JP2016160381A - Curable epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable epoxy resin composition capable of forming a cured product excellent in transparency, heat resistance, thermal shock resistance, and adhesiveness.SOLUTION: The curable epoxy resin composition contains a siloxane derivative (A) having two or more epoxy groups in the molecule and an acrylic resin (B). The acrylic resin (B) is a polymer containing an acrylic monomer and a styrenic monomer as monomer components and having an epoxy group in a side chain. In the curable epoxy resin composition, it is preferable that the ratio of the siloxane derivative (A) having two or more epoxy groups in the molecule is 65-95 wt.% and the ratio of the acrylic resin (B) is 5-35 wt.% based on the total amount (100 wt.%) of the siloxane derivative (A) having two or more epoxy groups in the molecule and the acrylic resin (B).SELECTED DRAWING: None

Description

  The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition, And an optical semiconductor device in which an optical semiconductor element is bonded to an electrode with the curable epoxy resin composition.

  In an optical semiconductor device, an epoxy resin that forms a transparent cured product (resin cured product) by curing is widely used. The epoxy resin is mainly used as a sealant for sealing and protecting an optical semiconductor element in an optical semiconductor device, and an adhesive for bonding and fixing the optical semiconductor element and a metal electrode. (Referred to as die attach paste, die bond, etc.).

  As an epoxy resin used in an optical semiconductor device, for example, a composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin is known (see Patent Document 1). However, when the composition is used as a sealant or a die attach paste agent in an optical semiconductor device, coloring of the cured product (encapsulant or adhesive) proceeds by light or heat emitted from the optical semiconductor element. There has been a problem that the light extraction efficiency of the optical semiconductor device is lowered.

  In addition, as an epoxy resin used in the optical semiconductor device, a liquid alicyclic epoxy resin such as 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate is known. However, the cured products of these alicyclic epoxy resins are susceptible to various stresses, so that cracks are likely to occur. For example, the above alicyclic epoxy resins can be used as sealants and die attach pastes in optical semiconductor devices. When used, especially in high-temperature environments (for example, when heated at extremely high temperatures, such as in a reflow process, or when exposed to high temperatures for long periods of time), or with a thermal cycle (heating and cooling periodically) When a thermal shock such as (repeat) is applied, there has been a problem that the light intensity is likely to decrease.

  When using the above alicyclic epoxy resin as a die attach paste agent, an inorganic substance such as a filler may be blended in order to suppress cracking against thermal shock. The light emitted from the optical semiconductor element due to the decrease in transparency is absorbed by the cured product, and as a result, the light extraction efficiency of the optical semiconductor device decreases.

  Furthermore, when the above-described alicyclic epoxy resin is used as a die attach paste agent, the cured product does not have sufficient adhesive force for fixing the optical semiconductor element and the electrode in the optical semiconductor device, and the optical semiconductor device On the other hand, when stress due to thermal shock or the like is applied, the optical semiconductor element may be peeled off from the electrode, and a crack may be remarkably generated in the sealing material of the optical semiconductor element.

  As a material for solving the above-mentioned various problems in the case of using an alicyclic epoxy resin, for example, Patent Document 2 includes a composition containing an alicyclic epoxy compound and an acrylic resin, and the acrylic resin is A curable epoxy resin composition which is a polymer containing an acrylic monomer and a styrene monomer as essential monomer components and having an epoxy group in the side chain is disclosed.

JP 2000-344867 A International Publication No. 2014/109212

  According to the curable epoxy resin composition disclosed in Patent Document 2, it is possible to form a cured product excellent in transparency, heat resistance, thermal shock resistance, and adhesiveness. However, in the future, it is expected that the optical semiconductor element mounted on the optical semiconductor device will have higher luminance, and the optical semiconductor device is expected to be used in a harsher environment. In addition, it is required to suppress yellowing due to heating at a very high level.

Accordingly, it is an object of the present invention to provide transparency, heat resistance, thermal shock resistance (characteristics in which a cured product is hardly cracked when a thermal shock is applied, or a decrease in luminous intensity of an optical semiconductor device when a thermal shock is applied. It is an object of the present invention to provide a curable epoxy resin composition capable of forming a cured product excellent in adhesive properties and a property that is difficult to occur.
Another object of the present invention is to provide a cured product excellent in transparency, heat resistance, thermal shock resistance, and adhesiveness.
Furthermore, another object of the present invention is to prevent problems such as energization characteristics at high temperatures of the optical semiconductor device and reflow resistance (the occurrence of cracks in the sealing material and a decrease in luminous intensity of the optical semiconductor device even after the reflow process). It is an object of the present invention to provide a resin composition for sealing an optical semiconductor (encapsulant for an optical semiconductor element) capable of improving characteristics) and thermal shock resistance.
Furthermore, another object of the present invention is to provide a resin for an adhesive that can improve the light extraction efficiency, thermal shock resistance, and heat resistance of an optical semiconductor device, particularly when used as a die attach paste agent in an optical semiconductor device. The object is to provide a composition (adhesive).
Furthermore, another object of the present invention is to provide an optical semiconductor device that has high light extraction efficiency and is excellent in energization characteristics at high temperatures, reflow resistance, and thermal shock resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable epoxy resin composition containing a siloxane derivative having two or more epoxy groups in a molecule and an acrylic resin having a specific structure as essential components, It has been found that a cured product excellent in transparency, heat resistance, thermal shock resistance and adhesiveness can be formed, and is useful as a sealant for optical semiconductor elements and a die attach paste in optical semiconductor devices. Was completed.

That is, the present invention includes a siloxane derivative (A) having two or more epoxy groups in the molecule, and an acrylic resin (B),
The curable epoxy resin composition, wherein the acrylic resin (B) is a polymer containing an acrylic monomer and a styrene monomer as monomer components and having an epoxy group in a side chain I will provide a.

  Furthermore, the ratio of the siloxane derivative (A) having two or more epoxy groups in the molecule to the total amount (100% by weight) of the siloxane derivative (A) having two or more epoxy groups in the molecule and the acrylic resin (B) is The curable epoxy resin composition is provided in an amount of 65 to 95% by weight and an acrylic resin (B) ratio of 5 to 35% by weight.

  Furthermore, the said curable epoxy resin composition which further contains a hardening | curing agent (C) and a hardening accelerator (D), or a hardening catalyst (E) is provided.

  Moreover, this invention provides the hardened | cured material obtained by hardening the said curable epoxy resin composition.

  Furthermore, the said curable epoxy resin composition which is a resin composition for optical semiconductor sealing is provided.

  Moreover, this invention provides the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the said curable epoxy resin composition.

  Furthermore, the said curable epoxy resin composition which is a resin composition for adhesive agents is provided.

  Moreover, this invention provides the optical semiconductor device by which the optical semiconductor element was adhere | attached on the electrode with the hardened | cured material of the said curable epoxy resin composition.

  Since the curable epoxy resin composition of the present invention has the above-described configuration, a cured product excellent in transparency, heat resistance, thermal shock resistance, and adhesiveness can be formed by curing the resin composition. . In particular, the cured product has very excellent heat resistance, and yellowing due to heating hardly occurs. For this reason, by using the curable epoxy resin composition of the present invention as an encapsulant for optical semiconductor elements, it is possible to improve the current-carrying characteristics, reflow resistance, and thermal shock resistance of the optical semiconductor device at high temperatures. Moreover, the light extraction efficiency, thermal shock resistance, and heat resistance of an optical semiconductor device can be improved by using the curable epoxy resin composition of the present invention as a die attach paste agent in the optical semiconductor device. Therefore, an optical semiconductor device with high durability and quality can be obtained by using the curable epoxy resin composition of the present invention.

It is the schematic which shows one Embodiment of the optical semiconductor device by which the optical semiconductor element was sealed with the hardened | cured material of the curable epoxy resin composition of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. It is an example of the surface temperature profile (temperature profile in one heat processing among two heat processing) of the optical semiconductor device in the solder heat resistance test of an Example.

<Curable epoxy resin composition>
The curable epoxy resin composition of the present invention comprises a siloxane derivative (A) having two or more epoxy groups in the molecule (sometimes referred to as “siloxane derivative (A)”) and an acrylic resin (B) as essential components. It is a composition (curable composition) included as. The curable epoxy resin composition of the present invention may contain other components as required in addition to the siloxane derivative (A) and the acrylic resin (B).

[Siloxane derivative (A) having two or more epoxy groups in the molecule]
The siloxane derivative (A) in the curable epoxy resin composition of the present invention is a compound having a skeleton composed of siloxane bonds (—Si—O—Si—) having two or more epoxy groups in the molecule (siloxane). Compound). The siloxane skeleton (Si—O—Si skeleton) in the siloxane derivative (A) is not particularly limited, and examples thereof include a cyclic siloxane skeleton; a linear silicone, a cage-type or ladder-type polysilsesquioxane, and the like. Examples include a polysiloxane skeleton. Among these, as the siloxane skeleton, a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the light intensity of the optical semiconductor device. That is, the siloxane derivative (A) is preferably a cyclic siloxane having two or more epoxy groups in the molecule and a linear silicone having two or more epoxy groups in the molecule.

  When the siloxane derivative (A) is a cyclic siloxane having two or more epoxy groups in the molecule, the number of Si—O units forming the siloxane ring (equal to the number of silicon atoms forming the siloxane ring) is particularly Although not limited, 2-12 are preferable and 4-8 are more preferable from a viewpoint of improving the heat resistance and light resistance of hardened | cured material.

  Although the weight average molecular weight of a siloxane derivative (A) is not specifically limited, From a viewpoint of improving the heat resistance and light resistance of hardened | cured material, 100-3000 are preferable, More preferably, it is 180-2000. In addition, the said weight average molecular weight of a siloxane derivative (A) is computed from the molecular weight of standard polystyrene conversion measured by GPC (gel permeation chromatography) method.

  The number of epoxy groups in the molecule of the siloxane derivative (A) is not particularly limited as long as it is 2 or more. However, from the viewpoint of improving the heat resistance and light resistance of the cured product, 2 to 4 (2, 3 or 4) is preferred.

  The epoxy equivalent of the siloxane derivative (A) is not particularly limited, but is preferably 180 to 2000, more preferably 180 to 1500, and still more preferably 180 to 1000 from the viewpoint of improving the heat resistance and light resistance of the cured product. . The epoxy equivalent is a value measured according to JIS K7236.

  The epoxy group possessed by the siloxane derivative (A) is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, an epoxy composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. Group (alicyclic epoxy group) is preferable, and among them, a cyclohexene oxide group is particularly preferable.

Examples of the siloxane derivative (A) include a siloxane compound represented by the following formula (I).

In formula (I), R ^a is the same or different and represents an epoxy group-containing group or an alkyl group. Provided that at least two R ^a in formula (I) (e.g. one to four) is a group containing an epoxy group. The above-mentioned group containing an epoxy group is a group containing at least one epoxy group (oxirane ring), for example, a linear or branched aliphatic group having a carbon-carbon unsaturated double bond such as an alkenyl group. A group in which at least one double bond of a hydrocarbon group is epoxidized, or a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond (for example, cycloalkenyl group; cyclohexenylethyl group, etc. A group in which at least one double bond of the alkenylalkyl group or the like is epoxidized. More specifically, for example, 1,2-epoxyethyl group (epoxy group), 1,2-epoxypropyl group, 2,3-epoxypropyl group (glycidyl group), 2,3-epoxy-2-methylpropyl Group (methylglycidyl group), 3,4-epoxybutyl group, 3-glycidyloxypropyl group, 3,4-epoxycyclohexylmethyl group, 2- (3,4-epoxycyclohexyl) ethyl group and the like. Among these, a group in which at least one double bond of a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond is epoxidized is preferable. Examples of the alkyl group include straight chain or branched chain groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group. An alkyl group etc. are mentioned. Especially, a C1-C10 linear or branched alkyl group is preferable.

  In formula (I), n shows the integer of 2-12. Particularly, n is preferably 4 to 8, more preferably 4 or 5, from the viewpoint of the thermal shock resistance of the cured product, the reflow resistance and the thermal shock resistance of the optical semiconductor device.

More specifically, the siloxane derivative (A) is, for example, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6. , 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-cyclotetra Siloxane, 2,4,8-tri [2- (3- {Oxavicic [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, silsesquioxane having two or more epoxy groups in the molecule, and the like. More specifically, for example, a cyclic siloxane having two or more epoxy groups in the molecule represented by the following formula.

  Examples of the siloxane derivative (A) include alicyclic epoxy group-containing silicone resins described in JP-A-2008-248169, and at least two epoxy functional groups in one molecule described in JP-A-2008-19422. An organopolysilsesquioxane resin having a functional group can also be used.

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

  The siloxane derivative (A) is, for example, a trade name “X-40-2678”, “X-40-2670”, “X-40-2720” (above) which is a cyclic siloxane having two or more epoxy groups in the molecule. Commercial products such as Shin-Etsu Chemical Co., Ltd.) are available. The siloxane derivative (A) can be produced by a known or conventional method.

  Although content (blending amount) of the siloxane derivative (A) in the curable epoxy resin composition of the present invention is not particularly limited, it is 10 to 98 wt% with respect to the total amount (100 wt%) of the curable epoxy resin composition. % Is preferable, more preferably 15 to 95% by weight, still more preferably 20 to 90% by weight. By controlling the content of the siloxane derivative (A) within the above range, the thixotropy of the curable epoxy resin composition is increased, and the heat resistance, light resistance, and transparency of the cured product tend to be further improved.

  Although content (blending amount) of the siloxane derivative (A) in the curable epoxy resin composition of the present invention is not particularly limited, the total amount of the compound (epoxy compound) having an epoxy group contained in the curable epoxy resin composition ( 100 to 100% by weight), preferably 40 to 98% by weight, more preferably 50 to 95% by weight, and still more preferably 60 to 92% by weight. By setting the content of the siloxane derivative (A) to 40% by weight or more, the thixotropy of the curable epoxy resin composition is increased, and the heat resistance, light resistance, and transparency of the cured product tend to be further improved. . On the other hand, when the content of the siloxane derivative (A) is 98% by weight or less, the thermal shock resistance and adhesiveness of the cured product tend to be further improved.

[Acrylic resin (B)]
The acrylic resin (B) in the curable epoxy resin composition of the present invention contains an acrylic monomer and a styrene monomer as essential monomer components, and has a polymer having an epoxy group in the side chain ( Copolymer). That is, the acrylic resin (B) is a polymer containing a structural unit derived from an acrylic monomer and a structural unit derived from a styrene monomer as essential structural units, and having an epoxy group in the side chain. .

［式（１）中、Ｒ¹は、水素原子又はメチル基を示す。Ｒ²は、アルキレン基を示す。］ As the acrylic monomer that is an essential monomer component of the acrylic resin (B), a known or conventional acrylic monomer can be used, and is not particularly limited. For example, (meth) acrylic acid Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as t-butyl acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate (for example, (meth) acrylic acid alkyl esters having an alkyl group having 1 to 18 carbon atoms) Etc.) (Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc.) Kill; glycidyl (meth) acrylate, an epoxy group-containing acrylic monomer such as a compound represented by the following formula (1) (for example, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc.); γ-trimethoxy Silyl group-containing acrylic monomers such as silane (meth) acrylate and γ-triethoxysilane (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxy Examples include amide group-containing acrylic monomers such as methyl (meth) acrylamide; aldehyde group-containing acrylic monomers such as acrolein and methacrolein. In addition, an acrylic monomer can also be used individually as a monomer component of an acrylic resin (B), and can also be used in combination of 2 or more type. Among them, the acrylic monomer is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms or an epoxy group-containing acrylic monomer, more preferably an alkyl group having 1 to 4 carbon atoms. (Meth) acrylic acid alkyl ester having glycidyl (meth) acrylate, and a compound represented by the following formula (1). In this specification, “(meth) acryl” means acryl and / or methacryl (any one or both of acryl and methacryl), and other similar expressions are also synonymous.

[In Formula (1), R < ¹ > shows a hydrogen atom or a methyl group. R ² represents an alkylene group. ]

R ² in the above formula (1) is, for example, methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group. C1-C10 alkylene group etc. are mentioned.

  As the styrene monomer which is an essential monomer component of the acrylic resin (B), a known or commonly used aromatic vinyl monomer (a monomer having a styrene skeleton) can be used, and is not particularly limited. For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, ethylstyrene, trimethylstyrene, pentamethylstyrene, diethylstyrene, isopropylstyrene, butyl Alkyl styrene such as styrene (3-t-butylstyrene, 4-t-butylstyrene, etc.); chlorostyrene (o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc.), dichlorostyrene (2,4-dichloro) Styrene, 2,5-dichlorostyrene, etc.), trichlorostyrene, bromostyrene 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, etc.), halogenated styrene such as fluorostyrene (2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, etc.), p-iodostyrene; methoxystyrene, Alkoxy styrene such as methoxymethyl styrene, dimethoxy styrene, ethoxy styrene, vinyl phenyl allyl ether; hydroxy styrene, methoxy hydroxy styrene, acetoxy styrene, α-methyl styrene, α-methyl-p-methyl styrene, 1,1-diphenylethylene, p- (N, N-diethylaminoethyl) styrene, p- (N, N-diethylaminomethyl) styrene, vinylnaphthalene, [(4-ethenylphenyl) methyl] oxirane, 4- (glycidyloxy) styrene, etc. It is below. In addition, a styrene-type monomer can also be used individually as a monomer component of an acrylic resin (B), and can also be used in combination of 2 or more type. Of these, styrene is preferred as the styrene monomer.

  The epoxy group that the acrylic resin (B) has in the side chain is usually a structure derived from a monomer having an epoxy group in the molecule (sometimes referred to as “epoxy group-containing monomer”). The epoxy group-containing monomer may be a known or commonly used monomer having a polymerizable functional group and an epoxy group in the molecule, and is not particularly limited. For example, glycidyl (meth) acrylate , Epoxy group-containing acrylic monomers such as compounds represented by the above formula (1) (for example, 3,4-epoxycyclohexylmethyl (meth) acrylate), 4-hydroxybutyl (meth) acrylate glycidyl ether; Styrenic monomers having an epoxy group such as 4-ethenylphenyl) methyl] oxirane, 4- (glycidyloxy) styrene; 4-vinylepoxycyclohexane, diglycidyl fumarate, diepoxycyclohexylmethyl fumarate, allyl glycidyl ether Etc. In addition, an epoxy-group containing monomer can also be used individually by 1 type as a monomer component of an acrylic resin (B), and can also be used in combination of 2 or more type. Among these, glycidyl methacrylate and 3,4-epoxycyclohexylmethyl acrylate are preferable as the epoxy group-containing monomer.

  The acrylic resin (B) is not particularly limited, but may contain a monomer other than the above-described monomers (sometimes referred to as “other monomers”) as a monomer component. Examples of the other monomers include unsaturated nitrile compounds such as (meth) acrylonitrile; olefins such as ethylene, propylene, isoprene and isobutene; conjugated dienes such as butadiene; vinyl chloride; vinylidene chloride; Unsaturated acid anhydrides; vinyl esters such as vinyl acetate and vinyl propionate, and various vinyl compounds such as isobutyl vinyl ether, methyl vinyl sulfide, N-vinyl carbazole, and methyl vinyl ketone. In addition, another monomer can also be used individually as a monomer component of an acrylic resin (B), and can also be used in combination of 2 or more type.

  The ratio of the acrylic monomer to the total amount (100% by weight) of the monomer constituting the acrylic resin (B) is not particularly limited, but is preferably 45 to 98% by weight, more preferably 60 to 95% by weight, More preferably, it is 65 to 90% by weight. That is, the proportion (content) of the structural unit derived from the acrylic monomer in the acrylic resin (B) is not particularly limited, but is 45% with respect to the total structural unit (100% by weight) of the acrylic resin (B). It is preferably -98% by weight, more preferably 60-95% by weight, still more preferably 65-90% by weight. By setting the proportion of the acrylic monomer (the proportion of the structural unit derived from the acrylic monomer) to 45% by weight or more, the heat resistance and adhesiveness of the cured product tend to be further improved. On the other hand, when the ratio is 98% by weight or less, the ratio of the styrene monomer as the monomer component is relatively increased, and the adhesiveness of the cured product tends to be further improved.

  Although the ratio of the styrene-type monomer with respect to the whole quantity (100 weight%) of the monomer which comprises an acrylic resin (B) is not specifically limited, 1-50 weight% is preferable, More preferably, it is 5-45 weight%, More preferably, it is 10 to 40% by weight. That is, the proportion (content) of the structural unit derived from the styrenic monomer in the acrylic resin (B) is not particularly limited, but is 1 with respect to the total structural unit (100 wt%) of the acrylic resin (B). -50 wt% is preferable, more preferably 5-45 wt%, still more preferably 10-40 wt%. By setting the ratio of the styrene monomer (the ratio of the structural unit derived from the styrene monomer) to 1% by weight or more, the adhesiveness of the cured product tends to be further improved. On the other hand, when the ratio is 50% by weight or less, the heat resistance and adhesiveness of the cured product tend to be further improved.

  The ratio of the epoxy group-containing monomer to the total amount (100% by weight) of the monomer constituting the acrylic resin (B) is not particularly limited, but is preferably 5 to 50% by weight, more preferably 15 to 45% by weight. More preferably, it is 25 to 40% by weight. That is, the proportion (content) of the structural unit derived from the epoxy group-containing monomer in the acrylic resin (B) is not particularly limited, but with respect to the total structural unit (100 wt%) of the acrylic resin (B), 5 to 50 weight% is preferable, More preferably, it is 15 to 45 weight%, More preferably, it is 25 to 40 weight%. By setting the proportion of the epoxy group-containing monomer (the proportion of the structural unit derived from the epoxy group-containing monomer) to 5% by weight or more, the solubility in the curable epoxy resin composition becomes higher, and the cured product There is a tendency for transparency to be further improved. On the other hand, when the ratio is 50% by weight or less, the thermal shock resistance tends to be further improved without the cured product becoming too hard.

  The ratio of the other monomer to the total amount (100% by weight) of the monomer constituting the acrylic resin (B) is not particularly limited, but is less than 10% by weight (for example, 0% by weight or more and less than 10% by weight). Is preferred, and more preferably less than 5% by weight. That is, the ratio (total ratio) of the acrylic monomer, the styrene monomer, and the epoxy group-containing monomer with respect to the total amount (100% by weight) of the monomer constituting the acrylic resin (B) is particularly limited. However, it is preferably 90% by weight or more (for example, 90 to 100% by weight), more preferably 95% by weight or more. When the ratio of the other monomer is 10% by weight or more, the heat resistance, transparency, adhesiveness, and thermal shock resistance of the cured product may be lowered.

  The acrylic resin (B) can be produced by polymerizing (copolymerizing) an acrylic monomer, a styrene monomer, an epoxy group-containing monomer, and, if necessary, other monomers. it can. Examples of the method for producing the acrylic resin (B) include known or conventional polymer production methods, and are not particularly limited. For example, the acrylic resin (B) is prepared by advancing the radical polymerization reaction (radical copolymerization reaction) of the above monomers. Examples thereof include a method for producing the resin (B).

  The polymerization reaction of the monomer constituting the acrylic resin (B) can be allowed to proceed in the absence of a solvent, or can be allowed to proceed in the presence of a solvent (polymerization solvent). Examples of the polymerization solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane, 1,2, and the like. A halogenated hydrocarbon such as dichloroethane; an ether such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; a ketone such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; an ester such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; Amides such as N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Alcohols such as methanol, ethanol, isopropyl alcohol and butanol Various organic solvents such as dimethyl sulfoxide. In addition, a polymerization solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Moreover, as a polymerization solvent, an epoxy compound (for example, a siloxane derivative (A) or other epoxy compounds described later) as a constituent component of the curable epoxy resin composition can also be used. Obtaining a mixture of an epoxy compound and an acrylic resin (B) in one step by using an epoxy compound as a polymerization solvent and advancing the polymerization reaction of the monomer constituting the acrylic resin (B) in the polymerization solvent Can do. Compared with a method using a well-known and commonly used organic solvent as a solvent, such a method removes the polymerization solvent from the acrylic resin (B) and dissolves (re-dissolves) in the epoxy compound, or the acrylic resin (B This is advantageous in terms of productivity and cost, because it is possible to eliminate the trouble of dissolving the epoxy compound in the polymerization solvent containing) and then removing the polymerization solvent. The epoxy compound used as the polymerization solvent may be a partial amount of the epoxy compound constituting the curable epoxy resin composition, or may be the total amount (the total amount excluding the acrylic resin (B)). .

  Although the usage-amount of the said polymerization solvent is not specifically limited, 10-800 weight part is preferable with respect to 100 weight part of whole quantity of the monomer which comprises an acrylic resin (B), More preferably, it is 50-700 weight part. is there. In addition, when using an epoxy compound as a polymerization solvent, the usage-amount of an epoxy compound can be set suitably so that the mixture of the epoxy compound and acrylic resin (B) of a desired composition may be obtained.

  The polymerization reaction of the monomer constituting the acrylic resin (B) can be allowed to proceed in the presence of a polymerization initiator. Examples of the polymerization initiator include known or conventional polymerization initiators, and are not particularly limited. Examples thereof include 2,2′-azobisisobutyronitrile (AIBN), benzoyl peroxide, and isobutyryl peroxide. Can be mentioned. In addition, a polymerization initiator can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Although the usage-amount of the said polymerization initiator is not specifically limited, 0.1-5 weight part is preferable with respect to 100 weight part of whole quantity of the monomer which comprises an acrylic resin (B), More preferably, it is 0.2. ~ 3 parts by weight. By setting the amount of the polymerization initiator used to be 0.1 parts by weight or more, the molecular weight of the acrylic resin (B) does not become too small, and the crosslinked structure in the cured product does not become too loose. There is a tendency to improve. On the other hand, by setting the amount of the polymerization initiator used to 5 parts by weight or less, the molecular weight of the acrylic resin (B) is not excessively increased, and a crosslinked structure is formed in the cured product appropriately and densely. Thermal shock resistance tends to be further improved.

  The polymerization reaction of the monomer constituting the acrylic resin (B) may be allowed to proceed in the presence of a known or commonly used polymerization inhibitor such as methoxyhydroquinone or hydroquinone for the purpose of controlling the molecular weight. A polymerization inhibitor can also be used individually by 1 type, and can also be used in combination of 2 or more type. Although the usage-amount of a polymerization inhibitor is not specifically limited, 0.01-5 weight part is preferable with respect to 100 weight part of whole quantity of the monomer which comprises an acrylic resin (B), More preferably, it is 0.1-0.1 weight part. 1 part by weight.

  The temperature (polymerization temperature) at which the polymerization reaction of the monomer constituting the acrylic resin (B) proceeds can be appropriately selected depending on the type of the polymerization initiator used, and is not particularly limited, but is preferably 0 to 150 ° C., more Preferably it is 80-130 degreeC. During the polymerization reaction, the polymerization temperature can be controlled to be constant, or can be controlled to vary stepwise or continuously. Further, the time for allowing the polymerization reaction to proceed (polymerization time) is not particularly limited, but is preferably 1 to 900 minutes, and more preferably 60 to 480 minutes.

  The polymerization reaction of the monomer constituting the acrylic resin (B) can be allowed to proceed under normal pressure, or can be allowed to proceed under increased pressure or reduced pressure. Moreover, the said polymerization reaction is although it does not specifically limit, It is preferable to advance in inert gas atmosphere, such as nitrogen atmosphere and argon atmosphere.

  After completion of the polymerization reaction, the acrylic resin (B) is separated from the acrylic resin (B) by a known or conventional method (for example, reprecipitation, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc.) And a separation means combining these, etc.). As described above, when an epoxy compound is used as the polymerization solvent, a mixture of the epoxy compound and the acrylic resin (B) can be generated in one step by the above polymerization reaction, so that the acrylic resin (B) This is advantageous in terms of cost.

  Although the weight average molecular weight of an acrylic resin (B) is not specifically limited, 500-100000 are preferable, More preferably, it is 1000-60000, More preferably, it is 3000-50000, Most preferably, it is 30000-40000. By setting the weight average molecular weight to 100000 or less, the compatibility with the siloxane derivative (A) is improved, and the transparency, adhesiveness, thermal shock resistance and the like of the cured product tend to be further improved. On the other hand, when the weight average molecular weight is 500 or more, the heat resistance and thermal shock resistance of the cured product tend to be further improved.

  Although the number average molecular weight of an acrylic resin (B) is not specifically limited, 200-50000 are preferable, More preferably, it is 400-30000, More preferably, it is 1000-30000, Most preferably, it is 10000-30000. By setting the number average molecular weight to 50000 or less, the compatibility with the siloxane derivative (A) decreases, and the transparency, adhesiveness, thermal shock resistance and the like of the cured product tend to be further improved. On the other hand, when the number average molecular weight is 200 or more, the heat resistance and thermal shock resistance of the cured product tend to be further improved. In addition, the weight average molecular weight and number average molecular weight of an acrylic resin (B) are computed from the molecular weight of standard polystyrene conversion measured by GPC method.

  In the curable epoxy resin composition of the present invention, the acrylic resin (B) can be used alone or in combination of two or more.

  The content (blending amount) of the acrylic resin (B) in the curable epoxy resin composition of the present invention is not particularly limited, but is 1 to 40 weights with respect to the total amount (100% by weight) of the curable epoxy resin composition. % Is preferable, and more preferably 3 to 30% by weight. By setting the content of the acrylic resin (B) to 1% by weight or more, the thermal shock resistance and adhesiveness of the cured product tend to be further improved. On the other hand, when the content of the acrylic resin (B) is 40% by weight or less, the transparency of the cured product tends to be further improved.

  The ratio of the acrylic resin (B) to the total amount (100% by weight) of the siloxane derivative (A) and the acrylic resin (B) is not particularly limited, but is preferably 5 to 35% by weight, more preferably 8 to 32% by weight. It is. That is, the ratio of the siloxane derivative (A) to the total amount (100 wt%) of the siloxane derivative (A) and the acrylic resin (B) is not particularly limited, but is preferably 65 to 95 wt%, more preferably 68 to 92. % By weight. By setting the proportion of the acrylic resin (B) to 5% by weight or more, the thermal shock resistance and adhesiveness of the cured product tend to be further improved. On the other hand, when the proportion of the acrylic resin (B) is 35% by weight or less, the transparency of the cured product tends to be further improved.

  Although the ratio of the acrylic resin (B) to the total amount (100% by weight) of the epoxy compound contained in the curable epoxy resin composition of the present invention is not particularly limited, it is preferably 1 to 50% by weight, more preferably 5 to 45%. % By weight, more preferably 8-40% by weight. When the ratio of the acrylic resin (B) is 1% by weight or more, the thermal shock resistance and adhesiveness of the cured product tend to be further improved. On the other hand, when the ratio of the acrylic resin (B) is 50% by weight or less, the transparency of the cured product tends to be further improved.

  The curable epoxy resin composition of the present invention may contain an epoxy compound other than the siloxane derivative (A) and the acrylic resin (B) (sometimes referred to as “other epoxy compounds”). As other epoxy compounds, known or commonly used epoxy compounds (epoxy resins) can be used, and are not particularly limited, and examples thereof include alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds.

  The ratio of the siloxane derivative (A) and the acrylic resin (B) to the total amount (100% by weight) of the epoxy compound contained in the curable epoxy resin composition of the present invention (the total amount of the siloxane derivative (A) and the acrylic resin (B) The ratio is not particularly limited, but is preferably 60% by weight or more (for example, 60 to 100% by weight), more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more. Preferably it is 95 weight% or more. By making the said ratio into the said range, there exists a tendency for transparency, heat resistance, thermal shock resistance, and adhesiveness of hardened | cured material to coexist at a higher level.

[Curing agent (C)]
The curable epoxy resin composition of the present invention may contain a curing agent (C). The curing agent (C) is a compound having a function of curing the curable epoxy resin composition by reacting with an epoxy compound such as a siloxane derivative (A) or an acrylic resin (B). As the curing agent (C), a known or conventional curing agent can be used as a curing agent for epoxy resin, and is not particularly limited. For example, acid anhydrides (acid anhydride curing agents), amines ( Amine curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, etc. Can be mentioned.

  As the acid anhydrides (acid anhydride-based curing agents) as the curing agent (C), known or conventional acid anhydride-based 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 (C in the curable epoxy resin composition of the present invention (C ) 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 (C), 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 (C), 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 (C) 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 (C), 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 (C) include liquid polymercaptan and polysulfide resin.

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

  Among these, as the curing agent (C), acid anhydrides (acid anhydride curing agents) are preferable from the viewpoint of heat resistance and transparency of the cured product. In addition, the hardening | curing agent (C) can also be used individually by 1 type in the curable epoxy resin composition of this invention, 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 (C). 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 (C) in the curable epoxy resin composition of the present invention is not particularly limited, but is 50 with respect to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition. -200 weight part is preferable, More preferably, it is 80-150 weight part. More specifically, when acid anhydrides are used as the curing agent (C), 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 (C) into 50 weight part or more, hardening can fully be advanced and there exists a tendency which the toughness of hardened | cured material improves more. On the other hand, by setting the content of the curing agent (C) to 200 parts by weight or less, coloring tends to be further suppressed and a cured product excellent in hue tends to be obtained.

[Curing accelerator (D)]
The curable epoxy resin composition of the present invention may contain a curing accelerator (D). The curing accelerator (D) is a compound having a function of accelerating the reaction rate when the epoxy compound reacts with the curing agent (C). The curing accelerator (D) may be a known or conventional curing accelerator, and is not particularly limited. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, , Phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (for example, phenol Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, etc. Tertiary amines; Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Acid esters; phosphines such as triphenylphosphine and tris (dimethoxy) phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organometallic salts such as zinc octylate, tin octylate and zinc stearate; Examples thereof include metal chelates such as aluminum acetylacetone complex.

  In addition, a hardening accelerator (D) 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. Further, as the curing accelerator (D), trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “U-CAT 12XD” ( (Developed product) (San Apro Co., Ltd.); trade names "TPP-K", "TPP-MK" (Hokuko Chemical Co., Ltd.); trade name "PX-4ET" (Nippon Chemical Industry ( It is also possible to use a commercial product such as a product manufactured by Co., Ltd.

  Although content (blending amount) of the curing accelerator (D) in the curable epoxy resin composition of the present invention is not particularly limited, with respect to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition, 0.01-5 weight part is preferable, More preferably, it is 0.03-3 weight part, More preferably, it is 0.03-2 weight part. By setting the content of the curing accelerator (D) to 0.01 parts by weight or more, a more efficient curing promoting effect tends to be obtained. On the other hand, when the content of the curing accelerator (D) is 5 parts by weight or less, there is a tendency that coloring is further suppressed and a cured product having excellent hue is obtained.

[Curing catalyst (E)]
The curable epoxy resin composition of the present invention may further contain a curing catalyst (E) (for example, instead of the curing agent (C) and the curing accelerator (D)). The curing catalyst (E) in the curable epoxy resin composition of the present invention starts and / or accelerates a curing reaction (polymerization reaction) of a cationically polymerizable compound such as a siloxane derivative (A) or an acrylic resin (B). And a compound having a function of curing the curable epoxy resin composition. The curing catalyst (E) is not particularly limited. For example, a cationic polymerization initiator (photo cationic polymerization initiator, thermal cationic polymerization) that initiates polymerization by generating cationic species by light irradiation, heat treatment, or the like. Initiators, etc.), Lewis acid / amine complexes, Bronsted acid salts, imidazoles and the like.

  Examples of the photocationic polymerization initiator as the curing catalyst (E) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically. For example, triarylsulfonium hexafluorophosphate (for example, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate), sulfonium salt such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salt); diaryl iodonium hexafluorophosphate , Diaryl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodo Iodonium salts such as um [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; pyridinium salts such as N-hexylpyridinium tetrafluoroborate It is done. Moreover, as a photocationic polymerization initiator, for example, trade name “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, the United States) Commercial products such as Sartomer); trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.

  Examples of the thermal cationic polymerization initiator as the curing catalyst (E) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33” and “CP-66”. "CP-77" (manufactured by ADEKA); trade name "FC-509" (manufactured by 3M); trade name "UVE1014" (manufactured by GE); trade name "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” ( Commercially available products such as BASF) can be preferably used. Further, as the thermal cationic polymerization initiator, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketone Examples thereof include a compound of a chelate compound with a phenol and a phenol such as bisphenol S.

As the Lewis acid / amine complex as the curing catalyst (E), 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 (E), 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 (E), 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 (E) can be used singly or in combination of two or more. In addition, as above-mentioned, a commercial item can also be used as a curing catalyst (E).

  The content (blending amount) of the curing catalyst (E) in the curable epoxy resin composition of the present invention is not particularly limited, but is based on 100 parts by weight of the total amount of the cationic polymerizable compound contained in the curable epoxy resin composition. 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 0.05 to 8 parts by weight. By using the curing catalyst (E) within the above range, the curing rate of the curable epoxy resin composition is increased, and the heat resistance and transparency of the cured product tend to be improved in a balanced manner.

[Additive]
In addition to the above, the curable epoxy resin composition of the present invention may contain various additives within a range that does not impair the effects of the present invention. For example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained as the additive, the reaction can be allowed to proceed slowly. Other silane coupling agents such as silicone-based and fluorine-based antifoaming agents, leveling agents, and γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, as long as the viscosity and transparency are not impaired. , Surfactants, inorganic fillers such as silica and alumina, flame retardants, colorants, ion adsorbents, pigments, phosphors (for example, inorganic phosphor fine particles such as YAG phosphor fine particles, silicate phosphor fine particles, etc. ), A conventional additive such as a release agent can be used.

  Although the curable epoxy resin composition of this invention is not specifically limited, It can prepare by stirring and mixing each said component in the state heated as needed. In addition, the curable epoxy resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more stored separately. The components (each component may be a mixture of two or more components) can be used as a multi-component (for example, two-component) composition that is used by mixing at a predetermined ratio before use. . The stirring / mixing method is not particularly limited, and for example, known or commonly used 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 vacuum.

  Although the viscosity in 25 degreeC of the curable epoxy resin composition of this invention is not specifically limited, 100-50000 mPa * s is preferable, More preferably, it is 200-45000 mPa * s, More preferably, it is 300-40000 mPa * s. By controlling the viscosity at 25 ° C. within the above range, workability at the time of casting or coating is further improved, and there is a tendency that defects resulting from casting failure or coating failure are less likely to occur in the cured product. In addition, the said viscosity at 25 degrees C of a curable epoxy resin composition uses a digital viscometer (model number "DVU-EII type", the Tokimec Co., Ltd. product), rotor: Standard 1 degree 34'xR24, temperature: It is measured under the conditions of 25 ° C. and rotation speed: 0.5 to 10 rpm.

  The light transmittance of light having a wavelength of 450 nm [in terms of thickness 10 mm] of the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 80% or more (for example, 80% or more, less than 100%), more preferably. 82% or more. When the light transmittance is less than 80%, the transparency of the cured product may be lowered. The light transmittance can be measured using, for example, a spectrophotometer (for example, trade name “UV-2400”, manufactured by Shimadzu Corporation). In the curable epoxy resin composition of this invention, since the siloxane derivative (A) and acrylic resin (B) have high compatibility, the said light transmittance is high.

<Hardened product>
By curing the curable epoxy resin composition of the present invention, a cured product excellent in transparency, heat resistance, thermal shock resistance and adhesion (sometimes referred to as “cured product of the present invention”) is obtained. Can do. Although the heating temperature (curing temperature) in the case of hardening is not specifically limited, 45-200 degreeC is preferable, More preferably, it is 100-190 degreeC, More preferably, it is 100-180 degreeC. In addition, the heating time (curing time) for curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit value in the above range, curing is insufficient. On the contrary, when the curing temperature and the curing time are higher than the upper limit value in the above range, the resin component may be decomposed. Although the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased.

  The light transmittance of the cured product of the present invention having a wavelength of 450 nm [in terms of thickness of 3 mm] is not particularly limited, but is preferably 85% or more (for example, 85% or more and less than 100%), more preferably 90% or more. is there. When the total light transmittance is 85% or more, the light intensity emitted from the optical semiconductor device when the curable epoxy resin composition is used as an optical semiconductor element sealant or die attach paste agent in the optical semiconductor device. Tend to be higher. The light transmittance can be measured using, for example, a spectrophotometer (for example, trade name “UV-2400”, manufactured by Shimadzu Corporation). In the hardened | cured material of this invention, since the compatibility of the siloxane derivative (A) and acrylic resin (B) in a curable epoxy resin composition is high, the said light transmittance is high.

<Resin composition for optical semiconductor encapsulation>
The curable epoxy resin composition of the present invention is a resin composition for sealing an optical semiconductor (an optical semiconductor element) in an optical semiconductor device, that is, an optical semiconductor sealing resin composition (an optical semiconductor element sealing agent). ) Can be preferably used. By using the curable epoxy resin composition of the present invention as a resin composition for sealing an optical semiconductor, the optical semiconductor element was sealed with a cured product excellent in transparency, heat resistance, thermal shock resistance, and adhesiveness. An optical semiconductor device is obtained.

<Adhesive resin composition>
The curable epoxy resin composition of the present invention can also be preferably used as a resin composition for adhering and fixing a member or the like to an adherend, that is, a resin composition for an adhesive (adhesive). In particular, the curable epoxy resin composition of the present invention is a die attach paste (die bond agent) for bonding and fixing an optical semiconductor element to a metal electrode in an optical semiconductor device (for example, the optical semiconductor device shown in FIG. 1). Can be preferably used as an adhesive for forming the adhesive (die attach paste material) 105. By using the curable epoxy resin composition of the present invention as a die attach paste agent, an optical semiconductor device in which an optical semiconductor element is bonded to an electrode by a cured product excellent in transparency, heat resistance, thermal shock resistance, and adhesiveness Is obtained. In addition to the die attach paste agent, the curable epoxy resin composition (adhesive resin composition) of the present invention, for example, fixes a lens of a camera or the like to an adherend or bonds the lenses together. Adhesive for lenses; for fixing optical films (for example, polarizers, polarizer protective films, retardation films, etc.) to adherends, or bonding optical films together or optical films and other films. In particular, it can be used in various applications that require excellent transparency, heat resistance, thermal shock resistance, and adhesiveness, such as adhesives for optical films.

<Optical semiconductor device>
The optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition (resin composition for optical semiconductor encapsulation) of the present invention, or the curable property of the present invention. This is an optical semiconductor device in which an optical semiconductor element is bonded to an electrode with a cured product of an epoxy resin composition (adhesive resin composition). In the optical semiconductor device of the present invention, an optical semiconductor element is bonded to an electrode with a cured product of the curable epoxy resin composition (adhesive resin composition) of the present invention, and the optical semiconductor element is curable of the present invention. The optical semiconductor device sealed with the hardened | cured material of the epoxy resin composition (resin composition for optical semiconductor sealing) may be sufficient. Therefore, the optical semiconductor device of the present invention has high light extraction efficiency, excellent current-carrying characteristics at high temperatures, reflow resistance, and thermal shock resistance, and has high quality and durability.

  Sealing of the optical semiconductor element in the optical semiconductor device of the present invention can be carried out by a known or conventional method, and is not particularly limited. For example, the curable epoxy resin composition of the present invention is injected into a predetermined mold, It can be performed by heating and curing under predetermined conditions. Thereby, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the curable epoxy resin composition of this invention is obtained. The curing temperature and the curing time can be appropriately set within the same range as when the cured product is prepared. On the other hand, the adhesion of the optical semiconductor element to the electrode in the optical semiconductor device of the present invention can be carried out by a known or conventional method, and is not particularly limited. For example, the curable epoxy resin composition of the present invention is applied to the electrode in the optical semiconductor device. It can be performed by coating (applying) at a predetermined position and placing the optical semiconductor element on the curable epoxy resin composition, followed by heat curing under predetermined conditions. Thereby, the optical semiconductor device with which the optical semiconductor element was adhere | attached on the electrode with the hardened | cured material of the curable epoxy resin composition of this invention is obtained. In obtaining the optical semiconductor device of the present invention, as a method of injecting or coating the curable epoxy resin composition of the present invention, a known or conventional method can be used, and is not particularly limited. Examples thereof include a method using a dispenser, a printer, a spin coater, a bar coater and the like.

  The curable epoxy resin composition of the present invention is not limited to the above-mentioned optical semiconductor element sealing application or adhesive application, for example, electrical insulating material, laminated board, coating, ink, paint, sealant, resist, composite material , Transparent substrate, transparent sheet, transparent film, optical element, optical lens, optical member, stereolithography, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, etc. it can.

  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, "-" in Tables 1-3 means that the said component was not mix | blended. Moreover, the unit of the quantity (ratio) of the component shown to Tables 1-3 is a weight part.

Production Example 1
(Manufacture of acrylic resin)
A 300 ml reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and reflux condenser was charged with 100 parts by weight of butyl acetate, heated to 95 ° C. in a nitrogen gas atmosphere, and MMA (methyl methacrylate) 40 wt. Part, 30 parts by weight of styrene, 30 parts by weight of GMA (glycidyl methacrylate), 1 part by weight of AIBN (azobisisobutyronitrile), and 0.2 part by weight of MEHQ (paramethoxyphenol), and added at 95 ° C. for 45 minutes. Reacted. Thereafter, the mixture was kept at 120 ° C. for 45 minutes, then cooled, reprecipitated with methanol, collected by filtration, and then dried to obtain an acrylic resin (B1).

Production Examples 2-5
(Manufacture of acrylic resin)
Acrylic resins (B2) to (B5) were produced in the same manner as in Production Example 1 except that the types and amounts of the monomers used were changed as shown in Table 1.

  Table 1 shows the results of the weight average molecular weight and the number average molecular weight of the acrylic resins (B1) to (B5) calculated from the molecular weight in terms of standard polystyrene measured by the GPC method.

Production Example 6
(Manufacture of curing agent composition)
In the blending ratio shown in Table 2, the trade name “Rikacid MH-700” (curing agent, manufactured by Shin Nippon Rika Co., Ltd.), the trade name “U-CAT 18X” (curing accelerator, manufactured by San Apro Co., Ltd.), and Uniform ethylene glycol (additive, manufactured by Wako Pure Chemical Industries, Ltd.) using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd., the same shall apply hereinafter) The mixture was mixed and degassed to produce a curing agent composition (sometimes referred to as “K agent”).

Example 1
First, with the compounding ratio shown in Table 2, the trade name “X-40-2678” (siloxane derivative, manufactured by Shin-Etsu Chemical Co., Ltd.) and the acrylic resin (B1) obtained in Production Example 1 were revolved. The mixture was uniformly mixed using a stirrer and defoamed to prepare a mixture of a siloxane derivative and an acrylic resin.
Next, the mixture obtained above and the curing agent composition obtained in Production Example 6 are uniformly mixed using a self-revolving stirrer so as to achieve the blending ratio shown in Table 2, and defoamed. Thus, a curable epoxy resin composition was obtained.
Furthermore, after casting the curable epoxy resin composition obtained above on an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1, a 120 ° C. resin curing oven (trade name “ GPHH-201 "(manufactured by ESPEC CORP., The same shall apply hereinafter) was heated for 5 hours to obtain an optical semiconductor device in which the optical semiconductor element was sealed with a cured product of the curable epoxy resin composition. In FIG. 1, 100 is a reflector (light reflecting resin composition), 101 is a metal wiring (electrode), 102 is an optical semiconductor element, 103 is a bonding wire, 104 is a cured product (sealing material), and 105 is an adhesive. The material (die attach paste material) is shown.

Examples 2-7, Comparative Examples 1-10
A curable epoxy resin composition was produced in the same manner as in Example 1 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 2.
Further, an optical semiconductor device was manufactured in the same manner as in Example 1.

Example 8
First, the product name “X-40-2678” (siloxane derivative, manufactured by Shin-Etsu Chemical Co., Ltd.) and the acrylic resin (B1) obtained in Production Example 1 were mixed at the blending ratios shown in Table 3. Using the apparatus, the mixture was uniformly mixed and defoamed to produce a mixture of a siloxane derivative and an acrylic resin.
Next, in order to obtain the blending ratio shown in Table 3, the mixture obtained above and the trade name “SANAID SI-100L” (curing catalyst, manufactured by Sanshin Chemical Industry Co., Ltd.) The resulting mixture was uniformly mixed and defoamed to obtain a curable epoxy resin composition.
Further, the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm) shown in FIG. 1, and then heated in a resin curing oven at 120 ° C. for 5 hours. Thus, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable epoxy resin composition was obtained.

Examples 9-14, Comparative Examples 11-20
A curable epoxy resin composition was produced in the same manner as in Example 8, except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 3.
Further, an optical semiconductor device was manufactured in the same manner as in Example 8.

<Evaluation>
The following evaluation tests were conducted on the curable epoxy resin compositions and optical semiconductor devices obtained in the examples and comparative examples.

[Thixotropic]
The thixotropy of the curable epoxy resin composition was evaluated by calculating the following thixotropy index (TI). The results of the thixotropy index are shown in the “Thixotropy (TI)” column of Tables 2 and 3. In addition, it shows that high thixotropy is expressed, so that a thixotropy index is large.
[Thixotropic index (TI)] = [Viscosity of curable epoxy resin composition measured at 1 rpm (mPa · s)] / [Viscosity of curable epoxy resin composition measured at 10 rpm) (MPa · s)]
The above-mentioned “viscosity of curable epoxy resin composition measured at 1 rpm” is a rheometer (trade name “Physica MCR-302”, manufactured by Anton Paar) and a parallel plate (cone diameter: 25 mm, taper angle). = 0 °), the viscosity of the curable epoxy resin composition measured under the conditions of temperature: 25 ° C and rotation speed: 1 rpm. On the other hand, the “viscosity of the curable epoxy resin composition measured at a rotation speed of 10 rpm” is a rheometer (trade name “Physica MCR-302”, manufactured by Anton Paar) and a parallel plate (cone diameter: 25 mm, taper angle). = 0 °), the viscosity of the curable epoxy resin composition measured under the conditions of temperature: 25 ° C. and rotation speed: 10 rpm.

[Initial light transmittance]
The mold was filled with the curable epoxy resin composition and heated in a resin curing oven at 120 ° C. for 5 hours to obtain a cured product having a thickness of 3 mm. The light transmittance (thickness direction) of light having a wavelength of 450 nm of the obtained cured product was measured using a spectrophotometer (trade name “UV-2400”, manufactured by Shimadzu Corporation) (“initial light transmission”). Rate "). The results are shown in the column of “initial light transmittance [%]” in Tables 2 and 3.

[Energization test]
The total luminous flux of the optical semiconductor device was measured using a total luminous flux measuring device (trade name “Multispectral Radiation Measurement System OL771” manufactured by Optronic Laboratories), and this was defined as “0 hour total luminous flux”. Furthermore, the total luminous flux after flowing a current of 20 mA through the optical semiconductor device was measured for 100 hours in an 85 ° C. constant temperature bath (trade name “Small High Temperature Chamber ST-120B1”, manufactured by ESPEC Corporation). “Total luminous flux after 100 hours”. And luminous intensity retention was computed from the following formula. The results are shown in the columns of “Luminance retention rate [%]” in Tables 2 and 3.
{Luminance retention (%)}
= {Total luminous flux after 100 hours (lm)} / {total luminous flux after 0 hours (lm)} × 100

[Solder heat resistance test]
An optical semiconductor device (two were used for each curable epoxy resin composition) was left to stand for 192 hours under the conditions of 30 ° C. and 70% RH for moisture absorption treatment. Next, the optical semiconductor device was placed in a reflow furnace (trade name “UNI-5016F”, manufactured by Nippon Antom Co., Ltd., the same shall apply hereinafter) and heat-treated under the following heating conditions. Thereafter, the optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then again placed in a reflow furnace and heat-treated under the same conditions. That is, in the solder heat resistance test, the thermal history under the following heating conditions was given twice to the optical semiconductor device.
[Heating conditions (based on surface temperature of optical semiconductor device)]
(1) Preheating: 150 to 190 ° C. for 60 to 120 seconds (2) Main heating after preheating: 217 ° C. or more for 60 to 150 seconds, maximum temperature 260 ° C.
However, the rate of temperature increase when shifting from preheating to main heating was controlled to 3 ° C./second at the maximum.
FIG. 2 shows an example of a surface temperature profile (temperature profile in one of the two heat treatments) of the optical semiconductor device when heated by the reflow furnace.
After that, the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation, the same shall apply hereinafter), and a crack with a length of 90 μm or more occurred in the cured product by the heat treatment. It was confirmed whether or not. Of the two optical semiconductor devices, the number of optical semiconductor devices having a crack of 90 μm or more in the cured product is shown in the column of “Solder heat resistance test [number]” in Tables 2 and 3.

[Thermal shock test]
One cycle of exposure to an optical semiconductor device (two used for each curable epoxy resin composition) in an atmosphere of −40 ° C. for 30 minutes, followed by exposure to an atmosphere of 120 ° C. for 30 minutes A thermal shock tester (trade name “Small Thermal Shock Device TSE-11-A”, manufactured by Espec Co., Ltd.) was applied for 200 cycles. Thereafter, the length of the crack generated in the cured product in the optical semiconductor device due to the application of the thermal shock was observed using a digital microscope, and a crack having a length of 90 μm or more in the cured product among the two optical semiconductor devices. The number of optical semiconductor devices in which the occurrence occurred was measured. The results are shown in the column of “Thermal shock test [number]” in Tables 2 and 3.

[Comprehensive judgment 1]
As a result of each test, what satisfy | filled all the following (1-1)-(1-4) was determined as (circle) (good). On the other hand, when any of the following (1-1) to (1-4) was not satisfied, it was determined as x (defective).
(1-1) Initial light transmittance is 90% or more. (1-2) Current test: luminous intensity retention is 90% or more. (1-3) Solder heat resistance test: A crack having a length of 90 μm or more is found on the cured product. The number of generated optical semiconductor devices is 0. (1-4) Thermal shock test: The number of optical semiconductor devices where a crack with a length of 90 μm or more has occurred in the cured product is 0. This is shown in the column “1”. In addition, the said comprehensive determination 1 determines the suitability at the time of using a curable epoxy resin composition as a resin composition for optical semiconductor sealing (sealing agent of an optical semiconductor element).

[Light transmittance after aging at 120 ° C.]
The cured product (thickness: 3 mm) whose initial light transmittance was measured as described above was placed in an oven and aged at 120 ° C. for 200 hours. Thereafter, the light transmittance (thickness direction) of light having a wavelength of 450 nm was measured for the cured product after aging using a spectrophotometer (trade name “UV-2400”, manufactured by Shimadzu Corporation) (“aging”). Later light transmittance "). The results are shown in the columns of “Light transmittance after aging at 120 ° C. [%]” in Tables 2 and 3.

[Die share test]
A curable epoxy resin composition was applied onto an Ag-plated Cu substrate so that the adhesion area was 1.25 mm × 1.25 mm, and a 1.25 mm square Si chip was mounted. Next, this was heated at 150 degreeC for 2 hours, the curable epoxy resin composition was hardened, and the test sample was produced. About the said test sample, the die shear intensity | strength in 25 degreeC was evaluated at the speed | rate of 300 micrometers / second using the die shear tester (Brand name "DAGE 4000", Co., Ltd. product made from Arctec Co., Ltd.). The results are shown in the column of “Die shear test [N]” in Tables 2 and 3.

[Comprehensive judgment 2]
As a result of each test, what satisfy | filled all the following (2-1)-(2-3) was determined as (circle) (good). On the other hand, when any of the following (2-1) to (2-3) was not satisfied, it was determined as x (defective).
(2-1) Initial light transmittance is 90% or more (2-2) Light transmittance after aging at 120 ° C. is 85% or more (2-3) Die shear test: value where die shear strength exceeds 20 N Table 2 3 in the “overall determination 2” column. In addition, the comprehensive determination 2 is for determining whether or not the curable epoxy resin composition is used as a resin composition for an adhesive (adhesive, in particular, a die attach paste).

In addition, the component used in the present Example is as follows.
(Acrylic resin monomer)
ST: Styrene GMA: Glycidyl methacrylate MMA: Methyl methacrylate BMA: Butyl methacrylate BA: Butyl acrylate (polymerization initiator)
AIBN: Azobisisobutyronitrile (polymerization inhibitor)
MEHQ: Paramethoxyphenol (epoxy compound)
X-40-2678: trade name “X-40-2678” (siloxane derivative having two epoxy groups in the molecule), manufactured by Shin-Etsu Chemical Co., Ltd. X-40-2720: trade name “X-40-2720” "(Siloxane derivative having three epoxy groups in the molecule), X-E-40-2670 manufactured by Shin-Etsu Chemical Co., Ltd .: Trade name" X-40-2670 "(siloxane derivative having four epoxy groups in the molecule) Manufactured by Shin-Etsu Chemical Co., Ltd. Celoxide 2021P: Trade name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate), manufactured by Daicel Corporation (curing agent composition)
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. (curing catalyst)
Sun-Aid SI-100L: Trade name “Sun-Aid SI-100L” (curing catalyst), manufactured by Sanshin Chemical Industry Co., Ltd.

  As shown in Tables 2 and 3, the curable epoxy resin compositions (Examples 1 to 14) of the present invention are cured products having excellent transparency, heat resistance, thermal shock resistance, and adhesiveness by curing. In particular, it was confirmed to be useful as a resin composition for sealing an optical semiconductor and a die attach paste agent. Furthermore, it was confirmed that the curable epoxy resin composition of the present invention exhibits thixotropy as an unintended effect by using a siloxane derivative and an acrylic resin having a specific structure as essential components. Although the curable epoxy resin composition of the present invention contains a siloxane derivative having a relatively low adhesiveness as compared with an alicyclic epoxy compound (having no siloxane bond) as an essential component, it is suitable for an optical semiconductor device. It is presumed that the excellent thermal shock resistance and reflow resistance can be exhibited by the effect of the thixotropy.

100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor element 103: Bonding wire 104: Cured material (sealing material)
105: Adhesive (Die attach paste)

Claims (8)

Including a siloxane derivative (A) having two or more epoxy groups in the molecule, and an acrylic resin (B),
The curable epoxy resin composition, wherein the acrylic resin (B) is a polymer containing an acrylic monomer and a styrene monomer as monomer components and having an epoxy group in a side chain .   The ratio of the siloxane derivative (A) having two or more epoxy groups in the molecule to the total amount (100% by weight) of the siloxane derivative (A) having two or more epoxy groups in the molecule and the acrylic resin (B) is 65 to 65%. The curable epoxy resin composition according to claim 1, wherein 95% by weight and the proportion of the acrylic resin (B) is 5 to 35% by weight.   The curable epoxy resin composition according to claim 1 or 2, further comprising a curing agent (C) and a curing accelerator (D) or a curing catalyst (E).   Hardened | cured material obtained by hardening the curable epoxy resin composition as described in any one of Claims 1-3.   It is a resin composition for optical semiconductor sealing, The curable epoxy resin composition as described in any one of Claims 1-3.   An optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition according to claim 5.   It is a resin composition for adhesive agents, The curable epoxy resin composition as described in any one of Claims 1-3.   An optical semiconductor device in which an optical semiconductor element is bonded to an electrode with a cured product of the curable epoxy resin composition according to claim 7.

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