JP3484681B2 - Epoxy resin composition, method for producing epoxy resin mixture, and semiconductor encapsulating material - Google Patents

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 ,
Furthermore, a semiconductor encapsulating material that can be highly filled with an inorganic filler, is remarkably excellent in low water absorption and low linear expansion coefficient, and has excellent fluidity and is extremely easy to mold into a fine semiconductor chip. To provide.

[0008]

Means for Solving the Problems As a result of intensive investigations by the present inventors, a cyclic aliphatic hydrocarbon group was used as an epoxy resin.
Compounds bound to hydroxyl aromatic compounds as linking groups
A mixture of the product (a) and the biphenols (b),
Epoxy resin mixture obtained by reacting halohydrin
By using (A ') , it was found that the cured product has a low melt viscosity and excellent fluidity, and further, in addition to these components, the semiconductor encapsulating material containing an inorganic filler as an essential component is inorganic-filled. The material can be highly filled, has a low coefficient of water absorption and a low coefficient of linear expansion, which makes it excellent in solder crack resistance and fluidity, making it extremely easy to mold fine semiconductor chips. They found out that there was something and completed the present invention.

That is, according to the present invention, (1) a hydroxy group having a cycloaliphatic hydrocarbon group as a linking group is used.
Compound (a) combined with an aromatic compound and bipheno
By reacting a mixture with the group (b) with epihalohydrin
Obtained epoxy resin mixture (A ') and curing agent
An epoxy resin composition comprising (C) as an essential component, (2) hydroxy having a cycloaliphatic hydrocarbon group as a binding group
Compound (a) combined with an aromatic compound and bipheno
By reacting a mixture with the group (b) with epihalohydrin
Obtained epoxy resin mixture (A '), curing agent
The present invention relates to a semiconductor encapsulating material containing (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) ") .
(A ') is used. Here, the higher the content of polyglycidyl ether (A), the more the heat resistance and water resistance tend to improve, while the higher the content of diglycidyl ether (B), the higher the fluidity, The melt viscosity of the cured product tends to decrease.

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 epoxy resin mixture (A ') is
It 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 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. 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.

[0015]

[0016]

[0017]

The polyglycidyl ether (A) contained in the epoxy resin mixture (A ′) has a melt viscosity of 150 ° C. in view of the fluidity when used as a sealing material and the fillable amount of the filler. In the above, 0.1 to 10 poise is preferable, and in particular, the range of 0.1 to 2.0 poise is preferable from the viewpoint that this effect becomes remarkable. Also, the measuring equipment at this time is IC
It is an I-cone plate type 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 .

Glycidyl ether (B) is an epoxy resin.
In the fat mixture (A ′), due to the effect of low melt viscosity at the time of molding, fluidity is excellent, and defects such as breakage of a fine structure package or a gold wire 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.

The epoxy resin mixture (A ') used in the epoxy resin composition of the present invention is an epoxy resin mixture obtained by the method described in detail below , and comprises polyglycidyl ether (A) and diglycidyl ether (B). 2) and melt-mixed separately, the melt viscosity can be made extremely low without degrading other performances, and the desired epoxy resin mixture can be obtained very easily. The productivity of the mixture is dramatically improved .

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 mixture which is a mixture of a diglycidyl ether of biphenol and a polyglycidyl ether (A) can be very easily avoided by avoiding such a problem.
Compound (A ') is obtained.

[0024]

Below, the epoxy resin mixture (A ')
The manufacturing method of is detailed. The method for producing an epoxy resin mixture according to the present invention comprises a compound (a) having a cycloaliphatic hydrocarbon group as a linking group and a hydroxyl aromatic compound (hereinafter,
"Compound (a)") and biphenols (b)
And a reaction with a mixture of epihalohydrin and other conditions are not limited. For example, a mixture of (a) and (b) is added to the hydroxyl group in the mixture in an amount of 1 to Examples include a method of dissolving in 20 times equivalent, preferably 2 to 10 times equivalent of epihalohydrin, and reacting in the presence of an alkali metal hydroxide at a temperature condition of 10 to 120 ° C, preferably 50 to 90 ° C. 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. 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.

In order to obtain the above-mentioned compound (a) , a hydroxyaromatic compound and a cycloaliphatic unsaturated hydrocarbon represented by dicyclopentadiene, limonene and 3a, 4,7,7a-tetrahydroindene are used as a catalyst. And a method of polymerizing the compound 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 .

Further, as the biphenols (b), specifically indicate the compound 2 molecule binds directly coupling reaction phenols, but are not limited to specific compounds, 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, heat resistance,
Biphenol and 4,4′-hydroxy-3,3 ′, 5,5′-tetrabiphenyl are particularly preferable because of their excellent curability. Above all, as described above, when using biphenol, an epoxy resin composition having extremely excellent fluidity and heat resistance is obtained, and according to the production method of the present invention, an epoxy resin mixture (A ′) is very easily obtained. It is possible and preferable.

Epoxy resin mixture thus obtained
(A ′) is not particularly limited, but it is preferable that the melt viscosity at 150 ° C. be in the range of 0.1 to 2.0 poises from the viewpoint that the melt viscosity of the cured product becomes more remarkable.

The epoxy resin mixture (A ') preferably has a softening point of 70 ° C. or higher, from the viewpoint that the cured product will have excellent heat resistance.
Particularly preferably, it is 10 ° C.

Therefore, the epoxy resin mixture (A ') is
A range satisfying these conditions, that is, a melt viscosity at 150 ° C. in a range of 0.1 to 2.0 poise, and
It is preferable that the softening point is 70 ° C. or higher, and particularly 70 to 110 ° C., because these properties are well balanced.

Further, as described above, the epoxy resin mixture (A ') comprises 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 compound. The main component is diglycidyl ether (B), and the other components are polyglycidyl ether (A), which is a compound in which a cycloaliphatic hydrocarbon group is bonded to a hydroxyl aromatic compound as a binding group, and a biphenol. The mixture contains a polymerized product or a copolymerized product of a diglycidyl ether of a biphenol (B) and a compound having a cycloaliphatic hydrocarbon group as a linking group and a hydroxyl aromatic compound. Among them, the total amount of polyglycidyl ether (A) and diglycidyl ether (B) is 50-
90% by weight is preferable from the viewpoint that the effect of the present invention becomes remarkable, and is preferably 60 to 80% by weight.

In the epoxy resin composition of the present invention,
As the epoxy resin component , the epoxy resin mixture (A ') obtained by the production method of the present invention is used, and further, other epoxy resins may be used in an optional ratio within a range not impairing the effects of the present invention. It doesn't matter. Considering the degree of the effect of the present invention described above, the ratio of their use is 50 with respect to the total weight of the epoxy resin and the curing agent.
It is preferable to use the other epoxy resin together in an amount of not more than wt%.

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.

[0054]

[0055]

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[0059]

[0060]

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[0070]

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[0073]

Example 1 DCP resin (P1) (hydroxyl group 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, refinement is carried out by microfiltration, the solvent is distilled and recovered, and a brown epoxy resin mixture (E1) 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 2 120 g of biphenol and 147 of epichlorohydrin
Brown epoxy resin (E 2 ) 53 in the same manner as in Example 1 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 in the mixture.

Example 3 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
In the same manner as in Example 1 except that the H aqueous solution was replaced with 500 g, a brown epoxy resin mixture (E 3 ) 501 g was obtained.
Epoxy equivalent is 266 g / eq, softening point is 118 ° C., melt viscosity at 150 ° C. by an ICI cone plate type viscometer is 1.7 poise, glycidyl ether of DCP resin is 65% by weight, diglycidyl ether of biphenol is 16% by weight in the mixture. %Met.

Example 4 Biphenol was added to 4,4'-hydroxy-3,3,5,5 '.
-Tetramethylbiphenyl with 1 epichlorohydrin
520 g of a brown epoxy resin mixture (E 4 ) was obtained in the same manner as in Example 1 except that 180 g and a 20% NaOH aqueous solution were replaced with 560 g. Epoxy equivalent 250g / eq, softening point 86 ℃ , ICI cone plate viscometer 15
The melt viscosity at 0 ° C. was 0.4 poise, the glycidyl ether of DCP resin in the mixture was 68% by weight, and the diglycidyl ether of 4,4′-hydroxy-3,3,5,5′-tetramethylbiphenyl was 16% by weight. %Met.

Example 5 DCP resin (P1) was replaced with limonene-phenol resin (P1)
3) (489 g of a brown epoxy resin mixture (E 5 ) was obtained in the same manner as in Example 1 except that (hydroxyl equivalent 169 g / eq, softening point 89 ° C., melt viscosity 1.4 poise (150 ° C.)) was used instead. . Epoxy equivalent 249 g / eq, softening point 99 ° C, ICI
Melt viscosity at 150 ° C measured with a cone-plate type viscometer.
It was 3 poise, and the mixture contained 69% by weight of glycidyl ether of limonene-phenol resin and 19% of diglycidyl ether of biphenol.

Example 6 DCP resin (P1) was mixed with 3a, 4,7,7a-tetrahydroindene-phenol resin (P4) (hydroxyl equivalent 16
8 g / eq, a softening point of 93 ° C., ICI cone-plate type viscosity melt viscosity 1.8 poise (0.99 ° C.) by meter) was replaced in the same manner as in Example 1 brown epoxy resin mixture (E
6 ) Obtained 492 g. Epoxy equivalent 252 g / eq, softening point 100 ° C, 150 by ICI cone plate type viscometer
It has a melt viscosity of 0.4 poise and 3a, 4, in the mixture
The glycidyl ether of 7,7a-tetrahydroindene-phenol resin was 68% by weight, and the diglycidyl ether of biphenol was 15% by weight.

Example 7 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 (E) 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.
7 ) 502g was obtained. Epoxy equivalent 242 g / eq, softening point 108 ° C, ICI cone plate viscometer 150
The melt viscosity at 0.5 ° C. was 0.5 poise, and the glycidyl ether of dicyclopentadiene-cresol resin in the mixture was 66.
% By weight, and the diglycidyl ether of biphenol was 16% by weight.

Comparative Example 1 Epichlorohydrin was added to 870 without using biphenol.
g, brown epoxy resin (E8 ) 410 in the same manner as in Example 1 except that 410 g of 20% NaOH aqueous solution was used.
g was obtained. Epoxy equivalent 262g / eq, softening point 63g / eq,
The melt viscosity at 150 ° C. measured by an ICI cone and plate viscometer was 0.9 poise.

Comparative Example 2 Epichlorohydrin was added to 860 without using biphenol.
g, a brown epoxy resin (E9) 401 in the same manner as in Example 3 except that 410 g of a 20% aqueous NaOH solution was used.
g was obtained. Epoxy equivalent 280 g / eq, softening point 81 ° C, I
The melt viscosity at 150 ° C. measured by a CI cone plate type viscometer was 3.8 poise.

Examples 8 to 14 and Comparative Examples 3 to 5 Epoxy resin, a curing agent, and an accelerator were melt-mixed according to the formulations (weight basis) in Tables, and then cured at 175 ° C. for 5 hours to prepare cast plates. Then, heat resistance and water absorption were evaluated. The results are shown in Table 1.
1 and 2 in Table 1.

[0085]

[Table 3]

[0086]

[Table 4] (1 in Table 1 and 2 in Table 1 are blending amounts by weight, ECN ** is cresol novolac type epoxy resin “EPICLON N-665” (Dainippon Ink and Chemicals, Inc.)
Made, epoxy equivalent 211g / eq, softening point 68 ° C, melt viscosity 3.2 at 150 ° C by ICI cone plate type viscometer.
Phenol novolac resin * is "Phenolite TD-2131" (manufactured by Dainippon Ink and Chemicals, Inc., hydroxyl group equivalent 104 g / eq, softening point 80 ° C, melt viscosity 1.5 ps).

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

Examples 15 to 22 and Comparative Examples 6 to 8 According to the formulations (weight basis) in Table 2 , they were mixed at room temperature with a mixer, kneaded with a twin-screw roll at 70 to 100 ° C., cooled and pulverized to form molding materials And The obtained molding material is made into tablets, which are then transferred to a low-pressure transfer molding machine at 175 ° C. and 70
6m for solder crack test under the condition of kg / cm2, 120 seconds
A 6 mm chip was encapsulated in a 16 pSOP package. The following heat resistance evaluation of the sealed test element,
Water resistance evaluation, fluidity evaluation, and solder crack test and solder moisture resistance test were performed. The test results are shown in Table 2.

Solder crack test: Sealed test element
Treat the child for 72 hours in an environment of 85-85% RH,
After immersing in a solder bath at 240 ℃ for 10 seconds
External cracks were observed at. Heat resistance test and water resistance test: According to the formulation (weight basis) in the table
After melt mixing the epoxy resin with the curing agent and the accelerator, 1
Hardened at 75 ℃ for 5 hours to make a casting plate, heat resistance and water absorption
The rate was evaluated. Flowability test: 17 using a mold according to EMMI standard
Measure the spiral flow at 5 ℃ and 70kg / cm ²
It was Void test: Use an ultrasonic testing machine for the sealed test element
The void occurrence rate was visually observed.

[0095]

[Table 7]

[0096]

[Table 8] ( 1 in Table 2 and 2 in Table 2 are blended amounts by weight, ECN ** is cresol novolak type epoxy resin “EPICLON N-665” (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent) 211 g / eq, softening point 68 ° C, I
It has a melt viscosity of 150 poise measured by a CI cone-plate viscometer of 3.2 poise), and the brominated epoxy resin *** is "EPI
CLON 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 novolac resin * is“ pheno Light TD-2131 "(manufactured by Dainippon Ink and Chemicals, Inc., hydroxyl equivalent 104 g / eq,
It has a softening point of 80 ° C. and a melt viscosity of 1.5 ps. )

[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.

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Claims (8)

(57) [Claims] 1. A cyclic aliphatic hydrocarbon group as a linking group
A compound (a) combined with a droxyl aromatic compound;
A mixture of phenols (b) and epihalohydrin
An epoxy resin composition comprising an epoxy resin mixture (A ') obtained by reaction and a curing agent (C) as essential components. 2. An epoxy resin mixture (A ′) at 150 ° C.
The epoxy resin composition according to claim 1, wherein the melt viscosity is in the range of 0.1 to 2.0 poise at. Wherein the epoxy resin mixture (A ') a softening point of 70 ° C. or more is claim 1 or 2 epoxy resin composition according to. 4. The epoxy resin mixture (A ′) comprises a compound (a) having a cycloaliphatic hydrocarbon group as a linking group bonded to a hydroxyl aromatic compound and a biphenol (b) in a weight fraction. , (A) / (b) = 95/5 to 30/7
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is used at a ratio of 0 and reacted with epihalohydrin. 5. The cyclic aliphatic hydrocarbon group is based on an unsaturated bond in the molecular skeleton of dicyclopentadiene, limonene, or 3a, 4,7,7a-tetrahydroindene.
Claim 1 epoxy resin composition wherein the valent hydrocarbon group. 6. hydroxyaromatic compound is phenol or cresol in which claim 1 epoxy resin composition. 7. biphenols biphenol- or 4,4'-hydroxy-3,3 ', epoxy resin composition according to claim 1, wherein 5,5'-tetramethyl biphenyl. 8. The eppo according to any one of claims 1 to 7.
A xy resin composition and an inorganic filler (D) as essential components
A semiconductor encapsulating material characterized by the following .