JP2002212271A - Curing agent for epoxy resin, and epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing agent for epoxy resins which has a low melt viscosity and gives a cured product having excellent low stress properties and low hygroscopicity, and to provide a composition and a semiconductor sealing composition which use this curing agent. SOLUTION: The epoxy resin curing agent comprises (a) 30-99 pts.wt. phenolic resin having a hydrocarbon group having reduced polarity between the phenolic nuclei to be represented by formula (I), (b) 1-70 pts.wt. thiodiphenolic compound to be represented by formula (II), and (c) 0-100 pts.wt. polyhydric phenolic compound having a structure other than those of components (a) and (b). The epoxy resin composition and the semiconductor sealing composition use the curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curing agent for an epoxy resin which gives a cured product having a low melt viscosity, excellent low hygroscopicity and low stress, and excellent moldability. The present invention relates to an epoxy resin composition and an epoxy resin composition for encapsulating a semiconductor.

[0002]

2. Description of the Related Art Epoxy resins are used in a wide variety of fields because of their excellent cured physical properties and ease of handling.
Also, various types of curing agents can be used for the epoxy resin, and the curing properties vary greatly depending on the selection of the curing agent. Therefore, the epoxy resins are properly used according to the purpose of each application. recent years,
As the use conditions of the polymer material become severe, various properties required for the polymer material have become severe.
Even in applications where a curing agent for epoxy resin is used, various commonly used curing agents are no longer able to sufficiently satisfy the required characteristics. For example, an epoxy resin composition using a novolak type phenol 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 semiconductor devices has advanced, and the size of semiconductor elements and the size of packages have been reduced.
Thinning is progressing, and the mounting method is also shifting to surface mounting. In this case, since the entire semiconductor device is exposed to a high temperature near the melting temperature of solder at the time of mounting, a large stress is applied to the entire package due to rapid expansion of the moisture absorbed by the package, thereby causing a problem of cracking. . Epoxy resins and curing agents for sealing materials having good solder crack resistance are required to have low moisture absorption and low stress, that is, low elastic modulus. In addition, by highly filling an inorganic filler such as fused silica powder, low hygroscopicity and low stress,
In other words, although it is widely practiced to improve the coefficient of thermal expansion, the high filling of inorganic filler impairs the fluidity during molding, so epoxy resins and curing agents for sealing materials have low melt viscosities. Something has been required. The combination of a cresol novolak type epoxy resin and a phenol novolak resin curing agent, which are mainly used at present, cannot be said to have sufficient low hygroscopicity and low stress, that is, low elastic modulus and low melt viscosity. Recently, in order to solve these problems, by using a phenol resin having a less polar hydrocarbon group between phenol nuclei such as dicyclopentadiene phenol resin or xylylene phenol resin as a curing agent, low moisture absorption is achieved. Improvements in properties and low stress have also been made, but these phenolic 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, curability will be reduced and moldability will be deteriorated, resulting in reduced productivity. Although it is possible to increase the addition amount of a curing accelerator to improve curability,
In this case, the storage stability as a sealing material is deteriorated, which is not practical.

[0003]

The object of the present invention is to provide a curing agent for an epoxy resin which has a low melt viscosity, is excellent in low stress and low moisture absorption, and gives a cured product excellent in moldability. Epoxy resin composition and epoxy resin composition for semiconductor encapsulation for epoxy resin, using the curing agent, giving a cured product with low melt viscosity, excellent low hygroscopicity and low stress, and excellent moldability. The purpose is to provide things.

[0004]

The present inventors have made various studies to solve the above-mentioned problems, and as a result, as a curing agent for an epoxy resin, a specific low-polarity hydrocarbon group between phenol nuclei was used. The object has been achieved by using a phenolic resin and a thiodiphenol compound in combination. The present invention provides: 1. (a) a phenolic resin 3 having a less polar hydrocarbon group between phenol nuclei represented by the following general formula (I):
0 to 99 parts by weight General formula (I)

[0005]

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(Wherein R ¹ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or an alkoxy group. And Z is a divalent hydrocarbon group having 1 to 20 carbon atoms to which a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom may be bonded, which may be the same or different from each other, And at least one Z in one molecule is a divalent hydrocarbon group having 5 to 20 carbon atoms to which a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom may be bonded, and n is an average value And p is the same or different and p is an integer of 0 to 3.) (b) A thiodiphenol compound represented by the following general formula (II) 1 to 70 parts by weight General formula (II)

[0007]

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(Wherein R ² may be the same or different and each represents an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group or an alkoxy group. And q is the same or different and is an integer of 0 to 3.) (c) 0 to 100 parts by weight of a polyhydric phenol compound having a structure other than the component (a) and the component (b) A curing agent for epoxy resin. 2. (A) As a phenol resin having a less polar hydrocarbon group between phenol nuclei, in the general formula (I),
At least one Z in one molecule has the following general formula (III)
Or the curing agent for epoxy resin according to item 1, wherein at least one kind of phenol resin having a skeleton represented by the structural formulas (1) to (3) is used. General formula (III)

[0009]

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(Wherein R ³ is an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group or an alkoxy group, and the total number of carbon atoms of a plurality of R ³ is 1 to 14, and r is an integer of 0 to 10.) Structural formula (1)

[0011]

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Structural formula (2)

[0013]

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Structural formula (3)

[0015]

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3. (B) As thiodiphenol compounds, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide and bis (4-hydroxy-3,5-dimethylphenyl)
3. The curing agent for epoxy resin as described in 1 or 2, wherein at least one kind of thiodiphenol selected from sulfides is used. 4. Item 4. The curing agent for an epoxy resin described in any one of Items 1 to 3, wherein (a) a compounding amount of a phenol resin having a less polar hydrocarbon group between phenol nuclei is 45 to 90 parts by weight, b) 10 to 55 parts by weight of the thiodiphenol compound, (c) component (a) and (b)
A curing agent for an epoxy resin in which a polyhydric phenol compound having a structure other than the components is 0 to 100 parts by weight. 5. An epoxy resin composition comprising, as an essential component, an epoxy resin and the curing agent for an epoxy resin described in any one of items 1 to 4. 6. Epoxy resin produced from at least one phenol compound selected from biphenol, tetramethylbiphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) propane, terpene phenol and cresol novolak resin, and epihalohydrin And an epoxy resin composition for semiconductor encapsulation comprising the epoxy resin curing agent according to any one of items 1 to 4 as an essential component. 7. Crushable and / or spherical, fused and / or crystalline silica powder as the epoxy resin, the curing agent for the epoxy resin described in any one of Items 4 to 4, and the inorganic filler as the inorganic filler. An epoxy resin composition for semiconductor encapsulation formulated as an essential component at 95% by weight. 8. The amount of the epoxy resin curing agent used was set to an amount such that the group reacting with the epoxy group in the entire curing agent was 0.5 to 2.0 mol per 1 mol of the epoxy group in the entire epoxy resin component. Item 8. The epoxy resin composition for semiconductor encapsulation according to any one of Items 6 to 7. About.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The proportion of each component of the curing agent for epoxy resin of the present invention is as follows: (a) 30 to 99 parts by weight of a phenol resin having a less polar hydrocarbon group between phenol nuclei; b) 1 to 70 parts by weight of a thiodiphenol compound, and (c) 0 to 100 parts by weight of a polyhydric phenol compound having a structure other than the components (a) and (b). These components of the epoxy resin curing agent of the present invention may be used after mixing and preparing a mixed curing agent in advance, or when mixing various components during production of the epoxy resin composition, The respective components of the curing agent may be separately added and mixed at the same time.

(A) If the amount of the phenolic resin having a less polar hydrocarbon group between the phenol nuclei is less than 30 parts by weight, the low hygroscopicity and the low stress become insufficient. If the amount of the (b) thiodiphenol compound is less than 1 part by weight, the curability is lowered, so that sufficient moldability cannot be obtained. If the amount is more than 70 parts by weight, the low hygroscopicity becomes insufficient. From the balance of the above various properties, the use ratio of the component (a) and the component (b) is (a) 30 to 9
(B) 1 to 70 parts by weight with respect to 9 parts by weight, preferably (b) 5 to 5 parts with respect to (a) 40 to 95 parts by weight.
5 parts by weight, more preferably 45 to 90 parts by weight of (a) and 10 to 55 parts by weight of (b). (C)
A polyphenol compound having a structure other than (a) and (b)
If the amount is more than 00 parts by weight, the effect of the present invention cannot be sufficiently exhibited. One of the components of the curing agent for an epoxy resin of the present invention, (a) a phenolic resin having a less polar hydrocarbon group between the phenol nuclei represented by the general formula (I) is represented by the general formula (I) The production method is not particularly limited as long as it has a structure represented by the general formula (I), but generally, an addition condensation reaction between various phenol compounds and a carbonyl compound, an addition reaction with a diene compound, A method in which a phenol resin is oligomerized by a reaction such as a condensation reaction with a compound having an alkyl group or a dialkoxyalkyl group is used.

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

Examples of the compound having a carbonyl group used for oligomerizing these phenol compounds include various aldehydes or ketones having 5 to 15 carbon atoms, such as benzaldehyde, cyclohexanecarboxaldehyde, Octal, cyclohexanone, acetophenone and the like can be mentioned. A good cured product can be obtained by using this ratio and a curing agent,
It is particularly preferable for semiconductor encapsulation.

The diene compound includes, for example, divinylbenzene, norbornene, diisopropenylbenzene, terpenes and the like. Examples of the compound having a dihydroxyalkyl group or a dialkoxyalkyl group include 4,4'-dihydroxymethylbiphenyl,
2,6-dihydroxymethylnaphthalene, 4,4'-dimethoxymethylbiphenyl, 2,6-dimethoxynaphthalene and the like can be mentioned.

The reaction with a carbonyl compound, a diene compound, a compound having a hydroxyalkyl group or an alkoxyalkyl group for oligomerizing the phenol compound to form a phenol resin is performed by a general reaction method. That is, the reaction is performed at a temperature of 20 to 200 ° C. for 30 minutes to 20 hours in the presence of an acidic catalyst. At the time of the reaction, in order to adjust the molecular weight of (a) a phenol resin having a less polar hydrocarbon group between phenol nuclei to be produced,
The amount of the phenol compound used is 1 to 20 moles per 1 mole of the compound having a carbonyl compound, a diene compound, a dihydroxyalkyl group or a dialkoxyalkyl group. Further, the produced phenolic resin can be treated by a method such as recrystallization, reprecipitation, extraction, or distillation to adjust the molecular weight. In addition, the obtained phenol resin can be subjected to a condensation reaction with aldehydes such as formaldehyde and acetaldehyde under acidic conditions to adjust the softening point and the melt viscosity again. Among various phenolic resins having a less polar hydrocarbon group between phenol nuclei, the following formulas (IV) to (VI) are used from the viewpoint of easy availability and curing properties.
Resins as shown in I) are preferred. General formula (IV)

[0023]

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(Where m ¹ is a number of 0 to 8 on average) General formula (V)

[0025]

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(Where m ² is a number from 0 to 8 on average) General formula (VI)

[0027]

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(Wherein m ³ is a number of 0 to 8 on average) General formula (VII)

[0029]

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[0030] (wherein, ^{m 4} is a number from 0 to 8 in the average value)

The thiodiphenol compound (b), which is a component of the curing agent for epoxy resin of the present invention, has the general formula (I)
There is no restriction as long as the structure is represented by I), for example,
Bis (4-hydroxyphenyl) sulfide, bis (2
-Hydroxyphenyl) sulfide, 2-hydroxyphenyl-4'-hydroxyphenyl sulfide, bis (4-hydroxy-3-methylphenyl) sulfide,
Bis (4-hydroxy-3,5-dimethylphenyl) sulfide, bis (4-hydroxy-2-methyl-5-t
tert-butylphenyl) sulfide, bis (4-hydroxy-3-methyl-5-tert-butylphenyl)
Sulfide, bis (4-hydroxy-3,5-di-te
rt-butylphenyl) sulfide, etc.
Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide and bis (4-hydroxy-
3,5-Dimethylphenyl) sulfide is preferred, and bis (4-hydroxyphenyl) sulfide is more preferred.

The curing agent for epoxy resin of the present invention includes:
For fine adjustment of characteristics, the components (c) and (a) and (b)
A polyhydric phenol compound having a structure other than the above can be mixed and used. Examples of other polyhydric phenol compounds include, for example, phenol novolak resin, cresol novolak resin, various phenol resins such as bisphenol A novolak resin, various phenols, and various aldehydes such as acetaldehyde and propionaldehyde. Various phenolic resins such as polyhydric phenolic resins obtained by the condensation reaction are exemplified.

The epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent for an epoxy resin of the present invention as essential components, but there is no special designation for this epoxy resin. Epoxy resin can be used. Examples of the epoxy resin used include bisphenol F and bisphenol A.
D, biphenol, tetramethylbiphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) propane, terpene diphenol, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcinol, methylresorcinol, bisphenol S, thiodiphenol, Dihydroxy diphenyl ether, dihydroxy naphthalene, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin,
Terpene phenolic resin, phenol aralkyl resin,
Various phenols such as naphthol novolak resins, various phenol compounds such as polyhydric phenol resins obtained by a condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal; Various modified resins such as epoxy resin, diaminodiphenylmethane, xylenediamine, etc., produced from a modified phenol resin obtained by polycondensation of heavy oils or pitches, formaldehyde polymer and phenol in the presence of an acid catalyst, and epihalohydrin Epoxy resins produced from an amine compound and epihalohydrin, epoxy resins produced from epihalohydrin with various carboxylic acids such as methylhexahydrophthalic acid and dimer acid, and the like are included.

In the epoxy resin composition for encapsulating a semiconductor of the present invention, biphenol, tetramethylbiphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) propane, terpene diphenol and cresol are used as epoxy resins. It is preferable to use an epoxy resin produced from at least one phenol compound selected from novolak resins and epihalohydrin. The amount of the epoxy resin curing agent used is such that the amount of the group reacting with the epoxy in the entire curing agent is 0.5-2.
The amount to be 0 mol is preferable, and more preferably 0.7 to
1.2 mol.

Various additives can be added to the epoxy resin composition of the present invention, similarly to other general epoxy resin compositions. Examples of the various additives include a curing accelerator, an inorganic filler, a coupling agent, a flame retardant, a plasticizer, a reactive diluent, a pigment, and the like, and can be appropriately added as needed. 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 tetra. Phosphonium salts such as phenylborate and methyltricyanoethylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-
2-methylimidazole, 2,4-dicyano-6- [2
Imidazoles such as -methylimidazolyl- (1)]-ethyl-S-triazine and 2,4-dicyano-6- [2-undecylimidazolyl- (1)]-ethyl-S-triazine; 1-cyanoethyl-2 Imidazolium salts such as undecyl imidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetraphenylborate, 2-ethyl-1,4-dimethylimidazolium tetraphenylborate, Amines such as 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, tetramethylbutylguanidine, N-methylpiperazine, 2-dimethylamino-1-pyrroline, and ammonium salts such as triethylammonium tetraphenylborate , 1,5-diazabi Black (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5
Examples include diazabicyclo compounds such as nonene and 1,4-diazabicyclo (2,2,2) -octane, and tetraphenylborate, phenol salts, phenol novolak salts, and 2-ethylhexanoate salts of the diazabicyclo compounds. Among these compounds that serve as curing accelerators, phosphine compounds, imidazole compounds, diazabicyclo compounds, and salts thereof are preferable. Examples of the filler include fused silica, crystalline silica, glass powder, alumina, calcium carbonate and the like. In addition, the epoxy resin composition for semiconductor encapsulation of the present invention contains, as an inorganic filler, a crushable and / or spherical, fused and / or crystalline silica powder filler in an amount of 80 to 95% by weight of the whole composition.
It is preferable to mix them. Examples of the flame retardant include halogenated flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, phosphorus-based flame retardants such as phosphates and phosphines, and nitrogen-based flame retardants such as melamine derivatives. Flame retardants and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide. However, recently, from the viewpoint of deterioration of characteristics and environmental protection,
It is desired not to incorporate the above flame retardant. Since the cured product of the epoxy resin composition for semiconductor encapsulation of the present invention has excellent flame retardancy, it is not necessary to add these flame retardants or the amount thereof can be reduced. The epoxy resin curing agent of the present invention has a low melt viscosity, is excellent in low hygroscopicity and low stress, and gives a cured product excellent in moldability. Furthermore, the epoxy resin composition of the present invention using the curing agent has a low melt viscosity, and is excellent in low hygroscopicity and low stress, and gives a cured product excellent in moldability. It can be advantageously used for applications such as sealing, lamination, and painting, and is particularly useful for semiconductor encapsulation.

[0036]

EXAMPLES Examples of the production of each component of the epoxy resin curing agent of the present invention, examples of the epoxy resin curing agent of the present invention, examples of the epoxy resin composition of the present invention, and comparative examples are given below. .

(A) Production Examples 1 to 4 of phenol resin having a less polar hydrocarbon group between phenol nuclei Phenol and phenol were placed in a three-neck flask having a capacity of 5 liters equipped with a thermometer, a stirrer, and a condenser. Cyclohexanone, 4,4'-dimethoxymethylbiphenyl, 2,6-
Dihydroxymethylnaphthalene or limonene and paratoluenesulfonic acid or silicotungstic acid were charged in the amounts shown in Table 1, and the reaction was carried out at 120 ° C. for 10 hours. Subsequently, the reaction was stopped by neutralization with caustic soda, and then unreacted phenol was completely distilled off under reduced pressure to obtain a crude phenol resin. Thereafter, the crude phenol resin was dissolved in methyl isobutyl ketone, washed with water to remove the reaction catalyst and the like, and methyl isobutyl ketone was removed under reduced pressure to obtain a desired phenol resin. The hydroxyl group equivalents and softening points of these phenolic resins are shown in Table 1. Production Example 5 A purified phenol resin was obtained from the phenol resin obtained in Production Example 4 by a recrystallization method using toluene as a solvent. Table 1 shows the hydroxyl equivalent and the softening point of the phenol resin.

[0038]

[Table 1]

Examples 1 to 6 of curing agents for epoxy resins (a) As phenol resins having a less polar hydrocarbon group between phenol nuclei, phenol resins of the above Production Examples 1 to 5 and terpene phenol novolak resins, (b) )
As shown in Table 2, the thiodiphenol compound and the general phenol novolak resin as the polyhydric phenol compound having a structure other than the components (c), (a) and (b) were melt-mixed as shown in Table 2 and cured for each epoxy resin. An agent was manufactured.
Table 2 shows the melt viscosities, hydroxyl equivalents and softening points of these epoxy resin curing agents.

[0040]

[Table 2]

(Note) * 1: Japan Epoxy Resin Company, Epicure MP402, hydroxyl equivalent 175 g / eq, softening point 125
C * 2: Gunei Chemical Co., Ltd. Product name REGITOP PSM426
1, hydroxyl equivalent: 103 g / eq, softening point: 85 ° C. Epoxy resin compositions Examples 7 to 12 and Comparative Examples 1 to 3 As shown in Table 3, epoxy resin derived from tetramethylbiphenol as an epoxy resin Epoxy resin derived from biphenol and tetramethylbiphenol, or epoxy resin derived from ortho-cresol novolak resin, curing agent for each epoxy resin produced in Examples 1 to 6 as curing agent for epoxy resin, general phenol Novolak resin, phenolic resin of Production Example 2, or phenolic resin of Production Example 6, epoxy resin derived from tetrabromobisphenol A as a brominated epoxy resin, silica powder as an inorganic filler, and triphenylphosphine as a curing accelerator , And antimony trioxide as a flame retardant aid Epoxysilane as the coupling agent, using carnauba wax, respectively as a release agent, were blended with each epoxy resin composition. Next, each compound was melt-kneaded at a temperature of 70 to 120 ° C. for 5 minutes using a mixing roll. Each of the obtained molten mixtures was taken out into a thin plate, cooled, and then pulverized to obtain each molding material. Each of these molding materials was molded by a transfer molding machine at a mold temperature of 175 ° C and a molding time of 180 seconds to obtain each test piece, which was post-cured at 180 ° C for 8 hours. In addition, the spiral flow to examine the fluidity of each molding material, the hardness at the time of demolding heat to examine the moldability of each molding material, were also measured, and the moisture absorption of each test specimen after post cure,
Table 3 shows the results of the tests on the elastic modulus and the flame retardancy. Further, Table 3 shows the results of a test on the solder crack resistance of the simulated semiconductor device sealed with each molding material. Thereby, each of the molding materials of Examples 7 to 12 has moldability (high hardness during demolding heat), inductivity (that is, high spiral flow), and moisture resistance (that is, compared to the molding materials of Comparative Examples 1 to 3). It was excellent in balance between low hygroscopicity) and low stress (that is, low elastic modulus), and also excellent in solder crack resistance. Examples 7 to 12
Each molding material contained no harmful halogen-based flame retardant and was excellent in flame retardancy.

[0042]

[Table 3]

(Note) The mixing ratio is part by weight. * 1: A; Cresol novolak type epoxy resin (Epicoat 180S6, trade name of Japan Epoxy Resin Co., Ltd.)
2, epoxy equivalent: 210 (g / eq.)) * 2: B: tetramethylbiphenol type epoxy resin (trade name, Epikote XY4, manufactured by Japan Epoxy Resin Co., Ltd.)
000H, epoxy equivalent: 192 (g / eq.)) * 3: C: mixture of biphenol-type epoxy resin and tetramethylbiphenol-type epoxy resin (Japan Epoxy Resin Co., Ltd. Epicoat YL6121H, epoxy equivalent: 171 (g / eq.)) )) * 4: D; phenol aralkyl resin (Mitsui Toatsu Co., Ltd., trade name XL255-3L, hydroxyl equivalent: 170 (g / e)
q. ), Softening point: 71 ° C.) * 5: E: phenol novolak resin (trade name, Gunei Chemical Co., Ltd., Regitop PSM4261, hydroxyl equivalent: 103)
(G / eq.), Softening point: 85 ° C) * 6: Brominated epoxy resin (Japan Epoxy Resin Co., Ltd. Epicoat 5050, epoxy equivalent: 385)
(G / eq.), Bromine content: 48%) * 7: Spherical fused silica powder (trade name of Nippon Aerosil Co., Ltd.)
ELSIL BF100) * 8: Epoxysilane (brand name KB, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 9: Measured by Shore D * 10: Moisture absorption after 85 hours at 85 ° C and 85% RH for 300 hours * 11: Solder at 80 ° C and 16 QFPs at 85 ° C and 85% RH for 300 hours and then 260 ° C solder It was immersed in a bath for 10 seconds to determine the number of cracks. * 12: UL94

[0044]

The curing agent for epoxy resin and the epoxy resin composition of the present invention have a low melt viscosity, a low moisture absorption and a low stress, and provide a cured product having excellent moldability. It can be advantageously used for the use of the epoxy resin composition for stopping.

Continued on front page F-term (reference) 4J002 CC032 CC042 CD041 CD051 CD061 CD071 EJ038 EJ046 EJ048 EN026 EV006 EV047 FD142 FD146 FD147 FD148 GJ00 GQ00 4J036 AA02 AD07 AD08 AE05 AE07 AF06 DA01 DA06 DB06 EB01 EB07 DD07 EC01

Claims (8)

[Claims] (A) 30 to 99 parts by weight of a phenol resin having a less polar hydrocarbon group between phenol nuclei represented by the following general formula (I): (Wherein R ¹ 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; Are the same or different and are each a divalent hydrocarbon group having 1 to 20 carbon atoms to which a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom may be bonded, and one molecule At least one of Z is a nitrogen atom,
An oxygen atom, a phosphorus atom or a divalent hydrocarbon group having 5 to 20 carbon atoms to which a sulfur atom may be bonded, n is a number of 0 to 8 on average, and p is the same as each other And may be different and are an integer of 0 to 3. (B) 1 to 70 parts by weight of a thiodiphenol compound represented by the following general formula (II): (Wherein R ² may be the same or different from each other, and is an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group or an alkoxy group, and q May be the same or different and are integers of 0 to 3.) (c) An epoxy comprising 0 to 100 parts by weight of a polyhydric phenol compound having a structure other than the component (a) and the component (b) Curing agent for resin. 2. (a) As a phenol resin having a less polar hydrocarbon group between phenol nuclei, in formula (I), at least one Z in one molecule has the following general formula (III) or structural formula 2. The method according to claim 1, wherein at least one phenol resin having a skeleton of (1) to (3) is selected from phenol resins.
The curing agent for epoxy resins described in the above. General formula (III) (Wherein R ³ is an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group or an alkoxy group, and the total number of carbon atoms of a plurality of R ³ is 1
And r is an integer of 0-10. ) Structural formula (1) Structural formula (2) Structural formula (3) (3) As the thiodiphenol compound,
Bis (4-hydroxyphenyl) sulfide, bis (4
3. The method according to claim 1, wherein at least one kind of thiodiphenol selected from -hydroxy-3-methylphenyl) sulfide and bis (4-hydroxy-3,5-dimethylphenyl) sulfide is used. The described curing agents for epoxy resins. 4. The curing agent for an epoxy resin according to claim 1, wherein (a) a phenol resin having a less polar hydrocarbon group between phenol nuclei is compounded in an amount of 45 to 90. (B) 10 to 55 parts by weight of the thiodiphenol compound, and (c) 0 to 10 parts by weight of the polyhydric phenol compound having a structure other than the components (a) and (b).
A curing agent for an epoxy resin, in an amount of 100 parts by weight. 5. An epoxy resin, and claims 1 to 4.
An epoxy resin composition comprising the curing agent for epoxy resin described in any one of the above as an essential component. 6. Biphenol, tetramethylbiphenol, bis (4-hydroxyphenyl) methane, bis (4
An epoxy resin produced from at least one phenol compound selected from -hydroxyphenyl) propane, terpene phenol and cresol novolak resin, and epihalohydrin, and the epoxy resin according to any one of claims 1 to 4. Epoxy resin composition for semiconductor encapsulation comprising a curing agent as an essential component. 7. An epoxy resin, the epoxy resin curing agent according to claim 1, and a crushed and / or spherical, fused and / or crystalline silica powder as an inorganic filler. An epoxy resin composition for semiconductor encapsulation formulated as an essential component in an amount of 80 to 95% by weight of the composition. 8. The amount of the epoxy resin curing agent to be used is such that 0.5 to 2.0 mol of groups reacting with the epoxy groups in all curing agents are used per 1 mol of epoxy groups in all epoxy resin components. The epoxy resin composition for semiconductor encapsulation according to any one of claims 6 to 7, wherein the amount is an amount.