JPH1025333A - Epoxy resin composition for sealing semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new composition comprising a specific epoxy resin, a curing agent, an inorganic filler and a curing accelerator, capable of giving cured products having excellent heat resistant and low hygroscopicity, and useful for sealing semiconductors. SOLUTION: This epoxy resin composition contains (A) an epoxy resin having an epoxy equivalent of 220-370g/eq and obtained by the reaction of (i) a terpene phenolic resin having a phenolic hyroxyl group equivalent of 150-280g/eq with (ii) an epihalohydrin, (B) a phenolic and/or modified phenolic epoxy resin curing agent, (C) an inorganic filler in an amount of 60-95wt.% based on the whole amount of the composition, and (D) a curing accelerator as essential components. The terpene phenolic resin (i) is produced from (a) 20-80wt.% of a terpene phenolic compound of formula I [R<1> is a 1-10C hydrocarbon, a (substituted) aromatic, a (substituted) aralkyl, an alkoxy, a halogen; (m) is 0-2], (b) 10-60wt.% of a terpene phenolic compound of formula II [R<2> is the same as R<1> ; (n) is 0-2], and (c) 0-40wt.% of one or more other terpene phenolic compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an epoxy resin composition for encapsulating a semiconductor. More specifically, the present invention provides an epoxy resin obtained by a reaction between a specific terpene phenolic resin and epihalohydrin in a specific epoxy resin curing agent, an inorganic filler and a curing accelerator. The present invention relates to a novel epoxy resin composition for semiconductor encapsulation that gives an excellent cured product.

[0002]

2. Description of the Related Art In recent years, as semiconductor devices have become more highly integrated,
Various characteristics required for a sealing material for a semiconductor element have become severe, and crack resistance during immersion in a solder bath has become an important issue. However, epoxy resin compositions generally used at present have not been able to sufficiently satisfy required characteristics. That is, semiconductor devices have been highly integrated and semiconductor elements have been significantly increased in size. On the other hand, packages themselves have been reduced in size and thickness. In addition, the mounting of semiconductor devices has also shifted to surface mounting. In surface mounting, when a semiconductor device is directly immersed in a solder bath and exposed to a high temperature, the moisture absorbed expands, a large stress is applied to the entire package, and cracks are easily formed in the sealing material. Therefore, a sealing material having good solder crack resistance is required to have high heat resistance (that is, a high glass transition temperature) and low moisture absorption, and is based on a cresol novolac type epoxy resin which is mainly used at present. In the case of a sealing material, both heat resistance and low hygroscopicity have become insufficient.

[0003] With respect to each of the epoxy resin and the curing agent, studies on high heat resistance and low moisture absorption have been widely conducted, and various proposals have been made. For example, Japanese Unexamined Patent Publication
JP-A-301946 or JP-A-4-248828 proposes an epoxy resin or a curing agent into which a hydrophobic group such as a dicyclopentadiene skeleton or a xylene skeleton has been introduced, and JP-A-61-47725. It has been proposed to use a tetramethyl biphenol type epoxy resin.

[0004]

However, the epoxy resin proposed in the above publication cannot be said to have a sufficiently low hygroscopic effect, and the heat resistance is inferior, so that the solder crack resistance is sufficiently improved. Not. An object of the present invention is to provide a novel epoxy resin composition for semiconductor encapsulation that gives a cured product having excellent heat resistance and low moisture absorption.

[0005]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that an epoxy resin produced from a specific terpene phenol resin and epihalohydrin can be cured with a specific epoxy resin. It has been found that an epoxy resin composition mixed with an agent, an inorganic filler and a curing accelerator gives a cured product having excellent heat resistance and low moisture absorption, and has completed the present invention.

That is, the present invention provides: (A) (1) 20 to 80% by weight of a terpene phenol compound represented by the following general formula (I), (2) 10 to 10% by weight of a terpene phenol compound represented by the following general formula (II)
Epoxy equivalents 220 to 370 g obtained by reacting a terpene phenol resin having a phenolic hydroxyl equivalent of 150 to 280 g / eq with epihalohydrin, comprising 60% by weight and 0 to 40% by weight of a terpene phenol compound having another structure (3). / Eq, (b) a phenolic and / or modified phenolic epoxy resin curing agent, (c) an inorganic filler of 60 to 95% by weight of the total amount of the composition, and (d) a curing accelerator. Epoxy resin composition for semiconductor encapsulation formulated as

[0007]

Embedded image

(Wherein R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group or a halogen atom. And may be the same or different.
Is an integer of 0 to 2, and may be the same or different.

[0009]

Embedded image

(Wherein R ² represents a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group or a halogen atom. And may be the same or different.
Is an integer of 0 to 2, and may be the same or different.

2. As the component (a), (1) 20 to 80% by weight of a terpene phenol compound where m = 0 in the general formula (I), and (2) n = 0 in the general formula (II)
10 to 60% by weight of a terpene phenol compound having the following structure:
A phenolic hydroxyl equivalent of 150 to 2
An epoxy equivalent of 22 obtained by reacting a terpene phenol resin having 40 g / eq with epihalohydrin
2. The epoxy resin composition for semiconductor encapsulation according to item 1, wherein an epoxy resin having 0 to 310 g / eq is used.

3. As the component (a), (1) 20 to 80% by weight of a terpene phenol compound represented by the general formula (I) wherein R ¹ is a methyl group and m is 1 or 2;
(2) In the general formula (II), R ² is a methyl group;
Is 1 or 2, and the terpene phenol compound is 10 to 60.
Phenolic hydroxyl equivalent of 1% by weight and (3) 0 to 40% by weight of a terpene phenol compound having another structure.
2. The epoxy resin composition for semiconductor encapsulation according to item 1, wherein an epoxy resin having an epoxy equivalent of 230 to 350 g / eq obtained by reacting a terpene phenol resin having 60 to 260 g / eq with epihalohydrin is used.

4. The component (b) is selected from terpene phenol resins, phenol aralkyl resins, dicyclopentadiene phenol resins, and active ester-modified phenol resins obtained by esterifying all or part of the phenolic hydroxyl groups of phenol resins. The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 3, wherein at least one epoxy resin curing agent is used.

5. As the component (c), 7 of the total amount of the composition
0-93% by weight of crushed and / or spherical, molten and / or
Or the epoxy resin composition for semiconductor encapsulation according to any one of items 1 to 4, wherein a crystalline silica powder filler is used. Hereinafter, the present invention will be described in detail.

The epoxy resin (a) used in the present invention comprises (1) 20 to 80% by weight of a terpene phenol compound represented by the following general formula (I), and (2) a terpene phenol compound represented by the following general formula (II). Terpene phenol compounds 10 to 6
220 to 370 g / epoxy equivalent obtained by the reaction of a terpene phenol resin having a phenolic hydroxyl equivalent of 150 to 280 g / eq and epihalohydrin, which comprises 0 to 40% by weight of a terpene phenol compound having 0% by weight and (3) other structures. It is an epoxy resin having eq.

[0016]

Embedded image

(Wherein R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group or a halogen atom. And may be the same or different.
Is an integer of 0 to 2, and may be the same or different.

[0018]

Embedded image

(Wherein R ² represents a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group or a halogen atom. And may be the same or different.
Is an integer of 0 to 2, and may be the same or different.

The terpene phenol resin as a raw material can be obtained by adding a terpene compound to a phenol compound in the presence of an acidic catalyst. Examples of the starting terpene compound include terpene hydrocarbons, terpene alcohols, terpene aldehydes, etc. Among them, cyclic terpenes such as limonene, dipentene, terpinolene, pinene, terpinene, and mentadien are preferable. Also,
Examples of the raw material phenol compound include phenol, cresol, xylenol, ethyl phenol, propyl phenol, butyl phenol, butyl cresol, phenyl phenol, benzyl phenol, methoxy phenol, bromo phenol and the like. Among them, phenol, cresol and xylenol are preferable.

The addition reaction between the terpene compound and the phenol compound is carried out by using the phenol compound in an amount of 1 to 10 mol, preferably 1.5 to 6 mol, per mol of the terpene compound, at 40 to 160 ° C. in the presence of an acidic catalyst. At a temperature of 1 to 1
Perform for 0 hours. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or a complex thereof, and activated clay. The catalyst is usually used in an amount of 1.5 to 6% by weight based on the total amount of the terpene compound and the phenol compound.

The reaction solvent may not be used, but usually a solvent such as an aromatic hydrocarbon, an alcohol or an ether is used. Among the obtained terpene phenolic resins, resins having a phenolic hydroxyl equivalent of 150 to 240 g / eq obtained by the reaction of phenol and terpene compound, or phenolic hydroxyl obtained by reaction of cresol or xylenol with the terpene compound Equivalent to 160
Particularly preferred is a resin of ~ 260 g / eq. The phenolic hydroxyl group equivalent can be measured by the acetylation method shown in JIS K0070. In order to obtain a resin having a desired structure and composition, it is necessary to adjust the use ratio of the phenol compound and the terpene compound, the type of the catalyst, the reaction conditions, and the like. In addition, the resin after production is distilled, extracted,
It may be processed by a method such as recrystallization to obtain desired properties.

Next, by reacting the terpene phenol resin with epihalohydrin in the presence of an alkali metal hydroxide, the desired epoxy resin can be obtained. Representative examples of the reaction are described in detail below. First, a terpene phenolic resin is added in an amount of 2 per mole of the phenolic hydroxyl group.
Dissolve in epihalohydrin in an amount corresponding to 20 mol to make a homogeneous solution. Then, while stirring the solution, 0.8 to 2 moles of alkali metal hydroxide per mole of 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 3 when the reaction is carried out under normal pressure.
0 to 105 ° C. and about 30 to 8 in the case of a reaction under reduced pressure.
0 ° C. During the reaction, the reaction solution is azeotroped while maintaining a predetermined temperature as needed, and the condensate obtained by cooling the volatilizing vapor is separated into oil / water, and the oil component from which water has been removed is fed to the reaction system. It is dehydrated from the reaction system by the returning method. The addition of alkali metal hydroxide suppresses the rapid reaction,
Add in small portions intermittently or continuously over 0.5-8 hours. The total reaction time is usually about 1 to 10 hours. After completion of the reaction, insoluble by-product salts are removed by filtration or removed by washing with water, and unreacted epihalohydrin is removed by distillation under reduced pressure to obtain the desired epoxy resin.

In this reaction, epichlorohydrin or epibromohydrin is usually used as epihalohydrin, and caustic soda or potassium hydroxide is usually used as alkali metal hydroxide. In this reaction, tetramethylammonium chloride,
Quaternary ammonium salts such as tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6- (trisdimethylaminomethyl) phenol; 2-ethyl-4-methylimidazole and 2-phenylimidazole Catalysts such as imidazoles; phosphonium salts such as ethyltriphenylphosphonium iodide; and phosphines such as triphenylphosphine may be used.

Further, in this reaction, ethanol,
Alcohols such as isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; and inert organic solvents such as aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide may be used. Further, when the amount of the saponified halogen in the epoxy resin obtained as described above is too large, the epoxy resin can be re-processed to obtain a purified epoxy resin in which the amount of the saponified halogen is sufficiently reduced. That is, the crude epoxy resin is redissolved in an inert organic solvent such as isopropanol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, propylene glycol monomethyl ether, dimethyl sulfoxide, and the alkali metal hydroxide is solid or aqueous solution. At a temperature of about 30 to 120 ° C,
After performing the ring closure reaction for 8 hours, excess alkali metal hydroxide and by-product salts are removed by a method such as water washing, and the organic solvent is removed by distillation under reduced pressure to obtain a purified epoxy resin. .

The epoxy resin used in the epoxy resin composition for encapsulating a semiconductor of the present invention is an epoxy resin having an epoxy equivalent of 220 to 370 g / eq produced as described above. The epoxy equivalent obtained by the reaction between the terpene phenol resin obtained by the reaction and epihalohydrin is 220 to 310 g / e.
The epoxy resin represented by q is preferable, or the epoxy resin obtained by reacting terpene phenol resin obtained by reaction of cresol or xylenol with terpene compound with epihalohydrin has an epoxy equivalent of 230 to 350 g / eq.

The epoxy equivalent is measured according to JIS.
It can be measured by the perchloric acid titration method described in K7236. In the production of this epoxy resin, it is necessary to adjust the type, the use ratio, the production conditions and the like of each raw material so that the epoxy equivalent of the epoxy resin finally obtained falls within a target range.

Further, the epoxy resin composition for semiconductor encapsulation of the present invention comprises the above specific terpene phenol resin,
Epoxy resins other than epihalohydrin resin prepared from epihalohydrin can be mixed and used. Other epoxy resins that can be mixed include, for example, bisphenol A, bisphenol F, bisphenol AD, hydroquinone, methylhydroquinone,
Dimethylhydroquinone, dibutylhydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenylether, phenol novolak resin,
Various phenols such as cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolak resin, and various phenols, and various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal. And epoxy resins produced from epihalohydrin and various phenolic compounds such as polyhydric phenolic resins obtained by the condensation reaction of

In order to make the cured product flame-retardant, a part of the epoxy resin used can be a brominated epoxy resin. As the brominated epoxy resin, for example,
Examples include an epoxy resin produced from a brominated bisphenol A or a brominated phenol novolak resin and epihalohydrin, and an epoxy resin produced by reacting a low molecular epoxy resin with a brominated bisphenol A.
The use ratio of these other epoxy resins is preferably 50% by weight or less based on the total amount of the epoxy resin components. If the proportion of the epoxy resin other than the epoxy resin produced from the specific terpene phenol resin and epihalohydrin is too large, the effect of the present invention cannot be sufficiently exerted.

The epoxy resin curing agent (b) used in the epoxy resin composition for semiconductor encapsulation of the present invention is a phenolic and / or modified phenolic epoxy resin curing agent. Examples of the phenolic epoxy resin curing agent include bisphenol A, bisphenol F, bisphenol AD, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, phenol novolak resin, cresol novolak resin, and bisphenol A Various polyphenols such as novolak resin, dicyclopentadiene phenol resin, terpene phenol resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin, and various phenols with benzaldehyde, hydroxybensaldehyde, croton Polyhydric phenol resin obtained by condensation reaction with various aldehydes such as aldehyde and glyoxal Include various phenolic resins such as the of.

Examples of the modified phenolic epoxy resin curing agent include active ester compounds obtained by esterifying all or a part of the phenolic hydroxyl groups of phenolic resins, such as by benzoation or acetate formation. Among these epoxy resin curing agents, terpene phenol resins, phenol aralkyl resins, dicyclopentadiene phenol resins, and all or a part of the phenolic hydroxyl groups of these phenol resins are converted to benzoates or acetates due to their curing properties and the like. And at least one epoxy resin curing agent selected from active ester compounds obtained by esterification.

The amount of the epoxy resin curing agent (b) used in the epoxy resin composition for semiconductor encapsulation of the present invention is based on 1 mol of the epoxy group in the total epoxy resin component and the total amount of the epoxy resin curing agent component. The amount in which the total of the groups reacting with the epoxy group is 0.5 to 1.5 mol is preferable, and more preferably the amount is 0.7 to 1.3 mol. Next, (c) an inorganic filler is blended with the epoxy resin composition for semiconductor encapsulation of the present invention. Examples of the type of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, and calcium carbonate. Its shape is crushed or spherical. Various inorganic fillers may be used alone or in combination of two or more. Among various inorganic fillers, crushed or spherical fused silica or crystalline silica is preferable, and the amount used is 6% of the total amount of the composition.
The content is 0 to 95% by weight, more preferably 70 to 93% by weight, and still more preferably 75 to 92% by weight. The (d) curing accelerator used in the epoxy resin composition of the present invention is a compound that promotes a reaction between an epoxy group in the epoxy resin and an active group in the curing agent.

Examples of the curing accelerator include phosphine compounds such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, and tris (cyanoethyl) phosphine; tetraphenylphosphonium tetraphenylborate; Phosphonium salts such as methyltributylphosphonium teratophenylborate and methyltricyanoethylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2- Methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine, 2,4-
Dicyano-6- [2-undecylimidazolyl-
(1)] imidazoles such as -ethyl-S-triazine, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetraphenylborate, Imidazolium salts such as 2-ethyl-1,4-dimethylimidazolium tetraphenylborate, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, tetramethylbutylguanidine, N-methylpiperazine, Amines such as dimethylamino-1-pyrroline; ammonium salts such as triethylammonium tetraphenylborate;
-Diazabicyclo (5,4,0) -7-undecene,
1,5-diazabicyclo (4,3,0) -5-nonene,
Examples thereof include diazabicyclo compounds such as 1,4-diazabicyclo (2,2,2) -octane, tetraphenylborate, phenol salts, phenol novolak salts, and 2-ethylhexanoate salts of the diazabicyclo compounds.
Among the compounds to be those curing accelerators, phosphine compounds, imidazole compounds, diazabicyclo compounds,
And their salts are preferred. These curing accelerators are used alone or as a mixture of two or more, and the amount used is
It is 0.1 to 7% by weight based on all epoxy resin components.

[0034] The epoxy resin composition for semiconductor encapsulation of the present invention may optionally contain a coupling agent, a plasticizer, a pigment, a solvent, a flame retardant, and the like, if necessary. Further, antimony trioxide, phosphoric acid and the like can be appropriately blended as a flame retardant auxiliary. Since the epoxy resin composition for semiconductor encapsulation of the present invention gives a cured product having excellent heat resistance and low moisture absorption, it can be advantageously used in the field of semiconductor encapsulation.

[0035]

The following are examples of the production of terpene phenolic resins,
The present invention will be described in more detail with reference to Production Examples of the epoxy resin used in the epoxy resin composition for semiconductor encapsulation of the present invention, and Examples and Comparative Examples of the epoxy resin composition for semiconductor encapsulation of the present invention. However, the present invention is not limited to the embodiments unless it exceeds the gist. Production Example 1 (Terpene phenol resin) A phenol (680 g) and limonene (320 g) were charged into a three-liter three-necked flask equipped with a thermometer, a stirrer, and a condenser, and dried at 100 ° C under reduced pressure to remove water of crystallization. 10 g of silicotungstic acid was added, and the mixture was stirred at 80 ° C. for 7 hours to carry out a reaction. Subsequently, 1000 g of methyl isobutyl ketone was added to the reaction mixture, and after washing with water to remove the catalyst and the like, unreacted phenol and methyl isobutyl ketone were removed under reduced pressure to obtain the desired terpene phenol resin A8.
05 g were obtained. This terpene phenolic resin A is HPL
When analyzed by C, the content of the compound represented by the general formula (I) (m = 0) was 37%, the content of the compound represented by the general formula (II) (n = 0) was 20%, The phenolic hydroxyl equivalent by the acetylation method was 198 g / eq.

Production Example 2 (Terpene phenol resin) After completely dissolving 500 g of the terpene phenol resin obtained in Production Example 1 in 600 g of toluene at 100 ° C.,
The solution was cooled to ℃ and kept for one day to recrystallize. The crystals were separated by filtration and toluene was removed under reduced pressure to obtain 228 g of a purified terpene phenol resin B. Further, toluene was removed from the filtrate under reduced pressure to obtain 261 g of residual terpene phenol resin C. This purified terpene phenol resin B has a compound (m = 0) content of 65 represented by the general formula (I).
%, The content of the compound represented by the general formula (II) (n = 0) is 31%, and the phenolic hydroxyl equivalent is 164 g.
/ Eq. In addition, residual terpene phenolic resin C
Is a compound represented by the general formula (I) (m = 0) having a content of 13% and a compound represented by the general formula (II) (n =
0) was 11%, and the phenolic hydroxyl equivalent was 243 g / eq.

Production Example 3 (terpene phenol resin) The same reaction and post-treatment as in Production Example 1 except that 640 g of cresol was used in place of 680 g of phenol to obtain 893 g of terpene phenol resin D. This terpene phenolic resin D has the general formula (I)
The content of the compound represented by the formula (R ¹ ＣＨCH ₃ , m = 1) is 43%, and the compound represented by the general formula (II) (R ² ＣC
H ₃ , n = 1) was 25%, and the phenolic hydroxyl equivalent was 205 g / eq.

Production Examples 4 to 7 (Epoxy Resin) Each of the terpene phenol resins produced above was placed in a three-liter three-necked flask equipped with a thermometer, a stirrer, and a condenser, in an amount shown in Table 1 in the amount of epichlorohydrin. 650 g,
And 250 g of isopropyl alcohol at 35 ° C.
Then, 95 g of a 48.5% by weight aqueous sodium hydroxide solution was added dropwise over 1 hour. During this period, the temperature was gradually raised so that the temperature in the system reached 65 ° C. at the end of the dropping. Thereafter, the reaction was carried out at 65 ° C. for 30 minutes. After the completion of the reaction, the product was washed with water to remove by-product salts and excess sodium hydroxide. Next, 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 250 g of methyl isobutyl ketone, 4 g of a 48.5% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted at a temperature of 65 ° C. for 1 hour. After the completion of the reaction, sodium phosphate monobasic was added to neutralize the excess sodium hydroxide, and washed with water to remove by-product salts. Then
Methyl isobutyl ketone was completely removed under reduced pressure to obtain each epoxy resin. Table 1 shows the epoxy equivalents and softening points of these epoxy resins.

[0039]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 to 3 (Epoxy resin compositions for encapsulating semiconductors) As shown in Table 2, (a) each epoxy resin produced in Production Examples 4 to 7 as an epoxy resin, Epoxy resin derived from tetramethylbiphenol, or ortho-cresol novolak type epoxy resin, and brominated bisphenol A type epoxy resin as a brominated epoxy resin,
(B) a phenol novolak resin, a phenol aralkyl resin, a terpene phenol novolak resin, or a benzoated phenol novolak resin as an epoxy resin curing agent; (c) a crushed fused silica powder or a spherical fused silica powder as an inorganic filler; Trisphenylphosphine or 1,5-diazabicyclo (5,4,0) -7-undecene is used as a curing accelerator, antimony trioxide is used as a flame retardant auxiliary, epoxysilane is used as a surface treatment agent for a filler, and a release agent. , Each epoxy resin composition was compounded using carnauba wax.

Next, each composition was 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 shape and pulverized to obtain each molding material. Using each of these molding materials, a mold temperature of 180 ° C. and a molding time of 160 sec.
Each test piece was molded in 300 seconds and post-cured at 180 ° C. for 8 hours. In addition, the gel time of each molding material was measured. The results of testing the gel time of each molding material, the molding time, the moisture absorption after post-curing of the test piece, and the glass transition temperature are as shown in Table 2, and Examples 1 to 5
Each of the molding materials (1) and (2) had an excellent balance of heat resistance (high glass transition temperature) and low hygroscopicity as compared with the molding materials of Comparative Examples 1 to 3.

[0042]

[Table 2]

Notes to Table 2 E: Orthocresol novolak type epoxy resin (Eicoat 180S65, trade name of Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 213 g / eq) F: Epoxy resin derived from tetramethylbiphenol (Yuka Shell Epoxy Co., Ltd.) Product name Epicoat YX4
000H, epoxy equivalent: 193 g / eq) G: phenol novolak resin (manufactured by Gunei Chemical Co., hydroxyl equivalent: 103 g / eq, softening point: 85 ° C.) H: phenol aralkyl resin (Mitsui Toatsu Co., Ltd. trade name: MILEX XL225LL, hydroxyl group) Equivalent: 173 g / e
q, softening point: 78 ° C) I: Terpene phenol novolak resin (Yuka Kasper Epoxy Co., Ltd., Epicure MP402, hydroxyl equivalent:
175 g / eq, softening point: 128 ° C) J: Benzoated phenol novolak resin (Yuka Kasper Epoxy Co., Ltd., Epicur YLH626, active group equivalent: 182 g / eq, softening point: 68 ° C) K: Crushed fused silica powder ( L: Spherical fused silica powder (Nippon Aerosil trade name EL)
SIL100) M: Triphenylphosphine N: 1,5-diazabicyclo (5,4,0) -7-undecene * 1: Brominated bisphenol A type epoxy resin (Yuika Shell Epoxy Corp., Epicoat 5050, epoxy equivalent: 385 g) / Eq, bromine content: 49%) * 2: Antimony trioxide * 3: Carnauba wax * 4: Epoxysilane (Shin-Etsu Chemical Co., Ltd. brand name KBM)
-403) * 5: Calculated from the transition point of the thermal expansion curve using TMA. * 6: Moisture absorption after 168 hours at 85 ° C and 85% RH

[0044]

The epoxy resin composition for encapsulating a semiconductor of the present invention can provide a cured product having excellent heat resistance and low hygroscopicity, and thus can be advantageously used in semiconductor encapsulation applications.

Continued on the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical display location H01L 23/29 H01L 23/30 R 23/31

Claims (5)

[Claims] (A) (1) 20 to 80% by weight of a terpene phenol compound represented by the following general formula (I):
(2) A phenolic hydroxyl group equivalent of 150 to 280 g / eq consisting of 10 to 60% by weight of a terpene phenol compound represented by the following general formula (II) and (3) 0 to 40% by weight of a terpene phenol compound having another structure. An epoxy resin having an epoxy equivalent of 220 to 370 g / eq obtained by reacting a terpene phenol resin with epihalohydrin; (b) a phenolic and / or modified phenolic epoxy resin curing agent; An epoxy resin composition for encapsulating a semiconductor, comprising 95% by weight of an inorganic filler and (d) a curing accelerator as essential components. Embedded image (Wherein, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group or a halogen atom. And m may be 0 to 2
Which may be the same or different.) (Wherein, R ² represents a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group or a halogen atom. N may be 0 to 2;
Which may be the same or different) 2. Component (a) includes (1) general formula (I)
In which the terpene phenol compound 20 with m = 0
80% by weight, (2) 10 to 60% by weight of a terpene phenol compound in which n = 0 in the general formula (II), and (3)
A phenolic hydroxyl equivalent of 150 to 240 g comprising 0 to 40% by weight of a terpene phenol compound having another structure.
Epoxy equivalent obtained by the reaction of a terpene phenol resin having a / eq and an epihalohydrin of 220 to 3
The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein an epoxy resin having 10 g / eq is used. 3. The component (a) includes (1) a compound represented by the general formula (I):
Wherein R ¹ is a methyl group and m is 1 or 2, 20 to 80% by weight of a terpene phenol compound, (2) in the general formula (II), R ² is a methyl group, and n is 1 or 2
10 to 60% by weight of a terpene phenol compound having the following structure:
Phenolic hydroxyl equivalent of 160 to 26% by weight
Epoxy equivalent 230 obtained by the reaction of terpene phenol resin having 0 g / eq with epihalohydrin
The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein an epoxy resin having a weight of from 350 g / eq to 350 g / eq is used. 4. An active ester-modified phenol obtained by esterifying all or a part of phenolic hydroxyl groups of a terpene phenol resin, a phenol aralkyl resin, a dicyclopentadiene phenol resin, and phenol resins as the component (b). The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 3, wherein at least one type of epoxy resin curing agent selected from resins is used. 5. Component (c) is 70% of the total amount of the composition.
The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 4, wherein a crushed and / or spherical, fused and / or crystalline silica powder filler is used in an amount of up to 93% by weight.