JP2016212269A - Antireflection material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection material which can prevent deterioration in the total luminous flux of a light source while having a sufficient antireflection function, and to provide an optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material.SOLUTION: There are provided an antireflection material formed of a resin layer in which an inorganic filler and a nano filler are dispersed, where the inorganic filler forms irregularities for suppressing reflection on the surface of the resin layer; and an optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material.SELECTED DRAWING: Figure 2

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. There is known a method of scattering incident light by floating and forming irregularities on the surface (for example, see Patent Document 1 or 2).

Japanese Patent No. 5082259 JP 2000-114605 A

  However, when the methods of Patent Documents 1 and 2 are applied to an optical semiconductor sealing resin, it has been found difficult to secure the total luminous flux of the light source while providing a sufficient antireflection function. . That is, when a sufficient amount of inorganic filler is added to obtain a sufficient antireflection function, the total luminous flux of the light source is greatly reduced, while the inorganic filler is reduced in order to prevent a decrease in the total luminous flux of the light source. In this case, it was revealed that there was a trade-off relationship that sufficient antireflection performance could not be obtained.

Accordingly, an object of the present invention is to provide an antireflection material capable of preventing a decrease in the total luminous flux of a light source while having a sufficient antireflection function.
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 one of the reasons why sufficient antireflection ability cannot be obtained when the amount of inorganic filler is reduced, uniform unevenness is not formed on the entire resin layer surface due to aggregation of inorganic fillers, so that incident light is efficiently generated. On the other hand, if the blending amount is increased so that antireflection performance can be obtained on the entire resin layer surface even if the inorganic filler is aggregated, the inorganic filler itself absorbs light and the total luminous flux is greatly reduced. The present inventors have found out.
As a result of intensive studies to solve the above problems, the present inventors have blended nanofillers in addition to inorganic fillers in the resin layer constituting the antireflection material, which suppresses aggregation of inorganic fillers and adds a small amount. However, it has been found that a sufficient antireflection function is provided. As a result, an antireflection material having a sufficient antireflection function is provided without significantly reducing the total luminous flux of the light source, and it has been found that it is extremely suitable as a material for sealing an optical semiconductor element in an optical semiconductor device. The present invention has been completed.

That is, the present invention is an antireflection material comprising a resin layer in which an inorganic filler and a nanofiller are dispersed, wherein the inorganic filler forms irregularities that suppress reflection on the surface of the resin layer. Provide anti-reflective material.
The present invention also provides the antireflection material, wherein the inorganic filler and the nanofiller are uniformly dispersed in the resin layer and then float near the upper surface of the resin layer to form the unevenness on the surface. To do.
The present invention also provides the antireflection material, wherein the inorganic filler is a hollow body.
In addition, the present invention provides the antireflection material, wherein the inorganic filler and the nanofiller are substantially in contact under the concave portion rather than under the concave and convex portion.
The present invention also provides the antireflection material, wherein the nanofiller is a nanoinorganic filler.
The present invention also provides the antireflection material, wherein the resin layer is made of a transparent curable resin composition.
In the present invention, the curable resin composition comprises at least one curable compound selected from the group consisting of an epoxy resin (A), a silicone resin (B), and an acrylic resin (C). The antireflection material is provided.
Moreover, this invention provides the said antireflection material which is a resin composition for optical semiconductor sealing.
Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material.

  Since the antireflection material of the present invention has the above-described configuration, a sufficient antireflection function can be obtained even when the amount of the inorganic filler is reduced, and a significant decrease in the total luminous flux of the light source can be prevented. Therefore, by using the antireflection material of the present invention as a material for sealing the optical semiconductor element in the optical semiconductor device, a high-quality optical semiconductor device (for example, sufficient brightness while suppressing gloss) can be obtained. .

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 characterized in that an inorganic filler and a nanofiller are dispersed in a resin layer, and the inorganic filler forms irregularities that suppress reflection on the surface of the resin layer.
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 an inorganic filler, 3 is a nano filler. As shown in FIG. 1, the inorganic filler 2 and the nanofiller 3 are mainly present near the upper surface of the resin layer 1. The inorganic filler 2 is in contact with the upper surface of the resin layer 1 to form a concavo-convex shape, and incident light is scattered to suppress gloss due to total reflection. As shown in FIG. 1, the nanofiller 3 is present near the surface of the inorganic filler 2 and is considered to suppress aggregation by suppressing the interaction between the inorganic fillers 2. Therefore, by using the nanofiller 3, the inorganic filler 2 can reach the entire upper surface of the resin layer 1 even with a small amount, so that uniform and fine irregularities are formed on the surface of the resin layer. Can scatter incident light. Needless to say, the antireflection material of the present invention is not limited to this embodiment.
Hereinafter, each component will be described in detail.

[Inorganic filler]
The inorganic filler in the antireflection material of the present invention exists near the surface of the resin layer and has a function of forming irregularities on the resin layer surface for scattering incident light.

  As the inorganic filler that can be used in the antireflection material of the present invention, a known or conventional inorganic filler can be used, and is not particularly limited. For example, inorganic glass [for example, borosilicate glass, borosilicate soda glass, silicate Soda 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, Powders such as magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, fosterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, talc, These molded body (e.g., spheronized beads, etc.) and the like. Further, as the inorganic filler, a known or commonly used surface treatment for the above-mentioned inorganic filler [for example, a surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone. Etc.]. 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 an inorganic filler, an inorganic glass or silica (silica filler) is preferable from a viewpoint that an unevenness | corrugation can be efficiently formed in the resin layer surface.

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

  Moreover, as an inorganic filler, since specific gravity is small and it is easy to float in a resin layer, what has a hollow body structure is used preferably. Furthermore, by using a hollow inorganic filler, the inorganic filler present in the vicinity of the resin layer surface is hardly distributed on the concave and convex portions, and is distributed so as to be substantially in contact with the concave portions. Can be made. 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 nanofiller, and 4 is an inorganic filler that is a hollow body (hereinafter sometimes referred to as “hollow body inorganic filler”). As shown in FIG. 2, the hollow inorganic filler 4 and the nanofiller 3 are mainly present near the upper surface of the resin layer 1. The hollow inorganic filler 4 is in contact with the upper surface of the resin layer 1 to form a concavo-convex shape, and the incident light is scattered to suppress gloss due to total reflection. It is considered that the nanofiller 3 exists near the surface of the hollow inorganic filler 4 as in the first embodiment of FIG. 1 and suppresses aggregation by suppressing the interaction between the hollow inorganic fillers 4. Therefore, by using the nanofiller 3, the hollow inorganic filler 4 can be spread over the entire upper surface of the resin layer 1 even in a small amount, so that uniform and fine irregularities are formed on the resin layer surface. Incident light can be scattered efficiently. Further, the hollow inorganic filler 4 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 formed on the surface of the resin layer. Thereby, since the hollow body inorganic filler 4 hardly appears on the surface of the resin layer 1, reflection by the hollow body inorganic filler 4 itself is suppressed, and a higher antireflection function can be exhibited. Needless to say, the antireflection material of the present invention is not limited to this embodiment.

  The hollow inorganic filler is not particularly limited. For example, inorganic glass [for example, borosilicate glass, borosilicate soda glass, sodium silicate glass, aluminum silicate glass, quartz, etc.], metal oxide such as silica, alumina, zirconia, etc. , Inorganic hollow particles composed of inorganic materials such as metal salts such as calcium carbonate, barium carbonate, nickel carbonate, calcium silicate, etc. (including natural products such as shirasu balloon); inorganic composed of hybrid materials of inorganic and organic materials- Organic hollow particles etc. are mentioned. In addition, the hollow portion (the space inside the hollow particles) of the hollow inorganic filler may be in a vacuum state or may be filled with a medium. In particular, in order to improve the light scattering efficiency 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.

  In the case of using a hollow inorganic filler, the hollowness ratio (ratio of the volume of voids 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 inorganic filler tends to float in the resin layer and tends to be efficiently distributed under the concave and convex portions.

  The shape of the inorganic filler is not particularly limited, and examples thereof include powder, spherical shape, crushed shape, fibrous shape, needle shape, scale shape, and the like. Among these, spherical inorganic fillers are preferable from the viewpoint of dispersibility, and spherical inorganic fillers (for example, spherical inorganic fillers having an aspect ratio of 1.2 or less) are particularly preferable.

  Although the center particle diameter of an inorganic filler is not specifically limited, From a viewpoint that it becomes easy to form a uniform fine uneven | corrugated shape on the resin layer surface, 0.1-100 micrometers is preferable, More preferably, it is 1-50 micrometers. In addition, the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.

  The specific gravity of the inorganic filler 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, one kind of inorganic filler can be used alone, or two or more kinds can be used in combination. The inorganic filler can also be produced by a known or conventional production method. For example, FB series such as trade names “FB-910”, “FB-940”, “FB-950” (hereinafter referred to as “electrochemical”). Kogyo Co., Ltd.), trade names "MSR-2212", "MSR-25" (above, Tatsumori Co., Ltd.), trade names "HS-105", "HS-106", "HS-107" Commercial products such as (manufactured by Micron) can also be used.
Moreover, as a hollow body inorganic filler, it can also manufacture by a well-known thru | or conventional manufacturing method, for example, brand name "Sphericel (trademark) 110P8", "Sphericel (trademark) 25P45", "Sphericel (trademark) 34P30". "Sphericel (trademark) 60P18", "Q-CEL (trademark) 5020", "Q-CEL (trademark) 7014", "Q-CEL (trademark) 7040S" (above, manufactured by Potters Barottini Co., Ltd.) , Trade names “Glass Microballoon”, “Fuji Balloon H-40”, “Fuji Balloon H-35” (manufactured by Fuji Silysia Chemical Co., Ltd.), trade names “Cell Star Z-20”, “Cell Star Z-27” ”,“ Cell Star CZ-31T ”,“ Cell Star Z-36 ”,“ Cell Star Z-39 ”,“ "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.

  The content (blending amount) of the inorganic filler in the antireflection material of the present invention is usually 0.1 to 30 parts by weight, preferably with respect to the resin composition (100 parts by weight) constituting the antireflection material. 0.5 to 25 parts by weight, more preferably 1 to 20 parts by weight. When the content of the inorganic filler is 0.1 part 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 is 30 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 sufficient decrease in total luminous flux is prevented and sufficient illuminance Tends to be secured.

[Nano filler]
The antireflection material of the present invention is characterized in that a nanofiller is blended in the resin layer in addition to the inorganic filler. As shown in the enlarged schematic view of the embodiment of the antireflection material of the present invention in FIGS. 1 and 2, the nano filler 3 is distributed near the surface of the inorganic filler 2 or the hollow inorganic filler 4, and the inorganic fillers The nano filler 3 rotates and flows relatively freely on the surface of the inorganic filler and functions as a bearing between the inorganic filler particles to improve lubricity, thereby aggregating the inorganic filler. It is thought to suppress. Needless to say, the antireflection material of the present invention is not limited to this embodiment.
As described above, by using the nano filler in the antireflection material of the present invention, even if the amount of the inorganic filler is small, aggregation is suppressed and the inorganic filler is distributed over the entire resin surface. Can be formed on the resin surface, so that a sufficient antireflection function can be imparted while suppressing a significant decrease in the total luminous flux due to the inorganic filler itself.

  As the nanofiller that can be used in the antireflection material of the present invention, known or conventional nanoparticles can be used, and are not particularly limited. For example, inorganic glass [for example, borosilicate glass, borosilicate soda glass, sodium silicate soda] Glass, aluminum silicate glass, quartz, etc.], nano-inorganic fillers composed of inorganic substances such as metal oxides such as silica, alumina, zirconia, and metal salts such as calcium carbonate, barium carbonate, nickel carbonate, calcium silicate; styrenic resin , Acrylic resin, silicone resin, acrylic-styrene resin, vinyl chloride resin, vinylidene chloride resin, amide resin, urethane resin, phenol resin, styrene-conjugated diene resin, acrylic-conjugated diene resin , Such as polymers such as olefin resins (including cross-linked products of these polymers) Nano organic filler is constituted by the object; nano-inorganic constituted by a hybrid material of the inorganic and organic - organic fillers, and the like. In addition, the said nano filler may be comprised from the single material, and may be comprised from 2 or more types of materials. Among these, as the nanofiller, a nanoinorganic filler is preferable from the viewpoint of being easily adsorbed on the surface of the inorganic filler, and silica (nanosilica filler) is more preferable from the viewpoint of availability and manufacturability.

The nanofiller has been subjected to a known or conventional surface treatment [for example, surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone]. In particular, those subjected to silane coupling treatment are preferable. By applying such a surface treatment, compatibility with the components of the resin layer and dispersibility are improved, and thickening of the resin due to the addition of the nanofiller is suppressed, thereby making it easy to ensure fluidity.
The silane coupling agent is preferably a silane coupling agent having a hydrophobic functional group such as alkyl, vinyl, acryloyl, methacryloyl, phenyl, etc. from the viewpoint of improving the fluidity by suppressing the thickening of the resin layer. Those having vinyl, methacryloyl and phenyl are preferred. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, vinyl-tris (2-methoxy) silane, vinyltriacetoxysilane, 2-methacryloxyethyl triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxy-propylmethyldimethoxysilane, triethoxyphenylsilane, trimethoxyphenylsilane, dimethoxydiphenylsilane, Examples thereof include methyldiethoxyphenylsilane and dimethoxymethylphenylsilane.

  The nano filler may be added as a dry powder, or may be added as a slurry dispersed in an organic solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclocyclohexanone, etc.) Moreover, you may use what was previously disperse | distributed to the epoxy resin etc. Since it is easy to add to and disperse in the resin composition, it is preferable to use a resin previously dispersed in the resin.

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

  The nanofiller has a center particle diameter of 1 to 100 nm, but from the viewpoint of sufficiently suppressing the aggregation of the inorganic filler, the center particle diameter is preferably 5 to 70 nm, more preferably 10 to 50 nm. In addition, the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.

  In the antireflection material of the present invention, the nanofiller can be used alone or in combination of two or more. The nanofiller can also be produced by a known or conventional production method. For example, trade names “Admanano YA010C-SM1”, “Admanano YA010C-SP3”, “Admanano YA050C-SM1”, “Admanano YA050C-SP3” can be used. Commercially available products such as Admanano series (above, manufactured by Admatechs Co., Ltd.) can also be used.

  The content (blending amount) of the nano filler in the antireflection material of the present invention is usually 0.01 to 20 parts by weight, preferably with respect to the resin composition (100 parts by weight) constituting the antireflection material. 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight. When the content of the nanofiller is 0.01 parts by weight or more, aggregation of the inorganic filler is suppressed, and a uniform uneven shape is easily formed on the entire surface of the resin layer. On the other hand, when the nanofiller is added in an amount of more than 20 parts by weight, not only the cost increases, but the total luminous flux may decrease.

  The nano filler content (blending amount) with respect to 100 parts by weight of the inorganic filler in the antireflection material of the present invention is not particularly limited, but is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the inorganic filler. 5-150 weight part is more preferable, More preferably, it is 1-100 weight part. When the content of the nanofiller with respect to the inorganic filler is 0.1 part by weight or more, aggregation of the inorganic filler is suppressed and a uniform uneven shape is easily formed on the entire surface of the resin layer. On the other hand, when the nanofiller is added in an amount of more than 200 parts by weight with respect to the inorganic filler, not only the cost increases, but the total luminous flux may decrease.

[Resin layer]
The resin constituting the resin layer in the antireflection material of the present invention is not particularly limited, but is suitable as a sealing material for an optical semiconductor element in an optical semiconductor device, that is, a resin composition for optical semiconductor sealing. Can be preferably used, for example, cured by heat or light, has high transparency, durability (for example, characteristics that transparency is not easily lowered by heating, high temperature heat and thermal shock are applied) In addition, a curable resin that gives a cured product that is also excellent in cracks and properties that do not easily peel off from the adherend can be used.

As such a curable resin, a known or commonly used resin composition having thermosetting property or photo-curing property can be used without particular limitation. For example, an epoxy resin (epoxy compound) (“epoxy resin (A)” At least one selected from the group consisting of a silicone resin (silicone compound) (referred to as “silicone resin (B)”), and an acrylic resin (acrylic compound) (referred to as “acrylic resin (C)”). A composition containing a seed curable compound is preferred. Examples of such a composition include a composition containing an epoxy resin (A) (curable epoxy resin composition), a composition containing a silicone resin (B) (curable silicone resin composition), and an acrylic resin (C ) (A curable acrylic resin composition). Hereinafter, the composition of these embodiments will be described. However, the curable resin composition of this invention is not limited to the composition of the following aspects.
Further, the antireflection material of the present invention is not limited to the use of the resin composition for sealing an optical semiconductor, and can be applied to, for example, various optical members described later, and is a resin suitable for each use. (For example, it is applicable also to polyolefin resin, polyester resin, polyamide resin, polyurethane resin, etc.).

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 the epoxy resin (A) as an essential component. The curable epoxy resin composition of the present invention further contains a curing agent (D) and a curing accelerator (E) or a curing catalyst (F) as essential components. That is, the curable epoxy resin composition of the present invention is a composition containing an epoxy resin (A), a curing agent (D), and a curing accelerator (E) as essential components, or an epoxy resin (A) and a curing catalyst. It is a composition containing (F) as an essential component. The curable epoxy resin composition of the present invention may contain other components other than the essential components described above.

1-1. Epoxy resin (A)
The epoxy resin (A) in the curable epoxy resin composition of the present invention is a compound having one or more epoxy groups (oxirane rings) in the molecule, and is arbitrarily selected from known or commonly used epoxy compounds. Can do. Examples of the epoxy resin (A) include an aromatic epoxy compound (aromatic epoxy resin), an aliphatic epoxy compound (aliphatic epoxy resin), an alicyclic epoxy compound (alicyclic epoxy resin), and a heterocyclic epoxy compound. (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, From a sclerosing | hardenable viewpoint, a cyclohexene oxide group (adjacent which comprises a cyclohexane ring) 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 [o, o- (2,3 -Epoxypropoxy) cyclohexyl] methane, bis [o, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, Bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane, hydrogenated bisphenol F type epoxy resin (hydrogenated bisphenol Hydrogenated biphenol type epoxy resin; hydrogenated novolak type epoxy resin (for example, hydrogenated phenol novolak type epoxy resin, hydrogenated cresol novolak type epoxy resin, hydrogenated cresol novolak type epoxy resin of bisphenol A) Etc.); Hydrogenated naphthalene type epoxy resin; Hydrogenated epoxy resin of epoxy resin obtained from trisphenol methane 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 resin (A), bisphenol A type epoxy resin, isocyanurate having one or more epoxy groups in the molecule, in terms of allowing the curing of the curable epoxy resin composition to 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 resin (A) 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 resin (A) can be used alone or in combination of two or more. In addition, an epoxy resin (A) 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 resin (A) 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 resin (A) to 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.

  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.

  Although the ratio of the alicyclic epoxy compound to the total amount of the epoxy compound contained in the curable epoxy resin composition of the present invention (total epoxy compound; for example, total amount of epoxy resin (A)) (100% by weight) 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. Curing agent (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 a function of curing the curable epoxy resin composition by reacting with the epoxy compound. The curing agent (D) is not particularly limited, and those well known and commonly used as curing agents for epoxy resins can be used. For example, acid anhydrides (acid anhydride-based curing agents), amines (amine-based) Curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenol curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, and the like. .

  As the acid anhydrides (acid anhydride curing agents) as the curing agent (D), known or commonly used acid anhydride curing agents can be used, and are 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 Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydrous Nadic acid, anhydrous methyl nadic acid, methyl hydride Dic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride Examples include acid copolymers and alkylstyrene-maleic anhydride copolymers. 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. On the other hand, for a solid acid anhydride at 25 ° C., for example, by dissolving in a liquid acid anhydride at 25 ° C. to form a liquid mixture, the curing agent (D in the curable epoxy resin composition of the present invention (D ) Tends to be improved. As the acid anhydride curing agent, saturated monocyclic hydrocarbon dicarboxylic acid anhydrides (including those in which a substituent such as an alkyl group is bonded to the ring) are preferable from the viewpoint of heat resistance and transparency of the cured product.

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

  As the phenols (phenolic curing agents) as the curing agent (D), known or conventional phenolic curing agents can be used, and are not particularly limited. For example, novolac type phenol resins, novolac type cresol resins, paraxylylene-modified phenols. Examples thereof include aralkyl resins such as resins, paraxylylene / metaxylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.

  Examples of the polyamide resin as the curing agent (D) include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.

  As the imidazole (imidazole curing agent) as the curing agent (D), a known or commonly used imidazole curing agent can be used, and is not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanate Nu 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)] -Ethyl-s-triazine and the like.

  Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (D) include liquid polymercaptans and polysulfide resins.

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

  Among these, as the curing agent (D), acid anhydrides (acid anhydride curing agents) are preferable from the viewpoint of curability, heat resistance of the cured product, and transparency. In addition, in the curable epoxy resin composition of this invention, a hardening | curing agent (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Moreover, a commercial item can also be used as a hardening | curing agent (D). For example, as commercial products of acid anhydrides, trade names “Licacid MH-700” and “Licacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.); trade name “HN-5500” (Hitachi Chemical Industries) Etc.).

  The content (blending 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 The total amount of the resin (A)) is preferably 50 to 200 parts by weight, more preferably 75 to 150 parts by weight, and still more preferably 100 to 120 parts by weight with respect to 100 parts by weight. More specifically, when acid anhydrides are used as the curing agent (D), 0.5 to 1. per epoxy group equivalent in all epoxy compounds contained in the curable epoxy resin composition of the present invention. It is preferable to use it at a ratio of 5 equivalents. By making content of a hardening | curing agent (D) into 50 weight part or more, hardening can be advanced more efficiently and there exists a tendency for the toughness of hardened | cured material to improve more. 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) and excellent in hue is easily obtained.

1-3. Curing accelerator (E)
The curing accelerator (E), which is one of the essential components of the curable epoxy resin composition of the present invention, has a reaction rate of the reaction of the epoxy compound (particularly the reaction between the epoxy resin (A) and the curing agent (D)). It is a compound having a function to promote. As the curing accelerator (E), 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, a hardening accelerator (E) can also be used individually by 1 type in a curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type.

  Examples of the curing accelerator (E) in the curable epoxy resin composition of the present invention include 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 (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, The total amount of the epoxy resin (A)) 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 (E) 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 (E) 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. Curing catalyst (F)
The curing catalyst (F), which is one of the essential components of the curable epoxy resin composition of the present invention, is curable by initiating and / or accelerating the curing reaction (polymerization reaction) of a cationically polymerizable compound such as an epoxy compound. It is a compound having a function of curing the epoxy resin composition. Although it does not specifically limit as a curing catalyst (F), For example, the cationic polymerization initiator (thermal cation polymerization initiator) which generate | occur | produces a cationic seed | species by heat and starts superposition | polymerization, a Lewis acid amine complex, a Bronsted acid Examples thereof include salts and imidazoles.

  Specifically, examples of the curing catalyst (F) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33”, “CP-66”, “CP-77” (manufactured by ADEKA); trade name “FC-509” (manufactured by 3M); trade name “UVE1014” (manufactured by GE); trade names “Sun Aid SI-60L”, “Sun Aid” "SI-80L", "Sun-Aid SI-100L", "Sun-Aid SI-110L", "Sun-Aid SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd.); trade name "CG-24-61" (BASF Corporation) (Commercially available products) can be preferably used. Furthermore, as the curing catalyst (F), for example, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or a diketone and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid Alternatively, a compound of a chelate compound with a diketone and a phenol such as bisphenol S is also included.

As the Lewis acid / amine complex as the curing catalyst (F), a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited. For example, BF ₃ .n-hexylamine, BF ₃ · monoethylamine, 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 · diethylamine, BF ₄ · piperidine, BF ₄ · triethylamine, BF ₄ · aniline, PF ₅ · ethylamine, PF ₅ · isopropylamine, PF ₅ · butylamine, PF ₅ · laurylamine, PF ₅ · benzylamine, AsF _5. Laurylamine etc. are mentioned.

  As the Bronsted acid salts as the curing catalyst (F), known or commonly used Bronsted acid salts can be used, and are not particularly limited. For example, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphoniums. Examples include salts.

  As the imidazoles as the curing catalyst (F), known or conventional imidazoles can be used, and are not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl Imidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4 - Mino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine, etc. Is mentioned.

  In the curable epoxy resin composition of the present invention, the curing catalyst (F) can be used singly or in combination of two or more. In addition, as above-mentioned as a curing catalyst (F), a commercial item can be used, for example.

  The content (blending 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 The total amount of the resin (A)) 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, and particularly preferably 0 to 100 parts by weight. 0.05 to 8 parts by weight. By setting the content of the curing catalyst (F) to 0.01 parts by weight or more, the curing reaction tends to proceed more sufficiently. On the other hand, by setting the content of the curing catalyst (F) to 15 parts by weight or less, there is a tendency that a cured product having no color (or little) and excellent in hue is easily obtained. That is, by controlling the content of the curing catalyst (F) within the above range, the curing rate of the curable epoxy resin composition is improved, and a cured product having a good balance between transparency and durability is easily obtained. Tend.

  In addition, the curable epoxy resin composition of this invention may contain substantially the photocationic polymerization initiator which generate | occur | produces the seeds (acid etc.) of cationic polymerization by irradiation of light. When the curable epoxy resin composition of the present invention contains a photocationic polymerization initiator, the content thereof is, for example, the total amount of epoxy compounds contained in the curable epoxy resin composition (total epoxy compounds; for example, epoxy resin (A )) To 100 parts by weight, for example, about 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

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 includes a curing agent (D) and a curing accelerator (E), it further includes a polyhydric alcohol in that curing can proceed more efficiently. It is preferable. 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.

  The content (blending 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, epoxy resin ( The total amount of A) 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 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.

1-6. 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 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.

1-7. 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.

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. It is a thing. 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— (silalkylene bond: R ^A represents an alkylene group) Included polyorganosiloxysilalkylene; curable polysiloxanes such as polyorganosiloxane that does not contain the above-mentioned silalkylene bond as the main chain.

  As the silicone resin (B), a known or commonly used curable silicone resin (curable polysiloxane) can be used as the curable compound, and is not particularly limited. For example, an addition type (addition reaction curable type) Silicone resin, condensation type (condensation reaction curing type) silicone resin, and the like. When the curable silicone resin composition of the present invention contains the former, it can be used as an addition reaction curable silicone resin composition, and when it contains the latter, it can be used as a condensation reaction curable silicone resin composition. it can. Hereinafter, the addition reaction curable silicone resin composition and the condensation reaction curable silicone resin composition will be described. However, the curable silicone resin composition of the present invention is not limited thereto. For example, an addition type silicone resin and It may be a silicone resin composition that contains both condensation type silicone resins and cures by addition reaction and condensation reaction. That is, curing of the curable silicone resin composition in the curing step may proceed by at least one reaction selected from the group consisting of an addition reaction and a condensation reaction.

2-1. Addition reaction curable silicone resin composition The addition reaction curable silicone resin composition contains, for example, a polysiloxane (B1) having two or more alkenyl groups in the molecule as the silicone resin (B), and further required. Depending on the case, a curable silicone resin composition containing polysiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule, a metal curing catalyst, or the like may be mentioned.

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

  Examples of the polyorganosiloxane (B1-1) include those having a molecular structure of linear or branched (linear, partially branched, network, etc. partially branched). In addition, polyorganosiloxane (B1-1) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Two or more polyorganosiloxanes (B1-1) having different molecular structures can be used in combination, for example, a linear polyorganosiloxane (B1-1) and a branched polyorganosiloxane (B1-). 1) can be used in combination.

  Examples of the alkenyl group that the polyorganosiloxane (B1-1) has in the molecule include substituted or unsubstituted alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group. Examples of the substituent include a halogen atom, a hydroxy group, and a carboxy group. Among these, as the alkenyl group, a vinyl group is preferable. The polyorganosiloxane (B1-1) may have only one alkenyl group, or may have two or more alkenyl groups. Although the alkenyl group which polyorganosiloxane (B1-1) has is not specifically limited, It is preferable that it is a thing couple | bonded with the silicon atom.

  Although the group couple | bonded with silicon atoms other than the alkenyl group which polyorganosiloxane (B1-1) has is not specifically limited, For example, a hydrogen atom, a monovalent organic group, etc. are mentioned. Examples of the monovalent organic group include alkyl groups [eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.], cycloalkyl groups [eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, etc. Cyclohexyl group, cyclododecyl group, etc.], aryl group [eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.], cycloalkyl-alkyl group [eg, cyclohexylmethyl group, methylcyclohexyl group, etc.], aralkyl group [For example, a benzyl group, a phenethyl group, etc.], a halogenated hydrocarbon group in which one or more hydrogen atoms in a hydrocarbon group are substituted with a halogen atom [for example, a chloromethyl group, a 3-chloropropyl group, 3, 3, 3 Monovalent substituted or unsubstituted carbonization such as -halogenated alkyl group such as trifluoropropyl group] Containing group, and the like. In the present specification, the “group bonded to a silicon atom” usually means a group not containing a silicon atom.

  In addition, the group bonded to the silicon atom may have a hydroxy group or an alkoxy group.

  The property of polyorganosiloxane (B1-1) is not particularly limited, and may be liquid or solid.

As 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
The polyorganosiloxane represented by these is preferable. In the above average unit formula, R ⁷ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the specific examples described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated carbonization) Hydrogen group, etc.). However, a part of R ⁷ is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 2 or more in the molecule. For example, the ratio of the alkenyl group to the total amount of R ⁷ (100 mol%) is preferably 0.1 to 40 mol%. By controlling the ratio of the alkenyl group to the above range, the curability of the curable silicone resin composition tends to be further improved. Further, as R ⁷ other than the alkenyl group, an alkyl group (particularly 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. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.

  In the above average unit formula, a1 is 0 or positive number, a2 is 0 or positive number, a3 is 0 or positive number, a4 is 0 or positive number, a5 is 0 or positive number, and (a1 + a2 + a3) is positive Is a number.

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

  Examples of the polyorganosiloxysilalkylene (B1-2) include those having a molecular structure such as a straight chain or a branched chain (a linear chain having a partial branch, a branched chain, a network, etc.). In addition, polyorgano siloxysil alkylene (B1-2) can also be used individually by 1 type, and can also be used in combination of 2 or more type. For example, two or more kinds of polyorganosiloxysilalkylene (B1-2) having different molecular structures can be used in combination, for example, linear polyorganosiloxysilalkylene (B1-2) and branched polyorgano Siloxysilalkylene (B1-2) can also be used in combination.

  Examples of the alkenyl group that polyorganosiloxysilalkylene (B1-2) has in the molecule include the specific examples described above, and among them, a vinyl group is preferable. Further, the polyorganosiloxysilalkylene (B1-2) may have only one alkenyl group or may have two or more alkenyl groups. The alkenyl group of the polyorganosiloxysilalkylene (B1-2) is not particularly limited, but is preferably bonded to a silicon atom.

  Although the group couple | bonded with silicon atoms other than the alkenyl group which polyorganosiloxysil alkylene (B1-2) has is not specifically limited, For example, a hydrogen atom, a monovalent organic group, etc. are mentioned. As a monovalent organic group, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group etc. are mentioned, for example. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.

  In addition, the group bonded to the silicon atom may have a hydroxy group or an alkoxy group.

  The property of polyorganosiloxysilalkylene (B1-2) is not particularly limited, and may be liquid or solid.

As polyorganosiloxysilalkylene (B1-2), the following average unit formula:
(R ⁸ ₂ SiO _2/2 ) _{b 1} (R ⁸ ₃ SiO _1/2 ) _{b 2} (R ⁸ SiO _3/2 ) _{b 3} (SiO _4/2 ) _{b 4} (R ^A ) _{b 5} (ZO _1/2 ) _{b 6}
A polyorganosiloxysilalkylene represented by the formula is preferred. 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 specific examples (for example, alkyl group, alkenyl group, aryl group, aralkyl group, alkyl halide) Group). However, a part of R ⁸ is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 2 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 ratio of the alkenyl group to the above range, the curability of the curable silicone resin composition tends to be further improved. Further, R ⁸ other than an alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

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

  In the 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 a methyl group is particularly preferable.

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

As described above, the addition reaction curable silicone resin composition is a polysiloxane having one or more (preferably two or more) hydrosilyl groups (Si—H) in the molecule (“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 polyorganosiloxysil alkylene. In this specification, the hydrosilyl group-containing polyorganosiloxysilalkylene has one or more hydrosilyl groups in the molecule, and in addition to —Si—O—Si— (siloxane bond) as a main chain, —Si—R ^A polysiloxane containing A-Si- (silalkylene bond: ^RA represents an alkylene group). And the hydrosilyl group containing polyorganosiloxane in this specification is a polysiloxane which has 1 or more hydrosilyl groups in a molecule | numerator, and does not contain the said silalkylene bond as a principal chain. As R ^A (alkylene group), as described above, for example, a linear or branched C _1-12 alkylene group may be mentioned, and preferably a linear or branched C _2-4 alkylene group ( In particular, ethylene group).

  Examples of the hydrosilyl group-containing polyorganosiloxane include those having a molecular structure of linear or branched (linear, partially branched, networked, etc. partially branched). In addition, the said hydrosilyl group containing polyorganosiloxane can also be used individually by 1 type, and can also be used in combination of 2 or more type. Two or more hydrosilyl group-containing polyorganosiloxanes having different molecular structures can be used in combination. For example, a linear hydrosilyl group-containing polyorganosiloxane and a branched hydrosilyl group-containing polyorganosiloxane may be used in combination. it can.

  Among the groups bonded to the silicon atom of the hydrosilyl group-containing polyorganosiloxane, groups other than hydrogen atoms are not particularly limited. For example, the monovalent substituted or unsubstituted hydrocarbon group described above, more specifically, an alkyl group , Aryl group, aralkyl group, halogenated hydrocarbon group and the like. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable. Moreover, the said hydrosilyl group containing polyorganosiloxane may have an alkenyl group (for example, vinyl group) as a group couple | bonded with silicon atoms other than a hydrogen atom.

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

The hydrosilyl group-containing polyorganosiloxane has 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 ) _{c 5}
The polyorganosiloxane represented by these is preferable. In the above average unit formula, R ⁹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and a hydrogen atom, the above-mentioned specific examples (for example, alkyl group, alkenyl group, aryl Group, aralkyl group, halogenated alkyl group and the like). However, a part of R ⁹ is a hydrogen atom (hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in a range in which one or more (preferably two or more) hydrosilyl groups are present 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 proportion of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. R ⁹ other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

  In the 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 a methyl group is particularly preferable.

  In the above average unit formula, c1 is 0 or positive, c2 is 0 or positive, c3 is 0 or positive, c4 is 0 or positive, c5 is 0 or positive, and (c1 + c2 + c3) is positive Is a number.

As described above, the hydrosilyl group-containing polyorganosiloxysilalkylene is a polyorganosiloxane having one or more hydrosilyl groups in the molecule and containing a silalkylene bond as a main chain in addition to a siloxane bond. In addition, as an alkylene group in the said silalkylene bond, a _C2-4 alkylene group (especially ethylene group) is preferable, for example. The hydrosilyl group-containing polyorganosiloxysilalkylene is less likely to produce a low molecular weight ring in the production process than the hydrosilyl group-containing polyorganosiloxane, and is not easily decomposed by heating or the like to produce a silanol group (—SiOH). Therefore, when the above hydrosilyl group-containing polyorganosiloxysilalkylene is used, the surface tackiness of the cured product of the curable silicone resin composition tends to be low, and it tends to be more difficult to yellow.

  Examples of the hydrosilyl group-containing polyorganosiloxysilalkylene include those having a molecular structure of linear or branched (linear, partially branched, network, etc. having a partial branch). In addition, the said hydrosilyl group containing polyorganosiloxy silalkylene can also be used individually by 1 type, and can also be used in combination of 2 or more type. Two or more hydrosilyl group-containing polyorganosiloxysil alkylenes having different molecular structures can be used in combination, for example, a linear hydrosilyl group-containing polyorganosiloxysil alkylene and a branched hydrosilyl group-containing polyorganosiloxysil alkylene. Can also be used in combination.

  Although the group couple | bonded with silicon atoms other than the hydrogen atom which the said hydrosilyl group containing polyorganosiloxysil alkylene has is not specifically limited, For example, a monovalent organic group etc. are mentioned. As a monovalent organic group, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group etc. are mentioned, for example. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.

  The property of the hydrosilyl group-containing polyorganosiloxysilalkylene is not particularly limited, and may be liquid or solid.

Examples of the hydrosilyl group-containing polyorganosiloxysilalkylene include 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
A polyorganosiloxysilalkylene represented by the formula is preferred. In the above average unit formula, R ¹⁰ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and the hydrogen atom and the above-described specific examples (for example, an alkyl group, an alkenyl group, an aryl group) Aralkyl group, halogenated alkyl group, etc.). However, a part of R ¹⁰ is a hydrogen atom, and the ratio thereof is controlled within a range of 1 or more (preferably 2 or more) in the molecule. For example, the ratio of hydrogen atoms to the total amount of R ¹⁰ (100 mol%) is preferably 0.1 to 50 mol%, more preferably 5 to 35 mol%. By controlling the proportion of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. R ¹⁰ other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group). In particular, the ratio of aryl groups (particularly phenyl groups) to the total amount of R ¹⁰ (100 mol%) is preferably 5 mol% or more (for example, 5 to 80 mol%), more preferably 10 mol% or more.

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

  In the 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 a methyl group is particularly preferable.

  In the above average unit formula, d1 is a positive number, d2 is a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is a positive number, d6 is 0 or a positive number. Among these, d1 is preferably 1 to 50, d2 is preferably 1 to 50, d3 is preferably 0 to 10, d4 is preferably 0 to 5, and d5 is preferably 1 to 30.

  As the hydrosilyl group-containing polysiloxane in the addition reaction curable silicone resin composition, only the hydrosilyl group-containing polyorganosiloxane can be used, or only the hydrosilyl group-containing polyorganosiloxysil alkylene can be used, Moreover, hydrosilyl group-containing polyorganosiloxane and hydrosilyl group-containing polyorganosiloxysilalkylene can be used in combination. When the hydrosilyl group-containing polyorganosiloxane and the hydrosilyl group-containing polyorganosiloxysilalkylene are used in combination, these ratios are not particularly limited and can be set as appropriate.

  Although the said addition reaction curable silicone resin composition is not specifically limited, The composition (formulation composition) that an alkenyl group will be 0.2-4 mol with respect to 1 mol of hydrosilyl groups which exist in curable resin composition. ), More preferably 0.5 to 1.5 mol, still more preferably 0.8 to 1.2 mol. By controlling the ratio of hydrosilyl group and alkenyl group within the above range, the cured product has more heat resistance, transparency, thermal shock resistance, reflow resistance, and barrier property against corrosive gas (for example, SOx gas). There is a tendency to improve.

  The addition reaction curable silicone resin composition may include a metal curing catalyst as described above. Examples of metal curing catalysts include well-known hydrosilylation catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Specifically, platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported catalyst Activated carbon, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, platinum olefin complexes, platinum carbonyl complexes such as platinum-carbonylvinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes and platinum-cyclo Platinum-based catalyst such as platinum-vinylmethylsiloxane complex such as vinylmethylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, etc., and palladium-based catalyst containing palladium atom or rhodium atom instead of platinum atom in the platinum-based catalyst Or a rhodium-type catalyst is mentioned. Among these, as the hydrosilylation catalyst, a platinum vinylmethylsiloxane complex, a platinum-carbonylvinylmethyl complex, or a complex of chloroplatinic acid, an alcohol, and an aldehyde is preferable because the reaction rate is good.

  In addition, in the said addition reaction curable silicone resin composition, a metal curing catalyst (hydrosilylation catalyst) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The content (blending amount) of the metal curing catalyst (hydrosilylation catalyst) in the addition reaction curable silicone resin composition is not particularly limited, but the total amount of alkenyl groups contained in the addition reaction curable silicone resin composition is 1 mol. On the other hand, it is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol, more preferably 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻³ mol. By setting the content to 1 × 10 ⁻⁸ mol or more, there is a tendency that a cured product can be formed more efficiently. On the other hand, when the content is 1 × 10 ⁻² mol or less, there is a tendency that a cured product having a more excellent hue (less coloring) can be obtained.

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

2-2. Condensation reaction curable silicone resin composition The condensation reaction curable silicone resin composition includes, for example, two or more silanol groups (Si-OH) or silalkoxy groups (Si-OR) in the molecule as the silicone resin (B). And a curable silicone resin composition containing a metal curing catalyst and the like, if necessary. The polysiloxane (B2) may have only one of a silanol group and a silalkoxy group, or may have both a silanol group and a silalkoxy group. When it has both a silanol group and a silalkoxy group, the total number of these should just be 2 or more in a molecule | numerator.

As polysiloxane (B2), the polyorganosiloxane represented by the following average compositional formula is mentioned, for example.
R ¹¹ _e Si (OR ¹² ) _f (OH) _g O _{(4-efg) / 2}
[In the above average composition formula, R ¹¹ is the same or different and represents a monovalent organic group having 1 to 20 carbon atoms. R ¹² is the same or different and represents a monovalent organic group having 1 to 4 carbon atoms. e is a number from 0.8 to 1.5, f is a number from 0 to 0.3, and g is a number from 0 to 0.5. f + g is a number from 0.001 to less than 1.2. E + f + g is a number of 0.801 or more and less than 2. ]

Examples of the monovalent organic group as R ¹¹ in the average composition formula include, for example, a monovalent aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, etc.); a monovalent aromatic hydrocarbon group (for example, Aryl groups, etc.); monovalent heterocyclic groups; monovalent groups formed by combining two or more of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and the like. . These monovalent organic groups may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom). Among them, as R ^11, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms preferably. Examples of the monovalent organic group as R ¹² in the average composition formula include, for example, a monovalent aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, etc.) that may have a substituent. Is mentioned. Especially, as R < ¹² >, a C1-C4 alkyl group and a C2-C4 alkenyl group are preferable.

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

  The condensation reaction curable silicone resin composition may include a metal curing catalyst as described above. Examples of such metal curing catalysts include known or conventional condensation reaction catalysts, such as organic titanate esters, organic titanium chelate compounds, organic aluminum compounds, organic zirconium compounds, organic tin compounds, and metal salts of organic carboxylic acids. Amine compounds or salts thereof, quaternary ammonium salts, lower fatty acid salts of alkali metals, dialkylhydroxylamines, guanidyl group-containing organosilicon compounds, and the like. Among these, an organic zirconium compound is preferable from the viewpoint of reactivity. These can also be used individually by 1 type and can also be used in combination of 2 or more type. The content (blending amount) of the metal curing catalyst (condensation reaction catalyst) in the condensation reaction curable silicone resin composition is not particularly limited, but is, for example, about 0.1 part by weight relative to 100 parts by weight of the total amount of polysiloxane (B2). It can select suitably in the range of 01-20 weight part.

  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-described addition reaction curable silicone resin composition, condensation reaction curable silicone resin composition, etc.) may contain other components. As another component, what was illustrated as a component which the curable epoxy resin composition of this invention may contain, etc. are mentioned, for example. The content 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 encapsulating an optical semiconductor, it is preferable that the phosphor described above is included. The phosphor content (blending amount) in the curable silicone resin composition of the present invention is not particularly limited, and is 0.5 to 20% by weight relative to the total amount (100% by weight) of the curable silicone resin composition. It can select suitably in the range of.

  Although the curable silicone 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 silicone 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. Moreover, as a curable silicone resin composition of this invention or its component, a commercial item can also be used as it is.

3. Curable Acrylic Resin Composition The curable acrylic resin composition (sometimes referred to as “the curable acrylic resin composition of the present invention”) includes a curable composition containing an acrylic resin (C) as an essential component. It is a thing. 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 group selected from the group consisting of an acryloyl group and a methacryloyl group) in the molecule. Examples of the acrylic resin (C) include (meth) acryloyl compounds having only one (meth) acryloyl group in the molecule; polyfunctional (meth) acryloyl compounds having two or more (meth) acryloyl groups in the molecule. It is done. The (meth) acryloyl compound having only one (meth) acryloyl group in the molecule includes a monofunctional (meth) acryloyl compound having no polymerizable functional group other than the (meth) acryloyl group, In addition to the acryloyl group, a polyfunctional (meth) acryloyl compound having one or more other polymerizable functional groups such as an epoxy group, an oxetanyl group, a vinyl group, and a vinyloxy group. Acrylic resin (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, content of the acrylic resin (C) in the curable acrylic resin composition of this invention is not specifically limited, It can select suitably.

  The curable acrylic resin composition of this invention may contain the initiator for advancing the polymerization reaction of an acrylic resin (C), for example. Examples of the initiator include known or conventional polymerization initiators such as a thermal polymerization initiator. These can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, 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. As another component, what was illustrated as a component which the curable epoxy resin composition of this invention may contain, etc. are mentioned, for example. The content 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 encapsulating an optical semiconductor, it is preferable that the phosphor described above is included. The phosphor content (blending amount) in the curable acrylic 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 acrylic resin composition. It can select suitably in the range of.

  Although the curable acrylic 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. The curable acrylic 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. Moreover, as a curable acrylic resin composition of this invention, or its structural component, it is also possible to use a commercial item as it is.

[Uneven shape]
The antireflection material of the present invention exhibits an antireflection function by scattering the incident light by forming the irregular shape on the surface of the inorganic filler (and nanofiller) near the surface of the resin layer.
The method of making the said inorganic filler (and nano filler) exist in the surface vicinity of the said resin layer is not specifically limited, For example, resin after disperse | distributing an inorganic filler and a nano filler uniformly to the resin composition which comprises a resin layer. Examples include a method of levitating above the layer; a method of applying a resin containing an inorganic filler and a nanofiller to the surface of the resin layer after the resin layer is cured. In order to make the nanofiller uniformly exist on the surface of the inorganic filler and efficiently prevent aggregation, a method in which the inorganic filler and the nanofiller float on the resin layer is preferable. In addition, although a nano filler has the property to disperse | distribute uniformly in a resin layer, it is thought that a nano filler floats together in the state adsorb | sucked to the inorganic filler surface.
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 2 is an inorganic filler. The inorganic filler 2 may be a hollow inorganic filler. In addition, illustration of a nano filler is abbreviate | omitted.
FIG. 3A is a schematic view showing a state where the inorganic filler 2 and the nanofiller are uniformly dispersed in the resin layer 1 (the nanofiller is not shown). The inorganic filler 2 and the nano filler 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.
FIG. 3B is a schematic view showing that the inorganic filler 2 and nanofiller uniformly dispersed in the resin layer 1 float on the upper surface (the nanofiller is not shown). The inorganic filler 2 and the nanofiller may be floated before the resin is cured, or may be floated during the curing (for example, heating). In the case of floating before curing, for example, the resin layer 1 in which the inorganic filler 2 and the nano filler are uniformly dispersed can be allowed to stand at room temperature for 0 to 48 hours.
FIG. 3C is a schematic view showing a state where the inorganic filler 2 and the nano filler are uniformly distributed on the upper surface of the resin layer 1 (the nano filler and the uneven shape are not shown). The antireflection material of the present invention can be produced by curing, for example, the resin layer 1 on which the inorganic filler 2 and the nanofiller have floated on the upper surface.

[Curing process]
The inorganic filler and nanofiller are allowed to float while curing the resin layer in which the inorganic filler and nanofiller are uniformly dispersed as shown in FIG. 3A, or the inorganic filler and nanofiller shown in FIG. The antireflective material of the present invention can be obtained by curing the resin layer that has floated to form a cured product (hereinafter sometimes referred to as “cured product of the present invention”).
As the curing means, known or conventional means such as heat treatment or light irradiation 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. If the curing temperature and curing time are lower than the lower limit of the above range, curing will be insufficient. Conversely, if the curing temperature and curing time are higher than the upper limit of the above range, the inorganic filler and nanofiller will cure sufficiently before floating on the upper surface. Moreover, since decomposition | disassembly of a resin component may occur, neither is preferable. 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.
In the case of curing by light irradiation, for example, light (radiation) including i-line (365 nm), h-line (405 nm), g-line (436 nm), etc. is irradiated at an illuminance of 10 to 1200 mW / cm ² . The antireflection material of the present invention can be obtained by irradiating with a light amount of 20 to 2500 mJ / cm ² . From the viewpoint of suppressing deterioration of the resin layer due to radiation and from the viewpoint of productivity, the irradiation light amount is preferably ^{20 to} 600 mJ / cm ² , more preferably ²⁰ to 300 mJ / cm ² . For irradiation, a high-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, laser light, or the like can be used as an irradiation source.

[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 on the surface, and since incident light is scattered and total reflection does not occur, gloss is suppressed and visibility is improved. Can do. The concavo-convex arithmetic average surface roughness Ra formed on the antireflection material of the present invention is preferably in the range of 0.1 to 1.0 μm, and more preferably in the range of 0.2 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 uniformly dispersed in the inorganic filler and nanofiller shown in FIG. 3A prepared by the above-described method is injected into a predetermined mold, and if necessary After allowing to stand for a predetermined time and allowing the inorganic filler and nanofiller to sufficiently float on the upper surface, heat curing or photocuring can be performed under predetermined conditions. Alternatively, the inorganic filler and the nanofiller may be levitated while being cured. 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 can particularly exhibit an excellent antireflection function without reducing the total luminous flux. 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 1-4 is a weight part.

Production Example 1
100 parts by weight of a curing agent (trade name “Licacid MH-700”, 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 filler (trade name “Sphericel 110P8”, manufactured by Potters Barotini Co., Ltd.), and nano silica filler (trade name “Admanano YA010C-SM1”) ”, Manufactured by Admatechs Co., Ltd.) A lead frame (InGaN device) of an optical semiconductor shown in FIG. , 3.5 mm × 2.8 mm), and then heated in a resin curing oven at 120 ° C. for 5 hours to produce an optical semiconductor device in which the optical semiconductor element is sealed with the antireflection material of the present invention. . 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 2-13, Comparative Examples 1-7
An optical semiconductor device was manufactured in the same manner as in Example 1 except that the compositions of the hollow filler and the nanosilica filler were changed as shown in Tables 1 and 2.

Examples 14-26
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, and the nanosilica filler were changed as shown in Table 3.

Example 27
Curable silicone resin composition (trade name “OE-6630A / B” (curable silicone resin, manufactured by Toray Dow Corning Co., Ltd.) 100 parts by weight, hollow filler (trade name “Sphericel 110P8”, Potters Barotini It is obtained by mixing 10 parts by weight and 1 part by weight of nano silica filler (trade name “Admanano YA010C-SM1”, manufactured by Admatechs) using a self-revolving stirrer and degassing. The resulting curable silicone resin composition was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 4 and then heated in a resin curing oven at 150 ° C. for 1 hour. An optical semiconductor device in which an optical semiconductor element was sealed with the antireflection material of the invention was manufactured.

Examples 28-33
An optical semiconductor device was manufactured in the same manner as in Example 27 except that the composition of the curable silicone resin composition was changed as shown in Table 4.

Example 34
Curable acrylic resin composition (trade name “TB3030”, curable acrylic resin, manufactured by ThreeBond Co., Ltd.) 100 parts by weight, hollow filler (trade name “Sphericel 110P8”, manufactured by Potters Ballotini Co., Ltd.) 10 weight Part, and 1 part by weight of nanosilica filler (trade name “Admanano YA010C-SM1”, manufactured by Admatechs Co., Ltd.) using a self-revolving stirrer and defoamed to obtain a curable acrylic resin composition Is cast into an optical semiconductor lead frame (InGaN device, 3.5 mm × 2.8 mm) shown in FIG. 4 and then left to stand at room temperature for 24 hours. Further, a high-pressure mercury lamp (UVC-02516S1AA02: manufactured by USHIO INC.) , Illuminance of 120 mW / cm ² , irradiation light quantity of 199 mJ / cm ² ), and an optical semiconductor device in which the optical semiconductor element is sealed with the antireflection material of the present invention. (An optical semiconductor device in which an optical semiconductor element is sealed with an antireflection material) was manufactured.

[Evaluation]
The optical semiconductor device manufactured above was evaluated as follows. The results are shown in Tables 1 to 4, 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 (2) above is 0.10 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 1-4 is demonstrated below.
(Hollow filler)
Sphericel 110P8: Trade name "Sphericel 110P8", Potters Ballotini 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.

(Nanosilica filler)
YA010C-SM1: Trade name “Admanano YA010C-SM1”, Admanex YA010C-SP3: Trade name “Admanano YA010C-SP3”, Admanex YA050C-SM1: Trade name “Admanano YA010C-SM1” , YA050C-SP3 manufactured by Admatechs Co., Ltd .: trade name “Admanano YA050C-SP3”, manufactured by Admatechs Co., Ltd.

(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)
MH-700: Trade name “Licacid MH-700” [4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30], manufactured by Shin Nippon 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. SI-100L: trade name" Sun Aid SI-100L ", manufactured by San Apro Co., Ltd.

(Silicone resin)
OE-6630A / B: trade name “OE-6630A / B” [addition reaction curable silicone resin], manufactured by Toray Dow Corning Co., Ltd. KER-2500A / B: trade name “KER-2500A / B” [addition reaction Curable silicone resin (methyl rubber)], manufactured by Shin-Etsu Chemical Co., Ltd. SCR-1012A / B: trade name "SCR-1012A / B" [addition reaction curable silicone resin (modified silicone)], Shin-Etsu Chemical Co., Ltd. ETERLED GD1012A / B: Product name “ETERLED GD1012A / B” [addition reaction curable silicone resin (including polyorganosiloxysilalkylene)], ETERLED GD1130A / B: “ETERLED GD1130A / B” [ Addition reaction curable silicone resin (polyorganosiloxane) X-21-5841: trade name “X-21-5841” [condensation reaction curable silicone resin (silicone two-component RTV rubber)], manufactured by Shin-Etsu Chemical Co., Ltd. KF-9701: Trade name “KF-9701” [Condensation reaction curable silicone resin (modified silicone oil)], manufactured by Shin-Etsu Chemical Co., Ltd.

(acrylic resin)
TB3030: Trade name “TB3030” [curable acrylic resin], manufactured by ThreeBond Co., Ltd.)

As shown in Tables 1-4, according to the optical semiconductor device provided with the antireflection material according to the example to which the hollow filler and the nanosilica filler are added, the reflection of the fluorescent lamp is an evaluation of either ◯ or △, It was confirmed to have an excellent antireflection function.
In addition, the arithmetic average surface roughness Ra of the optical semiconductor device of the example of the present invention and the comparative example 2 in which the reflection of the fluorescent lamp was evaluated as ◯ or Δ was in the range of 0.10 to 1.0 μm. It was confirmed that an appropriate uneven shape 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, the optical semiconductor devices of Comparative Examples 1 and 3 to 6 to which no nanosilica filler was added were also added with 10 parts by weight of the hollow filler as in Examples 3 and 5 to 13 that were comprehensively determined to be good. Regardless, the reflection of the fluorescent lamp was evaluated as x (defect), and the value of the arithmetic average surface roughness Ra was low (0.1 μm or less). As a result of agglomeration of the hollow filler, it was considered that a uniform and fine uneven shape was not formed on the surface.
Further, the optical semiconductor device of Comparative Example 2 to which a large amount (50 parts by weight) of a hollow filler was added was not suitable as an optical semiconductor device because the total luminous flux was significantly reduced.
Further, in the optical semiconductor device of Comparative Example 7 in which only the nanosilica filler was added and no hollow filler was added, the reflection of the fluorescent lamp was evaluated as x (defect), and the value of the arithmetic average surface roughness Ra was low. (0.02 μm). Since the hollow filler was not added, it was thought that the uneven | corrugated shape was not formed in the surface.

  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: Inorganic filler (not hollow)
3: Nanofiller 4: Inorganic filler (hollow body)
100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor element 103: Bonding wire 104: Sealing material (antireflection material)

Claims (9)

  An antireflection material comprising a resin layer in which an inorganic filler and a nanofiller are dispersed, wherein the inorganic filler forms irregularities that suppress reflection on the surface of the resin layer.   The antireflection material according to claim 1, wherein the inorganic filler and the nanofiller are uniformly dispersed in the resin layer, and then float near the upper surface of the resin layer to form the unevenness on the surface.   The antireflection material according to claim 1, wherein the inorganic filler is a hollow body.   The antireflection material according to claim 3, wherein the inorganic filler and the nanofiller are substantially in contact with a lower portion of the concave portion than a lower portion of the concave portion.   The anti-reflection material according to any one of claims 1 to 4, wherein the nano filler is a nano inorganic filler.   The antireflection material according to claim 1, wherein the resin layer is made of a transparent curable resin composition.   The said curable resin composition consists of a composition containing the at least 1 sort (s) of curable compound selected from the group which consists of an epoxy resin (A), a silicone resin (B), and an acrylic resin (C). Antireflection material as described in 4.   The antireflective material of any one of Claims 1-7 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 8.

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