JPH111546A - Epoxy resin composition and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition excellent in blocking resistance and moldability and capable of giving a cured product excellent in mechanical strength, etc., by using a low-viscosity epoxy resin or a specific bisphenol-based epoxy resin, together with a specific multi-function-type epoxy resin. SOLUTION: This composition is obtained by including (A) 10-90 wt.% of a low-viscosity epoxy resin having the melt viscosity of <=0.3 poises at 150 deg.C, e.g. an epoxidized product of 4,4-dihydroxydiphenylmethane, or a bisphenol-based epoxy resin of formula I [R8-10 are each methyl, etc.; G is glycidyl: (q) is 0-15] and 90-10 wt.% of n aralkyl-based epoxy resin of formula II [A is a (substituted) benzene ring, etc.; R1 is methyl, etc.; (m) is 0-2; (n) is 1-15], each based on the total weight of epoxy resins, (B) a hardener (e.g. a polyhydric phenol compound, etc.), and (C) an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is excellent in blocking resistance, excellent in moldability such as rapid curability and fluidity, and excellent in mechanical strength, heat resistance, low moisture absorption, crack resistance and the like. The present invention relates to an epoxy resin composition for encapsulating an electronic component such as a semiconductor element that gives a cured product, and an electronic component using the same.

[0002]

2. Description of the Related Art A resin composition containing an epoxy resin as a main component is widely used in electric and electronic fields such as casting, sealing, and laminates. In recent years, as electronic components have become smaller and thinner,
A lower viscosity epoxy resin composition is desired. Conventional epoxy resin compositions often have a relatively high viscosity, which causes resin to not flow completely into minute gaps between parts or to cause molding defects such as entrapment of air bubbles, resulting in poor insulation and moisture resistance. There were problems such as deterioration.

In particular, in the field of semiconductors, as a method of mounting components on a printed circuit board, a shift from a conventional pin insertion method to a surface mounting method is progressing. In the surface mounting method, the entire package is heated to the solder temperature, and package cracks due to thermal shock have become a major problem. Furthermore, in recent years, high integration of semiconductor devices, enlargement of device size, and miniaturization of wiring width are also rapidly progressing, and the problem of package cracking is becoming more serious. As methods for preventing package cracks, there are methods such as toughening of the resin structure, high strength due to high filling of silica, and low water absorption.

[0004] In order to overcome the above problems, an epoxy resin excellent in low viscosity has been desired. As the low-viscosity epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin and the like are generally and widely used. However, among these epoxy resins, those having low viscosity are liquid at room temperature and are difficult to handle. Furthermore, these epoxy resins are not sufficient in heat resistance, mechanical strength, and toughness.

[0005] Against this background, many epoxy resin compositions using a crystalline epoxy resin that is solid at normal temperature have recently been proposed. Japanese Patent Publication No. 4-7365 proposes an epoxy resin composition for semiconductor encapsulation containing a biphenyl-based epoxy resin as a main component as an improvement in handling workability, heat resistance, toughness and the like. , Low viscosity and curability are not sufficient. Also, JP-A-6-3
Japanese Patent No. 45850 proposes using a bisphenol F type solid epoxy resin as a main ingredient. The bisphenol F type epoxy resin has the characteristic of being excellent in low viscosity, but there is room for improvement in blocking properties due to the softness of the epoxy resin composition.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an epoxy resin composition having excellent blocking resistance, excellent moldability such as rapid curability and fluidity, and mechanical strength and heat resistance. An object of the present invention is to provide an epoxy resin composition for providing a cured product excellent in low moisture absorption, crack resistance and the like, particularly for encapsulating electronic components such as surface-mounted semiconductor devices, and an electronic component using the same. .

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and have found that a low viscosity epoxy resin or a specific bisphenol type epoxy resin is used in combination with a specific polyfunctional epoxy resin. The present inventors have found that the above object can be achieved, and have reached the present invention.

That is, the present invention relates to an epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein a low-viscosity epoxy resin having a melt viscosity at 150 ° C. of 0.3 poise or less is used as an epoxy resin component. An aralkyl-type epoxy resin represented by the following general formula (1) is used in an amount of 10 to 90% by weight in the epoxy resin component.
An epoxy resin composition containing 0 to 10% by weight.

Embedded image (In the formula, A represents a benzene ring or a naphthalene ring which may be substituted simultaneously or separately with a hydrocarbon group having 1 to 6 carbon atoms, and R ₁ and R ₂ represent a hydrogen atom or methyl which may be the same or different. G represents a glycidyl group, and m represents 1
Or an integer of 2 and n represents a number of 1 to 15)

Further, the present invention provides an epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein a bisphenol type epoxy resin represented by the following general formula (3) is used as an epoxy resin component: Middle one
An epoxy resin composition comprising 0 to 90% by weight, and 90 to 10% by weight of an aralkyl type epoxy resin represented by the following general formula (1) in all epoxy resin components.

Embedded image (Wherein, R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a methyl group which may be the same or different, G represents a glycidyl group,
q shows the number of 0-15)

Embedded image (In the formula, A represents a benzene ring or a naphthalene ring which may be substituted simultaneously or separately with a hydrocarbon group having 1 to 6 carbon atoms, and R ₁ and R ₂ represent a hydrogen atom or methyl which may be the same or different. G represents a glycidyl group, and m represents 1
Or an integer of 2 and n represents a number of 1 to 15)

Further, the present invention is an electronic component sealed with a cured product of the above epoxy resin.

Hereinafter, the present invention will be described in detail. The low-viscosity epoxy resin used in the epoxy resin composition of the present invention is not particularly limited, but typically includes a bifunctional epoxy resin represented by the following general formula (2).

Embedded image (Wherein, G represents a glycidyl group, R ₃ represents a monovalent group, p represents an integer of 0 to 4, X represents a single bond or a divalent group, and q represents a number of 0 to 15. Indicates)

In the general formula (2), examples of the monovalent group R ₃ include a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms. 3rd, 5th or 3 'position from the viewpoint,
It is not preferred that the 5′-position is simultaneously a secondary or tertiary carbon substituent having 3 or more carbon atoms. The linking group X is a single bond or a divalent group, for example, an oxygen atom, a sulfur atom, a ketone group, a sulfone group, or a hydrocarbon group represented by the following general formula (a) or (b), Preferably a single bond, oxygen atom, sulfur atom, methylene group, ethylidene group or 1,4-
It is a phenylenebisisopropylidene group.

Embedded image (Wherein, R ₄ and R ₅ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms)

Embedded image (Wherein, R ₆ and R ₇ represent a hydrogen atom or a methyl group)

As such a low-viscosity epoxy resin,
For example, epoxidized 4,4'-dihydroxydiphenylmethane, epoxidized 3,3'-dimethyl-4,4'-dihydroxydiphenylmethane, 3,3 ', 5
Epoxidized product of 5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 2,2 ', 3,3', 5
Epoxidized product of 5'-hexamethyl-4,4'-dihydroxydiphenylmethane, 2,2'-dimethyl-5,
Epoxidized product of 5'-di-tert-butyl-4,4'-dihydroxydiphenylmethane, 1,4-bis (4-
Hydroxycumyl) epoxidized benzene, 1,4-
Epoxidized bis (3-methyl-4-hydroxycumyl) benzene, 1,4-bis (3,5-dimethyl-4-)
Hydroxycumyl) epoxidized benzene, 4,4 '
Epoxidized dihydroxydiphenyl ether,
Epoxidized 4,4'-dihydroxydiphenyl sulfide, epoxidized 2,2'-dimethyl-5,5-ditert-butyl-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetra Methyl-
Epoxidized 4,4'-dihydroxybiphenyl,
Epoxidized products of 2,5-ditert-butyl-hydroquinone, epoxidized products of 1,7-naphthalenediol and the like can be mentioned.

The low-viscosity epoxy resin used in the epoxy resin composition of the present invention is not limited to the above-mentioned epoxy resin.
For example, hydroquinones such as hydroquinone, 2,5-ditertiarybutylhydroquinone, 2,5-ditertiary amylhydroquinone, catechols, resorcinols, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxy Diglycidyl ethers such as naphthalene diols such as naphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene may be used.

The viscosity of the low-viscosity epoxy resin used in the epoxy resin composition of the present invention is at most 0.3 poise at 150 ° C., preferably at most 0.2 poise. If the viscosity is higher than 0.3 poise, it is difficult to increase the filling rate of the inorganic filler, and improvement in performance such as crack resistance cannot be expected.

An epoxy resin usable in the same manner as the low-viscosity epoxy resin used in the epoxy resin composition of the present invention is a bisphenol-type epoxy resin represented by the general formula (3). In the general formula (3), R ₈ , R
₉ and R ₁₀ represent a hydrogen atom or a methyl group which may be the same or different, preferably R ₈ and R ₉ are methyl groups,
R ₁₀ is a hydrogen atom or a methyl group. The average number of repetitions q is 0 to 15, preferably 0 to 5. The bisphenol-type epoxy resin represented by the general formula (3) is 1
The melt viscosity at 50 ° C. may be 0.3 poise or less.

The low-viscosity epoxy resin or the bisphenol type epoxy resin represented by the general formula (3) can be synthesized by reacting a compound having a phenolic hydroxyl group represented by a bisphenol compound with epichlorohydrin. it can. This reaction can be performed in the same manner as a usual epoxidation reaction. When a bisphenol compound is used, for example, after dissolving the bisphenol compound in an excess of epichlorohydrin, the solution is dissolved in an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like.
To 150 ° C., preferably 60 to 120 ° C. for 1 to 10 hours. At this time, the amount of the alkali metal hydroxide used is 0.8 to 2 mol, preferably 0.9 to 1.2 mol, per 1 mol of the hydroxyl group of the bisphenol compound. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain a desired product. It can be an epoxy resin.

Depending on the conditions at the time of synthesis, a mixture containing a multimer of a dimer or more of a bisphenol compound can be obtained, but from the viewpoint of low viscosity, the higher the monomer content of the bisphenol compound, the better. The content of the monomer is preferably 50% by weight or more. 5 monomer content
If the amount is less than 0% by weight, the content of the dimer or higher multimer increases and the viscosity increases.

The synthesized epoxy resin is preferably used after being crystallized and solidified. The melting point range of the epoxy resin is preferably 40 to 150C, more preferably 50 to 130C. If the temperature is lower than 40 ° C., there is a problem of blocking during storage, and if the temperature is higher than 150 ° C., the melt mixing property with a curing agent or other additives is inferior, and the workability at the time of preparing the epoxy resin composition is reduced. The melting point here is
This is a value obtained by a capillary method at a heating rate of 2 ° C./min.

The purity of the low-viscosity epoxy resin or the bisphenol-type epoxy resin represented by the general formula (3), particularly the amount of hydrolyzable chlorine, is preferably smaller than the viewpoint of improving the reliability of the electronic component to be sealed. There is no particular limitation, but preferably 1000 ppm or less. In addition, the hydrolyzable chlorine referred to in the present invention refers to a value measured by the following method. That is, 0.5 g of a sample is placed in 30 ml of dioxane.
After adding 10 ml of 1N-KOH and boiling under reflux for 30 minutes, the mixture was cooled to room temperature, further added with 100 ml of 80% acetone water, and subjected to potentiometric titration with a 0.002 N-AgNO ₃ aqueous solution.

In the epoxy resin composition of the present invention, the content of the low-viscosity epoxy resin or the bisphenol type epoxy resin represented by the general formula (3) is 10 to 90% by weight, preferably 30 to 90% by weight, based on all epoxy resin components. % To 80% by weight
It is. If the content of these epoxy resins is less than 10% by weight, a cured product having excellent crack resistance cannot be obtained, the effect of lowering the viscosity is small, and the filling rate of the inorganic filler cannot be increased. On the other hand, when the content exceeds 90% by weight, the blocking resistance of the epoxy resin composition decreases.

Next, the aralkyl-type epoxy resin represented by the general formula (1) can be synthesized by reacting an aralkyl-type polyhydric phenol resin with epichlorohydrin. In the general formula (1), A represents a benzene ring or a naphthalene ring, and these rings have 1 to 6 carbon atoms.
May be substituted. Preferably, A
Is a benzene ring or a naphthalene ring substituted or unsubstituted with a methyl group. R ₁ and R ₂ are a hydrogen atom or a methyl group, which may be the same or different. m is 1 or 2, and the average number of repetitions n is 1 to 15,
Preferably it is 1-5. In addition, A present in one molecule
May be either a benzene ring or a naphthalene ring or both. In the general formula (1), the glycidyl group is ring-opened during epoxidation to partially form an oligomer, which is also included in the aralkyl-type epoxy resin of the general formula (1).

Such an aralkyl type epoxy resin is
It can be synthesized by reacting an aralkyl polyhydric phenol resin represented by the following general formula (4) with epichlorohydrin.

Embedded image (In the formula, A represents a benzene ring or a naphthalene ring which may be substituted simultaneously or separately with a hydrocarbon group having 1 to 6 carbon atoms, and R ₁ and R ₂ represent a hydrogen atom or methyl which may be the same or different. M represents an integer of 1 or 2; n represents 1 to 1
Indicate the number of 5)

The aralkyl-type polyhydric phenol resin represented by the general formula (4) can be synthesized by reacting an alkyl-substituted or unsubstituted phenolic hydroxyl group-containing substance with an aromatic crosslinking agent.

The phenolic hydroxyl group-containing substance includes alkyl-substituted or unsubstituted phenols.
Is a benzene ring, for example, phenol, o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, tert-butylphenols, allylphenols, phenylphenols, 2,6-xylenol, When A is a naphthalene ring, examples thereof include 1-naphthol and 2-naphthol.

The aromatic cross-linking agent includes those having a benzene skeleton and those having a biphenyl skeleton.
The compound having a benzene skeleton may be any of an o-form, an m-form and a p-form, but is preferably an m-form or a p-form.
-Body. Examples of the aromatic crosslinking agent having a benzene skeleton include p-xylylene glycol, α, α′-dimethoxy-p-xylene, α, α′-diethoxy-p-xylene, and α, α′-diisopropoxy-p -Xylene,
α, α′-dibutoxy-p-xylene, m-xylylene glycol, α, α′-dimethoxy-m-xylene,
α, α'-diethoxy-m-xylene, α, α'-diisopropoxy-m-xylene, α, α'-dibutoxy-
m-xylene, 1,4-di (α-hydroxyethyl) benzene, 1,4-di (α-methoxyethyl) benzene,
1,4-di (α-ethoxyethyl) benzene, 1,4-
Di (α-isopropoxyethyl) benzene, 1,4-di (2-hydroxy-2-propyl) benzene, 1,4-
Di (2-methoxy-2-propyl) benzene, 1,4-
Di (2-ethoxy-2-propyl) benzene, 1,4-
Di (2-isopropoxy-2-propyl) benzene,
1,3-di (α-hydroxyethyl) benzene, 1,3
-Di (α-methoxyethyl) benzene, 1,3-di (2
-Hydroxy-2-propyl) benzene, 1,3-di (2-methoxy-2-propyl) benzene, 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-
Divinylbenzene, 1,2-di (2-propenyl) benzene, 1,3-di (2-propenyl) benzene, 1,4
-Di (2-propenyl) benzene and the like.

Examples of the aromatic crosslinking agent having a biphenyl skeleton include 4,4'-dihydroxymethylbiphenyl, 2,4'-dihydroxymethylbiphenyl,
2′-dihydroxymethylbiphenyl, 4,4′-dimethoxymethylbiphenyl, 2,4′-dimethoxymethylbiphenyl, 2,2′-dimethoxymethylbiphenyl,
4,4′-diisopropoxymethylbiphenyl, 2,
4'-diisopropoxymethylbiphenyl, 2,2'-
Diisopropoxymethyl biphenyl, 4,4'-dibutoxymethyl biphenyl, 2,4'-dibutoxymethyl biphenyl, 2,2'-dibutoxymethyl biphenyl,
4,4′-di (α-hydroxyethyl) biphenyl,
4,4′-di (α-methoxyethyl) biphenyl, 4,
4′-di (α-ethoxyethyl) biphenyl, 4,4 ′
-Di (α-isopropoxyethyl) biphenyl, 4,
4'-di (2-hydroxy-2-propyl) biphenyl, 4,4'-di (2-methoxy-2-propyl) biphenyl, 4,4'-di (2-ethoxy-2-propyl)
Biphenyl, 4,4'-di (2-isopropoxy-2-
Propyl) biphenyl, 2,4′-di (α-hydroxyethyl) biphenyl, 2,4′-di (α-methoxyethyl) biphenyl, 2,4′-di (2-hydroxy-2-
Propyl) biphenyl, 2,4′-di (2-methoxy-
2-propyl) biphenyl, 2,4′-divinylbiphenyl, 2,2′-divinylbiphenyl, 4,4′-divinylbiphenyl, 2,4′-di (2-propenyl) biphenyl, 2,2′-di ( 2-propenyl) biphenyl,
4,4′-di (2-propenyl) biphenyl and the like. The substitution position of a functional group such as a methylol group for biphenyl is 4,4′-position, 2,4′-position or 2,2′-position.
The preferred compound as the aromatic cross-linking agent is the 4,4'-isomer, and the compound containing 50% by weight or more of the 4,4'-isomer in the total cross-linking agent is particularly preferable. If the amount is less than this, there are drawbacks such as a decrease in the curing speed when used as an epoxy resin, and the resulting cured product becomes brittle.

In the general formula (4), the average number of repetitions n is 1 to 15. The value of n can be easily adjusted by changing the molar ratio of the phenolic hydroxyl group-containing compound and the aromatic crosslinking agent when they are reacted. That is, the more the phenolic hydroxyl group-containing compound is used relative to the aromatic crosslinking agent, the smaller the value of n can be controlled. The larger the value of n, the higher the softening point and viscosity of the obtained resin. Further, the viscosity decreases as the value of n decreases, but the number of unreacted phenolic hydroxyl group-containing compounds during synthesis increases,
Resin production efficiency decreases. The molar ratio of the two should be such that the aromatic cross-linking agent is practically 1 mol or less per 1 mol of the phenolic hydroxyl group-containing compound, and is preferably 0.1 to 1 mol.
0.9 mole. When the amount of the aromatic crosslinking agent is less than 0.1 mol, the amount of the unreacted phenolic hydroxyl group-containing compound increases.

The softening point of the aralkyl epoxy resin of the general formula (1) is preferably from 50 to 120 ° C., more preferably from 60 to 100 ° C. When the softening point is lower than 50 ° C., the effect of improving the blocking resistance of the epoxy resin composition is small, and when the softening point is higher than 120 ° C., the inorganic filler cannot be highly filled due to an increase in viscosity.

In the epoxy resin composition of the present invention, the content of the aralkyl type epoxy resin is 10 to 90% by weight, preferably 30 to 70% by weight, based on all epoxy resin components.
It is. If the content of the aralkyl type epoxy resin is less than 10% by weight, the effect of improving the blocking resistance of the epoxy resin composition is small, and if it exceeds 90% by weight, the filling rate of the inorganic filler cannot be increased due to the increase in viscosity.

Further, the epoxy resin composition of the present invention comprises:
In addition to the low-viscosity epoxy resin and the aralkyl-type epoxy resin used as essential components of the present invention, a general epoxy resin having two or more epoxy groups in a molecule can be used in combination. Examples of such an epoxy resin include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and tris- (4 -Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4
-Hydroxyphenyl) ethane, phenol novolak, o-cresol novolak and the like, phenols having three or more valences, and glycidyl ether compounds each derived from halogenated bisphenols such as tetrabromobisphenol A and the like. These epoxy resins may be used alone or in combination of two or more.

The curing agent for the epoxy resin composition of the present invention is not particularly limited, and a conventionally known epoxy resin curing agent can be used, and is preferably a polyhydric phenolic compound. As polyhydric phenolic compounds,
In addition to those known as epoxy resin curing agents,
Polyhydric phenolic compounds having an aralkyl-type structure can be used. The polyhydric phenolic compound having an aralkyl-type structure can be synthesized by reacting a polyhydric phenolic hydroxyl group-containing compound having an alkyl-substituted or unsubstituted benzene ring or naphthalene ring with a specific aromatic crosslinking agent.

The polyhydric phenolic hydroxyl group-containing compound includes, for example, bisphenol A, bisphenol F,
Bisphenol S, fluorene bisphenol, 4,
Divalent phenols such as 4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, catechol, naphthalene diols, and tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis ( 4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, tri- or more phenols represented by polyvinylphenol, and further phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, fluorene Bivalent phenols such as bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, catechol, naphthalene diol and formaldehyde, acetaldehyde, benzaldehyde, p-hydrido Roxybenzaldehyde, p
-Xylylene glycol, p-xylylene glycol dimethyl ether, divinylbenzene, diisopropenylbenzene, dimethoxymethylbiphenyls, divinylbiphenyl, polyhydric phenolic compounds synthesized by reaction with diisopropenylbiphenyls, etc. Is mentioned. These curing agents may be used alone or in combination of two or more.

The softening point of the polyhydric phenol compound as a curing agent is preferably from 40 to 150 ° C., more preferably from 50 to 120 ° C. If the softening point of the polyhydric phenolic compound is lower than 40 ° C., there is a problem of blocking during storage, and if it exceeds 150 ° C., there is a problem in kneading properties and moldability in preparing the epoxy resin composition. The melt viscosity at 150 ° C. is preferably 20 poise or less, more preferably 5 poise or less. If it is higher than this, there is a problem in kneadability and moldability during preparation of the epoxy resin composition.

In the epoxy resin composition of the present invention, as an inorganic filler, for example, silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, One or two or more kinds of powders such as mullite and titania or spherical beads thereof are mixed. For high packing of the inorganic filler, spherical fused silica is preferably used. Further, silica having several kinds of particle size distributions is used in combination. The average particle size of the silica to be combined is preferably 0.5 to 100 μm. The compounding amount of these inorganic fillers is preferably 70% by weight or more,
It is more preferably at least 80% by weight. If the amount of the inorganic filler is less than 70% by weight, the effect of improving the solder heat resistance is small.

Further, the epoxy resin composition of the present invention may contain a conventionally known curing accelerator. Examples of such a curing accelerator include amines,
There are imidazoles, organic phosphines, Lewis acids, etc., and specifically, 1,8-diazabicyclo (5,4,0)
Tertiary amines such as undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl Imidazoles such as imidazole and 2-heptadecyl imidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; tetraphenylphosphonium / tetraphenylborate; tetraphenylphosphonium / ethyl Tetra-substituted phosphonium / tetra-substituted borate such as triphenyl borate, tetrabutyl phosphonium / tetrabutyl borate, 2
And tetraphenylboron salts such as -ethyl-4-methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. Usually, the compounding amount is based on 100 parts by weight of the epoxy resin.
0.2 to 10 parts by weight.

The epoxy resin composition of the present invention may further contain a thermoplastic oligomer from the viewpoint of improving the fluidity during molding and improving the adhesion to a lead frame or the like. The thermoplastic oligomers, for example, C ₅ system and the C ₉ based petroleum resins, styrene resins, indene resins, indene-styrene copolymer resin, indene
Styrene / phenol copolymer resin, indene / coumarone copolymer resin, indene / benzothiophene copolymer resin, and the like are included, and the blending amount is 2 to 30 parts by weight based on 100 parts by weight of the epoxy resin.

If necessary, the epoxy resin composition of the present invention may further contain, for example, a flame retardant such as a brominated epoxy, a release agent such as carnauba wax or an ester wax, an epoxy silane, an amino silane, an ureido silane, or a vinyl silane. , Coupling agents such as alkyl silanes, organic titanates and aluminum alcoholates, coloring agents such as carbon black, flame retardant aids such as antimony trioxide, low stress agents such as silicone oil, higher fatty acids, higher fatty acid metal salts, etc. And the like.

Usually, the epoxy resin composition of the present invention is obtained by sufficiently mixing raw materials of a predetermined blending amount by a mixer or the like, kneading them by a mixing roll, an extruder, etc., cooling and pulverizing to obtain a molding material. be able to.

As a method for sealing an electronic component using the molding material obtained in the present invention, a low pressure transfer molding method is the most common, but an injection molding method or a compression molding method is also possible.

[0041]

The present invention will be described more specifically with reference to examples and comparative examples. Examples 1 to 6, Comparative Examples 1 to 5 The following epoxy resin components, curing agents, flame retardants and inorganic fillers, and triphenylphosphine as a curing accelerator,
Using γ-aminopropyltriethoxysilane as a silane coupling agent and other additives shown in Table 1,
An epoxy resin composition was prepared by kneading at the mixing ratio shown in Table 1. The numerical values in Table 1 are shown in parts by weight.

Epoxy resin A: Epoxidized product of 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane (ESLV-80X manufactured by Nippon Steel Chemical Co., Ltd.)
Y: epoxy equivalent 193, hydrolyzable chlorine 250 pp
m, melting point 78 ° C., melt viscosity at 150 ° C. 0.08 poise) Epoxy resin B: epoxidized 2,2 ′, 3,3 ′, 5,5′-hexamethyl-4,4′-dihydroxydiphenylmethane (new Nippon Steel Chemical, GK-8001; epoxy equivalent 209, hydrolyzable chlorine 250 ppm, melting point 1
Epoxy resin C: Epoxidized product of 1,4-bis (3-methyl-4-hydroxycumyl) benzene (ESLV-90CR; manufactured by Nippon Steel Chemical; epoxy) Equivalent: 256, hydrolyzable chlorine: 660 ppm, melting point: 90 ° C., melt viscosity at 150 ° C .: 0.19 poise) Epoxy resin D: 2,2′-dimethyl-5,5′-ditert-butyl-4,4′-dihydroxy Epoxy compound of diphenyl sulfide (Nippon Steel Chemical, ESLV
-120TE; epoxy equivalent 251, hydrolyzable chlorine 3
80 ppm, melting point 108 ° C, melt viscosity at 150 ° C
Epoxy resin E: Epoxidized product of 4,4'-dihydroxydiphenyl ether (ESLV-, manufactured by Nippon Steel Chemical Co., Ltd.)
80DE; epoxy equivalent 174, hydrolyzable chlorine 350
ppm, melting point 78 ° C., melt viscosity at 150 ° C. 0.06 poise) Epoxy resin F: 3,3 ′, 5,5′-tetramethyl-
Epoxidized 4,4'-dihydroxybiphenyl
(YX4000HK, manufactured by Yuka Shell Epoxy; epoxy equivalent: 195, hydrolyzable chlorine: 450 ppm, melting point: 105
Epoxy resin G: 2-naphthol aralkyl type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., ESN-185; epoxy equivalent 280, hydrolyzable chlorine 200 ppm, softening point 85 ° C,
Melt viscosity at 150 ° C. 4.6 poise) Epoxy resin H: o-cresol novolak type epoxy resin (manufactured by Nippon Kayaku, EOCN-1020-55; epoxy equivalent 196, hydrolyzable chlorine 400 ppm, softening point 55 ° C., 150) Epoxy resin I: o-cresol novolak type epoxy resin (EOCN-1020-70, manufactured by Nippon Kayaku; epoxy equivalent 200, hydrolyzable chlorine 400 ppm, softening point 70 ° C, 150 ° C) (Melt viscosity of 3.4 poise)

Curing agent A: phenol novolak (manufactured by Gunei Chemical Co., Ltd., PSM-4261; OH equivalent: 103, softening point: 8)
Curing agent B: Phenol aralkyl type resin (manufactured by Mitsui Toatsu, XL-225-LL; OH equivalent 174, softening point 75)
° C) Brominated epoxy A: Novolac type brominated epoxy (BREN-S, manufactured by Nippon Kayaku; epoxy equivalent: 284, hydrolyzable chlorine: 600 ppm, softening point: 84 ° C) Silica A: spherical silica (average particle size: 30 µm) Silica B : Spherical silica (average particle size: 16 μm) Silica C: Spherical silica (average particle size: 0.6 μm)

Next, these epoxy resin compositions were mixed with 17
After molding at 5 ° C. and post-curing at 175 ° C. for 12 hours to obtain a cured product test piece, it was subjected to various physical property measurements. The glass transition point was determined by a thermomechanical measuring device at a heating rate of 10 ° C./min. The water absorption was measured when a disk having a diameter of 50 mm and a thickness of 3 mm was formed using an epoxy resin composition, post-cured, and allowed to absorb moisture at 85 ° C. and 85% RH for 24 hours and 100 hours. . Crack generation rate is QFP-80pin (14 × 20 × 2.5mm
t) is molded and post-cured, and then subjected to the same condition as the water absorption rate of 85.
After absorbing moisture for a predetermined time under the condition of 85 ° C. and 85% RH,
After being immersed in a solder bath at 0 ° C. for 10 seconds, the state of the package was observed and determined. The blocking property was defined as the weight ratio of the agglomerated composition after the pulverized epoxy resin composition was left at 25 ° C. for 24 hours. Table 2 shows the measurement results of various physical properties.

From Table 2, it can be seen that Examples 1 to 6 satisfying the conditions specified in the present invention are all excellent in blocking resistance, excellent in moldability such as rapid curability and fluidity, and have good mechanical strength, heat resistance, It can be seen that a cured product excellent in low moisture absorption, crack resistance and the like is provided. On the other hand, Comparative Examples 1 to 5, which do not satisfy the conditions defined in the present invention, do not have all of the above-mentioned characteristics as excellent as Examples. That is, in Comparative Examples 1 and 2,
Since it does not contain an aralkyl-type epoxy resin, the blocking resistance is lower than that of the examples. Comparative Example 3
In Examples 4 and 4, since the low-viscosity epoxy resin having a melt viscosity at 150 ° C. of 0.3 poise or less was not contained, the fluidity of the epoxy resin composition was lower than that of the examples, and the inorganic filler had a high viscosity. Not suitable for filling. In Comparative Example 5, since no aralkyl-type epoxy resin was contained, the blocking resistance was lower than in the examples, and the crack resistance of the cured product was lower than in the examples.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

The epoxy resin composition of the present invention is excellent in moldability such as rapid curability and fluidity, has good blocking resistance as a composition, and has mechanical strength, heat resistance and low moisture absorption. When a cured product excellent in heat resistance and crack resistance is provided and applied to encapsulation of electronic components such as semiconductor elements, crack resistance is greatly improved and excellent solder heat resistance is exhibited.

Claims (4)

[Claims] 1. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein, as the epoxy resin component, a low-viscosity epoxy resin having a melt viscosity at 150 ° C. of 0.3 poise or less is contained in all epoxy resin components. An epoxy resin composition containing 10 to 90% by weight, and 90 to 10% by weight of an aralkyl type epoxy resin represented by the following general formula (1) in all epoxy resin components. Embedded image (In the formula, A represents a benzene ring or a naphthalene ring which may be substituted simultaneously or separately with a hydrocarbon group having 1 to 6 carbon atoms, and R ₁ and R ₂ represent a hydrogen atom or methyl which may be the same or different. G represents a glycidyl group, and m represents 1
Or an integer of 2 and n represents a number of 1 to 15) 2. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler, wherein a bisphenol type epoxy resin represented by the following general formula (3) is used as an epoxy resin component in an amount of 10 to 90 in all epoxy resin components. An epoxy resin composition characterized by containing 90 to 10% by weight of an aralkyl-type epoxy resin represented by the following general formula (1) in all epoxy resin components. Embedded image (Wherein, R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a methyl group which may be the same or different, G represents a glycidyl group,
q represents a number from 0 to 15) (In the formula, A represents a benzene ring or a naphthalene ring which may be substituted simultaneously or separately with a hydrocarbon group having 1 to 6 carbon atoms, and R ₁ and R ₂ represent a hydrogen atom or methyl which may be the same or different. G represents a glycidyl group, and m represents 1
Or an integer of 2 and n represents a number of 1 to 15) 3. The epoxy resin composition according to claim 1, wherein the curing agent is a polyhydric phenolic compound having a softening point of 40 to 150 ° C. 4. An electronic component sealed with a cured product of the epoxy resin composition according to claim 1.