JPWO2018070300A1 - Anti-reflective material - Google Patents

Abstract

The present invention can prevent a decrease in the total luminous flux of a light source while having a sufficient antireflection function, and has an antireflective material having high heat resistance (particularly, hot water resistance) and an optical semiconductor element sealed by the antireflective material. An object is to provide a stopped optical semiconductor device. The present invention is an antireflective material comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein the surface of the cured product is provided with irregularities that suppress reflection. An optical semiconductor device in which an optical semiconductor element is sealed with an anti-reflective material and the anti-reflective material.

Description

  The present invention relates to an antireflective material. The present invention also relates to an optical semiconductor device in which an optical semiconductor element is sealed by the antireflective material. The present invention also relates to a resin composition suitable for producing the antireflective material, and a method for producing an antireflective material using the resin composition. Priority is claimed on Japanese Patent Application No. 2016-200397, filed on October 11, 2016, the content of which is incorporated herein by reference.

In recent years, in various indoor or outdoor display boards, traffic signals, large display units, etc., adoption of a light emitting device (optical semiconductor device) using an optical semiconductor element (LED element) as a light source is in progress. Generally as such an optical semiconductor device, the optical semiconductor device is mounted on a board | substrate (substrate for optical semiconductor element mounting), and also the optical semiconductor device by which this optical semiconductor element was sealed by the transparent sealing material spreads. doing. The sealing material in such an optical semiconductor device is subjected to anti-reflection treatment on the surface in order to prevent deterioration of visibility due to total reflection of incident light such as illumination light from the outside and sunlight. There is.
Conventionally, as a method of imparting an antireflective function to the surface of a resin layer, there is known a method of dispersing incident light by dispersing an inorganic filler such as glass beads or silica in a resin (see, for example, Patent Document 1) ).

JP 2007-234767

  However, when the method of patent document 1 is applied to resin for optical semiconductor sealing, it turned out that it is difficult to ensure the total luminous flux of a light source, providing sufficient antireflection function. That is, when an inorganic filler of a sufficient amount to obtain a sufficient antireflection function is blended, the total luminous flux of the light source is significantly reduced, while the blending amount of the inorganic filler is small to prevent the reduction of the total luminous flux of the light source It became clear that there is a trade-off relation that sufficient anti-reflection ability can not be obtained in the case of

  Further, in recent years, the output of optical semiconductor devices has been increased, and the sealing material in such optical semiconductor devices has high heat resistance (in particular, heat resistance. Hereinafter, when simply referred to as "heat resistance", Durability such as “hot water resistance” is also required.

Therefore, an object of the present invention is to provide an antireflective material capable of preventing the reduction of the total luminous flux of the light source while having a sufficient antireflective function, and having high heat resistance, in particular, hot water resistance.
Another object of the present invention is to provide the above-mentioned antireflective material which is for sealing an optical semiconductor.
Furthermore, another object of the present invention is to provide an optical semiconductor device in which an optical semiconductor element is sealed by the above-mentioned antireflective material.
Another object of the present invention is to provide a resin composition suitable for producing the above-mentioned antireflective material, and a method for producing the above-mentioned antireflective material using the resin composition.

As one of the reasons why sufficient antireflective ability can not be obtained when the amount of the inorganic filler is reduced, it does not spread over the entire resin layer due to the sedimentation of the inorganic filler, and as a result, uniform unevenness is not formed on the entire surface When the compounding amount is increased so that the reflection preventing ability can be obtained on the entire surface of the resin layer even when the inorganic filler settles, the inorganic filler itself absorbs the light. The inventor has found that the total luminous flux is significantly reduced.
The inventors of the present invention have intensively studied to solve the above-mentioned problems, and as a result, when a hydrophobic porous inorganic filler is blended as a filler in a resin layer constituting an antireflective material, a sufficient antireflective function is imparted even with a small amount of addition. It also has high heat resistance. As a result, an antireflective material having a sufficient antireflective function and excellent heat resistance without significantly reducing the total luminous flux of the light source is provided, and it is extremely useful as a material for sealing an optical semiconductor element in an optical semiconductor device. It has been found that it is suitable and the present invention has been completed.

  That is, the present invention is an anti-reflection material comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein the surface of the cured product is formed with an unevenness suppressing the reflection. Provide an anti-reflective material.

  In the antireflective material, preferably, the hydrophobic porous inorganic filler is uniformly dispersed over the entire cured product, and forms irregularities on the surface to suppress reflection.

In the antireflective material, the hydrophobic porous inorganic filler is obtained by treating the surface of the porous inorganic filler with a hydrophobic treatment, and the specific surface area of the porous inorganic filler before the hydrophobic treatment is 200 m ² / g or more. It may be.

  In the antireflective material, the average particle diameter of the hydrophobic porous inorganic filler may be 1 μm to 20 μm.

  In the antireflective material, the content of the hydrophobic porous inorganic filler may be 4 to 40% by weight with respect to the total amount (100% by weight) of the antireflective material.

  In the antireflection material, the resin composition may be made of a transparent curable resin composition.

  In the antireflective material, the curable resin composition may be composed of a composition containing an epoxy resin.

  The antireflective material may be for sealing an optical semiconductor.

  In addition, the present invention provides an optical semiconductor device in which an optical semiconductor element is sealed by the anti-reflection material.

  The present invention also provides a resin composition in which a hydrophobic porous inorganic filler is dispersed, which is used for the production of the above-mentioned antireflective material.

  The resin composition may be liquid.

  The amount of components volatilized during curing with respect to the total amount (100% by weight) of the resin composition may be 10% by weight or less.

  In addition, the present invention provides a method for producing an antireflective material having a surface on which irregularities are formed to suppress reflection, characterized in that the resin composition is cured.

Since the antireflective material of the present invention has the above-mentioned constitution, a sufficient antireflective function can be obtained even when the blending amount of the hydrophobic porous inorganic filler is reduced, and the significant decrease of the total luminous flux of the light source is prevented. It also has excellent heat resistance, especially hot water resistance. Therefore, by using the anti-reflection material of the present invention as a material for sealing the optical semiconductor element in the optical semiconductor device, it is high quality (for example, it has high durability with sufficient brightness while suppressing gloss) An optical semiconductor device is obtained.
Moreover, since the resin composition of this invention has the said structure, it is very suitable for manufacturing the said anti-reflective material.

It is a schematic diagram showing one embodiment of an optical semiconductor device containing an antireflective material of the present invention. The left figure (a) is a perspective view, and the right figure (b) is a cross-sectional view.

<Anti-Reflection Material and Resin Composition>
The antireflective material of the present invention is composed of a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, and the hydrophobic porous inorganic filler forms irregularities on the surface of the cured product to suppress reflection. It is characterized by
The resin composition of the present invention is characterized in that a hydrophobic porous inorganic filler is dispersed, and is used for producing the above-mentioned antireflective material.

Due to the porous structure of the hydrophobic porous inorganic filler, the apparent volume for the resin composition is increased as compared to the non-porous filler, so even small additions will spread throughout the resin composition or its cured product, It can be uniformly dispersed, and uniform and fine irregularities can be formed on the surface of the cured product. In addition, the resin composition infiltrates into the porous structure, and the apparent specific gravity difference between the hydrophobic porous inorganic filler and the resin composition decreases, whereby the dispersed state becomes stable and the hydrophobic porous inorganic filler The interaction between the surfaces is suppressed and aggregation is difficult, and the hydrophobic porous inorganic filler can uniformly spread over the resin composition or the entire cured product thereof, so that uniform and fine irregularities are formed on the cured product surface. It can be formed to scatter incident light efficiently.
Moreover, since the surface of the hydrophobic porous inorganic filler exhibits hydrophobicity, the cured product containing the same exhibits high heat resistance that is not easily deteriorated even under severe heating conditions such as boiling water, and is excellent in durability.
In the present specification, a small amount (small amount) of the addition amount (use amount) of the hydrophobic porous inorganic filler means a small amount in weight conversion, and a small amount in the volume (volume) conversion Absent.

When a hydrophobic porous inorganic filler is used, reflection can be efficiently suppressed even if the amount used is reduced compared to a non-porous filler, so the light ray of the hydrophobic porous inorganic filler itself A sufficient anti-reflection function can be secured while suppressing a significant decrease in the total luminous flux due to absorption.
Each component will be described in detail below.

[Hydrophobic porous inorganic filler]
The hydrophobic porous inorganic filler in the antireflective material or resin composition of the present invention is uniformly dispersed throughout the resin composition or the entire cured product thereof, and as a result of the dispersed state being stabilized, the surface of the cured product is obtained. The present hydrophobic porous inorganic filler has a function of forming asperities for scattering incident light.

  The hydrophobic porous inorganic filler which can be used for the antireflective material or resin composition of the present invention is an inorganic filler having a smaller apparent specific gravity than the true specific gravity of the filler and having a porous structure in the inside thereof, the surface thereof Means that it has been treated hydrophobic.

  As a porous inorganic filler (a porous inorganic filler before the surface is subjected to a hydrophobic treatment) constituting the hydrophobic porous inorganic filler, known or commonly used ones can be used, and it is not particularly limited. Inorganic glass [eg borosilicate glass, sodium borosilicate glass, sodium silicate glass, aluminosilicate glass, quartz etc.], silica, alumina, zircon iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, pho Powders such as stellite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline sainite, cristobalite, wollastonite, diatomaceous earth, talc, etc., having a porous structure, or moldings thereof (for example, And spherical beads etc.).

The hydrophobic porous inorganic filler is a known or commonly used hydrophobic surface treating agent [for example, a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol or the like to the above-mentioned porous inorganic filler before hydrophobizing treatment] And a surface treatment with a hydrophobic surface treatment agent such as an organosilicon compound. By performing such hydrophobic surface treatment, the compatibility and dispersibility with the components of the resin composition can be improved, and the heat resistance of the cured product can be improved.
From the viewpoint of improving the compatibility and dispersibility with the components of the resin composition and improving the heat resistance of the cured product, as a hydrophobic surface treatment agent, an organosilicon compound (for example, trimethylchlorosilane, hexamethyldisiloxane, etc.) Among them, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, silcon oil and the like are preferable, and polydimethylsiloxane and the like are more preferable.
Among them, as a hydrophobic porous inorganic filler, it is dispersed uniformly throughout the resin composition or the cured product thereof, and it is possible to efficiently form asperities on the surface of the cured product and to exhibit excellent heat resistance. And hydrophobic porous inorganic glass or hydrophobic porous silica (hydrophobic porous silica filler) is preferable.

  The hydrophobic porous silica is not particularly limited. For example, known or commonly used porous silica such as fused silica, crystalline silica, high purity synthetic silica, colloidal silica, etc. is treated with the above-mentioned hydrophobic surface treating agent Can be used.

  Moreover, as the hydrophobic porous inorganic filler, an inorganic substance constituting the above-mentioned hydrophobic porous inorganic filler, a styrene resin, an acrylic resin, a silicone resin, an acrylic-styrene resin, a vinyl chloride resin, a vinylidene chloride resin Hydrophobic porous material made of an organic hybrid material such as a polymer of resin, amide resin, urethane resin, phenol resin, styrene-conjugated diene resin, acrylic-conjugated diene resin, olefin resin, cellulose resin, etc. Inorganic-organic fillers and the like can also be used.

  The said hydrophobic porous inorganic filler may be comprised from a single material, and may be comprised from 2 or more types of materials. Among them, as the hydrophobic porous inorganic filler, it can be uniformly dispersed throughout the resin composition or the entire cured product thereof to efficiently form irregularities on the surface of the cured product, and has high heat resistance, and Hydrophobic porous silica (hydrophobic porous silica filler) is more preferable from the viewpoint of availability and easiness of production.

  The shape of the hydrophobic porous inorganic filler is not particularly limited, and examples thereof include powder, sphere, crushed, fibrous, needle, and scaly. Among them, spherical or spherical in view of the fact that the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the entire cured product thereof to facilitate formation of a uniform and fine uneven shape on the surface of the cured product. Crushed hydrophobic porous inorganic fillers are preferred.

  The average particle size (central particle size) of the hydrophobic porous inorganic filler is not particularly limited, but the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the cured product thereof to obtain a cured product. The thickness is preferably 1 to 20 μm, and more preferably 2 to 15 μm from the viewpoint of easily forming a uniform and fine uneven shape on the surface. In addition, the said average particle diameter (central particle diameter) means the volume particle diameter (median volume diameter) in 50% of integration value in the particle size distribution measured by the laser diffraction and the scattering method.

  The hydrophobic porous inorganic filler porous structure can be specified by various parameters such as specific surface area, oil absorption, etc., and each has a grade of hydrophobic porous having parameters suitable for the antireflective material or resin composition of the present invention. The quality inorganic filler can be selected without particular limitation. The above parameters can also be evaluated by the parameters of the porous inorganic filler before being subjected to hydrophobic treatment.

Although the specific surface area of the porous inorganic filler (porous inorganic filler before the surface is subjected to hydrophobic treatment) constituting the hydrophobic porous inorganic filler is not particularly limited, the hydrophobic porous inorganic filler is a resin composition or It is preferably 200 m ² / g or more from the viewpoint of uniformly dispersing uniformly throughout the cured product, facilitating formation of a uniform and fine uneven shape on the surface of the cured product, and efficiently preventing reflection. ~2000m more preferably ² / g, more preferably from 200~1500m ² / g, particularly preferably 200~1000m ² / g. If the specific surface area is 200 m ² / g or more, the hydrophobic porous inorganic filler tends to be uniformly dispersed throughout the resin composition or the entire cured product thereof to improve the anti-reflection function of the surface of the cured product. is there. On the other hand, when the specific surface area is 2000 m ² / g or less, the viscosity increase and thixotropic property of the resin composition containing the hydrophobic porous inorganic filler are suppressed, and the fluidity in the production of the antireflective material is secured. Tend to The above-mentioned specific surface area can be determined from the adsorption isotherm of nitrogen at -196 ° C based on the BET equation according to JIS K6430 Annex E for the porous inorganic filler before the surface is treated to be hydrophobic. The adsorption specific surface area is meant.

  The oil absorption of the hydrophobic porous inorganic filler is not particularly limited, but the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the entire cured product thereof, and is uniform and fine on the surface of the cured product. The concentration is preferably 10 to 2000 mL / 100 g, and more preferably 100 to 1000 mL / 100 g from the viewpoint of facilitating formation of an uneven shape and efficiently preventing reflection. When the oil absorption amount is 10 mL / 100 g or more, the hydrophobic porous inorganic filler tends to be uniformly dispersed throughout the resin composition or the entire cured product thereof, and to easily form an uneven shape on the surface of the cured product. There is. On the other hand, when the oil absorption is 2000 mL / 100 g or less, the mechanical strength of the hydrophobic porous inorganic filler tends to be improved. In addition, the oil supply amount of the hydrophobic porous inorganic filler is the amount of oil absorbed by 100 g of the filler, and can be measured in accordance with JIS K5101.

  In the antireflective material or resin composition of the present invention, the hydrophobic porous inorganic filler can be used singly or in combination of two or more. The hydrophobic porous inorganic filler can also be produced by a known or commonly used production method, for example, under the trade names "Silo Hobik 702", "Silo Hobik 4004", "Silo Hobik 505", " Silo Hobik series such as Silo Hobik 100, Silo Hobik 200, Silo Hobik 704, Silo Hobic 507, and Silo Hobic 603 (all manufactured by Fuji Silysia Chemical Ltd.) , Aerosil series such as "Aerosil RX200" and "Aerosil RX300" (above, made by Evonik Degussa Co., Ltd.), Sansu such as "Sunsphere H-121-ET" and "Sunsphere H-51-ET" Commercially available products such as Fair ET series (manufactured by AGC S ITEC Co., Ltd.) can also be used.

  The content (blending amount) of the hydrophobic porous inorganic filler in the antireflective material or resin composition of the present invention is not particularly limited, but is preferably based on the total amount (100% by weight) of the antireflective material or resin composition Is 4 to 40% by weight, more preferably 4 to 35% by weight, and still more preferably 4 to 30% by weight. When the content of the hydrophobic porous inorganic filler is 4% by weight or more, the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the entire cured product constituting the antireflective material, and is thus cured. It becomes easy to form uniform uneven | corrugated shape on the whole surface of a thing. On the other hand, when the content of the hydrophobic porous inorganic filler is 40% by weight or less, when the antireflective material or resin composition of the present invention is used as, for example, a sealing material for optical semiconductor devices There is a tendency that sufficient illuminance can be secured by preventing a drop.

  The content (blended amount) of the hydrophobic porous inorganic filler in the antireflective material or resin composition of the present invention is usually 5 to 80% by weight based on the resin composition (100 parts by weight) constituting the antireflective material. Part, preferably 5 to 70 parts by weight, more preferably 5 to 60 parts by weight. When the content of the hydrophobic porous inorganic filler is 5 parts by weight or more, the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition constituting the antireflective material or the cured product thereof, and cured. It becomes easy to form uniform uneven | corrugated shape on the whole surface of a thing. On the other hand, when the content of the hydrophobic porous inorganic filler is 80 parts by weight or less, when the antireflective material or resin composition of the present invention is used, for example, as a sealing material for optical semiconductor devices There is a tendency that sufficient illuminance can be secured by preventing a drop.

[Resin composition]
Although the resin composition which comprises the hardened | cured material in the anti-reflective material of this invention is not specifically limited, It is suitable as a sealing material of the optical semiconductor element in an optical semiconductor device, ie, resin composition for optical semiconductor sealing. Can be used, for example, they are cured by heat or light, have high transparency, durability (for example, transparency is not easily reduced even by heating, high temperature heat and thermal shock are added). It is possible to suitably use a curable resin composition which gives a cured product which is excellent also in characteristics such as cracking and peeling off from an adherend, which are difficult to occur.

As such a curable resin composition, a known or commonly used resin composition having a thermosetting property or a light curing property can be used without particular limitation. For example, an epoxy resin (epoxy compound) Selected from the group consisting of A), silicone resin (silicone compound) (referred to as "silicone resin (B)"), and acrylic resin (acrylic compound) (referred to as "acrylic resin (C)") It is preferable that it is a composition containing at least one curable compound. As such a curable resin composition, for example, a composition containing an epoxy resin (A) (curable epoxy resin composition), a composition containing a silicone resin (B) (curable silicone resin composition), an acrylic resin The composition (curable acrylic resin composition) containing resin (C) is mentioned. Hereinafter, the curable resin composition of these aspects is demonstrated. However, the curable resin composition of the present invention is not limited to the composition of the following aspects.
In addition, the antireflective material of the present invention is not limited to the application of the resin composition for encapsulating an optical semiconductor, and is also applicable to, for example, various optical members described later, and a resin suitable for each application (For example, it is applicable also to polyolefin resin, polyester resin, polyamide resin, polyurethane resin, etc.).
As a resin composition which comprises the hardened | cured material in the anti-reflective material of this invention, the curable epoxy resin composition which is excellent in heat resistance, transparency, durability, etc., a curable silicone resin composition, and a curable acrylic resin composition Preferably, a curable epoxy resin composition is more preferred.

1. Curable epoxy resin composition The above-mentioned curable epoxy resin composition (sometimes referred to as "the curable epoxy resin composition of the present invention") is a curable composition containing an epoxy resin (A) as an essential component. The curable epoxy resin composition of the present invention further comprises a curing agent (D) and a curing accelerator (E), or a curing catalyst (F) as essential components. That is, the curable epoxy resin composition of the present invention is a composition comprising the epoxy resin (A), the curing agent (D) and the curing accelerator (E) as essential components, or the epoxy resin (A) and the curing catalyst (F) is a composition containing as an essential component. The curable epoxy resin composition of the present invention may contain other components other than the above-mentioned essential components.

1-1. Epoxy resin (A)
The epoxy resin (A) in the curable epoxy resin composition of the present invention is a compound having one or more epoxy groups (oxirane ring) in the molecule, and can be optionally selected from known or common epoxy compounds. Can. As an epoxy resin (A), For example, an aromatic epoxy compound (aromatic epoxy resin), an aliphatic epoxy compound (aliphatic epoxy resin), an alicyclic epoxy compound (alicyclic epoxy resin), a heterocyclic epoxy compound (Heterocyclic epoxy resin), a siloxane derivative having one or more epoxy groups in the molecule, and the like.

  Examples of the aromatic epoxy compound include aromatic glycidyl ether epoxy resins [eg, bisphenol A epoxy resin, bisphenol F epoxy resin, biphenol epoxy resin, novolac epoxy resin (eg phenol novolac epoxy resin, Cresol novolac epoxy resin, cresol novolac epoxy resin of bisphenol A, etc., naphthalene type epoxy resin, epoxy resin obtained from trisphenol methane etc.] and the like.

  As said aliphatic epoxy compound, an aliphatic glycidyl ether type epoxy compound [for example, aliphatic polyglycidyl ether etc.] etc. are mentioned.

  The above-mentioned alicyclic epoxy compound is a compound having one or more alicyclic (aliphatic hydrocarbon ring) and one or more epoxy groups in the molecule (however, one epoxy group is in the above-mentioned molecule). The above-mentioned siloxane derivatives are excluded). As the alicyclic epoxy compound, for example, (i) at least one alicyclic epoxy group (an epoxy group composed of two adjacent carbon atoms constituting an alicyclic ring and an oxygen atom) in a molecule (preferably) Is a compound having two or more; (ii) a compound having an epoxy group directly bonded to an alicyclic ring by a single bond; (iii) a compound having an alicyclic ring and a glycidyl group.

  The alicyclic epoxy group contained in the compound (i) having at least one alicyclic epoxy group in the molecule (i) is not particularly limited, but among them, from the viewpoint of curability, a cyclohexene oxide group (adjacent which constitutes a cyclohexane ring (Epoxy group) composed of two carbon atoms and an oxygen atom). In particular, as the compound having at least one alicyclic epoxy group in the molecule (i), a compound having two or more cyclohexene oxide groups in the molecule is preferable from the viewpoint of the transparency of the cured product and heat resistance, Preferably it is a compound represented by following formula (1).

  In formula (1), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of carbon-carbon double bonds are epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like And the like. In addition, substituents, such as an alkyl group, may be couple | bonded with one or more of the carbon atom which comprises the alicyclic ring (alicyclic epoxy group) in Formula (1).

  Examples of the compound in which X in the formula (1) is a single bond include (3,4,3 ′, 4′-diepoxy) bicyclohexyl.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. As a C1-C18 linear or branched alkylene group, a methylene group, a methyl methylene group, dimethyl methylene group, ethylene group, a propylene group, trimethylene group etc. are mentioned, for example. Examples of the divalent alicyclic hydrocarbon group include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, and a 1,3-dicarboxylic acid group. Examples thereof include divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.

  The alkenylene group in the above-mentioned alkenylene group (sometimes referred to as “epoxidized alkenylene group”) in which part or all of the carbon-carbon double bond is epoxidized is, for example, vinylene group, propenylene group, 1-butenylene group Linear or branched alkenylene groups (including alkapolyenylene groups) having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like . In particular, as the above-mentioned epoxidized alkenylene group, an alkenylene group in which all of carbon-carbon double bonds are epoxidized is preferable, and more preferably, all of carbon-carbon double bonds are epoxidized and each having 2 to 4 carbon atoms It is an alkenylene group.

  Especially as said coupling group X, the coupling group containing an oxygen atom is preferable, and, specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-, epoxidation is carried out And alkenylene groups; groups in which a plurality of these groups are linked; and groups in which one or more of these groups are linked to one or more of divalent hydrocarbon groups. Examples of the divalent hydrocarbon group include those exemplified above.

Representative examples of the compound represented by the above formula (1) include 2,2-bis (3,4-epoxycyclohexan-1-yl) propane, bis (3,4-epoxycyclohexylmethyl) ether, , 2-bis (3,4-epoxycyclohexan-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexan-1-yl) ethane, the following formula (1-1) The compound etc. which are represented by-(1-10) are mentioned. In the following formulas (1-5) and (1-7), l and m each represent an integer of 1 to 30. R in the following formula (1-5) is an alkylene group having 1 to 8 carbon atoms, and is methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene And linear or branched alkylene groups such as heptylene group and octylene group. Among these, C1-C3 linear or branched alkylene groups, such as a methylene group, ethylene group, a propylene group, and an isopropylene group, are preferable. N1 to n6 in the following formulas (1-9) and (1-10) each represent an integer of 1 to 30.

As a compound which has an epoxy group directly bonded to the above (ii) alicyclic by a single bond, for example, a compound represented by the following formula (2) and the like can be mentioned.

In the formula (2), R ′ is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from a p-valent alcohol in the structural formula, and p and q each represent a natural number. Examples of the p-valent alcohol [R ′ (OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms), and the like. p is preferably 1 to 6, and q is preferably 1 to 30. When p is 2 or more, q in the respective groups in () (within the outer parentheses) may be the same or different. Specific examples of the compound represented by the above formula (2) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, And trade name "EHPE 3150" (manufactured by Daicel Co., Ltd.) and the like.

  As a compound which has the above-mentioned (iii) alicyclic ring and a glycidyl group, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5] -Dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] propane, hydrogenated bisphenol A epoxy resin (hydrogenated bisphenol A epoxy resin), etc .; bis [2- (2,3-epoxy) Propoxy) cyclohexyl] methane, [2- (2,3-epoxypropoxy) cyclohexyl] [4- (2,3-epoxypropoxy) cyclohexyl] methane, bis [4- (2,3-epoxy) Propoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane, bisphenol F type epoxy Hydrogenated fat (hydrogenated bisphenol F type epoxy resin), etc .; hydrogenated biphenol type epoxy resin; hydrogenated novolac type epoxy resin (eg hydrogenated phenol novolac type epoxy resin, hydrogenated cresol novolac type epoxy resin, bisphenol A hydrogenated cresol novolac epoxy resin etc. of A); a hydrogenated naphthalene epoxy resin; a hydrogenated epoxy resin of an epoxy resin obtained from trisphenolmethane, etc. may be mentioned.

  As said alicyclic epoxy compound, others, for example, a 1,2,8,9- diepoxy limonene etc. are mentioned.

  As the above-mentioned heterocyclic epoxy compound, for example, heterocyclic ring other than epoxy group (oxirane ring) [for example, tetrahydrofuran ring, tetrahydropyran ring, morpholine ring, chroman ring, isochroman ring, tetrahydrothiophene ring, tetrahydrothiopyran ring] Ring, aziridine ring, pyrrolidine ring, piperidine ring, piperazine ring, indoline ring, 2,6-dioxabicyclo [3.3.0] octane ring, 1,3,5-triazacyclohexane ring, 1,3,5 Nonaromatic heterocyclic rings such as triazacyclohexa-2,4,6-trione ring (isocyanuric ring); aromatic heterocyclic rings such as thiophene ring, pyrrole ring, furan ring, pyridine ring etc.] and epoxy And compounds having a group.

  As the above-mentioned heterocyclic epoxy compound, for example, isocyanurate having one or more epoxy groups in the molecule (hereinafter sometimes referred to as "epoxy group-containing isocyanurate") can be preferably used. The number of epoxy groups contained in the molecule of the above-mentioned epoxy group-containing isocyanurate is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3.

  As said epoxy group containing isocyanurate, the compound represented by following formula (3) is mentioned, for example.

Wherein ^{(3), R X, R} Y, and R ^Z (R ^X ~R ^Z) are the same or different, represent a hydrogen atom or a monovalent organic group. However, at least one of R ^{X to} R ^Z is a monovalent organic group containing an epoxy group. Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group and the like); a monovalent aromatic hydrocarbon group (for example an aryl group and the like); Cyclic groups; aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and monovalent groups formed by combining two or more of aromatic hydrocarbon groups, and the like. The monovalent organic group may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group or a halogen atom). As a monovalent organic group containing an epoxy group, the monovalent group containing the below-mentioned epoxy groups, such as an epoxy group, a glycidyl group, 2-methyl epoxy propyl group, a cyclohexene oxide group, etc. are mentioned, for example.

  More specifically, as the epoxy group-containing isocyanurate, a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a table by the following formula (3-3) And the like.

In the above formulas (3-1), (3-2), and (3-3) (formulas (3-1) to (3-3)), R ¹ and R ² are the same or different, A hydrogen atom or a C1-C8 alkyl group is shown. As the alkyl group having 1 to 8 carbon atoms, for example, a straight chain such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like Examples include chain or branched alkyl groups. Among them, linear or branched alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group, propyl group and isopropyl group are preferable. It is particularly preferable that R ¹ and R ² in the above formulas (3-1) to (3-3) are a hydrogen atom.

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

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

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

  The above-mentioned epoxy group-containing isocyanurate can be used after being modified in advance by adding a compound that reacts with the epoxy group, such as alcohol or acid anhydride.

  As the above-mentioned siloxane derivative having one or more epoxy groups in the molecule (sometimes referred to as "epoxy group-containing siloxane derivative"), a siloxane skeleton composed of siloxane bonds (Si-O-Si) in the molecule It is a compound which it has and has one or more epoxy groups. As the siloxane skeleton, for example, cyclic siloxane skeleton; polysiloxane skeleton such as linear or branched silicone (linear or branched polysiloxane), cage type or ladder type polysilsesquioxane, etc. It can be mentioned. The number of epoxy groups contained in the molecule of the epoxy group-containing siloxane derivative is not particularly limited, but is preferably 2 to 4 and more preferably 3 or 4.

  The epoxy group contained in the epoxy group-containing siloxane derivative is not particularly limited, but at least one is effective in that the curable epoxy resin composition can be efficiently cured, and a cured product having more excellent strength can be obtained. It is preferably an alicyclic epoxy group, and it is particularly preferable that at least one of the epoxy groups is a cyclohexene oxide group.

  As said epoxy group containing siloxane derivative, the compound (cyclic siloxane) represented by following formula (4) is mentioned, for example.

In said Formula (4), R < ³ > is the same or different and shows the monovalent organic group containing an alkyl group or an epoxy group. However, among R ^{3 in} the compound represented by the formula (4), at least one (preferably at least two) is an epoxy group-containing monovalent organic group (in particular, an alicyclic epoxy group-containing one) Organic group). Further, p in the formula (4) represents an integer of 3 or more (preferably an integer of 3 to 6). In addition, several R ³ may be the same or different.

The monovalent organic group containing an epoxy group is, for example, an epoxy group, a glycidyl group, a methyl glycidyl group, a group represented by -A-R ⁴ [A represents an alkylene group, and R ⁴ represents an alicyclic epoxy Indicates a group. ] Is mentioned. As said A (alkylene group), C1-C18 linear or branched alkylene groups, such as a methylene group, a methyl methylene group, a dimethyl methylene group, ethylene group, a propylene group, a trimethylene group, etc. are mentioned, for example Be Examples of R ⁴ include cyclohexene oxide and the like.

  More specifically, examples of the epoxy group-containing siloxane derivative include 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6, 6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,2,4,6,6,8 Hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6,8-dipropyl-2,4,6,8-tetramethyl -Cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,6-dipropyl-2,4,6,8-tetramethyl-cyclo Tetrasiloxane, 2,4,8-tri [2- (3- { Xabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tri [2- (3- {oxabicyclo [4.1] .0] Heptyl}) ethyl] -6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetra [2- (3- {oxabicyclo [4.1] .0] Heptyl}) ethyl] -2,4,6,8-Tetramethyl-cyclotetrasiloxane and the like.

Moreover, as said epoxy group containing siloxane derivative, the compound (chain polysiloxane) represented by following formula (5) is mentioned, for example.

In the above formula (5), R ⁵ and R ⁶ are the same or different and each is an epoxy group-containing monovalent organic group, an alkoxy group (for example, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or ethoxy group) Etc.), alkyl groups (eg, alkyl groups having 1 to 4 carbon atoms such as methyl and ethyl), and aryl groups (eg, aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl) Show. However, at least one (preferably at least two) of R ⁵ and R ⁶ in the compound represented by the formula (5) is a monovalent organic group containing an epoxy group. As a monovalent organic group containing an epoxy group, the same group as the thing in the said Formula (4) is mentioned. In particular, from the viewpoint of curability, it is preferable that one or both of R ^{6 be} a monovalent organic group containing an epoxy group. Moreover, q in Formula (5) shows an integer greater than or equal to 1 (for example, the integer of 1-500). The structures in the brackets attached with q may be identical to or different from each other. In addition, when two or more types exist as the structure in the parenthesis to which q is attached, the addition form is not particularly limited, and may be a random type or a block type.

  As the epoxy group-containing siloxane derivative, for example, a silicone resin having an epoxy group (for example, an alicyclic epoxy group-containing silicone resin described in JP-A-2008-248169), a silsesquioxane having an epoxy group, and the like Sun (for example, the organopolysilsesquioxane resin etc. which have at least 2 epoxy functional group in 1 molecule of Unexamined-Japanese-Patent No. 2008-19422 etc.) etc. are mentioned.

  Among them, as the epoxy resin (A), a bisphenol A type epoxy resin, an isocyanurate having one or more epoxy groups in the molecule, in that curing of the curable epoxy resin composition can proceed more efficiently. Novolak type epoxy resins, alicyclic epoxy compounds, aliphatic epoxy compounds, and siloxane derivatives having one or more epoxy groups in the molecule are preferable. In particular, the curable epoxy resin composition of the present invention contains an alicyclic epoxy compound as an essential component as the epoxy resin (A), in that a cured product excellent in transparency and durability can be obtained with high productivity. It is preferable to include. The alicyclic epoxy compound is preferably a compound having a cyclohexene oxide group in the molecule (in particular, a compound having two or more cyclohexene oxide groups in the molecule), more preferably represented by the formula (1) (In particular, compounds represented by formula (1-1)).

  In the curable epoxy resin composition of the present invention, the epoxy resin (A) can be used singly or in combination of two or more. In addition, an epoxy resin (A) can also be manufactured by a well-known thru | or a usual method, and a commercial item can also be used.

  The content (blending amount) of the epoxy resin (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is 25 to 99.% with respect to the total amount (100% by weight) of the curable epoxy resin composition. 8% by weight (eg, 25 to 95% by weight) is preferable, more preferably 30 to 90% by weight, still more preferably 35 to 85% by weight, and particularly preferably 40 to 60% by weight. By setting the content of the epoxy resin (A) to 25% by weight or more, curing tends to be able to proceed more efficiently. On the other hand, when the content of the epoxy resin (A) is 99.8 wt% or less, the strength of the cured product tends to be further improved.

  The content (blending amount) of the alicyclic epoxy compound in the curable epoxy resin composition of the present invention is not particularly limited, but it is 20 to 99.% with respect to the total amount (100% by weight) of the curable epoxy resin composition. 8% by weight is preferable, more preferably 40 to 95% by weight (eg, 40 to 60% by weight), still more preferably 50 to 95% by weight, particularly preferably 60 to 90% by weight, most preferably 70 to 85% by weight It is. By setting the content of the alicyclic epoxy compound to 20% by weight or more, curing can be advanced more efficiently, and the transparency and durability of the cured product tend to be further improved. On the other hand, when the content of the alicyclic epoxy compound is 99.8 wt% or less, the strength of the cured product tends to be further improved.

  The ratio of the alicyclic epoxy compound to the total amount of epoxy compounds (all epoxy compounds; for example, the total amount of epoxy resin (A)) (100% by weight) contained in the curable epoxy resin composition of the present invention is not particularly limited. 40 to 100% by weight (for example, 40 to 90% by weight) is preferable, more preferably 80 to 100% by weight, still more preferably 90 to 100% by weight, and particularly preferably 95 to 100% by weight. By setting the proportion of the alicyclic epoxy compound to 40% by weight or more, curing can be advanced more efficiently, and the transparency and durability of the cured product tend to be further improved.

1-2. Hardener (D)
The curing agent (D) which is one of the essential components of the curable epoxy resin composition of the present invention is a compound having a function of curing the curable epoxy resin composition by reacting with the epoxy compound. The curing agent (D) is not particularly limited, and any well-known and commonly used curing agent for epoxy resins can be used. For example, acid anhydrides (acid anhydride curing agents), amines (amines) Curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenol curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazide and the like .

  As the acid anhydrides (acid anhydride based curing agent) as the curing agent (D), known or commonly used acid anhydride based curing agents can be used and are not particularly limited. For example, methyltetrahydrophthalic anhydride (4 -Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc., methyl hexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methyl Endo methylene tetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, anhydrous Nadic acid, methyl nadic acid anhydride, methyl hydride Dicic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic acid anhydride, vinyl ether-maleic anhydride An acid copolymer, an alkylstyrene-maleic anhydride copolymer, etc. are mentioned. Among them, acid anhydride [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl endo methylene tetrahydrophthalic anhydride, etc.] which is liquid at 25 ° C. is preferable from the viewpoint of handleability. On the other hand, the acid anhydride solid at 25 ° C. is, for example, dissolved in acid anhydride liquid at 25 ° C. to form a liquid mixture, the curing agent (D in the curable epoxy resin composition of the present invention) Tend to be improved as the From the viewpoints of heat resistance and transparency of the cured product, as the acid anhydride curing agent, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those in which a substituent such as an alkyl group is bonded to the ring) are preferable.

  As the amines (amine-based curing agent) as the curing agent (D), known or commonly used amine-based curing agents can be used and are not particularly limited. For example, ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, Aliphatic polyamines such as dipropylenediamine, diethylaminopropylamine, polypropylenetriamine; mensenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-amino Alicyclic polyamines such as ethyl piperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; m-phenylene diamine, p-phenylene diamine, tri N-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyl tolylene-2,4-diamine, 3,5-diethyl tolylene-2,6- Examples thereof include mononuclear polyamines such as diamine, and biphenylene diamine, aromatic polyamines such as 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, 2,6-naphthylenediamine, and the like.

  As the phenols (phenolic curing agent) as the curing agent (D), known or commonly used phenolic curing agents can be used and are not particularly limited. For example, novolak type phenol resin, novolac type cresol resin, paraxylylene modified phenol And resins, aralkyl resins such as paraxylylene / metaxylylene modified phenolic resin, terpene modified phenolic resin, dicyclopentadiene modified phenolic resin, triphenolpropane and the like.

  As a polyamide resin as a hardening | curing agent (D), the polyamide resin etc. which have any one or both of a primary amino group and a secondary amino group in a molecule | numerator are mentioned, for example.

  As the imidazoles (imidazole-based curing agents) as the curing agent (D), known or commonly used imidazole-based curing agents can be used and are not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanate Nu 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)] And -ethyl-s-triazine and the like.

  Examples of polymercaptans (polymercaptan curing agents) as the curing agent (D) include liquid polymercaptans and polysulfide resins.

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

  Among them, as the curing agent (D), acid anhydrides (acid anhydride based curing agent) are preferable in view of curability, heat resistance of cured product, and transparency. In addition, in the curable epoxy resin composition of this invention, a hardening | curing agent (D) can also be used individually by 1 type, and can also be used combining 2 or more types. Moreover, a commercial item can also be used as a hardening | curing agent (D). For example, as commercial products of acid anhydrides, trade names "Rikasid MH-700", "Rikasid MH-700F" (all manufactured by Shin Nippon Rika Co., Ltd.); trade name "HN-5500" (Hitachi Chemical Co., Ltd.) Manufactured by Co., Ltd., and the like.

  The content (blending amount) of the curing agent (D) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of epoxy compounds contained in the curable epoxy resin composition (all epoxy compounds; It is preferably 50 to 200 parts by weight, more preferably 75 to 150 parts by weight, and still more preferably 100 to 120 parts by weight with respect to 100 parts by weight of the total amount of the resin (A). More specifically, when acid anhydrides are used as the curing agent (D), it is preferably 0.5 to 1. per equivalent of epoxy group in all epoxy compounds contained in the curable epoxy resin composition of the present invention. It is preferable to use at a ratio of 5 equivalents. By setting the content of the curing agent (D) to 50 parts by weight or more, curing can be advanced more efficiently, and the toughness of the cured product tends to be further improved. On the other hand, when the content of the curing agent (D) is 200 parts by weight or less, there is a tendency that a cured product having no color (or a small amount) and excellent in hue tends to be obtained.

1-3. Hardening accelerator (E)
The curing accelerator (E), which is one of the essential components of the curable epoxy resin composition of the present invention, is the reaction rate of the reaction of the epoxy compound (in particular, the reaction of the epoxy resin (A) with the curing agent (D)). It is a compound having a promoting function. As the curing accelerator (E), any well-known and commonly used curing accelerator for epoxy resins can be used, and it is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 ( DBU), and salts thereof (eg, phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) And their salts (eg, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborates, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, Tertiary amines such as N, N-dimethylcyclohexylamine; 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methane Imidazoles such as limidazole; phosphines such as phosphoric acid ester and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organic metal salts such as tin octylate and zinc octylate; metal chelates etc. It can be mentioned.

  In addition, in the curable epoxy resin composition of this invention, a hardening accelerator (E) can also be used individually by 1 type, and can also be used combining 2 or more types.

  As a curing accelerator (E) in the curable epoxy resin composition of the present invention, for example, trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X "," 12XD "(developed product, manufactured by San-Apro Ltd.); trade names" TPP-K "," TPP-MK "(manufactured by Hokuko Chemical Co., Ltd.); trade name" PX- " Commercial products such as 4ET (manufactured by Nippon Chemical Industrial Co., Ltd.) can be used.

  The content (blending amount) of the curing accelerator (E) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of epoxy compounds contained in the curable epoxy resin composition (all epoxy compounds; It is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 100 parts by weight of the epoxy resin (A). It is 0.25 to 2.5 parts by weight. By setting the content of the curing accelerator (E) to 0.05 parts by weight or more, a more sufficient curing promoting effect tends to be obtained. On the other hand, when the content of the curing accelerator (E) is 5 parts by weight or less, there is a tendency that a cured product having no color (or a small amount) and excellent in hue tends to be obtained.

1-4. Curing catalyst (F)
The curing catalyst (F) which is one of the essential components of the curable epoxy resin composition of the present invention is curable by initiating and / or accelerating the curing reaction (polymerization reaction) of a cationically polymerizable compound such as an epoxy compound. It is a compound having a function of curing an epoxy resin composition. The curing catalyst (F) is not particularly limited, but, for example, a cationic polymerization initiator (thermal cationic polymerization initiator) which generates cationic species by heat to initiate polymerization, a Lewis acid / amine complex, a Bronsted acid Salts, imidazoles and the like can be mentioned.

  Specifically, examples of the curing catalyst (F) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes and the like, under the trade names “PP-33”, “CP-66”, "CP-77" (all manufactured by ADEKA); trade name "FC-509" (manufactured by 3M); trade name "UVE 1014" (manufactured by G. E.); trade name "Sun Aid SI-60L" SI-80 L "," San Aid SI-100 L "," San Aid SI-110 L "," San Aid SI-150 L "(above, Sanshin Chemical Industry Co., Ltd. product); Brand name" CG-24-61 "(BASF AG) Commercial products, such as (made) can be used preferably. Furthermore, as the curing catalyst (F), for example, a compound of a chelate compound of a metal such as aluminum or titanium with acetoacetic acid or diketones and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium with acetoacetic acid Or compounds of chelate compounds with diketones and phenols such as bisphenol S.

The Lewis acid-amine complex as a curing catalyst (F), can be a known or conventional Lewis acid-amine complex curing catalyst is not particularly limited, for example, BF ₃ · n-hexylamine, BF ₃ · monoethylamine, BF ₃ · benzylamine, BF ₃ · diethylamine, BF ₃ · piperidine, BF ₃ · triethylamine, BF ₃ · aniline, BF ₄ · n-hexylamine, BF ₄ · monoethylamine, BF ₄ · benzylamine , BF ₄ · diethylamine, BF ₄ · piperidine, BF ₄ · triethylamine, BF ₄ · aniline, PF ₅ · ethylamine, PF ₅ · isopropylamine, PF ₅ · butylamine, PF ₅ · laurylamine, PF ₅ · benzylamine, AsF ₅ · laurylamine etc. may be mentioned.

  As Brönsted acid salts as curing catalyst (F), known or common Brönsted acid salts can be used, and it is not particularly limited. For example, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphoniums Salt etc. are mentioned.

  As imidazoles as a curing catalyst (F), known or common imidazoles can be used, and it is not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl Imidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-one Undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4 - Mino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine and the like Can be mentioned.

  In the curable epoxy resin composition of the present invention, the curing catalyst (F) may be used alone or in combination of two or more. In addition, as above-mentioned, as a curing catalyst (F), a commercial item can be used, for example.

  The content (blending amount) of the curing catalyst (F) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of epoxy compounds contained in the curable epoxy resin composition (all epoxy compounds; The amount is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, particularly preferably 0 with respect to 100 parts by weight of the total amount of the resin (A). It is .05 to 8 parts by weight. By setting the content of the curing catalyst (F) to 0.01 parts by weight or more, the curing reaction tends to be able to proceed more sufficiently. On the other hand, when the content of the curing catalyst (F) is 15 parts by weight or less, a cured product having no color (or less) and excellent in hue tends to be easily obtained. That is, by controlling the content of the curing catalyst (F) in the above range, the curing speed of the curable epoxy resin composition is improved, and a cured product having excellent balance of transparency and durability can be easily obtained. Tend.

  In addition, the curable epoxy resin composition of this invention may substantially contain the photocationic polymerization initiator which generate | occur | produces the seed | species (acid etc.) of cationic polymerization by irradiation of light. When the curable epoxy resin composition of the present invention contains a cationic photopolymerization initiator, its content is, for example, the total amount of epoxy compounds contained in the curable epoxy resin composition (all epoxy compounds; for example, epoxy resins (A For example, about 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the total amount of

1-5. Polyhydric alcohol The curable epoxy resin composition of the present invention may contain a polyhydric alcohol. In particular, when the curable epoxy resin composition of the present invention contains a curing agent (D) and a curing accelerator (E), it further contains a polyhydric alcohol in that curing can proceed more efficiently. Is preferred. As polyhydric alcohols, known or commonly used polyhydric alcohols can be used, and although not particularly limited, for example, ethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol and the like.

  Among them, as the polyhydric alcohol, an alkylene glycol having 1 to 6 carbon atoms is preferable, and a carbon 1 to 6 alkylene glycol is preferable in that a cured product which can control curing well and is less likely to cause cracking and peeling is easily obtained. It is a number 2-4 alkylene glycol.

  A polyhydric alcohol can also be used individually by 1 type in the curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type.

  The content (blending amount) of the polyhydric alcohol in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of epoxy compounds contained in the curable epoxy resin composition (all epoxy compounds; 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 5 parts by weight per 100 parts by weight of A) -2.5 parts by weight. By setting the content of the polyhydric alcohol to 0.05 parts by weight or more, curing tends to be able to proceed more efficiently. On the other hand, when the content of the polyhydric alcohol is 5 parts by weight or less, the curing reaction rate tends to be easily controlled.

1-6. Phosphor The curable epoxy resin composition of the present invention may contain a phosphor. When the curable epoxy resin composition of the present invention contains a phosphor, it is particularly preferably used as a sealing application (sealing material application) of an optical semiconductor element in an optical semiconductor device, that is, as a resin composition for optical semiconductor sealing. it can. As the above-mentioned phosphors, known or commonly used phosphors (in particular, phosphors used in sealing applications for optical semiconductor devices) can be used, and there is no particular limitation. For example, general formula A ₃ B ₅ O ₁₂ : M [Wherein, A represents one or more elements selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm, and B is selected from the group consisting of Al, Ga, and In] And at least one element selected from the group consisting of Ce, Pr, Eu, Cr, Nd, and Er]. (For example, Y ₃ Al ₅ O ₁₂ : Ce phosphor fine particles, (Y, Gd, Tb) ₃ (Al, Ga) ₅ O ₁₂ : Ce phosphor fine particles etc.), silicate based phosphor fine particles (for example, (Sr, Ca, Ba) ₂ SiO ₄ : Eu, etc. can be mentioned. The phosphor may be, for example, one whose surface is modified with an organic group (for example, a long chain alkyl group, a phosphate group or the like) or the like in order to improve the dispersibility. In the curable epoxy resin composition of the present invention, one kind of phosphor may be used alone, or two or more kinds may be used in combination. Moreover, a commercial item can be used as fluorescent substance.

  The content (blending amount) of the phosphor in the curable epoxy resin composition of the present invention is not particularly limited, and 0.5 to 20% by weight based on the total amount (100% by weight) of the curable epoxy resin composition It can select suitably in the range of.

1-7. Other Components The curable epoxy resin composition of the present invention may contain other components other than the above, as long as the curing property, transparency and the like are not adversely affected. As the above-mentioned other components, for example, silicone resin having linear or branched chain, silicone resin having alicyclic ring, silicone resin having aromatic ring, cage type / ladder type / random type silsesquioxane, Silane coupling agents, such as (gamma)-glycidoxy propyl trimethoxysilane, silicone type and a fluorine-type antifoamer etc. are mentioned. The content (blending amount) of the above other components is not particularly limited, but is preferably 5% by weight or less (eg, 0 to 3% by weight) based on the total amount (100% by weight) of the curable epoxy resin composition .

  The curable epoxy resin composition of the present invention is not particularly limited, and can be prepared, for example, by stirring and mixing the above-mentioned components in a heated state as required. The curable epoxy resin composition of the present invention may be a one-component composition in which a mixture of all the components in advance is used as it is, for example, a component divided into two or more It may be a composition of a multi-liquid system (for example, a two-liquid system) which is mixed and used at a predetermined ratio immediately before use. The method of stirring and mixing is not particularly limited. For example, various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and known and commonly used stirring and mixing means such as revolution type stirring devices can be used. Moreover, after stirring and mixing, you may degas under pressure reduction or under a vacuum.

2. Curable silicone resin composition The curable silicone resin composition (sometimes referred to as "the curable silicone resin composition of the present invention") comprises a curable composition comprising a silicone resin (B) as an essential component as a curable compound. It is a thing. The curable silicone resin composition of the present invention may contain components other than the silicone resin (B).

As the silicone resin (B), for example, in addition to -Si-O-Si- (siloxane bond) as a main chain, -Si- ^RA -Si- (sil alkylene bond: ^RA represents an alkylene group) And curable polysiloxanes such as polyorganosiloxanes containing no silalkylene bond as a main chain.

  Further, as the silicone resin (B), a curable silicone resin (curable polysiloxane) which is known or commonly used as a curable compound can be used and is not particularly limited. For example, addition type (addition reaction curing type) And silicone resins of condensation type (condensation reaction curing type). When the curable silicone resin composition of the present invention contains the former, it can be used as an addition reaction curable silicone resin composition, and when it contains the latter, it can be used as a condensation reaction curable silicone resin composition it can. Hereinafter, these addition reaction curable silicone resin composition and condensation reaction curable silicone resin composition will be described, but the curable silicone resin composition of the present invention is not limited to these, and, for example, addition type silicone resin and It may be a silicone resin composition which cures by addition reaction and condensation reaction which contains both of condensation type silicone resins. That is, curing of the curable silicone resin composition in the curing step may proceed by at least one reaction selected from the group consisting of addition reaction and condensation reaction.

2-1. Addition reaction curable silicone resin composition The above addition reaction curable silicone resin composition contains, for example, a polysiloxane (B1) having two or more alkenyl groups in the molecule as the silicone resin (B), and further necessary. According to the above, a curable silicone resin composition containing a polysiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule, a metal curing catalyst, and the like can be mentioned.

The above-mentioned polysiloxane (B1) is classified into polyorganosiloxane (B1-1) and polyorganosiloxysil alkylene (B1-2). In the present specification, polyorganosiloxycyl alkylene (B1-2) has two or more alkenyl groups in the molecule, and in addition to -Si-O-Si- (siloxane bond) as a main chain, -Si -R ^a -Si- (silalkylene bond: R ^a represents an alkylene group) polysiloxane containing. And polyorganosiloxane (B1-1) in this specification is a polysiloxane which has a 2 or more alkenyl group in a molecule | numerator, and does not contain the said silalkylene bond as a principal chain.

  The polyorganosiloxane (B1-1) includes those having a linear or branched molecular structure (a partially branched linear, branched, network, etc.) molecular structure. In addition, polyorganosiloxane (B1-1) can also be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, two or more kinds of polyorganosiloxanes (B1-1) having different molecular structures can be used in combination, and examples thereof include linear polyorganosiloxane (B1-1) and branched polyorganosiloxane (B1-). It can also be used in combination with 1).

  As an alkenyl group which polyorganosiloxane (B1-1) has in a molecule | numerator, substituted or unsubstituted alkenyl groups, such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, are mentioned. Examples of the substituent include a halogen atom, a hydroxy group and a carboxy group. Among them, a vinyl group is preferable as the alkenyl group. Moreover, polyorganosiloxane (B1-1) may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups. Although the alkenyl group which polyorganosiloxane (B1-1) has is not specifically limited, It is preferable that it is couple | bonded with the silicon atom.

  Although the group couple | bonded with silicon atoms other than the alkenyl group which polyorganosiloxane (B1-1) has is not specifically limited, For example, a hydrogen atom, monovalent organic group, etc. are mentioned. As a monovalent organic group, for example, an alkyl group [for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group etc.], a cycloalkyl group [for example, cyclopropyl group, cyclobutyl group, cyclopentyl group] , Cyclohexyl group, cyclododecyl group, etc.], aryl group [eg, phenyl group, tolyl group, xylyl group, naphthyl group etc.], cycloalkyl-alkyl group [eg, cyclohexyl methyl group, methylcyclohexyl group etc.], aralkyl group [Eg, benzyl group, phenethyl group etc.], a halogenated hydrocarbon group in which at least one hydrogen atom in the hydrocarbon group is substituted with a halogen atom [eg, chloromethyl group, 3-chloropropyl group, 3,3,3 -Halogenated alkyl group such as trifluoropropyl group etc.] or the like, monovalent substituted or unsubstituted carbonization Containing group, and the like. In the present specification, “a group bonded to a silicon atom” usually refers to a group not containing a silicon atom.

  Moreover, you may have a hydroxy group and an alkoxy group as group couple | bonded with the silicon atom.

  The property of the polyorganosiloxane (B1-1) is not particularly limited, and may be liquid or solid.

As polyorganosiloxane (B1-1), the following average unit formula:
^{_{(R 7 SiO 3/2) a1 (}} R 7 2 SiO 2/2) a2 (R 7 3 SiO 1/2) a3 (SiO 4/2) a4 (ZO 1/2) a5
The polyorganosiloxane represented by is preferable. In the above average unit formula, R ⁷ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the specific examples described above (eg, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated carbon, etc. Hydrogen group etc.). However, a part of R ⁷ is an alkenyl group (in particular, a vinyl group), and the ratio thereof is controlled to a range of 2 or more in the molecule. For example, the ratio of alkenyl groups relative to the total amount of R ⁷ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R ⁷ other than an alkenyl group, an alkyl group (especially a methyl group) and an aryl group (especially a phenyl group) are preferable.

  In the above average unit formula, Z is a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.

  In the above average unit formula, a1 is 0 or a positive number, a2 is 0 or a positive number, a3 is 0 or a positive number, a4 is 0 or a positive number, a5 is 0 or a positive number, and (a1 + a2 + a3) is a positive It is a number.

The polyorganosiloxycyl alkylene (B1-2) is a polyorganosiloxane having a silalkylene bond in addition to the siloxane bond as a main chain, as described above, having two or more alkenyl groups in the molecule. As the alkylene group in the above-mentioned silalkylene bond, a C _2-4 alkylene group (in particular, an ethylene group) is preferable. The polyorganosiloxycyl alkylene (B1-2) is less likely to form a ring having a low molecular weight in the production process compared to the polyorganosiloxane (B1-1), and is decomposed by heating or the like to form a silanol group (-SiOH) When the polyorganosiloxycyl alkylene (B1-2) is used, the surface tackiness (tackiness) of the cured product of the curable silicone resin composition tends to be low, and yellowing tends to occur more easily.

  As polyorganosiloxycyl alkylene (B1-2), those having a linear or branched (a partially branched linear, branched, network, etc.) molecular structure can be mentioned. In addition, polyorgano siloxy syl alkylene (B1-2) can also be used individually by 1 type, and can also be used in combination of 2 or more type. For example, two or more kinds of polyorganosiloxysil alkylene (B1-2) having different molecular structures can be used in combination, for example, linear polyorganosiloxysil alkylene (B1-2) and branched polyorgano. It can also be used in combination with siloxycyl alkylene (B1-2).

  Although the above-mentioned specific example is mentioned as an alkenyl group which polyorgano siloxy cyl alkylene (B1-2) has in a molecule | numerator, Especially, a vinyl group is preferable. The polyorganosiloxycyl alkylene (B1-2) may have only one type of alkenyl group or may have two or more types of alkenyl groups. Although the alkenyl group which polyorganosiloxy cyl alkylene (B1-2) has is not specifically limited, It is preferable that it is couple | bonded with the silicon atom.

  Although the group couple | bonded with silicon atoms other than the alkenyl group which polyorgano siloxy cyl alkylene (B1-2) has is not specifically limited, For example, a hydrogen atom, monovalent organic group, etc. are mentioned. As a monovalent organic group, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group etc. are mentioned, for example. Among them, alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferable.

  Moreover, you may have a hydroxy group and an alkoxy group as group couple | bonded with the silicon atom.

  The property of the polyorganosiloxycyl alkylene (B1-2) is not particularly limited, and may be liquid or solid.

As polyorganosiloxycyl alkylene (B1-2), the following average unit formula:
(R ⁸ ₂ SiO _2/2 ) _{b 1} (R ⁸ ₃ SiO _1/2 ) _{b 2} (R ⁸ SiO _3/2 ) _{b 3} (SiO _4/2 ) _{b 4} (R ^A ) _{b 5} (ZO _1/2 ) _{b 6}
The polyorganosiloxycyl alkylene represented by is preferable. In the above average unit formula, R ⁸ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the specific examples described above (eg, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated alkyl) Groups, etc.). However, a part of R ⁸ is an alkenyl group (especially a vinyl group), and the ratio thereof is controlled to a range of 2 or more in the molecule. For example, the ratio of the alkenyl group to the total amount (100 mol%) of R ⁸ is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R ⁸ other than an alkenyl group, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable.

In the above average unit formula, R ^A is an alkylene group as described above. Particularly preferred is an ethylene group.

  In the above average unit formula, Z is a hydrogen atom or an alkyl group as described above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.

  In the above average unit formula, b1 is a positive number, b2 is a positive number, b3 is 0 or a positive number, b4 is 0 or a positive number, b5 is a positive number, and b6 is 0 or a positive number. Among them, b1 is preferably 1 to 200, b2 is preferably 1 to 200, b3 is preferably 0 to 10, b4 is preferably 0 to 5 and b5 is preferably 1 to 100. In particular, when (b3 + b4) is a positive number, the mechanical strength of the cured product tends to be further improved.

The addition reaction curable silicone resin composition is, as described above, a polysiloxane ("hydrosilyl group-containing polysiloxane") further having one or more (preferably two or more) hydrosilyl groups (Si-H) in the molecule. May be included). The hydrosilyl group-containing polysiloxane is classified into a hydrosilyl group-containing polyorganosiloxane and a hydrosilyl group-containing polyorganosiloxysil alkylene. In the present specification, the hydrosilyl group-containing polyorganosiloxysil alkylene has one or more hydrosilyl groups in the molecule, and in addition to -Si-O-Si- (siloxane bond) as the main chain, -Si-R ^A— Si— (a silalkylene bond: R ^A represents an alkylene group). The hydrosilyl group-containing polyorganosiloxane in the present specification is a polysiloxane having one or more hydrosilyl groups in the molecule and containing no silalkylene bond as a main chain. As R ^A (alkylene group), as described above, for example, a linear or branched C _1-12 alkylene group may be mentioned, and preferably a linear or branched C _2-4 alkylene group ( In particular, it is an ethylene group).

  Examples of the hydrosilyl group-containing polyorganosiloxane include those having a linear or branched (a partially branched linear, branched, network, etc.) molecular structure. The hydrosilyl group-containing polyorganosiloxanes may be used alone or in combination of two or more. Two or more kinds of hydrosilyl group-containing polyorganosiloxanes having different molecular structures can be used in combination, for example, a combination of a linear hydrosilyl group-containing polyorganosiloxane and a branched hydrosilyl group-containing polyorganosiloxane it can.

  Among the groups bonded to the silicon atom of the hydrosilyl group-containing polyorganosiloxane, groups other than hydrogen atoms are not particularly limited, but, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups, more specifically alkyl groups And aryl groups, aralkyl groups, halogenated hydrocarbon groups and the like. Among them, alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferable. The hydrosilyl group-containing polyorganosiloxane may have an alkenyl group (for example, a vinyl group) as a group bonded to a silicon atom other than a hydrogen atom.

  The properties of the hydrosilyl group-containing polyorganosiloxane are not particularly limited, and may be liquid or solid. Among them, a liquid is preferable, and a liquid having a viscosity at 25 ° C. of 0.1 to 1000,000,000 mPa · s is more preferable.

As the above hydrosilyl group-containing polyorganosiloxane, the following average unit formula:
(R ⁹ SiO _3/2 ) _{c 1} (R ⁹ ₂ SiO _2/2 ) _{c 2} (R ⁹ ₃ SiO _1/2 ) _{c 3} (SiO _4/2 ) _{c 4} (ZO _1/2 ) _{c 5}
The polyorganosiloxane represented by is preferable. In the above average unit formula, R ⁹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and a hydrogen atom, the specific examples described above (for example, an alkyl group, an alkenyl group, an aryl) Groups, aralkyl groups, halogenated alkyl groups etc.). However, a part of R ⁹ is a hydrogen atom (a hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in such a range that one or more (preferably 2 or more) hydrosilyl groups are contained in the molecule. For example, the ratio of hydrogen atoms to the total amount of R ⁹ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the proportion of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. Further, as R ⁹ other than a hydrogen atom, an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable.

  In the above average unit formula, Z is a hydrogen atom or an alkyl group as described above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.

  In the above average unit formula, c1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is 0 or a positive number, and (c1 + c2 + c3) is a positive It is a number.

The above hydrosilyl group-containing polyorganosiloxysil alkylene is a polyorganosiloxane having a silalkylene bond in addition to a siloxane bond as a main chain, as described above, having one or more hydrosilyl groups in the molecule. In addition, as an alkylene group in the said sil alkylene bond, a _C2-4 alkylene group (especially ethylene group) is preferable, for example. The hydrosilyl group-containing polyorganosiloxycyl alkylene is less likely to form a ring having a low molecular weight in the production process as compared to the hydrosilyl group-containing polyorganosiloxane, and is less likely to be decomposed by heating or the like to form a silanol group (-SiOH) Therefore, when the above-mentioned hydrosilyl group-containing polyorganosiloxysil alkylene is used, the surface tackiness of the cured product of the curable silicone resin composition tends to be low, and yellowing tends to occur more easily.

  As the hydrosilyl group-containing polyorganosiloxycyl alkylene, those having a linear or branched (a partially branched linear, branched, network, etc.) molecular structure can be mentioned. The above hydrosilyl group-containing polyorganosiloxycyl alkylene can be used alone or in combination of two or more. Two or more kinds of hydrosilyl group-containing polyorganosiloxysil alkylenes having different molecular structures can be used in combination, for example, linear hydrosilyl group-containing polyorganosiloxysil alkylene and branched hydrosilyl group-containing polyorganosiloxy alkylene And can be used in combination.

  Although the group couple | bonded with silicon atoms other than the hydrogen atom which the said hydrosilyl group containing polyorgano siloxy cyl alkylene has is not specifically limited, For example, monovalent organic group etc. are mentioned. As a monovalent organic group, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group etc. are mentioned, for example. Among them, alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferable.

  The properties of the hydrosilyl group-containing polyorganosiloxycyl alkylene are not particularly limited, and may be liquid or solid.

As the above hydrosilyl group-containing polyorganosiloxycyl alkylene, the following average unit formula:
^{_{(R 10 2 SiO 2/2) d1}} (R 10 3 SiO 1/2) d2 (R 10 SiO 3/2) d3 (SiO 4/2) d4 (R A) d5 (ZO 1/2) d6
The polyorganosiloxycyl alkylene represented by is preferable. In the above average unit formula, R ¹⁰ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and a hydrogen atom and the specific examples described above (for example, an alkyl group, an alkenyl group, an aryl group , Aralkyl groups, halogenated alkyl groups and the like). However, a part of R ¹⁰ is a hydrogen atom, and the ratio thereof is controlled in a range of 1 or more (preferably 2 or more) in the molecule. For example, the ratio of hydrogen atoms to the total amount of R ¹⁰ (100 mol%) is 0.1 to 50 mol% by weight, more preferably 5 to 35 mol%. By controlling the proportion of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. Further, as R ¹⁰ other than a hydrogen atom, an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable. In particular, the ratio of the aryl group (particularly, phenyl group) to the total amount (100 mol%) of R ¹⁰ is preferably 5 mol% or more (for example, 5 to 80 mol%), more preferably 10 mol% or more.

In the above average unit formula, R ^A is an alkylene group as described above. Particularly preferred is an ethylene group.

  In the above average unit formula, Z is a hydrogen atom or an alkyl group as described above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.

  In the above average unit formula, d1 is a positive number, d2 is a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is a positive number, and d6 is 0 or a positive number. Among them, d1 is preferably 1 to 50, d2 is preferably 1 to 50, d3 is preferably 0 to 10, d4 is preferably 0 to 5 and d5 is preferably 1 to 30.

  As the hydrosilyl group-containing polysiloxane in the addition reaction-curable silicone resin composition, only a hydrosilyl group-containing polyorganosiloxane can be used, or only a hydrosilyl group-containing polyorganosiloxysilalkylene can be used. In addition, the hydrosilyl group-containing polyorganosiloxane and the hydrosilyl group-containing polyorganosiloxysilalkylene can be used in combination. When the hydrosilyl group-containing polyorganosiloxane and the hydrosilyl group-containing polyorganosiloxycyl alkylene are used in combination, the ratio thereof is not particularly limited, and can be set appropriately.

  The addition reaction-curable silicone resin composition is not particularly limited, but a composition (formulation composition) in which 0.2 to 4 moles of alkenyl groups are contained per 1 mole of hydrosilyl groups present in the curable resin composition. Is more preferably 0.5 to 1.5 mol, further preferably 0.8 to 1.2 mol. By controlling the ratio between the hydrosilyl group and the alkenyl group in the above range, the heat resistance, transparency, thermal shock resistance and reflow resistance of the cured product, and the barrier property against corrosive gas (for example, SOx gas etc.) are further enhanced. There is a tendency to improve.

  The addition reaction curable silicone resin composition may contain a metal curing catalyst as described above. Examples of the metal curing catalyst include well-known hydrosilylation catalysts such as platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, etc. Specifically, fine platinum powder, platinum black, fine platinum-supported silica powder, supported platinum Activated carbon, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., olefin complexes of platinum, carbonyl complexes of platinum such as platinum-carbonylvinylmethyl complex, platinum-divinyl tetramethyl disiloxane complex, platinum-cyclo Platinum vinyl methyl siloxane complex such as vinyl methyl siloxane complex, platinum-based catalyst such as platinum-phosphine complex, platinum-phosphite complex, and palladium-based catalyst containing palladium atom or rhodium atom instead of platinum atom in the above-mentioned platinum-based catalyst Or rhodium based catalysts. Among them, as the hydrosilylation catalyst, a platinum vinyl methyl siloxane complex, a platinum-carbonyl vinyl methyl complex, a complex of chloroplatinic acid with an alcohol, and an aldehyde are preferable because the reaction rate is good.

  In the addition reaction curable silicone resin composition, one metal curing catalyst (hydrosilylation catalyst) can be used alone, or two or more can be used in combination.

The content (compounding amount) of the metal curing catalyst (hydrosilylation catalyst) in the addition reaction curable silicone resin composition is not particularly limited, but the total amount of alkenyl groups contained in the addition reaction curable silicone resin composition is 1 mole. On the other hand, 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol is preferable, and more preferably 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻³ mol. By setting the content to 1 × 10 ⁻⁸ mol or more, a cured product tends to be able to be formed more efficiently. On the other hand, by setting the content to 1 × 10 ⁻² mol or less, there is a tendency to be able to obtain a cured product having a better hue (less coloring).

  The addition reaction curable silicone resin composition may contain components other than those described above.

2-2. Condensation reaction curable silicone resin composition As the above condensation reaction curable silicone resin composition, for example, as a silicone resin (B), two or more silanol groups (Si-OH) or silalkoxy groups (Si-OR) may be contained in the molecule. And a curable silicone resin composition containing a metal curing catalyst and the like as required. The polysiloxane (B2) may have only one of a silanol group and a silalkoxy group, or may have both a silanol group and a silalkoxy group. When having both a silanol group and a silalkoxy group, the total number of these may be two or more in the molecule.

As a polysiloxane (B2), the polyorganosiloxane represented by the following average composition formula is mentioned, for example.
R ¹¹ _e Si (OR ¹² ) _f (OH) _g O _{(4-efg) / 2}
[In the above average composition formula, R ¹¹ is the same or different and are each a monovalent organic group having 1 to 20 carbon atoms. R <^12> is the same or different, and shows a C1-C4 monovalent organic group. e is a number of 0.8 to 1.5, f is a number of 0 to 0.3, and g is a number of 0 to 0.5. f + g is a number of 0.001 or more and less than 1.2. Moreover, e + f + g is a number of 0.801 or more and less than 2. ]

As a monovalent organic group as R ¹¹ in the above average composition formula, for example, a monovalent aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group and the like); a monovalent aromatic hydrocarbon group (for example, Aryl group etc.) monovalent heterocyclic group; aliphatic hydrocarbon group, alicyclic hydrocarbon group, and monovalent group formed by combining two or more of aromatic hydrocarbon group, etc. may be mentioned . These monovalent organic groups may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group or a halogen atom). Among them, as R ^11, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms preferably. Moreover, as a monovalent organic group as R ¹² in the above average composition formula, for example, a monovalent aliphatic hydrocarbon group (eg, an alkyl group, an alkenyl group, etc.) which may have a substituent, etc. Can be mentioned. Among them, as R ¹² , an alkyl group having 1 to 4 carbon atoms and an alkenyl group having 2 to 4 carbon atoms are preferable.

  In the condensation reaction-curable silicone resin composition, the polysiloxane (B2) can be used alone or in combination of two or more.

  The condensation reaction curable silicone resin composition may contain a metal curing catalyst as described above. As such a metal curing catalyst, known or commonly used condensation reaction catalysts may be mentioned. For example, organic titanate, organic titanium chelate compound, organic aluminum compound, organic zirconium compound, organic tin compound, metal salt of organic carboxylic acid And amine compounds or salts thereof, quaternary ammonium salts, lower fatty acid salts of alkali metals, dialkylhydroxylamines, guanidyl group-containing organosilicon compounds and the like. Among them, organic zirconium compounds are preferable from the viewpoint of reactivity. One of these may be used alone, or two or more may be used in combination. The content (compounding amount) of the metal curing catalyst (condensation reaction catalyst) in the above condensation reaction curable silicone resin composition is not particularly limited, but for example, 0. 0. to 100 parts by weight of the total amount of the polysiloxane (B2). It can select suitably in the range of 01-20 weight part.

  The condensation reaction curable silicone resin composition may contain components other than those described above.

  The curable silicone resin composition of the present invention (for example, the above-mentioned addition reaction curable silicone resin composition, condensation reaction curable silicone resin composition, etc.) may contain other components. As another component, what was illustrated as a component which the curable epoxy resin composition of this invention may contain is mentioned, for example. The content is also not particularly limited, and can be appropriately selected. For example, when the curable silicone resin composition of the present invention is a resin composition for encapsulating an optical semiconductor, it is preferable to include the above-mentioned phosphor. The content (blending amount) of the phosphor in the curable silicone resin composition of the present invention is not particularly limited, and 0.5 to 20% by weight based on the total amount (100% by weight) of the curable silicone resin composition It can select suitably in the range of.

  The curable silicone resin composition of the present invention is not particularly limited, and can be prepared, for example, by stirring and mixing the above-mentioned components in a heated state as required. The curable silicone resin composition of the present invention may be a one-component composition in which one in which all the components are mixed in advance is used as it is, for example, a component divided into two or more It may be a composition of a multi-liquid system (for example, a two-liquid system) which is mixed and used at a predetermined ratio immediately before use. The method of stirring and mixing is not particularly limited. For example, various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and known and commonly used stirring and mixing means such as revolution type stirring devices can be used. Moreover, after stirring and mixing, you may degas under pressure reduction or under a vacuum. Moreover, it is also possible to use a commercial item as it is as a curable silicone resin composition or its component of this invention.

3. Curable acrylic resin composition The curable acrylic resin composition (sometimes referred to as "the curable acrylic resin composition of the present invention") comprises a curable composition containing an acrylic resin (C) as an essential component as a curable compound. It is a thing. The curable acrylic resin composition of the present invention may contain components other than the acrylic resin (C).

  Examples of the acrylic resin (C) include compounds having one or more (meth) acryloyl groups (at least one group selected from the group consisting of acryloyl groups and methacryloyl groups) in the molecule. Examples of the acrylic resin (C) include (meth) acryloyl compounds having only one (meth) acryloyl group in the molecule; and polyfunctional (meth) acryloyl compounds having two or more (meth) acryloyl groups in the molecule. Be The (meth) acryloyl compound having only one (meth) acryloyl group in the molecule includes a monofunctional (meth) acryloyl compound having no polymerizable functional group other than the (meth) acryloyl group; In addition to an acryloyl group, a polyfunctional (meth) acryloyl compound having one or more other polymerizable functional groups such as an epoxy group, an oxetanyl group, a vinyl group and a vinyloxy group is further included. Acrylic resin (C) can also be used individually by 1 type, and can also be used combining 2 or more types. In addition, content of the acrylic resin (C) in the curable acrylic resin composition of this invention is not specifically limited, It is possible to select suitably.

  The curable acrylic resin composition of the present invention may contain, for example, an initiator for promoting the polymerization reaction of the acrylic resin (C). Examples of the initiator include known or commonly used polymerization initiators such as a thermal polymerization initiator. One of these may be used alone, or two or more may be used in combination. Further, the content of the initiator is not particularly limited, and can be appropriately selected.

  The curable acrylic resin composition of the present invention may contain other components. As another component, what was illustrated as a component which the curable epoxy resin composition of this invention may contain is mentioned, for example. The content is also not particularly limited, and can be appropriately selected. For example, when the curable acrylic resin composition of the present invention is a resin composition for encapsulating an optical semiconductor, it is preferable to include the above-mentioned phosphor. The content (blending amount) of the phosphor in the curable acrylic resin composition of the present invention is not particularly limited, and 0.5 to 20% by weight with respect to the total amount (100% by weight) of the curable acrylic resin composition It can select suitably in the range of.

  The curable acrylic resin composition of the present invention is not particularly limited, and can be prepared, for example, by stirring and mixing the above-mentioned components in a heated state as necessary. The curable acrylic resin composition of the present invention may be a one-component composition in which one in which all the components are mixed in advance is used as it is, for example, a component divided into two or more It may be a composition of a multi-liquid system (for example, a two-liquid system) which is mixed and used at a predetermined ratio immediately before use. The method of stirring and mixing is not particularly limited. For example, various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and known and commonly used stirring and mixing means such as revolution type stirring devices can be used. Moreover, after stirring and mixing, you may degas under pressure reduction or under a vacuum. Moreover, it is also possible to use a commercial item as it is as a curable acrylic resin composition or its component of this invention.

[Cured product and uneven shape]
In the antireflective material of the present invention, the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the entire cured product thereof, and as a result of the dispersed state being stabilized, it is present on the surface of the cured product The hydrophobic porous inorganic filler forms asperities and scatters incident light to exhibit an antireflective function. In addition, the porous structure on the surface of the hydrophobic porous inorganic filler can also scatter incident light, and the antireflection function is further improved.
In addition, since the surface of the hydrophobic porous inorganic filler exhibits hydrophobicity, a cured product containing the same exhibits high heat resistance, particularly heat resistance water resistance, which is difficult to deteriorate even under severe heating conditions such as boiling water, and is durable Excellent.
The method for spreading the hydrophobic porous inorganic filler over the entire cured product is not particularly limited. For example, the hydrophobic porous inorganic filler is uniformly dispersed in the resin composition constituting the cured product and then cured. Etc. In order to produce the antireflective material of the present invention efficiently, it is preferable to uniformly disperse the hydrophobic porous inorganic filler and then to cure it.
Although the one aspect | mode of the manufacturing method of the anti-reflective material of this invention is demonstrated below, this invention is not limited to this.

  A hydrophobic porous inorganic filler can be added to the resin composition, and the resin composition can be uniformly dispersed by mixing and stirring. The method of mixing and stirring is not particularly limited, and, for example, various known mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and known and commonly used stirring and mixing means such as a revolution type stirring device can be used. Moreover, after stirring and mixing, you may degas under pressure reduction or under a vacuum.

  The property of the resin composition before curing of the present invention is not particularly limited, but is preferably liquid. The resin composition before curing to form the antireflective material of the present invention can exhibit an antireflective function with a small amount of addition by using a hydrophobic porous inorganic filler, and therefore no solvent such as toluene is used. Both are easy to become liquid and are preferable.

[Curing process]
An antireflective material according to the present invention is obtained by curing a resin composition in which a hydrophobic porous inorganic filler is uniformly dispersed to obtain a cured product (hereinafter sometimes referred to as "cured product of the present invention"). Can.
The amount of components that volatilize during curing is preferably 10 wt% or less, more preferably 8 wt% or less, with respect to the total amount (100 wt%) of the resin composition before curing. Preferably it is 5 weight% or less. When the amount of components volatilized during curing is 10% by weight or less, dimensional stability of the cured product is enhanced, which is preferable. The resin composition before curing of the present invention can exhibit an anti-reflection function with a small amount of addition by using a hydrophobic porous inorganic filler, and therefore, it does not use any volatile component such as a solvent (toluene etc.) And can reduce the amount of components that volatilize during curing.

As means for curing, known or conventional means such as heat treatment or light irradiation treatment can be used. Although the temperature (hardening temperature) at the time of hardening by heating is not specifically limited, 45-200 degreeC is preferable, More preferably, it is 50-190 degreeC, More preferably, it is 55-180 degreeC. Moreover, the time (hardening time) heated at the time of hardening is not specifically limited, However, 30 to 600 minutes are preferable, More preferably, it is 45 to 540 minutes, More preferably, it is 60 to 480 minutes. If the curing temperature and the curing time are lower than the lower limit of the above range, curing will be insufficient. If the upper limit is above the above range, decomposition of the resin component may occur. Although the curing conditions depend on various conditions, for example, when the curing temperature is raised, the curing time can be appropriately adjusted by shortening the curing time, and when the curing temperature is lowered, prolonging the curing time or the like. Further, curing can be performed in one step or in multiple steps of two or more steps.
In the case of curing by light irradiation, for example, light (radiation) including i-line (365 nm), h-line (405 nm), g-line (436 nm), etc., illuminance 10 to 1200 mW / cm ² , irradiation The antireflection material of the present invention can be obtained by irradiation with a light amount of 20 to 2500 mJ / cm ² . From the viewpoint of suppressing deterioration of a cured product due to radiation and from the viewpoint of productivity, the irradiation light amount of radiation is preferably 20 to 600 mJ / cm ² , more preferably ²⁰ to 300 mJ / cm ² . For the irradiation, a high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a laser beam or the like can be used as an irradiation source.

[Anti-reflective material]
The antireflective material of the present invention, as described above, has high heat resistance (in particular, heat resistant water resistance) in addition to high transparency and excellent antireflective function, so it is used for applications for forming optical materials Can be suitably used as a resin. The optical material is a material that exhibits various optical functions such as light diffusivity, light transparency, and light reflectivity. By using the antireflective material of the present invention, an optical member comprising at least the cured product (optical material) of the present invention can be obtained. In addition, the said optical member may be comprised only from the anti-reflective material of this invention, and the anti-reflective material of this invention may be used only for one part. Examples of the optical member include a member that exhibits various optical functions such as light diffusivity, light transparency, and light reflectivity, and a member that constitutes an apparatus or device using the above optical function, and is particularly limited. For example, optical semiconductor devices, organic EL devices, adhesives, electrical insulation materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical Examples thereof include known or commonly used optical members used in various applications such as lenses, optical molding, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, optical pickup sensors and the like.

The antireflective material according to the present invention has fine and uniform asperities formed on the surface by the hydrophobic porous inorganic filler, as a result of the hydrophobic porous inorganic filler being uniformly dispersed throughout the cured product, Since the incident light is scattered in the uneven shape and total reflection does not occur, the gloss can be suppressed and the visibility can be improved. The range of 0.1-1.0 micrometers is preferable, and, as for arithmetic mean surface roughness Ra of the uneven | corrugated shape formed in the anti-reflective material of this invention, the range of 0.2-0.8 micrometers is more preferable. If the arithmetic mean surface roughness Ra of the concavo-convex shape is in this range, there is a tendency that a sufficient antireflection function can be exhibited without significantly reducing the total luminous flux.
In the present invention, the arithmetic mean surface roughness Ra is a numerical value defined by JIS B 0601-2001, and means one measured and calculated by the method described in the examples described later.

  The resin composition which comprises the anti-reflective material of this invention can be preferably used, for example as a resin composition for optical semiconductor sealing. That is, the resin composition of the present invention can be preferably used as a composition for sealing an optical semiconductor element in an optical semiconductor device (an encapsulant for an optical semiconductor element in an optical semiconductor device). The optical semiconductor device (for example, 104 in FIG. 1 is anti-reflective of this invention with the photo-semiconductor element sealed by the anti-reflective material manufactured using the resin composition (resin composition for optical semiconductor sealing) of this invention) An optical semiconductor device made of a material is obtained. The optical semiconductor element can be sealed, for example, by injecting a resin composition in which a hydrophobic porous inorganic filler is uniformly dispersed into a predetermined mold, and heat curing or photocuring under predetermined conditions. The curing temperature, the curing time, the conditions for photocuring, and the like can be appropriately set in the same range as in the preparation of the above-mentioned antireflective material. The optical semiconductor device of the present invention described above can exhibit an excellent antireflection function without particularly reducing the total luminous flux, and has high heat resistance (in particular, hot water resistance). In the present specification, “the optical semiconductor device according to the present invention” means that the antireflective material according to the present invention is used for at least a part of constituent members (for example, a sealing material, a die bonding material, etc.) of the optical semiconductor device. It means an optical semiconductor device.

  EXAMPLES The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples. In addition, the unit of the component which comprises the resin composition shown to Table 1, 2 is a weight part.

Production Example 1
100 parts by weight of a curing agent (trade name "Rikasid MH-700", manufactured by Shin Nippon Rika Co., Ltd.), 0.5 part by weight of a curing accelerator (trade name "U-CAT 18X", manufactured by San Apro Ltd.), One part by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) is mixed using a revolution-revolution type stirring device (trade name "Awatori Neritaro AR-250, manufactured by Shinky Co., Ltd., the same applies hereinafter), An epoxy curing agent (K agent) was produced.

Example 1
100 parts by weight of an alicyclic epoxy compound (trade name "Celoxide 2021 P", manufactured by Daicel Co., Ltd.) and 101.5 parts by weight of the epoxy curing agent obtained in Production Example 1 are mixed using a self-revolution stirring device, Degassing to produce a curable epoxy resin composition.
100 parts by weight of the curable epoxy resin composition obtained above, and 20 parts by weight of a hydrophobic porous inorganic filler (trade name "Silo Hobic 702, manufactured by Fuji Silysia Chemical Ltd.)" A curable epoxy resin composition obtained by mixing, degassing and using is cast on a lead frame (InGaN element, 3.5 mm × 2.8 mm) of an optical semiconductor shown in FIG. 1, and then a resin of 150 ° C. By heating in a curing oven for 5 hours, an optical semiconductor device having an optical semiconductor element sealed with the antireflective material of the present invention was manufactured. In FIG. 1, 100 is a reflector, 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, 104 is a sealing material (antireflection material), and a hydrophobic porous inorganic filler is shown throughout 104 Are uniformly dispersed, and a uniform and fine uneven shape is formed by the hydrophobic porous inorganic filler present on the upper surface thereof (the uneven shape is not shown).

Examples 2 to 13 and Comparative Examples 1 to 13
The same as Example 1, except that the compositions of the curable epoxy resin composition, the hydrophobic porous inorganic filler, and the porous inorganic filler (not hydrophobized) were changed as shown in Tables 1 and 2. , Manufactured an optical semiconductor device.

[Evaluation]
The following evaluation was performed about the optical semiconductor device manufactured above. The results are shown in each of Tables 1 and 2.

(1) Hot water resistance test (heat resistance in boiling water)
The optical semiconductor devices obtained in Examples and Comparative Examples were immersed in boiling water for 30 minutes, and then the appearance was visually evaluated. The case where the appearance was the same as before the test was ○, and the case where it became cloudy was x.

(2) Reflection of fluorescent lamp When a fluorescent lamp is turned on to the upper surface (the upper surface of the sealing material 104 of FIG. 1) of the optical semiconductor device obtained in the embodiment and the comparative example, reflection is prevented when reflection is observed. The sharpness of the fluorescent light reflected in the material was evaluated in three steps by visual observation.
The case where the outline of the fluorescent lamp can not be recognized is ○, the case where the outline can be recognized while being unclear is Δ, and the case where the outline can be clearly recognized is ×.
(3) Arithmetic mean surface roughness Ra
The upper surface (the upper surface of the sealing material 104 of FIG. 1) of the optical semiconductor device obtained in the example and the comparative example is used as a laser microscope (trade name “shape measurement laser microscope VK-8710”, manufactured by Keyence Corporation) It was measured.

(4) Total luminous flux For each optical semiconductor device obtained in the examples and comparative examples, the total luminous flux when energized under the conditions of 5 V and 20 mA is a total luminous flux measuring machine (trade name “multi-spectroscopic emission measuring system OL771”, It measured using the optotronic laboratory company make.

(5) Comprehensive Judgment For each of the optical semiconductor devices obtained in Examples and Comparative Examples, when all of the following (a) to (d) are satisfied, O (good), the following (a) to (d) The case where one of the conditions was not satisfied was determined to be x (defective).
(A) The hot water resistance measured in the above (1) is ○.
(B) The reflection of the fluorescent lamp measured in (2) is ○ or Δ.
(C) The arithmetic average surface roughness Ra measured in (3) above is 0.10 to 1.0 μm.
(D) The total luminous flux measured in (4) above is 0.60 lm or more.

Each component which comprises the anti-reflective material shown to Table 1, 2 is demonstrated below.
(Hydrophobic porous inorganic filler)
Silo Hobic 702: trade name “Silo Hobik 702”, a product of Fuji Silysia Chemical Co., Ltd., porous silica filler which has been hydrophobically surface-treated with polydimethylsiloxane, volume average particle diameter: 4.1 μm, hydrophobic surface treatment Specific surface area of the porous silica filler before being made: 350 m ² / g; oil absorption: 170 mL / 100 g
Silo Hobic 4004: trade name "Silo Hobic 4004," manufactured by Fuji Silysia Chemical Ltd., porous silica filler hydrophobically surface treated with polydimethylsiloxane, volume average particle diameter: 8.0 μm, hydrophobic surface treatment Specific surface area of the porous silica filler before being made: 350 m ² / g; oil absorption: 165 mL / 100 g
Silo Hobic 505: trade name “Silo Hobic 505, manufactured by Fuji Silysia Chemical Ltd., porous silica filler hydrophobically surface-treated with polydimethylsiloxane, volume average particle diameter: 3.9 μm; hydrophobic surface treatment Specific surface area of the porous silica filler before being made: 500 m ² / g; oil absorption: 110 mL / 100 g

(Porous inorganic filler)
Silysia 430: trade name "Silysia 430" manufactured by Fuji Silysia Chemical Ltd., volume average particle diameter: 4.1 μm; specific surface area: 350 m ² / g; average pore diameter: 17 nm; pore volume: 1.25 mL / g Oil absorption: 230 mL / 100 g
Silososphere C-1504: trade name "Silosphere C-1504" manufactured by Fuji Silysia Chemical Ltd., volume average particle diameter: 4.5 μm; specific surface area: 520 m ² / g; average pore diameter: 12 nm; pore volume : 1.5 mL / g; oil absorption: 290 mL / 100 g
Sunsphere H-52: trade name "Sunsphere H-52", manufactured by AGC S IT Co., Ltd., volume average particle diameter: 5 μm; specific surface area: 700 m ² / g; average pore diameter: 10 nm; pore volume: 2 mL Oil absorption: 300 mL / 100 g

(Epoxy resin)
Celloxide 2021 P: trade name "Ceroxide 2021 P" [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate], manufactured by Daicel Corporation YD-128: trade name "YD-128" [bisphenol A type epoxy] Resin], Nippon Steel & Sumikin Chemical Co., Ltd. TEPIC-VL: trade name "TEPIC-VL" [triglycidyl isocyanurate], Nissan Chemical Industries Co., Ltd. 152: trade name "152" [phenol novolac epoxy resin ], Mitsubishi Chemical Co., Ltd. YL7410: trade name "YL7410" [aliphatic epoxy compound], Mitsubishi Chemical Co., Ltd. X-22-169AS: trade name "X-22-169AS" [modified silicone oil (both ends) (Polydimethylsiloxane having cyclohexene oxide group) Chemical Industry Co., Ltd. X-40-2670: trade name "X-40-2670" [cyclic siloxanes having a cyclohexene oxide group], manufactured by Shin-Etsu Chemical Co., Ltd.

(Epoxy curing agent)
MH-700: trade name "Rikasid MH-700" [4-methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30], Shin Nippon Chemical Co., Ltd. U-CAT 18X: trade name "U-CAT" 18X "[hardening accelerator], manufactured by San Apro Ltd. Ethylene glycol: manufactured by Wako Pure Chemical Industries, Ltd.

As shown in Table 1, according to the optical semiconductor device provided with the anti-reflection material according to the embodiment to which the hydrophobic porous inorganic filler is added, all of the hot water resistance tests are ○, and the reflection of the fluorescent light is ○. Or 評 価, the arithmetic average surface roughness Ra is in the range of 0.10 to 1.0 μm, the total luminous flux is in the range of 0.60 lm or more, excellent anti-reflection function and illuminance, excellent heat resistance, in particular, hot water resistance It has been confirmed that it combines.
On the other hand, as shown in Table 2, although the optical semiconductor device of the comparative example which mix | blended the porous inorganic filler which is not hydrophobized treated shows the outstanding antireflection function and illumination intensity, all of the hot water resistance tests are x. It was inferior to the hot water resistance.

The variations of the present invention described above are additionally described below.
[1] A reflection preventing material comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, which is characterized in that the surface of the cured product is formed with irregularities to suppress reflection, Prevention material.
[2] The antireflective material according to the above [1], wherein the hydrophobic porous inorganic filler is uniformly dispersed over the entire cured product, and irregularities are formed on the surface to suppress reflection.
[3] A porous inorganic filler (a porous inorganic filler before the surface is subjected to a hydrophobic treatment) constituting the hydrophobic porous inorganic filler is an inorganic glass [eg, borosilicate glass, borosilicate glass, sodium silicate glass , Aluminum silicate glass, quartz etc], silica, alumina, zircon iron oxide, zinc oxide, zirconium oxide, magnesium oxide, magnesium oxide, titanium oxide, aluminum oxide, forsterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline At least one powder selected from the group consisting of cynite, cristobalite, wollastonite, diatomaceous earth, and talc, having a porous structure, or a molded product thereof (eg, spherical beads etc.) The antireflective material according to the above [1] or [2].
[4] The hydrophobic porous inorganic filler is at least one selected from the group consisting of metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols, and organic silicon compounds as the porous inorganic fillers. The antireflective material according to the above [3], which has been subjected to surface treatment with a hydrophobic surface treatment agent of a certain type.
[5] The antireflective material according to the above [4], wherein the hydrophobic surface treatment agent is an organosilicon compound.
[6] The organosilicon compound is at least one selected from the group consisting of trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, and silcon oil. The antireflective material according to the above [5], which is a species (preferably, polydimethylsiloxane).
[7] At least one member (preferably, hydrophobic porous) selected from the group consisting of hydrophobic porous inorganic glass and hydrophobic porous silica (hydrophobic porous silica filler) The antireflective material according to any one of the above [1] to [6], which is a silica filler).
[8] At least one porous silica selected from the group consisting of fused silica, crystalline silica, high purity synthetic silica, and colloidal silica is treated with the hydrophobic surface treatment agent. The antireflective material according to the above [7], which is
[9] The shape of the hydrophobic porous inorganic filler is at least one selected from the group consisting of powder, sphere, fracture, fiber, needle, and scale (preferably sphere or fracture) The antireflective material as described in any one of the above [1] to [8].
[10] The hydrophobic porous inorganic filler is obtained by treating the surface of the porous inorganic filler with a hydrophobic treatment, and the specific surface area of the porous inorganic filler before the hydrophobic treatment is 200 m ² / g or more (preferably 200) ~2000m ² / g, more preferably 200~1500m ² / g, more preferably from 200~1000m ² / g), the above-mentioned [1] - antireflective member according to any one of [9].
[11] The antireflective material according to any one of the above [1] to [10], wherein the average particle diameter of the hydrophobic porous inorganic filler is 1 to 20 μm (preferably 2 to 15 μm).
[12] The antireflection according to any one of the above [1] to [11], wherein the oil absorption of the hydrophobic porous inorganic filler is 10 to 2000 mL / 100 g (preferably 100 to 1000 mL / 100 g). Material.
[13] The content of the hydrophobic porous inorganic filler is 4 to 40% by weight (preferably 4 to 35% by weight, more preferably 4 to 30% by weight) based on the total amount (100% by weight) of the antireflective material The antireflective material according to any one of the above [1] to [12].
[14] The content (compounding amount) of the hydrophobic porous inorganic filler is 5 to 80 parts by weight (preferably 5 to 70 parts by weight, more preferably) to the resin composition (100 parts by weight) constituting the antireflective material The antireflective material according to any one of the above [1] to [13], which is 5 to 60 parts by weight).

［式（１）中、Ｘは単結合又は連結基（１以上の原子を有する２価の基）を示す。式（１）における脂環を構成する炭素原子の１以上には、置換基（好ましくはアルキル基）が結合していてもよい。］
［２１］前記式（１）で表される化合物が、２，２−ビス（３，４−エポキシシクロヘキサン−１−イル）プロパン、ビス（３，４−エポキシシクロヘキシルメチル）エーテル、１，２−ビス（３，４−エポキシシクロヘキサン−１−イル）エタン、１，２−エポキシ−１，２−ビス（３，４−エポキシシクロヘキサン−１−イル）エタン、及び下記式（１−１）〜（１−１０）で表される化合物からなる群から選ばれる少なくとも１種の脂環式エポキシ化合物である、上記［２０］に記載の反射防止材。

［式（１−５）、（１−７）中のｌ、ｍは、それぞれ１〜３０の整数を表す。式（１−５）中のＲは炭素数１〜８のアルキレン基である。下記式（１−９）、（１−１０）中のｎ１〜ｎ６は、それぞれ１〜３０の整数を示す。］
［２２］前記脂環式エポキシ化合物が、上記式（１−１）で表される化合物を含む、上記［２１］に記載の反射防止材。
［２３］前記エポキシ樹脂（Ａ）の含有量（配合量）が、硬化性エポキシ樹脂組成物の全量（１００重量％）に対して、２５〜９９．８重量％（例えば、２５〜９５重量％）（好ましくは３０〜９０重量％、より好ましくは３５〜８５重量％、さらに好ましくは４０〜６０重量％）である、上記［１７］〜［２２］のいずれか１つに記載の反射防止材。
［２４］前記脂環式エポキシ化合物の含有量（配合量）が、硬化性エポキシ樹脂組成物の全量（１００重量％）に対して、２０〜９９．８重量％（好ましくは４０〜９５重量％（例えば、４０〜６０重量％）、より好ましくは５０〜９５重量％、さらに好ましくは６０〜９０重量％、最も好ましくは７０〜８５重量％）である、上記［１８］〜［２３］のいずれか１つに記載の反射防止材。
［２５］前記硬化性エポキシ樹脂組成物に含まれるエポキシ化合物の全量（１００重量％）に対する脂環式エポキシ化合物の割合が、４０〜１００重量％（例えば、４０〜９０重量％）（好ましくは８０〜１００重量％、より好ましくは９０〜１００重量％、さらに好ましくは９５〜１００重量％）である、上記［１８］〜［２４］のいずれか１つに記載の反射防止材。
［２６］前記硬化性エポキシ樹脂組成物が、さらに、硬化剤（Ｄ）及び硬化促進剤（Ｅ）、又は、硬化触媒（Ｆ）（好ましくは、硬化剤（Ｄ）及び硬化促進剤（Ｅ））を含む、上記［１７］〜［２５］のいずれか１つに記載の反射防止材。
［２７］前記硬化剤（Ｄ）が、酸無水物類（酸無水物系硬化剤）、アミン類（アミン系硬化剤）、ポリアミド樹脂、イミダゾール類（イミダゾール系硬化剤）、ポリメルカプタン類（ポリメルカプタン系硬化剤）、フェノール類（フェノール系硬化剤）、ポリカルボン酸類、ジシアンジアミド類、及び有機酸ヒドラジドからなる群から選ばれる少なくとも１種（好ましくは、酸無水物系硬化剤）である、上記［２６］に記載の反射防止材。
［２８］前記酸無水物系硬化剤が、２５℃で液状の酸無水物、又は２５℃で固体状の酸無水物を２５℃で液状の酸無水物に溶解させた液状の混合物である、上記［２７］に記載の反射防止材。
［２９］前記硬化剤（Ｄ）の含有量（配合量）が、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物の全量１００重量部に対して、５０〜２００重量部（好ましくは７５〜１５０重量部、より好ましくは１００〜１２０重量部）である、上記［２６］〜［２８］のいずれか１つに記載の反射防止材。
［３０］前記硬化促進剤（Ｅ）の含有量（配合量）が、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物の全量１００重量部に対して、０．０５〜５重量部（好ましくは０．１〜３重量部、より好ましくは０．２〜３重量部、さらに好ましくは０．２５〜２．５重量部）である、上記［２６］〜［２９］のいずれか１つに記載の反射防止材。
［３１］前記硬化性エポキシ樹脂組成物が、多価アルコール（好ましくは炭素数２〜４のアルキレングリコール）を含む、上記［１７］〜［３０］のいずれか１つに記載の反射防止材。
［３２］前記多価アルコールの含有量（配合量）が、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物の全量１００重量部に対して、０．０５〜５重量部（好ましくは０．１〜３重量部、より好ましくは０．２〜３重量部、さらに好ましくは０．２５〜２．５重量部）である、上記［３１］に記載の反射防止材。
［３３］前記硬化性エポキシ樹脂組成物が、蛍光体を含む、上記［１］〜［３２］のいずれか１つに記載の反射防止材。
［３４］前記蛍光体の含有量（配合量）が、硬化性エポキシ樹脂組成物の全量（１００重量％）に対して、０．５〜２０重量％である、上記［３３］に記載の反射防止材。[15] The antireflective material according to any one of the above [1] to [14], wherein the resin composition is a transparent curable resin composition.
[16] The curable resin composition comprises a composition comprising at least one curable compound selected from the group consisting of an epoxy resin (A), a silicone resin (B), and an acrylic resin (C). The antireflective material as described in the above [15].
[17] The antireflective material according to the above [16], wherein the curable resin composition comprises a composition containing an epoxy resin (A) (curable epoxy resin composition).
[18] The epoxy resin (A) is a bisphenol A epoxy resin, isocyanurate having one or more epoxy groups in the molecule, novolac epoxy resin, alicyclic epoxy compound, aliphatic epoxy compound, and in the molecule The antireflective member according to the above [16] or [17], which is at least one selected from the group consisting of siloxane derivatives having one or more epoxy groups (preferably, an alicyclic epoxy compound).
[19] The anti-reflection as described in the above [18], wherein the alicyclic epoxy compound contains a compound having a cyclohexene oxide group in a molecule (preferably a compound having two or more cyclohexene oxide groups in the molecule). Material.
[20] The antireflective material according to the above [19], wherein the alicyclic epoxy compound contains a compound represented by the following formula (1).

[In Formula (1), X shows a single bond or a coupling group (bivalent group which has one or more atoms). A substituent (preferably an alkyl group) may be bonded to one or more of the carbon atoms constituting the alicyclic ring in the formula (1). ]
[21] The compound represented by the above formula (1) is 2,2-bis (3,4-epoxycyclohexan-1-yl) propane, bis (3,4-epoxycyclohexylmethyl) ether, 1,2- Bis (3,4-epoxycyclohexan-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexan-1-yl) ethane, and the following formulas (1-1) to ( The antireflective material as described in the above [20], which is at least one alicyclic epoxy compound selected from the group consisting of compounds represented by 1-10).

[L and m in formulas (1-5) and (1-7) each represent an integer of 1 to 30] R in Formula (1-5) is a C1-C8 alkylene group. N1 to n6 in the following formulas (1-9) and (1-10) each represent an integer of 1 to 30. ]
[22] The antireflective material according to the above [21], wherein the alicyclic epoxy compound contains a compound represented by the above formula (1-1).
[23] The content (blending amount) of the epoxy resin (A) is 25 to 99.8% by weight (eg, 25 to 95% by weight) based on the total amount (100% by weight) of the curable epoxy resin composition The antireflective material according to any one of the above [17] to [22], which is preferably 30 to 90% by weight, more preferably 35 to 85% by weight, still more preferably 40 to 60% by weight. .
[24] The content (blending amount) of the alicyclic epoxy compound is 20 to 99.8% by weight (preferably 40 to 95% by weight) based on the total amount (100% by weight) of the curable epoxy resin composition (For example, 40 to 60% by weight), more preferably 50 to 95% by weight, still more preferably 60 to 90% by weight, and most preferably 70 to 85% by weight) The antireflective material as described in 1 or 2.
[25] The ratio of the alicyclic epoxy compound to the total amount (100% by weight) of the epoxy compound contained in the curable epoxy resin composition is 40 to 100% by weight (eg, 40 to 90% by weight) (preferably 80) The antireflective material according to any one of the above [18] to [24], which is 100 to 100% by weight, more preferably 90 to 100% by weight, and still more preferably 95 to 100% by weight.
[26] The curable epoxy resin composition further comprises a curing agent (D) and a curing accelerator (E), or a curing catalyst (F) (preferably a curing agent (D) and a curing accelerator (E) The antireflective material according to any one of the above [17] to [25], which comprises
[27] The curing agent (D) is an acid anhydride (acid anhydride curing agent), an amine (amine curing agent), a polyamide resin, an imidazole (imidazole curing agent), a polymercaptans (poly A mercaptan-based curing agent), at least one selected from the group consisting of phenols (phenol-based curing agent), polycarboxylic acids, dicyandiamides, and organic acid hydrazide (preferably, an acid anhydride-based curing agent); The antireflective material as described in [26].
[28] The acid anhydride curing agent is an acid anhydride which is liquid at 25 ° C., or a liquid mixture in which a solid acid anhydride is dissolved at 25 ° C. in an acid anhydride which is liquid. The antireflective material as described in the above [27].
[29] The content (blending amount) of the curing agent (D) is 50 to 200 parts by weight (preferably 75 to 150 parts by weight) with respect to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition The antireflective material according to any one of the above [26] to [28], which is part (more preferably 100 to 120 parts by weight).
[30] The content (blending amount) of the curing accelerator (E) is 0.05 to 5 parts by weight (preferably 0) with respect to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition. 1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, still more preferably 0.25 to 2.5 parts by weight), according to any one of the above [26] to [29] Anti-reflective material.
[31] The antireflective material according to any one of the above [17] to [30], wherein the curable epoxy resin composition contains a polyhydric alcohol (preferably an alkylene glycol having 2 to 4 carbon atoms).
[32] The content (blending amount) of the polyhydric alcohol is preferably 0.05 to 5 parts by weight (preferably 0.1 to 10 parts by weight) with respect to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition. The antireflective material according to the above [31], which is 3 parts by weight, more preferably 0.2 to 3 parts by weight, and still more preferably 0.25 to 2.5 parts by weight.
[33] The antireflective material according to any one of the above [1] to [32], wherein the curable epoxy resin composition contains a phosphor.
[34] The reflection according to the above [33], wherein the content (blending amount) of the phosphor is 0.5 to 20% by weight with respect to the total amount (100% by weight) of the curable epoxy resin composition Prevention material.

[35] The above-mentioned [3], wherein the arithmetic mean surface roughness Ra of the concavo-convex shape formed on the anti-reflection material is in the range of 0.1 to 1.0 μm (preferably in the range of 0.2 to 0.8 μm) The antireflective material as described in any one of 1]-[34].
[36] The antireflective material according to any one of the above [1] to [35], which is for encapsulating an optical semiconductor.
[37] An optical semiconductor device in which the optical semiconductor element is sealed with the antireflective material according to the above [36].

[38] A resin composition in which a hydrophobic porous inorganic filler is dispersed, which is used for the production of the antireflective material according to any one of the above [1] to [36].
[39] The resin composition according to [38], which is liquid.
[40] The resin composition according to the above [38] or [39], wherein the amount of the component that volatilizes during curing relative to the total amount (100% by weight) of the resin composition is 10% by weight or less.
[41] A method for producing an antireflective member, wherein the resin composition according to any one of the above [38] to [40] is cured, and the surface is provided with irregularities for suppressing reflection.

  The antireflective material of the present invention is suitable as a resin (used for forming an optical material) for an optical material because it has high heat resistance, particularly high heat resistance, in addition to high transparency and excellent antireflective function. It can be used for Examples of the optical member include a member that exhibits various optical functions such as light diffusivity, light transparency, and light reflectivity, and a member that constitutes an apparatus or device using the above optical function, and is particularly limited. For example, optical semiconductor devices, organic EL devices, adhesives, electrical insulation materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical Examples thereof include known or commonly used optical members used in various applications such as lenses, optical molding, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, optical pickup sensors and the like.

100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor device 103: Bonding wire 104: Sealing material (antireflection material)

Claims (13)

  What is claimed is: 1. An antireflective member comprising: a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein the surface of the cured product is provided with irregularities to suppress reflection.   The antireflective material according to claim 1, wherein the hydrophobic porous inorganic filler is uniformly dispersed over the entire cured product, and the surface has irregularities to suppress reflection. The hydrophobic porous inorganic filler is obtained by treating the surface of a porous inorganic filler with a hydrophobic treatment, and the specific surface area of the porous inorganic filler before the hydrophobic treatment is 200 m ² / g or more. The antireflective material as described in 2.   The antireflection material according to any one of claims 1 to 3, wherein an average particle diameter of the hydrophobic porous inorganic filler is 1 μm to 20 μm.   The antireflective material according to any one of claims 1 to 4, wherein the content of the hydrophobic porous inorganic filler is 4 to 40 wt% with respect to the total amount (100 wt%) of the antireflective material.   The antireflective material according to any one of claims 1 to 5, wherein the resin composition is made of a transparent curable resin composition.   The antireflective material according to claim 6, wherein the curable resin composition comprises a composition containing an epoxy resin.   The antireflective material according to any one of claims 1 to 7, which is for sealing an optical semiconductor.   The optical semiconductor device by which the optical semiconductor element was sealed by the anti-reflective material of Claim 8.   A resin composition having a hydrophobic porous inorganic filler dispersed therein, which is used for the production of the antireflective material according to any one of claims 1 to 8.   The resin composition according to claim 10, which is liquid.   The resin composition according to claim 10 or 11, wherein the amount of the component that volatilizes during curing to the total amount (100% by weight) of the resin composition is 10% by weight or less.   A method for producing an antireflective member, comprising: a surface on which a surface asperity for suppressing reflection is formed, wherein the resin composition according to any one of claims 10 to 12 is cured.

Images