JP7481802B2 - Anti-reflective material - Google Patents

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 encapsulated with 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. This application claims priority from Japanese Patent Application No. 2016-200397, filed in Japan on October 11, 2016, the contents of which are incorporated herein by reference.

In recent years, light-emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources have been increasingly adopted for various indoor or outdoor display boards, traffic signals, large display units, etc. As such optical semiconductor devices, optical semiconductor devices in which optical semiconductor elements are mounted on a substrate (substrate for mounting optical semiconductor elements) and the optical semiconductor elements are further encapsulated with a transparent encapsulant are generally in widespread use. The encapsulant in such optical semiconductor devices has an anti-reflection treatment applied to its surface in order to prevent a decrease in visibility due to total reflection of incident light such as external illumination light or sunlight.
Conventionally, as a method for imparting an anti-reflection function to the surface of a resin layer, a method is known in which incident light is scattered by dispersing inorganic fillers such as glass beads and silica in the resin (see, for example, Patent Document 1).

Patent Publication 2007-234767

However, when the method of Patent Document 1 is applied to a resin for sealing optical semiconductors, it has been found to be difficult to ensure the total luminous flux of the light source while providing sufficient anti-reflection function. In other words, it has been revealed that there is a trade-off between the fact that when a necessary and sufficient amount of inorganic filler is blended to obtain sufficient anti-reflection function, the total luminous flux of the light source is significantly reduced, and when the amount of inorganic filler is reduced to prevent the reduction in the total luminous flux of the light source, sufficient anti-reflection performance cannot be obtained.

In addition, in recent years, optical semiconductor devices have become increasingly powerful, and the encapsulating materials used in such optical semiconductor devices are required to have durability, such as high heat resistance (especially hot water resistance; hereafter, when simply referring to "heat resistance," this is also intended to include "hot water resistance").

Therefore, an object of the present invention is to provide an antireflection material which has sufficient antireflection function, is capable of preventing a decrease in the total luminous flux of a light source, and has high heat resistance, particularly hot water resistance.
Another object of the present invention is to provide the above antireflection material for use in encapsulating optical semiconductor devices.
It is still another object of the present invention to provide an optical semiconductor device in which an optical semiconductor element is encapsulated with the above-mentioned antireflection 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.

The inventors have discovered that one of the reasons why sufficient anti-reflection performance cannot be obtained when the amount of inorganic filler is reduced is that the inorganic filler settles and does not spread throughout the entire resin layer, and as a result, uniform unevenness is not formed over the entire surface, and incident light is not scattered efficiently. On the other hand, when the amount is increased so that anti-reflection performance can be obtained over the entire resin layer surface even if the inorganic filler settles, the inorganic filler itself absorbs light, resulting in a significant decrease in total luminous flux.
As a result of intensive research to solve the above problems, the present inventors found that when a hydrophobic porous inorganic filler was blended as a filler in the resin layer constituting the antireflective material, a sufficient antireflective function was imparted even with a small amount of addition, and furthermore, the antireflective material had high heat resistance. As a result, an antireflective material having both sufficient antireflective function and excellent heat resistance without significantly reducing the total luminous flux of the light source was provided, and it was found to be extremely suitable as a material for sealing an optical semiconductor element in an optical semiconductor device, leading to the completion of the present invention.

That is, the present invention provides an antireflective material comprising a cured resin composition having a hydrophobic porous inorganic filler dispersed therein, characterized in that the surface of the cured material has irregularities formed thereon to suppress reflection.

In the anti-reflective material, the hydrophobic porous inorganic filler is preferably uniformly dispersed throughout the cured material, forming irregularities on the surface that suppress reflection.

In the antireflection material, the hydrophobic porous inorganic filler may be a porous inorganic filler whose surface has been subjected to a hydrophobic treatment, and the specific surface area of the porous inorganic filler before the hydrophobic treatment may be 200 m ² /g or more.

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 relative to the total amount of the antireflective material (100% by weight) may be 4 to 40% by weight.

In the anti-reflective material, the resin composition may be a transparent curable resin composition.

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

The anti-reflective material may be used for sealing optical semiconductors.

The present invention also provides an optical semiconductor device in which an optical semiconductor element is encapsulated with the anti-reflective material.

The present invention also provides a resin composition having a dispersed hydrophobic porous inorganic filler, which is characterized by being used for producing the antireflective material.

The resin composition may be in liquid form.

The amount of components that volatilize during curing relative to the total amount (100% by weight) of the resin composition may be 10% by weight or less.

The present invention also provides a method for producing an anti-reflective material having a surface with irregularities that suppress reflection, characterized by curing the resin composition.

Since the antireflection material of the present invention has the above-mentioned constitution, even if the blending amount of the hydrophobic porous inorganic filler is reduced, sufficient antireflection function is obtained, and a significant decrease in the total luminous flux of the light source can be prevented, and the antireflection material of the present invention also has excellent heat resistance, particularly hot water resistance. Therefore, by using the antireflection material of the present invention as a material for sealing the optical semiconductor element in an optical semiconductor device, a high-quality optical semiconductor device (e.g., sufficient brightness while suppressing gloss and having high durability) can be obtained.
Furthermore, since the resin composition of the present invention has the above-mentioned configuration, it is extremely suitable for producing the above-mentioned antireflective material.

1 is a schematic diagram showing one embodiment of an optical semiconductor device including an antireflection material of the present invention, in which (a) on the left side is a perspective view and (b) on the right side 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 is characterized in that the hydrophobic porous inorganic filler forms irregularities on the surface of the cured product that suppress reflection.
The resin composition of the present invention is characterized in that it contains a hydrophobic porous inorganic filler dispersed therein, and is used for producing the above-mentioned antireflection material.

The porous structure of the hydrophobic porous inorganic filler increases the apparent volume of the resin composition compared to a non-porous filler, so that even a small amount of the filler can be added to spread throughout the resin composition or its cured product, and uniformly dispersed, forming uniform and fine irregularities on the surface of the cured product. In addition, the resin composition is permeated into the porous structure, and the apparent specific gravity difference between the hydrophobic porous inorganic filler and the resin composition is reduced, so that the dispersion state becomes stable, and the interaction between the surfaces of the hydrophobic porous inorganic filler is suppressed, making it difficult to aggregate, and the hydrophobic porous inorganic filler can be uniformly spread throughout the resin composition or its cured product, so that uniform and fine irregularities can be formed on the surface of the cured product to efficiently scatter incident light.
Furthermore, since the hydrophobic porous inorganic filler has a hydrophobic surface, a cured product containing the filler exhibits high heat resistance and is resistant to deterioration even under harsh heating conditions such as boiling water, and has excellent durability.
In this specification, the addition amount (amount used) of the hydrophobic porous inorganic filler being small (low) means that it is small in terms of weight, and does not mean that it is small in terms of capacity (volume).

When a hydrophobic porous inorganic filler is used, reflection can be effectively suppressed even if a smaller amount is used compared to a non-porous filler, so that a sufficient anti-reflection function can be ensured while suppressing a significant decrease in total luminous flux due to light absorption by the hydrophobic porous inorganic filler itself.
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 its cured product, and as a result of the stable dispersion state, the hydrophobic porous inorganic filler present on the surface of the cured product functions to form irregularities for scattering incident light.

The hydrophobic porous inorganic filler that can be used in the antireflective material or resin composition of the present invention means an inorganic filler that has an apparent specific gravity smaller than the true specific gravity of the filler, has a porous structure inside, and has a hydrophobic surface.

The porous inorganic filler constituting the hydrophobic porous inorganic filler (porous inorganic filler before the surface is hydrophobically treated) may be any known or conventional material, and is not particularly limited. Examples of such materials include inorganic glass (e.g., borosilicate glass, borosilicate soda glass, silicate soda glass, aluminum silicate glass, quartz, etc.), silica, alumina, zircon iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, fosterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline cystine, cristobalite, wollastonite, diatomaceous earth, talc, and other powders having a porous structure, or molded bodies thereof (e.g., spherical beads, etc.).

The hydrophobic porous inorganic filler is a porous inorganic filler before the hydrophobic treatment described above that has been subjected to a surface treatment with a known or conventional hydrophobic surface treatment agent [e.g., hydrophobic surface treatment agents such as metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols, and organosilicon compounds]. By subjecting the filler to such a hydrophobic surface treatment, 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 compatibility and dispersibility with the components of the resin composition and improving the heat resistance of the cured product, the hydrophobic surface treatment agent is preferably an organosilicon compound (e.g., trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, silicone oil, etc.), and more preferably polydimethylsiloxane, etc.
Among these, the hydrophobic porous inorganic filler is preferably hydrophobic porous inorganic glass or hydrophobic porous silica (hydrophobic porous silica filler) from the viewpoints of being able to disperse uniformly throughout the resin composition or the cured product thereof, efficiently forming irregularities on the surface of the cured product, and exhibiting excellent heat resistance.

The hydrophobic porous silica is not particularly limited, and examples of the hydrophobic porous silica that can be used include known or conventional porous silica such as fused silica, crystalline silica, high-purity synthetic silica, and colloidal silica that have been treated with the above-mentioned hydrophobic surface treatment agent.

In addition, examples of hydrophobic porous inorganic fillers that can be used include hydrophobic porous inorganic-organic fillers that are composed of a hybrid material of an inorganic substance constituting the above-mentioned hydrophobic porous inorganic filler and an organic substance such as a polymer, such as a styrene-based resin, an acrylic-based resin, a silicone-based resin, an acrylic-styrene-based resin, a vinyl chloride-based resin, a vinylidene chloride-based resin, an amide-based resin, a urethane-based resin, a phenol-based resin, a styrene-conjugated diene-based resin, an acrylic-conjugated diene-based resin, an olefin-based resin, or a cellulose resin.

The hydrophobic porous inorganic filler may be composed of a single material or two or more materials. Among them, hydrophobic porous inorganic fillers are more preferably hydrophobic porous silica (hydrophobic porous silica filler) from the viewpoints of being uniformly dispersed throughout the resin composition or its cured product, being able to efficiently form irregularities on the surface of the cured product, having high heat resistance, and being easily available and easy to manufacture.

The shape of the hydrophobic porous inorganic filler is not particularly limited, but examples include powder, spheres, crushed, fibrous, needle-like, and scaly shapes. Among these, spherical or crushed hydrophobic porous inorganic fillers are preferred, from the viewpoint that the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or its cured product, making it easier to form a uniform and fine uneven shape on the surface of the cured product.

The average particle size (median particle size) of the hydrophobic porous inorganic filler is not particularly limited, but is preferably 1 to 20 μm, more preferably 2 to 15 μm, from the viewpoint that the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or its cured product, and it becomes easy to form a uniform and fine uneven shape on the surface of the cured product. Note that the above average particle size (median particle size) means the volume particle size (median volume diameter) at an integrated value of 50% in the particle size distribution measured by a laser diffraction/scattering method.

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

The specific surface area of the porous inorganic filler (porous inorganic filler before the surface is hydrophobically treated) constituting the hydrophobic porous inorganic filler is not particularly limited, but from the viewpoint that the hydrophobic porous inorganic filler spreads and disperses uniformly throughout the resin composition or its cured product, and easily forms a uniform and fine uneven shape on the surface of the cured product, and efficiently prevents reflection, it is preferably 200 m ² /g or more, more preferably 200 to 2000 m ² /g, even more preferably 200 to 1500 m ² /g, and particularly preferably 200 to 1000 m ² /g. If the specific surface area is 200 m ² /g or more, the hydrophobic porous inorganic filler spreads and disperses uniformly throughout the resin composition or its cured product, and the anti-reflection function of the surface of the cured product tends to be improved. On the other hand, by having a specific surface area of 2000 m ² /g or less, the viscosity increase and thixotropy of the resin composition containing the hydrophobic porous inorganic filler are suppressed, and the flowability when manufacturing the anti-reflective material tends to be ensured. The specific surface area refers to the nitrogen adsorption specific surface area of the porous inorganic filler before the surface is subjected to hydrophobic treatment, which is determined based on the BET equation from the nitrogen adsorption isotherm at −196° C. in accordance with JIS K6430, Appendix E.

The oil absorption of the hydrophobic porous inorganic filler is not particularly limited, but is preferably 10 to 2000 mL/100 g, more preferably 100 to 1000 mL/100 g, from the viewpoint that the hydrophobic porous inorganic filler spreads and disperses uniformly throughout the resin composition or its cured product, making it easier to form a uniform and fine uneven shape on the surface of the cured product, and efficiently preventing reflection. If the oil absorption is 10 mL/100 g or more, the hydrophobic porous inorganic filler spreads and disperses uniformly throughout the resin composition or its cured product, making it easier to form an uneven shape on the surface of the cured product. On the other hand, if the oil absorption is 2000 mL/100 g or less, the mechanical strength of the hydrophobic porous inorganic filler tends to be improved. The oil supply amount of the hydrophobic porous inorganic filler is the amount of oil absorbed by 100 g of filler, and can be measured in accordance with JIS K5101.

In the anti-reflective material or resin composition of the present invention, the hydrophobic porous inorganic filler may be used alone or in combination of two or more. The hydrophobic porous inorganic filler may be manufactured by a known or conventional manufacturing method, or may be a commercially available product such as the Silo Hobic series (product names: Silo Hobic 702, Silo Hobic 4004, Silo Hobic 505, Silo Hobic 100, Silo Hobic 200, Silo Hobic 704, Silo Hobic 507, Silo Hobic 603) (all manufactured by Fuji Silysia Chemical Co., Ltd.), the Aerosil series (product names: Aerosil RX200, Aerosil RX300) (all manufactured by Evonik Degussa), and the Sunsphere ET series (product names: Sunsphere H-121-ET, Sunsphere H-51-ET) (all manufactured by AGC Si-Tech Co., Ltd.).

The content (mixture 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 4 to 40% by weight, more preferably 4 to 35% by weight, and even more preferably 4 to 30% by weight, based on the total amount (100% by weight) of the antireflective material or resin composition. 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 entire resin composition or the cured product constituting the antireflective material, making it easier to form a uniform uneven shape over the entire surface of the cured product. On the other hand, when the content of the hydrophobic porous inorganic filler is 40% by weight or less, there is a tendency that a significant decrease in total luminous flux is prevented and sufficient illuminance can be ensured when the antireflective material or resin composition of the present invention is used, for example, as an encapsulant for an optical semiconductor device.

The content (mixture amount) of the hydrophobic porous inorganic filler in the antireflective material or resin composition of the present invention is usually 5 to 80 parts by weight, preferably 5 to 70 parts by weight, and more preferably 5 to 60 parts by weight, relative to the resin composition (100 parts by weight) constituting the antireflective material. 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 entire cured product thereof, making it easier to form a uniform uneven shape over the entire surface of the cured product. 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 as, for example, an encapsulant for an optical semiconductor device, there is a tendency that a significant decrease in total luminous flux is prevented and sufficient illuminance can be ensured.

[Resin composition]
The resin composition constituting the cured product in the antireflective material of the present invention is not particularly limited, but a resin composition suitable as an encapsulant for an optical semiconductor element in an optical semiconductor device, i.e., a resin composition for encapsulating an optical semiconductor, can be preferably used. For example, a curable resin composition that is cured by heat or light to give a cured product that has high transparency and excellent durability (e.g., the property that transparency is not easily reduced even when heated, the property that cracks or peeling from the adherend is not easily caused even when high-temperature heat or thermal shock is applied, etc.) can be preferably used.

As such a curable resin composition, known or commonly used resin compositions having thermosetting or photosetting properties can be used without any particular limitation. For example, a composition containing at least one curable compound selected from the group consisting of an epoxy resin (epoxy compound) (referred to as "epoxy resin (A)"), a silicone resin (silicone compound) (referred to as "silicone resin (B)"), and an acrylic resin (acrylic compound) (referred to as "acrylic resin (C)") is preferable. Examples of such a curable resin composition include a composition containing an epoxy resin (A) (curable epoxy resin composition), a composition containing a silicone resin (B) (curable silicone resin composition), and a composition containing an acrylic resin (C) (curable acrylic resin composition). Hereinafter, the curable resin composition of these aspects will be described. However, the curable resin composition of the present invention is not limited to the composition of the following aspects.
Furthermore, the antireflection material of the present invention is not limited to use as a resin composition for sealing optical semiconductors, but can also be applied to, for example, various optical members described below, and can also be applied to resins suitable for each application (for example, polyolefin resins, polyester resins, polyamide resins, polyurethane resins, etc.).
As the resin composition constituting the cured product in the antireflective material of the present invention, a curable epoxy resin composition, a curable silicone resin composition, or a curable acrylic resin composition, each of which has excellent heat resistance, transparency, durability, etc., is preferred, and 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 contains 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 containing an epoxy resin (A), a curing agent (D), and a curing accelerator (E) as essential components, or a composition containing an epoxy resin (A) and a curing catalyst (F) as essential components. The curable epoxy resin composition of the present invention may contain other components in addition to 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 rings) in the molecule, and can be arbitrarily selected from known or commonly used epoxy compounds. Examples of the epoxy resin (A) include aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), alicyclic epoxy compounds (alicyclic epoxy resins), heterocyclic epoxy compounds (heterocyclic epoxy resins), and siloxane derivatives having one or more epoxy groups in the molecule.

Examples of the aromatic epoxy compounds include aromatic glycidyl ether epoxy resins (e.g., bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenol type epoxy resins, novolac type epoxy resins (e.g., phenol novolac type epoxy resins, cresol novolac type epoxy resins, cresol novolac type epoxy resins of bisphenol A), naphthalene type epoxy resins, epoxy resins derived from trisphenolmethane, etc.).

Examples of the aliphatic epoxy compounds include aliphatic glycidyl ether-based epoxy compounds [e.g., aliphatic polyglycidyl ethers, etc.].

The alicyclic epoxy compound is a compound having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more epoxy groups in the molecule (however, the above-mentioned siloxane derivatives having one or more epoxy groups in the molecule are excluded). Examples of the alicyclic epoxy compound include (i) a compound having at least one (preferably two or more) alicyclic epoxy group (an epoxy group consisting of two adjacent carbon atoms and an oxygen atom that constitute an alicyclic ring) in the molecule; (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, etc.

The alicyclic epoxy group of the compound having at least one alicyclic epoxy group in the molecule (i) is not particularly limited, but from the viewpoint of curability, a cyclohexene oxide group (an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting a cyclohexane ring) is preferable. In particular, from the viewpoint of transparency and heat resistance of the cured product, a compound having two or more cyclohexene oxide groups in the molecule is preferable as the compound having at least one alicyclic epoxy group in the molecule (i), and more preferably a compound represented by the 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 some or all of the carbon-carbon double bonds have been epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and groups in which multiple of these are linked together. In addition, a substituent such as an alkyl group may be bonded to one or more of the carbon atoms constituting the alicyclic ring (alicyclic epoxy group) in formula (1).

An example of a compound in which X in formula (1) is a single bond is (3,4,3',4'-diepoxy)bicyclohexyl.

Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups. Examples of the linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Examples of the divalent alicyclic hydrocarbon group include divalent cycloalkylene groups (including cycloalkylidene groups) such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene.

Examples of the alkenylene group in the alkenylene group in which some or all of the carbon-carbon double bonds have been epoxidized (sometimes referred to as "epoxidized alkenylene group") include linear or branched alkenylene groups (including alkapolyenylene groups) having 2 to 8 carbon atoms, such as vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, and octenylene group. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds have been epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds have been epoxidized.

As the linking group X, in particular, a linking group containing an oxygen atom is preferred, and specific examples include -CO-, -O-CO-O-, -COO-, -O-, -CONH-, an epoxidized alkenylene group; a group in which a plurality of these groups are linked; and a group in which one or more of these groups are linked to one or more divalent hydrocarbon groups. Examples of divalent hydrocarbon groups include those exemplified above.

Representative examples of the compound represented by the above formula (1) include 2,2-bis(3,4-epoxycyclohexyl-1-yl)propane, bis(3,4-epoxycyclohexylmethyl)ether, 1,2-bis(3,4-epoxycyclohexyl-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexyl-1-yl)ethane, and compounds represented by the following formulas (1-1) to (1-10). In the following formulas (1-5) and (1-7), l and m each represent an integer of 1 to 30. In the following formula (1-5), R is an alkylene group having 1 to 8 carbon atoms, and examples of such linear or branched alkylene groups include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, an s-butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Among these, linear or branched alkylene groups having 1 to 3 carbon atoms, such as a methylene group, an ethylene group, a propylene group, an isopropylene group, etc., are preferred. In the following formulas (1-9) and (1-10), n1 to n6 each represent an integer of 1 to 30.

Examples of the above-mentioned (ii) compound having an epoxy group directly bonded to an alicyclic ring via a single bond include compounds represented by the following formula (2).

In 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 p-valent alcohols [R'(OH) _p ] include polyhydric alcohols (alcohols having 1 to 15 carbon atoms, etc.) such as 2,2-bis(hydroxymethyl)-1-butanol. p is preferably 1 to 6, and q is preferably 1 to 30. When p is 2 or more, the qs in the groups in ( ) (in the outer parentheses) may be the same or different. Specific examples of the compound represented by formula (2) include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol [for example, trade name "EHPE3150" (manufactured by Daicel Corporation)], etc.

Examples of the above-mentioned (iii) compounds having an alicyclic ring and a glycidyl group include, 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 type epoxy resin (hydrogenated bisphenol A type epoxy resin), etc.; bis[2-(2,3-epoxypropoxy)cyclohexyl]methane, [2-(2,3-epoxypropoxy)cyclohexyl][4-(2,3-epoxypropoxy)cyclohexyl]methane, bis[4-(2,3-epoxy [0036] Examples of such epoxy resins include hydrogenated bisphenol F type epoxy resins (hydrogenated bisphenol F type epoxy resins), bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane, bisphenol F type epoxy resins, and the like; hydrogenated biphenol type epoxy resins; hydrogenated novolac type epoxy resins (e.g., hydrogenated phenol novolac type epoxy resins, hydrogenated cresol novolac type epoxy resins, hydrogenated cresol novolac type epoxy resins of bisphenol A, and the like); hydrogenated naphthalene type epoxy resins; and hydrogenated epoxy resins of epoxy resins obtained from trisphenolmethane.

Other examples of the alicyclic epoxy compounds include 1,2,8,9-diepoxylimonene.

Examples of the heterocyclic epoxy compounds include compounds having a heterocycle other than an epoxy group (oxirane ring) in the molecule [for example, non-aromatic heterocycles such as a tetrahydrofuran ring, tetrahydropyran ring, morpholine ring, chroman ring, isochroman ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, aziridine ring, pyrrolidine ring, piperidine ring, piperazine ring, indoline ring, 2,6-dioxabicyclo[3.3.0]octane ring, 1,3,5-triazacyclohexane ring, and 1,3,5-triazacyclohexa-2,4,6-trione ring (isocyanuric ring); aromatic heterocycles such as a thiophene ring, pyrrole ring, furan ring, and pyridine ring] and an epoxy group.

As the heterocyclic epoxy compound, for example, an 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 in the molecule of the epoxy group-containing isocyanurate is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.

Examples of the above-mentioned epoxy group-containing isocyanurate include compounds represented by the following formula (3).

In formula (3), R ^X , R ^Y , and R ^Z (R ^X to R ^Z ) are the same or different and each represents a hydrogen atom or a monovalent organic group. However, at least one of R ^X to R ^Z is a monovalent organic group containing an epoxy group. Examples of the monovalent organic group include monovalent aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups, etc.); monovalent aromatic hydrocarbon groups (e.g., aryl groups, etc.); monovalent heterocyclic groups; and monovalent groups formed by combining two or more of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The monovalent organic group may have a substituent (e.g., a substituent such as a hydroxy group, a carboxy group, or a halogen atom). Examples of the monovalent organic group containing an epoxy group include monovalent groups containing an epoxy group described below, such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group, and a cyclohexene oxide group.

More specifically, examples of the epoxy group-containing isocyanurate include a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3).

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 and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and octyl. Of these, linear or branched alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and isopropyl are preferred. It is particularly preferred that R ¹ and R ² in the above formulas (3-1) to (3-3) are hydrogen atoms.

Representative examples of compounds 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-methylpropenyl)-3,5-bis(2-methylepoxypropyl) isocyanurate, etc.

Representative examples of compounds 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-methylepoxypropyl) isocyanurate, etc.

Representative examples of compounds represented by the above formula (3-3) include triglycidyl isocyanurate, tris(2-methylepoxypropyl) isocyanurate, etc.

The epoxy group-containing isocyanurate may be modified in advance by adding a compound that reacts with the epoxy group, such as an alcohol or an acid anhydride.

The above-mentioned siloxane derivatives having one or more epoxy groups in the molecule (sometimes referred to as "epoxy group-containing siloxane derivatives") are compounds having a siloxane skeleton formed by siloxane bonds (Si-O-Si) in the molecule and having one or more epoxy groups. Examples of the above-mentioned siloxane skeletons include cyclic siloxane skeletons; linear or branched silicones (linear or branched polysiloxanes), and polysiloxane skeletons such as cage-type or ladder-type polysilsesquioxanes. The number of epoxy groups that the above-mentioned epoxy group-containing siloxane derivatives have in the molecule is not particularly limited, but is preferably 2 to 4, and more preferably 3 or 4.

The epoxy groups contained in the epoxy group-containing siloxane derivative are not particularly limited, but it is preferable that at least one of the epoxy groups is an alicyclic epoxy group, and it is particularly preferable that at least one of the epoxy groups is a cyclohexene oxide group, in order to efficiently cure the curable epoxy resin composition and to obtain a cured product with superior strength.

Examples of the above-mentioned epoxy group-containing siloxane derivatives include compounds (cyclic siloxanes) represented by the following formula (4):

In the above formula (4), R ³ may be the same or different and represents an alkyl group or a monovalent organic group containing an epoxy group. However, at least one (preferably at least two) of the R ³ in the compound represented by formula (4) is a monovalent organic group containing an epoxy group (particularly, a monovalent organic group containing an alicyclic epoxy group). Furthermore, p in formula (4) represents an integer of 3 or more (preferably an integer of 3 to 6). Note that multiple R ³ may be the same or different.

Examples of the monovalent organic group containing an epoxy group include an epoxy group, a glycidyl group, a methylglycidyl group, and a group represented by -A-R ⁴ [A represents an alkylene group, and R ⁴ represents an alicyclic epoxy group.]. Examples of A (alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms, such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of R ⁴ include a cyclohexene oxide group.

More specifically, examples of the epoxy group-containing siloxane derivatives 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]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, ]heptyl})ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,8-tri[2-(3-{oxabicyclo[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, the epoxy group-containing siloxane derivative may, for example, be a compound (chain polysiloxane) represented by the following formula (5).

In the above formula (5), R ⁵ and R ⁶ are the same or different and represent a monovalent organic group containing an epoxy group, an alkoxy group (e.g., an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group or an ethoxy group), an alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group), or an aryl group (e.g., an aryl group having 6 to 12 carbon atoms, such as a phenyl group or a naphthyl group). However, at least one (preferably at least two) of R ⁵ and R ⁶ in the compound represented by formula (5) is a monovalent organic group containing an epoxy group. Examples of the monovalent organic group containing an epoxy group include the same groups as those in the above formula (4). In particular, from the viewpoint of curability, it is preferable that either one or both of R ⁶ is a monovalent organic group containing an epoxy group. In addition, q in formula (5) represents an integer of 1 or more (e.g., an integer of 1 to 500). The structures in the parentheses to which q is added may be the same or different. When there are two or more types of structures in the parentheses with q, the addition form is not particularly limited, and may be a random type or a block type.

Other examples of the epoxy group-containing siloxane derivatives include silicone resins having epoxy groups (e.g., alicyclic epoxy group-containing silicone resins described in JP 2008-248169 A), silsesquioxanes having epoxy groups (e.g., organopolysilsesquioxane resins having at least two epoxy functional groups in one molecule described in JP 2008-19422 A), etc.

Among them, as the epoxy resin (A), bisphenol A type epoxy resin, isocyanurate having one or more epoxy groups in the molecule, novolac type epoxy resin, alicyclic epoxy compound, aliphatic epoxy compound, and siloxane derivative having one or more epoxy groups in the molecule are preferred, because they can more efficiently proceed the curing of the curable epoxy resin composition. In particular, the curable epoxy resin composition of the present invention preferably contains an alicyclic epoxy compound as an essential component as the epoxy resin (A), because they can produce a cured product having excellent transparency and durability with high productivity. As the alicyclic epoxy compound, in particular, a compound having a cyclohexene oxide group in the molecule (in particular, a compound having two or more cyclohexene oxide groups in the molecule) is preferred, and more preferably, a compound represented by formula (1) (in particular, a compound represented by formula (1-1)).

In the curable epoxy resin composition of the present invention, the epoxy resin (A) may be used alone or in combination of two or more kinds. The epoxy resin (A) may be produced by a known or conventional method, or a commercially available product may be used.

The content (amount) of epoxy resin (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 25 to 99.8% by weight (e.g., 25 to 95% by weight) relative to the total amount (100% by weight) of the curable epoxy resin composition, more preferably 30 to 90% by weight, even more preferably 35 to 85% by weight, and particularly preferably 40 to 60% by weight. By making the content of epoxy resin (A) 25% by weight or more, curing tends to proceed more efficiently. On the other hand, by making the content of epoxy resin (A) 99.8% by weight or less, the strength of the cured product tends to be further improved.

The content (amount) of the alicyclic epoxy compound in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 20 to 99.8% by weight, more preferably 40 to 95% by weight (e.g., 40 to 60% by weight), even more preferably 50 to 95% by weight, particularly preferably 60 to 90% by weight, and most preferably 70 to 85% by weight, based on the total amount (100% by weight) of the curable epoxy resin composition. By making the content of the alicyclic epoxy compound 20% by weight or more, curing can be promoted more efficiently, and the transparency and durability of the cured product tend to be improved. On the other hand, by making the content of the alicyclic epoxy compound 99.8% by weight or less, the strength of the cured product tends to be improved.

The ratio of the alicyclic epoxy compound to the total amount of epoxy compounds (total 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, but is preferably 40 to 100% by weight (for example, 40 to 90% by weight), more preferably 80 to 100% by weight, even more preferably 90 to 100% by weight, and particularly preferably 95 to 100% by weight. By making the ratio of the alicyclic epoxy compound 40% by weight or more, curing can be made to proceed 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 that has the function of curing the curable epoxy resin composition by reacting with an epoxy compound. The curing agent (D) is not particularly limited, and a well-known and conventional curing agent for epoxy resins can be used, such as acid anhydrides (acid anhydride curing agent), amines (amine curing agent), polyamide resins, imidazoles (imidazole curing agent), polymercaptans (polymercaptan curing agent), phenols (phenol curing agent), polycarboxylic acids, dicyandiamides, and organic acid hydrazides.

As the acid anhydride (acid anhydride-based curing agent) as the curing agent (D), known or conventional acid anhydride-based curing agents can be used, and are not particularly limited. For example, methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methyl-end methylene tetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, heptane anhydride, Examples of the acid anhydride include hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, 4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer, etc. Among them, from the viewpoint of handling, acid anhydrides that are liquid at 25° C. [e.g., methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl end methylene tetrahydrophthalic anhydride, etc.] are preferred. On the other hand, with regard to an acid anhydride that is solid at 25° C., for example, by dissolving it in an acid anhydride that is liquid at 25° C. to form a liquid mixture, the handling property as the curing agent (D) in the curable epoxy resin composition of the present invention tends to be improved. As the acid anhydride-based curing agent, from the viewpoint of heat resistance and transparency of the cured product, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those having a substituent such as an alkyl group bonded to the ring) are preferred.

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

As the phenol (phenol-based hardener) used as the hardener (D), known or conventional phenol-based hardeners can be used, and examples thereof include, but are not limited to, aralkyl resins such as novolac-type phenolic resins, novolac-type cresol resins, paraxylylene-modified phenolic resins, paraxylylene-metaxylylene-modified phenolic resins, terpene-modified phenolic resins, dicyclopentadiene-modified phenolic resins, and triphenolpropane.

Examples of polyamide resins as curing agents (D) include polyamide resins having either or both of a primary amino group and a secondary amino group in the molecule.

As the imidazoles (imidazole-based curing agents) as the curing agent (D), known or conventional imidazole-based curing agents can be used, and are not particularly limited. Examples of such curing agents include, but are not limited to, 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 ... ethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine, and the like.

Examples of polymercaptans (polymercaptan-based hardeners) as the hardener (D) include liquid polymercaptan, polysulfide resin, etc.

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

Among them, as the curing agent (D), acid anhydrides (acid anhydride-based curing agents) are preferred from the viewpoints of curability, heat resistance of the cured product, and transparency. In the curable epoxy resin composition of the present invention, the curing agent (D) may be used alone or in combination of two or more. In addition, commercially available products may be used as the curing agent (D). For example, commercially available acid anhydrides include those sold under the trade names "RIKACID MH-700" and "RIKACID MH-700F" (both manufactured by New Japan Chemical Co., Ltd.); and those sold under the trade name "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.).

The content (amount) of the curing agent (D) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 50 to 200 parts by weight, more preferably 75 to 150 parts by weight, and even more preferably 100 to 120 parts by weight, relative to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition (total epoxy compounds; for example, the total amount of epoxy resin (A)). More specifically, when an acid anhydride is used as the curing agent (D), it is preferable to use it in a ratio of 0.5 to 1.5 equivalents per equivalent of epoxy groups in all epoxy compounds contained in the curable epoxy resin composition of the present invention. By making the content of the curing agent (D) 50 parts by weight or more, curing can be promoted more efficiently, and the toughness of the cured product tends to be improved. On the other hand, by making the content of the curing agent (D) 200 parts by weight or less, it tends to be easy to obtain a cured product that is free of (or has little) coloring and has excellent color.

1-3. Curing accelerator (E)
The curing accelerator (E), which is one of the essential components of the curable epoxy resin composition of the present invention, is a compound having the function of accelerating the reaction rate of the reaction of epoxy compounds (particularly, the reaction between the epoxy resin (A) and the curing agent (D)). As the curing accelerator (E), a well-known and conventional curing accelerator for epoxy resins can be used, and is not particularly limited. Examples of the curing accelerator include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and salts thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate salt, formate salt, tetraphenylborate salt, etc.); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and salts thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate salt, formate salt, tetraphenylborate salt, etc.); tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphoric acid esters and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organic metal salts such as tin octoate and zinc octoate; and metal chelates.

In addition, in the curable epoxy resin composition of the present invention, the curing accelerator (E) may be used alone or in combination of two or more types.

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

The content (amount) of the curing accelerator (E) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, even more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight, relative to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition (total epoxy compounds; for example, the total amount of epoxy resin (A)). By making the content of the curing accelerator (E) 0.05 parts by weight or more, it tends to be possible to obtain a more sufficient curing acceleration effect. On the other hand, by making the content of the curing accelerator (E) 5 parts by weight or less, it tends to be possible to obtain a cured product that is free of (or has little) coloring and has excellent color.

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, initiates and/or accelerates the curing reaction (polymerization reaction) of a cationic polymerizable compound such as an epoxy compound, thereby forming a curable The curing catalyst (F) is a compound having a function of curing an epoxy resin composition. The curing catalyst (F) is not particularly limited, but examples thereof include cationic polymerization initiators (thermal cationic polymerization initiators) that generate cationic species by heat and initiate polymerization. initiator), Lewis acid-amine complexes, Bronsted acid salts, imidazoles, etc.

Specifically, examples of the curing catalyst (F) include aryl diazonium salts, aryl iodonium salts, aryl sulfonium salts, and allene ion complexes. Commercially available products that can be preferably used include those under the trade names "PP-33", "CP-66", and "CP-77" (all manufactured by ADEKA CORPORATION); "FC-509" (manufactured by 3M); "UVE1014" (manufactured by G.E.); "SAN-AID SI-60L", "SAN-AID SI-80L", "SAN-AID SI-100L", "SAN-AID SI-110L", and "SAN-AID SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.); and "CG-24-61" (manufactured by BASF). Further, examples of the curing catalyst (F) include compounds of a chelate compound of a metal such as aluminum or titanium with acetoacetic acid or a diketone and a silanol such as triphenylsilanol, and compounds of a chelate compound of a metal such as aluminum or titanium with acetoacetic acid or a diketone and a phenol such as bisphenol S.

As the Lewis acid-amine complex as the curing catalyst (F), a known or conventional Lewis acid-amine complex curing catalyst can be used, and examples thereof include, but are not limited to, _BF3.n -hexylamine, _{BF3.monoethylamine} , _{BF3.benzylamine} , _{BF3.diethylamine, BF3.piperidine, BF3.triethylamine, BF3.aniline, BF4.n - hexylamine , BF4.monoethylamine} , _{BF4.benzylamine , BF4.diethylamine} , _{BF4.piperidine} , BF4.triethylamine, BF4.aniline, _{PF5.ethylamine} , PF5.isopropylamine _{, PF5.butylamine , PF5.laurylamine , PF5.benzylamine} , _{AsF5.laurylamine} , and the like.

As the Brønsted acid salts used as the curing catalyst (F), known or conventional Brønsted acid salts can be used, and examples thereof include, but are not limited to, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphonium salts, etc.

As the imidazoles used as the curing catalyst (F), known or conventional imidazoles can be used, and are not particularly limited. Examples of such imidazoles include, but are not limited to, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2 -undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine, and the like.

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. As described above, for example, a commercially available product may be used as the curing catalyst (F).

The content (amount) of the curing catalyst (F) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, even more preferably 0.05 to 10 parts by weight, and particularly preferably 0.05 to 8 parts by weight, relative to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition (total epoxy compounds; for example, the total amount of epoxy resin (A)). By setting the content of the curing catalyst (F) to 0.01 parts by weight or more, there is a tendency that the curing reaction can be progressed more sufficiently. On the other hand, by setting the content of the curing catalyst (F) to 15 parts by weight or less, there is a tendency that a cured product with no (or little) coloring and excellent color tone is easily obtained. In other words, by controlling the content of the curing catalyst (F) within the above range, the curing speed of the curable epoxy resin composition is improved, and a cured product with an excellent balance of transparency and durability is easily obtained.

The curable epoxy resin composition of the present invention may substantially contain a cationic photopolymerization initiator that generates an initiating species (such as an acid) for cationic polymerization upon irradiation with light. When the curable epoxy resin composition of the present invention contains a cationic photopolymerization initiator, the content thereof is, 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 epoxy compounds contained in the curable epoxy resin composition (total epoxy compounds; for example, the total amount of epoxy resin (A)).

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 is preferable that the composition further contains a polyhydric alcohol, since the curing can proceed more efficiently. As the polyhydric alcohol, any known or commonly used polyhydric alcohol can be used, and examples thereof include, but are not limited to, 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 these, the polyhydric alcohol is preferably an alkylene glycol having 1 to 6 carbon atoms, more preferably an alkylene glycol having 2 to 4 carbon atoms, since the curing can be well controlled and a cured product that is less susceptible to cracking or peeling can be obtained.

In the curable epoxy resin composition of the present invention, the polyhydric alcohol may be used alone or in combination of two or more kinds.

The content (amount) of the polyhydric alcohol in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, even more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight, relative to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition (total epoxy compounds; for example, the total amount of epoxy resin (A)). By making the content of the polyhydric alcohol 0.05 parts by weight or more, there is a tendency for the curing to proceed more efficiently. On the other hand, by making the content of the polyhydric alcohol 5 parts by weight or less, there is a tendency for the reaction rate of the curing to be easily controlled.

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 can be particularly preferably used for sealing an optical semiconductor element in an optical semiconductor device (for sealing material use), that is, as an optical semiconductor sealing resin composition. The phosphor may be any known or conventional phosphor (particularly a phosphor used for sealing optical semiconductor elements), and may include, but is not limited to, _{YAG-based phosphor fine particles (e.g., Y3Al5O12 :} Ce phosphor _fine particles, (Y,Gd,Tb)3(Al,Ga)5O12:Ce phosphor fine particles, etc.) represented by the general formula A3B5O12:M [wherein A represents one or more elements selected from the group consisting of Y, Gd, Tb, La _, Lu, Se, and Sm, B represents one or more elements selected from the group consisting of Al, Ga, _and In, and M represents one or more elements selected from the group consisting of _Ce , _Pr , Eu, Cr _, Nd, and Er _] , silicate _- based phosphor fine particles (e.g., (Sr,Ca,Ba) _2SiO4 :Eu, etc.). The phosphor may be surface-modified with an organic group (e.g., a long-chain alkyl group, a phosphate group, etc.) to improve dispersibility. In the curable epoxy resin composition of the present invention, one type of phosphor may be used alone, or two or more types may be used in combination. Commercially available products may be used as the phosphor.

The content (mixture amount) of the phosphor in the curable epoxy resin composition of the present invention is not particularly limited and can be appropriately selected in the range of 0.5 to 20% by weight relative to the total amount (100% by weight) of the curable epoxy resin composition.

1-7. Other Components The curable epoxy resin composition of the present invention may contain other components other than those described above, as long as they do not have a significant adverse effect on the curability, transparency, etc. Examples of the other components include linear or branched silicone resins, alicyclic silicone resins, aromatic silicone resins, cage/ladder/random silsesquioxanes, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, silicone or fluorine-based defoamers, etc. The content (mixture amount) of the other components is not particularly limited, but is preferably 5% by weight or less (e.g., 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, but can be prepared, for example, by stirring and mixing the above-mentioned components in a heated state as necessary. The curable epoxy resin composition of the present invention may be a one-liquid composition in which all of the components are mixed in advance and used as is, or a multi-liquid (e.g., two-liquid) composition in which, for example, two or more divided components are mixed in a predetermined ratio just before use. The method of stirring and mixing is not particularly limited, and for example, known or conventional stirring and mixing means such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and self-revolving stirring devices can be used. After stirring and mixing, degassing may be performed under reduced pressure or vacuum.

2. Curable Silicone Resin Composition The above-mentioned curable silicone resin composition (sometimes referred to as the "curable silicone resin composition of the present invention") is a curable composition that contains a silicone resin (B) as a curable compound as an essential component. The curable silicone resin composition of the present invention may contain components other than the silicone resin (B).

Examples of the silicone resin (B) include curable polysiloxanes such as polyorganosiloxysilalkylenes containing, in addition to -Si-O-Si- (siloxane bond) as the main chain, -Si-R ^A -Si- (silalkylene bond: R ^A represents an alkylene group); and polyorganosiloxanes not containing the above-mentioned silalkylene bond as the main chain.

In addition, as the silicone resin (B), a known or commonly used curable silicone resin (curable polysiloxane) can be used as a curable compound, and is not particularly limited, but examples thereof include addition type (addition reaction curing type) silicone resin and condensation type (condensation reaction curing type) silicone resin. 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. Below, these addition reaction curable silicone resin compositions and condensation reaction curable silicone resin compositions will be explained, but the curable silicone resin composition of the present invention is not limited to these, and may be, for example, a silicone resin composition that contains both an addition type silicone resin and a condensation type silicone resin and is cured by an addition reaction and a condensation reaction. That is, the curing of the curable silicone resin composition in the above curing step may proceed by at least one reaction selected from the group consisting of an addition reaction and a condensation reaction.

2-1. Addition reaction curable silicone resin composition Examples of the addition reaction curable silicone resin composition include curable silicone resin compositions that contain, as the silicone resin (B), a polysiloxane (B1) having two or more alkenyl groups in the molecule, and, if necessary, further contain a polysiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule, a metal curing catalyst, etc.

The polysiloxane (B1) is classified into polyorganosiloxane (B1-1) and polyorganosiloxysilalkylene (B1-2). In this specification, polyorganosiloxysilalkylene (B1-2) is a polysiloxane having two or more alkenyl groups in the molecule and containing -Si-R ^A -Si- (silalkylene bond: R ^A represents an alkylene group) in addition to -Si-O-Si- (siloxane bond) as the main chain. And, polyorganosiloxane (B1-1) in this specification is a polysiloxane having two or more alkenyl groups in the molecule and not containing the above-mentioned silalkylene bond as the main chain.

Examples of polyorganosiloxanes (B1-1) include those having a linear or branched molecular structure (linear with some branches, branched, mesh-like, etc.). The polyorganosiloxanes (B1-1) can be used alone or in combination of two or more. Two or more polyorganosiloxanes (B1-1) having different molecular structures can be used in combination. For example, a linear polyorganosiloxane (B1-1) and a branched polyorganosiloxane (B1-1) can be used in combination.

The alkenyl group contained in the polyorganosiloxane (B1-1) molecule may be a substituted or unsubstituted alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, or a hexenyl group. Examples of the substituent include a halogen atom, a hydroxyl group, and a carboxyl group. Among these, the alkenyl group is preferably a vinyl group. The polyorganosiloxane (B1-1) may have only one type of alkenyl group, or may have two or more types of alkenyl groups. The alkenyl group contained in the polyorganosiloxane (B1-1) is not particularly limited, but is preferably bonded to a silicon atom.

The groups bonded to the silicon atoms other than the alkenyl groups in the polyorganosiloxane (B1-1) are not particularly limited, but examples thereof include hydrogen atoms, monovalent organic groups, etc. Examples of monovalent organic groups include monovalent substituted or unsubstituted hydrocarbon groups such as alkyl groups [e.g., methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, etc.], cycloalkyl groups [e.g., cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cyclododecyl groups, etc.], aryl groups [e.g., phenyl groups, tolyl groups, xylyl groups, naphthyl groups, etc.], cycloalkyl-alkyl groups [e.g., cyclohexylmethyl groups, methylcyclohexyl groups, etc.], aralkyl groups [e.g., benzyl groups, phenethyl groups, etc.], and halogenated hydrocarbon groups in which one or more hydrogen atoms in the hydrocarbon group are substituted with halogen atoms [e.g., halogenated alkyl groups such as chloromethyl groups, 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, etc.]. In this specification, the term "group bonded to a silicon atom" generally refers to a group that does not contain a silicon atom.

The silicon atom may also have a hydroxyl group or an alkoxy group bonded to it.

The properties of the polyorganosiloxane (B1-1) are not particularly limited and may be liquid or solid.

The polyorganosiloxane (B1-1) may be represented by the following average unit formula:
( ^R7SiO3/ ₂ ) _{a1 (} ^R72SiO2 / ₂ ⁾ _a2 (R73SiO1/ ₂ ) _a3 ( _{SiO4/2 ) a4} (ZO1 _/2 ) _a5
In the above average unit formula, R ⁷ is the same or different, and is a monovalent substituted or unsubstituted hydrocarbon group, and the above-mentioned specific examples (e.g., alkyl group, alkenyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.) can be mentioned. However, a part of R ⁷ is an alkenyl group (particularly a vinyl group), and the ratio is controlled to a range of 2 or more in the molecule. For example, the ratio of alkenyl groups to the total amount of R ⁷ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of alkenyl groups to the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R ⁷ other than the alkenyl group, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is 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 preferred.

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 number.

As described above, the polyorganosiloxysilalkylene (B1-2) is a polyorganosiloxane having two or more alkenyl groups in the molecule and containing a silalkylene bond in addition to a siloxane bond as the main chain. The alkylene group in the silalkylene bond is preferably a C _2-4 alkylene group (particularly an ethylene group). The polyorganosiloxysilalkylene (B1-2) is less likely to produce low molecular weight rings in the production process compared to the polyorganosiloxane (B1-1), and is also less likely to decompose by heating or the like to produce silanol groups (-SiOH). Therefore, when the polyorganosiloxysilalkylene (B1-2) is used, the surface adhesion (tackiness) of the cured product of the curable silicone resin composition is lowered, and it tends to be less likely to yellow.

Examples of polyorganosiloxysilalkylenes (B1-2) include those having a linear or branched molecular structure (linear with some branches, branched, mesh-like, etc.). The polyorganosiloxysilalkylenes (B1-2) can be used alone or in combination of two or more. For example, two or more polyorganosiloxysilalkylenes (B1-2) having different molecular structures can be used in combination, for example, linear polyorganosiloxysilalkylenes (B1-2) and branched polyorganosiloxysilalkylenes (B1-2) can be used in combination.

The alkenyl group contained in the polyorganosiloxysilalkylene (B1-2) molecule includes the specific examples mentioned above, with vinyl groups being preferred. The polyorganosiloxysilalkylene (B1-2) may have only one type of alkenyl group, or may have two or more types of alkenyl groups. The alkenyl group contained in the polyorganosiloxysilalkylene (B1-2) is not particularly limited, but is preferably bonded to a silicon atom.

The groups bonded to the silicon atoms other than the alkenyl groups in the polyorganosiloxysilalkylene (B1-2) are not particularly limited, but examples thereof include hydrogen atoms and monovalent organic groups. Examples of the monovalent organic groups include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups. Among these, alkyl groups (particularly methyl groups) and aryl groups (particularly phenyl groups) are preferred.

The silicon atom may also have a hydroxyl group or an alkoxy group bonded to it.

The properties of the polyorganosiloxysilalkylene (B1-2) are not particularly limited and may be liquid or solid.

The polyorganosiloxysilalkylene (B1-2) may have the following average unit formula:
( ^R82SiO2/ ₂ ⁾ _b1 ( ^R83SiO1 / ₂ ) _b2 ( _{R8SiO3/2 ) b3 ( SiO4/2} ) _b4 ( ^RA ) _b5 (ZO1 _/2 ) _b6
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 thereof include the above-mentioned (e.g., alkyl group, alkenyl group, aryl group, aralkyl group, halogenated alkyl group, etc.). However, a part of R ⁸ is an alkenyl group (particularly a vinyl group), and the ratio is controlled to a range of 2 or more in the molecule. For example, the ratio of alkenyl groups to the total amount of R ⁸ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of alkenyl groups to the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R ⁸ other than the alkenyl group, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferable.

In the above average unit formula, R ^A is an alkylene group as described above, and is particularly preferably an ethylene group.

In the above average unit formula, Z is, as above, 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 preferred.

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. Of these, 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.

As described above, the addition reaction curable silicone resin composition may further contain a polysiloxane having one or more (preferably two or more) hydrosilyl groups (Si-H) in the molecule (sometimes referred to as "hydrosilyl group-containing polysiloxane"). The hydrosilyl group-containing polysiloxane is classified into hydrosilyl group-containing polyorganosiloxane and hydrosilyl group-containing polyorganosiloxysilalkylene. In this specification, the hydrosilyl group-containing polyorganosiloxysilalkylene is a polysiloxane having one or more hydrosilyl groups in the molecule and containing -Si-R ^A -Si- (silalkylene bond: R ^A represents an alkylene group) in addition to -Si-O-Si- (siloxane bond) as the main chain. And, the hydrosilyl group-containing polyorganosiloxane in this specification is a polysiloxane having one or more hydrosilyl groups in the molecule and not containing the above-mentioned silalkylene bond as the main chain. As mentioned above, examples of R ^A (alkylene group) include linear or branched C _1-12 alkylene groups, and preferably linear or branched C _2-4 alkylene groups (particularly ethylene group).

The hydrosilyl group-containing polyorganosiloxane may have a molecular structure of a linear or branched chain (linear with some branches, branched chain, mesh-like, etc.). The hydrosilyl group-containing polyorganosiloxane may be used alone or in combination of two or more. Two or more hydrosilyl group-containing polyorganosiloxanes having different molecular structures may be used in combination, for example, a linear hydrosilyl group-containing polyorganosiloxane and a branched hydrosilyl group-containing polyorganosiloxane may be used in combination.

Among the groups bonded to silicon atoms in the hydrosilyl group-containing polyorganosiloxane, the groups other than hydrogen atoms are not particularly limited, but examples thereof include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups, more specifically, alkyl groups, aryl groups, aralkyl groups, halogenated hydrocarbon groups, etc. Among these, alkyl groups (particularly methyl groups) and aryl groups (particularly phenyl groups) are preferred. In addition, the hydrosilyl group-containing polyorganosiloxane may have an alkenyl group (e.g., 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. Of these, liquid is preferable, and a liquid having a viscosity of 0.1 to 1000000000 mPa·s at 25°C is more preferable.

The hydrosilyl group-containing polyorganosiloxane may be represented by the following average unit formula:
( ^R9SiO3 _/2 ) _c1 ( ^R92SiO2 / ₂ ) _c2 ( ^R93SiO1 _{/ 2} ) _c3 ( _{SiO4/2 ) c4} (ZO1 _/2 ) _c5
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 examples thereof include hydrogen atoms and the above-mentioned specific examples (e.g., alkyl groups, alkenyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, etc.). However, a part of R ⁹ is a hydrogen atom (hydrogen atoms constituting a hydrosilyl group), and the ratio is controlled to a range in which there is one or more (preferably two or more) hydrosilyl groups in the molecule. For example, the ratio of hydrogen atoms to the total amount (100 mol%) of R ⁹ is preferably 0.1 to 40 mol%. By controlling the ratio of hydrogen atoms to the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R ⁹ other than a hydrogen atom, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferable.

In the above average unit formula, Z is, as above, 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 preferred.

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 number.

As described above, the hydrosilyl group-containing polyorganosiloxysilalkylene is a polyorganosiloxane having one or more hydrosilyl groups in the molecule and containing a silalkylene bond in addition to a siloxane bond as the main chain. The alkylene group in the silalkylene bond is preferably, for example, a C _2-4 alkylene group (particularly, an ethylene group). The hydrosilyl group-containing polyorganosiloxysilalkylene is less likely to produce low molecular weight rings in the production process compared to the hydrosilyl group-containing polyorganosiloxane, and is less likely to decompose by heating or the like to produce silanol groups (-SiOH). Therefore, when the hydrosilyl group-containing polyorganosiloxysilalkylene is used, the surface adhesion of the cured product of the curable silicone resin composition is reduced and tends to be less likely to yellow.

The above hydrosilyl group-containing polyorganosiloxysil alkylenes include those having a linear or branched molecular structure (linear with some branches, branched, mesh-like, etc.). The above hydrosilyl group-containing polyorganosiloxysil alkylenes can be used alone or in combination of two or more. Two or more hydrosilyl group-containing polyorganosiloxysil alkylenes having different molecular structures can be used in combination, for example, a linear hydrosilyl group-containing polyorganosiloxysil alkylene and a branched hydrosilyl group-containing polyorganosiloxysil alkylene can be used in combination.

The groups bonded to the silicon atoms other than hydrogen atoms of the hydrosilyl group-containing polyorganosiloxysilalkylene are not particularly limited, but examples thereof include monovalent organic groups. Examples of monovalent organic groups include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups. Among these, alkyl groups (particularly methyl groups) and aryl groups (particularly phenyl groups) are preferred.

The properties of the above hydrosilyl group-containing polyorganosiloxysilalkylene are not particularly limited and may be liquid or solid.

The hydrosilyl group-containing polyorganosiloxysilalkylene has the following average unit formula:
( ^R102SiO2 _{/ 2 ) d1} ( ^R103SiO1 / ₂ ) _d2 (R10SiO3/ ₂ ) _d3 (SiO4 ^/ ₂ ) _d4 ( ^RA ) _d5 (ZO1 _/2 ) _d6
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 examples thereof include hydrogen atoms and the above-mentioned specific examples (e.g., alkyl groups, alkenyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, etc.). However, a part of R ¹⁰ is a hydrogen atom, and the ratio is controlled to a range of 1 or more (preferably 2 or more) in the molecule. For example, the ratio of hydrogen atoms to the total amount (100 mol%) of R ¹⁰ is preferably 0.1 to 50 mol%, more preferably 5 to 35 mol%. By controlling the ratio of hydrogen atoms to the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R ¹⁰ other than hydrogen atoms, alkyl groups (particularly methyl groups) and aryl groups (particularly phenyl groups) are preferred. In particular, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of R ¹⁰ is preferably 5 mol% or more (e.g., 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, and is particularly preferably an ethylene group.

In the above average unit formula, Z is, as above, 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 preferred.

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 the hydrosilyl group-containing polyorganosiloxane can be used, only the hydrosilyl group-containing polyorganosiloxysilalkylene can be used, or 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 polyorganosiloxysilalkylene are used in combination, the ratio of these is not particularly limited and can be set appropriately.

The addition reaction curable silicone resin composition is not particularly limited, but preferably has a composition (mixture) such that 0.2 to 4 moles of alkenyl groups are present per mole of hydrosilyl groups in the curable resin composition, more preferably 0.5 to 1.5 moles, and even more preferably 0.8 to 1.2 moles. By controlling the ratio of hydrosilyl groups to alkenyl groups within the above range, the heat resistance, transparency, thermal shock resistance, and reflow resistance of the cured product, as well as barrier properties against corrosive gases (such as SOx gas, etc.), tend to be improved.

The addition reaction curable silicone resin composition may contain a metal curing catalyst as described above. Examples of metal curing catalysts include well-known hydrosilylation reaction catalysts such as platinum catalysts, rhodium catalysts, and palladium catalysts. Specific examples include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum olefin complexes, platinum carbonyl complexes such as platinum-carbonylvinylmethyl complexes, platinum vinylmethylsiloxane complexes such as platinum-divinyltetramethyldisiloxane complexes and platinum-cyclovinylmethylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, and palladium catalysts or rhodium catalysts containing palladium atoms or rhodium atoms instead of platinum atoms in the platinum catalysts. Among these, as the hydrosilylation catalyst, platinum vinylmethylsiloxane complex, platinum carbonylvinylmethyl complex, and complexes of chloroplatinic acid with alcohols or aldehydes are preferred because of their favorable reaction rates.

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

The content (amount) of the metal curing catalyst (hydrosilylation catalyst) in the addition reaction curable silicone resin composition is not particularly limited, but is preferably 1×10 ^-8 to 1×10 ^-2 mol, more preferably 1.0×10 ^-6 to 1.0×10 ^-3 mol, per mol of the total amount of alkenyl groups contained in the addition reaction curable silicone resin composition. By making the content 1×10 ^-8 mol or more, it tends to be possible to form a cured product more efficiently. On the other hand, by making the content 1×10 ^-2 mol or less, it tends to be possible to obtain a cured product with better hue (less coloration).

The addition reaction curable silicone resin composition may contain other components.

2-2. Condensation reaction curable silicone resin composition The condensation reaction curable silicone resin composition includes, for example, a curable silicone resin composition containing a polysiloxane (B2) having two or more silanol groups (Si-OH) or silalkoxy groups (Si-OR) in the molecule as the silicone resin (B), and further containing a metal curing catalyst or the like as necessary. 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 both a silanol group and a silalkoxy group are present, the total number of these groups may be two or more in the molecule.

Examples of the polysiloxane (B2) include polyorganosiloxanes represented by the following average composition formula:
^R11eSi ( _OR12 ) _f ( ^OH ) _{gO (4-efg)/2}
[In the above average composition formula, R ¹¹ is the same or different and represents a monovalent organic group having 1 to 20 carbon atoms. R ¹² is the same or different and represents a monovalent organic group having 1 to 4 carbon atoms. e is a number from 0.8 to 1.5, f is a number from 0 to 0.3, and g is a number from 0 to 0.5. f+g is a number from 0.001 to less than 1.2. In addition, e+f+g is a number from 0.801 to less than 2.]

Examples of the monovalent organic group as R ¹¹ in the above average composition formula include monovalent aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups, etc.); monovalent aromatic hydrocarbon groups (e.g., aryl groups, etc.); monovalent heterocyclic groups; and monovalent groups formed by combining two or more of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. These monovalent organic groups may have a substituent (e.g., a hydroxyl group, a carboxyl group, a halogen atom, etc.). Among these, R ¹¹ is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Examples of the monovalent organic group as R ¹² in the above average composition formula include monovalent aliphatic hydrocarbon groups (e.g., alkyl groups, alkenyl groups, etc.) which may have a substituent. Among these, R ¹² is preferably an alkyl group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms.

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

The condensation reaction curable silicone resin composition may contain a metal curing catalyst as described above. Examples of such metal curing catalysts include known or conventional condensation reaction catalysts, such as organic titanate esters, organic titanium chelate compounds, organic aluminum compounds, organic zirconium compounds, organic tin compounds, metal salts of organic carboxylic acids, amine compounds or their salts, quaternary ammonium salts, lower fatty acid salts of alkali metals, dialkylhydroxylamine, and guanidyl group-containing organic silicon compounds. Among these, organic zirconium compounds are preferred from the viewpoint of reactivity. These can be used alone or in combination of two or more. The content (mixture amount) of the metal curing catalyst (condensation reaction catalyst) in the condensation reaction curable silicone resin composition is not particularly limited, but can be appropriately selected, for example, from the range of 0.01 to 20 parts by weight relative to 100 parts by weight of the total amount of polysiloxane (B2).

The condensation reaction curable silicone resin composition may contain other components than those mentioned 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. Examples of other components include those exemplified as components that may be contained in the curable epoxy resin composition of the present invention. The content is not particularly limited and can be selected appropriately. For example, when the curable silicone resin composition of the present invention is a resin composition for sealing optical semiconductors, it is preferable to contain the above-mentioned phosphor. The content (mixture amount) of the phosphor in the curable silicone resin composition of the present invention is not particularly limited and can be selected appropriately in the range of 0.5 to 20% by weight based on the total amount (100% by weight) of the curable silicone resin composition.

The curable silicone resin composition of the present invention is not particularly limited, but can be prepared, for example, by stirring and mixing the above-mentioned components in a heated state as necessary. The curable silicone resin composition of the present invention may be a one-liquid composition in which all of the components are mixed in advance and used as is, or a multi-liquid (e.g., two-liquid) composition in which, for example, two or more divided components are mixed in a predetermined ratio just before use. The method of stirring and mixing is not particularly limited, and for example, known or conventional stirring and mixing means such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and self-revolving stirring devices can be used. After stirring and mixing, the mixture may be degassed under reduced pressure or vacuum. In addition, as the curable silicone resin composition of the present invention or its components, commercially available products can be used as they are.

3. Curable acrylic resin composition The above-mentioned curable acrylic resin composition (sometimes referred to as the "curable acrylic resin composition of the present invention") is a curable composition containing an acrylic resin (C) as a curable compound as an essential component. 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; polyfunctional (meth)acryloyl compounds having two or more (meth)acryloyl groups in the molecule. The above-mentioned (meth)acryloyl compounds having only one (meth)acryloyl group in the molecule include monofunctional (meth)acryloyl compounds having no polymerizable functional groups other than the (meth)acryloyl group, and polyfunctional (meth)acryloyl compounds having one or more other polymerizable functional groups such as epoxy groups, oxetanyl groups, vinyl groups, and vinyloxy groups in addition to the (meth)acryloyl group. The acrylic resin (C) can be used alone or in combination of two or more types. The content of the acrylic resin (C) in the curable acrylic resin composition of the present invention is not particularly limited and can be appropriately selected.

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 initiators include known or commonly used polymerization initiators such as thermal polymerization initiators. These can be used alone or in combination of two or more. The content of the initiator is not particularly limited and can be selected appropriately.

The curable acrylic resin composition of the present invention may contain other components. Examples of other components include those exemplified as components that may be contained in the curable epoxy resin composition of the present invention. The content is not particularly limited and can be selected appropriately. For example, when the curable acrylic resin composition of the present invention is a resin composition for sealing optical semiconductors, it is preferable to contain the above-mentioned phosphor. The content (mixture amount) of the phosphor in the curable acrylic resin composition of the present invention is not particularly limited and can be selected appropriately in the range of 0.5 to 20% by weight based on the total amount (100% by weight) of the curable acrylic resin composition.

The curable acrylic resin composition of the present invention is not particularly limited, but 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-liquid composition in which all of the components are mixed in advance and used as is, or a multi-liquid (e.g., two-liquid) composition in which, for example, two or more divided components are mixed in a predetermined ratio just before use. The method of stirring and mixing is not particularly limited, and for example, known or conventional stirring and mixing means such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and self-revolving stirring devices can be used. After stirring and mixing, the mixture may be degassed under reduced pressure or vacuum. In addition, as the curable acrylic resin composition of the present invention or its components, commercially available products can be used as they are.

[Cured product and uneven shape]
In the antireflection material of the present invention, the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the cured product thereof, and as a result of the stable dispersion state, the hydrophobic porous inorganic filler present on the surface of the cured product forms an uneven shape and exhibits an antireflection function by scattering incident light. In addition, the porous structure on the surface of the hydrophobic porous inorganic filler can also scatter incident light, further improving the antireflection function.
In addition, since the hydrophobic porous inorganic filler has a hydrophobic surface, a cured product containing the filler exhibits high heat resistance, particularly hot water resistance, and is resistant to deterioration even under harsh heating conditions such as boiling water, and is therefore excellent in durability.
The method for dispersing the hydrophobic porous inorganic filler throughout the cured product is not particularly limited, and examples thereof include a method in which the hydrophobic porous inorganic filler is uniformly dispersed in a resin composition constituting the cured product and then cured. In order to efficiently produce the antireflective material of the present invention, a method in which the hydrophobic porous inorganic filler is uniformly dispersed and then cured is preferred.
One embodiment of the method for producing an antireflective material of the present invention will be described below, but the present invention is not limited thereto.

A hydrophobic porous inorganic filler can be added to the resin composition and mixed and stirred to disperse it uniformly. The method of mixing and stirring is not particularly limited, and for example, known or conventional stirring and mixing means such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and self-revolving stirrers can be used. After stirring and mixing, the mixture may be degassed under reduced pressure or vacuum.

The properties of the resin composition before curing of the present invention are not particularly limited, but it is preferably liquid. The resin composition before curing that forms the antireflective material of the present invention is preferably liquid because it can exhibit antireflective function with the addition of a small amount of hydrophobic porous inorganic filler, without using a solvent such as toluene.

[Curing process]
The antireflective material of the present invention can be obtained by curing the resin composition in which the hydrophobic porous inorganic filler is uniformly dispersed to form a cured product (hereinafter, sometimes referred to as the "cured product of the present invention").
The amount of the components volatilized during curing relative to the total amount (100% by weight) of the resin composition before curing is not particularly limited, but is preferably 10% by weight or less, more preferably 8% by weight or less, and even more preferably 5% by weight or less. The amount of the components volatilized during curing of 10% by weight or less is preferable because the dimensional stability of the cured product is high. The resin composition before curing of the present invention can exhibit an anti-reflective function with a small amount of addition by using a hydrophobic porous inorganic filler, so that it is easy to become liquid even without using a volatile component of a solvent (toluene, etc.), and the amount of the components volatilized during curing can be reduced.

As the curing means, known or conventional means such as heating treatment and light irradiation treatment can be used. The temperature (curing temperature) when curing by heating is not particularly limited, but is preferably 45 to 200 ° C, more preferably 50 to 190 ° C, and even more preferably 55 to 180 ° C. The time for heating when curing (curing time) is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and even more preferably 60 to 480 minutes. If the curing temperature and curing time are lower than the lower limit of the above range, the curing will be insufficient, and conversely, if they are higher than the upper limit of the above range, decomposition of the resin component may occur, so neither is preferable. The curing conditions depend on various conditions, but can be appropriately adjusted, for example, by shortening the curing time when the curing temperature is high, and lengthening the curing time when the curing temperature is low. The curing can be performed in one stage or in multiple stages of two or more stages.
When curing is performed by irradiation with light, the antireflective material of the present invention can be obtained by irradiating light (radiation) including, for example, i-rays (365 nm), h-rays (405 nm), g-rays (436 nm), etc., at an illuminance of 10 to 1200 mW/cm ² and an exposure dose of 20 to 2500 mJ/cm ^2. From the viewpoint of suppressing deterioration of the cured product due to radiation and from the viewpoint of productivity, the exposure dose of radiation is preferably 20 to 600 mJ/cm ² , more preferably 20 to 300 mJ/cm ^2. For irradiation, a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a laser beam, etc. can be used as an irradiation source.

[Anti-reflective material]
As described above, the antireflective material of the present invention has high transparency and excellent antireflective function, as well as high heat resistance (particularly hot water resistance), and therefore can be suitably used as a resin for optical materials (used for forming optical materials). Optical materials are materials that exhibit various optical functions such as light diffusion, light transmission, and light reflectivity. By using the antireflective material of the present invention, an optical member containing at least the cured product (optical material) of the present invention can be obtained. The optical member may be composed only of the antireflective material of the present invention, or may be one in which the antireflective material of the present invention is used only in a part thereof. Examples of optical members include members that exhibit various optical functions such as light diffusibility, light transmittance, and light reflectivity, and members that constitute devices or equipment that utilize the above-mentioned optical functions. Examples of optical members include, but are not limited to, known or commonly used optical members used in various applications such as optical semiconductor devices, organic EL devices, adhesives, electrical insulating materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, photolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors.

The antireflective material of the present invention has a fine and uniform uneven shape formed by the hydrophobic porous inorganic filler on its surface as a result of the hydrophobic porous inorganic filler being uniformly dispersed throughout the entire cured product, and the uneven shape scatters incident light and does not cause total reflection, so that the gloss can be suppressed and visibility can be improved. The arithmetic mean surface roughness Ra of the uneven shape formed on the antireflective material of the present invention is preferably in the range of 0.1 to 1.0 μm, more preferably in the range of 0.2 to 0.8 μm. If the arithmetic mean surface roughness Ra of the uneven shape is within this range, there is a tendency that sufficient antireflective function can be exhibited without significantly impairing 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 a value measured and calculated by the method described in the examples below.

The resin composition constituting the antireflective material of the present invention can be preferably used, for example, as a resin composition for sealing optical semiconductors. 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 (sealing material for an optical semiconductor element in an optical semiconductor device). An optical semiconductor device in which an optical semiconductor element is sealed by an antireflective material manufactured using the resin composition of the present invention (resin composition for sealing an optical semiconductor device) (for example, an optical semiconductor device in which 104 in FIG. 1 is composed of the antireflective material of the present invention) can be obtained. The sealing of the optical semiconductor element can be performed, 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, curing time, photocuring conditions, etc. can be appropriately set within the same range as when preparing the above-mentioned antireflective material. The above-mentioned optical semiconductor device of the present invention can particularly exhibit excellent antireflective function without reducing the total luminous flux, and has high heat resistance (particularly hot water resistance). In addition, in this specification, the "optical semiconductor device of the present invention" means an optical semiconductor device in which the antireflective material of the present invention is used in at least a part of the constituent members of the optical semiconductor device (for example, a sealing material, a die bonding material, etc.).

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The units of the components constituting the resin compositions shown in Tables 1 and 2 are parts by weight.

Production Example 1
An epoxy curing agent (agent K) was produced by mixing 100 parts by weight of a curing agent (product name "RIKACID MH-700", manufactured by New Japan Chemical Co., Ltd.), 0.5 parts by weight of a curing accelerator (product name "U-CAT 18X", manufactured by San-Apro Ltd.), and 1 part by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) using a planetary stirring device (product name "Awatori Rentaro AR-250", manufactured by Thinky Corporation; the same applies hereinafter).

Example 1
A curable epoxy resin composition was produced by mixing 100 parts by weight of an alicyclic epoxy compound (product name "Celloxide 2021P", manufactured by Daicel Corporation) and 101.5 parts by weight of the epoxy curing agent obtained in Production Example 1 using a planetary stirring apparatus and degassing the mixture.
100 parts by weight of the curable epoxy resin composition obtained above and 20 parts by weight of a hydrophobic porous inorganic filler (product name "Sylo Hobic 702", manufactured by Fuji Silysia Chemical Co., Ltd.) were mixed using a rotary and revolutionary stirrer, degassed, and the resulting curable epoxy resin composition was poured into an optical semiconductor lead frame (InGaN element, 3.5 mm x 2.8 mm) shown in Figure 1, and then heated for 5 hours in a resin curing oven at 150°C to produce an optical semiconductor device in which an optical semiconductor element is encapsulated with the antireflection material of the present invention. In Figure 1, 100 denotes a reflector, 101 denotes metal wiring, 102 denotes an optical semiconductor element, 103 denotes a bonding wire, and 104 denotes an encapsulant (antireflection material), and the hydrophobic porous inorganic filler is uniformly dispersed throughout 104, and the hydrophobic porous inorganic filler present on the upper surface of the composition forms a uniform and fine uneven shape (the uneven shape is not shown).

Examples 2 to 13, Comparative Examples 1 to 13
An optical semiconductor device was manufactured in the same manner as in Example 1, except that the compositions of the curable epoxy resin composition, the hydrophobic porous inorganic filler, and the porous inorganic filler (not subjected to hydrophobic treatment) were changed as shown in Tables 1 and 2.

[evaluation]
The optical semiconductor device manufactured as described above was subjected to the following evaluations. The results are shown in Tables 1 and 2.

(1) Hot water resistance test (heat resistance in boiling water)
The optical semiconductor devices obtained in the Examples and Comparative Examples were immersed in boiling water for 30 minutes, and then visually evaluated for appearance. When the appearance was the same as before the test, it was marked with an ◯, and when it was cloudy, it was marked with an X.

(2) Reflection of Fluorescent Light When a lit fluorescent light was shone on the top surface (top surface of encapsulant 104 in FIG. 1 ) of the optical semiconductor devices obtained in the Examples and Comparative Examples, the clarity of the fluorescent light reflected in the anti-reflection material was visually evaluated on a three-level scale.
The cases where the outline of the fluorescent light was not discernible were marked with an ◯, the cases where the outline was vague but discernible were marked with a △, and the cases where the outline was clearly discernible were marked with an ×.
(3) Arithmetic mean surface roughness Ra
The upper surfaces of the optical semiconductor devices obtained in the examples and comparative examples (the upper surface of the encapsulant 104 in FIG. 1) were measured using a laser microscope (product name "Shape Measuring Laser Microscope VK-8710", manufactured by Keyence Corporation).

(4) Total Luminous Flux For each of the optical semiconductor devices obtained in the Examples and Comparative Examples, the total luminous flux was measured when a current of 5 V and 20 mA was applied using a total luminous flux meter (product name "Multi-spectroradiometry system OL771", manufactured by Optronic Laboratories, Inc.).

(5) Overall Judgment For each optical semiconductor device obtained in the Examples and Comparative Examples, if all of the following (a) to (d) were satisfied, it was judged as ◯ (good), and if any of the following (a) to (d) were not satisfied, it was judged as × (bad).
(a) The hot water resistance measured in the above (1) is ◯.
(b) The reflection of fluorescent lights measured in (2) above is ◯ or Δ.
(c) The arithmetic mean 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 constituting the anti-reflective material shown in Tables 1 and 2 will be described below.
(Hydrophobic porous inorganic filler)
SiloHorbic 702: Trade name "SiloHorbic 702", manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler hydrophobically surface-treated with polydimethylsiloxane, volume average particle size: 4.1 μm; specific surface area of porous silica filler before hydrophobic surface treatment: 350 m ² /g; oil absorption: 170 mL/100 g
SiloHorbic 4004: Product name "SiloHorbic 4004", manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler hydrophobically surface-treated with polydimethylsiloxane, volume average particle size: 8.0 μm; specific surface area of porous silica filler before hydrophobic surface treatment: 350 m ² /g; oil absorption: 165 mL/100 g
Silo Hobic 505: Trade name "Silo Hobic 505", manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler hydrophobically surface-treated with polydimethylsiloxane, volume average particle size: 3.9 μm; specific surface area of porous silica filler before hydrophobic surface treatment: 500 m ² /g; oil absorption: 110 mL/100 g

(Porous inorganic filler)
Sylysia 430: Trade name "Sylysia 430", manufactured by Fuji Silysia Chemical Co., Ltd., volume average particle size: 4.1 μm; specific surface area: 350 m ² /g; average pore size: 17 nm; pore volume: 1.25 mL/g; oil absorption: 230 mL/100 g
Sylosphere C-1504: Product name "Sylosphere C-1504", manufactured by Fuji Silysia Chemical Ltd., volume average particle size: 4.5 μm; specific surface area: 520 m ² /g; average pore size: 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 Si-Tech Co., Ltd., volume average particle size: 5 μm; specific surface area: 700 m ² /g; average pore size: 10 nm; pore volume: 2 mL/g; oil absorption: 300 mL/100 g

(Epoxy resin)
CELLOXIDE 2021P: Trade name "CELLOXIDE 2021P" [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate], manufactured by Daicel Corporation. YD-128: Trade name "YD-128" [Bisphenol A type epoxy resin], manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. TEPIC-VL: Trade name "TEPIC-VL" [Triglycidyl isocyanurate], manufactured by Nissan Chemical Industries, Ltd. 152: Trade name "152" [Phenol novolac type epoxy resin], manufactured by Mitsubishi Chemical Corporation. YL7410: Trade name "YL7410" [Aliphatic epoxy compound], manufactured by Mitsubishi Chemical Corporation. X-22-169AS: Trade name "X-22-169AS" [Modified silicone oil (polydimethylsiloxane having cyclohexene oxide groups at both ends)], manufactured by Shin-Etsu Chemical Co., Ltd. X-40-2670: Trade name "X-40-2670" [cyclic siloxane having a cyclohexene oxide group], manufactured by Shin-Etsu Chemical Co., Ltd.

(Epoxy hardener)
MH-700: Trade name "Rikacid MH-700" [4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride = 70/30], manufactured by New Japan Chemical Co., Ltd. U-CAT 18X: Trade name "U-CAT 18X" [curing accelerator], manufactured by San-Apro Co., Ltd. Ethylene glycol: Manufactured by Wako Pure Chemical Industries, Ltd.

As shown in Table 1, in the optical semiconductor device equipped with the antireflection material according to the embodiment to which the hydrophobic porous inorganic filler was added, the hot water resistance test was rated as ◯ in all cases, the fluorescent light reflection was rated as ◯ or △ in all cases, the arithmetic mean surface roughness Ra was in the range of 0.10 to 1.0 μm, and the total luminous flux was 0.60 lm or more, and it was confirmed that the optical semiconductor device combined excellent antireflection function and illuminance with excellent heat resistance, especially hot water resistance.
On the other hand, as shown in Table 2, the optical semiconductor device of the comparative example, which contained a porous inorganic filler that had not been hydrophobized, exhibited excellent anti-reflection function and illuminance, but was rated x in all hot water resistance tests, and was therefore poor in hot water resistance.

Variations of the present invention described above are given below.
[1] An antireflective material comprising a cured product of a resin composition having a hydrophobic porous inorganic filler dispersed therein, the antireflective material being characterized in that the cured product has a surface on which irregularities that suppress reflection are formed.
[2] The anti-reflective material according to the above [1], wherein the hydrophobic porous inorganic filler is uniformly dispersed throughout the cured material, forming irregularities on the surface that suppress reflection.
[3] The antireflection material according to the above [1] or [2], wherein the porous inorganic filler constituting the hydrophobic porous inorganic filler (the porous inorganic filler before the surface is subjected to hydrophobic treatment) is at least one powder selected from the group consisting of inorganic glass [e.g., borosilicate glass, borosilicate soda glass, silicate soda glass, aluminum silicate glass, quartz, etc.], silica, alumina, zircon iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, fosterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline cyanite, cristobalite, wollastonite, diatomaceous earth, and talc, and has a porous structure, or a molded product thereof (e.g., spherical beads, etc.).
[4] The anti-reflective material according to the above [3], wherein the hydrophobic porous inorganic filler is a porous inorganic filler that has been surface-treated with at least one hydrophobic surface treatment agent selected from the group consisting of metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols, and organosilicon compounds.
[5] The anti-reflective material according to the above [4], wherein the hydrophobic surface treatment agent is an organosilicon compound.
[6] The anti-reflective material according to the above [5], wherein the organosilicon compound is at least one selected from the group consisting of trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, and silcon oil (preferably polydimethylsiloxane).
[7] The antireflection material according to any one of the above [1] to [6], wherein the hydrophobic porous inorganic filler is at least one selected from the group consisting of hydrophobic porous inorganic glass and hydrophobic porous silica (hydrophobic porous silica filler) (preferably, hydrophobic porous silica filler).
[8] The antireflection material according to the above-mentioned [7], wherein the hydrophobic porous silica filler is at least one type of porous silica selected from the group consisting of fused silica, crystalline silica, high-purity synthetic silica, and colloidal silica, which has been treated with the hydrophobic surface treatment agent.
[9] The antireflective material according to any one of the above [1] to [8], wherein the hydrophobic porous inorganic filler has at least one shape selected from the group consisting of powder, spheres, crushed, fibrous, needles, and scales (preferably spherical or crushed).
[10] The antireflective material according to any one of the above [1] to [9], wherein the hydrophobic porous inorganic filler is a porous inorganic filler whose surface has been hydrophobized, and the specific surface area of the porous inorganic filler before the hydrophobic treatment is 200 m ² /g or more (preferably 200 to 2000 m ² /g, more preferably 200 to 1500 m ² /g, and even more preferably 200 to 1000 m ² /g).
[11] The antireflective material according to any one of the above [1] to [10], wherein the average particle size of the hydrophobic porous inorganic filler is 1 to 20 μm (preferably 2 to 15 μm).
[12] The antireflective material according to any one of the above [1] to [11], wherein the hydrophobic porous inorganic filler has an oil absorption of 10 to 2000 mL/100 g (preferably 100 to 1000 mL/100 g).
[13] The antireflective material according to any one of the above [1] to [12], wherein the content of the hydrophobic porous inorganic filler relative to the total amount (100% by weight) of the antireflective material is 4 to 40% by weight (preferably 4 to 35% by weight, more preferably 4 to 30% by weight).
[14] The antireflective material according to any one of the above [1] to [13], wherein the content (blending amount) of the hydrophobic porous inorganic filler relative to the resin composition (100 parts by weight) constituting the antireflective material is 5 to 80 parts by weight (preferably 5 to 70 parts by weight, more preferably 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 anti-reflective material according to any one of the above [1] to [14], wherein the resin composition is a transparent curable resin composition.
[16] The anti-reflective material according to the above [15], wherein the curable resin composition comprises a composition containing at least one curable compound selected from the group consisting of an epoxy resin (A), a silicone resin (B), and an acrylic resin (C).
[17] The antireflective material according to the above [16], wherein the curable resin composition is a composition (curable epoxy resin composition) containing an epoxy resin (A).
[18] The antireflective material according to the above [16] or [17], wherein the epoxy resin (A) is at least one selected from the group consisting of bisphenol A type epoxy resins, isocyanurates having one or more epoxy groups in the molecule, novolac type epoxy resins, alicyclic epoxy compounds, aliphatic epoxy compounds, and siloxane derivatives having one or more epoxy groups in the molecule (preferably alicyclic epoxy compounds).
[19] The anti-reflective material according to the above [18], wherein the alicyclic epoxy compound includes a compound having a cyclohexene oxide group in the molecule (preferably a compound having two or more cyclohexene oxide groups in the molecule).
[20] The anti-reflective material according to the above [19], wherein the alicyclic epoxy compound includes a compound represented by the following formula (1):

[In formula (1), X represents a single bond or a linking group (a divalent group having one or more atoms). One or more of the carbon atoms constituting the alicyclic ring in formula (1) may be bonded to a substituent (preferably an alkyl group).]
[21] The antireflective material according to the above [20], wherein the compound represented by formula (1) is at least one alicyclic epoxy compound selected from the group consisting of 2,2-bis(3,4-epoxycyclohexyl)propane, bis(3,4-epoxycyclohexylmethyl)ether, 1,2-bis(3,4-epoxycyclohexyl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexyl)ethane, and compounds represented by the following formulas (1-1) to (1-10):

[In formulas (1-5) and (1-7), l and m each represent an integer from 1 to 30. R in formula (1-5) is an alkylene group having 1 to 8 carbon atoms. In the following formulas (1-9) and (1-10), n1 to n6 each represent an integer from 1 to 30.]
[22] The antireflective material according to the above [21], wherein the alicyclic epoxy compound includes a compound represented by the above formula (1-1).
[23] The antireflective material according to any one of the above [17] to [22], wherein the content (blending amount) of the epoxy resin (A) is 25 to 99.8% by weight (e.g., 25 to 95% by weight) (preferably 30 to 90% by weight, more preferably 35 to 85% by weight, and even more preferably 40 to 60% by weight) relative to the total amount (100% by weight) of the curable epoxy resin composition.
[24] The antireflection material according to any one of the above [18] to [23], wherein the content (blending amount) of the alicyclic epoxy compound is 20 to 99.8% by weight (preferably 40 to 95% by weight (e.g., 40 to 60% by weight), more preferably 50 to 95% by weight, even more preferably 60 to 90% by weight, and most preferably 70 to 85% by weight) relative to the total amount (100% by weight) of the curable epoxy resin composition.
[25] The antireflective material according to any one of the above [18] to [24], wherein the ratio of the alicyclic epoxy compound to the total amount (100 wt%) of the epoxy compounds contained in the curable epoxy resin composition is 40 to 100 wt% (e.g., 40 to 90 wt%) (preferably 80 to 100 wt%, more preferably 90 to 100 wt%, and even more preferably 95 to 100 wt%).
[26] The antireflective material according to any one of the above [17] to [25], wherein 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)).
[27] The antireflective material according to the above [26], wherein the curing agent (D) is at least one selected from the group consisting of acid anhydrides (acid anhydride-based curing agents), amines (amine-based curing agents), polyamide resins, imidazoles (imidazole-based curing agents), polymercaptans (polymercaptan-based curing agents), phenols (phenol-based curing agents), polycarboxylic acids, dicyandiamides, and organic acid hydrazides (preferably, an acid anhydride-based curing agent).
[28] The anti-reflective material according to the above [27], wherein the acid anhydride-based curing agent is an acid anhydride that is liquid at 25°C, or a liquid mixture obtained by dissolving an acid anhydride that is solid at 25°C in an acid anhydride that is liquid at 25°C.
[29] The antireflective material according to any one of the above [26] to [28], wherein the content (blending amount) of the curing agent (D) is 50 to 200 parts by weight (preferably 75 to 150 parts by weight, more preferably 100 to 120 parts by weight) per 100 parts by weight of the total amount of the epoxy compounds contained in the curable epoxy resin composition.
[30] The antireflective material according to any one of the above [26] to [29], wherein the content (blending amount) of the curing accelerator (E) is 0.05 to 5 parts by weight (preferably 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, and even more preferably 0.25 to 2.5 parts by weight) relative to 100 parts by weight of the total amount of the epoxy compounds contained in the curable epoxy resin composition.
[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 antireflective material according to the above [31], wherein the content (blending amount) of the polyhydric alcohol is 0.05 to 5 parts by weight (preferably 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, and even more preferably 0.25 to 2.5 parts by weight) relative to 100 parts by weight of the total amount of the epoxy compounds contained in the curable epoxy resin composition.
[33] The anti-reflective material according to any one of the above [1] to [32], wherein the curable epoxy resin composition contains a phosphor.
[34] The anti-reflective material according to the above [33], wherein the content (blending amount) of the phosphor is 0.5 to 20% by weight relative to the total amount (100% by weight) of the curable epoxy resin composition.

[35] The antireflective material according to any one of the above [1] to [34], wherein the arithmetic mean surface roughness Ra of the uneven shape formed on the antireflective material is in the range of 0.1 to 1.0 μm (preferably, in the range of 0.2 to 0.8 μm).
[36] The antireflection material according to any one of the above [1] to [35], which is for sealing an optical semiconductor device.
[37] An optical semiconductor device in which an optical semiconductor element is encapsulated with the antireflection material according to [36] above.

[38] A resin composition having a hydrophobic porous inorganic filler dispersed therein, which is used for producing the antireflective material according to any one of [1] to [36] above.
[39] The resin composition according to [38] above, which is liquid.
[40] The resin composition according to [38] or [39] above, wherein the amount of components that volatilize 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 material having a surface having projections and recesses for suppressing reflection, comprising curing the resin composition according to any one of [38] to [40] above.

The anti-reflective material of the present invention has high transparency and excellent anti-reflective function, as well as high heat resistance, especially hot water resistance, and can therefore be suitably used as a resin for optical materials (used in applications for forming optical materials). Examples of optical components include components that exhibit various optical functions such as light diffusion, light transmission, and light reflectivity, and components that constitute devices and equipment that utilize the above optical functions, and are not particularly limited. For example, known or conventional optical components used in various applications such as optical semiconductor devices, organic EL devices, adhesives, electrical insulating materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, photo-molding, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors are exemplified.

100: Reflector (light reflecting resin composition)
101: Metal wiring (electrode)
102: Optical semiconductor element 103: Bonding wire 104: Sealing material (anti-reflection material)

Claims (7)

An anti-reflective material for encapsulating optical semiconductors, comprising a cured product of a resin composition having a hydrophobic porous inorganic filler dispersed therein, the cured product having a surface formed with irregularities for suppressing reflection,
The oil absorption of the hydrophobic porous inorganic filler is 100 to 2000 mL/100 g;
The average particle size of the hydrophobic porous inorganic filler is 1 μm to 20 μm;
1. An anti-reflective material for encapsulating optical semiconductor devices, wherein the thickness of the anti-reflective material is greater than the average particle size of the hydrophobic porous inorganic filler . 2. The anti-reflective material for encapsulating optical semiconductor devices according to claim 1, wherein the hydrophobic porous inorganic filler is uniformly dispersed throughout the cured product, forming irregularities on the surface thereof for suppressing reflection. 3. The anti-reflective material for encapsulating optical semiconductor devices according to claim 1, wherein the hydrophobic porous inorganic filler has a surface that has been subjected to a hydrophobic treatment, and the specific surface area of the porous inorganic filler before the hydrophobic treatment is 200 ^m2 /g or more. 4. The antireflective material for encapsulating optical semiconductor devices according to claim 1 , wherein the content of said hydrophobic porous inorganic filler is 4 to 40% by weight based on the total amount (100% by weight) of the antireflective material. 5. The antireflection material for encapsulating optical semiconductor devices according to claim 1 , wherein the resin composition is a transparent curable resin composition. 6. The antireflection material for encapsulating optical semiconductor devices according to claim 5 , wherein the curable resin composition comprises a composition containing an epoxy resin. An optical semiconductor device comprising an optical semiconductor element encapsulated with the antireflection material for optical semiconductor encapsulation according to any one of claims 1 to 6 .

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