TWI607054B - Curable epoxy resin composition - Google Patents

Description

Curable epoxy resin composition

The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, and a light obtained by sealing the optical semiconductor element with the cured product of the curable epoxy resin composition. Semiconductor device.

In recent years, high output of optical semiconductor devices has been progressing, and resins for such optical semiconductor devices are required to have high heat resistance and light resistance. In the past, as a sealing resin having high heat resistance, for example, a composition containing a monoallyl isocyanate diglycidyl ester and a bisphenol A type epoxy resin is known (see Patent Document 1). However, the above composition is used as a high output blue. In the case of a sealant for a white light semiconductor, coloring due to light and heat emitted from the optical semiconductor element causes absorption of light that should be originally output, and as a result, the luminance of light output from the optical semiconductor device is lowered.

As a sealant having high heat resistance and light resistance and not easily yellowing, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanoic acid is known, (3,4- An epoxy group) an adduct of 3,4-epoxycyclohexylmethyl epoxide and ε-caprolactone, and an alicyclic skeleton such as 1,2,8,9-dicyclooxynonene An alicyclic epoxy resin. However, these alicyclic epoxy resins The various stresses of the cured product are weak, and problems such as cracking (cracking) occur when hot pressing such as a cold heat cycle (periodic repeated heating and cooling) is applied.

Further, an optical semiconductor device (for example, a surface mount type optical semiconductor device) generally passes through a reflow step for connecting electrodes of the optical semiconductor device to the wiring substrate by soldering. In recent years, a solder which is a bonding material uses a high-melting-free lead-free solder, so that the heat treatment in the reflow step becomes higher (for example, the peak temperature is 240 to 260 ° C). In this case, in the conventional optical semiconductor device, the sealing material is peeled off from the lead frame of the optical semiconductor device due to the heat treatment in the reflow step, and there is a problem that cracks or the like are deteriorated.

Therefore, in addition to high heat resistance and light resistance, the sealing material in the optical semiconductor device is required to have a property of being less likely to be cracked when heat is applied (also referred to as "heat-resistant"), and The reflow step is also less susceptible to cracking and peeling when subjected to heat treatment. In particular, in recent years, from the viewpoint of ensuring higher reliability of the sealing material, moisture absorption under high humidity conditions for a certain period of time (for example, 168 hours at 30 ° C, 70% RH; at 60 ° C, 60 After 40 hours of the condition of %RH, etc., when the heat treatment is performed by the reflow step, cracks and peeling are unlikely to occur (this characteristic is also referred to as "water absorption reflow resistance").

[Previous Technical Literature] [Patent Document]

Patent Document 1 Japanese Patent Laid-Open Publication No. 2000-344867

Accordingly, it is an object of the present invention to provide a high resistance A curable epoxy resin composition of a cured product having excellent heat resistance, light resistance, and heat repellency, and particularly excellent moisture absorption reflow resistance.

Further, another object of the present invention is to provide a cured product which has high heat resistance, light resistance, and heat repellency, and is particularly resistant to moisture reflow.

Further, another object of the present invention is to provide an optical semiconductor device capable of suppressing deterioration such as reduction in luminance, and in particular, capable of suppressing a decrease in luminance when heated in a reflow step after being stored in a high-humidity condition.

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

That is, the present invention provides a curable epoxy resin composition characterized by comprising: an alicyclic epoxy compound, and a core-shell type acrylic acid polymerization having a solubility parameter (Fedors method) of 19.5 to 21.5 [MPa ^1/2 ]. And 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 outer shell is 60 to 120 ° C, and the core-shell type acrylic acid The content of the polymer particles is 1 to 30 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound, and the viscosity at 25 ° C is 60 to 6000 mPa. s.

Further, the above curable epoxy resin composition containing a compound represented by the following formula (I) is also provided.

In the formula (I), 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. ]

Furthermore, the above-mentioned curable epoxy resin composition of the compound represented by the following formula (1) is also provided.

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

Furthermore, the curable epoxy resin composition of the compound represented by the following formula (2-1) is also provided as the alicyclic epoxy compound.

Further, the above-mentioned curable epoxy resin composition containing a hardener, a hardening accelerator, or a curing catalyst is further provided.

Further, the present invention provides a cured product obtained by curing the curable epoxy resin composition.

Further, a resin composition for optical semiconductor sealing, which is a curable epoxy resin composition as described above, is also provided.

Further, the present invention provides an optical semiconductor device in which an optical semiconductor element is sealed by a cured product of the curable epoxy resin composition.

The curable epoxy resin composition of the present invention has the above-described configuration, and by curing the resin composition, it is possible to form a hardening having high heat resistance, light resistance, and heat repellency, and particularly excellent moisture absorption reflow resistance. Things. Therefore, when the curable epoxy resin composition of the present invention is used as a resin composition for photo-semiconductor sealing, it is possible to obtain brightness even when stored in a reflow step, particularly after storage under high-humidity conditions. High quality optical semiconductor devices that are not easily reduced.

100‧‧‧Reflector (resin composition for light reflection)

101‧‧‧Metal wiring

102‧‧‧Optical semiconductor components

103‧‧‧ bonding line

104‧‧‧ hardened material (sealing material)

Fig. 1 is a schematic view showing an embodiment of an optical semiconductor device in which an optical semiconductor element is sealed using the curable epoxy resin composition of the present invention. The figure (a) on the left side is a perspective view, and the figure (b) on the right side is a cross-sectional view.

Fig. 2 is a view showing an example of the surface temperature curve (temperature curve of primary heating in two heating) of the optical semiconductor device in the measurement of the brightness maintenance rate after reflow after the embodiment.

[Formation of the Invention]

<Curable epoxy resin composition>

The curable epoxy resin composition of the present invention comprises at least: an alicyclic epoxy compound, and 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 It is a resin composition of core-shell type acrylic polymer particles having a glass transition temperature of 60 to 120 ° C which is an acrylic polymer of 60 to 120 ° C.

[alicyclic epoxy compound]

The alicyclic epoxy compound which 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 a molecule (within one molecule). Specific examples of the alicyclic epoxy compound include (i) a compound having an epoxy group composed of two carbon atoms and an oxygen atom which are adjacent to each other in the alicyclic ring, and (ii) an epoxy group directly A compound which is bonded to an alicyclic ring by a single bond or the like.

The above (i) has a compound having an epoxy group (alicyclic epoxy group) composed of two carbon atoms and an oxygen atom adjacent to the alicyclic ring, and can be arbitrarily selected from the conventionally known compounds. Among them, the above alicyclic epoxy group is preferably an oxycyclohexane group.

The above (i) has a compound having an epoxy group composed of two carbon atoms and an oxygen atom adjacent to the alicyclic ring, and particularly preferably has oxidized cyclohexane from the viewpoint of transparency and heat resistance. A compound represented by the following formula (1) (alicyclic epoxy compound).

In the above formula (1), X represents a monovalent organic group. Examples of the above monovalent organic group include a hydrocarbon group (monovalent hydrocarbon group), an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, a decyloxy group, an alkylthio group, an alkenethio group, and an aromatic sulfur. Base, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkoxycarbonyl group, epoxypropyl group, epoxy group, cyano group, isocyanate group, amine methyl group, isothiocyanate An ester group or a group in which these groups are bonded to a linking group to be described later.

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 them are bonded.

The aliphatic hydrocarbon group may, for example, be an alkyl group, an alkenyl group or an alkynyl group. The alkyl group may, for example, be a C _1-20 alkyl group 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 or a dodecyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a methallyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a 1-pentene group. A C _2-20 alkenyl group such as a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group or a 5-hexenyl group. Examples of the alkynyl group include a C _2-20 alkynyl group such as an ethynyl group and a propynyl group.

The alicyclic hydrocarbon group may, for example, be a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cyclododecyl group; a C _3-12 cycloalkenyl group such as a cyclohexenyl group; A C _4-15 bridged cyclic hydrocarbon group such as a bicycloheptyl group or a bicycloheptenyl group.

Examples of the aromatic hydrocarbon group include a C _6-14 aryl group (particularly a C _6-10 aryl group) such as a phenyl group or a naphthyl group.

Further, examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are bonded to each other 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 to each other include a C _6-18 aralkyl group such as a benzyl group or a phenethyl group, and a C _6-10 aryl-C _2-6 alkenyl group such as a propylene phenyl group. And a C _2-4 alkenyl substituted aryl group such as a C _1-4 alkyl group such as a tolyl group or a styryl group.

The above hydrocarbon group may have a substituent. The carbon number of the substituent in the above hydrocarbon group is not particularly limited, but is preferably 0 to 20, more preferably 0 to 10. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxyl group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group or the like. Alkoxy group (especially C _1-6 alkoxy group); alkenyloxy group such as allyloxy group (especially C _2-6 alkenyloxy group); phenoxy group, tolyloxy group, naphthyloxy group, etc. An aryloxy group (particularly a C _6-14 aryloxy group) which may have a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom or a C _1-4 alkoxy group in the aromatic ring; An aralkoxy group such as a methyloxy group or a phenethyloxy group (particularly a C _7-18 aralkyloxy group); an ethoxy group, a propenyloxy group, a (meth) acryloxy group, a benzamidine group An oxy group such as an oxy group (especially a C _1-12 decyloxy group); a fluorenyl group; an alkylthio group such as a methylthio group or an ethylthio group (particularly a C _1-6 alkylthio group); an allylthio group or the like Sulfur-based (especially C _2-6 alkenylthio); phenylthio, tolylthio, naphthylthio, etc., may have a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom in the aromatic ring. An arylthio group of a substituent such as a C _1-4 alkoxy group (particularly a C _6-14 arylthio group); an aralkylthio group such as a benzylthio group or a phenethylthio group ( In particular, C _7-18 aralkylthio group; carboxyl group; alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group (especially C _1-6 alkoxy group) An aryloxycarbonyl group such as a phenoxycarbonyl group, a tolyloxycarbonyl group or a naphthyloxycarbonyl group (particularly a C _6-14 aryloxy-carbonyl group); an aralkoxycarbonyl group such as a benzyloxycarbonyl group (especially C _7-18 aralkyloxy-carbonyl); amine group; mono or dialkylamino group such as methylamino, ethylamino, dimethylamino, diethylamino (especially mono or di-C _{1- 6} alkylamino); acetamino group, propylamino group, benzylamino group, etc. amide group (especially C _1-11 guanamine group); epoxy group, epoxy propyl group, epoxide group An epoxy group-containing group such as a oxy group or an oxycyclohexane group; an oxetane group containing an oxetane group; an ethyl oxetyl group; a propyl fluorenyl group; The fluorenyl group; a pendant oxy group; a group in which two or more kinds are bonded to a C _1-6 alkylene group as needed.

Among the compounds represented by the above formula (1), a compound represented by the following formula (2) (alicyclic epoxy compound) is preferred 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 (having a divalent group of 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 bond, a guanamine group, and a plurality of groups (for example, a carbonyloxy group) which are bonded to each other.

Department of formula Y a single bond aliphatic epoxy compound (2) in the ring include, for example: 3,4,3 ', 4' - bicyclo-biphenyl cyclohexane ((3,3 ', 4,4 ' -Dioctyloxy)bicyclohexane). Commercially available products of such alicyclic epoxy compounds can be used.

The divalent hydrocarbon group may, for example, be a linear or branched alkylene group having a carbon number of 1 to 18, a divalent alicyclic hydrocarbon group or the like. Examples of the linear or branched chain 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. Wait. The divalent alicyclic hydrocarbon group may, for example, be 1,2-cyclopentadienyl, 1,3-cyclopentadienyl, cyclopentylene, 1,2-cyclohexanediyl, 1,3-cyclohexane A divalent cycloalkanediyl group (including a cycloalkylene group) such as a 1,4-cyclohexanediyl group or a cyclohexylene group.

The above-mentioned linking group Y is particularly preferably a linking group containing an oxygen atom, and specific examples thereof include -CO-, -O-CO-O-, -COO-, -O-, -CONH-; A plurality of linked groups; a group in which one or two or more of these bases are bonded to one or two or more divalent hydrocarbon groups. The divalent hydrocarbon group may be exemplified as described above.

Representative examples of the alicyclic epoxy compound represented by the above formula (2) include compounds represented by the following formulas (2-1) to (2-10). Further, l and m in the following formulas (2-5) and (2-7) each represent an integer of 1 to 30. The R group in the following formula (2-5) is an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a butylene group, and an isobutylene group. A linear or branched chain alkylene group such as a secondary butylene group, a pentylene group, a hexylene group, a heptylene group or a octylene group. Among them, a linear or branched chain alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group or an isopropylidene group is preferable. In the following formulas (2-9) and (2-10), n1 to n6 each represent an integer of 1 to 30.

For the alicyclic epoxy compound represented by the above formulas (2-1) to (2-10), for example, a product such as "CELLOXIDE 2021P" or "CELLOXIDE 2081" (manufactured by Daicel) can be used. Sale.

The compound represented by the following formula (3) is exemplified as the compound in which the (ii) epoxy group is directly bonded to the alicyclic ring by a single bond.

In the formula (3), R ' is a group obtained by removing p -OH from a p-valent alcohol, and p and n are natural numbers. The p-valent alcohol [R ' -(OH) _p ] may, for example, be a polyhydric alcohol such as 2,2-bis(hydroxymethyl)-1-butanol or the like (an alcohol having 1 to 15 carbon atoms). p is preferably from 1 to 6, and n is preferably from 1 to 30. In the case where p is 2 or more, the n of each of the bases (in the parentheses) may be the same or different. Specific examples of the above compound include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. The product name is "EHPE 3150" (manufactured by Daicel).

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, the alicyclic epoxy compound is particularly preferably 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanoate represented by the above formula (2-1), and the trade name "CELLOXIDE" 2021P" ((share) made by Daicel).

The content (adjusted amount) of the alicyclic epoxy compound in the curable epoxy resin composition of the present invention is not particularly limited, but is equivalent to the epoxy group-containing compound contained in the curable epoxy resin composition. The total amount (all epoxy compounds) is 100% by weight, preferably 50 to 100% by weight, more preferably 60 to 100% by weight, still more preferably 70 to 100% by weight, particularly preferably 80 to 100% by weight. When the content of the alicyclic epoxy compound is less than 50% by weight, the heat resistance and light resistance of the cured product may be lowered.

[core-shell acrylic polymer particles]

The core-shell type acrylic polymer particles, which are essential components of the curable epoxy resin composition of the present invention, have a core-shell structure composed of an inner core and a shell layer (shell) covering a single layer or a plurality of layers of the core, the core Both of the outer shell layers are polymer particles composed of an acrylic polymer (a polymer having an acrylic monomer as an essential monomer component). The curable epoxy resin composition of the present invention, as described later, can form a cured product which is excellent in usability at room temperature and excellent in hygroscopicity by containing the core-shell type acrylic polymer particles.

In the present specification, the acrylic polymer constituting the core of the core-shell type acrylic polymer particles is referred to as "acrylic polymer (C)", and the outer shell of the core-shell type acrylic polymer particles is formed. The olefin polymer is referred to as "acrylic polymer (S)". The core-shell type acrylic polymer particles are not particularly limited, but preferably the acrylic polymer (C) and the acrylic polymer (S) have different compositions.

The solubility parameter (δ) of the core-shell type acrylic polymer particles calculated by the Fedors method at 25 ° C (referred to as "solubility parameter (Fedors method)") is 19.5 to 21.5 [MPa ^1/2 ], preferably 19.7. ~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 lowered, and the heat resistance and moisture absorption reflow of the cured product are improved. Sex and heat resistance will be reduced. In general, a monomer which causes a low solubility parameter (for example, an alkyl (meth)acrylate having a long-chain alkyl group) has a tendency to lower the glass transition temperature, and is particularly useful when a large amount of such a monomer unit is contained. There is a tendency that the heat resistance, moisture absorption reflow resistance, and impact resistance of the cured product are lowered. On the other hand, if the solubility parameter (Fedors method) of the core-shell type acrylic polymer particles is more than 21.5 [MPa ^1/2 ], the compatibility with the alicyclic epoxy compound is lowered, and the cured product is resistant to moisture absorption. Weldability will decrease. In general, a single system having a high solubility parameter has a hydrophilic functional group (for example, a carboxyl group or a nitrile group), and when such a monomer unit is contained in a large amount, the moisture absorption reflow resistance of the cured product tends to be lowered. The solubility parameter (Fedors method) of the core-shell type acrylic polymer particles can be calculated by, for example, calculating the solubility parameter (Fedors method) of the acrylic polymer (C) and the acrylic polymer (S), and then weighting the average Calculated. Further, 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 above acrylic polymer (C) is 60 to 120 ° C, preferably 70 to 110 ° C, more preferably 80 to 100 ° C. When the glass transition temperature of the acrylic polymer (C) is less than 60 ° C, the heat resistance of the cured product is lowered. On the other hand, when the glass transition temperature of the acrylic polymer (C) is more than 120 ° C, for example, when a large amount of a monomer component (for example, (meth)acrylic acid or the like) which contributes to a high glass transition temperature is present, the cured product There is a reduced resistance to moisture reflow. Here, the glass transition temperature of the acrylic polymer (C) means a calculated value calculated by the following formula of Fox (refer to Bull. Am. Phys. Soc., 1 (3) 123 (1956)). In the formula of the following Fox, Tg represents the glass transition temperature (unit: K) of the acrylic polymer, and W _i represents the weight fraction of the monomer i with respect to the total amount of the monomers constituting the acrylic polymer. Further, Tg _i represents the glass transition temperature (unit: K) of the homopolymer of monomer i. The following formula of Fox shows a case where 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

The glass transition temperature of the above homopolymer can be a value described in various documents, and for example, the value described in "POLYMER HANDBOOK 3rd Edition" (issued by John Wiley & Sons, Inc.) can be used. Among them, for the undocumented matter in the literature, the value of the glass transition temperature measured by DSC using a homopolymer obtained by polymerizing a monomer in a usual manner can be employed.

Among them, the glass transition temperature of the acrylic polymer (C) can be controlled by the composition of the monomers constituting the acrylic polymer (C).

The glass transition temperature of the above acrylic polymer (S) is 60 to 120 ° C, preferably 70 to 115 ° C. Glass transition of acrylic polymer (S) If the shift temperature 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 acrylic polymer (S) is more than 120 ° C, for example, when a large amount of a monomer component (for example, (meth)acrylic acid or the like) which contributes to a high glass transition temperature is present, the cured product The moisture absorption reflow resistance may be lowered, and the long-term storage stability may be deteriorated due to viscosity change or the like. Here, the glass transition temperature of the acrylic polymer (S) means a calculated value calculated by the following formula of Fox, and can be calculated in the same manner as the glass transition temperature of the acrylic polymer (C). Further, the glass transition temperature of the acrylic polymer (S) can be controlled by the composition of the monomers constituting the acrylic polymer (S).

In the above-mentioned core-shell type acrylic polymer particles, the difference between the glass transition temperature of the acrylic polymer (C) and the glass transition temperature of the acrylic polymer (S) [glass transition temperature of the acrylic polymer (S) - acrylic polymer (C The glass transition temperature] is not particularly limited, but is preferably -5 to 60 ° C, more preferably 0 to 55 ° C. When the difference in the glass transition temperature is controlled to the above range, the adhesion of the curable epoxy resin composition at the time of curing is improved, and the moisture absorption reflow resistance of the cured product is improved, and the heat resistance of the cured product is further improved. There will be a tendency to improve.

The acrylic polymer (C) and the acrylic polymer (S) are each an acrylic polymer 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, and n-propyl (meth)acrylate. Isopropyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, butyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylate Heptyl ester, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, decyl (meth)acrylate, (alkyl) (meth)acrylate, alkyl (meth)acrylate such as octadecyl (meth)acrylate; cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6] decan-8-acrylate, (meth) acrylate, dicyclopentadienyl esters having an aliphatic cyclic (alicyclic) of (A Acrylate; (meth) acrylate having an aromatic ring such as phenyl (meth) acrylate or benzyl (meth) acrylate; N-methyl-2,2,6,6-tetramethyl Piperidinyl (meth) acrylate, etc. Acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, etc. (meth) acrylate having a hydroxyl group; (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate, methyl epoxypropyl (meth) acrylate; (meth) acrylate N, A (meth) acrylate having an amine group such as N-dimethylaminoethyl ester; (meth)acrylic acid; (meth)acrylamide or the like. In the present specification, "(meth)acrylic" means acrylic acid and/or methacrylic acid (either or both of acrylic acid and methacrylic acid).

The monomer constituting the acrylic polymer (C) or the acrylic polymer (S) may be used in combination with a monomer other than the acrylic monomer. Examples of the monomer other than the acrylic monomer include an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene; and a vinyl cyanide monomer such as acrylonitrile or methacrylonitrile; a monomer having a carboxyl group such as crotonic acid, itaconic acid, fumaric acid or maleic acid; vinyl pyridine, vinyl alcohol, and ethyl Vinyl monomers such as alkenyl imidazole, vinyl pyrrolidone, vinyl acetate, 1-vinylimidazole; monomethyl meconate, monoethyl ikonate, monopropyl itaconate, and itaconic acid Icitol esters such as butyl ester, dimethyl ikonate, diethyl itaconate, dipropyl itaconate, dibutyl itaconate; monomethyl fumarate, fumaric acid Monoethyl ester, monopropyl methacrylate, monobutyl butyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, anti Fumarate such as dibutyl phthalate; monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate And maleic acid maleate such as dimethyl maleate, diethyl maleate, dipropyl maleate or dibutyl maleate.

Further, as the monomer constituting the acrylic polymer (C) or the acrylic polymer (S), a polyfunctional monomer having two or more polymerizable functional groups (for example, an aliphatic carbon-carbon double bond or the like) may be used. Examples of the polyfunctional monomer include divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diallyl maleate, and cyanuric acid. Allyl ester, diallyl phthalate, butanediol diacrylate, and the like.

The ratio of the acrylic monomer to the total amount (100% by weight) of the monomers constituting the acrylic polymer (C) is not particularly limited, but is preferably 70 to 100% by weight. In particular, the acrylic polymer (C) is substantially a polymer composed only of an acrylic monomer (for example, a polymer having a ratio of acrylic monomers of 98 to 100% by weight based on the total amount of the monomers) It is preferred. The monomer constituting the above acrylic polymer (C) is preferably a (meth) propyl group having an alkyl group having 1 to 4 carbon atoms. The alkyl olefinate is more preferably methyl methacrylate, butyl acrylate or butyl methacrylate.

The ratio of the acrylic monomer to the total amount (100% by weight) of the monomers constituting the acrylic polymer (S) is not particularly limited, but is preferably 70 to 100% by weight. In particular, the acrylic polymer (S) is a polymer consisting essentially only of an acrylic monomer (for example, a polymer having a ratio of acrylic monomers of 98 to 100% by weight based on the total amount of the monomers) It is preferred. The monomer constituting the above acrylic polymer (S) is preferably an alkyl (meth)acrylate having a carbon number of 1 to 4, (meth)acrylic acid, more preferably methyl methacrylate. , butyl acrylate, butyl methacrylate, methacrylic acid.

That is, the core-shell type acrylic polymer particles are preferably a polymer composed of substantially only an acrylic monomer (for example, an acrylic single sheet with respect to the total amount of monomers constituting the core-shell type acrylic polymer particles). The shell-shell type acrylic polymer particles are formed by a ratio of 98 to 100% by weight of the polymer.

When a monomer constituting the acrylic polymer (C) or the acrylic polymer (S) is used in a large amount, a vinyl cyanide monomer such as (meth)acrylonitrile is used, since the monomer has high polarity, moisture resistance of the cured product Reflowability tends to decrease and is less preferred. Further, when a monomer constituting the acrylic polymer (C) or the acrylic polymer (S) is used in a large amount, an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene is used, and the cured product changes. It is easy to color and is not good. Therefore, the ratio of the vinyl cyanide monomer to the aromatic vinyl monomer is preferably relative to the total amount (100% by weight) of the monomers constituting the above acrylic polymer (C) (or the acrylic polymer (S)). 5 weights The amount is preferably 5% or less, more preferably 2% by weight or less, and particularly preferably substantially not (actively not formulated as a monomer component).

Further, the core-shell type acrylic polymer particles preferably do not contain butadiene rubber from the viewpoint of suppressing coloration and deterioration of the cured product. Further, the core-shell type acrylic polymer particles preferably contain no polyoxyxene rubber from the viewpoint of compatibility and cost.

The ratio (weight ratio) of the acrylic polymer (C) to the acrylic polymer (S) in the core-shell type acrylic polymer particles [acrylic polymer (C) / acrylic polymer (S)] is not particularly limited, However, it is preferably from 1/0.1 to 1/200, more preferably from 1/0.3 to 1/120, and even more preferably from 1/0.4 to 1/10. When the ratio of the acrylic polymer (C) to the acrylic polymer (S) is outside the above range, it is difficult to obtain an adhesion force to the adherend which will be described later, and heating is used to promote the effect of thickening. As a result, there is a result. The effect of improving the usability of the curable epoxy resin composition and the effect of improving the moisture reflow resistance of the cured product are not obtained.

Particularly preferred embodiments of the core-shell type acrylic polymer particles include, for example, alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (particularly methyl methacrylate or butyl methacrylate). As an essential monomer component, the acrylic polymer (C) having a glass transition temperature of 60 to 120 ° C is regarded as an inner core, and an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (especially A) is used. As a necessary monomer component, a methacrylic acid polymer (S) having a glass transition temperature of 60 to 120 ° C and a monomer composition different from the acrylic polymer (C) is used as a monomer component. Core-shell type acrylic polymer particles of the outer shell. The above acrylic polymer (S) preferably further comprises a monomer having a hydroxyl group (for example, having a hydroxyl group) The (meth) acrylate) and/or a monomer having a carboxyl group (for example, (meth)acrylic acid) is used as a monomer component. Wherein, the outer casing may be a single layer or a plurality of layers. The proportion of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is preferably 60% by weight or more based on the total amount (100% by weight) of the monomer components constituting the acrylic polymer (C). More preferably, it is 80% by weight or more. Further, the total amount (100% by weight) of the monomer components constituting the acrylic polymer (S) has a ratio of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, preferably 60% by weight or more. More preferably, it is 80% by weight or more.

The content of the alkali metal ions (for example, Na ions, K ions, and the like) 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, still more preferably 1 ppm or less. When the content of the alkali metal ions is more than 10 ppm, the insulating properties of the cured product may be lowered. The content of the above alkali metal ion can be measured, for example, using an inductively coupled plasma luminescence analyzer or an ion chromatograph. Further, the content of the above alkali metal ion can be controlled, for example, by selecting a polymerization initiator and an emulsifier used for polymerization.

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 diameter is less than 5 μm, it is easy to fly and cause static electricity, which may be difficult to use. On the other hand, when the average secondary particle diameter is more than 50 μm, the time load may be large when dispersed into primary particles. The average secondary particle diameter can be measured, for example, by an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Further, the average secondary particle diameter can be controlled, for example, by 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. Moreover, 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, still more preferably 1 μm or less. When the volume average primary particle diameter is less than 200 nm, the dispersibility may be lowered. On the other hand, when the volume average primary particle diameter is more than 8 μm, the transparency of the cured product may be lowered. The volume average primary particle diameter can be measured, for example, by using a laser diffraction/scattering type particle size distribution measuring apparatus (for example, trade name "LA-910W", manufactured by Horiba, Ltd.). Further, the volume average primary particle diameter can be controlled, for example, by the conditions at the time of monomer emulsification.

The monodispersity (ratio of the volume average primary particle diameter Dv to the number average primary particle diameter Dn [Dv/Dn]) of the core-shell type acrylic polymer particles is not particularly limited, but is preferably 3.0 or less, and more preferably It is 2.0 or less, and more preferably 1.5 or less. When Dv/Dn is more than 3.0, the moisture repellent reflow resistance and the heat repellency of the cured product may be lowered. The Dv/Dn can be measured, for example, by using a laser diffraction/scattering type particle size distribution measuring apparatus (for example, trade name "LA-910W", manufactured by Horiba, Ltd.). Further, the above Dv/Dn can be controlled, for example, by the conditions at the time of monomer emulsification.

The core-shell type acrylic polymer particles can be produced by a known method for producing core-shell type polymer particles. The core-shell type acrylic polymer particles can be obtained by coating the core with an outer shell, and examples thereof include a method of coating an acrylic polymer constituting the outer shell on the surface of the inner core, or an acrylic polymer constituting the inner core as a main layer. A component, a method of graft-polymerizing an acrylic polymer (branched component) constituting a shell, and the like. More specifically, the above-described core-shell type acrylic polymer particles can be produced, for example, according to the method disclosed in International Publication No. 2010/090246.

In the curable epoxy resin composition of the present invention, the core-shell type acrylic polymer particles may be used alone or in combination of two or more. As the core-shell type acrylic polymer particles, commercially available products such as "METABLEN KP-0917", "METABLEN KP-0930", and "METABLEN KP-0950" (above, Mitsubishi Rayon Co., Ltd.) can be used. .

The content (adjusted amount) of the core-shell type acrylic polymer particles is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, per 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 less likely to be obtained, and the moisture absorption reflow resistance and the heat repellency of the cured product are deteriorated. On the other hand, when the content of the core-shell type acrylic polymer particles is more than 30 parts by weight, the curable epoxy resin composition becomes sticky and becomes difficult to use.

The curable epoxy resin composition of the present invention comprising the alicyclic epoxy compound and the core-shell type acrylic polymer particles as essential components can be supplied with high heat resistance, light resistance, and heat repellency. In particular, it is a cured product excellent in moisture absorption reflow resistance. These effects in the above-mentioned cured product (especially, the effect of improving moisture absorption reflow resistance) are presumed to be that the core-shell type acrylic polymer particles in the curable epoxy resin composition have a core-shell structure, and Glass turn of the outer casing The temperature and solubility parameters are controlled to a specific range, and the adhesion to the adherend of the cured product (especially the silver electrode in the optical semiconductor device, etc.) is mainly promoted, and further the adhesion is promoted by heat (gelation). The effect produced by maintaining (fixing) the shape before it is completely hardened. When a general acrylic polymer (linear polymer or the like) is used instead of the core-shell type acrylic polymer particles, the above-mentioned adhesion enhancement and the effect of thickening by heating are not obtained. For example, a resin composition which is markedly low in viscosity by heating is easily deformed by the shape at the time of curing, and is liable to cause a problem due to such deformation (for example, low moisture reflow resistance). Moreover, since the curable epoxy resin composition of the present invention containing the core-shell type acrylic polymer particles has a low viscosity at room temperature as will be described later, the usability is also excellent.

Further, the tackifying effect of the above-mentioned curable epoxy resin composition by heating is presumably, in particular, by the above-mentioned core-shell type acrylic polymer when heated (particularly near the Tg of the inner core or the outer shell, specifically It is swelled when heated at 80 to 90 ° C, and the solubility parameter (Fedors method) of the core-shell type acrylic polymer is controlled to a specific range, and the alicyclic epoxy compound can be easily impregnated into the swelled core-shell type acrylic acid. The effect obtained by the outer layer (surface layer) of the polymer particles.

[Trimeric isocyanate monoallyl epoxide ester compound]

The curable epoxy resin composition of the present invention preferably further comprises a compound represented by the following formula (I) (monoallyl isocyanate diglycidyl ester compound). In the case where the above-mentioned monoallyl isocyanate diglycidyl ester compound is contained, the moisture absorption reflow resistance and the heat repellency of the cured product are particularly improved.

In the above formula (I), 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. Examples of the alkyl group having 1 to 8 carbon atoms include a linear chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. Or a branched chain alkyl group. Among them, a linear or branched chain alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. R ¹ and R ² in the above formula (I) are particularly preferably a hydrogen atom.

Representative examples of the above-mentioned monoallyl isocyanate diglycidyl ester compound include: monoallyl isocyanate diglycidyl ester, 1-allyl-3,5-bis (2) -Methylcyclooxypropyl)trimeric isocyanate, 1-(2-methylpropenyl)-3,5-diepoxypropyl trimer isocyanate, 1-(2-methylpropenyl)-3, 5-bis(2-methylepoxypropyl)trimeric isocyanate. Further, the monoallyl isocyanate diglycidyl ester compound may be used alone or in combination of two or more.

Further, the above-mentioned trimeric isocyanate monoallyl epoxide compound may be modified by using an alcohol or an acid anhydride or the like and a compound which reacts with an epoxy group.

The content (adjusted amount) of the above-mentioned monoallyl isocyanate diglycidyl ester compound is not particularly limited, and is preferably 3 to 50 parts by weight based on 100 parts by weight of the alicyclic epoxy compound. More preferably, it is 5 to 45 parts by weight, and more preferably 10 to 40 parts by weight. Trimeric isocyanate monoallyl ester When the content of the diglycidyl ester compound is more than 50 parts by weight, the solubility of the monoallyl isocyanate diglycidyl ester compound in the curable epoxy resin composition is lowered, and the cured product is cured. A situation in which physical properties have an adverse effect. On the other hand, when the content of the monoallyl isocyanate diglycidyl ester compound is less than 3 parts by weight, the moisture absorption reflow resistance and the hot stamping resistance of the cured product may be insufficient.

The curable epoxy resin composition of the present invention may further contain a hardener, a hardening accelerator, or a hardening catalyst.

[hardener]

The hardener in the curable epoxy resin composition of the present invention is a compound having an action of hardening a compound having an epoxy group. As the curing agent, a known to conventional curing agent can be used as the curing agent for the epoxy resin. As the curing agent, among them, an acid anhydride which is liquid at 25 ° C is preferable, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and dodecenyl succinic anhydride. Methyl endomethylenetetrahydrophthalic anhydride or the like. Further, for example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dianhydride are equal to a normal temperature (about 25 ° C) solid anhydride, which can be dissolved by A curing agent of the present invention is used as a liquid mixture in a liquid state at room temperature (about 25 ° C). Further, the curing agent may be used alone or in combination of two or more. As described above, as the curing agent, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (also included in the viewpoint of heat resistance, light resistance, and crack resistance (characteristic of occurrence of cracking) of the cured product is preferable. A substituent such as an alkyl group is bonded to the ring).

Further, in the present invention, as the curing agent, it is also possible to use The product names are "RIKACID MH-700", "RIKACID MH-700F" (above is New Japan Physical and Chemical Co., Ltd.), and the product name is "HN-5500" (Hitachi Chemical Industry Co., Ltd.).

The content (the amount of the curing agent) of the curing agent is not particularly limited, but is preferably 50 in terms of the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention. ~200 parts by weight, more preferably 100 to 145 parts by weight. More specifically, it is preferably used in an amount of from 0.5 to 1.5 equivalents per 1 equivalent of the epoxy group of the epoxy group-containing compound contained in the curable epoxy resin composition of the present invention. When the content of the curing agent is less than 50 parts by weight, the curing may be insufficient, and the strength of the cured product tends to be lowered. On the other hand, when the content of the curing agent is more than 200 parts by weight, the cured product may be colored, and the color tone may be deteriorated.

[hardening accelerator]

The hardening accelerator in the curable epoxy resin composition of the present invention has a function of promoting the curing rate when the compound having an epoxy group is cured by a curing agent. As the hardening accelerator, a known hardening accelerator can be used, and examples thereof include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and salts thereof (for example, phenates). , octanoate, p-toluenesulfonate, formate, tetraphenyl borate); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and salts thereof (eg, phenates, Octanoate, p-toluenesulfonate, formate, tetraphenylborate); benzyldimethylamine, 2,4,6-glucos(dimethylaminomethyl)phenol, N,N-di a tertiary amine such as methylcyclohexylamine; an imidazole such as 2-ethyl-4-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole; a phosphine such as a phosphate or triphenylphosphine Class; tetra(p-tolyl)boronic acid An anthracene compound such as tetraphenylphosphonium; an organic metal salt such as tin octylate or zinc octoate; a metal chelate compound. The curing accelerator may be used alone or in combination of two or more.

Further, in the present invention, as the curing accelerator, the trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", "U-" may be used. CAT 18XD", "12XD" (opening product) (above is SAN-APRO (share) system), trade name "TPP-K", "TPP-MK" (above, Beixing Chemical Industry Co., Ltd.), trade name Commercial products such as "PX-4ET" (Japan Chemical Industry Co., Ltd.).

The content (adjusted amount) of the hardening accelerator is not particularly limited, but is preferably 0.05 to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 2.5 parts by weight. When the content of the hardening accelerator is less than 0.05 parts by weight, the hardening promoting effect may be insufficient. On the other hand, when the content of the hardening accelerator is more than 5 parts by weight, the cured product may be colored and the color tone may be deteriorated.

[hardening catalyst]

In the curable epoxy resin composition of the present invention, a curing catalyst or a curing accelerator may be used instead of the curing catalyst. As in the case of using a curing agent and a hardening accelerator, a compound having an epoxy group can be subjected to a hardening reaction by using a curing catalyst to obtain a cured product. The hardening catalyst is not particularly limited, and a cationic catalyst (cationic polymerization initiator) which initiates polymerization by irradiation with ultraviolet rays or heat treatment may be used. Moreover, the curing catalyst can be used alone or in combination. The above combination is used.

Examples of the cationic catalyst which generates a cationic species by irradiation with ultraviolet rays include hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, hexafluoroalginate and the like. The cation catalyst can be preferably used, for example, under the trade name "UVACURE 1590" (Daicel-Cytec Co., Ltd.), trade names "CD-1010", "CD-1011", and "CD-1012" (above is Sartomer, USA) Manufactured under the trade name "IRGACURE 264" (manufactured by Ciba Japan Co., Ltd.) and trade name "CIT-1682" (made by Japan Soda Co., Ltd.).

The cationic catalyst which generates a cationic species by heat treatment may, for example, be an aryldiazonium salt, an arylsulfonium salt, an arylsulfonium salt, a heavy olefin-ion complex, or the like, and a trade name may be preferably used. PP-33", "CP-66", "CP-77" (above is made by ADEKA), trade name "FC-509" (3M system), product name "UVE1014" (made by GE), trade name "San Aid SI-60L", "San Aid SI-80L", "San Aid SI-100L", "San Aid SI-110L" (above is Sanshin Chemical Industry Co., Ltd.), trade name "CG-24" -61" (made by Ciba Japan) and other commercial products. Further, it may be a chelate compound of a metal such as aluminum or titanium with acetonitrile or a diketone, a compound of sterol such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and acetonitrile or diketone. a chelate compound, a compound of a phenol such as bisphenol S.

The content (adjusted amount) of the curing catalyst is not particularly limited, but is preferably 0.01 to 15 with respect to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. The parts by weight are more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, particularly It is preferably 0.1 to 10 parts by weight. By using a curing catalyst within the above range, a cured product excellent in heat resistance, light resistance, and transparency can be obtained.

[Epoxy propyl ether epoxy compound without aromatic ring]

The curable epoxy resin composition of the present invention may further contain, as an epoxy compound, a glycidyl ether epoxy compound having no aromatic ring, in addition to the above alicyclic epoxy compound. The above-mentioned epoxy propyl ether-based epoxy compound having no aromatic ring is preferred in that it can improve the crack resistance without impairing the high heat resistance of the cured product, and in particular, it does not impair the high heat resistance of the cured product. It is preferred to improve the crack resistance of the light and light resistance.

The epoxy propyl ether epoxy compound having no aromatic ring described above contains an aliphatic epoxy propyl ether epoxy compound and a compound obtained by hydrogenating an aromatic epoxy propyl ether epoxy compound. As the epoxy propyl ether epoxy compound having no aromatic ring, for example, the trade names "EPICLON 703", "EPICLON 707", "EPICLON 720", and "EPICLON 725" (made by DIC) can be preferably used. "YH-300", "YH-315", "YH-324", "PG-202", "PG-207", "SUN THOTO ST-3000" (Nippon Steel Chemical Co., Ltd.), trade name "RIKARESIN DME-100", "RIKARESIN HBE-100" (Nippon Chemical and Chemical Co., Ltd.), trade name "DENACOL EX-212", "DENACOL EX-321" (Nagase ChemteX (share) system), trade name " Commercial products such as YX8000" and "YX8034" (Mitsubishi Chemical Co., Ltd.). Further, the epoxy propyl ether-based epoxy compound having no aromatic ring may be used alone or in combination of two or more.

The content of the epoxy propyl ether epoxy compound without an aromatic ring The amount (measured amount) is not particularly limited, but is preferably 10% by weight based on 100% by weight of the total of the epoxy group-containing compound (all epoxy compounds) contained in the curable epoxy resin composition. 70% by weight, more preferably 20 to 50% by weight.

[Polyol compound]

The curable epoxy resin composition of the present invention may also contain a polyol compound. It is preferable to include the above polyol compound in order to further improve the heat resistance and crack resistance of the cured product. The polyol compound is a polymer (oligomer or polymer) having a number average molecular weight of 2 or more hydroxyl groups in a molecule (in one molecule) of 200 or more, and includes, for example, a polyether polyol, a polyester polyol, Polycarbonate polyols and the like. Further, the above polyol compounds may be used alone or in combination of two or more.

For the polyester polyol, for example, the trade names "Placcel 205", "Placcel 205H", "Placcel 205U", "Placcel 205BA", "Placcel 208", "Placcel 210", "Placcel 210CP", "Placcel 210BA" can be used. , Placcel 212, Placcel 212CP, Placcel 220, Placcel 220CPB, Placcel 220NP1, Placcel 220BA, Placcel 220ED, Placcel 220EB, Placcel 220EC, Placcel 230 , Placcel 230CP, Placcel 240, Placcel 240CP, Placcel 210N, Placcel 220N, Placcel L205AL, Placcel L208AL, Placcel L212AL, Placcel L220AL, Placcel L230AL , "Placcel 305", "Placcel 308", "Placcel 312", "Placcel L312AL", "Placcel Commercial products such as "320", "Placcel L320AL", "Placcel L330AL", "Placcel 410", "Placcel 410D", "Placcel 610", "Placcel P3403", "Placcel CDE9P" (above (Daicel)) .

For the polyether polyol, for example, the trade name "PEP-101" (FREUND Industries Co., Ltd.), trade names "Adeka Pluronic L", "Adeka Pluronic P", "Adeka Pluronic F", "Adeka Pluronic R" can be used. , "Adeka Pluronic TR", "Adeka PEG" (above (made by Adeka)), trade names "PEG#1000", "PEG#1500", "PEG#11000" (above is Nippon Oil Co., Ltd.) , the trade name "NEWPOL PE-34", "NEWPOL PE-61", "NEWPOL PE-78", "NEWPOL PE-108", "PEG-200", "PEG-600", "PEG-2000", " PEG-6000", "PEG-10000", "PEG-20000" (above is Sanyo Chemical Industry Co., Ltd.), trade names "PTMG1000", "PTMG1800", "PTMG2000" (above is Mitsubishi Chemical Corporation) ), and "PTMG Prepolymer" (Mitsubishi Resin Co., Ltd.) and other commercial products.

For the polycarbonate polyol, for example, the trade names "Placcel CD205PL", "Placcel CD205HL", "Placcel CD210PL", "Placcel CD210HL", "Placcel CD220PL", and "Placcel CD220HL" (above: Daicel) , trade names "UH-CARB50", "UH-CARB100", "UH-CARB300", "UH-CARB90(1/3)", "UH-CARB90(1/1)", "UC-CARB100" (above) For Ube Industries Co., Ltd., the trade names are "PCDL T4671", "PCDL T4672", "PCDL T5650J", "PCDL T5651", "PCDL T5652" (above is Asahi Kasei CHEMICALS) Commercial products such as system).

As the polyol compound, a polyhydric alcohol compound, a polyester polyol, or a polyol compound other than a polycarbonate polyol (also referred to as "another polyol compound") may be used. For the above other polyol compounds, for example, the 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" (The above is Nippon Steel Chemical Co., Ltd.)苯), phenoxy resin such as "jER1256", "jER4250", "jER4275" (above: Mitsubishi Chemical Co., Ltd.); trade name "EPOTOHTO YD-014", "EPOTOHTO YD-017", "EPOTOHTO YD" -019", "EPOTOHTO YD-020G", "EPOTOHTO YD-904", "EPOTOHTO YD-907", "EPOTOHTO YD-6020" (above is Nippon Steel Chemical Co., Ltd.), trade name "jER1007", Bisphenol type polymer ring having an epoxy equivalent of more than 1000 g/eq, such as "jER1009", "jER1010", "jER1005F", "jER1009F", "jER1006FS", "jER1007FS" (above, Mitsubishi Chemical Co., Ltd.) Oxygen resin; trade name "Poly bd R-45HT", "Poly bd R-15HT", "Poly ip", "KRASOL" (above is Idemitsu Kosan Co., Ltd.), trade name "α-ω polybutan Olediol G-1000" a polybutadiene having a hydroxyl group such as "α-ω polybutadiene diol G-2000" or "α-ω polybutadiene diol G-3000" (above, manufactured by Japan Soda Co., Ltd.); "Hitaloid 3903", "Hitaloid 3904", "Hitaloid 3905", "Hitaloid 6500", "Hitaloid 6500B", "Hitaloid 3018X" (above is Hitachi Chemical Industry Co., Ltd.), trade name "ACRYDIC" DL-1537", "ACRYDIC BL-616", "ACRYDIC AL-1157", "ACRYDIC A-322", "ACRYDIC A-817", "ACRYDIC A-870", "ACRYDIC A-859-B", " ACRYDIC A-829", "ACRYDIC A-49-394-IM" (above is DIC (share) system), trade names "Dianal SR-1346", "Dianal SR-1237", "Dianal AS-1139" (above) It is a commercial item such as an acrylic polyol such as Mitsubishi Rayon Co., Ltd.).

The content (adjusted amount) of the above-mentioned polyol compound is not particularly limited, but is 100 parts by weight based on the total amount of the epoxy group-containing compound (all epoxy compounds) contained in the curable epoxy resin composition. It is preferably 1 to 50 parts by weight, 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 is more than 50 parts by weight, the Tg of the cured product may be too low, the volume change due to heating may increase, and the optical semiconductor device may not be bright. 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 also contain rubber particles. Examples of the rubber particles include particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). In addition, the rubber particles include, for example, rubber particles having a multilayer structure (core-shell structure) composed of an inner core portion having rubber elasticity and an outer shell layer covering at least one layer of the core portion. As the rubber particles having the above-described core-shell structure, it is preferred to have a hydroxyl group and/or a carboxyl group as a surface and an alicyclic type. a functional group reactive with an epoxy compound, having an average particle diameter of 10 to 500 nm, a maximum particle diameter of 50 to 1000 nm, and a refractive index of the rubber particle and a cured product of the hardenable epoxy resin composition containing the rubber particle The difference in rate is within ±0.02. The amount of the rubber particles to be added is appropriately adjusted as necessary, and is not particularly limited, but is preferably 0.5 to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. 30 parts by weight, more preferably 1 to 20 parts by weight. When the amount of the rubber particles used is less than 0.5 part by weight, the crack resistance of the cured product tends to be lowered. On the other hand, when the amount of the rubber particles used is more than 30 parts by weight, the heat resistance and transparency of the cured product are obtained. There will be a tendency to decrease.

[additive]

In addition to the above, the curable epoxy resin composition of the present invention may contain various additives insofar as the effects of the present invention are not impaired. When the above-mentioned additive is a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or propylene trichloride, the reaction can be carried out slowly. Others, in the range which does not impair viscosity and transparency, can be used as a polyfluorene-based and fluorine-based antifoaming agent, a leveling agent, γ-glycidoxypropyltrimethoxydecane and 3-mercaptopropyl group. A decane coupling agent such as trimethoxy decane, a surfactant, an inorganic filler such as cerium oxide or aluminum oxide, a flame retardant, a coloring agent, an antioxidant, an ultraviolet absorber, an ion sorbent, a pigment, a phosphor, and a mold release Conventional additives such as agents.

The curable epoxy resin composition of the present invention is not particularly limited, and can be stirred by heating the above components as needed. Mix to modulate. Moreover, the curable epoxy resin composition of the present invention can be used as a material in which each component is previously mixed, and one liquid system is used as it is. The composition may be used as a composition of a multi-liquid system (for example, a two-liquid system) in which two or more components are separately stored and used in a predetermined ratio before use.

The curable epoxy resin composition of the present invention has a viscosity at 25 ° C of 60 to 6000 mPa. s, preferably 100~5500mPa. s, more preferably 150~5000mPa. s. The viscosity at 25 ° C is less than 60 mPa. s, the heat resistance of the cured product tends to decrease. On the other hand, the viscosity at 25 ° C is greater than 6000 mPa. In s, there is a tendency that the flowability is lowered, and the cured product tends to have a problem of poor casting. Further, the viscosity of the curable epoxy resin composition at 25 ° C can be, for example, a digital viscometer (model "DVU-EII type", manufactured by Tokyo Keiki Co., Ltd.), rotor: standard 1 ° 34 ' × R24, Temperature: 25 ° C, rotation speed: 0.5 ~ 10 rpm conditions.

<hardened matter>

By curing the curable epoxy resin composition of the present invention, it is possible to obtain heat-resistant, light-resistant, and heat-resistant properties, and in particular, a cured product excellent in moisture absorption reflow resistance. The heating temperature (hardening temperature) at the time of hardening is not particularly limited, but is preferably 45 to 200 ° C, more preferably 100 to 190 ° C, still more preferably 100 to 180 ° C. Further, the time (hardening time) for heating during curing is not particularly limited, but is preferably from 30 to 600 minutes, more preferably from 45 to 540 minutes, still more preferably from 60 to 480 minutes. When the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening may be insufficient. Conversely, when the curing temperature is higher than the upper limit of the above range, the decomposition of the resin component may occur. Either one is not good. The hardening conditions are dependent on various conditions and can be achieved, for example, by increasing the hardening temperature. The hardening time is shortened, and the hardening time is lowered in the case of lowering the hardening temperature, and the like is appropriately adjusted.

<Resin composition for optical semiconductor sealing>

The curable epoxy resin composition of the present invention can be preferably used as a resin composition for encapsulating a photo-semiconductor. By using the resin composition for encapsulating the optical semiconductor, it is possible to obtain a cured product having high heat resistance, light resistance, and heat repellency, and particularly excellent moisture absorption reflow resistance, and the optical semiconductor element is sealed. Optical semiconductor device. In the case where the optical semiconductor device is equipped with an optical semiconductor device having a high output and a high luminance, the luminance is less likely to decrease with time, and in particular, even when it is heated in a reflow step after being stored under high-humidity conditions, brightness is less likely to occur. Reduce the degradation.

<Optical semiconductor device>

The optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is sealed by a cured product of a curable epoxy resin composition (a resin composition for optical semiconductor sealing) of the present invention. The sealing of the optical semiconductor element is carried out by injecting the curable epoxy resin composition prepared by the above method into a specific molding die and heating and hardening under specific conditions. Thereby, an optical semiconductor device in which the optical semiconductor element is sealed with a cured product of the curable epoxy resin composition can be obtained. The hardening temperature and the hardening time can be set to the same range as when the cured product is prepared.

In particular, the curable epoxy resin composition of the present invention can be preferably used as a sealant which is used in a state in which a certain space is injected and hardened. This is because the curable epoxy resin composition of the present invention is hardened in a certain space as described above, even when a high temperature is applied (for example, In the case of the heat generated by the reflow step and the load generated by the hot stamping (for example, the hot and cold cycle), it is also possible to exhibit the effect of being less likely to cause peeling and cracking. Therefore, the curable epoxy resin composition of the present invention can be preferably used as a sealant such as a PLCC sealing material for forming an LED, an inner sealing material for a bullet-type LED, and a flip chip sealing material.

The curable epoxy resin composition of the present invention is not limited to the sealing use of the above-described optical semiconductor element, and can be used, for example, for an adhesive, an electrical insulating material, a laminate, a coating, an ink, a coating, a sealant, and a resist. Agent, composite material, transparent substrate, transparent sheet, transparent film, optical element, optical lens, optical member, photosensitive etching processing, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory And other uses.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples.

Manufacturing example 1

(Manufacture of acrylic polymer emulsion (E1), acrylic polymer powder (P1))

585.0 g of ion-exchanged water was prepared and stirred in a 2 liter separable flask equipped with a stirrer, a reflux cooling tube, an injection pump, a temperature control device, and a nitrogen introduction tube.

Further, 453.5 g of methyl methacrylate, 71.5 g of n-butyl methacrylate, 5.25 g of di-2-ethylhexylsulfosuccinate, and 262.5 g of ions were homogenized (25,000 rpm). The water was exchanged for emulsification, and the monomer mixture (M1) was prepared. 10% of the monomer mixture (M1) was placed in the flask, and then the temperature was raised to 80 ° C under a nitrogen atmosphere. Next, 0.30 g of a previously prepared aqueous solution of ammonium persulfate (dissolved in 15.0 g of ion-exchanged water) was placed in the flask and held for 60 minutes to form seed particles. Next, the remaining monomer mixture (M1) was dropped into the flask in which the seed particles were formed for 180 minutes, and the mixture was kept for 1 hour after the dropwise addition, and the polymerization in the first stage was completed.

Next, 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 were homogenized (25,000 rpm). The monomer mixture obtained by the emulsification treatment was dropped into the flask for 90 minutes, and the mixture was kept for 1 hour after the dropwise addition, and the polymerization in the second stage was completed to obtain an acrylic polymer emulsion (E1) having an average particle diameter of 0.84 μm. Due to the composition of the acrylic monomer in the acrylic polymer emulsion (E1), the core component formed by the polymerization of the first stage has a glass transition temperature of 90.6 ° C and a solubility parameter (Fedors method) of 20.45, after the second stage. The glass transition temperature of the outer shell component formed by the polymerization was 106.9 ° C, and the solubility parameter (Fedors method) was 20.66.

The obtained acrylic polymer emulsion (E1) was subjected to spray drying treatment to obtain an acrylic polymer powder (P1).

Manufacturing example 2~6

The acrylic polymer emulsions (E2) to (E6) and the acrylic polymer powders (P2) to (P6) were obtained in the same manner as in Production Example 1 except that the raw material composition and the polymerization conditions described in Table 1 were changed. .

Manufacturing Example 7

(Manufacture of acrylic polymer emulsion (E7), acrylic polymer powder (P7))

Equipped with a mixer, reflux cooling tube, injection pump, temperature control device In a 2 liter separable flask equipped with a nitrogen gas introduction tube, 624 g of ion-exchanged water was prepared 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) for the polymerization of the first stage. 40.0 g of the above monomer mixture (M7) was placed in the above flask, and then the temperature was raised to 80 ° C under a nitrogen atmosphere. Next, 0.32 g of a previously prepared aqueous solution of ammonium persulfate (dissolved in 16.0 g of ion-exchanged water) was placed in the flask and held for 60 minutes to form seed particles. Next, it took 210 minutes to homogenize (25000 rpm) to the remaining 520.0 g of the monomer mixture (M7), 5.6 g of di-2-ethylhexylsulfosuccinate, and 280.0 g of ion exchange. The mixture obtained by emulsification treatment of water was dropped into the flask in which the seed particles were formed, and the mixture was kept for 1 hour to complete the polymerization in the first stage.

Next, for 90 minutes, 233.9 g of methyl methacrylate, 6.1 g of methacrylic acid, 2.4 g of ammonium di-2-ethylhexylsulfosuccinate, and 120.0 were homogenized (25,000 rpm). The monomer mixture obtained by emulsification treatment of g-exchanged water of g was dropped into the flask, and after the dropwise addition, the mixture was kept for 1 hour, and the polymerization in the second stage was completed to obtain an acrylic polymer emulsion (E7) having an average particle diameter of 0.81 μm. Due to the composition of the acrylic monomer in the above acrylic polymer emulsion (E7), the core component formed by the polymerization of the first stage has a glass transition temperature of 90.6 ° C, and the solubility parameter (Fedors method) is 20.45, after the second stage. The glass transition temperature of the outer shell component formed by the polymerization was 106.9 ° C, and the solubility parameter (Fedors method) was 20.66.

Spray drying of the obtained acrylic polymer emulsion (E7) The acrylic polymer powder (P7) was obtained.

Manufacturing Example 8

(Manufacture of acrylic polymer emulsion (E8), acrylic polymer powder (P8))

585.0 g of ion-exchanged water was prepared and stirred in a 2 liter separable flask equipped with a stirrer, a reflux cooling tube, an injection pump, a temperature control device, and a nitrogen introduction tube.

Further, 672.75 g of methyl methacrylate, 71.5 g of n-butyl methacrylate, 5.72 g of methacrylic acid, and 7.5 g of di-2-ethylhexylsulfosuccinic acid were homogenized (25,000 rpm). Ammonium and 375.0 g of ion-exchanged water were emulsified to prepare a monomer mixture (M8), and 10% of the monomer mixture (M8) was placed in the flask, and then the temperature was raised to 80 ° C in a nitrogen atmosphere. Next, 0.30 g of a previously prepared aqueous solution of ammonium persulfate (dissolved in 15.0 g of ion-exchanged water) was placed in the flask and held for 60 minutes to form seed particles. Next, the remaining monomer mixture (M8) was dropped into the above-mentioned flask in which the seed particles were formed, and the mixture was kept for 1 hour after the dropwise addition, and the polymerization was terminated to obtain an acrylic polymer emulsion (E8) having an average particle diameter of 0.62 μm. . Due to the composition of the acrylic monomer in the above acrylic polymer emulsion (E8), the glass transition temperature was 95.3 ° C, and the solubility parameter (Fedors method) was 20.52.

The obtained acrylic polymer emulsion (E8) was subjected to spray drying treatment to obtain an acrylic polymer powder (P8).

Example 1

100 parts by weight of an alicyclic epoxy compound (trade name "CELLOXIDE 2021P", manufactured by Daicel), and 10 parts by using a self-rotating rotary stirring device (trade name "AR-250", manufactured by THINKY) The parts by weight of the acrylic polymer powder (P1) are uniformly mixed and defoamed to obtain an agent A.

110 parts by weight of a curing agent (anhydride) (trade name "MH-700F", manufactured by Nippon Chemical and Chemical Co., Ltd.), 0.5 using a self-rotating rotary stirring device (trade name "AR-250", manufactured by THINKY). A part by weight of a hardening accelerator (trade name "U-CAT 18XD", manufactured by SAN-APRO Co., Ltd.), and 3 parts by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) are uniformly mixed and defoamed. , get B agent.

The A agent and the B agent obtained above were used in a ratio of [A agent/B agent] (weight ratio) = 100/100, and a self-rotating revolution type stirring device (trade name "AR-250", (stock) THINKY) was used. The mixture was uniformly mixed and defoamed to obtain a curable epoxy resin composition.

Next, the curable epoxy resin composition obtained above was extended to the lead frame (InGaN element, 3.5 mm × 2.8 mm) of the optical semiconductor shown in Fig. 1, and then dried in an oven at 120 ° C (resin-hardened oven). After heating for 5 hours, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable epoxy resin composition was obtained. In the first drawing, 100 is a reflector (a resin composition for light reflection), 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 to 14 and Comparative Examples 1 to 8

The composition of the agent A and the agent B was changed to the composition shown in Table 2 and Table 3, and the same procedure as in Example 1 was carried out to prepare a curable epoxy resin composition. Further, an optical semiconductor device was produced in the same manner as in the first embodiment. In addition, as shown in Table 2 and Table 3, in Example 2 and Comparative Example 2, the B agent was not used as a constituent component of the curable epoxy resin composition, and only the A agent was used.

<evaluation>

The following evaluation test was carried out using the optical semiconductor devices obtained in the examples and the comparative examples.

[Power-on test]

The total luminous flux (the "initial total luminous flux") of the optical semiconductor devices (10 for each curable epoxy resin composition) obtained in the examples and the comparative examples was measured using a total luminous flux measuring machine. Next, the total luminous flux after the current of 20 mA was flown into the optical semiconductor device was measured in a thermostat at 60 ° C and 90% RH for 1000 hours (the "total luminous flux after 1000 hours"). Then, the luminance maintenance ratio is calculated by the following equation, and the number of optical semiconductor devices in which the luminance maintenance ratio is less than 90% among the ten optical semiconductor devices is calculated. The results are shown in Tables 2 and 3.

(Brightness maintenance rate (%)) =100×(total luminous flux after 1000 hours (lm))/(initial total luminous flux (lm))

[Brightness maintenance rate after reflow]

The total luminous flux (the "initial total luminous flux") of the optical semiconductor devices (10 for each curable epoxy resin composition) obtained in the examples and the comparative examples was measured using a total luminous flux measuring machine. Next, put The optical semiconductor device was allowed to stand for 168 hours under conditions of 30 ° C and 70% RH to absorb moisture, and then placed in a reflow furnace and heated under the following heating conditions. Then, the optical semiconductor device was taken out to room temperature and allowed to cool, and then placed in a reflow furnace and heated under the same conditions. That is, in this test, the thermal history of the following heating conditions was applied to the optical semiconductor device twice.

[heating conditions (based on the surface temperature of the optical semiconductor device)]

(1) Preheating: heating at 150~190 °C for 60~120 seconds

(2) Formal heating after preliminary heating: heating at 217 ° C or higher for 60 to 150 seconds, maximum temperature 260 ° C

However, the temperature increase rate from the preparatory heating to the main heating is controlled to a maximum of 3 ° C / sec.

Fig. 2 is a view showing an example of a surface temperature profile of a semiconductor device (a temperature profile of primary heating in two heating) when heated in a reflow furnace.

Then, the total luminous flux of the optical semiconductor device (the "total luminous flux after reflow") was measured. Next, the luminance maintenance ratio is calculated by the following equation, and the number of optical semiconductor devices in which the luminance maintenance ratio is less than 90% in the ten optical semiconductor devices is calculated. The results are shown in Tables 2 and 3.

(Brightness 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 the examples and the comparative examples (10 for each of the curable epoxy resin compositions) were brightened after the above reflow soldering The degree of maintenance was measured under the same conditions for heat treatment. Next, the heat-treated optical semiconductor device was placed in red ink (aqueous) at 25 ° C for 4 hours. Then, it was taken out from the red ink, and a red microscope (VHX-900, manufactured by KEYENCE) was used to observe whether the red ink was soaked into the inside of the optical semiconductor device (the electrode was dyed red in the case of saturation). Among the ten optical semiconductor devices, the number of optical semiconductor devices that were saturated with red ink was calculated. The results are shown in Tables 2 and 3. The red ink impregnation suggests that the hardened material is peeled and/or cracked.

[Hot rush test]

The total luminous flux (the "initial total luminous flux") of the optical semiconductor device (10 for each curable epoxy resin composition) obtained in the examples and the comparative examples was measured using a total luminous flux measuring machine. Next, the film was exposed to an environment of -40 ° C for 15 minutes, and then exposed to an environment of 120 ° C for 15 minutes as a heat of 1 cycle, and the above-mentioned optical semiconductor device was applied for 1000 cycles using a thermal punching tester. Then, the total luminous flux of the optical semiconductor device (the "total luminous flux after thermal flushing") was measured. Then, the luminance maintenance ratio is calculated by the following equation, and the number of optical semiconductor devices in which the luminance maintenance ratio is less than 90% among the ten optical semiconductor devices is calculated. The results are shown in Tables 2 and 3.

(Brightness maintenance rate (%)) =100×(total luminous flux after thermal flushing (lm))/(initial total luminous flux (lm))

Moreover, the components used in the examples, comparative examples, and production examples are as follows.

MMA: Methyl methacrylate

n-BMA: n-butyl methacrylate

BA: n-butyl acrylate

i-BMA: isobutyl methacrylate

MAA: Methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

CEL2021P (CELLOXIDE 2021P): 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanoic acid, manufactured by Daicel

MA-DGIC: triallyl isocyanate monoallyl epoxide, Siguo Chemical Industry Co., Ltd.

CELLOXIDE 3000: 1,2,8,9-dicyclooxynonene, (share) made by Daicel

YD-128: bisphenol A epoxy resin, Nippon Steel Chemical Co., Ltd.

Z-6040: decane coupling agent, Dow Corning Toray

SI-100L (San Aid SI-100L): aryl sulfonium salt, Sanshin Chemical Industry Co., Ltd.

MH-700F (RIKACID MH-700F): Hardener, New Japan Physical and Chemical Co., Ltd.

U-CAT 18XD: hardening accelerator, SAN-APRO (share) system

Ethylene glycol: Wako Pure Chemical Industries Co., Ltd.

Test machine

. Resin hardening oven

ESPEC (share) system GPHH-201

. Thermostat

ESPEC (stock) system small high temperature box ST-120B1

. Total luminous flux measuring machine

Multi-channel spectroradiometric system OL771 manufactured by Optronic Laboratories

. Hot punching test machine

ESPEC (stock) system small hot and cold flushing device TSE-11-A

. Reflow furnace

Japan ANTOM (share) system, UNI-5016F

[Industry Utilization]

The curable epoxy resin composition of the present invention can be preferably used as a resin composition for optical semiconductor sealing (particularly, a PLCC sealing material for forming an LED, an inner sealing material for a bullet-type LED, a flip chip sealing material, etc.) Agent). Further, the curable epoxy resin composition of the present invention can also be used for, for example, an adhesive, an electrically insulating material, a laminate, a coating, an ink, a coating, a sealant, a resist, a composite material, a transparent substrate, and a transparent Sheets, transparent films, optical elements, optical lenses, optical components, photosensitive etching, electronic paper, touch panels, solar cell substrates, optical waveguides, light guides, holographic memory, etc.

Claims (8)

A curable epoxy resin composition comprising: an alicyclic epoxy compound, a core-shell type acrylic polymer having a solubility parameter of 19.5 to 21.5 [MPa ^1/2 ] at 25 ° C calculated by the Fedors method And 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 outer shell is 60 to 120 ° C, and the core-shell type acrylic acid is polymerized. The content of the particles is from 1 to 30 parts by weight based on 100 parts by weight of the alicyclic epoxy compound, and the total amount of the monomer components constituting the acrylic polymer constituting the core of the core-shell type acrylic polymer particles. 100% by weight, the proportion of the aromatic vinyl monomer is 5% by weight or less, and has carbon with respect to 100% by weight of the total of the monomer components constituting the acrylic polymer constituting the core of the core-shell type acrylic polymer particles. The ratio of alkyl methacrylate of 1 to 4 alkyl groups is 80% by weight or more, and the viscosity of the curable epoxy resin composition at 25 ° C is 60 to 6000 mPa. s. The curable epoxy resin composition of claim 1, which further comprises a compound represented by the following formula (I): In the formula (I), 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 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 claim 1 or 2, wherein the alicyclic epoxy compound is a compound represented by the following formula (2-1) The curable epoxy resin composition according to claim 1 or 2, further comprising a hardener and a hardening accelerator, or a hardening catalyst. A curable epoxy resin composition according to claim 1 or 2, which is a resin composition for sealing a photo-semiconductor. A cured product obtained by hardening a curable epoxy resin composition according to any one of claims 1 to 6. An optical semiconductor device obtained by sealing an optical semiconductor element with a cured product of a curable epoxy resin composition according to any one of claims 1 to 6.