JP6010550B2 - 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 high heat resistance and light resistance are required for resins used in such optical semiconductor devices. Conventionally, as a sealing resin 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-power blue / white light semiconductor, coloring progresses due to light and heat emitted from the optical semiconductor element, and light that should be output is absorbed. As a result, there has been a problem that the luminous intensity of the light output from the optical semiconductor device is reduced.

  3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) as sealants that have high heat resistance and light resistance and are resistant to yellowing A liquid alicyclic epoxy resin having an alicyclic skeleton such as an adduct of cyclohexanecarboxylate and ε-caprolactone and 1,2,8,9-diepoxylimonene is known. 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 has been a problem of deterioration such that the sealing material is peeled off from the lead frame of the optical semiconductor device or a crack is generated by the heat treatment in the reflow process. .

  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, it is a certain time under high humidity conditions (for example, 168 hours under conditions of 30 ° C. and 70% RH; under conditions of 60 ° C. and 60% RH). It is demanded that cracks and peeling are not likely to occur even when heat treatment is performed in a reflow process after moisture absorption (such as 40 hours) (this characteristic is sometimes referred to as “moisture absorption reflow resistance”).

JP 2000-344867 A

Accordingly, an object of the present invention is to provide a curable epoxy resin composition that provides a cured product having high heat resistance, light resistance, and thermal shock resistance, and particularly excellent in moisture absorption reflow resistance.
Another object of the present invention is to provide a cured product having high heat resistance, light resistance, and thermal shock resistance, and particularly excellent in moisture absorption reflow resistance.
Another object of the present invention is to provide an optical semiconductor device in which deterioration such as a decrease in luminous intensity is suppressed, and in particular, a decrease in luminous intensity is suppressed when heated in a reflow process after being stored under high humidity conditions. It is in.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable epoxy resin composition containing a specific amount of an alicyclic epoxy compound and a specific core-shell type polymer particle and having a specific viscosity has a high heat resistance. The present invention has been completed by finding that a cured product having excellent heat resistance, light resistance, and thermal shock resistance, and particularly excellent in moisture absorption and reflow resistance can be formed.

That is, the present invention contains an alicyclic epoxy compound and core-shell acrylic polymer particles having a solubility parameter (Fedors method) of 19.5 to 21.5 [MPa ^1/2 ], and the core-shell acrylic polymer The glass transition temperature of the acrylic polymer constituting the particle core is 60 to 120 ° C., the glass transition temperature of the acrylic polymer constituting the shell is 60 to 120 ° C., and the content of the core-shell type acrylic polymer particles is the alicyclic ring Provided is a curable epoxy resin composition that is 1 to 30 parts by weight with respect to 100 parts by weight of the formula epoxy compound and has a viscosity at 25 ° C. of 60 to 6000 mPa · s.

［式（Ｉ）中、Ｒ¹及び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。］Furthermore, the said curable epoxy resin composition containing the compound represented by following formula (I) is provided.

[In Formula (I), R < ¹ > and R < ² > are the same or different and show a hydrogen atom or a C1-C8 alkyl group. ]

［式（１）中、Ｘは１価の有機基を示す。］Furthermore, the said alicyclic epoxy compound provides the said curable epoxy resin composition which is a compound represented by following formula (1).

[In the formula (1), X represents a monovalent organic group. ]

Furthermore, the said alicyclic epoxy compound provides the said curable epoxy resin composition which is a compound represented by a following formula (2-1).

  Furthermore, the said curable epoxy resin composition containing a hardening | curing agent and a hardening accelerator, or a hardening catalyst 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, by curing the resin composition, it has high heat resistance, light resistance, and thermal shock resistance, and particularly excellent in moisture absorption reflow resistance. A cured product can be formed. For this reason, when the curable epoxy resin composition of the present invention is used as a resin composition for encapsulating an optical semiconductor, the luminous intensity is lowered even when it is heat-treated in a reflow process after being stored under a high humidity condition. It is difficult to obtain a high-quality optical semiconductor device.

It is the schematic which shows one Embodiment of the optical semiconductor device which sealed the optical semiconductor element using 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 heating of two heatings) in the luminous intensity maintenance factor measurement after the reflow of an Example.

<Curable epoxy resin composition>
The curable epoxy resin composition of the present invention has an alicyclic epoxy compound, a solubility parameter (Fedors method) of 19.5 to 21.5 [MPa ^1/2 ], and a glass transition temperature of an acrylic polymer constituting the core. The resin composition contains at least core-shell type acrylic polymer particles having a glass transition temperature of 60 to 120 ° C. and a glass transition temperature of the acrylic polymer constituting the shell of 60 to 120 ° C.

[Alicyclic epoxy compounds]
The alicyclic epoxy compound that is an essential component of 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). Specific examples of the alicyclic epoxy compound include (i) a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and (ii) an alicyclic ring. Examples include compounds in which an epoxy group is directly bonded by a single bond.

  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 having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (i) described above, the following formula having a cyclohexene oxide group, particularly from the viewpoint of transparency and heat resistance: The compound (alicyclic epoxy compound) represented by (1) is preferable.

  In the above formula (1), X represents a monovalent organic group. Examples of the monovalent organic group include a hydrocarbon group (monovalent hydrocarbon group), an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, an alkylthio group, an alkenylthio group, and an arylthio group. An aralkylthio group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, a glycidyl group, an epoxy group, a cyano group, an isocyanate group, a carbamoyl group, an isothiocyanate group; Examples include a group bonded to a group.

  Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include C _1-20 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group, and a dodecyl group. Examples of the alkenyl group include a vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, C _2-20 alkenyl groups such as 3-pentenyl group, 4-pentenyl group, 5-hexenyl group and the like can be mentioned. Examples of the alkynyl group include C _2-20 alkynyl groups such as ethynyl group and propynyl group.

Examples of the alicyclic hydrocarbon group include a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a _cyclododecyl group; a C _3-12 cyclo group such as a cyclohexenyl group. An alkenyl group; a C _4-15 bridged cyclic hydrocarbon group such as a bicycloheptanyl group and a bicycloheptenyl group.

As said aromatic hydrocarbon group, _C6-14 aryl groups (especially _C6-10 aryl group), such as a phenyl group and a naphthyl group, etc. are mentioned, for example.

Examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. Examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded include, for example, C _7-18 aralkyl groups such as benzyl group and phenethyl group, and C _6-10 aryl-C _2-6 alkenyl groups such as cinnamyl group. And C _1-4 alkyl-substituted aryl groups such as a tolyl group and C _2-4 alkenyl-substituted aryl groups such as a styryl group.

The hydrocarbon group may have a substituent. Although carbon number of the substituent in the said hydrocarbon group is not specifically limited, 0-20 are preferable, More preferably, it is 0-10. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Especially C _1-6 alkoxy group); alkenyloxy group such as allyloxy group (particularly C _2-6 alkenyloxy group); C _1-4 alkyl on aromatic ring such as phenoxy group, tolyloxy group, naphthyloxy group, etc. Group, C _2-4 alkenyl group, halogen atom, aryloxy group which may have a substituent such as C _1-4 alkoxy group (especially C _6-14 aryloxy group); benzyloxy group, phenethyloxy aralkyloxy group (particularly, C _7-18 aralkyloxy group) of the group or the like; an acetyl group, propionyloxy group, (meth) Akuriroiruo Shi group, an acyloxy group such as a benzoyloxy group (in particular, C _1-12 acyloxy group); a mercapto group; methylthio group, an alkylthio group such as an ethylthio group (particularly, C _1-6 alkylthio group); arylthio alkenylthio groups such as Group (especially C _2-6 alkenylthio group); C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group on the aromatic ring such as phenylthio group, tolylthio group, naphthylthio group, etc. An arylthio group (particularly a C _6-14 arylthio group) optionally having a substituent such as aralkylthio group (particularly a C _7-18 aralkylthio group) such as a benzylthio group or a phenethylthio group; a carboxyl group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl alkoxycarbonyl group such as a group (in particular, C _1-6 alkoxy - Carbonyl group); phenoxycarbonyl group, a tolyl group, an aryloxycarbonyl group such as a naphthyloxycarbonyl group (particularly, C _6-14 aryloxy - carbonyl group); aralkyloxycarbonyl group such as benzyloxycarbonyl group (especially, C _7-18 aralkyloxy - carbonyl group); an amino group; methylamino group, ethylamino group, dimethylamino group, mono- or dialkylamino groups such as diethylamino group (especially, mono- or di -C _1-6 alkylamino group) Acyl group such as acetylamino group, propionylamino group and benzoylamino group (especially C _1-11 acylamino group); epoxy group-containing group such as epoxy group, glycidyl group, glycidyloxy group and cyclohexene oxide group; ethyl oxetanyloxy Oxetanyl group such as a group Yumoto; oxo group; an acetyl group, a propionyl group, benzoyl group, etc. bonded groups via a C _1-6 alkylene group, depending These demands have 2 or more thereof.

Among the compounds represented by the above formula (1), a compound represented by the following formula (2) (alicyclic epoxy compound) is particularly preferable from the viewpoint of heat resistance and light resistance of the cured product.

  In the above formula (2), Y 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 groups are linked (for example, a carbonyloxy group). .

  Examples of the alicyclic epoxy compound in which Y in the formula (2) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane ((3,3 ′, 4,4′-diepoxy) Bicyclohexyl). A commercial item can also be used as such an alicyclic epoxy compound.

  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-cyclohexene group. And divalent cycloalkylene groups (including cycloalkylidene groups) such as a silylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  The linking group Y is particularly preferably a linking group containing an oxygen atom, specifically, for example, —CO—, —O—CO—O—, —COO—, —O—, —CONH—; A group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include those exemplified above.

Typical examples of the alicyclic epoxy compound represented by the above formula (2) include compounds represented by the following formulas (2-1) to (2-10). In the following formulas (2-5) and (2-7), l and m each represent an integer of 1 to 30. R in the following formula (2-5) is an alkylene group having 1 to 8 carbon atoms, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group. , A linear or branched alkylene group such as a hexylene 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 (2-9) and (2-10) each represent an integer of 1 to 30.

  Examples of the alicyclic epoxy compounds represented by the above formulas (2-1) to (2-10) include commercially available products such as “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation). Can also be used.

Examples of the compound (ii) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include a compound represented by the following formula (3).

In the formula (3), R ′ is a group obtained by removing p —OH from a p-valent alcohol, and p and n represent natural numbers. 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 may be used alone or in combination of two or more. Among them, as the alicyclic epoxy compound, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate represented by the above formula (2-1), trade name “Celoxide 2021P” (Co., Ltd.) Daicel) is particularly preferable.

  Although content (blending amount) of the alicyclic epoxy compound in the curable epoxy resin composition of the present invention is not particularly limited, the total amount of the compound having an epoxy group contained in the curable epoxy resin composition (total epoxy compound). 50-100 weight% is preferable with respect to 100 weight%, More preferably, it is 60-100 weight%, More preferably, it is 70-100 weight%, Most preferably, it is 80-100 weight%. If content of an alicyclic epoxy compound is less than 50 weight%, the heat resistance of a hardened | cured material and light resistance may fall.

[Core-shell type acrylic polymer particles]
The core-shell type acrylic polymer particle, which is an essential component of 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, and the core The shell layer is a polymer particle 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 can form a cured product having excellent handling properties at room temperature and excellent moisture absorption resistance by containing the above core-shell type acrylic polymer particles.

  In this specification, the acrylic polymer constituting the core of the core-shell type acrylic polymer particle is “acrylic polymer (C)”, and the acrylic polymer constituting the core of the core-shell type acrylic polymer particle is “acrylic polymer (S)”. May be called. Although it does not specifically limit in the said core-shell type acrylic polymer particle, It is preferable that an acrylic polymer (C) and an acrylic polymer (S) have a different composition.

The solubility parameter (δ) (referred to as “solubility parameter (Fedors method)”) at 25 ° C. calculated by the Fedors method of the core-shell type acrylic polymer particles is 19.5 to 21.5 [MPa ^1/2 ], The pressure is preferably 19.7 to 21.3 [MPa ^1/2 ], more preferably 20.0 to 21.0 [MPa ^1/2 ]. When the solubility parameter (Fedors method) of the core-shell type acrylic polymer particles is less than 19.5 [MPa ^1/2 ], the compatibility with the alicyclic epoxy compound is reduced, the heat resistance of the cured product, and the moisture absorption resistance Reflow property and thermal shock resistance are reduced. 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 exceeds 21.5 [MPa ^1/2 ], the compatibility with the alicyclic epoxy compound is reduced, or the moisture absorption reflow resistance of the cured product is reduced. Decreases. 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 is calculated by, for example, calculating the solubility parameter (Fedors method) of acrylic polymer (C) and acrylic polymer (S), respectively, and calculating a weighted average thereof. Can do. The solubility parameter (Fedors method) of the core-shell type acrylic polymer particles is controlled by the composition of the monomers constituting the core-shell type acrylic polymer particles.

The glass transition temperature of the acrylic polymer (C) 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 an acrylic polymer (C) is less than 60 degreeC. On the other hand, when the glass transition temperature of the acrylic polymer (C) 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. Reflowability may be reduced. The glass transition temperature of the acrylic polymer (C) 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.

  In addition, the glass transition temperature of acrylic polymer (C) is controlled by the composition of the monomer which comprises acrylic polymer (C).

  The glass transition temperature of the acrylic polymer (S) is 60 to 120 ° C, preferably 70 to 115 ° C. The heat resistance of hardened | cured material falls that the glass transition temperature of an acrylic polymer (S) is less than 60 degreeC. On the other hand, when the glass transition temperature of the acrylic polymer (S) 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 the moisture absorption resistance of the cured product 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 (S) 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 (C). In addition, the glass transition temperature of acrylic polymer (S) is controlled by the composition of the monomer which comprises acrylic polymer (S).

  Difference between glass transition temperature of acrylic polymer (C) and glass transition temperature of acrylic polymer (S) in the above-mentioned core-shell type acrylic polymer particles [glass transition temperature of acrylic polymer (S) −glass transition temperature of acrylic polymer (C)] Although it does not specifically limit, -5-60 degreeC is preferable, More preferably, it is 0-55 degreeC. 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 (C) and the acrylic polymer (S) 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 (C) and the acrylic polymer (S) include 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 rings, such as acrylic acid dicyclopentadienyl (Meth) acrylic acid ester having (alicyclic); (meth) acrylic acid ester having an aromatic ring such as phenyl (meth) acrylate and benzyl (meth) acrylate; N-methyl-2,2,6, (Meth) acrylic acid ester having a heterocyclic ring such as 6-tetramethylpiperidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy (meth) acrylate (Meth) acrylic acid ester having a hydroxyl group such as butyl or glycerol mono (meth) acrylate; (Meth) acrylic acid ester having an epoxy group such as glycidyl toluate and methyl glycidyl (meth) acrylate; (meth) acrylic acid ester having an amino group such as (meth) acrylic acid N, N-dimethylaminoethyl; (Meth) acrylic acid; (meth) acrylamide and the like. In the present specification, “(meth) acryl” means acrylic and / or methacrylic (any one or both of acrylic and methacrylic).

  As the monomer constituting the acrylic polymer (C) and the acrylic polymer (S), a monomer other than the acrylic monomer 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 (C) and an acrylic polymer (S), the polyfunctional monomer which has a 2 or more polymerizable functional group (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 with respect to the total amount (100% by weight) of the monomer constituting the acrylic polymer (C) is not particularly limited, it is preferably 70 to 100% by weight. In particular, the acrylic polymer (C) is a polymer substantially composed 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 the monomer constituting the acrylic polymer (C), (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.

  Although the ratio of the acrylic monomer with respect to the total amount (100% by weight) of the monomer constituting the acrylic polymer (S) is not particularly limited, it is preferably 70 to 100% by weight. In particular, the acrylic polymer (S) is a polymer substantially composed only of an acrylic monomer (for example, a polymer having a ratio of acrylic monomer to 98 to 100% by weight with respect to the total amount of monomers). It is preferable that As a monomer which comprises the said acrylic polymer (S), the (meth) acrylic-acid alkylester 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 is a polymer substantially composed of only an acrylic monomer (for example, the ratio of the acrylic monomer to the total amount of monomers constituting the core-shell type acrylic polymer particle) It is preferable that the core-shell type acrylic polymer particles are formed by a polymer having a weight of 98 to 100% by weight.

  When a large amount of vinyl cyanide monomer such as (meth) acrylonitrile is used as a monomer constituting the acrylic polymer (C) and the acrylic polymer (S), the monomer has high polarity, so that it is cured. This is not preferable because the moisture absorption reflow resistance of the product tends to decrease. Further, when a large amount of aromatic vinyl monomer such as styrene, α-methylstyrene, vinyltoluene or the like is used as a monomer constituting the acrylic polymer (C) or acrylic polymer (S), 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 (C) (or acrylic polymer (S)) 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 the said core-shell type acrylic polymer particle does not contain a butadiene rubber from a viewpoint of suppressing coloring and deterioration of hardened | cured material. Moreover, it is preferable that the said core-shell type acrylic polymer particle does not contain silicone rubber from a viewpoint of compatibility or cost.

  The ratio (weight ratio) of the acrylic polymer (C) and the acrylic polymer (S) in the core-shell type acrylic polymer particles (acrylic polymer (C) / acrylic polymer (S)) is not particularly limited, but is 1 / 0.1 to 0.1 1/200 is preferable, more preferably 1 / 0.3 to 1/120, still more preferably 1 / 0.4 to 1/10. When the ratio of the acrylic polymer (C) and the acrylic polymer (S) is out of the above range, it is difficult to obtain the effect of improving the adhesion to the adherend described later and quickly increasing the viscosity by heating, and as a result, a 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 particles, for example, an alkyl ester having a C1-C4 alkyl group (particularly methyl methacrylate, butyl methacrylate) and an essential monomer component are used. Monomer having an acrylic polymer (C) having a glass transition temperature of 60 to 120 ° C. as a core and having an alkyl group having 1 to 4 carbon atoms (particularly methyl methacrylate and butyl methacrylate) Examples include core-shell type acrylic polymer particles having a glass transition temperature of 60 to 120 ° C. as a component and having an acrylic polymer (S) having a monomer composition different from that of the acrylic polymer (C) as a shell. The acrylic polymer (S) 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 with respect to the total amount (100% by weight) of the monomer component constituting the acrylic polymer (C) 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 (S) 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 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 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 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 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 (ratio of volume average primary particle diameter Dv to number average primary particle diameter Dn [Dv / Dn]) is not particularly limited, but is preferably 3.0 or less, more preferably 2 0.0 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 can be produced using a known or conventional method for producing core-shell type polymer particles. The core-shell type acrylic polymer particles can be obtained by coating the core with a shell. For example, the core-shell type acrylic polymer particles can be obtained by coating the surface of the core with an acrylic polymer constituting the shell, or using the acrylic polymer constituting the core as a trunk component. Examples thereof include a method of graft polymerization of an acrylic polymer (branch component) constituting the shell. More specifically, the core-shell type acrylic polymer particles 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 can be used singly or in combination of two or more. As the core-shell type acrylic polymer particles, commercially available products such as trade names “METABBRENE KP-0917”, “METABBRENE KP-0930”, “METABBRENE KP-0950” (manufactured by Mitsubishi Rayon Co., Ltd.) are used. You can also.

  The content (blending amount) of the core-shell type acrylic polymer particles 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. When the content of the core-shell type acrylic polymer particles is less than 1 part by weight, the effect of adding the core-shell type acrylic polymer particles is difficult to obtain, and the moisture absorption reflow resistance and thermal shock resistance of the cured product become poor. On the other hand, when the content of the core-shell type acrylic polymer particles 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 and the core-shell type acrylic polymer particles as essential components has high heat resistance, light resistance, and thermal shock resistance, and in particular, moisture absorption reflow resistance. Gives a cured product with excellent properties. These effects in the cured product (especially the effect of improving moisture absorption reflow resistance) are that the core-shell type acrylic polymer particles in the curable epoxy resin composition have a core-shell structure, and the glass transition temperature and solubility of the core and shell. By controlling the parameters within a specific range, the adhesion of cured products to adherends (especially silver electrodes in optical semiconductor devices, etc.) is improved. ) And the shape is presumed to be retained (fixed) before being completely cured. When a general acrylic polymer (such as a linear polymer) is used in place of the core-shell type acrylic polymer particles, the above-described adhesive improvement and thickening effect 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 the present invention containing the core-shell type acrylic polymer particles has a relatively low viscosity at room temperature as described later, it is excellent in handleability.

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

[Monoallyl diglycidyl isocyanurate compound]
The curable epoxy resin composition of the present invention preferably further contains a compound represented by the following formula (I) (monoallyl diglycidyl isocyanurate compound). When the monoallyl diglycidyl isocyanurate compound is included, the moisture absorption reflow resistance and the thermal shock resistance of the cured product tend to be further improved.

In the above formula (I), R ¹ and 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 (I) are particularly preferably hydrogen atoms.

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

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

  Although content (blending amount) of the monoallyl diglycidyl isocyanurate compound is not particularly limited, it is preferably 3 to 50 parts by weight, more preferably 5 to 45 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound. More preferably, it is 10 to 40 parts by weight. When the content of the monoallyl diglycidyl isocyanurate compound exceeds 50 parts by weight, the solubility of the monoallyl diglycidyl isocyanurate compound in the curable epoxy resin composition is lowered, and the physical properties of the cured product may be adversely affected. . On the other hand, when the content of the monoallyl diglycidyl isocyanurate compound is less than 3 parts by weight, the moisture absorption reflow resistance and thermal shock resistance of the cured product may be insufficient.

  The curable epoxy resin composition of the present invention may further contain a curing agent and a curing accelerator, or a curing catalyst.

[Curing agent]
The curing agent in the curable epoxy resin composition of the present invention is a compound having a function of curing a compound having an epoxy group. As said hardening | curing agent, a well-known thru | or usual hardening | curing agent can be used as a hardening | curing agent for epoxy resins. Among these curing agents, acid anhydrides that are liquid at 25 ° C. are preferable, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, and methylendomethylenetetrahydrophthalic anhydride. . In addition, solid acid anhydrides at room temperature (about 25 ° C.) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride are liquid at room temperature (about 25 ° C.). It can be used as a curing agent in the present invention by dissolving in an acid anhydride to form a liquid mixture. In addition, a hardening | curing agent can be used individually by 1 type or in combination of 2 or more types. As described above, as the curing agent, from the viewpoint of heat resistance, light resistance, and crack resistance (characteristics that hardly cause cracks) of a cured product, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (an alkyl group or the like in the ring). And those having the substituents bonded thereto are preferred.

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

  Although it does not specifically limit as content (blending amount) of a hardening | curing agent, 50-200 weight part with respect to the whole quantity (100 weight part) of the compound which has the epoxy group contained in the curable epoxy resin composition of this invention. Is more preferable, and 100 to 145 parts by weight is more preferable. More specifically, it is preferably used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in the compound having all epoxy groups contained in the curable epoxy resin composition of the present invention. . When content of a hardening | curing agent 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 exceeds 200 weight part, hardened | cured material may color and a hue may deteriorate.

[Curing accelerator]
The curing accelerator in the curable epoxy resin composition of the present invention is a compound having a function of accelerating the curing rate when a compound having an epoxy group is cured by the curing agent. As the curing accelerator, known or conventional curing accelerators can be used. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and salts thereof (for example, phenol salts) Octylate, p-toluenesulfonate, formate, tetraphenylborate salt); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), and salts 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; phosphoric acid Ester, phosphines such as triphenylphosphine; tetraphenylphosphonium tetra (p- tolyl) phosphonium compounds such as borate, tin octylate, organic metal salts such as zinc octylate; metal chelate and the like. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

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

  The content (blending amount) of the curing accelerator is not particularly limited, but is 0.05 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. More preferably, it is 0.1-3 weight part, More preferably, it is 0.2-3 weight part, Most preferably, it is 0.25-2.5 weight part. If the content of the curing accelerator is less than 0.05 parts by weight, the curing acceleration effect may be insufficient. On the other hand, when content of a hardening accelerator exceeds 5 weight part, hardened | cured material may color and a hue may deteriorate.

[Curing catalyst]
In the curable epoxy resin composition of the present invention, a curing catalyst can be used instead of the above-mentioned curing agent and curing accelerator. Similarly to the case of using a curing agent and a curing accelerator, by using a curing catalyst, the curing reaction of the compound having an epoxy group can be advanced to obtain a cured product. Although it does not specifically limit as said curing catalyst, The cationic catalyst (cationic polymerization initiator) which generate | occur | produces a cationic seed | species by performing ultraviolet irradiation or heat processing, and starts superposition | polymerization can be used. In addition, a curing catalyst 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 Ciba Japan Co., Ltd.) and trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.

  Examples of the cation catalyst that generates a cation species by performing heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, and allene-ion complexes, and trade names “PP-33”, “ CP-66 "," CP-77 "(manufactured by ADEKA Corporation), 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 "(manufactured by Sanshin Chemical Industry Co., Ltd.), trade name" CG-24-61 "(Ciba Japan) (Commercially available products) 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 is not particularly limited, but is 0.01 to 15 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. More preferably, it is 0.01-12 weight part, More preferably, it is 0.05-10 weight part, Especially preferably, it is 0.1-10 weight part. By using a curing catalyst within the above range, a cured product having excellent heat resistance, light resistance and transparency can be obtained.

[Glycidyl ether epoxy compound having no aromatic ring]
The curable epoxy resin composition of the present invention may further contain a glycidyl ether epoxy compound having no aromatic ring in addition to the alicyclic epoxy compound as an epoxy compound. The inclusion of the glycidyl ether-based epoxy compound having no aromatic ring is preferable because it can improve the crack resistance without impairing the high heat resistance of the cured product, and in particular, the high heat resistance and light resistance of the cured product. It is preferable at the point which can improve crack resistance, without impairing.

  Examples of the glycidyl ether epoxy compound having no aromatic ring include aliphatic glycidyl ether epoxy compounds and compounds obtained by nuclear hydrogenation of aromatic glycidyl ether epoxy compounds. Examples of the glycidyl ether-based epoxy compound having no aromatic ring include, for example, trade names “EPICLON 703”, “EPICLON 707”, “EPICLON 720”, “EPICLON 725” (manufactured by DIC Corporation), trade names “YH-300”, “ “YH-315”, “YH-324”, “PG-202”, “PG-207”, “Santoto ST-3000” (manufactured by Nippon Steel Chemical Co., Ltd.), trade names “Rikaresin DME-100”, “ Rica Resin HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.), trade names “Denacol EX-212”, “Denacol EX-321” (manufactured by Nagase ChemteX Corporation), trade names “YX8000”, “YX8034” ( Commercial products such as Mitsubishi Chemical Corporation) can be preferably used. In addition, the glycidyl ether type epoxy compound which does not have an aromatic ring can be used individually by 1 type or in combination of 2 or more types.

  The content (blending amount) of the glycidyl ether-based epoxy compound having no aromatic ring is not particularly limited, but is 100% by weight based on the total amount of the compound having an epoxy group (total epoxy compound) contained in the curable epoxy resin composition. The content is preferably 10 to 70% by weight, more preferably 20 to 50% by weight.

[Polyol compound]
The curable epoxy resin composition of the present invention may contain a polyol compound. The inclusion of the polyol compound is preferable in that the heat resistance and crack resistance of the cured product can be further improved. The polyol compound is a polymer (oligomer or polymer) having a number average molecular weight of 200 or more having two or more hydroxyl groups in the molecule (in one molecule). For example, polyether polyol, polyester polyol, polycarbonate polyol, etc. included. In addition, the said polyol compound can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polyester polyol include, for example, trade names "Placcel 205", "Placcel 205H", "Placcel 205U", "Placcel 205BA", "Placcel 208", "Placcel 210", "Placcel 210CP", "Placcel 210BA", “Plaxel 212”, “Plaxel 212CP”, “Plaxel 220”, “Plaxel 220CPB”, “Plaxel 220NP1”, “Plaxel 220BA”, “Plaxel 220ED”, “Plaxel 220EB”, “Plaxel 220EC”, “Plaxel 230”, “Plaxel 230CP”, “Plaxel 240”, “Plaxel 240CP”, “Plaxel 210N”, “Plaxel 220N”, “Plaxel L205AL”, “Plaxel L208A” ”,“ Plaxel L212AL ”,“ Plaxel L220AL ”,“ Plaxel L230AL ”,“ Plaxel 305 ”,“ Plaxel 308 ”,“ Plaxel 312 ”,“ Plaxel L312AL ”,“ Plaxel 320 ”,“ Plaxel L320AL ”,“ Plaxel L330AL ” , “Plaxel 410”, “Plaxel 410D”, “Plaxel 610”, “Plaxel P3403”, “Plaxel CDE9P” (above, manufactured by Daicel Corporation) can be used.

  Examples of the polyether polyol include trade name “PEP-101” (manufactured by Freund Sangyo Co., Ltd.), trade names “Adeka Pluronic L”, “Adeka Pluronic P”, “Adeka Pluronic F”, “Adeka Pluronic R”. , “Adeka Pluronic TR”, “Adeka PEG” (above, manufactured by ADEKA Corporation), trade names “PEG # 1000”, “PEG # 1500”, “PEG # 11000” (above, manufactured by NOF Corporation) , “New Pole PE-34”, “New Pole PE-61”, “New Pole PE-78”, “New Pole PE-108”, “PEG-200”, “PEG-600”, “PEG-” 2000 ”,“ PEG-6000 ”,“ PEG-10000 ”,“ PEG-20000 ”(manufactured by Sanyo Chemical Industries, Ltd.), trade name“ TMG1000 "," PTMG1800 "," PTMG2000 "(or, Mitsubishi Chemical Co., Ltd.), can be used" PTMG prepolymer "(manufactured by Mitsubishi Plastics Inc.), and commercial products.

  Examples of the polycarbonate polyol include trade names “Placcel CD205PL”, “Plaxel CD205HL”, “Plaxel CD210PL”, “Plaxel CD210HL”, “Plaxel CD220PL”, “Plaxel CD220HL” (manufactured by Daicel Corporation) Names “UH-CARB50”, “UH-CARB100”, “UH-CARB300”, “UH-CARB90 (1/3)”, “UH-CARB90 (1/1)”, “UC-CARB100” (above, Ube) Manufactured by Kosan Co., Ltd.), trade names such as “PCDL T4671”, “PCDL T4672”, “PCDL T5650J”, “PCDL T5651”, “PCDL T5652” (above, manufactured by Asahi Kasei Chemicals) be able to.

  As the polyol compound, a polyol compound other than the polyether polyol, polyester polyol, and polycarbonate polyol (sometimes referred to as “other polyol compound”) may be used. Examples of the other polyol compounds include trade names “YP-50”, “YP-50S”, “YP-55U”, “YP-70”, “ZX-1356-2”, “YPB-43C”, "YPB-43M", "FX-316", "FX-310T40", "FX-280S", "FX-293", "YPS-007A30", "TX-1016" (Nippon Steel Chemical Co., Ltd. )), Phenoxy resins such as “jER1256”, “jER4250”, “jER4275” (manufactured by Mitsubishi Chemical Corporation); product names “Epototo YD-014”, “Epototo YD-017”, “Epototo” "YD-019", "Epototo YD-020G", "Epototo YD-904", "Epototo YD-907", "Epototo YD-6020" Epoxy equivalents such as “JER1007”, “jER1009”, “jER1010”, “jER1005F”, “jER1009F”, “jER1006FS”, “jER1007FS” (above, manufactured by Mitsubishi Chemical Corporation) Is 1000 g / eq. Bisphenol type polymer epoxy resin exceeding the product name: “Poly bd R-45HT”, “Poly bd R-15HT”, “Poly ip”, “KRASOL” (above, manufactured by Idemitsu Kosan Co., Ltd.), trade name “α Polybutadienes having a hydroxyl group such as -ω polybutadiene glycol G-1000 "," α-ω polybutadiene glycol G-2000 "," α-ω polybutadiene glycol G-3000 "(Nippon Soda Co., Ltd.); “Hitaroid 3903”, “Hitaroid 3904”, “Hitaroid 3905”, “Hitaroid 6500”, “Hitaroid 6500B”, “Hitaroid 3018X” (manufactured by Hitachi Chemical Co., Ltd.), trade name “Acridick DL-1537” , “Acridick BL-616”, “Acridick AL -1157 "," Acridic A-322 "," Acridic A-817 "," Acridic A-870 "," Acridic A-859-B "," Acridic A-829 "," Acridic A " -49-394-IM "(above, manufactured by DIC Corporation), trade names" Dianar SR-1346 "," Dianar SR-1237 "," Dianar AS-1139 "(above, Mitsubishi Rayon Co., Ltd.) Commercially available products such as acrylic polyols, etc.) can be used.

  Although the content (blending amount) of the polyol compound is not particularly limited, it is 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of compounds having epoxy groups (total epoxy compound) contained in the curable epoxy resin composition. Is preferable, more preferably 1.5 to 40 parts by weight, still more preferably 5 to 30 parts by weight. When the content of the polyol compound exceeds 50 parts by weight, the Tg of the cured product is excessively lowered, the volume change due to heating is increased, and problems such as non-lighting of the optical semiconductor device may occur. When the content of the polyol compound is less than 1 part by weight, the heat resistance and light resistance of the cured product may be insufficient.

[Rubber particles]
The curable epoxy resin composition of the present invention may contain rubber particles. Examples of the rubber particles include particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, particulate SBR (styrene-butadiene rubber), and the like. Examples of the rubber particles include 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. As the rubber particles having the core-shell structure, in particular, the surface has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with an alicyclic epoxy compound, an average particle size of 10 to 500 nm, and a maximum particle size of 50. It is preferable that the difference between the refractive index of the rubber particles and the refractive index of the cured product of the curable epoxy resin composition containing the rubber particles is within ± 0.02. The blending amount of the rubber particles can be appropriately adjusted as necessary, and is not particularly limited, but is 0 with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition. The amount is preferably 5 to 30 parts by weight, more preferably 1 to 20 parts by weight. If the amount of rubber particles used is less than 0.5 parts by weight, the crack resistance of the cured product tends to be reduced. On the other hand, if the amount of rubber particles used exceeds 30 parts by weight, the heat resistance and transparency of the cured product are reduced. Tend 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 used as the additive, the reaction can be allowed to proceed slowly. In addition, silicone and fluorine antifoaming agents, leveling agents, and silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane as long as the viscosity and transparency are not impaired. Use conventional additives such as surfactants, inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, UV absorbers, ion adsorbents, pigments, phosphors, mold release agents, etc. Can do.

  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 viscosity at 25 ° C. of the curable epoxy resin composition of the present invention is 60 to 6000 mPa · s, preferably 100 to 5500 mPa · s, and more preferably 150 to 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, a cured product having excellent heat resistance, light resistance, and thermal shock resistance, and particularly excellent in moisture absorption reflow resistance 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 optical semiconductor encapsulation. 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 set in the same range as at the time of preparing the cured product.

  In particular, the curable epoxy resin composition of the present invention can be preferably used as a sealant used in an embodiment in which it is cured after being poured into a certain space. The curable epoxy resin composition of the present invention is cured even in a case where a load due to high temperature (for example, thermal history in a reflow process) or thermal shock (for example, cooling / heating cycle) is applied after curing in the above-described fixed space. This is because the effect of hardly causing peeling or cracking can be exhibited. Therefore, the curable epoxy resin composition of the present invention is particularly preferably used as a sealing agent for forming a PLCC sealing material for LEDs, an inner sealing material for bullet-type LEDs, a flip chip sealing material, and the like. be able to.

  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.

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, 5.25 g of ammonium di-2-ethylhexylsulfosuccinate, 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 the mixture was held for 1 hour after the dropping, thereby completing the first stage polymerization.
Next, a monomer obtained by emulsifying 219.3 g of methyl methacrylate, 5.7 g of methacrylic acid, 2.25 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 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 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).

Example 1
100 parts by weight of an alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation) and 10 parts by weight of an acrylic polymer powder (P1) were mixed into a self-revolving stirrer (trade name “Noritaro Awatori” AR-250 "(manufactured by Shinky Co., Ltd.) was mixed uniformly and defoamed to obtain agent A.
110 parts by weight of curing agent (acid anhydride) (trade name “MH-700F”, manufactured by Shin Nippon Rika Co., Ltd.), curing accelerator (trade name “U-CAT 18XD”, manufactured by San Apro Co., Ltd.) 0.5 Part by weight and 3 parts by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.) Were mixed and defoamed to obtain agent B.
The above-obtained agent A and agent B were mixed at a ratio of [agent A / agent B] (weight ratio) = 100/100, with a self-revolving stirrer (trade name “Awatori Nerita AR-250”, ) Manufactured by Shinky Co., Ltd.) and uniformly 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 which sealed the optical semiconductor element 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 1-8
A curable epoxy resin composition was prepared in the same manner as in Example 1 except that the compositions of Agent A and Agent B were changed to the compositions shown in Tables 2 and 3. In addition, an optical semiconductor device was fabricated in the same manner as in Example 1. As shown in Tables 2 and 3, in Example 2 and Comparative Example 2, B agent was not used as a constituent component of the curable epoxy resin composition, and only A agent was used.

<Evaluation>
The following evaluation tests were performed using the optical semiconductor devices obtained in the examples and comparative examples.

[Energization test]
The total luminous fluxes of the optical semiconductor devices (10 used for each curable epoxy resin composition) obtained in the examples and comparative examples were measured using a total luminous flux measuring instrument (referred to as “initial total luminous flux”). Further, the total luminous flux after a current of 20 mA was passed through the optical semiconductor device for 1000 hours in a thermostat at 60 ° C. and 90% RH was measured (referred to as “total luminous flux after 1000 hours”). Then, the luminous intensity maintenance rate was calculated from the following formula, and the number of optical semiconductor devices having a luminous intensity maintenance rate of less than 90% among the 10 optical semiconductor devices was measured. The results are shown in Tables 2 and 3.
(Luminance maintenance rate (%))
= 100 × (total luminous flux after 1000 hours (lm)) / (initial total luminous flux (lm))

[Luminance maintenance rate after reflow]
The total luminous fluxes of the optical semiconductor devices (10 used for each curable epoxy resin composition) obtained in the examples and comparative examples were measured using a total luminous flux measuring instrument (referred to as “initial total luminous flux”). Furthermore, the optical semiconductor device was placed in a condition of 30 ° C. and 70% RH for 168 hours to absorb moisture, then placed in a reflow furnace and heated under the following heating conditions. Thereafter, the optical semiconductor device was taken out in a room temperature environment and allowed to cool, and then placed in a reflow furnace again and heated under the same conditions. That is, in this 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 the surface temperature profile of the optical semiconductor device during heating in the reflow furnace (temperature profile in one of the two heating operations).
Thereafter, the total luminous flux of the optical semiconductor device was measured (referred to as “total luminous flux after reflow”). Then, the luminous intensity maintenance rate was calculated from the following formula, and the number of optical semiconductor devices having a luminous intensity maintenance rate of less than 90% among the 10 optical semiconductor devices was measured. The results are shown in Tables 2 and 3.
(Luminance maintenance rate (%))
= 100 × (total luminous flux after reflow (lm)) / (initial total luminous flux (lm))

[Red ink test (after reflow)]
The optical semiconductor devices obtained in Examples and Comparative Examples (10 used for each curable epoxy resin composition) were heat-treated under the same conditions as the measurement of the luminous intensity maintenance rate after the reflow. Next, the optical semiconductor device after the heat treatment was immersed in red ink (aqueous) at 25 ° C. for 4 hours. Thereafter, the digital ink is taken out from the red ink and whether or not the red ink penetrates into the inside of the optical semiconductor device (when it penetrates, the electrode is dyed red) is a digital microscope (VHX-900, manufactured by Keyence Corporation). Was used to observe. Of the ten optical semiconductor devices, the number of optical semiconductor devices into which the red ink penetrated was measured. The results are shown in Tables 2 and 3. The penetration of the red ink suggests that the cured product is peeled and / or cracked.

[Thermal shock test]
The total luminous fluxes of the optical semiconductor devices (10 used for each curable epoxy resin composition) obtained in the examples and comparative examples were measured using a total luminous flux measuring instrument (referred to as “initial total luminous flux”). Furthermore, a thermal shock tester was used for thermal shock in which the optical semiconductor device was exposed to a −40 ° C. atmosphere for 15 minutes and then exposed to a 120 ° C. atmosphere for 15 minutes as one cycle. 1000 cycles were given. Thereafter, the total luminous flux of the optical semiconductor device was measured (referred to as “total luminous flux after thermal shock”). Then, the luminous intensity maintenance rate was calculated from the following formula, and the number of optical semiconductor devices having a luminous intensity maintenance rate of less than 90% among the 10 optical semiconductor devices was measured. The results are shown in Tables 2 and 3.
(Luminance maintenance rate (%))
= 100 × (total luminous flux after thermal shock (lm)) / (initial total luminous flux (lm))

In addition, the component used by the Example, the comparative example, and the manufacture example is as follows.
MMA: methyl methacrylate n-BMA: n-butyl methacrylate BA: n-butyl acrylate i-BMA: i-butyl methacrylate MAA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate 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. Celoxide 3000: 1, 2, 8, 9- Diepoxy limonene, manufactured by Daicel Corporation YD-128: bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd. Z-6040: silane coupling agent, manufactured by Toray Dow Corning Co., Ltd., SI-100L (Sun-Aid SI) -100L): Ally Sulphonium salt, MH-700F (Rikacid MH-700F) manufactured by Sanshin Chemical Industry Co., Ltd .: Curing agent, U-CAT 18XD manufactured by Shin Nippon Rika Co., Ltd., curing accelerator, manufactured by San Apro Co., Ltd. Ethylene glycol: Jun Wako Made by Yakuhin 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

  The curable epoxy resin composition of the present invention is an optical semiconductor sealing resin composition (particularly for forming a PLCC sealing material for LEDs, an inner sealing material for bullet-type LEDs, a flip chip sealing material, etc.) It can be preferably used as a sealing agent. In addition, the curable epoxy resin composition of the present invention includes, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, a resist, a composite material, a transparent substrate, a transparent sheet, a transparent film, and an optical element. , Optical lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and the like.

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

Claims (8)

An alicyclic epoxy compound and core-shell type acrylic polymer particles having a solubility parameter (Fedors method) of 19.5 to 21.5 [MPa ^1/2 ],
The glass transition temperature of the acrylic polymer constituting the core of the core-shell type acrylic polymer particles is 60 to 120 ° C., and the glass transition temperature of the acrylic polymer constituting the shell is 60 to 120 ° C.,
The ratio of the aromatic vinyl monomer to the total amount (100% by weight) of the monomer component constituting the acrylic polymer constituting the core of the core-shell type acrylic polymer particle is 5% by weight or less,
Difference between the glass transition temperature of the acrylic polymer constituting the core of the core-shell type acrylic polymer particle and the glass transition temperature of the acrylic polymer constituting the shell of the core-shell type acrylic polymer particle [of the acrylic polymer constituting the shell of the core-shell type acrylic polymer particle Glass transition temperature-Glass transition temperature of acrylic polymer constituting core of core-shell type acrylic polymer particles] is -5 to 60 ° C,
The content of the core-shell type acrylic polymer particles is 1 to 30 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound,
A curable epoxy resin composition having a viscosity at 25 ° C. of 60 to 6000 mPa · s. Furthermore, the curable epoxy resin composition of Claim 1 containing the compound represented by a following formula (I).

[In Formula (I), R < ¹ > and R < ² > are the same or different and show a hydrogen atom or a C1-C8 alkyl group. ] The curable epoxy resin composition according to claim 1 or 2, wherein the alicyclic epoxy compound is a compound represented by the following formula (1).

[In the formula (1), X represents a monovalent organic group. ] The curable epoxy resin composition according to any one of claims 1 to 3, wherein the alicyclic epoxy compound is a compound represented by the following formula (2-1).

  Furthermore, the curable epoxy resin composition of any one of Claims 1-4 containing a hardening | curing agent and a hardening accelerator, or a hardening catalyst. Hardened | cured material of the curable epoxy resin composition of any one of Claims 1-5.   It is a resin composition for optical semiconductor sealing, The curable epoxy resin composition of any one of Claims 1-5.   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 7.

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