JPH07247409A - Epoxy resin composition, production of epoxy resin mixture and material for sealing semiconductor - Google Patents

Abstract

PURPOSE:To obtain the subject composition, consisting essentially of a specific epoxy resin and a curing agent, capable of highly filling an inorganic filler therein, having a low water absorptivity and a low linear expansion coefficient, excellent in solder crack resistance and fluidity and readily molded into fine semiconductor chips. CONSTITUTION:This epoxy resin composition consists essentially of (A) an epoxy resin using (i) a polyglycidyl ether of a compound bound through a cyclic aliphatic hydrocarbon group (preferably a bivalent hydrocarbon group based on an unsaturated bond in a molecular skeleton of dicyclopentadiene, limonene or 3a,4,7,7a-tetrahydroindene) as a connecting group to a hydroxyl aromatic compound (preferably phenol or cresol) and (ii) a diglycidyl ether of biphenols (preferably biphenol or 4,4'-hydroxy-3,3',5,5'-tetramethylbiphenyl) in combination and (B) a curing agent (preferably a phenolic curing agent).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition containing a specific epoxy resin and a curing agent as essential components and having an excellent balance of water resistance and heat resistance, as well as moldability and solder resistance during surface mounting. The present invention relates to a semiconductor encapsulating material having excellent crackability and the like.

[0002]

2. Description of the Related Art Recently, science and technology have been rapidly advancing mainly in the electronics industry, and in particular, semiconductor-related technology has been remarkably advancing. In semiconductors, wiring has become finer and chips have been made thinner with the increase in the degree of integration of memories. With the improvement in the degree of integration, the mounting method is also shifting from through-hole mounting to surface mounting.

In an automated surface mounting line, a semiconductor package, which has absorbed moisture during lead wire soldering, undergoes a rapid temperature change, which causes cracks in the resin molding portion, leading to mounting failure, and also an interface between lead wire resins. Deteriorates, and as a result, the moisture resistance decreases.

An epoxy resin is mainly used as a semiconductor encapsulating resin used in the above resin molding part, and an ortho-cresol novolac type epoxy resin (hereinafter simply referred to as "ECN") is generally used as the epoxy resin. (Abbreviated) is used. But with ECN,
The semiconductor package has a strong hygroscopic property, and as a result, there is a problem that cracking is unavoidable during immersion in the solder bath as described above.

Therefore, conventionally, in order to improve the moisture resistance of the semiconductor sealing resin, for example, JP-A-61-293219 has been proposed.
The publication discloses a composition comprising a combination of an epoxidized product of a dicyclopentadiene-modified phenol resin (hereinafter abbreviated as "DCP resin") and a phenol novolac resin.

[0006]

However, the cured product using the epoxidized DCP resin has improved water resistance as compared with ECN, and has a low melt viscosity, but still reaches a satisfactory level. Not not. In particular, in the use of epoxy resin compositions for semiconductor encapsulation materials, in view of the more stringent requirements of recent years, we have achieved higher filling of inorganic fillers and further lower water absorption and lower linear expansion coefficient. In order to achieve this, a lower melt viscosity is required, but the above DC
The epoxidized product of P resin is not yet sufficient, and these requirements have not been satisfied.

The problem to be solved by the present invention is to provide an epoxy resin composition capable of imparting excellent fluidity with a low melt viscosity and a method for producing the same, and further, to enable high filling of an inorganic filler to reduce water absorption. It is an object of the present invention to provide a semiconductor encapsulating material which has a significantly low coefficient of linear expansion and is excellent in fluidity and which is extremely easy to mold into a fine semiconductor chip.

[0008]

Means for Solving the Problems As a result of intensive investigations by the present inventors, polyglycidyl ether of a compound in which a cycloaliphatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a bonding group, and a biphenol are used as an epoxy resin. By using a mixture of diglycidyl ether of, the cured product, it is found that the low melt viscosity and excellent flowability, further, in addition to these components, a semiconductor encapsulating material with an inorganic filler as an essential component The inorganic filler can be highly filled, and has a low coefficient of water absorption and a low coefficient of linear expansion, so that it is excellent in solder crack resistance and excellent in fluidity and can be molded into fine semiconductor chips. They have found that it is extremely easy and have completed the present invention.

That is, the present invention provides (1) an epoxy resin composition comprising an epoxy resin and a cured product as essential components, wherein the epoxy resin is (A) a hydroxyl aromatic compound having a cyclic aliphatic hydrocarbon group as a binding group. A polyglycidyl ether of a compound bound with
(B) an epoxy resin composition characterized by being used in combination with a diglycidyl ether of a biphenol, (2) a compound (a) in which a cyclic aromatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a bonding group, A method for producing an epoxy resin mixture, which comprises reacting a mixture with a biphenol (b) with epihalohydrin, and (3) a compound in which a cyclic aliphatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a bonding group. Of the polyglycidyl ether (A), diglycidyl ether of a biphenol or an alkyl-substituted biphenol (B), a curing agent (C), and an inorganic filler (D) as essential components.

The epoxy resin composition of the present invention comprises, as an epoxy resin, a polyglycidyl ether (hereinafter referred to as "polyglycidyl ether (A)" of a compound in which a cycloaliphatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a bonding group. A) ") and (B) diglycidyl ether of biphenols (hereinafter abbreviated as" diglycidyl ether (B) ") are used together, but the content of polyglycidyl ether (A) is The higher the value is, the more the heat resistance and the water resistance tend to be improved. On the other hand, the higher the content of the diglycidyl ether (B) is, the more the fluidity is improved, and the melt viscosity of the cured product is decreased.

From the point of excellent balance of these, polyglycidyl ether (A) and diglycidyl ether (B)
(A) / (B) = 95/5 to 30/70
Is preferred. Among them, the synergistic effect of each compound makes it possible to obtain a cured product having extremely outstanding heat resistance, water resistance and low melt viscosity (A) / (B) =
It is preferably 90/10 to 50/50.

The above-mentioned polyglycidyl ether (A)
The use method of the diglycidyl ether (B) is not particularly limited, and the individually synthesized ones may be melt-mixed and used, or the cycloaliphatic hydrocarbon group may be bonded. You may use it as an epoxy resin mixture obtained by making epihalohydrin react with the mixture of the compound (a) couple | bonded with the hydroxyl aromatic compound as a group, and a biphenol (b).

The cycloaliphatic hydrocarbon group constituting the polyglycidyl ether (A) used in the present invention is not particularly limited, but those having a cyclohexane ring or a cyclohexene ring in the skeleton thereof are cured products. It is preferable because it has an excellent effect of improving water resistance. Among these, since this effect is particularly remarkable, specifically, dicyclopentadiene, limonene, or 3a, 4, 7, 7
A divalent hydrocarbon group based on an unsaturated bond in the molecular skeleton of a-tetrahydroindene is preferred. These compounds may be used alone or in combination of two or more kinds. Further, among these, a divalent hydrocarbon group based on an unsaturated bond in the molecular skeleton of dicyclopentadiene is preferable because the heat resistance and moisture resistance of the cured product can be further improved.

On the other hand, the hydroxy aromatic compound constituting the polyglycidyl ether (A) is a benzene ring, naphthalene ring or anthracene ring in which one or more hydroxyl groups are substituted, and examples thereof include phenol or bisphenol. A, bisphenols such as bisphenol F, cresols, alkyl-substituted phenols such as p-tert-butylphenol, aromatic hydrocarbons containing two or more phenolic hydroxyl groups such as resorcin, 1-naphthol, 2-naphthol, 1, Examples thereof include naphthols such as 6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene, and hydroxyanthracenes such as 1-hydroxyanthracene and 2-hydroxyanthracene, but are not particularly limited, but polyglycidyl ether is particularly preferable. Melt viscosity is low, specifically from the viewpoint of fluidity is excellent phenol or cresol preferred.

The above polyglycidyl ether (A) is
Although the production method thereof is not particularly limited, for example, a hydroxyl aromatic compound and an alicyclic unsaturated hydrocarbon represented by dicyclopentadiene, limonene and 3a, 4,7,7a-tetrahydroindene are used. A method of obtaining a polyglycidyl ether (A) by polymerizing using a catalyst to obtain a polymer containing a phenolic hydroxyl group (first step), and then subjecting the polymer to glycidyl etherification with epihalohydrin (second step) Can be mentioned.

The catalyst that can be used in the first step is, for example, AlCl ₃ , BF ₃ , ZnCl ₂ , H ₂ S.
Lewis acids such as O ₄ , TiCl ₄ and H ₃ PO ₄ can be mentioned.
As a specific method of the first step, for example, a hydroxyl aromatic compound is heated and melted, a catalyst is added thereto and uniformly dissolved, and then 50 to 180 ° C., preferably 80 to 15 ° C.
Examples thereof include a method of dropping an alicyclic unsaturated hydrocarbon at 0 ° C. The ratio of each raw material to be used is not particularly limited, but the ratio of the catalyst to 0.1 mol to the alicyclic unsaturated hydrocarbon is 0.1.
001 to 0.1 mol, preferably 0.005 to 0.10.
0.1 to 1 mole of hydroxyl aromatic compound
It is 0.0 mol, preferably 0.3 to 4 mol. Also,
In the first step, the hydroxyl aromatic compound may be added to the melt-mixed alicyclic unsaturated hydrocarbon and the catalyst.

Next, in the second step, for example, the polymer obtained in the first step is added to the hydroxyl group of the polymer in an amount of 1 to
Examples include a method of dissolving in 20 equivalents, preferably 2 to 10 times, of epihalohydrin, and reacting in the presence of an alkali metal hydroxide under the temperature condition of 10 to 120 ° C, preferably 50 to 90 ° C. The alkali metal hydroxide is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The amount of the alkali metal hydroxide used is preferably 0.9 to 1.2 equivalents with respect to the hydroxyl group of the polymer obtained in the first step. The epihalohydrin is not particularly limited here, but epichlorohydrin, epibromohydrin,
Examples include epiiodohydrin.

The polyglycidyl ether (A) thus obtained has a melt viscosity of preferably 0.1 to 10 poise at 150 ° C. in view of the fluidity when used as a sealing material and the fillable amount of the filler. Above all, the range of 0.1 to 2.0 poise is preferable from the viewpoint that this effect becomes remarkable. The measuring instrument at this time is an ICI cone-plate viscometer.

In the diglycidyl ether (B) used in the present invention, biphenols are those having one phenolic hydroxyl group in each aromatic nucleus of the biphenyl structure, for example, biphenol, 4,4 '. -Hydroxy-3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-hydroxy-3,3', 5,5'-tetrachlorobiphenyl, 4,4'-hydroxy-3,
3 ', 5,5'- tetrabromobiphenyl etc. are mentioned. As the diglycidyl ether (B), those obtained by reacting these biphenols with epichlorohydrin, specifically, 4,4′-di (2,3-epoxypropoxy) -biphenyl, 4,4′-di (2,3-Epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-di (2,3-epoxypropoxy) -3,3', 5,5'-tetrachloro Biphenyl,
4,4'-di (2,3-epoxypropoxy) -3,
3 ', 5,5'- tetrabromobiphenyl etc. are mentioned. Among these, 4,4'-di (2,3-epoxypropoxy) -biphenyl and 4,4'-di (2,3-epoxypropoxy) are excellent in heat resistance and curability.
-3,3 ', 5,5'-Tetramethylbiphenyl is preferred.

At this time, in view of the effect of obtaining the melt viscosity of the glycidyl ether (B), the melt viscosity at 150 ° C. is preferably 0.2 poise or less. Further, as a commercially available product of diglycidyl ether (B) satisfying this melt viscosity,
For example, "Epicoat YX-" manufactured by Yuka Shell Epoxy Co., Ltd.
4000 "or" YX- "manufactured by Yuka Shell Epoxy Co., Ltd.
4000H "or the like is used.

Since the diglycidyl ether (B) is usually crystalline, it has good workability such as charging and kneading. In a mixed system with polyglycidyl ether (A),
Due to the effect of low melt viscosity at the time of molding, the fluidity is excellent, and defects such as breakage of fine structure packages and gold wires can be reduced.
Further, it is also effective in increasing the amount of the inorganic filler compounded, and it is effective in improving the solder crack resistance during surface mounting by reducing the water absorption rate and also in decreasing the linear expansion coefficient.

In the epoxy resin composition of the present invention, as the epoxy resin used, as described above, the polyglycidyl ether (A) and the diglycidyl ether (B) separately synthesized are melt-mixed and used. However, it can be used as an epoxy resin mixture obtained by the method for producing an epoxy resin mixture of the present invention, which will be described in detail below, after the polyglycidyl ether (A) and the diglycidyl ether (B) are individually synthesized. Compared with the case of melt mixing, the melt viscosity can be made extremely low without degrading other performances, and furthermore, the target epoxy resin mixture can be obtained very easily, and the productivity of the epoxy resin mixture is dramatically improved. It is preferable from the viewpoint of improving

That is, as the diglycidyl ether (B), for example, diglycidyl ether of biphenol is preferable as compared with diglycidyl ether of tetramethylbiphenol because of its excellent fluidity, heat resistance and curability. Diglycidyl ether has a melting point of 1
Since it is as high as about 80 ° C, polyglycidyl ether (A)
In addition to being difficult to mix with, it was difficult to manufacture the diglycidyl ether (B) itself due to crystallization during the epoxidation step due to poor solvent solubility. Therefore, according to the production method of the present invention, an epoxy resin which is a mixture of a diglycidyl ether of biphenol and a polyglycidyl ether (A) can be obtained very easily by avoiding such problems.

Therefore, the epoxy resin composition of the present invention is
A reaction product of a mixture of a compound (a) having a cycloaliphatic hydrocarbon group as a binding group bonded to a hydroxyl aromatic compound and a biphenol (b) and epihalohydrin (hereinafter, simply referred to as "reaction product"). ), And a curing agent are most preferably used as essential components.

The method for producing the epoxy resin mixture of the present invention for obtaining the reaction product will be described in detail below. The method for producing an epoxy resin mixture of the present invention is a compound (a) having a cycloaliphatic hydrocarbon group as a binding group and a hydroxyl aromatic compound bonded thereto (hereinafter, abbreviated as "compound (a)").
And a biphenol (b) are allowed to react with epihalohydrin, and other conditions are not limited. For example, a mixture of (a) and (b) It is dissolved in 1 to 20 times equivalent, preferably 2 to 10 times equivalent of epihalohydrin with respect to the hydroxyl group,
Under the temperature condition of 0 to 120 ° C, preferably 50 to 90 ° C,
A method of reacting in the presence of an alkali metal hydroxide can be mentioned. The alkali metal hydroxide is not particularly limited, but examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide. The amount of the alkali metal hydroxide used is preferably 0.8 to 1.2 equivalents to the hydroxyl group.

Further, as a preferable method for efficiently obtaining the desired epoxy resin mixture in a high yield, the following methods are specifically mentioned. That is, the mixture is dissolved in epichlorohydrin in an amount of 3 to 7 times equivalent to hydroxyl groups, and then 1.0 to 1.0 to the hydroxyl groups at a temperature of 60 to 80 ° C.
1.1 equivalent of 20% sodium hydroxide aqueous solution is added dropwise with stirring over 3 to 5 hours. After completion of the dropping, the mixture is stirred for 1 hour and left to stand for liquid separation to discard the saline solution in the lower layer. afterwards,
Unreacted epichlorohydrin is recovered by distillation. Then, methyl isobutyl ketone or toluene is added and dissolved, and then washed with water to remove inorganic impurities, and the solvent is distilled and recovered to obtain a desired epoxy resin mixture.

Here, the mixing ratio of the compound (a) and the biphenols (b) is not particularly limited, but in order to obtain an appropriate softening point for improving fluidity and workability. In order to improve the balance between heat resistance and water absorption, (a) / (b) = 95/5 to 30/70 in weight ratio.
Is preferred. Further, in order to further improve these characteristics, the range of 90/10 to 50/50 is particularly preferable.

The cyclic aliphatic hydrocarbon group constituting the compound (a) used in the method for producing the epoxy resin mixture of the present invention is not particularly limited, and the cyclic aliphatic hydrocarbon group constituting the above polyglycidyl ether (A) is used. Aliphatic hydrocarbon groups are mentioned.

Specifically, those having a cyclohexane ring or a cyclohexene ring in the skeleton are preferable from the viewpoint of excellent effect of improving the water resistance of the cured product, and among them, this effect is particularly remarkable. 2 based on unsaturated bonds in the molecular skeleton of dicyclopentadiene, limonene, or 3a, 4,7,7a-tetrahydroindene
A valent hydrocarbon group is preferred. These compounds may be used alone or in combination of two or more kinds. Furthermore,
Of these, a divalent hydrocarbon group based on an unsaturated bond in the molecular skeleton of dicyclopentadiene is preferable because the moisture resistance of the cured product is further improved and the heat resistance of the cured product is significantly improved.

Similarly, as the hydroxyaromatic compound constituting the compound (a), any of the hydroxyaromatic compounds constituting the above-mentioned polyglycidyl ether (A) can be mentioned, and specifically, one or two hydroxyl groups can be mentioned. Examples thereof include a benzene ring, a naphthalene ring, or an anthracene ring substituted with one or more. More specifically, for example, phenol or bisphenols such as bisphenol A and bisphenol F, alkyl-substituted phenols such as cresol and p-tert-butylphenol, and aromatic hydrocarbons containing two or more phenolic hydroxyl groups such as resorcin. 1
-Naphthols such as naphthol, 2-naphthol, 1,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; and hydroxyanthracenes such as 1-hydroxyanthracene and 2-hydroxyanthracene, and particularly the melt viscosity of polyglycidyl ether. In particular, phenol or cresol is preferable because of its low viscosity and excellent fluidity.

To obtain the compound (a), the hydroxyaromatic compound, dicyclopentadiene, limonene and 3a, 4,7,7a-tetrahydroindene, as described above in the production of the polyglycidyl ether (A), are used. A method of polymerizing an alicyclic unsaturated hydrocarbon represented by the formula (1) with a catalyst to obtain an addition polymer containing a phenolic hydroxyl group.

Specifically, the hydroxyl aromatic compound is heated and melted, and a catalyst is added thereto to uniformly dissolve it,
The alicyclic unsaturated hydrocarbon is added dropwise at 50 to 180 ° C, preferably 80 to 150 ° C. As for the usage ratio of each raw material,
Although not particularly limited, the catalyst is 0.001 to 0.1 mol, preferably 0.1 to 0.1 mol with respect to 1 mol of the alicyclic unsaturated hydrocarbon.
005 to 0.10 mol, and the hydroxyl aromatic compound is 0.1 to 10.0 mol, preferably 0.3 to 4 mol. Further, in this reaction, the hydroxyl aromatic compound may be added to the place where the alicyclic unsaturated hydrocarbon and the catalyst are melt-mixed.

The catalyst used here is, for example, AlC.
l ₃ , BF ₃ , ZnCl ₂ , H ₂ SO ₄ , TiCl ₄ , H ₃ P
Examples thereof include Lewis acids such as O ₄ .

As the biphenols (b), any of the above-mentioned phenols can be used, and specifically, a compound in which two molecules of phenols are bound by a direct coupling reaction is shown and is not limited to a specific compound. It's not something
For example biphenol, 4,4'-hydroxy-3,
3 ', 5,5'-tetrabiphenyl, 4,4'-hydroxy-3,3', 5,5'-tetrachlorobiphenyl,
4,4'-hydroxy-3,3 ', 5,5'-tetrabromobiphenyl and the like can be mentioned. Among them, biphenol, 4,4′-hydroxy-3,3 ′, 5,5′-tetrabiphenyl are particularly preferable because they have excellent heat resistance and curability. Above all, as described above, when using biphenol, an epoxy resin composition having extremely excellent fluidity and heat resistance can be obtained, and according to the production method of the present invention, an epoxy resin mixture can be extremely easily prepared. preferable.

The epoxy resin mixture thus obtained is not particularly limited, but has a melt viscosity at 150 ° C. of 0.1 because the low melt viscosity of the cured product becomes more remarkable.
It is preferably in the range of up to 2.0 poise.

Further, the softening point of the epoxy resin mixture is 70 ° C. from the viewpoint that the cured product has excellent heat resistance.
It is preferably above the temperature range, and particularly preferably 70 to 110 ° C.

Therefore, the reactant has a melt viscosity of 0.1 at 150 ° C., that is, a range satisfying these conditions.
To 2.0 poise and softening point of 70 ° C
Above all, it is preferable that the temperature is 70 to 110 [deg.] C. because these characteristics are well balanced.

Further, as described above, the epoxy resin mixture contains a polyglycidyl ether (A) of a compound in which a cycloaliphatic hydrocarbon group is bonded to a hydroxyl aromatic compound and a diglycidyl ether of a biphenol ( B) as a main component, and as another component, a copolymer of a polyglycidyl ether (A) of a compound in which a cycloaliphatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a binding group and a biphenol, Alternatively, it contains a copolymer of a diglycidyl ether of a biphenol (B) and a compound in which a cycloaliphatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a binding group, and polyglycidyl is contained in the mixture. Ether (A)
It is preferable that the total amount of the diglycidyl ether (B) and the diglycidyl ether (B) is 50 to 90% by weight, from the viewpoint that the effect of the present invention becomes remarkable, and it is preferably 60 to 80% by weight.

In the epoxy resin composition of the present invention,
As the epoxy resin component, a mixture of polyglycidyl ether (A) and diglycidyl ether (B) or an epoxy resin mixture obtained by the production method of the present invention is used, but the effect of the present invention is not impaired. Other epoxy resins may be used together in an arbitrary ratio within the range. Considering the degree of the effect of the present invention described above, it is preferable to use other epoxy resins in combination at 50% by weight or less based on the total weight of the epoxy resin and the curing agent.

The epoxy resin that can be used in combination is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, BPA novolac type epoxy resin, naphthol novolac type. Epoxy resin, biphenol type epoxy resin, brominated phenol novolac type epoxy resin, brominated BPA type epoxy resin, cresol-naphthol co-compressed novolac type epoxy resin, dihydroxynaphthalene type epoxy resin, glycidyl amine type tetrafunctional epoxy resin, etc. You can Among these, the cresol novolac type epoxy resin is preferable because it is excellent in heat resistance and curability.

The curing agent used in the epoxy resin composition of the present invention is also not particularly limited, but examples thereof include phenol novolac type resins, alkyl-substituted phenol novolac type resins, BPA novolac type resins, and xyloc type phenols. Hardeners, dihydroxynaphthalene, phenol-naphthol cocondensed novolac resins, naphthol novolak resins, naphthol-based hardeners such as dihydroxynaphthalene novolac resins, aliphatic amines such as diethylenetriamine and triethylenetetraamine, diaminodiphenylamine, diaminodiphenylsulfone, etc. Aromatic amines, polyamide resins and modified products thereof, acid anhydride type curing agents such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride and pyroperitic anhydride Anjiamido, imidazole, BF
Examples include latent curing agents such as 3 complexes and guanidine derivatives. These curing agents may be used alone or in combination of two or more.

Of these, a phenol-based curing agent is preferable because of its excellent curability. As a use ratio of the curing agent, usually, the epoxy group of the epoxy resin and the active hydrogen in the curing agent are in the equivalent ratio of the former / the latter = 0.8 to 1.2, preferably used in the equivalent ratio. You can

Further, if necessary, a curing accelerator may be used, and as the usable one, a known curing accelerator for an epoxy resin may be used, and examples thereof include tertiary phosphines, imidazoles, and Tertiary amines and the like can be used. Specifically, examples of the tertiary phosphines preferably include triethylphosphine, tributylphosphine, triphenylphosphine, and the like. Examples of the tertiary amines include dimethylethanolamine, dimethylbenzylamine, 2,
4,6-Tris (dimethylamino) phenol, 1,8
Preferred examples include diazabicyclo [5,4,0] undecene. Examples of imidazoles include 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole,
1-vinyl-2-methylimidazole, 1-propyl-
2-methylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-
Cyanoethyl-2-ethyl-4-methylimidazole,
1-Cyanoethyl-2-undecylimidazole, 1-
Cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-
Examples thereof include phenyl-4-methyl-5-hydroxymethylimidazole. Among these, 2-methylimidazole, diazabicycloundecene (DBU), triphenylphosphine, and dimethylbenzylamine are excellent in heat resistance, water resistance, electrical characteristics, and the like, and are excellent in stability in semiconductor encapsulation material applications. And mixtures thereof are preferred.

The proportion of the curing accelerator used is not particularly limited, but it is usually 0. 0 with respect to the resin component in the composition.
It is in the range of 05 to 0.30% by weight, preferably 0.5 to 0.20% by weight.

In the epoxy resin composition of the present invention, an inorganic filler may be used in each of the above components, if necessary. Examples of the inorganic filler include fused or crystalline silica powder, glass fiber, carbon fiber and carbonic acid. Calcium, quartz, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, diatomaceous earth, calcined clay, carion, mica,
Examples include asbestos, pulp, wood flour and the like. The blending ratio of the inorganic filler can be appropriately selected according to the purpose of use, but is usually 50 to 90% by weight with respect to the entire composition.
And the range of 65 to 85% by weight is preferable. Furthermore, in the case of using a high filling of 73 to 85% by weight, the moisture resistance of the cured product becomes extremely remarkable, which is more preferable.

If necessary, flame retardants such as antimony trioxide and hexabromobenzene, coloring agents such as carbon black and red iron oxide, releasing agents such as natural wax and synthetic wax, and low stress such as silicone oil and rubber. It can be obtained by appropriately mixing various additives such as additives. Further, as the flame retardant, a brominated phenol novolac type epoxy resin or a brominated BPA type epoxy resin exemplified as the other epoxy resins which can be used in combination can be used as the flame retardant.

Further, in order to prepare a molding material from the epoxy resin composition of the present invention, the epoxy resin, the curing agent, the curing accelerator, and other additives are sufficiently and uniformly mixed with a mixer or the like, and then a heat roll is further added. Alternatively, it can be obtained by melt-kneading with a kneader or the like and performing transfer molding or injection molding.

The semiconductor encapsulating material of the present invention is the epoxy resin composition of the present invention containing the above-mentioned epoxy resin and curing agent as essential components, and further containing an inorganic filler as an essential component. Similarly, the other epoxy resin as exemplified above and the curing agent may be used together in an arbitrary ratio, and similarly, if necessary, other curing accelerators and additives as exemplified above. May be used.

As the inorganic filler used in the semiconductor encapsulating material of the present invention, any of the above-mentioned ones can be used, but in general, silica powder filler and the like can be preferably used. The compounding ratio of the inorganic filler used in the epoxy resin composition for encapsulant of the present invention is usually 50 with respect to the entire semiconductor encapsulant.
Is 90 to 90% by weight, and particularly preferably 65 to 85% by weight.

To prepare a molding material using the semiconductor encapsulating material of the present invention, an epoxy resin, a phenol resin, a curing accelerator, an inorganic filler, and other additives are sufficiently uniformly mixed with a mixer or the like. Alternatively, it can be obtained by melt-kneading with a hot roll or a kneader and performing low-pressure transfer molding or injection molding.

[0051]

The present invention is described in detail below with reference to examples, but the present invention is not limited thereto. Each test method in Examples and Comparative Examples is as follows.

[Evaluation method] Glass transition temperature: A test piece was cut out and a viscoelasticity measuring device (D
Measured by MA). Water absorption rate: Calculated from the weight increase rate after treatment for 300 hours under the conditions of 85 ° C. and 85% RH.

Gel time: Measure the time to gelation on a cure plate at 175 ° C. Melt viscosity: It is the viscosity measured by an ICI cone plate type viscometer at 150 ° C. at the time of compounding.

Example 1 Dicyclopentadiene-phenol polyadduct type epoxy resin (E1) (epoxy equivalent: 263 g / eq, softening point: 65 ° C., melt viscosity at 150 ° C. by ICI cone plate viscometer: 0.8 poise: Dainippon Ink and Chemicals, Inc., EPICLON EXA-7200)) 56 parts by weight 4,4′-di (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethyl-biphenol (E2 ) (Epoxy equivalent 194 g / eq, softening point 105 ° C., melt viscosity at 150 ° C. 0.1 poise: “YX-4000H” manufactured by Yuka Shell Epoxy Co., Ltd.) 14 parts by weight Phenol novolac resin (H1) Equivalent weight 104 g / eq, softening point 80 ° C .: Dainippon Ink and Chemicals, Inc. Phenolite TD-2131) 30 parts by weight Triphenylphosphine 0.7 parts by weight After melting mixed and cured 5 hours at 175 ° C. to create a cast plate were evaluated heat resistance and water resistance. The results are shown in Table 1-1.

Example 2 Evaluations were made in the same manner as in Example 1 except that the epoxy resin and the curing agent were changed to the following. The results are shown in Table 1-1.

Epoxy resin (E1) 34 parts by weight Epoxy resin (E2) 34 parts by weight Phenol novolac resin (H1) 32 parts by weight Triphenylphosphine 0.7 parts by weight

Example 3 Evaluations were made in the same manner as in Example 1 except that the epoxy resin and the curing agent were changed to the following. The results are shown in Table 1-1.

Epoxy resin (E1) 41 parts by weight Epoxy resin (E2) 17 parts by weight Phenol-aralkyl resin (H2) (hydroxyl equivalent 175 g / eq, softening point 75 ° C., melt viscosity at 150 ° C. 3.1 poise, Mitsui Higashi Pressure Chemical Co., Ltd. Millex "XL-225-LL") 42 parts by weight Triphenylphosphine 0.7 parts by weight

Example 4 Evaluations were made in the same manner as in Example 1 except that the following epoxy resin and curing agent were used. The results are shown in Table 1-1.

Dicyclopentadiene-cresol polyaddition type epoxy resin (E3) (epoxy equivalent 280 g / eq, softening point 58 ° C., melt viscosity at 150 ° C. 0.7 poise) 56 parts by weight Epoxy resin (E2) 14 parts by weight Parts Phenol novolac resin (H1) 30 parts by weight Triphenylphosphine 0.7 parts by weight

Example 5 Evaluations were made in the same manner as in Example 1 except that the epoxy resin and the curing agent were changed to the following. The results are shown in Table 1-1.

3a, 4,7,7a-Tetrahydroindene-phenol polyadduct type epoxy resin (E4) (epoxy equivalent: 275 g / eq, softening point: 60 ° C., melt viscosity of 150 ° C. measured by an ICI cone plate type viscometer. 5 Poise: EPICLON EXA-7861L manufactured by Dainippon Ink and Chemicals, Inc. 41 parts by weight Epoxy resin (E2) 28 parts by weight Phenol novolac resin (H1) 31 parts by weight Triphenylphosphine 0.7 parts by weight

Example 6 Evaluations were made in the same manner as in Example 1 except that the epoxy resin and the curing agent were changed to the following. The results are shown in Table 1-1.

Limonene-phenol polyaddition type epoxy resin (E5) (epoxy equivalent 250 g / eq, softening point 56 ° C., melt viscosity at 150 ° C. by ICI cone plate viscometer 0.4 poise) 55 parts by weight epoxy resin (E2) 14 parts by weight Phenol novolac resin (H1) 31 parts by weight Triphenylphosphine 0.7 parts by weight

Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that the epoxy resin and the curing agent were changed to the following. The results are shown in Table 1-2.

Epoxy resin (E1) 72 parts by weight Phenol novolac resin (H1) 28 parts by weight Triphenylphosphine 0.7 parts by weight

Comparative Example 2 Evaluation was made in the same manner as in Example 1 except that the epoxy resin and the curing agent were changed to the following. The results are shown in Table 1-2.

Epoxy resin (E2) 65 parts by weight Phenol novolac resin (H1) 35 parts by weight Triphenylphosphine 0.7 parts by weight

Comparative Example 3 Evaluation was made in the same manner as in Example 1 except that the epoxy resin and the curing agent were changed to the following. The results are shown in Table 1-2.

Epoxy resin (E1) 60 parts by weight Phenol-aralkyl resin (H2) 40 parts by weight Triphenylphosphine 0.6 parts by weight

Comparative Example 4 Orthocresol novolac type epoxy resin (E6) (epoxy equivalent: 208 g / eq, softening point: 67 ° C., melt viscosity at 150 ° C. by ICI cone plate type viscometer 3.0 poise: Dainippon Ink and Chemicals ( EPICLON N-665) 67 parts by weight Phenol novolac resin (H1) 33 parts by weight Triphenylphosphine 0.7 parts by weight

[0072]

[Table 1] (In 1 of Table 1, the blending amount is based on weight)

[0073]

[Table 2] (In 2 of Table 1, the blending amount is based on weight)

Example 7 DCP resin (P1) (hydroxyl equivalent 169 g / eq, softening point 9
320 g of melt viscosity 1.7 poise (150 ° C.) by ICI cone plate type viscometer and biphenol 80 at 0 ° C.
g was dissolved in 1070 g of epichlorohydrin, and 510 g of 20% NaOH aqueous solution was added dropwise at 70 ° C. while stirring for 3 hours. Then, stirring is continued for 1 hour, and the mixture is allowed to stand still and the lower layer saline is discarded. Excess epichlorohydrin was recovered by distillation, and methyl isobutyl ketone 8 was added to the crude resin.
Inorganic impurities are removed by adding 00 g and 200 g of water. Then, after dehydration by heating, it is refined by microfiltration and the solvent is distilled and recovered to obtain a brown epoxy resin mixture (E7) 5
00g was obtained.

The epoxy resin mixture has an epoxy equivalent of 2
53 g / eq, softening point 108 ° C., melt viscosity at 150 ° C. by an ICI cone plate type viscometer of 0.4 poise, 68% by weight of polyglycidyl ether of DCP resin and 17% by weight of diglycidyl ether of biphenol in the mixture.
Met.

Example 8 120 g of biphenol and 147 of epichlorohydrin
Brown epoxy resin (E8) 53 in the same manner as in Example 7 except that 0 g and a 20% NaOH aqueous solution were replaced with 700 g.
0 g was obtained. Epoxy equivalent 231g / eq, softening point 120
C., the melt viscosity at 150.degree. C. measured by an ICI cone and plate viscometer was 0.2 poise, the glycidyl ether of DCP resin was 63% by weight, and the diglycidyl ether of biphenol was 24% by weight.

Example 9 DCP resin (P1) was replaced with DCP resin (P2) (hydroxyl group equivalent 172 g / eq, softening point 101 ° C., melt viscosity 5.5 poise (150 ° C.) by ICI cone plate type viscometer) 320
g, epichlorohydrin 1060 g, 20% NaO
501 g of a brown epoxy resin mixture (E9) was obtained in the same manner as in Example 7 except that the H aqueous solution was changed to 500 g.
Epoxy equivalent of 266 g / eq, softening point of 118 g / eq, melt viscosity at 150 ° C. by ICI cone plate viscometer 1.7
Poise, the glycidyl ether of DCP resin was 65% by weight and the diglycidyl ether of biphenol was 16% by weight in the mixture.

Example 10 Biphenol was added to 4,4'-hydroxy-3,3,5,5.
520 g of a brown epoxy resin mixture (E10) was obtained in the same manner as in Example 7 except that 5180 g of epichlorohydrin and 560 g of 20% NaOH aqueous solution were used in place of 5′-tetramethylbiphenyl. Epoxy equivalent 250g / e
q, softening point 86 g / eq, melt viscosity at 150 ° C. by an ICI cone plate viscometer of 0.4 poise, glycidyl ether of DCP resin in the mixture is 68% by weight, 4,
The diglycidyl ether of 4'-hydroxy-3,3,5,5'-tetramethylbiphenyl was 16% by weight.

Example 11 DCP resin (P1) was replaced with limonene-phenol resin (P
4) Brown epoxy resin mixture (E11) 489 g in the same manner as in Example 7 except that 3) (hydroxyl equivalent 169 g / eq, softening point 89 ° C., melt viscosity 1.4 poise (150 ° C.)) was used.
Got Epoxy equivalent 249 g / eq, softening point 99 g / eq, I
The melt viscosity at 150 ° C. measured by a CI cone plate type viscometer was 0.3 poise, and the glycidyl ether of the limonene-phenol resin was 69% by weight and the diglycidyl ether of biphenol was 19% in the mixture.

Example 12 DCP resin (P1) was mixed with 3a, 4,7,7a-tetrahydroindene-phenol resin (P4) (hydroxyl equivalent 16
8 g / eq, softening point 93 ° C., melt viscosity 1.8 poise (150 ° C.) measured by an ICI cone plate type viscometer) except that a brown epoxy resin mixture (E) was used.
12) Obtained 492 g. Epoxy equivalent 252g / eq, softening point 100g / eq, 1 by ICI cone plate viscometer
The melt viscosity at 50 ° C. is 0.4 poise and 3a in the mixture,
The glycidyl ether of 4,7,7a-tetrahydroindene-phenol resin was 68% by weight, and the diglycidyl ether of biphenol was 15% by weight.

Example 13 DCP resin (P1) was replaced with dicyclopentadiene-cresol resin (P5) (hydroxyl group equivalent: 174 g / eq, softening point: 99).
C., melt viscosity by ICI cone plate viscometer 2.
3 poises (150 ℃), add epichlorohydrin to 105
A brown epoxy resin mixture (E1) was prepared in the same manner as in Example 7 except that 0 g and a 20% NaOH aqueous solution were replaced with 500 g.
3) 502g was obtained. Epoxy equivalent 242 g / eq, softening point 108 g / eq, 15 by ICI cone plate type viscometer
The melt viscosity at 0 ° C. is 0.5 poise, and the glycidyl ether of the dicyclopentadiene-cresol resin in the mixture is 6
6% by weight, diglycidyl ether of biphenol is 16
% By weight.

Comparative Example 5 Epichlorohydrin was added to 870 without using biphenol.
g, a brown epoxy resin mixture (E1) in the same manner as in Example 7 except that 410 g of 20% NaOH aqueous solution was used.
4) 410 g was obtained. Epoxy equivalent 262 g / eq, softening point 63 g / eq, ICI cone plate viscometer 150
The melt viscosity at 0 ° C. was 0.9 poise.

Comparative Example 6 860 was added to epichlorohydrin without using biphenol.
g, a brown epoxy resin mixture (E9) in the same manner as in Example 9 except that the 20% NaOH aqueous solution was changed to 410 g.
401 g was obtained. Epoxy equivalent 280g / eq, softening point 81
g / eq, melt viscosity at 150 ° C. measured by ICI cone and plate viscometer was 3.8 poise.

Composition Examples 14-21, Comparative Examples 7-9
The test results of are shown in Table 1-1 and Table-2-2. Regarding the test content, an epoxy resin, a curing agent, and an accelerator were melt-mixed in accordance with the formulation (weight basis) in the table and then cured at 175 ° C. for 5 hours to prepare a cast plate, and heat resistance and water absorption were evaluated.

[0085]

[Table 3]

[0086]

[Table 4] (In Table 1 and 2 of Table 2, the blending amount is on a weight basis, and ECN ** is a cresol novolak type epoxy resin “EPICLON”.
N-665 "(manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 211 g / eq, softening point 68 ° C., melt viscosity at 150 ° C. 3.2 poise by ICI cone plate type viscometer), phenol novolak resin * Is "Phenolite TD-213
1 "(Dainippon Ink and Chemicals, Inc., hydroxyl equivalent 10
4 g / eq, softening point 80 ° C., melt viscosity 1.5 ps. )

Table 3 shows the test results of Examples 21 to 26 and Comparative Examples 10 to 13. Next, the composition of Table 3 (weight basis)
Mix at room temperature with a mixer according to
The mixture was kneaded with a shaft roll, cooled, and then ground to obtain a molding material.
The obtained molding material is made into a tablet, and a 6 mm × 6 mm chip for solder crack test is prepared with a low pressure transfer molding machine under the conditions of 175 ° C., 70 kg / cm 2, 120 seconds.
It was sealed in a pSOP package. The following heat resistance evaluation, water resistance evaluation, fluidity evaluation of the sealed test element,
In addition, a solder crack test and a solder moisture resistance test were performed.

Solder crack test: The sealed test element was treated in an environment of 85 ° C. and 85% RH for 72 hours, then immersed in a solder bath at 240 ° C. for 10 seconds, and then external cracks were observed with a microscope.

Heat resistance test, water resistance test: same as the above composition Flowability test: 17 using a mold according to EMMI standard
The spiral flow was measured under the conditions of 5 ° C. and 70 kg / cm ² .

Void test: The sealed test element was visually observed for the void occurrence rate using an ultrasonic testing machine.

[0091]

[Table 5]

[0092]

[Table 6]

Table 2 shows the test results of Examples 27 to 34 and Comparative Examples 14 to 16. Next, in accordance with the composition (weight basis) in Table 4, they were mixed at room temperature with a mixer, kneaded at 70 to 100 ° C. with a biaxial roll, cooled and pulverized to obtain a molding material. The obtained molding material is made into a tablet, and a 6 mm × 6 mm chip for solder cracking test is put into 16p with a low-pressure transfer molding machine under the conditions of 175 ° C., 70 kg / cm 2, and 120 seconds.
It was sealed in an SOP package. The sealed test element was subjected to the following heat resistance evaluation, water resistance evaluation, fluidity evaluation, and solder crack test and solder moisture resistance test.

Solder crack test: The sealed test element was treated in an environment of 85 ° C. and 85% RH for 72 hours, then immersed in a solder bath at 240 ° C. for 10 seconds, and then external cracks were observed with a microscope.

[0095]

[Table 7]

[0096]

[Table 8] (In Table 1 and 2 in Table 4, the blending amount is based on weight, and ECN ** is a cresol novolak type epoxy resin "EPICLON".
N-665 "(Dainippon Ink and Chemicals, Inc., epoxy equivalent 211g / eq, softening point 68 ° C, melt viscosity 3.2 poise at 150 ° C by ICI cone plate type viscometer), brominated epoxy resin *** means "EPICLON 153" (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 400 g / eq, softening point 68 ° C, melt viscosity 1.0 poise at 150 ° C, bromine content 48%, phenol novolak Resin * is "Phenolite TD-2131" (Dainippon Ink and Chemicals, Inc., hydroxyl equivalent 104g / eq, softening point 80 ° C, melt viscosity 1.5ps
Is. )

[0097]

EFFECTS OF THE INVENTION According to the present invention, a method for easily obtaining an epoxy resin mixture imparting excellent low melt viscosity to a cured product, an epoxy resin composition having the above characteristics, and a high inorganic filler It is possible to provide a semiconductor encapsulating material that can be filled, is remarkably excellent in low water absorption and low linear expansion coefficient, has excellent fluidity, and is extremely easy to mold into a fine semiconductor chip.

Claims (23)

[Claims] 1. An epoxy resin composition comprising an epoxy resin and a cured product as essential components, wherein the epoxy resin comprises (A) a compound of a compound in which a cyclic aliphatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a bonding group. An epoxy resin composition comprising a combination of glycidyl ether and (B) a diglycidyl ether of a biphenol. 2. The weight fraction of polyglycidyl ether (A) and diglycidyl ether (B) is (A) /
The composition according to claim 1, wherein (B) = 95/5 to 30/70. 3. An epoxy resin is obtained by reacting a mixture of a compound (a) having a cycloaliphatic hydrocarbon group as a binding group with a hydroxyl aromatic compound and a biphenol (b) with epihalohydrin. The epoxy resin composition according to claim 1, which is an epoxy resin mixture. 4. The epoxy resin composition according to claim 3, wherein the epoxy resin has a melt viscosity at 150 ° C. in the range of 0.1 to 2.0 poise. 5. The composition according to claim 3, wherein the epoxy resin has a softening point of 70 ° C. or higher. 6. An epoxy resin comprising a compound (a) having a cycloaliphatic hydrocarbon group as a binding group bonded to a hydroxyl aromatic compound and a biphenol (b) in a weight fraction of (a) / The composition according to claim 3, 4 or 5, which is used in a ratio of (b) = 95/5 to 30/70 and reacted with epihalohydrin. 7. A cycloaliphatic hydrocarbon group based on an unsaturated bond in the molecular skeleton of dicyclopentadiene, limonene, or 3a, 4,7,7a-tetrahydroindene.
The composition according to claim 1, 2, 3, 4, 5, or 6, which is a valent hydrocarbon group. 8. The epoxy resin composition according to claim 7, wherein the hydroxyaromatic compound is phenol or cresol. 9. The composition according to claim 7, wherein the biphenol is biphenol or 4,4′-hydroxy-3,3 ′, 5,5′-tetramethylbiphenyl. 10. A compound (a) in which a cyclic aromatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a bonding group,
A process for producing an epoxy resin mixture, which comprises reacting a mixture with a biphenol (b) with epihalohydrin. 11. The cycloaliphatic hydrocarbon group is a divalent hydrocarbon group based on an unsaturated bond in the molecular skeleton of dicyclopentadiene, limonene, or 3a, 4,7,7a-tetrahydroindene. 10. The manufacturing method according to 10. 12. The method according to claim 11, wherein the hydroxyaromatic compound is phenol or cresol. 13. The method according to claim 11, wherein the biphenol is biphenol or 4,4′-hydroxy-3,3 ′, 5,5′-tetramethylbiphenyl. 14. A compound (a) in which a cyclic aromatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a bonding group,
The weight fraction with the mixture with the biphenols (b) is
(A) / (b) = 95/5 to 30/70.
The manufacturing method according to 0, 11, 12, 13 or 14. 15. A polyglycidyl ether (A) of a compound in which a cyclic aromatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a binding group, a diglycidyl ether of a biphenol (B), and a curing agent (C). A semiconductor encapsulating material containing, as an essential component, an inorganic filler (D). 16. The weight fraction of polyglycidyl ether (A) and diglycidyl ether (B) is (A) /
The semiconductor encapsulating material according to claim 15, wherein (B) = 95/5 to 30/70. 17. A compound (a) in which a polyglycidyl ether (A) and a diglycidyl ether (B) are bonded to a hydroxyl aromatic compound with a cycloaliphatic hydrocarbon group as a binding group, and a biphenol (b). The semiconductor encapsulating material according to claim 16, which is a reaction product obtained by reacting epihalohydrin with the mixture of. 18. The semiconductor encapsulating material according to claim 17, wherein the reaction product has a melt viscosity at 150 ° C. in the range of 0.1 to 2.0 poise. 19. The semiconductor encapsulating material according to claim 17, wherein the reaction product has a softening point of 70 ° C. or higher. 20. The cycloaliphatic hydrocarbon group is a divalent hydrocarbon group based on an unsaturated bond in the molecular skeleton of dicyclopentadiene, limonene, or 3a, 4,7,7a-tetrahydroindene. 15, 16, 17, 18
Alternatively, the semiconductor encapsulating material according to Item 19. 21. The semiconductor encapsulating material according to claim 20, wherein the hydroxyaromatic compound is phenol or cresol. 22. The method according to claim 20, wherein the biphenol is biphenol or 4,4′-hydroxy-3,3 ′, 5,5′-tetramethylbiphenyl. 23. The reaction product comprises a compound (a) having a cycloaliphatic hydrocarbon group as a binding group bonded to a hydroxyl aromatic compound and a biphenol (b) in a weight fraction (a). The semiconductor encapsulating material according to any one of claims 17 to 22, which is used by reacting with epihalohydrin at a ratio of / (b) = 95/5 to 30/70.