KR20190059969A - Antireflective material - Google Patents

Abstract

An object of the present invention is to provide an antireflection material having a sufficient antireflection function and capable of preventing a reduction in the total luminous flux of a light source and having a high heat resistance (particularly, heat resistance water resistance), and an antireflection material And an optical semiconductor device.
The present invention relates to an antireflection material comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein an antireflection layer for suppressing reflection is formed on the surface of the antireflection material, And the optical semiconductor device is sealed by ashes.

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. 2016-200397, 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 making high output, and the sealing material in such an optical semiconductor device is considered to include high heat resistance (particularly, heat resistance water resistance, hereinafter simply referred to as "heat resistance" ) Is also required.

Accordingly, an object of the present invention is to provide an antireflection material having a sufficient antireflection function, capable of preventing the reduction of the total luminous flux of a light source, and having high heat resistance, particularly heat 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 antireflective member and a method for producing the antireflective member 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 for solving the above problems, the present inventors have found that when a hydrophobic porous inorganic filler is incorporated as a filler in a resin layer constituting an antireflection member, a sufficient antireflection function is imparted even in the case of addition of a small amount, . As a result, it has been found that an antireflection material having a sufficient antireflection function and excellent heat resistance without significantly lowering the total light flux of the light source is provided, and it is very suitable as a material for sealing an optical semiconductor element in an optical semiconductor device. .

That is, the present invention provides an antireflection material comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein unevenness for suppressing reflection is formed on the surface of the cured product .

In the above-mentioned antireflection material, the hydrophobic porous inorganic filler is preferably uniformly dispersed throughout the cured product, and forms irregularities on the surface to suppress reflection.

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

In the antireflection material, the hydrophobic porous inorganic filler may have an average particle diameter of 1 to 20 탆.

In the antireflection material, the content of the hydrophobic porous inorganic filler relative to the total amount (100 wt%) of the antireflection material may be 4 to 40 wt%.

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

In the antireflection material, the curable resin composition may include a composition containing an epoxy resin.

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.

In addition, the present invention provides a resin composition in which a hydrophobic porous inorganic filler is dispersed, which is used for the production of the antireflective member.

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 antireflective member of the present invention has the above-described structure, a sufficient antireflection function can be obtained even when the amount of the hydrophobic porous inorganic filler to be incorporated is reduced, and a significant decrease in the total light of the light source can be prevented. It also has heat-resistant water. 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 while having high gloss and high durability) Device is obtained.

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

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 antireflective member of the present invention is characterized in that the hydrophobic porous inorganic filler is composed of a cured product of a resin composition in which the hydrophobic porous inorganic filler is dispersed, and the hydrophobic porous inorganic filler forms irregularities on the surface of the cured product to suppress reflection.

Further, the resin composition of the present invention is characterized in that a hydrophobic porous inorganic filler is dispersed and used for producing the above-mentioned antireflection material.

The porous structure of the hydrophobic porous inorganic filler increases the apparent volume of the resin composition as compared with the non-porous filler. Therefore, even when a small amount of the filler is added to the resin composition or the cured product thereof, Fine irregularities can be formed on the surface of the cured product. In addition, the resin composition seeps into the porous structure, and the apparent specific gravity difference between the hydrophobic porous inorganic filler and the resin composition is lowered, so that the dispersed state is stabilized and the interaction of the surfaces of the hydrophobic porous inorganic filler is suppressed, , The hydrophobic porous inorganic filler can be spread uniformly throughout the resin composition or the cured product thereof, so that uniform and fine irregularities can be formed on the surface of the cured product to efficiently scatter the incident light.

Further, since the surface of the hydrophobic porous inorganic filler exhibits hydrophobicity, the cured product containing the same exhibits high heat resistance, which is hard to deteriorate even under severe heating conditions such as boiling water, and is excellent in durability.

In the present specification, the addition amount (amount of use) of the hydrophobic porous inorganic filler 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.

When the hydrophobic porous inorganic filler is used, the reflection can be effectively suppressed even when the amount of use is reduced, as compared with the non-porous filler. Therefore, the hydrophobic porous inorganic filler itself can sufficiently suppress The reflection prevention function can be secured.

Hereinafter, each component will be described in detail.

[Hydrophobic porous inorganic filler]

The hydrophobic porous inorganic filler 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 hydrophobic porous inorganic filler Thereby forming irregularities for scattering the incident light.

The hydrophobic porous inorganic filler that can be used in the antireflective member or the resin composition of the present invention is an inorganic filler having an apparent specific gravity smaller than that of the filler and having a porous structure therein and means that the surface is subjected to hydrophobic treatment do.

As the porous inorganic filler constituting the hydrophobic porous inorganic filler (the porous inorganic filler before the surface is subjected to the hydrophobic treatment), it is possible to use a publicly known or publicly known one. Examples thereof include inorganic glass (for example, borosilicate glass, Silica, alumina, zirconium oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, posteriorite, stearate, spinel, clay, kaolin , Dolomite, hydroxyapatite, nepherinecinite, cristobalite, wollastonite, diatomaceous earth, talc and the like, having a porous structure, or a molded product thereof (for example, spherical beads, etc.) have.

The hydrophobic porous inorganic filler is obtained by adding a hydrophobic surface treating agent (for example, a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, an organic silicon compound, etc.) to the porous inorganic filler before the hydrophobic treatment described above Etc.] was carried out. By carrying out such a hydrophobic surface treatment, the compatibility with the components of the resin composition and the dispersibility are improved, and the heat resistance of the cured product can be improved.

From the viewpoint of improving the compatibility with the components of the resin composition and dispersibility and improving the heat resistance of the cured product, examples of the hydrophobic surface treatment agent include organic silicon compounds (e.g., trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane , Octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, silicone oil, etc.), and polydimethylsiloxane and the like are more preferable.

Among them, as the hydrophobic porous inorganic filler, from the viewpoints of being able to widely disperse and uniformly disperse throughout the resin composition or the cured product thereof, to efficiently form irregularities on the surface of the cured product and to exhibit excellent heat resistance, the hydrophobic porous inorganic glass Or hydrophobic porous silica (hydrophobic porous silica filler).

The hydrophobic porous silica is not particularly limited, and for example, a known or publicly known porous silica such as fused silica, crystalline silica, high purity synthetic silica, colloidal silica and the like treated with the hydrophobic surface treating agent may be used.

As the hydrophobic porous inorganic filler, it is also possible to use an inorganic filler which is obtained by mixing an inorganic material constituting the hydrophobic porous inorganic filler with an inorganic filler such as a styrene resin, an acrylic resin, a silicone resin, an acryl-styrene resin, a vinyl chloride resin, a vinylidene chloride resin, A hydrophobic porous inorganic inorganic filler composed of a hybrid material of an organic material such as a urethane resin, a phenol resin, a styrene-conjugated diene resin, an acryl-conjugated diene resin, an olefin resin or a polymer such as a cellulose resin may be used.

The hydrophobic porous inorganic filler may be composed of a single material or may be composed of two or more kinds of materials. Among them, the hydrophobic porous inorganic filler is widely dispersed and uniformly dispersed throughout the resin composition or its cured product to efficiently form irregularities on the surface of the cured product, and has a high heat resistance, , Hydrophobic porous silica (hydrophobic porous silica filler) is more preferable.

The shape of the hydrophobic porous inorganic filler is not particularly limited, and examples thereof include powder, spherical, crushed, fibrous, needle-like, scaly and the like. Among them, spherical or crushed hydrophobic porous inorganic fillers are preferable from the viewpoint that the hydrophobic porous inorganic filler 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 Do.

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

The hydrophobic porous inorganic filler porous structure can be selected by various parameters such as specific surface area, oil absorption amount, and the like. The hydrophobic porous inorganic filler having a parameter suitable for the antireflection material or resin composition of the present invention can be selected without particular limitation . In addition, the parameter may be evaluated as a parameter of the porous inorganic filler before the hydrophobic treatment.

The specific surface area of the porous inorganic filler constituting the hydrophobic porous inorganic filler (the porous inorganic filler before the surface is subjected to the hydrophobic treatment) is not particularly limited, but the hydrophobic porous inorganic filler is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof , from the viewpoint of uniformity in the cured product surface, and easy to form a fine concavo-convex shape, effectively prevent the reflection, 200m ² / g or more is preferable, and 200 to 2000m ² / g is more preferable, and from 200 to 1500m ² / g, and particularly preferably 200 to 1000 m ² / g. If the specific surface area is 200 m ² / g or more, the hydrophobic porous inorganic filler is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof, and the function of preventing surface reflection 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 hydrophobic porous inorganic filler is increased and the thixotropic property is suppressed, and the fluidity at the time of producing the antireflective material tends to be secured. The specific surface area of the porous inorganic filler before the surface was subjected to the hydrophobic treatment was determined based on the nitrogen adsorption specific surface area determined based on the BET equation from the adsorption isotherm of nitrogen at -196 캜 according to JIS K6430 Annex E. it means.

The oil-absorbing amount of the hydrophobic porous inorganic filler is not particularly limited, but the hydrophobic porous inorganic filler 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, , It is preferably 10 to 2000 mL / 100 g, more preferably 100 to 1000 mL / 100 g. If the oil absorption amount is 10 mL / 100 g or more, the hydrophobic porous inorganic filler tends to become widespread and uniformly dispersed throughout the resin composition or the cured product of the resin composition to easily form a concavo-convex shape 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 hydrophobic porous inorganic filler tends to be improved. The feed amount of the hydrophobic porous inorganic filler is the amount of oil absorbed by 100 g of filler and can be measured in accordance with JIS K5101.

In the antireflective member or the resin composition of the present invention, the hydrophobic porous inorganic filler may be used singly or in combination of two or more kinds. The hydrophobic porous inorganic filler may be produced by a known or common manufacturing method. For example, the hydrophobic porous inorganic filler may be manufactured by a method known in the art, such as "Silo Foobic 702", "Silo Foobic 4004", "Silo Foobic 505", "Silo Foobic 100" (Manufactured by Fuji Silicia Chemical Co., Ltd.) such as "Foobic 200", "Silo Foobic 704", "Silo Foobic 507" and "Silo Foobic 603" (Commercially available from Ebonic Degussa), "Sanspecia H-121-ET" and "Sanspearia H-51-ET" Quot; manufactured by ITEC Co., Ltd.) may be used.

The content (blend amount) of the hydrophobic porous inorganic filler in the antireflective member or the resin composition of the present invention is not particularly limited, but is preferably 4 to 40 parts by weight, based on the total amount (100 wt%) of the antireflective member or the resin composition By weight, more preferably 4 to 35% by weight, and still more preferably 4 to 30% by weight. The content of the hydrophobic porous inorganic filler is 4% by weight or more so that the hydrophobic porous inorganic filler is uniformly dispersed and uniformly spread over the entirety of the cured product constituting the resin composition or the antireflective member to form uniform irregularities on the entire surface of the cured product It becomes easier to do. On the other hand, when the content of the hydrophobic porous inorganic filler is 40 wt% or less, remarkable deterioration of the whole 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 do.

The content (blending amount) of the hydrophobic porous inorganic filler in the antireflective member or the resin composition of the present invention is usually 5 to 80 parts by weight based on the resin composition (100 parts by weight) constituting the antireflection member, 5 to 70 parts by weight, more preferably 5 to 60 parts by weight. The content of the hydrophobic porous inorganic filler is 5 parts by weight or more so that the hydrophobic porous inorganic filler is uniformly dispersed and uniformly dispersed throughout the resin composition or the cured product thereof constituting the antireflective material to form uniform irregularities on the entire surface of the cured product It becomes easier to do. On the other hand, when the content of the hydrophobic porous inorganic filler is 80 parts by weight or less, remarkable deterioration of the total internal 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 do.

[Resin composition]

The resin composition constituting the cured product of the antireflection material of the present invention is not particularly limited, but it is preferably usable as a sealing material of an optical semiconductor element in a photosemiconductor device, that is, a resin composition for optical semiconductor encapsulation (For example, a property that transparency does not easily deteriorate even by heating, a crack or an exfoliation from an adherend even if a high-temperature heat or a thermal shock is applied), which is hardened by heat or light, Hardly occurs, etc.) can be suitably used as the curable resin composition.

As such a curable resin composition, a known or publicly known resin composition having a thermosetting property or a photo-curable property can be used without particular limitation, and examples thereof include an epoxy resin (epoxy compound) (referred to as "epoxy resin (A)") Is a composition comprising at least one kind of curing compound selected from the group consisting of a silicone compound (referred to as "silicone resin (B)") and an acrylic resin (referred to as "acrylic resin (C) desirable. Examples of such a curable resin composition include a composition comprising a composition (curable epoxy resin composition) containing an epoxy resin (A), a composition (curable silicone resin composition) containing a silicone resin (B) (A curable acrylic resin composition). Hereinafter, the curable resin composition of these embodiments will be described. However, the curable resin composition of the present invention is not limited to the composition of the following embodiments.

The antireflection material of the present invention is not limited to the use of the resin composition for optical semiconductor encapsulation. For example, the antireflective material of the present invention can be applied to various optical members described later, and may be a resin suitable for each application (for example, a polyolefin resin , Polyester resin, polyamide resin, polyurethane resin, etc.).

As the resin composition constituting the cured product of the antireflection material of the present invention, a curable epoxy resin composition, a curable silicone resin composition and a curable acrylic resin composition having excellent heat resistance, transparency and durability are preferable, and a curable epoxy resin composition is preferred desirable.

1. Curable Epoxy Resin Composition

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

1-1. The epoxy resin (A)

The epoxy resin (A) in the curable epoxy resin composition of the present invention is a compound having at least one epoxy group (oxirane ring) in the molecule, and can be arbitrarily selected from known and publicly known epoxy compounds. Examples of the epoxy resin (A) include aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), alicyclic epoxy compounds (alicyclic epoxy resins), heterocyclic epoxy compounds (heterocyclic epoxy resins) And siloxane derivatives having at least one epoxy group in the molecule.

Examples of the aromatic epoxy compound include aromatic glycidyl ether type epoxy resins (for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, novolac type epoxy resin (for example, Phenol novolak type epoxy resin, cresol novolak type epoxy resin, cresol novolak type epoxy resin of bisphenol A), epoxy resins obtained from naphthalene type epoxy resins and trisphenol methane], and the like.

As the aliphatic epoxy compound, for example, an aliphatic glycidyl ether-based epoxy compound [for example, an aliphatic polyglycidyl ether] and the like can be given.

The alicyclic epoxy compound is a compound having at least one alicyclic ring (aliphatic hydrocarbon ring) and at least one epoxy group in the molecule (except for the siloxane derivative having at least one epoxy group in the molecule described above). 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 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.

Examples of the above-mentioned heterocyclic epoxy compound include compounds having a heterocyclic ring (for example, a tetrahydrofuran ring, a tetrahydropyran ring, a morpholine ring, a chroman ring, an isochroman ring, a tetrahydrofuran ring, A thiophene ring, a tetrahydrothiopyran ring, an aziridine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, an indoline ring, a 2,6-dioxabicyclo [3.3.0] Nonaromatic heterocycle such as a triazacyclohexane ring and a 1,3,5-triazacyclochexa-2,4,6-trione ring (isocyanuric ring); An aromatic heterocycle such as a thiophene ring, a pyrrole ring, a furan ring and a pyridine ring], and a compound having an epoxy group.

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

Examples of the epoxy group-containing isocyanurate include a compound represented by the following formula (3).

In the formula (3), R ^X , R ^Y and R ^Z (R ^X to R ^Z ) are the same or different and represent a hydrogen atom or a monovalent organic group. Provided that at least one of R ^x to R ^z is a monovalent organic group containing an epoxy group. Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group (e.g., an alkyl group, an alkenyl group, etc.); A monovalent aromatic hydrocarbon group (e.g., an aryl group and the like); A monovalent heterocyclic group; And monovalent groups formed by bonding two or more of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The monovalent organic group may have a substituent (for example, a substituent such as a hydroxy group, a carboxyl group or a halogen atom). Examples of the monovalent organic group containing an epoxy group include a monovalent group containing an epoxy group described later such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group, and a cyclohexene oxide group.

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

In the formulas (3-1), (3-2) and (3-3), R ¹ and R ² are the same or different and each represents a hydrogen atom Or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include linear or branched groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, Chain alkyl group. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferable. It is particularly preferable that R ¹ and R ² in the formulas (3-1) to (3-3) are hydrogen atoms.

Representative examples of the compound represented by the formula (3-1) include monoaryl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- 2-methylpropenyl) -3,5-diglycidyl isocyanurate, and 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate. have.

Representative examples of the compound represented by the formula (3-2) include diarylmonoglycidylisocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3 Bis (2-methylpropenyl) -5- (2-methylpropoxy) isocyanurate, and the like. have.

Representative examples of the compound represented by the above formula (3-3) include triglycidylisocyanurate and tris (2-methylepoxypropyl) isocyanurate.

The epoxy group-containing isocyanurate may be modified by adding a compound which reacts with an epoxy group such as an alcohol or an acid anhydride beforehand.

The siloxane derivative having at least one epoxy group in the molecule (sometimes referred to as "epoxy group-containing siloxane derivative") has a siloxane skeleton composed of a siloxane bond (Si-O-Si) in the molecule and has one epoxy group Or more. Examples of the siloxane skeleton include a cyclic siloxane skeleton; (Straight chain or branched chain polysiloxane) of linear or branched chain, polysiloxane skeleton such as cage-type or ladder-type polysilsesquioxane, and the like. The number of epoxy groups contained in the molecule of the epoxy group-containing siloxane derivative is not particularly limited, but is preferably 2 to 4, and more preferably 3 or 4.

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

The epoxy group-containing siloxane derivative includes, for example, a compound represented by the following formula (4) (cyclic siloxane).

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

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

More specifically, examples of the epoxy group-containing siloxane derivatives include 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6,8 , 8-hexamethylcyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,2,4,6,6,8-hexamethyl -Cyclotetrasiloxane, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6,8-dipropyl-2,4,6,8-tetramethyl- Tetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane , 2,4,8-tri [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 8-tri [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6-propyl-2,4,6,8- tetramethyl-cyclotetrasiloxane, 2,4,6,8 -Tetra [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,8-tetramethyl-cyclotetrasiloxane.

As the epoxy group-containing siloxane derivative, for example, a compound represented by the following formula (5) (chain polysiloxane) can be mentioned.

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

Examples of the epoxy group-containing siloxane derivatives include silicon resins having an epoxy group (for example, silicone resins containing alicyclic epoxy groups described in JP-A-2008-248169), silsesquioxane having an epoxy group For example, an organopolysiloxane resin having at least two epoxy functional groups in a molecule described in JP-A-2008-19422), and the like.

Among them, as the epoxy resin (A), bisphenol A type epoxy resin, isocyanurate having at least one epoxy group in the molecule, novolak type epoxy resin , Alicyclic epoxy compounds, aliphatic epoxy compounds, and siloxane derivatives having at least one epoxy group in the molecule. In particular, it is preferable that the curable epoxy resin composition of the present invention contains an alicyclic epoxy compound as an essential component as the epoxy resin (A) because a cured product having excellent transparency and durability can be obtained with high productivity. As the alicyclic epoxy compound, a compound having a cyclohexene oxide group in the molecule (particularly, a compound having two or more cyclohexene oxide groups in the molecule) is preferable, and a compound represented by the formula (1) Particularly a compound represented by the formula (1-1)).

In the curable epoxy resin composition of the present invention, the epoxy resin (A) may be used singly or in combination of two or more. The epoxy resin (A) may be produced by a method known to those skilled in the art, or a commercially available product may be used.

The content (blend amount) of the epoxy resin (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 25 to 99.8 wt% (for example, 100 wt%) based on the total amount of the curable epoxy resin composition , Preferably 25 to 95% by weight, more preferably 30 to 90% by weight, still more preferably 35 to 85% by weight, particularly preferably 40 to 60% by weight. When the content of the epoxy resin (A) is 25% by weight or more, curing tends to proceed more efficiently. On the other hand, when the content of the epoxy resin (A) is 99.8% by weight or less, the strength of the cured product tends to be further improved.

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

The ratio of the alicyclic epoxy compound to the total amount of the epoxy compound (total epoxy compound; for example, the total amount of the epoxy resin (A)) (100 wt%) contained in the curable epoxy resin composition of the present invention is particularly limited But is preferably 40 to 100% by weight (for example, 40 to 90% by weight), more preferably 80 to 100% by weight, still more preferably 90 to 100% by weight, particularly preferably 95 to 100% Weight%. When the proportion of the alicyclic epoxy compound is 40% by weight or more, the curing can proceed more efficiently and the transparency and durability of the cured product tends to be further improved.

1-2. The hardener (D)

The curing agent (D), which is one of the essential components of the curable epoxy resin composition of the present invention, is a compound having an action of curing the curable epoxy resin composition by reacting with an epoxy compound. The curing agent (D) is not particularly limited, and a curing agent for epoxy resins can be used, and examples thereof include acid anhydrides (acid anhydride type curing agent), amines (amine type curing agent), polyamide resin, (Imidazole-based curing agent), polymeric captan (polymeric curable curing agent), phenol (phenolic curing agent), polycarboxylic acid, dicyandiamide, organic acid hydrazide and the like.

As the acid anhydrides (acid anhydride-based curing agent) as the curing agent (D), there can be used an acid anhydride-based curing agent of known or conventional type, and there is no particular limitation, and examples thereof include methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride , 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride), dodecenylsuccinic anhydride, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride , Maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, anhydrous pyromellitic acid, anhydrous trimellitic acid, benzophenonetetracarboxylic acid anhydride, anhydrous nadic acid, anhydrous methyl nadic acid , Methylnadic anhydride anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, anhydrous adipic acid, anhydrous sebacic acid, Methylcyclohexene tetracarboxylic acid anhydride, vinyl ether-maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer, and the like. Among them, acid anhydrides (for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methylendomethylenetetrahydrophthalic anhydride and the like) which are liquid at 25 ° C are preferable from the viewpoint of handling. On the other hand, the acid anhydrides which are solid at 25 DEG C are dissolved in an acid anhydride in liquid state at 25 DEG C to form a liquid mixture, whereby handling properties of the curing agent (D) in the curable epoxy resin composition of the present invention are improved . As the acid anhydride-based curing agent, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including a ring to which a substituent such as an alkyl group is bonded) is preferable from the viewpoint of heat resistance and transparency of the cured product.

As the amine (amine-based curing agent) as the curing agent (D), there can be used an amine-based curing agent of a known or common type and there is no particular limitation, and examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, , Aliphatic polyamines such as dipropylenediamine, diethylaminopropylamine, and polypropylenetriamine; (Aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis 3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5- Monomolecular polyamines such as 4-diamine and 3,5-diethylolthrylene-2,6-diamine, biphenylene diamine, 4,4-diaminodiphenylmethane, 2,5-naphthylene diamine, And aromatic polyamines such as naphthylene diamine.

As the phenol (phenol-based curing agent) as the curing agent (D), a phenol-based curing agent which is publicly known or publicly available can be used and is not particularly limited. Examples thereof include novolak type phenol resin, novolak type cresol resin, Aralkyl resins such as phenol resin and paraxylylene-meta-xylylene-modified phenol resin, terpene-modified phenol resin, dicyclopentadiene-modified phenol resin and triphenolpropane.

As the polyamide resin as the curing agent (D), for example, a polyamide resin having either or both of a primary amino group and a secondary amino group in a molecule can be given.

As imidazoles (imidazole-based curing agents) as the curing agent (D), there can be used an imidazole-based curing agent which is publicly known or commonly used, and there are no particular limitations. Examples thereof include 2-methylimidazole, Methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, Methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6- [2- Methylimidazolyl- (1)] -ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- .

Examples of the polymeric capsules (polymer-capper-based curing agent) as the curing agent (D) include polymeric polymers such as liquid mercaptans and polysulfide resins.

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

Among them, acid anhydrides (acid anhydride-based curing agent) are preferable as the curing agent (D) from the viewpoints of curability, heat resistance of the cured product, and transparency. In the curable epoxy resin composition of the present invention, the curing agent (D) may be used singly or in combination of two or more kinds. As the curing agent (D), a commercially available product may also be used. For example, commercially available products of acid anhydrides include trade names "Ricaside MH-700" and "Ricaside MH-700F" (manufactured by Shin-Nihon Rika Co., Ltd.); Trade name " HN-5500 " (manufactured by Hitachi Kasei Kogyo Co., Ltd.).

The content (amount) of the curing agent (D) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, epoxy resin A ) Is preferably from 50 to 200 parts by weight, more preferably from 75 to 150 parts by weight, and still more preferably from 100 to 120 parts by weight, based on 100 parts by weight of the total amount of the resin (A). More specifically, when acid anhydrides are used as the curing agent (D), it is preferable to use the acid anhydrides in a proportion of 0.5 to 1.5 equivalents per equivalent of the epoxy group in all the epoxy compounds contained in the curable epoxy resin composition of the present invention desirable. When the content of the curing agent (D) is 50 parts by weight or more, the curing can proceed more efficiently and the toughness of the cured product tends to be further improved. On the other hand, when the content of the curing agent (D) is 200 parts by weight or less, there is a tendency that a cured product having no color (or little color) and excellent color tends to be obtained.

1-3. Curing accelerator (E)

The curing accelerator (E), which is an essential component of the curable epoxy resin composition of the present invention, is a compound having a function of accelerating the reaction rate of the epoxy compound (in particular, the reaction of the epoxy resin (A) and the curing agent (D)) . As the curing accelerator (E), a curing accelerator for epoxy resin can be used, and it is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and Salts (e.g., phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts and the like); Diazabicyclo [4.3.0] nonene-5 (DBN) and its salts (for example, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts and the like); 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.

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

Examples of the curing accelerator (E) in the curable epoxy resin composition of the present invention include U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X , &Quot; 12XD " (developed product) (manufactured by SANA PRO Co., Ltd.); Trade names " TPP-K ", " TPP-MK " (manufactured by Kakogaku Kagaku Co., Ltd.); Quot; PX-4ET " (manufactured by NIPPON KAGAKU KOGYO CO., LTD.) And the like can be used.

The content (amount) of the curing accelerator (E) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, Is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 2.5 parts by weight, based on 100 parts by weight of the total amount of . When the content of the curing accelerator (E) is 0.05 parts by weight or more, a sufficient curing acceleration effect tends to be obtained. On the other hand, when the content of the curing accelerator (E) is 5 parts by weight or less, there is a tendency that a cured product having no color (or little color) and excellent in color tends to be obtained.

1-4. The curing catalyst (F)

The curing catalyst (F), which is one of the essential components of the curable epoxy resin composition of the present invention, initiates and / or accelerates the curing reaction (polymerization reaction) of a cationic polymerizable compound such as an epoxy compound to cure the curable epoxy resin composition Lt; / RTI > The curing catalyst (F) is not particularly limited, and examples thereof include cationic polymerization initiators (thermal cationic polymerization initiators) which generate cationic species by heat to initiate polymerization, Lewis acid-amine complexes, Bronsted acid salts, Diazoles and the like.

Specific examples of the curing catalyst (F) include aryldiazonium salts, aryl iodonium salts, arylsulfonium salts and allene-ion complexes. Examples of the curing catalysts (F) &Quot; CP-77 " (manufactured by ADEKA Corporation); Trade name " FC-509 " (made by 3M); Trade name " UVE1014 " (G. E.); San Aid SI-60L "," Sanade SI-80L "," Sanade SI-100L "," Sanade SI-110L "and" Sanade SI-150L "(above, SANSHIN KAGAKU KOGYO CO., LTD. My); Quot; and " CG-24-61 " (manufactured by BASF) can be preferably used. As the curing catalyst (F), for example, a compound of a metal such as aluminum or titanium, a chelate compound of acetoacetic acid or diketones, a silanol compound such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or Chelate compounds of diketones and compounds of phenols such as bisphenol S and the like.

As the Lewis acid-amine complex as the curing catalyst (F), a known or common Lewis acid-amine complex system curing catalyst can be used, and although not particularly limited, for example, BF ₃ n-hexylamine, BF ₃ ethylamine, BF ₃ · benzylamine, BF ₃ · diethylamine, BF ₃ · piperidine, BF ₃ · triethylamine, BF ₃ · aniline, BF ₄ · n- hexylamine, BF ₄ · monoethylamine, BF ₄ benzylamine, BF ₄揃 diethylamine, BF ₄揃 piperidine, BF ₄揃 triethylamine, BF ₄揃 aniline, PF ₅揃 ethylamine, PF ₅揃 isopropylamine, PF ₅揃 butylamine , PF ₅ laurylamine, PF ₅ benzylamine, AsF ₅ laurylamine, and the like.

As the Bronsted acid salts as the curing catalyst (F), known or publicly known Bronsted acid salts can be used without particular limitation, and examples thereof include aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphonium salts And the like.

As the imidazoles as the curing catalyst (F), there can be used imidazoles of known or common use, and there are no particular limitations. For example, 2-methylimidazole, 2-ethyl- 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1- Ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazolyl- ( 1] -ethyl-s-triazine and 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)] -ethyl-s-triazine.

In the curable epoxy resin composition of the present invention, the curing catalyst (F) may be used singly or in combination of two or more kinds. As described above, a commercially available product can be used as the curing catalyst (F), for example.

The content (amount) of the curing catalyst (F) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, epoxy resin Is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the total amount of . When the content of the curing catalyst (F) is 0.01 part by weight or more, the curing reaction tends to proceed more sufficiently. On the other hand, when the content of the curing catalyst (F) is 15 parts by weight or less, there is a tendency that a cured product having no color (or little color) and excellent color tends to be obtained. That is, by controlling the content of the curing catalyst (F) within the above range, the curing speed of the curable epoxy resin composition is improved, and a cured product excellent in balance of transparency and durability tends to be obtained.

In addition, the curable epoxy resin composition of the present invention may substantially contain a cationic photopolymerization initiator that generates cationic polymerization initiator (acid or the like) upon irradiation of light. When the curable epoxy resin composition of the present invention contains a photo cationic polymerization initiator, the content thereof may vary depending on, for example, the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, epoxy resin (A) For example, about 0.01 to 20 parts by weight, and preferably about 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the inorganic filler.

1-5. Polyhydric alcohol

The curable epoxy resin composition of the present invention may contain a polyhydric alcohol. In particular, when the curable epoxy resin composition of the present invention contains the curing agent (D) and the curing accelerator (E), it is preferable that the curable epoxy resin composition further contains a polyhydric alcohol in order to allow curing to proceed more efficiently. As polyhydric alcohols, there may be used polyhydric alcohols of known or common type, and there is no particular limitation, and examples thereof include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, Diol, 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 curable epoxy resin composition of the present invention, the polyhydric alcohol may be used singly or in combination of two or more.

The content (blend amount) of the polyhydric alcohol in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, Is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 2.5 parts by weight, based on 100 parts by weight of the total amount of the binder 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.

1-6. Phosphor

The curable epoxy resin composition of the present invention may contain a phosphor. When the curable epoxy resin composition of the present invention contains a phosphor, it can be particularly preferably used as a sealing application (sealing material application) 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 curable epoxy resin composition of the present invention, one kind of fluorescent material may be used alone, or two or more kinds of fluorescent materials may be used in combination. As the phosphor, a commercially available product can be used.

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

1-7. Other ingredients

The curable epoxy resin composition of the present invention may contain other components than the above insofar as the curing property and transparency are not adversely affected. 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, Silane coupling agents such as trimethoxysilane, silicone-based and fluorine-based defoaming agents, and the like. The content (amount) of the other components is not particularly limited, but is preferably 5% by weight or less (for example, 0 to 3% by weight) based on the total amount (100% by weight) of the curable epoxy resin composition.

The curable epoxy resin composition of the present invention is not particularly limited, but can be prepared, for example, by stirring and mixing the above-mentioned 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.

2. Curable silicone resin composition

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

As the silicone resin (B), for example, in addition to -Si-O-Si- (siloxane bond) as a main chain, -Si-R ^A -Si- (alkylalkylene bond: R ^A represents an alkylene group) A polyorganosiloxysilane; And a curable polysiloxane such as a polyorganosiloxane which does not contain the alkylalkylene bond as the main chain.

As the silicone resin (B), a known or publicly known curable silicone resin (curable polysiloxane) can be used as the curable compound and is not particularly limited. For example, silicone resin of addition type (addition reaction curing type), condensation type Reactive curing type) silicone resin. When the curable silicone resin composition of the present invention contains an electron, it can be used as an addition reaction curable silicone resin composition, and when the latter is included, it can be used as a condensation reaction curable silicone resin composition. The addition reaction curable silicone resin composition and the condensation reaction curable silicone resin composition will be described below. However, the curable silicone resin composition of the present invention is not limited to these examples. For example, both the addition silicone resin and the condensation silicone resin Or a silicone resin composition which is cured by addition reaction and condensation reaction. That is, the curing of the curable silicone resin composition in the curing step may be carried out by at least one kind of reaction selected from the group consisting of addition reaction and condensation reaction.

2-1. Addition reaction curable silicone resin composition

Examples of the addition curable silicone resin composition include polysiloxane (B1) having two or more alkenyl groups in the molecule as a silicone resin (B) and, if necessary, one or more (preferably two Or more) polysiloxane having a hydrosilyl group or a metal curing catalyst, and the like.

The polysiloxane (B1) is classified into a polyorganosiloxane (B1-1) and a polyorganosiloxysilane (B1-2). In the present specification polyorganosiloxane Sicily alkylene (B1-2) is, have at least two alkenyl in the molecule, in addition to the -Si-O-Si- (siloxane bond) as a main chain, -Si-R ^A - Is a polysiloxane containing Si- (alkylalkylene bond: R ^A represents an alkylene group). The polyorganosiloxane (B1-1) in the present specification is a polysiloxane having two or more alkenyl groups in the molecule and not containing the alkylene bond as the main chain.

Examples of the polyorganosiloxane (B1-1) include those having a molecular structure of a straight chain, branched chain (straight chain having a branch, a branched chain, a mesh, etc.). The polyorganosiloxane (B1-1) may be used singly or in combination of two or more. In addition, two or more kinds of polyorganosiloxanes (B1-1) having different molecular structures may be used in combination. For example, a linear polyorganosiloxane (B1-1) and a branched polyorganosiloxane (B1 -1) may be used in combination.

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

The group bonded to the silicon atom other than the alkenyl group of the polyorganosiloxane (B1-1) is not particularly limited, and examples thereof include a hydrogen atom and a monovalent organic group. Examples of the monovalent organic group include an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group), a cycloalkyl group (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group A cyclohexyl group, a cyclododecyl group, etc.), an aryl group (e.g., a phenyl group, a tolyl group, a xylyl group or a naphthyl group), a cycloalkylalkyl group (e.g., a cyclohexylmethyl group, a methylcyclohexyl group , A halogenated hydrocarbon group in which at least one hydrogen atom in the hydrocarbon group is substituted with a halogen atom (e.g., a chloromethyl group, a 3-chloropropyl group, a 3,3 , A halogenated alkyl group such as a 3-trifluoropropyl group, etc.], and the like. In the present specification, the term "group bonded to a silicon atom" generally refers to a group not containing a silicon atom.

The group bonded to the silicon atom may have a hydroxy group or an alkoxy group.

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

As the polyorganosiloxane (B1-1), the following average unit formula:

^{_{(R 7 SiO 3/2) a1 (}} R 7 2 SiO 2/2) a2 (R 7 3 SiO 1/2) a3 (SiO 4/2) a4 (ZO 1/2) a5

Is preferably a polyorganosiloxane. In the above average unit formula, R ⁷ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the above-mentioned specific examples (for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a halogenated hydrocarbon group, . Provided that a part of R < ⁷ > is an alkenyl group (especially a vinyl group), and the ratio is controlled to be in a range of two or more in the molecule. For example, the ratio of the alkenyl group to the total amount (100 mol%) of R ⁷ is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group within the above range, the curability of the curable silicone resin composition tends to be further improved. As R ⁷ other than an alkenyl group, an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable.

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

A2 is 0 or a positive number; a3 is 0 or a positive number; a4 is 0 or a positive number; a5 is 0 or a positive number; and (a1 + a2 + a3) is a positive number.

As described above, the polyorganosiloxysilylalkylene (B1-2) is a polyorganosiloxane having two or more alkenyl groups in the molecule and containing a siloxane bond as a main chain and a silane linkage. Further, as the alkylene group in said chamber alkylene bond, preferably a C _{2- 4} alkyl group (particularly an ethylene group). The polyorganosiloxysilylalkane (B1-2) is less likely to generate a low molecular weight ring in the production process as compared with the polyorganosiloxane (B1-1), and is decomposed by heating or the like to be a silanol group (- SiOH), when the polyorganosiloxy alkylene (B1-2) is used, the surface tackiness (tackiness) of the cured product of the curable silicone resin composition tends to be low and yellowing hardly occurs.

Examples of the polyorganosiloxysilylalkylene (B1-2) include those having a molecular structure of straight chain, branched chain (straight chain, branched chain, net-like chain having some branches, etc.). The polyorganosiloxysilylalkylene (B1-2) may be used singly or in combination of two or more. For example, two or more kinds of polyorganosiloxysilylenes (B1-2) having different molecular structures can be used in combination. For example, straight-chain polyorganosiloxysilylenes (B1-2) The chain polyorganosiloxysilylalkylene (B1-2) may also be used in combination.

As the alkenyl group having the polyorganosiloxysilylalkylene (B1-2) in the molecule, the above-mentioned specific examples can be mentioned, and among them, a vinyl group is preferable. The polyorganosiloxysilylalkylene (B1-2) may have only one alkenyl group or may have two or more alkenyl groups. The alkenyl group of the polyorganosiloxysilylalkylene (B1-2) is not particularly limited, but is preferably an alkenyl group bonded to a silicon atom.

The group bonded to the silicon atom other than the alkenyl group of the polyorganosiloxysilylalkylene (B1-2) is not particularly limited, and examples thereof include a hydrogen atom and a monovalent organic group. Examples of monovalent organic groups include monovalent substituted or unsubstituted hydrocarbon groups described above. Among them, an alkyl group (especially a methyl group) and an aryl group (particularly a phenyl group) are preferable.

The group bonded to the silicon atom may have a hydroxy group or an alkoxy group.

The property of the polyorganosiloxysilylalkylene (B1-2) is not particularly limited and may be a liquid state or a solid state.

Examples of the polyorganosiloxysilylalkylene (B1-2) include the following average unit formula:

^{_{(R 8 2 SiO 2/2) b1}} (R 8 3 SiO 1/2) b2 (R 8 SiO 3/2) b3 (SiO 4/2) b4 (R A) b5 (ZO 1/2) b6

Is preferably a polyorganosiloxysilane represented by the following general formula In the above average unit formula, R ⁸ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the above-mentioned specific examples (for example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, . However, a part of R ⁸ is an alkenyl group (in particular, a vinyl group), and the ratio thereof is controlled within a range of two or more in the molecule. For example, the ratio of the alkenyl group to the total amount of R ⁸ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group within the above range, the curability of the curable silicone resin composition tends to be further improved. As R ⁸ other than an alkenyl group, an alkyl group (especially a methyl group) and an aryl group (particularly a phenyl group) are preferable.

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

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

B3 is 0 or a positive number; b4 is 0 or a positive number; b5 is a positive number; and b6 is 0 or a positive number. Among them, b1 is preferably from 1 to 200, b2 is preferably from 1 to 200, b3 is preferably from 0 to 10, b4 is preferably from 0 to 5, and b5 is preferably from 1 to 100. In particular, when (b3 + b4) is positive, the mechanical strength of the cured product tends to be further improved.

As described above, the addition reaction-curable silicone resin composition may further contain a polysiloxane having one or more (preferably two or more) hydrosilyl groups (Si-H) in the molecule (referred to as " hydrosilyl group-containing polysiloxane " May be included). The hydrosilyl group-containing polysiloxane is classified into a hydrosilyl group-containing polyorganosiloxane and a hydrosilyl group-containing polyorganosiloxysilane. In the present specification, the hydrosilyl group-containing polyorganosiloxysilane has at least one hydrosilyl group in the molecule, and in addition to -Si-O-Si- (siloxane bond) as a main chain, -Si-R ^A -Si - (alkylalkylene bond: R ^A represents an alkylene group). The hydrosilyl group-containing polyorganosiloxane in the present specification is a polysiloxane having at least one hydrosilyl group in the molecule and not containing the alkylene bond as the main chain. In addition, R ^A (alkylene) As in the same manner as described above, for example, there may be mentioned straight-chain or branched C _{1- 12} alkylene group, preferably a linear or branched C _2- C ₄ alkylene group (in particular, Ethylene group).

Examples of the hydrosilyl group-containing polyorganosiloxane include those having a molecular structure of straight chain, branched chain (straight chain, branched chain, meshed chain having some branches, etc.). The hydrosilyl group-containing polyorganosiloxane may be used singly or in combination of two or more. Two or more hydrosilyl group-containing polyorganosiloxanes having different molecular structures may be used in combination. For example, a combination of a linear hydrosilyl group-containing polyorganosiloxane and a branched chain hydrosilyl group-containing polyorganosiloxane You may.

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

The properties of the hydrosilyl group-containing polyorganosiloxane are not particularly limited and may be a liquid phase or a solid phase. Among them, it is preferable to be liquid, and it is more preferable that the liquid has a viscosity at 25 ° C of 0.1 to 1,000,000,000 mPa · s.

As the hydrosilyl group-containing polyorganosiloxane, the following average unit formula:

(R ⁹ SiO _3/2 ) _{c 1} (R ⁹ ₂ SiO _2/2 ) _{c 2} (R ⁹ ₃ SiO _1/2 ) _{c 3} (SiO _4/2 ) _{c 4} (ZO _1/2 ) _c5

Is preferably a polyorganosiloxane. In the average unit formula, R ⁹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and is a hydrogen atom, the above-mentioned specific examples (e.g., an alkyl group, an alkenyl group, An alkyl group, a halogenated alkyl group, etc.). Provided that a part of R ⁹ is a hydrogen atom (a hydrogen atom constituting a hydrosilyl group), and the ratio is controlled to be within a range of one or more (preferably two or more) hydrosilyl groups in the molecule. For example, the ratio of hydrogen atoms to the total amount of R ⁹ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. As R ⁹ other than a hydrogen atom, an alkyl group (especially a methyl group) and an aryl group (particularly a phenyl group) are preferable.

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

C2 is 0 or a positive number; c3 is 0 or a positive number; c4 is 0 or a positive number; c5 is 0 or a positive number; and (c1 + c2 + c3) is a positive number.

The hydrosilyl group-containing polyorganosiloxylalkylene is a polyorganosiloxane having at least one hydrosilyl group in the molecule and containing a siloxane bond as a main chain, as described above. The Examples of the alkylene group in said chamber alkylene bond, for example _2- C ₄ alkylene group (particularly an ethylene group) is preferred. The hydrosilyl group-containing polyorganosiloxylalkylene is less likely to generate a low-molecular-weight ring in the production process as compared with the hydrosilyl group-containing polyorganosiloxane, and is decomposed by heating or the like to produce a silanol group (-SiOH ). When the hydrosilyl group-containing polyorganosiloxyl alkylene is used, the surface hardness of the cured product of the curable silicone resin composition tends to be lowered and yellowing hardly occurs.

Examples of the hydrosilyl group-containing polyorganosiloxylalkylene include those having a molecular structure of straight chain, branched chain (straight chain, branched chain, mesh-like chain having some branches, etc.). The hydrosilyl group-containing polyorganosiloxyl alkylene may be used singly or in combination of two or more. Containing hydrosilyl group-containing polyorganosiloxysilylenes having different molecular structures can be used in combination. For example, a combination of a linear hydrosilyl group-containing polyorganosiloxysilylene and a branched chain hydrosilyl group- The polyorganosiloxysilylene may be used in combination.

The group bonded to the silicon atom other than the hydrogen atom of the hydrosilyl group-containing polyorganosiloxy alkylene is not particularly limited, and examples thereof include monovalent organic groups. Examples of monovalent organic groups include monovalent substituted or unsubstituted hydrocarbon groups described above. Among them, an alkyl group (especially a methyl group) and an aryl group (particularly a phenyl group) are preferable.

The properties of the hydrosilyl group-containing polyorganosiloxylalkylene are not particularly limited and may be a liquid phase or a solid phase.

As the hydrosilyl group-containing polyorganosiloxylalkylene, the following average unit formula:

^{_{(R 10 2 SiO 2/2) d1}} (R 10 3 SiO 1/2) d2 (R 10 SiO 3/2) d3 (SiO 4/2) d4 (R A) d5 (ZO 1/2) d6

Is preferably a polyorganosiloxysilane represented by the following general formula Wherein R ¹⁰ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group and is a hydrogen atom and the above-mentioned specific examples (e.g., an alkyl group, an alkenyl group, an aryl group, An alkyl group, a halogenated alkyl group, etc.). Provided that a part of R < ¹⁰ > is a hydrogen atom, and the ratio thereof is controlled to be in the range of one or more (preferably two or more) in the molecule. For example, the ratio of hydrogen atoms to the total amount (100 mol%) of R ¹⁰ is preferably 0.1 to 50 mol%, more preferably 5 to 35 mol%. By controlling the ratio of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. As R ¹⁰ other than a hydrogen atom, an alkyl group (particularly methyl group) and an aryl group (particularly, a phenyl group) are preferable. The proportion of the aryl group (especially phenyl group) relative to the total amount (100 mol%) of R ¹⁰ is preferably 5 mol% or more (for example, 5 to 80 mol%), more preferably 10 mol% or more to be.

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

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

D2 is a positive number; d3 is 0 or a positive number; d4 is 0 or a positive number; d5 is a positive number; and d6 is 0 or a positive number. Among them, d1 is preferably from 1 to 50, d2 is preferably from 1 to 50, d3 is preferably from 0 to 10, d4 is preferably from 0 to 5, and d5 is preferably from 1 to 30. [

As the hydrosilyl group-containing polysiloxane in the addition reaction-curable silicone resin composition, only the hydrosilyl group-containing polyorganosiloxane may be used, only the hydrosilyl group-containing polyorganosiloxysilane may be used, or the hydrosilyl group- Containing polyorganosiloxane and a hydrosilyl group-containing polyorganosiloxysilane may be used in combination. When the hydrosilyl group-containing polyorganosiloxane and the hydrosilyl group-containing polyorganosiloxysilane are used in combination, their ratio is not particularly limited and can be suitably set.

The addition reaction curable silicone resin composition is not particularly limited, but it is preferably a composition (compounding composition) in which the alkenyl group is 0.2 to 4 moles relative to 1 mole of the hydrosilyl group present in the curable resin composition, more preferably 0.5 To 1.5 mol, and more preferably 0.8 to 1.2 mol. By controlling the ratio of the hydrosilyl group and the alkenyl group within the above range, the heat resistance, transparency, thermal shock resistance and downflow resistance of the cured product and the barrier property against the corrosive gas (for example, SOx gas) tend to be further improved .

The addition reaction curable silicone resin composition may include a metal curing catalyst as described above. Examples of the metal curing catalyst include well known hydrosilylation catalysts such as platinum-based catalysts, rhodium-based catalysts and palladium-based catalysts. Specific examples thereof include platinum fine powders, platinum black, platinum-supported silica fine powders, platinum- Complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonyl complexes such as platinum-carbonylvinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum- Based catalyst such as a platinum-vinylmethylsiloxane complex, a platinum-phosphine complex and a platinum-phosphite complex, and a palladium-based catalyst or a rhodium-based catalyst containing a palladium atom or a rhodium atom in place of the platinum- . Among them, the hydrosilylation catalyst is preferable because a platinum vinylmethylsiloxane complex, a platinum-carbonylvinylmethyl complex, a chloroplatinic acid, and an alcohol or an aldehyde complex have a good reaction rate.

In addition, in the addition reaction-curable silicone resin composition, the metal curing catalyst (hydrosilylation catalyst) may be used singly or in combination of two or more.

The content (blend amount) of the metal curing catalyst (hydrosilylation catalyst) in the addition reaction-curable silicone resin composition is not particularly limited, but is preferably 1 to 5 mol per 1 mol of the total amount of alkenyl groups contained in the addition- × 10 ^-8 to 1 × 10 ^-2 is the mole, more preferably 1.0 × 10 ^-6 to 1.0 × 10 ^{- 3} mol of a. When the content is 1 x 10 < ^-8 > mol or more, the cured product tends to be formed more efficiently. On the other hand, when the content is less than 1 x 10 < ^-2 > mol, a cured product having better color (less coloring) tends to be obtained.

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

2-2. Condensation reaction curable silicone resin composition

Examples of the condensation-curable silicone resin composition include silicone resin (B), polysiloxane (B2) having two or more silanol groups (Si-OH) or silanol groups (Si-OR) And a curable silicone resin composition containing a metal curing catalyst or the like as required. The polysiloxane (B2) may have only either a silanol group or a silanol group, and may have both a silanol group and a silanol group. In the case of having both a silanol group and a silyloxy group, the total number of these groups may be two or more in the molecule.

As the polysiloxane (B2), for example, a polyorganosiloxane represented by the following average compositional formula can be given.

R ¹¹ _e Si (OR ¹² ) _f (OH) _g O _{(4- e f ) / 2}

[In the above average composition formula, R ¹¹ is the same or different and represents a monovalent organic group having 1 to 20 carbon atoms. R ¹² is the same or different and represents a monovalent organic group having 1 to 4 carbon atoms. e represents a number of 0.8 to 1.5, f represents a number of 0 to 0.3, and g represents a number of 0 to 0.5. f + g is a number of 0.001 or more and less than 1.2. Also, e + f + g is a number of not less than 0.801 and not more than 2.]

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

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

The condensation reaction-curable silicone resin composition may contain a metal curing catalyst as described above. Examples of such a metal curing catalyst include condensation reaction catalysts of known or common use, and examples thereof include organic titanic acid esters, organic titanium chelate compounds, organoaluminum compounds, organic zirconium compounds, organotin compounds, metal salts of organic carboxylic acids, Amine compounds or salts thereof, quaternary ammonium salts, alkali metal lower fatty acid salts, dialkylhydroxylamines, guanidyl group-containing organosilicon compounds, and the like. Among them, organic zirconium compounds are preferable from the viewpoint of reactivity. These may be used singly or in combination of two or more. The content (blending amount) of the metal curing catalyst (condensation reaction catalyst) in the condensation reaction-curable silicone resin composition is not particularly limited. For example, 0.01 to 20 parts by weight Range.

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

The curable silicone resin composition of the present invention (for example, the above-mentioned addition reaction curable silicone resin composition, condensation reaction curable silicone resin composition, etc.) may contain other components. Examples of other components include those exemplified as components that may contain the curable epoxy resin composition of the present invention. The content thereof is not particularly limited and can be appropriately selected. For example, when the curable silicone resin composition of the present invention is a resin composition for optical semiconductor encapsulation, it preferably contains the above-mentioned fluorescent substance. The content (amount) of the fluorescent material in the curable silicone resin composition of the present invention is not particularly limited and may be appropriately selected within the range of 0.5 to 20% by weight based on the total amount (100% by weight) of the curable silicone resin composition.

The curable silicone resin composition of the present invention is not particularly limited, and can be prepared, for example, by stirring and mixing the above-mentioned respective components under heating in accordance with necessity. Further, the curable silicone resin composition of the present invention may be a one-liquid composition in which all of the components are mixed in advance, and for example, two or more divided components 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. As the curable silicone resin composition or its constituent components of the present invention, commercially available products can be used as they are.

3. Curable acrylic resin composition

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

Examples of the acrylic resin (C) include compounds having at least one (meth) acryloyl group (at least one kind of group selected from the group consisting of acryloyl group and methacryloyl group) in the molecule. As the acrylic resin (C), a (meth) acryloyl compound having only one (meth) acryloyl group in the molecule; (Meth) acryloyl groups having two or more (meth) acryloyl groups in the molecule. The (meth) acryloyl compound having only one (meth) acryloyl group in the molecule may be exemplified by a monofunctional (meth) acryloyl compound having no polymerizable functional group other than the (meth) acryloyl group, (Meth) acryloyl group having at least one polymerizable functional group such as an epoxy group, an oxetanyl group, a vinyl group and a vinyloxy group in addition to a (meth) acryloyl group. The acrylic resin (C) may be used singly or in combination of two or more kinds. The content of the acrylic resin (C) in the curable acrylic resin composition of the present invention is not particularly limited and can be appropriately selected.

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

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

The curable acrylic resin composition of the present invention is not particularly limited, and can be prepared, for example, by stirring and mixing the above-mentioned respective components under heating in accordance with necessity. The curable acrylic resin composition of the present invention may be a one-liquid composition in which all of the components are mixed in advance, or may be a composition in which two or more components are 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. As the curable acrylic resin composition or its constituent components of the present invention, commercially available products can be used as they are.

[Shape of cured product and unevenness]

The antireflection material of the present invention is characterized in that the hydrophobic porous inorganic filler is widely dispersed and uniformly dispersed throughout the resin composition or the cured product thereof and the dispersed state is stabilized so that the hydrophobic porous inorganic filler present on the surface of the cured product has a concavo- And the reflection preventing function is exhibited by scattering the incident light. In addition, the porous structure on the surface of the hydrophobic porous inorganic filler can also scatter incident light, thereby further improving the antireflection function.

Further, since the surface of the hydrophobic porous inorganic filler exhibits hydrophobicity, the cured product containing the same exhibits high heat resistance, in particular, heat resistance water resistance, which is hard to deteriorate even under severe heating conditions such as boiling water, and is excellent in durability.

The method for spreading the hydrophobic porous inorganic filler over the entirety of the cured product is not particularly limited and includes, for example, a method of uniformly dispersing the hydrophobic porous inorganic filler in the resin composition constituting the cured product, followed by curing have. In order to efficiently produce the antireflective member of the present invention, a method of uniformly dispersing and then curing the hydrophobic porous inorganic filler 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 hydrophobic porous inorganic filler may be 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.

The shape of the resin composition before curing of the present invention is not particularly limited, but it is preferably liquid. Since the resin composition before curing to form the antireflection material of the present invention can exhibit antireflection function by the addition of a small amount by using a hydrophobic porous inorganic filler, it is easy to form a liquid phase without using a solvent such as toluene, Do.

[Curing Process]

The antireflection material of the present invention can be obtained by curing a resin composition in which the hydrophobic porous inorganic filler 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 hydrophobic porous inorganic filler, it is liable to become a liquid phase without using a volatile component of a solvent (toluene or the like) It is possible to reduce the amount of the constituents.

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 has high transparency and excellent antireflective function as well as high heat resistance (in particular, heat resistance water), and therefore can be used as an optical material (used for forming an optical material) It can be suitably used. 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 hydrophobic porous inorganic filler on its surface as a result of the fact that the hydrophobic porous inorganic filler is widely dispersed and uniformly dispersed throughout the cured product and the incident light It is not scattered to cause total internal reflection, so that gloss can be suppressed and 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. An optical semiconductor device in which an optical semiconductor element is sealed by an antireflection material produced by using the resin composition (resin composition for optical semiconductor encapsulation) of the present invention (for example, 104 in FIG. 1 is an antireflection material Is obtained. The sealing of the optical semiconductor element can be carried out, for example, by injecting a resin composition in which a hydrophobic porous inorganic filler is uniformly dispersed into a predetermined mold, and curing 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 luminous flux and has a high heat resistance (particularly, heat resistance water 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.

Production Example 1

, 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 an alicyclic epoxy compound (trade name " Celloxide 2021P ", Daicel Co., Ltd.) and 101.5 parts by weight of the epoxy curing agent obtained in Production Example 1 were mixed using a self-propulsive 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 hydrophobic porous inorganic filler (trade name " Silo Foobic 702 ", manufactured by Fuji Silysia Chemical Co., Ltd.) were mixed using a self- The curable epoxy resin composition was molded into 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, Thereby manufacturing a photosemiconductor device in which semiconductor elements are sealed. 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 is uniform and fine irregularities are formed by the hydrophobic porous inorganic filler existing on the upper surface thereof (uneven shape is not shown).

Examples 2 to 13 and Comparative Examples 1 to 13

The optical semiconductor device was fabricated in the same manner as in Example 1 except that the composition of the curable epoxy resin composition, the hydrophobic porous inorganic filler, and the porous inorganic filler (not subjected to hydrophobic treatment) was 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) Heat resistance test (heat resistance in boiling water)

EXAMPLES The optical semiconductor devices obtained in Examples and Comparative Examples were immersed in boiling water for 30 minutes, and then evaluated for appearance. The case where the appearance was the same as that before the test was evaluated as & cir &

(2) projection of 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 represented by?, A case where the outline is not clear and?, And a case where the outline can be recognized clearly is indicated by?.

(3) 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).

(4) 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 >

(5) 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 hot water resistance measured in the above (1) is?.

(b) The projection of the fluorescent lamp measured in the above (2) is? or?.

(c) the arithmetic average surface roughness Ra measured in the above (3) is 0.10 to 1.0 占 퐉.

(d) The total light flux measured in the above (4) is 0.60 lm or more.

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

(Hydrophobic porous inorganic filler)

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

(Porous inorganic 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

(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.

TEPIC-VL: trade name "TEPIC-VL" [triglycidylisocyanurate], manufactured by Nissan Kagaku Kogyo Co., Ltd.

152: trade name " 152 " [phenol novolak type epoxy resin], manufactured by Mitsubishi Chemical Corporation

YL7410: trade name " YL7410 " [aliphatic epoxy compound], manufactured by Mitsubishi Chemical Corporation

X-22-169 AS: a trade name " X-22-169AS " [denatured silicone oil (polydimethylsiloxane having cyclohexene oxide groups at both ends)], Shinetsu Chemical Industry Co.,

X-40-2670: trade name "X-40-2670" [cyclic siloxane having a cyclohexene oxide group], manufactured by Shin-Etsu Chemical Co.,

(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.

As shown in Table 1, according to the optical semiconductor device having the antireflection member according to the embodiment to which the hydrophobic porous inorganic filler is added, the resistance to water heat resistance test is all ◯, the projection of fluorescent light is evaluated to be ◯ or Δ, It was confirmed that the average surface roughness Ra was in the range of 0.10 to 1.0 占 퐉 and the total light flux was in the range of 0.60 lm or more and excellent antireflection function and roughness and excellent heat resistance,

On the other hand, as shown in Table 2, the optical semiconductor device of the comparative example in which the porous inorganic filler not subjected to the hydrophobic treatment was mixed exhibited excellent antireflection function and roughness, but the heat resistance water test was X, .

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

[1] An antireflective member comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein the surface of the cured product has irregularities for suppressing reflection.

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

[3] The porous inorganic filler constituting the hydrophobic porous inorganic filler (the porous inorganic filler before the surface is subjected to the hydrophobic treatment) may be an inorganic filler (for example, borosilicate glass, sodium borosilicate glass, sodium silicate glass, aluminum silicate glass, Zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, forsterite, stearate, spinel, clay, kaolin, dolomite, hydroxyapatite, nephelinsinite, cristobalite, [1] or [2], wherein the powder is at least one kind of powder selected from the group consisting of wollastonite, diatomaceous earth and talc and has a porous structure, or a molded product thereof (for example, .

[4] The hydrophobic porous inorganic filler as described in any one of [1] to [4], wherein the hydrophobic porous inorganic filler is a hydrophilic porous filler having a surface of at least one hydrophobic surface treatment agent selected from the group consisting of metal oxides, silane coupling agents, titanium coupling agents, organic acids, polyols and organic silicon compounds The anti-reflective material according to the above [3], wherein the treatment is carried out.

[5] The antireflective material according to the above-mentioned [4], wherein the hydrophobic surface treating agent is an organic silicon compound.

[6] The organic silicon compound according to any one of [1] to [4], wherein the organosilicon compound is at least one selected from the group consisting of trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, (Preferably polydimethylsiloxane). The antireflection material according to the above-mentioned [5]

[7] The method according to any one of [1] to [5], wherein the hydrophobic porous inorganic filler is at least one selected from the group consisting of hydrophobic porous inorganic glass and hydrophobic porous silica (hydrophobic porous silica filler) 6]. ≪ / RTI >

[8] The method according to the above [7], wherein the hydrophobic porous silica filler 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 is treated with the hydrophobic surface treating agent. .

[9] The method according to [1], wherein the hydrophobic porous inorganic filler is at least one (preferably spherical or crushed) selected from the group consisting of powder, spherical, crushed, To [8].

[10] The hydrophobic porous inorganic filler, will have the surface of the porous inorganic filler the hydrophobic treatment, the specific surface area of the porous inorganic filler prior to the hydrophobic treatment is more preferably 200m ² / g or more (preferably from 200 to 2000m ² / g, Is 200 to 1500 m ² / g, and more preferably 200 to 1000 m ² / g).

[11] The antireflective material according to any one of [1] to [10], wherein the hydrophobic porous inorganic filler has an average particle diameter of 1 to 20 μm (preferably 2 to 15 μm).

[12] The antireflective material according to any one of [1] to [11], wherein the hydrophobic porous inorganic filler has an oil absorption of 10 to 2000 mL / 100 g (preferably 100 to 1000 mL / 100 g).

(13) The hydrophobic porous inorganic filler as described in any one of (1) to (3), wherein the hydrophobic porous inorganic filler has a content of 4 to 40% by weight (preferably 4 to 35% by weight, more preferably 4 to 30% An antireflective member according to any one of [1] to [12] above.

[14] The content (mixing amount) of the hydrophobic porous inorganic filler relative to the resin composition (100 parts by weight) constituting the antireflection material is 5 to 80 parts by weight (preferably 5 to 70 parts by weight, more preferably 5 to 70 parts by weight, 60 parts by weight). The antireflection material according to any one of [1] to [13] above.

[15] The antireflective material according to any one of [1] to [14], wherein the resin composition comprises a transparent curable resin composition.

[16] The curable resin composition according to the above [15], wherein the curable resin composition comprises a composition comprising at least one curable compound selected from the group consisting of an epoxy resin (A), a silicone resin (B) and an acrylic resin (C) .

[17] The antireflection material according to the above-mentioned [16], wherein the curable resin composition comprises a composition (curable epoxy resin composition) comprising an epoxy resin (A).

[18] The epoxy resin composition according to any one of [1] to [5], wherein the epoxy resin (A) is at least one epoxy resin selected from the group consisting of bisphenol A type epoxy resin, isocyanurate having at least one epoxy group in the molecule, novolak type epoxy resin, alicyclic epoxy compound, The antireflective material according to the item [16] or [17], wherein the antireflective material is at least one kind selected from the group consisting of siloxane derivatives having at least one alicyclic epoxy group (preferably an alicyclic epoxy compound).

[19] The antireflection material as described in the above [18], wherein the alicyclic epoxy compound comprises a compound having a cyclohexenecoxide group in the molecule (preferably a compound having two or more cyclohexenoxide groups in the molecule).

[20] The antireflection material according to the above-mentioned [19], wherein the alicyclic epoxy compound comprises 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).)

[21] The positive resist composition as described in any one of [1] to [3], wherein the compound represented by the formula (1) is 2,2-bis (3,4-epoxycyclohexan- (3,4-epoxycyclohexan-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4- Is at least one alicyclic epoxy compound selected from the group consisting of compounds represented by formulas (1) to (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 following formulas (1-9) and (1-10) each represent an integer of 1 to 30.]

[22] The antireflective material according to the above-mentioned [21], wherein the alicyclic epoxy compound comprises the compound represented by the formula (1-1).

It is preferable that the content (blending amount) of the epoxy resin (A) is 25 to 99.8 wt% (for example, 25 to 95 wt%) based on the total amount (100 wt%) of the curable epoxy resin composition 30] to 90% by weight, more preferably 35 to 85% by weight, and still more preferably 40 to 60% by weight.

The content (blending amount) of the alicyclic epoxy compound is preferably 20 to 99.8% by weight (preferably 40 to 95% by weight (for example, 40 to 95% by weight (based on the total amount of the curable epoxy resin composition) (18) to (23), wherein the content of the component (B) is 60% by weight or less, Antireflective material.

The proportion of the alicyclic epoxy compound to the total amount (100% by weight) of the epoxy compound contained in the curable epoxy resin composition is preferably 40 to 100% by weight (for example, 40 to 90% by weight) Is from 80 to 100% by weight, more preferably from 90 to 100% by weight, and still more preferably from 95 to 100% by weight.

[26] The curable epoxy resin composition according to any one of [1] to [3], wherein the curable epoxy resin composition further comprises a curing agent (D) and a curing accelerator (E), or a curing catalyst (F) (preferably a curing agent (D) 17] The antireflection material described in any one of [17] to [25].

The curing agent (D) may be at least one selected from the group consisting of acid anhydrides (acid anhydride type curing agent), amines (amine type curing agent), polyamide resin, imidazoles (imidazole type curing agent), polymeric captan (polymer captan type curing agent) (Preferably an acid anhydride-based curing agent) selected from the group consisting of phenols (phenol-based curing agents), polycarboxylic acids, dicyandiamides and organic acid hydrazides. .

[28] The antireflection coating composition according to the above [27], wherein the acid anhydride-based curing agent 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 a liquid acid anhydride at 25 ° C. ashes.

The amount (mixing amount) of the curing agent (D) is preferably 50 to 200 parts by weight (preferably 75 to 150 parts by weight, more preferably 20 to 100 parts by weight) based on 100 parts by weight of the total amount of the epoxy compound contained in the curable epoxy resin composition (100 to 120 parts by weight per 100 parts by weight of the antireflection film).

The amount (mixing amount) of the curing accelerator (E) is preferably 0.05 to 5 parts by weight (preferably 0.1 to 3 parts by weight, more preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight) based on 100 parts by weight of the total amount of the epoxy compound contained in the curable epoxy resin composition , 0.2 to 3 parts by weight, and more preferably 0.25 to 2.5 parts by weight in terms of weight of the antireflective layer.

[31] The antireflective member according to any one of [17] to [30], wherein the curable epoxy resin composition comprises a polyhydric alcohol (preferably an alkylene glycol having 2 to 4 carbon atoms).

The amount (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 0.1 to 3 parts by weight, 0.2 to 3 parts by weight, more preferably 0.25 to 2.5 parts by weight).

[33] The antireflection material according to any one of [1] to [32], wherein the curable epoxy resin composition comprises a phosphor.

[34] The antireflective material according to the above item [33], wherein the content (amount) of the phosphor is 0.5 to 20% by weight based on the total amount (100% by weight) of the curable epoxy resin composition.

Any one of the above-mentioned [1] to [34], 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) .

[36] The antireflection material according to any one of [1] to [35], which is used for sealing a semiconductor optical device.

[37] An optical semiconductor device in which an optical semiconductor element is sealed by an antireflection material as described in [36] above.

[38] A resin composition comprising a hydrophobic porous inorganic filler dispersed therein, which is used for producing the antireflective member according to any one of [1] to [36].

[39] The resin composition according to the above [38], which is a liquid.

[40] The resin composition according to the above [38] or [39], 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.

[41] A method for producing an antireflective member, which comprises curing the resin composition according to any one of [38] to [40], wherein unevenness for suppressing reflection on the surface is formed.

The antireflective 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 heat resistance, especially heat 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 (13)

An antireflective member comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein the surface of the cured product has irregularities for suppressing reflection. The antireflective member according to claim 1, wherein the hydrophobic porous inorganic filler is uniformly dispersed throughout the cured product, and unevenness is formed on the surface to suppress reflection. The antireflective member according to claim 1 or 2, wherein the hydrophobic porous inorganic filler has a surface of the porous inorganic filler treated with a hydrophobic property and a specific surface area of the porous inorganic filler before the hydrophobic treatment is 200 m ² / g or more. The antireflective member according to any one of claims 1 to 3, wherein the hydrophobic porous inorganic filler has an average particle diameter of 1 占 퐉 to 20 占 퐉. The antireflective member according to any one of claims 1 to 4, wherein the content of the hydrophobic porous inorganic filler relative to the total amount (100 wt%) of the antireflective member is 4 to 40 wt%. The antireflective member according to any one of claims 1 to 5, wherein the resin composition comprises a transparent curable resin composition. 7. The antireflection material according to claim 6, wherein the curable resin composition comprises a composition comprising an epoxy resin. 8. The antireflective member according to any one of claims 1 to 7, which is used for sealing the optical semiconductor. An optical semiconductor device in which an optical semiconductor element is sealed by the antireflection material according to claim 8. 9. A resin composition comprising a hydrophobic porous inorganic filler dispersed therein, which is used for producing the antireflective member according to any one of claims 1 to 8. The resin composition according to claim 10, wherein the resin composition is a liquid. The resin composition according to claim 10 or 11, 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. A method for producing an antireflective member, the method comprising: curing the resin composition according to any one of claims 10 to 12;

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