JP6046497B2 - Curable epoxy resin composition - Google Patents

Description

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

  In recent years, the output of optical semiconductor devices has been increased, and in such an optical semiconductor device, a resin (encapsulant) that covers the optical semiconductor element is required to have high heat resistance and light resistance. Conventionally, as a sealing agent for forming a sealing material having high heat resistance, 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 for a high-output blue / white light semiconductor, the coloring of the sealant proceeds by light and heat emitted from the optical semiconductor element and should be output originally. As a result, the light is absorbed, and as a result, the intensity of the light output from the optical semiconductor device is lowered with time.

  3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4 as a sealing agent that forms a cured product (sealing material) that has high heat resistance and light resistance and is not easily yellowed -Liquid alicyclic epoxy resins having an alicyclic skeleton such as an adduct of epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and ε-caprolactone and 1,2,8,9-diepoxylimonene are known. ing. However, the cured products of these alicyclic epoxy resins are susceptible to various stresses, and cracks are generated when a thermal shock such as a cooling cycle (repeating heating and cooling periodically) is applied. Etc. had occurred.

  In addition, an optical semiconductor device (for example, a surface-mount type optical semiconductor device) generally undergoes a reflow process for bonding an electrode of the optical semiconductor device to a wiring board by soldering. In recent years, lead-free solder having a high melting point has been used as a solder as a bonding material, and heat treatment in a reflow process has become a higher temperature (for example, a peak temperature of 240 to 260 ° C.). . Under such circumstances, in the conventional optical semiconductor device, there is a problem of deterioration such that the sealing material is peeled off from the lead frame of the optical semiconductor device due to the heat treatment in the reflow process, or the sealing material is cracked. Has occurred.

  For this reason, the sealing material in the optical semiconductor device has high heat resistance and light resistance, and also has a characteristic that cracks are not easily generated when a thermal shock is applied (sometimes referred to as “thermal shock resistance”), and Further, there is a demand for characteristics in which cracks and peeling are unlikely to occur even when heat treatment is performed in the reflow process. In particular, in recent years, from the viewpoint of ensuring higher reliability of the sealing material, the optical semiconductor device is kept under high humidity conditions for a certain period of time (for example, 168 hours under conditions of 30 ° C. and 70% RH; 60 ° C., 60% RH). The above-mentioned cracks and peeling are not likely to occur even when heat treatment is performed in the reflow process after absorbing moisture after being placed under the above conditions (for 40 hours, etc.) (this characteristic is sometimes referred to as “moisture absorption reflow resistance”). ) Is required.

JP 2000-344867 A

Accordingly, an object of the present invention is to have a high heat resistance, light resistance, and thermal shock resistance, and in particular, it is possible to form a cured product capable of improving the current-carrying characteristics and moisture absorption reflow resistance of an optical semiconductor device at high temperatures. A curable epoxy resin composition is provided.
Another object of the present invention is to provide a cured product having high heat resistance, light resistance, and thermal shock resistance, and in particular, capable of improving current-carrying characteristics and moisture absorption reflow resistance at high temperatures of an optical semiconductor device. provide.
In addition, another object of the present invention is to improve durability and quality, which is excellent in current-carrying characteristics at high temperature, further suppresses deterioration such as a decrease in luminous intensity when heat-treated in a reflow process after being stored under high humidity conditions. The object is to provide a high optical semiconductor device.

  As a result of intensive studies to solve the above problems, the present inventor has a high curable epoxy resin composition containing an alicyclic epoxy compound, a specific amount of specific core-shell polymer particles, and a specific leveling agent. The inventors have found that a cured product having heat resistance, light resistance, and thermal shock resistance, in particular, capable of improving current-carrying characteristics and moisture absorption reflow resistance of an optical semiconductor device at a high temperature can be formed, and the present invention has been completed. .

That is, the present invention relates to an alicyclic epoxy compound (A), core-shell type acrylic polymer particles (B) having a solubility parameter (Fedors method) of 19.5 to 21.5 [MPa ^1/2 ], And at least one leveling agent (C) selected from the group consisting of a leveling agent and a fluorine-based leveling agent,
The glass transition temperature of the acrylic polymer constituting the core of the core-shell type acrylic polymer particles (B) is 60 to 120 ° C., and the glass transition temperature of the acrylic polymer constituting the shell is 60 to 120 ° C.,
The content of the core-shell type acrylic polymer particles (B) is 1 to 30 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A), and a curable epoxy resin composition is provided.

［式中、Ｒ¹、Ｒ²は、同一又は異なって、水素原子又は炭素数１〜８のアルキル基を示す。］
で表されるモノアリルジグリシジルイソシアヌレート化合物（Ｄ）を含む前記の硬化性エポキシ樹脂組成物を提供する。 Further, the following formula (1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
The said curable epoxy resin composition containing the monoallyl diglycidyl isocyanurate compound (D) represented by these is provided.

［式（２）中、Ｒ³は、置換基を有していてもよい直鎖又は分岐鎖状のアルキル基を示す。Ｒ⁴は、置換基を有していてもよい直鎖若しくは分岐鎖状のアルキル基、置換基を有していてもよいアラルキル基、ポリエーテル鎖を含む有機基、又はポリエステル鎖を含む有機基を示す。］
で表される構造単位を有するシリコーン系重合体（Ｃ１）、下記式（３）

［式（３）中、Ｒ⁵は、水素原子、フッ素原子、又は、水素原子の一部若しくは全部がフッ素原子で置換されていてもよい炭素数１〜４の直鎖若しくは分岐鎖状のアルキル基を示す。Ｒ⁶は、フッ素化アルキル基を示す。］
で表される構造単位を有する含フッ素アクリル系重合体（Ｃ２）、及び下記式（４）

［式（４）中、Ｒ¹⁹は、３価の直鎖又は分岐鎖状の炭化水素基を示す。Ｒ²⁰は、フッ素化アルキル基を示す。ｚは、１〜３０の整数を示す。］
で表される構造単位を有する含フッ素ポリエーテル系重合体（Ｃ３）からなる群より選択された少なくとも１種の重合体を含むレベリング剤である前記の硬化性エポキシ樹脂組成物を提供する。 Furthermore, the leveling agent (C) is represented by the following formula (2):

[In formula (2), R ³ represents an optionally substituted straight or branched chain alkyl group. R ⁴ is a linear or branched alkyl group which may have a substituent, an aralkyl group which may have a substituent, an organic group containing a polyether chain, or an organic group containing a polyester chain Indicates. ]
Silicone polymer (C1) having a structural unit represented by the following formula (3)

[In the formula (3), R ⁵ represents a hydrogen atom, a fluorine atom, or a linear or branched alkyl having 1 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a fluorine atom. Indicates a group. R ⁶ represents a fluorinated alkyl group. ]
And a fluorine-containing acrylic polymer (C2) having a structural unit represented by the following formula (4):

[In the formula (4), R ¹⁹ represents a trivalent linear or branched hydrocarbon group. R ²⁰ represents a fluorinated alkyl group. z shows the integer of 1-30. ]
The curable epoxy resin composition is a leveling agent comprising at least one polymer selected from the group consisting of a fluorine-containing polyether polymer (C3) having a structural unit represented by:

  Furthermore, the curable epoxy resin composition is provided in which the alicyclic epoxy compound (A) is a compound having a cyclohexene oxide group.

で表される化合物である前記の硬化性エポキシ樹脂組成物を提供する。 Furthermore, the alicyclic epoxy compound (A) is represented by the following formula (I-1)

The said curable epoxy resin composition which is a compound represented by these is provided.

  Furthermore, the said curable epoxy resin composition containing a rubber particle is provided.

  Furthermore, the said curable epoxy resin composition containing a hardening | curing agent (E) and a hardening accelerator (F), or a hardening catalyst (G) is provided.

  Moreover, this invention provides the hardened | cured material obtained by hardening | curing 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.

  Since the curable epoxy resin composition of the present invention has the above-described configuration, it has high heat resistance, light resistance, and thermal shock resistance by curing the resin composition. A cured product capable of improving characteristics and moisture absorption reflow resistance can be formed. For this reason, when the curable epoxy resin composition of the present invention is used as a resin composition for optical semiconductor encapsulation, deterioration such as a decrease in luminous intensity is unlikely to occur especially under severe conditions at high temperatures. It is possible to obtain an optical semiconductor device having high durability and high quality, which is less likely to deteriorate such as a decrease in luminous intensity even when heat treatment is performed in a reflow process after storage under conditions.

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 an alicyclic epoxy compound (A) and core-shell type acrylic polymer particles (B) having a solubility parameter (Fedors method) of 19.5 to 21.5 [MPa ^1/2 ]. ) (Simply referred to as “core-shell type acrylic polymer particles (B)”) and at least one leveling agent (C) selected from the group consisting of silicone leveling agents and fluorine leveling agents (simply referred to as “leveling”). A resin composition (curable composition) at least.

[Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in the molecule (in one molecule). As the alicyclic epoxy compound (A), specifically, (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, (Ii) A compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and the like.

  The compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (i) is arbitrarily selected from known or commonly used compounds. Can be used. Especially, as said alicyclic epoxy group, a cyclohexene oxide group is preferable.

As the compound (i) having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, a compound having a cyclohexene oxide group is preferable from the viewpoint of transparency and heat resistance. In particular, a compound (alicyclic epoxy compound) represented by the following formula (I) is preferable.

  In the above formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked.

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

  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 a cyclohexylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

  As the linking group X, a linking group containing an oxygen atom is particularly preferable. Specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-; A group in which a plurality of 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.

Typical examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10). In the following formulas (I-5) and (I-7), l and m each represent an integer of 1 to 30. R in the following formula (I-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 (I-9) and (I-10) each represent an integer of 1 to 30.

Examples of the compound (ii) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).

In the formula (II), R ′ is a group obtained by removing p —OH from a p-valent alcohol, and p and n each represent a natural number. Examples of the p-valent alcohol [R ′-(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (such as alcohols having 1 to 15 carbon atoms). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each () (in parentheses) may be the same or different. Specifically, as the above compound, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, trade name “EHPE3150” (Co., Ltd.) Daicel) and the like.

  In the curable epoxy resin composition of the present invention, the alicyclic epoxy compound (A) can be used singly or in combination of two or more. In addition, as the alicyclic epoxy compound (A), for example, commercially available products such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) may be used.

  As the alicyclic epoxy compound (A), 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate represented by the above formula (I-1) [for example, trade name “Celoxide 2021P” (( Etc.) are particularly preferred.

  Although content (blending amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, it is 10 to 98 with respect to the curable epoxy resin composition (100% by weight). % By weight is preferred, more preferably 15 to 95% by weight, and still more preferably 20 to 95% by weight. When content of an alicyclic epoxy compound (A) remove | deviates from the said range, the heat resistance and light resistance of hardened | cured material may become inadequate.

  Further, the content (blending amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, but the curable epoxy resin composition of the present invention is a curing agent (E ) As an essential component, it is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, still more preferably 20 to 70% by weight, based on the curable epoxy resin composition (100% by weight). It is. On the other hand, when the curable epoxy resin composition of the present invention contains a curing catalyst (G) described later as an essential component, the content (blending amount) of the alicyclic epoxy compound (A) is determined by the curable epoxy resin composition. The amount is preferably 25 to 98% by weight, more preferably 30 to 95% by weight, and still more preferably 35 to 95% by weight with respect to the product (100% by weight).

  The content (blending amount) of the alicyclic epoxy compound (A) with respect to the total amount of the compounds having an epoxy group contained in the curable epoxy resin composition (total epoxy compound) (100 wt%) is not particularly limited, but 60 % By weight or more (for example, 60 to 100% by weight) is preferable, more preferably 65% by weight or more, and still more preferably 70% by weight or more. When the content of the alicyclic epoxy compound (A) is less than 60% by weight, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be lowered.

[Core-shell type acrylic polymer particles (B)]
The core-shell type acrylic polymer particle (B) in the curable epoxy resin composition of the present invention has a core-shell structure comprising a core and a single-layer or multi-layer shell layer (shell) covering the core, Both shell layers are polymer particles composed of an acrylic polymer (a polymer having an acrylic monomer as an essential monomer component). As described later, the curable epoxy resin composition of the present invention contains core-shell type acrylic polymer particles (B), thereby forming a cured product having excellent handleability at room temperature and excellent moisture absorption resistance. it can.

  In this specification, the acrylic polymer constituting the core of the core-shell type acrylic polymer particle (B) is referred to as “acrylic polymer [core]”, and the acrylic polymer constituting the core of the core-shell type acrylic polymer particle is referred to as “acrylic polymer [ Shell] ”. The core-shell type acrylic polymer particles are not particularly limited, but the acrylic polymer [core] and the acrylic polymer [shell] preferably have different compositions.

The solubility parameter (δ) at 25 ° C. (referred to as “solubility parameter (Fedors method)”) calculated by the Fedors method of the core-shell type acrylic polymer particles (B) is 19.5 to 21.5 [MPa ^1/2 ]. Yes, preferably 19.7 to 21.3 [MPa ^1/2 ], more preferably 20.0 to 21.0 [MPa ^1/2 ]. If the solubility parameter (Fedors method) of the core-shell type acrylic polymer particles (B) is less than 19.5 [MPa ^1/2 ], the compatibility with the alicyclic epoxy compound (A) may be reduced, Reduces heat resistance, moisture absorption reflow resistance, and thermal shock resistance. In general, monomers resulting from low solubility parameters (eg, (meth) acrylic acid alkyl esters having long chain alkyl groups) tend to lower the glass transition temperature, so such monomer units When a large amount of is contained, the heat resistance, moisture absorption reflow resistance and impact resistance of the cured product tend to be reduced. On the other hand, when the solubility parameter (Fedors method) of the core-shell type acrylic polymer particles (B) exceeds 21.5 [MPa ^1/2 ], the compatibility with the alicyclic epoxy compound (A) is reduced, or the cured product Hygroscopic reflow resistance of the is reduced. In general, a monomer resulting from a high solubility parameter has a hydrophilic functional group (for example, carboxyl group or nitrile group). Reflowability tends to decrease. The solubility parameter (Fedors method) of the core-shell type acrylic polymer particles (B) is calculated by, for example, calculating the solubility parameter (Fedors method) of the acrylic polymer [core] and the acrylic polymer [shell], respectively, and calculating a weighted average thereof. can do. The solubility parameter (Fedors method) of the core-shell type acrylic polymer particles (B) is controlled by the composition of the monomers constituting the core-shell type acrylic polymer particles (B).

The glass transition temperature of the acrylic polymer [core] is 60 to 120 ° C, preferably 70 to 110 ° C, more preferably 80 to 100 ° C. The heat resistance of hardened | cured material falls that the glass transition temperature of acrylic polymer [core] is less than 60 degreeC. On the other hand, when the glass transition temperature of the acrylic polymer [core] exceeds 120 ° C., for example, there are many monomer components (for example, (meth) acrylic acid, etc.) that contribute to a high glass transition temperature. Reflowability may be reduced. The glass transition temperature of the acrylic polymer [core] means a calculated value calculated by the following Fox equation (see Bull. Am. Phys. Soc., 1 (3) 123 (1956)). Wherein the following Fox, Tg is the glass transition temperature of the acrylic polymer (unit: K) indicates, W _i represents the weight fraction of the monomer i for the monomer total amount constituting the acrylic polymer. Further, Tg _i is the glass transition temperature of the homopolymer of monomer i (unit: K) shows a. The following Fox formula shows the formula when the acrylic polymer is a copolymer of monomer 1, monomer 2,..., And monomer n.
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n
As the glass transition temperature of the homopolymer, values described in various documents can be adopted, for example, values described in “POLYMER HANDBOOK 3rd edition” (published by John Wiley & Sons, Inc.) can be adopted. In addition, about the thing which is not described in literature, the value of the glass transition temperature measured by DSC of the homopolymer obtained by superposing | polymerizing a monomer by a conventional method is employable.

  The glass transition temperature of the acrylic polymer [core] is controlled by the composition of the monomers constituting the acrylic polymer [core].

  The glass transition temperature of the acrylic polymer [shell] is 60 to 120 ° C, preferably 70 to 115 ° C. The heat resistance of hardened | cured material falls that the glass transition temperature of acrylic polymer [shell] is less than 60 degreeC. On the other hand, when the glass transition temperature of the acrylic polymer [shell] exceeds 120 ° C., for example, there are many monomer components (for example, (meth) acrylic acid, etc.) that contribute to a high glass transition temperature, so that the cured product has moisture absorption resistance. In some cases, the reflowability may decrease, and the long-term storage stability may deteriorate due to thickening or the like. The glass transition temperature of the acrylic polymer [shell] means a value calculated by the above Fox equation, and can be calculated in the same manner as the glass transition temperature of the acrylic polymer [core]. The glass transition temperature of the acrylic polymer [shell] is controlled by the composition of the monomers constituting the acrylic polymer [shell].

  Difference between glass transition temperature of acrylic polymer [core] and glass transition temperature of acrylic polymer [shell] in core-shell type acrylic polymer particles (B) [glass transition temperature of acrylic polymer [shell]-glass transition of acrylic polymer [core] The temperature] is not particularly limited, but is preferably -5 to 60 ° C, more preferably 0 to 55 ° C. By controlling the difference in the glass transition temperature within the above range, the adhesion of the curable epoxy resin composition at the time of curing is improved, the moisture absorption reflow resistance of the cured product is improved, and the heat resistance of the cured product is further improved. Tend to improve.

  The acrylic polymer [core] and the acrylic polymer [shell] are acrylic polymers each composed of an acrylic monomer (acrylic monomer) as an essential monomer component.

Examples of the acrylic monomer constituting the acrylic polymer [core] and acrylic polymer [shell] include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth ) I-propyl acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n- (meth) acrylate Heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, i-nonyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid alkyl esters such as dodecyl, stearyl (meth) acrylate; cyclohexyl (meth) acrylate, (meth) Acrylic acid t- butyl cyclohexyl (meth) acrylate, isobornyl (meth) acrylic acid tricyclo [5.2.1.0 ^2.6] decan-8-yl, (meth) aliphatic, such as acrylic acid dicyclopentadienyl (Meth) acrylic acid ester having a ring (alicyclic ring); (meth) acrylic acid ester having an aromatic ring such as phenyl (meth) acrylate and benzyl (meth) acrylate; N-methyl-2,2,6 , 6- (Tetramethylpiperidyl (meth) acrylate) -containing (meth) acrylic acid ester; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 4- (Meth) acrylic acid ester having a hydroxyl group such as hydroxybutyl and glycerol mono (meth) acrylate; ) (Meth) acrylic acid ester having an epoxy group such as glycidyl acrylate and methyl glycidyl (meth) acrylate; (meth) acrylic acid ester having an amino group such as N, N-dimethylaminoethyl (meth) acrylate; (Meth) acrylic acid; (meth) acrylamide etc. are mentioned. In the present specification, “(meth) acryl” means acrylic and / or methacrylic (any one or both of acrylic and methacrylic).

  As monomers constituting the acrylic polymer [core] and acrylic polymer [shell], monomers other than acrylic monomers can be used in combination. Examples of monomers other than the acrylic monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyl toluene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; crotonic acid , Monomers having a carboxyl group such as itaconic acid, fumaric acid and maleic acid; vinyl monomers such as vinyl pyridine, vinyl alcohol, vinyl imidazole, vinyl pyrrolidone, vinyl acetate and 1-vinyl imidazole; monomethyl itaconate, mono Itaconic esters such as ethyl itaconate, monopropyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dipropyl itaconate, dibutyl itaconate; monomethyl fumarate, monoethyl fumarate, monopropyl fumarate , Monobutyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, etc. fumarate; monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, dimethyl maleate , Maleate esters such as diethyl maleate, dipropyl maleate and dibutyl maleate.

  Moreover, as a monomer which comprises the said acrylic polymer [core] and acrylic polymer [shell], the polyfunctional monomer which has two or more polymerizable functional groups (for example, an aliphatic carbon-carbon double bond etc.). The body can also be used. Examples of the polyfunctional monomer include divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, and the like.

  Although the ratio of the acrylic monomer to the total amount (100% by weight) of the monomer constituting the acrylic polymer [core] is not particularly limited, it is preferably 70 to 100% by weight. In particular, the acrylic polymer [core] is a polymer substantially composed of only an acrylic monomer (for example, a polymer whose ratio of acrylic monomer to the total amount of monomers is 98 to 100% by weight). It is preferable that As the monomer constituting the acrylic polymer [core], (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl methacrylate, butyl acrylate, methacrylic acid are more preferable. Butyl.

  The ratio of the acrylic monomer to the total amount (100% by weight) of the monomer constituting the acrylic polymer [shell] is not particularly limited, but is preferably 70 to 100% by weight. In particular, the above-mentioned acrylic polymer [shell] is a polymer composed substantially of only an acrylic monomer (for example, a polymer whose ratio of the acrylic monomer to the total amount of the monomer is 98 to 100% by weight. It is preferable that As a monomer which comprises the said acrylic polymer [shell], the (meth) acrylic acid alkyl ester and (meth) acrylic acid which have a C1-C4 alkyl group are preferable, More preferably, methyl methacrylate, They are butyl acrylate, butyl methacrylate, and methacrylic acid.

  That is, the core-shell type acrylic polymer particle (B) is a polymer substantially composed only of an acrylic monomer (for example, acrylic based on the total amount of monomers constituting the core-shell type acrylic polymer particle (B)). Polymers having a monomer ratio of 98 to 100% by weight) are preferably core-shell type acrylic polymer particles.

  When a large amount of vinyl cyanide monomer such as (meth) acrylonitrile is used as a monomer constituting the acrylic polymer [core] and the acrylic polymer [shell], the monomer has high polarity and is cured. This is not preferable because the moisture absorption reflow resistance of the product tends to decrease. In addition, when a large amount of an aromatic vinyl monomer such as styrene, α-methylstyrene, vinyltoluene or the like is used as a monomer constituting the acrylic polymer [core] and the acrylic polymer [shell], the cured product is colored. Since it becomes easy, it is not preferable. Therefore, the ratio of the vinyl cyanide monomer and the aromatic vinyl monomer to the total amount (100% by weight) of the monomer constituting the acrylic polymer [core] (or acrylic polymer [shell]) is 5% by weight. The following is preferable, more preferably 2% by weight or less, and it is particularly preferable that it is not substantially contained (not actively blended as a monomer component).

  Moreover, it is preferable that a core-shell type acrylic polymer particle (B) does not contain a butadiene rubber from a viewpoint of suppressing coloring and deterioration of hardened | cured material. Moreover, it is preferable that a core-shell type acrylic polymer particle (B) does not contain a silicone rubber from a viewpoint of compatibility or cost.

  The ratio (weight ratio) [acrylic polymer [core] / acrylic polymer [shell]] of acrylic polymer [core] and acrylic polymer [shell] in the core-shell type acrylic polymer particles (B) is not particularly limited, but is 1 / 0.0. 1-1000 is preferable, More preferably, it is 1 / 0.3 to 1/120, More preferably, it is 1 / 0.4 to 1/10. If the ratio of the acrylic polymer [core] and the acrylic polymer [shell] is out of the above range, it will be difficult to obtain the effect of improving the adhesion to the adherend described below and quickly increasing the viscosity by heating. As a result, the curable epoxy resin The effect of improving the handleability of the composition and improving the moisture absorption reflow resistance of the cured product may not be obtained.

  As a particularly preferable specific embodiment of the core-shell type acrylic polymer particle (B), for example, a monomer having an essential alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (particularly, methyl methacrylate or butyl methacrylate). A methacrylic acid alkyl ester (especially methyl methacrylate, butyl methacrylate) having an acrylic polymer [core] having a glass transition temperature of 60 to 120 ° C. as a core and an alkyl group having 1 to 4 carbon atoms is essential. Examples of the polymer component include core-shell type acrylic polymer particles having a monomer component, an acrylic polymer [shell] having a glass transition temperature of 60 to 120 ° C. and a monomer composition different from that of the acrylic polymer [core]. The acrylic polymer [shell] further includes a monomer having a hydroxyl group (for example, a (meth) acrylic acid ester having a hydroxyl group) and / or a monomer having a carboxyl group (for example, (meth) acrylic acid). It is preferably contained as a monomer component. The shell may be a single layer or a multilayer. The ratio of the alkyl methacrylate having 1 to 4 carbon atoms to the total amount (100% by weight) of the monomer component constituting the acrylic polymer [core] is preferably 60% by weight or more, more preferably 80%. % By weight or more. Further, the ratio of the alkyl methacrylate having a C 1-4 alkyl group to the total amount (100% by weight) of the monomer component constituting the acrylic polymer [shell] is preferably 60% by weight or more, more preferably. Is 80% by weight or more.

  The content of alkali metal ions (for example, Na ions, K ions, etc.) in the core-shell type acrylic polymer particles (B) is not particularly limited, but is preferably 10 ppm or less, more preferably 5 ppm or less, and even more preferably 1 ppm or less. . If the content of alkali metal ions exceeds 10 ppm, the insulating properties of the cured product may be deteriorated. The content of the alkali metal ions can be measured using, for example, an ICP emission analyzer or ion chromatography. In addition, content of the said alkali metal ion can be controlled by selection of the polymerization initiator and emulsifier used for superposition | polymerization, for example.

  The average secondary particle diameter of the core-shell type acrylic polymer particles (B) is not particularly limited, but is preferably 5 to 50 μm. When the average secondary particle size is less than 5 μm, it is easy to fly and static electricity easily occurs, which may be difficult to handle. On the other hand, if the average secondary particle diameter exceeds 50 μm, there may be a large time load when dispersed in the primary particles. The said average secondary particle diameter can be measured using electron microscopes, such as a scanning electron microscope (SEM) and a transmission electron microscope (TEM), for example. The average secondary particle diameter can be controlled by, for example, granulation conditions, drying conditions (temperature, air volume), and the like.

  The volume average primary particle diameter (Dv) of the core-shell type acrylic polymer particles (B) is not particularly limited, but is preferably 200 nm or more, and more preferably 500 nm or more. Further, the volume average primary particle diameter of the core-shell type acrylic polymer particles (B) is preferably 8 μm or less, more preferably 5 μm or less, and further preferably 1 μm or less. If the volume average primary particle diameter is less than 200 nm, the dispersibility may decrease. On the other hand, if the volume average primary particle diameter exceeds 8 μm, the transparency of the cured product may be lowered. The volume average primary particle size can be measured using, for example, a laser diffraction / scattering particle size distribution analyzer (for example, trade name “LA-910W”, manufactured by Horiba, Ltd.). In addition, the said volume average primary particle diameter can be controlled by the conditions at the time of emulsification of a monomer, etc., for example.

  The monodispersity of the core-shell type acrylic polymer particles (B) (the ratio of the volume average primary particle diameter Dv to the number average primary particle diameter Dn [Dv / Dn]) is not particularly limited, but is preferably 3.0 or less, more preferably Is 2.0 or less, more preferably 1.5 or less. When Dv / Dn exceeds 3.0, the moisture absorption reflow resistance and thermal shock resistance of the cured product may decrease. The Dv / Dn can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus (for example, trade name “LA-910W”, manufactured by Horiba, Ltd.). The Dv / Dn can be controlled by, for example, the conditions during the emulsification of the monomer.

  The core-shell type acrylic polymer particles (B) can be produced by using a known or conventional method for producing core-shell type polymer particles. The core-shell type acrylic polymer particles (B) can be obtained by coating the core with a shell. For example, the core-shell type acrylic polymer particles (B) can be obtained by coating the surface of the core with an acrylic polymer that constitutes the shell, or the acrylic polymer that constitutes the core. Examples thereof include a method of graft polymerization of an acrylic polymer (branch component) constituting the shell as a component. More specifically, the core-shell type acrylic polymer particles (B) can be produced, for example, according to the method disclosed in International Publication 2010/090246.

  In the curable epoxy resin composition of the present invention, the core-shell type acrylic polymer particles (B) can be used singly or in combination of two or more. As the core-shell type acrylic polymer particles (B), commercially available products such as trade names “METABBRENE KP-0917”, “METABBRENE KP-0930”, “METABBRENE KP-0950” (manufactured by Mitsubishi Rayon Co., Ltd.) are available. It can also be used.

  The content (blending amount) of the core-shell type acrylic polymer particles (B) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). When the content of the core-shell type acrylic polymer particles (B) is less than 1 part by weight, the effect of adding the core-shell type acrylic polymer particles (B) is difficult to obtain, and the moisture absorption reflow resistance and thermal shock resistance of the cured product are poor. Become. On the other hand, when the content of the core-shell type acrylic polymer particles (B) exceeds 30 parts by weight, the curable epoxy resin composition is thickened and handling is not easy.

  The curable epoxy resin composition of the present invention containing the alicyclic epoxy compound (A) and the core-shell type acrylic polymer particles (B) as essential components has high heat resistance, light resistance, and thermal shock resistance. Gives a cured product excellent in moisture absorption and reflow resistance. These effects (particularly, the effect of improving moisture absorption reflow resistance) in the cured product are as follows. The core-shell type acrylic polymer particles (B) in the curable epoxy resin composition have a core-shell structure, and the glass transition temperature between the core and the shell. By controlling the solubility parameter within a specific range, mainly the adhesion of the cured product to the adherend (especially a silver electrode in an optical semiconductor device) is improved, and further, the viscosity is rapidly increased by heating ( It is presumed that the effect is due to the shape being held (fixed) before being completely cured. In the case where a general acrylic polymer (linear polymer or the like) is used instead of the core-shell type acrylic polymer particles (B), the above-described effects of improving adhesiveness and thickening by heating cannot be obtained. For example, since the resin composition that is remarkably reduced in viscosity by heating is easily deformed in shape, it is liable to cause defects (for example, reduced moisture absorption reflow resistance) due to such deformation. Moreover, since the curable epoxy resin composition of this invention containing a core-shell type acrylic polymer particle (B) has a comparatively low viscosity at room temperature as mentioned later, it is excellent also in handleability.

  In addition, the thickening effect by heating of the above-mentioned curable epoxy resin composition is particularly when the core-shell type acrylic polymer (B) is heated (particularly in the vicinity of Tg of the core or shell, specifically 80 to 90 ° C. Core-shell type in which the alicyclic epoxy compound (A) is swollen by being controlled to a specific range in the solubility parameter (Fedors method) of the core-shell type acrylic polymer (B). It is presumed that this is an effect obtained by being able to easily penetrate into the shell layer (surface layer) of acrylic polymer particles.

[Leveling agent (C)]
The leveling agent (C) constituting the curable epoxy resin composition of the present invention is at least one leveling agent selected from the group consisting of a silicone leveling agent (polysiloxane leveling agent) and a fluorine leveling agent. . By including the leveling agent (C), the curable epoxy resin composition of the present invention can form a cured product having excellent heat resistance, light resistance, and crack resistance, and using the cured product. The produced optical semiconductor device is unlikely to have a decrease in light intensity over time.

(Silicone leveling agent)
The silicone leveling agent is a leveling agent containing a compound having a polysiloxane skeleton. As the silicone leveling agent, known or conventional silicone leveling agents can be used, and are not particularly limited. For example, trade names “BYK-300”, “BYK-301 / 302”, “BYK-306”, “ BYK-307 "," BYK-310 "," BYK-315 "," BYK-313 "," BYK-320 "," BYK-322 "," BYK-323 "," BYK-325 "," BYK- " 330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-341 "," BYK-344 "," BYK-345 / 346 "," BYK-347 "," BYK- " 348 "," BYK-349 "," BYK-370 "," BYK-375 "," BYK-377 "," BYK-378 "," BYK-UV3500 "," YK-UV3510 ”,“ BYK-UV3570 ”,“ BYK-3550 ”,“ BYK-SILCLEAN3700 ”,“ BYK-SILCLEAN3720 ”(manufactured by Big Chemie Japan Co., Ltd.); trade names“ AC FS 180 ”,“ AC "FS 360", "AC S 20" (manufactured by Algin Chemie); trade names "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL" -403 "," Polyflow KL-404 "(manufactured by Kyoeisha Chemical Co., Ltd.); trade names" KP-323 "," KP-326 "," KP-341 "," KP-104 "," KP- 110 ”,“ KP-112 ”(manufactured by Shin-Etsu Chemical Co., Ltd.); trade name“ LP-7001 ”, LP-7002 ”,“ 8032 ADDIIVE ”,“ 57 ADDIIVE ”,“ L-7604 ”,“ FZ-2110 ”,“ FZ-2105 ”,“ 67 ADDITION ”,“ 8618 ADDIIVE ”,“ 3 ADDITIVE ”,“ 56 Commercial products such as “ADDITIVE” (made by Toray Dow Corning Co., Ltd.) can be used.

As the compound having a polysiloxane skeleton, in particular, a silicone polymer having at least a structural unit (repeating structural unit) represented by the following formula (2) (hereinafter referred to as “silicone polymer (C1)”) Is preferred). In other words, the silicone leveling agent is preferably a leveling agent containing at least the silicone polymer (C1).

R ³ in the above formula (2) represents a linear or branched alkyl group which may have a substituent. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), an isobutyl group, a s-butyl group, a t-butyl group, and pentyl. C1-C30 linear or branched alkyl groups, such as group, are mentioned.

In R ³ , the substituent that the linear or branched alkyl group may have is not particularly limited. For example, a hydroxyl group that may be protected with a protecting group [for example, a hydroxyl group, A substituted oxy group (for example, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group)], a carboxyl group that may be protected with a protecting group [for example, a —COOR ^a group, etc .: R ^a Represents a hydrogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and a hexyl group. A linear or branched alkyl group having 1 to 6 carbon atoms], acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl , Propenyl group, an epoxy group, such as glycidyl groups.

R ⁴ in the above formula (2) is a linear or branched alkyl group which may have a substituent, an aralkyl group which may have a substituent, an organic group containing a polyether chain, Or the organic group containing a polyester chain | strand is shown. Examples of the linear or branched alkyl group represented by R ^4, is not particularly limited, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group (n- butyl group), an isobutyl group, s- butyl C1-C30 linear or branched alkyl groups, such as a group, t-butyl group, and pentyl group. The aralkyl group is not particularly limited, and examples thereof include a benzyl group, a methylbenzyl group, a phenethyl group, a methylphenethyl group, a phenylpropyl group, and a naphthylmethyl group.

In R ⁴ , the substituent that the linear or branched alkyl group may have and the substituent that the aralkyl group may have are not particularly limited. For example, in R ³ described above, Examples thereof include the exemplified substituents.

The organic group containing a polyether chain in R ⁴ is a monovalent organic group containing at least a polyether structure. The polyether structure in the organic group containing a polyether chain is not particularly limited as long as it has a structure having a plurality of ether bonds. For example, polyethylene glycol structure (polyethylene oxide structure), polypropylene glycol structure (polypropylene oxide structure) And polyoxyalkylene structures such as polybutylene glycol (polytetramethylene glycol) structures and polyether structures derived from multiple types of alkylene glycol (or alkylene oxide) (for example, poly (propylene glycol / ethylene glycol) structures). It is done. In addition, the addition form of each alkylene glycol in the polyether structure derived from a plurality of types of alkylene glycols may be a block type (block copolymer type) or a random type (random copolymer type). Also good.

  The organic group containing the polyether chain may be an organic group consisting only of the polyether structure, or one or two or more of the polyether structure and one or two or more linking groups (one or more atoms may be bonded). It may be an organic group having a structure in which a divalent group) is linked. Examples of the linking group in the organic group containing a polyether chain include, for example, a divalent hydrocarbon group (particularly, a linear or branched alkylene group), a thioether group (—S—), an ester group (—COO—). ), An amide group (—CONH—), a carbonyl group (—CO—), a carbonate group (—OCOO—), a group in which two or more of these are bonded, and the like.

In addition, the organic group containing the polyether chain is the substituent exemplified in the above R ³ (for example, hydroxyl group, carboxyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, etc. For example, as an organic group containing such a polyether structure, an organic group having the above substituent at the terminal (end on the opposite side to the silicon atom in the formula (2)) may be mentioned. It is done.

The organic group containing a polyester chain in R ⁴ is a monovalent organic group containing at least a polyester structure. The polyester structure in the organic group containing a polyester chain is not particularly limited as long as it has a structure having a plurality of ester bonds, and examples thereof include an aliphatic polyester structure, an alicyclic polyester structure, and an aromatic polyester structure. .

  More specifically, examples of the polyester structure include a polyester structure formed by polymerization of polycarboxylic acid (particularly dicarboxylic acid) and polyol (particularly diol). The polycarboxylic acid is not particularly limited, and examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides and esters); adipic acid and sebacic acid Aliphatic dicarboxylic acids such as azelaic acid, succinic acid, fumaric acid, maleic acid (including derivatives such as acid anhydrides and esters); 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 -Cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, highmic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, Has an alicyclic structure such as 2,7-decahydronaphthalenedicarboxylic acid A carboxylic acid (including derivatives such as acid anhydrides and esters). Examples of the polyol include, but are not limited to, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4- Butanediol (tetramethylene glycol), neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4- Trimethyl-1,6-hexanediol, 3-methylpentanediol, diethylene glycol, dipropylene glycol, hexylene glycol (2-methylpentane-2,4-diol), 3-methyl-1,5-pentanediol, 2- Methyl-1,5-pentanediol, 2,3,5-trime 1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, Diols (including their derivatives) such as 8-octanediol, 1,12-dodecanediol, xylylene glycol, 1,3-dihydroxyacetone, polybutadienediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A ); 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, bis (hydroxymethyl) tricyclo [5.2.1.0] ] 5-membered ring diol such as decane, 1,2-cyclohexanediol 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol (1,2-dimethylolcyclohexane), 1,3-cyclohexanedimethanol (1,3-dimethylolcyclohexane), 1, Diols having an alicyclic structure such as 4-membered diol such as 4-cyclohexanedimethanol (1,4-dimethylolcyclohexane), 2,2-bis- (4-hydroxycyclohexyl) propane, and hydrogenated bisphenol A (these Derivatives), polyols having three or more hydroxyl groups such as glycerin, trimethylolpropane, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, pentaerythritol (including these derivatives), and the like. . Each of the polyester structures may be formed from a single polyol or polycarboxylic acid, or may be formed from two or more polyols or polycarboxylic acids.

  Examples of the polyester structure include a polyester structure formed by polymerization of hydroxycarboxylic acid and a polyester structure formed by polymerization (ring-opening polymerization) of a lactone that is a cyclic ester of the hydroxycarboxylic acid. The hydroxycarboxylic acid is not particularly limited. For example, p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid (salicylic acid), 3-methoxy-4-hydroxybenzoic acid (vanillic acid), 4 -Methoxy-3-hydroxybenzoic acid (isovanillic acid), 3,5-dimethoxy-4-hydroxybenzoic acid (syringic acid), 2,6-dimethoxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid 4-methyl-3-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 4-phenyl-3-hydroxybenzoic acid, 2-phenyl-4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3,4-dihydroxycinnamic acid (caffeic acid), (E) -3- (4-hydroxy-3-methoxy-phenyl) Nyl) propane-2-enolic acid (ferulic acid), hydroxy aromatic carboxylic acids such as 3- (4-hydroxyphenyl) -2-propenonic acid (coumaric acid); hydroxy such as glycolic acid, lactic acid, tartaric acid, citric acid Aliphatic carboxylic acid etc. are mentioned. Although it does not specifically limit as said lactone, For example, (gamma) -butyrolactone, (delta) -valerolactone, (epsilon) -caprolactone, (xi) -enanthlactone, (eta) -caprolactone, etc. are mentioned. The polyester structure may be formed from a single hydroxycarboxylic acid or lactone, or may be formed from two or more hydroxycarboxylic acids or lactones.

  The polyester structure is not limited to the structure exemplified above. For example, the polyester structure formed by polymerization of the above polycarboxylic acid and polyol, the polyester structure formed by polymerization of hydroxycarboxylic acid, and the polymerization of lactone. A structure in which two or more of the formed polyester structures are combined may be used.

  The organic group containing the polyester chain may be an organic group consisting only of the polyester structure, or an organic group having a structure in which one or two or more of the polyester structures and one or two or more connecting groups are connected. It may be. Examples of the linking group in the organic group containing a polyester chain include a divalent hydrocarbon group (particularly, a linear or branched alkylene group), a thioether group (—S—), and an ester group (—COO—). Amide group (—CONH—), carbonyl group (—CO—), carbonate group (—OCOO—), a group in which two or more of these are bonded, and the like.

The organic group containing the polyester chain is the substituent exemplified in the above R ³ (for example, hydroxyl group, carboxyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, etc.) For example, examples of the organic group including such a polyester structure include an organic group having the above substituent at the terminal (end on the opposite side to the silicon atom in Formula (2)).

  The silicone polymer (C1) may be a polymer having only a structural unit represented by the formula (2) as a repeating structural unit, or a structure other than the structural unit represented by the formula (2). It may be a polymer having units. The structural unit other than the structural unit represented by the formula (2) in the silicone polymer is not particularly limited, and examples thereof include a structural unit having a hydrosilyl group (Si—H). The silicone polymer (C1) may be a polymer having only one type of structural unit represented by the formula (2), or two or more types of structural units represented by the formula (2). It may be a polymer. Moreover, the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (2) may be sufficient.

Specific examples of the silicone polymer (C1) include polymers represented by the following formulas (2a) to (2e) (polydimethylsiloxane or modified polydimethylsiloxane).

The silicone polymer (C1) represented by the above formula (2a) is polydimethylsiloxane. The x1 (the number of repeating dimethylsilyloxy structural units [—Si (CH ₃ ) ₂ —O—]) in the formula (2a) is not particularly limited, but preferably 2 to 3000, more preferably 3 to 1500.

The silicone-based polymer (C1) represented by the above formula (2b) is a polydimethylsiloxane modified polyether in which a polyether structure is introduced into the side chain of the polydimethylsiloxane. R ⁷ in formula (2b) represents a hydrogen atom or a methyl group. R ⁸ represents a hydrogen atom or a linear or branched alkyl group which may have a substituent. In addition, as a substituent in R < ⁸ >, the substituent illustrated in the above-mentioned R < ³ > is mentioned. Although q1 (the number of repeating methylene structural units) in the formula (2b) is not particularly limited, for example, it can be appropriately selected from the range of 1-30. Moreover, r1 (the number of repeating oxyethylene structural units or oxypropylene structural units) is not particularly limited, but can be appropriately selected from a range of 2 to 3000, for example. Moreover, although y1 (The repeating number of the structural unit containing a polyether structure (polyether side chain)) in Formula (2b) is not specifically limited, 1-3000 are preferable, More preferably, it is 3-1500. Furthermore, x2 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 2 to 3000, and more preferably 3 to 1500. The addition form of the structural unit having a polyether structure and the dimethylsilyloxy structural unit in the silicone polymer (C1) represented by the formula (2b) may be a block type or a random type. May be. Moreover, when y1 is an integer greater than or equal to 2, the structural unit which has the polyether structure enclosed by the parenthesis to which y1 was attached | subjected may be the same respectively, and may differ.

The silicone polymer (C1) represented by the above formula (2c) is a polydimethylsiloxane long-chain alkyl-modified product (polymethylsiloxane) in which a side chain of polydimethylsiloxane is introduced with an alkyl group that is longer than a methyl group. Alkylsiloxane). R ⁹ in the formula (2c) represents a linear or branched alkyl group having 2 or more carbon atoms. Y2 (the number of repeating methylalkylsilyloxy structural units) in the formula (2c) is not particularly limited, but is preferably 2 to 3000, more preferably 3 to 1500. Further, x3 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 0 to 3000, and more preferably 2 to 1500. In addition, the addition form of the methylalkylsilyloxy structural unit and the dimethylsilyloxy structural unit in the silicone-based polymer (C1) represented by the formula (2c) may be a block type or a random type. Also good. In addition, the methylalkylsilyloxy structural units surrounded by parentheses with y2 may be the same or different.

  The silicone polymer (C1) represented by the above formula (2d) is an aralkyl modified product of polydimethylsiloxane in which an aralkyl group is introduced into the side chain of polydimethylsiloxane. Although q2 (the number of repeating methylene structural units) in the formula (2d) is not particularly limited, for example, it can be appropriately selected from the range of 1-30. Further, y3 (the number of repeating methylaralkylsilyloxy structural units) is not particularly limited, but is preferably 2 to 3000, and more preferably 3 to 1500. Further, x4 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 0 to 3000, and more preferably 2 to 1500. The addition form of the methylaralkylsilyloxy structural unit and the dimethylsilyloxy structural unit in the silicone-based polymer (C1) represented by the formula (2d) may be a block type or a random type. Also good. The methylaralkylsilyloxy structural units enclosed in parentheses with y3 may be the same or different.

The silicone-based polymer (C1) represented by the above formula (2e) is a polyester modified body of polydimethylsiloxane in which a polyester structure is introduced into the side chain of polydimethylsiloxane. R ¹⁰ and R ¹¹ in formula (2e) are the same or different and represent a divalent organic group (for example, a divalent hydrocarbon group). R ¹² represents a hydrogen atom or a linear or branched alkyl group which may have a substituent. As the substituent in R ^12, include the substituents exemplified in R ³ above. Although q3 (the number of repeating methylene structural units) in formula (2e) is not particularly limited, it can be appropriately selected from the range of 1 to 30, for example. Moreover, r2 (the repeating number of the condensation structure of a polyol and polycarboxylic acid) is not particularly limited, but can be appropriately selected from a range of 2 to 3000, for example. Moreover, although y4 (The repeating number of the structural unit containing a polyester structure (polyester side chain)) in Formula (2e) is not specifically limited, 1-3000 are preferable, More preferably, it is 3-1500. Furthermore, x5 (the number of repeating dimethylsilyloxy structural units) is not particularly limited, but is preferably 2 to 3000, and more preferably 3 to 1500. In addition, in the silicone polymer (C1) represented by the formula (2e), the addition form of the structural unit having a polyester structure and the dimethylsilyloxy structural unit may be a block type or a random type. Also good. Moreover, when y4 is an integer greater than or equal to 2, the structural unit containing the polyester structure enclosed by the parenthesis to which y4 was attached | subjected may be the same respectively, and may differ.

  The silicone polymer (C1) can be obtained by a known or conventional production method, and the production method is not particularly limited. For example, the monomer having a structure corresponding to the structural unit represented by the formula (2) Or a compound having a predetermined structure with respect to the reactive group of a silicone polymer having a reactive group in the side chain (such as polydimethylsiloxane having a reactive group in the side chain) (for example, A compound having a polyether structure or a polyester structure) can be produced by a method of reacting and bonding them. Moreover, a commercial item can also be used as said silicone type polymer (C1).

(Fluorine leveling agent)
The fluorine-based leveling agent is a leveling agent containing a compound having a fluorinated alkyl group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The fluorine-based leveling agent may be a known or commonly used fluorine-based leveling agent, and is not particularly limited. For example, a trade name “BYK-340” (manufactured by BYK Japan Japan Co., Ltd.); a trade name “AC 110a” "AC 100a" (manufactured by Algin Chemie); trade names "Megafuck F-114", "Megafuck F-410", "Megafuck F-444", "Megafuck EXP TP-2066", "Mega Fuck F-430, Mega Fuck F-472SF, Mega Fuck F-477, Mega Fuck F-552, Mega Fuck F-553, Mega Fuck F-554, Mega Fuck F -555 "," Megafuck R-94 "," Megafuck RS-72-K "," Megafuck RS-75 "," Mega "Fuck F-556", "Mega Fuck EXP TF-1367", "Mega Fuck EXP TF-1437", "Mega Fuck F-558", "Mega Fuck EXP TF-1537" (manufactured by DIC Corporation); Trade names “FC-4430”, “FC-4432” (manufactured by Sumitomo 3M Limited); trade names “Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, "Factent 150CH", "Factent AK", "Factent 501", "Factent 250", "Factent 251", "Factent 222F", "Factent 208G", "Factent 300", "Furgent 310", "Furgent 400SW" (above Product name “PF-136A”, “PF-156A”, “PF-151N”, “PF-636”, “PF-6320”, “PF-656”, “PF-6520” , “PF-651”, “PF-652” (above, manufactured by Kitamura Chemical Sangyo Co., Ltd.) can also be used.

As the compound having a fluorinated alkyl group, in particular, a fluorinated acrylic polymer (hereinafter referred to as “fluorinated acrylic polymer (C2) having at least a structural unit (repeating structural unit) represented by the following formula (3)”: ) ”Or a fluorine-containing polyether polymer having at least a structural unit (repeating structural unit) represented by the following formula (4) (hereinafter referred to as“ fluorine-containing polyether polymer (C3) ”) Is sometimes preferred). That is, the fluorine leveling agent is preferably a leveling agent containing at least the fluorine-containing acrylic polymer (C2) or a leveling agent containing at least the fluorine-containing polyether polymer (C3).

R ⁵ in the above formula (3) is a hydrogen atom, a fluorine atom, or a linear or branched alkyl having 1 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a fluorine atom. Indicates a group. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, and a t-butyl group.

R ⁶ in the above formula (3) represents a fluorinated alkyl group (an alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms). The fluorinated alkyl group is not particularly limited, and examples thereof include a difluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, and a 2,2,3,3-tetrafluoropropyl group. Perfluoroethylmethyl group, 2,2,3,3,4,4-hexafluorobutyl group, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl group, 1,1-dimethyl-2 , 2,3,3,3-pentafluoropropyl group, 2- (perfluoropropyl) ethyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 1,1-dimethyl -2,2,3,3,4,4-hexafluorobutyl group, 1,1-dimethyl-2,2,3,3,4,4,4-heptafluorobutyl group, 2- (perfluorobutyl) Ethyl group, 2,2,3,3 4,4,5,5,6,6-decafluorohexyl group, perfluoropentylmethyl group, 1,1-dimethyl-2,2,3,3,4,4,5,5-octafluoropentyl group, 1,1-dimethyl-2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2- (perfluoropentyl) ethyl group, 2,2,3,3,4,4 , 5,5,6,6,7,7-dodecafluoroheptyl group, perfluorohexylmethyl group, 2- (perfluorohexyl) ethyl group, 2,2,3,3,4,4,5,5 6,6,7,7,8,8-tetradecafluorooctyl group, perfluoroheptylmethyl group, 2- (perfluoroheptyl) ethyl group, 2,2,3,3,4,4,5,5 6,6,7,7,8,8,9,9-hexadecafluorononyl group, perf Orooctylmethyl group, 2- (perfluorooctyl) ethyl group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10 -Octadecafluorodecyl group, perfluorononylmethyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3 , 3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridodeca A linear or branched alkyl group having 1 to 30 carbon atoms in which a part of hydrogen atoms such as a fluorooctyl group is substituted with a fluorine atom; a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group , Heptafluoroisopropyl group, nonafluoro-n-butyl group, nonaflu Carbon such as oroisobutyl group, nonafluoro-s-butyl group, nonafluoro-t-butyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group Examples thereof include linear or branched perfluoroalkyl groups having a number of 1 to 30. Among these, as R ⁶ , a perfluoroalkyl group is preferable.

  The fluorine-containing acrylic polymer (C2) may be a polymer having only a structural unit represented by the formula (3) as a repeating structural unit, or a structure represented by the formula (3). It may be a polymer having a structural unit other than the unit. The fluorine-containing acrylic polymer (C2) may be a polymer having only one type of structural unit represented by the formula (3), or 2 structural units represented by the formula (3). It may be a polymer having more than one species. Moreover, the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (3) may be sufficient.

  The structural unit other than the structural unit represented by the formula (3) that the fluorine-containing acrylic polymer (C2) may have is not particularly limited, and the monomer component of the acrylic polymer (single amount) Examples of the body component include structural units derived from known or commonly used monomers. Examples of the monomer include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and pentyl acrylate (including those having a functional group such as a hydroxyl group or a carboxyl group); methacrylic acid Methacrylic acid esters such as methyl, ethyl methacrylate, propyl methacrylate and butyl methacrylate (including those having functional groups such as hydroxyl and carboxyl groups); acrylamides such as acrylamide and N-methylacrylamide; methacrylamide and the like Examples include methacrylamides; allyl compounds; vinyl compounds such as aromatic vinyl compounds, vinyl ethers, and vinyl esters. Further, an ester of polyalkylene glycol ether and acrylic acid or methacrylic acid can also be used as the monomer.

Specific examples of the fluorine-containing acrylic polymer (C2) include a fluorine-containing acrylic polymer represented by the following formula (3a).

R ¹³ in the formula (3a) represents a hydrogen atom or a methyl group. R ¹⁴ represents a linear or branched alkyl group. Although it does not specifically limit as said linear or branched alkyl group, For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (n-butyl group), an isobutyl group, s-butyl group, t -C1-C30 linear or branched alkyl groups, such as a butyl group and a pentyl group, are mentioned.

R ¹⁵ in the formula (3a) represents a hydrogen atom or a methyl group. R ¹⁶ represents a perfluoroalkyl group. Examples of the perfluoroalkyl group is not particularly limited, for example, perfluoroalkyl groups such as exemplified as R ⁶ in the formula (3) below.

R ¹⁷ in formula (3a) represents a hydrogen atom or a methyl group. R ¹⁸ represents an organic group containing a polyether chain. The organic group having a polyether chain is not particularly limited, and examples thereof include those exemplified as R ⁴ in the above formula (2).

  R, s, and t in Formula (3a) each represent an integer of 1 to 3000.

  The fluorine-containing acrylic polymer (C2) can be obtained by a known or conventional production method, and the production method is not particularly limited. For example, the structural unit represented by the formula (3) is obtained by polymerization. It can be produced by a method of polymerizing a monomer to be provided (for example, perfluoroalkyl acrylate or perfluoroalkyl methacrylate). Moreover, a commercial item can also be used as said fluorine-containing acrylic polymer (C2).

R ¹⁹ in the above formula (4) represents a trivalent linear or branched hydrocarbon group. Examples of the trivalent linear or branched hydrocarbon group include methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, and heptane. , Groups in which three hydrogen atoms have been removed from a linear or branched alkane such as 2-methylheptane, 3-methylheptane, octane, nonane and decane. Especially, the group remove | excluding three hydrogen atoms from a C1-C10 linear or branched alkane is preferable.

R ²⁰ in the above formula (4) represents a fluorinated alkyl group. The fluorinated alkyl group may be any alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms, and is not particularly limited. Examples thereof include those exemplified as R ⁶ in the above formula (3). Can be mentioned. Among them, R ²⁰ is preferably an alkyl group in which a part of hydrogen atoms are substituted with fluorine atoms.

  In the above formula (4), z (the number of repeating methylene structural units) represents an integer of 1-30. Among these, an integer of 1 to 10 is preferable.

  The fluorine-containing polyether polymer (C3) may be a polymer having only the structural unit represented by the formula (4) as the repeating structural unit, or represented by the formula (4). It may be a polymer having a structural unit other than the structural unit. The fluorine-containing polyether polymer (C3) may be a polymer having only one type of structural unit represented by the formula (4), or the structural unit represented by the formula (4). The polymer which has 2 or more types may be sufficient. Moreover, the polymer which has 2 or more types of structural units other than the structural unit represented by Formula (4) may be sufficient.

The structural unit other than the structural unit represented by the formula (4) that the fluorine-containing polyether polymer (C3) may have is not particularly limited, and for example, an oxyethylene unit [—OCH ₂ Examples thereof include oxyalkylene structural units such as CH ₂ —] and oxypropylene units [—OCH (CH ₃ ) CH ₂ —].

Specific examples of the structural unit represented by the above formula (4) include a structural unit represented by the following formula. R ²¹ in the following formula represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, etc.). R ²⁰ and z in the following formula are the same as described above.

Specific examples of the fluorine-containing polyether polymer (C3) include a fluorine-containing polyether polymer represented by the following formula (4a).

  U, v, and w in Formula (4a) each represent an integer of 1 to 50. Especially, it is preferable that the sum of u and w is an integer of 2-80, More preferably, it is an integer of 4-30, More preferably, it is an integer of 6-14. Moreover, it is preferable that v is an integer of 2-50, More preferably, it is an integer of 5-20.

  The fluorinated polyether polymer (C3) can be obtained by a known or conventional production method, and the production method is not particularly limited. For example, the structural unit represented by the formula (4) by polymerization. Can be produced by a method of polymerizing (for example, ring-opening polymerization) a monomer (for example, a cyclic ether compound such as an epoxy compound or an oxetane compound). Moreover, a commercial item can also be used as said fluorine-containing polyether type polymer (C3).

  The non-volatile content (blending amount) of the leveling agent (C) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable epoxy resin composition (100 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.1 to 4 parts by weight. If the content of the leveling agent (C) (in terms of non-volatile content) is less than 0.1 parts by weight, the crack resistance of the cured product may be lowered. On the other hand, if the content of the leveling agent (C) (in terms of non-volatile content) exceeds 10 parts by weight, the transparency and heat resistance of the cured product may decrease.

  In particular, the content (blending amount) of the silicone polymer (C1), the fluorinated acrylic polymer (C2), and the fluorinated polyether polymer (C3) in the curable epoxy resin composition of the present invention is as follows. Although not particularly limited, it is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. Parts, more preferably 0.1 to 4 parts by weight. When the content of the silicone polymer (C1), the fluorinated acrylic polymer (C2), and the fluorinated polyether polymer (C3) is less than 0.1 parts by weight, the crack resistance of the cured product is reduced. May decrease. On the other hand, if the content exceeds 10 parts by weight, the transparency and heat resistance of the cured product may be lowered. The “content (blending amount) of the silicone polymer (C1), the fluorine-containing acrylic polymer (C2), and the fluorine-containing polyether polymer (C3)” means the silicone polymer (C1). In the case where two or more kinds of fluorine-containing acrylic polymer (C2) and fluorine-containing polyether polymer (C3) are contained, it means the total of these contents (total content).

  Since the curable epoxy resin composition of the present invention contains the specific leveling agent (C) described above, an optical semiconductor device obtained by sealing an optical semiconductor element with a cured product of the resin composition is excellent. It exhibits heat resistance and crack resistance and suppresses a decrease in light intensity over time (particularly, a decrease in light intensity of an optical semiconductor device that emits high-luminance light). Such an effect improves the adhesion of the curable epoxy resin composition of the present invention (or its cured product) to an optical semiconductor element or a package material (for example, a reflector material) by including a leveling agent (C). This is presumed to be due to this.

[Monoallyldiglycidyl isocyanurate compound (D)]
The curable epoxy resin composition of the present invention may further contain a monoallyl diglycidyl isocyanurate compound (D) represented by the following formula (1). When the curable epoxy resin composition of the present invention contains the monoallyl diglycidyl isocyanurate compound (D), the toughness of the cured product is improved, and the thermal shock resistance and moisture absorption reflow resistance (especially reflow after moisture absorption). There is a tendency that the crack resistance (characteristics that hardly cause cracks) in the heat treatment in the process is further improved.

The formula (1), R ^1, R ² are the same or different, represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include 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 formula (1) are particularly preferably hydrogen atoms.

  Representative examples of the monoallyl diglycidyl isocyanurate compound (D) include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methyl And propenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, and the like. In addition, a monoallyl diglycidyl isocyanurate compound (D) can be used individually by 1 type or in combination of 2 or more types.

  The monoallyl diglycidyl isocyanurate compound (D) may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.

  The content (blending amount) of the monoallyl diglycidyl isocyanurate compound (D) is not particularly limited, but is 5 with respect to the total amount (100% by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. -60 wt% is preferable, more preferably 8-55 wt%, still more preferably 10-50 wt%. When the content of the monoallyl diglycidyl isocyanurate compound (D) exceeds 60% by weight, the solubility of the monoallyl diglycidyl isocyanurate compound (D) in the curable epoxy resin composition is lowered, and the physical properties of the cured product are reduced. There may be adverse effects. On the other hand, if the content of the monoallyl diglycidyl isocyanurate compound (D) is less than 5% by weight, the thermal shock resistance and moisture absorption reflow resistance of the cured product may be lowered.

  Further, the content (blending amount) of the monoallyl diglycidyl isocyanurate compound (D) relative to the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (D) is particularly Although not limited, 5 to 60 weight% is preferable, More preferably, it is 8 to 55 weight%, More preferably, it is 10 to 50 weight%. When the content of the monoallyl diglycidyl isocyanurate compound (D) exceeds 60% by weight, the solubility of the monoallyl diglycidyl isocyanurate compound (D) in the curable epoxy resin composition is lowered, and the physical properties of the cured product are reduced. There may be adverse effects. On the other hand, if the content of the monoallyl diglycidyl isocyanurate compound (D) is less than 5% by weight, the thermal shock resistance and moisture absorption reflow resistance of the cured product may be lowered.

[Curing agent (E)]
The curable epoxy resin composition of the present invention may contain a curing agent (E). The curing agent (E) is a compound having a function of curing a compound having an epoxy group. As the curing agent (E), a known or conventional curing agent can be used as a curing agent for epoxy resin. As the curing agent (E), an acid anhydride which is liquid at 25 ° C. is preferable, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, and methylendomethylenetetrahydrophthalic anhydride. Can be mentioned. In addition, solid acid anhydrides at room temperature (about 25 ° C.) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride are also liquid at room temperature (about 25 ° C.). It can be preferably used as the curing agent (E) in the curable epoxy resin composition of the present invention by dissolving it in an acid anhydride. In addition, a hardening | curing agent (E) can be used individually by 1 type or in combination of 2 or more types. As described above, as the curing agent (E), from the viewpoint of heat resistance, light resistance and crack resistance of the cured product, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (a substituent such as an alkyl group is bonded to the ring) Are also preferable).

  In the present invention, as the curing agent (E), trade names “Rikacid MH-700”, “Rikacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.); trade names “HN-5500” (Hitachi) Commercial products such as Kasei Kogyo Co., Ltd. can also be used.

  Although content (blending amount) of a hardening | curing agent (E) is not specifically limited, 50-200 weight part is preferable with respect to 100 weight part of whole quantity of the compound which has an epoxy group contained in curable epoxy resin composition, More preferably, it is 100-145 weight part. More specifically, it is preferably used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in all compounds having epoxy groups contained in the curable epoxy resin composition of the present invention. When content of a hardening | curing agent (E) is less than 50 weight part, hardening will become inadequate and there exists a tendency for the toughness of hardened | cured material to fall. On the other hand, when content of a hardening | curing agent (E) exceeds 200 weight part, hardened | cured material may color and hue may deteriorate. In addition, when using 2 or more types as a hardening | curing agent (E), it is preferable that the total amount of these hardening | curing agents (E) satisfy | fills the said range.

[Curing accelerator (F)]
The curable epoxy resin composition of the present invention may contain a curing accelerator (F). A hardening accelerator (F) is a compound which has a function which accelerates | stimulates a cure rate, when the compound which has an epoxy group hardens | cures with a hardening | curing agent (E). As the curing accelerator (F), a known or conventional curing accelerator can be used. 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); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, octyl) Acid salt, p-toluenesulfonate, formate, tetraphenylborate salt); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Le, phosphines such as triphenyl phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p- tolyl) borate, organic metal salts such as zinc octylate and tin octylate; metal chelate and the like. A hardening accelerator (F) can be used individually by 1 type or in combination of 2 or more types.

  In the present invention, as the curing accelerator (F), trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “12XD”. (Developed product) (San Apro Co., Ltd.); Trade name “TPP-K”, “TPP-MK” (Hokuko Chemical Co., Ltd.); Trade name “PX-4ET” (Nippon Chemical Industry) Commercial products such as (manufactured by Co., Ltd.) can also be used.

  Although content (blending amount) of a hardening accelerator (F) is not specifically limited, 0.01-5 with respect to the whole quantity (100 weight part) of the compound which has an epoxy group contained in a curable epoxy resin composition. Part by weight is preferred, more preferably 0.03 to 3 parts by weight, and still more preferably 0.03 to 2 parts by weight. When the content of the curing accelerator (F) is less than 0.01 parts by weight, the curing accelerating effect may be insufficient. On the other hand, when content of a hardening accelerator (F) exceeds 5 weight part, hardened | cured material may color and a hue may deteriorate.

[Curing catalyst (G)]
The curable epoxy resin composition of the present invention may further contain a curing catalyst (G) (for example, instead of the curing agent (E) and the curing accelerator (F)). The curing catalyst (G) is a compound having a function of initiating and / or promoting a curing reaction of a compound having an epoxy group. Although it does not specifically limit as a curing catalyst (G), The cationic catalyst (cationic polymerization initiator) which generate | occur | produces a cationic seed | species by giving an ultraviolet irradiation or heat processing, and starts superposition | polymerization is mentioned. In addition, a curing catalyst (G) can be used individually by 1 type or in combination of 2 or more types.

  Examples of the cation catalyst that generates cation species by ultraviolet irradiation include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and the like. Examples of the cationic catalyst include trade names “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, manufactured by Sartomer, USA); Commercial products such as trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can also be preferably used.

  Examples of the cation catalyst that generates a cation species by performing heat treatment include aryl diazonium salts, aryl iodonium salts, aryl sulfonium salts, and allene-ion complexes, 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 name“ Sun-Aid SI-60L ” "Sun-Aid SI-80L", "Sun-Aid SI-100L", "Sun-Aid SI-110L", "Sun-Aid SI-150L" (above, manufactured by Sanshin Chemical Industry Co., Ltd.); trade name "CG-24-61" Commercial products such as (made by BASF) can be preferably used. Furthermore, a chelate compound of a metal such as aluminum or titanium and a acetoacetate or diketone compound and a silanol such as triphenylsilanol, or a chelate compound of a metal such as aluminum or titanium and acetoacetate or diketone and bisphenol S The compound with phenols, such as these, may be sufficient.

  The content (blending amount) of the curing catalyst (G) is not particularly limited, but is 0.01 to 15 parts by weight with respect to 100 parts by weight of the total amount of the compound having an epoxy group contained in the curable epoxy resin composition. More preferably, it is 0.01-12 weight part, More preferably, it is 0.05-10 weight part, Especially preferably, it is 0.05-8 weight part. By using the curing catalyst (G) within the above range, a cured product having excellent heat resistance, light resistance and transparency can be obtained.

[Rubber particles]
The curable epoxy resin composition of the present invention may further contain rubber particles. Examples of the rubber particles include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, particulate SBR (styrene-butadiene rubber). The rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion. The rubber particles are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component (monomer component), and an epoxy such as an alicyclic epoxy compound (A) on the surface. Rubber particles having a hydroxyl group and / or a carboxyl group (either one or both of a hydroxyl group and a carboxyl group) as a functional group capable of reacting with a compound having a group are preferred. When there is no hydroxyl group and / or carboxyl group on the surface of the rubber particles, the cured product becomes clouded by a thermal shock such as a cold cycle and the transparency is lowered, which is not preferable.

  The polymer constituting the core portion having rubber elasticity in the rubber particles is not particularly limited, but (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are used. The essential monomer component is preferred. The polymer constituting the core portion having rubber elasticity is, for example, aromatic vinyl such as styrene and α-methylstyrene, nitrile such as acrylonitrile and methacrylonitrile, conjugated diene such as butadiene and isoprene, ethylene, propylene, Isobutene or the like may be contained as a monomer component.

  Especially, the polymer which comprises the said core part which has the rubber elasticity contains 1 type, or 2 or more types selected from the group which consists of aromatic vinyl, a nitrile, and a conjugated diene with a (meth) acrylic acid ester as a monomer component. It is preferable to include it in combination. That is, as the polymer constituting the core part, for example, (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene and other binary copolymers; (meth) acrylic acid ester / aromatic And terpolymers such as group vinyl / conjugated dienes. The polymer constituting the core part may contain silicone such as polydimethylsiloxane and polyphenylmethylsiloxane, polyurethane, and the like.

  The polymer constituting the core part includes, as other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc. One monomer (one molecule) may contain a reactive crosslinking monomer having two or more reactive functional groups.

  The core part of the rubber particles is a core part composed of a (meth) acrylic ester / aromatic vinyl binary copolymer (particularly butyl acrylate / styrene). It is preferable in that the rate can be easily adjusted.

  The glass transition temperature of the polymer constituting the core part of the rubber particles is not particularly limited, but is preferably less than 60 ° C. (for example, −150 ° C. or more and less than 60 ° C.), more preferably −150 to 15 ° C., and even more preferably. Is −100 to 0 ° C. When the glass transition temperature of the polymer is 60 ° C. or higher, the crack resistance of the cured product (characteristics that hardly cause cracks with respect to various stresses) may decrease. The glass transition temperature of the polymer constituting the core portion means a calculated value calculated by the Fox equation, for example, the same as the glass transition temperature of the acrylic polymer [core] in the core-shell type acrylic polymer particles described above. Can be measured.

  The core part of the rubber particles can be produced by a commonly used method. For example, it can be produced by a method of polymerizing the monomer by an emulsion polymerization method. In the emulsion polymerization method, the whole amount of the monomer may be charged all at once and polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently for polymerization. Further, a polymerization method using seed particles may be used.

  The polymer constituting the shell layer of the rubber particles is preferably a polymer different from the polymer constituting the core portion. In addition, as described above, the shell layer preferably has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as the alicyclic epoxy compound (A). Thereby, especially with respect to the hardened | cured material which can improve adhesiveness in an interface with an alicyclic epoxy compound (A), and hardened the curable epoxy resin composition containing the rubber particle which has this shell layer. , Excellent crack resistance can be exhibited. Moreover, the fall of the glass transition temperature of hardened | cured material can also be prevented.

  The polymer constituting the shell layer preferably contains (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate as an essential monomer component. For example, when butyl acrylate is used as the (meth) acrylic acid ester in the core part, (meth) acrylic acid esters other than butyl acrylate (for example, (meth) acrylic) as the monomer component of the polymer constituting the shell layer It is preferable to use methyl acid, ethyl (meth) acrylate, butyl methacrylate and the like. Examples of the monomer component that may be contained in addition to the (meth) acrylic acid ester include aromatic vinyl such as styrene and α-methylstyrene, and nitrile such as acrylonitrile and methacrylonitrile. In the rubber particles, as a monomer component constituting the shell layer, it is preferable to contain the monomer alone or in combination of two or more, together with (meth) acrylic acid ester, and particularly at least aromatic vinyl. Is preferable in that the refractive index of the rubber particles can be easily adjusted.

  Further, the polymer constituting the shell layer forms a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component. , Hydroxyl group-containing monomers (eg, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate) and carboxyl group-containing monomers (eg, α, β-unsaturated acids such as (meth) acrylic acid, It is preferable to contain an α, β-unsaturated acid anhydride such as maleic anhydride).

  It is preferable that the polymer which comprises the shell layer in the said rubber particle contains 1 type, or 2 or more types selected from the said monomer in combination with (meth) acrylic acid ester as a monomer component. That is, the shell layer is formed of, for example, a ternary copolymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / α, β-unsaturated acid. A shell layer composed of a polymer or the like is preferable.

  Further, the polymer constituting the shell layer includes, as the other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, trimethyl, as well as the above-described monomer. A reactive crosslinking monomer having two or more reactive functional groups may be contained in one monomer (one molecule) such as allyl cyanurate, diallyl phthalate, or butylene glycol diacrylate.

  Although the glass transition temperature of the polymer which comprises the shell layer of the said rubber particle is not specifically limited, 60-120 degreeC is preferable, More preferably, it is 70-115 degreeC. When the glass transition temperature of the polymer is less than 60 ° C., the heat resistance of the cured product may be lowered. On the other hand, when the glass transition temperature of the polymer exceeds 120 ° C., the crack resistance of the cured product may be lowered. The glass transition temperature of the polymer constituting the shell layer means a calculated value calculated by the Fox equation, for example, the same as the glass transition temperature of the acrylic polymer [core] in the core-shell type acrylic polymer particles described above. Can be measured.

  The rubber particles (rubber particles having a core-shell structure) can be obtained by covering the core portion with a shell layer. Examples of the method of coating the core part with a shell layer include a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a copolymer constituting the shell layer, and the above method And a method in which the core part having rubber elasticity obtained by the above method is used as a trunk component and each component constituting the shell layer is used as a branch component for graft polymerization.

  The average particle diameter of the rubber particles is not particularly limited, but is preferably 10 to 500 nm, and more preferably 20 to 400 nm. The maximum particle size of the rubber particles is not particularly limited, but is preferably 50 to 1000 nm, more preferably 100 to 800 nm. If the average particle diameter exceeds 500 nm or the maximum particle diameter exceeds 1000 nm, the dispersibility of the rubber particles in the cured product may be reduced, and crack resistance may be reduced. On the other hand, if the average particle size is less than 10 nm or the maximum particle size is less than 50 nm, the effect of improving the crack resistance of the cured product may be difficult to obtain.

  Although the refractive index of the said rubber particle is not specifically limited, 1.40-1.60 are preferable, More preferably, it is 1.42-1.58. The difference between the refractive index of the rubber particles and the refractive index of the cured product obtained by curing the curable epoxy resin composition (the curable epoxy resin composition of the present invention) containing the rubber particles is ± 0.03. Is preferably within. When the difference in refractive index exceeds ± 0.03, the transparency of the cured product decreases, sometimes it becomes cloudy, the light intensity of the optical semiconductor device tends to decrease, and the function of the optical semiconductor device is lost. There is.

  The refractive index of the rubber particles is, for example, 1 g of rubber particles cast into a mold and compression molded at 210 ° C. and 4 MPa to obtain a flat plate having a thickness of 1 mm. And using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate solution, It can be determined by measuring the refractive index at 20 ° C. and sodium D line.

  The refractive index of the cured product of the curable epoxy resin composition of the present invention is, for example, a test piece having a length of 20 mm × width of 6 mm × thickness of 1 mm from a cured product obtained by the heat curing method described in the section of cured product below. And using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate solution, It can be determined by measuring the refractive index at 20 ° C. and sodium D line.

  The content (blending amount) of the rubber particles in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. On the other hand, 0.5-30 weight part is preferable, More preferably, it is 1-20 weight part. When the content of the rubber particles is less than 0.5 parts by weight, the crack resistance of the cured product tends to decrease. On the other hand, when the content of the rubber particles exceeds 30 parts by weight, the heat resistance of the cured product tends to decrease.

[Additive]
In addition to the above, the curable epoxy resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. For example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is included as the additive, the reaction can be allowed to proceed slowly. In addition, as long as the viscosity and transparency are not impaired, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, surfactants, inorganic fillers such as silica and alumina, flame retardants, colorants, Conventional additives such as antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors (for example, inorganic phosphor particles such as YAG phosphor fine particles and silicate phosphor fine particles), release agents, etc. 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. These components can also be used as a multi-liquid composition (for example, a two-liquid system) that is used by mixing them at a predetermined ratio before use. The stirring / mixing method is not particularly limited, and 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 vacuum.

  Although not particularly limited, when rubber particles are blended in the curable epoxy resin composition of the present invention, the rubber particles are prepared by dispersing the rubber particles in the alicyclic epoxy compound (A) in advance (the composition is referred to as “rubber”). It is preferable to blend in a state of “sometimes referred to as a“ particle dispersed epoxy compound ””. That is, when rubber particles are blended in the curable epoxy resin composition of the present invention, the curable epoxy resin composition of the present invention comprises the rubber particle-dispersed epoxy compound, the core-shell type acrylic polymer (B), the leveling agent ( It is preferable to prepare by mixing C) and other components as necessary. Such a preparation method can particularly improve the dispersibility of the rubber particles in the curable epoxy resin composition. However, the blending method of the rubber particles is not limited to the above method, and may be a method of blending alone.

(Rubber particle dispersed epoxy compound)
The rubber particle-dispersed epoxy compound is obtained by dispersing the rubber particles in the alicyclic epoxy compound (A). The alicyclic epoxy compound (A) in the rubber particle-dispersed epoxy compound may be the total amount of the alicyclic epoxy compound (A) constituting the curable epoxy resin composition, or may be a partial amount. There may be. Similarly, the rubber particles in the rubber particle-dispersed epoxy compound may be the total amount of rubber particles constituting the curable epoxy resin composition, or may be a partial amount.

  The viscosity of the rubber particle-dispersed epoxy compound can be adjusted, for example, by using a reactive diluent in combination (that is, the rubber particle-dispersed epoxy compound may further contain a reactive diluent). As the reactive diluent, for example, an aliphatic polyglycidyl ether having a viscosity at room temperature (25 ° C.) of 200 mPa · s or less can be preferably used. Examples of the aliphatic polyglycidyl ether having a viscosity (25 ° C.) of 200 mPa · s or less include, for example, cyclohexanedimethanol diglycidyl ether, cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. , Trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, and the like.

  The amount of the reactive diluent used can be appropriately adjusted and is not particularly limited, but is preferably 30 parts by weight or less with respect to 100 parts by weight of the total amount of the alicyclic epoxy compound (A) and the rubber particles, More preferably, it is 25 parts by weight or less (for example, 5 to 25 parts by weight). When the amount used exceeds 30 parts by weight, it tends to be difficult to obtain desired performance such as crack resistance.

  The manufacturing method of the said rubber particle dispersion | distribution epoxy compound is not specifically limited, A well-known and usual method can be used. For example, after the rubber particles are dehydrated and dried to form powder, the rubber particles are mixed and dispersed in the alicyclic epoxy compound (A), or the emulsion of rubber particles and the alicyclic epoxy compound (A) are directly mixed. Then, the method of dehydrating etc. is mentioned.

  Although the viscosity in 25 degreeC of the curable epoxy resin composition of this invention is not specifically limited, 60-6000 mPa * s is preferable, More preferably, it is 100-5500 mPa * s, More preferably, it is 150-5000 mPa * s. There exists a tendency for the heat resistance of hardened | cured material to fall that the viscosity in 25 degreeC is less than 60 mPa * s. On the other hand, when the viscosity at 25 ° C. exceeds 6000 mPa · s, the handleability at the time of casting tends to be lowered, or a defect derived from poor casting tends to occur in the cured product. The viscosity at 25 ° C. of the curable epoxy resin composition is, for example, using a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24, temperature : Measured under conditions of 25 ° C. and rotation speed: 0.5 to 10 rpm.

<Hardened product>
By curing the curable epoxy resin composition of the present invention, it is excellent in heat resistance, light resistance, and thermal shock resistance, and in particular, it is possible to improve current-carrying characteristics and moisture absorption reflow resistance of optical semiconductor devices at high temperatures. A cured product can be obtained. 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.

<Resin composition for optical semiconductor encapsulation>
The curable epoxy resin composition of the present invention can be preferably used as a resin composition for sealing an optical semiconductor (optical semiconductor element) in an optical semiconductor device, that is, a resin composition for optical semiconductor sealing. An optical semiconductor in which an optical semiconductor element is sealed with a cured product having high heat resistance, light resistance, and thermal shock resistance, and particularly excellent in moisture absorption and reflow resistance, by using the resin composition for sealing an optical semiconductor. A device is obtained. Even if the above optical semiconductor device is provided with a high-output, high-brightness optical semiconductor element, the light intensity is unlikely to decrease with time, especially when it is heated in a reflow process after being stored under high humidity conditions. However, deterioration such as a decrease in luminous intensity is unlikely to occur.

<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 sealing) of the present invention. The optical semiconductor element is sealed by injecting the curable epoxy resin composition prepared by the above-described method into a predetermined mold and heat-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 is obtained. The curing temperature and the curing time can be appropriately set within the same range as when the cured product is prepared.

  The curable epoxy resin composition of the present invention is not limited to the above-mentioned optical semiconductor element sealing application, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, a resist, a composite material, It can also be used for applications such as transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members, optical modeling, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc. .

  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 combination of the corresponding component or the corresponding operation was not performed.

Production Example 1
(Manufacture of acrylic polymer emulsion (E1) and acrylic polymer powder (P1))
In a 2 liter separable flask equipped with a stirrer, a reflux condenser, a dropping pump, a temperature controller, and a nitrogen introduction tube, 585.0 g of ion-exchanged water was charged and stirred.
Separately, 453.5 g of methyl methacrylate, 71.5 g of n-butyl methacrylate, 5.3 g of ammonium di-2-ethylhexyl sulfosuccinate, and 262.5 g of ion-exchanged water were emulsified with a homogenizer (25000 rpm) to give a monomer. A mixture (M1) was prepared, 10% of the monomer mixture (M1) was charged into the flask, and then heated to 80 ° C. in a nitrogen atmosphere. Next, an aqueous solution of 0.30 g of ammonium persulfate prepared in advance (dissolved in 15.0 g of ion exchange water) was charged all at once into the flask and held for 60 minutes to form seed particles. Further, the remaining monomer mixture (M1) was dropped into the flask in which the seed particles were formed over 180 minutes, and held for 1 hour after the dropping to complete the first stage polymerization.
Next, a monomer obtained by emulsifying 219.3 g of methyl methacrylate, 5.7 g of methacrylic acid, 2.3 g of ammonium di-2-ethylhexylsulfosuccinate, and 112.5 g of ion-exchanged water with a homogenizer (25000 rpm). The mixture was dropped into the flask over 90 minutes and held for 1 hour after dropping to finish the second stage polymerization, and an acrylic polymer emulsion (E1) having an average particle size of 0.84 μm was obtained. From the composition of the acrylic monomer in the acrylic polymer emulsion (E1), the glass transition temperature of the core component formed by the first stage polymerization is 90.6 ° C., the solubility parameter (Fedors method) is 20.45, The glass transition temperature of the shell component formed by the second stage polymerization is 106.9 ° C., and the solubility parameter (Fedors method) is 20.66.
The obtained acrylic polymer emulsion (E1) was spray-dried to obtain an acrylic polymer powder (P1).

Production Examples 2-6
Acrylic polymer emulsions (E2) to (E6) and acrylic polymer powders (P2) to (P6) were prepared in the same manner as in Production Example 1 except that the raw material compositions and polymerization conditions described in Table 1 were changed. Obtained.

Production Example 7
(Manufacture of acrylic polymer emulsion (E7) and acrylic polymer powder (P7))
624 g of ion-exchanged water was charged into a 2 liter separable flask equipped with a stirrer, a reflux condenser, a dropping pump, a temperature controller, and a nitrogen introduction tube, and stirred.
Separately, 483.7 g of methyl methacrylate and 76.3 g of n-butyl methacrylate were mixed to prepare a monomer mixture (M7) used for the first stage polymerization. 40.0 g of the monomer mixture (M7) was charged into the flask, and then heated to 80 ° C. in a nitrogen atmosphere. Next, an aqueous solution of 0.32 g of ammonium persulfate prepared in advance (dissolved in 16.0 g of ion exchange water) was charged all at once into the flask and held for 60 minutes to form seed particles. Further, 520.0 g of the remaining monomer mixture (M7), 5.6 g of ammonium di-2-ethylhexylsulfosuccinate, and 280.0 g of ion-exchanged water were homogenizer (25000 rpm) in the flask in which the seed particles were formed. The mixture obtained by the emulsification treatment was added dropwise over 210 minutes and held for 1 hour to complete the first stage polymerization.
Next, 233.9 g of methyl methacrylate, 6.1 g of methacrylic acid, 2.4 g of ammonium di-2-ethylhexylsulfosuccinate, and 120.0 g of ion-exchanged water are emulsified in the flask using a homogenizer (25000 rpm). The resulting monomer mixture was added dropwise over 90 minutes, and held for 1 hour after the addition, and the second stage polymerization was completed to obtain an acrylic polymer emulsion (E7) having an average particle size of 0.81 μm. From the composition of the acrylic monomer in the acrylic polymer emulsion (E7), the glass transition temperature of the core component formed by the first stage polymerization is 90.6 ° C., the solubility parameter (Fedors method) is 20.45, The glass transition temperature of the shell component formed by the second stage polymerization is 106.9 ° C., and the solubility parameter (Fedors method) is 20.66.
The obtained acrylic polymer emulsion (E7) was spray-dried to obtain an acrylic polymer powder (P7).

Production Example 8
(Manufacture of acrylic polymer emulsion (E8) and acrylic polymer powder (P8))
In a 2 liter separable flask equipped with a stirrer, a reflux condenser, a dropping pump, a temperature controller, and a nitrogen introduction tube, 585.0 g of ion-exchanged water was charged and stirred.
Separately, 672.75 g of methyl methacrylate, 71.5 g of n-butyl methacrylate, 5.72 g of methacrylic acid, 7.5 g of ammonium di-2-ethylhexylsulfosuccinate, and 375.0 g of ion-exchanged water were emulsified with a homogenizer (25000 rpm). The monomer mixture (M8) was prepared by treatment, 10% of the monomer mixture (M8) was charged into the flask, and then heated to 80 ° C. in a nitrogen atmosphere. Next, an aqueous solution of 0.30 g of ammonium persulfate prepared in advance (dissolved in 15.0 g of ion exchange water) was charged all at once into the flask and held for 60 minutes to form seed particles. Further, the remaining monomer mixture (M8) was dropped into the flask in which the seed particles were formed over 270 minutes, held for 1 hour after the dropping, the polymerization was terminated, and the average particle size was 0.62 μm. An acrylic polymer emulsion (E8) was obtained. From the composition of the acrylic monomer in the acrylic polymer emulsion (E8), the glass transition temperature of the acrylic polymer constituting the acrylic polymer emulsion (E8) is 95.3 ° C., and the solubility parameter (Fedors method) is 20.52. .
The obtained acrylic polymer emulsion (E8) was spray-dried to obtain an acrylic polymer powder (P8).

Production Example 9
(Manufacture of rubber particles)
In a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Here, a monomer mixture composed of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion of the rubber particles. Were added together and emulsified by stirring for 20 minutes, and then 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour to perform the first seed polymerization. Subsequently, 180.5 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, the remaining amount (about 95% by weight) of butyl acrylate 180.5 g, styrene 48.89 g, divinylbenzene 7.33 g and 0.95 g of sodium dioctyl sulfosuccinate were added to form the core part. The dissolved monomer mixture was continuously added over 2 hours to perform the second seed polymerization, and then aged for 1 hour to obtain a core part.
Next, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, 0.3 g of sodium dioctylsulfosuccinate was dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid and 0.3 g of allyl methacrylate. The monomer mixture was continuously added over 30 minutes to perform seed polymerization. Then, it aged for 1 hour and formed the shell layer which coat | covers a core part.
Next, the mixture was cooled to room temperature (25 ° C.) and filtered through a plastic mesh having an opening of 120 μm to obtain a latex containing rubber particles having a core-shell structure. The obtained latex was frozen at −30 ° C., dehydrated and washed with a suction filter, and then blown and dried at 60 ° C. overnight to obtain rubber particles. The resulting rubber particles had an average particle size of 254 nm and a maximum particle size of 486 nm.

The average particle size and the maximum particle size of the rubber particles are “Nanotrac ^™ ” type nanotrack particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) based on the dynamic light scattering method. ) Was used to measure the sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is 0 The maximum particle size at the time of exceeding 0.000 was defined as the maximum particle size. In addition, as said sample, what disperse | distributed 1 weight part of rubber particle dispersion | distribution epoxy compounds obtained by the following manufacture example 10 to 20 weight part of tetrahydrofuran was used.

Production Example 10
(Manufacture of rubber particle-dispersed epoxy compounds)
Using a dissolver with 10 parts by weight of the rubber particles obtained in Production Example 9 heated to 60 ° C. under a nitrogen stream, the product name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4) -Epoxy) cyclohexanecarboxylate (manufactured by Daicel Corporation) dispersed in 80 parts by weight (1000 rpm, 60 minutes) and vacuum degassed to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C .: 530 mPa · s). It was.
The viscosity (viscosity at 25 ° C.) of the rubber particle-dispersed epoxy compound obtained above (10 parts by weight of rubber particles dispersed in 80 parts by weight of celoxide 2021P) is a digital viscometer (trade name “ DVU-EII type "(manufactured by Tokimec Co., Ltd.).

Production Example 11
(Manufacture of curing agent composition)
In the blending ratio (unit: parts by weight) 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, San Apro ( Co., Ltd.), and 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 mixture was uniformly mixed and defoamed to obtain a curing agent composition (sometimes referred to as “K agent”).

Example 1
First, the product name “Celoxide 2021P” (alicyclic epoxy compound, manufactured by Daicel Corporation) and acrylic polymer powder (P1) and the acrylic polymer powder (P1) at a blending ratio (unit: parts by weight) shown in Table 2 are subjected to revolving stirring. Using an apparatus (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), uniformly mixing, defoaming, alicyclic epoxy compound and acrylic polymer powder (core-shell type acrylic polymer) Particles).
Next, the mixture obtained above so as to have the blending ratio (unit: parts by weight) shown in Table 2, the trade name “BYK-300” (silicone leveling agent, manufactured by Big Chemie Japan Co., Ltd.), The curing agent composition obtained in Production Example 11 is uniformly mixed and defoamed using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.). A curable epoxy resin composition was obtained. Table 2 shows the viscosity at 25 ° C. of the curable epoxy resin composition measured by the method described above.
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 in an oven (resin curing oven) at 120 ° C. By heating for 5 hours, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the said curable epoxy resin composition was obtained. In FIG. 1, 100 is a reflector (light reflecting resin composition), 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a cured product (sealing material).

Examples 2-14, Comparative Examples 1-7
A curable epoxy resin composition was prepared 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. In Example 14, the rubber particle-dispersed epoxy compound obtained in Production Example 10 was used as a constituent component of the epoxy resin. In addition, when compounding monoallyl diglycidyl isocyanurate (MA-DGIC, Shikoku Kasei Kogyo Co., Ltd.) as an epoxy resin, in order to dissolve MA-DGIC, the epoxy is obtained by stirring at 80 ° C. for 1 hour. Mixing of resin or epoxy resin and acrylic polymer powder was performed.
Further, an optical semiconductor device was fabricated in the same manner as in Example 1.

Example 15
First, the product name “Celoxide 2021P” (alicyclic epoxy compound, manufactured by Daicel Co., Ltd.) and acrylic polymer powder (P1) and the acrylic polymer powder (P1) at the blending ratio (unit: part by weight) shown in Table 3 Using a device (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), the mixture was uniformly mixed and degassed to obtain a mixture of an alicyclic epoxy compound and an acrylic polymer powder. .
Next, the mixture obtained above and a trade name “BYK-300” (silicone-based leveling agent, manufactured by Big Chemie Japan Co., Ltd.) so as to have a blending ratio (unit: parts by weight) shown in Table 3; Using the product name "Sun-Aid SI-100L" (curing catalyst, manufactured by Sanshin Chemical Industry Co., Ltd.) and a self-revolving stirrer (trade name "Awatori Nerita AR-250", manufactured by Shinky Corporation) Were mixed uniformly 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 in an oven (resin curing oven) at 120 ° C. By heating for 5 hours, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the said curable epoxy resin composition was obtained.

Examples 16 to 27, Comparative Examples 8 to 14
A curable epoxy resin composition was prepared in the same manner as in Example 15 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 3. In Example 26, the rubber particle-dispersed epoxy compound obtained in Production Example 10 was used as a constituent component of the epoxy resin. In addition, when compounding monoallyl diglycidyl isocyanurate (MA-DGIC, Shikoku Kasei Kogyo Co., Ltd.), in order to dissolve MA-DGIC, by stirring for 1 hour at 80 ° C., an epoxy resin, or Then, the epoxy resin and the acrylic polymer powder were mixed.
Further, an optical semiconductor device was manufactured in the same manner as in Example 15.

<Evaluation>
The following evaluation tests were carried out on the optical semiconductor devices obtained in the examples and comparative examples.

[Energization test]
The total luminous flux of the optical semiconductor devices obtained in the examples and comparative examples was measured using a total luminous flux measuring machine, and this was defined as “total luminous flux for 0 hour”. Further, the total luminous flux after a current of 40 mA was passed through the optical semiconductor device in an 85 ° C. constant temperature bath for 100 hours was measured, and this was designated as “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]
The optical semiconductor devices (two used for each curable epoxy resin composition) obtained in the examples and comparative examples were left to stand for 192 hours under the conditions of 30 ° C. and 70% RH for moisture absorption treatment. Subsequently, the said optical semiconductor device was put into the reflow furnace, and it heat-processed on 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.
Thereafter, the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Co., Ltd.), whether or not a crack having a length of 90 μm or more occurred in the cured product, and It was evaluated whether or not electrode peeling (peeling of the cured product from the electrode surface) occurred. Of the two optical semiconductor devices, the number of optical semiconductor devices having a crack of 90 μm or longer in the cured product is shown in the column of “Solder heat resistance test [number of cracks]” in Tables 2 and 3, The number of generated optical semiconductor devices is shown in the column of “Solder heat resistance test [number of electrode peeling]” in Tables 2 and 3.

[Thermal shock test]
The optical semiconductor devices obtained in the examples and comparative examples (two were used for each curable epoxy resin composition) were exposed in an atmosphere of −40 ° C. for 30 minutes, and then in an atmosphere of 120 ° C. A thermal shock with one cycle of exposure to 30 minutes was applied for 500 cycles using a thermal shock tester. Then, the length of the crack which arose in the hardened | cured material in an optical semiconductor device was observed using a digital microscope (brand name "VHX-900", the Keyence Co., Ltd. product), and hardening was carried out among two optical semiconductor devices. The number of optical semiconductor devices in which cracks having a length of 90 μm or more occurred in the object was measured. The results are shown in the column of “thermal shock test [number of cracks]” in Tables 2 and 3.

[Comprehensive judgment]
As a result of each test, what satisfy | filled all the following (1)-(4) was determined as (circle) (good). On the other hand, when any of the following (1) to (4) was not satisfied, it was determined as x (defective).
(1) Current test: luminous intensity retention of 80% or more (2) Solder heat resistance test: No. of optical semiconductor devices having cracks of 90 μm or more in cured product (3) Solder heat resistance test: The number of optical semiconductor devices in which electrode peeling occurred was zero (4) Thermal shock test: The number of optical semiconductor devices in which cracks of 90 μm or more occurred in the cured product was zero. It is shown in the “determination” column.

In addition, the component used by the Example and the comparative example is as follows.
(Epoxy resin)
CEL2021P (Celoxide 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, manufactured by Daicel Corporation MA-DGIC: monoallyl diglycidyl isocyanurate, manufactured by Shikoku Chemicals Co., Ltd. YD-128 : Bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd. (leveling agent)
BYK-300: Silicone leveling agent (including silicone polymer (C1)), Big Chemie Japan Co., Ltd. AC FS 180: Silicone leveling agent (including silicone polymer (C1)), Algin Chemie BYK-340: Fluorine leveling agent (including fluorinated acrylic polymer (C2)), Big Chemie Japan Co., Ltd. AC 110a: Fluorine leveling agent (including fluorinated polyether polymer (C3)) , Made by Algin Chemie (curing agent composition)
MH-700 (Licacid MH-700): 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Rika Co., Ltd. U-CAT 18X: curing accelerator, manufactured by San Apro Co., Ltd. Glycol: Wako Pure Chemical Industries, Ltd. (curing catalyst)
SI-100L (Sun-Aid SI-100L): Curing catalyst, manufactured by Sanshin Chemical Industry Co., Ltd.

Test equipment ・ Resin curing oven ESPH Co., Ltd. GPH-201
-Thermostatic chamber ESPEC Co., Ltd. Small high temperature chamber ST-120B1
・ Total luminous flux measuring machine Optronic Laboratories Multi-spectral Radiation Measurement System OL771
・ Thermal shock tester Espec Co., Ltd. Small thermal shock device TSE-11-A
-Reflow furnace manufactured by Nippon Antom Co., Ltd., UNI-5016F

100: Reflector (resin composition for light reflection)
101: Metal wiring 102: Optical semiconductor element 103: Bonding wire 104: Hardened material (sealing material)

Claims (10)

Formula (I)

[In the formula (I), X is a single bond or a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group selected from the group consisting of a plurality of these groups linked together. Indicates a group. ]
In the alicyclic epoxy compound represented as (A), the solubility parameter core-shell acrylic polymer particles (Fedors method) is ^{19.5~21.5 [MPa 1/2] (B)} , a silicone-based leveling agent And at least one leveling agent (C) selected from the group consisting of fluorine-based leveling agents,
The glass transition temperature of the acrylic polymer constituting the core of the core-shell type acrylic polymer particles (B) is 60 to 120 ° C., and the glass transition temperature of the acrylic polymer constituting the shell is 60 to 120 ° C.,
Content of a core-shell type acrylic polymer particle (B) is 1-30 weight part with respect to 100 weight part of alicyclic epoxy compounds (A), The curable epoxy resin composition characterized by the above-mentioned. Further, the following formula (1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
The curable epoxy resin composition of Claim 1 containing the monoallyl diglycidyl isocyanurate compound (D) represented by these. Leveling agent (C) is represented by the following formula (2)

[In formula (2), R ³ represents an optionally substituted straight or branched chain alkyl group. R ⁴ is a linear or branched alkyl group which may have a substituent, an aralkyl group which may have a substituent, an organic group containing a polyether chain, or an organic group containing a polyester chain Indicates. ]
Silicone polymer (C1) having a structural unit represented by the following formula (3)

[In the formula (3), R ⁵ represents a hydrogen atom, a fluorine atom, or a linear or branched alkyl having 1 to 4 carbon atoms in which part or all of the hydrogen atoms may be substituted with a fluorine atom. Indicates a group. R ⁶ represents a fluorinated alkyl group. ]
And a fluorine-containing acrylic polymer (C2) having a structural unit represented by the following formula (4):

[In the formula (4), R ¹⁹ represents a trivalent linear or branched hydrocarbon group. R ²⁰ represents a fluorinated alkyl group. z shows the integer of 1-30. ]
The curable epoxy resin composition according to claim 1 or 2, which is a leveling agent comprising at least one polymer selected from the group consisting of a fluorine-containing polyether polymer (C3) having a structural unit represented by object. The alicyclic epoxy compound (A) is represented by the following formula (I-1)

Curable epoxy resin composition according to any one of claims 1 to 3 in a compound represented by. Furthermore, the curable epoxy resin composition of any one of Claims 1-4 containing a rubber particle. Furthermore, the curable epoxy resin composition of any one of Claims 1-5 containing a hardening | curing agent (E), a hardening accelerator (F), or a hardening catalyst (G). The content of the alicyclic epoxy compound (A) with respect to the total amount of 100% by weight of the compound having an epoxy group contained in the curable epoxy resin composition is 60% by weight or more. The curable epoxy resin composition described. Hardened | cured material of the curable epoxy resin composition of any one of Claims 1-7.   It is a resin composition for optical semiconductor sealing, The curable epoxy resin composition of any one of Claims 1-7.   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 9.

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