JPH08109243A - Epoxy resin composition for sealing of semiconductor - Google Patents

Abstract

PURPOSE: To improve the fluidity, soldering crack resistance, low hygroscopicity, and heat resistance by incorporating a particular epoxy resin, an epoxy resin curing agent, an inorganic filler, and a curing accelerator. CONSTITUTION: 20 to 90 pts.wt. 4,4'-bisphenol F epoxy resin of the formula I (wherein m is 0 to 0.5 on the average), 10 to 80 pts.wt. polyhydric phenol epoxy resin of the formula II (wherein R is a 1-10C alkyl, a (substd.) phenyl, a (substd.) aralkyl, a 1-10C alkoxy, or a halogen, k is 0 to 4, G is glycidyl, Z is a 5-15C divalent hydrocarbon residue, and n is 0 to 5 on the average) with a hydrocarbon residue having a low polarity being interposed between the phenyl nuclei, an epoxy resin curing agent in an amt. of 0.5 to 2.0mol, in terms of total amt. of groups reactive with the epoxy group, per mol of epoxy group in the whole epoxy resin component, 60 to 95wt.%, based on the whole compsn., inorg. filler, and 0.1 to 7wt.%, based on the epoxy resin, curing accelerator are mixed together.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for encapsulating a semiconductor, which gives a cured product having excellent fluidity and solder crack resistance.

[0002]

2. Description of the Related Art Epoxy resin compositions are used for adhesion, casting, encapsulation, lamination, because of their excellent cured properties and ease of handling.
It is used in a wide range of fields such as molding and painting. There are many types of epoxy resins, and the cured physical properties vary greatly depending on the selection, so they are used properly according to the field of use and purpose.

In recent years, as the use conditions of polymer materials have become severer, various characteristics required for polymer materials have become strict, and various epoxy resins generally used satisfy the required characteristics sufficiently. I can't.

For example, an epoxy resin composition is used for encapsulating a semiconductor, and the required performance is also in this field.
It's getting tougher. That is, as the degree of integration of semiconductor devices has increased, the size of semiconductor elements has increased significantly, and the packages themselves have become smaller and thinner. In addition, the mounting of semiconductor devices is also shifting to surface mounting, and in surface mounting, semiconductor devices are directly immersed in a solder bath and exposed to high temperatures, which causes a large expansion of the entire package due to the rapid expansion of absorbed moisture. Stress is applied and the sealing material cracks. Therefore, an epoxy resin composition for a sealing material having good solder crack resistance is required to have high heat resistance (that is, high glass transition temperature), low hygroscopicity and low stress.

It is widely practiced to improve the low hygroscopicity and low stress (that is, low coefficient of thermal expansion) by highly filling an inorganic filler such as fused silica powder,
Although it has a great effect on improving the solder crack resistance, the epoxy resin for the encapsulant is also required to have a low melt viscosity because high flow of the inorganic filler impairs the flowability during molding. It was

The cresol novolac type epoxy resin which is mainly used at present has become insufficient in terms of low hygroscopicity and low melt viscosity.

[0007] Researches for lowering moisture absorption of epoxy resins have been widely conducted. A typical method is to introduce a hydrophobic group such as a dicyclopentane skeleton or a xylene skeleton (JP-A-60-112813 and JP-A-62-20).
1922, etc.), a certain degree of low moisture absorption effect can be obtained, but since it is not sufficient in terms of low melt viscosity, it cannot be highly filled with an inorganic filler, and solder crack resistance is not sufficient. Not improved.

Further, with the miniaturization and thinning of the package, the epoxy resin composition for encapsulant is required to have high fluidity, and the demand for low melt viscosity of the epoxy resin is becoming more severe. .

Although the bisphenol A type epoxy resin and the bisphenol F type epoxy resin have a very low viscosity, generally, these epoxy resins are liquid at room temperature,
It cannot be used for epoxy resin compositions for encapsulants used in powder form. Further, the low hygroscopicity and heat resistance of these epoxy resins are not sufficient.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an epoxy resin composition for semiconductor encapsulation which gives a cured product having excellent fluidity and solder crack resistance.

[0011]

As a result of various studies to solve the above-mentioned problems, the present inventors have found that a specific bisphenol F type epoxy resin as an epoxy resin and a hydrocarbon having a small polarity between the phenyl nucleus. The object could be achieved by using a mixture of specific epoxy resins having groups.

That is, the epoxy resin composition for semiconductor encapsulation of the present invention is an epoxy resin composition containing at least an epoxy resin, an epoxy resin curing agent, an inorganic filler and a curing accelerator. Of the general formula (I)

[0013]

Embedded image (In the formula, m is an average value of 0 to 0.5.) 4,4′-bisphenol F type epoxy resin 20
~ 90 parts by weight and the following general formula (II)

[0014]

[Chemical 4] (In the formula, R is an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and each R is mutually They may be the same or different, k is an integer of 0 to 4, each k may be the same as or different from each other, G is a glycidyl group,
Z is a divalent hydrocarbon group having 5 to 15 carbon atoms, and each Z may be the same as or different from each other. n is an average value and is a number of 0-5. ) Is used, and an epoxy resin having an epoxy resin as a main component, which is composed of 10 to 80 parts by weight of a polyhydric phenol resin-based epoxy resin in which a hydrocarbon group having less polarity is interposed between phenyl nuclei, is used. It is a composition.

Since a general bisphenol F type epoxy resin is a mixture of three kinds of isomers of 2,2'-form, 2,4'-form and 4,4'-form, its 2,2 ' The two isomers of the -form and the 2,4'-form hinder the crystallization of the 4,4'-form, are liquid at room temperature, and have high viscosity, and further give a cured product having low heat resistance. is there.

On the other hand, the 4,4'-bisphenol F type epoxy resin represented by the general formula (I) used in the present invention [hereinafter, referred to as "4,4'-bisphenol F"
It may be abbreviated as "type epoxy resin (I)". ] Is
Since it is composed only of 4,4′-form, it is a crystal (solid) at room temperature, and the average value of m in the general formula (I) is in the range of 0 to 0.5. It is possible to provide a cured product having low viscosity, excellent fluidity, and relatively excellent heat resistance.

Further, the above-mentioned general formula (II) used in the present invention
Represented by a polyhydric phenol resin-based epoxy resin in which a hydrocarbon group having less polarity is interposed between phenyl nuclei [hereinafter,
This may be abbreviated as “hydrocarbon group-mediated polyphenolic epoxy resin (II)”. ] Is a hydrocarbon group having less polarity between phenyl nuclei [in the general formula (II)
Z-] is interposed, a cured product having excellent low hygroscopicity and relatively excellent heat resistance is provided.

The epoxy resin used in the present invention is
20 to 90 parts by weight, preferably 30 to 80 parts by weight of the specific 4,4′-bisphenol F type epoxy resin (I) and the specific hydrocarbon group-containing polyhydric phenol resin-based epoxy resin (II) The epoxy resin composition of the present invention is excellent in the fluidity of the composition and is low in viscosity because it is an epoxy resin containing 10 to 80 parts by weight, preferably 20 to 70 parts by weight, as the main component. It is possible to provide a cured product having a well-balanced moisture absorption rate, heat resistance, and solder crack resistance. When the ratio of the 4,4′-bisphenol F type epoxy resin (I) is too large, the composition has excellent fluidity, but the cured product has high hygroscopicity, and the hydrocarbon group-containing multi-component is high. If the proportion of the hydric phenol resin-based epoxy resin (II) is too large, the hygroscopicity of the cured product will be low, but the fluidity of the composition will be poor, so the proportion of both will be within the above range.

The 4,4'-bisphenol F type epoxy resin (I) can be produced by subjecting 4,4'-bisphenol F and epihalohydrin to a condensation reaction in the presence of an alkali.

A typical example of the method for producing the 4,4'-bisphenol F type epoxy resin (I) is described in detail below. First, 4,4'-bisphenol F is dissolved in an amount of epihalohydrin corresponding to 3 to 20 mol per mol of the phenolic hydroxyl group to form a uniform solution. Then
While stirring the solution, an alkali metal hydroxide in an amount of 1 to 2 mol per mol of the phenolic hydroxyl group is added as a solid or an aqueous solution and reacted. This reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is usually about 30 to 105 ° C. in the case of reaction under normal pressure and about 30 to 80 ° C. in the case of reaction under reduced pressure. is there. In the reaction, the reaction solution is azeotroped while maintaining a predetermined temperature if necessary, and the condensate obtained by cooling the vaporizing vapor is separated into oil and water, and the oil content excluding water is returned to the reaction system. It is dehydrated from the reaction system depending on the method. The addition of the alkali metal hydroxide is intermittently or continuously added little by little over 1 to 8 hours in order to suppress a rapid reaction. The total reaction time is usually 1 to
It is about 10 hours.

After completion of the reaction, the insoluble by-product salt is removed by filtration or washed with water, and the unreacted epihalohydrin is removed by distillation under reduced pressure to remove the desired 4,4'-bisphenol F type epoxy resin ( I) is obtained.

Epichlorohydrin or epibromohydrin is usually used as the epihalohydrin in this reaction, and NaOH or KOH is usually used as the alkali metal hydroxide.

In this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6- (trisdimethylaminomethyl) phenol; A catalyst such as imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine may be used.

Further, in this reaction, alcohols such as ethanol and isopropanol; acetone,
Ketones such as methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; inert organic solvents such as aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide may be used.

Furthermore, 4, obtained as described above,
When the amount of the saponifiable halogen of the 4'-bisphenol F type epoxy resin is too large, it can be reprocessed to obtain a purified epoxy resin having a sufficiently reduced amount of the saponifiable halogen. For example, the crude epoxy resin is isopropanol, methyl ethyl ketone, methyl isobutyl ketone,
It is redissolved in an inert organic solvent such as toluene, xylene, dioxane, propylene glycol monomethyl ether or dimethylsulfoxide, and an alkali metal hydroxide is added as a solid or an aqueous solution, and the temperature is about 30 to 120 ° C. at 0.5.
After the ring-closing reaction was carried out for ~ 8 hours, excess alkali metal hydroxide and by-product salts were removed by a method such as washing with water, and the organic solvent was distilled off under reduced pressure to give purified 4,4 '. A bisphenol F type epoxy resin is obtained.

Next, the hydrocarbon group-containing polyhydric phenol resin-based epoxy resin (II) is represented by the following general formula (III), and has various types of polyphenylene resin-based epoxy resin having a less polar hydrocarbon group between phenyl nuclei. It can be produced by subjecting a polyhydric phenol resin and epihalohydrin to a condensation reaction in the presence of an alkali.

[0027]

Embedded image (In the formula, R is an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and each R is mutually They may be the same or different, k is an integer of 0 to 4, each k may be the same or different, and Z is a divalent hydrocarbon group having 5 to 15 carbon atoms. And each Z may be the same as or different from each other, and n is an average value of 0 to 5.)

The polyhydric phenolic resin represented by the above general formula (III), which is a raw material for producing the hydrocarbon group-mediated polyhydric phenolic epoxy resin (II) used in the present invention, can be prepared by various methods. Although it can be produced, in general, various phenol compounds which may have the same substituents and / or substituent atoms as R in the general formula (II),
Oligomerization using a reaction such as an addition condensation reaction with a carbonyl group-containing compound, an addition reaction with a compound having an unsaturated bond, or a condensation reaction with α-hydroxyalkylbenzenes or α-alkoxyalkylbenzenes,
A method of resinification is used.

Examples of the raw material phenol compound include phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol,
Examples include butylcresol, phenylphenol, benzylphenol, methoxyphenol, bromophenol and the like.

Examples of the carbonyl group-containing compound used for oligomerizing these phenol compounds include various aldehydes or ketones having 5 to 15 carbon atoms, specifically, benzaldehyde, cyclohexanone, acetophenone, naphthaldehyde. And so on.

As the compound having the unsaturated bond,
For example, divinylbenzene, diisopropenylbenzene, dicyclopentadiene, norbornene, terpenes and the like can be mentioned.

Further, as α-hydroxyalkylbenzenes or α-alkoxyalkylbenzenes, for example, α, α'-dihydroxyxylene, α, α'-dihydroxyxylene,
α'-dihydroxydiisopropylbenzene, α, α '
-Dimethoxyxylene, α, α′-dimethoxydiisopropylbenzene and the like can be mentioned.

The reaction with a compound having a carbonyl group, a compound having an unsaturated bond, α-hydroxyalkylbenzenes or α-alkoxyalkylbenzenes used for oligomerizing these phenol compounds to form a resin is a general reaction. A method is used. That is, in the presence of an acidic catalyst, at a temperature of 20 to 200 ° C.
Incubate for 20 hours.

Among the polyhydric phenol resins represented by the general formula (III) thus produced, dicyclopentadiene phenol resin and terpene phenol resin are available from the viewpoints of availability and cured physical properties. Phenol aralkyl resin, phenol cyclohexanone resin and the like are preferable.

The reaction of the polyhydric phenol resin represented by the general formula (III) with epihalohydrin for producing the hydrocarbon group-mediated polyhydric phenol resin epoxy resin (II) used in the present invention is The polyhydric phenol resin represented by the general formula (III) may be subjected to a condensation reaction with one or a mixture of two or more kinds and epihalohydrin in the presence of an alkali. Since the reaction for producing the 4,4′-bisphenol F type epoxy resin (I) and the method according to the embodiment are used as the embodiment, detailed description thereof will be omitted.

Since the hydrocarbon group-mediated polyphenolic epoxy resin (II) is already on the market, the present invention can be carried out using the commercially available product.

The epoxy resin in the epoxy resin composition for semiconductor encapsulation of the present invention includes the 4,4'-bisphenol F type epoxy resin (I) and the hydrocarbon group-containing polyhydric phenol resin-based epoxy resin ( II) and may be separately produced or obtained and mixed and used,
A mixture of each of the epoxy resins, 4,4′-bisphenol F, and a polyhydric phenol resin represented by the general formula (III) was reacted with epihalohydrin to produce a mixture of both epoxy resins. , Mixtures thereof may be used.

As described above, the mixing ratio of the 4,4'-bisphenol F type epoxy resin (I) and the hydrocarbon group-containing polyhydric phenol resin type epoxy resin (II) is 2 in the former case.
The latter is 10 to 80 parts by weight, preferably 20 to 70 parts by weight with respect to 0 to 90 parts by weight, preferably 30 to 80 parts by weight.

The epoxy resin in the epoxy resin composition for semiconductor encapsulation of the present invention includes 4,4'-bisphenol F type epoxy resin (I) and hydrocarbon group-containing polyphenolic epoxy resin (II). An epoxy resin having an epoxy resin as a main component, which is composed of the above ratio of
It is preferable to use only the epoxy resins (I) and (II), but other epoxy resins can be mixed and used.

Other epoxy resins which can be mixed and used include, for example, bisphenol A, bisphenol AD, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, dihydroxydiphenylether, dihydroxynaphthalene, phenol novolac resin, Cresol novolac resin, bisphenol A novolac resin,
Various phenols such as dicyclopentadiene phenol resin, terpene phenol resin, phenol aralkyl resin, naphthol novolac resin, brominated bisphenol A, brominated phenol novolac resin, and various phenols, hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc. Of various phenolic compounds such as polyhydric phenolic resins obtained by condensation reaction with various aldehydes, and an epoxy resin produced from epihalohydrin; various amine compounds such as diaminodiphenylmethane, aminophenol, and xylenediamine, Epoxy resin produced from epihalohydrin; epoxy resin produced from various carboxylic acids such as methylhexahydrophthalic acid and dimer acid, and epihalohydrin And the like.

The proportion of these other epoxy resins used is
4,4'-Bisphenol F type epoxy resin (I) and hydrocarbon group-containing polyphenolic epoxy resin (II)
Is 100 parts by weight or less, preferably 50 parts by weight or less. If the proportion of the other epoxy resin used is too large, the effects of the present invention will not be sufficiently exhibited.

Next, an epoxy resin curing agent is added to the epoxy resin composition for semiconductor encapsulation of the present invention as an essential component. The epoxy resin curing agent is not particularly limited, and a general epoxy resin curing agent is used. Agents can be used.

Examples of the epoxy resin curing agent used include bisphenol A, bisphenol F, bisphenol AD, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, phenol novolac resin, cresol novolac resin, Various phenols such as bisphenol A novolac resin, dicyclopentadiene phenol resin, terpene phenol resin, phenol aralkyl resin, naphthol novolac resin, brominated bisphenol A, brominated phenol novolac resin; various phenols, hydroxybenzaldehyde, croton Many compounds obtained by condensation reaction with various aldehydes such as aldehydes and glyoxal Various phenolic resins such as phenolic resins; active ester compounds obtained by esterifying all or part of the phenolic hydroxyl groups of these various phenols (resins) with benzoate or acetate and the like; methyltetrahydrophthalic anhydride Acids, acid anhydrides such as hexahydrophthalic anhydride, pyromellitic dianhydride, and methyl nadic acid; amines such as diethylenetriamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and dicyandiamide.

Among these various epoxy resin curing agents, various phenols (resins) or active ester compounds thereof are preferable from the viewpoint of cured physical properties and the like.

The amount of the epoxy resin curing agent used in the epoxy resin composition for semiconductor encapsulation of the present invention is such that the epoxy group in the epoxy resin curing agent component is 1 mol of the epoxy group in the total epoxy resin component. The amount in which the total amount of the groups that react with the groups is 0.5 to 2.0 mol is preferable, and the amount is more preferably 0.7 to 1.2 mol.

Next, the epoxy resin composition for semiconductor encapsulation of the present invention is blended with an inorganic filler. Examples of the kind of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, calcium carbonate and the like. Its shape is a crush type or a spherical shape. Various inorganic fillers may be used alone or in combination of two or more, and among them, fused silica or crystalline silica is preferable. The amount used is 60 to 95% by weight of the entire composition.
And more preferably 80 to 93% by weight.

A curing accelerator is added to the epoxy resin composition for semiconductor encapsulation of the present invention, and the curing accelerator causes the reaction between the epoxy group in the epoxy resin and the active group in the curing agent. It is a accelerating compound.

Examples of the curing accelerator include phosphine compounds such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine; tetraphenylphosphonium tetraphenylborate, Phosphonium salts such as methyltributylphosphonium tetraphenylborate and methyltricyanoethylphosphonium tetraphenylborate; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-
Undecyl imidazole, 1-cyanoethyl-2-methyl imidazole, 2,4-dicyano-6- [2-methyl imidazolyl- (1)]-ethyl-S-triazine,
Imidazoles such as 2,4-dicyano-6- [2-undecylimidazolyl- (1)]-ethyl-S-triazine; 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanate Nurate, 2-ethyl-4-methylimidazolium tetraphenylborate, 2-ethyl-1,4-dimethylimidazolium tetraphenylborate and other imidazolium salts; 2,4,6-tris (dimethylaminomethyl) phenol, benzyl Amines such as dimethylamine, tetramethylbutylguanidine, N-methylpiperazine and 2-dimethylamino-1-pyrroline; ammonium salts such as triethylammonium tetraphenylborate; 1,5-diazabicyclo (5,4,0) -7 −
Undecene, 1,5-diazabicyclo (4,3,0)-
5-nonene, 1,4-diazabicyclo (2,2,2)-
Diazabicyclo compounds such as octane; tetraphenylborate, phenol salt, phenol novolac salt, 2-ethylhexanoate, etc. of these diazabicyclo compounds.

Among these compounds which act as curing accelerators, phosphine compounds, imidazole compounds, diazabicyclo compounds and salts thereof are preferred.

These curing accelerators are used alone or in admixture of two or more, and the amount used is 0.1 to 7% by weight, preferably 1 to 5% by weight, based on the epoxy resin. Is.

If necessary, a coupling agent, a plasticizer, a pigment and the like can be appropriately added to the epoxy resin composition for semiconductor encapsulation of the present invention. Also, as a flame retardant aid,
Antimony trioxide, phosphoric acid, etc. can be appropriately mixed.

Since the epoxy resin composition for semiconductor encapsulation of the present invention gives a cured product having excellent fluidity and solder crack resistance, it can be advantageously used in the field of semiconductor encapsulation.

The epoxy resin production examples, examples and comparative examples will be described in more detail below.

Production Example 1 of Bisphenol F-type Epoxy Resin Content of 3000 ml equipped with thermometer, stirrer and cooling tube
Add 4,4'-bisphenol F20 to a 3-necked flask.
0 g, epichlorohydrin 1295 g, and isopropyl alcohol 504 g were charged, the temperature was raised to 35 ° C. to uniformly dissolve, and 190 g of a 48.5 wt% sodium hydroxide aqueous solution was added dropwise over 1 hour. During that time, the temperature was gradually raised so that the temperature inside the system became 65 ° C. at the end of the dropping. Then, the reaction was carried out by holding at 65 ° C. for 30 minutes. After completion of the reaction, the by-product salt and excess sodium hydroxide were removed by washing with water. Then, excess epichlorohydrin and isopropyl alcohol were distilled off from the product under reduced pressure to obtain a crude epoxy resin.

This crude epoxy resin was dissolved in 400 g of methyl isobutyl ketone, 6 g of a 48.5 wt% sodium hydroxide aqueous solution was added, and the mixture was reacted at a temperature of 65 ° C. for 1 hour. After the reaction was completed, sodium phosphate monobasic was added to neutralize excess sodium hydroxide, and the product was washed with water to remove by-product salts. Then, methyl isobutyl ketone was completely removed under reduced pressure to obtain 4,4′-bisphenol F type epoxy resin.

This epoxy resin has an epoxy equivalent of 164
g / eq. It was a yellowish white crystalline solid having a melting point of 51 ° C. and an average value of m in the general formula (I) of 0.1.

Production Example a of Hydrocarbon Group-Mediated Polyphenolic Epoxy Resin 200 g of 4,4′-bisphenol F used in Production Example 1
In place of the above, 360 g of dicyclopentadiene phenol resin (DCP-5000 manufactured by Mitsui Toatsu Chemicals, Inc.) was used to react with epichlorohydrin in the same manner as in Production Example 1 and post-treated to obtain an epoxy resin.

This epoxy resin has an epoxy equivalent of 255
g / eq. Is a yellow-red solid having a softening point of 62 ° C., R in the general formula (II) is a hydrogen atom, Z is a group represented by the following formula, k is 0, and n is 1.2. It was an epoxy resin.

[0059]

[Chemical 6]

Production Example b of Hydrocarbon Group-Mediated Polyphenolic Resin Epoxy Resin 4,200 g of 4,4′-bisphenol F used in Production Example 1
In place of the above, 350 g of phenol aralkyl resin (Mirex XL225LL manufactured by Mitsui Toatsu Chemical Co., Inc.) was used to react with epichlorohydrin in the same manner as in Production Example 1 and post-treated to obtain an epoxy resin.

This epoxy resin has an epoxy equivalent of 252
g / eq. Is a yellow-red solid having a softening point of 64 ° C., R in the general formula (II) is a hydrogen atom, Z is a group represented by the following formula, k is 0, and n is 2.1. It was an epoxy resin.

[0062]

[Chemical 7]

Production Example c of Hydrocarbon Group-Mediated Polyphenol Resin Epoxy Resin 200 g of 4,4′-bisphenol F used in Production Example 1
In place of the above, 330 g of a terpene phenol resin (YP-90 manufactured by Yasuhara Chemical Co., Ltd.) was used to react with epichlorohydrin in the same manner as in Production Example 1 and post-treated to obtain an epoxy resin.

This epoxy resin has an epoxy equivalent of 233
g / eq. Is a yellow-red solid having a softening point of 60 ° C., R in the general formula (II) is a hydrogen atom, Z is a group represented by the following formula, k is 0, and n is 0.1. It was an epoxy resin.

[0065]

Embedded image

Examples 1 to 5 and Comparative Examples 1 to 3 As shown in Table 1, as an epoxy resin, the epoxy resin obtained in Production Example 1, each epoxy resin obtained in Production Examples a to c, and cresol novolac. -Type epoxy resin and brominated epoxy resin, respectively, commercially available phenol novolak resin (A) and commercially available terpene phenol novolac resin (B) as epoxy resin curing agents, and commercially available crush type melting as inorganic filler Silica powder (Examples 1 to 5 and Comparative Example 1 were 8 based on the total composition).
2% by weight, and 75% by weight for each of the compositions in Comparative Examples 2 and 3), triphenylphosphine as a curing accelerator, antimony trioxide as a flame retardant aid, and surface treatment of an inorganic filler. Each epoxy resin composition was compounded by using commercially available epoxysilane as an agent and carnauba wax as a release agent.

Then, the respective blends were melt mixed for 5 minutes at a temperature of 70 to 130 ° C. using a mixing roll. Each of the obtained molten mixtures was taken out in a sheet form and pulverized to obtain each molding material.

Each of these molding materials was molded by a low-pressure transfer molding machine at a mold temperature of 180 ° C. for a molding time of 180 seconds to obtain each test piece, which was post-cured at 180 ° C. for 8 hours. In addition, the spiral flow of each molding material was measured.

Spiral flow of each molding material and solder crack resistance after post-curing of each test piece, moisture absorption rate,
The results of testing the glass transition temperature are shown in Table 1, and the molding materials of Examples 1 to 5 have fluidity (that is, high spiral flow) as compared with the molding materials of Comparative Examples 1 to 3.
And the solder crack resistance was well balanced and excellent.

[0070]

[Table 1]

Note to Table 1: * 1 ... Orthocresol novolac type epoxy resin (Yuka Kachel Epoxy Co., Ltd. trade name Epicoat 18
OH65, epoxy equivalent 205) * 2 ... Brominated bisphenol A type epoxy resin (Yukaka Shell Epoxy Co., Ltd., trade name Epicoat 5050,
Epoxy equivalent 385, bromine content 49%) * 3 ... A: Phenol novolac resin (manufactured by Gunei Chemical Co., hydroxyl equivalent 103, softening point 85 ° C) * 4 ... B: Terpene phenol novolac resin (oiled Ciel Epoxy Co., Ltd. Product name Epicure MP40
2, hydroxyl equivalent 175, softening point 130 ° C.) * 5 ... Fracturing type fused silica powder (Tatsumori company trade name RD-
8) * 6 ... Shin-Etsu Chemical Co., Ltd. trade name KBM-403 * 7 ... 16 44-pin FPPs are absorbed at 85 ° C. and 85% RH for 300 hours, then immersed in a solder bath at 260 ° C. for 10 seconds to remove cracks. The number of occurrences was calculated. * 8 ... Moisture absorption after 85 hours at 85 ° C and 85% RH for 300 hours Moisture absorption * 9 ... Determined from the transition point of the thermal expansion curve using TMA.

As is clear from Table 1, the compositions of the Examples are more fluid than the compositions of the Comparative Examples, and the fluidity of the compositions, the hygroscopicity of the cured product, the solder crack resistance and the heat resistance (glass transition). The temperature is balanced and excellent.

[0073]

The epoxy resin composition of the present invention is excellent in fluidity, and the cured product has excellent balance in solder crack resistance, low moisture absorption and heat resistance (glass transition temperature). It is advantageously used for semiconductor encapsulation.

Continuation of front page (51) Int.Cl. ⁶ Identification number In-house reference number FI Technical indication location H01L 23/31 (72) Inventor Yoshinori Nakanishi 1 Shiohama-cho, Yokkaichi-shi, Mie Yukasei Shell Epoxy Co., Ltd.

Claims (1)

[Claims] 1. An epoxy resin composition containing at least an epoxy resin, an epoxy resin curing agent, an inorganic filler and a curing accelerator, wherein the epoxy resin is represented by the following general formula (I): (In the formula, m is an average value of 0 to 0.5.) 4,4′-bisphenol F type epoxy resin 20
~ 90 parts by weight and the following general formula (II): (In the formula, R is an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and each R is mutually They may be the same or different, k is an integer of 0 to 4, each k may be the same as or different from each other, G is a glycidyl group,
Z is a divalent hydrocarbon group having 5 to 15 carbon atoms, and each Z may be the same as or different from each other. n is an average value and is a number of 0-5. ) Is used, and an epoxy resin having an epoxy resin as a main component, which is composed of 10 to 80 parts by weight of a polyhydric phenol resin-based epoxy resin in which a hydrocarbon group having less polarity is interposed between phenyl nuclei, is used. Epoxy resin composition for semiconductor encapsulation.