JP7128112B2 - Antireflection material - Google Patents

Description

The present invention relates to antireflective materials. The present invention also relates to an optical semiconductor device in which an optical semiconductor element is encapsulated with the antireflection material. The present invention also relates to a resin composition suitable for producing the antireflection material and a method for producing the antireflection material using the resin composition. This application claims priority of Japanese Patent Application No. 2016-200398 filed in Japan on October 11, 2016, and the contents thereof are incorporated herein.

2. Description of the Related Art In recent years, light-emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources have been increasingly used in various indoor or outdoor display boards, traffic signals, units for large displays, and the like. As such an optical semiconductor device, in general, an optical semiconductor device in which an optical semiconductor element is mounted on a substrate (substrate for mounting an optical semiconductor element) and the optical semiconductor element is sealed with a transparent sealing material is widely used. is doing. The surface of the encapsulant in such an optical semiconductor device is subjected to antireflection treatment in order to prevent deterioration of visibility due to total reflection of incident light such as illumination light and sunlight from the outside. there is
Conventionally, as a method of imparting an antireflection function to the surface of a resin layer, a method of scattering incident light by dispersing an inorganic filler such as glass beads or silica in a resin is known (see, for example, Patent Document 1). ).

JP 2007-234767

However, when the method of Patent Literature 1 is applied to the resin for optical semiconductor encapsulation, it has been found difficult to secure the total luminous flux of the light source while imparting a sufficient antireflection function. In other words, when the necessary and sufficient amount of inorganic filler is blended to obtain a sufficient antireflection function, the total luminous flux of the light source is greatly reduced. It has been clarified that there is a trade-off relationship that sufficient antireflection performance cannot be obtained when

In recent years, the output of optical semiconductor devices has been increasing, and the encapsulating material in such optical semiconductor devices has been subjected to thermal shock such as thermal cycles (periodic repetition of heating and cooling). In some cases, cracks occur, causing the problem of non-lighting. For this reason, a sealing material for an optical semiconductor device is required to have a property that cracks are unlikely to occur even when a thermal shock is applied (sometimes referred to as "thermal shock resistance").

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an antireflection material capable of preventing a decrease in the total luminous flux of a light source while having a sufficient antireflection function and having high thermal shock resistance.
Another object of the present invention is to provide the antireflection material for optical semiconductor encapsulation.
Further, another object of the present invention is to provide an optical semiconductor device in which an optical semiconductor element is encapsulated with the antireflection material.
Another object of the present invention is to provide a resin composition suitable for producing the antireflection material, and a method for producing the antireflection material using the resin composition.

One of the reasons why sufficient antireflection performance cannot be obtained when the amount of the inorganic filler is reduced is that the inorganic filler does not spread over the entire resin layer due to sedimentation, and as a result, uniform unevenness is not formed on the entire surface. Therefore, the incident light is not efficiently scattered, but if the amount of the inorganic filler is increased so that the entire surface of the resin layer has antireflection performance even if the inorganic filler settles, the inorganic filler itself absorbs light. The inventors have determined that the total luminous flux is significantly reduced.
As a result of intensive studies to solve the above problems, the present inventor found that when a porous filler was added as a filler in the resin layer constituting the antireflection material, a sufficient antireflection function was imparted even with a small amount of addition. I found Furthermore, when an alicyclic epoxy resin in which rubber particles having a specific structure are dispersed is used as the resin layer, it has been found to be excellent in thermal shock resistance. As a result, an antireflection material that has both a sufficient antireflection function and excellent thermal shock resistance without significantly reducing the total luminous flux of a light source is provided, and can be used as a material for encapsulating an optical semiconductor element in an optical semiconductor device. We have found that it is extremely suitable, and have completed the present invention.

That is, the present invention provides an antireflection material comprising a cured product of a resin composition in which a porous filler (A) is dispersed, wherein the porous filler (A) has unevenness that suppresses reflection on the surface of the cured product. form,
The resin composition contains a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride curing agent (C), and a curing accelerator (D),
The rubber particles have a core-shell structure, are composed of a polymer containing a (meth)acrylic acid ester as an essential monomer component, and have hydroxyl groups and/or carboxyl groups on their surfaces as functional groups capable of reacting with an alicyclic epoxy resin. having an average particle size of 10 nm to 500 nm, a maximum particle size of 50 nm to 1000 nm, and a difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition being within ±0.02;
Provided is an antireflection material characterized in that the content of the porous filler (A) is 4 to 40% by weight with respect to the total amount (100% by weight) of the antireflection material.

In the antireflection material, the porous filler (A) is preferably dispersed uniformly over the entire cured product to form unevenness on the surface that suppresses reflection.

In the antireflection material, the resin composition may further contain a nonporous filler (F) having a specific surface area of 10 m ² /g or less, in which case the total amount of the antireflection material (100% by weight) The total content of the porous filler (A) and the nonporous filler (F) is preferably 20 to 60% by weight.

In the antireflection material, the porous filler (A) may be an inorganic porous filler.

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

The antireflection material may be for optical semiconductor encapsulation.

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

The present invention also provides a resin composition in which a porous filler (A) is dispersed, which is used for the production of the antireflection material,
Contains a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride-based curing agent (C), and a curing accelerator (D),
The rubber particles have a core-shell structure, are composed of a polymer containing a (meth)acrylic acid ester as an essential monomer component, and have hydroxyl groups and/or carboxyl groups on their surfaces as functional groups capable of reacting with an alicyclic epoxy resin. having an average particle size of 10 nm to 500 nm, a maximum particle size of 50 nm to 1000 nm, and a difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition being within ±0.02;
Provided is a resin composition in which the content of the porous filler (A) is 4 to 40% by weight with respect to the total amount (100% by weight) of the resin composition.

The resin composition may be liquid.

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

Furthermore, the present invention provides a method for producing an antireflection material having unevennesses formed on the surface thereof for suppressing reflection, characterized by curing the resin composition.

Since the antireflection material of the present invention has the above structure, a sufficient antireflection function can be obtained even when the amount of the porous filler (A) is reduced, and a significant decrease in the total luminous flux of the light source can be prevented. It also has excellent thermal shock resistance. Therefore, by using the antireflection material of the present invention as a material for encapsulating an optical semiconductor element in an optical semiconductor device, high quality (for example, sufficient brightness while suppressing gloss and high durability) can be obtained. An optical semiconductor device is obtained.
Moreover, since the resin composition of the present invention has the above constitution, it is extremely suitable for producing the above antireflection material.

BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows one Embodiment of the optical semiconductor device containing the antireflection material of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view.

<Antireflection material and resin composition>
The antireflection material of the present invention comprises a cured product of a resin composition in which a porous filler (A) is dispersed. The resin composition contains a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride curing agent (C), and a curing accelerator (D), and the rubber The particles have a core-shell structure, are composed of a polymer containing a (meth)acrylic acid ester as an essential monomer component, and have hydroxyl groups and/or carboxyl groups on the surface as functional groups capable of reacting with an alicyclic epoxy resin. , an average particle size of 10 nm to 500 nm, a maximum particle size of 50 nm to 1000 nm, a difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition is within ±0.02, and antireflection It is characterized in that the content of the porous filler (A) is 4 to 40% by weight with respect to the total amount (100% by weight) of the material.
Further, the resin composition of the present invention comprises a rubber particle-dispersed epoxy compound (B) in which a porous inorganic filler is dispersed and rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride-based curing agent (C), and It contains a curing accelerator (D), the rubber particles have a core-shell structure, are composed of a polymer containing (meth)acrylic acid ester as an essential monomer component, and have a functional surface capable of reacting with an alicyclic epoxy resin. It has a hydroxyl group and/or a carboxyl group as a group, has an average particle size of 10 nm to 500 nm and a maximum particle size of 50 nm to 1000 nm, and has a refractive index between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition. The difference is within ±0.02, and the content of the porous filler (A) with respect to the total amount (100% by weight) of the resin composition is 4 to 40% by weight, and for producing the antireflection material is used for

Due to the porous structure of the porous filler (A), the apparent volume with respect to the resin composition increases compared to non-porous fillers. It can be dispersed uniformly, and can form uniform and fine irregularities on the surface of the cured product. In addition, the resin composition permeates into the porous structure, and the difference in apparent specific gravity between the porous filler (A) and the resin composition decreases, thereby stabilizing the dispersion state and increasing the amount of the porous filler (A). The interaction between the surfaces of is suppressed and it becomes difficult to aggregate, and the porous filler (A) can spread uniformly throughout the resin composition or its cured product, so that uniform and fine unevenness is formed on the surface of the cured product. It can be formed to efficiently scatter incident light.
In this specification, the addition amount (use amount) of the porous filler (A) is small (small) means that it is small in terms of weight, and does not mean that it is small in terms of capacity (volume). do not have.

When the porous filler (A) is used, reflection can be efficiently suppressed even if the amount used is small compared to a non-porous filler, so the light beam of the porous filler (A) itself can be suppressed. A sufficient antireflection function can be ensured while suppressing a significant decrease in the total luminous flux due to absorption.

In addition, the resin composition contains a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride-based curing agent (C), and a curing accelerator (D), The rubber particles have a core-shell structure and are composed of a polymer containing (meth)acrylic acid ester as an essential monomer component, and have hydroxyl groups and/or carboxyl groups as functional groups capable of reacting with alicyclic epoxy resins on the surface. and having an average particle size of 10 nm to 500 nm and a maximum particle size of 50 nm to 1000 nm, wherein the difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition is ±0 .02 or less, the rubber component is not eluted from the rubber particles, the glass transition temperature of the cured product obtained by curing the resin composition is not greatly lowered, and the transparency is not impaired. Not at all. The cured product obtained by curing the resin composition containing the rubber particle-dispersed epoxy compound (B) maintains excellent heat resistance and transparency, and exhibits excellent crack resistance ( thermal shock resistance) can be exhibited.
Each component will be described in detail below.

[Porous filler (A)]
The porous filler (A) in the antireflection 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 surface of the cured product The existing porous filler (A) functions to form unevenness for scattering incident light.

The porous filler (A) that can be used in the antireflection material or resin composition of the present invention means an inorganic or organic filler having an apparent specific gravity smaller than the true specific gravity of the filler and having a porous structure inside. . Hereinafter, they may be referred to as "inorganic porous filler (A1)" and "organic porous filler (A2)", respectively.

As the inorganic porous filler (A1), known or commonly used fillers can be used without particular limitation, but examples include inorganic glass [e.g., borosilicate glass, sodium borosilicate glass, sodium silicate glass, aluminum silicate glass , quartz, etc.], silica, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, silicon nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, Powders of aluminum oxide, calcium sulfate, barium sulfate, forsterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nephelinsinite, cristobalite, wollastonite, diatomaceous earth, talc, etc., which have a porous structure. or molded products thereof (for example, spherical beads, etc.). In addition, the inorganic porous filler (A1) may be subjected to a known or commonly used surface treatment for the inorganic porous filler described above [for example, metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyol, silicone, etc. surface treatment with a surface treatment agent, etc.] may also be mentioned. By applying such a surface treatment, it may be possible to improve the compatibility and dispersibility with the components of the resin composition. Among them, as the inorganic porous filler (A1), a porous inorganic glass or a porous filler is selected from the viewpoint that it spreads uniformly over the entire resin composition or a cured product thereof and can efficiently form unevenness on the surface of the cured product. Silica (porous silica filler) is preferred.

Porous silica is not particularly limited, and known or commonly used porous silica such as fused silica, crystalline silica, high-purity synthetic silica, and colloidal silica can be used. The porous silica may be subjected to known or conventional surface treatment [for example, surface treatment with a hydrophobic surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, an organic silicon compound, etc. ] can also be used. In this specification, porous silica surface-treated with a hydrophobic surface-treating agent may be referred to as "hydrophobic porous silica".
From the viewpoint of improving the compatibility and dispersibility with the components of the resin composition and improving the heat resistance (for example, hot water resistance) of the cured product, hydrophobic porous silica is preferable. , Organosilicon compounds (e.g., trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, silcon oil, etc.) are preferable, and polydimethylsiloxane, etc. are more preferable. preferable.

As the organic porous filler (A2), known or commonly used fillers can be used without particular limitation, but examples include styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, and vinyl chloride resins. Polymers such as resins, vinylidene chloride resins, amide resins, urethane resins, phenol resins, styrene-conjugated diene resins, acrylic-conjugated diene resins, olefin resins, cellulose resins (including crosslinked products of these polymers) ), polymer porous sintered bodies, polymer foams, organic porous fillers such as gel porous bodies, and the like.
In addition, an inorganic-organic porous filler or the like composed of a hybrid material of the inorganic substance and the organic substance can also be used.

The porous filler (A) may be composed of a single material, or may be composed of two or more kinds of materials. Among them, as the porous filler (A), an inorganic porous filler ( A1) is preferable, porous silica (porous silica filler) is more preferable from the viewpoint of availability and ease of production, and hydrophobic porous silica is more preferable from the viewpoint of heat resistance (e.g., hot water resistance) of the cured product. (Hydrophobic porous silica filler) is more preferred.

The shape of the porous filler (A) is not particularly limited, but examples thereof include powder, spherical, pulverized, fibrous, needle-like, scale-like, and the like. Among them, the porous filler (A) spreads uniformly throughout the resin composition or the cured product thereof, and from the viewpoint that it becomes easy to form a uniform and fine irregular shape on the surface of the cured product, spherical, or A crushed porous filler (A) is preferred.

The median particle diameter of the porous filler (A) is not particularly limited, but the porous filler (A) spreads evenly throughout the resin composition or its cured product, and uniformly fine particles are formed on the surface of the cured product. The thickness is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, from the viewpoint of facilitating the formation of a smooth uneven shape. The median particle size means a volume particle size (median volume diameter) at an integrated value of 50% in a particle size distribution measured by a laser diffraction/scattering method.

The porous structure of the porous filler (A) can be specified by various parameters such as specific surface area, pore volume, and oil absorption. The filler (A) can be selected without particular restrictions.

The specific surface area of the porous filler (A) is not particularly limited. It is preferably 10 to 2000 m ² /g, more preferably 100 to 1000 m ² /g, from the viewpoints of facilitating the formation of irregularities and effectively preventing reflection. When the specific surface area is 10 m ² /g or more, the porous filler (A) is dispersed evenly throughout the resin composition or its cured product, and the antireflection function of the surface of the cured product tends to be improved. be. On the other hand, when the specific surface area is 2000 m ² /g or less, the viscosity increase and thixotropy of the resin composition containing the porous filler (A) are suppressed, and the fluidity in producing the antireflection material is ensured. tend to The above specific surface area means the nitrogen adsorption specific surface area obtained based on the BET formula from the nitrogen adsorption isotherm at −196° C. in accordance with JIS K6430 Annex E.
In the case of the porous filler (A) surface-treated with a hydrophobic surface treatment agent, the above-mentioned "specific surface area" means the specific surface area of the porous filler (A) before the surface treatment. .

The pore volume of the porous filler (A) is not particularly limited. It is preferably 0.1 to 10 mL/g, more preferably 0.2 to 5 mL/g, from the viewpoint of facilitating the formation of a smooth uneven shape and efficiently preventing reflection. When the pore volume is 0.1 mL/g or more, the porous filler (A) is uniformly dispersed throughout the resin composition or its cured product to form unevenness on the surface of the cured product. tends to be easier. On the other hand, when the pore volume is 5 mL/g or less, the mechanical strength of the porous filler (A) tends to improve. The pore volume of the porous filler (A) can be obtained by measuring the pore distribution by a mercury intrusion method (porosimeter method).

The oil absorption of the porous filler (A) is not particularly limited. It is preferably 10 to 2000 mL/100 g, more preferably 100 to 1000 mL/100 g, from the viewpoint of facilitating the formation of uneven shapes and efficiently preventing reflection. When the oil absorption is 10 mL/100 g or more, the porous filler (A) is dispersed uniformly throughout the resin composition or its cured product, and tends to easily form unevenness on the surface of the cured product. There is On the other hand, when the oil absorption is 2000 mL/100 g or less, the mechanical strength of the porous filler (A) tends to improve. The amount of oil supplied to the porous filler (A) is the amount of oil absorbed by 100 g of the filler, and can be measured according to JIS K5101.

In the antireflection material of the present invention, the porous filler (A) can be used singly or in combination of two or more. In addition, the porous filler (A) can be produced by a known or commonly used production method. 320", "Silycia 350", "Silycia 358", "Silycia 430", "Silycia 431", "Silycia 440", "Silycia 450", "Silycia 470", "Silycia 435", "Silycia 445", "Silycia 436”, “Sylysia 446”, “Sylysia 456”, “Sylysia 530”, “Sylysia 540”, “Sylysia 550”, “Sylysia 730”, “Sylysia 740”, “Sylysia 770”, etc., product names Sylosphere series such as "Silosphere C-1504", "Silosphere C-1510" (manufactured by Fuji Silysia Chemical Co., Ltd.), trade names "Sunsphere H-31", "Sunsphere H-32", “Sunsphere H-33”, “Sunsphere H-51”, “Sunsphere H-52”, “Sunsphere H-53”, “Sunsphere H-121”, “Sunsphere H-122”, “Sunsphere Fair H-201" and other Sunsphere H series (manufactured by AGC Si Tech Co., Ltd.), etc. Porous inorganic fillers that have not been subjected to hydrophobic surface treatment, trade names "Silophobic 702", "Silohobic 4004 , "Silohobic 505", "Silohobic 100", "Silohobic 200", "Silohobic 704", "Silohobic 507", "Silohobic 603", etc. (manufactured by Fuji Silysia Chemical Co., Ltd.), trade names "Aerosil RX200", "Aerosil RX300" and other Aerosil series (manufactured by Evonik Degussa), trade names "Sunsphere H-121-ET", "Suns Commercially available products such as hydrophobic porous silica such as Sunsphere ET series (manufactured by AGC Si Tech Co., Ltd.) such as Fair H-51-ET can also be used.

The content (amount) of the porous filler (A) in the antireflection material or resin composition of the present invention is 4 to 40% by weight with respect to the total amount (100% by weight) of the antireflection material or resin composition. Yes, preferably 4 to 35% by weight, more preferably 4 to 30% by weight. When the content of the porous filler (A) is 4% by weight or more, the porous filler (A) spreads uniformly throughout the resin composition or the cured product constituting the antireflection material thereof, and is cured. It becomes easy to form a uniform uneven shape on the entire surface of the object. On the other hand, since the content of the porous filler (A) is 40% by weight or less, when the antireflection material or resin composition of the present invention is used, for example, as a sealing material for an optical semiconductor device, the total luminous flux is significantly reduced. There is a tendency to prevent a decrease and ensure sufficient illuminance.

The content (amount) of the porous filler (A) in the antireflection material or resin composition of the present invention is usually 5 to 80 parts by weight with respect to the resin composition (100 parts by weight) constituting the antireflection material. parts, preferably 5 to 70 parts by weight, more preferably 5 to 60 parts by weight. When the content of the porous filler (A) is 5 parts by weight or more, the porous filler (A) spreads uniformly throughout the resin composition or the cured product constituting the antireflection material thereof, and is cured. It becomes easy to form a uniform uneven shape on the entire surface of the object. On the other hand, since the content of the porous filler (A) is 80 parts by weight or less, when the antireflection material or resin composition of the present invention is used, for example, as a sealing material for an optical semiconductor device, the total luminous flux is significantly increased. There is a tendency to prevent a decrease and ensure sufficient illuminance.

[Resin composition]
The resin composition constituting the cured product in the antireflection material of the present invention is a rubber particle-dispersed epoxy compound (B) obtained by dispersing rubber particles in an alicyclic epoxy resin (hereinafter referred to as "rubber particle-dispersed epoxy (sometimes referred to as "compound (B)"), an acid anhydride curing agent (C), and a curing accelerator (D), the rubber particles having a core-shell structure, and a (meth)acrylic acid ester is an essential monomer component, has a hydroxyl group and / or a carboxyl group as a functional group that can react with an alicyclic epoxy resin on the surface, has an average particle size of 10 nm to 500 nm, and a maximum particle size of 50 nm to 1000 nm, and the difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition is within ±0.02. The resin composition is suitable as a sealing material for optical semiconductor elements in optical semiconductor devices, that is, as a resin composition for sealing optical semiconductors. (For example, it is resistant to deterioration in transparency due to heat or light, and resistant to cracking or peeling from adherends even when subjected to high-temperature heat or thermal shock.) It is particularly resistant to thermal shock. Gives an excellent cured product.

[Rubber particle-dispersed epoxy compound (B)]
The rubber particle-dispersed epoxy compound (B) in the present invention has a core-shell structure and is composed of a polymer containing a (meth)acrylic acid ester as an essential monomer component. Rubber particles having a hydroxyl group and/or a carboxyl group as a group and having an average particle size of 10 nm to 500 nm and a maximum particle size of 50 nm to 1000 nm, wherein the refractive index of the rubber particles and the cured product of the resin composition. is dispersed in an alicyclic epoxy resin.

(rubber particles)
The rubber particles in the present invention have a multilayer structure (core-shell structure) consisting of a core portion having rubber elasticity and at least one shell layer covering the core portion. Moreover, it is composed of a polymer containing (meth)acrylic acid ester as an essential monomer component, and has a hydroxyl group and/or a carboxyl group on the surface as functional groups capable of reacting with an alicyclic epoxy resin. If hydroxyl groups and/or carboxyl groups are not present on the rubber particle surface, the cured product becomes cloudy due to thermal shock such as a thermal cycle, which is not preferable because the transparency is lowered.

A (meth)acrylic acid ester such as methyl (meth)acrylate, ethyl (meth)acrylate, or butyl (meth)acrylate is essential as a monomer component constituting the polymer of the core portion having rubber elasticity. Examples of monomer components that may be contained in addition to (meth)acrylic acid esters include silicones such as dimethylsiloxane and phenylmethylsiloxane, aromatic vinyls such as styrene and α-methylstyrene, and nitriles such as acrylonitrile and methacrylonitrile. , conjugated dienes such as butadiene and isoprene, urethane, ethylene, propylene, and isobutene.

In the present invention, the monomer component constituting the core portion having rubber elasticity includes (meth)acrylic acid ester and one or more selected from silicone, aromatic vinyl, nitrile, and conjugated diene in combination. For example, binary copolymers such as (meth) acrylate/aromatic vinyl, (meth) acrylate/conjugated diene; (meth) acrylate/aromatic vinyl/conjugated diene, etc. A terpolymer of the above can be mentioned.

In the core portion having rubber elasticity, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc. are added in addition to the above monomer components. It may contain reactive cross-linking monomers having two or more reactive functional groups in one corresponding monomer.

The monomer component constituting the core portion having rubber elasticity in the present invention is, among others, a (meth)acrylic acid ester/aromatic vinyl binary copolymer (especially butyl acrylate/styrene). This is preferable in that the refractive index of the rubber particles can be easily adjusted.

The core portion having rubber elasticity can be produced by a commonly used method, for example, a method of polymerizing the above monomers by emulsion polymerization. As the emulsion polymerization method, the total amount of the above monomers may be charged at once and polymerized, or after a part of the above monomers is polymerized, the rest may be added continuously or intermittently for polymerization. , polymerization methods using seed particles may be used.

The shell layer is preferably made of a polymer different from the polymer constituting the core portion. In addition, the shell layer has hydroxyl groups and/or carboxyl groups as functional groups capable of reacting with the alicyclic epoxy resin. As a result, it is possible to improve the adhesiveness at the interface with the alicyclic epoxy resin, and by curing the resin composition containing the rubber particles having the shell layer, it has excellent crack resistance and is cloudy. A transparent cured product can be obtained without Moreover, it can prevent that the glass transition temperature of hardened|cured material falls.

As a monomer component constituting the shell layer, a (meth)acrylic acid ester such as methyl (meth)acrylate, ethyl (meth)acrylate, or butyl (meth)acrylate is essential. When the meth)acrylate is butyl acrylate, the shell layer is composed of a (meth)acrylate other than butyl acrylate (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, butyl methacrylate, etc.). is preferably used. Examples of monomer components that may be contained in addition to (meth)acrylic acid esters include aromatic vinyls such as styrene and α-methylstyrene, and nitriles such as acrylonitrile and methacrylonitrile. In the present invention, it is preferable that the monomer components constituting the shell layer include (meth)acrylic acid ester and the above-mentioned monomers alone or in combination of two or more, and in particular, at least aromatic vinyl is included. is preferable in that the refractive index of the rubber particles can be easily adjusted.

Furthermore, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid as monomer components having hydroxyl groups and/or carboxyl groups as functional groups capable of reacting with alicyclic epoxy resins It is preferable to contain a monomer corresponding to an α,β-unsaturated acid such as α,β-unsaturated acid such as maleic anhydride.

In the present invention, the monomer component constituting the shell layer preferably contains (meth)acrylic acid ester and one or more selected from the above monomers in combination. acid ester/aromatic vinyl/hydroxyalkyl (meth)acrylate, (meth)acrylic acid ester/aromatic vinyl/α,β-unsaturated acid terpolymer, (meth)acrylic acid ester/hydroxyalkyl ( Binary copolymers such as meth)acrylates, (meth)acrylates/α,β-unsaturated acids (preferably (meth)acrylates/hydroxyalkyl (meth)acrylates, (meth)acrylates/α , a binary copolymer of β-unsaturated acid, etc.).

In addition to the above monomers, the shell layer contains divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, and butylene glycol diacrylate, as in the core portion. A reactive cross-linking monomer having two or more reactive functional groups may be contained in one monomer corresponding to, for example.

The method of coating the core portion with the shell layer includes, for example, a method of coating the surface of the core portion having rubber elasticity obtained by the above method with the copolymer constituting the shell layer, and the above method. A method of graft-polymerizing the obtained core portion having rubber elasticity as a trunk component and each component constituting the shell layer as a branch component can be exemplified.

The average particle size of the rubber particles in the present invention is about 10-500 nm, preferably about 20-400 nm. Also, the maximum particle size of the rubber particles is about 50 to 1000 nm, preferably about 100 to 800 nm. When the average particle size exceeds 500 nm, or when the maximum particle size of the rubber particles exceeds 1000 nm, the transparency of the cured product tends to decrease and the luminous intensity of the optical semiconductor tends to decrease. On the other hand, when the average particle size is less than 10 nm, or when the maximum particle size of the rubber particles is less than 50 nm, crack resistance tends to decrease.

The refractive index of the rubber particles in the present invention is, for example, about 1.40 to 1.60, preferably about 1.42 to 1.58. Further, the difference between the refractive index of the rubber particles and the refractive index of the cured product obtained by curing the resin composition containing the rubber particles is within ±0.02, especially within ±0.018. is preferred. If the difference in refractive index exceeds ±0.02, the transparency of the cured product is reduced, and sometimes it becomes cloudy, and the luminous intensity of the optical semiconductor tends to decrease, which may result in the loss of the function of the optical semiconductor. .

For the refractive index of the rubber particles, for example, 1 g of rubber particles is cast into a mold and compression-molded at 210° C. and 4 MPa to obtain a flat plate with a thickness of 1 mm. is cut out, and a prism and the test piece are brought into close contact using monobromonaphthalene as an intermediate liquid, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) is used, It can be determined by measuring the refractive index at 20° C. and the sodium D line.

The refractive index of the cured product of the resin composition is obtained by, for example, cutting out a test piece having a length of 20 mm, a width of 6 mm, and a thickness of 1 mm from the cured product obtained by the heat curing method described in the section of the optical semiconductor device below. A multi-wavelength Abbe refractometer (trade name: "DR-M2", manufactured by Atago Co., Ltd.) was used with monobromonaphthalene being used as a liquid, and the prism and the test piece were brought into close contact with each other. It can be obtained by measuring the refractive index at the D line.

(alicyclic epoxy resin)
The alicyclic epoxy resin in the present invention is a compound having one or more alicyclic (aliphatic hydrocarbon ring) and one or more epoxy groups in the molecule. As the alicyclic epoxy compound, for example, (i) at least one (preferably (ii) a compound having an epoxy group directly bonded to an alicyclic ring with a single bond; (iii) a compound having an alicyclic ring and a glycidyl group. The alicyclic epoxy resin used in the present invention is preferably liquid at room temperature (25° C.) from the viewpoint of workability during preparation and casting.

The alicyclic epoxy group of the above-mentioned (i) compound having at least one alicyclic epoxy group in the molecule is not particularly limited, but from the viewpoint of curability, a cyclohexene oxide group (adjacent An epoxy group composed of two carbon atoms and an oxygen atom) is preferred. In particular, (i) the compound having at least one alicyclic epoxy group in the molecule is preferably a compound having two or more cyclohexene oxide groups in the molecule from the viewpoint of the transparency and heat resistance of the cured product. A compound represented by the following formula (1) is preferable.

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 part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and these and a group in which a plurality of is linked. One or more carbon atoms constituting the alicyclic ring (alicyclic epoxy group) in formula (1) may be bonded with a substituent such as an alkyl group.

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

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

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

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

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

Examples of the (ii) compound having an epoxy group directly bonded to an alicyclic ring with 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, and p and q each represent a natural number. Examples of the p-valent alcohol [R'(OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis(hydroxymethyl)-1-butanol. p is preferably 1-6, and q is preferably 1-30. When p is 2 or more, q in each group in ( ) (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (2) include a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol [for example, , trade name “EHPE3150” (manufactured by Daicel Corporation), etc.] and the like.

Examples of the compound (iii) having an alicyclic ring and a glycidyl group include 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-epoxy) Propoxy)cyclohexyl]methane, [2-(2,3-epoxypropoxy)cyclohexyl][4-(2,3-epoxypropoxy)cyclohexyl]methane, bis[4-(2,3-epoxy) propoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane, hydrogenated bisphenol F type epoxy resin (hydrogenated bisphenol F type epoxy resin ) etc.; hydrogenated biphenol type epoxy resin; hydrogenated novolak type epoxy resin (for example, hydrogenated phenol novolac type epoxy resin, hydrogenated cresol novolac type epoxy resin, hydrogenated cresol novolak type epoxy resin of bisphenol A, etc.); naphthalene-type epoxy resins; hydrogenated epoxy resins of epoxy resins obtained from trisphenolmethane;

Other examples of the alicyclic epoxy compound include 1,2,8,9-diepoxylimonene and the like.

These alicyclic epoxy resins can be used alone or in combination of two or more. can also be used.

The rubber particle-dispersed epoxy compound (B) in the present invention is obtained by dispersing the above rubber particles in the above alicyclic epoxy resin. The amount of the rubber particles can be adjusted as necessary. For example, the amount is about 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the total amount of the rubber particle-dispersed epoxy compound (B). %. When the amount of rubber particles used is less than 0.5% by weight, the crack resistance tends to decrease, while when the amount of rubber particles used exceeds 30% by weight, heat resistance and transparency tend to decrease. be.

The viscosity of the rubber particle-dispersed epoxy compound (B) is preferably 400 mPa·s to 50,000 mPa·s at 25° C., more preferably 500 mPa·s to 10,000 mPa·s. When the viscosity (25°C) of the rubber particle-dispersed epoxy compound (B) is less than 400 mPa·s, the transparency tends to decrease, while the rubber particle-dispersed epoxy compound (B) has a viscosity (25°C) of 50000 mPa·s. , the productivity tends to decrease in both the production of the rubber particle-dispersed epoxy compound (B) and the production of the resin composition.

The viscosity of the rubber particle-dispersed epoxy compound (B) can be adjusted by using a reactive diluent. As the reactive diluent, an aliphatic polyglycidyl ether having a viscosity of 200 mPa·s or less at normal temperature (25° C.) can be preferably used. Examples of the aliphatic polyglycidyl ether include cyclohexanedimethanol diglycidyl ether, cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and polypropylene glycol. Diglycidyl ether and the like can be mentioned.

The amount of the reactive diluent used can be adjusted as appropriate. For example, 30 parts by weight or less, preferably 25 parts by weight or less (for example, 5 to 25 parts by weight). When the amount of the reactive diluent used exceeds 30 parts by weight, it tends to be difficult to obtain the desired performance such as crack resistance.

The method for producing the rubber particle-dispersed epoxy compound (B) in the present invention is not particularly limited, and a well-known and commonly used method can be used. Examples include a method of mixing and dispersing in a cyclic epoxy resin, and a method of directly mixing and dehydrating a rubber particle emulsion and an alicyclic epoxy resin.

The amount of the rubber particle-dispersed epoxy compound (B) used is preferably about 20 to 100% by weight, more preferably about 50 to 100% by weight, of the total epoxy group-containing resin contained in the resin composition. Preferably. If the amount of the rubber particle-dispersed epoxy compound (B) used is less than 20% by weight of the total epoxy group-containing resin, the resulting cured product tends to have reduced crack resistance.

The resin composition according to the present invention contains at least three components, a rubber particle-dispersed epoxy compound (B), an acid anhydride curing agent (C), and a curing accelerator (D), as essential components. A mode in which two components, the compound (B) and the curing catalyst (E), are essential components may also be used.

[Acid anhydride curing agent (C)]
The acid anhydride curing agent (C) has a function of curing compounds having epoxy groups. As the acid anhydride curing agent (C) in the present invention, a well-known and commonly used curing agent for epoxy resins can be used. The acid anhydride curing agent (C) in the present invention is preferably an acid anhydride that is liquid at 25° C., such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride , methylendomethylenetetrahydrophthalic anhydride, and the like. Further, for example, acid anhydrides that are solid at room temperature (25°C), such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexenedicarboxylic anhydride, are liquid acid anhydrides at room temperature (25°C). It can be used as the acid anhydride curing agent (C) in the present invention by dissolving it in a substance to form a liquid mixture.

In addition, in the present invention, as the acid anhydride curing agent (C), trade name "Likacid MH-700" (manufactured by Shin Nippon Rika Co., Ltd.), trade name "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.) etc. can also be used.

The amount of the acid anhydride curing agent (C) used is, for example, 50 to 150 parts by weight, preferably 52 to 145 parts by weight, based on 100 parts by weight of the compound having all epoxy groups contained in the resin composition. Particularly preferably, it is about 55 to 140 parts by weight. More specifically, it is preferably used in a proportion of 0.5 to 1.5 equivalents per equivalent of epoxy groups in all epoxy group-containing compounds contained in the resin composition. When the amount of the acid anhydride curing agent (C) used is less than 50 parts by weight, the effect tends to be insufficient and the toughness of the cured product tends to decrease. exceeds 150 parts by weight, the cured product may be colored and the hue may be deteriorated.

[Curing accelerator (D)]
The curing accelerator (D) is a compound having a function of accelerating the curing rate when the epoxy group-containing compound is cured by the acid anhydride curing agent (C). As the curing accelerator (D) in the present invention, a well-known and commonly used curing accelerator can be used, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and salts thereof ( phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and salts thereof (such as phosphonium salts, sulfonium salts, quaternary ammonium salts, iodonium salts); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylcyclohexylamine and other tertiary amines; 2-ethyl- imidazoles such as 4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphoric acid esters and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; octylic acid Organic metal salts such as tin and zinc octylate; metal chelates; These can be used individually or in mixture of 2 or more types.

In the present invention, as the curing accelerator (D), trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", "12XD ( Developed product)” (both manufactured by San-Apro Co., Ltd.), trade names “TPP-K” and “TPP-MK” (both manufactured by Hokko Chemical Industry Co., Ltd.), trade name “PX-4ET” (Nippon Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) can also be used.

The amount of curing accelerator (D) used is, for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the compound having all epoxy groups contained in the resin composition. parts, particularly preferably 0.2 to 3 parts by weight, most preferably about 0.25 to 2.5 parts by weight. If the amount of the curing accelerator (D) used is less than 0.05 parts by weight, the curing acceleration effect may be insufficient. A hardened|cured material may color and a hue may deteriorate.

[Curing catalyst (E)]
The curing catalyst (E) in the present invention functions to initiate polymerization of the epoxy compound in the rubber particle-dispersed epoxy compound (B). As the curing catalyst (E) in the present invention, a cationic polymerization initiator that generates cationic species by UV irradiation or heat treatment to initiate polymerization of the rubber particle-dispersed epoxy compound (B) is preferred.

Examples of cationic polymerization initiators that generate cationic species upon irradiation with ultraviolet rays include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, and hexafluoroalzenate salts. UVACURE 1590” (manufactured by Daicel Cytec Co., Ltd.), trade names “CD-1010”, “CD-1011”, “CD-1012” (manufactured by Sartomer, USA), trade name “Irgacure 264” (Ciba Japan Co., Ltd. ), trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) and the like can be suitably used.

Examples of cationic polymerization initiators that generate cationic species by heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, and the like. , “CP-66”, “CP-77” (manufactured by ADEKA Corporation), trade name “FC-509” (manufactured by 3M Co., Ltd.), trade name “UVE1014” (manufactured by G.E. Co., Ltd.) , trade names “San-Aid SI-60L”, “San-Aid SI-80L”, “San-Aid SI-100L”, “San-Aid SI-110L” (manufactured by Sanshin Chemical Industry Co., Ltd.), trade name “CG-24-61” (manufactured by Ciba Japan Co., Ltd.) and the like can be suitably used. Furthermore, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketones and a silanol such as triphenylsilanol, or a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketones and bisphenol S It may be a compound with phenols such as

As the curing catalyst (E) in the present invention, a hexafluorophosphate salt is particularly preferable because of its low toxicity, ease of handling, and excellent versatility.

The amount of the curing catalyst (E) used is, for example, 0.01 to 15 parts by weight, preferably 0.01 to 12 parts by weight, based on 100 parts by weight of the compound having all epoxy groups contained in the resin composition. , particularly preferably about 0.05 to 10 parts by weight, most preferably about 0.1 to 10 parts by weight. By using within this range, a cured product having excellent heat resistance, transparency and weather resistance can be obtained.

[Nonporous filler (F)]
The resin composition constituting the antireflection material of the present invention may contain a nonporous filler (F). By including the nonporous filler (F) in the resin composition in the antireflection material of the present invention, the thermal shock resistance of the cured product is further improved.

The nonporous filler (F) that can be used in the antireflection material of the present invention means an inorganic or organic filler that does not have a porous structure and has a specific surface area of 10 m ² /g or less. Hereinafter, they may be referred to as "inorganic nonporous filler (F1)" and "organic nonporous filler (F2)", respectively.

As the inorganic nonporous filler (F1) that can be used in the antireflection material of the present invention, a known or commonly used inorganic nonporous filler can be used, and is not particularly limited. silicate glass, borosilicate soda glass, sodium silicate glass, aluminum silicate glass, quartz, etc.], silica, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, silicon nitride, boron nitride, aluminum hydroxide, Iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, forsterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nephelinsinite, cristobalite, wollastonite , powders such as diatomaceous earth and talc, or molded bodies thereof (for example, spherical beads). As the nonporous filler (F), known or commonly used surface treatments for the above inorganic fillers [e.g., metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols, silicones, etc.] Surface treatment with a treating agent, etc.] may also be mentioned. By applying such a surface treatment, it may be possible to improve the compatibility and dispersibility with the components of the resin composition. Among them, as the inorganic nonporous filler (F1), inorganic nonporous glass or nonporous silica (nonporous silica filler) is preferable from the viewpoint that excellent thermal shock resistance can be imparted to the cured product.

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

Moreover, as the inorganic nonporous filler (F1), one having a hollow body structure may be used. Examples of the hollow inorganic nonporous filler include, but are not limited to, inorganic glass [e.g., borosilicate glass, borosilicate soda glass, soda silicate glass, aluminum silicate glass, quartz, etc.], silica, alumina, zirconia, and the like. Inorganic hollow particles (including natural products such as shirasu balloons) composed of inorganic substances such as metal oxides, calcium carbonate, barium carbonate, nickel carbonate, calcium silicate, etc.; hybrid materials composed of inorganic and organic substances and inorganic-organic hollow particles. In addition, the hollow portion (internal space of the hollow particles) of the hollow inorganic nonporous filler may be in a vacuum state or may be filled with a medium. For this purpose, hollow particles filled with a medium having a low refractive index (for example, an inert gas such as nitrogen or argon, or air) are preferred.
When a hollow inorganic nonporous filler is used, its hollowness (ratio of void volume to the total volume of the inorganic filler) is not particularly limited, but is preferably 10 to 90% by volume, more preferably 30 to 90% by volume. .

As the organic nonporous filler (F2), known or commonly used fillers can be used without particular limitation, but examples include styrene-based resins, acrylic resins, silicone-based resins, acrylic-styrene-based resins, and vinyl chloride. resins, vinylidene chloride resins, amide resins, urethane resins, phenolic resins, styrene-conjugated diene resins, acrylic-conjugated diene resins, olefin resins, cellulose resins, etc. and organic nonporous fillers composed of organic substances such as
Inorganic-organic nonporous fillers composed of hybrid materials of the above inorganic and organic substances can also be used.

The nonporous filler (F) may be composed of a single material, or may be composed of two or more kinds of materials. Among them, as the nonporous filler (F), the inorganic nonporous filler (F1) is preferable from the viewpoint of imparting excellent thermal shock resistance to the cured product. Nonporous silica (nonporous silica filler) is more preferred.

The shape of the nonporous filler (F) is not particularly limited, but examples thereof include powder, spherical, pulverized, fibrous, needle-like, scale-like and the like. Among them, spherical or crushed nonporous fillers (F) are preferable from the viewpoint that the nonporous fillers (F) improve the thermal shock resistance of the cured product.

The median particle diameter of the nonporous filler (F) is not particularly limited, but from the viewpoint that the nonporous filler (F) improves the thermal shock resistance of the cured product, it is preferably 0.1 to 100 μm, more preferably 1 to 50 μm. The median particle size means a volume particle size (median volume diameter) at an integrated value of 50% in a particle size distribution measured by a laser diffraction/scattering method.

In the antireflection material of the present invention, the nonporous filler (F) can be used singly or in combination of two or more. In addition, the inorganic filler can be produced by a known or commonly used production method. Kogyo Co., Ltd.), trade names “MSR-2212”, “MSR-25” (manufactured by Tatsumori Co., Ltd.), trade names “HS-105”, “HS-106”, “HS-107” (above, manufactured by Micron) and other commercial products can also be used.
In addition, the hollow inorganic nonporous filler can be produced by a known or commonly used production method. ) 34P30”, “Sphericel (trademark) 60P18”, “Q-CEL (trademark) 5020”, “Q-CEL (trademark) 7014”, “Q-CEL (trademark) 7040S” (above, Potters Barrottini Co., Ltd. ), trade names “Glass Microballoon”, “Fuji Balloon H-40”, “Fuji Balloon H-35” (manufactured by Fuji Silysia Chemical Co., Ltd.), trade names “Cellstar Z-20”, “Cellstar Z-27”, “Selstar CZ-31T”, “Selstar Z-36”, “Selstar Z-39”, “Selstar Z-39”, “Selstar T-36”, “Selstar PZ-6000” (Tokai Kogyo Co., Ltd.), trade name “Cyrax Fine Balloon” (manufactured by Fine Balloon Co., Ltd.), trade name “Super Balloon BA-15”, “Super Balloon 732C” (manufactured by Showa Chemical Industry Co., Ltd.) ) can be used.

When the resin composition in the antireflection material of the present invention contains the nonporous filler (F), the content (blended amount) is not particularly limited, but the resin composition (100 parts by weight) constituting the antireflection material ), preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight. When the content of the nonporous filler (F) is 10 parts by weight or more, the thermal shock resistance of the cured product constituting the antireflection material tends to be improved. On the other hand, since the content of the nonporous filler (F) is 200 parts by weight or less, when the antireflection material of the present invention is used, for example, as a sealing material for an optical semiconductor device, a significant decrease in total luminous flux is prevented. to ensure sufficient illuminance.

When the resin composition in the antireflection material of the present invention contains a nonporous filler (F), the total content (total compounding amount) of the porous filler (A) and the nonporous filler (F) is particularly Although not limited, it is preferably 20 to 60% by weight with respect to the total amount (100% by weight) of the antireflection material. When the total content of the porous filler (A) and the nonporous filler (F) is 20% by weight or more, the thermal shock resistance of the cured product constituting the antireflection material tends to be improved. On the other hand, when the total content of the porous filler (A) and the nonporous filler (F) is 60 parts by weight or less, the antireflection material of the present invention is used, for example, as a sealing material for an optical semiconductor device. There is a tendency to prevent a significant drop in total luminous flux and ensure sufficient illuminance.

[Polyhydric alcohol]
The resin composition of the present invention may contain a polyhydric alcohol. In particular, when the resin composition of the present invention contains an acid anhydride curing agent (C) and a curing accelerator (D), it further contains a polyhydric alcohol in that curing can proceed more efficiently. is preferred. As the polyhydric alcohol, known or commonly used polyhydric alcohols can be used without particular limitation. Examples include ethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol and the like.

Among them, as the polyhydric alcohol, alkylene glycol having 1 to 6 carbon atoms is preferable, more preferably carbon, in that curing can be well controlled and a cured product that is less likely to crack or peel off can be obtained. It is an alkylene glycol of numbers 2-4.

In the resin composition of the present invention, polyhydric alcohols can be used singly or in combination of two or more.

The content (blended amount) of the polyhydric alcohol in the resin composition of the present invention is not particularly limited, but the total amount of epoxy compounds contained in the resin composition (total epoxy compounds; for example, total amount of alicyclic epoxy resin) is 100. It is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight. is. By setting the polyhydric alcohol content to 0.05 parts by weight or more, there is a tendency that curing can proceed more efficiently. On the other hand, by setting the content of the polyhydric alcohol to 5 parts by weight or less, there is a tendency to easily control the reaction rate of the curing.

[Phosphor]
The resin composition of the present invention may contain a phosphor. When the resin composition of the present invention contains a phosphor, it can be particularly preferably used for encapsulating optical semiconductor elements in optical semiconductor devices (sealing material applications), that is, as a resin composition for encapsulating optical semiconductors. As the phosphor, known or commonly used phosphors ₍ especially phosphors used for _{encapsulation} of optical semiconductor elements) can be used, and there is no particular _limitation . [Wherein, A represents one or more elements selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm, and B is selected from the group consisting of Al, Ga, and In and M represents one or more elements selected from the group consisting of Ce, Pr, Eu, Cr, Nd, and Er]. (e.g., _Y3Al5O12 :Ce phosphor fine particles, (Y, Gd, Tb) _{3 (} Al, Ga) _5O12 : _Ce phosphor fine particles, etc.), silicate _- based phosphor fine particles (e.g., (Sr, Ca, Ba) ₂ SiO ₄ :Eu, etc.) and the like. The surface of the phosphor may be modified with an organic group (for example, a long-chain alkyl group, a phosphoric acid group, etc.), for example, in order to improve dispersibility. In the resin composition of the present invention, the phosphor can be used singly or in combination of two or more. Moreover, a commercial item can be used as fluorescent substance.

The content (blended amount) of the phosphor in the resin composition of the present invention is not particularly limited, and is appropriately selected in the range of 0.5 to 20% by weight with respect to the total amount (100% by weight) of the resin composition. be able to.

The resin composition according to the present invention may contain an alicyclic epoxy resin containing no rubber particles in addition to the rubber particle-dispersed epoxy compound (B). As the alicyclic epoxy resin, an alicyclic epoxy resin represented by the above formula (1) can be mentioned. The amount of the alicyclic epoxy resin containing no rubber particles used is preferably less than 70% by weight, especially less than 60% by weight, of the total epoxy group-containing resin contained in the resin composition. is preferred. If the amount of the alicyclic epoxy resin containing no rubber particles exceeds 70% by weight of the total epoxy group-containing resin, the resulting cured product tends to have reduced crack resistance.

Furthermore, the resin composition according to the present invention includes glycidyl ether-based epoxy compounds having aromatic rings such as bisphenol A type and bisphenol F type; Epoxy compounds; glycidyl ester-based epoxy compounds; glycidylamine-based epoxy compounds; polyol compounds, oxetane compounds, vinyl ether compounds, and other epoxy resins other than alicyclic epoxy resins may be contained. The amount of the epoxy resin other than the alicyclic epoxy resin used is preferably less than 70% by weight, more preferably less than 60% by weight, of the total epoxy group-containing resin contained in the resin composition. preferable. If the amount of the epoxy resin other than the alicyclic epoxy resin used exceeds 70% by weight of the total epoxy group-containing resin, the crack resistance of the resulting cured product tends to decrease.

Moreover, even an epoxy compound that exhibits a solid state at room temperature (25° C.) may be contained as long as it exhibits a liquid state after blending. Examples of epoxy compounds that are solid at room temperature (25° C.) include solid bisphenol-type epoxy compounds, novolak-type epoxy compounds, glycidyl esters, triglycidyl isocyanurate, and 2,2-bis(hydroxymethyl)-1-butanol. 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct (trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd.) and the like can be mentioned. These epoxy compounds can be used individually or in combination of 2 or more types.

In the present invention, among others, in addition to the acid anhydride curing agent (C), the curing catalyst (E), and the curing catalyst (E), a glycidyl ether-based epoxy compound having no aromatic ring and/or a liquid at 25 ° C. It is preferable to include a polyol compound (except for polyether polyol) that exhibits a high degree of heat resistance in terms of improving crack resistance without impairing high heat resistance. It is preferable to contain it because crack resistance can be improved without impairing high heat resistance and light resistance.

[Glycidyl ether-based epoxy compound having no aromatic ring]
Glycidyl ether epoxy compounds having no aromatic ring in the present invention include aliphatic glycidyl ether epoxy compounds and compounds obtained by hydrogenating the nucleus of aromatic glycidyl ether epoxy compounds. For example, trade names "EPICLON703", "EPICLON707", "EPICLON720", "EPICLON725" (manufactured by DIC Corporation), trade names "YH-300", "YH-315", "YH-324", "PG- 202”, “PG-207”, “Suntote ST-3000” (manufactured by Tohto Kasei Co., Ltd.), trade names “Rikaresin DME-100”, “Rikaresin HBE-100” (manufactured by Shin Nippon Rika Co., Ltd.), products Commercially available products such as "Denacol EX-212" and "Denacol EX-321" (manufactured by Nagase ChemteX Corporation) and trade names "YX8000" and "YX8034" (manufactured by Japan Epoxy Resin Co., Ltd.) are preferably used. can do.

The amount of the glycidyl ether-based epoxy compound having no aromatic ring to be used is, for example, about 10 to 60 parts by weight, preferably about 20 to 50 parts by weight, per 100 parts by weight of the alicyclic epoxy resin.

[Polyol compound exhibiting liquid state at 25°C]
The polyol compound that exhibits a liquid state at 25° C. in the present invention includes polyol compounds other than polyether polyols, such as polyester polyols and polycarbonate polyols.

As polyester polyols, for example, trade names "PLAXEL 205", "PLAXEL 205H", "PLAXEL 205U", "PLAXEL 205BA", "PLAXEL 208", "PLAXEL 210", "PLAXEL 210CP", "PLAXEL 210BA", " Praxel 212", "Praxel 212CP", "Praxel 220", "Praxel 220CPB", "Praxel 220NP1", "Praxel 220BA", "Praxel 220ED", "Praxel 220EB", "Praxel 220EC", "Praxel 230", " Praxel 230CP", "Praxel 240", "Praxel 240CP", "Praxel 210N", "Praxel 220N", "Praxel L205AL", "Praxel L208AL", "Praxel L212AL", "Praxel L220AL", "Praxel L230AL", " Praxel 305", "Praxel 308", "Praxel 312", "Praxel L312AL", "Praxel 320", "Praxel L320AL", "Praxel L330AL", "Praxel 410", "Praxel 410D", "Praxel 610", " Commercially available products such as PLAXEL P3403" and PLAXEL CDE9P (manufactured by Daicel Chemical Industries, Ltd.) can be used.

Polycarbonate polyols include, for example, trade names "PLAXEL CD205PL," "PLAXEL CD205HL," "PLAXEL CD210PL," "PLAXEL CD210HL," "PLAXEL CD220PL," and "PLAXEL CD220HL" (manufactured by Daicel Chemical Industries, Ltd.). "UH-CARB50", "UH-CARB100", "UH-CARB300", "UH-CARB90 (1/3)", "UH-CARB90 (1/1)", "UC-CARB100" (Ube Industries, Ltd.) ), trade names "PCDL T4671", "PCDL T4672", "PCDL T5650J", "PCDL T5651", "PCDL T5652" (manufactured by Asahi Kasei Chemicals Corporation), and other commercially available products can be used.

The amount of the polyol compound that is liquid at 25° C. is, for example, about 5 to 50 parts by weight, preferably about 10 to 40 parts by weight, per 100 parts by weight of the rubber particle-dispersed epoxy compound (B).

[Other ingredients]
The resin composition of the present invention may contain other components other than those mentioned above as long as the curability, transparency, etc. are not adversely affected. Examples of the above other components include silicone resins having straight or branched chains, silicone resins having an alicyclic ring, silicone resins having an aromatic ring, cage-type/ladder-type/random-type silsesquioxanes, Silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, silicone-based and fluorine-based defoaming agents, leveling agents, surfactants, fillers, flame retardants, coloring agents, antioxidants, UV absorbers, Examples include ion adsorbents, pigments, release agents, and the like. The content (blending amount) of the other components is not particularly limited, but is preferably 5% by weight or less (eg, 0 to 3% by weight) relative to the total amount (100% by weight) of the resin composition.

Although the resin composition of the present invention is not particularly limited, it can be prepared, for example, by stirring and mixing each of the above-described 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 premixed and used as it is, or, for example, a component divided into two or more components. It may be a multi-liquid system (for example, two-liquid system) composition that is used by mixing at a predetermined ratio immediately before use. Stirring and mixing methods are not particularly limited, and known or commonly used stirring and mixing means such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and rotation-revolution stirrers can be used. Moreover, after stirring and mixing, defoaming may be performed under reduced pressure or vacuum.

[Cured product and uneven shape]
In the antireflection material of the present invention, the porous filler (A) is uniformly dispersed throughout the resin composition or its cured product, and as a result of the stable dispersion state, it exists on the surface of the cured product. The porous filler (A) exhibits an antireflection function by forming unevenness and scattering incident light. In addition, the porous structure on the surface of the porous filler (A) can also scatter incident light, further improving the antireflection function.
In addition, since the resin composition contains the rubber particle-dispersed epoxy compound (B), a cured product containing this has excellent thermal shock resistance.
The method for uniformly spreading the porous filler (A) over the entire cured product is not particularly limited. and the like. In order to efficiently produce the antireflection material of the present invention, a method of uniformly dispersing the porous filler (A) and then curing it is preferred.
One aspect of the method for producing the antireflection material of the present invention will be described below, but the present invention is not limited thereto.

The porous filler (A) and, if necessary, the nonporous filler (F) are added to the resin composition, and mixed and stirred to uniformly disperse them. The mixing/stirring method is not particularly limited, and known or commonly used stirring and mixing means such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and rotation-revolution stirrers can be used. Moreover, after stirring and mixing, defoaming may be performed under reduced pressure or vacuum.
When the nonporous filler (F) is dispersed in the cured product together with the porous filler (A), the thermal shock resistance of the cured product can be further improved.

The properties of the resin composition before curing of the present invention are not particularly limited, but are preferably liquid. The resin composition before curing that forms the antireflection material of the present invention can exhibit an antireflection function by adding a small amount by using the porous filler (A), so it does not use a solvent such as toluene. Both tend to become liquid, which is preferable.

[Curing process]
Obtaining the antireflection material of the present invention by curing the resin composition in which the porous filler (A) is uniformly dispersed to obtain a cured product (hereinafter sometimes referred to as the “cured product of the present invention”). can be done.
The amount of components volatilized during curing is not particularly limited to the total amount (100% by weight) of the resin composition before curing, but is preferably 10% by weight or less, more preferably 8% by weight or less, and further Preferably, it is 5% by weight or less. When the amount of components volatilized during curing is 10% by weight or less, the dimensional stability of the cured product is increased, which is preferable. By using the porous filler (A), the resin composition before curing of the present invention can exhibit an antireflection function with the addition of a small amount. and the amount of components volatilized during curing can be reduced.

As curing means, known or commonly used means such as heat treatment and light irradiation treatment can be used. The temperature for curing by heating (curing temperature) is not particularly limited, but is preferably 45 to 200.degree. C., more preferably 50 to 190.degree. C., still more preferably 55 to 180.degree. The time for heating during 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. When the curing temperature and curing time are lower than the lower limit of the above range, the curing becomes insufficient. The curing conditions depend on various conditions, but can be adjusted as appropriate by, for example, shortening the curing time when the curing temperature is raised and lengthening the curing time when the curing temperature is lowered. Moreover, curing can be carried out in one step or in multiple steps of two or more steps.
In the case of curing by light irradiation, for example, light (radiation) including i-line (365 nm), h-line (405 nm), g-line (436 nm), etc. is irradiated at an illuminance of 10 to 1200 mW/cm ² . The antireflection material of the present invention can be obtained by irradiation with a light amount of 20 to 2500 mJ/cm ² . From the viewpoint of suppressing deterioration of the cured product due to radiation and from the viewpoint of productivity, the irradiation light amount 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, or the like can be used as an irradiation source.

[Anti-reflection material]
As described above, the antireflection material of the present invention has high transparency, excellent antireflection function, and high thermal shock resistance, so it is suitable as a resin for optical materials (used for forming optical materials). can be used for An optical material is a material that exhibits various optical functions such as light diffusing properties, light transmitting properties, and light reflecting properties. By using the antireflection 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 antireflection material of the present invention, or may be partially composed of the antireflection material of the present invention. Examples of the optical member include members exhibiting various optical functions such as light diffusion, light transmission, and light reflectivity, and members constituting devices and equipment utilizing the above optical functions. For example, 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, optics Known or commonly used optical members used in various applications such as lenses, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors are exemplified.

In the antireflection material of the present invention, as a result of the porous filler (A) being evenly dispersed throughout the cured product, the surface thereof has fine and uniform irregularities formed by the porous filler (A), Since incident light is scattered by the uneven shape and total reflection does not occur, glossiness can be suppressed and visibility can be improved. The arithmetic mean surface roughness Ra of the irregularities formed on the antireflection 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 a sufficient antireflection 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 the value measured and calculated by the method described in Examples below.

The resin composition constituting the antireflection material of the present invention can be preferably used, for example, as a resin composition for optical semiconductor encapsulation. That is, the resin composition of the present invention can be preferably used as a composition for encapsulating an optical semiconductor element in an optical semiconductor device (a sealing material for an optical semiconductor element in an optical semiconductor device). An optical semiconductor device (for example, 104 in FIG. An optical semiconductor device composed of a protective material is obtained. The optical semiconductor element can be sealed, for example, by injecting a resin composition in which the porous filler (A) is uniformly dispersed into a predetermined molding die, and heat-curing or photo-curing it under predetermined conditions. The curing temperature, curing time, photocuring conditions, and the like can be appropriately set within the same range as in the preparation of the antireflection material. The above-described optical semiconductor device of the present invention can exhibit an excellent antireflection function without reducing the total luminous flux. In addition, since the resin composition of the present invention contains a rubber particle-dispersed epoxy compound (B) and, if necessary, a nonporous filler (F), a cured product containing this has excellent thermal shock resistance. . In this specification, the "optical semiconductor device of the present invention" means that the antireflection material of the present invention is used for at least a part of the constituent members of the optical semiconductor device (e.g., encapsulant, die bonding material, etc.). means an optical semiconductor device.

EXAMPLES The present invention will be described in more detail below based on 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.

The average particle diameter and the maximum particle diameter of the rubber particles were measured using a ^Nanotrac particle size distribution analyzer (trade name: UPA-EX150, Nikkiso Co., Ltd. ) was used to measure the following samples, and in the resulting particle size distribution curve, the cumulative average diameter, which is the particle diameter when the cumulative curve reaches 50%, is the average particle diameter, and the frequency (%) of the particle size distribution measurement results is The maximum particle size at the time when the content exceeded 0.00% was defined as the maximum particle size.
sample:
A sample was prepared by dispersing 1 part by weight of rubber particle-dispersed epoxy compound (B) in 20 parts by weight of tetrahydrofuran.

The refractive index of the rubber particles was measured by casting 1 g of rubber particles into a mold and compression molding at 210° C. and 4 MPa to obtain a flat plate with a thickness of 1 mm. , Using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state in which monobromonaphthalene is used as an intermediate liquid and the prism and the test piece are in close contact, the test The refractive index at the sodium D line at 20° C. on the piece was measured.

The viscosity of the rubber particle-dispersed epoxy compound (B) obtained in Production Example (5 parts by weight of rubber particles dispersed in 100 parts by weight of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.)) was measured using a digital viscosity type (product Viscosity at 25° C. was measured using the name “DVU-EII type” manufactured by Tokimec Co., Ltd.).

Production example 1
A 1 L polymerization vessel equipped with a reflux condenser was charged with 500 g of ion-exchanged water and 0.68 g of sodium dioctylsuccinate, and the temperature was raised to 80° C. while stirring under a nitrogen stream. Here, a monomer mixture consisting of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion was added all at once. After addition and stirring for 20 minutes to emulsify, 9.5 mg of potassium peroxodisulfate is added and stirred for 1 hour for initial seed polymerization, followed by addition of 180.5 mg of potassium peroxodisulfate, Stir for 5 minutes. 180.5 g of butyl acrylate, 48.89 g of styrene, 7.33 g of divinylbenzene, and 0.95 g of sodium dioctyl succinate are added to the remainder (about 95% by weight) required to form the core portion. The dissolved monomer mixture was continuously added over 2 hours to conduct a second seed polymerization, followed by aging for 1 hour to obtain a core portion.

Then, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. The polymer mixture was continuously added over 30 minutes for seed polymerization, followed by aging for 1 hour to form a shell layer covering the core portion.

Then, the mixture was cooled to room temperature (25° C.) and filtered through a plastic mesh with an opening of 120 μm to obtain a latex containing particles having a core-shell structure. The resulting latex was frozen at minus 30°C, dehydrated and washed with a suction filter, and then air-dried at 60°C for a whole day and night to obtain rubber particles (1). The obtained rubber particles (1) had an average particle size of 254 nm, a maximum particle size of 486 nm, and a refractive index of 1.500.

5 parts by weight of the obtained rubber particles (1) were dissolved in 100 parts by weight of Celloxide 2021P (manufactured by Daicel Chemical Industries, Ltd.) using a dissolver (1000 rpm, 60 minutes) while being heated to 60°C under a nitrogen stream. and deaerated under vacuum to obtain a rubber particle-dispersed epoxy compound (B-1) (viscosity at 25° C.: 559 mPa·s).

Production example 2
Rubber particles (2) were obtained in the same manner as in Production Example 1, except that 2.7 g of 2-hydroxyethyl methacrylate was used instead of 1.5 g of acrylic acid. The obtained rubber particles (2) had an average particle size of 261 nm, a maximum particle size of 578 nm, and a refractive index of 1.500.
Furthermore, in the same manner as in Production Example 1, a rubber particle-dispersed epoxy compound (B-2) (viscosity at 25° C.: 512 mPa·s) was obtained.

Production example 3
A 1 L polymerization vessel equipped with a reflux condenser was charged with 500 g of ion-exchanged water and 1.3 g of sodium dioctylsuccinate, and the temperature was raised to 80° C. while stirring under a nitrogen stream. Here, a monomer mixture consisting of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion was added all at once. After addition and stirring for 20 minutes to emulsify, 12 mg of potassium peroxodisulfate was added and stirred for 1 hour for initial seed polymerization, followed by the addition of 228 mg of potassium peroxodisulfate and stirring for 5 minutes. . 180.5 g of butyl acrylate, 48.89 g of styrene, 7.33 g of divinylbenzene and 1.2 g of sodium dioctyl succinate were added to the remainder (about 95% by weight) required to form the core portion. The dissolved monomer mixture was continuously added over 2 hours to conduct a second seed polymerization, followed by aging for 1 hour to obtain a core portion.

Then, rubber particles (3) were obtained in the same manner as in Production Example 1, except that the amount of acrylic acid used was changed from 1.5 g to 2.0 g. The obtained rubber particles (3) had an average particle size of 108 nm, a maximum particle size of 289 nm, and a refractive index of 1.500.
Furthermore, in the same manner as in Production Example 1, a rubber particle-dispersed epoxy compound (B-3) (viscosity at 25° C.: 1036 mPa·s) was obtained.

Production example 4
Curing agent (trade name “Rikashid MH-700”, manufactured by Shin Nippon Rika Co., Ltd.) 100 parts by weight, curing accelerator (trade name “U-CAT 18X”, manufactured by San-Apro Co., Ltd.) 0.5 parts by weight, and 1 part by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) is mixed using a rotation-revolution stirring device (trade name “Awatori Mixer AR-250”, manufactured by Thinky Co., Ltd., the same applies hereinafter), An epoxy curing agent (K agent) was produced.

Example 1
100 parts by weight of the rubber particle-dispersed epoxy compound (B-1) obtained in Production Example 1 and 101.5 parts by weight of the epoxy curing agent obtained in Production Example 4 were mixed using a rotation-revolution stirrer, followed by defoaming. Then, a curable epoxy resin composition was produced.
100 parts by weight of the curable epoxy resin composition obtained above and 20 parts by weight of a porous filler (trade name “Sylysia 430” manufactured by Fuji Silysia Chemical Co., Ltd.) are mixed using a rotation-revolution stirring device, After the curable epoxy resin composition obtained by defoaming was poured into the optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in Fig. 1, it was cured in a resin curing oven at 150°C for 5 hours. By heating, an optical semiconductor device in which an optical semiconductor element was encapsulated with the antireflection material of the present invention was manufactured. In FIG. 1, 100 is a reflector, 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a sealing material (antireflection material). It is dispersed, and the porous filler present on the upper surface thereof forms a uniform and fine uneven shape (the uneven shape is not shown).

Examples 2-15, Comparative Examples 1-5
An optical semiconductor device was manufactured in the same manner as in Example 1, except that the compositions of the curable epoxy resin composition, porous filler, and nonporous filler were changed as shown in Tables 1 and 2.

[evaluation]
The optical semiconductor device manufactured above was evaluated as follows. The results are shown in Tables 1 and 2, respectively.

(1) Reflection of Fluorescent Lamp When the top surface of the optical semiconductor devices obtained in Examples and Comparative Examples (the top surface of the encapsulant 104 in FIG. 1) is illuminated with a fluorescent lamp and the reflection is observed, the anti-reflection effect is observed. The vividness of the fluorescent light reflected on the material was visually evaluated on a three-grade scale.
The case where the outline of the fluorescent lamp could not be recognized was evaluated as ◯, the case where the outline was obscure but could be recognized as Δ, and the case where the outline could be clearly recognized as ×.

(2) Arithmetic mean surface roughness Ra
The top surface of the optical semiconductor device obtained in Examples and Comparative Examples (the top surface of the sealing material 104 in FIG. 1) was examined using a laser microscope (trade name “Shape measurement laser microscope VK-8710” manufactured by Keyence Corporation). It was measured.

(3) Total luminous flux For each optical semiconductor device obtained in Examples and Comparative Examples, the total luminous flux when energized under the conditions of 5 V and 20 mA was measured (manufactured by Optronic Laboratories, Inc.).

(4) Thermal Shock Test The optical semiconductor devices obtained in Examples and Comparative Examples (two devices were used for each curable epoxy resin composition) were exposed to an atmosphere of −40° C. for 30 minutes, followed by , 100° C. for 30 minutes, and 200 cycles of thermal shock were applied using a thermal shock tester. After that, a current of 10 mA was applied to the optical semiconductor devices, and the number of optical semiconductor devices that did not light up (unlighted optical semiconductor devices) was counted. Before the thermal shock test, it was confirmed that all the optical semiconductor devices would light up. The results are shown in the column of "Thermal shock test [number of non-lighting]" in Tables 1 and 2.

(5) Refractive Index Difference Test The curable epoxy resin compositions obtained in Examples 1 to 15 and Comparative Examples 3 to 5 were cast into molds and heated at 150° C. for 5 hours. A test piece of 20 mm length × 6 mm width × 1 mm thickness is cut out from the obtained cured product, and the prism and the test piece are brought into close contact using monobromonaphthalene as an intermediate liquid, and a multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by Atago Co., Ltd.), the refractive index of the cured product was measured by measuring the refractive index at 20 ° C. at the sodium D line, and the refractive index difference was calculated according to the following formula. . The results are shown in the column of "refractive index difference from rubber particles" in Tables 1 and 2.
Refractive index difference = [refractive index of rubber particles] - [refractive index of cured product]

(6) Comprehensive Judgment For each optical semiconductor device obtained in Examples and Comparative Examples, ○ (good) if all of the following (a) to (d) are satisfied, and (a) to (d) below. A case in which either condition was not satisfied was determined to be x (defective).
(a) The reflection of the fluorescent lamp measured in (1) above is ◯ or Δ.
(b) The arithmetic mean surface roughness Ra measured in (2) above is 0.10 to 1.0 μm.
(c) The total luminous flux measured in (3) above is 0.60 lm or more.
(d) In (4) above, the number of unlit optical semiconductor devices is zero.

Each component constituting the antireflection material shown in Tables 1 and 2 will be described below.

(Rubber particle-dispersed epoxy compound (B))
B-1: Rubber particle-dispersed epoxy compound (B-1) produced in Production Example 1
B-2: Rubber particle-dispersed epoxy compound (B-2) produced in Production Example 2
B-3: Rubber particle-dispersed epoxy compound (B-3) produced in Production Example 3

(Epoxy resin)
Celoxide 2021P: trade name “Celoxide 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.

(epoxy curing agent)
MH-700: Product name “Rikashid MH-700” [4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride = 70/30], manufactured by Shin Nippon Rika Co., Ltd. U-CAT 18X: Product name “U-CAT 18X" [curing accelerator], manufactured by San-Apro Co., Ltd. Ethylene glycol: manufactured by Wako Pure Chemical Industries, Ltd. SI-100L: trade name "San-Aid SI-100L", manufactured by San-Apro Co., Ltd.

(Porous silica filler)
Silysia 430: trade name “Silysia 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
Cylosphere C-1504: trade name “Cylosphere C-1504”, manufactured by Fuji Silysia Chemical Co., Ltd., volume average particle diameter: 4.5 μm; specific surface area: 520 m ² /g; average pore diameter: 12 nm; : 1.5 mL/g; oil absorption: 290 mL/100 g
Sunsphere H-52: trade name "Sunsphere H-52", manufactured by AGC S.I.Tec 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
Cyrophobic 702: trade name “Cylophobic 702”, manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler hydrophobically treated with polydimethylsiloxane, volume average particle size: 4.1 μm; hydrophobic surface treatment Specific surface area of porous silica filler before treatment: 350 m ² /g; oil absorption: 170 mL/100 g
Cylophobic 4004: trade name “Cylophobic 4004”, manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler hydrophobically treated with polydimethylsiloxane, volume average particle size: 8.0 μm; hydrophobic surface treatment Specific surface area of porous silica filler before treatment: 350 m ² /g; oil absorption: 165 mL/100 g
Cyrophobic 505: trade name “Cylophobic 505”, manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler hydrophobically treated with polydimethylsiloxane, volume average particle size: 3.9 μm; hydrophobic surface treatment Specific surface area of porous silica filler before treatment: 500 m ² /g; oil absorption: 110 mL/100 g

(Non-porous silica filler)
Fused spherical silica: manufactured by Tatsumori Co., Ltd., volume average particle size: 5 μm

As shown in Table 1, a predetermined amount of the porous silica filler of the present invention is added, and the antireflection material according to the example produced from the resin composition containing the rubber particle-dispersed epoxy compound (B) is provided. According to the semiconductor device, the reflection of the fluorescent lamp is either ○ or △, the arithmetic mean surface roughness Ra is in the range of 0.10 to 1.0 μm, and the total luminous flux is 0.60 lm or more. The number of unlighted optical semiconductor devices in the thermal shock test was 0, and it was confirmed that while having an excellent antireflection function, it exhibited good illuminance and also had excellent thermal shock resistance. .
On the other hand, as shown in Table 2, the optical semiconductor devices provided with the antireflection materials of Comparative Examples 1 and 2, which do not use the rubber particle-dispersed epoxy compound (B), exhibited excellent antireflection function and good illuminance. In the thermal shock resistance test, the number of non-lighting optical semiconductor devices was 2 in each case, and it was confirmed that the thermal shock resistance was poor. In addition, the antireflection materials of Comparative Example 3, in which only the nonporous silica filler was blended without the porous silica filler, and Comparative Example 4, in which the blending amount of the porous silica filler was less than the range specified by the present invention, were provided. The optical semiconductor device was inferior in antireflection function. In Comparative Example 3, the nonporous silica filler sedimented, and in Comparative Example 4, the blending amount of the porous silica filler was insufficient. Furthermore, in the optical semiconductor device provided with the antireflection material of Comparative Example 5, in which the blending amount of the porous silica filler is larger than the range specified by the present invention, the total luminous flux is 0.48 lm or more while exhibiting a good antireflection function. , the illuminance decreased significantly. It is believed that the light was absorbed because the amount of the porous silica filler was large.

Variations of the invention described above are appended below.
[1] An antireflection material comprising a cured product of a resin composition in which a porous filler (A) is dispersed, wherein the porous filler (A) forms unevenness that suppresses reflection on the surface of the cured product,
The resin composition contains a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride curing agent (C), and a curing accelerator (D),
The rubber particles have a core-shell structure, are composed of a polymer containing a (meth)acrylic acid ester as an essential monomer component, and have hydroxyl groups and/or carboxyl groups on their surfaces as functional groups capable of reacting with an alicyclic epoxy resin. having an average particle size of 10 nm to 500 nm, a maximum particle size of 50 nm to 1000 nm, and a difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition being within ±0.02;
An antireflection material characterized in that the content of the porous filler (A) is 4 to 40% by weight with respect to the total amount (100% by weight) of the antireflection material.
[2] The antireflection material according to [1] above, in which the porous filler (A) is uniformly dispersed over the entire cured product, and the surface has unevenness that suppresses reflection.
[3] The above-mentioned [1] or [2], wherein the porous filler (A) is at least one selected from the group consisting of an inorganic porous filler (A1) and an organic porous filler (A2). anti-reflective material.
[4] The antireflection material according to [3] above, wherein the porous filler (A) is an inorganic porous filler (A1).
[5] The inorganic porous filler (A1) is inorganic glass [e.g., borosilicate glass, borosilicate soda glass, sodium silicate glass, aluminum silicate glass, quartz, etc.], silica, alumina, zircon, calcium silicate, calcium phosphate, carbonate Calcium, magnesium carbonate, silicon carbide, silicon nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, forsterite, steatite, spinel, At least one powder selected from the group consisting of clay, kaolin, dolomite, hydroxyapatite, nephelinsinite, cristobalite, wollastonite, diatomaceous earth, and talc and having a porous structure, or a molded product thereof ( For example, spherical beads, etc.) (preferably porous inorganic glass or porous silica, more preferably porous silica).
[6] The inorganic porous filler (A1) is surface-treated with at least one surface treatment agent selected from the group consisting of metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols, and silicones. The antireflection material according to any one of the above [3] to [5], which is applied with
[7] The above [5] or [6], wherein the porous silica is at least one kind of porous silica selected from the group consisting of fused silica, crystalline silica, high-purity synthetic silica, and colloidal silica. Anti-reflective material.
[8] The porous silica is 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 The antireflection material according to any one of the above [5] to [7], which is surface-treated (hydrophobic porous silica) with an organic silicon compound).
[9] The hydrophobic surface treatment agent is selected from the group consisting of trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, and silcon oil. The antireflection material according to [8] above, which is at least one organosilicon compound (preferably polydimethylsiloxane).
[10] The organic porous filler (A2) is styrene resin, acrylic resin, silicone resin, acrylic-styrene resin, vinyl chloride resin, vinylidene chloride resin, amide resin, urethane resin, phenol Porous macromolecules composed of at least one organic material selected from the group consisting of styrene-conjugated diene-based resins, acrylic-conjugated diene-based resins, olefin-based resins, and cellulose resins (including crosslinked products of these polymers) The antireflection material according to any one of [3] to [9] above, which is a sintered body, a polymer foam, or a gel porous body.
[11] The shape of the porous filler (A) is at least one (preferably spherical or crushed) selected from the group consisting of powder, spherical, crushed, fibrous, acicular, and scale-like. , The antireflection material according to any one of the above [1] to [10].
[12] The antireflection material according to any one of [1] to [11] above, wherein the porous filler (A) has a median particle size of 0.1 to 100 μm (preferably 1 to 50 μm). .
[13] Any one of the above [1] to [12], wherein the porous filler (A) has a specific surface area of 10 to 2000 m ² /g (preferably 100 to 1000 m ² /g). Anti-reflective material.
[14] Any one of the above [1] to [13], wherein the porous filler (A) has a pore volume of 0.1 to 10 mL/g (preferably 0.2 to 5 mL/g) The antireflection material described in .
[15] The antireflection according to any one of [1] to [14] above, wherein the porous filler (A) has an oil absorption of 10 to 2000 mL/100 g (preferably 100 to 1000 mL/100 g). material.
[16] The content (blending amount) of the porous filler (A) is 4 to 35% by weight (preferably 4 to 30% by weight) relative to the total amount (100% by weight) of the antireflection material or resin composition. ), the antireflection material according to any one of the above [1] to [15].
[17] The content (blended amount) of the porous filler (A) is 5 to 80 parts by weight (preferably 5 to 70 parts by weight) with respect to the resin composition (100 parts by weight) constituting the antireflection material. , more preferably 5 to 60 parts by weight), the antireflection material according to any one of the above [1] to [16].

[18] The antireflection material according to any one of [1] to [17] above, wherein the resin composition is a transparent curable resin composition.
[19] A binary copolymer in which the core portion in the core-shell structure is selected from the group consisting of (meth)acrylate/aromatic vinyl and (meth)acrylate/conjugated diene; or (meth)acrylic acid The antireflection material according to any one of [1] to [18] above, which is composed of a terpolymer of ester/aromatic vinyl/conjugated diene.
[20] The reflection according to [19] above, wherein the core portion in the core-shell structure is composed of a (meth)acrylate/aromatic vinyl binary copolymer (preferably butyl acrylate/styrene). prevention material.
[21] The above-mentioned [19] or [20], wherein the core portion in the core-shell structure further contains a reactive cross-linking monomer (preferably divinylbenzene) having two or more reactive functional groups in one monomer. anti-reflective material.
[22] The antireflection material according to any one of [1] to [21] above, wherein the shell layer in the core-shell structure is made of a polymer different from the polymer forming the core portion in the core-shell structure. .
[23] The shell layer in the core-shell structure consists of (meth)acrylic acid ester/aromatic vinyl/hydroxyalkyl (meth)acrylate and (meth)acrylic acid ester/aromatic vinyl/α,β-unsaturated acid. A terpolymer selected from the group, or a binary copolymer selected from the group consisting of (meth)acrylic acid ester/hydroxyalkyl (meth)acrylate, (meth)acrylic acid ester/α,β-unsaturated acid (preferably a binary copolymer), the antireflection material according to any one of the above [1] to [22].
[24] The above-mentioned [23], wherein the shell layer in the core-shell structure further contains a reactive cross-linking monomer (preferably allyl (meth)acrylate) having two or more reactive functional groups in one monomer. Anti-reflective material.
[25] The antireflection material according to any one of [1] to [24] above, wherein the rubber particles have an average particle size of 20 to 400 nm.
[26] The antireflection material according to any one of [1] to [25] above, wherein the rubber particles have a maximum particle size of 100 to 800 nm.
[27] The antireflection according to any one of [1] to [26] above, wherein the rubber particles have a refractive index of 1.40 to 1.60 (preferably 1.42 to 1.58). material.
[28] Any one of the above [1] to [27], wherein the difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition is within ±0.018. Anti-reflective material.

［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。］
［３２］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種を含む、上記［３１］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。式（１－９）、（１－１０）中のｎ１～ｎ６は、それぞれ１～３０の整数を示す。］
［３３］前記式（１）で表される化合物が、上記式（１－１）で表される化合である、上記［３２］に記載の反射防止材。
［３４］前記（ii）脂環に直接単結合で結合したエポキシ基を有する化合物が、下記式（２）で表される化合物である、上記［２９］～［３３］のいずれか１つに記載の反射防止材。

［式（２）中、Ｒ'は、ｐ価の有機基であり、ｐ、ｑはそれぞれ自然数を表す。］
［３５］前記ゴム粒子の配合量が、ゴム粒子分散エポキシ化合物（Ｂ）全量（１００重量％）に対して、０．５～３０重量％（好ましくは１～２０重量％程度）である、上記［１］～［３４］のいずれか１つに記載の反射防止材。
［３６］前記ゴム粒子分散エポキシ化合物（Ｂ）の２５℃における粘度が、４００ｍＰａ・ｓ～５００００ｍＰａ・ｓ（好ましくは５００ｍＰａ・ｓ～１００００ｍＰａ・ｓ）である、上記［１］～［３５］のいずれか１つに記載の反射防止材。
［３７］前記ゴム粒子分散エポキシ化合物（Ｂ）の使用量が、樹脂組成物中に含有される全エポキシ基含有樹脂の２０～１００重量％（好ましく５０～１００重量％）である、上記［１］～［３６］のいずれか１つに記載の反射防止材。
［３８］前記酸無水物硬化剤（Ｃ）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［１］～［３７］のいずれか１つに記載の反射防止材。
［３９］前記酸無水物硬化剤（Ｃ）の使用量が、樹脂組成物中に含有する全エポキシ基を有する化合物１００重量部に対して、５０～１５０重量部（好ましくは５２～１４５重量部、より好ましくは、５５～１４０重量部）である、上記［１］～［３８］のいずれか１つに記載の反射防止材。
［４０］前記酸無水物硬化剤（Ｃ）の使用量が、樹脂組成物中に含有する全てのエポキシ基を有する化合物におけるエポキシ基１当量当たり、０．５～１．５当量となる割合である、上記［１］～［３９］のいずれか１つに記載の反射防止材。
［４１］硬化促進剤（Ｄ）の使用量が、樹脂組成物中に含有する全エポキシ基を有する化合物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、特に好ましくは０．２～３重量部、最も好ましくは０．２５～２．５重量部）である、上記［１］～［４０］のいずれか１つに記載の反射防止材。[29] The alicyclic epoxy resin comprises (i) a compound having at least one (preferably two or more) alicyclic epoxy groups in the molecule; (ii) an epoxy group directly bonded to the alicyclic ring with a single bond and (iii) at least one compound selected from the group consisting of compounds having an alicyclic ring and a glycidyl group.
[30] The antireflection material according to [29] above, wherein the alicyclic epoxy group of (i) the compound having at least one alicyclic epoxy group in the molecule is a cyclohexene oxide group.
[31] The antireflection material according to [30] above, wherein the (i) compound having at least one alicyclic epoxy group in the molecule is 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). A substituent (preferably an alkyl group) may be bonded to one or more carbon atoms constituting the alicyclic ring in formula (1). ]
[32] The compound represented by formula (1) is 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, bis(3,4-epoxycyclohexylmethyl)ether, 1,2- Bis(3,4-epoxycyclohexan-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, and the following formulas (1-1) to ( The antireflection material according to [31] above, which contains at least one compound selected from the group consisting of compounds represented by 1-10).

[l and m in formulas (1-5) and (1-7) each represent an integer of 1 to 30. R in formula (1-5) is an alkylene group having 1 to 8 carbon atoms. n1 to n6 in formulas (1-9) and (1-10) represent integers of 1 to 30, respectively. ]
[33] The antireflection material according to [32] above, wherein the compound represented by formula (1) is a compound represented by formula (1-1) above.
[34] Any one of [29] to [33] above, wherein (ii) the compound having an epoxy group directly bonded to the alicyclic ring with a single bond is a compound represented by the following formula (2): Antireflection material as described.

[In formula (2), R' is a p-valent organic group, and p and q each represent a natural number. ]
[35] The amount of the rubber particles is 0.5 to 30% by weight (preferably about 1 to 20% by weight) with respect to the total amount (100% by weight) of the rubber particle-dispersed epoxy compound (B). [1] The antireflection material according to any one of [34].
[36] Any one of the above [1] to [35], wherein the rubber particle-dispersed epoxy compound (B) has a viscosity of 400 mPa·s to 50000 mPa·s (preferably 500 mPa·s to 10000 mPa·s) at 25°C. or the antireflection material according to claim 1.
[37] The above [1], wherein the rubber particle-dispersed epoxy compound (B) is used in an amount of 20 to 100% by weight (preferably 50 to 100% by weight) of the total epoxy group-containing resin contained in the resin composition. ] The antireflection material according to any one of [36].
[38] The acid anhydride curing agent (C) 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. The antireflection material according to any one of [1] to [37] above.
[39] The amount of the acid anhydride curing agent (C) used is 50 to 150 parts by weight (preferably 52 to 145 parts by weight) per 100 parts by weight of the compound having all epoxy groups contained in the resin composition. , more preferably 55 to 140 parts by weight), the antireflection material according to any one of [1] to [38].
[40] The amount of the acid anhydride curing agent (C) used is 0.5 to 1.5 equivalents per equivalent of epoxy groups in all epoxy group-containing compounds contained in the resin composition. The antireflection material according to any one of [1] to [39] above.
[41] The amount of the curing accelerator (D) used is 0.05 to 5 parts by weight (preferably 0.1 to 3 parts by weight) per 100 parts by weight of the compound having all epoxy groups contained in the resin composition. parts, particularly preferably 0.2 to 3 parts by weight, most preferably 0.25 to 2.5 parts by weight).

[42] The antireflection material according to any one of [1] to [41] above, wherein the resin composition further contains a nonporous filler (F) having a specific surface area of 10 m ² /g or less. .
[43] The antireflection material according to [42] above, wherein the nonporous filler (F) is a nonporous silica filler.
[44] The content (blended amount) of the nonporous filler (F) is 10 to 200 parts by weight (preferably 20 to 150 parts by weight) with respect to the resin composition (100 parts by weight) constituting the antireflection material. Part), the antireflection material according to the above [42] or [43].
[45] The total content (total compounding amount) of the porous filler (A) and the nonporous filler (F) is 20 to 60% by weight with respect to the total amount of the antireflection material (100% by weight). , The antireflection material according to any one of the above [42] to [44].

[46] The antireflection material according to any one of [1] to [45] above, wherein the resin composition contains a polyhydric alcohol (preferably an alkylene glycol having 2 to 4 carbon atoms).
[47] The content (blended amount) of the polyhydric alcohol is 0.05 to 5 parts by weight (preferably 0.1 to 3 parts by weight) with respect to 100 parts by weight of the total epoxy compound contained in the resin composition. , more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight), the antireflection material according to [46] above.
[48] The antireflection material according to any one of [1] to [47] above, wherein the resin composition contains a phosphor.
[49] The antireflection material according to [48] above, wherein the content (blended amount) of the phosphor is 0.5 to 20% by weight with respect to the total amount (100% by weight) of the resin composition.
[50] The resin composition contains, in addition to the rubber particle-dispersed epoxy compound (B), an alicyclic epoxy resin containing no rubber particles (preferably an alicyclic epoxy resin represented by the above formula (1)). The antireflection material according to any one of [1] to [49] above.
[51] The above [ 50].
[52] The above [1] to [1] to [1], wherein the resin composition contains an epoxy resin other than an alicyclic epoxy resin (preferably a glycidyl ether epoxy compound having an aromatic ring such as bisphenol A type or bisphenol F type) 51].
[53] The above [52], wherein the amount of the epoxy resin other than the alicyclic epoxy resin used is less than 70% by weight (preferably less than 60% by weight) of the total epoxy group-containing resin contained in the resin composition. ].

[54] The above [1 ] The antireflection material according to any one of [53].
[55] The antireflection material according to any one of [1] to [54] above, which is for optical semiconductor encapsulation.
[56] An optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material according to [55] above.

[57] A resin composition in which a porous filler (A) is dispersed, which is used for producing the antireflection material according to any one of [1] to [55] above. hand,
Contains a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride-based curing agent (C), and a curing accelerator (D),
The rubber particles have a core-shell structure, are composed of a polymer containing a (meth)acrylic acid ester as an essential monomer component, and have hydroxyl groups and/or carboxyl groups on their surfaces as functional groups capable of reacting with an alicyclic epoxy resin. having an average particle size of 10 nm to 500 nm, a maximum particle size of 50 nm to 1000 nm, and a difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition being within ±0.02;
A resin composition in which the content of the porous filler (A) is 4 to 40% by weight with respect to the total amount (100% by weight) of the resin composition.
[58] The resin composition according to [57] above, which is liquid.
[59] The resin composition according to the above [57] or [58], wherein the amount of components volatilized during curing is 10% by weight or less relative to the total amount (100% by weight) of the resin composition.
[60] A method for producing an antireflection material having surface irregularities that suppress reflection, comprising curing the resin composition according to any one of [57] to [59] above.

In addition to high transparency and excellent antireflection function, the antireflection material of the present invention has high thermal shock resistance, so it can be suitably used as a resin for optical materials (used for forming optical materials). can be done. Examples of the optical member include members exhibiting various optical functions such as light diffusion, light transmission, and light reflectivity, and members constituting devices and equipment utilizing the above optical functions. For example, 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, optics Known or commonly used optical members used in various applications such as lenses, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors are exemplified.

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

Claims (10)

An antireflection material comprising a cured product of a resin composition in which a porous filler (A) is dispersed, wherein the porous filler (A) is uniformly dispersed throughout the cured product, and the porous The filler (A) forms irregularities that suppress reflection on the surface of the cured product,
The resin composition contains a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride curing agent (C), and a curing accelerator (D),
The rubber particles have a core-shell structure, are composed of a polymer containing a (meth)acrylic acid ester as an essential monomer component, and have hydroxyl groups and/or carboxyl groups on their surfaces as functional groups capable of reacting with an alicyclic epoxy resin. having an average particle size of 10 nm to 500 nm, a maximum particle size of 50 nm to 1000 nm, and a difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition being within ±0.02;
The content of the porous filler (A) is 4 to 40% by weight with respect to the total amount of the antireflection material (100% by weight) ,
The antireflection material, wherein the porous filler (A) has an oil absorption of 100 to 2000 mL/100 g . The resin composition further contains a nonporous filler (F) having a specific surface area of 10 m ² /g or less, and the porous filler (A) and the nonporous The antireflection material according to claim 1 , wherein the total content of filler (F) is 20-60% by weight. The antireflection material according to claim 1 or 2 , wherein the porous filler (A) is an inorganic porous filler. The antireflection material according to any one of claims 1 to 3 , wherein the resin composition comprises a transparent curable resin composition. The antireflection material according to any one of claims 1 to 4 , which is for optical semiconductor encapsulation. An optical semiconductor device in which an optical semiconductor element is encapsulated with the antireflection material according to claim 5 . A resin composition in which a porous filler (A) is dispersed, characterized by being used for the production of the antireflection material according to any one of claims 1 to 5 ,
Contains a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin, an acid anhydride-based curing agent (C), and a curing accelerator (D),
The rubber particles have a core-shell structure, are composed of a polymer containing a (meth)acrylic acid ester as an essential monomer component, and have hydroxyl groups and/or carboxyl groups on their surfaces as functional groups capable of reacting with an alicyclic epoxy resin. having an average particle size of 10 nm to 500 nm, a maximum particle size of 50 nm to 1000 nm, and a difference between the refractive index of the rubber particles and the refractive index of the cured product of the resin composition being within ±0.02;
The content of the porous filler (A) is 4 to 40% by weight with respect to the total amount (100% by weight) of the resin composition ,
The resin composition , wherein the porous filler (A) has an oil absorption of 100 to 2000 mL/100 g . The resin composition according to claim 7 , which is liquid. 9. The resin composition according to claim 7 , wherein the amount of components volatilized during curing is 10 % by weight or less relative to the total amount (100% by weight) of the resin composition. 10. A method for producing an antireflection material having surface irregularities that suppress reflection, comprising curing the resin composition according to any one of claims 7 to 9 .

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