JP2017126045A - Antireflection material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection material that exhibits satisfactorily antireflection function even left at a normal temperature for a certain period of time (for example, two hours or more) before resin is cured, and an optical semiconductor device including an optical semiconductor element encapsulated by the antireflection material.SOLUTION: The antireflection material includes a resin layer in which at least one kind of inorganic filler (A) selected from the group consisting of a porous filler (A1) and a hollow body filler (A2) is dispersed, and the inorganic filler (A) forms convexoconcave for suppressing reflection on the surface of the resin layer. The resin layer is a cured product of curable epoxy resin composition containing epoxy compound (B) and acid anhydride hardener (C) including cross-linking cyclic hydrocarbon ring. An optical semiconductor device including an optical semiconductor element encapsulated by the antireflection material is also provided.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an antireflection material. The present invention also relates to an optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material.

In recent years, in various indoor or outdoor display boards, traffic signals, large display units, etc., a light emitting device (optical semiconductor device) using an optical semiconductor element (LED element) as a light source has been advanced. As such an optical semiconductor device, in general, an optical semiconductor device in which an optical semiconductor element is mounted on a substrate (substrate for mounting an optical semiconductor element) and the optical semiconductor element is sealed with a transparent sealing material is widespread. doing. The sealing material in such an optical semiconductor device is subjected to antireflection treatment on its surface in order to prevent a decrease in visibility due to total reflection of incident light such as illumination light from outside and sunlight. Yes.
Conventionally, as a method for imparting an antireflection function to the surface of a resin layer, an inorganic filler having a specific gravity smaller than that of a resin such as glass beads, silica, and hollow particles is dispersed in the resin, and the resin layer surface is cured before or during curing. A method of scattering incident light by floating and forming irregularities on the surface is known (for example, see Patent Document 1).

JP 2000-114605 A

  In the method of Patent Document 1, a resin composition in which an inorganic filler is uniformly dispersed in a resin is cast in a light-emitting device, and the inorganic filler is floated on the upper surface of the resin by allowing it to stand at room temperature for a certain period of time, followed by heating. The antireflection material is formed by curing. In order to sufficiently float the inorganic filler on the upper surface of the resin layer, it is necessary to leave it at room temperature for a certain time (for example, 2 hours or more) before heating, but the inventors tried the method of Patent Document 1. However, it has been found that the antireflection function of the obtained antireflection material deteriorates, for example, if it is left for 2 hours or longer before heat curing.

Accordingly, an object of the present invention is to provide an antireflection material that exhibits a sufficient antireflection function even if it is left at room temperature for a certain period of time (for example, 2 hours or more) before the resin is cured.
Moreover, the other object of this invention is to provide the said antireflection material which is a resin composition for optical semiconductor sealing.
Furthermore, another object of the present invention is to provide an optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material.

  As a result of intensive studies to solve the above problems, the present inventors have adopted a curable epoxy resin composition as a curable composition constituting a resin layer constituting an antireflective material, and further, crosslinked as an epoxy curing agent. When an acid anhydride curing agent having a cyclic hydrocarbon ring is used and a hollow filler or a porous filler is blended as an inorganic filler, even if it is left at room temperature for 2 hours or more before the resin is cured, sufficient reflection is achieved. The present inventors have found that an antireflection material having a prevention function is provided and is extremely suitable as a material for sealing an optical semiconductor element in an optical semiconductor device, and have completed the present invention.

  That is, the present invention comprises a resin layer in which at least one inorganic filler (A) selected from the group consisting of a porous filler (A1) and a hollow filler (A2) is dispersed, and the inorganic filler (A) Is an antireflective material that forms irregularities to suppress reflection on the surface of the resin layer, and the resin layer contains an epoxy compound (B) and an acid anhydride curing agent (C) having a crosslinked cyclic hydrocarbon ring. Provided is an antireflection material which is a cured product of a curable epoxy resin composition.

  In the antireflection material, the inorganic filler (A) is dispersed uniformly in the curable epoxy resin composition and then floats near the upper surface of the curable epoxy resin composition to form the irregularities on the surface. Can do.

  In the antireflection material, the content of the inorganic filler (A) with respect to the total amount (100% by weight) of the antireflection material may be 0.5 to 40% by weight.

  In the antireflection material, the antireflection material before curing may be liquid.

  In the antireflection material, the amount of components that volatilize during curing relative to the total amount (100 wt%) of the antireflection material before curing may be 10 wt% or less.

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

  The antireflection material may be an optical semiconductor sealing resin composition.

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

  Since the antireflection material of the present invention has the above-described configuration, a sufficient antireflection function can be obtained and the total luminous flux of the light source can be secured even when left at room temperature for 2 hours or more before the resin is cured. Therefore, by using the antireflection material of the present invention as a material for sealing an optical semiconductor element in an optical semiconductor device, a high-quality optical semiconductor device (for example, sufficient brightness while suppressing gloss) can be efficiently obtained. Can be manufactured.

It is an expansion schematic diagram of the reflection preventing material which concerns on the 1st Embodiment of this invention. It is an expansion schematic diagram of the reflection preventing material which concerns on the 2nd Embodiment of this invention. It is the schematic which shows the process of the manufacture example of the antireflection material of this invention. It is the schematic which shows one Embodiment of the optical semiconductor device containing the reflection preventing material of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view.

<Antireflection material>
The antireflection material of the present invention is an acid anhydride in which at least one inorganic filler (A) selected from the group consisting of a porous filler and a hollow filler has an epoxy compound (B) and a crosslinked cyclic hydrocarbon ring. Dispersed in a resin layer that is a cured product of a curable epoxy resin composition containing a curing agent (C), the inorganic filler (A) forms irregularities that suppress reflection on the surface of the resin layer. To do.

FIG. 1 is an enlarged schematic view of an antireflection material according to the first embodiment of the present invention. 1 is a resin layer, 2 is a porous filler. As shown in FIG. 1, among the porous fillers 2 dispersed in the resin layer 1, the porous filler 2 existing in the vicinity of the upper surface of the resin layer 1 comes into contact with the upper surface of the resin layer 1, thereby forming an uneven shape. The incident light is scattered and the gloss caused by total reflection is suppressed. 1st Embodiment is an aspect distributed so that the porous filler 2 may contact more under a convex part rather than under a concave-convex shaped recessed part.
Due to the porous structure of the porous filler 2, the apparent volume with respect to the resin layer is increased as compared with a filler that is not porous, and therefore, irregularities can be formed on the surface of the resin layer even with a small amount of addition. Further, the resin layer 1 penetrates into the porous structure of the porous filler 2 and the apparent specific gravity difference between the porous filler and the resin layer is reduced, so that the dispersed state is stabilized and the porous filler 2 Since the interaction between the surfaces is suppressed and aggregation becomes difficult and the porous filler 2 can spread over the entire upper surface of the resin layer 1, uniform and fine irregularities are formed on the surface of the resin layer for efficient incidence. Light can be scattered. In the first embodiment, the surface of the porous filler 2 itself is likely to appear on the upper surface of the resin layer 1. However, since the incident light is scattered by the porous structure of the surface of the porous filler 2, it is not porous. Gloss due to reflection can be more efficiently suppressed as compared with the case where a filler is used.

FIG. 2 is an enlarged schematic view of an antireflection material according to the second embodiment of the present invention. 1 is a resin layer, 3 is a hollow body filler. As shown in FIG. 2, the hollow filler 3 is mainly present near the upper surface of the resin layer 1. The hollow filler 3 forms an uneven shape by being in contact with the upper surface of the resin layer 1, and incident light is scattered to suppress gloss due to total reflection.
In the second embodiment, the hollow filler is distributed so as to be in contact with the lower portion of the concave portion than the lower portion of the concave and convex portion. The hollow filler 3 is distributed so as to be more in contact with the bottom of the concave portion than under the concave and convex portion formed on the surface of the resin layer, so that the hollow filler 3 is less likely to appear on the surface of the resin layer 1. Therefore, reflection by the hollow filler 3 itself is suppressed, and a higher antireflection function can be exhibited.

As explained in the first and second embodiments, when a porous filler or a hollow filler is used, reflection is efficient even if the amount used is small compared to an inorganic filler that is neither porous nor hollow. Therefore, a sufficient antireflection function can be ensured while suppressing a significant decrease in the total luminous flux due to light absorption of the porous filler or the hollow filler itself.
Needless to say, the antireflection material of the present invention is not limited to the first and second embodiments.
Hereinafter, each component will be described in detail.

[Inorganic filler (A)]
The inorganic filler (A) in the antireflection material of the present invention has a function of forming irregularities on the surface of the resin layer that are present near the surface of the resin layer and scatter incident light. The inorganic filler (A) is at least one selected from the group consisting of a porous filler (A1) and a hollow filler (A2).
Since each hollow body filler (A2) has a hollow inside thereof, it is preferably used for the antireflection material of the present invention because it has a small specific gravity and easily floats in the resin layer.

[Porous filler (A1)]
The porous filler (A1) that can be used in the antireflection material of the present invention means an inorganic filler that has an apparent specific gravity smaller than the true specific gravity of the filler and has a porous structure therein.

  As the porous filler (A1), known or commonly used ones can be used, and are not particularly limited. For example, inorganic glass [for example, borosilicate glass, borosilicate soda glass, sodium silicate glass, aluminum silicate glass, Quartz, etc.], silica, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, silicon nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, oxidation Powders of aluminum, calcium sulfate, barium sulfate, fosterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, talc, etc. and have a porous structure Also , Or their molded (e.g., spheronized beads, etc.) and the like. Further, as the porous filler (A1), a known or commonly used surface treatment for the above-mentioned porous filler [for example, surface treatment of metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyol, silicone, etc. And the like subjected to surface treatment with an agent]. By performing such a surface treatment, there are cases where compatibility and dispersibility with the components of the resin layer can be improved. Especially, as a porous filler (A1), a porous inorganic glass or porous silica (porous silica filler) is preferable from a viewpoint that an unevenness | corrugation can be efficiently formed in the resin layer surface.

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

  The porous filler (A1) may be composed of a single material, or may be composed of two or more materials. Especially, as a porous filler (A1), an unevenness | corrugation can be efficiently formed in the resin layer surface, and a porous silica (porous silica filler) is more preferable from a viewpoint of availability or manufacture ease.

  The shape of the porous filler (A1) is not particularly limited, and examples thereof include powder, spherical shape, crushed shape, fibrous shape, needle shape, and scale shape. Among these, spherical or crushed porous fillers are preferable from the viewpoint of easily forming a uniform fine uneven shape on the surface of the resin layer.

  The center particle diameter of the porous filler (A1) is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, from the viewpoint that it is easy to form a uniform and fine uneven shape on the surface of the resin layer. It is. The central particle diameter means a volume particle diameter (median volume diameter) at an integrated value of 50% in a particle size distribution measured by a laser diffraction / scattering method.

  The porous structure of the porous filler (A1) can be specified by various parameters such as specific surface area, pore volume, oil absorption, etc., each having a grade suitable for the antireflection material of the present invention. The filler can be selected without particular limitation.

The specific surface area of the porous filler (A1) is not particularly limited, but is 10 to 2000 m ² / g from the viewpoint of easily forming a uniform and fine uneven shape on the resin layer surface and efficiently preventing reflection. More preferably, it is 100-1000 m < ² > / g. When the specific surface area is 10 m ² / g or more, the antireflection function on the surface of the porous filler (A1) tends to be improved. On the other hand, when the specific surface area is 2000 m ² / g or less, the viscosity increase and thixotropy of the resin composition containing the porous filler (A1) are suppressed, and the fluidity when producing the antireflection material is secured. There is a tendency to. In addition, the said specific surface area means the nitrogen adsorption specific surface area calculated | required based on BET type | formula from the adsorption isotherm of nitrogen in -196 degreeC based on JISK6430 appendix E.

  The pore volume of the porous filler (A1) is not particularly limited, but from the viewpoint of easily forming a uniform fine uneven shape on the surface of the resin layer and efficiently preventing reflection, 0.1 to 10 mL / g is preferable, and more preferably 0.2 to 5 mL / g. If the pore volume is 0.1 mL / g or more, the porous filler (A1) tends to form an uneven shape on the surface of the resin layer. On the other hand, when the pore volume is 5 mL / g or less, the mechanical strength of the porous filler (A1) tends to be improved. The pore volume of the porous filler (A1) can be determined by measuring the pore distribution by the mercury intrusion method (porosimeter method).

  The oil absorption amount of the porous filler (A1) is not particularly limited, but is preferably 10 to 2000 mL / 100 g from the viewpoint of facilitating formation of a uniform and fine uneven shape on the surface of the resin layer and efficiently preventing reflection. More preferably, it is 100-1000 mL / 100g. If the oil absorption is 10 mL / 100 g or more, the porous filler (A1) tends to form an uneven shape on the resin layer surface. On the other hand, when the oil absorption is 2000 mL / 100 g or less, the mechanical strength of the porous filler (A1) tends to be improved. In addition, the amount of oil supply of the porous filler (A1) is the amount of oil absorbed by 100 g of the filler, and can be measured according to JIS K5101.

  In the antireflection material of the present invention, the porous filler (A1) can be used alone or in combination of two or more. The porous filler (A1) can also be produced by a known or conventional production method. For example, the trade names “Silicia 250N”, “Silicia 256”, “Silicia 256N”, “Silicia 310”, “Silicia” 320 ”,“ Silicia 350 ”,“ Silicia 358 ”,“ Silicia 430 ”,“ Silicia 431 ”,“ Silicia 440 ”,“ Silicia 450 ”,“ Silicia 470 ”,“ Silicia 435 ”,“ Silicia 445 ”,“ Silicia ” 436 ”,“ Silicia 446 ”,“ Silicia 456 ”,“ Silicia 530 ”,“ Silicia 540 ”,“ Silicia 550 ”,“ Silicia 730 ”,“ Silicia 740 ”,“ Silicia 770 ”, etc. "Cylos Sphere C-1504" Cyros sphere series such as “Cylos Sphere C-1510” (above, manufactured by Fuji Silysia Chemical Co., Ltd.), trade names “Sunsphere H-31”, “Sunsphere H-32”, “Sunsphere H-33”, Suns such as "Sunsphere H-51", "Sunsphere H-52", "Sunsphere H-53", "Sunsphere H-121", "Sunsphere H-122", "Sunsphere H-201" Commercial products such as Fair H series (AGC S-Tech Co., Ltd.) can also be used.

[Hollow filler (A2)]
When the hollow body filler (A2) is used in the antireflection material of the present invention, as shown in FIG. 2, the hollow body filler (A2) present near the resin layer surface is not formed on the convex and concave portions. Almost no distribution and distribution so as to be substantially in contact with the concave portion, and the hollow filler (A2) hardly appears on the surface of the resin layer. It is suppressed and a higher antireflection function can be exhibited.

  Although it does not specifically limit as said hollow body filler (A2), For example, inorganic glass [For example, borosilicate glass, borosilicate sodium glass, sodium silicate glass, aluminum silicate glass, quartz, etc.], silica, alumina, zirconia, etc. Inorganic hollow particles (including natural products such as Shirasu Balloon) composed of inorganic materials such as metal salts such as metal oxides, calcium carbonate, barium carbonate, nickel carbonate, calcium silicate, etc .; composed of hybrid materials of inorganic and organic materials Examples include inorganic-organic hollow particles. In addition, the hollow part (the space inside the hollow particles) of the hollow filler (A2) may be in a vacuum state or may be filled with a medium, but particularly for improving light scattering efficiency. For this, hollow particles filled with a medium having a low refractive index (for example, an inert gas such as nitrogen or argon or air) are preferable.

  Further, as the hollow filler (A2), a known or commonly used surface treatment for the above-mentioned hollow filler [for example, surface treatment of metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyol, silicone, etc. And the like subjected to surface treatment with an agent]. By performing such a surface treatment, there are cases where compatibility and dispersibility with the components of the resin layer can be improved. Especially, as a hollow body filler (A2), a hollow body inorganic glass or hollow body silica (hollow body silica filler) is preferable from a viewpoint that an unevenness | corrugation can be efficiently formed in the resin layer surface.

  When using a hollow body filler (A2), the hollow ratio (ratio of the volume of the voids relative to the total volume of the inorganic filler) is not particularly limited, but is preferably 10 to 90% by volume, more preferably 30 to 90% by volume. When the hollow ratio is in this range, the hollow filler (A2) tends to float in the resin layer and tends to be efficiently distributed under the concave and convex portions.

  Although the shape of a hollow body filler (A2) is not specifically limited, For example, powder, spherical shape, crushed shape, fibrous shape, needle shape, scale shape, etc. are mentioned. Among these, from the viewpoint of dispersibility, a spherical hollow filler is preferable, and a true hollow filler (for example, a spherical hollow filler having an aspect ratio of 1.2 or less) is particularly preferable.

  The center particle diameter of the hollow filler (A2) is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, from the viewpoint that it is easy to form a uniform and fine uneven shape on the surface of the resin layer. It is. The central particle diameter means a volume particle diameter (median volume diameter) at an integrated value of 50% in a particle size distribution measured by a laser diffraction / scattering method.

  The specific gravity of the hollow filler (A2) is not particularly limited, but it is preferably lighter than the specific gravity of the resin layer from the viewpoint that it is easy to efficiently float on the surface of the resin layer.

  In the antireflection material of the present invention, the hollow filler (A2) can be used alone or in combination of two or more. The hollow filler (A2) can also be produced by a known or conventional production method. For example, trade names “Sphericel ™ 110P8”, “Sphericel ™ 25P45”, “Sphericel ™ 34P30. "," Sphericel (trademark) 60P18 "," Q-CEL (trademark) 5020 "," Q-CEL (trademark) 7014 "," Q-CEL (trademark) 7040S "(Potters Barottini Co., Ltd.) ), Trade names "Glass Microballoon", "Fuji Balloon H-40", "Fuji Balloon H-35" (Fuji Silysia Chemical Ltd.), trade names "Cell Star Z-20", "Cell Star Z-" 27 ”,“ Cell Star CZ-31T ”,“ Cell Star Z-36 ”,“ Cell Star Z-39 ”,“ Cell "Star Z-39", "Cell Star T-36", "Cell Star PZ-6000" (manufactured by Tokai Kogyo Co., Ltd.), trade name "Syracx Fine Balloon" (made by Fine Balloon), trade name Commercial products such as “Super Balloon BA-15” and “Super Balloon 732C” (manufactured by Showa Chemical Industry Co., Ltd.) can be used.

  As the inorganic filler (A), only one of the porous filler (A1) and the hollow filler (A2) may be used, or the porous filler (A1) and the hollow filler (A2) are used in combination. May be.

  The content (blending amount) of the inorganic filler (A) in the antireflection material of the present invention is 0.5 to 40% by weight, preferably 0.5%, based on the total amount (100% by weight) of the antireflection material. It is -35 weight%, More preferably, it is 0.5-30 weight%. When the content of the inorganic filler (A) is 0.5% by weight or more, it becomes easy to form a uniform uneven shape on the entire surface of the resin layer constituting the antireflection material. On the other hand, when the content of the inorganic filler (A) is 40% by weight or less, when the antireflection material of the present invention is used as, for example, a sealing material for an optical semiconductor device, a significant decrease in the total luminous flux is prevented. There is a tendency to ensure sufficient illuminance.

  The content (blending amount) of the inorganic filler (A) in the antireflection material of the present invention is usually 0.1 to 80 parts by weight with respect to the resin composition (100 parts by weight) constituting the antireflection material. The amount is preferably 0.5 to 70 parts by weight, more preferably 1 to 60 parts by weight. When content of an inorganic filler (A) is 0.1 weight part or more, it becomes easy to form uniform uneven | corrugated shape on the whole surface of the resin layer which comprises an antireflection material. On the other hand, when the content of the inorganic filler (A) is 80 parts by weight or less, when the antireflection material of the present invention is used as, for example, a sealing material for an optical semiconductor device, a significant decrease in the total luminous flux is prevented. There is a tendency to ensure sufficient illuminance.

  When the antireflection material of the present invention contains a porous filler (A1), the content (mixing amount) of the porous filler (A1) is preferably 4 to the total amount (100% by weight) of the antireflection material. It is 40% by weight, more preferably 4 to 35% by weight, still more preferably 4 to 30% by weight. When the content of the porous filler (A1) is 4% by weight or more, it becomes easy to form a uniform uneven shape on the entire surface of the resin layer constituting the antireflection material. On the other hand, when the content of the porous filler (A1) is 40% by weight or less, when the antireflection material of the present invention is used as, for example, a sealing material for an optical semiconductor device, a significant decrease in the total luminous flux is prevented. There is a tendency to secure sufficient illuminance.

  When the antireflection material of the present invention contains a hollow body filler (A2), the content (blending amount) of the hollow body filler (A2) is preferably 0.00 with respect to the total amount (100% by weight) of the antireflection material. It is 5 to 40% by weight, more preferably 0.5 to 30% by weight, and still more preferably 0.5 to 20% by weight. When the content of the hollow filler (A2) is 0.5% by weight or more, it becomes easy to form a uniform uneven shape on the entire surface of the resin layer constituting the antireflection material. On the other hand, when the content of the hollow filler (A2) is 40% by weight or less, when the antireflection material of the present invention is used as, for example, a sealing material for an optical semiconductor device, a significant decrease in the total luminous flux is prevented. There is a tendency to secure sufficient illuminance.

[Resin layer]
The resin constituting the resin layer in the antireflective material of the present invention is a curable epoxy resin composition containing an epoxy compound (B) and an acid anhydride curing agent (C) having a crosslinked cyclic hydrocarbon ring as essential components. (Hereinafter, it may be referred to as “the curable epoxy resin composition of the present invention.”) (Hereinafter, it may be referred to as “the cured product of the present invention”). The curable epoxy resin composition of the present invention may contain other components other than the essential components described above.

1-1. Epoxy compound (B)
The epoxy compound (B) in the curable epoxy resin composition of the present invention is a compound having one or more epoxy groups (oxirane rings) in the molecule, and is arbitrarily selected from known or commonly used epoxy compounds. Can do. Examples of the epoxy compound (B) include aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), alicyclic epoxy compounds (alicyclic epoxy resins), and heterocyclic epoxy compounds. (Heterocyclic epoxy resin), siloxane derivatives having one or more epoxy groups in the molecule, and the like.

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

  Examples of the aliphatic epoxy compound include aliphatic glycidyl ether type epoxy compounds [for example, aliphatic polyglycidyl ether and the like].

  The alicyclic epoxy compound is a compound having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more epoxy groups in the molecule (provided that one epoxy group is present in the molecule). The siloxane derivative having the above is excluded). Examples of the alicyclic epoxy compound include (i) at least one alicyclic epoxy group (an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring) in the molecule (preferably (Ii) a compound having an epoxy group bonded directly to the alicyclic ring with a single bond; (iii) a compound having an alicyclic ring and a glycidyl group.

  Although it does not specifically limit as an alicyclic epoxy group which the compound which has at least one alicyclic epoxy group in the above-mentioned (i) molecule | numerator has, In particular, it is a cyclohexene oxide group (adjacent which comprises a cyclohexane ring from a sclerosing | hardenable viewpoint. And an epoxy group composed of two carbon atoms and an oxygen atom). In particular, (i) the compound having at least one alicyclic epoxy group in the molecule is preferably a compound having two or more cyclohexene oxide groups in the molecule from the viewpoint of transparency and heat resistance of the cured product. A compound represented by the following formula (1) is preferable.

  In formula (1), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include divalent hydrocarbon groups, alkenylene groups in which some or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected.

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

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, etc., straight chain or branched chain alkenylene groups having 2 to 8 carbon atoms (including alkapolyenylene groups) and the like. . In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

  The linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation. An alkenylene group; a group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, 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-epoxycyclohexane-1-yl) propane, bis (3,4-epoxycyclohexylmethyl) ether, , 2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, the following formula (1-1) The compound etc. which are represented by-(1-10) are mentioned. In the following formulas (1-5) and (1-7), l and m each represent an integer of 1 to 30. R in the following formula (1-5) is an alkylene group having 1 to 8 carbon atoms, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene. And linear or branched alkylene groups such as a group, a heptylene group, and an octylene group. Among these, C1-C3 linear or branched alkylene groups, such as a methylene group, ethylene group, a propylene group, an isopropylene group, are preferable. N1 to n6 in the following formulas (1-9) and (1-10) each represent an integer of 1 to 30.

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

In the formula (2), R ′ is a group obtained by removing p hydroxyl groups (—OH) from a p-valent alcohol (p-valent organic group) in the structural formula, and p and q each represent a natural number. Examples of the p-valent alcohol [R ′ (OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably from 1 to 6, and q is preferably from 1 to 30. When p is 2 or more, q in each () (inside the parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (2) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

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

  Other examples of the alicyclic epoxy compound include 1,2,8,9-diepoxy limonene.

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

  As the heterocyclic epoxy compound, for example, isocyanurate having one or more epoxy groups in the molecule (hereinafter sometimes referred to as “epoxy group-containing isocyanurate”) can be preferably used. Although the number of the epoxy groups which the said epoxy group containing isocyanurate has in a molecule | numerator is not specifically limited, 1-6 pieces are preferable, More preferably, it is 1-3.

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

In Formula (3), R ^X , R ^Y , and R ^Z (R ^{X to} R ^Z ) are the same or different and represent a hydrogen atom or a monovalent organic group. However, at least one of R ^{X to} R ^Z is a monovalent organic group containing an epoxy group. Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group); a monovalent aromatic hydrocarbon group (for example, an aryl group); A cyclic group; a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Note that the monovalent organic group may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom). Examples of the monovalent organic group containing an epoxy group include monovalent groups containing an epoxy group described later such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group, and a cyclohexene oxide group.

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

In the above formula (3-1), formula (3-2), and formula (3-3) (formulas (3-1) to (3-3)), R ¹ and R ² are the same or different, A hydrogen atom or an alkyl group having 1 to 8 carbon atoms is shown. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and octyl groups. Examples thereof include a chain or branched alkyl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable. R ¹ and R ² in the above formulas (3-1) to (3-3) are particularly preferably hydrogen atoms.

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

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

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

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

  As a siloxane derivative having one or more epoxy groups in the molecule (sometimes referred to as “epoxy group-containing siloxane derivative”), a siloxane skeleton composed of siloxane bonds (Si—O—Si) in the molecule is used. And a compound having at least one epoxy group. Examples of the siloxane skeleton include a cyclic siloxane skeleton; a linear or branched silicone (linear or branched polysiloxane), a polysiloxane skeleton such as a cage-type or ladder-type polysilsesquioxane, and the like. Can be mentioned. The number of epoxy groups in the molecule of the epoxy group-containing siloxane derivative is not particularly limited, but is preferably 2 to 4, more preferably 3 or 4.

  Although the epoxy group which the said epoxy group containing siloxane derivative has is not specifically limited, at least 1 piece is a point which can harden a curable epoxy resin composition efficiently and the hardened | cured material excellent in intensity | strength is obtained. An alicyclic epoxy group is preferred, and among them, at least one of the epoxy groups is particularly preferably a cyclohexene oxide group.

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

In said formula (4), R < ³ > is the same or different and shows the monovalent | monohydric organic group containing an alkyl group or an epoxy group. However, 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 (in particular, 1 containing an alicyclic epoxy group). Valent organic group). Moreover, p in Formula (4) shows an integer greater than or equal to 3 (preferably an integer of 3-6). The plurality of R ³ may be the same or different.

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

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

  Examples of the epoxy group-containing siloxane derivative include compounds represented by the following formula (5) (chain polysiloxane).

In said formula (5), R < ⁵ >, R < ⁶ > is the same or different and is a monovalent organic group containing an epoxy group, an alkoxy group (for example, C1-C4 alkoxy groups, such as a methoxy group, an ethoxy group, etc.). Etc.), an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group), or an aryl group (for example, an aryl group having 6 to 12 carbon atoms such as a phenyl group or a naphthyl group). Show. However, at least one (preferably at least two) of R ⁵ and R ⁶ in the compound represented by the formula (5) is a monovalent organic group containing an epoxy group. Examples of the monovalent organic group containing an epoxy group include the same groups as those in the above formula (4). In particular, from the viewpoint of curability, it is preferable that either one or both of R ^{6 is} a monovalent organic group containing an epoxy group. Moreover, q in Formula (5) shows an integer greater than or equal to 1 (for example, an integer of 1 to 500). The structures in parentheses marked with q may be the same or different. In addition, when two or more kinds of structures in parentheses with q are present, the additional form is not particularly limited, and may be a random type or a block type.

  Other examples of the epoxy group-containing siloxane derivative include a silicone resin having an epoxy group (for example, an alicyclic epoxy group-containing silicone resin described in JP-A-2008-248169) and a silsesquioxy having an epoxy group. Sun (for example, organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in JP-A-2008-19422) and the like.

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

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

  Although content (blending amount) of the epoxy compound (B) in the curable epoxy resin composition of the present invention is not particularly limited, it is 25 to 99.99 with respect to the total amount (100% by weight) of the curable epoxy resin composition. It is preferably 8% by weight (for example, 25 to 95% by weight), more preferably 30 to 90% by weight, still more preferably 35 to 85% by weight, and particularly preferably 40 to 60% by weight. By setting the content of the epoxy compound (B) to 25% by weight or more, curing tends to proceed more efficiently. On the other hand, there exists a tendency for the intensity | strength of hardened | cured material to improve more by making content of an epoxy compound (B) 99.8 weight% or less.

  Although content (blending amount) of the alicyclic epoxy compound in the curable epoxy resin composition of the present invention is not particularly limited, it is 20 to 99. with respect to the total amount (100% by weight) of the curable epoxy resin composition. 8% by weight is preferable, more preferably 40 to 95% by weight (for example, 40 to 60% by weight), still more preferably 50 to 95% by weight, particularly preferably 60 to 90% by weight, and most preferably 70 to 85% by weight. It is. By setting the content of the alicyclic epoxy compound to 20% by weight or more, curing can proceed more efficiently, and the transparency and durability of the cured product tend to be further improved. On the other hand, when the content of the alicyclic epoxy compound is 99.8% 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, total amount of the epoxy compound (B)) (100% by weight) contained in the curable epoxy resin composition of the present invention is not particularly limited. 40 to 100% by weight (for example, 40 to 90% by weight), more preferably 80 to 100% by weight, still more preferably 90 to 100% by weight, and particularly preferably 95 to 100% by weight. By setting the ratio of the alicyclic epoxy compound to 40% by weight or more, the curing can proceed more efficiently, and the transparency and durability of the cured product tend to be further improved.

1-2. Acid anhydride curing agent having a crosslinked cyclic hydrocarbon ring (C)
The acid anhydride curing agent (C) having a crosslinked cyclic hydrocarbon ring, which is one of the essential components of the curable epoxy resin composition of the present invention (hereinafter referred to as “crosslinked cyclic acid anhydride curing agent (C)”). Is a compound having a function of curing the curable epoxy resin composition by reacting with the epoxy compound.

  The crosslinked cyclic acid anhydride curing agent (C) has at least a crosslinked cyclic hydrocarbon ring structure and an acid anhydride group (—C (═O) —O—C (═O) —) in the molecule. In the curable epoxy resin composition of the present invention, a known or commonly used crosslinked cyclic acid anhydride curing agent (C) can be used. Among these, a crosslinked cyclic acid anhydride curing agent (C) that is liquid (liquid) at 25 ° C. is preferable in that a uniform mixture with the epoxy compound (B) described later can be efficiently prepared. In the present specification, “liquid at 25 ° C.” means a state at normal pressure. When the liquid crosslinked cyclic acid anhydride curing agent (C) is used at 25 ° C., the productivity of the curable epoxy resin composition of the present invention tends to be further improved.

In order to uniformly distribute the inorganic filler (A) on the upper surface of the resin layer, it is necessary to leave the curable epoxy resin composition of the present invention at room temperature for a certain time (for example, 2 hours or more) before heating. When the inventors tried the method of Patent Document 1, it was found that the antireflection function of the obtained antireflection material deteriorates when left, for example, for 2 hours or more before heat curing.
In view of the above problems, the present inventors have studied various epoxy resin compositions, and as a result, by using a crosslinked cyclic acid anhydride curing agent (C) as a curing agent, a crosslinked cyclic hydrocarbon is obtained. When the curable epoxy resin composition of the present invention is allowed to stand for a certain period of time (for example, 2 hours or more) at room temperature before heat curing as compared with the case where an anhydride curing agent having no ring is used, the present invention It has been found that it is possible to suppress a decrease in the antireflection function of an antireflection material made of a cured product.
By using the cross-linked cyclic acid anhydride curing agent (C), even if it is left for 2 hours or more before heat curing, the mechanism of action that can suppress the decrease in the antireflection function is unknown, but the cross-linked ring The portion of the crosslinked cyclic hydrocarbon ring of the formula acid anhydride curing agent (C) becomes three-dimensionally bulkier than other acid anhydride curing agents, and various physical properties (viscosity of the curable epoxy resin composition of the present invention). It is speculated that the inorganic filler (A) is uniformly distributed so as to appropriately exhibit the antireflection function even if it is left to stand for 2 hours or more before heat curing. Needless to say, the inference does not limit the present invention.

The “crosslinked cyclic hydrocarbon ring” possessed by the crosslinked cyclic acid anhydride curing agent (C) is a hydrocarbon ring having a total of 6 to 30 carbon atoms, preferably 7 to 14 carbon atoms, having a crosslinked portion. There is no particular limitation, for example, pinane, bornane, norpinane, norbornane, bicycloheptane ring (for example, bicyclo [2.2.1] heptane ring), bicycloheptene ring (for example, bicyclo [2.2.1] hepta-2) -Ene ring etc.), bicyclic hydrocarbon rings such as bicyclooctane ring (for example, bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring); homobredan, adamantane, tricyclo [ 5.2.1.0 ^2,6 ] a tricyclic hydrocarbon ring such as a decane ring. In addition, the bridged cyclic hydrocarbon ring includes, for example, a dimer hydrogenated product [for example, a cycloalkadiene dimer hydrogenated product such as cyclopentadiene, cyclohexadiene, cycloheptadiene ( For example, perhydro-4,7-methanoindene and the like, dimers of butadiene (vinylcyclohexene) and hydrogenated products thereof, and the like] are also included. Further, the bridged cyclic hydrocarbon ring includes, for example, a condensed cyclic hydrocarbon ring, for example, a condensed ring in which a plurality of 4- to 8-membered cycloalkane rings such as perhydronaphthalene (decalin) and perhydroindene rings are condensed. Etc. are also included.

The bridged cyclic hydrocarbon ring may have a substituent. Examples of the bridged cyclic hydrocarbon ring having the substituent include groups in which part or all of the hydrogen atoms bonded to the carbon atoms constituting the bridged cyclic hydrocarbon ring are substituted with a substituent. Examples of the substituent include a halogen atom [eg, fluorine atom, chlorine atom, bromine atom, etc.], alkyl group [eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t- C1-C4 linear or branched alkyl group such as butyl group], oxo group, hydroxy group, substituted oxy group [for example, C _1-6 alkoxy group, C _6-14 aryloxy group, C _7-15 aralkyloxy group, C _1-11 acyloxy group, etc.], carboxy group, substituted oxycarbonyl group [for example, C _1-6 alkoxycarbonyl group, C _6-14 aryloxycarbonyl group, C _7-15 aralkyloxycarbonyl group Group, etc.], substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group and the like. In addition, the said substituent (for example, a hydroxy group, a carboxy group, an amino group, etc.) may be protected by a protective group commonly used in the field of organic synthesis.

  Examples of the substituted or unsubstituted carbamoyl group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, and t-butyl group. 10, more preferably 1 to 3) alkyl group, or a carbamoyl group having an acyl group of 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 3) such as an acetyl group or a benzoyl group, or the like An unsubstituted carbamoyl group etc. are mentioned. Examples of the substituted or unsubstituted amino group include 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group (preferably 1-10, more preferably 1-3) an amino group having an alkyl group, such as an alkyl group, acetyl group, benzoyl group, etc., having 1-20 carbon atoms (preferably 1-10, more preferably 1-3), etc., Or an unsubstituted amino group etc. are mentioned.

  The number of carbon atoms in the case where the bridged cyclic hydrocarbon ring is a substituted bridged cyclic hydrocarbon ring is not particularly limited, and is, for example, 6 to 30.

  More specifically, examples of the crosslinked cyclic acid anhydride curing agent (C) include compounds represented by the following formula (A).

Ring Z in the formula (A) represents an optionally substituted bridged cyclic hydrocarbon ring (including a condensed cyclic hydrocarbon ring) having 6 to 30 carbon atoms, preferably 7 to 14 carbon atoms.
The bridged cyclic hydrocarbon ring represented by ring Z and the substituent that the bridged cyclic hydrocarbon ring may have are the same as described above.
In formula (A), k is the same or different and represents 0 or 1.

  Specific examples of the compound represented by the formula (A) include a compound represented by the following formula. Each compound represented by the following formula includes various stereoisomers.

  In the curable epoxy resin composition of the present invention, the crosslinked cyclic acid anhydride curing agent (C) can be used singly or in combination of two or more. The crosslinked cyclic acid anhydride curing agent (C) can also be produced by a known or conventional method. For example, the trade name “Licacid HNA-100” (manufactured by Shin Nippon Rika Co., Ltd.); Commercial products such as “MHAC-P” (manufactured by Hitachi Chemical Co., Ltd.) can also be used.

  As the crosslinked cyclic acid anhydride curing agent (C), a compound represented by the following formula may be used alone or in combination of two or more in terms of further improving the antireflection function of the antireflection material of the present invention. Particularly preferred.

The curable epoxy resin composition of the present invention may contain an acid anhydride curing agent other than the crosslinked cyclic acid anhydride curing agent (C) as long as the effects of the present invention are not impaired. As the acid anhydride curing agent other than the crosslinked cyclic acid anhydride curing agent (C), a known or commonly used acid anhydride curing agent can be used, and is not particularly limited. For example, methyltetrahydrophthalic anhydride (4- Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride), dodecenyl succinic anhydride, methyl end Methylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, 4- (4-Methyl-3-pentenyl) tetrahydro anhydride Examples include phosphoric acid, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer, and the like. . Among these, acid anhydrides [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] that are liquid at 25 ° C. are preferable from the viewpoint of handleability.
When an acid anhydride curing agent other than the crosslinked cyclic acid anhydride curing agent (C) is included, the content of the cyclic cyclic acid anhydride curing agent (C) is 100 weights in order to secure the effect of the present invention. 100 parts by weight or less is preferable with respect to parts, and 50 parts by weight or less is more preferable.

  The content (blending amount) of the crosslinked cyclic acid anhydride curing agent (C) in the curable epoxy resin composition of the present invention is not particularly limited, but is the total amount of epoxy compound contained in the curable epoxy resin composition (total amount). 50 to 200 parts by weight, preferably 75 to 150 parts by weight, and more preferably 100 to 120 parts by weight with respect to 100 parts by weight of the epoxy compound; for example, the total amount of the epoxy compound (B). More specifically, a cross-linked cyclic acid anhydride curing agent (0.5 to 1.5 equivalents per 1 epoxy group equivalent in all epoxy compounds contained in the curable epoxy resin composition of the present invention ( C) is preferably used. By setting the content of the crosslinked cyclic acid anhydride curing agent (C) to 50 parts by weight or more, curing can proceed more efficiently and the antireflection function tends to be further improved. On the other hand, by setting the content of the crosslinked cyclic acid anhydride curing agent (C) to 200 parts by weight or less, there is a tendency that a cured product having no color (or little) and excellent in hue is easily obtained.

1-3. Curing accelerator (D)
The curable epoxy resin composition of the present invention may contain a curing accelerator (D). A hardening accelerator (D) is a compound which has a function which accelerates | stimulates the reaction rate of reaction of an epoxy compound (especially reaction of an epoxy compound (B) and a bridge | crosslinking cyclic acid anhydride hardening | curing agent (C)). As the curing accelerator (D), those well known and commonly used as curing accelerators for epoxy resins can be used, and are not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 ( DBU), and salts thereof (eg, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) ), And salts thereof (eg, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, Tertiary amines such as N, N-dimethylcyclohexylamine; 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazoles such as ruimidazole; phosphines such as phosphate esters and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organometallic salts such as tin octylate and zinc octylate; Can be mentioned.

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

  Examples of the curing accelerator (D) in the curable epoxy resin composition of the present invention include, for example, trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT”. 18X "," 12XD "(developed product) (above, manufactured by San Apro Corporation); trade names" TPP-K "," TPP-MK "(above, manufactured by Hokuko Chemical Co., Ltd.); trade name" PX- " Commercially available products such as “4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) can be used.

  The content (blending amount) of the curing accelerator (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, The total amount of the epoxy compound (B)) is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 100 parts by weight. 0.25 to 2.5 parts by weight. By setting the content of the curing accelerator (D) to 0.05 parts by weight or more, there is a tendency that a more sufficient curing acceleration effect can be obtained. On the other hand, when the content of the curing accelerator (D) is 5 parts by weight or less, there is a tendency that a cured product having no color (or little) and excellent in hue is easily obtained.

1-4. Polyhydric alcohol The curable epoxy resin composition of the present invention may contain a polyhydric alcohol. In particular, when the curable epoxy resin composition of the present invention contains a crosslinked cyclic acid anhydride curing agent (C) and a curing accelerator (D), the curing can proceed more efficiently. Further, it preferably contains a polyhydric alcohol. As the polyhydric alcohol, known or conventional polyhydric alcohols can be used, and are not particularly limited. For example, ethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, Examples include 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol.

  Among them, the polyhydric alcohol is preferably an alkylene glycol having 1 to 6 carbon atoms, more preferably carbon in terms of being able to control curing well and obtaining a cured product that is less prone to cracking and peeling. It is an alkylene glycol of formula 2-4.

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

  Although the content (blending amount) of the polyhydric alcohol in the curable epoxy resin composition of the present invention is not particularly limited, the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, epoxy compound ( The total amount of B) is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 100 parts by weight. -2.5 parts by weight. By setting the content of the polyhydric alcohol to 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.

1-5. Phosphor The curable epoxy resin composition of the present invention may contain a phosphor. When the curable epoxy resin composition of the present invention contains a phosphor, it is particularly preferably used as an optical semiconductor device sealing application (sealing material application) in an optical semiconductor device, that is, an optical semiconductor sealing resin composition. it can. As the phosphor, a known or commonly used phosphor (in particular, a phosphor used for sealing an optical semiconductor element) can be used, and is not particularly limited. For example, the general formula A ₃ B ₅ O ₁₂ : M [Wherein, A represents one or more elements selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm, and B is selected from the group consisting of Al, Ga, and In. YAG phosphor fine particles represented by the following formula: M represents one or more elements selected from the group consisting of Ce, Pr, Eu, Cr, Nd, and Er] (For example, Y ₃ Al ₅ O ₁₂ : Ce phosphor fine particles, (Y, Gd, Tb) ₃ (Al, Ga) ₅ O ₁₂ : Ce phosphor fine particles, etc.), silicate type phosphor fine particles (for example, (Sr, Ca, Ba) ₂ SiO ₄ : Eu and the like. In addition, the surface of the phosphor may be modified with an organic group (for example, a long-chain alkyl group, a phosphate group, etc.) to improve dispersibility, for example. In the curable epoxy resin composition of the present invention, the phosphor may be used alone or in combination of two or more. Moreover, a commercial item can be used as a fluorescent substance.

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

1-6. Other Components The curable epoxy resin composition of the present invention may contain other components other than those described above within a range that does not adversely affect the curability and transparency. Examples of the other components include a silicone resin having a linear or branched chain, a silicone resin having an alicyclic ring, a silicone resin having an aromatic ring, a cage type / ladder type / random type silsesquioxane, Examples include silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, silicone-based and fluorine-based antifoaming agents, and the like. The content (blending amount) of the other components is not particularly limited, but is preferably 5% by weight or less (for example, 0 to 3% by weight) with respect to the total amount (100% by weight) of the curable epoxy resin composition. .

  Although the curable epoxy resin composition of this invention is not specifically limited, For example, it can prepare by stirring and mixing each above-mentioned component in the state heated as needed. In addition, the curable epoxy resin composition of the present invention may be a one-component composition that uses a mixture of all the components in advance, or, for example, a component divided into two or more. It may be a multi-liquid composition (for example, a two-liquid system) used by mixing at a predetermined ratio immediately before use. The method of stirring and mixing is not particularly limited, and for example, known or conventional stirring and mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under reduced pressure or under vacuum.

[Uneven shape]
The antireflection material of the present invention exhibits the antireflection function by scattering the incident light by forming the irregular shape on the surface of the inorganic filler (A) near the surface of the resin layer.
The method of allowing the inorganic filler (A) to be present in the vicinity of the surface of the resin layer is, for example, after the inorganic filler (A) is uniformly dispersed in the resin composition constituting the resin layer, and if necessary, the resin layer For example, a method of rising to the top.
Hereinafter, one embodiment of the method for producing an antireflection material of the present invention will be described, but the present invention is not limited thereto.

FIG. 3 is a schematic view showing a process of a production example of the antireflection material of the present invention. 1 is a resin layer and 4 is an inorganic filler. The inorganic filler 4 may be a porous filler, a hollow filler, or a mixture thereof, but is preferably a hollow filler having a small specific gravity and easy to float.
FIG. 3A is a schematic view showing a state in which the inorganic filler 4 is uniformly dispersed in the resin layer 1. The inorganic filler 4 can be added to the resin layer 1 and mixed and stirred to be uniformly dispersed. The mixing / stirring method is not particularly limited. For example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under reduced pressure or under vacuum.

  The properties of the antireflection material before curing of the present invention are not particularly limited, but are preferably liquid. Since the resin composition before curing forming the antireflection material of the present invention can exhibit an antireflection function with a small amount of addition by using a porous filler and / or a hollow filler, a solvent such as toluene is used. Even if it is not used, it is liable to become liquid and is preferable.

FIG. 3B is a schematic view showing a state where the inorganic filler 4 uniformly dispersed in the resin layer 1 floats on the upper surface. It is preferable that the inorganic filler 4 is levitated before the resin is cured in order to exhibit an excellent antireflection function. For example, the resin layer 1 in which the inorganic filler 4 is uniformly dispersed can be left at room temperature for 2 to 48 hours.
FIG. 3C is a schematic diagram showing a state in which the inorganic filler 4 is uniformly distributed on the upper surface of the resin layer 1 (uneven shape is not shown). If necessary, the antireflection material of the present invention can be produced by, for example, curing the resin layer 1 on which the inorganic filler 4 floats on the upper surface.

[Curing process]
If necessary, the inorganic filler 4 shown in FIG. 3 (c) cures the resin layer levitated on the upper surface to obtain a cured product of the present invention, whereby the antireflection material of the present invention can be obtained. .
The amount of the component that volatilizes during curing relative to the total amount (100% by weight) of the antireflection material before curing is not particularly limited, but is preferably 10% by weight or less, more preferably 8% by weight or less, Preferably it is 5 weight% or less. When the amount of the component that volatilizes during curing is 10% by weight or less, the dimensional stability of the cured product is increased, which is preferable. Since the antireflection material before curing of the present invention can exhibit an antireflection function with a small amount of addition by using a porous filler and / or a hollow filler, a volatile component of a solvent (such as toluene) is used. Even if not, it tends to be liquid and the amount of components that volatilize during curing can be reduced.

  As the curing means, known or conventional means such as heat treatment can be used. Although the temperature (curing temperature) at the time of making it harden | cure by heating is not specifically limited, 45-200 degreeC is preferable, More preferably, it is 50-190 degreeC, More preferably, it is 55-180 degreeC. In addition, the heating time (curing time) for curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit value in the above range, curing is insufficient. On the contrary, when the curing temperature and the curing time are higher than the upper limit value in the above range, the resin component may be decomposed. Although the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased. Moreover, hardening can also be performed in one step and can also be performed in two or more steps.

[Anti-reflective material]
Since the antireflection material of the present invention has both high transparency and an excellent antireflection function as described above, it can be suitably used as a resin for optical materials (used for forming optical materials). An optical material is a material that exhibits various optical functions such as light diffusibility, light transmission, and light reflectivity. By using the antireflection material of the present invention, an optical member containing at least the cured product (optical material) of the present invention can be obtained. In addition, the said optical member may be comprised only from the reflection preventing material of this invention, and the reflection preventing material of this invention may be used for only one part. Examples of the optical member include a member that expresses various optical functions such as light diffusibility, light transmittance, and light reflectivity, and a member that constitutes a device or an apparatus using the optical function. For example, optical semiconductor devices, organic EL devices, adhesives, electrical insulating materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optics Examples thereof include known or conventional optical members used in various applications such as lenses, optical modeling, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors.

The anti-reflective material of the present invention has a fine and uniform concavo-convex shape formed of an inorganic filler (A) on the surface, and since incident light is scattered and total reflection does not occur, gloss is suppressed and visibility is improved. Can be improved. The concavo-convex arithmetic average surface roughness Ra formed on the antireflection material of the present invention is preferably in the range of 0.2 to 1.0 μm, and more preferably in the range of 0.3 to 0.8 μm. If the arithmetic average surface roughness Ra of the concavo-convex shape is in this range, there is a tendency that a sufficient antireflection function can be exhibited without significantly impairing the total luminous flux.
In the present invention, the arithmetic average surface roughness Ra is a numerical value defined by JIS B 0601-2001, and means a value measured and calculated by a method described in Examples described later.

  The antireflection material of the present invention can be preferably used, for example, as a resin composition for optical semiconductor encapsulation. That is, the antireflection material of the present invention can be preferably used as a composition for sealing an optical semiconductor element in an optical semiconductor device (an optical semiconductor element sealing material in an optical semiconductor device). An optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material (resin composition for encapsulating an optical semiconductor) of the present invention (for example, 104 in FIG. 4 is the antireflection material of the present invention). An optical semiconductor device comprised of: For sealing the optical semiconductor element, for example, a resin composition in which the inorganic filler (A) shown in FIG. 3 (a) prepared by the above method is uniformly dispersed is injected into a predetermined mold and left for a predetermined time. Then, it can be carried out by heat curing under predetermined conditions. The curing temperature, curing time, photocuring conditions, and the like can be set as appropriate within the same range as in the preparation of the antireflection material. The above-described optical semiconductor device of the present invention exhibits an excellent antireflection function even when left at room temperature for a sufficient time (for example, 2 hours or more) before curing of the curable epoxy resin composition of the present invention. can do. In the present specification, the “optical semiconductor device of the present invention” means that the antireflective 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.) of the optical semiconductor device. An optical semiconductor device is meant.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the unit of the component which comprises the resin composition shown to Tables 1-3 is a weight part.

Production Example 1
100 parts by weight of a curing agent (trade name “Licacid HNA-100”, manufactured by Shin Nippon Rika Co., Ltd.), 0.5 part by weight of a curing accelerator (trade name “U-CAT 18X”, manufactured by Sun Apro Co., Ltd.), and 1 part by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) is mixed using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinkey Co., Ltd., the same shall apply hereinafter), An epoxy curing agent (K agent) was produced.

Example 1
100 parts by weight of an alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation) and 101.5 parts by weight of the epoxy curing agent obtained in Production Example 1 were mixed using a self-revolving stirrer, Defoaming was carried out to produce a curable epoxy resin composition.
100 parts by weight of the curable epoxy resin composition obtained above, 2 parts by weight of a hollow body filler (trade name “Sphericel 110P8”, manufactured by Potters Barotini Co., Ltd.) are mixed using a revolving stirrer, The curable epoxy resin composition obtained by defoaming was cast into an optical semiconductor lead frame (InGaN device, 3.5 mm × 2.8 mm) shown in FIG. 4 and allowed to stand at room temperature for 2 hours, and then 150 ° C. The optical semiconductor device in which the optical semiconductor element was sealed with the antireflection material of the present invention was manufactured by heating in a resin curing oven for 5 hours. In FIG. 4, 100 is a reflector, 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, 104 is a sealing material (antireflection material), and the upper surface of 104 is uniform with a hollow filler. A fine uneven shape is formed (the uneven shape is not shown).

Examples 2 to 21 and Comparative Examples 1 to 6
An optical semiconductor device was manufactured in the same manner as in Example 1 except that the compositions of the curable epoxy resin composition, the curing agent, the hollow filler, the porous filler, and the inorganic filler were changed as shown in Tables 1 to 3. .

[Evaluation]
The optical semiconductor device manufactured above was evaluated as follows. The results are shown in Tables 1 to 3, respectively.

(1) Reflection of fluorescent lamp Anti-reflection when the reflected fluorescent lamp is applied to the upper surface of the optical semiconductor device (upper surface of the sealing material 104 in FIG. 4) obtained in the examples and comparative examples. The clearness of the fluorescent lamp reflected on the material was visually evaluated in three stages.
The case where the outline of the fluorescent lamp could not be recognized was indicated by ◯, the case where the outline could be recognized while being unclear, and the case where the outline could be clearly recognized was indicated by x.

(2) Arithmetic average surface roughness Ra
The upper surface (the upper surface of the sealing material 104 in FIG. 4) of the optical semiconductor device obtained in the example and the comparative example is used with a laser microscope (trade name “Shape Measurement Laser Microscope VK-8710”, manufactured by Keyence Corporation). It was measured.

(3) Total luminous flux About each optical semiconductor device obtained by the Example and the comparative example, the total luminous flux when energized under the conditions of 5 V and 20 mA is converted into a total luminous flux measuring machine (trade name “Multispectral Radiation Measurement System OL771”, Measured using Optronic Laboratories).

(4) Comprehensive judgment About each optical semiconductor device obtained by the Example and the comparative example, the case of satisfying all of the following (a) to (c): ○ (good), the following (a) to (c) The case where any of them was not satisfied was determined as x (defective).
(A) The reflection of the fluorescent lamp measured in the above (1) is ◯ or Δ.
(B) The arithmetic average surface roughness Ra measured in the above (2) is 0.20 to 1.0 μm.
(C) The total luminous flux measured in the above (3) is 0.30 lm or more.

Each component which comprises the antireflection material shown to Tables 1-3 is demonstrated below.
(Hollow filler)
Sphericel 110P8: Trade name "Sphericel 110P8", Potters Barotini Co., Ltd. Sphericel 60P18: Trade name "Sphericel 60P18", Potters Barotini Co., Ltd. Sphericel 34P30: Trade name "Sphericel Potters 34P30" Sphericel 25P45 manufactured by Co., Ltd .: trade name “Sphericel 25P45”, manufactured by Potters Ballotini Co., Ltd. Q-CEL 7040: trade name “Q-CEL 7040” manufactured by Potters Ballotini Co., Ltd.

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

(Inorganic filler)
Fused crushed silica: manufactured by Tatsumori Co., Ltd., volume average particle size: 6-7 μm
Fused spherical silica: manufactured by Tatsumori Co., Ltd., volume average particle size: 5 μm
Crystalline crushed silica: manufactured by Tatsumori Co., Ltd., average particle size: 5 μm

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

(Epoxy curing agent)
HNA-100: Trade name “Licacid HNA-100” [Methylnorbornane-2,3-dicarboxylic anhydride and norbornane-2,3-dicarboxylic anhydride mixture (content of succinic anhydride: 0.4% by weight) MH-700: trade name “Ricacid MH-700” [4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30], manufactured by Shinnippon Rika Co., Ltd. U-CAT 18X: Trade name “U-CAT 18X” [curing accelerator], manufactured by San Apro Co., Ltd. Ethylene glycol: manufactured by Wako Pure Chemical Industries, Ltd.

As shown in Tables 1 and 2, the antireflective material according to the example, in which a hollow body filler or a porous filler was added, and Ricacid HNA-100, which is an acid anhydride having a crosslinked cyclic hydrocarbon ring, was blended. According to the optical semiconductor device having the above, the reflection of the fluorescent lamp was evaluated as “Good”, and it was confirmed that it had an excellent antireflection function.
In addition, the arithmetic average surface roughness Ra of the optical semiconductor device of the example of the present invention in which the reflection of the fluorescent lamp was evaluated as “good” is in the range of 0.20 to 1.0 μm, and has an appropriate uneven shape. It was confirmed that was formed.
Further, the total luminous flux of the optical semiconductor device according to the example of the present invention was 0.30 lm or more, indicating a good illuminance.
On the other hand, in the optical semiconductor devices of Comparative Examples 2 to 4 to which a silica filler that is neither porous nor hollow is added, even if Ricacid HNA-100 is used as the curing agent, the reflection of the fluorescent lamp is x (defect). The value of the arithmetic average surface roughness Ra was low (0.2 μm or less), and showed only the antireflection function of Comparative Example 1 to which no filler was added.
Moreover, even if the optical semiconductor device of Comparative Examples 5 and 6 to which Ricacid MH-700F, which is an acid anhydride having no crosslinked cyclic hydrocarbon ring, is added, a porous filler or a hollow filler is used. Reflection was evaluated as x (defect), and the value of arithmetic average surface roughness Ra was also low (0.2 μm or less).

  Since the antireflection material of the present invention has both high transparency and an excellent antireflection function, the antireflection material can be suitably used as a resin for optical materials (used for forming optical materials). Examples of the optical member include a member that expresses various optical functions such as light diffusibility, light transmittance, and light reflectivity, and a member that constitutes a device or an apparatus using the optical function. For example, optical semiconductor devices, organic EL devices, adhesives, electrical insulating materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optics Examples thereof include known or conventional optical members used in various applications such as lenses, optical modeling, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors.

1: Resin layer 2: Porous filler 3: Hollow body filler 4: Inorganic filler (including porous filler and hollow body filler)
100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor element 103: Bonding wire 104: Sealing material (antireflection material)

Claims (6)

  It consists of a resin layer in which at least one inorganic filler (A) selected from the group consisting of a porous filler (A1) and a hollow filler (A2) is dispersed, and the inorganic filler (A) is the surface of the resin layer A curable epoxy resin composition comprising an anti-reflective material for forming irregularities to suppress reflection, wherein the resin layer contains an epoxy compound (B) and an acid anhydride curing agent (C) having a crosslinked cyclic hydrocarbon ring An antireflection material characterized by being a cured product of the above.   The inorganic filler (A) floats near the upper surface of the curable epoxy resin composition after being uniformly dispersed in the curable epoxy resin composition and forms the irregularities on the surface. The antireflection material as described.   The antireflection material according to claim 1 or 2, wherein the content of the inorganic filler (A) with respect to the total amount (100 wt%) of the antireflection material is 0.5 to 40 wt%.   The antireflection material according to claim 1, wherein the resin layer is made of a transparent curable resin composition.   The antireflective material of any one of Claims 1-4 which is a resin composition for optical semiconductor sealing.   An optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material according to claim 5.

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