JPH11322901A - Epoxy resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition to give a more superior crack- resistant package than conventional hardened substances especially in use as a semiconductor-sealing material with newly realized low hygroscopicity. SOLUTION: An epoxy resin composition comprises: an epoxy compound having more than two functional groups or the epoxy resin; a compound containing an ester more than two functional groups wherein 10 mol.%-100 mol.% of a hydroxyl group is esterified with an aliphatic acyl group or an ester-containing resin as a hardener; and a phosphine oxide derivative as an essential component of an accelerator represented by the formula (wherein R1 -R6 show each a hydrogen atom, an alkyl group, an aryl group and/or an aralkyl group which may be either all the same or different from each other).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device in which a semiconductor integrated circuit is encapsulated with an epoxy resin, and more particularly to an epoxy resin composition which imparts various physical properties sufficient for the purpose, particularly as a curing agent. The present invention relates to an epoxy resin composition obtained by using a compound or a resin having an ester group and combining a catalyst for rapidly reacting the ester group with an epoxy group, and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, integrated circuits (ICs) and large-scale integrated circuits (LSIs) are protected from dust, dust, heat, moisture, light or malfunction due to light in an external atmosphere by a sealing material for protecting them. Has been put to practical use. As this sealing material,
In recent years, the use of metal or ceramics has shifted to resin encapsulation, and epoxy resin encapsulation is now the mainstream. In particular, epoxy resin compositions using a phenol resin as a curing agent are often used in view of a balance between cost and physical properties. Encapsulants using these epoxy resin compositions are required to improve not only mechanical properties but also the following problems.

[0003] That is, the subject is to absorb moisture in the outside air, so that when exposed to soldering conditions, it is exposed to high temperatures and causes cracks due to explosive vaporization of moisture. Due to the partial occurrence of epoxy homopolymerization, the hydroxyl groups of the phenolic resin become excessive, resulting in inferior moisture resistance and electric characteristics.In addition to the original epoxy-phenolic resin network, the epoxy homopolymerized portion and the excess phenolic resin portion , The mechanical properties are degraded by the presence of, and corrosion of metal parts of the semiconductor and electric leakage occur due to mixing of free ions, particularly halogen ions. Of these, ionic impurities are particularly problems of purification and purity of the epoxy resin. However, it is possible to sufficiently bring out the original physical properties of the epoxy resin composition by modifying the resin and suppressing the side reaction.

However, as for the moisture absorption of the resin, as long as the curing reaction is caused by the reaction between the epoxy group and the hydroxyl group, it is a reaction that always generates a hydroxyl group as represented by the following reaction formula (II) (Formula 2). However, the hydrophilicity increases due to the hydroxyl group, and there is a limit in reducing the overall moisture absorption even if the basic skeleton is made hydrophobic.

[0005]

Embedded image (In the formula, A represents an epoxy residue, and B represents a phenol residue.)

As one method for solving this problem, use of a reaction between an epoxy group and an ester group as disclosed in Japanese Patent Application Laid-Open No. 62-53327 filed by Nishikubo et al. Can be considered. The publication discloses quaternary onium salts and crown ether complexes as preferable catalysts, and further describes the same paper (Synthetic Organic Chemistry, Vol. 49, No. 3, pp. 218-233 (1)).
991), the addition reaction of an epoxy compound with an ester and its application to polymer synthesis), specifically, the yield when each catalyst is used as a unit reaction is shown.
According to the report, the highest value is 91% of tetrabutylammonium chloride, but the yield is generally low. If these quaternary onium salts and crown ether complexes remain contained in the resin used as the encapsulant for the semiconductor integrated circuit, they not only cause undesirable results such as an electrical short circuit, but also cause contact with them. Needless to say, it also causes corrosion of metal parts, which is a serious defect as a product.

On the other hand, in a general addition reaction between an epoxy resin and a phenol resin, phosphines such as trialkylphosphines and triarylphosphines, imidazoles, tertiary amines and the like are used as catalysts. For immobilization, imidazoles and phosphines are often used. Of these, imidazoles have a reaction activity, but are liable to cause the epoxy homopolymerization which is a side reaction described above, and the above-mentioned problem is large. On the other hand, phosphines do not have these problems, but have a low curing rate. When imidazoles are used as a catalyst in epoxy / ester curing reactions, according to the above-mentioned literature by Nishikubo et al., The reaction yield of an addition reaction of an ester group to an epoxy group is about 50%, and the other is a single epoxy resin. Considering that it is a side reaction such as polymerization, it is not a catalyst that can obtain a sufficient cured product.

[0008] Further, in the follow-up test of the present inventors, when these imidazoles and phosphines are used as a curing catalyst, the ester by the aliphatic acyl group in the present invention does not substantially cause a curing reaction of the epoxy resin. (See the comparative example described later). Specifically, in the range of 150 to 200 ° C., which is the temperature usually used for curing, 10
This is a situation in which the resin composition does not gel for more than a minute and actually flows out before a cured product is obtained.

Further, the epoxy resin is cured with an ester,
A method has been proposed in which 10 to 90% of a phenol resin is esterified and used as a curing agent for use as a sealing material for a semiconductor integrated circuit (Japanese Patent Application Laid-Open No. 9-235451).
In this method, in producing an ester resin, a phenolic hydroxyl group of a phenol resin as a raw material is partially left to form a crosslinked portion by an easily reactable phenol portion at an early stage of curing, and a later after This is based on the idea that an ester group acts on an epoxy group by curing. However, in this publication, esters based on aliphatic acyl groups do not react with epoxy resins, and are limited to esters based on aromatic acyl groups.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to efficiently convert an ester-containing compound or an ester-containing resin with an aliphatic acyl group into a cured epoxy resin having low moisture absorption and excellent electrical properties. An epoxy resin composition for a semiconductor encapsulant, which is for reacting and having excellent crack resistance and electrical properties obtained thereby,
It is to provide a cured product and a semiconductor device.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by using a phosphine oxide derivative as a curing accelerator, and have completed the present invention. Was.

That is, the present invention relates to (1) (A) an epoxy compound or epoxy resin having two or more functional groups;
In an epoxy resin composition containing a bifunctional or more functional ester-containing compound or an ester-containing resin in which 10 mol% to 100 mol% of hydroxyl groups are esterified by an aliphatic acyl group as a curing agent, a general formula ( I) An epoxy resin composition comprising the phosphine oxide derivative represented by the chemical formula (3) as an essential component.

[0013]

Embedded image (Wherein, R _{1 to} R ₆ represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a carbon atom having _{6 to 1} carbon atoms)
0 represents an aryl group or an aralkyl group, which may be the same or different. )

(2) The epoxy resin according to (1), wherein (C) an organic and / or inorganic filler is contained in an amount of 100 parts by weight or more and 1900 parts by weight or less based on 100 parts by weight of (A + B). A resin composition, (3) a cured epoxy resin obtained by thermally curing the epoxy resin composition according to (1) or (2), (4) an epoxy resin according to (1) or (2). The present invention relates to a semiconductor device obtained by sealing a semiconductor integrated circuit using a resin composition.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin composition of the present invention comprises:
(A) an epoxy compound or epoxy resin having two or more functional groups, and (B) 10 mol% to 100 mol% of a hydroxyl group as a curing agent.
In an epoxy resin composition containing a bifunctional or more functional ester-containing compound or an ester-containing resin in which mol% is esterified by an aliphatic acyl group, the phosphine oxide derivative represented by the general formula (I) is used as a curing accelerator. An epoxy resin composition characterized by being an essential component.

The epoxy resin composition of the present invention using the phosphine oxide derivative represented by the general formula (I) as a curing accelerator as an essential component can be prepared by using a conventional imidazole or phosphine as a curing accelerator. Compared to,
Solving the above-mentioned problems and further, quickly reacting an ester group and an epoxy group with an aliphatic acyl group to give a cured product having high mechanical properties, particularly excellent flexibility, and excellent crack resistance and electrical properties. Were found for the first time by the present inventors. Furthermore, the present inventors have found that a resin composition obtained by adding an organic and / or inorganic filler to this resin composition is extremely excellent as a sealing material for a semiconductor integrated circuit.

[0017] To add further, the aforementioned Japanese Patent Laid-Open No.
In 235451, when a conventional catalyst for curing an epoxy resin is used, an ester based on an aliphatic acyl group has a very slow reaction with an epoxy group. Therefore, the ester used is limited to an ester based on an aromatic acyl group. However, in the present invention, the phosphine oxide derivative described above was found to sufficiently practically cure the reaction between the ester and the epoxy group by the aliphatic acyl group, and the present invention was achieved.

In the epoxy resin composition of the present invention,
As the bifunctional or higher functional epoxy compound or epoxy resin (hereinafter referred to as epoxy resin) as the component (A), any compound having two or more epoxy groups in one molecule can be used. Specifically, it has an epoxy group obtained by oxidation of olefins, glycidyl etherification of hydroxyl groups, glycidyl amination of 1,2 primary amines, glycidyl esterification of carboxylic acid, and the like.

The raw materials that can be epoxidized include:
For example, glycols such as ethylene glycol and polyethylene glycol; polyols such as glycerin, erythritol, pentaerythritol and 1,6-hexanediol; dihydroxybenzenes such as catechol, resorcinol and hydroquinone; 2,6-dihydroxynaphthalene; -Bis (4'-hydroxyphenyl) propane (bisphenol A), 2- (3'-hydroxyphenyl) -2- (4 "-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane (bisphenol F), Bis (4-hydroxyphenyl) sulfone (bisphenol S), bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) methylcyclohexane, bis (4-hydroxyphenyl) methylbenzene, 4,4′- Hydroxybiphenyl,
4,4′-dihydroxy-2,2 ′, 6,6′-tetramethylbiphenyl, 4,4′-dihydroxydiphenyl ether, 6,6′-dihydroxy-3,3,3 ′,
3′-tetramethyl-1,1-spirobiindane, 1,
3,3-trimethyl-1- (4-hydroxyphenyl)
Bisphenols such as -1-indan-6-ol; oligophenols such as tetraphenylolethane and naphthol-cresol resol condensate; phenol novolaks; cresol novolaks; Triphenol or higher: hereinafter abbreviated as VR); phenol aralkyls represented by general formula (III) (formula 4); naphthol aralkyls represented by general formula (IV) (formula 5); general formula (V) (Formula 6)
Phenolic resins such as a phenol-dicyclopentadiene copolymer resin (DPR resin) represented by: ethylenediamine, propylenediamine, hexamethylenediamine,
Aniline, 4,4'-diaminophenylmethane (MD
A) 4,4'-diaminodiphenyl ether 4,
4'-diaminodiphenylsulfone, 2,2-bis (4,4'-diaminophenyl) propane, m-xylylenediamine, p-xylylenediamine, 1,2-diaminocyclohexane, general formula (VI) ), Aliphatic and aromatic amines such as aniline aralkyl resin (trade name: Anilix, manufactured by Mitsui Chemicals, Inc.); m-aminophenol, p-aminophenol, 2- (4-aminophenyl)- 2- (4'-hydroxyphenyl) propane, 4-aminophenyl-4-hydroxyphenyl)
Aminophenols such as methane; carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, adipic acid, 1,3-dicarboxycyclohexane; salicylic acid,
Hydroxycarboxylic acids such as 4-hydroxybenzoic acid;
And the like.

[0020]

Embedded image (In the formula, R ₇ represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms or a phenyl group; And represents 3. The number n representing the number of repeating units is from 0 to
100, the average being in the range 0-50. Incidentally, an average of the number n of repeating units of 0 indicates that the compound is a bisphenol compound. )

[0021]

Embedded image (In the formula, n ′ indicating the number of repeating units is in the range of 0 to 50, and the average is in the range of 0 to 15. The average of the number of repeating units n ′ is 0, which means that the compound is a bisnaphthol body. Shown.)

[0022]

Embedded image (In the formula, R ₈ represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms or a phenyl group; To 3. The n 'indicating the number of repeating units is 0.
５０50, the average of which is in the range of 0-15. Incidentally, an average of the number n of repeating units of 0 indicates that the compound is a bisphenol compound. )

[0023]

Embedded image (Wherein, R ₉ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms, n ′ representing the number of repeating units is in the range of 0 to 50, and the average is 0 to 50) It is in the range of 15. In addition, an average of the number n of repeating units is 0 indicates that it is a bisaniline compound.)

The glycidylation of these epoxy raw materials having active hydrogen is performed by a known method. It is most common to react epichlorohydrin in the presence of a hydrogen halide acceptor, but when producing glycidyl esters, metal catalysts, especially TlN
It is also known that a method of reacting carboxylic acid methyl ester with glycidol using a thallium compound such as O ₃ and Tl (OCOCF ₃ ) ₃ as a catalyst is known. Among the epoxy resins used in the present invention, those preferably used as a sealing material for a semiconductor integrated circuit include the above-mentioned dihydroxybenzene, naphthalenes, bisphenols, oligophenols, novolaks or the general formula (III) or the general formula Glycidyl ethers derived from the compounds represented by (IV) and the general formula (V).

In the epoxy resin composition of the present invention,
(B) The curing agent is obtained by esterifying a compound having two or more hydroxyl groups in one molecule with an aliphatic acyl group in a range of 10 mol% to 100 mol%. And those having a hydroxyl group are esterified. In the present invention, the range of esterification of the esterified product used as a curing agent is 10 mol% to 100 mol%, preferably 50 mol% to 100 mol%, more preferably 80 mol% to 100 mol%. .

As the esterification method, a known method is used, and the specific method is as follows. That is, the esterifying agent used when esterifying the above-mentioned hydroxyl group may be any of an organic carboxylic anhydride, an organic carboxylic halide, and an organic carboxylic acid. What is necessary is just to select suitably according to the characteristic of the esterifying agent according to the carbon number of the ester to be induced. Specific examples of the esterifying agent include acetic anhydride, acetyl chloride, acetic acid, propionic anhydride, propionic chloride, propionic bromide, propionic acid, butyric anhydride, butyric chloride, butyric acid, valeric anhydride, and valeric chloride. Valeric acid bromide, valeric acid, pivalic acid chloride, pivalic acid, phenylacetic acid, phenylacetic acid chloride, 2-phenylpropionic acid, 3-phenylpropionic acid, o-tolylacetic acid, m-tolylacetic acid, p-tolylacetic acid, cumene Acids and the like can be mentioned. These esterifying agents can be used alone or in combination of two or more.

The amount used is 10 mol% based on the hydroxyl groups.
The upper limit is not particularly limited, and if the esterification is sufficiently advanced by using the excess, the excess esterifying agent may be removed after the completion of the reaction. From the viewpoint of cost and the like, the molar amount is 10 times or less, preferably 5 times or less, more preferably 3 times or less with respect to the hydroxyl group.
It is preferably at most twice the molar amount.

The specific reaction varies depending on the type of the esterifying agent, but for each case, a generally used reaction may be used for the organic carboxylic anhydride.
That is, after reacting an arbitrary amount of organic carboxylic anhydride to be esterified with respect to the hydroxyl group, the by-produced organic carboxylic acid, excess organic carboxylic anhydride is subjected to atmospheric distillation,
The desired ester compound is obtained by removal by any method such as vacuum distillation, washing with water, washing with a weak base such as carbonate, or a combination thereof. When partial esterification is performed, an esterified product obtained by esterifying an arbitrary amount with respect to the hydroxyl group, that is, 10 mol% or more in the resin composition of the present invention is used, so that 10 mol% or more of the organic carboxylic acid anhydride is used. In the case of complete esterification using a product, the upper limit thereof is not particularly limited as long as it is also used as a solvent in an equimolar amount or more with respect to the hydroxyl group. It may be used in a molar amount of not more than twice. This amount is the same in the case of a reaction using an organic carboxylic acid described later.

In general, the esterification reaction is often carried out in the presence of an organic base which is inert to the reaction of pyridine, piperidine, triethylamine or the like.
When the epoxy resin composition of the present invention is used in the electric and electronic fields such as a sealing material for a semiconductor integrated circuit, it is necessary to prevent the nitrogen-containing organic base from remaining. For this reason, it is desirable to finally introduce a washing step. However, since the reaction proceeds sufficiently even without using these organic bases, it is most desirable not to use an organic base.

The reaction temperature ranges from 60 ° C. to 200 ° C., preferably from 80 ° C. to 180 ° C., particularly preferably 100 ° C.
It is desirable to be in the range of ℃ to 160 ℃. The reaction time greatly depends on the type of the reaction substrate and the reaction temperature, but is about 1 hour to
It is within a range of 25 hours, and it is practically desirable to determine the end point while tracking the disappearance of the esterifying agent, the disappearance of the hydroxyl group, and the like by high performance liquid chromatography, gas chromatography, or the like. The solvent in the reaction may or may not be used. When the substance having a hydroxyl group as a raw material is sufficiently melted at the reaction temperature and the esterifying agent is liquid,
In addition, when melting at a reaction temperature or dissolving in a resin does not hinder the reaction, the reaction may be performed without a solvent.

If a solvent is required, any solvent inert to the reaction can be used. Examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, and diphenyl ether; N, N-dimethylformamide;
Aprotic polar solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethyl-2-imidazolidinone, dimethylsulfoxide and sulfolane; tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like Ethers, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in any combination.

The reaction is carried out at normal pressure, under pressure (in an autoclave),
Any of reduced pressure may be used, and the atmosphere of the reaction system is in air,
Any of inert gases such as nitrogen, argon and helium may be used, but preferably under a nitrogen atmosphere.

Next, the reaction when an organic carboxylic acid halide is used as the esterifying agent will be described.
Also in this case, a generally used technique can be used. That is, any amount of the organic carboxylic acid halide to be esterified with the hydroxyl group may be reacted. In this case, the by-product hydrogen halide is trapped in the system in the presence of a required amount of a base inert to the reaction of pyridine, piperazine, triethylamine, etc. However, it is conceivable that trapping is carried out using water or an alkali trap installed outside the reaction system.However, for the reasons described above, hydrogen halide gas is used during the reaction to avoid contamination with nitrogen-containing compounds and ionic compounds. A method in which the compound is rapidly released from the system is preferred.
At this time, it is more preferable to carry out the reaction under a stream of a gas which is also inert to the reaction.

When the partial esterification is carried out, the amount of the organic carboxylic acid halide to be used is an arbitrary amount with respect to the hydroxyl group, that is, in the resin composition of the present invention, an esterified product having at least 10 mol% esterified is used. Since 10 mol% or more of an organic carboxylic acid halide is used and an ester is completely esterified, an equimolar amount or a small excess with respect to the hydroxyl group may be used, and the use of a large excess is not particularly limited. Considering the economic efficiency, the volumetric efficiency of the reaction, and the complexity of the processing steps after the reaction, 10
Mol times or less, preferably 5 mols, more preferably 3 mols.
It may be used in the range of twice the mole. The reaction temperature, the use of a solvent in the reaction, and the form of the reaction may be in accordance with the case of the above-mentioned organic carboxylic anhydride.

In the case where an organic carboxylic acid is used as the esterifying agent, an organic carboxylic acid anhydride may be used, but an acid catalyst is required for the reaction. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and polyphosphoric acid; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, dimethylsulfonic acid, and diethylsulfonic acid; and trifluoromethane. Examples thereof include a super strong acid represented by sulfonic acid, an acidic ion exchange resin represented by alkane sulfonic acid type, and a super strong acid ion exchange resin represented by perfluoroalkane sulfonic acid type.

The amount of the superacid is 0.00001 to 5% by weight, preferably 0.0% to the weight of the raw material.
001 to 1% by weight, more preferably 0.001 to 0.1
In the range of 1 to 100% by weight, preferably 10 to 50% by weight in the case of ion exchange resins, and 0.01 to 10% by weight, preferably 0.1 to 5% by weight in other cases. Range. If the reaction time falls below this range, the reaction rate decreases, and the reaction is not completed in a practical reaction time. On the other hand, if it is larger than this range, the side reaction cannot be ignored, or it leads to an increase in cost including the complicated process of removing the catalyst.

The reaction has been described above with respect to the three types of esterifying agents. In any case, when it is necessary to obtain an esterified product having a higher degree of purification, a water washing step may be introduced after the completion of the reaction. Good. In that case toluene,
Washing may be performed using a water-washable solvent such as xylene, methyl isobutyl ketone, methyl ethyl ketone, or ethyl acetate until the washing wastewater is free of acidic components and ionic impurities.

The esterified product having an esterification rate of 10 to 100 mol% obtained as described above can be used as a curing agent for an epoxy resin in the same manner as a conventional phenol resin. That is, by using a bifunctional or more epoxy resin as a curing agent, it can be used as a thermosetting resin in the same field as a conventional epoxy-phenol cured product.

The most significant features of the cured product of the present invention are that, as compared with the conventional epoxy-phenol cured product, the moisture absorption is greatly reduced and the effect of having an ester group is obtained.
It is very flexible. Furthermore, since a cured product is formed in a form in which the hydroxyl group is esterified with respect to the epoxy-phenol cured product in which a hydroxyl group is generated in the structure after curing, the electric characteristics are also improved.

Conventionally, phenolic resins have been frequently used as curing agents, particularly in the field of sealing materials, but the improvement in performance has a great correlation with the decrease in moisture absorption. When the water contained in the resin is suddenly exposed to a high temperature of 200 ° C. or more as in the case of IR reflow, it is vaporized at once, generating a so-called steam explosive force, which causes cracks and various physical properties. This has an adverse effect, and in the worst case, it may lead to separation between the sealing material and the chip. The present invention contributes to solving this problem in terms of both low moisture absorption and crack resistance from the above-described features.

The mixing ratio of the epoxy resin to the curing agent is such that the ester group or the total of the ester group and the hydroxyl group is 1 mole equivalent of the epoxy group, that is, 0.5 to 1.5 mole equivalent of the active group to the epoxy group is preferable. Is 0.7 ~
1.3 molar equivalents. It is more preferable to adjust the molar ratio to obtain the optimum physical properties of the cured product before use. Even if the epoxy resin and the curing agent are used alone one by one,
A plurality may be used in combination.

The phosphine oxide derivative represented by the general formula (I) used as an essential component of the curing accelerator in the present invention will be described. In the general formula (I), the substituents R _{1 to} R ₆ may be the same or different, and each may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, And aryl groups or aralkyl groups of the formulas 6 to 10.

Specific examples include, for example, a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n
-Butyl group, sec-butyl group, tert-butyl group,
1-pentyl group, 2-pentyl group, 3-pentyl group, 2
-Methyl-1-butyl group, isopentyl group, tert-
Pentyl group, 3-methyl-2-butyl group, neopentyl group, n-hexyl group, 4-methyl-2-pentyl group, cyclopentyl group, cyclohexyl group, 1-heptyl group,
3-heptyl group, 1-octyl group, 2-octyl group, 2
Linear, branched or cyclic alkyl groups such as -ethyl-1-hexyl group, nonyl group or decyl group; aryl groups such as phenyl group; toluyl group, benzyl group, 1-phenylethyl group or 2-phenylethyl group; Aralkyl groups. Of these, preferred are methyl, ethyl, n-propyl, isopropyl, n-
An alkyl group having 1 to 6 carbon atoms such as a butyl group or a cyclohexyl group, more preferably a methyl group or an ethyl group.

The phosphine oxide derivative is GNKoian
etal.Journal of Generral Chemistry of The USSR, 5
As described in 5, 1453 (1985), it can be synthesized by reacting phosphorus oxytrichloride with three molecules of iminotrisamino (unsubstituted, monosubstituted, disubstituted) phosphorane. Further, if purification is necessary, it can be purified by a commonly used method such as column chromatography, distillation and recrystallization. The phosphine oxide derivative thus obtained is usually a solid.

In the epoxy resin composition of the present invention, the amount of the phosphine oxide derivative as a curing accelerator used is as follows:
0.001 to 25% (0. 0%) by weight based on the total epoxy resin composition (resin component: total of epoxy resin and curing agent).
001 to 25 g / 100 g), preferably 0.0
It is used in the range of 1 to 15%, more preferably 0.1 to 5%. When converted to a molar equivalent, 1.5 × 10 ⁻⁶ to 4.
5 × 10 ⁻² mol / 100 g, preferably 1.5 × 10 ⁻⁵
2.5 × 10 ⁻² , more preferably 1.5 × 10 ⁻⁴
It is in the range of 1.0 × 10 ^-2 mol / 100 g.

In the epoxy resin composition of the present invention, a known curing accelerator other than the phosphine oxide derivative, for example, an imidazole such as 2-methylimidazole, a phosphine such as triphenylphosphine, or the like is used as a phosphine. The oxide derivative may be used in the range of 0.5% by weight to 500% by weight (5 times weight). If the amount exceeds 500% by weight, the features of the present invention are lost.

In the epoxy resin composition of the present invention,
If necessary, organic and / or inorganic fillers and other additives may be added as a component (C) to the epoxy resin composition. In particular, when used as a sealing material for semiconductor integrated circuits, organic and / or inorganic fillers are used to improve their mechanical properties and reduce overall cost, and coloring agents such as carbon black are used to prevent malfunctions due to light. It is desirable to use a release agent, a coupling agent, a flame retardant, and the like. The amount of the organic and / or inorganic filler used is in the range of 100 parts by weight or more and 1900 parts by weight or less based on 100 parts by weight of (A + B).
From the viewpoint of mechanical strength, it is preferably at least 250 parts by weight, more preferably at least 550 parts by weight. Organic and / or inorganic fillers used include, for example, silica,
Examples thereof include powders such as alumina, silicon nitride, silicon carbide, talc, calcium silicate, calcium carbonate, mica, clay, and titanium white; and fibrous bodies such as glass fiber, carbon fiber, and aramid fiber. Among these, crystalline silica and / or fused silica are preferable for use as a sealing material. Further, in consideration of fluidity during molding of the resin composition, the shape is spherical or spherical and irregular. Mixtures are desirable.

Further, in the epoxy resin composition of the present invention, it is preferable to mix various additives in consideration of mechanical strength and heat resistance. For example, it is desirable to use a coupling agent in order to improve the adhesiveness between the resin and the inorganic filler, and examples of such a coupling agent include silane, titanate, aluminate, and zircoaluminate. Can be. Among them, a silane coupling agent is preferable, and a silane coupling agent having a functional group that reacts with an epoxy group is most preferable. Such coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2
-Aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltriethoxysilane, 3-glycol Sidoxypropyltrimethoxysilane, 3
-Glycidoxypropylmethyldimethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned, and these can be used alone or in combination of two or more kinds. Can be. It is desirable that these coupling agents are previously adsorbed on the surface of the inorganic filler or fixed by a reaction.

As a method for manufacturing a semiconductor device by sealing a semiconductor integrated circuit using the epoxy resin composition of the present invention, low-pressure transfer molding can be said to be the most common, but other methods such as injection molding , Compression molding, casting, etc., and special techniques such as using a solvent are also possible.

[0050]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Curing Agent Synthesis Example 1 In a glass container equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, a phenol aralkyl resin (trade name:
Millex XLC-4L, hydroxyl equivalent 169 g / eq:
507 g (3 mol) manufactured by Mitsui Chemicals, Inc. were charged, and the internal temperature was raised to 125 ° C. While maintaining the internal temperature at the same temperature, 336.9 g (3.3 mol) of acetic anhydride was added dropwise over 2 hours while stirring. Thereafter, the reaction was carried out for 2 hours while maintaining the temperature at 125 ° C., and the temperature was further raised to 140 ° C. 140-1
After aging at 50 ° C. for 2 hours, excess acetic anhydride and by-produced acetic acid were distilled off under reduced pressure at a maximum of 150 ° C./10 mmHg.

The resin obtained here was treated with toluene 1400
g and washed with hot water at 60 to 70 ° C. until the wastewater becomes neutral.
The residue was distilled under the condition of g to obtain 609 g of a resin in which hydroxyl groups were completely acetylated. The melt viscosity of this resin (according to the ICI cone type melt viscosity type; the same applies hereinafter) is 3.4 poise at 100 ° C., 1.0 poise at 125 ° C., 0.5 poise at 150 ° C., and the hydroxyl equivalent is 3000 g / eq. This was the result (not detectable).

Hardening Agent Synthesis Example 2 A phenol aralkyl resin (trade name: Millex XLC-4L, hydroxyl equivalent: 16) was placed in the same reactor as in Synthesis Example 1.
507 g (3 mol) of 9 g / eq: manufactured by Mitsui Chemicals, Inc. was charged, and the internal temperature was raised to 125 ° C. While maintaining the internal temperature at the same temperature, 245.0 g of acetic anhydride (2.4
Mol) was added dropwise over 2 hours. Thereafter, the reaction was carried out for 2 hours while maintaining the temperature at 125 ° C., and the temperature was further raised to 140 ° C. After aging at 140 to 150 ° C. for 2 hours, by-produced acetic acid was distilled off under reduced pressure at a maximum of 150 ° C./10 mmHg.

The resin obtained here was treated with toluene 1400
g and washed with hot water at 60 to 70 ° C. until the wastewater becomes neutral.
The residue was distilled under the condition of g to obtain 590 g of a resin in which the hydroxyl group was acetylated at 80 mol%. The melt viscosity of the resin (according to the ICI cone type melt viscosity type; the same applies hereinafter) at 125 ° C. was 1.
It was 0.7 poise at 2 poises and 150 ° C., and the hydroxyl equivalent was 880 g / eq.

Hardening Agent Synthesis Example 3 A phenol aralkyl resin (trade name: Millex XLC-4L, hydroxyl equivalent 16
507 g (3 mol) of 9 g / eq: manufactured by Mitsui Chemicals, Inc. was charged, and the internal temperature was raised to 125 ° C. While maintaining the internal temperature at the same temperature, 153.1 g of acetic anhydride (1.5
Mol) was added dropwise over 2 hours. Thereafter, the reaction was carried out for 2 hours while maintaining the temperature at 125 ° C., and the temperature was further raised to 140 ° C. After aging at 140 to 150 ° C. for 2 hours, by-produced acetic acid was distilled off under reduced pressure at a maximum of 150 ° C./10 mmHg.

The resin obtained here was treated with toluene 1400
g and washed with hot water at 60 to 70 ° C. until the wastewater becomes neutral.
The residue was distilled off under the condition of g to obtain 561 g of a resin having a hydroxyl group acetylated at 50 mol%. The melt viscosity of this resin (according to the ICI cone type melt viscosity type; the same applies hereinafter) at 125 ° C.
It was 1.1 poise at 0 poise and 150 ° C., and the hydroxyl equivalent was 359 g / eq.

Hardening Agent Synthesis Example 4 A phenol aralkyl resin (trade name: Millex XLC-4L, hydroxyl equivalent: 16) was placed in the same reactor as in Synthesis Example 1.
507 g (3 mol) of 9 g / eq: manufactured by Mitsui Chemicals, Inc. was charged, and the internal temperature was raised to 125 ° C. The internal temperature was kept at the same temperature, and 23.6 g of acetic acid chloride was added while stirring.
(0.3 mol) was added dropwise over 1 hour. Then 125 ° C
After performing the reaction for 2 hours while maintaining the temperature, the temperature was further raised to 140 ° C.

The reaction system was colored red by the hydrochloric acid produced as a by-product, but after aging at 140 to 150 ° C. for 2 hours, 1
The temperature was raised to 60 ° C., and the pressure was slightly reduced by a water aspirator. The hydrochloric acid by-produced was exhausted from the tip of the reflux cooler to the outside of the system, and was captured as it was by an alkali trap through the introduction pipe. The resin was discharged to obtain 520 g of a resin in which 10 mol% of hydroxyl groups were acetylated. The melt viscosity of this resin (according to the ICI cone type melt viscosity type; the same applies hereinafter) is 2.0 at 125 ° C.
The poise was 1.1 poise at 150 ° C., and the hydroxyl equivalent was 192 g / eq.

Example 1 Bisphenol A type diglycidyl ether (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy, epoxy equivalent: 184 g / eq) as an epoxy resin, and the acetylated phenol aralkyl resin (ester) of Synthesis Example 1 as a curing agent (Equivalent 211 g / eq = calculated value) One gram equivalent was sufficiently melt-kneaded at 80 ° C. to obtain a uniform resin mixture. In this resin mixture, R _{1 to} R ₆ in the general formula (I) are used.
Is a phosphine oxide derivative (P
ZO) was added and kneaded at 50 ° C. for 1 minute to obtain a resin composition.

10 g of this resin composition was taken and 2 cm × 5
cm × 0.7mm, 150 ℃ → 185 ℃ /
After obtaining a cured product under the conditions of 5 min, 185 ° C./5 min, and 150 kg / cm ² , after-curing is performed under the conditions of 185 ° C./8 Hr (nitrogen atmosphere) to mold a resin plate that has been sufficiently cured. did. Using this resin plate, a simple crack test was performed. According to the method, a vertical half was cut with scissors, and the number of generated cracks was visually counted. As a result, no crack occurred.

Further, a filler and other additives were added to the remaining 200 g of the resin composition in the proportions shown in Table 1 (Table 1), and the mixture was heated and kneaded with a roll to obtain a molding material for a sealing material. Obtained. Using a part of the molding material thus obtained, 150 ° C. → 185 ° C./5 min, 185 ° C./5 m
in, after obtaining a cured product under the conditions of 150 kg / cm ² ,
After-curing was performed under the conditions of 185 ° C./8 Hr (nitrogen atmosphere) to sufficiently advance the curing. Each physical property was measured using this cured product. Further, a test semiconductor device was prepared by low-pressure transfer molding using the same molding material, and a crack generation test using a solder bath was performed. The results are shown in Table 1 (Table 1). The gel time of the resin composition before the roll kneading was measured at 150 ° C. (same as below)

Example 2 The epoxy resin in Example 1 was replaced by the following formula (VII):
Tetraphenylolethane type epoxy resin (trade name:
A simple crack test of the resin composition was performed in the same manner as in Example 1 except that E1031S, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 189 g / eq), and it was confirmed that cracks did not occur. Thereafter, in the same manner as above, a molding material for a sealing material was obtained using the remaining resin composition, and physical properties of the cured product and a crack generation test of the test semiconductor device were performed. The results are shown in Table 1 (Table 1).

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Example 3 The epoxy resin in Example 1 was replaced with a naphthol-cresol resole condensation type epoxy resin represented by the following formula (VIII) (Chemical Formula 9) (trade name: EOCN7000, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 204 g / eq) ), A simple crack test of the resin composition was carried out in the same manner as in Example 1, and it was confirmed that no crack was generated. afterwards,
Further, in the same manner, a molding material for a sealing material was obtained using the remaining resin composition, and physical properties of a cured product and a crack generation test of a test semiconductor device were performed. The results are shown in Table 1 (Table 1).

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Example 4 The epoxy resin in Example 1 was replaced by a spirobiindane diphenol type epoxy resin represented by the formula (IX) (Chemical Formula 10) (trade name: SPIDG, manufactured by Mitsui Chemicals, Inc., epoxy equivalent: 233 g / eq) ), A simple crack test of the resin composition was carried out in the same manner as in Example 1, and it was confirmed that no crack was generated. Thereafter, in the same manner as above, a molding material for a sealing material was obtained using the remaining resin composition, and physical properties of the cured product and a crack generation test of the test semiconductor device were performed. The results are shown in Table 1 (Table 1).

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Examples 5 to 8 The curing agent in Examples 1 to 4 was changed to the acetylated phenol aralkyl resin obtained in Synthesis Example 2, and the epoxy group / functional group (hydroxyl group + ester group) = 1/1 mole In the same manner, a simple crack test of the resin composition was performed in the same manner, and it was confirmed that no crack was generated. Thereafter, in the same manner as above, a molding material for a sealing material was obtained using the remaining resin composition, and physical properties of the cured product and a crack generation test of the test semiconductor device were performed. The results are shown in Table 1 (Table 1).

Examples 9 to 12 The curing agent in Examples 1 to 4 was changed to the acetylated phenol aralkyl resin obtained in Synthesis Example 3, and the molar ratio of epoxy group / functional group (hydroxyl group + ester group) was 1/1. In the same manner, a simple crack test of the resin composition was performed in the same manner, and it was confirmed that no crack was generated. Thereafter, in the same manner as above, a molding material for a sealing material was obtained using the remaining resin composition, and physical properties of the cured product and a crack generation test of the test semiconductor device were performed. The results are shown in Table 1 (Table 2).

Examples 13 to 16 The curing agent in Examples 1 to 4 was changed to the acetylated phenol aralkyl resin obtained in Synthesis Example 4, and the epoxy group / functional group (hydroxyl group + ester group) = 1/1 mole was used. In the same manner, a simple crack test of the resin composition was performed in the same manner, and it was confirmed that no crack was generated. Thereafter, in the same manner as above, a molding material for a sealing material was obtained using the remaining resin composition, and physical properties of the cured product and a crack generation test of the test semiconductor device were performed. The results are shown in Table 1 (Table 2).

Comparative Examples 1-4 The phenol aralkyl resin (trade name: Millex XLC) before esterifying the curing agent in Examples 1-4 was used.
-4 L, hydroxyl equivalent 169 g / eq: Mitsui Chemicals, Inc.
) And triphenylphosphine (T
Although PP) was used, the curability was very poor, and the gel time could not be measured and a molded product could not be obtained. Therefore, the amount of triphenylphosphine was increased to 0.015 mol, and the gel time was measured. The results are shown in Table 1 (Table 3). As a result, since the gel time was almost the same as that of the example, a cured product was obtained from the resin composition in the same manner as in the example, and a simple crack test was performed. I was Furthermore, a molding material for a sealing material is obtained,
The cured physical properties and the crack generation test of the test semiconductor device were performed. The results are shown in Table 1 (Table 3).

Comparative Examples 5 to 8 The phenol aralkyl resin (trade name: Millex XLC) before esterifying the curing agent in Examples 1 to 4 was used.
-4 L, hydroxyl equivalent 169 g / eq: Mitsui Chemicals, Inc.
) And the curing accelerator was changed to 2-undecylimidazole (trade name: C11Z, manufactured by Shikoku Fine Chemical Co., Ltd.). However, since the curing property was very poor, the gel time could not be measured and a molded product could not be obtained. The amount of triphenylphosphine was increased to 0.015 mol and the gel time was measured. The results are shown in Table 1 (Table 3). As a result, since the gel time was almost the same as that of the example, a cured product was obtained from the resin composition in the same manner as in the example, and a simple crack test was performed. I was Further, a molding material for a sealing material was obtained, and physical properties of cured products and a crack generation test of a test semiconductor device were performed. The results are shown in Table 1 (Table 3).

Comparative Examples 9 to 12 A resin composition was obtained in the same manner as in Examples 1 to 4 except that triphenylphosphine was used in place of 0.015 mol of triphenylphosphine as a curing accelerator. In order to carry out a crack test, a molded product was obtained, but all flowed before curing, and a molded product could not be obtained. Therefore, the gel time was measured.
In, the test was stopped without gelation in 15 minutes.

COMPARATIVE EXAMPLES 13-16 A resin composition was obtained in the same manner as in Examples 5-8 except that triphenylphosphine was used in place of 0.015 mol of triphenylphosphine. In order to carry out a crack test, a molded product was obtained, but all flowed before curing, and a molded product could not be obtained. Therefore, the gel time was measured.
In, the test was stopped without gelation in 15 minutes.

Comparative Examples 17 to 20 A cured product was obtained from the resin composition in the same manner as in Examples 9 to 12, except that the curing accelerator was changed to 0.015 mol of triphenylphosphine, and a simple crack test was carried out. However, all test pieces were destroyed. Further, a molding material for a sealing material was obtained, and physical properties of cured products and a crack generation test of a test semiconductor device were performed. The results are shown in Table 1 (Table 5).

Comparative Examples 21 to 24 A cured product was obtained from the resin composition in the same manner as in Examples 13 to 16 except that the curing accelerator was changed to 0.015 mol of triphenylphosphine, and a simple crack test was performed. However, all test pieces were destroyed. Further, a molding material for a sealing material was obtained, and physical properties of cured products and a crack generation test of a test semiconductor device were performed. The results are shown in Table 1 (Table 5).

The test methods for various physical properties are as follows.・ Tg (glass transition temperature): TMA needle penetration method (Shimadzu T
Measured by MA-DRW DT-30. -Flexural strength and elastic modulus: according to JIS K-6911. Boiling water absorption: The weight increase after boiling for 2 hours in boiling water at 100 ° C. was measured. * V. P. S test: Test semiconductor device at 85 ° C, 8
After standing in a 5% constant temperature and humidity chamber for 168 hours, immediately
Fluorinert solution at 0 ° C (Sumitomo 3M Co., Ltd., F
C-70), and the number of semiconductors having cracks in the package resin was counted. The test value is shown as a fraction, the numerator is the number of cracked semiconductors, and the denominator is the number of subjects.

The various additives used in the test are as follows. -Inorganic filler: spherical fused silica (Halimic S-CO,
A mixture of 50 parts by weight of Micron Corporation and 50 parts by weight of amorphous fused silica (Hughes Rex RD-8, manufactured by Tatsumori Co., Ltd.). -Silane coupling material: (SZ-6083, manufactured by Toray Dow Corning Silicone Co., Ltd.)

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5] In addition, the value of the additive in a table | surface is a value with respect to 200 g of main agents + hardening | curing agents.

As described above in detail with reference to the examples and the like, the epoxy resin composition using the phosphine oxide derivative of the present invention as an essential curing accelerator and an ester compound as a curing agent is a conventional epoxy resin-phenol. Compared with the cured resin, it is greatly excellent in moisture absorption and excellent in flexibility, and is very advantageous in crack resistance.
For this reason, it can be seen that crack resistance is excellent particularly in a sealing material application of a semiconductor integrated circuit.

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The epoxy resin composition provided by the present invention can be used in industrial fields where epoxy resin compositions have been conventionally used. Epoxy resin-
It provides a package having better crack resistance than a cured phenol resin.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/29 H01L 23/30 R 23/31 (72) Inventor Tadahito No. 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Pref. Inventor: Sanji Takagi, 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Inside Mitsui Chemicals, Inc.

Claims (4)

[Claims] 1. An epoxy compound or epoxy resin (A) having two or more functional groups, and (B) one or more hydroxyl groups as a curing agent.
In an epoxy resin composition containing a bifunctional or more functional ester-containing compound or an ester-containing resin in which 0 mol% to 100 mol% is esterified by an aliphatic acyl group, a general formula (I) An epoxy resin composition comprising the phosphine oxide derivative represented by 1) as an essential component. Embedded image (Wherein R _{1 to} R ₆ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a carbon atom having _{6 to 1} carbon atoms)
0 represents an aryl group or an aralkyl group, which may be the same or different. ) 2. The epoxy resin composition according to claim 1, comprising (C) an organic and / or inorganic filler in an amount of 100 parts by weight or more and 1900 parts by weight or less based on 100 parts by weight of (A + B). 3. An epoxy resin cured product obtained by thermally curing the epoxy resin composition according to claim 1 or 2. 4. A semiconductor device obtained by sealing a semiconductor integrated circuit using the epoxy resin composition according to claim 1.