from 10 to 90% by weight, preferably from 15 to 80% by weight, more preferably from 18 to 70% by weight. On the other hand, when the curable epoxy resin composition of the present invention contains a curing catalyst (E) as an essential component, the amount (content) of the alicyclic epoxy compound (A) is relative to the white pigment ( C) The total amount (100% by weight) of the curable epoxy resin composition to be removed is preferably from 25 to 95% by weight, preferably from 30 to 92% by weight, more preferably from 35 to 90% by weight.

In particular, the curable epoxy resin composition of the present invention contains either or both of a decane derivative (G) and an alicyclic polyester resin (H) having two or more epoxy groups in the molecule. The amount (content) of the alicyclic epoxy compound (A) is not particularly limited, and the curable epoxy resin composition of the present invention contains a curing agent (D) as a necessity. In the case of the component, the total amount (100% by weight) of the curable epoxy resin composition from which the white pigment (C) is removed is preferably 5 to 90% by weight, preferably 8 to 80% by weight, more preferably 10 to 75% by weight. On the other hand, when the curable epoxy resin composition of the present invention contains either or both of the component (G) and the component (H) (particularly when both are contained), the curing catalyst (E) is contained as a necessity. In the case of the component, the amount (content) of the alicyclic epoxy compound (A) is 10 to 95% by weight based on the total amount (100% by weight) of the curable epoxy resin composition from which the white pigment (C) is removed. Preferably, it is preferably 15 to 85% by weight, more preferably 20 to 75% by weight.

Further, the alicyclic epoxy compound (A) is based on the total amount (100% by weight) of the alicyclic epoxy compound (A) and the isoallyl cyanopropyl diglycidyl ester compound (B). The amount (content) used is not particularly limited, and is preferably 50 to 95% by weight, more preferably 50 to 90% by weight, still more preferably 60 to 90% by weight, particularly preferably 70 to 90% by weight. When the amount of the alicyclic epoxy compound (A) used is less than 50% by weight, the solubility of the monoallyl cyanurate compound (B) is insufficient, and it is easy to stand at room temperature. The situation of precipitation. On the other hand, when the amount of the alicyclic epoxy compound (A) used is more than 95% by weight, the toughness of the cured product is low, and cracking is likely to occur.

[Isopropyl propylene glycol epoxide compound (B)]

The isomeric isocyanurate compound (B) which constitutes the curable epoxy resin composition of the present invention is the following general formula (1),

In the above formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. A linear or branched chain alkyl group having the same or the like. In particular, a linear or branched chain alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. R ¹ and R ² in the above formula (1) are particularly preferably a hydrogen atom.

As a representative example of the isoallyl cyanurate compound (B), an allyl cyanurate isoallyl diglycidyl ester or iso-cyanuric acid may be mentioned. 1-allyl-3,5-bis(2-methylepoxypropyl) ester, 1-(2-methylpropenyl)-3,5-digby propyl isophthalocyanate, different 1-(2-methylpropenyl)-3,5-bis(2-methylepoxypropyl) cyanurate or the like. Further, the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) can be used singly or in combination of two or more.

The isoallyl cyanuric propylene carbonate compound (B) can be arbitrarily mixed in a range soluble in the above alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) The ratio of the monoallyl diglycidyl ester compound (B) to the isocyanuric acid is not particularly limited, and the alicyclic epoxy compound (A): monoallyl diglycidyl isocyanurate The compound (B) is preferably 50:50 to 95:5 by weight, more preferably 50:50 to 90:10 by weight. When it is outside this range, the solubility of the isoallyl cyanurate compound (B) is difficult to obtain.

The allyl cyanuric acid monoallyl diglycidyl ester compound (B) may be used by preliminarily modifying a compound which reacts with an epoxy group such as an alcohol or an acid anhydride.

[white pigment (C)]

The white pigment (C), which is an essential component of the curable epoxy resin composition of the present invention, serves as a cured product obtained by curing the curable epoxy resin composition to exhibit high light reflectivity. In the case of the white pigment (C), a well-known or commonly used white pigment can be used without particular limitation, and examples thereof include glass, clay, mica, talc, kaolin, halloysite, zeolite, acid clay, and Inorganic white pigment such as activated clay, boehmite, pseudoboehmite, inorganic oxide or alkaline earth metal salt; styrene resin, benzoguanamine resin, urea- An organic white pigment (such as a plastic pigment) such as a resin pigment such as a cycline resin, a melamine-formalin resin or a guanamine resin; or a hollow particle having a hollow structure (balloon structure). These white pigments can be used singly or in combination of two or more.

Examples of the inorganic oxide include alumina, magnesia, cerium oxide, titanium oxide (rutile type titanium oxide, anatase type titanium oxide, and brookite type titanium oxide). Zirconium oxide, zinc oxide, cerium oxide (cerium oxide), and the like. Further, examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium citrate, calcium citrate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, and barium sulfate. Wait. Further, examples of the metal salt other than the alkaline earth metal salt include aluminum niobate, aluminum hydroxide, and zinc sulfide.

The hollow particles are not particularly limited, and examples thereof include inorganic glass (for example, sodium citrate calcium glass, aluminosilicate glass, sodium borosilicate glass, quartz, etc.), cerium oxide, and aluminum oxide. Metal oxidation Inorganic hollow particles (including natural materials such as white stone balloons) composed of inorganic substances such as metal salts such as calcium carbonate, barium carbonate, nickel carbonate, and calcium citrate; styrene resin, acrylic resin, and polyoxyl Resin, acrylic acid-styrene resin, vinyl chloride resin, vinylidene chloride resin, guanamine resin, urethane resin, phenol resin, styrene-conjugated double bond resin, acrylic acid - An organic hollow particle composed of an organic substance such as a conjugated double bond resin or a polymer such as an olefin resin (including a crosslinked body of the polymer); and an inorganic-organic hollow composed of a mixed material of an inorganic material and an organic material Particles, etc. Further, the hollow particles may be composed of a single material, or may be composed of two or more materials. Further, the hollow portion (the space inside the hollow particles) of the hollow particles may be in a vacuum state, or may be filled with a medium, in particular, a medium having a low refractive index from the viewpoint of improving the reflectance (for example, nitrogen, It is preferable that the hollow particles are filled with an inert gas such as argon or air.

Further, the white pigment (C) may be a surface treatment which is subjected to a well-known or usual surface treatment (for example, a surface treatment agent using a metal oxide, a decane coupling agent, a titanium coupling agent, an organic acid, a polyhydric alcohol, a polyfluorene oxide, or the like). Etc.) By performing such a surface treatment, it is possible to improve the compatibility and dispersibility of the white pigment (C) of the curable epoxy resin composition with other components.

In particular, the white pigment (C) is preferably an inorganic oxide or an inorganic hollow particle from the viewpoints of availability, heat resistance, and light resistance, and preferably contains alumina, magnesia, cerium oxide, and titanium oxide. One or more kinds of white pigments are selected from the group consisting of zirconium oxide, cerium oxide, and inorganic hollow particles. In particular, in the case of the white pigment (C), titanium oxide is preferred in terms of having a high refractive index.

The shape of the white pigment (C) is not particularly limited, and examples thereof include a spherical shape, a crushed shape, a fibrous shape, a needle shape, a scaly shape, and a whisker shape. In particular, from the viewpoint of dispersibility of the white pigment (C), a spherical white pigment is preferable, and a spherical white pigment (for example, a spherical white pigment having an aspect ratio of 1.2 or less) is particularly preferable.

The center particle diameter of the white pigment (C) is not particularly limited, and from the viewpoint of improving light reflectivity, it is preferably 0.1 to 50 μm. In particular, when an inorganic oxide is used as the white pigment (C), the central particle diameter of the inorganic oxide is not particularly limited, and is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, still more preferably 0.1 to 20 μm. It is 0.1~10μm, and the best is 0.1~5μm. On the other hand, when hollow particles (especially inorganic hollow particles) are used as the white pigment (C), the central particle diameter of the hollow particles is not particularly limited, and is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm. Moreover, the above-mentioned central particle size means that laser diffraction is used. The cumulative value of the particle size distribution measured by the scattering method is 50% of the particle diameter (median diameter).

The amount (mixing amount) of the white pigment (C) used in the curable epoxy resin composition of the present invention is not particularly limited, and is equivalent to the epoxy group-containing compound contained in the curable epoxy resin composition. The total amount (the total epoxy group-containing compound) is preferably from 80 to 500 parts by weight, preferably from 90 to 400 parts by weight, more preferably from 100 to 380 parts by weight, per 100 parts by weight. When the amount used is less than 80 parts by weight, the light reflectivity of the cured product tends to be low. On the other hand, when the amount used is more than 500 parts by weight, the toughness of the cured product tends to be low.

Further, the white pigment (C) can be produced by a known or usual production method. Also, in the case of white pigment (C), it is also commercially available. For example, you can use the 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, 堺Chemical Industries Co., Ltd.), trade name "Tipaque CR-50", "CR-50-2", "CR-60", " CR-60-2, CR-63, CR-80, CR-90, CR-90-2, CR-93, CR-95, CR-97 (The above, Ishihara Industry Co., Ltd.), the trade name "JR-301", "JR-403", "JR-405", "JR-600A", "JR-605", "JR-600E", " JR-603", "JR-805", "JR-806", "JR-701", "JRNC", "JR-800", "JR" (above, TAYCA (share) system), product name "TR" -600", "TR-700", "TR-750", "TR-840", "TR-900" (above, Fuji TITAN Industrial Co., Ltd.), trade name "KR-310", "KR- 380", "KR-380N" (above, TITAN Industrial Co., Ltd.), trade name "ST-410WB", "ST-455", "ST-4" Rutile titanium oxide such as 55WB", "ST-457SA", "ST-457EC", "ST-485SA15", "ST-486SA", "ST-495M" (above, TITAN Industrial Co., Ltd.); Product names "A-110", "TCA-123E", "A-190", "A-197", "SA-1", "SA-1L", "SSP Series", "CSB Series" (above,堺Chemical Industry Co., Ltd.), trade name "JA-1", "JA-C", "JA-3" (above, TAYCA (share) system), trade name "KA-10", "KA-15" Anatase-type titanium oxide, such as "KA-20", "STT-65C-S", "STT-30EHJ" (above, TITAN Industrial Co., Ltd.).

[hardener (D)]

The curing agent (D) constituting the curable epoxy resin composition of the present invention serves as a task for hardening a compound having an epoxy group. As the hardener (D), a known or commonly used hardener can be used as the hardener for the epoxy resin. In particular, the curing agent (D) is preferably an acid anhydride which is liquid at 25 ° C, and more specifically, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl group Succinic anhydride, methyl endomethylene tetrahydrophthalic anhydride, and the like. Further, for example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dibasic anhydride are equal to an acid anhydride having a solid temperature at room temperature (about 25 ° C), and are dissolved in a normal temperature (about 25 ° C). A mixture which is liquid in the form of a liquid acid anhydride can also be suitably used as the curing agent (D). Further, the curing agent (D) can be used singly or in combination of two or more. The hardener (D) is characterized by the resistance of a saturated monocyclic hydrocarbon dibasic acid (including a substituent such as an alkyl group bonded to the ring) from the viewpoint of heat resistance, light resistance, and crack resistance. good.

Further, in the present invention, the hardener (D) can also be used under the trade name "Rikacid MH-700" (Nippon Chemical and Chemical Co., Ltd.) and the trade name "HN-5500" (Hitachi Chemical Industry Co., Ltd.) Commercial product such as system).

The amount (content) of the curing agent (D) is not particularly limited, and is 50 to 200 by weight based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. Preferably, it is preferably from 100 to 145 parts by weight. More specifically, all of the epoxy group-containing compounds contained in the curable epoxy resin composition of the present invention are preferably used in an amount of from 0.5 to 1.5 equivalents per equivalent of the epoxy group of the compound. When the amount of the hardener (D) used is less than 50 parts by weight, the hardening system is not charged. The toughness of the hardened material has a tendency to be low. On the other hand, when the amount of the curing agent (D) used is more than 200 parts by weight, the cured product is colored and the hue is deteriorated.

[hardening accelerator (F)]

In the hardening accelerator (F) of the curable epoxy resin composition of the present invention, when the epoxy group-containing compound is cured by the curing agent (D), the curing accelerator (F) has a rate of promoting hardening. Functional compound. As the hardening accelerator (F), a known or commonly used hardening accelerator can be used without particular limitation, and, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) can be mentioned. And salts thereof (for example, phenates, octanoates, p-toluenesulfonates, formates, tetraphenylborates); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) And its salts (for example, phenates, octanoates, p-toluenesulfonates, formates, tetraphenylborates); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl) a tertiary amine such as phenol or N,N-dimethylcyclohexylamine; an imidazole such as 2-ethyl-4-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole a phosphine such as a phosphate ester or a triphenylphosphine; an anthracene compound such as tetraphenylphosphonium tetra(p-tolyl)borate; an organic metal salt such as tin octylate or zinc octylate; or a metal chelating agent. Further, the curing accelerator (F) can be used singly or in combination of two or more.

Further, in the present invention, the hardening accelerator (F) can also be used under the trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", and "U-CAT 18X". "12XD (developed product)" (above, SAN-APRO (share) system), trade name "TPP-K", "TPP-MK" (above, Beixing Chemical Industry Co., Ltd.), trade name "PX- Commercial product such as 4ET" (Nippon Chemical Industry Co., Ltd.).

The amount (content) of the curing accelerator (F) is not particularly limited, and is 0.05 to 5 based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. The parts by weight are preferably from 0.1 to 3 parts by weight, more preferably from 0.2 to 3 parts by weight, particularly preferably from 0.25 to 2.5 parts by weight. When the amount of the curing accelerator (F) used is less than 0.05 parts by weight, the hardening promoting effect may be insufficient. On the other hand, when the amount of the curing accelerator (F) used is more than 5 parts by weight, the cured product is colored and the hue is deteriorated.

[hardening catalyst (E)]

The curable epoxy resin composition of the present invention may contain a curing catalyst (E) instead of the above-mentioned curing agent (D). In the same manner as in the case of using the curing agent (D), a cured compound can be obtained by subjecting a compound having an epoxy group to a curing reaction by using a curing catalyst (E). The above-mentioned curing catalyst (E) is not particularly limited. For example, a cationic catalyst (cationic polymerization initiator) which can generate a cationic species by ultraviolet irradiation or heat treatment to start polymerization can be used.

Examples of the cationic catalyst for generating a cationic species by ultraviolet irradiation include hexafluoroantimonate, pentafluorohydroxyphthalate, hexafluorohydroxyphosphate, and hexafluoroarsenate. These cationic catalysts can be used singly or in combination of two or more. For the above cationic catalyst, for example, the product name "UVACURE 1590" (DAICEL .CYTEC), trade name "CD-1010", "CD-1011", "CD-1012" (above) can be used. A product of the trade name "IRGACURE 264" (manufactured by CIBA Japan Co., Ltd.) and the trade name "CIT-1682" (manufactured by Japan Soda Co., Ltd.).

Examples of the cationic catalyst for generating a cationic species by heat treatment include, for example, an aryldiazonium salt, an aryl iodonium salt, an arylsulfonium salt, and an allene-ion error. Compounds, etc. These cationic catalysts can be used singly or in combination of two or more. For the cation catalyst, for example, the product names "PP-33", "CP-66", "CP-77" (above, ADEKA), and the product name "FC-509" (3M) can be suitably used. )), the product name "UVE1014" (made by GE), the product name "SANEIDO SI-60L", "SANEIDO SI-80L", "SANEIDO SI-100L", "SANEIDO SI-110L", "SANEIDO SI-150L" ( The above is a commercial item such as Sankyo Chemical Industry Co., Ltd., and the trade name "CG-24-61" (manufactured by CIBA Japan Co., Ltd.). In the above cationic catalyst, a compound of a metal such as aluminum or titanium, a compound of acetonitrile acetic acid or a diketone, a compound of decyl alcohol such as triphenylsulfanol, or aluminum or titanium can be used. A compound of a metal and an acetonitrile acetic acid or a diketone, a compound of a phenol such as bisphenol S, or the like.

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

The curable epoxy resin composition of the present invention may contain a hafnoxy derivative (G) and/or an alicyclic polyester resin (H) having two or more epoxy groups in the molecule. In particular, the curable epoxy resin composition of the present invention contains an oxirane derivative having two or more epoxy groups in the molecule. Biological (G) and alicyclic polyester resins (H) are preferred. That is, the curable epoxy resin composition of the present invention is an allyl cyanurate monoallyl diglycidyl compound represented by the above formula (1) containing at least an alicyclic epoxy compound (A). (B) a decane derivative (G) having two or more epoxy groups in the molecule, an alicyclic polyester resin (H), a white pigment (C), a curing agent (D), and a hardening accelerator a resin composition of (F) or an allyl allyl diglycidyl compound (B) containing at least an alicyclic epoxy compound (A) and represented by the above formula (1), The resin composition having a cyclooxyl derivative (G) having two or more epoxy groups in the molecule, an alicyclic polyester resin (H), a white pigment (C), and a curing catalyst (E) is preferred.

[a oxane derivative (G) having two or more epoxy groups in the molecule]

As described above, the curable epoxy resin composition of the present invention may contain a hafnoxy derivative (G) having two or more epoxy groups in a molecule (in one molecule). The fluorinated alkane derivative (G) having two or more epoxy groups in the molecule is a compound having a siloxane skeleton and having two or more epoxy groups in the molecule. The fluorinated alkane derivative (G) having two or more epoxy groups in the molecule serves to improve the heat resistance, light resistance, and crack resistance of the cured product, and to suppress the luminosity of the optical semiconductor device.

The oxoxane skeleton having a cyclooxyalkylene derivative (G) having two or more epoxy groups in the molecule is not particularly limited, and examples thereof include a cyclic fluorinated alkane skeleton and a linear polycondensation. A polyoxane skeleton such as a helium oxygen, a basket or a ladder type polysilsesquioxane. In particular, from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the decrease in luminosity, the above-mentioned siloxane chain skeleton is preferably a cyclic oxime skeleton or a linear polyfluorene skeleton. That is, there are more than two in the molecule. The cyclooxyalkylene derivative (G) is a cyclic oxirane having two or more epoxy groups in the molecule and a linear chain having two or more epoxy groups in the molecule. Polyoxyl is preferred. In addition, the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule can be used singly or in combination of two or more.

The fluorinated alkane derivative (G) having two or more epoxy groups in the molecule is a cyclic oxirane having two or more epoxy groups, and forms a Si-O unit of a siloxane chain. The number (the number of the ruthenium atoms forming the oxime ring) is not particularly limited, and from the viewpoint of improving the heat resistance and light resistance of the cured product, it is preferably 2 to 12, more preferably 4 to 8.

The weight average molecular weight of the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, and from the viewpoint of heat resistance and light resistance of the cured product, it is preferably from 100 to 3,000. Jia is 180~2000. In addition, the weight average molecular weight of the oxoxane derivative (G) having two or more epoxy groups in the molecule can be, for example, GPC (gel permeation chromatography) method and can be converted into standard polystyrene. The value is measured in a manner.

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

The epoxy equivalent of the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule (in accordance with JIS K7236) is not particularly limited, and the heat resistance and light resistance of the cured product are 180°. 400 is preferred, preferably 240 to 400, and more preferably 240 to 350.

The epoxy group having a cyclooxyl derivative (G) having two or more epoxy groups in the molecule is not particularly limited, and the heat resistance and light resistance of the cured product are improved. It is preferred that the ring has two carbon atoms adjacent to each other and an epoxy group (alicyclic epoxy group) of an oxygen atom, and particularly preferably an epoxycyclohexane group.

The polyoxane derivative (G) having two or more epoxy groups in the molecule is specifically 2,4-di[2-(3-{oxabicyclo[4.1. 0]heptyl})ethyl]-2,4,6,6,8,8-hexamethyl-cyclotetraoxane, 4,8-di[2-(3-{oxabicyclo[4.1. 0] heptyl}) ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetraoxane, 2,4-di[2-(3-{oxabicyclo[4.1. 0]heptyl})ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 4,8-di[2-(3-{oxa) Bicyclo[4.1.0]heptyl})ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,8-tri[2- (3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetraoxane, 2,4,8-tri[2- (3-{oxabicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,6,8 -tetrakis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetraoxane, half of an epoxy group Oxane and the like. More specifically, for example, a cyclic oxirane having two or more epoxy groups in one molecule represented by the following formulas (S-1) to (S-7) can be given.

In addition, as the fluorinated alkane derivative (G) having two or more epoxy groups in the molecule, for example, an alicyclic epoxy group-containing polyfluorene oxide described in JP-A-2008-248169 can be used. An organic polysilsesquioxane resin having at least two epoxy functional groups in one molecule as described in JP-A-2008-19422.

In the case of the oxoxane derivative (G) having two or more epoxy groups in the molecule, for example, a cyclic oxirane having two or more epoxy groups in the molecule, and the trade name "X" can also be used. -40-2678" (Shin-Etsu Chemical Co., Ltd.), trade name "X-40-2670" (Shin-Etsu Chemical Co., Ltd.), trade name "X-40-2720" (Shin-Etsu Chemical Industry Co., Ltd.) Commercial product such as system).

The amount (content) of the oxoxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, and is relative to the component (A), the component (B), and the component (G). The total amount (100% by weight) is preferably 5 to 80% by weight, more preferably 8 to 78% by weight, still more preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. When the amount of the decane derivative (G) having two or more epoxy groups in the molecule is less than 5% by weight, the heat resistance and light resistance of the cured product may be lowered. On the other hand, when the amount of the oxoxane derivative (G) having two or more epoxy groups in the molecule is more than 80% by weight, the crack resistance of the cured product may be lowered.

An alicyclic epoxy compound (A), an isocyanurate monoallyl diglycidyl ester compound (B), relative to the total amount (100% by weight) of the epoxy group-containing compound (epoxy resin) The total amount of the oxoxane derivative (G) having two or more epoxy groups in the molecule is not particularly limited, and the heat resistance, light resistance, and crack resistance are improved by 30 weights. % or more (for example, 30 to 100% by weight) is preferable, and 40% by weight or more is particularly preferable.

[Cycloaliphatic Polyester Resin (H)]

The alicyclic polyester resin (H) is a polyester resin having at least an alicyclic structure (aliphatic ring structure). The alicyclic polyester resin (H) serves to improve the heat resistance, light resistance, and crack resistance of the cured product and to suppress the luminosity of the optical semiconductor device. In particular, from the viewpoint of improving the heat resistance, light resistance, and crack resistance of the cured product, the alicyclic polyester resin (H) is an alicyclic polyester having an alicyclic ring (alicyclic structure) in the main chain. good. That is, the alicyclic polyester resin (H) is preferably a polyester resin which constitutes a polymer main chain from a part or all of carbon atoms constituting the alicyclic ring. Further, the alicyclic polyester resin (H) can be used singly or in combination of two or more.

The alicyclic structure of the alicyclic polyester resin (H) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure and a crosslinked cyclic hydrocarbon structure (for example, a bicyclic hydrocarbon), and the like. The alicyclic ring (the carbon-carbon bond constituting the alicyclic ring) is preferably a saturated monocyclic hydrocarbon structure or a saturated crosslinked cyclic hydrocarbon structure composed entirely of a carbon-carbon single bond. Further, the alicyclic structure of the alicyclic polyester resin (H) may be either a constituent unit derived from a dicarboxylic acid or a constituent unit derived from a diol, or both It is introduced without particular limitation.

The alicyclic polyester resin (H) contains a constituent unit derived from a monomer component having an alicyclic structure. The monomer having the above alicyclic structure is exemplified by a diol or a dicarboxylic acid having an alicyclic structure which is well known or commonly used, and is not particularly limited, and examples thereof include 1,2-cyclohexanedicarboxylic acid. , 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, hemic acid, 1, a dicarboxylic acid having an alicyclic structure such as 4-decahydronaphthalene dicarboxylic acid, 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid or 2,7-decahydronaphthalene dicarboxylic acid (also including derivatives such as acid anhydrides), etc.; 1,2-dicyclopentanediol, 1,3-dicyclopentanediol, 1,2-dicyclopentanemethanol, 1,3-dicyclopentanemethanol 5-membered ring diol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexane, such as bis(hydroxymethyl)tricyclo[5.2.1.0]decane Alkanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis-(4-hydroxycyclohexyl)propane, etc. A diol having an alicyclic structure (including such a derivative) such as a 6-membered ring diol or a hydrogenated bisphenol A.

The alicyclic polyester resin (H) may also contain a constituent unit derived from a monomer component having no alicyclic structure. In the above, there is no alicyclic structure. The monomer component is not particularly limited, and examples thereof include aromatic dicarboxylic acids such as citric acid, isononanoic acid, decanoic acid, and naphthalene dicarboxylic acid (including derivatives such as acid anhydrides); and adipic acid. An aliphatic dicarboxylic acid (including a derivative such as an acid anhydride) such as azelaic acid, sebacic acid, succinic acid, fumaric acid or maleic acid; ethylene glycol, propylene glycol, 1,2- Propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane Glycol, diethylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl a diol such as 2-ethyl-1,3-propanediol, benzene dimethyl glycol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A (including these Derivatives) and so on. Further, in the monomer component having no alicyclic structure, an appropriate substituent (for example, an alkyl group, an alkoxy group, a halogen atom or the like) is bonded to the above dicarboxylic acid or diol having no alicyclic structure. Adult.

The ratio of the monomer unit having an alicyclic ring is not particularly limited, and is 10 mol% or more, based on the total monomer unit (total monomer component) (100 mol%) constituting the alicyclic polyester resin (H). (for example, 10 to 80 mol%), preferably 25 to 70 mol%, more preferably 40 to 60 mol%. When the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, and crack resistance of the cured product may be lowered.

In particular, the alicyclic polyester resin (H) is preferably an alicyclic polyester resin containing at least one or more constituent units represented by the following formulas (2) to (4).

(wherein R ³ represents a straight chain, a branched chain, or a cyclic alkyl group having 2 to 15 carbon atoms. Further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched group. a chain of alkyl groups having 1 to 4 carbon atoms, and two selected from R ⁴ to R ⁷ may be bonded to form a ring)

(wherein R ³ represents a straight chain, a branched chain, or a cyclic alkyl group having 2 to 15 carbon atoms. Further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched group. a chain of alkyl groups having 1 to 4 carbon atoms, and may also form a ring selected from two selected from R ⁴ to R ⁷ )

(wherein R ³ represents a straight chain, a branched chain, or a cyclic alkyl group having 2 to 15 carbon atoms. Further, R ⁴ to R ⁷ each independently represent a hydrogen atom or a linear or branched group. a chain of alkyl groups having 1 to 4 carbon atoms, and may also form a ring selected from two selected from R ⁴ to R ⁷ )

Preferred examples of the constituent units represented by the above formulas (2) to (4) include, for example, 4-methyl-1,2-cyclohexane derived from the following formula (5). a constituent unit of a carboxylic acid and ethylene glycol. The alicyclic polyester resin (H) having such a constituent unit can be obtained, for example, by polycondensing methyl hexahydrophthalic anhydride with ethylene glycol.

In addition, other preferable specific examples of the constituent units represented by the above formulas (2) to (4) include, for example, 1,4-cyclohexanedicarboxylic acid represented by the following formula (6). And a constituent unit of neopentyl glycol. The alicyclic polyester resin (H) having such a structural unit can be obtained, for example, by polycondensation of 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.

Further, the terminal structure of the alicyclic polyester resin (H) is not particularly limited, and may be a hydroxyl group or a carboxyl group, or may be a structure in which the hydroxyl group or the carboxyl group is appropriately modified (for example, the terminal hydroxyl group is a monocarboxylic acid or an acid anhydride). The structure of esterification, the structure in which the carboxyl group at the terminal is esterified with an alcohol, etc.).

The alicyclic polyester resin (H) has a constituent unit represented by the above formulas (2) to (4), and the total content of the constituent units (total content; total monomer unit constituting the constituent unit) It is not particularly limited, and is 20 mol% or more with respect to the total constituent unit of the alicyclic polyester resin (H) (100 mol%; the total monomer unit constituting the alicyclic polyester resin (H)) ( For example, 20 to 100 mol% is preferable, preferably 50 to 100 mol%, more preferably 80 to 100 mol%. When the content of the constituent unit represented by the above formulas (2) to (4) is less than 20 mol%, the heat resistance, light resistance, and crack resistance of the cured product may be lowered.

The number average molecular weight of the alicyclic polyester resin (H) is not particularly limited, and is preferably from 300 to 100,000, more preferably from 300 to 30,000. When the number average molecular weight of the alicyclic polyester resin (H) is less than 300, the toughness of the cured product is insufficient and the crack resistance is lowered. On the other hand, when the number average molecular weight of the alicyclic polyester resin (H) is more than 100,000, the compatibility with other components (for example, the hardener (D)) is low, and the mechanical properties of the cured product are adversely affected and the turtle is resistant. Cracking has a low situation. Further, the number average molecular weight of the alicyclic polyester resin (H) can be measured, for example, by a GPC (gel permeation chromatography) method and a value in terms of standard polystyrene.

In addition, the alicyclic polyester resin (H) can be used singly or in combination of two or more.

The alicyclic polyester resin (H) is not particularly limited and can be produced by a known or usual method. In more detail, for example, the alicyclic polyester resin (H) can be obtained by polycondensing the above dicarboxylic acid and a diol by a usual method, or by derivatizing the above dicarboxylic acid. The product (anhydride, ester, acid halide, etc.) is obtained by polycondensation with a diol by a usual method.

In the curable epoxy resin composition of the present invention, the amount (content) of the alicyclic polyester resin (H) is not particularly limited, and the curing agent (D) is an essential component, and the alicyclic ring is used. The total amount (100% by weight) of the polyester resin (H) and the curing agent (D) is preferably from 1 to 60% by weight, preferably from 5 to 30% by weight. When the compounding amount of the alicyclic polyester resin (H) is less than 1% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the compounding amount of the alicyclic polyester resin (H) is more than 60% by weight, the heat resistance of the cured product may be lowered.

On the other hand, in the case where the curable epoxy resin composition of the present invention contains the curing catalyst (E) as an essential component, the amount (content) of the alicyclic polyester resin (H) is not particularly limited, as opposed to The total amount (100% by weight) of the alicyclic polyester resin (H) and the hardening catalyst (E) is preferably from 50 to 99% by weight, preferably from 65 to 99% by weight. When the compounding amount of the alicyclic polyester resin (H) is less than 50% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the compounding amount of the alicyclic polyester resin (H) is more than 99% by weight, the heat resistance of the cured product may be lowered.

[leveling agent]

The curable epoxy resin composition of the present invention further comprises at least one type of leveling selected from the group consisting of a polyfluorene-based leveling agent (polyoxane-based leveling agent) and a fluorine-based leveling agent. The agent is better. The curable epoxy resin composition of the present invention can form a cured product exhibiting a higher degree of heat resistance, light resistance, and crack resistance by containing the above-mentioned leveling agent, and light made using the cured product can be formed. In semiconductor devices, it is less likely to cause luminosity caused by elapse of time.

(polyoxane leveling agent)

The polyoxo-based leveling agent is a leveling agent containing a compound having a polyoxyalkylene skeleton. The polyfluorene-based leveling agent can be a commonly used or commonly used polyfluorinated leveling agent, and is not particularly limited. For example, the product names "BYK-300" and "BYK-301/302" can be used. BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322, BYK-323, BYK -325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-341", "BYK-344", BYK-345/346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-375, BYK-377, BYK-378, "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" (above, BYK-Chemie Japan (share) system), trade name "AC FS 180", "AC FS 360", "AC S 20" (above, manufactured by Algin Chemie), trade name "POLYFLOW KL-400X", "POLYFLOW KL-400HF", "POLYFLOW KL-401", "POLYFLOW" KL-402", "POLYFLOW KL-403", "POLYFLOW KL-404" (above, Kyoeisha Chemical Co., Ltd.), trade name "KP-323", "KP-326", "KP-341" "KP-104", "KP-110", "KP-112" (above, Shin-Etsu Chemical Co., Ltd.), trade name "LP-7001", "LP-7002", "8032 ADDITIVE", " 57 ADDITIVE, L-7604, FZ-2110, FZ-2105, 67 ADDITIVE, 8618 ADDITIVE, 3 ADDITIVE, 56 ADDITIVE (above, TORAY.DOWCORNING) Commercial product such as system).

The compound having a polyoxyalkylene skeleton is, in particular, a polyfluorene-based polymer having at least a structural unit (repeated structural unit) represented by the following formula (7) (however, the component (C) is removed) It is better. That is, the above-mentioned polyoxane-based leveling agent is preferably a leveling agent containing at least the above-mentioned polyfluorene-based polymer.

R ⁸ in the above formula (7) represents a linear or branched chain alkyl group which may have a substituent. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl (n-butyl group), an isobutyl group, a second butyl group, and the like. A linear or branched chain alkyl group having 1 to 30 carbon atoms such as tributyl or pentyl.

In the above R ⁸ , a substituent which may have a linear or branched chain alkyl group is not particularly limited, and for example, a hydroxyl group which may also be protected by a protecting group [for example, a hydroxyl group, a substituted oxy group (for example) a carboxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group, etc., and a carboxyl group which may be protected by a protecting group [for example, a -COOR ^a group or the like: R ^a represents a hydrogen atom or The alkyl group may, for example, be a carbon number such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group or a hexyl group. 6 linear or branched chain alkyl], propylene fluorenyl, methacryl fluorenyl, acryloxy, methacryloxy, vinyl, propenyl, epoxy, epoxypropyl Wait.

R ⁹ in the above formula (7) represents a linear or branched chain alkyl group which may have a substituent, an aryloxy group which may have a substituent, an organic group containing a polyether chain, or a polyester. The organic base of the chain. The linear or branched chain alkyl group of the above R ⁹ is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), and a different one. a linear or branched chain alkyl group having 1 to 30 carbon atoms such as a butyl group, a second butyl group, a third butyl group or a pentyl group. In addition, the aryloxy group is not particularly limited, and examples thereof include a benzyl group, a methylbenzyl group, a phenethyl group, a methylphenethyl group, a phenylpropyl group, and a naphthylmethyl group.

The above R ⁹ may be a substituent having a linear or branched chain alkyl group or a substituent having an aryloxy group, and is not particularly limited, and examples thereof include the above R ⁸ . Illustrative substituents and the like.

The organic group containing a polyether chain in the above R ⁹ contains at least one organic group having a polyether structure. The polyether structure of the polyether chain-containing organic group is not particularly limited as long as it has a plurality of ether bonds, and examples thereof include a polyethylene glycol structure (polyethylene oxide structure). Polypropylene structure (polypropylene oxide structure), polytetramethylene glycol (tetramethylene glycol) structure, polyether structure of a plurality of alkylene glycol (or alkylene oxide) (for example, poly A polyoxyalkylene structure such as a (propylene glycol/ethylene glycol) structure or the like. Further, the addition form of the alkylene glycol in each of the polyether structures derived from the plurality of alkylene glycols may be a block type (block copolymerization type) or a random type ( Random copolymer type).

The organic group containing the polyether chain may be an organic group containing only the above polyether structure, or may have one or two or more and one or two or more linking groups having the above polyether structure (having one or more) The organic base of the structure of the divalent base of the atom. Examples of the linking group of the above-mentioned organic group containing a polyether chain include a divalent hydrocarbon group (particularly a linear or branched chain alkyl group), a thioether group (-S-), and an ester. a group (-COO-), a decylamino group (-CONH-), a carbonyl group (-CO-), a carbonate group (-OCOO-), or a combination of two or more of these groups.

Further, the above-mentioned organic group containing a polyether chain may have a substituent exemplified in the above R ⁸ (for example, a hydroxyl group, a carboxyl group, an acrylonitrile group, a methacryl fluorenyl group, an acryloxy group, a methacryl oxime). Examples of the organic group having such a polyether structure include an oxy group, a vinyl group, a propylene group, and the like, and the above-mentioned terminal (the end opposite to the ruthenium atom of the formula (7)) has the above-mentioned Substituent organic groups and the like.

The organic group containing a polyester chain in the above R ⁹ contains at least an organic group having a monovalent structure of the polyester. The polyester structure of the organic group containing the polyester chain is not particularly limited as long as it has a plurality of ester bonds, and examples thereof include an aliphatic polyester structure, an alicyclic polyester structure, and a fragrance. A family polyester structure, an aliphatic/aromatic polyester structure, an aliphatic/alicyclic polyester structure, an alicyclic/aromatic polyester structure, and the like.

More specifically, the polyester structure described above may be a polyester structure formed by polymerization of a polybasic acid (particularly a dicarboxylic acid) and a polyhydric alcohol (particularly a diol). The polybasic acid is not particularly limited, and examples thereof include aromatic dicarboxylic acids such as citric acid, isophthalic acid, decanoic acid, and naphthalene dicarboxylic acid (including derivatives such as acid anhydrides and esters); An aliphatic dicarboxylic acid such as adipic acid, sebacic acid, sebacic acid, succinic acid, fumaric acid or maleic acid (including derivatives of acid anhydrides and esters, etc.); 1,2-ring Hexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, seamic acid, 1 a dicarboxylic acid having an alicyclic structure such as 4-decahydronaphthalene dicarboxylic acid, 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid or 2,7-decahydronaphthalene dicarboxylic acid; An acid (including a derivative such as an acid anhydride or an ester) or the like. The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, and 2,3-butanediol. 1,4-butanediol (butanediol), neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2,6-hexanediol, 2-ethyl-1, 6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 3-methylpentanediol, diethylene glycol, dipropylene glycol, hexanediol (2-methylpentyl) Alkane-2,4-diol), 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl- 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,8-octanediol, 1,12-dodecanediol, benzodimethyldiol, 1,3 a diol such as dihydroxyacetone, polybutadiene diol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A (including such derivatives); 2-dicyclopentanediol, 1,3-dicyclopentanediol, 1,2-dicyclopentanemethanol, 1,3-dicyclopentanemethanol, bis(hydroxymethyl)tricyclo[5.2.1.0 a 5-membered ring diol such as decane, 1,2-cyclohexane diol, 1,3-cyclohexane diol, 1,4-cyclohexane diol, 1,2-cyclohexanedimethanol (1,2-dimethylolcyclohexane), 1,3-cyclohexanedimethanol (1,3-dimethylolcyclohexane), 1,4-cyclohexanedimethanol (1,4 a diol having an alicyclic structure such as a 6-membered ring diol such as dichloromethylcyclohexane or 2,2-bis-(4-hydroxycyclohexyl)propane or a hydrogenated bisphenol A (including these a derivative), glycerin, trimethylolpropane, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, neopentyl alcohol, etc. having more than 3 hydroxy groups a polyol (including such derivatives) or the like. The polyester structure may be formed of a single polyol or a polybasic acid, or may be formed of two or more kinds of polyols or polycarboxylic acids.

Further, the polyester structure may, for example, be a polyester structure formed by polymerization of a hydroxycarboxylic acid, or a polymerization (open-loop polymerization) of a lactone of a cyclic ester of the hydroxycarboxylic acid. The formed polyester structure or the like. The hydroxycarboxylic acid is not particularly limited, and examples thereof include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid (wille acid), and 3-methoxy-4-hydroxybenzoic acid (vanillic acid). ), 4-methoxy-3-hydroxybenzoic acid (isovanaic acid), 3,5-dimethoxy-4-hydroxybenzoic acid (syringic acid), 2,6-dimethyl Oxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 4-methyl-3-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 4-phenyl-3-hydroxyl Benzoic acid, 2-phenyl-4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3,4-dihydroxycinnamic acid (caffeic acid), (E)-3-(4-hydroxy-3-methyl a hydroxyaromatic carboxylic acid such as oxy-phenyl)propan-2-enol (ferulic acid) or 3-(4-hydroxyphenyl)-2-acrylic acid (coumaric acid); glycolic acid, lactic acid, A hydroxyaliphatic carboxylic acid such as tartaric acid or citric acid. The lactone is not particularly limited, and examples thereof include γ-butyrolactone, δ-valerolactone, ε-caprolactone, ξ-heptanolactone, and η-octanolactone. The polyester structure may be formed of a single hydroxycarboxylic acid or a lactone, or may be formed of two or more kinds of hydroxycarboxylic acids and lactones.

Further, the polyester structure is not limited to the above-exemplified structure, and may be, for example, a polyester structure formed by polymerization of the above polybasic acid and a polyhydric alcohol, or a polyester structure formed by polymerization of a hydroxycarboxylic acid. A structure in which two or more types of polyester structures formed by polymerization of lactones are combined.

The organic group containing the polyester chain may be an organic group containing only the polyester structure described above, or may have a structure in which one or two or more of the above polyester structures are bonded to one or two or more linking groups. Organic base. The linking group of the above-mentioned organic group containing a polyester chain may, for example, be a divalent hydrocarbon group (particularly a linear or branched chain alkyl group), a thioether group (-S-), an ester. a group (-COO-), a decylamino group (-CONH-), a carbonyl group (-CO-), a carbonate group (-OCOO-), or a combination of two or more of these groups.

Further, the above-mentioned organic chain-containing organic group may have a substituent exemplified in the above R ⁸ (for example, a hydroxyl group, a carboxyl group, an acrylonitrile group, a methacryl fluorenyl group, an acryloxy group, a methacryl oxime). Examples of the organic group having such a polyester structure include an oxy group, a vinyl group, a propylene group, and the like, and the above-mentioned organic group having the polyester (the opposite end to the atom of the formula (7)) Substituent organic groups and the like.

In the case of the repeating structural unit, the polyoxymethylene-based polymer may be a polymer having only the structural unit represented by the formula (7), or may be a structural unit other than the structural unit represented by the formula (7). polymer. The structural unit other than the structural unit represented by the formula (7) in the above polyfluorinated polymer is not particularly limited, and examples thereof include a structural unit having a hydrofluorenyl group (Si—H). In addition, the polyfluorene-based polymer may be a polymer having only one structural unit represented by the formula (7), or a polymer having two or more structural units represented by the formula (7). Further, a polymer other than the structural unit represented by the formula (7) may be used.

Specific examples of the above polysiloxane polymer include a polymer represented by the following formulas (7a) to (7e) (polydimethyl siloxane or modified polydimethyl decane). )Wait.

The polyfluorene-based polymer represented by the above formula (7a) is a polydimethylsiloxane. The x1 (the number of repetitions of the dimethyl nonyloxy structural unit [-Si(CH ₃ ) ₂ -O-]) of the formula (7a) is not particularly limited, and is preferably 2 to 3,000, more preferably 3 to 1,500. .

The polyoxymethylene-based polymer represented by the above formula (7b) is a polyether modified product of a polydimethylsiloxane having a polyether structure introduced into a side chain of polydimethylsiloxane. R ¹⁰ in the formula (7b) represents a hydrogen atom or a methyl group. Further, R ¹¹ represents a hydrogen atom or a linear or branched chain alkyl group which may have a substituent. Further, the substituent of R ¹¹ may, for example, be a substituent exemplified in the above R ⁸ . M1 (the number of repetitions of the methylene structural unit) of the formula (7b) is not particularly limited, and can be appropriately selected from the range of 1 to 30, for example. Further, n1 (the number of repetitions of the oxygen-extended ethyl structural unit or the oxygen-extended propyl structural unit) is not particularly limited, and can be appropriately selected from the range of 2 to 3,000, for example. Further, the y1 (the number of repetitions of the structural unit of the polyether structure (polyether side chain)) of the formula (7b) is not particularly limited, and is preferably from 1 to 3,000, more preferably from 3 to 1,500. Further, x2 (the number of repetitions of the dimethyl decyloxy structural unit) is not particularly limited, and is preferably 2 to 3,000, more preferably 3 to 1,500. Further, the addition form of the structural unit having a polyether structure and the dimethyl nonyloxy structural unit of the polyoxynene polymer represented by the formula (7b) may be a block type or a random form. type. Further, when y1 is an integer of 2 or more, the structural unit having a polyether structure surrounded by the brackets of y1 may be the same or different.

The polyoxyalkylene polymer represented by the above formula (7c) is a long-chain alkane of polydimethyloxane obtained by introducing an alkyl group having a longer chain than a methyl group in a side chain of polydimethylsiloxane. A modified group (polymethylalkyloxane). R ¹² in the formula (7c) represents a linear or branched chain alkyl group having 2 or more carbon atoms. The y2 of the formula (7c) (the number of repeating groups of the methylalkyl fluorenyl structural unit) is not particularly limited, and is preferably 2 to 3,000, more preferably 3 to 1,500. Further, x3 (the number of repetitions of the dimethyl decyloxy structural unit) is not particularly limited, and is preferably 0 to 3,000, more preferably 2 to 1,500. Further, the addition form of the methylalkyl fluorenyl structural unit and the dimethyl decyloxy structural unit of the polyfluorene-based polymer represented by the formula (7c) may be a block type or a random form. type. Further, each of the methylalkyl fluorenyl structural units surrounded by the y2 brackets may be the same or different.

The polyoxymethylene-based polymer represented by the above formula (7d) is an aralkyl modified product of polydimethylsiloxane having an aryloxy group introduced into a side chain of polydimethylsiloxane. M2 (the number of repetitions of the methylene structural unit) of the formula (7d) is not particularly limited, and can be appropriately selected from the range of 1 to 30, for example. Further, y3 (the number of repetitions of the methyl aralkylalkylene structural unit) is not particularly limited, and is preferably from 2 to 3,000, more preferably from 3 to 1,500. Further, x4 (the number of repetitions of the dimethyl decyloxy structural unit) is not particularly limited, and 0~3000 is better, preferably 2~1500. Further, the addition form of the methyl aralkyl fluorenyl structural unit and the dimethyl decyloxy structural unit of the polyfluorene-based polymer represented by the formula (7d) may be a block type or may be none. Regulations. Further, the methyl aralkyl sulfonium alkyl structural unit surrounded by the y3 brackets may be the same or different.

The polyoxymethylene-based polymer represented by the above formula (7e) is a polyester modified product of a polydimethylsiloxane having a polyester structure introduced into a side chain of polydimethylsiloxane. R ¹³ and R ¹⁴ in the formula (7e) are the same or different and represent a divalent organic group (for example, a divalent hydrocarbon group or the like). Further, R ¹⁵ represents a hydrogen atom or a linear or branched chain alkyl group which may have a substituent. Further, the substituent of R ¹⁵ may, for example, be a substituent exemplified in the above R ⁸ . M3 (the number of repetitions of the methylene structural unit) of the formula (7e) is not particularly limited, and can be appropriately selected, for example, from the range of 1 to 30. Further, n2 (the number of repetitions of the condensation structure of the polyhydric alcohol and the polybasic acid) is not particularly limited, and can be appropriately selected from the range of 2 to 3,000, for example. Further, y4 of the formula (7e) (the number of repetitions of the structural unit containing the polyester structure (polyester side chain)) is not particularly limited, and is preferably from 1 to 3,000, more preferably from 3 to 1,500. Further, x5 (the number of repetitions of the dimethyl decyloxy structural unit) is not particularly limited, and is preferably 2 to 3,000, more preferably 3 to 1,500. Further, the addition form of the structural unit having a polyester structure and the dimethyl decyloxy structural unit of the polyoxynoxy polymer represented by the formula (7e) may be a block type or a random type. . Further, when y4 is an integer of 2 or more, the structural unit containing the polyester structure surrounded by the brackets of y4 may be the same or different.

The polyoxosiloxane-based polymer can be obtained by a known or usual production method, and the production method thereof is not particularly limited, and for example, it can be carried out by using a monomer having a structure corresponding to the structural unit represented by the formula (7). a method of polymerizing a compound having a predetermined structure (for example, a compound having a polyether structure or a polyester structure) to a polyoxyalkylene polymer having a reactive group in a side chain (a poly group having a reactive group in a side chain) The reactive group of methyl oxane or the like is produced by a reaction or a bonding method. Further, as the above polyoxymethylene polymer, a commercially available product can also be used.

(fluorine leveling agent)

The fluorine-based leveling agent is a leveling agent containing a compound having a fluorinated alkyl group, and a part or all of a hydrogen atom of the fluorinated alkyl-based alkyl group is substituted with a fluorine atom. In the above-mentioned fluorine-based leveling agent, a fluorine-based leveling agent which is well-known or commonly used can be used, and it is not particularly limited. For example, the product name "BYK-340" (BYK-Chemie Japan Co., Ltd.) and the product can be used. "AC 110a", "AC 100a" (above, manufactured by Algin Chemie), trade name "MEGAFAC F-114", "MEGAFAC F-410", "MEGAFAC F-444", "MEGAFAC EXP TP-2066", " MEGAFAC F-430", "MEGAFAC F-472SF", "MEGAFAC F-477", "MEGAFAC F-552", "MEGAFAC F-553", "MEGAFAC F-554", "MEGAFAC F-555", "MEGAFAC" R-94", "MEGAFAC RS-72-K", "MEGAFAC RS-75", "MEGAFAC F-556", "MEGAFAC EXP TF-1367", "MEGAFAC EXP TF-1437", "MEGAFAC F-558" "MEGAFAC EXP TF-1537" (above, DIC (share) system), trade name "FC-4430", "FC-4432" (above, Sumitomo 3M (share) system), trade name "FTERGENT 100", "FTERGENT 100C", "FTERGENT 110", "FTERGENT 150", "FTERGENT 150CH", " FTERGENT AK, FTERGENT 501, FTERGENT 250, FTERGENT 251, FTERGENT 222F, FTERGENT 208G, FTERGENT 300, FTERGENT 310, FTERGENT 400SW (above, NEOS) System), trade names "PF-136A", "PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF- 651", "PF-652" (above, Bukchon Chemical Industry Co., Ltd.) and other commercial products.

The compound having a fluorinated alkyl group is, in particular, a fluorine-containing acrylic polymer having at least a structural unit (repeated structural unit) represented by the following formula (8), and at least having the following formula (9) The fluorine-containing polyether polymer of the structural unit (repeated structural unit) shown is preferable. In other words, the fluorine-based leveling agent is preferably a leveling agent containing at least the fluorine-containing acrylic polymer or a leveling agent containing at least the fluorine-containing polyether polymer.

R ¹⁶ in the above formula (8) represents a straight or branched chain alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom in a part or all of a hydrogen atom, a fluorine atom or a hydrogen atom. Examples of the linear or branched chain alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group. Wait.

R ¹⁷ in the above formula (8) represents a fluorinated alkyl group (an alkyl group in which a part or all of a hydrogen atom is substituted by a fluorine atom). The fluorinated alkyl group is not particularly limited, and examples thereof include difluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3. -tetrafluoropropyl, perfluoroethylmethyl, 2,2,3,3,4,4-hexafluorobutyl, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl 1,1-Dimethyl-2,2,3,3,3-pentafluoropropyl, 2-(perfluoropropyl)ethyl, 2,2,3,3,4,4,5,5 -octafluoropentyl, 1,1-dimethyl-2,2,3,3,4,4-hexafluorobutyl, 1,1-dimethyl-2,2,3,3,4,4 ,4-heptafluorobutyl, 2-(perfluorobutyl)ethyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, perfluoropentylmethyl, 1,1-Dimethyl-2,2,3,3,4,4,5,5-octafluoropentyl, 1,1-dimethyl-2,2,3,3,4,4,5 ,5,5-nonafluoropentyl, 2-(perfluoropentyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7-dodecylheptyl , perfluorohexylmethyl, 2-(perfluorohexyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecylfluorenyl , perfluoroheptylmethyl, 2-(perfluoroheptyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9 -hexadecafluorodecyl, perfluorooctylmethyl, 2-(perfluorooctyl)ethyl, 2,2,3,3,4,4,5,5,6,6,7,7,8 ,8,9,9,10,10-octadecylfluorenyl, perfluorodecylmethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4 , 4 ,4-heptafluorobutyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 3,3,4,4,5,5,6,6,7,7, a part of a hydrogen atom such as 8,8,8-tris(tetradecyl)fluoroindolyl is a linear or branched alkyl group having 1 to 30 carbon atoms which is substituted by a fluorine atom; trifluoromethyl, pentafluoroethyl Base, heptafluoro-n-propyl, heptafluoroisopropyl, nonafluoro-n-butyl, nonafluoroisobutyl, nonafluoro-t-butyl, nonafluoro-t-butyl, perfluoropentyl, all A straight-chain or branched-chain perfluoroalkyl group having 1 to 30 carbon atoms such as a fluorohexyl group, a perfluoroheptyl group, a perfluorodecyl group, a perfluorodecyl group or a perfluorodecyl group. In particular, in the case of the above R ¹⁷ , a perfluoroalkyl group is preferred.

In addition, the fluorine-containing acrylic polymer may be a polymer having only the structural unit represented by the formula (8), or may have a structure other than the structural unit represented by the formula (8). The polymer of the unit. In addition, the fluorine-containing acrylic polymer may be a polymer having only one structural unit represented by the formula (8), or a polymer having two or more structural units represented by the formula (8). Further, a polymer having two or more structural units other than the structural unit represented by the formula (8) may be used.

The structural unit other than the structural unit represented by the formula (8) in the fluorine-containing acrylic polymer is not particularly limited, and examples thereof include a monomer component (monomer component) as an acrylic polymer. It is derived from a structural unit of a well-known or commonly used monomer. Examples of the above-mentioned monomer include acrylates (including those having a hydroxyl group and a carboxyl group) such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and amyl acrylate; a methacrylate such as methyl acrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate (including a functional group having a hydroxyl group and a carboxyl group); acrylamide, N-methyl propylene A acrylamide such as decylamine; a methacrylamide such as methacrylamide; an allyl compound; an ethylene compound such as an aromatic vinyl compound, a vinyl ether or a vinyl ester. Further, a polyalkylene glycol ether, an ester of acrylic acid or methacrylic acid, or the like can be used as the above monomer.

Specific examples of the fluorine-containing acrylic polymer include a fluorine-containing acrylic polymer represented by the following formula (8a).

R ¹⁸ in the formula (8a) represents a hydrogen atom or a methyl group. Further, R ¹⁹ represents a linear or branched chain alkyl group. The linear or branched chain alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), and an isobutyl group. A linear or branched chain alkyl group having 1 to 30 carbon atoms such as dibutyl, tert-butyl or pentyl.

R ²⁰ in the formula (8a) represents a hydrogen atom or a methyl group. Further, R ²¹ represents a perfluoroalkyl group. The perfluoroalkyl group is not particularly limited, and examples thereof include a perfluoroalkyl group exemplified as R ¹⁷ in the above formula (8).

R ²² in the formula (8a) represents a hydrogen atom or a methyl group. Further, R ²³ represents an organic group containing a polyether chain. The organic group containing the polyether chain is not particularly limited, and examples thereof include those exemplified as R ⁹ in the above formula (7).

The r, s, and t systems of the formula (8a) each represent an integer of 1 to 3,000.

The fluorine-containing acrylic polymer can be obtained by a known or usual production method, and the production method thereof is not particularly limited, and for example, a monomer (for example, perfluoroalkyl acrylate and perfluoroalkyl methacrylate) can be used. The ester or the like is produced by a method of polymerization or the like, wherein the single system can supply a structural unit represented by the formula (8) by polymerization. Further, as the fluorine-containing acrylic polymer, a commercially available product can also be used.

R ²⁴ in the above formula (9) represents a trivalent linear or branched chain hydrocarbon group. The above-mentioned trivalent linear or branched chain hydrocarbon group may, for example, be methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane or 2-methylpentane. a linear or branched chain alkane of 3-methylpentane, heptane, 2-methylheptane, 3-methylheptane, octane, decane or decane, after removing three hydrogen atoms Base (alkane-triyl) and the like. In particular, it is preferred to remove three hydrogen atoms from a linear or branched chain alkane having 1 to 10 carbon atoms.

R ²⁵ in the above formula (9) represents a fluorinated alkyl group. For the above fluorinated alkyl group, a part or all based system is substituted with the fluorine atoms to hydrogen atoms is not particularly limited, and examples thereof include the above formula (8) as illustrated by R ¹⁷ and the like. In particular, in the case of R ²⁵ described above, an alkyl group in which a part of a hydrogen atom is substituted by a fluorine atom is preferred.

In the above formula (9), z (the number of repetitions of the methylene structural unit) is an integer of 1 to 30, particularly preferably an integer of 1 to 10.

Further, in the case of the repeating structure unit, the fluorine-containing polyether polymer may be a polymer having only the structural unit represented by the formula (9), or may have a structure other than the structural unit represented by the formula (9). The polymer of the building block. In addition, the fluorine-containing polyether polymer may be a polymer having only one structural unit represented by the formula (9), or may be a polymer having two or more structural units represented by the formula (9). . Further, a polymer having two or more structural units other than the structural unit represented by the formula (9) may be used.

The structural unit other than the structural unit represented by the formula (9) is not particularly limited, and examples thereof include an oxygen-extended ethyl unit [-OCH ₂ CH ₂ - An oxygen-extension alkyl structural unit such as an oxypropyl unit [-OCH(CH ₃ )CH ₂ -].

Specific examples of the structural unit represented by the above formula (9) include a structural unit represented by the following formula and the like. R ²⁶ in the following formula represents a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 to 4 (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group or the like). R ²⁵ and z in the following formula are the same as described above.

Specific examples of the fluorine-containing polyether polymer include a fluorine-containing polyether polymer represented by the following formula (9a).

In the formula (9a), u, v, and w each represent an integer of 1 to 50. In particular, the total of u and w is preferably an integer of 2 to 80, preferably an integer of 4 to 30, more preferably an integer of 6 to 14. Further, v is preferably an integer of 2 to 50, and preferably an integer of 5 to 20.

The fluorine-containing polyether polymer can be obtained by a known or usual production method, and the production method thereof is not particularly limited. For example, a monomer (for example, an epoxy compound, an oxetane compound, etc.) can be used. a cyclic ether compound or the like) produced by a method of polymerization (for example, ring-opening polymerization), wherein the single system can supply a structural unit represented by the formula (9) by polymerization, and the above-mentioned fluorine-containing polyether polymerization Commercially available products can also be used.

The nonvolatile content (adjusted amount) of the leveling agent of the curable epoxy resin composition of the present invention is not particularly limited, and is equivalent to the epoxy group contained in the curable epoxy resin composition. The total amount (100 parts by weight) of the compound is preferably 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 4 parts by weight. When the content of the leveling agent (in terms of nonvolatile matter) is less than 0.1 part by weight, the crack resistance of the cured product may be lowered. On the other hand, when the content of the leveling agent (in terms of nonvolatile matter) is more than 10 parts by weight, the heat resistance of the cured product may be lowered.

In particular, the content (mixing amount) of the polyfluorene-based polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer in the curable epoxy resin composition of the present invention is not particularly limited. The total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, more preferably 0.1 to 4 parts by weight. When the content of the polyfluorene-based polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer is less than 0.1 part by weight, the crack resistance of the cured product may be lowered. On the other hand, when the content is more than 10 parts by weight, the heat resistance of the cured product may be lowered. In addition, the content (the amount of the above-mentioned polyfluorinated polymer, the fluorine-containing acrylic polymer, and the fluorine-containing polyether polymer) means that the polyfluorene-based polymer and the above-mentioned In the case of two or more kinds of the fluoroacrylic polymer and the fluorine-containing polyether polymer, the total content (total content).

When the curable epoxy resin composition of the present invention contains the above-mentioned specific leveling agent, it is possible to exhibit a higher level of heat resistance and crack resistance by using a reflecting material containing a cured product of the above resin composition. In the optical semiconductor device including the reflective material, the luminosity caused by the lapse of time (especially, the luminosity of the optical semiconductor device that emits high-intensity light is lowered). It is estimated that the effect of the curable epoxy resin composition (or a cured product thereof) of the present invention on the sealing material (the sealing resin of the optical semiconductor element) is improved by the preparation of the leveling agent. .

[Polyol compound]

The curable epoxy resin composition of the present invention preferably further contains a polyol compound. The curable epoxy resin composition of the present invention can form a cured product which exhibits a higher degree of heat resistance and crack resistance by containing the above-described polyol compound, and an optical semiconductor device produced by using the cured product. It is not easy to cause luminosity caused by the passage of time. The polyol compound is a polymer (oligomer or polymer) having a number average molecular weight of 200 or more in a molecule (in one molecule), and includes, for example, a polyether polyol or a polyester polyol. Alcohol, polycarbonate polyol, and the like. Further, the above polyol compounds can be used singly or in combination of two or more.

The hydroxyl group (two or more hydroxyl groups) of the above polyol compound may be an alcoholic hydroxyl group or a phenolic hydroxyl group. In addition, the number of the hydroxyl groups (the number of hydroxyl groups in one molecule) of the polyol compound may be two or more, and is not particularly limited.

The position of the hydroxyl group (two or more hydroxyl groups) of the polyol compound is not particularly limited, and is at least present at the end of the polyol (end of the polymer main chain) from the viewpoint of reactivity with the curing agent and the like. Preferably, it is particularly preferred to be present at least at both ends of the polyol.

The polyol compound may be formed into a liquid curable epoxy resin composition after being blended with other components, and may be a solid or a liquid.

The number average molecular weight of the above polyol compound is 200 or more, and is not particularly limited, and is preferably from 200 to 100,000, more preferably from 300 to 50,000, still more preferably from 400 to 40,000. When the number average molecular weight is less than 200, there is a case where the cured product is peeled off or cracks are formed in the hardened material when passing through the solder reflow step. On the other hand, when the number average molecular weight is more than 100,000, the liquid curable epoxy resin composition may be precipitated or may not be dissolved. Further, the number average molecular weight of the above polyol compound means a number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

The polyhydric alcohol compound may, for example, be a polyester polyol (including a polyester polyol oligomer) having an ester skeleton (polyester skeleton) in a molecule, and have an ether skeleton (polyether skeleton) in the molecule. The polyether polyol (including a polyether polyol oligomer), a polycarbonate polyol having a carbonate skeleton (polycarbonate skeleton) in a molecule (including a polycarbonate polyol oligomer), and the like. The polyol compound may further contain, for example, a phenoxy resin, a bisphenol type polymer epoxy resin having an epoxy equivalent of more than 1000 g/eq., a polybutadiene having a hydroxyl group, an acrylic polyol, or the like.

The polyester polyol may, for example, be a polyester polyol obtained by condensation polymerization (for example, transesterification) of a polyhydric alcohol, a polybasic acid or a hydroxycarboxylic acid, or a ring-opening of a lactone. A polyester polyol obtained by polymerization or the like.

Examples of the polyol constituting the monomer component of the polyester polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, and 2-methyl-1,3-propanediol. 3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3 -methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol , 2,2,4-trimethyl-1,6-hexanediol, 2,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,2-di Hydroxymethylcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dodecanediol, polybutadiene diol, neopentyl Glycol, butanediol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexanediol, 1,2,6-hexanetriol, ditrimethylolpropane , mannitol, sorbitol, neopentyl alcohol, and the like. Examples of the polybasic acid constituting the monomer component of the polyester polyol include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, and hydrazine. Diacid, citric acid, 2,6-naphthalene dicarboxylic acid, p-nonanoic acid, isophthalic acid, citric acid, citraconic acid, 1,10-decane dicarboxylic acid, methyl hexahydrophthalic anhydride, hexahydroanthracene Anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyrogalic anhydride, 1,2,4-benzenetricarboxylic anhydride, and the like. Examples of the hydroxycarboxylic acid include lactic acid, malic acid, glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Examples of the lactones include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

The polyester polyol can be produced by a known or usual production method, and is not particularly limited. For example, condensation polymerization (polycondensation) of the above polyol and polybasic acid, condensation polymerization of the above hydroxycarboxylic acid, and the above lactone can be used. Manufactured by ring-opening polymerization or the like. Conditions during polymerization It is not particularly limited, and well-known or commonly used reaction conditions can be appropriately selected. Further, as the above polyol, polybasic acid or hydroxycarboxylic acid, well-known or commonly used derivatives (for example, hydroxy-based fluorenyl group, alkoxycarbonyl group, organodecyl group, alkoxyalkyl group, oxygen) can also be used. A protected derivative such as a heterocycloalkyl group or a carboxyl group is derivatized into a derivative such as an alkyl ester, an acid anhydride or an oxyhalide compound.

For the polyester polyol, for example, the trade names "PLACCEL 205", "PLACCEL 205H", "PLACCEL 205U", "PLACCEL 205BA", "PLACCEL 208", "PLACCEL 210", "PLACCEL 210CP", " PLACCEL 210BA", "PLACCEL 212", "PLACCEL 212CP", "PLACCEL 220", "PLACCEL 220CPB", "PLACCEL 220NP1", "PLACCEL 220BA", "PLACCEL 220ED", "PLACCEL 220EB", "PLACCEL 220EC", " PLACCEL 230", "PLACCEL 230CP", "PLACCEL 240", "PLACCEL 240CP", "PLACCEL 210N", "PLACCEL 220N", "PLACCEL L205AL", "PLACCEL L208AL", "PLACCEL L212AL", "PLACCEL L220AL", " PLACCEL L230AL", "PLACCEL 305", "PLACCEL 308", "PLACCEL 312", "PLACCEL L312AL", "PLACCEL 320", "PLACCEL L320AL", "PLACCEL L330AL", "PLACCEL 410", "PLACCEL 410D", " Commercial products such as PLACCEL 610", "PLACCEL P3403", and "PLACCEL CDE9P" (above, DAICEL).

The polyether polyol may, for example, be a polyether polyol obtained by an addition reaction of a cyclic ether compound to a polyhydric alcohol, and an ether polyol obtained by ring-opening polymerization of an alkylene oxide. Wait.

More specifically, the polyether polyol may, for example, be ethylene glycol, diethylene glycol, 1,2-propylene glycol (propylene glycol), 2-methyl-1,3-propanediol, or 1,3-. Propylene glycol, 1,4-butanediol (butanediol), 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentyl Glycol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6 - hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1 , 2-Dimethylolcyclohexane, 1,3-Dimethylolcyclohexane, 1,4-Dimethylmethylcyclohexane, 1,12-dodecanediol, Polybutadiene II Alcohol, neopentyl glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-dihydroxyacetone, hexanediol, 1,2,6-hexanetriol, ditrimethylolpropane, mannose a polymer of a polyol such as an alcohol, sorbitol or neopentyl alcohol; the above polyols with ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide , an adduct of an alkylene oxide such as 2,3-butylene oxide, tetrahydrofuran or epichlorohydrin; a ring-opening polymer of a cyclic ether such as tetrahydrofuran (for example, polybutane diol) and the like.

The polyether polyol can be produced by a known or usual production method, and is not particularly limited. For example, an addition reaction (open-loop addition polymerization) of a polyhydric alcohol can be carried out by a cyclic ether compound, and the alkylene oxide can be opened. Manufactured by ring polymerization (individual polymerization or copolymerization) or the like. The conditions at the time of polymerization are also not particularly limited, and well-known or commonly used reaction conditions are appropriately selected.

For the polyether polyol, for example, the trade name "PEP-101" (FREUND Industries Co., Ltd.) and the trade name "Adeka" can be used. Pulronic L", "Adeka pulronic P", "Adeka pulronic F", "Adeka pulronic R", "Adeka pulronic TR", "Adeka PEG" (above, Adeka), trade name "PEG#1000", "PEG#1500", "PEG#11000" (above, Nippon Oil Co., Ltd.), trade name "NEWPOL PE-34", "NEWPOL PE-61", "NEWPOL PE-78", "NEWPOL PE-108" ", PEG-200", "PEG-600", "PEG-2000", "PEG-6000", "PEG-10000", "PEG-20000" (above, Sanyo Chemical Industry Co., Ltd.), and products Commercial products such as "PTMG1000", "PTMG1800", "PTMG2000" (above, Mitsubishi Chemical Co., Ltd.), and "PTMG PREPOLYMER" (Mitsubishi Resin Co., Ltd.).

The above-mentioned polycarbonate polyol is a polycarbonate having two or more hydroxyl groups in its molecule. In particular, in view of the above polycarbonate polyol, a polycarbonate diol having two terminal hydroxyl groups in the molecule is preferred.

The above polycarbonate polyol can be obtained by the same phosgene method as the usual method for producing a polycarbonate polyol, or by a carbonate exchange reaction such as a dialkyl carbonate or a diphenyl carbonate (Special opening) It is synthesized by the like, etc., etc., etc., etc., etc., etc., etc., etc., etc., etc., and the like. Since the carbonate bond of the above polycarbonate polyol is not easily thermally decomposed, the cured resin containing a polycarbonate polyol exhibits excellent stability even under high temperature and high humidity.

Examples of the polyol used in the carbonate exchange reaction with the above dialkyl carbonate or diphenyl carbonate include, for example, 1,6-hexanediol, ethylene glycol, diethylene glycol, and 1 , 3-propanediol, 1,4-butanediol, 1,3- Butylene glycol, 2,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,8-octanediol 1,9-decanediol, 1,12-dodecanediol, butadienediol, neopentyl glycol, butanediol, propylene glycol, dipropylene glycol, and the like.

For the polycarbonate polyol, for example, the trade names "PLACCEL CD205PL", "PLACCEL CD205HL", "PLACCEL CD210PL", "PLACCEL CD210HL", "PLACCEL CD220PL", "PLACCEL CD220HL" can be used (above, DAICEL (shares) )), product name "UH-CARB50", "UH-CARB100", "UH-CARB300", "UH-CARB90(1/3)", "UH-CARB90(1/1)", "UC-CARB100" (The above, Ube Industries Co., Ltd.), trade names "PCDL T4671", "PCDL T4672", "PCDL T5650J", "PCDL T5651", "PCDL T5652" (above, Asahi Kasei CHEMICALS) Commercial products.

For the polyol compound other than the polyether polyol, the polyester polyol, and the polycarbonate polyol, for example, "YP-50", "YP-50S", "YP-55U", and "YP" can be used. -70", "ZX-1356-2", "YPB-43C", "YPB-43M", "FX-316", "FX-310T40", "FX-280S", "FX-293", "YPS" -007A30", "TX-1016" (above, Nippon Steel Chemical Co., Ltd.), the trade name "jER1256", "jER4250", "jER4275" (above, Mitsubishi Chemical Co., Ltd.) Resin; trade name "EpoTohto YD-014", "EpoTohto YD-017", "EpoTohto YD-019", "EpoTohto YD-020G", "EpoTohto YD-904", "EpoTohto YD-907", "EpoTohto YD-6020" (above, Nippon Steel Chemical Co., Ltd.), trade name "jER1007", "jER1009", "jER1010", "jER1005F", "jER1009F", "jER1006FS", "jER1007FS" (above) , bisphenol type polymer epoxy resin having an epoxy equivalent of more than 1000 g/eq., such as Mitsubishi Chemical Co., Ltd.; trade name "Poly bd R-45HT", "Poly bd R-15HT", "Poly ip" "KRASOL" (above, Idemitsu Kosan Co., Ltd.), trade name "α-ω polybutadiene diol G-1000", "α-ω polybutadiene diol G-2000", "α Polybutadiene having a hydroxyl group such as -ω polybutadiene diol G-3000" (above, manufactured by Nippon Soda Co., Ltd.); trade names "Hitaloid 3903", "Hitaloid 3904", "Hitaloid 3905", "Hitaloid 6500", "Hitaloid 6500B", "Hitaloid 3018X" (above, Hitachi Chemical Co., Ltd.), trade name "ACRYDIC DL-1537", "ACRYDIC BL-616", "ACRYDIC AL-1157", " ACRYDIC A-322", "ACRYDIC A-817", "ACRYDIC A-870", "ACRYDIC A-859-B", "ACRYDIC A-829", "ACRYDIC A-49-394-IM" (above, DIC A commercially available product such as an acrylic polyol such as "trade name", "DIANAL SR-1346", "DIANAL SR-1237", "DIANAL AS-1139" (above, Mitsubishi Rayon Co., Ltd.).

The amount (content) of the polyol compound to be used is not particularly limited, and is preferably from 1 to 50 parts by weight, preferably from 1.5 to the total amount (100 parts by weight) of the component (A) and the component (B). 40 parts by weight, more preferably 5 to 30 parts by weight. When the content of the polyol compound is more than 50 parts by weight, the Tg of the cured product is excessively lowered, and the volume change due to heating is increased, so that the optical semiconductor device may be defective in lighting or the like. When the content of the polyol compound is less than 1 part by weight, the light reflectivity may be lowered due to the passage of time.

When the curable epoxy resin composition of the present invention contains a nonoxyl derivative (G) having two or more epoxy groups in the molecule, the amount (content) of the above polyol compound is not particularly limited, and is not particularly limited. The total amount (100 parts by weight) of the component (A), the component (B), and the component (G) is preferably 1 to 50 parts by weight, more preferably 1.5 to 40 parts by weight, still more preferably 5 to 30 parts by weight. Parts by weight. When the content of the polyol compound is more than 50 parts by weight, the Tg of the cured product is excessively lowered, and the volume change due to heating is increased, so that the optical semiconductor device may be defective in lighting or the like. When the content of the polyol compound is less than 1 part by weight, the light reflectivity may be lowered due to the passage of time.

[Acrylic block copolymer]

The curable epoxy resin composition of the present invention preferably further contains an acrylic block copolymer. More specifically, when the curable epoxy resin composition of the present invention contains an acrylic block copolymer, an optical semiconductor device produced by using the curable epoxy resin composition is particularly high in brightness. In the case of high output power, luminosity is also less likely to have a tendency to fall. In other words, the cured product obtained by curing the curable epoxy resin composition of the present invention by using the acrylic block copolymer can exhibit higher level of heat resistance, light resistance, and crack resistance.

The above acrylic block copolymer contains a block copolymer containing an acrylic monomer as an essential monomer component. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. Methyl ester, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl stearate, etc. (meth) acrylate having an alicyclic structure such as cyclohexyl acrylate or cyclohexyl methacrylate; (meth) acrylate having an aromatic ring such as benzyl methacrylate; a (fluoro)alkyl ester of (meth)acrylic acid such as 2-trifluoroethyl acrylate; a carboxyl group-containing acrylic monomer having a carboxyl group in a molecule such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glycerin a hydroxyl group-containing acrylic monomer having a hydroxyl group in a molecule such as mono(meth)acrylate; glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxy ring of methacrylic acid Acrylic acid monomer having an epoxy group in a molecule such as hexylmethyl ester; allyl acrylate Allyl methacrylate or the like having an allyl group-containing acrylic monomer in the molecule; γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropyl three An oxiranyl-containing acrylic monomer having a hydrolyzable alkylene group in the molecule; 2-(2'-hydroxy-5'-methylpropenyloxyethylphenyl ester)-2H-benzotriene A UV-absorbing acrylic monomer having a benzotriazole-based ultraviolet absorbing group or the like.

Further, the acrylic block copolymer may be used as a monomer component other than the monomer other than the acrylic monomer. Examples of the monomer other than the acrylic monomer include an aromatic vinyl compound such as styrene or α-methylstyrene, a conjugated double bond such as butadiene or isoprene, and ethylene. An olefin such as propylene or isobutylene.

The acrylic block copolymer is not particularly limited, and examples thereof include a diblock copolymer containing two polymer blocks, three polymer block triblock copolymers, and four or more. A multi-block copolymer of a polymer block or the like.

In particular, in view of the improvement of heat resistance, light resistance, and crack resistance, the above-mentioned acrylic block copolymer is a polymer block [S] having a lower glass transition temperature (Tg) (soft embedded) Preferably, the polymer block [H] (hard block) having a higher Tg than the polymer block [S] is a block copolymer which is alternately arranged, preferably in the middle A triblock copolymer having a polymer block [S] and having an HSH structure of a polymer block [H] at both ends thereof is preferred. Further, the Tg of the polymer constituting the polymer block [S] of the above acrylic block copolymer is not particularly limited, and is preferably less than 30 °C. Further, the Tg system of the polymer constituting the polymer block [H] is not particularly limited, and is preferably 30 ° C or more. The above acrylic block copolymer has a plurality of polymer blocks [H], and the respective polymer blocks [H] may have the same composition or may be different. Similarly, the above acrylic block copolymer has a plurality of polymer blocks [S], and the respective polymer blocks [S] may have the same composition or may be different.

The monomer component constituting the polymer block [H] of the above-mentioned acrylic block copolymer (such as a triblock copolymer of the above-described HSH structure) is not particularly limited, and examples thereof include a homopolymer. Tg is a monomer of 30 ° C or more, and more specifically, methyl methacrylate, styrene, acrylamide, acrylonitrile, etc. are mentioned. On the other hand, the monomer component constituting the polymer block [S] of the above-mentioned acrylic block copolymer is not particularly limited, and examples thereof include a monomer having a Tg of less than 30 ° C in the homopolymer. More specifically, C _2-10 alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate, butadiene (1,4-butadiene), or the like can be given.

In a preferred embodiment of the curable epoxy resin composition of the present invention, the polymer block [S] is composed of butyl acrylate (BA) as a main monomer. The polymer, the polymer block [H] is a polymer composed of methyl methacrylate (MMA) as a main monomer, and polymethyl methacrylate-block-polybutyl acrylate-block- Polymethyl methacrylate terpolymer (PMMA-b-PBA-b-PMMA) and the like. The above PMMA-b-PBA-b-PMMA is preferred in terms of heat resistance, light resistance, and crack resistance. Further, for the purpose of improving the compatibility with the component (A) and the component (B), the PMMA-b-PBA-b-PMMA may have a hydrophilic group (for example, a hydroxyl group, if necessary). a monomer such as a carboxyl group or an amine group, for example, a hydroxyethyl (meth)acrylate, a hydroxypropyl (meth)acrylate, or a (meth)acrylic acid, which is obtained by copolymerizing a PMMA block and/or a PBA block. By.

The number average molecular weight of the above acrylic block copolymer is not particularly limited, and is preferably from 3,000 to 500,000, more preferably from 30,000 to 400,000. When the number average molecular weight is less than 3,000, the toughness of the cured product is insufficient and the crack resistance is lowered. On the other hand, when the number average molecular weight is more than 500,000, the compatibility with the alicyclic epoxy compound (A) is low, and the mechanical properties of the cured product are adversely affected, and the crack resistance is lowered.

The above acrylic block copolymer can be produced by a method of producing a well-known or commonly used block copolymer. On the above acrylic block The method for producing a polymer is, in particular, active polymerization (active radical polymerization, living anionic polymerization, living cationic polymerization, etc.) from the viewpoint of controlling the easiness of molecular weight, molecular weight distribution, and terminal structure of the acrylic block copolymer. ) is better. The above living polymerization system can be carried out by a well-known or usual method.

Further, for the above-mentioned acrylic block copolymer, for example, "Nanostrength M52N", "Nanostrength M22N", "Nanostrength M51", "Nanostrength M52", "Nanostrength M53" (made by ARKEMA, PMMA-b-PBA) can also be used. -b-PMMA), a commercial item such as "Nanostrength E21" and "Nanostrength E41" (manufactured by ARKEMA, PSt (polystyrene)-b-PBA-b-PMMA).

The amount (content) of the acrylic block copolymer is not particularly limited, and it is preferably 1 to 30 parts by weight based on the total amount (100 parts by weight) of the component (A) and the component (B). Preferably, it is 3 to 15 parts by weight, more preferably 5 to 10 parts by weight. When the amount of the acrylic block copolymer used is less than 1 part by weight, the toughness of the cured product may be insufficient, and the heat resistance and light resistance may be lowered. On the other hand, when the amount of the acrylic block copolymer used is more than 30 parts by weight, the compatibility with the alicyclic epoxy compound (A) is low, and the crack resistance of the cured product may be lowered.

When the curable epoxy resin composition of the present invention contains a cyclooxyalkylene derivative (G) having two or more epoxy groups in the molecule, the amount (content) of the acrylic block copolymer used is It is not particularly limited, and it is preferably 1 to 30 parts by weight, preferably 3 to 15 parts by weight, based on the total amount (100 parts by weight) of the component (A), the component (B), and the component (G). good It is 5 to 10 parts by weight. When the amount of the acrylic block copolymer used is less than 1 part by weight, the toughness of the cured product may be insufficient, and the heat resistance and light resistance may be lowered. On the other hand, when the amount of the acrylic block copolymer used is more than 30 parts by weight, the compatibility with the alicyclic epoxy compound (A) is low, and the crack resistance of the cured product may be lowered.

[Rubber particles]

The curable epoxy resin composition of the present invention may further contain rubber particles. Examples of the rubber particles include particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). Rubber particles. It is preferable that the rubber particles are rubber particles having a multilayer structure (core-shell structure) having a core portion and a shell layer of at least one layer, wherein the core portion has rubber elasticity; and the shell layer is coated with the rubber layer Nuclear part. The rubber particles are particularly preferably rubber particles containing a polymer and having a hydroxyl group and/or a carboxyl group (either or both of a hydroxyl group and a carboxyl group) on the surface, wherein the polymer is (meth) The acrylate is an essential monomer component; and the hydroxyl group and/or carboxyl group is a functional group capable of reacting with an epoxy group-containing compound such as the alicyclic epoxy compound (A). When the hydroxyl group and/or the carboxyl group are not present on the surface of the rubber particles, the cured product is likely to be cracked.

The polymer having a rubber-elastic core portion of the rubber particles is not particularly limited, and is preferably methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate. The acrylate is preferred as the necessary monomer component. A polymer constituting the above-mentioned rubber-elastic core portion, and further, for example, styrene, α-methylstyrene, or the like Aromatic ethylene (aromatic vinyl compound), nitrile such as acrylonitrile or methacrylonitrile, conjugated double bond such as butadiene or isoprene, ethylene, propylene, isobutylene or the like is contained as a monomer component.

In particular, the polymer constituting the above-mentioned rubber-elastic core portion is selected from the group consisting of aromatic vinyl, nitrile and conjugated double bonds in the case of a monomer component containing a (meth) acrylate. Kinds or more than two are preferred. In other words, the polymer constituting the core portion may, for example, be a binary copolymer of (meth) acrylate/aromatic ethylene or a (meth) acrylate/conjugated double bond; a terpolymer such as an acrylate/aromatic ethylene/conjugated double bond or the like. Further, the polymer constituting the core portion may contain fluorene or a polyurethane such as polydimethyl siloxane or polyphenylmethyl siloxane.

The polymer constituting the core portion may be divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, maleic acid as other monomer components. a diallyl ester, a triallyl cyanurate, a diallyl phthalate, a butanediol diacrylate, or the like, which contains a reactive group having two or more reactive functional groups in one monomer (one molecule) Joint monomer.

The core portion of the rubber particles is preferably a core portion containing a (meth) acrylate/aromatic ethylene binary copolymer (particularly butyl acrylate/styrene) from the viewpoint of heat resistance.

The core portion of the rubber particles can be produced by a method generally used, and can be produced, for example, by a method in which the monomer is polymerized by an emulsion polymerization method. In the emulsion polymerization method, the total amount of the above monomers may be added in a batch to be polymerized, or a part of the above monomers may be polymerized. After the combination, the residual portion is continuously or intermittently added for polymerization, and a polymerization method of the seed particles may also be used.

The polymer constituting the shell layer of the rubber particles is preferably a polymer which is different from the polymer constituting the core portion. In addition, as described above, the shell layer preferably has a hydroxyl group and/or a carboxyl group which can be a functional group reactive with a compound having an epoxy group such as an alicyclic epoxy compound (A). The adhesion to the interface with the alicyclic epoxy compound (A) can be improved, and the cured product obtained by curing the curable epoxy resin composition containing the rubber particles having the shell layer can be used. Excellent crack resistance. Further, it is also possible to prevent the glass transition temperature of the cured product from being lowered.

The polymer constituting the shell layer contains a (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate as an essential monomer component. It is better. For example, when butyl acrylate is used as the (meth) acrylate in the above-mentioned core portion, a (meth) acrylate other than butyl acrylate is used for the monomer component of the polymer constituting the shell layer (for example) Preferably, methyl (meth)acrylate, ethyl (meth)acrylate, butyl methacrylate or the like). Examples of the monomer component which may be contained in addition to the (meth) acrylate include aromatic vinyl such as styrene or α-methylstyrene, nitrile such as acrylonitrile or methacrylonitrile. In the above-mentioned rubber particles, it is preferable to contain the above-mentioned monomers alone or in combination of two or more kinds, in particular, heat resistance from the viewpoint of the (meth) acrylate. It is preferred to contain at least aromatic vinyl.

Further, the polymer constituting the shell layer has a hydroxyl group and/or a functional group capable of reacting with an epoxy group-containing compound such as an alicyclic epoxy compound (A) in terms of a monomer component. The carboxyl group is α which includes a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, an α,β-unsaturated acid such as (meth)acrylic acid, or maleic anhydride. A monomer such as a β-unsaturated acid anhydride is preferred.

The polymer constituting the shell layer of the rubber particles is preferably one or two or more selected from the above monomers in combination with the (meth) acrylate. That is, the shell layer includes, for example, three of (meth) acrylate/aromatic ethylene/hydroxyalkyl (meth) acrylate, (meth) acrylate/aromatic ethylene/α, β-unsaturated acid, and the like. A shell layer of a meta-copolymer or the like is preferred.

Further, the polymer constituting the shell layer may be divinylbenzene, allyl (meth)acrylate or ethylene glycol in addition to the above-mentioned monomers, in the same manner as the core component. In one monomer (one molecule) such as di(meth)acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate or butanediol diacrylate, Containing a reactive crosslinking monomer having two or more reactive functional groups.

The rubber particles (rubber particles having a core-shell structure) can be obtained by coating the core portion with a shell layer. In the method of coating the core portion with the shell layer, for example, a method of coating a copolymer constituting the shell layer by coating the surface of the core portion having rubber elasticity obtained by the above method; and A method in which a core portion having rubber elasticity obtained by the above method is used as a dry component, and each component constituting the shell layer is graft-polymerized as a branch component.

The average particle diameter of the rubber particles is not particularly limited, and is preferably 10 to 500 nm, more preferably 20 to 400 nm. Further, the maximum particle diameter of the rubber particles is not particularly limited, and is preferably 50 to 1000 nm, more preferably 100 to 800 nm. When the average particle diameter is more than 500 nm or the maximum particle diameter is more than 1000 nm, the dispersibility of the rubber particles in the cured product is lowered, and the crack resistance is lowered. On the other hand, when the average particle diameter is less than 10 nm or the maximum particle diameter is less than 50 nm, the effect of improving the crack resistance of the cured product is not easily obtained.

The content (adjusted amount) of the rubber particles of the curable epoxy resin composition of the present invention is not particularly limited, and is the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition. (100 parts by weight) is preferably 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight. When the content of the rubber particles is less than 0.5 part by weight, the crack resistance of the cured product tends to be low. On the other hand, when the content of the rubber particles is more than 30 parts by weight, the heat resistance of the cured product tends to be low.

[additive]

In addition to the above, the curable epoxy resin composition of the present invention can use various additives within a range not impairing the effects of the present invention. In the case of the additive, for example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or glycerin is used (the above polyol compound is removed), the reaction (curing reaction) can be gradually carried out. Further, in the range which does not adversely affect the effects of the present invention, a decane coupling agent such as γ-glycidoxypropyltrimethoxydecane, a surfactant, a cerium oxide, or an inorganic oxide such as alumina can be used. Common additives such as fillers, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, mold release agents, and the like.

<Modulation method of curable epoxy resin composition>

The method for producing the curable epoxy resin composition of the present invention is not particularly limited, and a well-known or commonly used method can be applied. Specifically, for example, a predetermined amount of an alicyclic epoxy compound (A), an isomeric isocyanate propylene carbonate compound (B), a white pigment (C), and a curing agent (D) may be mentioned. , a hardening accelerator (F), and any additives, or a predetermined amount of an alicyclic epoxy compound (A), an isomeric isocyanurate compound (B) Various kinds of mixers, kneaders, roll mills, bead mills, self-revolving stirring devices, etc., which are prepared by mixing a white pigment (C), a curing catalyst (E), and an optional additive, using a dissolver or a homogenizer. Stirring, mixing, etc. Further, after stirring and mixing, defoaming can also be carried out under reduced pressure or under vacuum.

More specifically, the curable epoxy resin composition of the present invention can be, for example, an alicyclic epoxy compound (A) or an isomeric isocyanurate compound ( B) an α-agent containing an epoxy group-containing compound such as a cyclooxyl derivative (G) having two or more epoxy groups in the molecule as an essential component, and a curing agent (D) and a curing accelerator The agent (F) or the hardening catalyst (E) contains the β agent as an essential component, and the α agent and the β agent are stirred at a predetermined ratio. Mix and modulate as necessary to perform defoaming under vacuum. Further, the alicyclic polyester resin (H) may be previously mixed (adapted) as a constituent component of the alpha agent and/or the beta agent, or may be used as an alpha agent or a beta agent when the alpha agent and the beta agent are mixed. The third component is blended. Further, similarly, the white pigment (C) may be previously mixed (adapted) as a constituent component of the alpha agent and/or the beta agent, or may be used as an alpha agent or a beta agent when the alpha agent and the beta agent are mixed. The third component is formulated.

Stirring when preparing the above α agent. The temperature at the time of mixing is not particularly limited, and is preferably from 30 to 150 ° C, preferably from 35 to 130 ° C. Further, stirring is carried out when the above-mentioned β agent (in the case of including two or more kinds of components) is prepared. The temperature at the time of mixing is not particularly limited, and is preferably from 30 to 100 ° C, preferably from 35 to 80 ° C. Stir. As the mixing system, various known devices, for example, various mixers such as a dissolver and a homogenizer, a kneader, a roll mill, a bead mill, a self-rotating stirring device, and the like can be used. Further, after stirring and mixing, defoaming can also be carried out under reduced pressure or under vacuum.

In particular, when the curable epoxy resin composition of the present invention contains a curing agent (D) as an essential component, a uniform composition is obtained by using an alicyclic polyester resin (H) and a hardener ( D) premixing to obtain the mixture (a mixture of the alicyclic polyester resin (H) and the hardener (D)), and then blending the mixture with the hardening accelerator (F) or other additives to prepare the β agent, Next, it is preferred to mix the β agent with an α agent. The temperature at which the alicyclic polyester resin (H) and the curing agent (D) are mixed is not particularly limited, and is preferably 60 to 130 ° C, preferably 90 to 120 ° C. The mixing time is not particularly limited and is preferably from 30 to 100 minutes, preferably from 45 to 80 minutes. The mixing system is not particularly limited and is preferably carried out under a nitrogen atmosphere. Further, the above-described well-known device can be used for the hybrid system.

The alicyclic polyester resin (H) and the curing agent (D) are not particularly limited, and may be further subjected to an appropriate chemical treatment (for example, hydrogenation, terminal modification of an alicyclic polyester, etc.). Further, in the mixture of the above alicyclic polyester resin (H) and the hardener (D), a part of the hardener (D) may also be combined with the alicyclic polyester resin (H) (for example, an alicyclic polyester resin) The reaction of the hydroxyl group of (H), etc.).

For the mixture of the alicyclic polyester resin (H) and the hardener (D), for example, "HN-7200" (manufactured by Hitachi Chemical Co., Ltd.) and "HN-5700" (Hitachi Chemical Co., Ltd.) can also be used. Commercial product such as industrial (stock) system.

<hardened matter>

The curable epoxy resin composition of the present invention can be cured by heating and/or by irradiation with light such as ultraviolet rays to form a cured product. The heating temperature (hardening temperature) and the heating time (hardening time) at the time of hardening are not particularly limited, and for example, conditions for forming a reflecting material to be described later can be employed.

The reflectance of the cured product of the curable epoxy resin composition of the present invention is not particularly limited. For example, the reflectance of light having a wavelength of 450 nm is preferably 90% or more, preferably 90.5% or more. In particular, the reflectance of light of 450 to 800 nm is preferably 90% or more, preferably 90.5% or more. In the above-mentioned reflectance, for example, a cured product (thickness: 3 mm) of the curable epoxy resin composition of the present invention can be used as a test piece, and a spectrophotometer (trade name "Spectrophotometer UV-2450", Shimadzu Corporation can be used. (Stock) system for measurement.

The cured product obtained by curing the curable epoxy resin composition of the present invention has high light reflectivity, is excellent in heat resistance and light resistance, and is strong. Therefore, since the cured product is not easily deteriorated and cracking is unlikely to occur, it is not easy to cause a decrease in reflectance due to elapse of time. Therefore, the curable epoxy resin composition of the present invention can be suitably used for LED packaging applications (components of LED packages, for example, reflective materials and packaging materials for optical semiconductor devices), subsequent use of electronic components, and liquid crystal display applications. (for example, a reflector, etc.), an ink for a white substrate, a sealant, or the like. its In particular, a curable resin composition for LED packaging (particularly, a curable resin composition for a reflector of an optical semiconductor device) can be suitably used.

<The curable resin composition for light reflection>

The curable epoxy resin composition for light reflection of the present invention comprises the curable epoxy resin composition of the present invention. In the present specification, the term "curable resin composition for light reflection" means a cured resin composition capable of forming a cured product having high light reflectivity by curing, and specifically, for example, a pair can be formed. A curable resin composition of a cured product having a reflectance of light having a wavelength of 450 nm of 80% or more. By using the curable resin composition for light reflection of the present invention, for example, an optical semiconductor including a reflective material formed of a cured product excellent in various physical properties such as light reflectivity, heat resistance, light resistance, and crack resistance can be obtained. Device. Since the above-mentioned reflective material is less likely to cause a decrease in reflectance due to the passage of time, the optical semiconductor device including the reflective material is particularly susceptible to luminosity when the optical semiconductor device having high output and high luminance is provided. And it is low and can play a high degree of trust.

<Optical semiconductor device>

The optical semiconductor device of the present invention includes at least an optical semiconductor device as a light source, and an optical semiconductor device including a cured material of a cured epoxy resin composition (curable resin composition for light reflection) of the present invention. Further, the above-mentioned reflective material is a member for reflecting the light emitted from the optical semiconductor element, improving the directivity of the light, and improving the efficiency of light extraction and brightness extraction. Fig. 1 is a view showing a composition having a curable epoxy resin of the present invention (hardening for light reflection) A schematic view of an example of an optical semiconductor device (optical semiconductor device of the present invention) of a reflective material formed of a cured product of the resin composition, (a) is a perspective view, and (b) is a cross-sectional view. In the first figure, reference numeral 1 denotes a reflective material, 2 denotes a metal wiring, 3 denotes an optical semiconductor element (LED element), 4 denotes a bonding wire, 5 denotes a sealing resin, and 6 denotes a sealing resin. The reflective material 1 surrounds the periphery of the sealing resin 5 in a ring shape, and has an inclined shape so that the diameter of the ring is enlarged upward. In the optical semiconductor device shown in FIG. 1, the light emitted from the optical semiconductor element 3 is reflected on the surface (reflection surface) of the reflective material 1, whereby the light from the optical semiconductor element 3 can be taken out with high efficiency.

The method for forming the above-mentioned reflective material can be any known or commonly used molding method, and is not particularly limited, and examples thereof include transfer molding, compression molding, injection molding, LIM molding (injection molding), and use of a dispenser. A method such as dam molding.

Specifically, for example, the curable epoxy resin composition (curable resin composition for light reflection) of the present invention can be injected into a predetermined molding die and heat-cured to form a reflective material. In the heating and hardening conditions at this time, for example, the heating temperature can be appropriately adjusted within a range of 80 to 200 ° C (preferably 80 to 190 ° C, more preferably 80 to 180 ° C), and it is 30 to 600 minutes (more) The heating time is appropriately adjusted within the range of 45 to 540 minutes, preferably 60 to 480 minutes. For example, when the heating temperature is increased, the heating time is preferably shortened, and when the heating temperature is lowered, the heating time is increased. It is better. When either or both of the heating temperature and the heating time are less than the above range, the curing tends to be insufficient. On the other hand, when either or both of the heating temperature and the heating time are larger than the above range, the resin is formed. There are cases of decomposition. Further, the heat curing treatment may be carried out in one stage, or may be divided into a plurality of stages and subjected to heat treatment to be hardened in stages.

In the present invention, in particular, in order to prevent foaming caused by a rapid hardening reaction and to alleviate stress deformation due to hardening and to improve toughness (crack resistance), the heat treatment is performed in a plurality of stages by division. Its hardening is better. Specifically, for example, when the hardener (D) is used, it is preferably heated at a temperature of 80 to 150 ° C (preferably 100 to 140 ° C) for 30 to 300 minutes (preferably 45 to 270) in the first stage. Minutes), and in the second stage, it is cured by heating at a temperature of 100 to 200 ° C (preferably 110 to 180 ° C) for 30 to 600 minutes (preferably 45 to 540 minutes). Further, for example, when the hardening catalyst (E) is used, it is preferably heated at a temperature of 30 to 150 ° C (preferably 40 to 140 ° C) for 30 to 300 minutes (preferably 45 to 1) in the first stage. 270 minutes), and in the second stage, it is cured by heating at a temperature of 60 to 200 ° C (preferably 80 to 180 ° C) for 30 to 600 minutes.

The optical semiconductor device of the present invention has at least a reflective material comprising a cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention, and can be used for a long period of time even when high-intensity light is output. And emit light with stability. In addition, the reflective material containing the cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention is a sealing property to the sealing resin (especially epoxy resin) of the optical semiconductor element. It is excellent, and it is less prone to problems such as low luminosity over time. Therefore, the optical semiconductor device of the present invention can exhibit high reliability as a long-life optical semiconductor device.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples. In addition, the blending amount of the polyoxane-based leveling agent ("BYK-300", "AC FS 180") and the fluorine-based leveling agent ("BYK-340", "AC 110a") in Tables 3 and 4 Indicates the quantity in terms of the product (the amount of the product itself). Further, "-" in Tables 1 to 4 indicates that the blending of the components is not performed.

Manufacturing example 1 (Manufacture of epoxy resin containing white pigment: Examples 1 to 9)

By using isoallyl propylene glycol monoallyl propylene carbonate (manufactured by Shikoku Chemicals Co., Ltd., trade name "MA-DGIC"), alicyclic epoxy compound (DAICEL, product, product) The name "CELLOXIDE 2021P" was mixed according to the formulation (mixing ratio) shown in Table 1 (unit: parts by weight), and stirred at 80 ° C for 1 hour to make isoallyl diglycidyl isocyanate Dissolved to obtain an epoxy resin (mixture). Next, the above-mentioned epoxy resin and white pigment (titanium oxide; manufactured by Nippon Chemical Industry Co., Ltd., trade name "TCR-52") are prepared according to the formulation (mixing ratio) (unit: weight) shown in Table 1. The dissolver was uniformly mixed, and kneaded under a predetermined condition (roll pitch: 0.2 mm, number of revolutions: Hertz), 3 passes using a roll mill to obtain an epoxy resin (epoxy) containing a white pigment. Resin composition).

Manufacturing Example 2 (Manufacture of epoxy resin containing white pigment: Comparative Examples 1 to 8)

An alicyclic epoxy compound (trade name "CELLOXIDE 2021P", DAICEL (share); trade name "EHPE3150", DAICEL (share) ), triglycidyl isocyanurate (trade name "TEPIC-PAS B26", Nissan Chemical Industry Co., Ltd.), according to the formulation shown in Table 1 (mixing ratio) (unit: parts by weight) The epoxy resin (mixture) was obtained by mixing (in the case of Comparative Examples 1, 2, 4 to 6, and 8, since the components of the epoxy resin were one type, they were directly used as the epoxy resin without mixing). Next, the epoxy resin and the white pigment (titanium oxide; trade name "TCR-52", manufactured by Nippon Chemical Industry Co., Ltd.) are used according to the formulation (mixing ratio) (unit: part by weight) shown in Table 1. The mixture was uniformly mixed with a dissolver, and kneaded under a predetermined condition (roll pitch: 0.2 mm, number of revolutions: 25 Hz, 3 passes) using a roll mill to obtain an epoxy resin containing a white pigment (epoxy resin composition). ()).

Manufacturing Example 3 (Manufacture of at least a hardener composition containing a curing agent (hereinafter referred to as "K agent"): Examples 1 to 6 and Comparative Examples 1 to 4)

A curing agent (anhydride) (manufactured by Nippon Chemical and Chemical Co., Ltd., trade name "Rikacid MH-700"), a hardening accelerator (SAN-APRO (manufactured by the company), trade name "U-CAT 18X"), and additives (and Manufactured in accordance with the formulation (mixing ratio) shown in Table 1 and used in a revolving stirring device (THINKY Co., Ltd., trade name "Stirring defoaming device", manufactured by Kokon Pure Chemical Industries, Ltd., under the trade name "ETHYLENE GLYCOL" AR-250") uniformly mixed and defoamed to obtain K agent.

Examples 1 to 9 and Comparative Examples 1 to 8 (Manufacture of curable epoxy resin composition)

As shown in Table 1, the formulation (unit: part by weight) of the epoxy resin containing the white pigment obtained in Production Example 1 was produced in Production Example 2. The obtained epoxy resin containing a white pigment, the K agent obtained in the production example 3, and the curing catalyst (manufactured by Sanshin Chemical Industry Co., Ltd., trade name "SANEIDO SI-100L") were used in a self-revolving stirring device ( The THINKY (stock) system and the product name "stirring and defoaming device AR-250" were uniformly mixed (2000 rpm, 5 minutes) and defoamed to obtain a curable epoxy resin composition.

(Manufacture of hardened materials)

The curable epoxy resin composition was cast into a mold, placed in an oven (trade name "GPHH-201", manufactured by ESPEC), and heated at 120 ° C for 5 hours to obtain a cured product.

Manufacturing Example 4 (Manufacture of epoxy resin containing white pigment: Examples 10 to 21, Comparative Examples 9 to 13)

By using isoallyl propylene glycol monoallylate (trade name "MA-DGIC", manufactured by Shikoku Chemicals Co., Ltd.), alicyclic epoxy compound (trade name "CELLOXIDE 2021P", DAICEL (share) system; trade name "EHPE3150", DAICEL (share)), iso-glycidyl isocyanurate (trade name "TEPIC-PAS B26", Nissan Chemical Industry Co., Ltd.), in the molecule a cyclooxygen derivative having two epoxy groups (trade name "X-40-2678", manufactured by Shin-Etsu Chemical Co., Ltd.) and a cyclooxygen derivative having three epoxy groups in the molecule (product "X-40-2720", Shin-Etsu Chemical Co., Ltd.), a cyclooxygen derivative having four epoxy groups in the molecule (trade name "X-40-2670", Shin-Etsu Chemical Co., Ltd.) , according to the formulation (mixing ratio) shown in Table 2 (unit: parts by weight), and further stirred at 80 ° C for 1 hour to make isoallyl cyanurate When the propyl ester was dissolved, an epoxy resin (mixture) was obtained (in the case of Comparative Examples 9 to 13, since the component of the epoxy resin was one type, the mixture was directly used as the epoxy resin without performing the mixing). Next, the epoxy resin and the white pigment (titanium oxide; trade name "TCR-52", manufactured by Nippon Chemical Industry Co., Ltd.) are used in accordance with the formulation (mixing ratio) (unit: part by weight) shown in Table 2. The dissolver was uniformly mixed and kneaded under a predetermined condition (roll pitch: 0.2 mm, number of revolutions: 25 Hz, 3 passes) using a roll mill to obtain an epoxy resin (epoxy resin composition) containing a white pigment. .

Manufacturing Example 5 (Manufacture of a hardener composition containing at least a hardener (K agent): Examples 10 to 21, Comparative Examples 9 to 13)

A mixture of a curing agent (anhydride) (trade name "Rikacid MH-700", manufactured by Hitachi Chemical Co., Ltd.), a curing agent (anhydride), and an alicyclic polyester resin (trade name "HN-7200", Hitachi Chemical Co., Ltd. Industrial (stock) system, mixture of hardener (anhydride) and alicyclic polyester resin (trade name "HN-5700", manufactured by Hitachi Chemical Co., Ltd.), hardening accelerator (trade name "U-CAT 18X" ", SAN-APRO (share) system), additives (trade name "ETHYLENE GLYCOL", and Wako Pure Chemical Industries, Ltd.) according to the formulation (distribution ratio) shown in Table 2 (unit: parts by weight), used from A revolving stirring apparatus (trade name "Stirring Defoaming Apparatus AR-250", manufactured by THINKY Co., Ltd.) was uniformly mixed and defoamed to obtain a K agent.

Examples 10 to 21 and Comparative Examples 9 to 13 (Manufacture of curable epoxy resin composition)

The epoxy resin containing the white pigment obtained in Production Example 4 was prepared in the formulation (unit: parts by weight) shown in Table 2, in Production Example 5. The obtained K agent was uniformly mixed (2000 rpm, 5 minutes) using a self-rotating stirring device (trade name "Stirring defoaming device AR-250", manufactured by THINKY Co., Ltd.) and defoamed to obtain a curable epoxy resin composition. Things.

(Manufacture of hardened materials)

The curable epoxy resin composition obtained above was placed in an oven (trade name "GPHH-201", manufactured by ESPEC Co., Ltd.), and heated at 120 ° C for 5 hours to obtain a cured product.

Manufacturing Example 6 (manufacture of rubber particles)

Into a 1 L polymerization vessel to which a reflux condenser was attached, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were added, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. Here, a monomer mixture (containing 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene) to form a core portion corresponding to a necessary amount of 5% by weight is added in batches, and stirred 20 After emulsification in a minute, 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour to carry out initial seed polymerization, followed by addition of 180.5 mg of potassium peroxodisulfate and stirring for 5 minutes. Here, a monomer mixture for forming a necessary portion of the core portion (about 95% by weight component) was used to dissolve 0.95 g of sodium octylsulfosuccinate in 180.5 g of butyl acrylate and 48.89 g of styrene. 7.3 g of divinylbenzene was added, and the second seed crystal polymerization was carried out continuously for 2 hours, followed by aging for 1 hour to obtain a core portion.

Next, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, 0.3 g of sodium dioctylsulfosuccinate was dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid, and 0.3 g of methacrylic acid. Propyl ester The monomer mixture was continuously added for seed polymerization for 30 minutes. Subsequently, it was aged for 1 hour to form a shell layer of the coated core portion.

Next, by cooling to room temperature (25 ° C) and filtering using a plastic mesh having a hole opening of 120 μm, a latex containing rubber particles having a core-shell structure was obtained, and the obtained latex was frozen at -30 ° C and used. After suctioning the filter for dehydration washing, it was air-dried at 60 ° C for one day and night to obtain rubber particles. The obtained rubber particles had an average particle diameter of 254 nm and a maximum particle diameter of 486 nm.

Further, the average particle size of the rubber particles, maximum particle size to a particle size based NANOTRACK using dynamic light scattering method as a "Nanotrac ^TM" principle of measurement in the form of distribution measuring apparatus (trade name "UPA-EX150", Nikkiso (shares) manufactured In the obtained particle size distribution curve, the cumulative average diameter of the particle diameter at the point where the cumulative curve is 50% is set as the average particle diameter, and the frequency (%) of the particle size distribution measurement result is more than 0.00%. The maximum particle size at the time point is set as the maximum particle diameter. In addition, 1 part by weight of the rubber particle-dispersed epoxy compound obtained in Production Example 7 was dispersed in 20 parts by weight of tetrahydrofuran, and it was used as a sample.

Manufacturing Example 7 (Manufacture of rubber particle-dispersed epoxy compound)

10 parts by weight of the rubber particles obtained in Production Example 6 were heated to 60 ° C under a nitrogen stream, and dispersed in 48 parts by weight of CELLOXIDE 2021P (3,4-epoxy ring) using a dissolver (1000 rpm, 60 minutes). Hexylmethyl (3,4-epoxy) decanecarboxylate, manufactured by DAICEL Co., Ltd., and subjected to vacuum defoaming to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C: 1023 mPa·s).

Further, the rubber particle-dispersed epoxy compound obtained in Production Example 7 (the viscosity of the resin particles dispersed in 48 parts by weight of CELLOXIDE 2021P (manufactured by DAICEL)) was used (viscosity at 25 ° C). It was measured by a digital viscometer (trade name "DVU-EII type", TOKIMEC (stock) system).

Manufacturing Example 8 (Manufacture of epoxy resin containing white pigment: Examples 22 to 41)

By using isoallyl propylene glycol monoallylate (trade name "MA-DGIC", manufactured by Shikoku Chemicals Co., Ltd.), alicyclic epoxy compound (trade name "CELLOXIDE 2021P", DAICEL (manufactured by the company), a cyclooxygen derivative having two epoxy groups in the molecule (trade name "X-40-2678", manufactured by Shin-Etsu Chemical Co., Ltd.), and three epoxy resins in the molecule. A sulfoxane derivative (trade name "X-40-2720", manufactured by Shin-Etsu Chemical Co., Ltd.), a cyclooxygen derivative having four epoxy groups in the molecule (trade name "X-40- 2670", Shin-Etsu Chemical Co., Ltd.), polyoxane-based leveling agent (trade name "BYK-300", BYK-Chemie Japan (share); trade name "AC FS 180", manufactured by Algin Chemie), Fluorine leveling agent (product name "BYK-340", BYK-Chemie Japan Co., Ltd.; trade name "AC 110a", manufactured by Algin Chemie), polycarbonate diol (trade name "PLACCEL CD220PL", DAICEL ( Co., Ltd.), polytetramethylene ether glycol (trade name "PTMG2000", manufactured by Mitsubishi Chemical Corporation), polycaprolactone polyol (trade name "PLACCEL 308", DAICEL (stock)), benzene Oxygen resin (trade name "YP-70", Nippon Steel Chemical (shares), Ltd.), a hydroxyl group-containing long-chain epoxy resin (trade name "EpoTohto YD-6020", manufactured by Nippon Steel Chemical (shares), Ltd.), the acrylic block copolymer (trade name "Nanostrength M52N", manufactured by ARKEMA), and the rubber particle-dispersed epoxy compound obtained in Production Example 7 were mixed according to the formulation (mixing ratio) (unit: part by weight) shown in Table 3, and stirred at 80 ° C for 1 hour. The allyl propylene glycol isoacetate is dissolved to obtain an epoxy resin (mixture). Next, the epoxy resin and the white pigment (titanium oxide; trade name "TCR-52", manufactured by Seiko Chemical Co., Ltd.) are formulated according to the formulation (mixing ratio) (unit: part by weight) shown in Table 3 and The mixture was uniformly mixed using a dissolver, and kneaded under a predetermined condition (roll pitch: 0.2 mm, number of revolutions: 25 Hz, 3 passes) using a roll mill to obtain an epoxy resin containing a white pigment (epoxy resin composition). ()).

Manufacturing Example 9 (Manufacture of K agent: Examples 22 to 41)

A mixture of a hardener (anhydride) and an alicyclic polyester resin (trade name "HN-7200", manufactured by Hitachi Chemical Co., Ltd.), and a hardening accelerator (trade name "U-CAT 18X", SAN-APRO (" (manufacturing system), additives (trade name "ETHYLENE GLYCOL", and Wako Pure Chemical Industries, Ltd.), according to the formula (mixing ratio) shown in Table 3 (unit: parts by weight) and using a self-propelled stirring device ( The product name "stirring defoaming device AR-250" and THINKY (manufactured by THINKY Co., Ltd.) were uniformly mixed and defoamed to obtain a K agent.

Example 22~41 (Manufacture of curable epoxy resin composition)

The blending prescription (unit: parts by weight) shown in Table 3, the epoxy resin containing the white pigment obtained in Production Example 8 and the K agent obtained in Production Example 9 were used in a revolving stirring apparatus (trade name "stirring off" The bubble device AR-250" and THINKY (manufactured by THINKY) were uniformly mixed (2000 rpm, 5 minutes) and defoamed to obtain a curable epoxy resin composition.

(Manufacture of hardened materials)

The curable epoxy resin composition obtained above was placed in an oven (trade name "GPHH-201", manufactured by ESPEC Co., Ltd.) and heated at 120 ° C for 5 hours to obtain a cured product.

Manufacturing Example 10 (Manufacture of epoxy resin containing white pigment: Examples 42 to 60, Comparative Examples 14 to 17)

By using isoallyl propylene glycol monoallylate (trade name "MA-DGIC", manufactured by Shikoku Chemicals Co., Ltd.), alicyclic epoxy compound (trade name "CELLOXIDE 2021P", DAICEL (share) system; trade name "EHPE3150", DAICEL (share) system, different three. Polyglycidyl polycyanate (trade name "TEPIC-PAS B26", Nissan Chemical Industry Co., Ltd.), a cyclooxygen derivative having two epoxy groups in the molecule (trade name "X-40-2678", manufactured by Shin-Etsu Chemical Co., Ltd.), and a cyclooxygen derivative having three epoxy groups in the molecule ( The product name "X-40-2720", Shin-Etsu Chemical Co., Ltd.), a cyclooxygen derivative having four epoxy groups in the molecule (trade name "X-40-2670", Shin-Etsu Chemical Industry Co., Ltd. )), polyfluorene-based leveling agent (trade name "BYK-300", BYK-Chemie Japan (stock); trade name "AC FS 180", manufactured by Algin Chemie), fluorine-based leveling agent (trade name) "BYK-340", BYK-Chemie Japan Co., Ltd.; trade name "AC 110a", manufactured by Algin Chemie), polycarbonate diol (trade name "PLACCEL CD220PL", DAICEL (share)), Polytetrachia Methyl ether glycol (trade name "PTMG2000" Mitsubishi Chemical Co., Ltd., polycaprolactone polyol (trade name "PLACCEL 308", DAICEL (stock)), phenoxy resin (trade name "YP-70", Nippon Steel Chemical Co., Ltd.) ), hydroxyl containing There are long-chain epoxy resins (trade name "EpoTohto YD-6020", manufactured by Nippon Steel Chemical Co., Ltd.), acrylic block copolymers (trade name "Nanostrength M52N", manufactured by ARKEMA), and rubber obtained in Production Example 7. The particle-dispersed epoxy compound was mixed according to the formulation (mixing ratio) (unit: part by weight) shown in Table 4, and further stirred at 80 ° C for 1 hour to dissolve isoallyl propylene glycol monoallyl diglycolate. The epoxy resin (mixture) was obtained (in the case of Comparative Examples 14 to 17, since the component of the epoxy resin was one type, the mixture was directly used as the epoxy resin without performing the mixing). Next, the above-mentioned epoxy resin and white pigment (titanium oxide; trade name "TCR-52", manufactured by 堺Chemical Industries Co., Ltd.) are formulated according to the formulation (mixing ratio) shown in Table 4 (unit: parts by weight) The mixture was uniformly mixed using a dissolver and kneaded under a predetermined condition (roll pitch: 0.2 mm, number of revolutions: 25 Hz, 3 passes) using a roll mill to obtain an epoxy resin (epoxy) containing a white pigment. Resin composition).

Manufacturing Example 11 (Manufacture of alicyclic polyester resin: Examples 42 to 60, Comparative Examples 14 to 17)

In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 172 parts by weight of 1,4-dioxane dicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 208 parts by weight of neopentyl glycol (Tokyo Chemical Industry Co., Ltd.) were added. )), 0.1 part by weight of tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.) and heated to 160 ° C, and heated from 160 ° C to 250 ° C in 4 hours. Next, the pressure was reduced to 5 mmHg over 1 hour, and further reduced to 0.3 mmHg or less, and then reacted at 250 ° C for 1 hour to obtain an alicyclic polyester resin.

Examples 42 to 60 and Comparative Examples 14 to 17 (Manufacture of curable epoxy resin composition)

The formulation (unit: parts by weight) shown in Table 4, the epoxy resin containing the white pigment obtained in Example 10, the alicyclic polyester resin obtained in Production Example 11, and the curing catalyst (trade name " SANEIDO SI-100L", manufactured by Sanshin Chemical Industry Co., Ltd.), uniformly mixed (2000 rpm, 5 minutes) using a self-propelled stirring device (trade name "Stirring defoaming device AR-250", THINKY (stock)) Further, defoaming was carried out to obtain a curable epoxy resin composition.

(Manufacture of hardened materials)

The cured epoxy resin composition obtained above was placed in an oven (trade name "GPHH-201", manufactured by ESPEC Co., Ltd.), and heated at 120 ° C for 5 hours to obtain a cured product.

<evaluation>

With respect to the cured product obtained in the examples and the comparative examples, the reflectance to light of 450 nm was measured according to the following procedure, and whether cracking occurred during reflow at the time of re-forming (cutting) was evaluated. The evaluation results are shown in Tables 1 to 4.

[reflectance evaluation]

The cured product obtained in the examples and the comparative examples was subjected to a cutting process to produce a test piece having a thickness of 3 mm. Next, the reflectance (designed as "initial reflectance") of each test piece of light having a wavelength of 450 nm was measured using a spectrophotometer (trade name "Spectrophotometer UV-2450", manufactured by Shimadzu Corporation). The results are shown in the column of "Initial Reflectance" in Tables 1 to 4.

[heat resistance test (heat aging 250 hours)]

After measuring the initial reflectance of the test piece (thickness: 3 mm) at 120 ° C for 250 hours, the reflectance of the light having a wavelength of 450 nm was measured. "Reflectance after heat aging (250 hours)"). Then, the reflectance retention ratio (before and after heat aging; 250 hours) was calculated according to the following formula. The results are shown in the columns of "Reflection retention rate before and after heating aging (250 hours)" in Tables 1 to 4.

[Reflection retention rate (before and after heat aging; 250 hours)] = [reflectance after heat aging (250 hours)] / [initial reflectance] × 100

[heat resistance test (heat aging 500 hours)]

The test piece (thickness: 3 mm) after measuring the initial reflectance was heated at 120 ° C for 500 hours, and then the reflectance of the light having a wavelength of 450 nm (the reflectance after "heating aging (500 hours)") was measured. Then, the reflectance retention ratio (before and after heating aging; 500 hours) was calculated according to the following formula. The results are shown in the columns of "Reflection retention rate before and after heating aging (500 hours)" in Tables 1 to 4.

[Reflection retention rate (before and after heating aging; 500 hours)] = [reflectance after heat aging (500 hours)] / [initial reflectance] × 100

[Light resistance test]

The test piece (thickness: 3 mm) after the initial reflectance was measured, and the ultraviolet ray having an intensity of 10 mW/cm ^{2 was applied} for 250 hours, and then the reflectance of the light having a wavelength of 450 nm (the "reflectance after ultraviolet aging") was measured. Then, the reflectance retention ratio (before and after ultraviolet aging) was calculated according to the following formula. The results are shown in the columns of "Resistance retention rate before and after UV aging" in Tables 1 to 4.

[Reflection retention rate (before and after UV aging)] = [Reflectance after ultraviolet aging] / [Initial reflectance] × 100

[Evaluation of the occurrence of cracks during cutting (evaluation of toughness)]

The test piece having a width of 5 mm, a length of 5 mm, and a thickness of 3 mm was produced by subjecting the cured product obtained in the examples and the comparative examples to cutting. For the cutting of the hardened material, a micro-cutting machine (trade name "BS-300CL", manufactured by MEIWAFOSIS Co., Ltd.) was used, and a digital microscope (trade name "VHX-900", manufactured by KEYENCE) was used to observe and confirm the cutting. Whether cracks are formed in the hardened material during processing. In the column of "the number of cracks at the time of cutting" in Tables 1 to 4, the number of test pieces in which 10 test pieces are produced per sample and the cracks can be confirmed (referred to as "crack" The number ") is displayed as the evaluation result. In addition, in Tables 1 to 4, when the number of cracked test pieces (the number of cracks) is n, it is displayed as "n/10".

[Evaluation of whether or not cracks occur during reflow (strength and toughness evaluation)]

A test piece (width: 5 mm × length: 5 mm × thickness: 3 mm) obtained by the above-described cutting process was used, and a reflow furnace (trade name "UNI-5016F", manufactured by ANTOM Co., Ltd.) was used to set 260 ° C to the highest temperature. The reflow treatment was carried out for 5 seconds and the total reflux time was set to 90 seconds. Subsequently, a digital microscope (trade name "VHX-900", manufactured by KEYENCE Co., Ltd.) was used to observe and confirm whether or not cracks occurred in the test piece due to the reflow treatment. In Tables 1 to 4, 10 test pieces were reflowed for each sample, and the number of the test pieces (the number of cracks) in which cracks were generated was determined as the evaluation result. In addition, in the column of "the number of cracks at the time of reflow" in Tables 1 to 4, it is possible to confirm that the number of cracks (the number of cracks) is n, and the method is "n/10". display.

[Overview]

The initial reflectance is 90% or more, and the reflectance retention rate in the heat resistance test (heat aging for 500 hours) is 90% or more, the reflectance retention rate in the light resistance test is 90% or more, and the presence or absence during cutting. The number of cracks in the crack evaluation (strength and toughness evaluation) and the presence or absence of crack evaluation (toughness evaluation) at the time of reflow was 0, and the overall judgment was ○ (good). On the other hand, the other factors are collectively determined to be × (bad). The results are shown in the column "Comprehensive judgment" in Tables 1 to 4.

Moreover, the components used in the examples and comparative examples are as follows.

[Epoxy resin]

CEL2021P (CELLOXIDE 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, DAICEL (manufactured by DAICEL)

MA-DGIC: Isopropyl diglycidyl isocyanurate, Siguo Chemical Industry Co., Ltd.

EHPE3150: 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by DAICEL

TEPIC-PAS B26: Triglycidyl isocyanurate, Nissan Chemical Industry Co., Ltd.

X-40-2678: a nonoxyl derivative having two epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

X-40-2720: a oxane derivative having three epoxy groups in the molecule, Shin-Etsu Chemical Co., Ltd.

X-40-2670: a cyclooxygen derivative having four epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

BYK-300: Polyoxane leveling agent (leveling agent containing polyfluorene-based polymer), BYK-Chemie Japan

AC FS 180: Polyoxane leveling agent (leveling agent containing lanthanide polymer), manufactured by Algin Chemie

BYK-340: Fluorine leveling agent (leveling agent containing fluoroacrylic polymer), BYK-Chemie Japan

AC 110a: Fluorine leveling agent (leveling agent containing fluoropolyether polymer), manufactured by Algin Chemie

CD220PL (PLACCEL CD220PL): polycarbonate diol, DAICEL (share) system

PTMG2000: polytetramethylene ether glycol, Mitsubishi Chemical Co., Ltd.

PLACCEL 308: Polycaprolactone polyol, DAICEL (share) system

YP-70: phenoxy resin, Nippon Steel Chemical Co., Ltd.

EpoTohto YD-6020: hydroxyl containing long-chain epoxy resin, Nippon Steel Chemical Co., Ltd.

M52N (Nanostrength M52N): acrylic block copolymer, manufactured by ARKEMA

[white pigment]

Titanium oxide, trade name "TCR-52", 堺Chemical Industry Co., Ltd.

[K agent]

MH-700(Rikacid MH-700): 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30, New Japan Physical and Chemical Co., Ltd.

HN-7200: a mixture of 4-methylhexahydrophthalic anhydride and an alicyclic polyester resin, manufactured by Hitachi Chemical Co., Ltd.

HN-5700: 4-methylhexahydrophthalic anhydride/3-methylhexahydrophthalic anhydride=70/30 mixture with alicyclic polyester resin, manufactured by Hitachi Chemical Co., Ltd.

18X (U-CAT 18X): hardening accelerator, SAN-APRO (share) system

Ethylene glycol: Wako Pure Chemical Industries Co., Ltd.

[hardening catalyst]

SANEIDO SI-100L: aryl sulfonium salt, Sanxin Chemical Industry Co., Ltd.

As shown in Tables 1 to 4, the cured product (Example) of the curable epoxy resin composition of the present invention has excellent light reflectivity, and does not cause cracking during cutting and reflow. Strong. Further, even after heat aging and ultraviolet aging, high light reflectivity can be maintained, and heat resistance and light resistance are excellent. In particular, in addition to the alicyclic ring. Oxygen compound and monoallyl diglycidyl isocyanurate, the alicyclic polyester resin is further contained (or further contains an alicyclic polyester resin and has a molecule in the molecule) In the case of two or more epoxy group deoxyalkylene derivatives (Examples 10 to 60), even after heating for a long time (500 hours), light reflectivity is hardly lowered, and excellent heat resistance is exhibited. Sex.

On the other hand, the cured product (comparative example) formed using the curable epoxy resin composition which does not satisfy the specification of the present invention has low light reflectivity and poor heat resistance and light resistance after heat aging and ultraviolet aging. Further, cracks are likely to occur during cutting and at the time of reflow, and the toughness is poor.

Industrial use possibility

The curable epoxy resin composition of the present invention can be suitably used as an LED package (a component of an LED package, for example, a reflective material or a package of an optical semiconductor device), an electronic component, and a liquid crystal display (for example, Reflector, etc.), ink for white substrates, sealant, etc.

1‧‧‧Reflecting material (reflecting material containing a cured product of the curable epoxy resin composition of the present invention)

2‧‧‧Metal wiring

3‧‧‧Optical semiconductor components

4‧‧‧ Bonding leads

5‧‧‧ sealing resin

6‧‧‧Packaging resin

1 is a schematic view showing an example of an optical semiconductor device including a reflective material of a cured product of a curable epoxy resin composition (curable resin composition for light reflection) of the present invention, and (a) is a perspective view. (b) is a sectional view.

Claims (14)

A curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A), an isomeric isocyanurate compound (B) represented by the following formula (1), White pigment (C), hardener (D), and hardening accelerator (F), [wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. A curable epoxy resin composition characterized by comprising an alicyclic epoxy compound (A), an isomeric isocyanurate compound (B) represented by the following formula (1), White pigment (C), and hardening catalyst (E), [wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. The curable epoxy resin composition according to claim 1 or 2, wherein the alicyclic epoxy compound (A) is a compound having a cyclohexene oxide group. The curable epoxy resin composition according to any one of claims 1 to 3, wherein the alicyclic epoxy compound (A) is represented by the following formula (I-1) Expressed as a compound. The curable epoxy resin composition according to any one of claims 1 to 4, further comprising a nonoxyl derivative (G) having two or more epoxy groups in the molecule. The curable epoxy resin composition according to any one of claims 1 to 5, further comprising an alicyclic polyester resin (H). The curable epoxy resin composition according to claim 6, wherein the alicyclic polyester resin (H) is an alicyclic polyester resin having an alicyclic ring in the main chain. The curable epoxy resin composition according to any one of claims 1 to 7, which further contains rubber particles. The curable epoxy resin composition according to any one of claims 1 to 8, further comprising at least one selected from the group consisting of a polyoxane-based leveling agent and a fluorine-based leveling agent. Leveling agent. The curable epoxy resin composition according to any one of claims 1 to 9, which further contains a polyol compound. The curable epoxy resin composition according to any one of claims 1 to 10, further comprising an acrylic block copolymer. A cured product obtained by hardening a curable epoxy resin composition according to any one of claims 1 to 11. A curable resin composition for light reflection, which comprises the curable epoxy resin composition according to any one of claims 1 to 11. An optical semiconductor device comprising at least an optical semiconductor element and a cured material of a cured product of a curable resin composition for light reflection according to claim 13 of the patent application.