JPH10182789A - Epoxy resin composition and semiconductor sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in preserving stability, flow property, forming property, reliability in moisture resistance and solder cracking resistance, and useful as a semiconductor sealing material by using a specific epoxy resin and a curing agent as indispensable compositions. SOLUTION: This epoxy resin composition is obtained by containing (A) an epoxy resin containing >=50wt.% compound having a crystalline state at a room temperature, containing a β position-substituted glycidyloxy group in its molecular structure and having preferably a structure of the formula [X is a condensed polycyclic hydrocarbon or a hydrocarbon obtained by bonding 2 aromatic nuclei through a joining group; R is an alkyl, an aryl, an acyl or H; (n)=0] and (B) a curing agent, preferably a phenolic compound, as indispensable components, and further preferably containing (C) an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel epoxy resin composition having excellent storage stability, fluidity, moldability, moisture resistance and solder crack resistance, and a semiconductor encapsulant using the same.

[0002]

2. Description of the Related Art In recent years, semiconductor packages have tended to be thinner in order to cope with higher packaging densities, and have a thickness of 1 mm.
The following TSOP type packages are also used: In order to cope with this, a material having high fluidity is required as a semiconductor encapsulating material.In addition, as the semiconductor mounting method is changed to a surface mounting method, it has excellent solder crack resistance, that is, the heat of the solder. Accordingly, there is a need for a low-water-absorbing material and a high-filling inorganic filler material in order to prevent cracks due to expansion of water in the sealing material.

[0003] Conventionally, crystalline epoxy resins have been studied as epoxy resins for semiconductor encapsulating materials, as low melting viscosity, high filling of inorganic fillers and good solder cracking resistance. For example, biphenyl-type epoxy resins, diglycidyl ether of dihydroxynaphthalene, diglycidyl ether of 4,4′-dihydroxybenzophenone, and the like are known.

[0004]

However, an epoxy composition for a semiconductor encapsulant using a biphenyl-type epoxy resin is inferior in curability, and inferior in solder heat resistance due to poor heat resistance and moisture resistance reliability. there were. Also, 1,5-, 1,4-, 2,6-dihydroxynaphthalene, 4,
Semiconductor encapsulating materials using epichlorohydrin such as 4′-dihydroxybenzophenone all have very poor solvent solubility, cause crystallization during the epoxidation step, and the obtained epoxy resin has a melting point of 150 ° C. or higher. For this reason, a curing reaction starts during melt-kneading or gelation occurs, so that there is a problem that the semiconductor encapsulating material cannot actually be adjusted.

[0005] Therefore, the problem to be solved by the present invention is:
Suitable melting point (70-1
An epoxy resin composition and a semiconductor encapsulation which have a crystallization temperature during the epoxidation step and exhibit more excellent curability, heat resistance and moisture resistance reliability than the biphenyl type. To provide a stopping material.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an epoxy resin having crystalline properties at room temperature and containing a β-substituted glycidyloxy group in the molecular structure is used as a main component. As a result, the present inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention comprises, as essential components, an epoxy resin (A) having crystalline properties at room temperature and containing a β-substituted glycidyloxy group in the molecular structure, and a curing agent (B). The present invention relates to an epoxy resin composition characterized by the following, and a semiconductor encapsulating material further comprising an inorganic filler (C) as an essential component in addition to the composition.

The epoxy resin (A) used in the present invention, which has crystalline properties at room temperature and contains a β-substituted glycidyloxy group in its molecular structure, is prepared from a compound capable of deriving a crystalline epoxy resin. Which is obtained by introducing a β-substituted glycidyloxy group into the molecular structure of the epoxy resin.

Here, the term "crystalline at normal temperature" in the epoxy resin (A) specifically means a crystalline state at 25 ° C.

The compound capable of deriving the crystalline epoxy resin in this case is not particularly limited as long as it is a compound having a chemical structure with high symmetry and high orientation. , 1,5-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, dihydroxynaphthalene isomers such as 2,6-dihydroxynaphthalene and alkyl-substituted dihydroxynaphthalene isomers,
Examples thereof include benzophenone structures such as 4,4'-dihydroxybenzophenone and bisphenols having a binding group of -SO2- such as bisphenol S.
Among them, from the viewpoint of heat resistance, moisture resistance reliability, etc.,
5-Dihydroxynaphthalene and 4,4'-dihydroxybenzophenone are preferred. These compounds are conventionally glycidylated with unsubstituted epihalohydrin alone,
Since the resulting epoxy compound has very high solvent solubility, crystallization (insolubilization) occurred during the epoxidation step. Therefore, it was difficult to obtain a target epoxy resin having a high purity. In addition, since the obtained epoxy resin also has a melting point exceeding 150 ° C., a kneading temperature higher than usual is required in a melt kneading step when used for a semiconductor encapsulating material, so that a crosslinking reaction occurs during kneading. Has progressed,
As a result, it was impossible to adjust the semiconductor sealing material.
In the present invention, all of these problems have been improved by replacing a part or all of the β-position unsubstituted glycidyloxy group glycidylated with unsubstituted epihalohydrin alone with a β-substituted glycidyloxy group. .

The structure of the epoxy resin (A) is not particularly limited as long as it is derived from the compound described above. However, in particular, β-substituted glycidyloxybenzophenone is preferred because of its excellent curability. Β-substituted glycidyloxynaphthalene is preferable from the viewpoint of excellent solubility, and further, a mixture of β-unsubstituted glycidyloxy-naphthalene and di-glycidyloxynaphthalene or di-β-substituted glycidylbenzophenone from the viewpoint of solvent solubility. And a mixture of β-substituted glycidyloxy-β-unsubstituted glycidyloxy-benzophenone and di-glycidyloxybenzophenone.

In the epoxy resin (A), it is particularly preferable that a β-unsubstituted glycidyloxy group and a β-substituted glycidyloxy group coexist. And the melting point can be arbitrarily adjusted. Specifically, the equivalent ratio of the glycidyloxy group to the β-substituted glycidyloxy group is 80 /
In the range 20-20 / 80, especially 35 / 65-65 / 35
Those in the range, the solvent solubility becomes remarkably good,
Further, the melting point suitable for semiconductor encapsulating materials is also in the optimum range, and furthermore, the moisture resistance reliability and the curability are extremely excellent.

Next, as described above, the melting point of the epoxy resin (A) can be reduced to 150 ° C., although it is crystalline at room temperature. As a particularly preferred melting point range, specifically, the Tg measured by DSC is 70 to 140.
° C.

Here, the β-substituted glycidyloxy group in the epoxy resin (A) has a substituent at the β-position, and the substituent includes an alkyl group, an aryl group, an allyl group and an aralkyl group. And the like, and an alkyl group is particularly preferable since the effect of the present invention is remarkable. In addition, these substituents preferably have 1 to 10 carbon atoms, and are most preferably alkyl groups having 1 to 10 carbon atoms.

It is preferable that the epoxy resin (A) has a melt viscosity at 150 ° C. of 0.5 poise or less, particularly 0.3 poise or less, since it has excellent fluidity and can be highly filled with an inorganic filler. .

The epoxy resin (A) generally has a molecular weight distribution, and is represented by the following formula 1, for example. In the case where the content of n = 0 in Formula 1 is 50% by weight or more, particularly, the melt viscosity is low, the fluidity is excellent, and the workability is excellent, and the cured product has excellent heat resistance and curability. It is preferable because it becomes. Particularly, when the content of n = 0 is 65% by weight or more, those effects become remarkable.

[0017]

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(Wherein X is a condensed polycyclic hydrocarbon group, or a hydrocarbon group in which two aromatic nuclei are bonded via a bonding group, and R is an alkyl group, an aryl group, an allyl group, an aralkyl group Or a hydrogen atom.)

Here, the fused polycyclic hydrocarbon group represented by X is 2
A hydrocarbon group in which two aromatic nuclei are bonded via a linking group,
Those exemplified as specific examples of the epoxy resin (A) β
A structural site bonded to a substituted or unsubstituted glycidyloxy group. For example, a condensed polycyclic hydrocarbon group includes a divalent hydrocarbon group having a naphthalene structure, while two aromatic nuclei form a bonding group. Examples of the hydrocarbon group bonded via a benzophenone structure include a divalent hydrocarbon group having a benzophenone structure and a bisphenol residue.

The epoxy resin (A) can reduce the amount of chlorine in the resin as compared with a conventional resin having only a β-position unsubstituted glycidyloxy group. Specifically, the total chlorine content is in the range of 800 ppm or less.

Among such epoxy resins (A), in particular, β-alkylglycidyloxynaphthalene or β-alkylglycidyloxybenzophenone represented by the following formula 2, wherein β-alkylglycidyloxy group and β-alkylglycidyloxy group In equivalent ratio with the alkyl glycidyloxy group,
Former / latter = 35 / 65-65 / 35,
And the melt viscosity at 150 ° C. is 0.3 poise or less, and the content of n = 0 in the formula 2 is 65% by weight or more,

[0022]

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(In the formula, X represents a hydrocarbon group having a naphthalene structure or a benzophenone structure, and R represents an alkyl group or a hydrogen atom.) The effect of the present invention is that the total chlorine content is 800 ppm or less. Is remarkable, which is preferable.

The method for producing the epoxy resin (A) is not particularly limited, but a compound capable of deriving a crystalline epoxy resin is used as a starting phenol compound, and all or part of epihalohydrins is used. , Β
And a method in which both are reacted by an ordinary method using β-substituted epihalohydrins in which the hydrogen atom at the position is substituted with a hydrocarbon group such as an alkyl group or a phenyl group. here,
As the raw material phenol compound, any of the compounds capable of deriving the above-mentioned crystalline epoxy resin can be used. Among them, dihydroxybenzophenone, particularly 4,4′-dihydroxybenzophenone, and heat resistance are particularly preferable in terms of excellent curability. Dihydroxynaphthalene,
Particularly preferred are 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and the like.

The β-substituted epihalohydrins include β
Substituents such as an alkyl group, an aryl group, an allyl group or an aralkyl group at the position, particularly epihalohydrin having an alkyl group having 1 to 10 carbon atoms as a substituent. Methyl epichlorohydrin, β-methyl epibromohydrin, β-methyl epifluorohydrin, β-phenyl epichlorohydrin and the like. The amount of the β-substituted epihalohydrin used may be determined by the epoxy equivalent of the target epoxy resin, molecular weight, melt viscosity, purity, or equivalent ratio with the glycidyl group, for example, when the purity is maximized. May be obtained by converting the total amount of epihalohydrins into β-substituted epihalohydrins. When the ratio of β-substituted glycidyloxy group to glycidyloxy group is 80/20 to 20/80 as described above, the ratio between β-substituted epihalohydrin and β-unsubstituted epihalohydrin Former / latter = 80 / 20-2 in molar ratio
What is necessary is just to set in the range of 0/80. Further, the ratio may be further adjusted in consideration of characteristics such as solvent solubility, melting point, purity, and curability that are desired to be obtained within this range. In addition, the β-unsubstituted epihalohydrin here includes epichlorohydrin, epibromohydrin, epiiodohydrin and the like.

In the present invention, a mixture of β-unsubstituted glycidyloxy-naphthalene and di-glycidyloxynaphthalene, or a mixture of di-glycidyloxynaphthalene is obtained by using β-substituted epihalohydrin and β-unsubstituted epihalohydrin in combination. A mixture of -β-substituted glycidylbenzophenone, β-substituted glycidyloxy-β-unsubstituted glycidyloxy-benzophenone, and di-glycidyloxybenzophenone can be easily obtained.

Next, an example of a method for producing the epoxy resin (A) will be specifically described below. First, 2 to 15 equivalents of β-substituted epichlorohydrin or a mixture of β-substituted epichlorohydrin and β-unsubstituted epichlorohydrin are added to the hydroxyl group in the polyhydric phenol compound capable of deriving a crystalline epoxy resin. And then dissolved in 0.8 to 1.2 equivalents of 10 to 10 hydroxyl groups in the polyhydric phenol compound.
A 50% aqueous NaOH solution is applied at a temperature of 50-80 ° C. for 3-5 hours. After lowering, stirring is continued at that temperature for about 0.5 to 2 hours, and after standing, the lower saline solution is discarded. Next, the excess epihalohydrin is recovered by distillation to obtain a crude resin.
An organic solvent such as toluene and MIBK is added thereto, and the resultant is washed with water.
The desired resin can be obtained through a dehydration-filtration-desolvation step. In addition, a solvent such as dioxane or DMSO may be used in the reaction for the purpose of reducing the amount of impurity chlorine.

Next, the curing agent (B) used in the present invention
Any compound known as a curing agent for an epoxy resin, such as a compound having active hydrogen in one molecule or a compound capable of causing self-polymerization of an epoxy group, can be used. In particular, phenolic compounds are preferred for use in semiconductor sealing materials. Any type of phenolic compound can be used. The type of the compound is not limited as long as it is a compound containing two or more phenolic hydroxyl groups in one molecule. Examples thereof include a phenol-formaldehyde polycondensate, a cresol novolak-formaldehyde polycondensate, a bisphenol A-formaldehyde polycondensate, and C1. C1 to C10 monoalkyl-substituted phenol-formaldehyde polycondensates, C1 to C10 dialkyl-substituted phenol-formaldehyde polycondensates, phenol and C1
To C10 monoalkyl-substituted phenol-formaldehyde copolycondensates, phenols and dicyclopentadiene,
Examples include polyadducts with cyclic dienes such as limonene and pinene, polyadducts of phenols and divinylbenzene, naphthol-formaldehyde polycondensates, naphthol-phenol polycondensates, and naphthol-cresol polycondensates. Among them, phenol-formaldehyde polycondensate, cresol novolak-formaldehyde polycondensate, and dicyclopentadiene-phenol polyadduct are particularly preferable because of excellent curability and heat resistance.

When each of the compounds described above is used as a curing agent, a curing accelerator can be appropriately used. As the curing accelerator, any known and commonly used curing accelerators can be used, and examples thereof include tertiary amines, imidazoles, organic acid metal salts, amine complex salts, phosphorus compounds such as triphenylphosphine, and the like. Not only one kind but also two or more kinds can be used in combination.

The epoxy resin composition of the present invention contains the above-mentioned epoxy resin (A) and curing agent (B) as essential components, and its use is not specified. And an inorganic filler (C) is used as an essential component. Of course, any epoxy resin composition can be used.

Examples of the inorganic filler (C) used in the present invention include silica, alumina, titanium white, aluminum hydroxide, talc, clay, glass fiber and the like.
Particularly, silica and alumina are preferred. These can also increase the filling amount by mixing those having different types, shapes (spherical or crushed) and particle sizes. The addition of the inorganic filler (C) is an essential component not only for increasing the mechanical strength of the cured product, but also for achieving a low water absorption and a low coefficient of linear expansion, and for enhancing the effect of preventing solder cracks. Therefore, the more the compounding amount, the more
It is preferable because the characteristics of the semiconductor sealing material are improved. It is particularly preferable to use the composition in the range of 80 to 95% by weight in the composition, since these characteristics become remarkable and the solder crack resistance is extremely excellent. If the amount of the inorganic filler is more than 95% by weight, the fluidity of the composition is significantly impaired, which results in poor molding, which is not preferable. On the other hand, when the amount of the inorganic filler is less than 80% by weight, the moisture resistance is poor and the effect of preventing solder cracking is impaired, which is not preferable.

The silica of the present invention is not particularly limited, and examples thereof include fused silica and crystalline silica. Fused silica is particularly preferred from the viewpoint of excellent fluidity. The particle size of the silica is not particularly limited, but a small particle size such as 5 microns or less may be preferable. In order to improve the fluidity, those having various particle size distributions can be used. In addition, the composition and the semiconductor encapsulating material of the present invention, in addition to the above-mentioned epoxy resin (A), which is an essential component, furthermore, as long as the properties of the composition of the present invention are not impaired.
Other epoxy resins may be used in combination.

As the epoxy resin used at this time, any known and commonly used epoxy resin can be used, for example, bisphenol A diglycidyl ether type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type epoxy resin Epoxy resin, bisphenol F novolak epoxy resin, brominated phenol novolak epoxy resin, naphthol novolak epoxy resin, naphthol and / or
Alternatively, a polycondensate-type epoxy resin of phenol and / or cresol and aldehydes, a bifunctional epoxy resin of tetramethylbiphenyl type, a condensate-type epoxy resin of hydroxybenzaldehyde with phenols and / or naphthols, tetrafunctional glycidyl of diaminodiphenylmethane type Examples thereof include amine-type and hydroxyaniline-type trifunctional epoxy resins, but are not limited thereto. Among these, orthocresol novolak type epoxy resin is particularly preferable from the viewpoint of excellent heat resistance, and tetramethylbiphenyl type bifunctional epoxy resin is preferable from the viewpoint of excellent fluidity.

If necessary, various known and commonly used additive components such as a coloring agent, a flame retardant, a release agent, a low-stress agent such as silicone oil or silicone resin, and a coupling agent may be appropriately compounded. it can.

In order to prepare a molding material or a semiconductor encapsulating material from the epoxy resin composition of the present invention, an epoxy resin, a curing agent, a curing accelerator, an inorganic filler and other additives are sufficiently mixed with a mixer or the like. After uniform mixing, the mixture is further melt-kneaded with a hot roll or kneader, cooled, pulverized,
Make tablets with a tableting machine. Further, as a method of molding the molding material, curing molding may be performed by a molding machine such as a transfer mold, a compression mold, and an injection mold.

The thus obtained epoxy resin composition and semiconductor encapsulant of the present invention have excellent storage stability and high purity with a small amount of impurity chlorine. Excellent in properties and solder crack resistance.

[0037]

Next, the present invention will be described in detail with reference to Production Examples, Examples and Comparative Examples. In the examples, all parts are by weight unless otherwise specified.

The melting point of the crystalline epoxy resin is DSC
(Heating rate 3 ° C./min). The content ratio (equivalent ratio) of each of the β-substituted glycidyloxy group and the β-unsubstituted glycidyloxy group in the epoxy resin is 13%.
It was calculated from the peak intensity ratio measured by C-NMR.

The melt viscosity is 50 Hz.
search equipment LTD. `` ICICONE & PLATE VIS
COMETER ".

The total chlorine content was measured by the following measuring method. After dissolving 0.3 g of the resin in 20 ml of n-BuOH, 1 g of metallic sodium is added, and heat treatment is performed at 120 ° C. for 3 hours. It was subjected to an appropriate method using an aqueous silver nitrate solution, and from the appropriate amount, the total chlorine content was calculated.

The gel time was determined when the mixture was heated and stirred at 175 ° C. and lost fluidity.

Production Example 1 160 g of 1,5-dihydroxynaphthalene was placed in a four-necked flask equipped with a decanter equipped with a stirrer, thermometer and condenser.
(1 mol), 194 g of epichlorohydrin and 522 g of β-methylepichlorohydrin are added and dissolved. Under reduced pressure, 167 g of a 48% aqueous NaOH solution was added dropwise at 70 ° C. with stirring over 3 hours. During that time, epichlorohydrin, β-methyl epichlorohydrin and water were distilled, and epichlorohydrin and β-
Methyl epichlorohydrin and water were separated, and epichlorohydrin and β-methyl epichlorohydrin were continuously returned to the flask. After the addition was completed, stirring was continued for 30 minutes, and then the pressure was returned to normal pressure. Thereafter, 180 g of water was added and the mixture was allowed to stand. The lower saline solution is discarded, and epichlorohydrin and β
-Methylepichlorohydrin was recovered by distillation at 150 ° C., and 400 g of MIBK was added to the crude resin.
200 g of aqueous OH solution was added, and the mixture was stirred at 80 ° C. for 3 hours. The lower aqueous layer was discarded. After that, MI
The BK layer is washed with 200 g of water, and the water is discarded.
After filtration, MIBK was desolvated at 150 ° C. to obtain 245 g of the desired epoxy resin (A). No crystallization was observed during this reaction step. The obtained epoxy resin (A) has crystal properties and has a melting point of 128 ° C. and 150 ° C.
Melt viscosity at ℃ is 0.05 poise, epoxy equivalent is 16
4 g / eq, the total chlorine amount was 490 ppm. As for the glycidyl group, the ratio was (β-methyl substitution) / (unsubstituted) = 47/53 (equivalent ratio). And n =
The content of zero substance was 81% by weight.

Production Example 2 326 g of the desired epoxy resin (B) was obtained in the same manner as in Production Example 1, except that 1,5-dihydroxynaphthalene was changed to 360 g of 4,4'-dihydroxybenzophenone. No crystallization was observed during this reaction step. The obtained epoxy resin (B) has crystalline properties and has a melting point of 117 ° C. and a melt viscosity at 150 ° C. of 0.03.
Poise, epoxy equivalent is 199 g / eq, total chlorine is 5
It was 40 ppm. For the glycidyl group,
(Β-methyl substitution) / (unsubstituted) = 44/56 (equivalent ratio). The content of the n = 0 substance was 72% by weight.

Production Comparative Example 1 The epihalohydrins used were epichlorohydrin 55
Epoxidation was carried out in the same manner as in Production Example 1 except that the amount was changed to 5 g alone, but severe crystallization occurred in the step of adding water to remove the lower saline solution layer. Therefore, since the liquid separation step became impossible, the generated crystal was filtered, washed with a solvent and water, and then dried to isolate a crystal. Since the melting point of this crystal was 178 ° C., the production evaluation of the sealing material could not be performed.

Production Comparative Example 2 The epihalohydrins used were epichlorohydrin 55
Epoxidation was carried out in the same manner as in Production Example 2 except that the amount was changed to 5 g alone, but crystallization occurred as in Production Comparative Example 1. The crystalline product isolated by filtration had a melting point of 189.
° C. Accordingly, the evaluation of the production of the sealing material could not be performed due to the high melting point.

Examples 1-2 and Comparative Examples 1-2 EPICLON N-665, an orthocresol novolak type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc .: melt viscosity at 150 ° C. 3.0 poise, epoxy) The following evaluations were made by comparing the equivalent of 208 g / eq) with YX-4000H, a tetramethylbiphenyl type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd .: melt viscosity 0.10 poise at 150 ° C., epoxy equivalent 195 g / eq). Was done.

Examples 1 and 2 and Comparative Examples 1 and 2 A mixture prepared according to the composition shown in Table 1 was kneaded with a hot roll at 100 ° C. for 8 minutes to obtain an epoxy resin composition. 1200 to 1400 kg
/ Cm2 at a pressure of 80 kg / cm 2 with a transfer molding machine.
Sealing was performed under the conditions of cm 2, a mold temperature of 175 ° C., and a molding time of 100 seconds, and a 20 mm-thick 20-pin flat package was prepared as an evaluation test piece. Thereafter, post-curing was performed at 175 ° C. for 8 hours. At that time, the gel time at 175 ° C. was used as an index of curability, and the index of fluidity was
175 ° C / 70kg / cm2, 120 using test mold
The spiral flow value was measured under the condition of seconds.

Using the test piece for evaluation thus obtained,
85% RH, 85% RH, moisture absorption under 300 hours condition, D
Glass transition temperature by MA, and 20 specimens were 85
After leaving it for 168 hours in an atmosphere of 85 ° C. and 85% RH to perform a moisture absorption process, the crack generation rate when the product was immersed in a 260 ° C. solder bath for 10 seconds was used as an index of the solder crack resistance. Further, as an index of the moisture resistance reliability, the package (no defective product) after immersion in the solder bath was used at 130 ° C. for 10 minutes.
PCT was performed under the condition of 0% RH, and the time until the cumulative failure rate became 50% was obtained.

153 is a tetrabromobisphenol A type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc., trade name: EPICLON 153, softening point 70 ° C., epoxy equivalent 401 g / eq), and TD-2131 is a phenol novolak resin ( Made by Dainippon Ink and Chemicals, Inc.
Phenolite TD-2131, softening point 80 ° C, hydroxyl equivalent 104 g / eq). The average particle size of the inorganic filler is 25.
μm spherical silica and crushed silica having an average particle size of 37 μm were used.

[0050]

[Table 1] Table 1

[0051]

According to the present invention, it has an appropriate melting point (within the range of 70 to 130 ° C.) usable for semiconductor encapsulating materials and does not cause crystallization during the epoxidation step. , And more excellent curability and heat resistance than biphenyl type,
An epoxy resin composition and a semiconductor encapsulating material exhibiting moisture resistance reliability can be provided.

The epoxy resin composition and the semiconductor encapsulant of the present invention have significantly superior surface crack resistance during surface mounting as compared with conventional epoxy resin compositions and semiconductor encapsulants using ECN. Can be applied to the device. Also, compared to epoxy resin composition using biphenyl type epoxy resin and semiconductor encapsulation material, it has better solder crack resistance during surface mounting, and also has remarkable curability, heat resistance, and moisture resistance reliability. Excellent.

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[Procedure amendment]

[Submission date] September 30, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 7

[Correction method] Change

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[Correction target item name] Claim 9

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[Formula 1] (Wherein, X is condensed polycyclic hydrocarbon group, or the two hydrocarbon radicals the aromatic nucleus are bonded via a binding contact group, R represents respectively
It independently represents an alkyl group, an aryl group, an allyl group, an acyl group, or a hydrogen atom. )

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] Claim 13

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[Formula 2] (In the formula, X represents a hydrocarbon group having a naphthalene structure or a benzophenone structure, and R represents an alkyl group or a hydrogen atom.) And the total chlorine content is 800 ppm or less. A composition as described.

[Procedure amendment 5]

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The epoxy resin (A) generally has a molecular weight distribution, and is represented by the following formula 1, for example. In the case where the content of n = 0 in Formula 1 is 50% by weight or more, particularly, the melt viscosity is low, the fluidity is excellent, and the workability is excellent, and the cured product has excellent heat resistance and curability. It is preferable because it becomes. Particularly, when the content of n = 0 is 65% by weight or more, those effects become remarkable. In the formula 1, R is independently an alkyl
Group, aryl group, allyl group, acyl group or hydrogen atom
And even if all R in one compound are the same,
The epoxy resin (A) may have different R
At least one of an alkyl group, an aryl group, and an allyl group
Or those containing compounds with acyl groups
is there.

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[0017]

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[Procedure amendment 7]

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(Wherein X is a condensed polycyclic hydrocarbon group, or a hydrocarbon group in which two aromatic nuclei are bonded via a bonding group, and R is each independently an alkyl group, an aryl group, an allyl Group, aralkyl group or hydrogen atom.)

[Procedure amendment 8]

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Here, X is a fused polycyclic hydrocarbon group , or
Is a hydrocarbon group in which two aromatic nuclei are bonded via a bonding group, a structural site bonded to a β-substituted or unsubstituted glycidyloxy group as exemplified as the specific example of the epoxy resin (A), For example, a condensed polycyclic hydrocarbon group includes a divalent hydrocarbon group having a naphthalene structure, while a hydrocarbon group in which two aromatic nuclei are bonded via a bonding group has a benzophenone structure Examples thereof include a divalent hydrocarbon group and a bisphenol residue.

[Procedure amendment 9]

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Among such epoxy resins (A), in particular, β-alkylglycidyloxynaphthalene or β-alkylglycidyloxybenzophenone represented by the following formula 2, wherein β-alkylglycidyloxy group and glycidyloxy In the equivalent ratio with the group , the former / the latter =
35/65 to 65/35 and 150
The melt viscosity at 0 ° C. is 0.3 poise or less, and the content of n = 0 in the formula 2 is 65% by weight or more,

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[0022]

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[Procedure amendment 11]

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The β-substituted epihalohydrins include β
Substituents such as an alkyl group, an aryl group, an allyl group or an aralkyl group at the position, particularly epihalohydrin having an alkyl group having 1 to 10 carbon atoms as a substituent. Methyl epichlorohydrin, β-methyl epibromohydrin, β-methyl epifluorohydrin, β-phenyl epichlorohydrin and the like. The amount of the β-substituted epihalohydrin used may be determined according to the epoxy equivalent of the target epoxy resin, molecular weight, melt viscosity, purity, or equivalent ratio with the β-unsubstituted glycidyl group. When it is improved, the total amount of epihalohydrins may be β-substituted epihalohydrins. When the ratio of β-substituted glycidyloxy group to glycidyloxy group is 80/20 to 20/80 as described above, the ratio between β-substituted epihalohydrin and β-unsubstituted epihalohydrin Former / latter = 8 in molar ratio
What is necessary is just to set in the range of 0/20-20/80. Further, the ratio may be further adjusted in consideration of characteristics such as solvent solubility, melting point, purity, and curability that are desired to be obtained within this range.
In addition, the β-unsubstituted epihalohydrin here includes epichlorohydrin, epibromohydrin, epiiodohydrin and the like.

Claims (16)

[Claims] 1. An epoxy resin (A) having a crystalline property at room temperature and containing a β-substituted glycidyloxy group in a molecular structure, and a curing agent (B) as essential components. A characteristic epoxy resin composition. 2. The composition according to claim 1, wherein the epoxy resin (A) has a β-substituted glycidyloxy group and a β-unsubstituted glycidyloxy group. 3. The abundance ratio between the β-substituted glycidyloxy group and the β-unsubstituted glycidyloxy group in the epoxy resin (A) is equivalent to the former / the latter = 80/20 to 20/8.
3. The composition according to claim 1, wherein the composition is in the range of 0. 4. The composition according to claim 1, wherein the epoxy resin (A) has a Tg measured by DSC in the range of 70 to 140 ° C. 5. The substituent according to claim 1, wherein the substituent located at the β-position in the β-substituted glycidyl group is an alkyl group.
A composition according to any one of the preceding claims. 6. The composition according to claim 1, wherein the epoxy resin (A) is β-substituted glycidyloxynaphthalene. 7. An epoxy resin (A) comprising di-β-substituted glycidyloxynaphthalene, β-substituted glycidyloxy-β-unsubstituted glycidyloxy-naphthalene, and di-β-substituted glycidyloxy-naphthalene.
The composition according to claim 6, which is a mixture of β-substituted glycidyloxynaphthalene. 8. The composition according to claim 1, wherein the epoxy resin (A) is β-substituted glycidyloxybenzophenone. 9. An epoxy resin (A) comprising di-β-substituted glycidylbenzophenone, β-substituted glycidyloxy-
β-unsubstituted glycidyloxy-benzophenone, and
The composition according to claim 9, which is a mixture of di-β-substituted glycidyloxybenzophenone. 10. The epoxy resin (A) having a melt viscosity at 150 ° C. of 0.5 poise or less.
The composition according to any one of claims 9 to 9. 11. The epoxy resin according to claim 1, wherein the epoxy resin (A) is represented by the following chemical structural formula (1), and the content of the compound having n = 0 is 50% by weight or more. A composition according to any one of the preceding claims. Formula 1 (Wherein, X is a condensed polycyclic hydrocarbon group, or a hydrocarbon group in which two aromatic nuclei are bonded via a bonding group, and R is an alkyl group, an aryl group, an allyl group, an acyl group, or a hydrogen atom. Represents.) 12. The method according to claim 1, wherein the total chlorine content in the epoxy resin (A) is 800 ppm or less.
A composition according to any one of the preceding claims. 13. The epoxy resin (A) is a β-alkylglycidyloxynaphthalene or a β-alkylglycidyloxybenzophenone represented by the following formula 2, wherein a β-alkylglycidyloxy group and a β-alkylglycidyloxy group are combined.
In the equivalent ratio with the alkyl glycidyloxy group, the former / the latter is in the range of 35/65 to 65/35 and 1
The melt viscosity at 50 ° C. is 0.3 poise or less, and the content of n = 0 in the following formula 2 is 65% by weight or more. (In the formula, X represents a hydrocarbon group having a naphthalene structure or a benzophenone structure, and R represents an alkyl group or a hydrogen atom.) And the total chlorine content is 800 ppm or less. A composition as described. 14. A semiconductor encapsulant, characterized in that the composition according to claim 1 further comprises an inorganic filler (C) as an essential component. 15. The semiconductor encapsulating material according to claim 14, wherein the weight ratio of the inorganic filler (C) to the semiconductor encapsulating material is in the range of 80 to 95% by weight. 16. The inorganic filler (C) is silica,
16. The semiconductor encapsulating material according to claim 14, which is a mixture of spherical silica and crushed silica.