JP5721519B2 - Phenol polymer, its production method and its use - Google Patents

Description

  The present invention relates to a phenolic polymer, a process for producing the same, and a use thereof. More specifically, the present invention relates to a phenolic polymer suitable for use in a semiconductor sealing material having a low melt viscosity and high flame retardancy, a composition thereof, and a method for producing the same.

  When used as a curing agent for epoxy resins, phenol aralkyl resins have excellent physical properties such as heat resistance, moisture resistance, mechanical properties, etc., and low viscosity resins can be produced and workability is good. And is used as a resin for surface mounting, particularly as a semiconductor sealing resin.

  Particularly in recent years, as semiconductor packages have become smaller, thinner and more complicated in shape, semiconductor sealing resins are increasingly required to have low viscosity. As a result of this improvement, it becomes possible to deal with packages with complex shapes, such as BGA, and because it is possible to increase the filling of the filler, it is advantageous in terms of flame resistance, solder heat resistance, and moisture resistance reliability. . Recently, in addition to this, there has been a movement to reduce or eliminate substances that may be harmful due to the importance of corporate activities in consideration of the global environment. Epoxy has excellent flame resistance without using halogenated flame retardants and antimony compounds. The demand for resin compositions is increasing, and phenol aralkyl resins used in applications ranging from general-purpose packages to advanced packages are also required to have excellent flame retardancy without using halogen flame retardants and antimony compounds. (For example, Patent Document 1).

  According to a recent invention, a modified product of a phenol aralkyl resin using an m-xylene-formalin-methanol condensate has been reported, which has higher fluidity than a phenol aralkyl resin but is flame retardant, heat resistant, The curability and softening point have the same characteristics as the conventional phenol aralkyl resin (Patent Document 2), but in the future, higher fluidity is required than ever for the above reasons. There is a need for an improved approach to further specialize high fluidity by narrowing down practical properties. In other words, the conventional improved approach is limited in improving the high fluidity so as to maintain all the practical characteristics of the current product, and considering only the minimum necessary practical characteristics in view of future needs trends. If various characteristic items were appropriately selected so that they could be maintained, there was room for further fluidization.

JP 5-97965 JP2009-242480

  An object of the present invention is to provide a phenolic polymer having a flame retardancy and a softening point equivalent to those of conventional phenol aralkyl resins and having a remarkably low viscosity, a composition thereof, and a method for producing the same.

  In the reaction of the phenols represented by the following general formula (1), the aromatic compound represented by the following general formula (2), and the condensate of m-xylene, formaldehyde and methanol, the molar ratio of the aromatic compound to the phenols Is a condensate of m-xylene, formaldehyde, and methanol having an oxygen content of 10 to 20 wt%, a viscosity at 25 ° C of 70 to 150 mPa · s, and a number average molecular weight of 200 to 350. Provided is a phenolic polymer obtained by reacting under the condition of 35 to 50 wt% of the similar weight.

(In formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and in formula (2), X is a halogen, OH group or OCH ₃ group.)

  The present invention provides an epoxy resin composition comprising the above-described phenolic polymer and an epoxy resin.

  In the reaction of the phenol represented by the general formula (1), the aromatic compound represented by the general formula (2), and the condensate of m-xylene / formaldehyde / methanol, the molar ratio of the aromatic compound to the phenol Is a condensate of m-xylene, formaldehyde, and methanol having an oxygen content of 10 to 20 wt%, a viscosity at 25 ° C of 70 to 150 mPa · s, and a number average molecular weight of 200 to 350. Provided is a method for producing a phenolic polymer obtained by reacting under the condition that 35 to 50 wt% of the similar weight is used.

  ADVANTAGE OF THE INVENTION According to this invention, the phenolic polymer effective for a molding material, various binders, a coating material, a laminated material, etc. and its manufacturing method are provided.

  According to the present invention, it is particularly useful as an epoxy resin curing agent, and particularly when used for semiconductor sealing, it forms an epoxy resin composition that has both extremely high fluidity while having both cold flow resistance and flame resistance. A phenolic polymer that can be used, and an epoxy resin composition thereof are provided.

  In the reaction with the phenol represented by the general formula (1), the aromatic compound represented by the general formula (2), and the condensate of m-xylene, formaldehyde and methanol, the present invention Of m-xylene / formaldehyde / methanol having a molar ratio of 0.10 to 0.20, an oxygen content of 10 to 20 wt%, a viscosity at 25 ° C. of 70 to 150 mPa · s, and a number average molecular weight of 200 to 350 Provided is a phenol polymer obtained by reacting the condensate under a condition that 35 to 50 wt% of the phenol is used.

  In the reaction with the phenol represented by the general formula (1), the aromatic compound represented by the general formula (2), and the condensate of m-xylene, formaldehyde and methanol, the present invention Of m-xylene / formaldehyde / methanol having a molar ratio of 0.10 to 0.20, an oxygen content of 10 to 20 wt%, a viscosity at 25 ° C. of 70 to 150 mPa · s, and a number average molecular weight of 200 to 350 Provided is a method for producing a phenol-based polymer obtained by reacting the condensate under the condition that 35 to 50 wt% of the phenol is used.

  Examples of the phenols represented by the general formula (1) include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6- Examples include monocyclic phenol compounds such as xylenol, 3,4-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, and the use of one or more of them. However, phenol is particularly preferable.

  The condensate of m-xylene / formaldehyde / methanol used in the present invention is an oligomer mixture having a structure in which m-xylene is crosslinked with a methylene group and having a reactive functional group capable of crosslinking via the methylene group. is there. These can be obtained by condensing m-xylene, formaldehyde, and methanol in the presence of an acidic catalyst, and an index of reactivity is given by oxygen content (Japanese Patent Laid-Open No. 10-168147). The oxygen content of the condensate of m-xylene / formaldehyde / methanol, viscosity at 25 ° C. and number average molecular weight depend on the ratio of m-xylene, formaldehyde and methanol as raw materials, but considering the balance between flame resistance and fluidity, The oxygen content is preferably 10 to 20 wt%, the viscosity at 25 ° C. is 70 to 150 mPa · s, and the number average molecular weight is preferably in the range of 200 to 350. This compound is commercially available and can be easily obtained. (For example, “Nikanol Y-100” manufactured by Fudou Co., Ltd.).

  Examples of the aromatic compound represented by the general formula (2) include 1,4-di (chloromethyl) benzene, 1,4-di (bromomethyl) benzene, 1,4-di (iodomethyl) benzene, 1,4- Examples include di (hydroxymethyl) benzene and 1,4-di (methoxymethyl) benzene. Of these aromatic compounds, 1,4-di (chloromethyl) benzene is preferably used from the viewpoint of availability.

  The phenolic polymer shown above is reacted with a phenol represented by the general formula (1), an aromatic compound represented by the general formula (2), and a condensate of m-xylene / formaldehyde / methanol. Can be obtained.

  In the reaction of the phenol represented by the general formula (1), the aromatic compound represented by the general formula (2), and the condensate of m-xylene / formaldehyde / methanol, an appropriate molecular weight and a curing agent for epoxy resin In order to obtain a phenolic polymer having an excellent performance as a molar ratio of aromatic compound to phenol, 0.10 to 0.20, preferably 0.12 to 0.15, m-xylene, formaldehyde, The methanol condensate may be reacted at 35-50 wt%, preferably 40-45 wt% of the weight of phenols.

The above reaction can be obtained by reacting at a temperature of about 60 to 150 ° C. for about 1 to 10 hours in the presence or absence of a catalyst. That is, in the formula (2), when X is an OH group or OCH ₃ group, it is necessary to carry out the reaction in the presence of an acid catalyst, and when X is a halogen in the formula (2), a slight amount is required. The reaction can be initiated by the presence of water and can be accelerated by the hydrogen halide produced by the reaction.

  Catalysts usable in the above reaction include inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, zinc chloride, and second chloride. Lewis acid catalysts such as tin and ferric chloride can be used alone or in combination.

  When the product phenolic polymer is used for electronic material applications such as semiconductor encapsulation, it is not preferable that the acid remains. Therefore, by using hydrochloric acid as the acid catalyst, the condensation reaction mixture is chlorinated under reduced pressure. Hydrogen is preferred because it can be easily removed.

  By removing low-boiling components such as unreacted raw materials, reaction byproducts, and catalysts from the condensation reaction mixture obtained by the condensation reaction, the phenolic polymer that is a reaction product can be recovered. Such a reaction product has an ICI melt viscosity at 150 ° C. of 10 to 60 mPa · s, preferably 20 to 40 mPa · s. The separation operation under reduced pressure, which is performed for removing unreacted raw materials in the reaction product, is usually performed at a temperature of 130 ° C. or higher, so that the molten reaction product obtained by the operation is used as it is. By quenching and solidifying, it can be isolated as an amorphous solid having a softening point (JIS K2207) of about 55 to 70 ° C. If the softening point is within the above temperature range, cold flow during storage is not a problem in practical use, but if the balance between high fluidity and cold flow resistance required by the present invention is further taken into consideration, the temperature range is 60 to 65. More preferably, it is ° C.

  The phenolic polymer, which is the reaction product thus obtained, has no cold flow during storage, has a low melt viscosity in the molding temperature range and excellent workability, and its cured product has excellent flame resistance. It can be used for molding materials, various binders, coating materials, laminated materials and the like. Therefore, it is useful as an epoxy resin curing agent, and when used as a curing agent in an epoxy resin-based semiconductor encapsulant, there is no cold flow, and an epoxy resin composition with excellent fluidity is obtained. Excellent.

  Examples of the epoxy resin that can be used with the phenolic polymer in the epoxy resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and biphenyl type. Epoxy resins, phenol biphenyl aralkyl type epoxy resins, epoxidized aralkyl resins with xylylene bonds such as phenol and naphthol, glycidyl ether type epoxy resins such as dicyclopentadiene type epoxy resin, dihydroxynaphthalene type epoxy resin and triphenolmethane type epoxy resin Epoxy compounds having two or more epoxy groups in one molecule such as glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, etc. It is below. These epoxy resins may be used alone or in combination of two or more. In consideration of moisture resistance, low elastic modulus during heat and flame retardancy, bifunctional epoxy resins such as bisphenol F type epoxy resin and biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, xylylene such as phenol and naphthol It is preferable to use a polyfunctional epoxy resin having many aromatic rings selected from epoxidized aralkyl resins by bonding.

  In curing the epoxy resin, it is preferable to use a curing accelerator in combination. As such a curing accelerator, a known curing accelerator for curing an epoxy resin with a phenol resin curing agent can be used. For example, a tertiary amine compound, a quaternary ammonium salt, an imidazole, a phosphine compound, a phosphonium A salt etc. can be mentioned. More specifically, tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 , 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, triphenylphosphine, tributylphosphine, tri (p -Phosphine compounds such as methylphenyl) phosphine and tri (nonylphenyl) phosphine, phosphonium salts such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphoniumtetranaphthoic acid borate, and triphenylphosphonio Enorato, it may be mentioned betaines like organic phosphorus compounds such as the reaction product of benzoquinone and triphenyl phosphine. Among these, from the viewpoint of low water absorption and reliability, use of a phosphine compound, a phosphonium salt, and a betaine-like organic phosphorus compound is preferable.

  In the epoxy resin composition of the present invention, an inorganic filler, a coupling agent, a release agent, a colorant, a flame retardant, a low stress agent, or the like can be added or reacted in advance if necessary. Other curing agents can be used in combination. Examples of such other curing agents include phenol novolak resins, phenol aralkyl resins, phenol biphenyl aralkyl resins, phenol naphthyl aralkyl resins, naphthol aralkyl resins, and triphenolmethane type novolak resins.

  When using the said epoxy resin composition for semiconductor sealing, addition of an inorganic filler is essential. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesia, barium sulfate, etc. Silica, crystalline silica, and barium sulfate are preferred. In order to increase the blending amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine packing.

  Examples of coupling agents include mercaptosilane-based, vinylsilane-based, aminosilane-based, and epoxysilane-based silane coupling agents and titanium coupling agents. Examples of mold release agents include carnauba wax, paraffin wax, and coloring. Examples of the agent include carbon black. Examples of the flame retardant include phosphorus compounds and metal hydroxides, and examples of the low stress agent include silicon rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.

  The mixing ratio of the phenolic polymer and the epoxy resin of the present invention is such that the equivalent ratio of hydroxyl group / epoxy group is 0.5 to 1.5, particularly 0.8 to 1.2, considering heat resistance, mechanical properties and the like. It is preferable that it exists in the range. Further, even when used in combination with another curing agent, it is preferable that the equivalent ratio of hydroxyl group / epoxy group is the above-mentioned ratio. The curing accelerator is preferably used in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin in consideration of curing characteristics and various physical properties. Furthermore, in an epoxy resin composition for semiconductor encapsulation, although it varies depending on the type of inorganic filler, considering the solder heat resistance, moldability (melt viscosity, fluidity), low stress, low water absorption, etc., it is inorganic. It is preferable to blend the filler in a proportion that occupies 60 to 93% by weight of the entire composition.

  As a general method for preparing an epoxy resin composition as a molding material, a predetermined proportion of each raw material is sufficiently mixed by, for example, a mixer, then kneaded by a hot roll or a kneader, and further cooled and solidified. Examples of the method include pulverization of a large size and tableting as necessary. The molding material thus obtained can be used for sealing a semiconductor by, for example, low-pressure transfer molding to manufacture a semiconductor device. Curing of the epoxy resin composition can be performed, for example, in a temperature range of 100 to 250 ° C.

  The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples.

[Example 1]
Phenol 1347.7 g (14.336 mol), 1,4-di (chloromethyl) benzene 350.0 g (2.000 mol), and Nikanol Y-100 (manufactured by Fudou Co., Ltd., number average molecular weight 270) 592. When 7g was charged into a four-necked flask with an outlet at the bottom and the temperature was raised, the system became a slurry state at 50 ° C, and evenly melted at 70 ° C, and generation of hydrogen chloride started. After holding for 1 hour, the temperature was raised, the temperature was kept at 95 ° C. for 2 hours, and then heat treatment was added at 150 ° C. for 1 hour. Hydrogen chloride produced in the reaction was volatilized out of the system as it was and trapped with alkaline water. At this stage, unreacted 1,4-di (chloromethyl) benzene did not remain, and it was confirmed by gas chromatography that all had reacted. After completion of the reaction, the pressure was reduced to remove hydrogen chloride remaining in the system and unreacted phenol out of the system. Finally, the residual phenol was not detected by gas chromatography by reducing the pressure to 150 ° C. at 30 torr. This reaction product was extracted while maintaining at 150 ° C. to obtain 1389.6 g of a pale yellowish brown and transparent phenol polymer (1).
The softening point of this phenolic polymer (1) based on JIS K 2207 was 61 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 20 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylated back titration method was 178 g / eq. After pulverizing this phenolic polymer (1) into particles of 3 mm or less, 150 g of this pulverized product was spread in a square space of 10 cm × 10 cm and left standing at 15 ° C. for 1 month with a load of 7 kg. Not observed.

[Example 2]
Epoxy resin represented by the following general formula (3) (Nippon Kayaku Co., Ltd. NC-3000P, phenol biphenyl aralkyl type, epoxy equivalent 272 g / eq), phenolic polymer (1) obtained in Example 1, molten Silica and phosphorus-based curing accelerator tetraphenylphosphonium tetra-p-methylphenylborate (Hokuko Sangyo Co., Ltd., TPP-MK) were blended in the proportions shown in Table 2 and mixed well, and then 2 at 85 ± 3 ° C. The molding composition was obtained by kneading with this roll for 3 minutes, cooling and grinding. This molding composition was molded at 175 ° C. for 2 minutes at a pressure of 100 kgf / cm 2 using a transfer molding machine, and then post-cured at 180 ° C. for 6 hours to obtain test pieces for measuring the glass transition temperature and for the flame retardancy test. .

(In the formula, G is a glycidyl group, and n is a number of 1 to 10.)

[Comparative Example 1]
A phenol aralkyl resin represented by the following general formula (4) (manufactured by Air Water Co., Ltd., HE100C-10) was used as the phenol polymer (2).
The softening point of this phenol polymer (2) based on JIS K 2207 was 63 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 100 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylated back titration method was 168 g / eq. After pulverizing this phenolic polymer (2) into particles of 3 mm or less, 150 g of this pulverized product was spread in a 10 cm × 10 cm square space and left to stand at 15 ° C. for 1 month under a load of 7 kg. Not observed.

(In the formula, n is a number of 1 to 8.)

[Comparative Example 2]
168.8 g (1.796 mol) of phenol, 77.0 g (0.440 mol) of 1,4-di (chloromethyl) benzene and 30.4 g of Nicanol Y-100 (manufactured by Fudou Co., Ltd., number average molecular weight 270) Is added to a four-necked flask with an outlet at the bottom, and when the temperature is raised, the system becomes a slurry at 50 ° C., dissolves uniformly at 70 ° C., and generation of hydrogen chloride begins. After holding for a period of time, the temperature was raised, the temperature was kept at 95 ° C. for 2 hours, and a heat treatment was further added at 150 ° C. for 1 hour. Hydrogen chloride produced in the reaction was volatilized out of the system as it was and trapped with alkaline water. At this stage, unreacted 1,4-di (chloromethyl) benzene and nicanol did not remain, and it was confirmed by gas chromatography that all had reacted. After completion of the reaction, the pressure was reduced to remove hydrogen chloride remaining in the system and unreacted phenol out of the system. Finally, the residual phenol was not detected by gas chromatography by reducing the pressure to 150 ° C. at 30 torr. The reaction product was withdrawn while maintaining at 150 ° C. to obtain 152.1 g of a pale yellowish brown and transparent phenol polymer (3).
The softening point of this phenol polymer (3) based on JIS K 2207 was 64 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 50 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 175 g / Eq. After pulverizing this phenolic polymer (3) into particles of 3 mm or less, 150 g of this pulverized product was spread in a 10 cm × 10 cm square space and left to stand at 15 ° C. for 1 month under a load of 7 kg. Not observed.

[Comparative Example 3]
In Example 2, a molding composition was prepared in the same manner except that the phenolic polymer (2) of Comparative Example 1 was used in place of the phenolic polymer (1) obtained in Example 1, and the glass transition was obtained therefrom. Test pieces for temperature measurement and flame retardancy test were obtained.

[Comparative Example 4]
In Example 2, a molding composition was prepared in the same manner except that the phenolic polymer (3) obtained in Comparative Example 2 was used instead of the phenolic polymer (1) obtained in Example 1. Test pieces for glass transition temperature measurement and flame retardancy test were obtained.

The physical properties of these molding materials were measured by the following method.
(1) Melt viscosity of the composition 2.5 g of the epoxy resin composition was tableted and measured with a high and low flow tester (temperature 175 ° C., orifice diameter 1 mm, length 1 mm).
(2) Afterflame time was measured and evaluated in accordance with UL-94 using a flame retardant thickness 1.6 mm × width 10 mm × length 135 mm sample.
These evaluation results are shown in Table 2.

  The phenolic polymers listed in Table 1 each had an equivalent softening point, and no cold flow was observed even in long-term storage assuming practical use. On the other hand, the melt viscosity [mPa · s] of the phenolic polymer of Example 1 is 0.2, and a comparative example in which the modification treatment with the same condensate of m-xylene, formaldehyde, and methanol as in Example 1 is performed. A significant reduction in viscosity was achieved by 40% lower than 0.5 of 2. From the above, it can be seen that the phenolic polymer provided by the present invention achieves a markedly low viscosity while having cold flow resistance equivalent to that of a conventional phenol aralkyl resin type curing agent.

In Table 2, it can be seen that the melt viscosity of Example 1 resin is exhibited as high fluidity when used as an epoxy resin composition. That is, the melt viscosity [Pa · s] of Example 2 is 0.7, which is a remarkably low viscosity corresponding to 70% of Comparative Example 4. In addition, since both Fmax and Ftotal are equivalent in the flame retardancy evaluation of the epoxy resin composition group in the table, the resin of Example 1 has the same cold flow resistance as that of a conventional phenol aralkyl resin type curing agent. It can be seen that in addition to the properties, the flame resistance is equivalent.
As described above, the phenolic polymer provided by the present invention imparts remarkable high fluidity while maintaining the cold flow resistance and flame resistance characteristics of the conventional phenol aralkyl resin type curing agent. It is difficult for these approaches to demonstrate these characteristics.

  The hardening | curing agent and composition which this invention provides are suitable for the high fluid type semiconductor sealing material use which combines cold flow resistance and flame resistance.

Claims (13)

In the reaction of the phenols represented by the following general formula (1), the aromatic compound represented by the following general formula (2), and the condensate of m-xylene, formaldehyde and methanol, the molar ratio of the aromatic compound to the phenols Is a condensate of m-xylene, formaldehyde, and methanol having an oxygen content of 10 to 20 wt%, a viscosity at 25 ° C of 70 to 150 mPa · s, and a number average molecular weight of 200 to 350. A phenolic polymer obtained by reacting under the condition that 35 to 50 wt% of the similar weight is used.
(In formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and in formula (2), X is a halogen, OH group or OCH ₃ group.)   The phenolic polymer according to claim 1, wherein the ICI melt viscosity at 150 ° C is 10 to 60 mPa · s, and the softening point is 55 to 70 ° C.   The phenolic polymer according to claim 1 or 2, wherein the phenol is phenol. Phenols represented by the following general formula (1), in the reaction of aromatic compounds, and m- xylene formaldehyde condensate methanol represented by the following general formula (2), the molar ratio of phenol aromatic compound Is a condensate of m-xylene, formaldehyde, and methanol having an oxygen content of 10 to 20 wt%, a viscosity at 25 ° C of 70 to 150 mPa · s, and a number average molecular weight of 200 to 350. A method for producing a phenolic polymer obtained by reacting under the condition that 35 to 50 wt% of the similar weight is used.
(In formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and in formula (2), X is a halogen, OH group or OCH ₃ group.)   The method for producing a phenolic polymer according to claim 4, wherein the ICI melt viscosity at 150 ° C is 10 to 60 mPa · s, and the softening point is 55 to 70 ° C.   The method for producing a phenolic polymer according to claim 4 or 5, wherein the phenol is phenol.   The hardening | curing agent for epoxy resins which consists of a phenol type polymer in any one of Claims 1-3.   The epoxy resin composition containing the hardening | curing agent for epoxy resins which consists of a phenolic polymer in any one of Claims 1-3, and an epoxy resin.   Furthermore, the epoxy resin composition of Claim 8 containing an inorganic filler.   Furthermore, the epoxy resin composition of Claim 8 or 9 containing a hardening accelerator.   The epoxy resin composition according to claim 8, which is for semiconductor encapsulation.   The epoxy resin hardened | cured material formed by hardening | curing the epoxy resin composition in any one of Claims 8-11.   The semiconductor device formed by sealing a semiconductor element using the epoxy resin composition of Claim 11.