KR20190059970A - Antireflective material - Google Patents

Abstract

The present invention provides an optical semiconductor device having a sufficient antireflection function and capable of preventing the reduction of the total luminous flux of a light source, an antireflection member having a high thermal shock resistance and an optical semiconductor element sealed by the antireflection member .
The present invention relates to an antireflective material comprising a cured product of a resin composition in which a porous filler (A) is dispersed, wherein the porous filler (A) forms irregularities for suppressing reflection on the surface of the cured product, (B), an acid anhydride-based curing agent (C) and a curing accelerator (D) in which rubber particles are dispersed in an alicyclic epoxy resin, the rubber particles have a core- Acrylic acid esters as essential monomer components and having a hydroxyl group and / or carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface and having an average particle diameter of 10 nm to 500 nm, a maximum particle diameter of 50 nm And the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within 0.02, and the amount of the porous filler (A) relative to the total amount of the antireflective material (100 wt% Provides an optical semiconductor device, the content of the optical semiconductor device sealed by the reflection preventing member, and the anti-reflective material, characterized in that 4 to 40% by weight.

Description

Antireflective material

The present invention relates to an antireflection material. Further, the present invention relates to an optical semiconductor device in which an optical semiconductor element is sealed by the antireflection material. Further, the present invention relates to a resin composition suitable for the production of the above-mentioned antireflection material, and a process for producing an antireflection material using the resin composition. The present application claims priority of Japanese Patent Application No. 2016-200398, filed on October 11, 2016, the contents of which are incorporated herein by reference.

2. Description of the Related Art In recent years, light emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as a light source have been employed in various indoor or outdoor display panels, traffic signals, large display units and the like. As such an optical semiconductor device, 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 by a transparent sealing material is popular. In the optical semiconductor device, the surface of the sealing material is subjected to antireflection treatment in order to prevent deterioration of visibility due to reflection of incident light such as illumination light or sunlight from the outside.

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).

Japanese Patent Application Laid-Open No. 2007-234767

However, when the method of Patent Document 1 is applied to a resin for optical semiconductor encapsulation, it has been found that it is difficult to secure a total light flux of a light source while giving a sufficient antireflection function. That is, when an inorganic filler is added in a necessary and sufficient amount to obtain a sufficient antireflection function, the entire light flux of the light source is significantly lowered. On the other hand, when the blending amount of the inorganic filler is reduced in order to prevent the reduction of the total light flux of the light source, It is clear that there is a trade-off relationship that the ability is not obtained.

Further, in recent years, the optical semiconductor device has been made more and more powerful, and the sealing material in such optical semiconductor devices is cracked (cracked) when a thermal shock such as a cooling / heating cycle (periodically repeating heating and cooling) Thus, a problem of becoming an auxiliary light has occurred. For this reason, the sealing material in the optical semiconductor device is required to have a property that cracks are less likely to occur (sometimes referred to as " thermal shock resistance ") even when a thermal shock is applied.

Accordingly, it is an object of the present invention to provide an antireflection member having a sufficient antireflection function, capable of preventing the reduction of the total luminous flux of a light source, and having a high thermal shock resistance.

Another object of the present invention is to provide the above-mentioned antireflection material for optical semiconductor sealing.

Another object of the present invention is to provide an optical semiconductor device in which an optical semiconductor element is sealed by the antireflection material.

Another object of the present invention is to provide a resin composition suitable for the production of the antireflection material, and a method for producing the antireflection material using the resin composition.

As one of the reasons why sufficient antireflection performance can not be obtained when the amount of the inorganic filler is reduced, the inorganic filler is not spread over the entire resin layer due to sedimentation and consequently uniform irregularities are not formed on the entire surface The present inventors have found that when the blending amount is increased so that the incident light is not efficiently scattered and the inorganic filler is settled even if the inorganic filler is settled down to obtain the antireflection performance over the entire surface of the resin layer, the inorganic filler itself absorbs the light, .

As a result of intensive studies to solve the above problems, the present inventors have found that when a porous filler is incorporated as a filler in a resin layer constituting an antireflection material, a sufficient antireflection function is imparted even by adding a small amount. Further, when an alicyclic epoxy resin in which rubber particles of a specific structure are dispersed is used as the resin layer, it has been found that the resin composition also has excellent thermal shock resistance. Thereby, an antireflection material having sufficient antireflection function and excellent thermal shock resistance without deteriorating the whole light flux of the light source is provided, and it is found that it is very suitable as a material for sealing the optical semiconductor element in the optical semiconductor device, And has reached the completion of the invention.

That is, the present invention relates to an antireflection material comprising a cured product of a resin composition in which a porous filler (A) is dispersed, wherein the porous filler (A)

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)

Wherein the rubber particles have a core shell structure and are composed of a polymer having a (meth) acrylate ester as an essential monomer component and having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface, A particle diameter of 10 nm to 500 nm and a maximum particle diameter of 50 nm to 1000 nm and the difference between the refractive index of the rubber particle and the cured product refractive index of the resin composition is within 0.02,

Wherein the content of the porous filler (A) relative to the total amount of the antireflective material (100 wt%) is 4 to 40 wt%.

In the antireflection material, the porous filler (A) is preferably uniformly dispersed throughout the cured product, and forms irregularities on the surface to suppress reflection.

In the antireflection material, the resin composition may further include a non-porous filler (F) having a specific surface area of 10 m ² / g or less. In this case, the total amount of the antireflection material (100 wt% The total content of the porous filler (A) and the non-porous 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 include a transparent curable resin composition.

The anti-reflection member may be for optical semiconductor sealing.

Further, the present invention provides an optical semiconductor device in which an optical semiconductor element is sealed by the antireflection material.

Further, the present invention is a resin composition in which a porous filler (A) is dispersed, which is used for producing the above-mentioned antireflection material,

A rubber particle-dispersed epoxy compound (B), an acid anhydride-based curing agent (C) and a curing accelerator (D) in which rubber particles are dispersed in an alicyclic epoxy resin,

Wherein the rubber particles have a core shell structure and are composed of a polymer having a (meth) acrylate ester as an essential monomer component and having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface, A particle diameter of 10 nm to 500 nm and a maximum particle diameter of 50 nm to 1000 nm and the difference between the refractive index of the rubber particle and the cured product refractive index of the resin composition is within 0.02,

Wherein the content of the porous filler (A) relative to the total amount (100 wt%) of the resin composition is 4 to 40 wt%.

The resin composition may be in a liquid state.

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

Further, the present invention provides a method for producing an antireflective material, wherein the resin composition is cured, wherein unevenness for suppressing reflection on the surface is formed.

Since the antireflection material of the present invention has the above-described structure, a sufficient antireflection function can be obtained even when the blending amount of the porous filler (A) is reduced, and a significant decrease in the total light of the light source can be prevented, . Therefore, by using the antireflective member of the present invention as a material for sealing an optical semiconductor element in an optical semiconductor device, it is possible to provide a high-quality optical semiconductor (for example, having sufficient brightness and high durability while suppressing gloss) Device is obtained.

Further, since the resin composition of the present invention has the above-described constitution, it is very suitable for producing the antireflective member.

1 is a schematic view showing an embodiment of an optical semiconductor device including an antireflective member of the present invention. The left side view (a) is a perspective view, and the right side view (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, wherein the porous filler (A) forms irregularities on the surface of the cured product to suppress reflection, (B), an acid anhydride-based curing agent (C) and a curing accelerator (D) in which rubber particles are dispersed in an alicyclic epoxy resin, the rubber particles have a core shell structure, And has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface and has an average particle diameter of 10 nm to 500 nm and a maximum particle diameter of 50 nm to 1000 nm , And the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within ± 0.02 and the difference between the refractive index of the porous filler (A) And the content is 4 to 40% by weight.

The resin composition of the present invention is a resin composition containing a rubber particle-dispersed epoxy compound (B), an acid anhydride-based curing agent (C) and a curing accelerator (D) in which a porous inorganic filler is dispersed and rubber particles are dispersed in an alicyclic epoxy resin (Meth) acrylic acid ester as essential monomer components and has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface thereof , The average particle diameter is 10 nm to 500 nm, the maximum particle diameter is 50 nm to 1000 nm, the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within ± 0.02, The content of the filler (A) is 4 to 40% by weight, and is used for producing the antireflective member.

Since the porous structure of the porous filler (A) increases the apparent volume of the resin composition as compared with the non-porous filler, even a small amount of the filler spreads widely throughout the resin composition or the cured product thereof, It is possible to form fine irregularities on the surface of the cured product. Further, the resin composition seeps into the porous structure, and the apparent specific gravity difference between the porous filler (A) and the resin composition is lowered, whereby the dispersed state is stabilized and the interaction of the surfaces of the porous filler (A) So that the porous filler (A) can be uniformly spread over the entirety of the resin composition or the cured product thereof, so that uniform and fine unevenness can be formed on the surface of the cured product to efficiently scatter the incident light.

In the present specification, the amount of the porous filler (A) to be added (used amount) means a small amount (less) means less in terms of weight conversion and does not mean that it is small in terms of volume (volume) conversion.

In the case of using the porous filler (A), reflection can be effectively suppressed even when the amount of use is reduced compared to a non-porous filler, so that the porous filler (A) , Sufficient antireflection function can be secured.

The resin composition preferably contains a rubber particle-dispersed epoxy compound (B), an acid anhydride-based curing agent (C) and a curing accelerator (D) in which rubber particles are dispersed in an alicyclic epoxy resin, And having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface and having an average particle diameter of 10 nm to 500 nm , Rubber particles having a maximum particle diameter of 50 nm to 1000 nm and the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within ± 0.02 is used so that the rubber component is not eluted from the rubber particle , The glass transition temperature of the cured product obtained by curing the resin composition is not significantly lowered and the transparency is not impaired. The cured product obtained by curing the resin composition containing the rubber particle-dispersed epoxy compound (B) can exhibit excellent crack resistance (thermal shock resistance) against thermal shock while maintaining excellent heat resistance and transparency.

Hereinafter, each component will be described in detail.

[Porous filler (A)]

The porous filler (A) in the antireflective member or the resin composition of the present invention is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof, and as a result of the stable dispersion state, the porous filler (A) present on the surface of the cured product A have the function of forming irregularities for scattering the incident light.

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

Examples of the inorganic porous filler (A1) include inorganic glass (for example, borosilicate glass, sodium borosilicate glass, sodium silicate glass, aluminum silicate glass, quartz, etc.) A metal oxide such as 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, Powder having a porous structure such as barium sulfate, barium sulfate, forsterite, stearate, spinel, clay, kaolin, dolomite, hydroxyapatite, nepherinecinite, cristobalite, wollastonite, diatomaceous earth and talc; (For example, spherical beads, etc.). As the inorganic porous filler (A1), it is possible to use an inorganic porous filler having a surface (for example, a metal oxide, a silane coupling agent, a titanium coupling agent, a surface treatment agent such as an organic acid, a polyol, Processing, etc.] have been carried out. By carrying out such a surface treatment, the compatibility with the component of the resin composition and the dispersibility can be improved in some cases. Among them, porous inorganic glass or porous silica (porous silica filler) is preferably used as the inorganic porous filler (A1) from the viewpoint that it can spread uniformly throughout the resin composition or the cured product thereof to efficiently form concavities and convexities on the surface of the cured product desirable.

The porous silica is not particularly limited, and for example, known or common porous silica such as fused silica, crystalline silica, high purity synthetic silica, colloidal silica and the like can be used. As the porous silica, there can be used a surface treated with a known or common surface treatment (for example, a surface treatment with a hydrophobic surface treating agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, an organic silicon compound, etc.) It can also be used. In the present specification, the porous silica surface-treated with the hydrophobic surface treatment agent may be referred to as " hydrophobic porous silica ".

Hydrophobic porous silica is preferable from the viewpoint of improving the compatibility with the components of the resin composition and dispersibility and improving the heat resistance (for example, heat resistance water) of the cured product. As the hydrophobic surface treatment agent, For example, trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, silicone oil and the like are preferable, and polydimethylsiloxane and the like are more preferable .

As the organic porous filler (A2), there can be used a publicly known or publicly known one, and there is no particular limitation, and examples thereof include styrene resin, acrylic resin, silicone resin, acryl- styrene resin, vinyl chloride resin, (Such as a crosslinked body of these polymers) such as a resin, an amide resin, a urethane resin, a phenol resin, a styrene-conjugated diene resin, an acryl-conjugated diene resin, an olefin resin and a cellulose resin And organic porous fillers such as a polymer porous sintered body, a polymer foam, and a gel porous body.

An inorganic-organic porous filler composed of a hybrid material of an inorganic material and an organic material may 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), the inorganic porous filler (A1) is preferable from the viewpoint that it can be widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof and efficiently form irregularities on the surface of the cured product, (Porous silica filler) is more preferable from the viewpoints of properties and ease of manufacture, and hydrophobic porous silica (hydrophobic porous silica filler) is more preferable from the viewpoint of the heat resistance (for example, heat resistance water) of the cured product.

The shape of the porous filler (A) is not particularly limited, and examples thereof include powder, spherical, crushed, fibrous, needle-like, scaly and the like. Among them, the spherical or crushed porous filler (A) is preferably used in view of the fact that the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof to easily form a fine uneven shape on the surface of the cured product. .

Although the center particle diameter of the porous filler (A) is not particularly limited, the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof to easily form a fine irregular shape on the surface of the cured product , It is preferably from 0.1 to 100 mu m, more preferably from 1 to 50 mu m. The center particle size means a volume particle diameter (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, oil absorption amount and the like, and the porous filler (A) having a grade suitable for the anti- You can choose without.

The specific surface area of the porous filler (A) is not particularly limited, but the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof to easily form fine unevenness on the surface of the cured product, From the viewpoint of effectively preventing reflection, it is preferably 10 to 2000 m ² / g, more preferably 100 to 1000 m ² / g. If the specific surface area is 10 m ² / g or more, the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof, and the antireflection function of the surface of the cured product tends to be improved. On the other hand, when the specific surface area is 2000 m ² / g or less, the viscosity of the resin composition containing the porous filler (A) is increased and the thixotropic property is suppressed, so that the fluidity at the time of producing the antireflection material tends to be secured. The specific surface area means the nitrogen adsorption specific surface area determined based on the BET equation from the adsorption isotherm of nitrogen at -196 캜, in accordance with Annex E of JIS K6430.

The "specific surface area" means the specific surface area of the porous filler (A) before the surface treatment in the case of the porous filler (A) surface-treated with the hydrophobic surface treatment agent.

The pore volume of the porous filler (A) is not particularly limited, but the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof to easily form fine unevenness on the surface of the cured product, From the viewpoint of effectively preventing reflection, it is preferably 0.1 to 10 mL / g, more preferably 0.2 to 5 mL / g. If the pore volume is 0.1 mL / g or more, the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof, and the concave-convex shape tends to be easily formed on the surface of the cured product. On the other hand, when the pore volume is 5 mL / g or less, the mechanical strength of the porous filler (A) tends to be improved. The pore volume of the porous filler (A) can be determined by measuring the pore distribution by mercury porosimetry (porosimetry).

The amount of oil absorbed by the porous filler (A) is not particularly limited, but the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product of the resin composition to easily form a fine uneven shape on the surface of the cured product, It is preferably from 10 to 2000 mL / 100 g, more preferably from 100 to 1000 mL / 100 g from the viewpoint of effectively preventing the problem. When the oil absorption amount is 10 mL / 100 g or more, the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof, and the concave and convex shape tends to be easily formed on the surface of the cured product. On the other hand, when the oil absorption amount is 2000 mL / 100 g or less, the mechanical strength of the porous filler (A) tends to be improved. The feed amount of the porous filler (A) is the amount of oil absorbed by the filler (100g), and can be measured in accordance with JIS K5101.

In the antireflection material of the present invention, the porous filler (A) may be used singly or in combination of two or more kinds. The porous filler (A) may be produced by a known or common production method. For example, the porous filler (A) may be produced by a method known in the art, for example, a trade name of "SiRiSiA 250N", "SiRiSiA 256", "SiRiSiA 256N" Saarisia 320 "," Saarisia 350 "," Saarisia 358 "," Saarisia 430 "," Saarisia 431 "," Saarisia 440 "," Saarisia 450 "," Saarisia 470 " 435 "," Siiricia 445 "," Siiricia 436 "," Siiricia 446 "," Siiricia 456 "," Siirisia 530 "," Siirisia 540 "," Siirisia 550 " , Saarisia series such as " Saarisia 740 ", " Saarisia 770 ", and Saarispaera series such as Saaris speara C-1504 and Saaris speara C- Quot ;, San Sphere H-31, San Sphere H-32 , "Sanspecia H-52", "Sanspecia H-52", "Sanspecia H-52", " (Manufactured by AGC Sightech Co., Ltd.), such as "SanSpore H-201" manufactured by Nippon Kayaku Co., Ltd., (Manufactured by Fuji Silicia Chemical Co., Ltd.) such as "Silo Fobic 100", "Silo Fobic 200", "Silo Fobic 704", "Silo Fobic 507", "Silo Fobic 603" (Commercially available from Ebonic Degussa), trade names "Sanspere H-121-ET", "Sanspere H-51-ET" And commercially available products such as hydrophobic porous silica such as Sanspere ET series (manufactured by AGC Sightech Co., Ltd.), etc. may be used.

The content (blending amount) of the porous filler (A) in the antireflective member or the resin composition of the present invention is 4 to 40% by weight based on the total amount (100% by weight) of the antireflective member or the resin composition, 4 to 35% by weight, more preferably 4 to 30% by weight. The content of the porous filler (A) is 4 wt% or more, whereby the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product constituting the antireflection material, . On the other hand, when the content of the porous filler (A) is 40 wt% or less, it is possible to prevent remarkable deterioration of the whole light flux when the antireflective material or the resin composition of the present invention is used as a sealing material for optical semiconductor devices, There is a tendency to be able to secure.

The content (blending amount) of the porous filler (A) in the antireflective member or the 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 member, Is 5 to 70 parts by weight, more preferably 5 to 60 parts by weight. The content of the porous filler (A) is 5 parts by weight or more, whereby the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product constituting the antireflection material, . On the other hand, when the content of the porous filler (A) is 80 parts by weight or less, remarkable deterioration of the total light is prevented when the antireflective material or the resin composition of the present invention is used as a sealing material for optical semiconductor devices, There is a tendency to be able to secure.

[Resin composition]

The resin composition constituting the cured product of the antireflection material of the present invention is a rubber particle-dispersed epoxy compound (B) in which rubber particles are dispersed in an alicyclic epoxy resin (hereinafter referred to as " rubber particle dispersion epoxy compound (B) "), an acid anhydride-based curing agent (C) and a curing accelerator (D), wherein the rubber particles have a core shell structure and a (meth) acrylic acid ester as an essential monomer component And has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface, has an average particle diameter of 10 nm to 500 nm and a maximum particle diameter of 50 nm to 1000 nm, And the difference in the refractive index of the cured product of the resin composition is within ± 0.02. The resin composition is suitable as a sealing material of an optical semiconductor element in an optical semiconductor device, that is, as a resin composition for optical semiconductor encapsulation. For example, the resin composition is cured by heat and has high transparency and durability A property that transparency is not easily lowered by light, a characteristic that cracks or peeling from an adherend are hard to occur even when high temperature heat or thermal shock is applied, and the like), and particularly, a cured product excellent in thermal shock resistance is given.

[Rubber particle-dispersed epoxy compound (B)]

The rubber particle-dispersed epoxy compound (B) in the present invention is composed of a polymer having a core shell structure and a (meth) acrylate ester as an essential monomer component, and a functional group capable of reacting with the alicyclic epoxy resin Is a rubber particle having a hydroxyl group and / or a carboxyl group and having an average particle diameter of 10 nm to 500 nm and a maximum particle diameter of 50 nm to 1000 nm and the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within 0.02 And rubber particles are dispersed in an alicyclic epoxy resin.

(Rubber particles)

The rubber particles in the present invention have a multilayer structure (core shell structure) including a core portion having rubber elasticity and at least one shell layer covering the core portion. Further, it is composed of a polymer having a (meth) acrylate ester as an essential monomer component, and has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface. When the hydroxyl group and / or the carboxyl group is not present on the surface of the rubber particle, the cured product is clouded by thermal shock such as a cooling / heating cycle and the transparency is lowered.

As the monomer component constituting the polymer of the core portion having rubber elasticity, a (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate is essential. Examples of the monomer component which may be contained in addition to the (meth) acrylate ester include silicone such as dimethylsiloxane and phenylmethylsiloxane, aromatic vinyl such as styrene and? -Methylstyrene, nitrile such as acrylonitrile and methacrylonitrile, Conjugated dienes such as butadiene and isoprene, urethane, ethylene, propylene and isobutene.

In the present invention, it is preferable that a monomer component constituting the core portion having rubber elasticity includes one or more kinds selected from silicone, aromatic vinyl, nitrile and conjugated diene in combination with (meth) acrylic acid ester And preferred examples thereof include bicyclic copolymers such as (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene; And ternary copolymers such as (meth) acrylic acid ester / aromatic vinyl / conjugated diene.

In addition to the above monomer components, the core portion having rubber elasticity may further contain, in addition to the monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, A reactive crosslinking monomer having two or more reactive functional groups in one monomer corresponding to diacrylate or the like may be contained.

The monomer component constituting the core portion having rubber elasticity in the present invention is preferably a binary copolymer of (meth) acrylic acid ester / aromatic vinyl (especially butyl acrylate / styrene) Can be adjusted.

The core portion having rubber elasticity can be produced by a commonly used method, and examples thereof include a method of polymerizing the monomer by emulsion polymerization. As the emulsion polymerization method, the total amount of the above-mentioned monomers may be fed in as a batch, or a part of the above-mentioned monomers may be polymerized and then the remaining may be continuously or intermittently added and polymerized. .

The shell layer preferably includes a polymer different from the polymer constituting the core portion. The shell layer has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin. Thereby, the adhesiveness at the interface of the alicyclic epoxy resin can be improved, and by curing the resin composition containing the rubber particles having the shell layer, a transparent cured product having excellent crack resistance and having no cloudiness can be obtained . Further, the glass transition temperature of the cured product can be prevented from lowering.

Examples of the monomer component constituting the shell layer include (meth) acrylic acid esters, such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) (Meth) acrylate other than butyl acrylate (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, butyl methacrylate, etc.) is preferably used as the shell layer in the case of butyl acrylate. Examples of the monomer component that may be contained in addition to the (meth) acrylic acid ester include aromatic vinyl such as styrene and? -Methylstyrene, nitrile such as acrylonitrile and methacrylonitrile, and the like. In the present invention, as the monomer component constituting the shell layer, it is preferable to contain the above monomers alone or in combination of two or more kinds together with the (meth) acrylic acid ester. Especially, And the refractive index of the rubber particles can be adjusted.

(Meth) acrylate such as 2-hydroxyethyl (meth) acrylate, and the like can be given as a monomer component having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin. Containing monomer such as an?,? -Unsaturated acid such as acrylic acid,?,? -Unsaturated acid anhydride such as maleic anhydride, and the like.

In the present invention, the monomer component constituting the shell layer preferably contains, in combination with (meth) acrylic acid ester, one or more selected from the above-mentioned monomers, and examples thereof include (meth) acrylic acid ester / (Meth) acrylate / hydroxyalkyl (meth) acrylate, (meth) acrylic ester / hydroxyalkyl (meth) acrylate, ternary copolymers such as (Meth) acrylate ester /?,? - unsaturated acid ester (preferably a (meth) acrylate ester / hydroxyalkyl (meth) acrylate, Bicyclic copolymers), and the like.

In addition to the above-mentioned monomer, the shell layer may contain, in addition to the above-mentioned monomer, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, And a reactive crosslinking monomer having two or more reactive functional groups in one monomer corresponding to phenylene glycol diacrylate and the like.

Examples of the method of covering the core portion with the shell layer include a method of coating the surface of the core portion having rubber elasticity obtained by the above method by coating a copolymer constituting the shell layer, A method in which a core portion is used as a stem component and each component constituting the shell layer is subjected to graft polymerization as a branch component.

The average particle diameter of the rubber particles in the present invention is about 10 to 500 nm, preferably about 20 to 400 nm. The maximum particle diameter of the rubber particles is about 50 to 1000 nm, preferably about 100 to 800 nm. When the average particle diameter exceeds 500 nm, or when the maximum particle diameter of the rubber particles exceeds 1000 nm, the transparency of the cured product decreases and the lightness of the optical semiconductor tends to decrease. On the other hand, when the average particle diameter is less than 10 nm, or when the maximum particle diameter of the rubber particles is less than 50 nm, the 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. 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, and preferably within ± 0.018. If the difference in the refractive index exceeds. + -. 0.02, the transparency of the cured product is lowered and, in some cases, it is opaque, the light intensity of the optical semiconductor tends to decrease, and the function of the optical semiconductor may be lost.

The refractive index of the rubber particles can be measured by, for example, molding 1 g of rubber particles into a mold and compression molding at 210 DEG C and 4 MPa to obtain a flat plate having a thickness of 1 mm and cutting a test piece having a length of 20 mm and a width of 6 mm from the obtained flat plate, Using a multi-wavelength Abbe refractometer (trade name " DR-M2 ", manufactured by Atago Co., Ltd.) under the condition that the prism and the test piece are in close contact with each other using monobromonaphthalene, the refractive index in a 20 DEG C sodium D line is measured .

The refractive index of the cured product of the resin composition is measured by cutting 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 described below and using monobromo Can be obtained by measuring the refractive index in a 20 DEG C sodium D line using a multi-wavelength Abbe refractometer (trade name " DR-M2 ", manufactured by Atago) under the condition that the prism and the test piece are in close contact with each other using naphthalene have.

(Alicyclic epoxy resin)

The alicyclic epoxy resin in the present invention is a compound having at least one alicyclic ring (aliphatic hydrocarbon ring) and at least one epoxy group in the molecule. Examples of the alicyclic epoxy compound include (i) a compound having at least one (preferably two or more) alicyclic epoxy groups (an epoxy group comprising two adjacent carbon atoms and oxygen atoms constituting alicyclic groups) in the molecule; (ii) a compound having an epoxy group directly bonded to the alicyclic ring; (iii) compounds having an alicyclic group and a glycidyl group. The alicyclic epoxy resin in the present invention preferably exhibits a liquid phase at normal temperature (25 캜) from the viewpoint of workability at the time of combination 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 among them, from the viewpoint of the curability, the cyclohexene oxide group (the two adjacent carbon atoms constituting the cyclohexane ring An epoxy group consisting of an atom and an oxygen atom). Particularly, a compound having at least one alicyclic epoxy group in the molecule (i) is preferably a compound having at least two cyclohexenecoxide groups in the molecule from the viewpoints of transparency and heat resistance of the cured product, ≪ / RTI >

In the formula (1), X represents a single bond or a linking group (a divalent group having at least one atom). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a 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, . A substituent such as an alkyl group may be bonded to at least one of the carbon atoms constituting the alicyclic epoxy group in the formula (1).

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

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

Examples of the alkenylene group in the alkenylene group in which a part or the whole of the carbon-carbon double bond is epoxidized (sometimes referred to as "epoxylated alkenylene group") include a vinylene group, a propenylene group, A straight or branched alkenylene group having 2 to 8 carbon atoms such as a butenylene group, a 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group and an octenylene group Prayer included). Particularly, as the above-mentioned epoxylated alkenylene group, an alkenylene group in which all carbon-carbon double bonds are epoxidized is preferable, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all carbon-carbon double bonds are epoxidized.

The linking group X is preferably a linking group containing an oxygen atom, specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-, an epoxyalkylene group; A plurality of these groups being connected; A group in which one or more of these groups is bonded to one or more of a divalent hydrocarbon group, and the like. 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) Bis (3,4-epoxycyclohexan-1-yl) ethane, the following formulas (1-1) to (1-10), and the like. In the following formulas (1-5) and (1-7), l and m each represent an integer of 1 to 30. R in the following formula (1-5) is an alkylene group having 1 to 8 carbon atoms, which may be a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a s-butylene group, a pentylene group, , A straight chain or branched chain alkylene group such as a heptylene group and an octylene group. Among them, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group is preferable. N1 to n6 in the following formulas (1-9) and (1-10) each represent an integer of 1 to 30;

Examples of the compound (ii) having an epoxy group bonded directly to the alicyclic ring in the above-mentioned group include, for example, a compound represented by the following formula (2).

In the formula (2), R 'is a group (p is an organic group) excluding p hydroxyl groups (-OH) from an alcohol of p number of structural units, and p and q each represent a natural number. Examples of the p-valent alcohol [R '(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol and the like (alcohols having 1 to 15 carbon atoms). p is preferably from 1 to 6, and q is preferably from 1 to 30. [ When p is 2 or more, q in each () parenthesized group may be the same or different. Specific examples of the compound represented by the formula (2) include a 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) For example, trade name " EHPE3150 " (manufactured by Daicel Chemical Industries, Ltd.).

Examples of the compound (iii) having an alicyclic group and a glycidyl group include 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2- Dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] propane, hydrogenated bisphenol A type epoxy resin (hydrogenated bisphenol A type epoxy resin); (2,3-epoxypropoxy) cyclohexyl] methane, [2- (2,3-epoxypropoxy) cyclohexyl] Bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane, bisphenol F type epoxy resins obtained by hydrogenating bis [4- (2,3-epoxypropoxy) cyclohexyl] (Hydrogenated bisphenol F type epoxy resin) and the like; Hydrogenated biphenol type epoxy resin; Hydrogenated novolak type epoxy resins (for example, hydrogenated phenol novolak type epoxy resins, hydrogenated cresol novolak type epoxy resins, hydrogenated cresol novolak type epoxy resins of bisphenol A, etc.); Hydrogenated naphthalene type epoxy resin; And hydrogenated epoxy resins of an epoxy resin obtained from trisphenol methane.

Examples of the alicyclic epoxy compound include 1,2,8,9-diepoxy limonene and the like.

These alicyclic epoxy resins may be used alone or in combination of two or more. For example, commercially available products such as "Celloxide 2021P" and "Celloxide 2081" (manufactured by Daicel Chemical Industries, Ltd.) It is possible.

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

The viscosity of the rubber particle-dispersed epoxy compound (B) is preferably from 400 mPa · s to 50,000 mPa · s at 25 ° C., and more preferably from 500 mPa · s to 10000 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. On the other hand, , The productivity tends to be lowered 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 占 퐏 or less at room temperature (25 占 폚) can be suitably used. The aliphatic polyglycidyl ether includes, for example, cyclohexanedimethanol diglycidyl ether, cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, and the like.

The amount of the reactive diluent to be used can be appropriately adjusted and is, for example, not more than 30 parts by weight, preferably not more than 25 parts by weight (for example, about 5 to 25 parts by weight) relative to 100 parts by weight of the rubber- to be. If the amount of the reactive diluent used exceeds 30 parts by weight, it tends to be difficult to obtain 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 known method can be used. For example, after the rubber particles are dewatered and dried to obtain a powder, an alicyclic epoxy resin Mixing and dispersing the rubber particle emulsion, and a method of directly mixing the rubber particle emulsion with the alicyclic epoxy resin and dewatering.

The amount of the rubber particle-dispersed epoxy compound (B) to be 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. When the amount of the rubber particle-dispersed epoxy compound (B) is less than 20% by weight of the total epoxy group-containing resin, the crack resistance of the resulting cured product tends to be lowered.

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

[Acid anhydride hardener (C)]

The acid anhydride curing agent (C) has an action of curing a compound having an epoxy group. As the acid anhydride curing agent (C) in the present invention, a curing agent for public use can be used as a curing agent for an epoxy resin. The acid anhydride curing agent (C) in the present invention is preferably an acid anhydride which is in a liquid phase at 25 ° C, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, Tetrahydrophthalic anhydride, and the like. The acid anhydrides in solid form at room temperature (25 DEG C) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic anhydride can be obtained by reacting an acid anhydride To give a liquid mixture, which can be used as the acid anhydride curing agent (C) in the present invention.

In the present invention, as the acid anhydride curing agent (C), there can be used an acid anhydride curing agent (C) such as "Ricaside MH-700" (manufactured by Shin-Nihon Rika K.K.), "HN-5500" Commercially available products may be used.

The amount of the acid anhydride curing agent (C) to be used is, for example, 50 to 150 parts by weight, preferably 52 to 145 parts by weight, particularly preferably 55 to 60 parts by weight, per 100 parts by weight of the compound having an epoxy group in the resin composition About 140 parts by weight. More specifically, it is preferably used in a proportion of 0.5 to 1.5 equivalents per equivalent of the epoxy group in the compound having all the epoxy groups contained in the resin composition. If the amount of the acid anhydride curing agent (C) used is less than 50 parts by weight, the effect becomes insufficient and the toughness of the cured product tends to deteriorate. On the other hand, And the color may be deteriorated.

[Curing accelerator (D)]

The curing accelerator (D) is a compound having a function of accelerating the curing rate when the compound having an epoxy group is cured by the acid anhydride curing agent (C). As the curing accelerator (D) in the present invention, it is possible to use a curing accelerator for a well-known purpose. Examples thereof include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) For example, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and its salts (for example, a phosphonium salt, a sulfonium salt, a quaternary ammonium salt, an iodonium salt); Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and N, N-dimethylcyclohexylamine; Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Phosphines such as phosphoric acid ester and triphenylphosphine; Phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; Organic metal salts such as tin octylate and zinc octylate; Metal chelates and the like. These may be used alone or in combination of two or more.

U-CAT SA 506 "," U-CAT SA 102 "," U-CAT 5003 "," U-CAT 18X "," 12XD (developed product) "as the curing accelerator (D) PX-4ET " (manufactured by NIPPON KAGAKU KOGYO CO., LTD.), Trade names " TPP-K ", " TPP- May be used.

The amount of the curing accelerator (D) to be used is, for example, from 0.05 to 5 parts by weight, preferably from 0.1 to 3 parts by weight, particularly preferably from 0.2 to 3 parts by weight, per 100 parts by weight of the total epoxy group- 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 part by weight, the curing accelerating effect may be insufficient. On the other hand, if the amount of the curing accelerator (D) exceeds 5 parts by weight, .

[Curing catalyst (E)]

The curing catalyst (E) in the present invention has an action of initiating polymerization of the epoxy compound in the rubber particle-dispersed epoxy compound (B). The curing catalyst (E) in the present invention is preferably a cationic polymerization initiator which generates cationic species by irradiation with ultraviolet rays or heat treatment to initiate polymerization of the rubber particle-dispersed epoxy compound (B).

Examples of the cationic polymerization initiator that generates cationic species by ultraviolet irradiation include hexafluoroantimonate salts, pentafluorohydroxy antimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and the like. CD-1011 ", " CD-1012 " (manufactured by Satomaru Co., Ltd.), trade names " IRGACURE " 264 (Product of Shiba, Japan), trade name "CIT-1682" (manufactured by Nippon Soda Co., Ltd.) can be suitably used.

Examples of the cationic polymerization initiator that generates a cationic species by subjecting to a heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, and allene-ion complexes. Examples of the cationic polymerization initiators include "PP-33" UV-1014 "(trade name, manufactured by GE Corporation), trade name" San-ai SI- Quot; CG-24-61 " (manufactured by Shiba, Japan) (trade name: SANAEI SI-110L, manufactured by SANSHIN KAGAKU KOGYO CO., LTD. (Trade name) manufactured by Kagaku Kogyo Co., Ltd. can be suitably used. In addition, a compound of a metal such as aluminum or titanium, a chelate compound of acetoacetic acid or a diketone and a silanol such as triphenylsilanol, a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or a diketone, Or a compound of phenols.

As the curing catalyst (E) in the present invention, a hexafluorophosphate salt is preferable because it is low in toxicity and easy to handle, and is excellent in versatility.

The amount of the curing catalyst (E) to be used is, for example, 0.01 to 15 parts by weight, preferably 0.01 to 12 parts by weight, particularly preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the compound having an epoxy group, Most preferably about 0.1 to 10 parts by weight. When used in this range, a cured product having excellent heat resistance, transparency and weather resistance can be obtained.

[Non-porous filler (F)]

The resin composition constituting the antireflection material of the present invention may contain the non-porous filler (F). When the resin composition of the antireflection material of the present invention contains the nonporous filler (F), the thermal shock resistance of the cured product is further improved.

The nonporous filler (F) usable in the antireflection material of the present invention means an inorganic or organic filler having no porous structure and having 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 non-porous filler (F1) that can be used in the antireflection material of the present invention, an inorganic, non-porous filler known to those skilled in the art can be used and is not particularly limited. Examples thereof include inorganic glass (for example, borosilicate 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, Zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulphate, forsterite, stearate, spinel, clay, kaolin, dolomite, hydroxyapatite, neperininositide, cristobalite, (For example, spherical beads, etc.), and the like. As the nonporous filler (F), it is possible to use a surface treatment (for example, a surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, Etc.] have been implemented. By carrying out such a surface treatment, the compatibility with the component of the resin composition and the dispersibility can be improved in some cases. Among them, as the inorganic non-porous filler (F1), inorganic nonporous glass or nonporous silica (non-porous silica filler) is preferable from the viewpoint of imparting excellent thermal shock resistance to a cured product.

As the nonporous silica, there is no particular limitation, and for example, a known or common nonporous silica such as fused silica, crystalline silica, high purity synthetic silica and the like can be used. As the nonporous silica, it is also possible to use those which have been subjected to a known or common surface treatment (for example, a surface treatment with a metal oxide, a silane coupling agent, a titanium coupling agent, a surface treatment agent such as an organic acid, have.

As the inorganic non-porous filler (F1), a material having a hollow structure may be used. The porous inorganic filler is not particularly limited, and examples thereof include inorganic glass (for example, borosilicate glass, sodium borosilicate glass, sodium silicate glass, aluminum silicate glass, quartz and the like), silica, alumina and zirconia Inorganic hollow particles (including natural materials such as Shirasu balloons) constituted by inorganic substances such as oxides, calcium carbonate, barium carbonate, nickel carbonate, and calcium silicate; And inorganic-organic hollow particles composed of a hybrid material of an inorganic material and an organic material. In order to improve the light scattering efficiency, a medium having a low refractive index (for example, nitrogen (e.g., nitrogen) or the like may be used. , Inert gas such as argon, air, or the like).

When the hollow inorganic filler is used, the hollow ratio (the volume ratio of the void relative to the volume of the entire inorganic filler) is not particularly limited, but is preferably 10 to 90% by volume, more preferably 30 to 90% Do.

As the organic non-porous filler (F2), there can be used a publicly known or publicly known one, and it is not particularly limited. For example, styrene resin, acrylic resin, silicone resin, acryl- styrene resin, vinyl chloride resin, (Including a crosslinked body of these polymers), such as an amide resin, an urethane resin, a phenol resin, a styrene-conjugated diene resin, an acryl-conjugated diene resin, an olefin resin and a cellulose resin Organic non-porous filler, and the like.

An inorganic-organic nonporous filler composed of a hybrid material of the inorganic material and the organic material may also be used.

The non-porous 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 giving the cured product excellent thermal shock resistance, and from the viewpoint of availability and easiness of production, Silica filler) is more preferable.

The shape of the non-porous filler (F) is not particularly limited, and examples thereof include powder, spherical, crushed, fibrous, needle-like, scaly and the like. Among them, the spherical or crushed non-porous filler (F) is preferable from the viewpoint that the non-porous filler (F) improves the thermal shock resistance of the cured product.

The center particle size of the nonporous filler (F) is not particularly limited, but is preferably 0.1 to 100 mu m, more preferably 1 to 50 mu m from the viewpoint that the nonporous filler (F) improves the thermal shock resistance of the cured product. The center particle size means a volume particle diameter (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) may be used singly or in combination of two or more kinds. The inorganic filler may be produced by a known or common manufacturing method. For example, an FB filler such as FB-910, FB-940 or FB-950 (trade name, manufactured by Denkagaku Kogyo Co., HS-105 "," HS-106 ", and" HS-107 "(trade names, manufactured by Dainippon Ink and Chemicals, Inc.), trade names" MSR-2212 "and" MSR- Commercially available from Micron Co.) can be used.

As the hollow inorganic phosphorus-free filler, it may be produced by a known or common manufacturing method. For example, Sphericel (trademark) 110P8, Sphericel (trademark) 25P45, Sphericel (trademark) Q-CEL (trademark) 7014, "" Q-CEL (trademark) 7040S "(manufactured by Pottsu Baratini Co., Ltd.)," Sphericel 60P18 " Fuji Balloon H-35 " (manufactured by Fuji Silysia Chemical Co., Ltd.), trade names " Cellstar Z-20 ", " Cellstar Z- Cellstar Z-39 "," Cellstar T-36 "," Cellstar PZ-31 "," Cellstar Z- Super Balloon BA-15 ", " Super Balloon 732C " (manufactured by Tokai Kogyo Co., Ltd., trade name; manufactured by Tokai Kogyo Co., (Manufactured by Kagaku Kogyo Co., Ltd.) can be used.

When the resin composition in the antireflection material of the present invention contains the nonporous filler (F), the content (blending amount) thereof is not particularly limited, but the resin composition (100 parts by weight) Preferably 10 to 200 parts by weight, and more preferably 20 to 150 parts by weight. When the content of the non-porous 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, when the content of the non-porous filler (F) is 200 parts by weight or less, remarkable deterioration of the whole light can be prevented to secure sufficient illuminance when the antireflective material of the present invention is used as a sealing material for optical semiconductor devices There is a tendency to be able to.

When the resin composition in the antireflection material of the present invention contains the non-porous filler (F), the total content (total amount) of the porous filler (A) and the non-porous filler (F) is not particularly limited, Is preferably 20 to 60% by weight based on the total amount of the barrier material (100% by weight). When the total content of the porous filler (A) and the non-porous filler (F) is 20 wt% or more, the thermal shock resistance of the cured product constituting the anti-reflective material tends to be improved. On the other hand, when the total content of the porous filler (A) and the non-porous filler (F) is 60 parts by weight or less, remarkable deterioration of the total light is obtained when the antireflective material of the present invention is used, for example, So that a sufficient illuminance can be secured.

[Polyhydric alcohols]

The resin composition of the present invention may contain a polyhydric alcohol. Particularly, when the resin composition of the present invention contains the acid anhydride curing agent (C) and the curing accelerator (D), it is preferable that the resin composition further contains a polyhydric alcohol in order to promote curing more efficiently. As the polyhydric alcohol, a known or common polyhydric alcohol can be used, and examples thereof include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, , Diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylol propane, glycerin, pentaerythritol, dipentaerythritol and the like.

Among them, the polyhydric alcohol is preferably an alkylene glycol having 1 to 6 carbon atoms, more preferably an alkylene glycol having 1 to 6 carbon atoms, more preferably an alkylene glycol having 1 to 6 carbon atoms, 2 to 4 alkylene glycols.

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

The content (blending amount) of the polyhydric alcohol in the resin composition of the present invention is not particularly limited, but it is preferable that the total amount of the epoxy compound (total epoxy compound; for example, the total amount of the alicyclic epoxy resin) Preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 2.5 parts by weight based on 100 parts by weight of the resin. When the content of the polyhydric alcohol is 0.05 parts by weight or more, curing tends to proceed more efficiently. On the other hand, when the content of the polyhydric alcohol is 5 parts by weight or less, the reaction rate of the curing tends to be easily controlled.

[Phosphor]

The resin composition of the present invention may contain a phosphor. When the resin composition of the present invention comprises a phosphor, it can be particularly preferably used as a sealing application (sealing material use) for an optical semiconductor device in a photosemiconductor device, that is, as a resin composition for optical semiconductor sealing. As the above-mentioned fluorescent material, there can be used known fluorescent materials (particularly fluorescent materials used in sealing applications of optical semiconductor devices), and there is no particular limitation. For example, a fluorescent material of the general formula A ₃ B ₅ O ₁₂ : M [ Wherein A represents at least one element selected from the group consisting of Y, Gd, Tb, La, Lu, Se and Sm; B represents at least one element selected from the group consisting of Al, Ga and In; (For example, Y ₃ Al ₅ O ₁₂ : Ce phosphor particulates, (Y, Gd (1), and (2) (Tb) ₃ (Al, Ga) ₅ O ₁₂ : Ce phosphor particulates and the like) and silicate-based phosphor particulates (for example, (Sr, Ca, Ba) ₂ SiO ₄ : Eu etc.). Further, the phosphor may be one whose surface has been modified by an organic group (for example, a long-chain alkyl group, a phosphoric group or the like) for improving dispersibility. In the resin composition of the present invention, one kind of fluorescent substance may be used alone, or two or more kinds of fluorescent substances may be used in combination. As the phosphor, a commercially available product can be used.

The content (blend amount) of the phosphor in the resin composition of the present invention is not particularly limited and may be appropriately selected in the range of 0.5 to 20 wt% based on the total amount (100 wt%) of the resin composition.

The resin composition according to the present invention may contain an alicyclic epoxy resin not containing 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 not containing rubber particles 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. When the use amount of the alicyclic epoxy resin not containing rubber particles exceeds 70% by weight of the total epoxy group-containing resin, the crack resistance of the resulting cured product tends to be lowered.

Also, the resin composition according to the present invention is a glycidyl ether-based epoxy compound having an aromatic ring such as bisphenol A type or bisphenol F type; A glycidyl ether-based epoxy compound having no aromatic ring such as hydrogenated bisphenol A type, aliphatic glycidyl type, etc.; Glycidyl ester-based epoxy compounds; Glycidylamine-based epoxy compounds; An epoxy resin other than an alicyclic epoxy resin such as a polyol compound, an oxetane compound, or a vinyl ether compound may be contained. The amount of the epoxy resin other than the alicyclic epoxy resin 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. If the amount of the epoxy resin other than the alicyclic epoxy resin exceeds 70% by weight of the total epoxy-containing resin, the crack resistance of the resulting cured product tends to be lowered.

Further, it may contain an epoxy compound which exhibits a solid at room temperature (25 ° C), or may be an epoxy compound that exhibits a liquid phase after compounding. Examples of the epoxy compound which exhibits a solid at room temperature (25 占 폚) include solid bisphenol epoxy compounds, novolac epoxy compounds, glycidyl esters, triglycidylisocyanurate, 2,2-bis (2-oxiranyl) cyclohexane adduct (trade name "EHPE3150", manufactured by Daicel Chemical Industries, Ltd.) of methyl- These epoxy compounds may be used alone or in combination of two or more.

In the present invention, in addition to the acid anhydride curing agent (C), the curing catalyst (E) and the curing catalyst (E), the glycidyl ether type epoxy compound having no aromatic ring and / (Excluding a polyether polyol) is preferable in that it can improve crack resistance without impairing high heat resistance, and particularly includes a glycidyl ether-based epoxy compound having no aromatic ring Is preferable in that crack resistance can be improved without impairing high heat resistance and light resistance.

[Glycidyl ether-based epoxy compound having no aromatic ring]

The glycidyl ether-based epoxy compound having no aromatic ring in the present invention includes a compound obtained by nucleophilic addition of an aliphatic glycidyl ether-based epoxy compound and an aromatic glycidyl ether-based epoxy compound. YH-300 "," YH-315 "," YH-324 "," PGIC-I "," EPICLON 701 "," EPICLON720 " (Manufactured by Shin-Nihon Rikagaku Co., Ltd.), "Rika Resin DME-100", "Rika Resin HBE-100" , Commercially available products such as "Denacol EX-212", "Denacol EX-321" (trade name, manufactured by Nagase ChemteX Corp.), "YX8000" and "YX8034" Can be used.

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

[Polyol compound showing liquid phase at 25 占 폚]

The polyol compound exhibiting a liquid phase at 25 占 폚 in the present invention includes a polyol compound other than the polyether polyol, and includes, for example, a polyester polyol and a polycarbonate polyol.

As the polyester polyol, for example, trade names "Flaxel 205", "Flaxel 205H", "Flaxel 205U", "Flaxel 205BA", "Flaxel 208", "Flaxel 210" , "Flexcell 210BA", "Flexcell 212", "Flexcell 212CP", "Flexcell 220", "Flexcell 220CPB", "Flexcell 220NP1", "Flexcell 220BA", "Flexcell 220ED" and " "Flexcell 220EB", "Flexcell 220EC", "Flexcell 230", "Flexcell 230CP", "Flexcell 240", "Flexcell 240CP", "Flexcell 210N", "Flexcell 220N" L205AL, L108AL, L108AL, L108AL, L102AL, L102AL, L102AL, L105AL, L105AL, L105AL, L108AL, L108AL, L108AL, , "Flockel 320", "Flockel L320AL", "Flockel L330AL", "Flockel 410", "Flockel 410D", "Flockel 610", "Flockel P3403", "Flockel CDE9P" (Manufactured by Sekigaku Kogyo Co., Ltd.) You can use a commercially available product.

Examples of the polycarbonate polyol include polyolefins such as those available under the trade names of "Fraxel CD205PL", "Fraxel CD205HL", "Fraxel CD210PL", "Fraxel CD210HL", "Fraxel CD220PL" (UH-CARB90), UH-CARB90 (1/1), UH-CARB90 (1/3), UH- PCDL T5651 " and " PCDL T5652 " (manufactured by Asahi Kasei Chemicals Co., Ltd.), which are commercially available under the trade names of UC-CARB100 (product of Ube Gosan Co., Ltd.), PCDL T4671, PCDL T4672, PCDL T5650J, Commercially available products can be used.

The amount of the polyol compound which exhibits a liquid phase at 25 占 폚 is about 5 to 50 parts by weight, preferably about 10 to 40 parts by weight, based on 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 as long as it does not adversely affect the curability and transparency. Examples of the other components include a silicone resin having a straight chain or a branched chain, a silicone resin having an alicyclic ring, a silicone resin having an aromatic ring, a silsesquioxane having a cage / ladder / random shape, A leveling agent, a surfactant, a filler, a flame retardant, a colorant, an antioxidant, an ultraviolet absorber, an ion adsorbent, a pigment, a release agent and the like can be given as a silane coupling agent such as a silane coupling agent such as trimethoxysilane and trimethoxysilane. The content (blending amount) of the other components is not particularly limited, but is preferably 5% by weight or less (e.g., 0 to 3% by weight) based on the total amount (100% by weight) of the resin composition.

The resin composition of the present invention is not particularly limited, and can be prepared, for example, by stirring and mixing the above-mentioned respective components under heating in accordance with necessity. In addition, the curable epoxy resin composition of the present invention may be a one-liquid composition in which all of the components are mixed in advance, and for example, components divided into two or more may be mixed at a predetermined ratio immediately before use (For example, a two-liquid system). The method of stirring and mixing is not particularly limited, and for example, it is possible to use known mixing means such as dissolver, homogenizer, etc., kneader, roll, bead mill and self-excited stirring device. Further, it may be degassed under reduced pressure or in vacuum after stirring and mixing.

[Shape of cured product and unevenness]

The antireflection material of the present invention is characterized in that the porous filler (A) is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof, and as a result of the stable dispersion state, the porous filler (A) Shape, and the reflection prevention function is exhibited by scattering the incident light. Further, the porous structure on the surface of the porous filler (A) can also scatter incident light, and also has an improved antireflection function.

Further, since the resin composition contains the rubber particle-dispersed epoxy compound (B), the cured product containing the epoxy compound (B) has excellent thermal shock resistance.

The method for uniformly spreading the porous filler (A) throughout the cured product is not particularly limited, and for example, a method of uniformly dispersing the porous filler (A) in the resin composition constituting the cured product and then curing And the like. In order to efficiently produce the antireflective member of the present invention, a method of uniformly dispersing and then curing the porous filler (A) is preferred.

Hereinafter, one mode of the method for producing an antireflective member of the present invention will be described, but the present invention is not limited thereto.

The porous filler (A) and, if necessary, the non-porous filler (F) are added to the resin composition and mixed and stirred to uniformly disperse the resin composition. The method of mixing and stirring is not particularly limited, and for example, known mixers such as dissolvers and homogenizers, kneaders, rolls, beads mills, and self-propulsive stirrers may be used. Further, it may be degassed under reduced pressure or in vacuum after stirring and mixing.

When the non-porous 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 shape of the resin composition before curing of the present invention is not particularly limited, but it is preferably liquid. The resin composition before curing to form the antireflective member of the present invention can exhibit an antireflection function by the addition of a small amount by using the porous filler (A), so that it becomes easy to form a liquid phase without using a solvent such as toluene, desirable.

[Curing Process]

The antireflection material of the present invention can be obtained by curing a resin composition in which the porous filler (A) is uniformly dispersed to obtain a cured product (hereinafter sometimes referred to as " cured product of the present invention ").

The amount of the component to be volatilized during curing with respect to the total amount (100% by weight) of the resin composition before curing is not particularly limited, but is preferably 10% by weight or less, more preferably 8% by weight or less, By weight or less. When the amount of the component volatilized during curing is 10% by weight or less, the dimensional stability of the cured product is enhanced, which is preferable. Since the resin composition before curing of the present invention can exhibit an antireflection function by the addition of a small amount by using the porous filler (A), the resin composition easily forms a liquid phase without using a volatile component of a solvent (toluene or the like) The amount of volatile components can be reduced.

As means for curing, publicly known means such as heat treatment and light irradiation treatment can be used. The temperature (curing temperature) at the time of curing by heating is not particularly limited, but is preferably 45 to 200 占 폚, more preferably 50 to 190 占 폚, and still more preferably 55 to 180 占 폚. The heating time (curing time) at the time of curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, further preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit of the above range, the curing becomes insufficient. On the contrary, when the curing temperature and the curing time are higher than the upper limit of the above range, the resin component may be decomposed. The curing condition depends on various conditions. For example, when the curing temperature is high, the curing time is short, and when the curing temperature is low, the curing time can be adjusted to a suitable value. The curing may be performed in one step or in multiple steps of two or more steps.

In the case of curing by light irradiation, light (radiation) containing i-line (365 nm), h-line (405 nm), g- line (436 nm) and the like is irradiated at an illuminance of 10 to 1200 mW / ² , and an irradiation light quantity of 20 to 2500 mJ / cm < ² > to obtain the antireflection material of the present invention. From the standpoint of suppressing the deterioration of the cured product by radiation and from the viewpoint of productivity, the irradiation dose of the radiation is preferably 20 to 600 mJ / cm ² , more preferably 20 to 300 mJ / cm ² . For the irradiation, a high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a laser beam, or the like can be used as an irradiation source.

[Antireflection material]

As described above, the antireflective material of the present invention can be suitably used as a resin for optical materials (used for forming an optical material) because it has high impact resistance in addition to high transparency and excellent antireflection function . The optical material is a material that exhibits various optical functions such as light diffusing property, light transmittance, and light reflectivity. By using the antireflection material of the present invention, an optical member including at least the cured product (optical material) of the present invention is obtained. The optical member may be composed only of the antireflective member of the present invention, or may be only partially used of the antireflective member of the present invention. Examples of the optical member include members that exhibit various optical functions such as light diffusing properties, light transmittance and light reflectivity, members that constitute apparatuses and apparatuses using the optical function, and the like, and are not particularly limited. For example, Optical semiconductor device, organic EL device, adhesive, electric insulating material, laminated plate, coating, ink, paint, sealant, resist, composite material, An optical member for public or public use which is used in various applications such as a panel, a solar cell substrate, an optical waveguide, a light guide plate, a holographic memory, an optical pickup sensor and the like.

The antireflective material of the present invention has a fine and uniform irregular shape formed by the porous filler (A) on its surface as a result that the porous filler (A) spreads uniformly over the entirety of the cured product and is dispersed. Since the incident light is scattered and the total reflection does not occur, the gloss can be suppressed and the visibility can be improved. The arithmetic mean surface roughness Ra of the concavo-convex shape formed in the antireflective member of the present invention is preferably in the range of 0.1 to 1.0 탆, more preferably in the range of 0.2 to 0.8 탆. When the arithmetic mean surface roughness Ra of the concave-convex shape is in this range, there is a tendency that a sufficient antireflection function can be exhibited without remarkably damaging the whole light flux.

In the present invention, the arithmetic average surface roughness Ra is a numerical value defined by JIS B 0601-2001, which means that it is measured and calculated by the method described in the following examples.

The resin composition constituting the antireflection material of the present invention can be suitably 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 (a sealing material for an optical semiconductor element in an optical semiconductor device) for sealing an optical semiconductor element in an optical semiconductor device. The optical semiconductor device in which the optical semiconductor element is sealed by the antireflection material produced using the resin composition (resin composition for optical semiconductor encapsulation) of the present invention (for example, Optical semiconductor device composed of ash) is obtained. The sealing of the optical semiconductor element can be carried out, for example, by injecting a resin composition in which the porous filler (A) is uniformly dispersed into a predetermined mold, and heating or curing the resin under predetermined conditions. The curing temperature, the curing time, and the conditions of photo-curing can be suitably set in the same range as in the preparation of the antireflection material. The optical semiconductor device of the present invention described above can exhibit an excellent antireflection function without lowering the total flux of light. In addition, since the resin composition of the present invention contains the rubber particle-dispersed epoxy compound (B) and, if necessary, the nonporous filler (F), the cured product containing the same has excellent thermal shock resistance. In the present specification, the "optical semiconductor device of the present invention" means an optical semiconductor device in which the antireflection material of the present invention is used for at least a part of constituent members (for example, a sealing material, a die bonding material, etc.) it means.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The units of components constituting the resin composition 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 ^TM type nano-track particle size distribution measuring apparatus (trade name: UPA-EX150, manufactured by Nikkiso Co., Ltd.) having a dynamic light scattering method as a measurement principle The following samples were measured, and the cumulative average diameter, which is the particle diameter at the time when the cumulative curve became 50%, was determined as the average particle diameter and the frequency (%) of the particle size distribution measurement result exceeded 0.00% The maximum particle diameter at the time point was defined as the maximum particle diameter.

sample:

1 part by weight of the rubber particle-dispersed epoxy compound (B) was dispersed in 20 parts by weight of tetrahydrofuran.

The refractive index of the rubber particles was obtained by molding rubber particles (1 g) into molds and compression-molding them at 210 DEG C and 4 MPa to obtain a flat plate having a thickness of 1 mm, cut out test pieces having a length of 20 mm and a width of 6 mm from the obtained flat plate, (Manufactured by Atago Co., Ltd.) using a multi-wavelength Abbe refractometer (trade name: DR-M2, manufactured by Atago Co., Ltd.) in a state in which the prism and the corresponding test piece were in close contact with each other using monobromonaphthalene. Was measured.

The viscosity of the rubber particle-dispersed epoxy compound (B) (5 parts by weight of rubber particles dispersed in 100 parts by weight of Celloxide 2021P (manufactured by Daicel Chemical Industries, Ltd.)) obtained in Production Example was measured with a digital dot- DVU-EII type ", manufactured by TOKIMEX Co., Ltd.).

Production Example 1

500 g of ion-exchanged water and 0.68 g of sodium dioctylsuccinate were charged into a 1 L polymerization vessel equipped with a reflux condenser, and the temperature was raised to 80 캜 while stirring under a nitrogen stream. To this was added a monomer mixture containing 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, and stirred for 20 minutes 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour to carry out the initial seed polymerization. Subsequently, 180.5 mg of potassium peroxodisulfate was added and the mixture was stirred for 5 minutes. A monomer mixture was prepared by dissolving 180.5 g of butyl acrylate (about 95% by weight) in the amount required to form the core portion, 48.89 g of styrene and 7.39 g of divinylbenzene and 0.95 g of sodium dioctylsuccinate Over a period of 2 hours to carry out a second seed polymerization, and then aged for 1 hour to obtain a core portion.

Subsequently, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. A monomer mixture obtained by dissolving 60 g of methyl methacrylate, 1.5 g of acrylic acid, and 0.3 g of sodium dioctylsuccinate in 0.3 g of allyl methacrylate was added to 30 Minute, followed by seed polymerization, and then aged for 1 hour to form a shell layer covering the core portion.

Subsequently, the mixture was cooled to room temperature (25 DEG C) and filtered through a plastic net having an eye size of 120 mu m to obtain a latex including particles having a core shell structure. The obtained latex was frozen at minus 30 캜, dehydrated and washed with a suction filter, and then blow-dried at 60 캜 for one day and night to obtain rubber particles (1). The rubber particles (1) thus obtained had an average particle diameter of 254 nm, a maximum particle diameter 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) under heating in a nitrogen stream at 60 캜 (B-1) (viscosity at 25 캜: 559 mPa s) was obtained.

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 rubber particles (2) thus obtained had an average particle diameter of 261 nm, a maximum particle diameter of 578 nm, and a refractive index of 1.500.

Further, a rubber particle-dispersed epoxy compound (B-2) (viscosity at 25 캜: 512 mPa)) was obtained in the same manner as in Production Example 1.

Production Example 3

500 g of ion-exchanged water and 1.3 g of sodium dioctylsuccinate were charged into a 1 L polymerization vessel equipped with a reflux condenser, and the temperature was raised to 80 캜 while stirring in a nitrogen stream. To this was added a monomer mixture containing 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, and stirred for 20 minutes And 12 mg of potassium peroxodisulfate was added and stirred for 1 hour to carry out the first seed polymerization. Then, 228 mg of potassium peroxodisulfate was added, followed by stirring for 5 minutes. To this was added a monomer mixture obtained by dissolving 180.5 g of butyl acrylate, 48.89 g of styrene, 7.33 g of divinylbenzene and 1.2 g of sodium dioctylsuccinic acid in an amount required to form the core portion (about 95% by weight) Over a period of 2 hours to carry out a second seed polymerization, and then aged 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 diameter of 108 nm, a maximum particle diameter of 289 nm, and a refractive index of 1.500.

Further, a rubber particle-dispersed epoxy compound (B-3) (viscosity at 25 캜: 1036 mPa s) was obtained in the same manner as in Production Example 1.

Production Example 4

, 100 parts by weight of a curing agent (trade name "RICASIDE MH-700", manufactured by Shin-Nippon Rika KK), 0.5 parts by weight of a curing accelerator (trade name "U- CAT 18X" (Manufactured by Kakinagaku Kogyo Co., Ltd.) were mixed by using a self-propulsive stirrer (trade name: "Awatolire Taro AR-250" .

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 self-propelled stirrer and defoamed to prepare a curable epoxy resin composition.

100 parts by weight of the curable epoxy resin composition obtained above and 20 parts by weight of a porous filler (trade name " Siriasia 430 ", manufactured by Fuji Silysia Chemical Co., Ltd.) were mixed using a self-propulsive stirrer and defoamed to obtain a curable epoxy resin The composition was cast in a lead frame (InGaN element, 3.5 mm x 2.8 mm) of the optical semiconductor shown in Fig. 1 and then heated in a resin curing oven at 150 deg. C for 5 hours, A sealed optical semiconductor device was manufactured. 1, reference numeral 100 denotes a reflector, 101 denotes a metal wiring, 102 denotes an optical semiconductor element, 103 denotes a bonding wire, and 104 denotes a sealing material (reflection preventing material) And a uniform and fine uneven shape is formed by the porous filler present on the upper surface thereof (uneven shape is not shown).

Examples 2 to 15 and Comparative Examples 1 to 5

An optical semiconductor device was produced in the same manner as in Example 1 except that the compositions of the curable epoxy resin composition, the porous filler and the non-porous filler were changed as shown in Tables 1 and 2. [

[evaluation]

The optical semiconductor device manufactured as described above was evaluated in the following manner. The results are shown in Tables 1 and 2, respectively.

(1) projection of a fluorescent lamp

The reflectance of the fluorescent lamp illuminated on the upper surface (the upper surface of the sealing material 104 in Fig. 1) of the optical semiconductor device obtained in the example and the comparative example was evaluated, and the clarity of the fluorescent lamp in the antireflective material was evaluated in three stages.

A case where the outline of the fluorescent lamp can not be recognized is indicated by o, a case where the outline can not be recognized clearly is indicated by A, and a case where the outline is clearly recognized is indicated by x.

(2) Arithmetic mean surface roughness Ra

The upper surface (the upper surface of the sealing material 104 in Fig. 1) of the optical semiconductor device obtained in Examples and Comparative Examples was measured using a laser microscope (trade name: Shape Measurement Laser Microscope VK-8710, manufactured by KEYENCE).

(3) Full beam

For each of the optical semiconductor devices obtained in the examples and the comparative examples, the total luminous flux at the time of energization under the conditions of 5 V and 20 mA was measured using a total luminous flux measuring instrument (trade name: "OL771", manufactured by Optron Laboratories) Lt; / RTI >

(4) Thermal shock test

Each of the optical semiconductor devices (used for each of the curable epoxy resin compositions) obtained in Examples and Comparative Examples was exposed for 30 minutes in an atmosphere of -40 占 폚 and then for 30 minutes in an atmosphere of 100 占 폚. One thermal shock was applied for 200 cycles using a thermal shock tester. Thereafter, a current of 10 mA was passed through the optical semiconductor device, and the number of optical semiconductor devices (sub-light-emitting optical semiconductor devices) which did not light was measured. In addition, before the thermal shock test, it was confirmed that all the optical semiconductor devices were turned on. The results are shown in the column of " Thermal Shock Test [Sub-lighting Number] " 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 molded into molds and heated at 150 占 폚 for 5 hours. A test piece having a length of 20 mm, a width of 6 mm and a thickness of 1 mm was cut out from the obtained cured product and a prism and a corresponding test piece were brought into close contact with each other using monobromonaphthalene as an intermediate liquid to prepare a multiwavelength Abbe refractometer ) Manufactured by Atago Co., Ltd.), the refractive index of the cured product was measured by measuring the refractive index at 20 占 폚 sodium D line, and the refractive index difference was calculated according to the following formula. The results are shown in the column of " difference in refractive index with rubber particles " in Tables 1 and 2.

Refractive index difference [refractive index of rubber particle] - [refractive index of cured product]

(6) Comprehensive judgment

(A) to (d) were satisfied with respect to each of the optical semiconductor devices obtained in the examples and the comparative examples was evaluated as satisfactory (good) and neither of the following (a) to (d) × (poor).

(a) The projection of the fluorescent lamp measured in the above (1) is? or?.

(b) The arithmetic mean surface roughness Ra measured in the above (2) is 0.10 to 1.0 占 퐉.

(c) the total light flux measured in the above (3) is 0.60 lm or more.

(d) In the above (4), the number of optical semiconductor devices such as negative light is zero.

Each component constituting the antireflection member 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) prepared in Production Example 1

B-2: Rubber particle-dispersed epoxy compound (B-2) prepared in Production Example 2

B-3: Rubber particle-dispersed epoxy compound (B-3) prepared in Preparation Example 3

(Epoxy resin)

(Trade name) "Celllock 2021P" [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate], "

YD-128: product name "YD-128" [bisphenol A type epoxy resin], Shinnitetsu Sumitomo Ginzoku Kogaku Co., Ltd.

(Epoxy curing agent)

MH-700: Rikacid MH-700 [4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30] manufactured by Shin-Nihon Rika Kogyo Co.,

U-CAT 18X: trade name " U-CAT 18X " [hardening accelerator]

Ethylene glycol: manufactured by Wako Pure Chemical Industries, Ltd.

SI-100L: Product name "SANEID SI-100L", manufactured by SANA PRO Co., Ltd.

(Porous silica filler)

Saisia 430: trade name " Saisia 430 ", manufactured by Fuji Silysia Chemical Co., Ltd., volume average particle diameter: 4.1 mu m; Specific surface area: 350 m ² / g; Average pore diameter: 17 nm; Pore volume: 1.25 mL / g; Oil absorption: 230mL / 100g

CYROSPACE C-1504: trade name " CYROSPACE C-1504 ", manufactured by Fuji Silysia Chemical Co., Ltd., volume average particle diameter: 4.5 mu m; Specific surface area: 520 m ² / g; Average pore diameter: 12 nm; Pore volume: 1.5 mL / g; Oil absorption: 290 mL / 100 g

Quot; Sanspeca H-52 ", manufactured by AGC Sightech Co., Ltd., volume average particle diameter: 5 탆; Specific surface area: 700 m ² / g; Average pore diameter: 10 nm; Pore volume: 2 mL / g; Oil absorption: 300mL / 100g

Silo Fobric 702: Silo Fobric 702, manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler having a hydrophobic surface treated with polydimethylsiloxane, volume average particle diameter: 4.1 탆; Specific surface area of porous silica filler before hydrophobic surface treatment: 350 m ² / g; Oil absorption: 170mL / 100g

Silo FoBic 4004: Silo FoBic 4004, manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler subjected to hydrophobic surface treatment with polydimethylsiloxane, volume average particle diameter: 8.0 mu m; Specific surface area of porous silica filler before hydrophobic surface treatment: 350 m ² / g; Oil absorption: 165mL / 100g

Silo Fobic 505: Product name "Silo Fobic 505", manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler subjected to hydrophobic surface treatment with polydimethylsiloxane, volume average particle diameter: 3.9 μm; The specific surface area of the porous silica filler before the hydrophobic surface treatment: 500 m ² / g; Oil absorption: 110mL / 100g

(Nonporous silica filler)

Molten spherical silica: manufactured by Tatsumori Co., Ltd. Volume average particle diameter: 5 탆

As shown in Table 1, the optical semiconductor device (1) comprising the antireflective material according to the example made of the resin composition containing the porous silica filler of the present invention in a predetermined amount and containing the rubber particle dispersion epoxy compound (B) , The projections of the fluorescent lamps are all O or DELTA, the arithmetic mean surface roughness Ra is in the range of 0.10 to 1.0 mu m, the total luminous flux is all 0.60 lm or more, and the number of optical semiconductor devices It was confirmed that all of them had excellent antireflection function, exhibited good roughness, and had excellent thermal shock resistance.

On the other hand, as shown in Table 2, the optical semiconductor device comprising the antireflection materials of Comparative Examples 1 and 2 without using the rubber particle dispersed epoxy compound (B) exhibited excellent antireflection function and good roughness, In the thermal shock test, it was confirmed that the number of optical semiconductor devices such as negative light was two in all and the thermal shock resistance was poor. In the optical semiconductor device of Comparative Example 3 in which the porous silica filler was not blended and only the pore-free silica filler was blended, and the antireflection material of Comparative Example 4 in which the blending amount of the porous silica filler was smaller than the predetermined range in the present invention, The anti-reflection function was poor. In Comparative Example 3, the non-porous silica filler was settled, and in Comparative Example 4, the amount of the porous silica filler was not sufficient, so that it was considered that the surface was uniform and fine unevenness was not formed. In the optical semiconductor device comprising the antireflective member of Comparative Example 5 in which the blending amount of the porous silica filler is larger than a predetermined range in the present invention, the antireflective function is exhibited, while the total light flux is 0.48 lm or more, . It is considered that light is absorbed because the blending amount of the porous silica filler is large.

The variations of the present invention described above will be described below.

[1] An antireflective material comprising a cured product of a resin composition in which a porous filler (A) is dispersed, wherein the porous filler (A) has irregularities for suppressing 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-based curing agent (C) and a curing accelerator (D)

Wherein the rubber particles have a core shell structure and are composed of a polymer having a (meth) acrylate ester as an essential monomer component and having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface, A particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm and the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within 0.02,

Wherein the content of the porous filler (A) relative to the total amount of the antireflective member (100 wt%) is 4 to 40 wt%.

[2] The antireflective material according to [1], wherein the porous filler (A) is uniformly dispersed throughout the cured product, and unevenness is formed on the surface to suppress reflection.

[3] The antireflective material according to [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).

[4] The antireflective material according to [3], wherein the porous filler (A) is an inorganic porous filler (A1).

The inorganic porous filler (A1) is preferably selected from inorganic glass (for example, borosilicate glass, sodium borosilicate glass, sodium silicate glass, aluminum silicate glass, quartz and the like), 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, stearate, spinel, clay, kaolin At least one kind of powder selected from the group consisting of dolomite, dolomite, hydroxyapatite, nepherinecinite, cristobalite, wollastonite, diatomaceous earth and talc and having a porous structure, or a molded product thereof (for example, (Beads or the like) (preferably porous inorganic glass or porous silica, more preferably porous silica). [3] or [4] The anti-reflective material.

[6] The porous inorganic filler as described in [1] above, wherein 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, The antireflection material according to any one of [3] to [5].

[7] The antireflection material as described in [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.

[8] The method for surface treatment of porous silica according to any one of the above items, wherein the porous silica is at least one hydrophobic surface treatment agent (preferably an organosilicon compound) selected from the group consisting of metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols and organic silicon compounds (Hydrophobic porous silica) obtained by the above-mentioned method (1).

[9] The hydrophobic surface treating agent according to any one of [1] to [6], wherein the hydrophobic surface treating agent is at least one selected from the group consisting of trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, (Preferably polydimethylsiloxane) of an organosilicon compound represented by the formula (1).

The organic porous filler (A2) may be at least one selected from the group consisting of a styrene resin, an acrylic resin, a silicone resin, an acryl-styrene resin, a vinyl chloride resin, a vinylidene chloride resin, an amide resin, a urethane resin, - a polymer porous sintered body composed of at least one kind of organic substance selected from the group consisting of a conjugated diene resin, an acryl-conjugated diene resin, an olefin resin and a cellulose resin (also including a crosslinked body of these polymers) The antiglare material according to any one of [3] to [9] above, which is a gel porous chain.

[11] The method according to [1], wherein the porous filler (A) is at least one (preferably spherical or crushed) selected from the group consisting of powder, spherical, crushed, To [10].

[12] The antireflection material as described in any one of [1] to [11], wherein the porous filler (A) has a median particle diameter of 0.1 to 100 μm (preferably 1 to 50 μm).

[13] The antireflective material according to any one of [1] to [12], wherein the specific surface area of the porous filler (A) is 10 to 2000 m ² / g (preferably 100 to 1000 m ² / g).

[14] The antireflective material according to any one of [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).

[15] The antireflective material according to any one of [1] to [14], wherein the amount of oil absorption of the porous filler (A) is 10 to 2000 mL / 100 g (preferably 100 to 1000 mL / 100 g).

The content (amount) of the porous filler (A) is 4 to 35 wt% (preferably 4 to 30 wt%) based on the total amount (100 wt%) of the antireflective material or the resin composition. The antireflection material according to any one of [1] to [15].

The amount (blending amount) of the porous filler (A) is 5 to 80 parts by weight (preferably 5 to 70 parts by weight, more preferably 5 To 60 parts by weight based on 100 parts by weight of the antireflection film.

[18] The antireflective member according to any one of [1] to [17], wherein the resin composition comprises a transparent curable resin composition.

[19] the core part of the core shell structure is selected from the group consisting of (meth) acrylic acid ester / aromatic vinyl and (meth) acrylic acid ester / conjugated diene; The antireflective material according to any one of [1] to [18], wherein the antireflective member is composed of a ternary copolymer of (meth) acrylic acid ester / aromatic vinyl / conjugated diene.

[20] The antireflective material according to the above-mentioned [19], wherein the core portion in the core shell structure is composed of a binary copolymer of (meth) acrylic acid ester / aromatic vinyl (preferably butyl acrylate / styrene).

[21] The method according to the above [19] or [20], wherein the core portion in the core shell structure further contains a reactive crosslinking monomer (preferably divinylbenzene) having at least two reactive functional groups in one monomer Prevention material.

[22] The antireflection film according to any one of the above [1] to [21], wherein the shell layer in the core shell structure comprises a polymer different from the polymer constituting the core portion in the core shell structure. ashes.

[23] The method for producing a core shell structure according to any one of [1] to [3], wherein the shell layer in the core shell structure is selected from the group consisting of (meth) acrylic ester / aromatic vinyl / hydroxyalkyl (meth) acrylate and (meth) acrylic acid ester / aromatic vinyl / Or a bidentate copolymer selected from the group consisting of (meth) acrylic ester / hydroxyalkyl (meth) acrylate, (meth) acrylic ester /?,? -Unsaturated acid The antireflective material according to any one of [1] to [22] above,

[24] The anti-reflective member according to [23], wherein the shell layer in the core shell structure further contains a reactive crosslinking monomer (preferably allyl (meth) acrylate) having at least two reactive functional groups in one monomer. .

[25] The antireflection material as described in any one of [1] to [24], wherein the rubber particles have an average particle diameter of 20 to 400 nm.

[26] The antireflection material as described in any one of [1] to [25], wherein the rubber particles have a maximum particle diameter of 100 to 800 nm.

[27] The antireflective material according to any one of [1] to [26], wherein the rubber particles have a refractive index of 1.40 to 1.60 (preferably 1.42 to 1.58).

[28] The antireflective material according to any one of [1] to [27], wherein the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within ± 0.018.

[29] The resin composition according to any one of [1] to [20], wherein the alicyclic epoxy resin is (i) a compound having at least one alicyclic epoxy group (preferably two or more) (ii) a compound having an epoxy group directly bonded to the alicyclic ring; And (iii) a compound having an alicyclic ring and a glycidyl group. The antireflective member according to any one of [1] to [28] above,

[30] The antireflection material as described in the item [29], wherein the (i) alicyclic epoxy group contained in the compound having at least one alicyclic epoxy group in the molecule is a cyclohexene oxide group.

[31] The antireflection material as described in the item [30], wherein the (i) compound having at least one alicyclic epoxy group in the molecule is a compound represented by the following formula (1).

[In the formula (1), X represents a single bond or a linking group (a divalent group having at least one atom). A substituent (preferably an alkyl group) may be bonded to at least one of the carbon atoms constituting the alicyclic group in the formula (1).)

When the compound represented by the formula (1) is at least one selected from the group consisting of 2,2-bis (3,4-epoxycyclohexan-1-yl) propane, bis (3,4-epoxycyclohexylmethyl) Bis (3,4-epoxycyclohexan-1-yl) ethane and the following formulas (1-1) to , And a compound represented by the following formula (1-10).

L and m in the formulas (1-5) and (1-7) each represent an integer of 1 to 30; R in the formula (1-5) is an alkylene group having 1 to 8 carbon atoms. N1 to n6 in the formulas (1-9) and (1-10) each represent an integer of 1 to 30.]

[33] The antireflective material according to the above [32], wherein the compound represented by the formula (1) is a compound represented by the formula (1-1).

[34] The antireflective member according to any one of the above items [29] to [33], wherein the compound (ii) having an epoxy group directly bonded to the alicyclic ring is a compound represented by the following formula (2).

[In the formula (2), R 'is an organic group of p, and p and q each represent a natural number.]

[1] to [3], wherein the amount of the rubber particles is 0.5 to 30% by weight (preferably about 1 to 20% by weight) based on the total amount of the rubber particle-dispersed epoxy compound (B) The antireflection material described in any one of [34] to [34].

In the above-mentioned [1] to [35], wherein the rubber particle-dispersed epoxy compound (B) has a viscosity at 25 ° C of from 400 mPa · s to 50,000 mPa · s (preferably from 500 mPa · s to 10000 mPa · s) Wherein the antireflective member described in any one of claims 1 to 3.

(1) to (36), wherein the amount of the rubber particle-dispersed epoxy compound (B) is 20 to 100% by weight (preferably 50 to 100% by weight) of the total epoxy group- Wherein the antireflective member is an antireflective member.

Wherein the acid anhydride curing agent (C) is a liquid mixture obtained by dissolving an acid anhydride in a liquid state at 25 ° C. or an acid anhydride in a solid state at 25 ° C. in an acid anhydride in a liquid state at 25 ° C. [ 37]. ≪ / RTI >

The amount of the acid anhydride curing agent (C) to be used is preferably 50 to 150 parts by weight (preferably 52 to 145 parts by weight, more preferably 55 to 150 parts by weight) per 100 parts by weight of the total epoxy group- 140 parts by weight based on 100 parts by weight of the antireflection film.

The use amount of the acid anhydride curing agent (C) is 0.5 to 1.5 equivalents per equivalent of the epoxy group in the compound having all the epoxy groups contained in the resin composition. Wherein the antireflective member described in any one of claims 1 to 3.

The amount of the curing accelerator (D) to be used is preferably 0.05 to 5 parts by weight (preferably 0.1 to 3 parts by weight, particularly preferably 0.2 to 3 parts by weight, more preferably 0.2 to 3 parts by weight) based on 100 parts by weight of the epoxy compound- By weight, and most preferably 0.25 to 2.5 parts by weight based on 100 parts by weight of the antireflection film.

[42] The antireflective member according to any one of the above items [1] to [41], wherein the resin composition further comprises a non-porous filler (F) having a specific surface area of 10 m ² / g or less.

[43] The antireflective material described in the above [42], wherein the non-porous filler (F) is a non-porous silica filler.

The amount (blending amount) of the nonporous filler (F) is 10 to 200 parts by weight (preferably 20 to 150 parts by weight) relative to the resin composition (100 parts by weight) The antireflective member described in [42] or [43].

(42) to (40), wherein the total content (summed amount) of the porous filler (A) and the non-porous filler (F) is 20 to 60% by weight based on the total amount [44] The antireflection material described in any one of [44] to [44].

[46] The antireflective member according to any one of [1] to [45], wherein the resin composition comprises a polyhydric alcohol (preferably an alkylene glycol having 2 to 4 carbon atoms).

The content (mixing amount) of the polyhydric alcohol is preferably 0.05 to 5 parts by weight (preferably 0.1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, more preferably 0.2 to 3 parts by weight) based on 100 parts by weight of the total amount of the epoxy compound contained in the resin composition. By weight, particularly preferably 0.25 to 2.5 parts by weight, based on 100 parts by weight of the antireflection film.

[48] The antireflective member described in any one of [1] to [47], wherein the resin composition comprises a phosphor.

[48] The antireflection material as described in the item [48], wherein the content (blending amount) of the phosphor is 0.5 to 20% by weight relative to the total amount (100% by weight) of the resin composition.

The resin composition preferably contains an alicyclic epoxy resin not containing rubber particles (preferably an alicyclic epoxy resin represented by the above formula (1)) in addition to the rubber particle-dispersed epoxy compound (B). The antireflection material according to any one of [1] to [49].

The use of the alicyclic epoxy resin containing no rubber particles is less than 70% by weight (preferably less than 60% by weight) of the total epoxy group-containing resin contained in the resin composition, Prevention material.

The resin composition according to any one of [1] to [5], wherein the resin composition contains an epoxy resin other than the alicyclic epoxy resin (preferably a glycidyl ether-based epoxy compound having an aromatic ring such as a bisphenol A- [51] The antireflective member described in any one of [51] to [51].

The use of the epoxy resin other than the alicyclic epoxy resin is less than 70% by weight (preferably less than 60% by weight) of the total epoxy group-containing resin contained in the resin composition, .

Any one of the above-mentioned [1] to [53], wherein the arithmetic mean surface roughness Ra of the concave-convex shape formed on the antireflection material is in the range of 0.1 to 1.0 μm (preferably in the range of 0.2 to 0.8 μm) ≪ / RTI >

[55] The antireflection material according to any one of the above-mentioned [1] to [54], which is used for sealing the optical semiconductor.

[56] An optical semiconductor device in which an optical semiconductor element is sealed by an antireflection material as described in [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]

A rubber particle-dispersed epoxy compound (B), an acid anhydride-based curing agent (C) and a curing accelerator (D) in which rubber particles are dispersed in an alicyclic epoxy resin,

Wherein the rubber particles have a core shell structure and are composed of a polymer having a (meth) acrylate ester as an essential monomer component and having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface, A particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm and the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within 0.02,

Wherein the content of the porous filler (A) relative to the total amount (100 wt%) of the resin composition is 4 to 40 wt%.

[58] The resin composition according to the above [57], which is a liquid.

[59] The resin composition according to the above [57] or [58], wherein the amount of the component to be volatilized during curing with respect to the total amount (100% by weight) of the resin composition is 10% by weight or less.

[60] A method for producing an antireflective member, the method comprising: curing the resin composition according to any one of [57] to [59], wherein unevenness for suppressing reflection is formed on the surface.

The antireflection material of the present invention can be suitably used as a resin for an optical material (used for forming an optical material) because it has high impact resistance in addition to high transparency and excellent antireflection function. Examples of the optical member include members that exhibit various optical functions such as light diffusing properties, light transmittance and light reflectivity, members that constitute apparatuses and apparatuses using the optical function, and the like, and are not particularly limited. For example, Optical semiconductor device, organic EL device, adhesive, electric insulating material, laminated plate, coating, ink, paint, sealant, resist, composite material, An optical member for public or public use which is used in various applications such as a panel, a solar cell substrate, an optical waveguide, a light guide plate, a holographic memory, an optical pickup sensor and the like.

100: Reflector (light-use resin composition)
101: metal wiring (electrode)
102: optical semiconductor element
103: Bonding wire
104: Sealing material (antireflection material)

Claims (11)

An antireflective material comprising a cured product of a resin composition in which a porous filler (A) is dispersed, wherein the porous filler (A) has a surface with irregularities for suppressing reflection,
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)
Wherein the rubber particles have a core shell structure and are composed of a polymer having a (meth) acrylate ester as an essential monomer component and having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface, A particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm and the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within 0.02,
Wherein the content of the porous filler (A) relative to the total amount of the antireflective member (100 wt%) is 4 to 40 wt%. The antireflective member according to claim 1, wherein the porous filler (A) is uniformly dispersed throughout the cured product and has irregularities for suppressing reflection on its surface. The porous film according to claim 1 or 2, wherein the resin composition further comprises a non-porous filler (F) having a specific surface area of 10 m ² / g or less, and the porous filler Wherein the total content of the non-porous filler (A) and the non-porous filler (F) is 20 to 60 wt%. The antireflective member according to any one of claims 1 to 3, wherein the porous filler (A) is an inorganic porous filler. The antireflective member according to any one of claims 1 to 4, wherein the resin composition comprises a transparent curable resin composition. The antireflective member according to any one of claims 1 to 5, which is used for sealing the optical semiconductor. An optical semiconductor device in which an optical semiconductor element is sealed by an antireflection member according to claim 6. A resin composition dispersed with a porous filler (A), which is used for the production of the antireflection material according to any one of claims 1 to 6,
A rubber particle-dispersed epoxy compound (B), an acid anhydride-based curing agent (C) and a curing accelerator (D) in which rubber particles are dispersed in an alicyclic epoxy resin,
Wherein the rubber particles have a core shell structure and are composed of a polymer having a (meth) acrylate ester as an essential monomer component and having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with the alicyclic epoxy resin on the surface, A particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm and the difference between the refractive index of the rubber particle and the refractive index of the cured product of the resin composition is within 0.02,
Wherein the content of the porous filler (A) relative to the total amount (100 wt%) of the resin composition is 4 to 40 wt%. The resin composition according to claim 8, wherein the resin composition is a liquid. The resin composition according to claim 8 or 9, wherein the amount of the component to be volatilized during curing with respect to the total amount (100% by weight) of the resin composition is 10% by weight or less. 10. A method for producing an antireflective member, the method comprising the steps of: curing the resin composition according to any one of claims 8 to 10;

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