JPH11106482A - Epoxy resin curing agent and epoxy resin composition for sealing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject curing agent capable of forming a cured material having a low melt viscosity, excellent in low moisture absorption and low stress property and useful for an epoxy resin composition for sealing a semiconductor by using a modified phenolic compound of which phenolic OH is partially etheri fied with a specific group. SOLUTION: This epoxy resin curing agent is (A) a modified phenolic compound of which phenolic OH is partially etherified by a group of formula I [Z<1> is H, a 1-10C alkyl, a (substituted) phenyl, a (substituted) aralkyl or an alkoxy; R<1> is Z<1> except for H or a halogen; (n<1> ) is 0-5] as a main component. The (A) component is obtained by e.g. dissolving a polyhydric phenol compound with a solvent as reaction medium to form a uniform solution, then adding a compound of formula II (R<3> , Z<3> and n<3> are R<1> , Z<1> and n<1> respectively; X is a halogen) and a hydroxide or a carbonate of an alkali metal into the solution, and reacting at 0-150 deg.C temperature for 1-10 hr while vigorously agitating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin curing agent which has a low melt viscosity and gives a cured product excellent in low moisture absorption and low stress. Furthermore, the present invention relates to an epoxy resin composition for providing a cured product having a low melt viscosity and excellent in low hygroscopicity and low stress, particularly an epoxy resin composition for semiconductor encapsulation.

[0002]

2. Description of the Related Art Epoxy resin compositions are widely used for bonding, casting, sealing, laminating, molding, painting and the like due to their excellent cured physical properties and ease of handling. In addition, many kinds of curing agents can be used for the epoxy resin, and the curing properties are greatly changed by the selection of the curing agent. In recent years, as the use conditions of polymer materials have become more severe, the characteristics required for the polymer materials have become severer, and various epoxy resins generally used can no longer sufficiently satisfy the required characteristics. Was. For example, an epoxy resin composition using a novolak type epoxy resin as a curing agent is used for semiconductor encapsulation, but the required performance is strict in this field as well. In other words, the integration of the semiconductor device has been advanced, and the size of the semiconductor element has been hardly increased, and the package itself has been reduced in size and thickness. In addition, the mounting of semiconductor devices has also shifted to surface mounting, and in surface mounting, the semiconductor device is directly immersed in a solder bath and exposed to high temperatures,
Due to the expansion of the absorbed moisture, a large stress is applied to the entire package, and cracks are formed in the sealing material. Therefore, for a sealing material having good solder crack resistance, high heat resistance, excellent low moisture absorption, and excellent low stress, that is, a low elastic modulus, are required. In addition, it is widely practiced to improve the low hygroscopicity and the low stress, that is, the low coefficient of thermal expansion by highly filling an inorganic filler such as a fused silica powder. Since the fluidity at the time is impaired, epoxy resins and curing agents for sealing materials have also been required to have low melt viscosities. The cresol novolak type epoxy resin and phenol novolak resin curing agent which are currently mainly used have become insufficient in heat resistance, low hygroscopicity and low stress, that is, low elastic modulus and low melt viscosity. Recently, to solve these problems, by using a phenol resin having a less polar hydrocarbon group introduced between phenol nuclei, such as a terpene phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin, as a curing agent. Improvements in low moisture absorption and low stress have also been made, but these resins have high melt viscosities and do not allow high loading of inorganic fillers. If the molecular weight of these resins is reduced in order to lower the melt viscosity, the crosslink density of the cured product will be reduced, and the heat resistance will be reduced. On the other hand, a curing agent having a low melt viscosity is strongly demanded for improving flowability in the field of powder coatings and for improving impregnation in the field of laminates.

[0003]

SUMMARY OF THE INVENTION The present invention provides an epoxy resin curing agent which gives a cured product having a low melt viscosity and excellent low moisture absorption and low stress, and further uses the epoxy resin curing agent. It is another object of the present invention to provide an epoxy resin composition for providing a cured product having a low melt viscosity and excellent in low hygroscopicity and low stress, particularly an epoxy resin composition for semiconductor encapsulation.

[0004]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, as a curing agent for an epoxy resin, a phenolic hydroxyl group of a polyhydric phenol compound is partially substituted with a specific group. The purpose was achieved by using an etherified modified phenol compound. The present invention provides an epoxy resin curing agent comprising, as a main component, a modified phenol compound obtained by partially etherifying a phenolic hydroxyl group of a polyhydric phenol compound with a group represented by the general formula (I). General formula (I)

[0005]

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(Wherein R ^{1 s} may be the same or different and each 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, , A halogen atom, Z ¹
May be the being the same or different, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group, n ¹ is It is an integer of 0-5. ) 2. 2. The epoxy resin curing agent according to item 1, wherein the polyhydric phenol compound is a compound represented by the general formula (II). General formula (II)

[0007]

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(Wherein R ² may be the same or different from each other and 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, , A halogen atom, Y
May be the same or different and are each a divalent hydrocarbon group having 1 to 15 carbon atoms, m is an integer of 0 to 20, and n ² is the same or different. And may be an integer of 0 to 4. ) 3. A compound in which the phenolic hydroxyl group of a polyhydric phenol compound is represented by the general formula (III): General formula (III)

[0009]

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Wherein X is a halogen atom, and R ³ is
They may be the same or different from each other and have 1 to 1 carbon atoms.
10 alkyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted aralkyl groups, alkoxy groups, or
A halogen atom, Z ² may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group; And n ³ is 0-5
Is an integer. 3. The epoxy resin curing agent according to any one of claims 1 to 2, wherein the epoxy resin curing agent is a modified phenol compound obtained by partial etherification by a dehydrohalogenation reaction. 4. 3. The polyhydric phenol compound is represented by the general formula (II), and the m = 0 component is a polyhydric phenol compound occupying 20% or less of the total polyhydric phenol compound. The epoxy resin curing agent according to any one of the above. 5. The modified phenol compound is a modified phenol compound obtained by etherifying 10 to 85% of the phenolic hydroxyl groups of the polyhydric phenol compound,
5. The epoxy resin curing agent according to any one of items 1 to 4. 6. (A) an epoxy resin; (b) an epoxy resin curing agent according to any one of items 1 to 5; (c) an inorganic filler; and (d) a curing accelerator. Resin composition. 7. (A) As an epoxy resin, an epoxy resin produced from at least one phenol compound selected from biphenol, tetramethylbiphenol, cresol novolak resin, phenolhydroxybenzaldehyde resin, and dicyclopentadiene phenol resin, and epihalohydrin is used. 7. The epoxy resin composition for sealing according to item 6, characterized in that: 8. (B) The amount of the epoxy resin curing agent is such that the total of groups reacting with the epoxy groups of all curing agent components is 0.5 to 1.5 mol per mol of epoxy groups in all epoxy resin components. Item 8. The epoxy resin composition for sealing according to item 7 or 7. 9. (C) As an inorganic filler, 60 to 9 of the total composition
5% by weight of pulverized and / or spherical, molten and / or
9. The epoxy resin composition for sealing according to any one of items 6 to 8, wherein a crystalline silica powder filler is used. 10. (D) A curing accelerator is compounded in an amount of 0.1 to 7.0 parts by weight based on 100 parts by weight of the epoxy resin.
Item 14. The epoxy resin composition for sealing described in any one of the above items. About.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin curing agent of the present invention comprises
There are no particular restrictions on the structure, production method, and the like of the polyhydric phenol compound as long as it is a modified phenol compound in which the phenolic hydroxyl group of the polyhydric phenol compound is partially etherified with the group represented by the general formula (I). Examples of the group represented by the general formula (I) include a benzyl group, an α-methylbenzyl group,
Ethylbenzyl group, α-dimethylbenzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2,4-dimethylbenzyl group, 2,5-dimethylbenzyl group, 3,5-dimethylbenzyl Group 2,4
5-trimethylbenzyl group, 4-ethylbenzyl group, 4
-Phenylbenzyl group, 3-methoxybenzyl group, 4-
Chlorobenzyl group, 2,5-dichlorobenzyl group and the like. There is no particular limitation on the structure and the like of the polyhydric phenol compound as a raw material of the modified phenol compound. For example, bisphenol A, bisphenol F, bisphenol AD, hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenylether, phenol novolak resin, cresol novolak resin, bisphenol A novolak Resin, phenol aralkyl resin, dicyclopentadiene phenol resin, terpene phenol resin,
Various phenols such as naphthol novolak resin,
Various phenols, hydroxybenzaldehyde,
And polyhydric phenol resins obtained by a condensation reaction with various aldehydes such as crotonaldehyde and glyoxal. Among these polyhydric phenol compounds, a compound represented by the general formula (II) is preferable in consideration of properties after modification. Furthermore, the general formula (I
As the polyhydric phenol compound represented by I), the compound component in which m = 0 in the general formula (II) desirably accounts for 20% or less of the entire polyhydric phenol compound. This is because the compound component where m = 0 in the general formula (II) has one phenolic hydroxyl group that contributes as a curing agent.
Although it has only two in the molecule, if even one of the phenolic hydroxyl groups is lost by etherification, it no longer functions as a curing agent.

The compound component in which m = 0 in the general formula (II) accounts for 20% of the total polyhydric phenol compound.
Polyhydric phenol compounds occupying the following are, for example, various phenols such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, phenol aralkyl resin, dicyclopentadiene phenol resin, terpene phenol resin, naphthol novolak resin, and the like. Phenols, hydroxybenzaldehyde, crotonaldehyde, polyhydric phenolic resin obtained by condensation reaction with various aldehydes such as glyoxal, for example, using various methods such as vacuum distillation method and solvent washing method, It can be obtained by selecting the reaction conditions for producing these resins. The partial etherification of the phenolic hydroxyl group of the polyhydric phenol compound is performed by using the compound represented by the general formula (III),
This is performed by a dehydrohalogenation reaction. Examples of the compound represented by the general formula (III) include, for example, benzyl chloride, benzyl bromide, α-methylbenzyl chloride, α-methylbenzyl bromide, α-ethylbenzyl chloride, α-dimethylbenzyl chloride, chloride 2 -Methylbenzyl, 3-methylbenzyl chloride, 4-methylbenzyl chloride, bromide 4
-Methylbenzyl, 2,4-dimethylbenzyl chloride, 2,5-dimethylbenzyl chloride, 3,5-dimethylbenzyl chloride, 2,4,5-trimethylbenzyl chloride, 4 chloride
-Ethylbenzyl, 4-phenylbenzyl chloride, chloride 3
-Methoxybenzyl, 4-chlorobenzyl chloride, 2,5-dichlorobenzyl chloride, 4-fluorobenzyl chloride and the like. The dehydrohalogenation reaction can be carried out by various methods using various conditions depending on the type and combination of the raw material polyhydric phenol compound and the compound represented by the general formula (III). The typical conditions and method of partial etherification are as follows: a polyhydric phenol compound is dissolved in a solvent as a reaction medium to form a uniform solution, and the compound represented by the general formula (III) is added to the solution. A metal hydroxide or an alkali metal carbonate is added, and the mixture is reacted at a temperature of 0 to 150 ° C. for 1 to 10 hours with vigorous stirring. After completion of the reaction, the unreacted compound represented by the general formula (III), by-product salt, solvent and the like are removed to obtain the desired modified phenol compound.

Solvents as a reaction medium in this reaction include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as dioxane and ethylene glycol dimethyl ether. And inert organic solvents such as aprotic polar solvents such as dimethylsulfoxide and dimethylformamide, and water. Examples of the alkali metal hydroxide in this reaction include sodium hydroxide, potassium hydroxide and the like. As the alkali metal carbonate in this reaction,
Examples include sodium carbonate and potassium carbonate. In this partial etherification reaction, the starting polyhydric phenol compound may use two or more different compounds, and the modified phenol compound starting from two or more different compounds and two or more different A modified phenol compound having an etherification ratio can be arbitrarily mixed and used. In this partial etherification reaction, it is desirable that 10 to 85% of the phenolic hydroxyl groups of the polyhydric phenol compound be etherified. If the etherification rate is 10% or less, the effect of reducing the viscosity and moisture absorption cannot be sufficiently obtained. When the etherification rate is 85% or more,
Since the phenolic hydroxyl group required for the curing reaction has been reduced, the curing speed has been remarkably slowed down, making it impractical.

The epoxy resin composition for sealing of the present invention comprises (a) an epoxy resin, (b) the epoxy resin curing agent described in any one of (1) to (5), (c) an inorganic filler, (D) An epoxy resin composition containing a curing accelerator as an essential component. The (a) epoxy resin is not particularly limited, and a general epoxy resin can be used. Examples of the epoxy resin (a) used include bisphenol A, bisphenol F, bisphenol AD, hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenylether, Phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, phenol aralkyl resin, dicyclopentadiene phenol resin, terpene phenol resin,
Various phenols such as naphthol novolak resin,
Various phenols, hydroxybenzaldehyde,
Crotonaldehyde, various phenolic compounds such as polyhydric phenolic resin obtained by condensation reaction with various aldehydes such as glyoxal and epoxy resin and diaminodiphenylmethane produced from epihalohydrin,
Epoxy resins produced from various amine compounds such as aminophenol and xylene diamine and epihalohydrin, epoxy resins produced from various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid and epihalohydrin, and the like. . Above all, considering availability, physical properties after curing, and the like, bisphenol A, bisphenol F, biphenol, tetramethylbiphenol, cresol novolak resin, bisphenol A novolak resin, phenol novolak resin, phenolhydroxybenzaldehyde resin, and dicyclohexane It is preferable to use an epoxy resin produced from at least one phenol compound selected from pentadiene phenol resins and epihalohydrin.
Further, in order to make the cured product flame-retardant, a part of the epoxy resin used is used as a brominated epoxy resin, for example, an epoxy resin produced from a brominated bisphenol A or a brominated phenol novolak resin and epihalohydrin, An epoxy resin produced by a reaction between a molecular epoxy resin and a brominated bisphenol A is exemplified.

The epoxy resin curing agent according to any one of the above items (b) used in the sealing epoxy resin composition of the present invention may be used alone or in combination with a phenolic epoxy resin curing agent. Any combination can be used. Phenol epoxy resin curing agents that can be used in combination are compounds having an average of two or more phenolic hydroxyl groups in one molecule, such as bisphenol A, bisphenol F, bisphenol AD, hydroquinone, resorcin, methylresorcin, biphenol, and tetramethyl. Biphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, phenol novolak resin,
Various polyphenols such as cresol novolak resin, bisphenol A novolak resin, phenol aralkyl resin, dicyclopentadiene phenol resin, terpene phenol resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin, and various phenols And various phenol resins such as polyhydric phenol resins obtained by a condensation reaction of the compounds with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde and glyoxal. The amount of the epoxy resin curing agent (b) used in the encapsulating epoxy resin composition of the present invention is such that the amount of epoxy group of all epoxy resin curing agent components is 1 mole of epoxy group in all epoxy resin components. The total number of reactive groups is 0.
An amount of 5 to 1.5 mol is preferable, and more preferably,
The amount is 0.7 to 1.3 mol. If it is 0.7 mol or less and 1.5 mol or more, it is not preferable because a sufficient cured product cannot be obtained.

The epoxy resin composition for sealing of the present invention comprises:
(C) An inorganic filler is blended. Examples of the kind of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, calcium carbonate and the like. The shape is a pulverized type or a spherical shape. Various inorganic fillers are used alone or in combination of two or more. Among various inorganic fillers, pulverized or spherical fused silica or crystalline silica is preferable, and its use amount is 60 to 95% by weight of the whole composition, more preferably 7 to 95% by weight.
0 to 93% by weight, more preferably 80 to 92% by weight.
% By weight.

The curing accelerator (d) used in the encapsulating 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, and methyltributylphosphonium. Phosphonium salts such as tetraphenylborate and methyltricyanoethylphosphonium tetraphenylborate;
-Methylimidazole, 2-phenylimidazole, 2
-Ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl (1)]-ethyl-S-triazine, 2, Imidazoles such as 4-dicyano-6- [2-undecylimidazolyl- (1)]-ethyl-S-triazine, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-
Imidazolium salts such as ethyl-4-methylimidazolium tetraphenylborate and 2-ethyl-1,4-dimethylimidazolium tetraphenylborate;
6-tris (dimethylaminomethyl) phenol, benzylmethylamine, tetramethylbutylguanidine, N
Amines such as -methylpiperazine, 2-dimethylamino-1-pyrroline, ammonium salts such as triethylammonium tetraphenylborate, 1,5-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo ( Diazabicyclo compounds such as 4,3,0) -5-nonene and 1,4-diazabicyclo (2,2,2) octane; tetraphenylborate, phenol salt, phenol novolak salt, and 2-ethylhexanoic acid of such diazabicyclo compounds Salt and the like. Among these compounds that serve as curing accelerators, phosphine compounds, imidazole compounds, diazabicyclo compounds, and salts thereof are preferable. These curing accelerators are used alone or as a mixture of two or more kinds, and the amount of use is 0.1 to 7% by weight based on all epoxy resin components. If it is less than 0.1% by weight, the curing is insufficient, and if it is more than 7% by weight, the storage stability of the composition is remarkably deteriorated.

The epoxy resin composition for sealing of the present invention comprises:
If necessary, a coupling agent, a plasticizer, a pigment, a solvent, a flame retardant, and the like can be appropriately blended. Further, antimony trioxide, phosphoric acid and the like can be appropriately blended as a flame retardant auxiliary. The epoxy resin curing agent of the present invention has a lower melt viscosity than conventional epoxy resin curing agents, and can provide a cured product excellent in low hygroscopicity and low stress. Furthermore, since the epoxy resin composition of the present invention has a low melt viscosity and can give a cured product having excellent low moisture absorption and low stress, it is advantageously used in the field of sealing, especially semiconductor sealing. can do.

[0019]

Examples The production examples of the modified phenol compound used as the epoxy resin curing agent of the present invention, and the examples and comparative examples of the epoxy resin composition for encapsulation of the present invention are described in more detail below.

Production Examples 1-6 of Modified Phenol Compounds Partially Etherified A polyhydric phenol compound and methyl isobutyl ketone were placed in a two-liter three-necked flask equipped with a thermometer, a stirrer, and a condenser. And the polyhydric ether was dissolved by stirring. Then, benzyl chloride (in the case of Production Example 6, 2,5-dimethylbenzyl chloride) and potassium carbonate were charged in the amounts shown in Table 1 and reacted at reflux temperature for 6 hours. After the reaction solution was washed with water to remove by-product salts and the like, methyl isobutyl ketone and unreacted benzyl chloride (in the case of Production Example 6, 2,5-dimethylbenzyl chloride) were removed under reduced pressure to obtain the desired modified phenol. The compound was obtained. The etherification rate, hydroxyl equivalent, softening point and melt viscosity of the resulting modified phenol compound were measured and are shown in Table 1.

[0021]

[Table 1]

(Note) The polyhydric phenol compounds A to D shown in Table 1
Is as follows. Polyhydric phenol compound A: phenol novolak resin, PSM4327 (Gunei Chemical Co., Ltd.) hydroxyl equivalent (g /
eq) 103, softening point (° C.) 93, m = 0 content * 5 (a
% GPC) 11.3, Melt viscosity (P) 4.8 Polyphenol compound B: phenol aralkyl resin,
Millex XL225LL (manufactured by Mitsui Toatsu Co.) hydroxyl equivalent (g / eq) 176, softening point (° C) 77, m = 0 content *
5 (a% GPC) 14.4, melt viscosity (P) 3.2 Polyhydric phenol compound C: phenol aralkyl resin,
Millex VR2210 (manufactured by Mitsui Toatsu), hydroxyl equivalent (g / eq) 105, softening point (° C) 61, m = 0 content *
5 (a% GPC) 9.8, melt viscosity (P) 0.6 Polyhydric phenol compound D: phenol novolak resin,
DL-92 (manufactured by Meiwa Chemical Co.) hydroxyl equivalent (g / eq) 1
06, softening point (° C.) 89, m = 0 content * 5 (a% GP
C) 6.4, melt viscosity (P) 2.4 * 1 {a + (b-1) (e / 100)} / (1-e / 10) obtained from the following equation.
0) = a 'a = hydroxyl equivalent of raw polyhydric phenol compound (actual measurement) a' = hydroxyl equivalent of modified phenol compound obtained by reaction (actual measurement) b = molecular weight of substituted ether group e = etherification ratio * 2 Acetylation method * 3 Ring and ball method * 4 ICI viscometer, 150 ° C * 5 Refers to m in general formula (II)

Example 1 Epoxy Resin Composition for Semiconductor Encapsulation
As shown in Tables 2 and 3, (a) an epoxy resin derived from tetramethylbiphenol as an epoxy resin, or an ortho-cresol novolak-type epoxy resin, and bromine as a brominated epoxy resin Bisphenol A epoxy resin, (b) modified phenolic compounds prepared in Preparation Examples 1 to 6 as epoxy resin curing agents, commercially available phenol novolak resin, (c) crushed fused silica powder as inorganic filler, (d) curing Using triphenylphosphine as an accelerator, antimony trioxide as a flame retardant auxiliary, epoxysilane as a filler surface treatment agent,
Each epoxy resin formulation was compounded using carnauba wax as a release agent. Next, each composition was melt-mixed at a temperature of 70 to 130 ° C. for 5 minutes 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 44-pin FPP (flat plastic package) in which each test piece and a simulated element are sealed is molded by a low-pressure transfer molding machine at a mold temperature of 175 ° C. and a molding time of 160 to 300 seconds. Obtained and post-cured at 180 ° C. for 8 hours. Further, the spiral flow of each molding material was measured.

[0024]

[Table 2]

[0025]

[Table 3]

(Note) Epoxy resin E: Epoxy resin derived from tetramethylbiphenol (Yuika Shell Epoxy Co., Ltd., Epicoat YX4000H, epoxy equivalent: 193 g / eq) Epoxy resin F: Orthocresol novolac type epoxy resin (Oil shell) Epoxy Coat 180S, manufactured by Epoxy
65, epoxy equivalent: 214 g / eq) Epoxy resin curing agent A: phenol novolak resin (PSM4327, manufactured by Gunei Chemical Co., Ltd., hydroxyl equivalent: 103 g / eq.)
eq) Epoxy resin curing agent B: phenol aralkyl resin (Mirex XL225LL, manufactured by Mitsui Toatsu Co., hydroxyl equivalent:
176 g / eq) * 1: Brominated bisphenol type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., BREN-S, epoxy equivalent: 285 g / eq) * 2: Pulverized fused silica powder (RD-8, manufactured by Tatsumori) * 3: Triphenylphosphine * 4: Antimony trioxide * 5: Carnauba wax * 6: Epoxysilane (KBM-4 manufactured by Shin-Etsu Chemical Co., Ltd.)
03) * 7: Calculated from the transition point of the thermal expansion curve using TMA. * 8: Measured according to JIS K6911. * 9: Moisture absorption after 24 hours at 85 ° C., 85% RH * 10: Moisture absorption after 85 hours at 85 ° C., 85% RH * 11: Moisture absorption of 16 44-pin FPPs at 85 ° C., 85% RH for 168 hours Then, it was immersed in a 260 ° C. solder bath for 10 seconds to determine the number of cracks. (Evaluation) Spiral flow measurement value of each molding material, glass transition temperature after post cure of each test piece, moisture absorption rate,
Table 2 shows the results of testing the flexural modulus and solder heat resistance.
The molding materials of Examples 1 to 6 have flowability (that is, high spiral flow), moisture resistance (that is, low hygroscopicity), and low stress as compared with the molding materials of Comparative Examples 1 to 3. (That is, low elastic modulus) and a cured product excellent in solder heat resistance.

[0027]

EFFECTS OF THE INVENTION The epoxy resin curing agent of the present invention has a low melt viscosity and can give a cured product having excellent low hygroscopicity and low stress. It can be used advantageously in applications. Furthermore, the epoxy resin composition for encapsulation of the present invention has a low melt viscosity and can give a cured product excellent in low moisture absorption and low stress, so that it is advantageous in encapsulation, especially in semiconductor encapsulation applications. Can be used.

Claims (10)

[Claims] 1. An epoxy resin curing agent comprising a modified phenol compound obtained by partially etherifying a phenolic hydroxyl group of a polyhydric phenol compound with a group represented by the general formula (I) as a main component. General formula (I) (In the formula, R ¹ may be the same or different, and may be an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group, or a halogen atom. And Z ^{1 s} may be the same or different from each other, and represent a hydrogen atom, a carbon atom 1
10 to 10 alkyl groups, substituted or unsubstituted phenyl groups,
Substituted or unsubstituted aralkyl group, an alkoxy group, n ¹ is an integer of 0 to 5. ) 2. The polyhydric phenol compound represented by the general formula (II)
The epoxy resin curing agent according to claim 1, which is a compound represented by the formula: Formula (II) (Wherein R ² may be the same or different from each other, and may be an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, an alkoxy group, or a halogen atom. and a, Y may be the being the same or different, is a divalent hydrocarbon group having 1 to 15 carbon atoms, m is an integer of 0 to 20, n ²
May be the same or different, and are an integer of 0 to 4. ) 3. A compound in which a phenolic hydroxyl group of a polyhydric phenol compound is represented by the general formula (III): General formula (III) (Wherein X is a halogen atom, R ³ may be the same or different, and may be an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group. , An alkoxy group or a halogen atom, Z ² may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted group. Wherein n ³ is an integer of 0 to 5), wherein n ³ is a modified phenol compound which is partially etherified by a dehydrohalogenation reaction. 3. The epoxy resin curing agent according to any one of 1 to 2. 4. The polyhydric phenol compound represented by the general formula (II)
The epoxy according to any one of claims 2 to 3, wherein m = 0 is a polyhydric phenol compound occupying 20% or less of the total polyhydric phenol compound. Resin curing agent. 5. The modified phenol compound according to claim 1, wherein the modified phenol compound is a modified phenol compound obtained by etherifying 10 to 85% of the phenolic hydroxyl groups of the polyhydric phenol compound. An epoxy resin curing agent described in 1. 6. An epoxy resin, (b) an epoxy resin curing agent according to any one of claims 1 to 5, (c) an inorganic filler, and (d) a curing accelerator. Epoxy resin composition for sealing. 7. An epoxy resin which is produced from at least one phenol compound selected from biphenol, tetramethylbiphenol, cresol novolak resin, phenolhydroxybenzaldehyde resin and dicyclopentadiene phenol resin as an epoxy resin, and epihalohydrin. The epoxy resin composition for sealing according to claim 6, wherein an epoxy resin is used. 8. (b) The total of the groups which react with the epoxy groups of all the curing agent components with respect to 1 mol of the epoxy groups in all the epoxy resin components is 0.5 to 1.5 mol. The epoxy resin composition for sealing according to claim 6 or 7, which is an amount. 9. The inorganic filler is characterized in that 60 to 95% by weight of the total composition of the milled and / or spherical, fused and / or crystalline silica powder filler is used. Item 10. The epoxy resin composition for sealing according to any one of Items 6 to 8. 10. A method according to claim 1, wherein (d) the curing accelerator is epoxy resin 10.
The epoxy resin composition for sealing according to any one of claims 6 to 9, wherein 0.1 to 7.0 parts by weight is blended with respect to 0 parts by weight.